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1994 NPRA
Question and Answer Session
On Refining and Petrochemical Technology
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47th Annual
NPRA Question and Answer
Session on Refining and
Petrochemical Technology

Conducted by the
National Petroleum Refiners Association
Suite 1000, 1899 L Street, N
Washington, D.C. 20036

© 1995 National Petroleum Refiners Association

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Typesetting/Layout by:
Right Angle Graphics
4207 Underwood St.
University Park, MD 20872
Printed in U.S.A.
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TABLE OF CONTENTS

Section Category Page Section Category Page

Introduction 5 IV. LIGHT OIL CATALYTIC PROCESSING

A. Alkylation - Sulfuric Acid . . . . . . . . . . . . . 140
I. GENERAL PROCESSING & SUPPORT OPERATIONS
Feed . . . . . . . . . . . . . . . . . . . . . . . 140
A. Treating and Desalting . . . . . . . . . . . . . . 8
Mechanical . . . . . . . . . . . . . . . . . . . . 142
B. Lube Oil Manufacturing . . . . . . . . . . . . . 20
General. . . . . . . . . . . . . . . . . . . . . . 143
C. Solvent Deasphalting . . . . . . . . . . . . . . . 22
B. Alkylation - Hydrofluoric Acid . . . . . . . . . . . 144
D. Crude Distillation . . . . . . . . . . . . . . . . . 22
Feed . . . . . . . . . . . . . . . . . . . . . . . 144
Mechanical . . . . . . . . . . . . . . . . . . . 22
Process . . . . . . . . . . . . . . . . . . . . . 145
Process . . . . . . . . . . . . . . . . . . . . . 23
E. Instrumentation . . . . . . . . . . . . . . . . . 27 Mechanical . . . . . . . . . . . . . . . . . . . . 146
F. Product Formulation . . . . . . . . . . . . . . . 31 General . . . . . . . . . . . . . . . . . . . . . . 146
G. Computer/Process Control . . . . . . . . . . . . 35 C. Reforming . . . . . . . . . . . . . . . . . . . . . 149
H. Miscellaneous . . . . . . . . . . . . . . . . . . 40 Feed . . . . . . . . . . . . . . . . . . . . . . . 149
Process . . . . . . . . . . . . . . . . . . . . . 153
II. HEAVY OIL PROCESSING Mechanical . . . . . . . . . . . . . . . . . . . . 162
A. Fluid Catalytic Cracking 49 D. Aromatic Extraction . . . . . . . . . . . . . . . . 167
Mechanical . . . . . . . . . . . . . . 49 E. Polymerization . . . . . . . . . . . . . . . . . . . 169
Catalysts . . . . . . . . . . . . . . . 54 F. Isomerization . . . . . . . . . . . . . . . . . . . 171
Process . . . . . . . . . . . . . . . . 65 G. Etherification . . . . . . . . . . . . . . . . . . . 173
Environmental Control . . . . . . . . 83
B. Residual Oil Upgrading-Delayed Coking 85 V. ENVIRONMENTAL CONTROL & ENERGY CONSERVATION
Mechanical . . . . . . . . . . . . . . 85 A. Sulfur Plant Operations . . . . . . . . . . . . . . 176
Process . . . . . . . . . . . . . . . . 86 Amine Plants . . . . . . . . . . . . . . . . . . . 176
C. Residual Oil Upgrading-Fluid Coking 90 Sulfur Plants . . . . . . . . . . . . . . . . . . . 186
D. Residual Oil Upgrading-Visbreaking 91 Tail Gas Plants . . . . . . . . . . . . . . . . . . 195
B. Environmental Control . . . . . . . . . . . . . . . 196
III. HYDROGEN PROCESSING
Air Emissions . . . . . . . . . . . . . . . . . . 196
A. Hydrogen Production . . . 92
NOx and SOx Emissions . . . . . . . . . . . . . 196
Hydrogen Manufacturing . 92
Hydrocarbon Emissions . . . . . . . . . . . . . 197
Hydrogen Purification . 98
Water Issues . . . . . . . . . . . . . . . . . . . 198
B. Hydrotreating . . . . 98
Mechanical . . . . . . . Secondary Treatment . . . . . . . . . . . . . . 198
98
Process . . . . . . . General. . . . . . . . . . . . . . . . . . . . . . 200
106
Catalysts . . . . . . . Solid and Chemical Wastes . . . . . . . . . . . 202
123
C. Hydrocracking . . . . . 130 C. Energy Conservation . . . . . . . . . . . . . . . . 206
Mechanical . . . . . . . 130 Process Heaters . . . . . . . . . . . . . . . . . 206
Process . . . . . . . . . 134 Exchangers . . . . . . . . . . . . . . . . . . . 206

Memorandum . . . . . . . . . . . . . . . . . . . . . . 208
Panel Biographies . . . . . . . . . . . . . . . . . . . . 209
Participation Index . . . . . . . . . . . . . . . . . . . . 213
Index to NPRA Q&A Topics . . . . . . . . . . . . . . . 215
References . . . . . . . . . . . . . . . . . . . . . . . . 222
Registration List . . . . . . . . . . . . . . . . . . . . . 267
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INTRODUCTION
JEFF K. UTLEY:
Good morning. My name is Jeff Utley. I am the Refin-
ery Manager for Flying J in North Salt Lake, Utah. I am
here this morning as Chairman of the NPRA Manufac-
turing Committee to welcome you to the 47th Annual
NPRA Question and Answer Session on Refining and
Petrochemical Technology.
It is great to see so many of you here this morning. It
was great to visit with you last night. I am involved in other
associations, as many of you are, within the industry, and
those associations have suffered some from the rationiza-
tion and downturn that our industry has seen in the last
few years. But in looking at the audience this morning and
visiting with you last night, this is a true testimony to the
value of the NPRA Q&A Session. Many of us are watching
very closely where we spend our dollars these days, and
1994 NPRA Q&A Session on Refining and Petrochemical Technology
judging from the size of the attendance, this is truly one
of the best returns on the dollar that we have to spend.
Before we begin the program this morning, I would just
like to make a few comments on some of the challenges
and issues facing our industry today. We as an industry are
about to embark on a new era that will see unprecedented
involvement of the government in our most basic proc-
esses and operations. The EPA will become intimately
involved in how we manufacture gasoline right down to
the individual components that can and cannot be put
into it, the distribution of gasoline, and finally to sell to
the end customer at the retail station.
The number of rules and regulations that involve our
business have multiplied at least by a hundred times, and
the penalties that we face for even one violation of any of
those new rules is a mere $25,000 a day. These rules affect
the most basic decisions that we make on a daily basis. For
example, what severity should I run on the reformer? How
will that affect my baseline? How will that affect the
benzene or aromatic content of my gasoline? Or at what
temperature should I run on the FCC reactor, or what
catalyst should I choose? How will that affect the sulfur
content, the olefin content, or the aromatic content of my
gasoline? In this new era, before any process change is
made, one will have to evaluate the impact on the gasoline
baseline.
In addition to these process questions, you have to back
up even further to ask what kind of crude should I run?
What will the change in crude do to my baseline?
I have heard and read a lot about these impacts and the
new regulations but I have not seen a lot discussed about
quality differences in crude. I believe that the crude quality
issues, combined with the baseline, are probably the great-
est threat to the future viability of our refineries. For
example, a refinery that processed the high quality crude
in 1990 will have a tremendously difficult time processing
a lower quality crude in 1995 and beyond.
When you stop to think that all these new regulations
come from a voluntary effort by our industry to change
the composition of our gasoline to reduce emissions, it is
scary to see what happens when a government mandate
takes the place of free market-driven fundamentals. On
top of the reformulated gasoline regulations we have re-
quirements for additives in gasoline. That is just around
the corner. Requirements for mass balancing to make sure
that the right amount of additives is put into gasoline.
That carries many rules and regulations and record-keep-
ing. I do not know what you guys are going to do with all
the records we are required to keep. We are going to rent
a storage shed on an acre of land. Refinery MACT is just
around the corner. It is going to require additional controls
on storage tanks, gasoline distribution facilities, process
vents, and you have to ask why. What is the risk? What is
the cost per ton of emission removed? We all see the
negative impacts from the news media on the public of
5
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the large fines and civil awards for incidents that do occur,
even though they are very, very rare. It makes you stop and
wonder, when an industry that has done so much to
improve the life for mankind around the world, why the
punishment is so great for a rare incident. It can be
depressing at times.
But I do look to the future with optimism and take an
awful lot of pride in what our industry has done. We are
the energy that fuels the worlds economy, and we will
continue to do so for the foreseeable future. Our products
from both refineries and the petrochemical plants are an
integral part of every day life. Our plants are cleaner and
more efficient and our products are better than ever before.
We have better science to predict the impacts of our
products on the human health and the environment be-
fore they are put on the market, and the government is
being forced to be more responsible for their regulations
in the form of risk assessment and funding before the rules
are put in place. There is progress being made to move
away from Command and Control regulations. However,
there is a lot more to do. I encourage each and every one
of you to get involved, to get involved with the NPRA’s
effort to represent our industry on the issues that are
coming at us. No issue is insignificant, and there are not
enough folks in the NPRA office to handle all the issues
that are coming at us. Get involved with your State
congressional delegations, with the state and local govern-
ments; become part of that process; become intimately
involved in that process. Get involved with the school
systems. Help educate the teachers who teach our kids.
Help educate the youth in America to what our industry
means to their daily lives. Bring them to your plants, and
go out and visit their classrooms. If we want to affect the
change in public attitude and opinion, this is where we
must start.
I would like to turn back to the meeting this morning,
and give you an idea of what kind of preparation went into
this meeting. A lot of you have been panelists before so
you know. To give you an idea, back in January there was
a call for panelist nominations. Those nominations were
submitted and then during the Annual Meeting, in the
Manufacturing Committee Meeting, the panelists were
selected. That was in March. About that same time, the
call for questions was sent out and generally we received
about 600 or 700 questions. From there, a screening
committee met in July and they used a tremendously
sophisticated, scientific method to whittle those questions
down to about 250 or so. From there they were sent out
to the panelists who had a chance to review them. The
panelists were asked to select about 30 or so questions each
to answer. These guys put an awful lot of their own time
late at night and on weekends, and if their wives and kids
are anything like mine, they just did not seem to under-
stand why they were putting in that extra time. There was
an awful lot of effort that went into the preparation of this
meeting. And please join me in giving the panelists a hand
for all their hard work.
Another group that we need to thank is the NPRA staff
They have put a lot of hours, a lot of hard work, and a lot
of worry into making certain this meeting is as successful
as it is. So please join me in giving the NPRA staff a hand.
Finally, it is my pleasure to introduce the moderator of
the meeting this morning. He is the Technical Director of
the NPRA, and he is the man responsible for coordinating
this meeting and many others with NPRA. Ladies and
Gentlemen, I present Terry Higgins.

Important Notice
The information and statements herein are believed to be reliable but are not to be construed as a warranty of
representation for which the participants assume legal responsibility. Users should undertake sufficient verification and
testing to determine the suitability for their own particular purpose of any information or products referred to herein.
NO WARRANTY OF FITNESS FOR A PARTICULAR PURPOSE IS MADE.
Nothing herein is to be taken as permission, inducement, or recommendation to practice any patented invention
without a license.

6 Introduction
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Background information on today’s panel can be found

in your program book. Note that Hersh Kohut of ARCO,
listed in the program, was unable to attend. The remaining
panelists starting from my far right are:

MICHAEL S. ARMBRESTER
Ashland Petroleum Company
Ashland, Kentucky
R. C. “BUZZ” BARLOW
Betz Process Chemicals, Inc.
The Woodlands, Texas
WILLIAM A. BOYCOTT
Frontier Refining Inc.
Cheyenne, Wyoming
PAUL L. CUNEO
TERRENCE HIGGINS:
Shell Development Company
Good Morning. Thank you very much, Jeff. We appre-
Houston, Texas
ciate your comments this morning, and as well the support
that the NPRA Manufacturing Committee provides this JAMES H. D’AURIA
meeting. UOP
I would like to thank STRATCO for sponsoring last Des Plaines, Illinois
night’s reception and Hart Publications for sponsoring the
JOHN T. DEATON
image magnification facilities in use today.
Clark Refining & Marketing Company
The schedule for the session is printed in your program
Blue Island, Illinois
books. Lunch will be served on Wednesday and Thursday
in the Constitution Ballroom, one flight up. The program B. W. “BILL” FELTROP
lists a 12:30 start time for lunch, but if I finish on time, Petrolite Corporation
lunch will be available by 12 Noon. Vegetarian meals are St. Louis, Missouri
available. Simply request one from one of the servers if
MICHAEL A. LAUX
desired.
Diamond Shamrock, Inc.
Throughout the next two and a halfdays, the panel will
Three Rivers, Texas
respond to questions submitted by industry and screened
by a panel of experts. I will not read the questions in their JOSEPH B. McLEAN
entirety, so bring your program books to the session. Engelhard Corporation
I will first call upon the panelists to respond to each Houston, Texas
question and then open the discussion to the floor. I
STEPHEN G. MENEGAZ
encourage your active participation. When commenting,
The Prichard Corporation
please state your name and company.
Houston, Texas
Approximately two weeks after the meeting, a copy of
the comments will be mailed to each participant for WILLIAM J. PORTER
corrections, additions, or deletions as deemed necessary. Chevron U.S.A. Products Company
After the return of the participants’ comments, they will Pascagoula, Mississippi
be printed and published in a hardback book by NPRA. SCOTT M. SAYLES
Each registrant at the 1994 NPRA Question and Answer Sinclair Oil Corporation
Session on Refining and Petrochemical Technology will Tulsa, Oklahoma
receive the bound transcript of the meeting. The bound
transcription includes a subject index which identifies STEVEN A. TREESE
pages where specific topics are covered. Unocal Corporation
Again, I encourage your participation. I also encourage Carson, California
you to take advantage of the hospitality provided through-
out the week by the various suppliers. These offer an The NPRA has received numerous positive comments
excellent opportunity to become better acquainted with as to the value of these sessions and transcripts. Any
those who serve our industry. The suppliers have experts criticisms or suggestions for improvement are welcomed.
available to discuss their products and answer questions. With these remarks, we are ready to begin the session.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 7

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I. GENERAL PROCESSING AND SUPPORT OPERATIONS
A. Treating and Desalting
QUESTION 1.
When feeding residual oil to the FCC and other down-
stream processes (coker hydrocracker), is it of more
benefit to have multiple stage desalting (2 or 3 stage)
of the crude oil or desalt the residual for Na removal?
What about purchased feed?
BARLOW:
The answer to this question will depend on the current
equipment that you have and your feedstock goals. I have
listed some advantages and disadvantages that we see with
residual desalting at the FCC charge or running it through
the crude unit.
The advantages of desalting the residual or FCC charge
would be: first of all, the size of the desalter can be smaller
because of the reduced throughput. Alternately, for a
similar size vessel you can increase your residence time and
the efficiency of the desalter. Purchased feed can be de-
salted without having to process it in the crude or feed
preparation units, which would avoid a potential reduc-
tion in crude throughput. Thirdly, if you are injecting
caustic in the desalted crude and you have a residual
desalter, you can continue to inject caustic and still get
reasonably good sodium removal.
The disadvantages are as follows: problems, costs and
training associated with building an additional process in
a second location. Adding a second desalter in a crude unit
is simply an extension of the existing process. Secondly,
corrosion protection, salt, solids and BS&W removal is
better with the second stage than with only a single stage
desalter. Thirdly, the residual can be more difficult to
desalt alone due to the lower gravity. If you double desalt
it with the crude, you have an inherent gravity enhance-
ment.
On the question about purchase feed, we have seen
problems with contamination by sea water, depending on
how that feed is transported, and we would recommend
reprocessing prior to the FCC unit.
CUNEO:
Yes, we believe very strongly in two stage desalting when
the residue is going to be fed to an FCC unit. We have
managed to justify these units basically on lower sodium
levels on equilibrium catalysts, benefits from reduced
fouling, energy consumption and corrosion.
8 General Processing and Support Operations
On the purchased feed question, in 1993, we commis-
sioned a new bielectric desalter to desalt purchased resi-
due.
FELTROP:
I agree especially with Mr. Cuneo’s comments on the
need for multiple stage desalting. Usually crude desalting
can be improved or upgraded significantly by adding a
multiple stage unit. This is especially true if downstream
requirements exist to have a low sodium level in your FCC
charge. Multiple stage desalting is definitely the preferred
route, but it can be, as Mr. Barlow has mentioned, an
expensive alternative.
Downstream desalting in front of an FCC is typically
justified when you have FCC feeds you are buying from
outside where you cannot control the sodium levels. It is
certainly dependent on the crude type that it has come
from. The economics vary, but we have several cases where
we have proven that a 0.1 ppm increase in feed sodium to
a typical 50,000 bbl/d FCC unit would cost the refiner
between $200 and $700 a day, depending on whether the
loss is taken as catalyst addition or conversion loss.
Quantifying generalized sodium effects on coker fur-
nace fouling is far more difficult and variable, but it is
another area that needs to be considered. Some exemplary
observations there would place the cost for a 20,000
bbl/day coker at between $25 and $100 per day per ppm
of feed sodium increase. Still more difficult is quantifying
a generalized sodium effect on other heavy oil catalyst
units, but the general belief is that sodium contributes
primarily to top bed fouling and could be a capacity issue
for those fixed bed units that are pressure drop run length
limited.
MENEGAZ:
We agree with all the previous comments regarding
multiple stage desalting. Additional desalting for marine-
shipped gas oil is a good idea. We know of several refiners
that run purchased gas oils without additional desalting,
and they have sodium levels of 0.6 wt% or higher. Most
of them complain of high catalyst makeup to maintain
activity.
Note that in residual cracking, equilibrium metals
rather than sodium generally sets the FCC catalyst
makeup rate. Added sodium on FCC catalyst above 0.4
wt% will definitely hurt yields and catalyst makeup rate.
TOC/INDEX

SAYLES: PORTER:
I agree with what has been said, with one additional We look at salt and water removal from crude as the key
point. If you have no need to desalt ahead of the crude parameters and also do a visual qualitative assessment of
unit and want to desalt your gas oil or atmospheric gas oil oil in the water. I generally agree with the numbers Mr.
hot rundown to downstream units, you can desalt those Feltrop reported. However, at the Pascagoula refinery, our
streams. I understand some desalters are operating at the salt removal in two-stage desalters has not consistently
rundown temperature of about 300°F and can be designed been at 99%.
to handle these streams at high salt removal levels.
TREESE:
QUESTION 2. In Unocal the target values are along the same lines as
Whatparameters and tools do refiners use to measure Mr. Feltrop mentioned. B&W is running 0.1% to 0.2%
desalter performance? What benchmarking values less than that. Chlorides and salt removal are 90% to 95%
have been established for each of these performance or greater. Oil in brine is less than l%, and usually the
indicators? criteria is a little bit more subjective: no visible oil in the
brine. We do have ways to handle the oil subsequently,
FELTROP: although we do not use the deoiling process.
We view the assessment of the performance of an For run length, we are usually shooting for greater than
operating desalter as a three part procedure. Initially, a 2 years, and with careful control of the process, at least in
determination is made of the optimum performance that one plant, we are now targeting for a 6 year run on the
can be expected with existing equipment and operational desalters.
conditions. This analysis results in a target or benchmark
for optimum performance capability at existing condi- ARMBRESTER:
tions. Secondly, determination of actual performance is Our desalter operating goals are fairly similar to those
made using detailed analytical procedures. Finally, after mentioned already. On salt content of the desalted crude,
determining what the desalter can do and what it is doing, we shoot for less than 1.5 lb/1,000 bbl, and that is
parametric optimization is indicated. Usually the data generally with less than 100 lb/1,000 bbl coming in with
indicates what is required for operational improvements. the raw crude. We look at water and basic sediment
Benchmark performance varies significantly based on de- individually, targeting 0.15% maximum on each of those,
sign. Single stage desalters should remove 90% to 95% of and we generally operate at less than 75 ppm oil and grease
incoming salt as levels go from 10 lb/l,000 bbl to upwards in the effluent water. We have achieved very good compli-
of 60 lb/l,000 bbl. Double stage desalters should achieve
ance with these goals using a water rate of 6% of the raw
99% removal and will handle salt levels of over 100
crude and about 5 ppm of desalting aid.
lb/l,000 bbl.
Oil outlet quality is generally measured in terms of
BARLOW:
BS&W and we should be able to achieve 0.2 wt% BS&W
We would agree that there are really no standard bench-
in almost all but the heaviest of crudes. On heavier crudes
marks, but there are some guidelines that you can use
this is at times dictated by economics rather than actual
across the industry. We would propose the attached list as
performance capabilities. The water effluent quality from
a starting point.
desalters is becoming more and more important with the
regulations that we are under. In general, effluent water
TOOLS BENCHMARK
total oil levels can be expected to be well below 200 ppm.
Much lower oil levels can be achieved but usually at the 1) Salt Out 0.2 - 2.0 PTB
expense of a deterioration of overhead performance. We 2) Salt Removal 90% - 98%
will discuss this further as a part of question 9. There are 3) Solids Removal 50% - 80%
known exceptions including heavy naphthenic acid crude 4) BS&W Out 0.1 - 1.0%
oils. 5) Na Removal 95%+
The last thing I wanted to mention is solids removal
6) Oil in Effluent Water 0% - 2%
efficiencies. They are highly dependent on the nature of
the incoming solids that come in with the crude and how 7) Oil and Grease in 100 to 1500 ppm
Effluent Water
the solids are defined analytically. It is feasible to use a
combination of equipment and chemicals to achieve a 8) Frac. O/H Chloride 0.1 to 0.5 ppm Cl -
Levels per 1,000 Barrels Crude
90% removal of solids in a desalter. More commonly,
however, reported solids removal efficiencies are in the 9) Iron Removal 50% - 75% Inorganic Iron
20% to 70% range with sufficiently oil free effluent brine. 10) Slop Production 0.1% - 1.0% of Crude Charge

1994 NPRA Q&A Session on Refining and Petrochemical Technology 9

TOC/INDEX
A parameter that we use that has not been mentioned,
depending on the purpose of the desalter and the specific
concerns for the plant, is sodium removal. We do monitor
that when appropriate. We also correlate the desalter
operation to the overhead chloride levels, iron removal and
the amount of slop handling capability of the desalter
itself. We see that, on the heavy crudes, one way to monitor
the performance is the amount of cutter, or Top Pump
Around used as an indicator of the impact on the overall
operation.
As a last comment, I would say that the standard
parameters are changing rapidly as we see refiners process-
ing cheap, lower quality, opportunity crudes. Each system
is really being proven individually with the different
changes in crude slates.
DEATON:
We look at three parameters across our single stage
desalter: percent salt removal daily, percent B&W in and
out daily, and percent filterable solids removal as needed.
Our percent salt removal currently runs between 88% and
92%. Desalted crude typically runs 1.5 to 3.0 lb/1,000
bbl. Our refinery lab runs salt tests by water extraction and
silver nitrate titration. Our BS&W typically runs between
0.3 and 0.4 wt% inlet with 0.2 wt% outlet, and our
refinery lab runs BS&W tests by 50% toluene dilution
and the centrifuge method.
Our filterable solids removal is typically 65% to 75%.
Our filterable solids are typically 30 to 40 1b/1,000 bbl
inlet, which are very low, with 10 lb/1,000 bbl outlet.
Filterable solids is the measure of colloidal material that
may not always settle out in a centrifuge. Our chemical
supplier runs filterable solids tests by toluene dilution,
using before and after weights on a 0.45 micron filtration
test.
QUESTION 3.
What are refiners doing to reduce/eliminate oil in the
desalter effluent water? What /eve/s are achieved and
what variables impact that level?
BARLOW:
Basically we see a broad cross section of levels of oil in
the desalter effluent water. Some people are as high as the
5% to 10% range and they are actually handling the
effluent downstream in a different separation system, or
simply in a separation tank. The levels we typically target
are less than 500 ppm oil and grease in the effluent water.
A lot of what you can do will depend on the associated
solids loading.
This problem is also changing rapidly with the different
types of crudes that refiners are processing. I will very
quickly go through a list of the different changes that we
attempt in order to improve overall operation and to
reduce and eliminate the oil:
10 General Processing and Support Operations
Improved level control is the first one. The use of
microwave sensors is more common and seems to be
more accurate these days than the old float type
devices.
Improved control systems with the new probes. They
can be used not only for level control, but we have
seen some success with their use as alarms or controls
for additional chemical pumps to control upsets.
We also see operator training and awareness as a
tremendous advantage.
Addition of new chemistry to the desalter; and there
will be more discussion on this a little bit later. Here
I am referring to wetting agents, reverse breakers and
emulsion polymers.
Addition of brine deoilers in the form of knock out
tanks and even modified desalters.
Slop oil injection location revisions.
Crude tank dewatering.
Improved oil movements where we monitor the
crude quality prior to processing in the desalter. One
example might be to segregate the high asphaltene
crudes from highly paraffin crudes, which help in
asphaltene deposition problems downstream.
Gravity enhancement with top pump around recycle.
Reduction in wash water rates to increase water
residence time. Sometimes you might go the other
way.
Desalter design modifications, which might include
larger vessels or a switch to a bielectric or another
grid type design.
BOYCOTT:
I agree with the previous comments on the effect of
desalter parameters on the oil content of the drain water.
We typically achieve less than 500 ppm oil and grease in
our effluent water. We do experience periodic problems
with the formation of emulsions caused by the presence
of coke fines in our recovered oil stream. These emulsions
carry oil with them in the effluent water stream. We have
been successful in treating this problem with wetting
agents and the introduction of some of our wash water in
the preheat train for better wetting of the fines.
DEATON:
In addition to the standard emulsion breakers, water
soluble cationic polymers can be used to agglomerate oil
with the polymers and water wet the solids, thus allowing
the solids to drop out oil free with the effluent water. These
polymers are injected into the desalter wash water at
treatment rates ranging from 0.5 to 2.0 ppm based on the
raw crude charge.
However, overfeeding polymers can tie up solids, cause
the desalter’s emulsion rag layer to grow in size, and show
up as excessive solids during mud washing. Also, overfeed-
ing polymers can lead to the buildup of solid polymeric
TOC/INDEX
material inside the desalter. It is critical not to exceed the
0.5 to 2.0 ppm dosage rate.
At one refinery, we injected these polymers on an as
needed basis when processing heavy west coast sour blends
with high filterable solids content ranging up to 200
lb/1,000 bbl. Oil in the effluent water frequently ran as
high as 10% before applying polymer. Within an hour
after injecting the polymer, oil in the effluent cleared up
and filterable solids removal returned to 60% to 70%.
ARMBRESTER:
I agree with most of the previous comments. I would
add a couple of things on some of the basics. We have our
operators monitor the rag layer location in the desalter
using tricock samplers or swing arm samplers and try to
run the rag layer as close to the grid as possible without
decreasing the voltage. We also monitor the desalter inlet
temperature since the emulsion is more difficult to break
at lower temperatures. Our actual target temperature for
1994 NPRA Q&A Session on Refining and Petrochemical Technology
the desalter inlet depends on the operating pressure, since
we want to prevent vaporization in the desalter.
FELTROP:
In addition to the traditional approaches that have been
mentioned, continuous mixing is often used in crude
tanks to assure that slugs of water do not hit the desalter.
This also helps with the solids. Several refiners are very
adamant in making sure they avoid the use of high pH
waters, anything that is greater than 8.5. Controlled slop
oil feeding is very important for stable operation of the
desalter. Usually a level of less than 3% is acceptable.
For processing crudes greater than 25° API, the meth-
ods that have been discussed will work. For crudes that are
less than 25° API, desalting at higher operating tempera-
tures, up to even 300°F, have seen a lot of success. Oper-
ating with lower mix valve pressures will trade off salt
removal for effluent quality. Continuous mud washing for
high solids content crudes is very important. There has
11
TOC/INDEX
been recent testing using very acidic, less than 6 pH wash
water for some specific crude slates that has shown success.
Polymers have already been mentioned. For processing
crudes between 20° and 25° API, these methods will be
successful usually to give you oil counts of less than 1,000
ppm.
Finally, for very difficult to treat crude slates like San
Joaquin Valley, we have developed specific chemical treat-
ment programs which will reduce oil undercarry from its
typical values of 3% to 5% to less than 1,000 ppm as well.
PORTER:
Most of the points I was going to make have already
been covered. In most cases, we see oil in the water in the
100 ppm range. With our more viscous crudes, though,
we do see a 1% to 2% range.
In addition to the problems that have been mentioned
that cause upset conditions, we also find that recovered oil
or recycled oil can cause desalter upsets.
We have been successful in converting to a bielectric
desalter in one application where a heavy crude was creat-
ing high oil in the effluent water. We are also evaluating
using a hydrocyclone to treat the effluent water on a
desalter with an oil undercarry problem.
TREESE:
We concentrate more on the basics of controlling and
improving the desalter operation as opposed to treating
the effluent water after it leaves the desalter.
The five main factors we concentrate on to reduce or
eliminate oil in the desalter water are: 1) maintaining
water below the grids; 2) continuous or daily mud washes;
3) optimizing the chemical treatment; 4) optimizing the
wash water rate; and 5) controlling and optimizing the
mixing valve pressure drop. Many of these factors have
been touched on already by the other panel members.
DENNIS GRANDLE (Agar Corporation, Inc.):
We found that replacing traditional level control instru-
mentation, like displacers or capacitance probes, with
energy absorption microwave probes, reduces oil under-
carry by 60% to 80%. This technology is capable of
measuring oil and water in small concentrations, prevent-
ing oil from going out the bottom with the waste water.
Typical payback is under six months when the operator
changes from traditional interface control to concentra-
tion measurement.
QUESTION 4.
Where are people sending their disulfide oil and Oflgas
that results from caustic regeneration? This question
has been asked at past NPRA P&A’s, but it may be
useful for us to know if there are any new develop-
ments/creative solutions. Disposal is becoming a big
12 General Processing and Support Operations
concern as we look to switching from sweetening to
extraction in light naphtha treating.
ARMBRESTER:
At the Catlettsburg refinery, we can reprocess the disul-
fide oil through the crude distillation unit or route it
directly to gasoline blending. Since the disulfide oil has a
very low octane rating, the reprocessing option is pre-
ferred. One option for handling the oxidizer off gas is to
route it to a fired heater or boiler.
D’AURIA:
The options for disposal of disulfide oil and offgas have
not changed greatly in recent years. We agree that as more
people go to extraction rather than sweetening this is
becoming an issue of greater concern. These streams,
however, are still relatively small in size, and there are a
number of good alternatives for in-refinery disposal. We
are aware of some chemical companies who sell disulfides
and have investigated the recovery of these from treating
units. This has generally not been attractive due to the
small size of the streams, as well as the number of contami-
nants that may exist in the oil.
The most common method of disposal of disulfide oil
today is sending the stream to a hydrotreater where the
disulfides are converted to H2S. Some refiners send this
stream to the FCC unit where the same conversion occurs.
Other refiners have been able to blend the oil in with their
heavier hydrocarbon streams.
The offgas from the disulfide separator is normally sent
to a place where it can burned. Most of the UOP designs
call for it to be sent directly to the heater firebox after
dilution with fuel gas. This gas will easily burn but it will
not support combustion by itself. The gas going to the
firebox is sent in a dedicated pipe near the burner, but not
directly into the burner. The system design incorporates
safety controls to prevent any flashback or explosive mix-
tures.
The gas should not be sent directly to the flare system
because of the presence of oxygen which can combine with
H2 S to form elemental sulfur and cause precipitation
problems in the flare. One alternative which has ben used
is to dilute the offgas with fuel gas, and send it in a separate
line directly to the tip of the flare. This allows the material
to be burned separately without entering the main flare
system.
LAUX:
What I would add to Mr. D’Auria’s comments is that
we mix fuel gas with our vent gas from the disulfide
separator in a 4: 1 ratio based on the air fed to the oxidizer
to ensure that the mixture is not explosive as it is traveling
to the furnace. We use a special waste gas burner in our
alkylation isostripper reboiler heater to burn this gas.
TOC/INDEX
As far as the disulfide oil, we tried routing that to our
naphtha hydrotreater, but we carried caustic into the unit
and plugged the reactor up. We now route our disulfide
oil to fuel oil.
MENEGAZ:
We agree with previous comments particularly Mr.
Laux’s. If you are going to send your disulfide oil over to
a hydrotreater, you had better be sure the sodium content
is less than 1 ppm. You can do that by using a coalescer or
a light hydrocarbon wash followed by a separator. The
crude unit is a less desirable choice since the disulfides will
thermally decompose and end up as mercaptans in the
naphtha and light oil draws. As a last resort, you can send
the disulfide oils over to the Claus unit, providing you
vaporize them first. The problem with this is that the
naphtha carrier from the Merox unit will give you some
color problems on the sulfur.
The offgas from the oxidizer is combusted in an incin-
erator or existing furnace. The burner tips foul, so an open
pipe with flame arrestors is sometimes substituted for a
burner tip.
TED KELLER (Ultramar Inc.):
You mentioned the liquid going to the Claus plant.
How about the vent gas going to the Claus plant?
MENEGAZ:
I would not really see any problem with that.
REBECCA FUSSELL (Fina Oil and Chemical Company):
We originally put our disulfide oil to our distillate
hydrotreater. Due to caustic carryover, we experienced a
major tube failure on our feed effluent exchangers. The
exchanger tubes are stainless steel. We now route that
material to gasoline blending. We are not sure how much
longer we are going to be able to do that, so we are trying
to find an alternative.
JOHN MITCHELL (Merichem Company):
It is Merichem’s experience that refiners have several
choices for DSO disposal. The three most common op-
tions are:
a) blend the DSO with fuel oil,
b) blend the DSO with the FCC feed, or
c) blend the DSO with the hydrotreater feed.
The DSO will contain trace amounts ofsodium, which
is a hydrotreater catalyst poison. If the DSO is to be
blended in with a hydrotreater stream, it should be sent to
a feed storage tank where the sodium can settle out. If the
DSO can not be sent to a storage tank, a small solvent
stream should be used in the DSO separator to better
separate the DSO from the caustic. The DSO/solvent
stream can then be water washed or passed through a sand
1994 NPRA Q&A Session on Refining and Petrochemical Technology
filter to completely remove any sodium prior to entering
the hydrotreater.
Merichem has found that most refiners will send the
off-gas to a furnace burner.
QUESTION 5.
Does anyone have experience with carbon bed com-
pression in a kerosene/gasoline sweetening system?
DEATON:
Carbon bed compression is a symptom of poor pre-
treatment which renders the carbon bed unable to accept
reimpregnation of catalyst.
One unit was operated to pretreatment level acid num-
bers of 0.015 mg KOH/ml. Carbon bed pressure drop
increased to about 50 psi before the carbon bed was hot
water washed to remove a soapy layer of sodium naphthen-
ates which caused the pressure drop. Catalyst reimpregna-
tion was required but the carbon bed would not adsorb
the catalyst A second bed was installed, pretreatment level
acid number was lowered to 0.01 mg KOH/ml, and the
pressure drop was limited to 20 psi before hot water
washing. Even with these steps, catalyst reimpregnation
was not successful. Finally, a third carbon bed was in-
stalled, pretreatment level acid number was lowered to
0.005 mg KOH/ml, and catalyst reimpregnation was
successful.
D’AURIA:
Carbon bed settling or bed compression can occur if
the loading is not done properly. We recommend a tele-
scoping sock where segments are removed as the bed is
progressively raised. In addition, the bottom of the reactor
typically contains an outlet collector, and you have to be
careful to properly pack the carbon material underneath
and around the arms of that collector, otherwise you could
get settling during operation.
Additionally, there are procedures sometimes used to
back flow through the bed, in order to alleviate high
pressure drop or channeling problems. If this is done too
frequently, it could lead to fines generation and compres-
sion or settling of the bed.
LAUX:
We found that if we wet load our charcoal beds we will
not have this kind of problem. We also do hot water washes
at just about every opportunity that we can, especially
whenever the pressure drop approaches the 20 psi crush
strength of the charcoal.
QUESTION 6.
What has been the industry experience using poly-
mers in heavy crude desalters to help clarify the
effluent water?
13
TOC/INDEX
BARLOW:
Our experience with polymers in heavy crude desalters
has been excellent. However, there are several concerns
that you have to observe and precautions that you need to
take in the application of these materials. We are aware of
at least one refiner that, in the past, has injected polymer
into the crude oil without making down the product. We
are not aware of how much they fed; they may have
actually overfed the product. The desalter was opened
during turnaround and the plant found a tremendous
amount of sludge. The sludge had shifted during an upset
and affected two of the lower electrodes, pulling them out
of position and creating electrical problems. An analysis
of that sludge did show substantial polymer levels.
Over the past few years we have been using polymers
in our programs. We have been evaluating different types
of polymers and also have developed our own line of
NOVUS polymers. Combining the specific polymer for a
specific application with a proper makedown system,
proper injection control, and injection into the wash water
has been very effective in addressing oil in the effluent
water. We now have a treatment history on over 15 units
with no reported problems similar to the one refinery I
referred to earlier.
The benefits of the NOVUS technology are obviously
less oil in the effluent. In extreme cases, 10% to 15% oil
in the effluent was reduced to 500 ppm oil through the
use of polymer technology. Another benefit is reduced
overall cost. Much of the primary chemical is being fed to
try to control oil in the effluent inefficiently. By using the
polymer you can reduce the amount of primary breaker
substantially, therefore reducing the chemical cost by as
much as 30% to 50%. A third benefit is also improved salt
removal, not necessarily due directly to the polymer; but,
by reducing the emulsion layer thickness and the amount
of oil in the effluent water, you can actually work the
desalter harder. The flexibility allows you to adjust water
levels, increase the mix valve delta P, and in some cases
increase the water wash injection rate.
FELTROP:
Using polymers to maintain clean effluent while proc-
essing heavy crude oil has generally been quite successful.
We have successfully used polymers having molecular
weights greater than 1 million for periods as long as five
years at several major refineries without serious incident.
I want to echo what Mr. Barlow said about the incident
that occurred several years ago with polymer addition. The
approach works, but it does require diligent monitoring
of all aspects involved.
MENEGAZ:
We agree with the previous comments. It appears that
satisfactory performance hinges on the correct polymer
14 General Processing and Support Operations
selection and an efficient mud washing system to remove
the settled solids.
PORTER:
We have a crude unit at one location that processes
heavy crude using a polymer. They believe it helps water
quality and results in a lower total chemical cost.
PAUL FEARNSIDE (Nalco/Exxon Energy Chemicals):
We are currently bringing out a new polymer technol-
ogy, different than the existing polymers. I would like to
share with you some of the performance improvements
that we see. These are units processing Cold Lake and
Lloyd Minister, very difficult type crudes. Oil in the
effluent before was 1% to 5%, afterwards less than 500
ppm. Solids removal was actually increased. Before it was
40% to 50%, afterwards 60% to 70% removal. We have
evaluated this new polymer in over ten desalters with no
reduction in filterable solids removal efficiency. In the rag
layer, there was actual reduction in the amount of solids
that were being held up. So we feel that this new technol-
ogy offers all the benefits of polymer types with what the
panel has said, but offers none of the bad aspects of them.
Overall program demulsifier costs have been reduced from
10% to 50% while improving effluent water quality.
QUESTION 7.
Are there any operators who have the low velocity type
desalters and have converted over to a bielectric type?
What performance improvements have been ob-
served? Would they recommend the changeover?
CUNEO:
Shell has replaced or converted five older desalter de-
signs with bielectric units, including three low velocity
units. For the constant vessel size, Petrolite advertised a
significant crude capacity advantage for the bielectric de-
sign. Our experience is that this claim is valid and the
increased capacity was achieved. I believe bielectric con-
version is a cost-effective way to debottleneck existing low
velocity desalters.
The three grid design of bielectric desalters provides
increased reliability and when properly configured the
electrical failure of any one grid does not seriously reduce
performance. Several of our applications have operated in
this mode for months rather than bringing the crude unit
down for repairs.
I believe that the bielectric desalter’s design is superior
for handling heavy crude oil and crude with high solids
content because the oil water inlet is located above the
desalter liquid phase interface. ‘When coupled with ad-
vanced level detection such as the Agar probe, I believe
this is the most effective way to achieve better brine quality
in environmentally sensitive applications.
TOC/INDEX
BARLOW:
The only thing I would add is some specific data
supporting the improved quality of the effluent. On a 38°
API high sulfur crude type, we saw a drop in oil in the
effluent from 9,000 ppm down to 500 ppm with this kind
of change. On a 20° API Lloyd Minister crude we saw a
drop from 5% to 30% oil in the effluent to 0% to 5% oil
in the effluent. And with a 16° API San Joaquin Valley
crude, oil in the effluent was reduced from 54% to 1%.
So we support this kind of modification.
FELTROP:
Over 50 desalters ofvarious designs have been converted
to Petreco’s bielectric design. Most have been converted to
increase throughput or improve performance on higher
viscosity crude oils. Typical performance improvements
include reduction in salt, BS&W, filterable solids, oil in
effluent water, improved on-line efficiency and economic
chemical optimization. Our Petreco Division is available
to provide a list of references for those who are interested.
PORTER:
We have converted two desalters to bielectric units for
different reasons. The first was to increase crude through-
put 25%. In the second case, we were feeding a very heavy
14° to 16° API gravity crude oil where the desalter per-
formance was not very good. Both of these were successful,
as we achieved the desired performance results.
HENRY JONES (Howe-Baker Engineers, Inc.):
We have converted many desalters, both of our original
design and that of others, to Howe-Baker’s current (state-
of-the-art) multi-grid, DEEPFIELD technology, In one
such instance we took a single-stage desalter that had two
vessels operating in parallel, converted the units to DEEP-
FIELD design and put the vessels back into service as a
two-stage desalter (i.e., doubling the desalting capacity of
each vessel without adversely affecting unit performance).
JAMES F. KELLY (CITGO Refining & Chemicals):
Mr. Porter, you mentioned that on your bielectric
desalter you had a 15° API gravity. Did you cut it with any
kind of cutter stock, or was the 15° API material going to
the desalter?
PORTER:
That was the API going to the desalter. After the
conversion, we did not need to cut it.
JAMES F. KELLY (CITGO Refining & Chemicals):
Did you get any increased throughput capacity from it?
PORTER:
We did not get it on that unit. It was the other unit we
targeted for increased capacity.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
QUESTION 8.
What systems are used to monitor the desalter inter-
face? How are they used to control the interface (auto-
mated or manual)?
BOYCOTT:
A number of different technologies may be applied to
desalter level detection. They are inclusive of: tricock
samplers, swing arms samplers, displacement floats, ca-
pacitance probes, energy absorption probes, and nuclear
level detectors.
Our desalter is equipped with an internal float for
interface level detection. However, this float has proven
extremely unreliable. As a result we typically resort to the
use of a system of five tricocks. Indications for the tricocks
dictate manual adjustments in effluent water rate for level
control. We have considered the installation of both nu-
clear density profilers, and energy absorption probes. We
have decided on the installation of an energy absorption
probe system in this service. With the installation of the
energy absorption probe system we will consider automat-
ion of the desalter interface level.
ARMBRESTER:
Ashland uses a displacer mounted in a slotted cage to
monitor the desalter interface level. All of our units are set
up to automatically control the interface level by adjusting
the control valve in the effluent water line. In some cases
this controller is board mounted, while in other units we
use a field mounted controller. All of these systems have
been very reliable.
In addition to the automated level controls, the opera-
tors routinely check the water interface level and the rag
layer thickness using a swing arm sampler or a set of tricock
samplers mounted at various elevations on the desalter.
FELTROP:
Displacer systems have been used with great success in
the industry and are generally used in an automatic mode.
This type of system does require manual calibration for
wide variations of crude oil and as such is not always
recommended for heavy crude oils. Capacitance probe
systems are the current recommendations for new desal-
ters due to their indifference to API gravity changes and
the probe’s high sensitivity to changes in interface eleva-
tion. The continuous proportional change in signal can be
employed to drive an automatic system. The third system
is the Agar probe system. This system is also reported to
operate in an automatic mode and is currently being tried
at several locations.
PORTER:
Most of our units use the Drexel Brooke Admittance
probe on automatic control. We have been very happy
with this control for the last ten years. We do use the
15
TOC/INDEX
manual taps referred to earlier as our backup. We recently
installed AGAR energy absorption probes on one of our
units, and are very pleased with the results. Overall, the
control has greatly improved, and we have seen a drop in
chemical usage as well.
TREESE:
Practices on our desalter interface controls in Unocal
refineries differ. You have heard most of the solutions that
we have used, and we have used most of them at one time
or another. At the San Francisco refinery, we are able to
get by with the traditional system of monitoring the
interface using a float, and it is operated on automatic. We
use a tricock system as a manual check on the accuracy of
the float.
At the Carson plant, we are using an Agar probe, which
is basically a microwave type device that measures the
difference in heating rates between oil and water. In effect,
it is providing a measure of the water concentration in the
oil. We have been very satisfied with that system since it
was installed. Again, we still have a tricock system that
provides a check on the probe.
Prior experience, that is things we tried that did not
quite work, included dP cells and capacitance probes. The
dP cells were generally poor in the application and the
capacitance probes got confused by the emulsion layer
within the desalter.
DENNIS GRANDLE (Agar Corporation, Inc.):
We now have systems installed successfully in over 75
desalters worldwide. Typically we see demulsifier reduc-
tion of 20% to 30% and reduced oil undercarry by 60%
to 80%. Use of Agar energy absorption microwave probes
allow the operator to automatically control the waste water
effluent valve.
Since the probes are capable of measuring the concen-
tration of water in oil over the range of 0% to l00%,
emulsions, layers, suspended oil or water droplets, etc. do
not affect the probes’ ability to perform. Energy absorp-
tion probes are not susceptible to fouling problems and
failures from asphaltenes or paraffins buildup like tradi-
tional level control technologies utilizing capacitance
probes, floats or displacers.
We also see an interesting phenomena with increased
operator awareness of what is going on in the unit. They
are taking more ownership of the vessel and are able to
better control and see what is happening for the first time.
HEROS DERGREGORIAN (Giant Refining Company):
The panel has been discussing automatic control of
interface. How is this achieved? Do you inject a constant
amount of water depending on the crude rate? You may
use an interface for diagnosis of the problem, but how do
you control that interface? Do you control the amount of
water injection or what?
16 General Processing and Support Operations
ARMBRESTER:
We are flow controlling the water injection to the crude
and then monitoring the interface level with a displacer
and allowing that level signal to control the effluent water
flow.
QUESTION 9.
What techniques have proven successful in eliminat-
ing residual sludge in desalters prior to entry?
PORTER:
The best technique we have found is not to get the
solids there in the first place. A few years back on one of
our desalters in Pascagoula, we did a chemical clean prior
to entry, and did not find oil but did find a fair amount
of mud. We do not know if the chemical cleaning removed
any of the mud, but we still found a fair amount. We
repaired the mud washing system and improved its opera-
tion. Recently we opened this desalter again following a
chemical cleaning. We were very pleased to find it oil and
solids free. So from my perspective, the best thing to do is
to keep your mud washing working properly to keep the
solids out and then chemical clean before entry.
SAYLES:
Our target is also sludge minimization in the desalters.
The internals, electrostaticgrid, baffles, and supports from
the desalters can cause low velocity zones that retain solids
even after water washing or chemical cleaning. We usually
have about 0.5% of the desalter’s volume remaining as
sludge when opened for inspection. When the desalters
are opened, we flush the remaining sludge into the sewer
with a fire hose.
TREESE:
Similar to the experiences of my fellow panel members,
Unocal uses a mud wash and chemical treatment with
chemicals developed specifically for the purpose of elimi-
nating residual sludge. At one plant we do employ a
continuous on-line mud wash that prevents sludge
buildup in the first place. That desalter comes out very
clean when we do open it up. This plant has the longest
cycle length on the desalter.
BARLOW:
We also strongly recommend focusing on the mud
wash system. A well operated mud wash system can reduce
the problem. However, even with some of the most suc-
cessful systems, cleaning is still required. Vessel degreasing
and degassing technology can be used to preclean the
vessel. Simply stated, this consists of injecting various
surface active chemicals into the desalter after shutdown.
The vessels can be filled with water and essentially “rolled”
with steam for extended periods. A mud wash system can
also be used at that time to help with circulation. This
TOC/INDEX

method has effectively reduced the amount of residual 2. The sediment wash system should be able to pro-
level of material in the desalter. vide 10 gallons per minute per nozzle in order to
be effective.
FELTROP: 3. The sediment wash water pump should be an open
I concur with the other panelists. The following proce- impeller, centrifugal type. Pumps with close me-
dural notes show how to effectively utilize the desalter chanical tolerances are not recommended as they
sediment wash system to minimize the amount of sludge may experience a rapid loss in efficiency.
buildup in the desalter during operation and prior to entry. The following is Petreco’s recommended method for
This procedure is to be used as a guide for the operation cleaning all traditional desalter/dehydrator vessels. It is to
of Petreco designed sediment wash systems. It is designed be used in conjunction with procedure T-3-4405, Safe
to be used in conjunction with any sediment wash system Work.
designed by or in conjunction with Petreco. Sediment 1. Either pump out or displace all remaining oil with
washing is the process through which accumulated sedi-
water. Displaced oil should be transferred to appro-
ment deposits are removed from a desalter. A sediment
priate storage vessels.
wash system utilizes high pressure water in conjunction
2. Open vent line to sewer, and inject steam into
with a series of nozzles located in the bottom of the desalter
water-filled vessel for 8 to 16 hours. Note: After
vessel. The high pressure water is used to agitate accumu-
completing this phase of the procedure, dispose of
lated sediment thereby suspending the sediment within
the lower reaches of the water phase. As water is injected contaminated water in accordance with applicable
via the sediment wash system, water is removed from the regulations.
desalter via the effluent water valve. The removed water 3. Fill vessel with chemical cleaner or diluent. Circu-
transports the sediments away from the desalter to the late cleaning medium for 8 to 16 hours. Note: After
waste water treatment facility. completing this phase of this procedure, dispose of
This procedure will describe both the recommended cleaning medium in accordance with applicable
sediment washing procedure and the recommended sedi- regulations.
ment wash system design. 4. Blind all process lines leading into and out of
1. Activate sediment wash while observing the clarity desalter.
of effluent water. The water clarity will become 5. Open all manways.
dark or oily in appearance. Important: It is ex-
tremely important that the sediment wash system
be utilized on a daily basis beginning the first day
of normal desalter operations. Failure to do so
could lead to large accumulations of sediment that
cannot be removed by sediment washing.
2. Continue sediment washing until the water clarity
returns to its initial clean state.
3. Record the elapsed time between initiating and
terminating the sediment washing.
4. Repeat steps 1 to 3 for 7 to 10 days.
5. Establish a sediment washing routine based on the
cumulative results of step 4. Important: Steps
should be taken to ensure that the sediment wash
routine is carried out on a daily basis in a correct,
uniform manner.
The following are sediment washing essentials:
1. Never derive sediment wash water from desalter
wash water. Doing so will deprive the desalter of
vital wash water during the periods within which
the sediment wash system is utilized. Desalting
efficiency is directly linked to wash water availabil-
ity. Petreco recommends using recycled effluent
water as the sediment wash water source. This type
of system does not take water away from the proc-
ess, and it does not add additional water to the
desalting process.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 17

TOC/INDEX
6. Inject steam to heat vessel for approximately 6
hours. Important: Never exceed 5 psig on vessel
when steam alone is being injected. Exceeding 5
psig will damage the teflon components (entrance
bushings and insulators) within the desalter.
7. Using a fire hose or larger water conduit, inject
water into the vessel via the top manway for ap-
proximately 8 hours or until the vessel is cool
enough to facilitate entry.
8. Obtain confined space entry permit for the vessel.
Note: Confined space entry requirements will vary
from refinery to refinery.
9. Drop lights into top manway of vessel to facilitate
the cleaning of the shield plates or electrodes in the
vicinity of the top manway.
10. Using a high pressure hose, remove sludge from the
electrode or shield plate before entering vessel.
11. Enter vessel via top manway. Using a high pressure
hose, remove sludge from the remainder of the
electrodes or shield plates. Note: Cleaning person-
nel will derive support from either the shield
plates/electrodes or custom-cut plywood or scaf-
fold boards. Important: Cleaning personnel should
remain on electrode supports at all times unless
custom-cut boards are being utilized.
12. Enter the bottom manway with lights. Thoroughly
clean the remainder of the vessel with high pressure
water.
13. After completing the high pressure water cleaning,
the internal components will remain coated in a
thin hydrocarbon film. This can be removed using
an oil soluble cleaner such as I-Chem’s TK-14 or
equal.
14. After all hydrocarbon has been removed from the
vessel, inject steam for 4 hours while venting to
heat up and dry out the vessel.
15. Install air mover or equivalent device to cool vessel
(approximately 8 hours).
At this point, the vessel will be ready for inspection by
Petreco personnel. It is very important that care be taken
to insure that the desalter vessel is properly cleaned prior
to each inspection. An unclean vessel does not promote a
proper inspection.
ARMBRESTER:
Ashland has used a desalter wash procedure on several
of our crude units to prepare the vessels for entry. In
general, the vessel is removed from service and blinded
from the process, then filled with water to float the remain-
ing oil out the top, where it is recovered in the slop oil
system. The water is then drained from the desalter and
the vessel is steamed out to remove more of the oil.
Following steamout, the desalter is again filled with water,
and circulation of the wash water is established through
the vessel using a skid-mounted pump. A cleaning agent
18 General Processing and Support Operations
designed for oil removal is then added to the circulating
water. After several hours of circulation, the wash water is
drained from the desalter for processing through the waste
water treatment plant. If necessary, the circulating wash is
repeated a second time, and when washing is complete,
the desalter is again filled with water for a final rinse. This
technique is effective for removing oil from the sludge in
the desalter, and makes for a much cleaner entry, but it
usually does not remove all of the solids. After the man-
ways are opened, the solids can be flushed out through the
bottom nozzles using a fire hose directed through the
vessel manways. We have successfully used cleaning agents
marketed by both Nalco and Petrolice for this service. The
temperature of the wash water varies between 120°F and
180°F, depending upon which cleaning chemical is used.
The one added benefit that has not been mentioned is
chat we have been able to get the benzene concentration
low enough to reduce the personal protective equipment
requirements for desalter entry.
QUESTION 1O.
Has anyone utilized an on stream chloride analyzer to
monitor desalter performance? Describe your experi-
ence.
FELTROP:
On-stream salt analyzers have been used to monitor
desalter performance, but these instruments measure con-
ductivity and not chlorides specifically. They must be
calibrated for the specific crude of interest and, therefore,
are usually used where the same crude is processed all the
time. These units are rather expensive at approximately
$100,000 for an installed cost.
QUESTION 11.
What methods are available to successfully control
high temperature corrosion either from naphthenic
acid or sulfur attack? Is there a maximum safe level
of either naphthenic acid or sulfur in the raw crude that
guarantees no corrosion? What monitoring tech-
niques are current/y used to combat these corrosion
problems?
FELTROP:
Metallurgy is one way to control either type of attack.
For naphthenic acid, the critical alloying element is mo-
lybdenum, a minimum of about 2.5%. The usual choice
is 317 stainless steel, which has a higher molybdenum
specification than 316. For sulfur attack, the critical ingre-
dient is chromium at about 12% to 14% as found in the
400 series stainless steels.
There are several other options for controlling
naphthenic acid attack. Blending with an acid free crude
so that the acids are diluted below a critical level is a
common practice. Keeping the acid number below 0.5 ml
TOC/INDEX
KOH/gm is usually accepted as safe, but we do know of
several cases where this level did not prove to be safe.
Neutralization of the acids followed by extraction is some-
times done. Inhibition with a chemical inhibitor is effec-
tive in some cases. Petrolite has an inhibitor which has
been proven to be very effective against naphthenic acid
attack.
Although the industry has traditionally accepted a safe
level of naphthenic acid to be that which gives a total acid
number of about 0.5 ml KOH/gm oil, there are case
histories of attack by crudes well below this level. Because
of the tremendous variety of sulfur compounds in crude
oil, it is difficult to correlate sulfur content with corrosiv-
ity. Corrosion coupons and electrical resistance probes of
the pertinent metallurgy can be used to monitor both
types of corrosion in some locations, and it is obviously
important that you have a good location to make sure you
get an accurate measurement.
MENEGAZ:
The best method for controlling this type of corrosion
is by the use of proven metallurgy. For naphthenic acid
corrosion, 316L or 317 high molybdenum content stain-
less steel has been successfully used to prevent corrosion.
For sulfur attack, 5% to 9% chrome has been used suc-
cessfully. Solutions, other than the metallurgy, include
crude blending to limit the total acid number below 1 mg
KOH/gm, corrosion inhibitors and neutralization with
caustic or amine. The 1993 NPRA Question and Answer
Session addressed this item.
One other item I would add is that to reduce corrosion,
you should limit the liquid velocities to under 10 ft/sec.
PORTER:
To avoid naphthenic acid corrosion of carbon steel, we
have long used 1.5 mg KOH/gm as a maximum neutrali-
zation number target in our distillates. Recently, though,
with some low sulfur crudes with moderate naphthenic
acid numbers, we have found that number to be too high.
We have not yet identified a new number, but we are
continuing to look at that. The only methods we are really
comfortable with are either dilution or metallurgy up-
grade. If we do not have the metallurgy required, then we
will dilute our crudes with a lower naphthenic acid mate-
rial to meet the target neutralization number.
As far as sulfur goes, we view about 0.3 wt% in the
crude as typically a safe level for utilizing carbon steel
metallurgy, except for the high temperature furnace tubes.
BARLOW:
I agree with most of what has been said so far. Focusing
a bit more on naphthenic acid corrosion, if you purchase
cheap opportunity crudes, you may not have the oppor-
tunity to metallurgy up, and there are inhibitors that can
reduce the corrosion rates. Monitoring is a real critical
1994 NPRA Q&A Session on Refining and Petrochemical Technology
element. Placement of the electrical resistant probes in the
right locations is critical and very difficult to assess. Also,
ultrasonic thickness measurements in high velocity areas
can reveal acid attack. Iron analysis in product streams
have been preformed and are used to try to predict and
document not only the attack by the acid but also the
result of inhibitors applications. We have also developed
a different technology in terms of feedstock analysis - a
specific naphthenic acid number for the fluid, which is a
proprietary test. It gives us a little better correlation to the
corrosion rate than just the total acid number, since the
total acid number does not really define the species for
you. We have had good success correlating in the
naphthenic acid number with corrosion due to different
crude blends.
DEATON:
I do not have anything to add regarding naphthenic
acid corrosion, but for sulfur, corrosion curves versus
temperatures are available for both carbon steel and the
various grades of chrome alloys. A general rule of thumb
is that doubling thesulfur content increases corrosion rates
by about 30%. At my refinery, we run a relatively low
sulfur content feed of about 0.8 wt% sulfur with 5 chrome
used for temperatures between 550° and 700°F, and 9
chrome for temperatures above 700°F. Corrosion moni-
toring consists of strategically located electronic resistance
corrosimeter probes coupled with periodic on stream ul-
trasonic thickness readings.
JAMES F. KELLY (CITGO Refining & Chemicals):
Do you have any maximum velocity recommenda-
tions?
MENEGAZ:
We made a recommendation of 10 ft/sec to avoid
erosion/corrosion with naphthenic acid.
JAMES F. KELLY (CITGO Refining & Chemicals):
Is that for neutralization numbers above 2? Is there a
correlation between velocity and acid number?
MENEGAZ:
I do not know of a correlation between velocity and
acid number. If we think there is going to be a naphthenic
acid corrosion problem, we want to hold the velocity at
10 ft/sec to avoid an erosion/corrosion situation.
QUESTION 12.
What methods and operating/economic philosophies
are employed to remove solids in a desalter? What
levels of performance (% removal) have been
achieved? Where are the solids disposed?
19
TOC/INDEX
BARLOW:
The most important parameter that we see in solids
removal is generating good contact between the wash
water and the solids entrained in the oil. The parameter
that we work with most often is mix valve delta P. Of
course, you try to get the maximum amount of mix
without creating a problem in the overall desalter opera-
tion, such as oily effluent, water carryover, or high B&W.
The more energy that you put into the crude water
mixture, the greater the solids removal will be. Oftentimes,
though, that method is not the most practical, and we
would certainly offer several chemical alternatives that
allow the oil coated solids to be wetted and stripped of
their oil coating. This methodology uses certain wetting
agents and so forth. The procedure allows the solids to be
removed in the water phase.
We also have a patented method of applying oil based
emulsion breakers in a split feed manner, both to the wash
water and to the oil. We have seen excellent results in
enhanced solid removal. With this technology, we have
seen increases in solids removal from about 30% up to
75% in some systems. When solids removal is a high
priority and economically justified, levels of removal in the
75% to 85% range can be achieved on a consistent basis.
CUNEO:
We do not currently operate any of our commercial
desalters with the objective of removing solids from crude,
but we typically observe about a 50% solids rejection to
brine. We have had several studies done by process chemi-
cal suppliers to look at solids removal for specific applica-
tions. To date, we have not employed any of those, being
concerned that there would be a significant increase in oil
undercarry in these applications.
DEATON:
The most common method is to use either oil soluble
or water soluble wetting agents. Wetting agents react with
surfactants that tie up oil and solids, and can effectively
deoil the solids and send them out with the desalter
effluent water. Typical percent filterable solids removal is
75%. Typical dosage rates range from 1 to 2 ppm based
on crude oil charge rate. Many demulsifier formulations
include wetting agents. In fact, all of the desalters that I
have worked on have contained wetting agents in the
demulsifier formulations. Indications that you need a
wetting agent are: large emulsion rag layers, oily effluent
water, poor solids removal, and water carryover. Once the
water is treated at the waste treatment plants, solids are
normally removed at the dissolved air floatation unit and
sent to a filter press and ultimately to incineration.
FELTROP:
Generally there are two broad profiles that bound the
range ofremoval philosophies. Refiners are strongly driven
20 General Processing and Support Operations
to remove solids via desalting if they have some combina-
tion of serious fouling problems or pressure drop capacity
limits; are eliminating effluent sludge at a coker; or are
eliminating effluent sludge as hazardous waste but have
solids related residual fuel product quality problems.
Conversely, refiners are strongly driven not to remove
solids by desalting if they have only moderate fouling that
does not impact capacity; they do not have solids related
residual fuel product specification problems and are elimi-
nating their dewatered effluent sludge as hazardous wastes.
Generally more refiners tend to fall closer to the latter
category than the former.
Costs of deviation from the governing philosophy typi-
cally range from hundreds of dollars per day for small
energy or process efficiency related effects to thousands of
dollars per day for capacity or product quality related
effects.
I wanted to make one note on the solids removal
determination. Appropriate procedures have been devel-
oped that measure water and toluene in soluble materials,
and with this evaluation most plants have shown little or
no removal of solids. There is a misconception that solids
collect in the desalter. That can easily be rejected when you
consider that 100 lb/l,000 bbl of solids in a 100,000
bbl/day desalter produces 120 cu ft/day of solids, and that
usually will fill your desalter up in less than a month. Based
on this, you need to be very careful in the way you analyze
the solids to make sure you are getting an accurate assess-
ment of the removal that is going on, because you can
make some erroneous judgments otherwise.
MARK BINFORD (Betz Process Chemicals, Inc.):
Regarding solids removal, and this also relates back to
questions 8 and 9, one of the applications that we have seen
for Agar probes is the use of a mud probe in the desalter.
We have found the mud probe to be a very effective tool
for managing solids removal, especially in regards to mud
wash frequency, duration and intensity. We do not have any
long term experience with the Agar mud probe, but are
encouraged by our experience thus far. I would be inter-
ested in Agar’s comments in terms of their long term
experience. We have seen it in operation for only about six
months, so we are not sure what its longevity will be.
B. Lube Oil Manufacturing
QUESTION 13.
What is your experience with fouling and corrosion
due to further degradation of NMP units?
CUNEO:
Shell Oil has utilized NMP as an extraction solvent in
its two high viscosity index (HVI) lube plants for about
ten years. Corrosion experience has been vastly different
TOC/INDEX
between the two. In one facility, there has been virtually
no corrosion. In the other, extensive corrosion was expe-
rienced initially in several major pieces of equipment:
reboilers, furnace, flash tower and transfer lines. The basic
difference in the operation of the two extraction units was
the control of chloride ingress into the process. At high
process temperatures in the extract furnace, NMP can
decompose into low molecular weight carbocyclic acids.
This process appears to be catalyzed by the presence of
chloride. Chloride introduction in the unit occurred when
waste water was being processed for NMP recovery. The
waste water, which contained up to 50 ppm of chloride,
was used to wash up solvent and oil spills.
Several steps were taken to bring the corrosion rate
under control. These include revised procedures for han-
dling waste water, use of amine neutralizing chemical to
maintain basic pH in the circulating solvent and upgrad-
ing the metallurgy at critical points in the unit.
QUESTION 14.
Are there any methods to predict the viscosity index
(VI) of the dewaxed oil on the so/vent extraction unit?
In ourprocess, we control the conditions of the solvent
extraction unit by the refractive index (RI) of the
refined oil (raffinate). We predict the VI of the de-
waxed oil by the RI of the raffinate, but the correlation
between the RI and the VI is not perfect.
ARMBRESTER:
Using the refractive index (RI) of raffinate to predict
the viscosity index of the dewaxed oil can be misleading,
since the RI is an average value of all the components in
the waxy distillate. Different molecular distributions can
give rise to the same RI but entirely different responses to
solvent extraction.
Ashland is presently exploring the use of our Infratane®
NIR technology to predict the viscosity index of the
dewaxed oil by analyzing the spectra of the raffinate, or
more preferably the waxy distillate feed stream to the
solvent extraction unit. The viscosity index of lab prepared
samples of waxy distillate, raffinate and dewaxed oil have
been correlated within a range of 1.1 to 1.7 index num-
bers. We believe that our NIR technology will allow
on-line adjustment of the solvent-treat ratio in the furfural
extraction unit based on analysis of the waxy distillate feed.
Ashland holds seven U.S. patents, with several others
pending, on the use of NIR technology in the refining
industry.
CUNEO:
We utilize a correlation between the raffinate API grav-
ity and the dewaxed oil viscosity index. The correlation
works wells as long as the source of crude processed
remains constant. When a change in crude source occurs,
an estimate is made for the extraction severity to be used
1994 NPRA Q&A Session on Refining and Petrochemical Technology
based on the aromatic content of the distillates. The
estimate would generally be conservative resulting in a
slight over extraction and higher than desired VI and a
consequent yield loss. We then adjust until the extraction
severity is where we need it.
PORTER:
Chevron manufactures lube base oils by hydrocracking
instead of solvent extraction. However, we also measure
the RI of the waxy hydrocrackate once per shift to monitor
the operation of the hydrocracker. The RI is used to
predict the dewaxed VI of the hydrocrackate. We also find
that the correlation between RI and the dewaxed VI is not
perfect. Thus, a sample of each lube oil cut from the
hydrocrackers is solvent dewaxed in the laboratory once a
day to obtain a dewaxed VI. The correlation is bias ad-
justed to reflect the results of the daily laboratory solvent
dewaxed VI. Thus, our correlation between RI and de-
waxed VI is continuously being updated to account for
any changes.
QUESTION 15.
A combination of solvent extraction and mild hydro-
treating is increasingly being adopted as a process
route to make high viscosity index lube oil base stocks
with improved yield and quality. Please share your
experience on this approach giving locations (if pos-
sible) of refineries adopting such practice.
CUNEO:
Shell Oil has practiced a combination of solvent ex-
traction and mild hydrotreating, hydrogen partial pres-
sure less than 1,500 psi, for more than twenty years.
Benefits resulting from this combination of processes are
numerous: increased product yield and higher feed rates
at the extraction unit resulting from less severe extraction
conditions; conversion of a significant portion of the
21
TOC/INDEX
remaining aromatics to naphthenes; and reduction in the
nitrogen content of the hydrotreated oils which improves
the oxidation stability of the base oils.
Types of catalysts employed have generally been cobalt
molybdenum or nickel molybdenum on an aluminum
base. Because the quality of the feed to the hydrotreater
has been upgraded by the extraction process, run lengths
for the catalysts have exceeded five years.
C. Solvent Deasphalting
QUESTION 16.
In view of increasing adoption of residual cracking,
what is the industry’s experience in revamping Sol-
vent Deasphalting (SDA) units to feedstock prepara-
tion units for secondary conversion processes?
LAUX:
We have fed the deasphalted oil from our McKee
propane deasphalting unit (PDA) and from our Three
Rivers Demex unit to both the hydrocrackers and to the
FCCUs. The Demex has not been revamped per se, but it
was built with extra solvent cooling capacity and runs with
a 5 to 1 solvent to feed ratio. Even without modifications,
our experience with feeding deasphalted oil to down-
stream conversion units is very good.
With our crudes, the total metals in the Demex feed are
around 100 ppm. The rejection is 75% to 85% at a 75%
Demex lift. The Conradson carbon in the feed runs
around 18%, and the weighted rejection is 50% to 60%.
In the FCC, the major concern obviously is Conradson
carbon. We run 2% to 3% in the combined FCC feed and
adjust the Demex lift to keep the regenerator temperature
at 1400°F while keeping gas oil inventory under control.
Typically, the Demex metals rejection has been high
enough that FCC catalyst metals are not a problem. We
run 1,000 ppm Ni and 2,000 ppm V at 0.3 1b/bbl of fresh
catalyst makeup depending somewhat on crude type.
When we started up our once through hydrocracker,
we decided to use it to process some demetalized oil
(DMO) even though the catalyst system had not been
designed for it. We fed DMO for about seven months at
less than 10% of the total hydrocracker feed. The metals
removal and Conradson carbon reduction were nearly
l00%, but very little conversion occurred even at the
2,400 psig system pressure. This helped the FCC heat
balance a great deal, and we were able to increase crude
charge significantly. We found that you need to keep a
close control on the asphaltene content, though, and
actually ended up deactivating our R-1 catalyst prema-
turely by over lifting in the Demex unit. We are now
getting ready for a reload, but with a catalyst system
specifically designed for feeding DMO.
22 General Processing and Support Operations
ARMBRESTER:
We have performed pilot evaluations of this option in
preparation for the restart of an idled SDA unit at
Catlettsburg. We believe this unit will provide additional
vacuum tower bottoms processing capability in our existing
RCC unit. A solvent will be selected with the objective of
producing a deasphalted oil (DAO) product with proper-
ties similar to the existing RCC feedstocks. DAO yields of
60% to 70% on Arabian light vacuum resid were obtained
in the pilot plant, with carbon and metals content compa-
rable to or better than Arabian light atmospheric resid.
Pilot plant cracking tests have shown the DAO to have
equivalent or only slightly poorer cracking yields than
atmospheric resid, while reducing RCC catalyst costs sig-
nificantly due to the lower metals content. Alternatively,
heavy crude oils could be charged to the refinery before
reaching bottoms processing limitations. Finding a suit-
able disposition for the SDA pitch product is obviously
the key to success for this processing scheme.
D. Crude Distillation
Mechanical
QUESTION 17.
Besides temperature control of hot water for carrying
out water wash of g/ass tubes in the crude furnace air
preheater, what alternative procedures or additional
instrumentation would aid in preventing breakage of
glass tubes during water wash operations?
HIGGINS:
The panel did not have an answer for this. In general,
they had no experience and were unfamiliar with the
operation. However, during our screening meeting at least
some attendees indicated that this is an important ques-
tion for some, so if you do have an answer or some insight,
please come forward.
No response.
QUESTION 18.
When coalescers fail to remove sufficient water from
a diesel stream to avoid a haze problem, what other
options have been found to be successful in solving
this problem?
LAUX:
Our diesel rundown streams go through electrostatic
coalescers or metercells before routing to salt towers for
final moisture removal. Because the coalescers operate at
120°F, the salt towers are not as effective as they might be.
We use a dehazing chemical about 10% of the time to
correct the haze problems at this high rundown tempera-
ture. We do this in the rundown tank before we transfer
TOC/INDEX
it to the finished product tank. We typically use about 10
1b/l,000 bbl.
McLEAN:
Coalescers generally remove about 70% or 80% of the
free water in a hydrocarbon stream. Options for further
treatment include additives to stabilize haze, vacuum or
salt driers, or switching from a steam stripper to a reboiled
stripper. Another option is to lower the pressure in the
stripper by installing a condenser and overhead pump to
achieve the necessary stripping efficiency without the use
of steam.
MENEGAZ:
Electrostatic coalescers are sometimes used in conjunc-
tion with phenolic or naphthenic acid removal. This
method will remove free water but not soluble water,
which still leaves you with the haze problem. A properly
designed and operated salt drier can dry fuel to a haze
point about 25°F below the temperature at which the fuel
enters the drier.
PORTER:
We use salt drying.
FELTROP:
I will comment briefly on the use of a dehazer since we
have covered the mechanical means very well.
Water haze can be effectively removed from diesel fuel
with the aid of specialized demulsifiers called dehazers.
These are designed to coalesce haze-causing quantities of
water, thus allowing the water to separate from the fuel.
Normally the use of a dehazer in conjunction with rolling
the tank to fully mix the dehazer will give superior results
in less time than settling alone. Dehazer use is also nor-
mally more convenient or less expensive than filtering or
reprocessing. If the problem is continuous and operational
or mechanical changes cannot be made to correct the
problem, the use of a dehazer, or you might call it an
emulsion preventative, on a continuous basis can be jus-
tified. The optimum chemical is selected using ASTM
D-4176 Procedure 2. Effectiveness really does depend on
the thorough mixing of the dehazer with the fuel being
treated.
Process
QUESTION 19.
What conditions in the crude overheadsystem impact
underdeposit corrosion? Has anyone experienced
specific problems at temperatures above the water
dew point? What practices exist to counter these
conditions?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
BARLOW:
Our research, modeling and field experiences indicate
that both underdeposit corrosion and corrosion ahead of
the water dew point in crude unit overheads are caused by
chloride salts precipitating before and around the water
dew point. The severity of the problem is determined by
the amount of scale present and the presence of an elec-
trolyte. Solid salts must have liquid water present from
absorption or condensation to be corrosive. However, they
can cause a pressure drop problem. The liquid salts can be
their own electrolyte, or can provide their own electrolytic
action.
Salt precipitation based on our modeling is controlled
by two factors. The first factor has to do with phase
equilibrium theory. The partial pressures of the vaporous
HCl and the neutralizing amine have a large impact on
that salt formation. The greater the quantity of either
component, the higher will be the temperature of precipi-
tation. This property is well documented in public domain
literature which discusses ammonium chloride salt pre-
cipitation.
The second factor is the base strength of the volatile
neutralizer. As a point of reference, any neutralizer with a
base strength equal to or greater than morpholine will form
a salt which is likely to precipitate well ahead of the water
dew point during normal operations. This second factor is
the primary controlling factor, based on our experience,
and salt formation potential is a key in selecting the proper
neutralizer. Selection of the key component neutralizers is
required as opposed to attempts at blending of traditional
amines in order to lower individual vapor pressures.
Utilizing this modeling theory in developing proprie-
tary technology, we have been able to virtually eliminate
underdeposit corrosion on several crude overheads.
BOYCOTT:
Conditions that impact underdeposit corrosion are:
overhead temperature and pressure,
wash water rate, quality, and point and type of
injection,
sulfur and chloride composition, and
neutralizing compound and application.
We have experienced underdeposit corrosion in our
overhead system. We believe that the contributing factors
have been wash water rate, distribution, and quality. We
have evidence of wash water maldistribution in the system.
We operate below the water dew point.
CUNEO:
I agree with the comments of both speakers, especially
Mr. Barlow. We have experienced very aggressive overhead
line and condenser bundle corrosion. Some life as short as
three to six months was associated with the presence of a
chloride salt and certain neutralizing amines where the
neutralizing amines had been added for corrosion control.
23
TOC/INDEX
As Mr. Barlow said, sometimes too much is not good.
Overdosing the neutralizing amine can actually cause
more aggressive corrosion.
DEATON:
This problem occurs when neutralizers and chloride
react to form salts above the dew point of the system such
that liquid water is not available to dissolve the salts. For
years Clark’s Blue Island Refinery suffered severe underde-
posit corrosion in the first crude overhead vapor versus
crude exchanger. The crude atmospheric tower top tem-
perature runs between 340°F and 350°F. Dew point cal-
culations showed the first exchanger to be dry. Based on
the recommendation of our chemical supplier, the neu-
tralizer injection point was moved from the top of the
crude overhead vapor line into the outlet of the first
vapor-to-crude exchanger. We then recirculated overhead
tail water back between the two exchangers and injected
the neutralizing amine into that water. Since changing
over to that program six years ago, we have not had any
more underdeposit corrosion problems.
At another refinery, I had a similar problem. We in-
jected a low melting point neutralizer without water into
the vapor line ahead of the first exchanger and injected our
normal neutralizer downstream of this exchanger along
with the circulating wash water.
FELTROP:
The deposits that are found on failed exchangers are
predominantly iron sulfide, which is the least soluble salt
likely to be in an overhead system. To determine the
conditions in the crude overhead which impact underde-
posit corrosion, one must determine what controls the
formation of the iron sulfide deposits. The solubility of
iron sulfide is dependent on pH and the amount of H2S
in the system. Iron sulfide solubility increases as pH
decreases and H2S concentration decreases.
The counter to eliminate iron sulfide deposits and the
resulting underdeposit corrosion is to operate the overhead
at conditions at which iron sulfide is soluble. These condi-
tions can be calculated through a definition of iron sulfide
as a function of pH and H2S concentration. The objective
is to operate the accumulator at the highest pH at which
the iron sulfide will have sufficient solubility to prevent
deposits. The required pH in most units is below 5.5.
While general corrosion may be slightly higher at these
pH levels, elimination of the deposits will result in sub-
stantially longer exchanger life and improved equipment
reliability. There are numerous examples of corrosion
problems on trays inside towers and in hot vapor lines
which are well above the dew point of water. These prob-
lems are primarily caused by amine chloride salts.
We echo the comments of the earlier panelists that you
need to be very careful with the injection of neutralizers,
and particularly in the overuse of those.
24 General Processing and Support Operations
LAUX:
Our crude atmospheric tower also has a top pum-
paround stream that exchanges heat with crude. The
return temperature is kept above 230°F to prevent water
condensation in the tower. The overhead vapors are con-
densed in four parallel fin fan bays with two inlet nozzles
per bay. Water with neutralizing amine is injected into
each nozzle through a restriction orifice to control the flow
to 5 gpm per nozzle. We also inject naphtha with an oil
soluble filming amine into each nozzle and into the main
vapor line at the top of the tower through restriction
orifices at 2.5 gpm per nozzle. This system gives us good
distribution of the chemicals and flush liquid, and we have
not seen any corrosion in our overhead system.
To monitor the effectiveness of the wash on-line, we
check the pass outlet temperatures. If there is a 20°F spread
between any pass, we pull the restriction orifices one at a
time and water wash the fouled passes until the delta T
comes back into the normal ranges of 5°F or less.
PORTER:
Most of my points have been covered by the previous
panelists, but I would like to make a comment on the
design of the overhead system. We think that is very
important. We prefer a vertical in-tube condenser with
continuous water wash.
SAYLES:
I agree with the comments of the prior speakers. We
have a tower that operates with a 200°F, or less, top tower
temperature with a water dew point within the tower. This
presented a challenge in keeping tray corrosion to a mini-
mum. Fortunately, our chemical vendors came up with an
interesting solution: a split chemical feed system. First,
filmer is fed into the reflux line to the top of the tower,
and then filmer and neutralizer are put in the overhead
line to protect the exchangers. This has worked fairly well.
We are into the end of a four year run, and an internal
inspection is planned.
TREESE:
The other panelists have touched on where the filming
amine goes in and where the water goes in. How effective
your corrosion control is going to be in the overhead
depends strongly on your specific case. In one refinery we
do not experience any significant corrosion problems at
temperatures above the water dew point. We do not do
anything special. Our corrosion inhibition is simply by
neutralizing with ammonia.
In another refinery, we think we do have a problem
above the dew point, and we think it is, as mentioned
before, due to the amine salts being formed within the
tubes from the amine neutralizer. We are fairly certain this
can be eliminated by moving the wash water injection
point further upstream; but in this case, where we have a
TOC/INDEX
tight approach on temperature, we are not willing to take
the loss in heat transfer efficiency. So we live with the
corrosion, and we accept, in effect, the one to one-and-a-
half year tube life on these exchangers. We can tolerate this
because the exchangers can be bypassed and changed out
on-line.
PAUL FEARNSIDE (Nalco/Exxon Energy Chemicals):
It has been our experience that some people have
experienced corrosion ahead of water dew point due to
sulfuric acid. That is being put into the unit two ways.
One is through sulfuric acid addition to sour water strip-
pers for pH control and then this water being used for
desalter wash water. The other is by using oxygenated wash
water to a desalter, allowing oxygen to ingress into the
crude unit and react with the H2S and form the resultant
SO4 in the overhead. It is very important that these not be
allowed to take place as it does not take very much SO4 to
push the sulfuric acid dew point ahead of the water dew
point.
The second point I would like to make has to do with
situations where you are using different amines to control
ammonia chloride salting ahead of the water dew point.
It has been our experience when using amines with base
strengths less than motpholine, that while they do control
and stop the injected amine salting ahead of water dew
point, they inadequately address the pH of the water dew
point. We have found that using those types of amines
typically takes one and a half to three times the
stoichiometric amount necessary to neutralize the chlo-
rides to elevate that water dew point pH up into a 4.5 or
greater pH range to stop dew point corrosion. This results
in drastically higher corrosion control program costs. So
you have to be careful when you are utilizing that technol-
ogy.
The third point is iffouling and underdeposit corrosion
is due to ammonia chloride subliming ahead of the water
dew point using an amine with less base strength than
ammonia (i.e., morpholine, pyridine, or picoline) will not
stop the ammonia chloride fouling and corrosion prob-
lem. In this case you either have to reduce the amount of
tramp ammonia or use amines with higher base strengths
to accomplish the straight forward chemical displacement
reaction of the ammonia. Once the ammonia is displaced
off the ammonia chloride, then the salt fouling and cor-
rosion problems will no longer exist.
QUESTION 20.
Has anyone experienced operating or maintenance
problems with structured packing in atmospheric or
vacuum crude columns which would make you think
twice about using them again? If so, what was the
nature ot the problem?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
SAYLES:
At one of our refineries the vacuum tower was retrofit-
ted with packing in 1988. We would choose packing
again. Packing reduced the top tower pressure from about
60 mmHg with trays to about 20 mmHg with packing.
The flash zone pressure was reduced from about 100
mmHg with trays to about 26 mmHg with packing. The
lower flash zone pressure allowed for a lower heater outlet
temperature while obtaining a lower bottoms yield. These
modifications were made in 1988 and the packing has not
been cleaned. Visual inspection of the packing from the
top and the bottom indicated the material was in good
shape.
At another location, initial operating problems with the
HVGO flush caused packing pluggage. After improving
the flush system the run time increased from 3 to 10 years.
LAUX:
I would echo the comments just made about the wash
oil rates. We have two towers at the Three Rivers refinery
that have packing in five different sections and have no
problem whatsoever. However, as reported in the 1988
NPRA Q&A transcript, our FCC main column at the
McKee refinery had a tremendous problem and we took
the packing out. That was due to poor liquid distribution.
The towers in Three Rivers were designed for a 0.15
gpm/sq ft coverage at the bottom of the grid, which
calculates back to typically about 0.5 gpm/sq ft at the top.
BOYCOTT
I agree with the previous comments on the performance
of packing and the criticality of liquid distribution and
maintenance of a wetted surface. Structured packing has
been installed in all sections of our vacuum tower. We have
had problems with the loss of a bed, specifically the wash
oil grid. We believe the problems stemmed from improper
grid installation and a unit upset. Modifications were
made to the bed unification and hold-down systems to try
to improve their structural integrity. The bed was unified
with through bolts. We did not consider elimination of
the structured packing for reasons of performance.
D’AURIA:
We are aware of seven incidents where there were some
problems with packing, not in operation but at turn-
arounds. In each one of these incidents, there was an auto
ignition that occurred in the packing bed. This occurred
even though the column had apparently been properly
steamed out. In all cases, the packing was either partially
or in some cases totally destroyed. In one case, there was
actually some damage to the column itself. It is thought
that the cause of this was pyrophoric iron sulfides, perhaps
also accelerated by coke or hydrocarbon that had not been
removed during the steaming operation. In two of the
25
TOC/INDEX
occurrences, the feedstock contained unusually high con-
centrations of iron.
Remedial actions that have been taken to avoid reoc-
currences are: 1) installation of a water wash capability
above the packing section to allow thorough washing prior
to opening the column, and 2) installation of delta P taps
across the packing section to monitor plugging of the bed
due to coking. We have not heard of any repeat incidents.
S. N. MATHUR (Hindustan Petroleum Corporation Ltd.):
The question referred to crude and vacuum towers.
Does anyone have experience with using structured pack-
ing in FCC fractionators, and what has been the operat-
ing and maintenance problems with these in FCC
fractionators?
LAUX:
As I mentioned, we did have structured packing in our
FCC main column at McKee. We took it out. I have also,
though, seen a completely packed tower at the Champlin
Refinery, now CITGO Refinery, in Corpus Christi, and
their operation is very good at this point.
PORTER:
We put structured packing in our FCC fractionator at
Pascagoula four years ago above the light cycle draw. We
have had good success.
26 General Processing and Support Operations
QUESTION 21.
Is there a crude API breakpoint that requires recycling
naphtha or distillates for viscosity reduction? What
are the desalter operating benefits to be realized?
MENEGAZ:
Recycle naphtha or distillates are used as cutter stock
co improve desalter performance by (1) increasing the
density difference between the crude and water and (2)
decreasing the crude viscosity. Desalter performance is
improved because both actions increase the settling veloc-
ity in accordance with Stokes Law. Although electrostatic
desalting without diluent has been done successfully down
to 12° API, diluent become increasingly attractive below
18° API due to performance improvements. Heavy Cali-
fornia crude such as San Joaquin Valley at 15° API have
been successfully desalted using 5% naphtha diluent.
Heavy Arabian atmospheric residual at 12° API has been
successfully desalted using naphtha diluent to raise the
gravity to 17° API. At h abasca tar sand bitumen at approxi-
mately 10° API and Boscan crude at 10° API have also
been successfully desalted using diluent. The cutter stock
should be selected co avoid asphaltene precipitation due
to crude incompatibility.
PORTER:
We think the desalter design and the oil viscosity at
operating temperature are also important variables in ad-
dition to API. In question 7, I described a desalter we
converted to a bielectric design that handles 14° to 16°
API gravity crude without cutter. That operating viscosity
is about 4 to 5 centistokes. For that unit it is probably at
the ragged edge, because when the operating temperature
drops, we do see a drop in performance.
In another low velocity type desalter, we find that we
have to add cutter to be above 20° API to get the unit to
perform satisfactorily.
FELTROP:
I agree with both of the comments. In general, the
ability to run a particular crude successfully through a
desalter is a function of API gravity, viscosity and tempera-
ture. Crudes heavier than 14° API usually require dilution
for viscosity reduction. This can be overcome to some
extent by increasing temperature as that will inherently
reduce viscosity.
Note, however, that API gravity is not the only variable
that affects crude oil viscosity. One 11.5° API gravity
South American crude requires no diluent as the viscosity
is 6.0 centistokes at 275°F. A lighter crude such as the ultra
waxy Chinese crude with a 36° API gravity requires dilu-
ent because the viscosity exceeds 50 centistokes at 300°F.
The desalter benefits include cleaner effluent, better salt
removal, lower desalted crude BS&W and the possibility
of higher net thruput in the same size vessel.
TOC/INDEX
BARLOW:
I think the previous panelists covered the subject well.
We see the need for cutter when the API gravity is 13°, or
less. A target of 17° is reasonable. Viscosity is a concern,
but the API is a good initial targeting method.
CUNEO:
Just one additional comment, when considering capital
projects, you can often trade off naphtha recycle for capital
costs on the desalting facility.
E. Instrumentation
QUESTION 22.
instruments that can be used to
Are there any reliable
measure pulsating flow from chemical injection
pumps?
BARLOW:
We do not find a great number of needs for reliable
automated measurement on pulsating flow chemical in-
jection pumps other than the control of the pump. When
we do run into those situations where we need measure-
ment, several instruments exist. One is the Pacesetter Plus
computerized chemical feed system. It comes with an
optional drawdown assembly or module that confirms and
verifies chemical injection rate as a function of a primary
flow signal or a treatment set point. It is a device located
at the suction or inlet to the chemical metering pump. It
operates essentially on the same principle as a pump
setting gauge or rate gauge commonly used manually to
check and calibrate pumps. Integrated electronics and
software permit a continuous monitoring and control
scheme and do ensure reliable chemical injection and
measurement on critical applications.
There also exist a number of commercially available
instruments designed for the purpose of measuring pul-
sating flows from positive displacement pumps. The in-
struments utilize a positive displacement measuring
approach whereby a piston or series of pistons are dis-
placed by the liquid or treatment solution being pumped.
The pistons’ action, with a known volume and reciprocat-
ing at some frequency based on flow, is converted, either
optically or mechanically, to an encoder which in turn
scales that measurement to an instrument signal.
BOYCOTT:
We use drawdown gauges on the suction of our positive
displacement pumps. They are checked and recorded
every shift. We have not found a need to go to any of the
more sophisticated instruments on our chemical injection
systems.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
CUNEO:
Where needed we have used Coreolis type meters by
Micro Motion on these types of applications with reason-
able success.
FELTROP:
I concur with those comments and would add on the
Coreolis meters that at low flow and high viscosity a
pulsation dampener added to the system is often necessary.
LAUX:
We agree with the simple suction level glass that Mr.
Boycott mentioned. It is the most economical thing to use.
KENNETH D. PETERS (UOP):
We do not feel that the cost and the complexity that
these instrumentation systems are currently justified in
almost any of our applications. We set the flow rate for
these small positive displacement pumps by measuring the
amount of liquid withdrawn from the calibrated sight glass
over a fixed time period. Certainly the key to reliability is
to keep that whole system free of any particulates and to
use stainless steel piping systems and filters to ensure that
the pump’s ball checks particularly do not get plugged. The
simplicity of this type ofsystem, when kept clean, provides
the reliability.
QUESTION 23.
What is the current experience of refiners using on-line
analyzers for certifying finished gasoline products?
ARMBRESTER:
The only location where we use an analyzer to actually
certify the gasoline blend is at our St. Paul, Minnesota
refinery where we use the NIR technology to analyze the
gasoline octane for certification on the product that we
ship across the rack. There is a significant portion of our
product at that plant that is transported by pipeline, and
the pipeline company does not accept the NIR certifica-
tion at this point. However, we do use it for the remainder
of our shipments.
At our Catlettsburg refinery, we use several on-line
analyzers as part of our computer control blending opera-
tion, but these instruments are not used to officially certify
the blends. However, we do use them for blending control
purposes and then certify the blend by laboratory analysis
of the finished product tank samples.
We have applied for a computer controlled in-line
blender exemption under the reformulated gasoline regu-
lations. Blends of reformulated gasoline (RFG) will still
require lab testing for certification, but the in-line blender
exemption would allow us to ship finished blends before
the laboratory analyses are complete.
Our Infratane® NIR technology is being used to pro-
vide on-line analysis of the gasoline octane, as well as the
27
TOC/INDEX
gasoline’s aromatic, olefin, oxygenate and benzene con-
tent. This analyzer is also capable of performing its own
calibration checks by periodically analyzing samples of
various gasoline prototype fuels. We are also using two
other analyzers in our gasoline blending operation: a
Hallikainen Model 1354 Kinetic Vapor Pressure analyzer,
and an ABB Process Analytics Model 3102 which reports
D-3710 distillation analysis.
BOYCOTT:
We monitor our blend RVP and octane with an on-line
NIR analyzer. Correlations indicate that the accuracy of
this analysis is comparable to our knock engines. We plan
to close the loop on blend control with this analyzer in the
future. At this point, I am not aware of any pipelines that
accept the NIR analyzer for certification of shipment, so
we continue to use our knock engines for final blend
certification. We are working to have the NIR results
accepted for this.
CUNEO:
We have on-line knock engines for octane measure-
ment at our largest locations. We have on-line Precision
Scientific KVP analyzers that have been correlated to RVP.
We also have an on-line distillation gas chromatograph
that we use for distillation. All of these are used for
certification.
We have obtained a waiver for in-line blending for
RFG. In that case, all of the properties except octane will
be off-line.
D’AURIA:
UOP’s Guided Wave division is seeing increasing inter-
est in the use of NIR techniques for on-line measurements.
There are currently more than 30 such NIR analyzers in
use on finished gasoline blending applications, and that
number is growing rapidly. Industry experience has been
very good with these analyzers. The NIR technique is not
yet an accepted standard for certification of finished gaso-
line. ASTM, however, does have a subcommittee actively
working on certification of this technique as a standard
practice.
LAUX:
Like the other panelists, we also are experimenting with
new analyzers, like the Infratane, NIR. We also have an
Applied Automation SimDist machine analyzing distilla-
tion points. We are using the ABB machine for RVP, but
we are waiting for certification as well. We are using these
analyzers to direct blend into a pipeline at our McKee
Refinery. Experience has been good.
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
In Europe, several refiners have obtained ISO 9000
certification of analyzer systems and used them for
28 General Processing and Support Operations
producing quality certificates on finished motor gasoline
(mogas), gas oil and fuel oil products.
In the USA, today many refiners use octane compara-
tors and RVP analyzers to blend directly to pipelines or
other off-plot destinations (this depends mainly on spe-
cific contractual arrangements the refiner has with the
purchaser). This will change with RFG which requires
laboratory samples (tank or composite). The “on-line
computer control” waiver option does provide a possibil-
ity of on-line certification.
QUESTION 24.
What instrument/control system changes are refiners
making to optimize reformulated gasoline blending?
TREESE:
Unocal is adding on-line analyzers for key blendstocks
and for the final blend header, as well as on-line optimi-
zation systems at each of our refineries. All of our blenders
are now DCS or computer-controlled. We have eight to
nine specifications to meet in California, not all of them
immediately, but within the next year.
For the blend header, we are planning to use Applied
Automation gas chromatography for on-line analysis of
RVP distillation points, benzene and aromatics. On-line
analyzers we considered, but rejected as not yet proven to
our satisfaction, are: GC for olefins, on-line x-ray for sulfur
and NIR for octane. Obviously we will reconsider these
analyzers in the future as we gain some confidence in them.
For key blend stocks, which comprise 5 out of some-
what over 20 stocks that we are going to be blending, we
are going to time-share one set of analyzers monitoring the
same properties as the blend. All our analyzers are going
to have an on-line reference stock that is used to calibrate
the analyzers roughly every hour to hour and a half. I did
not mention it, but we do have on-line knock engines for
the final blend octane rating.
PORTER:
We can blend reformulated gasoline on our existing
equipment, but because there are more variables to con-
trol, we cannot optimize it as well. At the Pascagoula
Refinery, we are strongly considering a project to integrate
our current blending models and do blend property con-
trol within a new instrumentation system to achieve better
optimization.
LAUX:
As mentioned in the previous question, we have several
new on-line analyzers installed that we believe will help us
optimize our RFG blending. We have also installed a new
Honeywell blend package with these analyzers and have
purchased an RFG blending LP (Wright Killen’s
WKBLEND).
TOC/INDEX
But, we have to master the techniques needed to use the
LP, especially at the blender’s level. It takes experience and
technical ability to master these complicated programs.
Our blenders are not at that level yet. It will take some time
to develop the intuition necessary to make changes to a
blend recipe with all the new specifications. Since the RFG
laws are very restrictive and the penalties for any noncom-
pliance are high, we do not intend to start using these
techniques immediately when we start blending RFG.
ARMBRESTER:
As I mentioned previously, we are using on-line analyz-
ers to determine octane, vapor pressure, D86 distillation,
aromatics, olefins, benzene and oxygenate values. The
NIR analyzer that we are using has been in service for
about four years at St. Paul and two years at Catlettsburg.
In the Catlettsburg blending operation, we are using
Honeywell’s Blend Ratio Control software in conjunction
with a multivariable critical property control program
developed by Oil Systems. The current properties of the
gasoline blender’s product are used to calculate the opti-
mum blend recipe for the remainder of the blend, using
another Oil Systems’ product known as MGBLEND. We
have also installed a higher level optimizer to perform
linear analysis of the refinery’s product demand and gaso-
line component availability, and then set blend schedules
and recipes which will maximize profit.
The simple and complex RFG models are now being
added to these software packages in preparation for RFG
blending. In addition, when we get to complex model
blending, we will need to add an on-line sulfur analyzer. I
might also mention that at St. Paul Park we are using the
Honeywell Blend Ratio Control, but some of the higher
level software packages in use at Catlettsburg are not being
implemented at St. Paul Park since the blending operation
is considerably less complex.
BOYCOTT
Although we are in a conventional gasoline area, we
have made significant efforts to improve the control and
optimization of our blending. They are inclusive of the
NIR analyzer already discussed, installation of a new
blending system inclusive of hardware modifications to
eliminate component bottlenecks, and increased emphasis
on consistent unit rundown parameters.
The result has been as much as a 75% reduction in RVP
and octane giveaway.
D’AURIA:
With the advent of advanced on-line analytical tech-
niques as well as the availability of powerful control
schemes, refiners are revamping their blenders with the
latest technology. As regulatory demands increase, in
both fuels production and quality documentation re-
quirements, refiners have turned to the NIR analytical
1994 NPRA Q&A Session Refining and Petrochemical Technology
technique for its capabilities and to advanced blend ratio
and blend property control systems for real time blending
optimization.
DAN HARTLEY (Haverly Systems, Inc.):
The blending systems that I see going in vary from
refinery to refinery, but the ones that I see going in mostly
involve software programs which optimize the recipe off-
line. Several of these programs are available in the market-
place. One that I am familiar with is Haverly Systems’ H
Boss. This information is downloaded to a multivariable
control system which controls the blend ratio control or
the in-line blender. Then the feedback from the product
lines is used to send information back to the multivariable
control system which then trims up the recipe. Some of
the software programs that optimize the recipe will also
optimize the blend schedule. With all the specifications
and regulations that are coming along, it is almost impos-
sible to do these things by hand, so I think this is where
everybody is heading.
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
Major changes include two areas: new analyzers to
measure RFG and regulated conventional properties and
reallocation of tankage and piping in off-site areas to
isolate conventional and RFG. A major change in control
system configuration and operation is required to opti-
mally segregate reformatted RFG and conventional gaso-
lines.
QUESTION 25.
Who performs hardware/software maintenance on the
newer generation DCS? Is it p/ant instrument main-
tenance (hour/y), salary p/ant staff/professional per-
sonnel, factory maintenance contract, or others?
ARMBRESTER:
Ashland has used a combination of these options at our
three refineries, depending on the maturity of the distrib-
uted control system. We have typically used contract
support engineers from the DCS equipment vendor to
provide expert assistance during the commissioning of the
system and the first year or two of operation, with plant
hourly personnel doing the hands-on work on the hard-
ware. As the expertise of our personnel has increased, we
have eliminated the use of the manufacturer’s local support
engineers. The ongoing maintenance support of the DCS
hardware and the lower level software is performed by our
hourly instrument technicians under the direction of in-
plant salaried personnel. The only exception to this is our
St. Paul Park refinery, where the hands-on work is per-
formed by salaried personnel, since we have no hourly
instrument technicians at this facility.
In all of our refineries, the higher level software, includ-
ing the advanced control systems, is maintained by the
29
TOC/INDEX
in-plant professional staff. We also maintain a service
contract with our DCS vendor for remote support of
system upgrades and trouble shooting.
BOYCOTT:
We have recently completed a conversion of our crude
unit from electronic instrumentation to a distributive
control system, inclusive of advanced controls and on-line
matrix optimizers. At this point, most of the support is
being provided by the technical personnel that installed
the system. We intend to continue to supply software
support with these people, but we are in the process of
training plant instrumentation people to provide the hard-
ware support.
PORTER:
We do not have a consistent approach at our refineries.
Generally, though, it is like we do at Pascagoula. The
hardware support is supplied by the I&E maintenance
people. The software support, software development and
control applications are done by our technical group. That
technical group is made up of ex-operators and engineers.
At a few sites, we do use contract factory personnel.
SAYLES:
We use technicians for hardware repair and professional
people for the software and DCS programming.
TREESE:
Generally we follow along the same lines. The hardware
maintenance is performed by hourly maintenance person-
nel that are part of specialized DCS and analyzer mainte-
nance crew. Software maintenance is performed by
salaried systems analysts and/or process control engineers.
We have had some systems analysts who were operators
that became very conversant with the systems; some of the
best actually have turned out to be computer programmers
that wanted to get into this end of the business.
I note we have used our computer systems suppliers
extensively in getting started and in setting up a lot of the
DCS systems, but I have found the more deeply we can
get involved, the smarter we become on the systems and
we experience on stream efficiency and reliability.
QUESTION 26.
Please comment on the use of flame scanners in
refinery process furnaces. Are they used just on new
units or also on existing plants? What type of flame
scanners are recommended for multiple fuel fired
furnaces?
BOYCOTT:
We have installed flame scanners on new installations.
We have not retrofitted existing furnaces with flame scan-
ners. I would like to point out that we have had false
30 General Processing and Support Operations
furnace shutdowns on our hydrogen plant reformer while
x-raying piping in adjacent units due to interference with
the flame scanners. We have attempted to use lead shield-
ing on the scanners to prevent this. Tests of the scanners
with shielding installed and the shutdowns bypassed indi-
cated that the shields would not prevent a shutdown. We
have been forced to develop procedures to bypass the flame
scanners’ shutdown trips while x-raying in the area.
DEATON:
My experience is with flame scanners installed on
forced draft upright, “can” type heaters. All of these heaters
have a single large burner mounted in the floor. There are
two flame scanners. One is a pilot flame scanner mounted
in the floor and aimed up at the pilot. The other is a main
burner flame scanner mounted in the wall and aimed at a
slight slope downward toward the main burner.
Each flame scanner has an instrument air purge
through the sight port to prevent debris from obscuring
the sight port. Both flame scanners have to show no flame
before the safety gas shutdown valve will close. Before the
pilot can be lit, a purge timer has to be satisfied. Then
before the main burner can be lit, the pilot flame scanner
has to be satisfied.
All of these scanners are on new heaters, but there is no
reason why scanners could not be installed in existing
heaters. Burners firing on fuel gas use scanners operating
in the ultraviolet range. Burners firing on fuel oil use
scanners operating in the infrared range. Furnaces with
combination fuel gas/fuel oil burners would probably
need three scanners: one UV pilot gas flame scanner, one
UV main burner gas flame scanner, and one IR oil flame
scanner.
ARMBRESTER:
Ashland uses flame scanners on all of our new boilers
and process heaters, as well as on most of he existing units.
For heaters and boilers which are fired with a single fuel,
we use an infrared detector, Fire Eye Model 45RM1 for
oil burners, and an ultraviolet detector, Fire Eye Model
45UV5-1000 for gas burners. On furnaces which fire a
combination of fuel gas and heavy fuel oil, we have used
an infrared spectrum scanner, Fire Eye Model 45RM2, but
we are now specifying the RM4 model, which is an
improved version of the RM2 scanner.
All of these scanners have provided very reliable service.
Loss of flame dry contacts are incorporated into our
protective shutdown scheme so that loss of flame will close
the fuel gas shutdown valve.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Have the flame scanners been installed in natural draft
furnaces?
TOC/INDEX
DEATON:
My experience, as I mentioned, was in forced draft
heaters. I have no experience with them in natural draft
heaters.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Are there any new type of flame scanners that will not
be affected by x-ray, preventing unnecessary shutdown of
the boilers?
BOYCOTT:
Out experience is strictly with the W scanners de-
signed for use with fuel gas. All of the flame scanners that
we have used are affected by x-rays.
ARMBRESTER:
I can comment on your first question. We have success-
fully used flame scanners on individual burners in both
forced draft and natural draft furnaces. However, we have
several box-style natural draft furnace with multiple
burner designs, on which we are not using flame scanners.
CURTIS CAVANAUGH (The Coastal Corporation):
We do have experience with a flame scanner on a
natural draft furnace at our MTBE facility in Cheyenne,
Wyoming, so there is experience with natural draft fur-
nace.
F. Product Formulation
QUESTION 27.
For an in-line gasoline blending system, is there a
flowmeter which can measure flow independent of
stream composition so that several different fluids
can be b/ended and measured through one meter
without recalibration?
CUNEO:
For in-line gasoline blending, we recommend the use
of turbine meters for the total flow after blending of all of
the components. We are also installing turbine meters on
the oxygenates and specific gravity analyzers on the total
gasoline blended to calculate the wt% oxygen.
ARMBRESTER:
Both turbine meters and vortex meters work well for
in-line gasoline blending service. The most important
requirement for an in-line blender meter is the ability to
provide accurate measurement over a wide range of flow
rates. Since the different materials being measured are all
gasoline streams, switching components from one meter
to another is not a problem. Modern control software,
such as Honeywell’s Blend Ratio Control, has the sophis-
tication to allow the operator to assign a specific blending
1994 NPRA Q&A Session on Refining and Petrochemical Technology
component and its associated properties to a given flow
meter and then perform temperature correction based on
the API gravity of the material flowing through the meter.
TREESE:
Our experience has been primarily using turbine flow
meters, which have good range-ability. They are relatively
insensitive to stream composition, or at least the compo-
sition differences among the stocks that we are blending
is consistent enough that it does not make a significant
difference to the meter.
JULIE VALENTINE (Micro Motion, Inc.):
The Micro Motion mass flow meter also offers in-
creased flexibility for in-line blending systems. The inde-
pendence from composition allows multiple products to
be metered through a single device which is useful for
spares, additional capacity, or changing additives. The
wide turndown of the meter, which is greatly increased
from what you would see with a turbine meter, at 100 to
1 turndown, also adds to the overall flexibility and can
significantly reduce project cost. We can also simultane-
ously measure the density of the stream, which allows for
product verification.
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
The question needs to be separated into two subjects:
component flowmeter and custody transfer meters. Al-
most all the refineries in the world we have studied and in
which we have done projects run many different compo-
nents through a flowmeter without any recalibration.
Most motor gasoline blending installations use turbines as
primary elements. They are viscosity sensitive, but the
viscosity differences between motor gasoline components
are negligible for measurement accuracy. Vortexes are gain-
ing popularity as primary elements; they have to be oper-
ated above a threshold Reynolds number. This is usually
accomplished with minimum fluid velocity, not recali-
brating the primary element.
The meters used to deliver motor gasoline (mogas) (or
any finished product) for custody purposes is a different
matter altogether. In this case, any significant stream
composition changes would have to be accounted for if
conventional meters are used. Some of the new coriales
technology-based meters should have a wider range of
applicability without recalibration, but we have not had
commercial experience with those meters at this time.
QUESTION 28.
What changes in unit operations will result from the
reformulated gasoline complex model versus opera-
tions under the EPA Simple Model? Are any refiners
planning to use the Complex Model prior to 1998 and
if so, how will fungibility be handled?
31
TOC/INDEX
D’AURIA:
The Simple Model correlates gasoline emissions with
RVP, oxygen, benzene and total aromatics, In addition,
there are caps placed on olefins, sulfur and T90 based at
the refinery’s baseline levels. For the Complex Model,
olefins, sulfur, E200, and E300 are added to the previous
parameters in the Simple Model equations.
When you compare the Simple and the Complex mod-
els, the two parameters that stand out are sulfur and
olefins. Sulfur plays a significant role in toxics and NO,
emissions under the Complex Model. Olefins also play a
significant role in NO, emissions, especially at olefin
concentrations above 15 vol% in the gasoline.
Changes in unit operations resulting from going from
the Simple Model to the Complex Model, clearly will be
those that control gasoline sulfur and olefin content. In
the case of sulfur, this means FCC feedstock hydrotreat-
ing, or heavy FCC gasoline sulfur reduction. Reducing
gasoline olefin content can be achieved by removing the
C5 olefins via alkylation or TAME production.
Looking further down the line, control of sulfur and
olefins will become even more important when you get
into the Phase II regulations, in the year 2000.
Another difference between the Simple and Complex
Models is that the tradeoff between benzene and aromatics
is about 50% greater for the Complex Model than it is for
the Simple Model. So as you move into the Complex
Model, you have the opportunity to go to higher total
aromatics levels in the gasoline, at a given benzene con-
centration.
We would not expect most refiners to use the Complex
Model prior to 1998, primarily due to the cost and the
complexity of segregating Complex Model gasoline from
Simple Model gasoline.
ARMBRESTER:
We agree with Mr. D’Auria’s comments regarding both
sulfur and olefin content being the major concerns. On
sulfur level of the gasoline, we also believe that we will
either need to reduce the FCC gasoline end point or
hydrotreat the FCC gasoline stream for sulfur removal.
The olefin content of the gasoline will also be an issue,
and as Mr. D’Auria mentioned, we are looking at reducing
the RVP of the FCC gasoline stream and using the C5’s as
feedstock to a TAME unit. That has the added benefit of
increasing alkylate and/or MTBE production, both of
which are desirable blending components for RFG.
We do not plan to use the Complex Model prior to
1998 due to the fungibility issue. If we were to go ahead
and implement Complex Model blending, that would
require our exchange partners to do so also.
PORTER:
We are not aware of any refiner who is going to be able
to use the Complex Model because of what was just
32 General Processing and Support Operations
mentioned, even though some refiners may find it easier
to meet the Complex Model than the Simple Model
requirements. It really depends on what your baseline was
back in 1990 versus the industry baseline on these key
parameters. Some refiners may not have to do anything.
However, if your refinery has changed considerably since
1990, and sulfur and olefin levels are higher, you may have
to make some changes.
SAYLES:
I agree with the other presenters that the Simple Model
will be used at least for the first two years; the Complex
Model is required in 1998 unless something changes. The
key difference here, for those of us who are conventional
gasoline producers, is what we have to do to make gasoline
that will allow us to take advantage of some of the breaks
built into the Complex Model. Some of the options are
adding ether production, maybe C5 alkylation, and ben-
zene reduction as discussed this morning.
TREESE:
Echoing the comments of the other panelists, we are
going to use the EPA Simple Model for RFG compliance.
In our case, we have a few different factors, perhaps, that
weigh in the decision. A primary issue for us is that
common carrier pipelines in California will not accept
Complex Model gasoline until 1998. Again, there are also
the exchange issues.
In addition, we will be subject to the California Air
Resources Board (CARB) specifications in addition to the
EPA. The CARB regulations are more strict, setting spe-
cific values for around eight to nine properties, as opposed
to EPA’s more performance-based specifications. We can-
not take advantage of the breaks that might be inherent in
the Complex Model. The CARB specifications are going
to control our production.
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
I would like to extend the question just a little bit and
ask about impacts in the off-site areas as a result of the
reformulated fuels requirements. It is clear that there are
going to be some additional grades of gasoline and addi-
tional components. There is a new RBOB component
coming along into the common carrier system. I know
that there are going to be some tankage impacts, but I have
not heard a lot of talk about big investments being made
yet. Are people able to make the necessary corrections
without spending a lot of money at this point? If so, is it
going to affect their storage and product disposition flexi-
bility?
LAUX:
One thing we are doing on that is adding some blenders
at our marketing terminals so we can blend plus from the
TOC/INDEX
supreme and the unleaded gasoline, and that frees up a
tank. We are avoiding building tanks that way.
ARMBRESTER:
I think tankage will be an issue, but perhaps a greater
issue will be logistics. If we are trying to increase the
number of grades ofgasoline without significantly increas-
ing tankage, then it is going to require much closer coor-
dination of gasoline shipments and sales.
QUESTION 29.
California Air Resources Board rules for diesel fuel
quality require reduction of aromatics to 10 vol% or
that the fuel meet the emission level of a standard
fuel. What measures have been taken to comply with
the rules? To what extent are additives being em-
ployed?
TREESE:
Initial compliance with the CARB diesel requirements
was met by providing 10% aromatics fuel. We later re-
ceived approval for several alternate formulations with
greater aromatics content, but with higher cetane num-
bers. We are using one of the alternate formulations cur-
rently. We add a cetane improver to meet the higher cetane
number requirement of the alternate formula:
CUNEO:
Our experience is basically the same. We have made
some CARB diesel at 10% aromatics. In looking at alter-
native formulations, we intend to use cetane improver as
well.
QUESTION 30.
With the advent of new fuels mandated by EPA and
some states, does anyone have tangible evidence
concerning effects this will have on gasoline proper-
ties such as corrosivity, additive compatibility, polym-
erization, etc.?
CUNEO:
We have made test blends of EPA gasoline and future
CARB gasoline. They passed all the required tests. We are
in the process of developing California additive certifica-
tion for 1995 for RFG.
D'AURIA:
We have not seen any published data on the changes in
properties such as corrosivity or additive compatibility.
The earlier corrosion problems associated with use of
alcohols have been mostly eliminated both by improve-
ments in the alcohol production processes and by upgrad-
ing the vehicle fuel system materials. The proposed
reduction in olefin content could help with respect to gum
or sediment formation.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
BARLOW:
We have some preliminary data that supported a pos-
sible increase in corrosivity in several oxygenated gasolines
blends. We are not prepared to say it is conclusive, and
there have been a lot of changes made, so we are basically
monitoring and continuing testing.
As far as diesel fuels are concerned, we think the low
sulfur fuel will exhibit better stability properties based on
the hydrotreating efforts required to reduce the sulfur
content. We are also taking a look at the corrosivity effect
of those fluids due to the removal of some trace polar
compounds that act as natural corrosion inhibitors. There
may be an increase, but, again, we are still doing a lot of
test work.
FELTROP:
Use of alcohols, such as ethanol or methanol, as oxy-
genates tend to increase the corrosivity of the gasoline.
This problem has been effectively addressed by treating
fuel grade alcohol with the corrosion inhibitor selected for
this purpose prior to gasoline blending. Because some
conventional fuel additive formulations are not compat-
ible with the lower level alcohols, additives for direct use
in the alcohol based alternative fuels like M85 and E85
must be specially formulated. At high oxygenate levels,
fewer compatibility problems arise since most deposit
control additives are soluble in the blended fuel, and
alcohol soluble corrosion inhibitors have been developed
for use directly in the alcohol.
SAYLES:
I agree.
QUESTI0N 31.
Have refiners experienced a deterioration in diesel
lubricity properties as a result of low sulfur diesel
production? Have lubricity additives been used/rec-
ommended? What lubricity test is being used? Are
these problems related to the ultra low sulfur (i. e. less
than 0.02 wt% sulfur) diesels, low aromatic diesels,
and/or the 0.05 wt% sulfur diesel?
FELTROP:
There is some evidence of deterioration in diesel fuel
lubricity with the shift to low sulfur production. While
fuel composition is implicated, it is not the exclusive
source of problems, because hardware type and duty cycles
are a factor as well. In particular, hydrotreating severity is
the primary factor. Much confusion remains in this area
as various test methods are evaluated in an attempt to
resolve the problems of precision and accuracy of data and
correlation with reported field problems.
Test methods under investigation are ASTM D-5001,
the Ball Oil Cylinder Lubricating Evaluation (BOCLE)
test, High Frequency Reciprocating Rigtest, modified
33
TOC/INDEX
BOCLE methods such as the U.S. Army’s Scuffing load
test and the Hadley constant loading Scuffing test. The
U.S. Army’s Scuffing load test has been widely used and
is reported to correlate with some field problems. How-
ever, the repeatability range of the method is quite large.
Lubricity additives have been developed and recom-
mended based on data from these tests. Lubricity additives
for diesel fuel are currently being used in North America,
especially in California.
PORTER:
Diesel injection equipment manufacturers, diesel users,
and diesel suppliers have expressed concern regrading the
lubriciry characteristics of No. 2-D low sulfur diesel man-
dated in 1993. One reason for their concern is that diesel
lubricity problems occurred in Sweden in 1991 when a very
severely hydrotreated low sulfur and low aromatics diesel
was mandated. Marginal diesel lubricity is also a concern
as it is not reality discernible in equipment operation, but
rather is a long term process resulting in equipment failure.
Lower lubricity appears to be related not to a specific
level of sulfur or aromatics, but co the severity of the
hydroprocessing used to make the product. It is not estab-
lished, however, what hydrotreating severity corresponds
to a reduced lubricity level that actually affects the opera-
tion of a diesel engine’s fuel system components such as
pumps and injectors. In our view, there is still not a clear
case that can be made of field damage in the U.S. caused
by lower lubricity of No. 2 diesel.
As Mr. Feltrop said, many lubricity tests are being used
but the most common test in the U.S. at this time is the
U.S. Army modified BOCLE. An ISO group is studying
methods and will make a recommendation later this year.
Lubricity additives are being used by some refiners
particularly in California. Chevron is monitoring lubricity
at their refineries and will add additives to reach a target
of a minimum scuffing load of 2,600 grams on the modi-
fied BOCLE test.
SAYLES:
We have been producing low sulfur diesel in this coun-
try for the last year or so. I have not been aware of a great
consumer outcry about engine failures. There has been,
however, an outcry for better lubricity tests. In the October
1994 issue, Lubrication Engineering, had a nice article
describing all the different tests, their good points and
their bad points.
Our concern is that the test has become the issue and
that the actual diesel engine performance has not. We will
continue to monitor the situation, but at this point we
have not seen lubricity as being a problem.
BARLOW:
We concur with what has been said so far. I would like
to add that there is a joint ISO/SAE task force currently
34 General Processing and Support Operations
underway trying to evaluate the appropriate tests. The goal
is to settle on one standard. Tests being reviewed are the
Lubrizol Modified BOCLE, the Southwest Research In-
stitute Modified BOCLE, the Exxon HFRR Test and the
BOTS (Ball on Three Seats) Test.
D’AURIA:
With the advent of reformulated diesels, refiners will
also need to be concerned about viscosity. Hydroprocess-
ing and reduction of aromatics content will reduce diesel
fuel viscosity. At the same time, engine manufacturers are
increasing fuel pressure and compression ratio in order to
reduce NO, and hydrocarbon emissions. The combina-
tion of these fuel and engine changes will reduce apparent
viscosity and lead to excessive fuel pump wear. The ulti-
mate resolution of these concerns will involve chemical
and mechanical changes, combined with improved test
methods that more clearly relate to actual engine condi-
tions.
ARTHUR J. SUCHANEK (Criterion Catalyst Company L.P.):
This question of lubricity continues to baffle me. Yes,
Mr. Porter is correct. There were problems in Sweden
several years ago when the first units were started up, and
those problems were found to be affected by the viscosity
and the viscosity was directly related to the front end cut
point. Once that was changed, there would seem to be no
problem.
I also agree with the comments on the fact of the
hydrotreating. Severe hydrotreating can cause some prob-
lems which can affect this. A year ago this month, we
started up a unit in Germany, which has been producing
10 ppm sulfur, 5% aromatics fuel for the Swedish Class 1
market with no problem at all on lubricity.
I sometimes think that maybe this problem is being
overblown. I do not think that the sulfur is the real
problem.
MAJED INTABI (Aramco):
From our experience, deterioration in lubricity had
been more of a concern with jet fuels containing hydro-
treated or hydrocracked fuels and was related to the accel-
erated wear of pumps and accessories in the aircraft fuel
system. Some airline companies used to request the addi-
tion of certain types of jet fuel chemicals as lubricity
improvers whenever hydrotreated or hydrocracked com-
ponents were present in the jet fuel blend.
BRUCE CAMPBELL (Petrolite Corporation):
While it appears that low sulfur diesel fuel lubricity is
not a wide spread concern, several regions have experi-
enced regular pump failures. Conventional corrosion in-
hibitors do not always provide sufficient lubricity
improvement and can cause adverse fuel/lubricity interac-
tions which may lead to pump seizures. This failure mode
TOC/INDEX
is usually associated with overtreatment scenarios.
Petrolite successfully remedied a severe pump failure prob-
lem in Canada by adding less than 10 ppm of a lubricity
agent.
QUESTION 32.
The concept of multigrading has been recent/y intro-
duced in paving bitumen (road asphalts). Can the
panel members elaborate on this particularly with
regard to production of such bitumens and their likely
application benefits?
DEATON:
The concept of multigrading was developed by the
government funded Strategic Highway Research Program,
also known as SHARP As a result of SHARP new asphalt
grades and specifications have been developed for different
sections of the country based on minimum and maximum
recorded road surface temperatures. The only way to meet
the new specifications is by adding polymer modifiers such
as SBS (styrene-butadiene-styrene) or SBR (styrene-buta-
diene-rubber). The addition of polymer modifiers in-
creases asphalt elasticity at lower temperatures and
enhances asphalt rigidity at higher temperatures. New
testing methods and new laboratory equipment will be
needed such as high shear testing and bending beam
rheometry. The new grades have not yet been mandated
by the federal government but have been left up to the
individual states. It is my understanding that Arizona and
Tennessee are two states that require the new grades.
CUNEO:
I am basically in agreement with the previous com-
ment. We find that we are going to be able to make some
of the lower grades through proper crude selection without
polymer modification. Some of the grades, where there is
a greater disparity between the high temperature and low
temperature property, will require either polymer modifi-
cation or other proprietary technology. Shell has been
marketing these multigrading proprietary technology as-
phalts in Europe, Canada and Australia.
SAYLES:
I agree with the comments that have been made pre-
viously. Just one other additional note, that SHARP is a
federal mandate, and from what I understand, the first use
of SHARP asphalt will be on federal highways.
G. Computer/Process Control
QUESTION 33.
What is the experience to date with tying “on-line”
rigorous process models into process control systems?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
CUNEO:
For years we have tied our rigorous process models into
on-line control systems by use of a separate computer
system for closed-loop, on-line optimization control. Cur-
rently in the more modern instrumentation packages,
there is the opportunity to integrate these models into the
TDC type of systems. We do not have any of those
applications currently running in refinery units but have
a few in chemical plants where they work very well.
D’AURIA:
UOP and SETPOINT have been working together to
develop on-line process models. Since 1991 we have im-
plemented 26 APC applications in process areas such as
Platforming, Penex, Pacol, and Phenol. In platforming
applications, we are now using process models to identify
reactor temperature requirements to meet octane targets,
to adjust heater limitations, to identify hydrogen recycle
demands to meet certain catalyst coking or life limitations,
and to lengthen catalyst life by improving regenerator
operation.
Optimization packages have been installed on Platform-
ing units, Penex units and Pacol units with the objective to
maximize the net profitability of those individual units. In
addition, we have two applications that will be coming on
stream later this year that will provide optimization of a
combination Platformer-Penex naphtha splitter processes.
PORTER:
We are presently piloting at Pascagoula a real-time
optimization model on one of our crude units. This will
be our first experience at this type of advanced control.
MOHAMMAO AL-SHAHRANI (Saudi Aramco):
Have multi-variable controls been used in such an
implementation?
CUNEO:
Yes, we use multi-variable control extensively in all of
the processes and find that it is a necessary platform for
implementation of on-line optimization as we have done
in crude units, olefin plants and catalytic cracking units.
LEE E. TURPIN (Honeywell Profimatics):
Profimatics has integrated rigorous kinetic process
models in about a dozen on-line advanced control pro-
jects. Most of these projects have been for on-line optimi-
zation. The kinetic models used are our standard SIM
series models for FCC, reformer and alkylation units.
These control packages continue to have a high percentage
on-stream time.
FRANK J. KLEINSCHROOT (SETPOINT, Inc.):
Mr. D’Auria did an excellent job describing the direct
use of rigorous process models in dynamic control systems.
35
TOC/INDEX
I would like to expand the description of steady state
rigorous models used to establish targets for a dynamic
control system.
The latest technology can be characterized as including
the following components:
a graphically configurable rigorous process model
based on a standard simulation package such as
AspenPlus and proprietary conversion models such
as UOP’s;
an equation-based optimization solution technique;
a graphically configurable optimization environ-
ment, such as SETPOINT’s MultiOpt-Xprt which
provides links between the process, other data
sources, and the modeling package; and
an on-line expert system to provide a high level
operator interface, and model-based reasoning capa-
bility in addition to diagnostic capability on the
optimization application itself.
SETPOINT has five projects in various stages of im-
plementation, including one completed application with
the new technology. It is running closed-loop and has
resulted in a measurable improvement of a key component
recovery in a range of operating modes.
The linkage between the on-line process models and
the process control system is handled by calculating a series
of setpoints and manipulated variable (MV) targets for
multivariable controllers. SETPOINT’s SMCA controller
allows direct specification of both SETPOINT’s and MV
targets along with hierarchial ranking specifying the order
these targets should be released in the presence of con-
straints.
SETPOINT and UOP have installed four other process
optimizers based on rigorous models on two catalytic
reformers, a Penex unit and a LAB complex. Several other
projects are underway and commercial negotiations are in
progress which will result in applying the new technology
on a broad process multi-unit scope including product-
blending systems.
QUESTION 34.
Comment on experience with model based closed-
loop process control. How have actual payouts com-
pared to projected payouts? What type of support staff
is necessary to keep these installations operational?
PORTER:
Chevron has installed a number of model-based closed-
loop process controllers for a variety of processes. In
essentially every installation, the expected benefits were
achieved and exceeded. The advanced control application
is only as valuable as the base instrumentation and analyzer
reliability. On-site control expertise is also required to keep
applications operational.
36 General Processing and Support Operations
TREESE:
Our experience is somewhat like Mr. Porter’s in our
applications of model-based, closed-loop control. Our
experience has been good when there is an on-line analyzer
available to update and correct the model on a regular
basis, and when the analyzer is maintained and accurate.
Actual payouts have been 50% to 150% of expected in
these cases. Daily or weekly review by a control engineer
is optimum. We want to say required, but it is hard to get
to the unit every day.
Our applications include viscosity of lube unit feed,
T90 and T95 of coker and crude unit products. We have
seen additional benefits of these models when combined
with the dynamic matrix control of the units. This is
especially evident in the coker, where the unit has to adjust
to the large swings resulting from the coking cycle.
BOYCOTT:
We installed a matrix controller on our crude unit in
February of this year. The post audit on the project was
just completed, and the actual payout was within 5% of
projected. Support for the model is provided by the proc-
ess engineering group. We have one engineer that provides
support for the matrix controller. It requires about 6 to 8
hours per week of his time.
CUNEO:
I agree with the comments that have been made pre-
viously. We have been doing the model-based advanced
process control for many, many years now. One of the
things that has not been mentioned is the importance of
ownership by the operating department. Unless they really
want to own these things and keep them operational, they
can let the maintenance and the support go downhill.
Ownership by operations is a critical factor.
D’AURIA:
We have implemented over 20 model-based closed-
loop process controls on Platforming units. Applications
include octane control, coke laydown, heater constraint
identification, and CCR regenerator optimization. Bene-
fits seen have been improved downstream blending, feed
maximization, and improved catalyst performance. RVI
refinery published a paper in the November, 1992 edition
of Fuel Reformulation in which they described their APC
implementation. RVI was able to control octane to within
0.2 RON deviation, and they were able to increase feed
rate by 5%. Similar benefits have been realized in other
applications. In all of these applications, the existing sup-
port staff has handled the model based control system.
LEE E. TURPIN (Honeywell Profimatics):
Profimatics has very successfully utilized our rigorous
kinetic based models for closed-loop process optimization
and control. Post implementation economic audits were
TOC/INDEX
not performed on most projects. The on-line optimization
of an FCC was reported by Conoco at the 1991 NPRA
Computer Conference. (Paper CC-91-130, On-Line Op-
timization for “SMART” FCC Controls, by John Gott,
Charles Roubidoux and Roland Heersink.) Also, Cor-
poven, S.A. reported benefits from on-line optimization
on their FCC reformer and alkylation units at the 1993
NPRA Computer Conference. (Paper CC-93-139, On-
Line Optimization at El Palito Refinery, by Rene’ Stram-
wasser and John Davis.)
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
On every post audit SETPOINT has undertaken, we
have always identified benefits which exceeded the payout
criteria for the project-usually resulting in less than one
year payouts when reinstrumentation hardware is not
included in costs.
QUESTION 35.
Are there any on-tine neural network applications
running either in a closed-loop or advisory mode?
What time frame was the training data taken from and
on what frequency was the data sampled? Was the
data exclusively process data (either instruments or
analyzers) or was laboratory data also used? What are
the benefits of the neural network compared to more
conventional control strategies?
BARLOW:
We are aware of several applications which use neural
network models ofvarious unit operations for closed-loop
control of parameters for the unit. One example I can give
is RVP control for the alkylate product in an alkylation
unit. The operating parameters of a DIB column were
used to model the RVP of the alkylate product, the DIB
bottoms. Hourly average data was centered on a snapshot
alkylate sample. The RVP of the alkylate was then ob-
tained in the laboratory. Data was gathered over several
weeks at various RVP levels. The neural network is now
used to control the operation of the DIB tower, based on
a predicted alkylate RVP which is later confirmed in the
lab.
We use neural networks in our PEAKS models for
alkylation units. These models have been used in advisory
modes to help unit operators control and stabilize fresh
acid makeup. The PEAKS models developed use both
process and laboratory data. The benefits of neural net-
works are their ability to correlate and recognize complex
nonlinear relationships. They can correlate multiple de-
pendent variables simultaneously. Our PEAKS models
have been generated with up to 115 independent variables
and 11 dependent variables. They also have the capability
to identify and utilize interaction between the inde-
pendent variables, which we consider a tremendous plus.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
CUNEO:
We have had very positive experience with Betz neural
network model for alkylation. It has been working very
well for us at our Wood River complex.
D’AURIA:
UOP is currently developing a closed-loop neural net-
work application to enhance model based control. We
believe a fundamental process knowledge is important in
the use of neural networks. The neural network does not
replace a conventional model but rather compensates for
the effect of unmeasured disturbances on the model accu-
racy. The network is trained with weeks of data of suffi-
ciently high frequency to capture the characteristic process
response behaviors. Both process and laboratory data are
used, with laboratory data mainly used for validation
purposes.
The reason for applying a neural network is to extract
the maximum benefit from process models to fit the
characteristics of an individual unit or group of units.
FRANK J. KLEINSCHROOT (SETPOINT, Inc.):
Neural Networks are a new tool for use in generating
automation benefits; they will not replace pheno-
menological models. They are not without fundamental
limitations. They require statistically significant distur-
bances in all active variables for every mode of operation
to have valid predictions. For many real situations, the
data requirements can not be met in any sort of reasonable
timeframe without intentional process movement. Where
chemical engineering-based phenomenological models
are applicable, neural networks generally should not be
expected to have equivalent performance, especially out-
side the range for which the network was developed. In
spite of all these difficulties, SETPOINT continues with
an active neural network development program and in-
tends to use this technology in appropriate situations.
QUESTION 36.
Is anyone using expert systems in refinery applica-
tions? Are there any closed-loop expert system appli-
cations? What are the benefits?
CUNEO:
At the present time we have no process applications in
refining. We have a few in our chemical side, predomi-
nantly in detergents and also additive manufacture. We
have one expert system that is currently being employed
by our mechanical engineering folks for pressure equip-
ment monitoring.
SAYLES:
Just a philosophical note. Expert systems we have seen
are rule based systems and are only as smart as the ques-
tions you can think to ask before they occur. As a rule based
37
TOC/INDEX
system, you require all the answers before you can deter-
mine the problem. Fortunately, we have operators and
supervisors who have years of experience to draw on and
can look at the same data and probably reach a conclusion
quicker than the machine, so at this point we have not
found expert systems to be desirable in operations.
DON HUSTEO (UOP):
Yes, refineries are using expert system applications.
Refineries are using expert systems for data analysis, alarm-
handling, diagnosis, scheduling, optimization, planning,
and monitoring. In fact, UOP is offering an on-line expert
system called the UOP CCR LHCS Diagnostic Advisor
which helps troubleshoot problems with the lock hopper
control system (LHCS) and CCR. Currently running
successfully in refineries, the Diagnostic Advisor helps
operation and maintenance personnel quickly trou-
bleshoot any alarms or abnormal events and provides
information on how to remedy the problem.
By “closed-loop expert system applications,” it is as-
sumed that the expert system plays a role in process control
by either manipulating setpoints directly or controlling
some aspect of plant operation. This would apply only to
those expert systems used for process control. Expert
systems for closed-loop process control are being used in
the areas of discrete part manufacturing and batch chemi-
cal operations to some degree, but they are even less
common in continuous refinery operations. Most refinery
expert system applications, however, are not developed for
process control applications and are designed for advisory
or interactive use.
Expert systems can be especially important in these
days of reduced refinery staffing where fewer personnel
can be easily overwhelmed by the increased level of process
information that is available. Any type of expert system
that can look at a large amount of refinery information
and condense this information into a useful summary or
action plan is very beneficial. Overall, listed below are
some of the major benefits of expert systems:
increased process on-stream time, improved process
operation, reduced off-spec product;
availability of technical expertise when the actual
human experts are not available;
ability to look continually and quickly examine large
amounts of process information 24 hours a day and
draw conclusions; and
ability to capture and document process knowledge
that may otherwise leave the company or refinery
when personnel leave and/or retire
FRANK J. KLEINSCHRODT (SETPOINT, Inc.):
SETPOINT is currently delivering two types of expert
system applications to refineries and plans are in place for
several others. The two current applications are in the area
of refinery scheduling (including upstream and down-
38 General Processing and Support Operations
stream feed and product disposition logistics) and refinery
optimization configuration and maintenance. Diagnostic
applications intended to improve advanced automation
system availability at reduced plant engineers’ time are the
current development directions.
QUESTION 37.
What qualifications do refiners fee/ will be required
in the future for the console operators?
ARMBRESTER:
Many of the qualifications of the console operators of
the future are the same as their counterparts of the past. It
is important that the operator have a good overall under-
standing of the process he is operating, including cause and
effect relationships between process variables, procedures
necessary to bring the unit back to a stable condition
following an upset, and a working knowledge of the equip-
ment in the field. In addition, the console operator of the
future will also need a good understanding of the control
system architecture and communication systems, since he
will be the first responder to system trouble alarms.
In addition to these points, the move toward distrib-
uted control systems, on-line analyzer systems and sophis-
ticated advance controls will require console operators to
develop some of the same skills that we usually look for in
a supervisor. Analysis and troubleshooting skills will be
critical since the DCS console operator is often required
to process large amounts of electronic data to determine
the cause of an operating problem and then initiate the
proper corrective action. Strong initiative and good lead-
ership and communications skills will also be important
since the console operator typically becomes the individ-
ual who directs the unit operation and manages the activi-
ties of the field operators.
In upset conditions, the console operator must be able
to grasp the importance of variables which are outside the
normal operating range and prioritize his own responses
so that the most critical problems are addressed first.
Console operators will also need a general understanding
of some basic chemical engineering principles, such as
distillation theory, reaction kinetics, heat and mass trans-
fer, etc., especially as they relate to the advance control
systems he is operating.
It will also be important for management to provide an
environment that is conducive to developing and main-
taining these qualities in the console operator. The control
system must be designed with the operator in mind, with
operating data and control screens organized in a way that
allows a good overview of the process. Alarms should be
set to allow early indication of process deviations from
normal conditions, without becoming a nuisance during
routine operation.
Training on dynamic process simulators can help pre-
pare operators for the real life situations they will face and
TOC/INDEX
provide refresher training on procedures which are used
infrequently. Rotation of operators between console and
field assignments will be important to maintain familiarity
with the field equipment and to avoid operator burn-out
in the higher stress environment of the control room.
CUNEO:
I agree with my colleague’s comments. We expect that
because of the necessity to work easily and efficiently in
the computer CRT based environment and being able to
function in self-directed workgroups we are probably go-
ing to need to go to either a two-year technical school
graduate or two years of college education.
PORTER:
At Pascagoula right now, we have 19 console operator
positions each shift. That is a large number to manage.
There are two prime considerations. Number one is plant
safety. I think Mr. Armbrester covered the skills required
in this area very well.
Number two is efficiency. With that many console
operators, you have to have a much better understanding
of what each other is doing and economics of the refinery
in order to optimize and be efficient.
CHARLES F. LeROY (CITGO Petroleum Corporation):
Mr. Porter says he has 19 board people; I have 11 board
positions at my plant, and we think that in the future we
can consolidate these down to 3 to 5 positions. Are your
people telling you that you will be able to consolidate your
19 down and run with 5 or 6 in the future?
PORTER:
No, we are not looking at any consolidations in the near
future. Our focus is on improved training.
CHARLES F. LeROY (CITGO Petroleum Corporation):
How many of you all have salaried board positions as
opposed to hourly board positions? Could the people on
the panel comment on that?
ARMBRESTER:
No, ours are hourly,
PORTER:
They are all hourly.
QUESTION 38.
Most refiners have implemented individual informa-
tion systems covering process, laboratory, planning,
maintenance, etc. (Islands of Information). What
plans and progress have been made to install Inte-
grated Information Systems allowing access to all
refinery information from a single work station?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
SAYLES:
Our first review of the data management requirements
in our refineries has found that the “Islands of Informa-
tion” were in fact continents. Our goal is to develop these
continents and make available to refinery personnel all
data required in an expanding government regulation
arena. We have an integrated information system using a
relational database which is designed to access multiple
database files and indices on multiple file servers using a
PC IAN. A single application is designed to access all
necessary database files from anywhere on the network.
One important aspect of these databases is that they
were designed around the natural work groups. Each of
these natural work groups is assigned the task of maintain-
ing all databases in their areas of responsibilities. Other
users have data viewing rights but cannot change the data.
Security and data integrity is maintained for all users
through a password protected, menu driven system, and
database applications controlling access to the network file
servers and files.
TREESE:
We are presently working toward company-wide inte-
gration of a system very much like what Mr. Sayles has
mentioned here. Right now, process and lab information
are available. I can pull those up at my desk. We are
working on getting accounting, procurement, and deliv-
ery information available on-line. That is presently being
implemented.
At one refinery, we have even gone so far as to imple-
ment our project management and control systems on-
line. In other words, the project can be submitted on the
computer. We will make the assignment, do all the status
reporting, cost reporting, cost tracking, etc. on-line. Ac-
cess is available to all the engineers on their PC. The
operations engineer can find out where his project is
immediately on-line. We are working with Morrison
Knudsen in developing the systems right now.
PORTER:
It sounds as if we are all moving in a similar direction.
At Pascagoula, we have all the real time process informa-
tion and laboratory information currently available to us
at one PC. In the near future, it will also contain process
safety management documents: P&IDS, equipment data,
maintenance history, operating procedures and instruc-
tions, refinery policies, and MSDS sheets.
ARMBRESTER:
We are also using the PCs and local area networks to
pull together all the information systems that we have
available in the refinery. Many of these applications were
developed on the corporate mainframe computer and are
still functional, so we are developing graphical interfaces
to make that information available across the PC network.
39
TOC/INDEX
We are using the same approach for our DEC-VAX
systems also, and in this way everyone in the plant will be
able to access the data that they need, regardless of what
system it is coming from, through one PC workstation.
We are also in the process ofdeveloping what we are calling
a universal database of all of our engineering documenta-
tion and regulatory compliance information.
CUNEO:
We are moving the same way. It is basically trying to
bring all the diverse sets of data together into one platform,
accessible through the PC.
DEATON:
Our experience is the same. I have nothing else to add.
LEE E. TURPIN (Honeywell Profimatics):
Through our direct experience, we recognize various
evolutionary stages to deploying a modern Integrated
Information System (IIS). Each stage provides successively
more integration and more benefits to the integrated
system, considered as a whole, and comes closer to the
ultimate IIS vision.
1. In the first stage, most integrated systems start as a
collection of individual systems that were justified
and driven by discrete business needs. Each system
serves the narrow needs of the local department,
but is unavailable to other users. At the first stage,
these are isolated, island systems that are useful
only to one (small) group within the enterprise.
2. The second stage is to build point-to-point con-
nectivity between individual systems on an as-
needed basis.
3. The third stage is to allow most users to access these
many different systems from their own office, us-
ing terminal emulation packages - the Windows
everywhere strategy. Users require training on each
system. To merge data stored in different systems
(maintenance and laboratory data, for example),
requires the user to logon to the different systems,
extract the data in some general format, and then
merge the data himself.
4. The fourth stage is to copy the data from the
separate systems into a single, central database for
general use by all users and applications. The data-
base becomes the integrating platform. It has the
disadvantage that the data may be stored in two
places and it is not always easy or appropriate to
replicate the data.
5. The fifth stage is to integrate different systems
using a client-server model, with each different
system represented by a server. A request for data,
made by a client, is processed by one to many
servers, each responsible for its bit of data. The
40 General Processing and Support Operations
client-server glue becomes responsible for integrat-
ing the data.
Experience says few refineries follow an identical ap-
proach, since the capabilities of the pre-existing systems
and the business incentives to integrate differ widely. Since
1991, we have implemented systems in three locations
that adopt a mixture of the fourth and fifth stages. In all
three systems, there is tight integration of the process,
laboratory, planning, product accounting functions. We
are currently planning an installation that permits the
tight integration of the maintenance functions, primarily
due to advances in maintenance software (SAP R/3 in this
case). We see that by year end 1995, a refinery user can sit
at a single workstation and seamlessly and transparently
pull information from all refinery and corporate sources,
analyze financial impacts of operational changes, and
directly inform everyone in the refinery of the results.
H. Miscellaneous
QUESTION 39.
HAZOPS reviews often identify the vapor space of cone
roof sour water tanks as potential fire/explosion haz-
ards because of the H2S, hydrocarbon and possibility
of pyrophoric iron sulfide. How are these hazards
being controlled?
LAUX:
We commissioned a revamped tank as a sour water
storage tank last year. Our HAZOP review considered this
tank to be the same as a gasoline tank from a fire or
explosion standpoint. We installed an internal floating
roof in the cone tank to alleviate the explosion hazard. We
also installed H2S sensors and alarms around the tank to
notify us of an excursion from a leak or a faulty level
controller that was allowing vapors to get to the tank.
PORTER:
Answers to a similar question at the 1991 NPRA
Question &Answer Session cover this topic in great detail.
An important factor in controlling vapor in the storage
tank is to degas the sour water before routing it to tankage.
This is accomplished by flashing the vapors from the
liquid in a low pressure vessel, usually vented to a reliefgas
or flare gas system. Minimizing vapor generation in the
storage tank can be enhanced by operating the flash drum
at less than 120°F.
Also, we do not like to use cone roofs in sour H2O
service. We strongly favor floating roof tanks with primary
and secondary seals. We maintain a layer of sponge oil on
top of the water that is changed out as necessary to
minimize odor problems.
TOC/INDEX
SAYLES:
We have cone roof tanks. Some of them have a gas
blanketing system, a floating roof, or both. Our sour water
tanks have, as Mr. Porter indicated, a sponge oil layer for
odor abatement. We find the sponge oil layer works well.
For the nitrogen purge, we have a vacuum breaking system
using about 2 oz of water pressure. Currently, the displaced
nitrogen is vented, but we are considering using a carbon
filter at some time in the future for additional odor
containment.
TREESE:
Our practices are pretty much like what has been
mentioned already. Our cone roof tanks, where we do have
them, are natural gas blanketed so they do not have the
same fire and explosion hazards that you would have in a
regular atmospheric vented tank. You still, of course, have
the problem of pyrophoric iron sulfide whenever you do
tank cleaning for removal from service.
Our preference is to hold sour water in floating roof
tanks with double seals. We do make sure that the water
is all degassed before it goes to those tanks.
ARMBRESTER:
Ashland’s foul water tanks are low pressure tanks de-
signed for 2 psig to 5 psig and are built to API Standard
620. These tanks have dome roofs, as opposed to cone
roofs, and the vapor space of the tank is blanketed with
refinery fuel gas. At our Catlettsburg refinery, the tank
vent gas is routed through a dedicated amine scrubber for
removal of H2S, and then the treated gas is incinerated
with the SCOT unit tail gas. At our Canton, Ohio refin-
ery, the tank vent gas is routed to the suction of the SCOT
unit booster blower and processed along with the tail gas
from Claus unit. In this case, a hydrogen rich stream is
used to blanket the foul water tanks which minimizes the
amount of hydrocarbon in the stream going to the SCOT
unit.
DEATON:
We had plans to convert an existing cone roof tank to
sour water service earlier this year. A nitrogen or fuel gas
pressurization system was planned along with a steam
eductor to remove H2 S and hydrocarbon vapors to the
flare. Internal coatings were to prevent formation of iron
sulfide. The reliability of the pressure control systems, the
danger of sucking air into the cone roof, the possibility of
iron sulfide formation upon coating failure, and the inher-
ent problems of putting steam in the flare caused us to
delay construction and explore the use of open floating
roof tank designs. Our investigation indicated that float-
ing roof designs utilizing a single mechanical shoe type seal
are safe and have been easy to maintain. Refiners who have
used foam pack type seals in this service have experienced
seal failure. A recommended practice with floating roof
1994 NPRA Q&A Session on Refining and Petrochemical Technology
tanks in sour water service is to maintain a 6 inch layer of
No. 2 oil on top of the sour water to help form a barrier
for H2S and to help lubricate the tank walls and roof seal.
QUESTION 40.
With the processing of heavier crude oils, the metals
levels (Ni and Va) in our refinery fuel oil are increas-
ing. What are the guidelines with respect to metal-
lurgy of tube hangers and tubes relative to vanadium
/eve/s in the refinery fuel oil?
CUNEO:
Our corrosion avoidance strategy is to keep the ash solid
by adding compounds to raise the melting point or to
restrict combinations ofvanadium and sodium ratios, and
temperatures to avoid melting. Temperatures below 970°F
will avoid melting. We do not believe that alloy selection
should be affected by vanadium levels, as no reasonable
alloy can resist the corrosive conditions if the ash deposits
are allowed to become molten.
D'AURIA:
When fuel oil vanadium content is above 50 wt ppm,
UOP’s standard calls for the use of chrome-nickel-nio-
bium material in the heater tube hangers (per ASTM
A560). In addition, we set a maximum tube wall tempera-
ture of 1,150°F. We are currently revising this policy so
that these standards apply to all heater designs where No.
6 fuel oil or heavier is being fired, rather than keying it on
expected vanadium content.
An alternative that is particularly applicable to retrofits
is the use of a sacrificial covering of wet wrap ceramic fiber
on the tube hangers to protect them from vanadium
attack.
ARMBRESTER:
This is a difficult question to answer because the high
temperature corrosion depends not only on vanadium
concentration but also on sodium sulfate, excess air, fire-
box temperature and sulfur content of the fuel oil. Gen-
erally speaking, if the level of vanadium is kept below 5%
of the total ash component, then the low melting point
salts or fluxes are suppressed, only forming high tempera-
ture melting salts. The metallurgy that is favorable for this
atmosphere are the high chrome materials such as RA330
and RA333, commonly used as tube supports and hang-
ers. The literature suggests that alloy 657 (50Cr-50Ni) be
used for heavy fuel oil containing 2% to 4% sulfur and 50
to 150 ppm vanadium. However, the percentage of accept-
able vanadium will be different depending on excess air
and temperature of the heater. These two parameters
determine whether a low or high melting salt will form
and whether it will melt or flux the oxide of the metal. The
higher the chromium to nickel ratio of the alloy, the less
susceptible the material will be to higher vanadium levels
41
TOC/INDEX
in the fuel oil. Because of the many parameters that must
be considered, each situation must be considered on an
individual design basis.
SAYLES:
I agree with what has been said before. The only thing
I will add is that in order to protect the hangers one step
further, we have a heater box temperature limit of about
1,600°F
DARRELL SCRUGGS (Kinetics Technology International Corporation):
To limit high temperature attack for metal tempera-
tures above 1,200°F, KTI follows the traditional guidelines
of vanadium plus sodium less than 100 ppm and vana-
dium itself less than 50 ppm. Above these limits a furnace
should use 50-50 chrome material for tube hangers and
supports or refractory lining.
The question was really addressed toward existing fur-
naces where you cannot necessarily retrofit with higher
alloys. For existing furnaces, KTI suggests you segregate
the fuel system where possible, such that fuel oil with high
metal content is used in lower temperature services or in
vertical cylindrical furnaces where the tube supports can
be shielded. High metal fuel oil should never be used in
high severity services such as steam reformers and catalytic
reformer furnaces.
KENNETH D. PETERS (UOP):
Particularly in the fired heater design for new CCR
Platforming units, with higher tube wall temperatures, we
have strongly pushed refiners away from firing fuel oils in
general. To design a Platfotming fired heater for these high
metals content fuel oils, instead of fuel gas, increases the
heater capital cost by about 40%. Since the charge heater
and interheaters in a Platforming unit represent about
20% to 25% of the overall capital cost of the unit, the cost
impact of fuel oil firing is significant. Due to this capital
cost impact, we encourage refiners to use fuel gas in this
application, and then fire this fuel oil in their heaters
having lower tube wall temperatures, where the cost dif-
ferential is smaller.
QUESTION 41.
What precautions are being taken to prevent water
contamination of MTBE during marine shipment? How
do you deal with wet MTBE to prevent resulting haze
in finished gasoline?
PORTER:
We have not had any problems that have resulted from
actual marine shipment. At Pascagoula, to avoid problems,
we have added dome roofs to our MTBE floating roof
tanks and inspect barges to insure they are water free before
loading. As far as dealing with wet MTBE, we have limited
the percentage in our gasoline blends to avoid a haze in
42 General Processing and Support Operations
the final product. We are aware ofa distillation system that
will remove soluble water from wet MTBE, but we have
not used it.
TREESE:
I do not have any comments necessarily on the marine
shipment. Marine shipment has not been a big problem
for us. We do get our MTBE wetter by collecting water
from rain. Wet MTBE can be blended off in gasoline and
still be bright and clear up to reasonable levels of water in
the MTBE, under maybe 2500 ppm. We now store all our
neat MTBE in covered tanks.
FELTROP:
Wet MTBE presents a unique haze problem in gasoline
blending. Up to 15,000 ppm of water is soluble in MTBE,
and MTBE with water content of 2,000 ppm or greater is
likely to produce a hazy gasoline blend. The resulting hazy
blends usually require several hours to clarify by static
settling. Dehazers can be effective in clarifying these hazy
blends within minutes to a few hours.
A more effective approach has been found where the
MTBE is known to be wet. In this case, the dehazer is
added to and mixed with the MTBE before blending with
the gasoline. This approach either prevents haze in the first
instance or greatly increases the rate of clarification. In
addition to faster responses, lower doses of dehazer are
typically required in the prevention method.
BARLOW:
Just to reiterate what has been said, we think the
primary problem is poor housekeeping. The resolution to
the primary problem is through improved housekeeping
procedures. If you have a problem after that, chemical
dehazers have been proven to be effective. We have used
50 ppm of a dehazer to eliminate a persistent water haze
(around 0.1 vol%) from an 85% gasoline/l5% MTBE
mixture.
DENNIS GRANDLE (Agar Corporation, Inc.):
We now have several installations where we are able to
measure the concentration of water in MTBE using en-
ergy absorption, microwave technology. We are able to
measure 2.1% now, even though the water is soluble in
the MTBE at low concentrations.
QUESTION 42.
How are refiners processing washwater and the sta-
bilized emulsions that result from turnaround clean-
ing and degassing programs?
FELTROP:
Waste streams from cleaning operations are often sent
to the waste water treatment plant along with the normal
TOC/INDEX
refinery process water streams. Solids and surfactants from
the cleaning waste streams may increase the stability of the
emulsions in the process waste water, upsetting the opera-
tion of the entire treatment plant. If possible, these turn-
around wastes should be segregated from the normal
streams flowing to the treatment system. This will make
it possible to tailor treatment of any wastes requiring
special handling without affecting normal plant opera-
tions. After initial separation of solids and oils from the
water, the streams can be mixed for additional primary or
secondary treatment.
Treatment of the wastes can be facilitated by precau-
tions taken during the cleaning procedure. Minimize the
amount of surfactants used to perform the cleanings.
Reduce the amount of solids from tank bottoms, heat
exchanger bundle cleanings, etc., that add fine solids to
the waste water. These solids attract oil which contributes
to the formation of emulsions and make treating the water
more difficult. For example, in the case of exchanger
cleaning, filtration of the waste water to remove solids may
provide sufficient pretreatment to allow mixing the waste
water into the general refinery sewer system.
During treatment of the segregated waste water from
cleanings, the use of additional chemical emulsion break-
ers or flocculants may be necessary to overcome the effect
of the higher solids in oil loadings. It may be necessary to
provide additional settling time to achieve expected results
with some waste waters. Even waste streams from the
cleaning of different process units may require different
handling, depending on the type and amount of solids and
surfactants occurring in the specific waste. The capacity to
treat these wastes separately from the normal refinery
waste waters will facilitate treatment with minimal effect
on overall operations.
SAYLES:
I agree with segregation of waste from cleaning solvent.
Most importantly, the operators need to know they must
keep the waste from these solvent cleaning solutions from
getting into the sewer system. If you have one truckload
of cleaning chemical go down the sewers, you will never
have it happen again.
TREESE:
In our refineries, we have dealt with emulsion from all
sources in two basic ways. One way is to dispose of the
emulsions directly to the coker using the MOSC process.
The second way, which is really our preferred way, is to use
emulsion breaking facilities. We break the emulsion with
heat and chemical first. That part has not been a particular
problem. Then we process the sludge in either the coker
or send it back to the crude unit along with recovered oil.
The water goes on to sour water stripping.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
ARMBRESTER:
Our procedures are similar to those that have already
been discussed. We try to segregate the wash water, hold
it for oil removal and then process the water slowly
through the benzene removal section of our waste water
treatment plant. The other thing we do is examine the
cleaning agent we plan to use and make sure it is compat-
ible with the waste water treatment plant operation. Two
of the primary things we check are the COD content and
the aquatic toxicity.
BARLOW:
We can not emphasize enough that a little bit of work
up front saves you a lot of headache in the end. After your
turnaround you must evaluate the compatibility of the
chemicals being used because often they are not very similar
to what you are already using in your systems. Secondly
from the standpoint of toxicity, they often carry different
concerns. Pre-evaluation of compatibility and dosages and
so forth will save you time and money. If done properly,
the degassing /degreasing programs can be quiet effective.
BOYCOTT:
Wash water from our turnaround cleaning is temporar-
ily stored to ensure the material is near neutral pH.
Depending on the makeup of the material, it is disposed
of in one of the following ways. If it is primarily water, it
is discharged to the oily water sewer at a controlled rate.
From this system, it is routed to the main API separator
in our waste water treatment plant. If the process or
chemical considerations raise toxicity concerns, we sample
and screen the material for toxicity. Secondly, if the mate-
rial contains greater than 10% oil, it is discharged to our
coker API separator, which runs in series with, and up-
stream of, the main API separator. This gives us two
opportunities to recover the oil. Thirdly, if the material
contains a stabilized emulsion, it is sent to a holding tank
to allow time for the emulsion to break. Oil and water are
drawn off of the tank for appropriate disposal. Remaining
emulsion is sent to the coker where we dispose of it in the
MOSC process.
QUESTION 43.
Have refiners experienced seal problems due to the
introduction of MTBE? Have the problems been expe-
rienced with pure MTBE streams or with gasoline
containing 11 to 75 percent MTBE as we//? If so, what
solutions have been implemented?
MENEGAZ:
Pure MTBE is much more aggressive than TAME or
ETBE on elastomeric seal materials. For pure MTBE, my
material experts tell me that high performance seals of
proprietary materials such as Zalak 250GT or Kalrez 4019
work very well. They are also horrendously expensive.
43
TOC/INDEX
However, they have had poor or mixed experience with
Viton, nitriles, teflon and fluorosilicones. This goes as well
for 11% to 15% MTBE. For oxygenated gasoline, highly
fluorinated elastomers such as Viton GLF, Viton GF, etc.
offer good resistance to attack.
SAYLES:
I agree with what has been said. I would just add that
we have been transferring 100% MTBE for more than
four years in our terminals and in our refineries. The hoses
we use are high density, high strength propylene, and the
seals that we have been using in our transfer pumps have
been Kalrez 4079, a DuPont trademark. After blending,
we have used conventional gasoline seals and hoses with-
out problems.
TREESE:
Our experience has been pretty much the same. Prob-
lems with neat MTBE and the seal elastomers are well
established. We have not had significant problems with
the blended gasoline containing MTBE up to 13%.
BOYCOTT
We have one pump and one tank in MTBE service. The
tank is equipped with twin seals, the primary being teflon
coated seal fabric and the secondary having a thiothane
wiper tip. The pump is equipped with tandem seals, the
primary being carbon rings, the secondary being teflon
O-rings. Both the tank and pump have been in MTBE
service for four years. We have not had any problems with
them.
D’AURIA:
We specify Kalrez 4079 in pump seals for both neat
MTBE as well as MTBE containing gasoline streams.
QUESTION 44.
What are the current experience and future plans for
commercializing/promoting biotechnology in the pe-
troleum refining and petrochemical industry?
FELTROP:
The primary refining and petrochemical applications
of biotechnology today are in waste treatment. These
involve using microorganisms developed through natural
selection, classical mutation or genetic engineering tech-
niques to convert waste materials from process sources
into innocuous or easily biodegraded compounds.
Specialized microorganisms can enhance the efficiency
of more conventional waste treatment operations signifi-
cantly. Some work has also been done on removing paraf-
fins from refined product streams using similar technology
to that reported for treating paraffinic crudes in produc-
tion. However, this application is not yet in commercial
application.
44 General Processing and Support Operations
To date, biotechnology has not been used in any of the
main processing units of a refinery. A process called bio-
catalytic desulfurization is currently under development
by Energy Biosystems. This process uses enzymes to selec-
tively remove organic sulfur from a range of petroleum
fractions in crude oil. As a biotechnology based process, it
operates near ambient temperature and pressure, offering
the potential for significant capital savings compared to
conventional hydroprocessing. The process does not use
hydrogen and is expected to have lower operating costs
than hydrodesulfurization. Biocatalytic desulfurization is
focused solely on sulfur removal and, therefore, does not
have some of the advantages of hydrotreating FCC feed-
stock, or the drawbacks of hydrotreating FCC gasoline.
Energy Biosystems expects to have a pilot plant in
operation at Petrolite facilities in St. Louis in late 1994 and
expects the first commercial unit into operation in 1996.
Ifsuccessful, biocatalytic desulfurization may pave the way
for other bioprocessing operations, such as nitrogen and
metals removal, aromatic saturation, reforming and vis-
cosity reduction.
MENEGAZ:
On the petrochemical side, there is a new strain of
ethanol-producing bacteria, Zymomonas mobilis, which
holds promise for converting xylose, a previously uncon-
vertible sugar. Xylose comprises about 40% of biomass.
This increases the range of potential feedstocks to very low
agricultural wastes and paper with a potential for reducing
ethanol costs substantially. Quadrex is planning one of
these biomass to ethanol plants up in Nebraska.
QUESTION 45.
What experience do refiners have in forming alliances
with suppliers? What key elements have proven suc-
cessful in maintaining a long term mutually beneficial
relationship?
TREESE:
In one refinery experience, a formal alliance was estab-
lished with our tool supplier. This arrangement has the
tool supplier manage our various tool rooms during turn-
arounds and also during normal periods. The effectiveness
of the arrangement is based upon having agreed upon
goals and identified performance measures. The objective
of the alliance was to reduce the total yearly tool cost for
the refinery, and that goal has been achieved.
Another alliance type of arrangement involved engi-
neering services. Depending on who you talk to, the
alliance was a success or a failure.
We have considered several alliances with suppliers over
the years, but our final arrangements or our final agree-
ments, if any, have generally fallen short of being what I
would call an alliance. They would still be characterized
as client/contractor arrangements, usually due to concern
TOC/INDEX
over financial controls on the alliance work scope. A lot of
it is related to establishing a comfortable level of trust
among all parties to the alliance.
FELTROP:
Petrolite’s experience with alliances span U.S. refining,
international refining and oil field areas. Supplier alliances
in the refining industry are relatively new concepts, but
we have been quite active in this area.
There are several types of alliances that have been
developed: single source, formal and informal alliances
and partnerships. Each type has a different level of risk.
We feel that the single source scenario is one that offers
low risk for the short term and puts the refiner at high risk
for the long term. Typically a single source scenario is one
where a bid or a chemical cost reduction approach is the
primary focus. This leaves the refiner vulnerable to limi-
tations in the ability to infuse new approaches and tech-
nology in the long term, resulting in a higher risk situation
for the overall operation.
Contrasting a formal alliance is a long-term commit-
ment which offers lower risks throughout. This scenario
allows two companies to work closely together to deter-
mine and prioritized what is best for the overall operation
and what is best for both companies so as to result in a
win/win situation.
As a former refiner who is now a supplier, my opinion
is that the key element in this is trust. This may seem
trivial, but it is true in every relationship that until we can
be honest enough to trust each other alliances will not be
successful.
The key elements for successful maintenance of a long-
term relationship include:
l A steering team is set up to manage the overall
alliance. Task forces are set up to address specific
opportunities or issues within the alliance. These
task forces are comprised typically of a Petrolite sales
engineer, an appropriate Petrolite technologist, cus-
tomer’s operations personnel and customer’s support
personnel as required.
l Relationships are better with our Technology per-
sonnel and our customer’s operational and technical
support personnel.
l Communication lines are open and fluid. Our cus-
tomer has direct access to our Technology Depart-
ment and vice versa. (Previously, our sales engineers
played a role as “gate keeper”.)
l There is a willingness to work on key issues but there
is a long payback period. This is a willingness to work
on the opportunities to give the greatest impact.
l Both companies are willing to devote more up front
resources.
l Both companies are getting good direction on each
other’s goals and needs.
l Commitment, shared goals and objectives are a must.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
l Performance should be based on mutually agreed
upon goals and standards.
l Clear understanding of priorities must be commu-
nicated.
l Common measurements for success need to be
established.
l It is important that a high level of candor be estab-
lished to identify those metrics that have the greatest
impact on operations.
l Regular review by Supplier and Customer manage-
ment provide routine control.
l Win/win situations are the ultimate goal.
McLEAN:
Speaking again from the supplier’s point of view, we are
doing a number of things aimed at moving relationships
with refiners into what we would truly call partnerships.
Some examples of these things include:
l Organization of our sales, technical service, R&D
and manufacturing staffinto specific customer focus
teams to better understand our customers’ needs and
then to respond with our services.
l We have adopted in our laboratories some specific
customer testing procedures in order to streamline
our product development programs.
l We have developed, in certain cases, custom catalyst
materials specific to individual customer’s needs.
l We have achieved ISO certification of our catalyst
manufacturing plants.
l We have also cooperated with and responded to
specific customer quality review and audit programs.
l Finally, an extension of our technical service capa-
bilities to work more towards helping to optimize a
customer’s operation rather than simply sell them a
product.
I think we recognize and strive for the mutual benefits
which can be achieved in moving from being simply a
qualified supplier to a preferred supplier and finally on to
a true partnership.
MENEGAZ:
There are three elements in maintaining a successful,
long-term alliance: (1) the alliance originates and operates
at the working level; (2) the alliance has a formal mecha-
nism for feedback, such as a report card, to assure that
expectations are being met and that the relationship is not
being taken for granted; and (3) the alliance is structured
to reward performance or share in the business successes.
PORTER:
Chevron has formed alliances with a few suppliers. The
focus of the process is establishing long-term agreements
with preferred suppliers to reduce the total cost of owner-
ship of services and materials. We are very satisfied with
our success so far.
45
TOC/INDEX
The key elements for a mutually beneficial relationship
are: 1) common definition of alliance, 2) clear expecta-
tions and objectives, 3) open and frequent communica-
tions, 4) documented plans and results, 5) audit at an early
stage, 6) similar company cultures with TQM process in
both organizations, 7) committed and credible team
members, and 8) strong sponsorship from both sides.
BARLOW:
As a supplier, we are rapidly gaining experience in
forming alliances with refiners. A significant portion of
our business is tied up in “alliances”-and I will use
quotations around that word because some might be
structured in a contract, some as a preferred supplier, some
as a sole supplier, and some actually as partnership type
structures. Our experience has shown that the actual key
elements of these alliances vary substantially from one
customer to another. Our goal is to try to work very closely
early on in the process with the customer to understand
what their goals are in forming the alliance. We then try
to stay in step with them, because we find that their goals
often change rapidly.
We have a definition of a partnership that we use and
that we would like to strive for in these alliances. Our
definition is a business relationship built on trust, which
you have heard said many times, with a legitimate struc-
ture for mutual problem solving as a vehicle for continu-
ous improvement in quality, productivity and profitability
for both parties. We find our most successful arrangements
work when we are focusing on profit improvement pro-
jects and not just cost reduction projects.
Trust is our number one key element. Other elements
that are required are:
Excellent communication, not just good communi-
cation. You must gain an understanding of each
other’s business needs.
You have to have a plan to resolve issues, because
they will arise.
You have to encourage an innovative attitude for
both parties. An ideal alliance is when a supplier
brings improvements to the customer as opposed to
being requested to bring improvements.
You have to have a proper commitment of resources,
because it does take an awful lot of effort to make it
work, and the responsibility for success of the alli-
ance has to be shared.
DEATON:
Both of Clark’s refineries began forming partnership
alliances with suppliers in August of 1993. Our goals are
to reduce costs, reduce the number of vendors, reduce
inventory, reduce paperwork, receive better service, reli-
able quality and consistent long-term pricing. All initial
agreements were for a period of one year. Savings of over
$52,000 were realized in the first quarter of 1994. Vendor
46 General Processing and Support Operations
discounts range from 5% to 10%. In addition, rebates
totalling an additional 4% have been negotiated with one
vendor should certain minimal levels of sales be reached.
To date, 30 commodities have been identified for possible
long-term agreements.
Areas where we have already been successful include
pipe, valve and fitting supplies, tools, portable equipment,
construction services, safety supplies, electrical supplies
and bearings. Areas that we are currently pursuing include
vacuum and hydroblast services, insulation, cylinder gases
and welding supplies, structural steel, motor repairs, cata-
lysts, commodity chemicals and process and water treating
chemicals.
KENNETH D. PETERS (UOP):
In 1990, UOP began a program to align our products
and work processes more closely with the needs of both
refiners and contractors. The first step was to conduct
formal customer satisfaction surveys, followed by a series
of in-depth interviews with specific clients and contractors
in order to clearly understand the needs of each and how
our products impacted their work processes. As a result of
these efforts, we have realigned our sales and service
functions to be more responsive to customer needs.
We have enhanced our development process to reduce
the time to commercialization through earlier customer
involvement. One example was sited in Jim D’Auria’s
earlier reference to customer involvement in solid bed
alkylation development.
UOP has formed alliances with other companies to
provide a more comprehensive portfolio of technologies
to the refining industry. Examples include our alliance
with Texaco for Alkad HF additive technology, with Foster
Wheeler for coking and visbreaking technology, with
CCIC for residual hydrotreating and with Unocal for
Unicracking.
More specifically UOP Engineering has changed and
greatly expanded the Schedule A package while at the same
time significantly reducing the time to produce this
Schedule A package. The key aspect of this program,
though, is the continuous measurement and adjustment
of these new systems to ensure their on-going alignment
with the changing needs of both refiners and contractors
in the future.
ARTHUR J. SUCHANEK (Criterion Catalyst Company L.P.):
In March of this year there was a very unique strategic
alliance formed among Syncrude of Canada, Criterion
Catalyst, Cat Tech, CRI and CRI-MET. The alliance was
formed to provide total fresh catalysts to Syncrude, also
regeneration of the catalysts, handling of the catalysts, and
then taking the final spent catalyst all the way back to their
final parts. Included in that alliance are joint R&D ele-
ments as well as continuous improvement in trust and
communication as was mentioned before.
TOC/INDEX
Roughly a year and a half ago, another alliance, which
we call a quality partnership, was formed with Lyondell,
now Lyondell-CITGO. This involved the same elements
as mentioned with tracking of units, joint R&D, and
various other technical functions.
DAVID M. JOHNSON (Chevron U.S.A. Products Company):
I will follow with a few comments on some of our
experience. We have several alliances of different types
ranging from vendor inventoried materials delivered di-
rectly to the process units to partnerships wherein vendor
supplies the chemicals, manages the inventory and pro-
vides the technical support on-site.
Some of the things we learned about these programs
over the last five years include the need for the supplier
side to have dedicated people assigned to the alliance who
understand why the alliance was formed, the purpose and
the reasons for the partnership and the vision to which we
are trying to achieve. On the other hand, the owner must
maintain his part and responsibility to the alliance in all
of the above areas.
We have found in certain instances, particularly in the
more mundane areas of the refinery, that communication
and trust elements broke down because we as the owner
were not holding up our side of the partnership. So I would
stress to anyone that when you enter one of these relation-
ships, not only does it take a lot of work up front to clearly
identify the vision and purpose of the alliance, but it also
requires ongoing effort to insure good communication
and ultimately success of the alliance.
QUESTION 46.
How are refiners with multiple locations training their
incoming refinery and R&D engineers? Is it done
jointly at a central location?
CUNEO:
Yes, we hire engineers into our multiple refineries. We
have six refineries that we manage as a common skill pool.
Hiring is basically weighted toward the large locations.
Historically we have had a training program which in-
cludes a lot of classroom training in the first three to five
years of a person’s career, probably on the order of 8 to 10
weeks a year. We are currently modifying that with the
intention to deliver most of that information through
on-line job helps or expert type of advice delivered through
their individual work station. We expect to get 7.5% to
80% of the material we historically taught in classrooms
available to them on-line.
With respect to the R&D engineers, we generally hire
people with advanced degrees, Master’s or PhD, in R&D.
They receive mostly on-the-job training. There are defined
opportunities for both groups as they progress in their
career to work in each other’s environment, either in the
1994 NPRA Q&A Session on Refining and Petrochemical Technology
technology center at Westhollow, or for R&D people to
get manufacturing assignments.
ARMBRESTER:
Ashland’s normal practice is to assign incoming engi-
neers to the central engineering or research group. This
allows the new employees to become familiar with the
company’s standard engineering policies and practices,
and to begin to develop their engineering skills under the
guidance of more experienced design and support engi-
neers. To further enhance their development, engineers are
often rotated into short-term training assignments in the
refinery operations, maintenance and technical groups.
Full-time assignments in the refinery are usually made
only after the employee has completed at least two years
of work in the central engineering department.
TREESE:
Each Unocal refinery trains incoming college graduates
slightly differently, but the objectives of the training are
essentially the same. That is, we want the incoming engi-
neer to gain as much practical experience in refining as
possible. This is accomplished by working in various
refinery groups and by contact with experienced engineers
in the forms of mentoring, joint engineering work or joint
engineering projects and seminars.
Much of our program depends on a learn-by-doing
approach. In our Los Angeles refinery, new engineers are
placed in two or three departments over a period of about
two years. Ideally, each engineer will spend several months
in operations, technical services and maintenance during
this period. However, frequently, job load dictates how
closely we can stick to that ideal. The program is admin-
istered by the Human Resources Department with input
from the chief engineer and the trainees.
At our San Francisco refinery, new engineers are moved
through a series of shorter assignments in more depart-
ments. Basically, they will spend a couple of weeks in about
every department. Again, the plan may be modified by job
loads. The San Francisco refinery plan lasts about a year
and a half and is administered by the Supervisor of Process
Engineering.
Unocal’s Research Department formerly ran a training
program with assignments of several months for each
engineer in two or three groups, similar to the way Los
Angeles Refinery runs their program. We have, on occa-
sion, swapped engineers among the refineries into Corpo-
rate and also between refineries and Research to gain
cross-pollination benefits in these areas.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
For all our new young engineers, Saudi Aramco has an
excellent three year program called the Professional Devel-
opment Program (PDP). The objectives are to:
47
TOC/INDEX
Introduce the Company’s main departments, busi-
ness locations and an overview of their respective
functions (Producing, Manufacturing, Engineering,
etc.);
Familiarize the new engineers with the Company
Engineering Standards with respect to safety, design,
material, inspection and testing, etc.;
Introduce the beginning engineer with real-life
working and business situations;
Assign each new engineer to a progressively increas-
ing degree of complexity in his respective field;
Enroll each new engineer in technical and manage-
ment courses to enhance both his technical and
management skills.
For each new engineer, an Individual Development
Plan and a Critical Task by his specific engineering disci-
pline (chemical, mechanical, electrical, etc.) are prepared
and discussed with him. His technical qualifications and
career objectives are balanced with current assignment
48 General Processing and Support Operations
openings at the various work locations. The three year
orientation is usually broken down into six assignments
(six months each). Special emphasis is placed on quickly
recognizing and rewarding performance. For example, the
engineer is given a detailed evaluation with personal con-
sultation at the end of each six month assignment. The
results are reflected in his salary within one month after
the evaluation.
Usually, the new engineer will be first assigned with one
of the engineering units. Later, he may rotate into one of
the other organizations within the refinery or other busi-
ness lines. By the end of this period, the engineer will be
prepared to fully participate in handling day to day prob-
lems encountered, in addition to other assignments. After
program completion, the engineer will be assigned to one
of the engineering support divisions. At this time, a new
development plan is prepared to help determine an appro-
priate career path (professional or management).
TOC/INDEX
II. HEAVY OIL PROCESSING
A. Fluid Catalytic Cracking
Mechanical
QUESTION l.
What are the relative merits and drawbacks of hot wall
and cold wall reactor designs?
MENEGAZ:
Both designs have been used successfully for many
years, but there are advantages and disadvantages to each.
The hot wall design requires 316 or 347 stainless steel
for the hotter sections such as the regenerated catalyst
standpipe, slide valve, and the lower riser. In this applica-
tion, stainless steel is prone to creep-induced cracking,
sigma phase formation, and polythionic stress corrosion
cracking. Several refiners have had problems with cracking
at the regenerated catalyst “Y” and switched to the cold
wall design. In the reactor area, temperatures are lower and
1¼ chrome 1/2 molybdenum is used very successfully.
However, as the vessel ages, thermal creep, carbide precipi-
tation, and other high temperature phenomena occur.
Several hot wall reactors built in the early 1950’s have
reached the end of their useful life, based either on calcu-
lation method or inspection, and they have been replaced.
The cold wall design has a normal skin temperature of
350°F to 450°F. At these temperatures, carbon steel works
well without metallurgical problems and the lifespan of
the shell is unlimited. The primary drawback for cold wall
designs is the reliability of the internal refractory.
Newer refraction installations are using more durable
refractory, better anchoring systems, and better quality
control during installation, and seeing significantly less
problems. Catastrophic failure on the run is a relative
rarity today. However, most refiners still do a lot of refrac-
tory replacement in the reactor at turnaround.
PORTER:
Cold wall reactor design has two major advantages:
1. It allows the use of a carbon steel shell which is
initially cheaper and greatly facilitates inspection,
repairs and modifications.
2. It minimizes the amount of thermal expansion that
must be accounted for in the design of connecting
piping and equipment.
The primary disadvantages to cold wall construction
are the additional weight and tendency, over time, for the
1994 NPRA Q&A Session on Refining and Petrochemical Technology
insulating refractory to become impregnated with coke.
Up to a point, the coke impregnation is not a problem,
and may even improve the insulating properties of the
material. Ultimately, however, the coke impregnation
causes separation from the wall and spalling of the refrac-
tory, and major repairs are necessary. As Mr. Menegaz said,
this disadvantage can be minimized by proper selection of
refractory material and anchoring system.
Mr. Menegaz has covered well my items regarding hot
wall design, The only additional point is that erosion-
resistant refractory is commonly used in hot wall reactors.
It is also subject to deterioration by coke impregnation,
but to a lesser extent than the thicker cold wall refractory.
McLEAN:
I have to agree with what Mr. Menegaz and Mr. Porter
have said, and will make an additional comment. On the
cold wail design, a critical parameter is paying careful
attention to the installation and curing procedure of the
refractory insulation. When this is done properly, lives of
5 to 10 years can be attained.
BOYCOTT:
Frontier’s FCC reactor was converted from a pseudo
hot wall to cold wall design in March 1994. Advantages
noted are:
Reactor wall temperatures were reduced from 850°F
to 350°F. This eliminated the carburization of the
carbon steel shell and extended the mechanical life
of the vessel.
Our previous system was ‘pseudo’ hot wall as it was
externally insulated and refractory lined. With this
system the stresses caused by differential thermal
expansion resulted in severe cracking of the refrac-
tory and a 2 to 3 thermal cycle life of the system.
With the current system, the lower temperature of
the shell has reduced the differential thermal expan-
sion of the shell and refractory. We anticipate that
this will reduce cracking of the refractory and in-
crease its life.
The selection and installation of refractory was criti-
cal in this conversion. We used a gunned, fused-silica
material with 3% needles. It was applied 5 in. thick
as a single component. Steer horns were used for
attachment.
Potential drawbacks are:
49
TOC/INDEX
Refractory selection and installation is critical. If
care is not taken, this system can become a high
maintenance area.
Careful consideration must be given to stresses in
associated piping due to the reduced thermal growth
of the reactor.
D’AURIA:
We have designed both hot wall and cold wall reactors.
We favor the hot wall design, however. A hot wall reactor
will be smaller for the same internal process diameter,
does not have the refractory repair requirements of a cold
wall reactor, and, in our experience, has a better on stream
efficiency. The cost difference that is cited for cold wall
reactor is valid for the vessel itself. We have found,
though, when you look at the entire reactor structure and
consider the larger size and weight of a cold wall reactor
and the impact this has on the foundations, that the cost
differential between a hot wall and cold wall installation
can be as low as $100,000. The higher on stream effi-
ciency, and the lack of problems with refractory, in the
hot wall design will tend to favor that design in most
instances.
DEATON:
We recently replaced our original carbon steel hot wall
reactor with a new 1¼ chrome 1/2 molybdenum hot wall
reactor. The top half of the new reactor has 410 stainless
steel cladding for corrosion protection, and the bottom
half is hexmesh lined for erosion protection.
A hot wall reactor design was preferred to avoid refrac-
tory maintenance problems inherent in the cold wall
reactor designs. The problem with the cold wall designs is
that hydrocarbon can cause coke formation behind the
refractory, thus leading to refractory spalling.
On the other hand, a cold wall design could help avoid
a metallurgy upgrade. Also, as Mr. D’Auria indicated, cold
wall designs require more robust foundation designs due
to the weight of the refractory. I believe that most refiners
favor a hot wall design.
JAN W. WELLS (Phillips 66 Company):
Have you noticed any difference in the coke accumu-
lation on the surface of the wail between the hot wall and
the cold wall design?
PORTER:
We have not seen any significant coke accumulation on
the refractory surface of either the hot or cold wall reactors.
FRANK ELVIN (Coastal Catalyst Technology, Inc.):
Have the panelists heard of anyone using cold wall but
with stainless?
50 Heavy Oil Processing
HIGGINS:
No response.
QUESTION 2.
During a recent FCCU turnaround, erosion and signifi-
cant wall thinning were discovered in areas of the
reactor overhead line. The erosion occurred near el-
bows on the downstream side of small internal weld
or p/ate protrusions. Have others experienced this?
What design or operational guidelines, such as maxi-
mum fluid velocity, are used to avoid significant reac-
tor transfer line erosion?
SAYLES:
A number of the units operating in this country were
built before the advent of zeolite catalysts. These units
built in the 1940’s were operated at much lower unit
throughputs than current operation. On most of the units
with which I am familiar, the reactor overhead line has not
been replaced.
The typical design considerations for these types of
units are 110 to 130 feet per second superficial vapor space
velocity, with an absolute maximum of about 190 feet per
second. We operate in the range of 130 to 150 feet per
second, and in this range we have not observed significant
erosion.
The reactor overhead line must be well insulated and
insulation repairs should be made as needed during the
run to limit heat loss, avoiding the potential of having
coking condensation, which causes coking in localized
areas. Localized coking causes a protrusion and on the
back side of the obstruction, there will be a swirling
motion or an eddy current. Erosion behind that obstruc-
tion occurs due to the flow interruption.
Before you think that erosion is occurring, make sure
that the reactor line is clean. In one case, the initial
inspection indicated we were observing erosion in the
overhead line. After cleaning the line, no erosion was
found. Apparently, coke deposits had laid down forming
an erosion surface that looked like line damage.
At another location, a 26-inch overhead line, installed
when the unit was built in 1946, cracked during routine
maintenance to remove coke. The line had an outer shell
of SA 201 and an inner lining of Type 430 stainless steel.
The line failed during normal coke chipping, using a
hand-held air-operated chip gun, at an ambient tempera-
ture of around 10°F. The fracture occurred in a horizontal
pipe section, was longitudinal for about 12 feet, then
turned circumferential at both ends. After the crack
formed, the line fortunately stayed in place, requiring
removal and replacement.
A metallurgical analysis indicated that during the 47
years of operation, the carbon from the outer line diffused
into the inner stainless steel liner, causing both of them to
become brittle. I believe that the steel on the outside of
TOC/INDEX
the line essentially turned into boiler plate iron, a very
brittle substance when cold.
We are familiar with low temperature embrittlement of
austenitic stainless and higher grade steels. We operate
units in the state of Wyoming, so we are familiar with
operating units in relatively cold temperatures and work-
ing on them in those conditions. To our knowledge, this
is the first time that we have observed or heard about
cracking in a reactor overhead line at those conditions.
McLEAN:
I want to add another issue here, regarding catalyst
carryover and the cause for the erosion. I think that if you
pay proper attention to the design and operation of the
cyclone system as well as the catalyst physical parameters,
you minimize the catalyst carryover and therefore mini-
mize the erosion potential, regardless of the other condi-
tions under which you are operating.
PORTER:
Our experience is similar to Mr. Sayle’s. We believe
velocities should be 100 to 120 feet per second to minimize
internal corrosion, but we have operated at 130 to 140 feet
per second without problems. Discontinuities in the line,
which create localized turbulence, and a high content of
catalyst in the reactor vapor will accelerate corrosion.
BOYCOTT:
I agree with the comments on velocity and dust loading
and note that we do experience fairly significant levels of
erosion in our reactor overhead line as a result of this
problem.
CUNEO:
We have also had some erosion in these types ofservices,
especially at high velocities. We have found that the appli-
cation of erosion-resistant refractory linings inside around
the bends is very effective in protecting from further
erosion.
MENEGAZ:
We would design a new unit for under 150 feet per
second. Above 175 feet per second, you are asking for
trouble with erosion. In certain cases, we design for much
lower velocities than 150 feet per second, and this is due
to pressure drop limitations which may affect the air
blower sizing.
QUESTION 3.
On a recent turnaround, we discovered significant oxi-
dation of the 1¼ Cr-1/2 MO nozzles on our regenerator
air ring. Has anyone eliminated this oxidation through
operating or equipment changes? Is oxygen enrich-
ment to 25% oxygen likely to exacerbate the problem?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
CUNEO:
We have observed significant increase in the oxidization
of chrome-molybdenum steels with increases in tempera-
ture. Although we do not have any direct experience with
oxygen enrichment up to 25%, we would expect that the
effect of oxygen content increase is small relative to the
temperature increase effect. To remedy that in our appli-
cations, we have moved to higher chrome-molybdenum
steels.
DEATON:
We recommend changing the air nozzles to 304 stain-
less steel. If you look at the oxidation rates for 1¼ chrome
l/2 molybdenum, it is 60 mils per year at 1,200°F com-
pared to less than 1 mil per year for 304 stainless steel. The
air nozzles on our regenerator are 304 stainless steel.
SAYLES:
We do not use oxygen enrichment. Our 304 H regen-
erator air ring nozzles have operated well over the last 8
years. Inspection after a 4-year run indicated a slight nozzle
ID enlargement which extrapolates into about 8 to 12
years of additional service. Low chromium content steels
(for example 1 1/4 chrome) have a very low high-tempera-
ture oxidatibn resistance and would not be recommended
for use in the regenerator.
Oxygen content should be limited to less than 25% to
prevent oxidation of the free carbon remaining in the steel.
The oxygen concentration should be calculated on the
amount of flowing air into which the oxygen is injected.
For example, on a unit which splits the air between
carrying air and burning air, injection of oxygen into the
burning air, 25% O2 based on the total air, could result in
a 33% O2 concentration in the air ring since 1/3 of the total
air is carrying air. The higher O2 content in the air ring
will cause accelerated metal oxidation.
GARY J. ANDERSON (Corhart Ceramics):
Many of you who are using ceramic nozzles in your
regenerators are aware that the ceramic technologies avail-
able are totally immune to oxidation, and we have appli-
cations for the materials that are using 40% oxygen
enrichment in molten steel or in molten copper. You have
a very vast safety margin at the temperatures we observe
in the FCCU.
Also, these materials are superior to erosion by a factor
of about 20.
QUESTION 4.
An Inconel 625 regenerator catalyst withdrawal/dump
nozzle failed recent/y in one of our refineries. What
nozzle metallurgy is recommended for this service, up
to 1,400°F?
51
TOC/INDEX
LAUX:
Our catalyst withdrawal nozzle is refractory lined carb-
on steel. It connects to a 1 l/4 chrome valve and line at the
regenerator. The line changes back to carbon steel about
20 feet away from the regenerator itself. We normally run
at 1,400°F and have not had a problem with this nozzle.
MENEGAZ:
Inconel 625 is not suitable above 1,200°F if sulfur is
present, and will embrittle with thermal cycling. Stainless
steel Type 321-H or 347-H solution annealed and ther-
mally stabilized has been recommended for this applica-
tion. I emphasize that the solution anneal and thermal
stabilization steps are necessary to protect against
polythionic acid corrosion.
ARMBRESTER:
On all of our FCC units, the catalyst withdrawal nozzle
is a carbon steel long weld neck nozzle welded into the
vessel shell, with a 304 stainless steel sleeve welded to the
nozzle at the I.D. of the shell and passing through the
refractory. This nozzle arrangement has provided very
good service, with only one repair required in over 20
years.
On the RCC unit at Catlettsburg, we use a true cold
wall installation, where the carbon steel nozzle is lined
with refractory, and a 304 stainless steel liner extends from
the nozzle flange to the inner face of the refractory. We
have not experienced any problems with this nozzle in over
10 years of operating experience.
Our regenerator dense bed temperatures on all of these
units are typically in the 1,300°F to 1,360°F range.
D’AURIA:
Inconel 625 is not suitable for this service. We recom-
mend the same setup that Mr. Laux described: a cold wall,
carbon steel nozzle, with transition to a low chrome set of
valves and line.
In addition, sometimes a finned pipe is used in this first
section of line to help with cooling.
Frequently air is introduced into the line, close to the
first block valve, to act both as a catalyst carrying medium
and also to help keep the pipe cool. The key variable is the
rate at which you unload catalyst. This rate should be
controlled to keep the process piping below its design
temperature. We have seen some people put a local skin
temperature indicator on the pipe so that the operator can
monitor the temperature as he is unloading catalyst.
MENEGAZ:
If you are adding air to your line for cooling, you better
keep the velocity downstream to less than 60 feet per
second or your transfer lines will wear out.
52 Heavy Oil Processing
QUESTION 5.
What experience do refiners have with corrosion of
heavy FCC naphtha pumparound circuit piping and
equipment? Our VRU (Vapor Recovery Unit) stripper
side reboiler recently experienced severe tube corro-
sion from the heavy naphtha pumparound side.
BARLOW:
Corrosion of the heavy FCC naphtha pumparound is
not considered a very common problem, based on our
experience. However, we have seen it in several units. The
problem is generally related to ammonium chloride depo-
sition. It is not unlike what you might experience in a
crude tower if conditions are set up properly. When salt
forms, and if the tower gets wet, the deposits can be
extremely corrosive, setting up a difficult environment.
Also, if the efficiency of the tower is affected, possibly
due to fouling, you can get water in the lower sections of
the tower which, again, by creating a wet, corrosive envi-
ronment, can cause severe tube corrosion in the VRU side
stripper reboiler. The problem is exacerbated if you have
high volumes of cooler temperature pumparounds return-
ing to the column, providing a source to condense water.
One process change that might exacerbate the problem
is the use of import feeds. If you import feeds and you have
contamination with chlorides, the formation of ammo-
nium chloride can be more severe. We would recommend
that if you do have this problem, you look at the tower
operating conditions and the handling of the feeds to the
unit first. If that does not work, then you should consider
applying a proprietary filmer to reduce corrosion and
disperse the salts.
CUNEO:
We agree. We have seen this type of corrosion in some
of our FCC main fractionators that have naphtha pum-
parounds near the top. We have experienced some mild
underside tray corrosion, which we have attributed to
ammonium chloride, and seen some significant corrosion
of column shells in the region by the naphtha draw, when
we thought we were operating a wet system.
FELTROP:
I agree with the comments on ammonium chloride,
and water in particular. Since both ammonia and H2S are
present, ammonium bisulfide is a possibility in these
situations. They are just several orders of magnitude less
temperature stable than ammonium chloride. Under cer-
tain partial pressure and temperature conditions, ammo-
nia and H2S, ammonium bisulfide could be the problem,
but we have not seen this in any FCC unit.
LAUX:
In our circuit, which is killed carbon steel and seamless
killed carbon steel tubes, we have not seen the problem.
TOC/INDEX
If you did have ammonium bisulfide, you would probably
be seeing hydrogen blistering as well, which might help
you to analyze the actual cause.
QUESTION 6.
We experience coke buildup at the reactor cyclone
inlet horns between the refractory and the metal. The
coke grows and causes the refractory to pull away
from the horn. What can be done to eliminate this
problem?
LAUX:
The solution that seems to work for us is simply to weld
every piece of hexmesh to the cyclone inlet horn. This
prevents the initial bulging which allows more coking and
further bulging.
McLEAN:
I agree with Mr. Law’s comment regarding the need to
weld every piece of hex. In addition, I emphasize that extra
effort should be made in pounding the refractory to make
sure that it is done right. Also, reactor and transfer line
coking in general can be minimized through the use of a
moderate to high matrix surface area catalyst. This has
been well documented in past Question and Answer Ses-
sions Transcripts, including 1986.
MENEGAZ:
I agree with the comments regarding the welding. The
weld should be a full fillet weld, not a tack weld. In
addition, the hexmesh should be the type that can be
placed flush against the wall.
PORTER:
I also support the comments on welding. In addition,
high quality workmanship is critical for installation of the
refractory.
SAYLES:
I have one additional note on how you install the
refractory. Wrap the refractory around the inlet horn to
avoid any open leading edges or install a bar or some device
at the leading edge of the refractory to seal the refractory
to the vessel wall. These measures are taken to prevent oil
from adsorbing under the refractory and forming coke.
The mechanism, which may allow coke to grow causing
refractory failure, is capillary action which draws the oil
into gaps between refractory and the vessel wall. Once in
place, the oil degrades into coke, further opening the gap
and repeating the process. Sealing the refractory edges
prevents this process from taking place.
BOYCOTT:
We have not experienced coke buildup under the re-
fractory in our cyclones; however, we have experienced a
1994 NPRA Q&A Session on Refining and Petrochemical Technology
similar problem in other areas of the reactor section. In
our experience, this problem occurs in areas of high con-
tour (i.e., a lack of adhesion due to difficulty of installa-
tion) or low velocity. It would appear that this example is
a case of poor adhesion. Where this occurs, we have had
success with the installation of a single component, hy-
draulic wear resistant refractory with 3% needles. S-bars
are used for adhesion. We have eliminated the use of hex
steel in these areas as we feel that the S-bars provide better
adhesion. Another consideration would be to sandblast
the base metal and apply a coating of phosbon mortar for
better adhesion.
I agree with the previous comments on installation.
Whichever system is used (S-bars or hexmesh), the instal-
lation is critical to service life. Welding of every biscuit is
necessary with hex steel.
D’AURIA:
In addition to the comments on the refractory, there is
also an operational consideration. If during start-up or
upsets, the temperature of the internals is allowed to get
too low, you can get condensation of hydrocarbon, which
can get behind the refractory and later cause coking. To
avoid this, we recommend that you allow sufficient time
for all of the reactor internals to come up to operating
temperature before introducing the feed.
DEATON:
I have a recommendation on how to avoid exposing the
edge bar of the hexmesh to the direct flow of the process.
This can be done by welding standoffs on the metal edge
of the inlet horn, and then welding strips of metal about
one inch wide to the stand-offs and mold it around the
edge of the inlet horn. Pack AA-22 refractory behind these
strips, and then weld S anchors on the strips and pack the
AA-22 into the S anchors. S anchors are preferred over
hexmesh because hexmesh has a tendency to be popped
loose in large sections, as inferred in the question.
It is very important that the refractory be prequalified
and that you have your own expert witnessing the anchor
and refractory installation. Poor welding, as well as too
much water in the refractory, can make the difference
between a problem area and one that provides trouble free
service.
QUESTION 7.
What inspection techniques are effective in monitor-
ing refractory wear in external cyclones? What areas
have been most prone to wear?
CUNEO:
For our hot wall external cyclone designs, we rely on
visual inspection and the maintenance history to monitor
the refractory wear. For cold wall designs, we would think
that infrared thermography would be useful.
53
TOC/INDEX
We have had few recent problems with our modern
design cyclones in this kind of service, although in the
past, heavily loaded cyclones historically eroded at the
inlet target area, and moderately loaded cyclones eroded
in the lower cone area.
SAYLES:
Although we do not have external cyclones, several
techniques are suggested:
Heat sensitive paint is an effective tool in determin-
ing temperature changes.
Thermal imaging or scanning has been used when
we suspect regenerator refractory problems.
Recent developments have allowed for fairly accu-
rate and inexpensive hand held pyrometers. The
drawback is you have to be close to the heat source
you are measuring. Close proximity might not be
possible for external cyclones.
Skin thermocouples in areas prone to erosion can be
welded to the vessel wall or skin. Areas to consider
are the dust bowl, lower 1/3 of the cone and the gas
outlet tube.
Catalysts
QUESTION 8.
How can olefins be reduced in FCC naphtha to meet
RFG standards?
MENEGAZ:
The typical FCC naphtha in the U.S. is 25 to 40 liquid
volume percent olefins. We envision refiners will meet the
RFG standards for naphtha olefins via one of three ap-
proaches. The first is to minimize naphtha olefin forma-
tion, similar to how West Coast refiners currently manage
bromine number. This would include the following:
1. Use a moderate riser temperature.
2. Maximize the catalyst-to-oil ratio to retrack naph-
tha olefins.
3. Increase the catalyst rare earth content to maximize
hydrogen transfer reactions which saturate olefins.
4. Minimize the catalyst matrix content consistent
with bottom upgrading goals.
5. Increase fresh catalyst additions to promote over-
cracking and higher hydrogen transfer. A higher
proportion of fresh catalyst in inventory will in-
crease the equilibrium unit cell size which, in turn,
promotes olefin saturation.
6. Increase HDS severity to increase hydrogen avail-
ability for hydrogen transfer reactions and to com-
pensate for the higher delta coke associated with
increasing catalyst activity and rare earth content.
54 Heavy Oil Processing
7. Use ZMS-5 to crack naphtha olefins. This effect is
most pronounced on C7 olefins and higher. This
may slightly increase C5 and C6 olefins.
The second route is to separate out the C5 olefins and
send them to an alkylation or TAME unit. The C5 olefins
are about a third of the naphtha olefin content. Acid
consumption in alkylating C5’s is minimized by making a
sharp cut in the depentanizer to avoid cyclopentenes and
by selective hydrogenation of the dienes. However, we
envision that many refiners will actually increase naphtha
olefins as a side effect of maximizing C4, olefins for the
alkylation and MTBE feed.
The third route is to hydrotreat the FCC naphtha,
which reduces olefin content at the expense of lower
octane and higher vapor pressure. Pilot plant work on a
West Coast naphtha indicated a R+M/2 loss of 5 numbers
for the C5 cut and 12 numbers for both the C6 and C7
cuts.
McLEAN:
I would agree with a lot of what Mr. Menegaz said. I
would reemphasize that this can be optimized by use of a
high rare earth, high hydrogen transfer, high activity cata-
lyst, and achieving conversion through catalyst activity
rather than reactor temperature or catalyst-to-oil ratio.
I would also extend the question and say that a more
difficult problem exists today for refiners who are trying
to maximize their light olefin yields while at the same time
minimizing the gasoline olefins. The use of a ZSM-5
additive may in fact help in this situation since ZSM-5
will crack with the C6 and heavier olefins in the gasoline
range down to materials in the C3 to C5 fraction, and this
is particularly beneficial if you do have separate C5 olefin
processing such as TAME or alkylation, as Mr. Menegaz
discussed.
Also, when you do this, you get a dilution effect. That
is, you are adding back more fractions of lower olefin and
high octane components, such as alkylate and ethers, so
you really have to look at this in terms of what the impact
is on the total pool and not just what comes directly out
of the FCC unit.
ARMBRESTER:
We agree with most of the comments that have been
made already. In addition, if you are increasing catalyst
rare earth content, our research indicates that you can
reduce olefin production possibly as much as 15%.
In terms of downstream processing, if you are going to
separate out the C5 olefins and use them for TAME
production, then the olefin content of the gasoline can be
reduced even further if you isomerize that C5 olefin stream
initially and then send it to the TAME unit.
Regarding hydrogenation or saturation of the olefins,
the work that we have done indicates that if you go to
TOC/INDEX
complete saturation, you could drop the octane number
by as much as 10 numbers.
CUNEO:
I agree with the comments about the operating vari-
ables in the cracking unit made by Mr. Menegaz. Our
experience is very similar. One thing he did not mention
was increasing catalyst-to-oil ratio, which can also help
increase catalytic hydrogen transfer and reduce olefins.
On the issue of hydrotreating the olefins, yes, they can
be fully saturated. If it is desired to hydrotreat the olefins
or the light naphtha, from the FCCU, only for sulfur
removal, this can be done in modern low pressure, high
space velocity units with much lower octane loss then
quoted, on the order of around 2 numbers.
QUESTION 9.
How can aromatics be reduced in FCC naphtha to meet
RFG standards?
McLEAN:
Most of the aromatics in the FCC naphtha originate as
ring structures in the feed, so there is little you can do to
change their cracking chemistry, aside from feed hydro-
treating. A small percentage are formed by dehydrocycli-
zation mechanisms which require a hydrogen transfer step
to assist in their formation, so it follows that a low hydro-
gen transfer catalyst will help to minimize this.
As we discussed in NPRA Paper AM-92-45, Engel-
hard’s IsoPlus 2000 catalyst reduced C6 to C9, aromatics
yield by 10% in a pilot plant study, relative to a base
RE-USY type catalyst. This was really a secondary benefit
for this ultra-low hydrogen transfer catalyst, which was
actually designed to be a maximum iso-olefins catalyst, but
aromatics reduction came along for the ride. However, it
is worth noting that, in this case, the concentration of
aromatics in the FCC naphtha actually increased because
1994 NPRA Q&A Session on Refining and Petrochemical Technology
the gasoline yield loss was higher than the aromatics
reduction. The actual reduction that you are going to
realize, again, will depend on your downstream processing
options and how much dilution effect you will have from
additional alkylate and ether production and things like
that.
For full light olefins processing schemes, pool aromatics
reductions can be very significant with these low hydrogen
transfer catalysts, and we have done some hypothetical
calculations that indicate this can be in the 30% to 40%
range.
Similar reasoning applies to the use of ZSM-5 additives,
which do not change the actual aromatics yield at all, but
they do change the concentration effect and, again, pro-
duce more light olefins for downstream processing.
Finally, since most of the FCC aromatics are in the back
end of the gasoline, end point reduction can also be used
and this, of course, is contingent on the options that you
have for disposal of the heavy end naphtha in other areas.
MENEGAZ:
Apart from conversion, different FCC catalyst types, to
my knowledge, do not seem to affect aromatic content
very much. The most effective method for controlling
aromatics is to reduce the gasoline T90 point and divert
the aromatics rich back end of the gasoline to distillates.
Unfortunately, this robs volume and octane from the
gasoline pool and creates problems for the distillate pool
as well.
SAYLES:
I agree with the comments on catalysts, and the only
thing that we can do with aromatics, if it turns out to be
a problem, is to reduce the naphtha in the pool.
ARMBRESTER:
We agree that the aromatics production is primarily a
result of the feed quality and the unit conversion level.
There are several options for post treating this stream,
including extraction, dealkylation, or hydrogenation, but
all of these are at a relatively high cost and have a high
difficulty level.
CUNEO:
We would agree with the previous comments.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
What are the technical limitations on the aromatics in
the product stream?
CUNEO:
We generally do not have a limit on FCC aromatics
alone. What we are trying to do is blend reformulated
gasoline to meet the EPA standards, and while the simple
model is in use, we cannot increase from the 1990 baseline.
55
TOC/INDEX
So, generally, refiners are looking at not being over 25%
to 28% vol in the total gasoline.
QUESTION 10.
What are the advantages/disadvantages of the various
vanadium passivation technologies:
a. tin;
b. separate particle trap in a dual particle system;
c. single particle catalyst system?
FELTROP:
Vanadium on FCC catalysts hurts the process in two
ways. First, it lowers the activity of the catalyst by reacting
with the zeolites and compromising the pore structure.
Secondly, it promotes undesirable dehydrogenation reac-
tions. Tin is effective in partially counteracting both of
these undesirable effects. Tin is advantageous in that it
can be added as a liquid, thus requiring a relatively
simpler and more flexible addition system than solid
particles. The big disadvantage is that cost effectiveness is
difficult to demonstrate.
Separate particle traps react selectively with vanadium
compounds, thus minimizing their contact with the zeo-
lites. One advantage of a separate particle vanadium trap
is that these can be added on an as-needed basis into the
catalyst. The primary disadvantage is that a more complex
addition system is required when added as a separate
particle.
Vanadium traps incorporated into the catalyst have the
advantage of being closer to the zeolite which they are
designed to protect. They also eliminate the need for a
separate injection system. One obvious disadvantage is the
loss of flexibility.
McLEAN:
I agree with the comments on the dual problems with
vanadium’s effect on activity and also dehydrogenation,
and the best way to deal with vanadium, therefore, de-
pends on which of these symptoms, or both, are the
primary problem.
For activity maintenance alone, a high matrix catalyst
with a high alumina content does a good job of immobi-
lizing vanadium and keeping it away from the zeolite. We
have commercial catalysts operating at vanadium levels in
the 4,000 ppm range, with equilibrium MAT activities in
the low 70’s, and equilibrium surface areas around 180,
with no vanadium trapping technology present other than
the catalyst matrix. If gas make is not a problem, this can
be the preferred approach.
We also make a separate particle vanadium trap that we
use blended with the active catalyst components and this
was introduced and described in NPRA Paper AM-93-30.
This trap has been used in about a dozen commercial units
around the world. The degree of impact varies proportion-
ately with the severity of the vanadium effect in the first
56 Heavy Oil Processing
place. That is, in units with high regenerator temperatures,
full burn operations with excess oxygen present, the vana-
dium deactivation is more severe to begin with, and
therefore the beneficial effects of the trap tend to show up
more. In one case, we saw an increase of 4 MAT numbers
relative to operations on the same catalyst without the trap
at about 5,000 ppm vanadium.
We prefer a separate particle trap for a number of
reasons. The interparticle mobility of vanadium allows a
separate particle to work and trap the vanadium well away
from the zeolite. The preferred manufacturing steps for
control of parameters such as porosity and attrition resis-
tance of the trap are easier to control in a separate particle
system where these can be optimized separately from what
you need to do to the zeolite-containing active particle. It
is also easier to adjust the trap inventory levels as unit
operations and vanadium levels can vary.
Finally, with respect to tin, its use for vanadium passi-
vation has been around a long time, and has never really
gained the same degree of acceptance as, for example,
nickel passivation technologies have.
PORTER:
The previous panelists have covered most of my com-
ments. We find that tin can mitigate only about 20% of
the deleterious effects of vanadium, so it is somewhat
limited in its effectiveness.
Also, the separate particle approach is diluting your
catalyst inventory, so you need to make sure the gains
offset that dilution.
ARMBRESTER:
We do agree that tin has been shown to be an effective
vanadium passivation additive, but we also agree with one
of the earlier comments that the cost effectiveness of that
additive is difficult to demonstrate commercially.
In addition, there is one major problem with tin in that
it is also an FCC catalyst poison, so your addition rates
have to be carefully balanced with the unit catalyst makeup
to be sure you do not get too much tin in the unit and
degrade the FCC yield structure.
On the separate particle trap, we have seen that to be
effective also, and in a laboratory scale, we have demon-
strated that this system is capable of trapping the vanadia.
We have seen an increase in catalyst activity as a result of
using the trap. One of the drawbacks here is that, in some
cases, the trap itself may be more expensive than the base
FCC catalyst.
We have very little direct experience with single particle
systems, except to note that catalyst formulations with
high quantities of active alumina appear to have improved
vanadium tolerance.
In addition, Ashland holds two patents on new va-
nadium passivation additives. One of these materials,
TOC/INDEX
marketed through Nalco Chemical Company, is presently
under commercial trial at our Canton, Ohio refinery,
BARLOW:
We have extensive experience with tin passivation. I
would agree with most of the comments stated so far. We
expect a reduction in the negative effects of vanadium in
terms of activity in the 20% to 40% range. We would
expect a reduction in terms of hydrogen production and
coke production due to vanadium in the range of about
65%.
I would caution that it is more difficult to prove vana-
dium passivation than it is to prove nickel passivation. We
generally find minimal incentive to treat below 2,000 ppm
on the equilibrium catalyst. That is roughly the breakpoint
where you should begin to be interested in the use of tin
passivation.
We have treated at levels in excess of 5,000 ppm vana-
dium, and the results at that level are very dramatic because
the percent reduction is readily discernible in unit data.
Also, it takes time to prove the vanadium passivation
program. It is usually a lot longer than a nickel passivation
program because the effects of vanadium in terms of
activity are not reversible; and you are primarily treating
the accumulating fresh vanadium, whereas in nickel pas-
sivation you are actually treating the nickel circulating in
the existing system.
QUESTION 11.
Discuss your experience wilh nickel passivation
liquids and/or catalyst trapping systems. What is the
typical ratio of the passivator-to-nickel content?
McLEAN:
Nickel tolerant catalysts are available which can mini-
mize the dehydrogenation effects of contaminant nickel.
A high zeolite content combined with a low surface area,
silica rich matrix is one way to do this. Certain matrix
materials can also be added which are effective at trapping
nickel by allowing it to agglomerate into larger crystallites,
reducing the surface dispersion and minimizing the dele-
terious catalytic dehydrogenation effects.
For many applications, such an approach may be a
preferred option, and the handling of a liquid passivator
can thereby be avoided. For example, this would tend to
be the case for feeds with very high nickel-to-vanadium
ratios, for highly reactive paraffinic feeds, and for units
with very high catalyst-to-oil ratios which do not demand
very high catalyst activity or matrix for bottoms upgrad-
ing. However, there are also many situations where use of
passivator is preferred.
Units which operate with high nickel typically also have
significant vanadium and also process heavy feeds where
bottoms upgrading selectivity of the catalyst is important.
For vanadium tolerance and bottoms cracking, an active
1994 NPRA Q&A Session on Refining and Petrochemical Technology
matrix catalyst is preferred. These active matrix sites can
have the deleterious side effect of maintaining deposited
nickel in a more highly dispersed state, which accentuates
dehydrogenation activity. This can be counteracted to a
large extent by use of a passivator. Antimony is the most
widely used, but bismuth and cerium materials have also
been used. These are added as liquid injected with the feed.
Reductions of up to 50% in the incremental hydrogen and
coke caused by the nickel have been reported. Antimony-
to-nickel ratios of equilibrium catalysts in our data base
vary widely, but most are in the 35% to 50% range on a
weight basis.
In summary, there is no single answer as to whether
catalyst or passivator is the best way to deal with nickel
effects; it depends on the situation.
MENEGAZ:
I do not want to turn my response into a commercial
for antimony, but I have been involved with several suc-
cessful experiences with this material.
As a very rough rule of thumb, the dry gas reduction
using antimony can be estimated as 60% of the hydrogen
make above 20 scf per barrel. A modest reduction in
regenerator temperature of 5°F to 8°F and a total dry gas
reduction are also seen occasionally.
Benefits are most pronounced on FCCU’s with long
riser and long postriser residence times. Response to ap-
plication is rapid, sometimes within one shift. A 0.25 to
0.40 antimony-to-nickel ratio is typical, although higher
dosages are used in anticipation of large changes in feed
metals. Higher dosages are justified if wet gas machine
capacity is limiting throughput.
To be effective, the antimony has to be injected prop-
erly in a slip stream of cycle oil downstream of the preheat
train. Otherwise, it will flash and plate out in the pipe and
exchangers. Antimony definitely ties up platinum pro-
moter, requiring higher promoter addition to control
afterburn.
PORTER:
Chevron has commercial experience with both bismuth
and antimony passivation technology and a wealth of
laboratory and pilot plant information obtained during
the development of the bismuth technology. Our data
indicate that bismuth and antimony are equally effective
in passivating nickel. Both have a deleterious effect on CO
promoter effectiveness and may require increased pro-
moter usage. Operating experience has shown that some-
what more attention must be paid to proper injection of
the bismuth liquid, but this far outweighs the hazardous
waste and toxicity problems associated with antimony.
A typical ratio of passivator-to-feed nickel is 0.6. The
proper dosage is application specific and requires tuning
as experience is gained.
57
TOC/INDEX
SAYLES:
We routinely operate our catalyst units with a sweet
atmospheric residual. We do not use a catalyst passivator.
Instead, we monitor the methane and the hydrogen-to-
methane ratio. Normally this is in the range of 0.3 to 0.4.
If the ratio gets above 0.6, we take some other action,
usually using a flushing catalyst or, in some cases, fresh
catalyst addition. We believe that by doing this, we main-
tain a better regenerator operation and the negative effect
of a metal passivator on combustion promoter is mini-
mized.
FELTROP:
Our experience is primarily with antimony, and it has
been very good. In addition to what has been said about
the particle size distribution in the antimony, we have seen
significant differences from one antimony product to
another. The fine dispersion in our particular product has
been proven more effective in laydown efficiency. The
environmental impact that was mentioned by Mr. Porter
is certainly a concern. It seems to be more of a concern
overseas than it is in the U.S. today. On the question of
antimony versus bismuth, we expect that there will be
more people using bismuth rather than antimony in the
future based on the environmental concerns.
LAUX:
I guess in the interest of keeping a balanced attack, I
vote for bismuth. We have been injecting it since May. We
changed crude and started feeding around 3 ppm nickel
into the FCCU. As the bismuth is injected, we have seen
a very good trend in reducing the hydrogen-to-methane
ratio. It took us about three weeks to see the response
because it does not happen as quickly as you might think.
I will endorse 0.6 lb of bismuth per pound of nickel in
the feed as the passivator-to-nickel ratio. Basically, all we
do is analyze the weekly feed composite for the nickel
content, and then adjust our next week’s injection rate
based on that number.
ARMBRESTER:
We routinely use antimony in our RCC unit at the
Catlettsburg refinery, with an antimony-to-nickel ratio in
the 0.15 to 0.2 range. At this ratio, we appear to get most
of the benefit in reduced hydrogen production, with a
minimum additive cost.
We have seen hydrogen production drop by 20% to
25%, and our hydrogen-to-methane ratio averages about
0.9, which is relatively low for this residual cracking
operation.
Due to the RCC unit’s elevated feed nozzle design and
the use of lift gas, active contaminating metal sites are
selectively carbonized in the lower riser before encounter-
ing feed. This allows relatively low antimony-to-nickel
58 Heavy Oil Processing
ratios in the RCC compared to more typical FCC opera-
tions.
Our experience with catalyst metal traps has been
mixed. One of our approved commercial RCC catalysts
contains a vanadium trap; and although we do not notice
any selectivity advantages when comparing this catalyst
with and without the vanadium trap, we have seen indi-
cations that the trap helps maintain unit catalyst activity.
During laboratory fixed fluidized bed testing of this
catalyst, with and without the vanadium trap, MAT activ-
ity was constant over repeated tests for the sample contain-
ing the vanadium trap, but dropped 4 vol% to 5 vol%
conversion without the trap.
Our experience with another vendor’s vanadium trap
has indicated neither increased MAT activity nor im-
proved product selectivity when using a vanadium trap in
FCCU service and processing up to 10% vacuum bot-
toms. In fact, hydrogen and coke yields increased when
this particular trap was added to the base catalyst. Inter-
estingly, though, metals did appear to preferentially accu-
mulate on the trap, but their activity did not appear to be
reduced.
BARLOW:
I guess I will add an endorsement for cerium as well as
antimony, just to further confuse the situation. We devel-
oped the cerium compound technology, primarily because
of the cost of and the environmental concerns over the
antimony programs. As the cost has come down, I think
the selection process is going to be driven more toward the
handling characteristic differences between the cerium
and the antimony.
The rest of my comments could probably apply to all
of the passivators.
Our experience with passivation of all the different
types of passivators is that there is a strong relationship
between laydown efficiency and the amount of passivator
that you try to feed on the unit. The laydown efficiency
of the passivator and the amount of active nickel in the
system ultimately relates to the antimony-to-nickel ratio
or the nickel-to-antimony ratio, depending on how you
report it. With an increase in attempts to laydown more
product, you have a lower laydown efficiency. We also see
that there is a maximum passivation efficiency that can be
achieved for each unit, and trying to feed more passivator
above that level simply results in the inefficient use of the
chemical but minimal further improvement in terms of
hydrogen and coke make reduction.
Our targets in terms of nickel-to-antimony ratio gen-
erally fall between 2.5 to 4.5, which is a wide range. How
that affects chemical demand is such that at about a 2.5
nickel-to-antimony ratio, you might feed four times the
amount of passivator than if you were able to get your
maximum efficiency at a 4.5 nickel-to-antimony ratio. So
TOC/INDEX
you can have a tremendous effect on program economics
with a good modeling and optimization approach.
D’AURIA:
I would like to expand on Mr. Armbrester’s comment
regarding lift gas. A lift gas system at the bottom of the
riser will contribute to nickel passivation, and reduce the
amount of liquid passivator required. As greater amounts
of residual are processed, and regenerated catalyst tem-
perature increases, an additional benefit from lift gas is
reduction of the steam partial pressure at the bottom of
the riser, with a corresponding reduction of hydrothermal
damage to the catalyst.
DEATON:
I have data for three nickel passivation liquids, with
performance being best with antimony, then bismuth, and
then cerium.
Antimony uses a simple chemical injection system, and
antimony laydown on catalyst is about 90%. For a catalyst
with a high nickel content of 3,000 ppm, hydrogen-to-
methane ratio was controlled at 0.8, with an antimony-
to-nickel ratio of 0.5. For another catalyst, with a lower
nickel content of 1,500 ppm, hydrogen-to-methane ratio
was controlled at 0.6, with an antimony-to-nickel ratio as
low as 0.25.
Bismuth works nearly as well as antimony, but the
injection system has to be watched closely or the injection
quill can plug. For the same catalyst with the high nickel
content of 3,000 ppm mentioned above, hydrogen-to-
methane ratio was controlled at 0.9, with a bismuth-to-
nickel ratio of 0.6. And for a catalyst with a relatively high
nickel content of 2,500 ppm, cerium controlled the hy-
drogen-to-methane ratio at 1.2, with a cerium-to-nickel
ratio of 0.7. Increasing the cerium-to-nickel ratio did not
lower the hydrogen-to-methane ratio.
WARREN S. LETZSCH (Stone & Webster Engineering Corp.):
With regards to the vanadium, two stage regeneration
will enhance vanadium passivation. In the first stage re-
generator, with partial oxidation, you are not pushing the
vanadium to V2O5, which is the form of the vanadium
that in fact deactivates the catalyst when it reacts with
water. In the second stage regenerator, there is excess
oxygen, but there is little water to create the vanadic acid
which attacks the zeolite. You have fairly high vanadium
levels and really minimize the catalyst deactivation. And
as Mr. McLean pointed out, single stage units with higher
temperatures (1,350°F+) and excess oxygen, are where the
catalyst really starts to deactivate.
All of the vanadium trap systems that have been dis-
cussed work, but my personal feeling is that the trap
technologies are increasingly more effective, and are really
worth considering. We think both systems, whether you
1994 NPRA Q&A Session on Refining and Petrochemical Technology
put it in the individual catalyst particle or have a separate
particle, are worth investigating.
Down the road, methods of removing the external
traps, in other words, the ones that are separate particles,
may be possible so a refiner can selectively withdraw the
vanadium from the unit. A process like the magnetic
separation that Refining Process Services is licensing is an
example of technology that you might see used in that
application.
With regard to the nickel passivation, if the nickel trap
is effective, what should be seen is the amount ofantimony
or the amount of bismuth that would stick on the catalyst
will go down. Typically, that is what we saw when the
nickel traps were working.
If you are not agglomerating the nickel or burying the
nickel in the catalyst surface, it is going to be available to
do dehydrogenation. When one or the other occurs, the
trap is being effective, and the antimony will only stick to
the nickel that is active. As an actual commercial example
of this, in a unit running 6,000 ppm nickel on the catalyst,
and using antimony, you would typically have about 3,000
ppm Sb on it. This is a fully active system at about the 0.5
ratio that people are used to. When the nickel trap is
incorporated into the catalyst and it is working, and the
same amount of antimony is added, what you find is that
the concentration of Sb is going down on the catalyst. It
went all the way down to 700 ppm or so, and that is about
where it leveled off. It was such a low number and the
hydrogen production was so low, the refiner decided to
take the antimony out of the unit, and the increase in
hydrogen was very small.
The result was about 0.15 wt% hydrogen with 6,000
ppm metals on the catalyst with no antimony in the unit
at all. So the catalyst traps can be very effective, and they
can work very well.
We suggest you want to look at that ratio (Sb/Ni) as
there is some scientific significance in how well the nickel
trap is really working in the unit. We have seen some very
good things with that technology.
GLENN GUGLIETTA (Grace Davison):
I would like to comment on nickel traps as well. The
Orion® family of catalysts has been used for four to five
years with excellent success. The typical antimony-to-
nickel ratio on Orion equilibrium catalysts is 0.12 to 0.16.
As Mr. Letzsch pointed out, this is a good indication of
the effectiveness of the nickel trap. Orion catalysts typi-
cally run about half the antimony that other catalysts
require. Davison is currently supplying its second genera-
tion of nickel tolerant catalysts, the Orion-LC family. One
refiner who runs 4,000 ppm nickel on equilibrium catalyst
found that they did not need to use antimony after they
switched to Orion-LC catalyst. The new generation of
nickel tolerant catalyst such as Orion-LC is showing ex-
cellent commercial results.
59
TOC/INDEX

G. ANDREW SMITH (INTERCAT, Inc.):
We have recently observed some impressive MAT num-
ber increases in an overseas FCC unit using a separate
particle that traps vanadium. The best way to maximize
the benefit and minimize the cost of using separate particle
additives is to inject them with the recently patented
INTERCAT solid additive feed system. In numerous
commercial accounts this technology has proven as effec-
tive as, if not better than, liquid injection systems used
with liquid additives.
In the use of nickel passivators, refiners need to learn
to look at not only the hydrogen-to-methane ratio but the
SCFB of hydrogen produced. In numerous accounts, the
H 2 /CH 4 ratio has been observed to increase, but the
hydrogen SCFB did not increase. This was due to lower
methane production.
since the vanadium trap will be in closer proximity to the
catalyst particle itself. Operations with high vanadium
mobility will show greater advantages with a dual particle
vanadium trap, since the more mobile vanadium species
will tend to destroy zeolite at a higher rate.
As far as commercial trials, we have seen operations
where the unit has increased vanadium on equilibrium
catalyst from 2,000 ppm up to 4,000 ppm, at constant
fresh catalyst addition rates, with no discernible losses in
activity. We have been able to corroborate activity reten-
RV Improves Zeolite Surface Area Retention

HEROS DERGREGORIAN (Giant Refining Company):

What is the minimum nickel on the equilibrium cata-
lyst that the passivator would affect as far as hydrogen
production?

BARLOW:
You can passivate at any level of nickel on your catalyst,
but the real question is what goal are you trying to achieve?
If you are running low ppm nickel on your catalyst and
you are not regenerator temperature limited nor wet gas
compressor limited, those are the major driving forces to
passivation. So if the limit is not there, then the economics
justifying the use of the passivator are minimal, even
though you get some yield improvement from hydrogen
and coke to other products. Practically speaking, if you are
below 800 ppm, I would say it is rare that you could justify
a passivator. Typically, levels are over 1,200 ppm before we
start seeing solid economics for a nickel passivator.

LAUX:
I agree. We used to run 800 ppm and then we switched
crudes. The equilibrium catalyst nickel jumped to about
1,500 to 1,600 ppm. At that point we saw that the
economics were favorable to start injecting the passivator.

JOSE MATOS (GRACE Davison):

With regards to vanadium tolerance, for the past couple
of years we have been conducting several commercial trials
with our RV technology. It is available in both the single
particle and the dual particle systems. We have found in
both our laboratory testing and commercial trials that the
potential for success ofvanadium traps is very unit specific
and is related to the vanadium mobility. Vanadium exhib-
its a tendency to be more or less mobile, depending on the
vanadium species and on the characteristics of the unit
operation.
We suspect that operations which have low vanadium
mobility would benefit more from single particle systems,
tion by looking at zeolite surface area. Laboratory data
show that both zeolite surface area retention and the
equilibrium catalyst activity retention are improved. This
is due primarily to migration of the vanadium to the
vanadium trap and away from the zeolite.
Through separation techniques in the laboratory on
commercial equilibrium catalyst sample, we have con-
firmed that vanadium on the trap has been in the order of
3 to 6 times higher than vanadium on the catalyst in the
dual particle system. We have observed vanadium concen-
trations in the levels of 12,000 ppm to 15,000 ppm on the
trap itself.

6O Heavy Oil Processing

TOC/INDEX
You should be aware that you must also consider the
effects of sulfur. There is a tendency to have sulfur com-
petition for the trap. The trap can react preferentially with
sulfur over vanadium. The RV technology developed by
GRACE Davison has demonstrated that sulfur does not
effectively react with our trap.
RAGHUNATH P. MEHROTRA (Indian Institute of Petroleum):
Catalyst based on modified zeolite is reported to be
more tolerant to nickel and vanadium. This catalyst sys-
tem minimizes the need for passivator. Is it more economi-
cal to use modified zeolite in these catalysts, or passivator
along with the traditional zeolite?
McLEAN:
I am not familiar with the particular modified zeolite
you mentioned. Most of the incorporated catalyst passi-
vation technologies deal more with alumina-based matrix
added materials than with changes in the zeolite itself.
JOHN PEARCE (Akzo Nobel):
I think the basic question most people have is whether
metals traps really work. I think the answer is very clear;
yes, they do, but what is probably not very clear is how
well they work in any particular application. That is very
location and operation specific. It is unfortunate that a lot
of the information needs to be generated by end unit
optimization itself rather than in the laboratory. As Warren
Letzsch suggested, this is becoming increasingly difficult
because the catalyst vendors are frequently introducing
improved materials, which also need to be evaluated every
time something new comes out.
On the more specific question of whether it is more
effective to put the trap in a loose additive or incorporate
it as part of the host catalyst, this is of course very compli-
cated, largely because the test methods used to evaluate the
effectiveness of these metals traps effectiveness in the
laboratory are not very representative of what actually
happens out on the operating unit. Nonetheless, I think
there is a growing body of commercial evidence that
suggests that the use of a loose or separate metals trap
additive, rather than incorporating the metals trap as part
or an element of the host catalyst, is more effective. The
loose additives appear to work a little better. This is
probably because the higher concentration of the metals
trap present in a loose additive prevents it from being
covered completely by the glues and binders which are
used to hold the FCC particles together.
I might add that the same argument holds true for
ZSM-5 additives as well as it does for metals trap additives.
H. DAVID SLOAN (The M. W. Kellogg Company):
The MAGNA CATTY Process, licensed either through
Refining Process Services (RPS) or The M.W. Kellogg
Company, selectively removes the most metals laden cata-
1994 NPRA Q&A Session on Refining and Petrochemical Technology
lyst from the circulatory inventory. MAGNA CATTM is
available in conjunction with The M.W. Kellogg Com-
pany catalytic cracker technology or from RPS.
Catalysts
QUESTION 12.
What is the effect on hydrogen production of old nickel
versus new nickel on equilibrium catalyst? Is there a
correlation between step changes in H2 yields with
spikes in the feed nickel in units operating with less
than 800 ppm Ni on catalyst?
TREESE:
On this question, I can relate a recent experience we
had at our FCCU. We had a sudden increase in the
vanadium and nickel content of the gas oil feed due to an
upset in the vacuum tower. Our nickel increased from 1
ppm up to 4 ppm in the feed. The high metals gas oil was
fed to the FCCU for about a month, causing a significant
increase in the hydrogen-to-methane volume ratio in the
dry gas.
The equilibrium catalyst typically contains 500 ppm of
vanadium and 300 ppm nickel. During the upset, the
vanadium on the catalyst increased to 1,200 ppm and the
nickel to 900 ppm. As a result, the hydrogen-to-methane
ratio in the dry gas went from 0.3 up to 1.0. The catalyst
MAT activity decreased, the coke and dry gas factors
increased.
The unit performance returned to normal within about
two weeks after the metals in the feedstock returned to
original levels. That was long before the metals on the
catalyst were brought back down to their normal levels a
couple of months later.
McLEAN:
Freshly-added metals are definitely more active with
respect to dehydrogenation. Correlations for determining
the activity of equilibrium catalyst metals were originally
published by ARCO in the early 1970’s. While the catalyst
and process technology have both advanced significantly
since then, the theory is still valid.
A corollary to this is that for a given nickel level, the
activity of that nickel is much higher when the concentra-
tion increases over a short period of time than if it is stable
or decreasing. Therefore, the spiking effect can give hydro-
gen yields which might be more typical of nickel levels
associated with much higher stable levels. For this reason,
we are aware of a number of refiners who have noted
positive benefits from control using antimony at nickel
levels similar to the 800 ppm mentioned in the question.
One way to think about this is that if you have feed related
spikes of, say 200 to 400 ppm, at the 800 ppm base level,
there is certainly a much higher percentage than if you are
61
TOC/INDEX
up at a couple of thousands parts per million. There you
might not notice the spiking effect as much. So, very
definitely, the answer is yes.
MENEGAZ:
I agree with Mr. McLean’s answer. I would like to add
a few additional comments.
There is a frequently quoted value of 1,000 cycles for
nickel life, where the activity decreases, say between 60%
to 90%. That corresponds roughly to five to eight days in
a typical FCCU. However, if you get any chlorides in your
system, they will reactivate the aged nickel by restoring the
surface area in a process that is similar to the oxychlorina-
tion procedure you see in reforming.
Finally, we do not have a correlation in the low nickel
range discussed, but several refiners have been curve fitting
their steady-state correlations for the units as part of their
FCCU simulation work.
SAYLES:
A quick increase of about 350 ppm in nickel increased
the regenerator temperature by 22°F; the conversion
dropped by about 1.0% to 1.5%. The C2 and lighter
increased by 0.12 and the naphtha yield dropped off by
0.1 to 0.8.
ARMBRESTER:
We agree with the general conclusion that the new
nickel is more active. We have seen several instances which
indicate this on both our FCC and RCC units at the
Catlettsburg refinery. The most recent example occurred
earlier this year when a crude change resulted in an imme-
diate 50% increase in the nickel content of the RCC feed.
Immediately after that, our total hydrogen production and
the hydrogen-to-methane ratio both increased by about
20%, and this occurred in spite of increasing catalyst
addition to maintain our normal level of 2,200 ppm nickel
on the catalyst.
We have seen similar instances on the FCC unit, which
typically has less than 1,000 ppm nickel on the catalyst,
but these occurred several years ago and I cannot quantify
the changes in hydrogen production.
BARLOW:
I agree with everything that has been said so far. We use
the ARCO correlations of the early 1970’s to calculate an
aging factor. Using the 800 ppm nickel as an example, in
a typical unit we would expect the equivalent of about 200
ppm ofeffective nickel to be actively producing hydrogen.
So if you have a 400 ppm spike in fresh nickel due to the
feed, you are essentially going to add two times more
additional hydrogen making capacity from the nickel as a
dehydrogenation catalyst.
I do want to point out that the effect is reduced if you
are currently using a nickel passivator; but nickel passiva-
62 Heavy Oil Processing
tors, as we talked about earlier, are about 50% effective.
So you still will see a spike, but the spike will be much
lower.
QUESTION 13.
in last year’s NPRA Q&A Session, it was stated that
oxygen enrichment necessitates increased catalyst
additions. Are some catalysts more tolerant of oxygen
enrichment than others? Has anyone developed a
good test to determine which catalysts can better
withstand the oxygen enrichment environment?
McLEAN:
The use of oxygen enrichment will accelerate the cata-
lyst deactivation rate due to a number of related effects.
Bulk regenerator temperatures will increase due to the
smaller nitrogen dilution effect. Catalyst particle tempera-
tures will probably increase by even more than what is
indicated by the bulk bed temperature, due to accelerated
burning kinetics, although there is not any good way to
directly measure this.
Since hydrothermal catalyst deactivation is caused by
the presence of steam at high temperatures, the effect of
concentrating the steam partial pressure formed from
hydrocarbon burning with lower nitrogen dilution will
also be present. The higher temperature and higher local-
ized oxygen concentration will also accentuate vanadium
mobility and, therefore, vanadium destruction of the zeo-
lite.
All of these things occurring simultaneously will in-
crease the catalyst deactivation rate. Commercial experi-
ence from one unit has shown deactivation rate increases
by 40% with the use of oxygen enrichment. This increases
the importance of activity and hydrothermal stability in
catalyst selection.
High levels of both zeolite and active, stable matrix are
employed to withstand these effects, without needing to
go to excessive catalyst addition rates. If the base case
catalyst is high Z to M ratio, it will probably be prudent
to consider lowering it, since there is a limit to how much
zeolite you can add and higher matrix catalysts will hold
up to the severe environment with more stability.
Concerning test methods, the discussion of how to
properly steam deactivate FCC catalysts in the laboratory
has been a source of many divergent opinions for a long
period of time. There are probably as many opinions as
there are companies represented in the room today.
Certainly, for the case with oxygen enrichment, a more
severe steaming treatment will be required to simulate
what the regenerator operation will do, with some combi-
nation of higher temperature, time, and/or steam partial
pressure.
It is always a good practice to make sure the deactiva-
tion severity used in testing matches reasonably well in
terms of MAT activity, zeolite and matrix properties and
TOC/INDEX
surface area retentions, with the known base catalyst in the
commercial unit. We have, in fact, worked with several oil
company R&D laboratories which have adjusted their
deactivation conditions when they are doing evaluations
based on units which do use oxygen enrichment.
SAYLES:
I agree with Mr. McLean’s comments. I would like to
add that the reason we would consider oxygen injection is
for additional carbon burning. Ordinarily, high coke units
would be processing a high metals feed.
During the investigation of oxygen enrichment, I
found the increased likelihood of deactivating the catalyst
due to increasing nickel and vanadium mobility interest-
ing. Since higher regenerator temperatures are likely, the
catalyst will further deactivate. Care should be taken to
minimize these combined effects.
KENT DAVIS (Grace Davison):
We have worked with a refiner in trying to determine
an appropriate deactivation method to model FCCU’s
that experience high catalyst particle temperatures in the
regenerator. Modifications to a standard steam deactiva-
tion protocol include changing the oxygen partial pressure
and both the time and temperature of the deactivation.
The modified techniques do seem to be effective in
identifying catalysts that have the highest activity and/or
activity retention after the more severe deactivation. The
downside, however, is that the protocols ignore the char-
acteristics of the catalyst that are contributing high particle
temperatures. These include inherent selectivity and
physical traits such as catalytic coke make and catalyst
stripability.
RANDALL HULL (BOC Gases):
We have a customer who has been using oxygen con-
tinuously in the regenerator for over ten years at fairly high
levels, 24% to 26% enrichment of the air. The leverage
effect of oxygen addition is fairly great. For example, at
2% enrichment, 21 mol% to 23 mol%, you get about a
10% increase in coke burning capacity. This particular
customer is operating in full combustion, and has a full
overhead flue gas handling system. The refiner was under
a severe velocity limitation, and the additional oxygen was
backing out about double the volume of air for each
volume of oxygen added to the regenerator. Although the
customer has not commented on catalyst deactivation per
se, they have seen less afterburn as a result of the reduced
velocities. They have also seen improved yields because of
lower CRC values and less catalyst fouling of the overhead
system.
Regarding the temperature increase, which direction-
ally would lead to deactivation, if you do not change any
of your other operating conditions on your FCCU, adding
oxygen will definitely change the heat balance. We have
1994 NPRA Q&A Session on Refining and Petrochemical Technology
seen roughly an increase of 5°F to 10°F in the dense bed
temperature, for every 1% enrichment level above 21%.
Refiners typically readjust the heat balance by reducing
feed preheat or, in some cases, if possible, increasing the
catalyst-to-oil ratios.
Additionally, if the refiner has additional capacity in the
vapor recovery wet gas system, we have seen refiners
increase their recycle of light cycle oils and naphthas to, in
effect, take care of the additional heat removal required
from the regenerator.
FRANK ELVIN (Coastal Catalyst Technology, Inc.):
In the 1970’s, a lot of the regenerator designs went from
10 psig to 35 psig. This resulted in doubling the oxygen
partial pressure of the inlet air going into the regenerator.
This did not result in additional hydrothermal deactiva-
tion, because the regenerator temperatures were kept
pretty much the same.
Similarly, if you double your oxygen partial pressure
due to oxygen enrichment and maintain your regenerator
temperatures constant, you should not see additional hy-
drothermal deactivation.
In a well designed regenerator, the oxygen content of
the flue gas and the oxygen content in the regenerator gas
is at the point of spent catalyst return, less than 3% oxygen,
whether you have 20% oxygen in the inlet air or you have
40% oxygen in the inlet air.
I have experience with a Gulf Coast FCCU that was
using between 500 and 1,000 tons per day of oxygen,
which was approximately 20,000 standard cubic feet per
minute. We enriched the air from 21% to 40%, and
maintained temperature with heat removal in the regen-
erator, and did not see deactivation as a result of oxygen
enrichment.
WARREN S. LETZSCH (Stone & Webster Engineering Corp.):
How you contact the catalyst and the air is going to be
very important. If you have countercurrent regeneration,
the higher oxygen concentration and the highly coked up
catalyst particles are really not going to see one another. If
the design is a sweep air system, spent catalyst is coming
right out of the stripper, and using the air to lift the catalyst
back up to the regenerator. If that is where the oxygen
enrichment is done, you could see quite a difference. In a
system with a high mix zone temperature, I think you are
going to tend to see more deactivation.
Typically, the regenerator temperature is going to be
around 7°F to 9°F for every percent oxygen that you raise
above 2l%, and this, as was stated earlier, is because of the
dilution effect (lack of nitrogen).
I cannot emphasize enough, and it was mentioned
before, the idea of mixing the oxygen so that it is coming
in uniformly. It should be pointed out that you can get
into severe metallurgical problems on your unit if you take
the oxygen concentrations too high. I hope nobody is
63
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really contemplating 40% oxygen; concentrations up to
27% are typically used in the unit.
JAN W. WELLS (Phillips 66 Company):
Has anybody observed any NOx problems when they
are using oxygen enrichment?
HIGGINS:
No comment.
QUESTION 14.
What mechanism is responsible for the production of
dienes in the LPG fraction of the FCCU products? What
catalyst orprocess variables are used to predict diene
production from the FCCU?
MENEGAZ:
Dienes are indicative of thermal rather than catalytic
cracking. Their formation is favored by high riser outlet
temperature, low catalyst-to-oil ratio, poor feed mixing,
excessive reactor vapor residence time, and octane cata-
lysts. Butadiene also appears to track with the percentage
of coker gas oil in the feed. Severely eroded feed nozzles
will also boost the butadiene level.
Developing a precise correlation has been difficult be-
cause of day to day swings in the butadiene content. Our
approach for estimating butadiene has been to establish a
baseline for a particular unit and use a linear correction
for the riser outlet temperature. We recommend 190 ppm
to 230 ppm butadiene per degree F as a good place to start
for FCCUs with conventional riser disengaging devices.
For close-coupled cyclones, we would use half of the
previous values. Further adjustments to the multiplier can
be made for feedstock, catalyst and mix zone temperature.
A 1987 panelist indicated that using a low hydrogen
transfer zero rare earth catalyst increased butadiene con-
tent 10 to 30 relative percent. Propadiene content is
generally less than 0.1%, so we treat it as a fixed percentage
of the butadiene content.
PORTER:
The major diene produced in the LPG fraction from
an FCCU is 1,3-butadiene. As Mr. Menegaz stated, this
compound is produced predominantly by thermal crack-
ing and hence is largely a function of riser temperature.
Our pilot plant data shows that butadiene yields start to
increase rapidly above 1,000°F and really take off above
1,025°F. To a lesser extent, butadiene yields are also de-
creased by the catalytic mechanism of hydrogen transfer,
for example by increasing catalyst-to-oil ratio. We have not
seen any measurable effect of catalyst type on diene pro-
duction at lower riser temperatures of about 950°F. How-
ever, butadiene yields are quite low in this temperature
range. We have not explored the effect of catalyst type at
higher reactor temperatures.
64 Heavy Oil Processing
SAYLES:
One thing that interests me about diene production is
that people utilizing close-couple cyclones indicate dienes
are reduced, those with improved feed nozzles indicate
dienes are reduced, and those with catalyst coolers indi-
cate lower diene production. In all three of those situ-
ations, the mix zone temperature or the ability of the
catalyst to contact the oils is radically improved. Perhaps
the question of diene production mechanism is not what
the riser outlet temperature is, but actually what the
conditions are in the mix zone. All of those situations
improve mix zone temperature control, and, as a result,
the oil is not exposed to regenerator temperature in
localized concentrations, but instead, is being dispersed
throughout the riser. The temperature is rapidly
quenched within the mix zone limiting the diene produc-
tion for a given riser outlet temperature.
Close-couple cyclones limit coke, reduce regenerator
temperature, increase catalyst circulation and improve mix
zone conditions by reducing the temperature. Catalyst
coolers also lower mix zone temperature. Multiple feed
nozzles reduce the mix zone temperature by reducing
coke/regenerator temperature, and improve mixing.
McLEAN:
I agree with all the comments that have been made, and
that the key parameter is how you can best measure the
thermal cracking that you are getting in a given unit. We
have seen in some cases, for example, the regenerator
temperature is a better correlating variable than the riser
temperature, probably because of these mix zone effects
that were discussed.
We have also seen very conclusively that installation of
advanced termination devices such as close-coupled cy-
clones can dramatically reduce dienes, even though the
reactor outlet temperatures are, in most cases, even
higher.
Concerning catalyst effects, it is true that there is a small
effect. A low hydrogen transfer catalyst producing more
light olefins will probably produce more compounds that
can thermally crack to diolefins at the same conditions. It
is also important to recognize that these types of catalysts
typically lower regenerator temperatures, and that may be
a more dominant catalyst effect than just looking at the
simple product distribution. So, in general, catalyst effects
are minor compared with these operating variables.
ARMBRESTER:
We agree with the comments made previously concern-
ing the importance of the mix zone temperature, and we
believe that improved feed nozzle designs, the use of lift
gas, and decreased regenerated catalyst temperatures can
all help to minimize the production of dienes.
TOC/INDEX
In terms of catalysts, we agree with an earlier comment
that the high rare earth and large unit cell size zeolites
should also help minimize diene production.
D’AURIA:
I do not think I can add much more to the discussion.
We agree dienes are thermally-cracked products and the
techniques for minimizing thermal cracking have all been
well covered.
DEATON:
One rule of thumb that I have used is an increase of
700 ppm of butadiene for every 10°F increase in reactor
temperature.
ROON MEEKER (YPF, S.A., Departamento Refinería La Plata):
Is there any relationship between ZSM-5 and dienes?
SAYLES:
We have tried ZSM-5 and we do observe a small
increase in diene production, about a 20% increase.
McLEAN:
A lot of times the critical parameter you are worried
about is the diene concentration in your butene stream,
and that should probably go down because you have made
so many more butenes with the ZSM-5.
HEROS DERGREGORIAN (Giant Refining Company):
Is there any relationship between the steam to the feed
nozzle and the diene production?
McLEAN:
Yes, there is for all the reasons we have discussed. The
proper dispersion and operation in the mix zone is a
variable.
HEROS DERGREGORIAN (Giant Refining Company):
So increasing the steam to the feed nozzle should
directionally reduce the production of the dienes?
McLEAN:
It does to a point.
GEORGE P. QUINN (Amoco Oil Company):
With respect to dienes, I agree with many of the com-
ments that were made by the panel. It is time and tempera-
ture. Amoco has been practicing a technology of quenching
the dilute phase for about five years now, basically reducing
the temperature by 50°F or more. We see in excess of 50%
reduction in butadiene production by quenching the dilute
phase. This also reduces the thermal reactions and reduces
the fuel gas make by about 1 wt%.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
We also see a reduction in the pentadienes in the
gasoline, which also enhances the oxidation stability of the
FCC gasoline.
MENEGAZ:
What reduction in pentadiene you are seeing?
GEORGE P. QUINN (Amoco Oil Company):
Testing conducted prior to introduction of dilute phase
quench, and testing with dilute phase quench showed a
significant reduction in pentadienes in FCC gasoline.
Without quenching the dilute phase, thermal reactions
typically produce 0.4 vol% pentadienes in FCC gasoline.
When the dilute phase is quenched to stop the thermal
reactions, the pentadiene production drops, and the con-
centration of pentadienes in FCC gasoline will drop to 0.2
vol%.
Process
QUESTION 15.
FCC licensors are now offering new technologies to
eliminate regenerator afterburn caused by maldis-
tribution of spent catalyst and oxygen. Please com-
ment on specific/actual results when using these new
technologies.
McLEAN:
FCC licensors have introduced designs for both new
and revamped units to reduce afterburn. These include
systems to improve distribution of spent catalyst as it is
introduced to the regenerator, and also to control the air
distribution profile. I know of one refiner who has in-
stalled designs from two different licensors and reports a
significant reduction in afterburn. CO promoter addi-
tions have been reduced but have not been totally elimi-
nated in these cases.
For new units, there are designs which have demon-
strated the ability to run in full combustion with no
promoter and manageable afterburn levels.
D’AURIA:
The key to preventing afterburn is proper matching of
the coke and air distribution in the regenerator, avoiding
areas of low coke and high air, which can lead to oxygen
breakthrough. We have installed spent catalyst inlet dis-
tributors, called “ski jumps”, into many units with very
good results. In one particular unit, after installing the ski
jumps we saw a reduction in the dense bed to dilute phase
delta T from 100°F to less than 25°F.
When installing ski jumps, you must take care to review
and adjust the air grid plugging pattern and the cyclone
dipleg discharge orientation to make sure that you are
65
TOC/INDEX
matching the inlet catalyst distribution with the inlet air
distribution.
QUESTION 16.
What conditions inside the regenerator have resulted
in significant afterburning? Have mechanical failures
been observed due to excessively high temperatures
in the regenerator? At what temperatures have these
failures been observed?
CUNEO:
A lot of the conditions that cause afterburn have been
addressed in the previous question about the proper con-
figuration of return of spent catalyst and the distribution
of the catalyst in the oxygen.
I would like to turn to the start-up issue. During
start-up, a problem can arise when high torch oil rates are
used to warm the regenerator bed if the oil is not also
evenly distributed around the bed. A second start-up
problem can occur when the catalyst circulation is being
established, because usually people go from total combus-
tion to partial combustion during this period. The transi-
tion period may have afterburn which can reach
temperatures over 1,400°F for a few minutes.
In Shell, we utilize water at the top of the regenerator
bed and torch oil lower in the bed to control afterburning
during the start-up period. Our regenerator cyclones are
now designed to accommodate short periods of afterburn-
ing up to 1,500°F.
In the past, we have seen cyclone hanger creep problems
which are likely the result of afterburn. The worst damage
that we have ever seen was when we let spray water contact
the body of the cyclones or the cyclone plenum in our
efforts to stay at lower temperature, which resulted in
cracking and warping of the cyclones.
D’AURIA:
Afterburning is primarily due to uneven distribution of
the coke and air in the regenerator with CO exiting the
catalyst bed at one point and oxygen exiting at another.
The subsequent combustion of the CO in the dilute phase,
with the accompanying very high heat release, can result
in temperatures of 1,800°F or more. We have seen in-
stances where this has been severe enough to cause defor-
mation of the stainless steel internals in the regenerator.
Fortunately, today afterburning is a fairly unusual prob-
lem, with most units operating in full CO combustion. In
bubbling bed regenerators, CO promoters are used to
catalyze the CO combustion; and in the UOP combustor
regenerators, we use a hot regenerated catalyst circulation
system to ensure full CO combustion.
BOYCOTT:
I agree with the previous comments on the causes of
afterburn. Frontier has noted increased afterburn in three
66 Heavy Oil Processing
instances: if CO promoter additions are too low, if excess
O2 falls below l%, and while running coker gas oil feed
to the unit. In the case of coker gas oil feed, increases in
dilute phase temperature of up to 60°F have been ob-
served. As a result, we limit the volume of coker gas oil fed
to the unit to ensure that we do not exceed the allowable
design temperature on the regenerator. No mechanical
failures have occurred.
The case of low excess O2 is interesting as low excess
O 2 must be maintained to keep NO, emissions at an
acceptable level. This will be addressed further in a later
question on NO, emissions.
LAUX:
In our UOP high efficiency regenerator, afterburning
does not occur very often. However, we do run one feed
stream that has about 10% Conradson carbon and an-
other feed stream with 0% Conradson carbon. If we lose
the good feed or spike the flow on the bad feed, we end
up in a transient partial burn situation, and we have very
high afterburning.
We have seen temperature spikes to over 1,750°F at
times. The durations, though, are usually very short, 30
minutes or so. We have not seen any failures that forced a
shutdown at these temperatures with the short duration.
However, we have seen loss of refractory on-line after such
an excursion. We have also had cracks develop in the
secondary cyclone outlet tubes that contributed to catalyst
losses.
McLEAN:
I agree with everything the other panelists have said. I
would also like to add one other comment, that we have
seen cases where a mechanical or a process or feed change
which results in a dramatic reduction in the regenerator
temperature can also give you an afterburn situation due
to the reduction in the kinetics of the coke and CO
burning reactions. In particular, we have seen this in a
couple of cases where people have done revamps, put in
things such as close-coupled cyclones and better feed
nozzles, which do have a very dramatic effect in reducing
regenerator temperature. They find out that they start
back up and experience a large afterburn situation and
have to dramatically increase promoter addition levels.
MENEGAZ:
I also agree with all the previous comments, particu-
larly Mr. D’Auria’s, that catastrophic afterburn is rela-
tively rare today, at least compared to the old days when
we had low temperature partial burn units. We know of
one refinery where there was a complete cyclone destruc-
tion followed by an excursion which exceeded 2,000°F
for several minutes.
TOC/INDEX
SAYLES:
The cyclone hangers usually set the maximum regen-
erator temperature. When significant afterburning occurs,
this limit may be reached.
On one unit we have observed cyclone hanger damage
due to a steam ring in the regenerator dome. During an
afterburning event the steam was turned on, wet steam
impacted and broke the cyclone hangers. An early start to
a planned shutdown was required to repair the cyclones.
The afterburning was traced to erosion of a spider air
grid which suffered loss, not only to the nozzles, but
sections of the grid had failed. The poor air distribution
caused incomplete combustion in the bed and severe
afterburning. The grid failure was due to erosion from an
imbalance in the air fed to the ring allowing catalyst to be
drawn into one side and blown out the other, cutting the
grid. The grid was repaired and unit completed a four year
run.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
STEVEN A. KALOTA (The M. K. Kellogg Company):
The panel’s comments are correct concerning air and
coke distribution. Kellogg incorporates a radial spent cata-
lyst distributor in its units to evenly distribute the coke
across the regenerator cross sectional area, which helps to
minimize the afterburning. We have applied this on side-
by-side and stack units also.
In terms of afterburning, we also can apply a multicell
kinetic regenerator model. We can break the regenerator
into segments and identify the coke air distribution in each
of those segments. And we use that to make adjustments
either to distribution of catalyst or to air in revamp situ-
ations to reduce the afterburning tendencies of units.
ROBERT GLENDINNING (ABB Lummus Crest, Inc.):
Lummus currently licenses the Texaco FCC process. In
a new unit design, the regenerator would have a deep fast
fluidized bed, which we think leads to excellent mixing
67
TOC/INDEX
between the gas and the catalyst and promotes a uniform
temperature distribution at the cyclone inlets. We agree
with the comments which have been made with regard to
how the spent catalyst is introduced to the regenerator. In
previous designs, the catalyst has been brought to the
regenerator by simple radial or tangential inlets which, in
some instances, did lead to greater spreads in the cyclone
inlet temperatures. A new vessel design these days would,
in fact, incorporate a spent catalyst distributor, which gives
very even distribution of the spent catalyst over the regen-
erator cross-section. The improved spent catalyst distribu-
tion, coupled with the bed mixing characteristics,
effectively eliminates afterburn.
Typically, the vessel operates with about 1% excess
oxygen, and typical afterburn is at about 10°F to 15°F.
DANIEL N. MYERS (UOP):
Our reduced crude conversion (RCC) units utilize two
stage regeneration which inherently gets away from prob-
lems of afterburning. In a two stage regenerator, the idea
is to burn the catalyst clean while minimizing the heat of
combustion of the coke deposit.
The first stage regenerator receives all the spent catalyst
and burns off about 75% to 80% of the coke deposit in
an oxygen deficient zone, so a lot of CO is generated. The
catalyst then moves on to the second stage where the
remainder of the coke deposit is burned off in an excess
air situation. All the coke is burned to CO2, so no after-
burning takes place.
Oxygen-containing flue gas from the second stage is
routed up through the first stage. Since not all the coke is
burned off the catalyst, the first stage operates like a
‘behind-in-burning’ bubbling bed regenerator. The
carbon bed provides a safeguard against afterburning-
there is no possibility of oxygen breakthrough. In fact,
instead of afterburning, the flue gas temperature and
dilute phase temperature actually run lower than the dense
phase temperature.
QUESTION 17.
Are there any new developments in the area of the
reactor catalyst stripper design in an FCCU? What has
been the experience with more than one steam injec-
tion point?
D'AURIA:
We have continued development of our stripper design
over the years, leading to the current staged stripping
system with multiple steam injection points. This system
is in use in about a half a dozen units and running very well.
Typically, these units observe very low steam usage, in the
order of 1.5 lb of steam per 1,000 lb of catalyst circulation.
In our newer unit designs, we combine the contained
riser disengaging system with catalyst prestripping up-
stream of the traditional stripper. Our new stripper system
68 Heavy Oil Processing
is designed for a lower catalyst flux to minimize voidage
and increase catalyst residence time. This helps to reduce
overcracking of the reaction products and also results in
less entrainment of hydrocarbons to the regenerator.
McLEAN:
Stripper design, along with feed injection and riser
termination, is one of the three major areas where refiners
are modernizing their FCC units today. Most units are
operating well over their original design throughput and
also with higher catalyst circulation rates, so that the
traffic through the stripper has increased dramatically
over the years. To get around this, people are employing
higher stripper length-to-diameter ratios, different inter-
nals designs, and in some cases the use of staged steam
introduction.
There are differences of opinion among licensors over
the use of multiple steam injection points. One of the
problems in analyzing commercial performance data on
some of these systems is strippers have usually been re-
vamped in combination with other things, such as newer,
improved feed nozzles, etc. Trying to get a back-to-back
comparison where the stripper is the only thing that was
changed is difficult. I am not aware of any.
SAYLES:
Our stripper designs are disk and doughnut types with
multiple steam injection. They have been in operation for
many years and work very well, based on the hydrogen in
coke that we see in the regenerator. The steam is injected
under the doughnut part of the system to prevent erosion
of the nozzles by the flowing catalysts.
As has been reported many times, you have to watch
the length-to-diameter (L to D) of the nozzles to avoid
catalyst erosion. We use an L to D of about 5 to keep
erosion to a minimum.
We use a maximum of 5 lb per 1,000 lb of catalyst.
Usually our steam injection is much lower than that. The
normal catalyst mass flow rate is in the range of 750 to
850 lb per min per sq ft of the superficial area.
STEVEN A. KALOTA (The M. W. Kellogg Company):
Other factors that go into stripper designing are much
like the regenerator. You need to consider catalyst distri-
bution and steam distribution, flux rate, the residence
time of the catalyst, and certainly that comes back into the
length-to-diameter ratio.
Kellogg uses the staged two distributor approach right
now. Baffle design is also important. We have done a lot
of work on baffles; and for most of you who are operating
up against flux limits, there is a new baffle design to handle
higher flux and give improved performance here.
We are trying to minimize the steam rates and L/D
ratios on the stripper, and to maintain hydrogen on coke
down to around the 6% level.
TOC/INDEX
DALIP S. SONI (ABB Lummus Crest, Inc.):
In trying to reduce hydrocarbons going to the regen-
erator, the riser termination device is very important. If
you remove most or all of the hydrocarbons there, that is
probably the best stripper you have, because once the
hydrocarbons go in the stripper, they further react and
produce dry gas and coke. Even if you recover hydrocar-
bons by stripping, you recover a lot of dry gas.
As most of the people here are aware, the earlier designs
used the T-top kind of separators which just sprayed
catalyst in the reactor and the catalyst entrained a lot of
hydrocarbons into the stripper. Then came the rough-cut
cyclone designs which were an improvement. However,
the rough-cut cyclones operate under positive pressure,
and some vapors are forced down the dipleg. In some of
the close-couple cyclone systems, the primary cyclone is
also under positive pressure.
In the Texaco close-couple cyclone system, the primary
cyclone is under negative pressure; i.e., pressure inside the
cyclone is less than pressure in the reactor vessel. There-
fore, the net flow of gas is up the dipleg, not down the
dipleg. That reduces, or almost eliminates, the hydrocar-
bon entering in the stripper. In one commercial installa-
tion, a temperature drop of 50°F was observed in the
regenerator after this close-couple system was put in
place.
MENEGAZ:
I heard mention of hydrogen on coke. Anybody who is
monitoring this on their unit might be tracking their feed
quality effects instead of the stripper performance.
PETER G. ANDREWS (Consultant, Engelhard Corporation):
The stripper situation has been discussed for many
years, but I would like to attack it from a different point
of view.
Many, if not all of you, have revamped your FCC units
and in most cases have increased the feed rate significantly.
Along with that, there has been a subtle change in your
C3+ liquid yield that you may or may not have noticed.
One unit, with which 1 am familiar, increased their feed
race (almost doubled it), and saw the C3+ liquid yield
decrease by 1.5% because they just could not get it out of
the overloaded stripper.
If you reduce your feed race to the original design and
compare C3+ liquid yield versus where you are today, you
will find that you have lost liquid yield, if the stripper is
too small for the new higher feed rate. Mr. McLean
elaborated on modernization--this is the word today.
QUESTION 18.
Several refiners have noted the loss of naphtha side-
draws while on-line. Upon shutdown, no damage was
found to fractionator internals which indicated the
cause to be tray salting. Has this experience with main
1994 NPRA Q&A Session on Refining and Petrochemical Technology
fractionator naphtha sidedraws become more
common? Have others tried on-line water washing to
alleviate the problem?
ARMBRESTER:
This question referred to loss of naphtha sidedraws
from the main fractionator due to tray salting. While our
fractionators do not have a naphtha sidedraw, we have seen
similar effects with the light cycle oil sidedraw. We have
experienced tray salting in the main fractionator trays on
both our RCC unit at Catlettsburg and on our Saint Paul,
Minnesota FCC unit when they are processing some
vacuum residua. There are several indicators of an ap-
proaching problem, including a high gasoline endpoint, a
reduction in the light cycle oil draw rate, and an increase
in the column flash zone pressure.
To alleviate this problem, we routinely wash the top
section of the main fractionator by injecting boiler feed
water into the top reflux stream. During this on-line wash,
we closely monitor the pressure drop through the tower,
the overhead temperature, and the light cycle oil sidedraw
stream. We terminate the boiler feed water after about 15
minutes, and then check the tower conditions to see if they
have returned to normal. If not, we repeat the washing
until we see conditions improve.
I might add that one thing we do to try to minimize
the salt deposits is to keep the main column overhead
temperature at least 10°F above the dew point.
CUNEO:
We have observed that you can have deposition of
ammonium chloride whenever temperatures are below
about 275°F, even if there is no liquid water present or
when you calculate the dew point is well above that
temperature.
We at Shell have had success with on-line water washing
to remove these salt deposits from the trays. This question
mentions that the sidedraw has been plugged. Usually,
there are a lot of earlier indicators of problems, as Mr.
Armbrester has mentioned. A good indicator would be
watching delta P trends, especially if you have a delta P
measurement across the top section of the column.
LAUX:
One source of main column salt deposition we have
seen came from refluxing overhead water back into the
column. Because that is usually the result of an instrument
failure, we do not see that salting is going to be any more
common these days. As mentioned, running the overhead
temperature coo low, below the ammonium chloride dew
point, will also cause salt deposition. This was also dis-
cussed in the 1985 NPRA Q&A Session. We operate at
over 250°F and have not had much of a problem there.
As mentioned, the water washing can be done on-line.
My experience is that you do need to pull all the liquid
69
TOC/INDEX
water out of the LCO draw in order to get the salts out of
the tower.
PORTER:
The previous comments have covered my points. When
necessary, we also water wash on-line.
SAYLES:
I agree.
MICHAEL BOBER, JR. (Mobil Research & Development Corp.):
One other indicator, going along with Mr. Armbrester’s
comments, would be the chloride content of the wash
water, which is easily checked to determine when the salt
is gone.
HEROS DERGREGORIAN (Giant Refining Company):
Has anybody related the problem of the fouling of the
salt deposit to a particular type of crude, especially Alaskan
crude?
CUNEO:
We have seen increased fouling with crudes that have
higher nitrogen contents; and West Coast crudes, includ-
ing Alaskan, tend to have a little higher nitrogen content
than some domestic sweet crudes like West Texas Interme-
diate. That can cause more ammonia to be formed in the
reactor.
PAUL FEARNSIDE (Nalco/Exxon Energy Chemicals):
We treat a number of FCC main fractionators with a
high detergent filming amine. Not only do we clean the
main fractionator on-line but have maintained salt-free
operations and allowed good FCC profitability because
of it.
QUESTION 19.
In a refinery operating both fluid catalytic cracking
and hydrocracking units, if there is a choice between
vacuum gas oil and coker gas oil feedstocks, what unit
is preferred to process coker gas oil? If it is preferable
to process coker gas oil in the hydrocracking unit,
what is the effect on catalyst life if total conversion is
employed?
D’AURIA:
From the point of view of unit operations, the pre-
ferred place to put coker gas oil is the FCC unit. The FCC
can more easily tolerate a difficult feed such as this. In the
FCC unit, the coker gas oil will convert perhaps 5 vol%
to 10 vol% less than straight-run VGO, and will increase
delta coke. These effects are not sever, however, and can
easily be handled by the FCCU. Many FCC units do
process 10% to 20% coker gas oil blended in with vac-
uum gas oil feed.
70 Heavy Oil Processing
When processing coker gas oil in a hydrocracker, heavy
molecules and contaminants are a major concern. The
endpoint should not exceed l,000°F, and 950°F is often
preferred to limit the nitrogen and polynuclear aromatics
in the feed. These materials can severely limit the hy-
drocracker catalyst life.
Depending on the actual contaminant level, inclusion
of 20% coker gas oil in a vacuum gas oil feed to a
hydrocracker, will shorten catalyst life by from 10% to
40% relative to a VGO only feed.
In addition, coker gas oils will produce a lower quality
product, particularly the distillate product.
McLEAN:
I think the way the question was posed almost presup-
posed that the answer was opposite to what Mr. D’Auria
just discussed. The choice would be case-specific, and it
would depend on factors such as the relative capacities,
what the quality of the base VGO is, what the constraints
on the FCCU are, and what is the cost of incremental
hydrogen consumption.
Coker gas oil will likely be a poorer quality feed to either
unit, so it is just a matter of balancing where it does the
least damage. In general, the use of unhydrotreated coker
gas oils as FCC feed will result in lower conversion and
lower product values. The ability to pump hydrogen into
this material in the hydrocracker can, in some cases,
improve the overall product slate from the combined
units.
One option to minimize the degradation of the hy-
drocracker operation could be to send some or all of the
hydrocracker bottoms to the FCC unit, which is discussed
in detail in Question Number 25, rather than recycling it
for total conversion.
PORTER:
I certainly agree that the coker gas oil is a very tough
feed. In general, coker gas oil is severely hydrogen deficient
relative to vacuum gas oil, and yields a much greater gain
through a hydrocracker. It takes a very high hydrogen
partial pressure and robust catalyst system to have an
acceptable fouling rate, particularly for the 800+°F coker
gas oil fraction. One other option would be to hydrotreat
the heavy coker gas oil fraction and then feed that product
to the FCCU.
MENEGAZ:
Feeding heavy coker gas oil to the catalytic cracker will
cause a substantial increase in bottoms fouling.
TREESE:
I think that where it is an option, it is probably best to
charge it to the hydrocracker and then not do total con-
version in the hydrocracker. Take a bleed stream of the
bottoms and send it to the FCCU as feed to kind of gain
TOC/INDEX
benefits in both units. However, as everybody has pointed
out, it depends on whether your hydrocracker can tolerate
it or not, and if you have enough hydrogen and enough
quench capability.
QUESTION 20.
What kinds of feed injection schemes are available
for FCC units with curved risers? Can modern nozzle
arrangements be installed without incurring exces-
sive erosion of the nozzles or riser? What performance
relative to a well-designed vertical riser can be ex-
pected?
D’AURIA:
UOP has revamped a number of curved riser FCC units
and we have installed modern radial feed injection nozzles,
preferably in the elevated portion of the riser, above the
curved section.
The mechanical integrity of the nozzles and the riser
has been good, with a few isolated cases of distributor tip
erosion observed.
The yield pattern has always improved when we have
performed these revamps. The degree of improvement
depends on the specific unit, the severity of the operation,
and the type of feedstock, but in every case we have seen
an improved yield pattern.
BOYCOTT:
We operate a 1943 UOP Model 2 unit with a curved
riser. Successive conversions from bayonet to shower head
to a high efficiency feed premix nozzle have not caused
any adverse effects on erosion in the system.
McLEAN:
The installation of new high pressure drop, high exit
velocity feed nozzle designs in a sloped, curved riser must
be done with great care. We know of at least one case where
a licenser declined co bid on such an installation, but it
has been done. It may depend on the specifics of the slope
and riser diameter.
Different combinations of inlet slope angles have been
employed relative to vertical risers. Also, an asymmetric
radial nozzle distribution pattern can be used to help
approach more uniform catalyst and feed distribution
across the riser cross section.
Performance benefits will be a function of many vari-
ables, including feed quality, base conversion level, exist-
ing nozzle design, steam rates, etc. Of course, other units
have also been revamped to include redesign to a vertical
configuration.
MENEGAZ:
I certainly agree with the previous comments, particu-
larly Mr. D’Auria’s regarding revamping. Radial nozzles
work well when placed in the vertical run far enough above
1994 NPRA Q&A Session on Refining and Petrochemical Technology
the bend for the catalyst to redistribute. Otherwise, the
uneven catalyst distribution leads to poor feed contacting
and hurts yields.
One refiner with J-bends recently improved his catalyst
contacting arrangement in the riser and saw the slurry
make drop from 6 liquid volume percent to 3 liquid
volume percent. 1 would say that their conversion is
definitely as good, if not better, than what would be
expected for a stacked unit running the same feed. They
have patented this system recently, and they will be offer-
ing it under license soon.
ROBERT GLENDINNING (ABB Lummus Crest, Inc.):
We have revamped two or three units where we have
installed high efficiency feed nozzles in curved riser sec-
tions, and typically the results have been fairly good. We
have seen conversion increases in the region of 4 vol% to
5 vol%, with 3 vol% to 4 vol% gasoline yield increases.
Erosion has not been a problem. We do not see any
particular problems with the installation of these nozzles
in a curved riser.
We have on one occasion simply replaced a curved riser
with a vertical riser. The feed injection and riser termina-
tion technology remained unaltered after the revamp. One
of the most impressive changes that, we saw in this appli-
cation was a fairly large drop in the regenerator tempera-
ture, in the region of about 30°F, which led to improved
catalyst-to-oil ratios and higher conversions.
LARRY LACIJAN (UOP):
As Mr. D’Auria mentioned, we prefer to locate our feed
distributors in an elevated position in the riser. In revamp
applications, we have a couple of concerns to share with
you. Number one, when we start putting the feed nozzles
up the riser in a Model 3 or other style curved riser
configuration, there is not a lot ofelevation left in the riser.
If you put the feed nozzles all the way up at the end of the
curve, you wind up close to the stripper and there is not a
lot of residence time left.
Our second concern is for loss of regenerated catalyst
slide valve delta I? In a conventional type UOP side-by-
side unit, when we locate the feed distributors up the riser,
of course, all of the head that is in the riser below that feed
distributor is now going to be subtracted from the regen-
erator catalyst slide valve. We have to be very careful about
how much slide valve differential we are willing to give up
versus the elevation of the feed distributor in the riser.
One way to counteract the loss of slide valve delta P is
to run a higher velocity in the bottom of the riser, to keep
the density down to regain some of the head. Of course,
that then brings in the complication of how much steam
your main column can handle.
So there are a series of issues here that have to be looked
at carefully when you do the revamp study.
71
TOC/INDEX
PETER G. ANDREWS (Consultant):
In my opinion, feed nozzles are number one under the
heading of modernization. I have seen significant yield
changes in various units from the several new feed nozzle
designs available today.
More recently, I am familiar with a refiner who had
plugging of feed nozzles and his yield pattern declined
significantly; he blamed the catalyst. But when the feed
nozzles were unplugged on-line, the unit yield pattern
returned back to normal. To me, the feed nozzles are the
heart of the FCCU.
Process
QUESTION 21.
What automatic shutdown features should he used in
a modern FCCU? Whatparameters trigger shutdowns,
and what actions do the shutdown system(s) take?
What design considerations are used to prevent nui-
sance shutdowns?
CUNEO:
The purpose of the automatic shutdown system for an
FCCU is to keep the oxygen out of the reactor and to keep
excessive fuel out of the regenerator.
We have four conditions which we use to automatically
shut down the unit. The first condition triggering a shut-
down is low differential pressure across the regenerator
catalyst slide valves. In that instance, we shut the slide
valves, shut off all hydrocarbon feed sources to the reactor,
and open emergency steam to the feed nozzles and riser.
The second situation triggering a shutdown is a low
reactor temperature which shuts off all hydrocarbon
sources to the reactor and, again, opens emergency steam
to the feed nozzles and riser.
72 Heavy Oil Processing
The third condition we use to trigger a shutdown is
spent catalyst standpipe valve low differential pressure, or
a low stripper bed level, which automatically will shut the
spent catalyst slide valve, shut the regenerator catalyst slide
valve, and, again, all sources of hydrocarbon to the reactor,
and open emergency steam to the feed nozzles and riser.
The fourth is loss of the main air blower for regenera-
tion air.
In order to provide high reliability in these systems, the
key ingredient is good purging of the differential pressure
taps so that they do not plug and indicate nuisance trips.
Our automatic shutdowns are very reliable and we do
routine checks of the shutdown instrumentation to ensure
that it functions properly when needed.
DEATON:
Automatic shutdown systems should mirror the shut-
down actions normally taken by the operators with totally
manual systems. These actions are (a) to close the reactor
feed valve and open a bypass valve to put feed into the
main fractionator, (b) open emergency steam to the riser,
and (c) close both the regenerator and spent catalyst slide
valves.
Although I have never worked on an FCCU with an
automatic shutdown system, engineers at Morrison-
Knudsen indicated to me that several existing units incor-
porate the following initiators in their automatic
shutdown systems: (a) low feed, usually set at 40% of
design; (b) low differential pressure across the catalyst slide
valves, usually set at 2 lb; (c) high and low differential
pressures between the reactor and regenerator, both usu-
ally set at 10 lb; (d) low level in the stripper; (e) failure of
slide valve hydraulic oil pressure; (f) continued loss of
boiler feed water to the steam drum, or a low level in the
steam drum.
And in addition to the shutdown items listed above,
the following actions must be taken upon loss of main air
blower flow: (a) activate the power assist on the air blower
check valve; and (b) close torch oil valves.
MENEGAZ:
Previous panelists have covered this topic very thor-
oughly, To minimize nuisance trips on low slide valve delta
P, the shutdown system may include timed delays to avoid
shutdown in the event of a momentary pressure spike.
Some refiners also supply two independent delta P systems
for each slide valve and arrange the shutdowns to occur
only if both taps read low pressure.
Newer installations have the shutdowns hardwired into
a PLC. Further, many installations have adopted a triple
modular redundant philosophy, which uses a two out of
three voting system to avoid spurious shutdowns due to a
PLC failure.
TOC/INDEX
PORTER:
We believe a safety interlock system is required in a
modern FCCU with slide valve control. At Pascagoula the
parameters that would trigger a plant shutdown are:
1. loss of main air to regenerator,
2. either catalyst slide valve in the closed position,
3. loss of delta P on either slide valve,
4. loss of level in regenerator flare gas waste heat
boiler, and
5. manual emergency shutdown button activated by
operators.
To prevent nuisance shutdowns you need redundancy
in all hardware and power supplies. We use a triple modu-
lar redundant system, that Mr. Menegaz described.
STEVEN A. KALOTA (The M. W. Kellogg Company):
An additional item that some of us licensers put in is a
hydraulic or air actuated cylinder on your air blower check
valves. If you lose the air blower flow, a rapper arm comes
down on that check valve shaft to make sure it closes. This
prevents backflow of catalyst into the air blower. The arm
mechanism is tied into the air blower shutdown logic
instrumentation.
QUESTION 22.
What methods are available for reducing the sulfur
content of FCC naphtha with minima/ impact on FCC
gasoline octane?
SAYLES:
We hope not to have to reduce sulfur in the FCC
naphtha but feel some sulfur reduction is likely. In review-
ing the different options available today, we still feel that
the reduction in naphtha end points is the first option.
The naphtha sulfur will be reduced by about 7.5 ppm for
every 1°F reduction in end point temperature for a virgin
feedstock. For hydrotreated feed, the sulfur content could
be reduced by about 2.6 ppm for every 1°F of end point
change. (Keyworth, “Offsetting the cost of Lower Sulfur
in Gasoline,” 1992 NPRA Annual Meeting.)
McLEAN:
This question can be answered in a very broad sense by
dividing the options into three categories: upstream, in,
and downstream of the FCC unit itself.
Upstream of the FCCU, an obvious option is feed
hydrotreating. It may be difficult to justify such an expen-
sive option solely on the basis of product sulfur reduction,
but other benefits such as higher conversion and through-
put should also be considered. The effect of catalyst feed
hydrotreating on octane is not straightforward and de-
pends on how the unit is operated. In many cases reactor
temperature and/or conversion increases can be used to
offset any inherent octane loss due to reduction in feed
aromaticity.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Within the FCC unit itself, the product sulfur distri-
bution is impacted by both catalyst type and operating
conditions. In general, combinations of conditions which
favor maximum gasoline selectivity also favor the lowest
gasoline sulfur content. This would include the use of a
high hydrogen transfer catalyst with a high degree of rare
earth exchange and a high zeolite-to-matrix ratio, along
with a low reactor temperature. Of course, the same
combination also favors gasoline yield at the expense of
octane. Conversely, lower rare earth catalysts and higher
reactor temperatures will increase both octane and gaso-
line sulfur. So to optimize the overall balance involves
tradeoffs which will be unit- and feed-specific.
The degree of overall variation in full range FCC
naphtha sulfur due to catalyst and process effects is rela-
tively small, usually within about ± 10% or 15%, and only
in rare cases will be significant enough to be a controlling
factor in how the unit is operated.
Catalytic additive technologies for reducing naphtha
sulfur content without impacting product yields have
been announced based on laboratory studies, but to this
point have not been fully commercially demonstrated.
Downstream, the first option that has been mentioned
is undercutting. Since most of the naphtha sulfur occurs
in the heavy end, this can give significant reductions. For
example, a T90 reduction from 390°F to 300°F can reduce
sulfur by up to 50%.
The impact of undercutting on octane is variable. It
depends on your specific curve. But a bigger problem can
be the disposition of the heavy naphtha.
The final option involves naphtha hydrofinishing. This
is being commercially practiced in a number of locations
to control either sulfur, olefin content, or both and is often
or usually done on a fractionated heavy naphtha feed.
Processes and catalysts have been developed which give
minimal octane loss, except at very high, 80% and higher,
sulfur removals. One such option was described by IFP in
NPRA Paper AM-92-21. Mobil has also announced a
process, described in NPRA Paper AM-94-39, which
combines hydrofinishing and catalytic technology for pre-
serving and actually increasing octane.
LAUX:
We agree with the comments. Basically, undercutting
seems like the best solution in our case. The concern about
what to do with the undercut material, since we run the
LCO through a hydrocracker, does not bother us at all.
Based on the curves that we see from our RFG testing, the
thing that you are going to end up with is a very good
response on sulfur, but very little impact on the octane.
ARMBRESTER:
Our preferred method to reduce sulfur in the FCC
naphtha would be through increased hydrotreating
73
TOC/INDEX
severity of the FCC feed, or moving to 100% hydrotreat-
ing of the FCC feed if you are not there already. This
method would carry the additional benefits of improving
the FCC yield structure, as well as reducing the sulfur
content of the cycle oil and the slurry oil products. And,
in addition, we would expect it to reduce the olefin
content of the cracked gasoline somewhat, which may be
beneficial from an RFG perspective.
A couple of panelists mentioned hydrotreating of the
naphtha. There are two options here. One is to go ahead
and cut the end point to remove most of the high sulfur
material and then hydrotreat that portion, or to hydrotreat
the full range gasoline. There is a significant octane penalty
associated with the full range hydrotreating; as much as 8
to 10 research octane numbers, and 3 to 4 motor octane
numbers.
In addition, there are some catalyst changes that may
be helpful. A catalyst with an active matrix and high rare
earths may reduce FCC gasoline sulfur by as much as 20%
to 25%, when compared to a low matrix activity, zero rare
earth USY catalyst.
The effect of the FCC catalyst type appears to be most
pronounced at high feed sulfur levels, and is minimal at
feed sulfur levels of 500 ppm or less.
DEATON:
We tested the sulfur content for various fractions of our
FCC gasoline. The heaviest 10% cut, above 385°F, con-
tained 69% of the sulfur in the full range gasoline.
Typically, we found that the heaviest 10% of FCC
gasoline has an octane equal to the octane for the entire
gasoline boiling range, so removing the heaviest material
by lowering the end point would have minimal impact on
octane. In our case, the light cycle oil goes to a hy-
drocracker so we do recover that heavier end of the FCC
gasoline.
TIMOTHY J. DOUGAN (Grace Davison):
I would like to expound on a catalytic alternative to
these process options. We have been able to catalytically
reduce the FCC naphtha sulfur in our circulating riser unit
by 15% to 35% without any octane loss with GSR tech-
nology. This represents a no capital alternative to some of
these other options that have been previously discussed.
The material has been manufactured commercially, and
we are currently evaluating possible trial sites. We hope to
have the first commercial use before the end of the year.
HERBERT WlZlG (Merichem Company):
In the C5 to 220°F boiling range of the full range
catalytic cracked naphtha, about 90% of the sulfur is
mercaptans that can be caustic extracted. Then the mer-
captan containing caustic can be regenerated with air,
catalyst, and temperature for maximum reuse, with the
74 Heavy Oil Processing
sulfur extracted in the form of disulfides which are sepa-
rated from the regenerated caustic.
RIK MILLER (The M. W. Kellogg Company):
In addition to the options that have been described thus
far, Kellogg offers Riser Quench Technology in which
naphtha is recycled to the upper section of the riser. This
technology reduces gasoline sulfur by about 20%, with an
increase in gasoline octane of about 1 RON and 0.5
MON.
ADRIAN HUMPHRIES (Akzo Nobel):
Among today’s current commercial FCC catalysts, we
see differences of about 25% to 30% in the ability to
control sulfur in gasoline. It is the midrange gasoline sulfur
compounds that are affected. We have commercial data
that shows that by using an FCC catalyst with a selective,
active matrix, you can remove a lot of the alkylthiophenes
and convert them to H2S.
QUESTION 23.
How can coking be avoided in the FCCU main frac-
tionator? How is the coking rate and slurry/steam
generator fouling affected by fractionator bottoms
temperature, residence time of the bottoms liquid,
FCC feed type (i.e., gas oil or residual), or other
variables?
MENEGAZ:
There appear to be several different types of fouling in
the bottoms in the slurry circuit, depending on the feed-
stock and operating conditions. These include:
1. Precipitation of asphaltenes, found most com-
monly when feeding residual. Poor feed mixing or
poor bottoms upgrading are occasionally to blame.
2. Coke polymerization, more commonly with paraf-
finic feeds. Inadequate bottoms cracking is a factor.
3. Hard coke spalling from the reactor transfer line,
or the fractionator internals.
4. Catalyst settling out of the flow stream. This will
combine with the slurry to make a very hard gunk
with time.
In addition to the above, we have seen numerous cases
where the fouling increases when running large amounts
of heavy coker gas oil. We attribute this to the higher
amount of coke precursors in the thermal cracked stocks.
To avoid coking and fouling problems, the following
are suggested:
As far as design goes,
1. properly insulate the reactor transfer line;
2. size the slurry circuit piping for 4 to 7 feet per
second to prevent catalyst saltation;
3. size the exchanger tubing for 6 to 10 feet per
second;
TOC/INDEX
4. and most importantly, in addition to the slurry
return line over the shed trays, provide a quench
line into the bottom of the tower. This line
quenches the bottom of the tower without hurting
slurry flashpoint. A 10°F reduction in bottoms
temperature will significantly reduce fouling due
to polymerization coking. A cooler bottoms tem-
perature will allow a longer residence time;
5. provide oversized coke strainers with easy access
and draining from grade; and
6. provide capability to flush unused circuits with
cycle oil.
As far as operation, operate at the maximum bottoms
temperature consistent with the feed type. This is deter-
mined by experience. Generally, this temperature is
around 680°F but will be lower with paraffinic feeds. Units
with bottoms quench can be operated at lower tempera-
tures and still achieve the desired gravity and flash points.
Consider changing the cracking severity or the catalyst or
the catalyst matrix content if the slurry gravity goes below
-6” or above +4° API. Avoid overfeeding antimony, and
consider antifoulants, if appropriate for the fouling type.
PORTER:
This question has been asked frequently in past meet-
ings, and much information can be found in past tran-
scripts. In general, the fouling tendency is heavily
influenced by bottoms temperature. Many FCC units,
including Chevron’s, limit bottoms temperature to about
680°F Some units run as high as 700°F without serious
fouling problems. Residence time is also a factor, and
Chevron targets a net bottoms rate of 5 vol% to 8 vol%
of feed. We believe that FCC feed properties have an effect
on fouling, but have not yet been able to correlate this
effect. We have not seen a significant difference between
gas oil and residual feeds.
SAYLES:
Fractionator coking is made up of three components:
(1) kinetic considerations, (2) inorganic solids, and (3)
coke management during the run.
Coking in the main fractionator is a function time,
temperature, FCCU severity, and chemical treatment pro-
grams. Our fractionator bottoms residence rime ranges
from about 10 to 20 minutes. The residence time was
calculated from the fractionator bottom volume and the
total liquid rate of HCGO plus wash. The maximum
bottoms temperature is about 700°F and is a function of
riser severity. Chemical treatment programs limit FCCU
bottoms circuit coking and fouling. The slurry pum-
paround circuit piping should have a velocity of between
3.5 to 8.5 fps with a good design value of 6 fps. These
velocities are high enough to prevent catalyst settling yet
low enough to prevent erosion.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Monitoring of the coking tendency in a heat-integrated
unit is determined by the pumparound temperature which
is determined by reboiler-fouling factors and the slurry
steam production. Other indications of fouling are the
frequency of bottoms flow reduction (due to pump suc-
tion screen cleaning, line pluggage, etc.), loss of fractiona-
tor quench, and less than -2 API slurry. Good insulation
is believed to be important in reducing fouling.
Inorganics in the main fractionator coke include cor-
rosion products, trash in the feed and catalyst losses.
Analytical testing of the solids in the coke can give an
indication of the fouling mechanism.
An interesting problem occurs when fresh feed enters
the main fractionator bottoms. Fresh feed can be intro-
duced to maintain bottoms level during an operational
upset, leaking feed/effluent exchanger, leakage into the
slurry loop or operator error. The use of low carbon residue
gas oils can cause asphaltene precipitation and coking at
the bottoms loop temperature of 625°F to 700°E High
Conradson carbon residual feeds can cause substantial
coke buildup when injected into the main fractionator
bottoms. Review of operating procedures to limit the use
of fresh feed into the fractionator bottoms to temperatures
below 600°F will greatly reduce coking tendency by this
mechanism.
Finally, coking will occur in the fractionator bottoms
despite all the precautions. The on-line coke management
program determines the success of the run. Mechanical
modifications such as easily cleaned screens before the
slurry pumps, seal oil flush systems, elevated internal slurry
suction inlet lines and avoiding low velocity areas, insure a
good tower wash rate and low shear slurry pumps will
improve operation. Screen cleaning should be done as
dictated by the pressure drop but should also be done at a
frequency of at least once per quarter. Quenching or rapid
bottoms temperature reductions should be avoided to pre-
vent coke spalling from the fractionator and piping walls
which can cause pluggage. If a rapid temperature loss
occurs, plan on more frequent slurry pump screen cleaning.
FELTROP:
I agree that coking can best be avoided by temperature
and velocity effects and keeping the catalyst carryover out
of the FCC unit. Mechanical solutions are no doubt the
best for fixing your FCCU if you have this problem.
One method useful for avoiding coking in the frac-
tionator is to control the bottoms temperature below
700°F I think that is a key variable.
Another way is to use process antifoulants in the bot-
toms pumparound circuit. The amount of antifoulant will
depend upon the desired temperatures. There is a practical
upper limit where the antifoulant cost will be excessive, or
the antifoulant will cease to be effective. It is important, if
you choose an antifoulant, to choose one that has high
temperature stability for your unit.
75
TOC/INDEX
Controlling the tower coking by either method has
generally reduced fouling in the bottoms pumparound
heat exchangers. In some cases, the use of antifoulants
allows higher bottoms temperatures while inhibiting the
fouling that would result. A more aggressive distillation
can upgrade useful gas oils from low value slurry oil.
Other variables will impact the coking and fouling
tendencies. Increased residence time will cause increased
fouling. Feeding reduced crude or vacuum residue to the
FCCU will increase fouling, all other operating aspects
being unchanged. High catalyst fines loadings can act as
agglomeration sites for the high boiling polyaromatics,
giving higher viscosity and more fouling potential.
LAUX:
Other people have discussed the temperature and ve-
locity effects and some of the feed effects. One other thing
you need to consider is conversion. At McKee, our feed is
very paraffinic. We run with an aniline point over 230°F
and we run around 85%+ conversion, with a very low
slurry yield. This tends to raise the concentration of poly-
cyclics and unconverted paraffins in the slurry. We have a
severe fouling problem. We clean two to three exchangers
per week in that circuit.
To minimize that coking and fouling, you have to
reduce your bottoms temperature as discussed, and reduce
the residence time at that temperature. Keep a high
enough exchanger tube velocity to avoid laydown.
At Three Rivers, we run at about 690°F in the bottoms,
with a 5 to 7 foot per second exchanger velocity. We also
monitor our slurry, checking for asphalrene content, and
any time that it gets up around 7 mg/ml, we will start
injecting an antifoulant. At Three Rivers, we typically do
not have to clean our steam generators at all during the
run.
McLEAN:
I agree with most of the comments regarding the me-
chanical effects the other panelists have made. I also would
like to note that I have been very well educated by Peter
Andrews that you cannot compare one main fractionator
operation with another in terms of comparing numbers.
You really have to look at what the operating window for
your unit is, based on the specifics of its design and feed
quality and conversion level.
I will make some comments on yield effects which can
lead to coke deposition problems if the bottoms yield is
either too high or too low. The presence of reactive, more
paraffinic compounds which continue to crack thermally
downstream of the reactor can cause this. You can also get
an antisolvent precipitation phenomenon, as a couple of
people have mentioned, where the presence of this paraf-
finic material causes deposition of the more aromatic
asphaltene molecules. This was also discussed in detail at
last year’s NPRA Q&A Session,
76 Heavy Oil Processing
This problem can be minimized by the use of a good
bottoms cracking catalyst with an active matrix to make
sure the reactive compounds are cracked out where they
are supposed to be, in the reactor. We have observed that
this problem diminishes commercially when changes to
better bottoms cracking catalysts have been made.
On the other end of the scale, there is a minimum
bottoms yield beyond which coking problems can occur.
This point of incipient coking can be determined by
increasing severity to the point where bottoms pump
screens begin to show pressure drop or require more
frequent cleaning, and then backing off and operating
somewhat below this point. Adjustments in the LCO draw
to alter bottoms yield and quality can also be used to
compensate.
BARLOW:
We feel that one of the strongest variables affecting
coking is the bottoms temperature. We see a tremendous
difference in the rate of coking in the bottoms and in the
fractionator slurry circuit between 680°F and 695°F. If you
are running 700°F, you are definitely in a high risk area.
However, we also acknowledge that running at a higher
bottoms temperature can improve your yield pattern and
structure and can be very economical. Cycle oil recovery
is much greater with a higher bottoms temperature.
One of the points I would like to stress is based on a lot
of effort analyzing the different feedstocks and the differ-
ing gas oils and residuals from the various crudes. We see
a tremendous impact on the coking rate in the main
fractionator based on feed quality changes.
We have focused on analytical techniques on the bot-
toms, although there are some limitations because of the
nature of the slurry in trying to apply these analytical
techniques. We have had success in correlating light cycle
oil and heavy cycle oil analyses with slurry stability, and,
again, I say correlating, so there is not always a direct
one-to-one relation. In terms of quality of the feed, we
look at aromatics and nitrogen content as well as the
reactor operating conditions. In terms of antifoulants,
which are obviously our business, we have moved away
from simply applying dispersants and trying to move or
maintain the coke particulate matter in suspension. We
have focused heavily on inhibitor technology, which
focusses on metal catalyzed polymerization growth
mechanisms, asphaltene precipitation and growth mecha-
nisms, and condensation type polymerization mecha-
nisms that are similar to what you see associated with light
cycle oil instability. Also, some high temperature ther-
mally-stable antifoulants have been very effective in severe
fouling conditions.
A paper on this subject “FCC Fouling Can Be Re-
duced-Even In the Slurry Loop” by R. E Freeman was
presented in June, 1987, at the 8th Katalistik’s FCC
Symposium.
TOC/INDEX
BHAGWAN B. PATIL (Hindustan Petroleum Corporation, Ltd.):
With the fractionator bottoms temperature being so
critical, is there a scheme for controlling it automatically?
Presently, we have a manual control by controlling bot-
toms quench flow. Do refiners utilize other controls on the
bottoms temperature?
MENEGAZ:
We have done the control on the bottoms quench
manually.
ARMBRESTER:
We use bottoms temperature control on all of our main
fractionators by controlling the slurry pumparound flows.
DELBERT F. TOLEN (Rocky Mountain Salvage & Equipment Co.):
I am going to disagree with Mr. McLean on something.
I have run three different catalytic crackers where we
recycled slurry to extinction without problems of coking
in the bottoms. Those slurry oils would run between -3”
and 0° API. A greater effect on slurry gravity and on
coking tendency was reactor temperature because as you
raised it, the slurry gravity would drop even in the total
recycle.
There is an enormous effect of recycle on the traffic in
the bottom of the tower, and most units have gone away
from recycle over the last ten years, so we are seeing more
coking tendencies in the bottom. The minimum API that
we used to run was a -5” API. If we dropped at all below
-5°, some place around a -8” or -9” gravity, you would
begin to get extreme polymerization of the materials in the
bottoms exchangers. So we always set the -5” API as an
absolute minimum on the entire bottoms. In three differ-
ent units we recycled slurry to extinction, so there is no
minimum slurry draw.
McLEAN:
I agree. Obviously, my comments did not apply to a
recycle operation. In recycle, you are not really drying up
the presence of those materials; you are actually concen-
trating them, and so obviously different rules will apply.
FRANK H. KHOUW (Shell International Petroleum):
If I may, I would like to extend the question from
coking in the fractionator to coking in the reactor riser.
I would like to ask the panel, and also the floor, whether
anyone has experienced reactor riser coking, and if the
answer is affirmative, is it more severe when processing
heavy feed? I would also like to know what the perceived
mechanism and what the solution to combatting coke
formation in the riser are?
MENEGAZ:
We are aware of a noncatalytic atmospheric residuum
treatment process where there was substantial coking in
1994 NPRA Q&A Session on Refining and Petrochemical Technology
the reactor. The heavier material was not processed in the
riser, and laid down as coke in the riser as a result.
ARMBRESTER:
We have experienced some coking in the riser on the
RCC unit, which obviously is a residual operation. The
coking problems occur in the area of the feed nozzles,
which are elevated in the RCC riser. I cannot give you an
answer on eliminating it other than trying to improve the
feed dispersion and minimize, backmixing in the feed
nozzle area.
LAUX:
The test is the hot heptane insolubles test, UOP
Method 614-80. It takes about 4 hours to run. We do this
test in our own laboratory.
QUESTION 24.
What have been recent experiences with advanced
process control on FCC units?
PORTER:
At our Pascagoula refinery, for the last two years we have
been using a DMC multivariable model-based predictive
controller on our FCCU. It controls our regenerator,
reactor and fractionator.
The primary benefits have been increased conversion
and improved fractionation. Operator acceptance has
been good.
McLEAN:
We are aware that advanced systems with on-line op-
timizers coupled to process models and controlling oper-
ating conditions are being used by a number of refiners.
To give an example, we know of one case where an
optimizer is being used to vary reactor temperature over a
range as wide as 970°F to 1,005°F in response to continual
updates using feed quality parameters and product values.
ARMBRESTER:
Ashland has installed advanced process controls on our
RCC unit and all of our FCC units, including the reac-
tor-regenerator sections, the main fractionators, and the
gas concentration units. Typical reactor-regenerator con-
trols include pressure balance controls for energy savings,
and carbon burn and reactor severity controls for unit
optimization. These controls have generally provided
good operation, with flue gas analyzer reliability and
operator acceptance being two of the biggest obstacles to
full utilization.
The main fractionator functions are directed toward
cut point controls for naphtha and cycle oil and heat
recovery optimization for the various cooling circuits.
These controls have also operated very well, except for a
77
TOC/INDEX

few cases where the physical limitations of the fractionator QUESTION 25.
have limited our optimization efforts. What is the yield pattern and naphtha octane expected
The gas concentration controls are intended to provide from an FCC processing hydrocracker fractionator bot-
product quality control, while minimizing energy con- toms?
sumption. These controls have also been very effective.
Related to this question and one that was addressed in LAUX:
the General Processing section, our experience with op- We process the unconverted gas oil from our 2,400 psig
erator acceptance has been that the acceptance is fairly once-through unicrackers through our FCCUs, both at
good on the controls that they do not consider critical, but Three Rivers and at McKee.
as you get into the FCC reactor-regenerator section, they At Three Rivers, the hydrocracker gas oil comprises up
are more reluctant to turn over those controls to the to 50% of the FCC feed slate at times, with demetallized
advanced control system. I think the training that you oil and some LVGO filling out the slate.
provide and their knowledge of the control functionality After our FCCU turnaround in January of this year, we
is very important to really achieve full utilization of these fed 50% hydrocracked gas oil to the FCCU at Three Rivers
controls. for nearly a month, as that was the only gas oil we had
stored during the turnaround. Compared to the yields
RONALD E. MARRELLI (Phillips Petroleum Company): from a 0% hydrocracked gas oil case with the same crude
For those who have put advanced controls on their slate, we saw about an 11% increase in conversion, and
catalytic crackers, have you added a distributed control the gasoline and LPG yields increased 8% and 4%, respec-
system first and then been able to quantify the economic tively. The gasoline research octane number dropped by
benefit of just the advanced control portion? about 1.5 numbers, but surprisingly, the motor octane
number did not drop at all. The propylene and butylene
CUNEO: yields actually increased by over 1 wt% each.
Yes. We have recently done that at our Norco unit. It The actual monthly averaged yield data is as follows:
was started up on a TDC system, and then this year, we
will put on the on-line optimization, so we are able to
MONTH 4/93 2/94
make that quantification. It has provided a very rapid
payout, even with the modern Honeywell TDC systems. Percent Hydrocracked 0.0 48.6
The cost for overlaying the optimization is very modest, API 24.1 28.0
and it is making us well over $1 million a year. Corrected Conversion LV% 73.7 85.4
LPG LV% 28.7 32.6
HEROS DERGREGORIAN (Giant Refining Company):
C3= WT% 4.64 5.72
In conjunction with optimizing the catalytic cracker
operation, is anybody using on-line analyzers to achieve C4= WT% 5.35 6.50
that? Corrected Gasoline LV% 54.1 62.7
RON 92.3 90.7
CUNEO: MON 80.2 80.1
Yes. We routinely use on-line analyzers around the flue
gas for oxygen, CO content, CO2, as well as on the gas
D’AURIA:
fractionation end point on naphtha, and concentrations
of propylene, ethylene, and butylenes in the gas plant. Hydrocracker bottoms are very hydrogen rich, they
convert very easily in the FCC unit, and they are very
ARMBRESTER: selective to gasoline range material. Compared with
We also use an on-line analyzer for flue gas composition straight run VGO, hydrocracker bottoms will convert
from the regenerator, and we have several analyzers in the 10% to 15% higher and yield 10% to 12% more gasoline.
gas concentration section looking at product purities. Due to the greater degree of saturation, the octane will
drop 1.5 to 2.0 numbers, and, ofcourse, the product sulfur
STEVEN M. FISCHER (CITGO Refining & Chemicals): content will be very low.
For those that run optimizers in addition to advanced
control systems, how often do you run the optimizer to QUESTION 26.
regenerate the new set points? Please comment on the effectiveness of the following
water wash cascade schemes for FCC gas plants:
CUNEO: a. fresh water to the interstage cooler, then to the high
We can get at least three or four solutions a day to pressure receiver and then to the main column over-
regenerate the set points. head;

78 Heavy Oil Processing

TOC/INDEX
b. water to the main column overhead, then to the infer-
stage cooler and then to the high pressure receiver; and
c. fresh wafer to the high pressure receiver, then to the
inferstage cooler and then to the main column over-
head.
FELTROP:
Of the three options presented, option b is clearly the
best. This is a concurrent flow scheme with the gas flow
from low pressure to high pressure. I assume that the water
from the high pressure separator goes to the sour water
stripper in this case.
Options a and c recycle water from the high pressure
separator to the main fractionator overhead, which is a
low pressure system. This results in releasing the ammo-
nia, H2 S, and HCN, and recycling them back through
the gas plant. The water from the high pressure separator
is in equilibrium with the gasses at high pressure. When
this water is injected back into the low pressure area, the
equilibrium is reestablished at the lower pressure, which
releases ammonia, H 2 S, and HCN back into the gas
plant.
Option b cascades the water in the direction of increas-
ing pressure and then leaves the system via the high
pressure separator water. This approach results in carrying
the maximum amount of ammonium bisulfide and cya-
nide out of the gas plant, and is clearly superior from a
corrosion standpoint.
There is an additional option that is equally effective
from a corrosion standpoint and offers additional cost
savings. This option uses the condensate water from the
main fractionator overhead as wash water for the interstage
and high pressure coolers. The recirculation loop to the
main fractionator overhead coolers provides a water wash
to remove ammonium bisulfide deposits from these cool-
ers. The water from the main fractionator overhead is not
corrosive since it is in equilibrium with the ammonia,
H2S, and HCN at low pressures, and is suitable for water
washing the higher pressure sections.
The major advantage of this approach is that no exter-
nal water is added to the system and it greatly reduces the
volume of water to be stripped at the sour water stripper.
It also eliminates the expense of preparing boiler feed
water.
In systems where cyanides are high and corrosion and
hydrogen blistering are potential problems, a water-sol-
uble filming inhibitor is added to the water at the main
fractionator. Since it stays with the water in the fractiona-
tor overhead, the interstage coolers and the high pressure
coolers are inhibited by addition of a single inhibitor;
whereas the use of an oil-soluble inhibitor requires addi-
tion to the fractionator overhead, interstage and high
pressure sections.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
PORTER:
I agree with Mr. Feltrop’s comments. At Pascagoula, we
utilize option b, without using any fresh water makeup.
As Mr. Feltrop described, we utilize the condensate from
condensing steam in the main fractionator overhead.
ARMBRESTER:
Ashland has successfully used water wash scheme a for
several years on our FCC unit at Saint Paul Park, with a
wash water rate of approximately 1 gpm to 1.5 gpm per
1,000 bbl/d of FCC charge. We routinely check the water
samples there for iron, chloride and cyanide content and,
as mentioned previously, one of the problems with this
scheme is the fact that you are dissolving contaminants at
high pressure and the possibility of releasing those again
in the low pressure section.
Our RCC unit at Catlettsburg has also achieved good
corrosion results using a modified scheme a. In this case,
the water from the high pressure receiver is not cascaded
to the main fractionator overhead, and we protect the
main fractionator overhead system simply by recirculating
the overhead wash water, with the makeup coming from
the reactor side.
We plan to convert this unit to water wash scheme b in
the near future, to reduce our water makeup rate and our
sour water stripping requirements.
Also on the RCC unit, we add air to the wet gas stream
for polysulfide production, and our water wash rates are
typically 2 gpm per 1,000 bpd of feed, with essentially
100% makeup water. In this unit, our monitoring efforts
include hydrogen probes at several locations in the inter-
stage and high pressure sections, and periodic water analy-
sis for pH, cyanide and thiocyanate content.
On our FCC unit at Catlettsburg, we historically have
used scheme c, but we recently switched over to scheme a
because we were experiencing corrosion problems in the
interstage area. This unit also uses air injection to the wet
gas stream, and a wash water rate of 2 gpm per 1,000 bpd
of feed.
BARLOW:
We have seen all the schemes used, but we also support
that the preferred method is b. Method b essentially
corresponds to increasing concentrations, thus reducing
the introduction of higher contaminant levels to the low
pressure areas. We see the greatest benefits of water wash-
ing in the high pressure section where, due to the partial
pressure, the concentration of dissolved ammonia and
HCN are highest.
We would prefer not to return the water from the high
pressure section at all to the main fractionator reflux
drums. This practice would cause H2 S, ammonia, and
HCN to flash off as the pressure is reduced at the reflux
drum and cause their concentration to build up in the
compression loop.
79
TOC/INDEX
CUNEO:
We agree that scheme b is by far the best for both
corrosion protection and minimizing the use of water.
DANIEL N. MYERS (UOP):
Wash water scheme a (sending the washwater to the
interstage cooler, then to the high pressure receiver and
then to the main column overhead) gives the water from
the high pressure section a chance to degas at the lower
pressure of the main column overhead receiver. This is
advantageous since it results in less gas going to the sour
water stripper.
QUESTION 27.
Please comment on desired washwafer rates and any
chemical additives that can further improve corrosion
control for FCC gas plants.
BARLOW:
The amount of washwater necessary depends on the
gas/vapor flow rate, the amount of water vapor already
present, and the amount and type of corrosives present. It
is adjusted primarily based on individual unit designs.
Ideally, the amount of washwater should be the minimum
needed to meet one or more of the following criteria, listed
in the order of importance:
Typically, use 2.0 gallons per minute, or approximately
1,000 lb per hour per million standard cubic feet of vapors
from the top of the main fractionator.
Adjust for a pH value in all the water draws between 8
and 8.5.
Try to maintain HCN content of all the water draws at
less than 20 ppm by weight.
Depending on the system, several different types of
water wash may have to be injected to meet these criteria.
For example, a slightly acidic sour water stream may be
used to depress pH values. In addition, polysulfide may
have to be added to the washwater to decrease the HCN
levels.
On the subject of polysulfide injection, continuous
injection of polysulfide solution into the washwater lowers
the HCN content of the condensates by forming thiocy-
anate. Polysulfide also reacts with some sulfide corrosion
products to produce a protective film on the steel surfaces.
Polysulfide injection should be considered if water wash-
ing by itself does not decrease the HCN concentration
below the recommended 20 ppm by weight. We have seen
several types of polysulfide solutions used, and several are
available. The majority prefer, in our experience, to use the
commercial 55% by weight ammonium polysulfide solu-
tion. It contains about 35% by weight polysulfide sulfur.
Sodium polysulfide solution is not recommended be-
cause it increases the pH of the sour water condensate and
reacts more slowly with cyanide, in comparison to ammo-
nium polysulfide. It is also considerably more expensive.
80 Heavy Oil Processing
We have extensive experience with the use of filming
inhibitors. Filming amines have been used for many years.
Both water- and oil-based inhibitors have been applied to
control general corrosion with good results. We also have
specific products that have been very effective at control-
ling hydrogen blistering and related cracking.
We also have a good track record at reducing fouling
from corrosion products that often affect reboiler and
column performance.
DEATON:
We use one gallon per minute of washwater injection
to the compressor aftercoolers per 1,000 bbl/d of FCC
charge. In addition to the water wash, we use an oil-soluble
filming amine in the compressor aftercoolers.
We have not seen any corrosion or hydrogen blistering
for several years by using this method ofcorrosion control.
FELTROP:
I agree with Mr. Deaton’s rule of thumb on the one gpm
per 1,000 bbl/d of feed to the unit. Our preference is a
water-soluble filming inhibitor, and combining this with
a concurrent water wash will give the best corrosion and
hydrogen blistering protection at a minimal cost.
There are cases where ammonium polysulfide can be
used effectively, but there are a couple of cautions with
that. The major one is knowing how much to add since it
requires a stoichiometric amount, according to the cya-
nide that is necessary. Excess polysulfide can lead to in-
creased corrosion, especially in high velocity areas. The
cyanide sampling procedure and analysis are sometimes
difficult to perform as well. Handling in cold weather can
be difficult, too.
SAYLES:
We agree with the amount of washwater needed, about
1.5 to 2.5 gpm per thousand barrels of FCC charge. One
thing that we have found that is critical is handling of the
wet gas compressor section. It depends on what your
corrosion products are. If a number of your corrosion
products fall out through your wet gas compressor system,
they do not go on into the vapor recovery system.
Previous comments have been on polysulfide and its
usage. One thing that we have found is that if you main-
tain the sulfur compounds at about the 200 mg per liter
level, cyanide is tied up; and we have not seen any hydro-
gen blistering or any corrosion on those lines.
LAUX:
I thoroughly agree with the 1 gpm per 1,000 rate. I have
seen a system where we reduced it down to 0.5 gpm per
1,000, or even a 0.25 gpm per 1,000 for sour water stripper
limitations, and added filming amines to try keeping the
corrosion down. It did not work. We corroded out the
primary adsorber.
TOC/INDEX
DENNIS K. NELSEN (Western Unichem):
We have developed a modified ammonium polysulfide
that has a sulfur content of 38%. The crystallization point
has been reduced from 40°F to -20°F which dramatically
improves handling properties. By increasing the amount
of modifier, we have a product with a -50°F crystallization
point. The modified ammonium polysulfide dosage is
controlled via a free cyanide analytical method developed
by Charles Taylor of Lyondell. Our standard control range
is 1 ppm to 5 ppm free cyanide in the water draws.
QUESTION 28.
At-sine sometimes must be removed from propylene
or FCC dry gas to make if more economical to process
in do downstream units. This is usually done by an arsine
guard bed that adsorbs the arsine. However, H2S,
when present, has historically been a poison to these
guard beds. Are there any materials that can be used
to solve these problems in processing these streams?
MENEGAZ:
Most materials which remove arsine-lead oxide,
nickel or copper-also have a stronger affinity for H2 S
than arsine. Caustic and amine treating upstream of the
guard beds can remove most of the H2S. One supplier
offers a manganese-based guard bed which supposedly will
remove arsine down to 1 ppb and is not affected by H2S.
We understand these materials have been used success-
fully in FCC service, and a similar copper-manganese
material has been used in natural gas service for three years
with satisfactory results. However, there is some question
as to whether the methyl acetylene in FCC propylene will
form copper acetylides, so we are hesitant to recommend
a copper-based material in FCC service at this time.
Most of the arsine guard bed materials we talked about
here present a disposal problem, especially if the arsine
content is above 5 wt%. We understand that some smelters
will take this material.
Aristech has a patent on in situ rejuvenation of lead
oxide guard beds which can extend the ultimate loading
capacity of arsine from 2% up to possibly as high as 6%.
They use this procedure to protect their Ziegler-Natta
catalysts in their polypropylene reactors. They discard the
bed after four rejuvenations and about 4% cumulative
arsine loading.
LAUX:
Our experience at our Mont Belvieu, Texas propylene
splitter facility is that arsine can be removed from the
propylene using a guard bed composed of about 40%
copper oxide, 40% zinc oxide, and 20% alumina. Arsine,
COS, H 2 S, and low molecular weight mercaptans are
effectively removed by this material. The sulfur com-
pounds are not a poison to this catalyst, but they do
occupy sites that could be used for arsine removal.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
There is an equation that predicts the bed life, and it is
two times the weight percent of arsenic deposited on the
spent catalyst plus the weight percent sulfur deposited
equals 5 weight percent total.
Depending on the concentration, it may be more eco-
nomical to remove the sulfur compounds upstream, as Mr.
Menegaz has mentioned. The COS can also be hydrolyzed
to H2S and CO2 over an aluminum bed and then removed
with amine or caustic.
ARMBRESTER:
Ashland sells a combined propane/propylene stream to
a neighboring plastics plant, and their feed preparation
system includes an arsine guard bed. Before transferring
this stream to the customer, it is processed through an
alumina treater for conversion of COS to H2S. To prevent
H2S poisoning of the customer’s arsine guard bed, we then
pass the stream through a vessel containing solid KOH
“walnuts”. The KOH treater is designed for an inlet H2S
concentration of 8 ppm to 10 ppm, and the outlet H2S
content is normally below the detection limit of our
laboratory equipment.
LEE W. MORRIS (Acreon Catalysts):
With copper-based and other arsine guard materials,
there is a competition between sulfur and arsine for the
catalytic active sites. This is important because sulfur
species are often present in excess of arsine levels.
Acreon offers a chemisorption product, MEP-191,
which is impervious to poisoning by sulfur species, includ-
ing H2 S and mercaptans. It has other benefits such as
extremely low hydrogenation potential, and no possibility
of forming explosive copper acetylides. It has been used in
approximately ten commercial plants.
QUESTION 29.
What benefits have you seen after converting to radial
feed nozzles?
D’AURIA:
The overall objective of the feed distribution system is
to produce a rapid and even contact of the catalyst and the
feed in the riser. Improved feed distribution will minimize
localized areas of overconversion, will decrease delta coke
and gas make, and will increase catalyst-to-oil and conver-
sion.
It is important to consider the uniformity of the catalyst
flow prior to feed injection as well as the feed injection
itself. The best feed distribution system will not compen-
sate for uneven catalyst flow.
The ability of the feed injectors to provide uniform
distribution of feed across the cross-sectional diameter of
the riser is very important. What is required is a total
system that delivers uniform catalyst flow, which is not too
81
TOC/INDEX
dense, and feed injection that does not produce too fine a
mist, which cannot penetrate uniformly across the riser.
Installation of radial feed nozzle systems will improve
conversion and selectivity to gasoline. The amount of
improvement is dependent on both the severity of the
operation as well as the type of feedstock. Generally,
greater improvements are realized when processing heavier
and more difficult to process feeds, and for operations at
higher regenerator temperatures.
When replacing a wye premix distributor with elevated
radial nozzles, the benefits that we are able to directly
attribute to the radial feed distributors generally are in the
form of 1 vol% to 3 vol% higher gasoline, and decreased
amounts of C2 minus material. Increased catalyst-to-oil
ratio, resulting from the decreased delta coke will also
increase conversion.
In many instances, however, installation of an im-
proved feed distribution system will allow improvements
or debottlenecking in another part of the plant, so that the
overall impact of such an installation can often be many
times greater than that attributed just to the feed distribu-
tor itself. It is important, therefore, to be realistic about
the benefits obtained from the feed distributor change
itself versus the secondary benefits from debottlenecking
other parts of the plant.
McLEAN:
All the major licensers are now offering radial nozzles
as their preferred design.
I agree with all of Mr. D’Auria’s comments about the
effects on reducing back mixing and improving distribu-
tion.
The degree of performance improvements will vary
depending on the feed quality, base conversion rate, steam
injection rate, and other factors. It is also, again, somewhat
difficult to find an operation where this was the only
change that was made as part of a revamp, so you get into
problems trying to isolate what is causing the effect. But
we do know of one case where this change was made and
nothing else was done, and what this refiner saw at the
same operating severity was a 40% to 50% reduction in
dry gas make. And, again, to back up what Mr. D’Auria
said, their next move was to increase the operating severity
in order to take advantage of the extra room this gave
them.
MENEGAZ:
I agree wholeheartedly with the comments that have
been made, particularly that the magnitude of the im-
provement that you see depends on where you start. The
improvement that you see can be masked by other
changes, such as improvements in the riser termination
device that are made at the same time.
The newer nozzle technologies, in relative terms, can
produce a Sauter Mean Diameter spray of 1, that is a
82 Heavy Oil Processing
relative number, as opposed to 2.35 for a slotted tip nozzle,
and a 7.80 for one of the older, showerhead types. The
yield improvements will be greater on heavy feeds because
they require finer atomization to achieve instantaneous
vaporization. Light feeds are less sensitive. As an extreme
example, one refiner processing a 28° API paraffinic feed-
stock in a UOP stacked unit with a showerhead nozzle
found that, except for improving his octane slightly, elimi-
nating dispersion steam did not appreciably affect his
operation.
VICENTE A. CITARELLA (Exxon Research & Engineering Company):
We have implemented over 40 feed injection system
upgrades of Exxon affiliates and licensed units, and we
would like to share that experience with you this morning.
We agree with the comment made earlier by Peter
Andrews that feed injection system improvements are the
most profitable FCC upgrades possible, with payout pe-
riods typically in the order of months.
Most of our units have been designed with radial feed
injection nozzles because of the feed/catalyst contacting
advantages this type of arrangement provides. In several
applications, we have converted units from axial to radial
feed nozzles. In each of these revamps, significant im-
provements in dry gas and coke yields were achieved.
Typically, conversion to the modern ER&E radial feed
nozzles have allowed an increase in naphtha yield of 3%
to 5% on feed. By adjusting operating conditions, this
advantage can be translated into the ability to process a
poorer quality feed, or permit an increase in feed rate. For
example, in one application this improvement in selectiv-
ity was utilized to permit an increase in residual processing
equivalent to a 2 wt% increase in feed Conradson carbon
content.
RIK MILLER (The M. W. Kellogg Company):
Regarding the differences in performance between axial
and radial feed injection systems, we have conducted fairly
extensive studies in both cold flow and commercial units
comparing axial to radial injection. We published the
results in a paper, which was referred to by Mr. Menegaz.
The paper is entitled, “New Developments in FCC Feed
Injection and Riser Hydrodynamics” and was presented
at the AICHE 1994 Spring National Meeting.
All other parameters being equal, converting from
axial to radial feed distribution, even without changing
the droplet size distribution or atomization quality, will
result in an increase in conversion of 2 vol% to 3 vol%.
This is largely due to the improvement in catalyst density
distribution across the riser that is obtained when you
inject the feed from a radial orientation up the riser, after
the catalyst has had a chance to re-establish its flow
profile. Axial injection of the feed at the bottom of the
riser, where the catalyst is changing direction, leads to
poor catalyst distribution.
TOC/INDEX
Where, in addition to changing from axial to radial
nozzles, there is also modernization to more updated
nozzle technology, such as our ATOMAXTM nozzles, we
have documented gasoline yield improvements of 3 vol%
to 6 vol%.
MENEGAZ:
What is the required pressure drop for the ATOMAXrM
nozzle?
RIK MILLER (The M. W. Kellogg Company):
The pressure drop used in the ATOMAX rM nozzle
depends on unit constraints, feed composition, and feed
type (i.e., VGO or residual application). Typically, they are
designed for a pressure drop of 30 to 60 psi.
DILIP DHARIA (Stone & Webster Engineering Corp.):
We have revamped a number of units where we have
replaced axial nozzles with the radial nozzles and improved
the yield performance; i.e., decrease in the dry gas, better
bottoms cracking, and improvement in the gasoline yield
of 3% to 8%. I will cite two examples in reference to the
effect of radial distribution of feed. In one revamp case,
one of the nozzles got plugged because of the leftover bolts
in the line, and when these bolts were removed after a few
months’ operation, the performance improved by 2% to
3% in terms of gasoline yield.
In another case, the unit originally had 12 feed nozzles
and we reduced them to 6 Stone and Webster nozzles and
still improved the performance. So in addition to the radial
distribution, nozzle design is also important.
Environmental Control
QUESTION 30.
What changes can be made to reduce NOx emissions
from the FCC regenerator?
BOYCOTT:
We have done extensive work on this subject due to
permit limitations. On a charge of straight-run gas oil, we
were able to develop excellent correlations between excess
O 2 and NO, emissions at constant coke make. Higher
excess O2 and higher coke make both lead to higher NO,
emissions. These correlations were of sufficient quality to
allow us to use surrogate parameter monitoring for NO,
emissions and defer the installation of a continuous emis-
sions monitor.
The addition of a SO, reduction additive did not
appear to have an impact on NO, emissions; however, the
addition of CO promoter did cause an increase in NO,
emissions.
Upon the introduction of coker gas oil feed, NO,
emissions increased and we were unable to develop corre-
1994 NPRA Q&A Session on Refining and Petrochemical Technology
lations to predict emissions. As a result of this and sub-
sequent operating permit modifications, we have installed
a continuous emissions monitor.
In conclusion, we have been successful in controlling
or reducing NO, emissions by controlling excess oxygen,
coke make and CO promoter additions.
D’AURIA:
The formation of NO, in the regenerator is influenced,
as Mr. Boycott said, by the oxidation severity. Higher levels
of excess oxygen and uses of CO promoter can, in some
cases, double the amount of NO, in the flue gas. Also,
there is some correlation with the amount of organic
nitrogen in the feed and the amount of NO, that might
appear in the regenerator.
Overall, careful control of the excess air and minimum
use of CO promoter are key variables to keep NO, from
getting too high.
The high efficiency regenerators that do not require the
use of CO promoters will minimize the formation of NOx.
ARMBRESTER:
I guess our studies here are a little different. We have
done some laboratory testing for NO, and our results
show that basically all of the NO, was related to the
fuel-bound nitrogen, and therefore, we think that remov-
ing nitrogen from the FCC feed is the item that will have
the biggest impact on overall NO, emissions from the
regenerator. This, of course, can be accomplished through
severe hydrotreating of the FCC feed.
McLEAN:
I agree with the comments on feed hydrotreating, CO
promoter and excess oxygen relationships. Also, not only
does the feed hydrotreating reduce the nitrogen level, but
typically it will result in a lower regenerator temperature
operation as well. So, it has a double barrel effect there.
Improving catalyst and air distribution has also been
mentioned as having a direct effect, as well as allowing you
to reduce promoter addition.
It should also be noted that partial burn units operating
without excess oxygen may minimize direct NO, forma-
tion in the regenerator. The NO, out of the CO boiler can
still be a problem in that case.
Finally, flue gas treatment options such as selective
catalytic reduction are available. We do know of one FCC
unit outside the United States which operates with a
selective catalytic reduction system on their FCC flue gas.
SAYLES:
I believe that there are three main mechanisms in NO,
formation, all three of which are more art than science at
this point. The mechanical processing of NO, has been
previously discussed. Good air mixing definitely reduces
83
TOC/INDEX
NOx. Surprisingly, incomplete combustion reduces NOx
significantly.
On the process side, the use of a CO boiler can control
the NO x formation from the stack of the FCC unit,
regardless of the regenerator conditions.
Finally, in the catalytic realm, promoter addition does
seem to increase NOx. We can not eliminate promoter
addition in our units, since we do not have CO boilers and
could not tolerate increased CO emission.
SOx reduction catalysts are interesting and can decrease
or increase NOx.
A good source of NOx data is in EPA Docket A79-09,
Item B-20.
JOHN T. HALEY (Grace Davison):
Several refiners in the industry have observed NOx
reduction of up to 40% with Grace Davison’s DESOX™.
Additionally, Grace Davison has been doing significant
research in this area. As a result of that research, we have
been conducting commercial evaluations of some prom-
ising new NOx reduction additives.
QUESTION 31.
What are the most important factors in maintaining
high stream time for FCC flue gas electrostatic pre-
cipitators?
CUNEO:
We see two key issues there. First and foremost is the
prevention of formation of liquid water and its contact
with the FCC catalyst. The second is preventive mainte-
nance around the mechanical equipment associated with
the precipitator. Because of the small particle size of the
catalyst at that point, it is extremely abrasive.
In order to keep liquid water away from the catalyst,
we closely control flue gas temperature, watch to make
sure that any purge air or fluffing air is dried, and make
sure that the body of the precipitator is well insulated. We
have to avoid depositing any sort of catalyst on the plates
and insure that it does not get wet at any time.
Excessively thick layers of catalyst on a plate can lead
to electrical arcing, breaking of wires, or shorting out of
entire cells.
With respect to the preventive maintenance, this is
important for mechanical reliability; particularly that of
rappers, draw-off bin vibrators, hopper rotary valves, and
conveyor bearings. Performance of these types of equip-
ment should be evaluated at least monthly, and preventive
maintenance done on a regular basis.
DEATON:
Three important factors are to maintain the ceramic
insulators, the rappers, and the catalyst removal systems
in good working order.
84 Heavy Oil Processing
Ceramic insulators encase the power supply to the
electrodes. When the ceramic is cracked due to thermal
shock or moisture, the electrodes short out. Wet catalyst
on an insulator can lead to electrical tracking and cause an
electrode to short out. A bank of insulators is protected by
a metal housing with filtered air purges to keep out catalyst
dust. The air purge supply usually has a heater which keeps
the air above its dew point. A good guideline is to heat the
air 40°F above ambient. Also, each insulator should have
a thermostatically controlled electric coil heater at its base.
Rappers should be regularly inspected by operators and
preventative maintenance people for proper timing. The
most common source of failure is failure of the timers’
printed circuit boards.
And, finally, as simple as it sounds, catalyst removal
systems need to be kept empty. If catalyst builds up into
the precipitator, it can short out the electrodes or bow the
collector plates, which can also lead to shorting out the
electrodes.
LAUX:
In addition to Mr. Cuneo’s comments on moisture
removal and exclusion, we think good inspection and
repair during turnarounds is also a major key to on stream
performance. We open up each precipitator during each
turnaround and do a thorough cleaning and inspection.
We typically replace all the wires every six years. We replace
about two to three insulators and repair the penthouse
seals every turnaround.
PORTER:
Most of the comments have been covered.
We believe in electrical segmentation so that loss of
efficiency is small if cells short out for any reason.
For ultimate reliability, the precipitator can be con-
structed as two parallel units, with inlet and outlet valves,
and enough capacity in each unit to maintain operation
of the FCC unit at reduced capacity and still meet stack
emission limits. One of the units can then be taken off line
for repairs without shutting down the FCC unit.
TREESE:
Most of the points we follow have been addressed here.
I will highlight that we have found frequent monitoring
of the automatic voltage controller is essential to keeping
the precipitator on-line. The older generation controllers
are mostly analog and require frequent power and spark
adjustments. Without the adjustments or monitoring, the
power input gets unstable, resulting in an increase in
sparking, wire failures, and opacity problems.
Also important is the frequent removal and emptying
of the collected catalyst fines in the hoppers to avoid
buildup and particle re-entrainment. All plugged hoppers
should be repaired as soon as possible.
TOC/INDEX
The value of more careful attention to the precipitators
can be seen in the failure frequency. We used to experience
five to six failures per year when we were not paying
adequate attention to the precipitators. Now that we are
monitoring the precipitators more closely, we are down to
less than one failure per year.
QUESTION 32.
What considerations limit inlet temperature for instal-
lations upstream of the CO boiler in partial burn units?
LAUX:
We took this question to mean, what are the precipita-
tor temperature limitations upstream of the CO boiler.
Typically, for the metallurgical design of the precipitator
itself, around 650°F is the usual number that I have seen.
How you correct a high temperature at this location
depends somewhat upon the design of your flue gas cooler.
If you have a box-type cooler, like we do at both McKee
and Three Rivers, soot blowers are absolutely essential.
They blow the catalyst off the tubes and return the heat
transfer coefficient to normal.
If you have a shell and tube heat exchanger with the flue
gas on the tube I.D., something that works well is shot
blasting the tubes with about 50 lb of walnut shells about
once a shift. This will usually reduce the cooler outlet
temperature to 80°F to 100°F with each blast.
B. Residual Oil Upgrading-Delayed Coking
Mechanical
QUESTION 33.
For refiners who dispose of waste sludge in cokers
during drum quench, what specialized equipment,
such as storage tanks and pumps, are used?
TREESE:
In Unocal we use cone roof tanks, generally with a
sloped bottom. We are using a rake in one tank. In another
tank we are using a flushing water distributor in the
bottom.
For level gauging in the tanks, we have used radar
gauges as well as conventional float level gauges. Some of
the tanks are blanketed with vapors sent to an odor
abatement system. Others are not blanketed. It is very
much a mixed bag on the tanks. We also have dilution
water and dual mixers in some of the tanks.
For pumps we use progressing cavity pumps, like
Moyno’s or some of the similar pumps.
For flow, we generally use one meter for both the water
and sludge. In one location, we started out with a magnetic
flow meter, but the element in it tended to foul, so we
replaced it with a Coriolis meter which has been working
1994 NPRA Q&A Session on Refining and Petrochemical Technology
well. At another location, we have used a standard orifice
meter, and I assume they have to replace the orifice
periodically.
At one refinery, for controls, a PLC times the events
and constantly monitors the drum overhead temperature,
feed tank level, the total sludge volume injected, and the
flow rate. If any of those reach preset limits, the injection
is automatically switched back over to water.
BOYCOTT:
We license the Mobil system for sludge coking. The
equipment basically is the same as Mr. Treese just de-
scribed.
I would reiterate that the tank must be well mixed. We
employ a large vertical mixer in our tank and use an orifice
meter for metering the injection of the sludge.
DEATON:
I have had good experience storing sludge in a specially
designed cone bottom tank. The cone bottom was heated
by electric panels to prevent freezing. There were also three
150 lb steam blast points in the cone bottom to dislodge
sludge, if necessary. The cone bottom fed into a positive
displacement pump with a progressing cavity barrel.
Tank capacity was about 2,000 barrels and was de-
signed with water and oil drawoff lines on the side of the
tank. Sludge was pumped into the tank over a period of
about two months, while water and oil were allowed to
separate and were drawn off. When there was no more
room for water and oil separation, the coker was switched
from anode grade operation to fuel grade operation, while
the sludge was disposed into the coke drums during drum
quench. The sludge was disposed over a period of about
one month. We typically injected about 50 barrels of
sludge into each coke drum, and each coke drum con-
tained about 250 tons of coke.
QUESTION 34.
We use a multiport valve to switch drums. What types
of valves are used downstream of the multiport valve
for positive isolation of drums? How often do the
multiport valves have to be removed for repair and
what are the most common repairs? Does anyone rely
on the multiport valve for positive shutoff while down-
stream valves are changed out or do you fake a unit
shutdown?
PORTER:
We use wedge plug valves downstream of our multiport
switch valves for positive isolation of coke drums. The
multiport valves are typically serviced only during major
unit shutdowns. This servicing normally consists of clean-
up followed by build-up and machining to return them to
original clearance/tolerance specifications. We do not rely
on the multiport switch valve for positive shutoff while
85
TOC/INDEX
the downstream valve is changed out, but rather take a unit
or module shutdown for the change out.
TREESE:
Our practice is almost identical. We use wedge style
valves. They are hydraulically-operated, and remotely-op-
erated, downstream of the Wilson-Snyder multiport valve.
And we expect the multiport to last from turnaround to
turnaround. At the turnaround, we do standard valve
maintenance and cleaning.
We would never use the multiport valve for isolation
by itself. We would take a shutdown first.
BOYCOTT:
We also use a Wilson-Snyder multiport valve for drum
switching. Gate valves downstream of the multiport valve
are used for isolation. We do not rely on the multiport
valve for positive isolation. The multiport valve is rebuilt
every 2 to 3 years.
CUNEO:
We use gate valves downstream of the multiport valve
for isolation, and like the other panelists, we would not
rely on the multiport valve for positive shutoff.
DEATON:
My experience is with wedge plug valves manufactured
by Stockham Valve Company. A manually-operated hand
wheel and gear assembly lifts the plug about one-half inch,
rotates through 90°, and then lowers the plug into position
with a rotation to grind coke solids as the plug seats. Steam
injection ports are located at the bottom of the valve body
and at the top of the valve bonnet to keep coke from
building up.
One key that I have found to long operation depends
on the ability of valve repair shops to lap the wedge plugs
into the valve seat in such a way that there are no crevices
or obtruding surfaces between the plugs and the valve seats
where coke can build up.
My experience with multiport switching valves is with
Wilson-Snyder valves. These valves remained operable
between shutdowns for heater burnout, which varied be-
tween 6 and 12 months. We kept a spare valve and changed
out valves each time we went down for heater burnout.
The valve that had been in service was sent out for
overhaul, and I was not aware of any unusual repairs.
When changing out a drum isolation valve downstream
of the multiport switching valve, I also recommend taking
a unit shutdown rather than relying on the multiport valve
for tight shut-off. Multiport valves frequently leak
through, and there is also the possibility that the operator
may not have properly seated the multiport valve. The risk
to personnel being burned by spraying black oil at tem-
peratures in excess of 900°F is too great.
86 Heavy Oil Processing
Process
QUESTION 35.
Has anyone found a specific relationship between
reduced cycle times and problems with coke drum
distortion, cracking of infernal clad layer, etc. ? Please
discuss any special procedures used to alleviate prob-
lems, i.e., quench safe, special quench distributors,
etc.
PORTER:
We have found a correlation between the total number
of cycles a drum has been through and the frequency of
drum cracks. We suggest you take this into account before
you reduce cycle time.
One way to reduce the cycle time is to quench at a faster
rate. We have analyzed the thermal stresses on the drums
during the cooling step and have determined that more
rapid cooling will ultimately shorten the life of the drums.
Faster cooling can also result in hot spots and possible
blowbacks. We have elected to find other ways to shorten
the cycle, and have not made major reductions in the drum
cooling time. We have not done anything else to alleviate
problems during the cooling step.
BOYCOTT:
During the past five years our coker has been expanded
from 4,500 bbl/d to 10,000 bbl/d. We have a three drum
operation with 16 ft diameter by 90 ft tangent to tangent
drums. As a result of the expansion, drum fill times have
been reduced from 20 to 24 hours to 10 to 12 hours. We
have not experienced increased drum distortion and crack-
ing problems since the cycle times were shortened. We
believe that we have been successful in avoiding worsened
problems by not sacrificing quench times. We believe that
this is the time of greatest stress on the drums, and so
proceed as slowly as possible. We typically quench for four
hours after steaming.
D'AURIA:
The predominant cause of coke drum failures is crack-
ing caused by thermal fatigue. The two portions of the
coking cycle most critical to minimizing potential thermal
fatigue are the preheat and the quench steps. Increasing
the preheat temperature prior to switching to hot feed will
minimize the thermal stresses at the feed cut-in point.
The quench portion of the cycle is the most severe, and
produces the greatest stresses. Increasing the quench rate,
to decrease cycle time will increase stress and is not very
advisable.
Foster Wheeler has developed a computer program that
models the quenching operation. This program can be
used to predict an optimum quench rate schedule that will
minimize the thermal gradients in the coke drum shell
during this very critical period. Use of this program will
TOC/INDEX
also minimize the load of quench vapors sent to the
downstream blowdown system.
LINDA D. LORD (The Coastal Corporation):
At one of our refineries, when we begin cooling a drum
we go through what is called the “big steam” step first,
before injecting water. I have seen recommendations to
discontinue the “big steam” step, but there is a payoff in
drum life. Has anybody else done this? That is, has anyone
eliminated the “big steam” step and seen any effect on
drum integrity or drum life from doing that?
BOYCOTT:
We maintain the steaming both to the fractionator and
then to blowdown prior to the quench cycle.
QUESTION 36.
What is the experience on using stripped sour water
as coke cutting water for coke drums with respect to
corrosion in the system? We experience severe cor-
rosion while using untreated water.
BARLOW:
We do not have direct experience with this method.
However, in stripped sour water, typical contaminants run
with H2S residual concentrations of less than 50 ppm, low
concentrations of tramp amines from the amine sweeten-
ing units and residual ammonia generated from some of
the water washes. We would not expect these contami-
nants to cause any significant corrosion concerns above
and beyond what is already normal in the coking system,
since H2S and ammonia are generally present at higher
levels. So we would expect this to be a reasonable water
source. However, there may be some odor concerns and
possibly some coke quality concerns, depending on the
contaminant levels.
CUNEO:
We have not yet done it either, but we would consider
stripped sour water as a good source for water. The only
issue would be the odor.
DEATON:
Clark’s Hartford refinery has used stripped sour water
for makeup to the jet water tank for over 20 years with no
side effects.
QUESTION 37.
What is considered the maximum coke drum velocity?
What can be done to eliminate the carryover of coke
fines at high drum velocities?
PORTER:
We consider design coke drum velocity to be maximum
and do not exceed it. At Pascagoula, we calculate velocity
1994 NPRA Q&A Session on Refining and Petrochemical Technology
on-line and make process adjustments so as not to exceed
that limit.
We do not think you can totally eliminate coke fines
carryover. You can reduce it by:
not exceeding the design velocity limit, especially
near the end of a fill, when disengaging space is low.
not exceeding proven coke drum outage limits. You
must know where your coke drum level is and
control it. This means you must take good care of
your drum level indicators and be sure to make
effective use of antifoam.
CUNEO:
I certainly agree with all of Mr. Porter’s comments, and
we would say it is also important to avoid any sudden
pressure surges during the drum switch.
QUESTION 38.
Are there any commercially proven green coke sam-
plers and/or methods which provide reliable results?
TREESE:
Unocal does not employ automatic samplers. We take
grab samples of the coke and composite them. And we do
not use any special equipment or techniques.
We are aware of at least one case where there is an
automatic sampling system from the conveyor belt, but I
do not have any details.
Certainly, the techniques employed for belt sampling
in the mining industry would be applicable for coke
sampling anywhere you are doing dry coke handling. At
least one of our plants has wet coke handling so it is not
possible to use belt sampling methods.
CUNEO:
We do not have any special samplers. We do try to
obtain a composite green coke by taking top, middle and
bottom samples out of the coke pile as part of the quality
assurance program on the green coke. Overall, this is fairly
reliable but there are, from time to time, problems with
the samples not being representative.
DEATON:
We and our coke purchaser are not aware of any coke
sampling methods other than using a shovel and bucket.
Our coke purchaser requests that we sample each rail car
in eight to ten different locations. He also specifies that
we dig down 2 ft to grab each sample. These samples are
then, of course, mixed and composited for the final rep-
resentative sample.
QUESTION 39.
Have problems been experienced with structured pack-
ing in a potential coking service such as the coker main
fractionator? Were any modifications made to help?
87
TOC/INDEX
D’AURIA:
The use of structured packing in the main fractionator
of the coker has to be considered very carefully. There are
certain areas where you can get into trouble, particularly
if you are running a very low recycle or ultra-low recycle
operation, defined as less than 5% recycle. At these low
recycle rates, Foster Wheeler does not recommend install-
ing packing in the wash section of the fractionator. The
low wash rates associated with low recycle operations will
not adequately wet the packing, and could result in plug-
ging and increased fractionator pressure drop. The mini-
mal recycle rate acceptable for the use of packing in this
area is about 7% to 8%. Sieve trays have been used
successfully at recycle rates as low as 4% to 5%, however,
tray fouling becomes a concern at low rates.
Recently Foster Wheeler has developed a new design
for these ultra-low recycle rates, which replaces the wash
zone trays with a direct contact spray chamber. Baffles are
located below the spray chamber to allow heat and mass
transfer to take place in the spray zone without the use of
packing or other internals. These chambers can be in-
cluded in new unit designs, or retrofitted into existing
units.
In actual operations, the spray chamber design has
allowed recycle ratios as low as 2% to be maintained. If
required, the spray chamber design allows for wash oil
turndown rates as low as 25%.
ANDREW W. SLOLEY (Glitsch, Inc.):
As regards structured packing and coker main frac-
tionators, we believe it is a proven device for heat removal
and moderate liquid rate loading zones in the main frac-
tionator HCGO pumparounds and higher sections. How-
ever, the application in the HCGO pumparound does take
some care to avoid the possibility of fouling from the coke
fine carryover. We know of no successful applications in
desuperheating and low liquid rate services.
QUESTION 40.
Has anyone found a correlation between feed compo-
sition (i.e., Conradson carbon residue, sodium) and
coking of heater tubes?
BARLOW:
Through our research efforts on coker furnace fouling,
we have been able to gain some genera! correlations be-
tween feed composition and coking of heater tubes. How-
ever, these correlations are not such that we have been able
to develop any predictive models. There is a lot of variabil-
ity in the analytical techniques as we!! as in the perform-
ance on the furnaces. Incident fouling of the furnaces
tends to contaminate our data, making it is very difficult
to draw direct correlations. A general correlation that we
see, is that the Conradson carbon value is an indicator of
the furnace fouling tendency. However, operating and
88 Heavy Oil Processing
mechanical factors have a greater impact on this. Also,
increased metals in the feed do correlate with an increased
tendency of the furnace tubes to foul. Specifically, iron and
sodium levels have been shown to correlate with increased
fouling in the furnace.
CUNEO:
I agree with everything that Mr. Barlow has said. Addi-
tional things that have to be taken into consideration are
heat flux, tube velocity, flow regime, the amount of vapori-
zation, and firing patterns in the furnaces.
D’AURIA:
There are correlations between feedstock composition
and heater tube coking. Higher feed Conradson carbon
content relates directly to heater tube coking. Sodium, and
other alkaline metals, act as catalysts to accelerate the rate
of coking in the heater tubes. Our specification is 10
weight ppm maximum sodium in the coker feedstock.
Heater run lengths of one year are normal when sodium
is held below this level, but operating data shows a rapid
increase in heater coking rate as feed sodium content
increases. For example, one refiner experienced an increase
in sodium from 10 to 17 weight ppm and saw heater run
lengths decrease from 1 year to 6 months.
In addition, our experience is that more paraffinic
crudes tend to give shorter heater coking cycles than the
naphthenic or aromatic types. This is due to the lower
solubility of asphaltenes in paraffinic feedstocks. As the
paraffinic feed cracks in the heater tube, there is a greater
tendency for the asphaltenes to drop out of solution and
form coke in the heater tubes and transfer lines.
QUESTION 41.
What strategies have you used to extend run times
between furnace decokings?
DEATON:
One method is to use some of the antifoulants that are
on the market today. Clark’s Hartford refinery has ex-
tended run times up to 20% by using a Petrolite product.
Also, steam or boiler feed water should be injected into
the heater passes. Our steam-to-oil ratio is 1.75 1b/bbl.
BARLOW:
We have seen the most significant improvements in
coker operation made by striving towards a steady, con-
tinuous operation; improving the reliability of the unit.
The biggest problems we have seen have been with what
we call “incident fouling” due to such events as pump
failure, strainer blockage, and harder furnace firing. Elimi-
nating or reducing these incidents greatly improves the
overall operation.
We have had success with our Betz Thermoflo anti-
foulant programs. We address coke formation through
TOC/INDEX
patented chemistries. We address the coke growth mecha-
nism by reducing the filamentous type coke formation.
We also incorporate dispersant packages that help move
particles through the system as they form.
BOYCOTT:
I agree with Mr. Barlow on the effect of steady opera-
tion on furnace fouling. As to other efforts to reduce
fouling, we inject distillate at a rate of 10% of unit charge
into our heater passes to increase pass velocities and reduce
coking. We also inject boiler feed water to maintain a
constant pass inlet pressure and provide mass flow in the
case of a loss of unit charge. The main effort we have made
to increase run length has been to provide for furnace
decoking with the unit on-line. We operate two furnaces
in parallel in coke drum service. We have installed valving
to allow one furnace to be decoked while the other remains
on-line. We do not use chemical injection in our furnace
passes to try to extend run lengths.
FELTROP:
I agree with Mr. Deaton’s comments, in particular on
the Clark’s Hartford refinery, where the high temperature
stable antifoulant has been shown to be successful, but the
costs are relatively high.
The particular problem at Hartford is inadequate de-
salting, and we are in the process of working with the
Hartford people to improve their desalting. We expect that
the use of that antifoulant will either be diminished sig-
nificantly or discontinued.
Sodium contents in the coker feed are a significant
contributor to this problem, and as mentioned by Mr.
Deaton, less than 10 ppm is a good rule of thumb. We
have seen cases where 40 ppm are certainly disastrous and
can result in run lengths of less than 1 month.
PORTER:
The pane! has covered all my comments, other than we
have tried antifoulants at several locations and have not
found them to be cost-effective. Currently, we are not
using antifoulants in any of our cokers.
TREESE:
I think I would reinforce the importance of stability of
the operation. We also do monitor tube skins fairly closely.
One thing we are trying that is a little bit different than
what has been mentioned is that we are working on
optimizing the heater excess oxygen. The thought here is
that improper excess oxygen results in poor flame patterns,
so you end up with a very high tube flux over a shorter
section of the heater tube. This would result in coking in
that region. From our standpoint, right now, the results
on this test are still pending.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
LINDA D. LORD (The Coastal Corporation):
On the subject of heater fouling, I have-heard of people
having good results from alonized tubes.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
My question is regarding the on-line decoking. What
are the typical problems you encounter during the on-line
decoking operation; and how long does this operation take?
BOYCOTT:
I should clarify myself. Our two furnaces are operated
in parallel. One furnace is taken off-line and receives a
standard decoking procedure. It is then brought back
on-line. The other furnace is then taken off-line for decok-
ing if necessary.
One problem we have had is coking of the furnace
isolation valves. We have been making modifications to
the steam purge on the isolation valves to try to ensure that
we can actually get the furnaces off-line and back on-line
as planned.
PORTER:
We do an on-line decoking. We call it a spall, where we
have a 4-pass furnace and we will take one of the passes
off-line and spall that pass using condensation.
SIM ROMERO (BP Oil Company):
Is there a preference to use boiler feed water or steam
when you on-line spall?
PORTER:
We use condensate.
QUESTION 42.
Does anyone add FCC slurry oil to the coker feed?
What percent of this feed is slurry oil? How does this
affect charge rate? Can you make anode grade coke?
CUNEO:
We do charge FCC slurry oil to our Norco coker while
we produce anode grade coke. The volume percent is not
a fixed number. It can range from 10% to 20% of total
charge. It is determined by the green coke quality. In order
to meet the green coke silica specification set by our
customers, the amount of fines in the slurry has to be
carefully controlled.
DEATON:
Refiners have added FCC slurry to the coker charge and
produced anode grade coke. Charge rate is not affected by
slurry in the feed. The typical maximum slurry content is
usually about 10% of the feed, although we are aware of
one refiner who has run the slurry content as high as 15%.
Coke produced from feed with too much slurry has a
tendency to “popcorn” in the calciner and this, in turn,
89
TOC/INDEX
reduces the vibrated bulk density and makes the coke
unacceptable for anode grade. Also, as Mr. Cuneo pointed
out, you must filter or settle the slurry to remove catalyst
fines and thus prevent exceeding the silica specification in
the anode grade coke.
McLEAN:
One thing that is common is for people to feed coker
gas oil back to the FCCU. They run the risk of building
up a very refractory recycle loop if they also feed FCC
slurry oil to the coker. One way you can minimize this
would be to hydrotreat the coker gas oil before it goes back
to the FCCU.
PORTER:
We feed FCC slurry at two locations. One of them
makes anode grade coke and feeds about 10% slurry to
the unit. The effect of slurry on coker feed rate depends
on the constraints that the particular coker is up against.
Slurry makes less coke and more liquid product than
residuum feed.
C. Residual Oil Upgrading-Fluid Coking
QUESTION 43.
What are the effects on coker operations and product
quality resulting from recovery of refinery F- and
K-wastes as coker feedstock? Specifically,
a. what is the maximum percentage (versus total coker
feed) of waste materials which can be used;
b. does the decision to use waste materials as feed limit
the operation to the production of “green” coke (as
opposed to anode-grade coke);
c. what are the typical impurities (metals, trace organics,
etc.) which can be expected to be present in coke
produced, at /east in part, from waste materials; and
d. what pretreatment, unit operations, material handling
equipment, etc. is typically required in order to feed
refinery wastes to the coker?
D’AURIA:
We are aware of several cokers which utilize structured
packing in the fractionation, wash zone and pumparound
sections of the main fractionator. The decreased pressure
drop associated with the use of structured packing allows
the unit’s operating pressure, and therefore its coke yield,
to be reduced. However, the use of structured packing
should be considered on a case-by-case basis.
For example, valve trays have historically been specified
for use in the coker’s main fractionator, with sieve trays
being utilized in the fractionator’s wash section. With the
advent of ultra-low recycle operations (less than 5% recy-
cle), the design of the fractionator’s wash section takes on
90 Heavy Oil Processing
additional importance since the performance of the wash
zone controls both the end point and the quality of the
coker’s HCGO product. Consequently, the use of packing
in the wash section of the main fractionator of an ultra-low
recycle coker is not recommended, since the low wash rates
associated with these operations will not adequately wet
the packing and could result in plugging of the packing
and increased fractionator pressure drop. If used in the
wash zone, the minimal acceptable recycle rate typically
considered for packing would be approximately 7% to
8%, which is much higher than current low-recycle coking
operations. With sieve trays, however, we have seen recycle
rates as low as 4% to 5%. However, there is an increased
tendency toward tray fouling at these low recycle rates.
For these reasons, recent Foster Wheeler cokers which
have been designed for ultra-low recycle operation have
replaced the wash zone trays with a direct contact spray
chamber. Baffles located below the spray chamber allow
heat and mass transfer to take place in the spray zone
without the use of packing or internals. These chambers
can be included in the original design of the unit or
retrofitted into existing units. In actual operations, the
spray chamber has allowed recycle ratios as low as 2% to
be maintained. Additionally, if required, the spray cham-
ber design allows wash oil turndown rates as low as 25%
of design to be maintained.
ALLAN M. EDELMAN (Exxon Research & Engineering Company):
Let me answer question number 43 for fluid coking
units. Refinery waste streams have been run to some of the
fluid coking units. The waste stream qualities vary signifi-
cantly, including water content, metals, and other impu-
rities. These streams can have an impact on the unit heat
balance, so large quantities can result in reduced residual
feed rates.
With respect to the first question, there is not a firm
maximum percentage of waste material that can be run.
We have to produce an adequate amount of coke for heat
balance, and have some product coke to purge the metals
and other impurities. So far, waste streams have been less
than 5% of the feed rate to commercial fluid coking units.
With respect to the second, there are no fluid coking
units that currently produce anode grade coke.
With respect to the third, most of the impurities from
the waste streams are concentrated in the product coke.
Some of the impurities can volatilize and leave the reactor
and/or leave the burner. High levels of volatile impurities
can lead to ammonium chloride deposits in the fractiona-
tor and possible deposits in the burner cyclones.
With respect to the fourth, the streams are usuaIly kept
well mixed to avoid solid settling, and strained to remove
large solids that would harm pumps or plug feed injectors.
Some locations dewater the streams to minimize heat load
and sour water production.
TOC/INDEX
D. Residual Oil Upgrading-Visbreaking
QUESTION 44.
What has been the experiences with using
deasphalted oils as visbreaker feeds? What conver-
sions have been achieved? Have operating problems
been experienced?
D'AURIA:
The simple answer is we do not know of anybody who
does this. UOP has designed a visbreaking unit which
processes the pitch, rather than the deasphalted oil, from
a Demex unit. This unit has been operating for a number
of years and gets about 6 wt% to 7 wt% conversion of the
pitch. The residual product from the visbreaker is blended
in with light cycle oil, about 40% light cycle oil, to make
No. 6 fuel oil. The unit was recently revamped to increase
its capacity to about 125% of the original design.
EARL ZICKEFOOSE (Scaltech, Inc.):
We work with numerous refineries on feeding hazard-
ous waste to cokers, and we have worked both on the feed
1994 NPRA Q&A Session on Refining and Petrochemical Technology
side and on the quench cycle side. We have found that
for the coker operation, the quench cycle side seems to
be the best way to go. If the waste has had all the free oil
removed and it has had a substantial reduction of particle
size, there are not any visual problems whenever you
dehead the drum. The traditional odor and hot spot
problems usually associated with the addition of the
rough sludge, either in the feed or quench cycle, are
eliminated by doing it that way.
Using a processed waste solid stream allows the injec-
tion of solids in the quench cycle to a much lower tem-
perature due to not having to volatilize the free oil.
We have had success adding from 0.05% to 0.1% of
coker production as waste solids. As an example, in a Gulf
Coast refinery, we routinely add 12 to 16 tons per day of
oil-free solids waste to the quench cycle of a 1,600 ton per
day coker, and we return 200 to 400 barrels per day of
clean oil to the refinery.
The process waste solids may be used when producing
anode grade, but may have to be fed at reduced rates due
to the higher ash content.
91
TOC/INDEX
III. HYDROGEN PROCESSING
A. Hydrogen Production
Hydrogen Manufacturing
QUESTION 1.
Is it possible to process butane over steam-methane
reforming (SMR) catalyst for production of hydrogen?
What is the penalty vis-a-vis SNR (naphtha) catalyst?
PORTER:
The catalyst vendors are best suited to advise you on
what to expect with your particular catalyst. In genera!,
some butane can be processed over SMR catalyst with
minor impact on the unit operation. The major factor in
evaluating the penalty is the percentage of butane in the
feed. There may be a slightly lower conversion and higher
coking rate with the butane feed. Coking can be controlled
by adjusting the steam to carbon ratio. If the plant is to be
switched from natural gas feed to butane feed perma-
nently, a catalyst change may be advisable. If the unit feed
quality is to be varied frequently, it may be advisable to
load a mixed charge of catalyst.
CUNEO:
I agree with Mr. Porter. Our only real experience with
butane over SMR catalysts has been limited to that which
is normally found in refinery vent gas strainers, which
would have been we!! less than 5%.
KEN CHLAPIK (ICI Katalco):
ICI Katalco as an operating company has a lot of
experience in operating feedstocks from natural gas
through naphtha. With respect to processing 100% bu-
tane, nonpromoted methane steam reforming catalysts
can operate without concerns for coking. The steam to
carbon ratio required is around 6 to 7. If you look at using
a lightly alkalized catalyst, this value can be lowered to
around 4 to 5. In most cases, these operating conditions
are either impractical or uneconomical for the overall
operation.
If we look at naphtha catalysts, the steam to carbon
ratio can be lowered even further; down to 2 to 2.5.
However, this is lower than steam limit for PSA-based
plants. Naphtha reforming catalyst is formulated to han-
dle the complexities of the hydrocarbons present in the
naphtha. In accomplishing this, the catalyst does lose some
of the methane reforming activity.
92 Hydrogen Processing
ICI Katalco has realized this and, as a result, has devel-
oped a dual feedstock catalyst that can handle the flexibil-
ity of the kind of operation that refiners are looking for,
i.e., the ability to process different feeds from natural gas
through LPG’s with very little change in overall reforming
activity. LPG feeds on this type of catalyst can operate at
steam to carbon ratios around 2.5 to 3. Prior to this ty!Je
of catalyst, the choice of catalyst meant there would be loss
of catalyst activity for methane reforming or the inability
to process the butane practically. We feel we have removed
this situation with our dual feedstock catalyst.
ANDERS NIELSEN (Haldor Topsoe A/S):
We agree it is only possible to steam reform butane over
a typical steam natural gas catalyst at a noneconomical
steam to carbon ratio. The steam naphtha reforming
catalyst, as we use it, is normally used for naphtha feed or
for alternating between naphtha and a lighter feed.
For processing of butane, we typically use an alkali
promoted catalyst in the top of the tubes and a natural gas
catalyst for the main part of the tube. We have supplied a
number of such units. A typical operation that has been
going on now for three years without problems has a steam
to carbon ratio of 3.5, an average heat flux of 24,000 BTU
per square foot inner tube surface. Of course, all the
butane is converted to methane, carbon oxides, and hy-
drogen in the top few feet of the tube, and that is the reason
you only need to have a special catalyst in this part of the
tubes.
DARRELL SCRUGGS (Kinetics Technology International Corp.):
As both catalyst suppliers have said, it is uneconomical
to feed butane over NG catalyst with high steam to carbon
ratios. We presume this is a question from someone that
wants to switch feed without taking the time to shut down
and change catalysts. Under those circumstances, with a
high steam to carbon ratio you can continue operation
under conditions that require, as Mr. Chlapik said, a steam
to carbon ratio of somewhere around 6 or 7 to 1. It also
requires a higher hydrogen recycle rate. The plant will be
limited in capacity mainly by the condensing capability of
the cooling train, particularly the process gas cooler. When
feeding 100% butane, capacity will be somewhere around
65% to 85% of the name plate capacity on natural gas.
There is really no penalty to initially design for feed-
stock flexibility of natural gas through butanes. There is
really no appreciable effect when feeding methane or
refinery gas over a dual feed type of catalyst. If you are
TOC/INDEX
running butane you need to be careful, not only as Mr.
Porter said for the heavy ends, but also to watch out for
the olefin content to make sure that you have a sufficiently
large Comox reactor (and for heat effects). You also must
be careful about steam-cracking in the feed preheat coil
because you must maintain a lower feed temperature of
under 1,000°E
A simpler solution might be to put in a prereformer
which allows operation with a wide range of feedstocks
over natural gas catalyst in the reformer.
ROSS BRUNSON (United Catalysts, Inc.):
One of the things to keep in mind is that in the last few
years, all of the major catalyst suppliers have developed an
intermediate type catalyst for butanes that apparently has
no penalty with respect to running straight natural gas
catalysts. If a particular refinery can limit the quantities of
CGS in the butane received, they can use this intermedi-
ately promoted catalyst. If they have to go to the full
naphtha catalyst, then they will run into some of these
activity penalties or limitations that will limit either
throughput or life with a particular charge of catalyst.
QUESTION 2.
Is more methanol formed over the new generation of
copper-promoted high temperature shift catalysts
than over the traditional types?
ARMBRESTER:
The short answer to this question is yes, the copper
promoted catalyst will produce more methanol than the
traditional catalysts do.
The methanol formation is kinetically driven and will
proceed to equilibrium at high reactor temperatures.
However, at the temperatures we typically see at the high
temperature shift reactor outlet, around 700°F to 750°F,
the equilibrium level of methanol is very low, in the 10
ppm range. If you were to use this catalyst in the low
temperature shift reactor, then the equilibrium level is
considerably higher, in the 100 ppm to 200 ppm range.
At our Saint Paul Park refinery, our hydrogen plant uses
a high temperature shift reactor and a PSA unit, so we do
not see a problem with methanol production.
KEN CHLAPIK (ICI Katalco):
I concur with most of Mr. Armbrester’s comments. I
first want to reference a question at last year’s NPRA Q&A
which covered methanol formation from low temperature
and medium temperature shift catalyst. To clarify this area,
once again, the copper on the high temperature shift
catalyst will promote methanol formation, but the equi-
librium level is extremely low compared to the level at the
operating conditions of a low temperature shift. In the low
temperature shift, however, the kinetics are not good
enough to reach the equilibrium level. In so saying, the
1994 NPRA Q&A Session on Refining and Petrochemical Technology
levels experienced are what Mr. Armbrester said, about
100 ppm to 200 ppm on a volume basis. At the high
temperature shift operating conditions, the kinetics are
strong enough to allow the equilibrium level to be
achieved but it is much lower, around 30 ppm to 60 ppm
by volume.
Is there an environmental concern about having 30
ppm to 60 ppm methanol taken out in condensate or
going to atmosphere out of a deaerator after exiting a high
temperature shift in a PSA based hydrogen plant?
ANDERS NIELSEN (Haldor Topsoe A/S):
I do not agree that the copper promoted shift should
make more methanol than a classic high temperature shift.
The copper promoted high temperature shift catalyst will
make methanol in the same amount as the traditional high
shift, which converts to equilibrium at the exit conditions.
QUESTION 3.
What burners or burner management systems are
recommended for hydrogen plants which have wide
ranges of operations, e.g., 20% to 100% of design
capacity? For hydrogen plants which use PSA offgas
as fuel, what burner/operating problems might be
expected with this fuel quality and low pressure?
ARMBRESTER:
Ashland uses Callidus burners in the hydrogen plant
at our Saint Paul Park refinery. The burner management
system that we use was designed in-house, and is con-
tained in a triple redundant, stand-alone PLC manufac-
tured by Triconex. We have flame scanners on each of the
four burners, and failure on any three of the burners will
trigger a heater shutdown. This unit, as I mentioned
earlier, does have a PSA which we have operated over a
wide range of production rates, approximately 25% to
100% of the design, and we have not seen any apparent
burner problems.
BOYCOTT:
Frontier operates a 5.5 MMSCFD hydrogen plant
through the range of 25% to 100% of design capacity. PSA
offgas is burned as fuel in the reforming furnace. The
Burner Management System is controlled by a local Allen-
Bradley PLC repeating on the TDC system. The BMS
controls all fuel gas, waste gas, air, etc. It also contains the
furnace shutdown trips. Regulatory feedback from the
TDC system is not required for a furnace trip. Other than
initial start-up problems, it has proven very reliable. The
waste gas is beneficial in reducing flame temperatures and
NO, emissions because of its high CO2 content. It has not
caused any problems in the operation of the unit at lower
rates. We do set the PSA cycle times below 40% of unit
design rate to maintain a constant waste gas pressure.
When reducing unit charge rate it is important to know
93
TOC/INDEX
the reforming furnaces’ minimum mass flow requirement
and maintain it with steam rate.
RONALD BREDEHOFT (Kinetics Technology International Corp.):
KTI typically designs for an operating range between
40% and l00%, and we have no operator intervention in
these kinds of turndowns.
One of the problems you have at the lower operating
conditions is unstable flames, and if they are unstable one
of the things that we do install is a dual gas system to each
of the burners and so you can turn off one of the sources
of gas as you turn down your burners.
Other than flame stability at the lower rates, the only
other problem is that you get a long lazy flame in some
older low NO, burners. The newer low NO, burners have
resolved that particular problem. Also, this gas is a very
clean gas so you do not really experience any plugging. In
hydrogen plants, we can install safe burner management
systems with or without flame sensors.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Is there any separate flame scanners on the burners,
different from the main burner?
ARMBRESTER:
Our heater has four main burners, each of which is
equipped with a flame scanner. Each of these burners also
has a companion pilot burner, but the pilot burners do not
have separate flame scanners.
BOYCOTT:
No, there is not.
HENRY JONES (Howe-Baker Engineers, Inc.):
We have not experienced any burner problems during
turndown operation to low rates in the range of 30% to
40% of design capacity. However, we do recommend that
if you turn your feed gas rate down below 50% of design
capacity, you leave your steam rate at approximately 50%
of design capacity. This helps your burner operation be-
cause the makeup fuel rate, per scf of hydrogen produced,
is increased somewhat.
QUESTION 4.
Is there any non-heavy metal corrosion inhibitor
which can be used in the hydrogen plant? Does anyone
have experience in using MDEA so/vent in the H2 plant
and what are the associated corrosion aspects?
MENEGAZ:
We are not aware of any non-heavy metal corrosion
inhibitors used successfully in this application. As far as
the second part of the question, MDEA alone probably
would not be the best choice ofsolvent for this application
because it would allow too much carbon dioxide to slip
94 Hydrogen Processing
into the hydrogen product. MEA has been used success-
fully in this application and there are probably some
formulated solvents that would work well here.
BARLOW:
We have been evaluating non-heavy metal corrosion
inhibitors for CO2 systems. They appear to have applica-
bility. We would evaluate their use on a case-by-case basis.
On these systems, expected reduction in corrosion rate is
in the range of 50% to 95%, depending on variables such
as rich loading, heat stable salts, oxygen contamination,
and so forth.
JAMES RONNANDER (Union Carbide Corporation):
Union Carbide has supplied UCARSOL® Solvents for
use in hydrogen plants since the mid-1980’s. The inlet CO2
level is usually 17.5 mole percent and the solvent reduces
the CO2 to approximately 100 ppmv in the product gas.
Concerning corrosion inhibitors, UCARSOL® Sol-
vents do not require any corrosion inhibitors. We have
seen corrosion in some of our plants when the regenerator
insulation has been stripped away or damaged which
results in condensation in the vapor phase of CO2 which
forms carbonic acid.
We have also seen cavitation problems caused by im-
proper flow and pump design. As mentioned by the panel,
if the solvent is not kept in good condition, this can also
create corrosion problems.
We have replaced MEA AmineGuardTM solvents with
UCARSOL® Solvents. Where there has been repairs and
CO2 has been allowed to get behind the repairs or the
flame spray stainless steel coatings, there can be significant
corrosion in these locations. It is extremely important in
CO2 service to do a good job with repairs.
KATHLEEN LEHAN (The Dow Chemical Company):
The GAS/SPEC Technology Group of The Dow
Chemical Company is a leader in hydrogen plant amine
unit applications utilizing MDEA-based specialty solvents
for CO2 removal. Specifically, GAS/SPEC™ (trademark of
The Dow Chemical Company) CS-Plus solvent is utilized
to consistently treat hydrogen streams containing 17.5 to
20.5 mole % CO2 down to less than 100 ppmv CO2. We
are not aware of any non-heavy metal corrosion inhibitors
which can be used in the hydrogen plant. However,
GAS/SPEC CS-Plus solvent does not require a corrosion
inhibitor.
The corrosion rate associated with GAS/SPEC CS-Plus
solvent is minimal, and therefore, not an issue if the
solvent is utilized per our recommended operating guide-
lines. If corrosion does occur, it is usually due to hot, wet
CO2 flashing out of solution, forming an acid and attack-
ing metallurgy. The areas most susceptible would be areas
with CO 2 loadings above recommendations or areas
where CO2 in solution experiences a sudden pressure drop
TOC/INDEX
and/or temperature increase. Such areas can be protected
from this type of corrosion through proper installation of
stainless steel.
QUESTION 5.
Does anyone have problems with vanadium plating out
in their Benfield process? What is the strength of the
vanadium in the system? What is the Benfield stripper
turnaround frequency? What types of internals are
used? Is there a suitable alternate to vanadium?
D’AURIA:
Vanadium acts as a passivating inhibitor by changing
valence state in solution. This means it is solution oriented
and will stay in solution under normal conditions. There
are two scenarios, however, where vanadium deposition
can occur. The first is when the iron concentration in the
circulating solution increases significantly above 100 ppm,
as a result of corrosion or erosion. Then vanadium will
precipitate in a vanadium-iron oxide complex.
The second source of precipitation could occur in the
regenerator overhead water wash system if the reflux water
becomes acidic. This precipitation can be avoided by
injecting a slip stream oflean solution into the reflux water
to keep the pH at 7 or higher in this area.
Regarding concentration, our operating manuals call
for the vanadium concentration in the circulating solution
to be about 0.7 wt%, calculated as vanadium pentoxide.
Small variations around this number are not a problem.
The frequency of turnarounds of the regenerator is
controlled by the associated equipment in the Benfield
unit, and by the related process units. Our experience is
that the average turnaround time for Benfield plants asso-
ciated with refinery hydrogen plants is about two years,
while those associated with fertilizer plants turnaround
about every three years.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Regarding internals, over 90% of the Benfield units use
packing. Packing has advantages of low pressure drop for
the process gas in the adsorber side of the unit, and lower
thermal energy requirements on the regenerator side. Vir-
tually all these units use random packing over structured.
Packing performance is an important parameter in the
Benfield process, and UOP maintains an active program
of evaluating different packing materials as they are devel-
oped by the vendors.
Finally, with respect to alternatives, we have looked for
them but we have so far not found any suitable alternative
to vanadium in this hot potassium carbonate service.
QUESTION 6.
What is the operating experience of using SCR NOX
reduction in steam/methane reforming furnaces?
McLEAN:
Selective Catalytic Reduction involves injection of am-
monia into a combustion product gas stream, and catalytic
reaction of the ammonia with NO, to form nitrogen and
water.
Engelhard’s Environmental Catalyst Group has sup-
plied a number of SCR units for various refinery process
heater applications. None of them, to this point, have been
on steam methane reformers, but I have been told by our
environmental people that there is nothing uniquely dif-
ferent that would be involved there, so it really should not
matter.
With respect to the ones that have been installed and
are operating, they have been designed for both natural
gas with refinery fuel gas as backup, as well as No. 2 and
No. 6 fuel oil firing. NOx reductions of 80% to 90% are
typical design conditions, with maximum ammonia slip
of 10 ppm.
TREESE:
The hydrogen plant at our Los Angeles refinery has a
Foster Wheeler designed SCR system that has worked well
for about four years. When opened recently, we found the
catalyst bed was about 80% plugged with refractory debris
out of the reforming furnace, yet our NOx emissions were
still in compliance during operation.
Temperature control to the SCR catalyst is sometimes
difficult under operating condition variations. The tem-
perature is a little bit at the mercy of what goes on in the
convection coils upstream. Luckily, the present catalysts,
in our experience, have been fairly forgiving.
ARMBRESTER:
Ashland installed a new hydrogen plant at our Saint
Paul Park refinery in 1993, and the heaters on this unit are
equipped with an SCR system. This unit has performed
very well, and stack testing has confirmed that our NO,
95
TOC/INDEX
emissions are in compliance with the regulatory limit of
0.0 137 lb of NOx per million BTU.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Is there any alternative to ammonia injection, like a
caustic or a substitute?
AMBRESTER:
We use ammonia.
TREESE:
You are referring to the ammonia injection upstream of
the SCR bed?
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
That is correct.
TREESE:
There are alternatives to straight anhydrous ammonia
injection. Some people have used aqueous ammonia in-
jection. There are also some systems looking at urea, or
various solutions. People are trying to work toward reduc-
ing the hazards inherent in handling the anhydrous am-
monia. Development is under way but I do not know of
any commercial applications yet.
SCOTT ADAIR (KTI Corporation):
KTI has supplied several steam reformers equipped
with SCR systems, and generally they perform quite well.
Care must be taken not to go fuel rich during operation,
as afterburning will occur on the SCR catalyst and cause
irreparable damage. Again, the main operating concern is
to watch ammonia slip, especially with high sulfur fuel gas
since this can lead to salting of the downstream heat
transfer surface, especially the air preheater.
Under typical operation, NOx can be controlled to 5
to 9 ppm.
RONALD BREDEHOFT (Kinetics Technology International Corp.):
If you have an existing reformer and you want to put
an SCR on it, that is usually a difficult job because the
standard conventional temperature window of 550°F to
650°F is in your convection section. KTI has worked with
Shell on a low temperature catalyst, and has installed one
of these low temperature catalysts on a unit. It will operate
around the 350°F+ range. The catalyst can be added as a
tail-end add-on to an existing reformer.
QUESTION 7.
What is the operating experience of having a forced
or induced draft fan shutdown in a steam/methane
reforming furnace application? What type of upset
occurs and what are the typical emergency procedures
applied?
96 Hydrogen Processing
DEATON:
At our Hartford refinery, the firebox operates at 0.35
inches of water negative draft. If the forced draft fan shuts
down, there is no automaticshutdown but flame impinge-
ment can occur. To prevent this, the damper on the forced
draft fan is opened 100% to allow more air to pull through
it, and the furnace stack damper is opened 100%. Usually,
the charge rate must also be reduced.
If the induced draft fan shuts down, the firebox devel-
ops positive pressure and the unit is forced to shutdown.
Automatic unit shutdown is initiated either on loss of the
induced draft fan motor, or on high pressure in the firebox.
Fuel gas is automatically closed to the burners, and feed
gas is automatically closed to the reactor furnace tubes.
Steam is left in the reactor furnace tubes until the heater
outlet drops to 600°F Nitrogen is then swept through the
reactor furnace tubes. If the induced draft fan cannot be
started up within five minutes, then the forced draft fan
is shut down to prevent cooling the furnace tubes too
quickly.
ARMBRESTER:
Our hydrogen plant at Saint Paul is also designed to
automatically shut down on loss of the induced draft fan,
and the trigger that we use is a two-of-two voting system
on the motor amperes for that fan. If this shutdown
occurs, the reformer feed gas is shut off and recycled to the
hydrotreating section and a reduced amount of steam
continues to flow through the heater passes to help cool
the tubes. The pressure swing absorbers will shut down on
low pressure, and gas from the reformer section is routed
to the flare.
This unit has only been in service for about one year,
and we have not yet had a shutdown of this nature. If we
were unable to restart the induced draft fan and proceed
with a normal relight of the furnace, then we would block
in the feed to the reformers and continue to steam the
heater tubes.
CUNEO:
In our units with induced draft fans, rather than a
complete shutdown we reduce the firing rate to that
which is predetermined to be acceptable for natural draft
operation. The operators then scale back the feed rate
accordingly.
PORTER:
We have induced draft fans on a number of our reform-
ing furnaces. Due to the size of the units, there are multiple
fans per furnace. As a result, loss of a fan is not as
significant as smaller units with a single fan.
Loss of a fan starves the furnace for oxygen. This can
cause the temperatures in the furnace to drop and stacks
to smoke. Emergency moves are made to reduce feed rate
TOC/INDEX
and fuel to the furnace. Usually, this can be done quickly
to restore normal operating conditions at a lower feed rate.
RAVI LAL (Kinetics Technology International Corp.):
A side fired and bottom fired reformer can be designed
to operate at reduced rates on loss of ID fans. For a top
fired furnace, there is an occasional concern that the
reformer must be shut down on loss of ID fan. In practice,
reformers can be designed to make loss of ID fans to be a
rare occurrence, with further precautions such as (a) dual
fans for very large reformers, in the 50 million standard
cubic feet per day range, (b) dual drives (electric and steam
turbine) or a steam ring in the stack which will allow
continued operation at reduced rates. Dropout doors on
the combustion air system can allow operation with loss
of the FD fan, but the burners must be designed to operate
with different draft conditions. If the plant is designed to
be shut down on loss of fan, the PLC shutdown system
should ramp to minimum steam flow through the tubes
and block out fuel gas and feed.
BEN CROMARTY (ICI Katalco):
There are different designs for the steam reformer, with
different design implications. Within ICI, we operate
both top fired reformers and terraced wall reformers, and
there is an operating difference between the two.
In the top fired case, if the ID fan fails then it is
important that the steam reformer is automatically
tripped, along the lines that have been described by the
panel.
With the terraced wall reformer, it is possible, depend-
ing on the reformer design, to operate without the fans.
Reformers of that design, without air preheat and, hence,
only induced draft fans, can be operated at around 60%
of plant load with fan failure.
So there is a difference between whether you have a top
fired reformer or a side fired or terraced wall type reformer.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Is there any blanketing requirement for the catalyst in
the event of an extended shutdown, or will the steam be
adequate?
DEATON:
As I mentioned, we keep steam in the tubes until we
drop to 600°F and at that time we would take the steam
out and purge and blanket with nitrogen. We have had the
unit down under nitrogen blanket for up to 45 days with
no ill effect on performance.
QUESTION 8.
We have experienced failure of our Manaurite XM
tubes on our H2 plant. The failure is in the catalyst
tubes on the outlet at the top of the heater and outside
of the firebox. The failure is on the main tube and not
1994 NPRA Q&A Session on Refining and Petrochemical Technology
on the pigtail. The tubes are top supported. The proc-
ess design outlet is 1,500°F Does anyone have expe-
rience with such a failure? If so, what was the remedy?
ARMBRESTER:
We experienced a tube failure similar to this at our Saint
Paul Park refinery. Initially, the problem was thought to
have been caused by thermal stress and to remedy the
problem, the metallurgy for the failed section of tubes
outside the heater was changed to Manaurite 900, since it
is a softer alloy than XM and can handle the thermal stress
better. However, after further investigation of the failure,
we believe that the primary mode of the tube failure was
a bending moment caused by a large temperature gradient
on the portion of the tubes that are outside the firebox.
The ambient air temperature produced preferential cool-
ing of the tubes, resulting in this bending moment. The
Manaurite 900 alloy may not provide any improvement
in protection against this type of failure.
ANDERS NIELSEN (Haldor Topsoe A/S):
First, we have used Manaurite XM as our standard tube
material for the last two or three years without problems,
but with a different design. We think the cause is that as
the inner tube surface is cooled when it is outside the
firebox, maybe by the top support, you enter into the
Bouduart carbon zone which can, and probably will, lead
to metal dusting, and this can result in rapid failure.
If that is the cause, you should see carbon and pitting
on the inside surface of the tubes in the cold part, and
maybe carbon in condensate. To remedy this situation,
insulation of the top of the tubes may help, and an overlay
of Inconel 600, the aluminum type, on the inside of the
tube, may also be a solution.
RUTH DAVIS (Air Products and Chemicals, Inc.):
Air Products has several small hydrogen plants in the
Far East where we experienced catastrophic tube failures
of the Manaurite XM variety. These tube failures were
within the furnace, and caused large longitudinal splits
along the tubes. Upon investigation of the cause of these
tube failures, we found that the metallurgical formulation
of one tube was not within specification, and therefore the
tube failed prematurely.
The Air Products/KTI alliance builds steam methane
reformer plants to supply hydrogen to refineries. Air Prod-
ucts owns and operates these plants. Our design specifica-
tion has designated that Manaurite XM is an acceptable
tube material in our furnaces, only after requalification of
the material quality control.
GLEN SCHEIRER (Exxon Research & Engineering Company):
Two Exxon hydrogen plants have had through wall
failures of the HP-45/Nb in the radiant tubes. These
occurred in both the tall and short tubes, above the inlet
97
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pigtail and below the internal insulation plug. The failures
were circumferential from inside to out. Independent
analysis concluded the failures most likely to be due to
thermal fatigue caused by refluxing of condensed steam
from the top of the uninsulated section of these tubes. The
thermal stresses were created locally as the condensate
flowed down into the hot zone and cooled the metal. The
problem was resolved by extending the external insulation
higher up around the tubes, consistent with the tempera-
ture limitation of the tube top flange material. The insu-
lation was installed with vents to avoid any combustible
accumulation, should there be a tube leak or a weld leak.
Intermittent on-line acoustical monitoring and inspec-
tion during turnarounds has demonstrated safe operation
for this fix for nearly eight years.
HENRY JONES (Howe-Baker Engineers, Inc.):
We have been utilizing catalyst tubes Manaurite XM
material since 1989. Other than the failure that Mr.
Armbrester talked about, we know of only one other such
case. This was a single tube failure, caused by direct flame
impingement on the tube, when a piece of debris that got
into a burner distorted the flame pattern.
We concur with the solution Mr. Armbrester described
if the problem was caused by thermal stress. Howe-Baker
is investigating other potential causes, and their potential
solutions, to problems like this one.
Hydrogen Purification
QUESTION 9.
Please discuss your experience with automatic purity
control for PSA units.
D’AURIA:
The purpose of automatic purity control systems on a
PSA unit is to allow the unit to operate at constant purity
levels in the product when the feed composition is chang-
ing. The automatic purity control uses a time delay in the
transfer of gases between the adsorbent beds to adjust the
PSA cycles. It brings the impurity level back to its set point
as the feed composition changes. The action is taken
before the product exits the unit, and thereby gives the
advantage of a feed forward type of control. Since the
entire control loop, however, is under feed back control,
the instability that sometimes is associated with feed for-
ward control is avoided in this type of system.
The automatic purity control allows the PSA unit to
operate at a maximum recovery point over a wide range of
conditions. The impact of changes in the process is mini-
mized and the system operates closer to the maximum
allowable impurity point. This results in greater hydrogen
recovery over a wide range of feed composition changes.
98 Hydrogen Processing
We have installed automatic purity controls on ten PSA
plants over the last five years, and we have had good
experience with them.
BOYCOTT:
I agree with Mr. D’Auria.
CUNEO:
We agree.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Regarding the condensate impurities, and primarily
chloride, is there any requirement that it should be free of
chloride. Can anyone elaborate on this?
DARRELL SCRUGGS (Kinetics Technology International Corp.):
A properly designed steam drum will not have any
significant chloride carryover. Unless you have a malop-
crating steam drum, the steam is not a source of concami-
nation for hydrogen plant catalyst. Steam drum internals
should achieve less than 1 ppm TDS for process steam.
Chemicals, blowdown, makeup, and level should be
monitored.
B. Hydrotreating
Mechanical
QUESTION 10.
What is the industry practice used to speed up the
pressurization of 2.25 Cr-1 MO reactors during start-
up? Is there any relationship between reactor skin
temperature and pressure used?
TREESE:
I wish I could say I had new news here, but there is no
way around the heatup and pressurization steps.
In recent years, the chemistry of the 2.25 Cr-1 MO steels
has been improved. This has improved their resistance to
chrome-molybdenum temperature embrittlement. How-
ever, heating up to the cold pressurization temperature
remains a required and necessary step in the unit start-up.
To speed up pressurization, it is necessary to speed up
heating at the cold pressuring temperature. This can be
done by maximizing the pressure, as limited by the cold
pressurization level, and maximizing the mass flow to the
reactor. Heater outlet temperatures should be adjusted so
the heatup is less than 75°F/hr or the differential between
the bed temperatures and the skin temperatures on the
outer wall is less than 150°F. Both restrictions are to avoid
thermal stresses within the reactor wall. Reactor skin
couples aid in monitoring metal temperatures so the re-
finer is able to make a safer decision on when to pressure
the reactors.
TOC/INDEX
Unocal practices in the heatup of 2.25 Cr steels vary
among our locations, depending on rhe vintage of the
reactors. The following guidelines are generally observed:
We keep the reactor below 20% of hydrotest pressure until
the wall temperature is over 250°F and this is sometimes
taken as 20% to 30% of full pressure, which is relatively
conservative. If you work it out, it is about 30%. Above
250°F to 275°F, the reactor is brought up to full pressure.
The exact pressure/temperature increase schedule for a
set of reactors is dependent on the reactor vintage and the
chemistry. On some of the newest reactors, you only need
to go to about 200°F before pressuring up. On old reactors
with known defects identified by detailed fracture me-
chanic’s analysis, we have actually gone all the way up to
350°F before pressuring up. The best guidelines you will
find are from your reactor manufacturer.
On very high pressure hydrotreating units, heatup time
is a problem. This is because a very large mass of catalyst
and reactor is present, and, generally, there is not a huge
volume of gas to heat it up, at least not compared to a
hydrocracker. Spiking the recycle gas with some methane
helps you get a little bit more molecular weight, a little bit
more mass through the reactors. That can help, but you
must keep in mind that you are limited in how fast you
can heat it up by some of the guidelines I mentioned
above.
LAUX:
We also follow our manufacturer’s recommendations on
the minimum pressurization temperature for these reac-
tors, even for 1993 vintage reactors, although this requires
heating up to 275°F before the pressure is raised to the 20%
limit, as Mr. Treese mentioned. That is about 500 psig for
our reactors. We do monitor skin thermocouples to give us
1994 NPRA Q&A Session on Refining and Petrochemical Technology
an indication of where we are. The actual heatup time to
get to the 275°F is about 24 hours, but we do not see any
reason to shortcut this step of the procedure.
PORTER:
We limit the operating pressure to one-quarter of the
design pressure when the external skin temperature of the
reactor at any location is below a specified minimum
pressurizing temperature. Each reactor is assigned a mini-
mum pressurizing temperature based upon its particular
steel, and takes into account “temper embrittlement” of
the 2¼ Cr-1 Mo material from long term operating
service.
SAYLES:
I agree with the comments that were made previously.
The one caution I have is to make sure everyone agrees on
the minimum temperature measurement point and the
minimum temperature value.
D'AURIA:
Our guidelines are similar to those already stated: the
reactor pressure should be limited to 20% of hydrostatic
test pressure, or 25% of operating pressure. This is for
21/4 chrome-l molybdenum reactors. For newer 3
chrome-l molybdenum reactors, this minimum tempera-
ture can be lowered to 200°F.
DEATON:
We do not take any shortcuts for pressurization during
start-up for fear of inducing brittle fracture. We follow
very strict guidelines for our Isomax hydrocracker, which
operates at 1,600 lb. Our guidelines are not to exceed 25%
of operating pressure, or 400 lb, until reactor skin tem-
perature is above 350°F. We watch the reactor bed tem-
peratures and know from experience that a 400°F bed
temperature corresponds to a 350°F wall temperature.
During the warmup period below 400°F, we raise bed
temperatures at a maximum rate of 50°F per hour. If we
are starting up in the dead of winter, when temperatures
are frequently near 0°F in Chicago, initially we raise the
bed temperatures at a very conservative 25°F per hour.
CHARLES McCOY (Consultant):
One serious point to add to what Mr. Treese and others
have said; skin temperatures must be measured, not just
on the shell of the reactor, but on nozzles and manways,
too. You have to get the whole reactor hot. You do nor
want any part of it to fail from brittle fracture.
On a more humorous side, two of our clients have come
up with interesting ways to speed this up. One refinery in
Australia has an idle boiler plant and they have steam
traced their reactor. They just fire up the idle boiler and
heat it up with steam while the rest of the plant is coming
33
TOC/INDEX
out of the shop. The Taiwanese, not to be outdone, put a
giant electric blanket on their reactor - and have a giant
electric plug into which to plug it.
ANOERS NIELSEN (Haldor Topsoe A/S):
When pressuring a vessel in 2.25 Cr-1 MO, you have to
consider the toughness of the material versus temperature,
as in some of the examples given by the panelists. However,
you have to consider two additional points. One, during
heatup, the delta T across the wall may be very significant.
Two, if the vessel has been operating in hydrogen at high
temperature, there will be hydrogen left in the material.
Such a vessel should never be exposed to a high pressure
at a low temperature. The hydrogen moves the toughness
versus temperature curve so that you need a higher tem-
perature in order to apply a certain pressure.
QUESTION 11.
Is a bed of spent hydrotreating catalyst a good feed
filter? If we install a pot in the feed line (to operate at
tow temperature with no hydrogen present) and
charge it with spent HDS catalyst, can we expect
significant removal of tramp solids?
TREESE:
We feel that cartridge or back flush filters are more
effective in removing filterable solids from the feed than
hydrotreating catalyst is. Filters also have the advantage of
being easily replaceable.
Assuming the cause of catalyst bed fouling is confirmed
to be filterable solids, it is questionable how effective a bed
of spent catalyst would be in trapping solids from the feed.
If the quantity of fines will cause a high pressure drop in
the reactor, they will also plug the filter bed. Perhaps, at
lower mass flux, a bed of catalyst can trap out some of the
larger particles in the feed, but some particles, that is
particles less than about 5 microns, will not be removed.
We have no experience with using catalysts or sand beds
to filter feed without the presence of hydrogen. We have
used spent catalyst and sand beds in guard reactor service,
in our Colorado Oil Shale Project, with flowing hydrogen
at 500°F with little success, but we had an abundance of
fines there.
We know of one licensee that uses l/32-inch sand in
bypassable guard reactors at about 300°F to trap solids in
a coker gas oil with some success.
LAUX:
We believe that the spent catalyst will plug up so
quickly, if you really had much of a fouling problem, it
would actually do you no good at all, and that the feed
filter system would be the better thing,
We do have a guard reactor on our lube hydrotreater
system that we take off-line to change out from time to
100 Hydrogen Processing
time. We have not had a lot of success, though, with
isolation valves in that service.
D'AURIA:
We do not think that a bed of spent hydrotreating
catalysts would make a good feed filter. As Mr. Laux said,
we would expect it might actually induce a more rapid
delta P buildup. As Mr. Treese mentioned, there are
specific metals scavenging catalysts and support materials
on the market, and we recommend using them for this
application.
QUESTION 12.
In our atmospheric residue desulfurization units using
Ronningen-Petter type feed filters with 25 micron
opening, we frequently faced excessive backwash.
Backwashing is done with residue feed only. On open-
ing the elements, waxy deposits were observed. On-
line washing with heavy gas oil was not effective.
During the problem period, our typical backwash fre-
quency was 2 to 5 minutes, while normally it was
around 30 to 40 minutes. Has anyone faced similar
problems and what are the suitable methods for clean-
ing such wax deposits?
PORTER:
At Pascagoula, we have not seen this problem in our
residual desulfurizer, which also has a Ronningen-Petter
type feed filter.
If your feed filter is plugging with waxy deposits and
not solids, I suggest you look at the viscosity of the material
you are trying to filter. Viscosity has a marked effect on
filter delta P and backwash frequency. You may have to
raise the operating temperature.
When we take our filters out of service, we generally
flush with middle distillate, rather than heavy gas oil, and
they come out clean.
D'AURIA:
I f waxy deposits are building up in the filter, this is an
indication that the filter is being operated too cold. To
prevent waxy deposits, the filter should be operated at least
10°F above the wax melt point. If the heavy gas oil being
used for backwash has a wax point above the filter tem-
perature, the backwash oil could also be contributing to
the waxy buildup.
Our normal recommendation is to use product mate-
rial as the backwash media, sending the wash stream on to
the product rundown tanks. We have successfully used this
practice for many years. The typical backwash frequency
is about one to two times per shift.
MEHMET Y. ASIM (Akzo Nobel Catalysts):
In our experience with atmospheric residual desul-
furizer, salt content of residual feeds has been identified as
TOC/INDEX
the primary culprit for excessive backwashing. In general,
more than 3 ppm of salt seems to be the critical level.
Therefore, we strongly recommend that you check the
desalter operation.
An excellent reference on this subject is an article by
Petrolite, entitled “Desalters Can Remove More Than
Salts and Sediment” (Oi1 and Gas Journal, April 11, 1988-
page 43).
ARTHUR J. SUCHANEK (Criterion Catalyst Company, L.P.):
I will echo what Mr. Asim said, but also add that one
might be looking at dissimilarity of crudes, which can
cause wax precipitation. I have seen that both on feed-
stocks and products coming from residual hydrotreaters.
PAUL VANCE (Acreon Catalysts):
If you are considering feed filters, I know of a firsthand
experience where a lot of money was spent on the feed
filter system and only after start-up did we find that the
upstream tank was full all the way to the suction nozzle
with scale. Cleaning the tank would have been a quick and
easy solution to that particular problem.
QUESTION 13.
Has anyone removedscale baskets from a hydrotreat-
ing reactor and compared operations before and af-
ter? If so, were there any noticeable differences?
Why?
BOYCOTT:
We have operated both with and without trash baskets
in our naphtha hydrotreater. This unit experiences signifi-
cant pressure drop problems due to the processing of coker
naphtha. I believe we will get into this subject in more
detail in Question 25.
The typical arrangement for our reactor is 3 ft trash
baskets with a graduated bed of inert spheres. The trash
baskets extend through the graduated bed and slightly into
the bed of catalyst. On one occasion, in order to try to
extend runs and due to the fouling problems, we installed
a guard bed of high surface area active support media in
this reactor. We did not use trash baskets when we installed
this bed. The results were almost identical to the runs
utilizing inert spheres and trash baskets, actually close
enough to be indistinguishable. Since that time, we have
gone back to the inert spheres and trash baskets.
I would point out that one useful test, and something
that we have considered, would be a run with the high
surface area, active support media with the trash baskets
installed.
CUNEO:
We have had experience both with and without the
trash baskets. In most cases, the baskets have been removed
because there was little or no accumulated scale. We have
1994 NPRA Q&A Session on Refining and Petrochemical Technology
observed no loss of performance in the cases where they
were removed.
D’AURIA:
The advantage of trash baskets is that they can extend
the time on stream before pressure drop becomes a prob-
lem. There are some drawbacks, the most significant being
poor liquid distribution. UOP does not recommend trash
baskets, but instead we prefer to install graded material at
the top of the reactor. This system provides trash removal
capability with better liquid distribution.
ARMBRESTER:
Our general practice is to use scale baskets in the light
hydrocarbon services where the coking tendency is small,
but in heavier services such as FCC feed hydrotreating, we
use a distributor plate which is primarily designed for
improved mixing and distribution of the feed and hydro-
gen, but also serves to protect the bed from scale and
debris.
We have had a couple of cases at our Saint Paul Park
refinery where we removed the scale baskets for one run.
We did see considerably faster buildup of pressure drop in
those reactors, and as a result, we have re-instituted the use
of the scale baskets.
We have one other case in which we removed the scale
baskets in a solvent hydrotreating reactor and replaced
them with a distributor plate, and in that case we have not
seen an increase in pressure drop.
BARLOW:
We have observed the use of baskets for many years,
and the comment that we would make is that, if you have
a pressure drop problem due primarily to migratory fou-
lant material, we would not recommend removing the
baskets. We have seen that done in one case, and the
subsequent run was disastrous due to high delta I? The
result was shortened run length. If it is not migratory
material, then other alternatives could be attempted.
LAUX:
We have removed the scale baskets from our Number
1 naphtha hydrotreater reactor and have not seen any
increase in the pressure drop buildup over the course of
the run. Based on that experience, we did not install any
on our new Number 2 naphtha hydrotreater reactor, and
we also deleted the scale baskets that were designed for the
first reactor in our hydrocracker. We have not seen any
increased pressure drop due to scale or trash in either of
these reactors either.
Our reasons for removing the baskets are that it does
allow us to load more catalyst, and it also makes for much
easier catalyst dump without the baskets inside the reactor.
101
TOC/INDEX
TREESE:
Our experience has been much the same. The scale
baskets have been of benefit where significant scale accu-
mulation is expected, just because they increase the area
of influx into the bed.
We have had experience where, when the reactor was
opened up, the scale baskets were found to be completely
filled with fines and scale material, and in that case, they
probably helped the unit stay on-line.
If there is really little scale coming into the reactor from
migratory materials, as Mr. Barlow mentioned, the scale
baskets probably are not effective and you would be better
off with a graded bed type design. A graded bed is good
enough for pressure drop protection.
Recently, we removed the scale baskets in the hydro-
treating reactor at one of our Unicrackers, and replaced
them with just a graded catalyst bed, and we have seen no
problems and no unusual pressure drop accumulation.
This is consistent with the fact there was no scale ever
collected in the scale baskets.
CHARLES M C COY (Consultant):
I have preached against scale baskets for a long time
because of the reasons that the panel has said. They may
or may not extend run length, but they definitely extend
the turnaround time. It takes a lot longer to get rid of the
pressure drop, and to clean up the reactor, if you have to
get those baskets out of there. I think Mr. Treese said it
right a moment ago: good bed grading will do the same
job and still not interfere with the turnaround.
BOYCOTT:
I would like to make one comment on the removal of
trash baskets during turnaround. The method that we
have found extremely successful is to chain the baskets
together and to the top head. We simply pull the baskets
out with the chain. This does not extend the turnaround
time.
QUESTION 14.
Dry ice blasting using CO2 pellets instead of sand is
now available for cleaning of reactor trash baskets,
etc. Would the panel please share their experience in
the use of this technique? What are the advan-
tages/disadvantages associated with it?
MENEGAZ:
Several refiners on the Gulf Coast use dry ice blasting
for cleaning the screens on their Platformers. The general
opinion is that the procedure takes about half the time of
doing it by hand with a brush, and results in a much better
job. The cleanup is minimal because the CO 2 pellets,
unlike grit, do not leave any debris.
Dry ice blasting is more expensive than sandblasting,
so it is restricted to special applications.
102 Hydrogen Processing
TREESE:
In Unocal we have not used dry ice blasting to clean
reactor scale baskets and trash baskets. The advantage is it
only removes the hard crust and it does not take away any
of the metal. It has been our evaluation so far that it is just
too expensive to be feasible for what we are trying to do.
We either hydroblast (sometimes using soda ash water) or
sandblast the reactor trash baskets during turnarounds; or,
as I noted before, we just eliminate them.
QUESTION 15.
What is the industry experience with the use of anti-
foolants for hydrocracking or hydrotreating reactor
effluent exchangers?
ARMBRESTER:
Ashland has about 14 years of experience with the use
of antifoulants in our distillate desulfurizer unit at
Catlettsburg. In 1980, we conducted a 90-day, side-by-
side test of two parallel heat exchange trains in this unit,
with one train treated with an antifoulant while the other
train was untreated. This unit was designed for blocked
out operation on either kerosene or diesel feed. The diesel
stream was a mixture of virgin diesel and light cycle oil
from the FCC unit. At the time of the testing, we had been
experiencing rapid fouling of the reactor feed/effluent
exchangers, resulting in excessive pressure drop through
the exchangers and increased firing duty on the reactor
charge heaters. Run lengths between exchanger cleanings
were typically four to eight months, resulting in excessive
downtime and high maintenance costs.
This side-by-side test demonstrated that run length
could be nearly doubled with the use of antifoulant, with
corresponding increases in heat transfer efficiency. Conse-
quently, we have used an antifoulant continuously since
that time.
In 1993, a new diesel desulfurizer was commissioned
at Catlettsburg to meet the low sulfur diesel requirements,
and this unit hydrotreats the mixed diesel/cycle oil stream
exclusively, with the original desulfurizer now used to treat
only kerosene.
We have used a Petrolite antifoulant at a 20 ppm treat
rate in the new DDS unit since the first day of operation,
and have now operated for more than 13 months with less
than a 10% decline in heat transfer. During the same time
frame, the kerosene treater has been operated at an anti-
foulant rate of 9.5 ppm, and the heat transfer has declined
by less than 5%.
BARLOW:
We are involved right now in treating over 50 hydro-
treaters. We have been involved historically in monitoring
and treating over 100 hydrotreaters.
I break this question down into two parts: feed side
fouling, and effluent side fouling of the feed/effluent
TOC/INDEX
exchangers. On the feed side fouling, we focus much of
our efforts away from the traditional use of dispersant
chemistries. Dispersant antifoulant chemistries are ap-
plied to try to prevent agglomeration of foulant material.
They are effective on iron sulfide type foulant materials,
but not as effective, or not as efficient, on polymeric
materials. We concentrate on feedstock characterization
and feedstock handling, as well as, applying the right
polymerization inhibitor, whether it is a free radical foul-
ing problem or a condensation fouling problem. You also
need to go upstream in your analysis if you are using
tankage. Take a look at the tank handling of your feeds
and what kind of oxygen intrusion you incur. Mixing of
feed is very important, too. You may have a straight-run
feed that does not have an oxygen-initiated polymeriza-
tion problem, but when you take that through tankage
and combine it with a cracked feed such as a coker
material, you can create a mess. So we have incorporated
mechanical and operational changes for feedstock han-
dling and inhibitor type antifoulants to provide solutions
to fouling problems.
On the effluent side, our primary experience focuses on
ammonium chloride deposition. Water wash is historically
used and is quite effective at controlling ammonium chlo-
ride deposition. If you do have underdeposit corrosion,
you may need to apply a filmer. At fairly low treatment
levels, an economical treatment program can be used to
control corrosion. If for some reason you have a water
handling constraint, you can use detergent/ dispersants to
essentially move the ammonium chloride downstream to
where you can better tolerate the deposition or remove it
from the system.
BOYCOTT:
We have experienced severe fouling of the feed side of
our naphtha hydrotreater feed/ effluent exchangers. This
problem is caused by the polymerization of gum precur-
sors in the coker naphtha charge to the unit. The coker
has been expanded twice. Prior to the first expansion the
concentration of coker naphtha in the hydrotreater was
10%. At that time, run lengths were not limited by
feed/effluent exchanger fouling. After the first coker ex-
pansion, the concentration of coker naphtha in the hydro-
treater charge increased to 15%. This caused a dramatic
increase in feed/effluent exchanger fouling. Runs were
limited to two to three months as a result of the fouling.
Two chemical addition systems were installed to address
this problem; an antioxidant in the coker naphtha run-
down stream and a dispersant in the naphtha hydrotreater
charge stream. Runs were increased to six to nine months.
After the second coker expansion, the concentration of
coker naphtha in the naphtha hydrotreater charge rose to
25%. At that point, the chemical additions proved ade-
quate and other measures were taken. These will be dis-
cussed in Question 25.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
DEATON:
In our naphtha hydrotreaters, fouling and corrosion on
the effluent side of the exchangers is due to ammonium
chloride salt deposits. To protect the effluent coolers, we
continuously water wash at a rate of about one gpm per
thousand barrels, which is sufficient to keep the stream
entering the coolers below the dew point.
On the feed side of the exchangers, we inject antifoulant
at a 12 ppm dosage rate. This antifoulant contains disper-
sants, corrosion inhibitors, and antioxidants. We regularly
import naphtha at about 10% of total naphtha charge
during the peak season and these feedstocks are often
thought to cause fouling because of oxygen-induced po-
lymerization,
We usually get a two year run on these exchangers
before they are pulled and cleaned.
FELTROP:
I do not have anything to add to the comments on
hydrotreaters, except to emphasize that depending on
your fouling mechanisms, appropriately chosen antifou-
lants can have a good economic incentive.
As for hydrocrackers, this is typically not a good appli-
cation for antifoulants. The main problem experienced in
reactor effluent exchangers is the deposition of ammo-
nium bisulfide and chloride salts. These salts can cause
corrosion and plugging of the exchangers.
Since these salts are water-soluble, water washing the
affected reactor efIIuent exchangers will control the prob-
lem. A corrosion inhibitor with good detergent properties
can also be used to alleviate the problem.
LAUX:
Like other people, our Number 1 naphtha hydrotreater
is fed a stream from an unblanketed storage tank. The
feed/effluent exchangers had a severe fouling problem on
the feed side. They actually would plug off. We monitored
pressure drop instead of heat transfer to determine run
length. Some runs were as short as six months. We then
started using an antifoulant, and since then we have not
had much of a fouling problem. Run lengths are up over
two years.
We have not seen any fouling on our McKee hy-
drocracker feed/effluent exchangers on the feed side in
over five years of operation. However, this unit is fed
directly from the crude units and there is no intermediate
tankage.
KENNETH D. PETERS (UOP):
The need for antifoulant injection can be reduced
significantly and most often eliminated by removing the
oxygen from the naphtha by process means or preventing
contact of the naphtha with the atmosphere.
Particularly in the design of some of our overseas units
that import significant quantities of naphtha by barge or
103
TOC/INDEX
tanker, we have had to add a reboiled oxygen stripper
column, rather than a gas stripper, to eliminate the poten-
tial oxygen fouling problem in hydrotreating combined
feed exchangers. Other than that, gas blanketing of the
intermediate storage tanks between the crude unit and the
naphtha hydrotreating unit seems to be mandatory to
prevent fouling of the combined feed exchangers.
HEROS DERGREGORIAN (Giant Refining Company):
In case of gas blanketing of the feed tank, has anybody
been successful to prevent feed side fouling? Also, is the
naphtha hydrotreater effluent exchanger, on the effluent
side, using inhibitors? Have they experienced any problem
in the reformers, as far as causing problems with catalyst
poisoning?
BOYCOTT:
Yes, with regard to gas blanketing of the charge tank.
This was one of a number of things that we did in
addressing the feed side fouling or our feed/effluent ex-
changers. We were successful in reducing the fouling, and
I am sure that had some effect on it.
JAMES KELLY (CITGO Refining and Chemicals):
Several people have mentioned fouling on the effluent
side. We at Corpus Christi, had a problem in our catalyst
feed hydrotreater, and we developed pressure drop on the
effluent side which we think was ammonium chloride. We
injected water and the pressure drop went away, but we
never could find the source of the chlorides. We could not
see the chlorides in the feed, and the hydrogen was clean.
Has anybody detected chlorides in the feed, organic or
inorganic?
ARTHUR J. SUCHANEK (Criterion Catalyst Company L.P.):
At the risk of having bricks or something thrown at me
by the additives people, there is something that is in
between the feed and the effluent. It is called the reactor,
and it is full of catalyst. I would suggest that you talk to
your additive suppliers to make sure what it is you are
buying as your additive, because sometimes they can cause
you troubles.
MOHAMMAO AL-SHAHRANI (Saudi Aramco):
Is there an oxygen scavenger that can be used to remove
oxygen from hydrocarbon?
BARLOW:
Yes, there is. Hydrazine compounds or hydroquinone
type compounds have been used. One drawback is that
they do not mix well, so we have developed some oil soluble
materials that work. But we find oxygen scavenging is
rather inefficient because you have to feed on a
stoichiometric amount, which is not cost effective when
dealing with a hydrotreater fouling problem. It is preferable
104 Hydrogen Processing
to feed an inhibitor to deal with the polymer precursors.
That has been our experience.
We have seen imported feed as a major problem, espe-
cially when barges have been used. There are a couple of
things we have done successfully to address this problem.
First we monitor filterable solids on that feed before it is
off loaded into the charge tanks. This gives you a very good
indication as to whether you have a polymer problem.
Second, when you do identify that there are polymer
precursors and you can get back to the source, putting in
inhibitors at the source, not dispersants ofcourse, has been
very cost effective.
QUESTION 16.
Is anyone injecting antifoulant chemicals into the
suction of reciprocating compressors (in hydrogen
service) to reduce fouling of compressor valves?
FELTROP:
Film forming type antifoulants are frequently injected
into the inlets of both reciprocating and turbine compres-
sors, to reduce fouling and vibration. The additives are
injected at a rate of 1 to 2 pints per million cubic feed of
gas, and the additive is diluted a minimum of 20 to 1 with
hydrocarbon, and injected with a spray nozzle or a quill.
SAYLES:
We have experienced fouling in hydrotreater recycle
compressor valves and in the unloader, which jams in the
open position. The fouling is believed to be due to ammo-
nium chloride and ammonium bisulfide formation. We
have evaluated the relative merits of using an additive or
an antifoulant, as opposed to increasing our washwater
rate, and decided to increase our washwater rate.
BARLOW:
We have seen success both ways, increasing washwater
rates and using antifoulants. Sometimes a foulant is not
simply a salt; there may be some organic polymers, al-
though it is a little more rare. In this case, we have experi-
ence feeding multifunctional antifoulants. One key in this
system is the injection and dispersion of the antifoulant. It
is very important to get proper distribution. We have
treated both centrifugal and reciprocating compressors.
KENNETH D. PETERS (UOP):
We have done two things to minimize the ammonium
chloride fouling. One is we have gone to a minimum of 3
vol% continuous water wash in the naphtha hydrotreater
reactor section, which tends to clean up most of the am-
monium chloride. Secondly, further to what I said yester-
day, we have converted our reciprocating machines, both
in the hydrotreater recycle gas and Platforming net gas
booster compressor service, from nonlubricated to syn-
thetically-lubricated machines. We have seen significant
TOC/INDEX
increases in the reliability and decreases of the fouling that
have occurred in the valves of these machines, with the
retrofitting of these lubrication systems.
We have had at least eight years experience now with
this. I refer you to my 1987 response, which was Question
18, page 83, in the Hydrotreating Mechanical Section of
the NPRA Q&A transcript.
BOYCOTT:
What is the injection point for the water wash stream
that you are putting on the reactor outlet?
KENNETH D.PETERS (UOP):
Our primary location is between the combined feed
exchangers and the air cooler. We also have secondary
water wash injection in the bundle of the combined feed
exchanger, or just ahead of the bundle, where we would
calculate the water dew point. We also have water injec-
tion, as an option, into the different passes of the air cooler
of the reactor section.
HEROS DERGREGORIAN (Giant Refining Company):
Does the 3 vol% injection cover the minimum require-
ment for ensuring that the water stays liquid as far as
partial pressure?
KENNETH D. PETERS (UOP):
We inject the water into the location so that it will be
in the water phase. So it is well beyond stoichiometric
requirements.
RONALD E. MARRELLI (Phillips Petroleum Company):
Are you injecting water ahead of the compressor and
going through the compressor with water?
KENNETH D. PETERS (UOP):
We do not inject water through the recycle gas com-
pressor. The injected water is condensed and recovered in
the product separator water boot.
RONALD E. MARRELLI (Phillips Petroleum Company):
Has anyone tried just elevating the temperature to keep
the ammonium chloride from depositing in the compres-
sor valves?
SAYLES:
Well, to answer your first question, we would not put
water through a reciprocating compressor. In answer to
the second question, we have not tried heating up the
recycle gas.
BOYCOTT:
We do not water wash our compressor. Regarding
temperature elevation, I would be concerned about the
1994 NPRA Q&A Session on Refining and Petrochemical Technology
compressor valves. We use a softseat valve in our compres-
sors that is sensitive to elevated temperatures.
BOB RODDEY (Roddey Engineering Services, Inc.):
Ammonium chloride deposits are very strange. They
can deposit in the suction of the compressor. When the
water in the vapor increases over the salt deposition, the
salt can decompose and then deposit again in the valves in
the compressor. It is very common in reformer regenera-
tions. When you have wet gas during the regeneration,
oftentimes the salts will move to the compressors and foul
them. This can also happen in hydrotreaters.
About the water injection rate, no one has mentioned
that you have to be sure that not all of the water is
vaporized, so it is dangerous to say, we inject a certain
percentage. You need to inject enough water so that 25%
to 50% of the water stays in the liquid phase, after it mixes
upstream of the fin fans.
CHARLES McCOY (Consultant):
When injecting three, four, or five percent water into
the effluent, you are making sour water. Stripping that
sour water costs you money. For chloride removal, it is
better to get the chloride out before the compressors,
either by water wash or solid adsorbent.
ADRIAN GRUIA (UOP):
Regarding Mr. McCoy’s comment, water injection is
needed despite the generation of sour water because, while
ammonium chloride may or may not be present, the
constituents which will form ammonium bisulfide, NH3
and H2S, are always in the reactor effluent from a hydro-
processing unit. The ammonium bisulfide does not exist
in the liquid form; by injecting water, the NH3 and H2S
are kept solution thus crystallization and deposition of the
ammonium bisulfide in the products condenser tubes is
avoided. If water were not injected, the tubes would plug
and the only way to get rid of the salts would be by heating
up the fin fan to sublime the ammonium bisulfide; you
do not really want to do that as a normal matter of course.
KENNETH D.PETERS (UOP):
We are treating all the Platforming unit net gas going to
the hydrotreaters with activated alumina treaters. Several
years ago, we found that the amount of organic chloride
coming in with the naphtha feed was then contributing to
significant corrosion in the downstream reactor effluent
section. We are aware of two units in Europe that both
ultimately developed holes in the reactor effluent lines, one
resulting in a fire and one in a complete depressure. We
later attributed these failures to organic chlorides in the
naphtha hydrotreating unit feed that formed the HCI and
caused the corrosion that then lead to the failures. There-
fore, we have maintained continuous water injection as a
105
TOC/INDEX
policy ever since, for naphtha hydrotreating unit reactor
sections.
HEROS DERGREGORIAN (Giant Refining Company):
Mr. Peters mentioned the organic chloride coming with
the naphtha feed. Is the source of the chloride crude oil
additives, or additives from a crude oil overhead system?
KENNETH D. PETERS (UOP):
We feel that the source of the organic chlorides in the
naphtha feed is primarily from the tertiary recovery of the
crude.
QUESTION 17.
Have there been any additional advancements in in-
creasing the reliability of hydrotreater reciprocating
compressors that often operate at unloaded condi-
tions, such as during start-up?
ARMBRESTER:
This question asked about additional advancements in
improving the reliability of reciprocating compressors
operating at unloaded conditions. I have a couple of
comments on things that you might consider, although I
am not sure any of them would be considered new
advancements.
The first one concerns the unloader itself. If you are
using a finger type unloader on the compressor, switching
to a plug style unloader will open up more volume at that
point, reduce the velocity in the valve, and cut down on
the heat generation.
Second, some of the reciprocating compressors are
designed with thermosyphon cooling systems, which may
not be adequate during unloaded operation. We have
converted most of our reciprocating compressors to a
circulating water cooling system, and we are now specify-
ing this equipment on any new installations.
106 Hydrogen Processing
The final point is that some of the manufacturers now
are including a timed cycling system with their compres-
sor package that will automatically load up the valve for
a short time and then unload it again. This allows some
cool makeup gas to enter the cylinder periodically and
prevent overheating while you are operating at unloaded
conditions.
KENNETH D. PETERS (UOP):
We believe it would be preferable to run these compres-
sors fully loaded during start-up to expedite reactor heatup
and to keep good distribution through all the equipment.
The fouling potential should be minimized, too, with
these reciprocating compressors running fully loaded.
Process
QUESTION 18.
We may be seeing contamination of naphtha hydro-
treater feed by oxygenates (i.e., ethers, phenols, etc.)
in years to come. What are the relative reaction rates
of sulfur, nitrogen and oxygen compounds? Which will
limit naphtha hydrotreater operation (i.e., fix mini-
mum catalyst temperature)?
CUNEO:
It is well known that sulfur and nitrogen compounds
have a wide range of hydrotreating reactivity. For instance,
in the sulfur, mercaptans react much faster than thio-
phenes, which in turn are more readily desulfurized than
dibenzothiophenes.
Our expectation is that, in general, the sulfur com-
pounds are more readily removed than the oxygenates, and
finally the nitrogen compounds. Thus, we believe that the
nitrogen removal, which we would recommend a limit for
reformer feed of less than 0.2 ppm, would limit the
hydrotreater severity, rather than oxygen contamination.
ARMBRESTER:
Our experience comes from treating coal liquids with
high nitrogen and phenolic content. Generally speaking,
the relative rates of removal are: HDS>HDN>HDO.
However, aromatic compounds are much tougher to treat
than nonaromatics, so in some cases, such as light naphtha
feeds containing alcohols and/or ethers, oxygen removal
may be easier than denitrification. For light distillate,
phenolic compounds are the most difficult to remove.
HDS requires no saturation of ring compounds, while
HDN requires it, and HDO proceeds both ways. Carbon
to heteroatom bond strengths also imply that HDO
would be more difficult than HDN, as indicated below:
(Aryl-S=300 kJ/mole, -NH=314, -0=387)
(Alkyl-S=287 kJ/mole, -NH=289, -0=347)
(literature values)
TOC/INDEX
For most conventional crude operations, sulfur content
will define the minimum catalyst temperature requirement
simply because it is the predominant heteroatom contami-
nant. Our operations at Catlettsburg, which use premium
nickel-molybdate catalysts to guard against nitrogen con-
taminants, are operated based on reformer charge sulfur
targets, and we have not observed any problems with
nitrogen carryover. We do not normally see measurable
levels of organic oxygen. Nitrogen and/or oxygen contents
could become defining factors, however, for:
1. units using cobalt-molybdate catalyst at low pres-
sure and high space velocity;
2. synthetic stocks, particularly coal or shale liquids,
where nitrogen generally becomes the limiting fac-
tor; and
3. rerun materials which may contain significant
amounts of phenols and/or MTBE.
MEHMET Y. ASIM (Akzo Nobel Catalysts):
I agree with what the panel members have already
stated. The only additional comment I have is that at the
March 1983 AIChE National Meeting in Houston, we
presented a paper titled “ Hydrotreating of Solvent Refined
Coal-I Naphtha”. Detailed kinetic studies, comparing
oxygen, sulfur, and nitrogen removal rates using cobalt-
molybdenum and nickel-molybdenum catalysts, were in-
cluded in this paper.
ROBERT W. MORSE (Acreon Catalysts):
We recently had a customer who had contamination of
about 20 ppm of oxygen in a naphtha hydrotreater, and it
was necessary for him to raise the inlet temperatures about
20°F to compensate for that oxygen.
SAFA GEORGE (Criterion Catalyst Company L.P.):
Two additional factors you have to consider include the
heat release due to removal of oxygen, as the amount of
oxygen that you find in naphthas containing oxygenates
would be significantly higher than feed sulfur content and
the additional water formed due to oxygen removal.
QUESTION 19.
Aromatics content of diesel fuels has become an
important consideration these days. We all agree that
FIA is not well suited on these cuts. What other meth-
ods are refiners using? What has been the experience
with these methods? How are the repeatability and
reproducibility?
PORTER:
In California, where we produce low aromatics diesel,
we use Supercritical Fluid Chromatography (SFC) to
measure diesel aromatics. Reproducibility is around 1 wt%.
Since California regulations are written using Fluorescence
Indicator Adsorption (FIA) to measure aromatics, SFC
1994 NPRA Q&A Session on Refining and Petrochemical Technology
aromatics must be “corrected” to FIA via the following
approved equation:
Equivalent FL4 Aromatics (LV%) = [0.916 x SFC
Aromatics (wt%)] + 1.33
TREESE:
One of our refineries uses ASTM D-1319, which em-
ploys a silicone gel column, to measure the aromatic
content of the diesel. It separates out the aromatics, satu-
rates, and olefins.
We also use ASTM D-5 186, which is the Supercritical
Fluid Chromatography (SFC) method that my colleague
just mentioned. The supercritical method is more accurate
than the ASTM D-l319 for CARB TF3 diesel.
We still use FIA on some units.
ARMBRESTER:
We also use ASTM D-5186 (SFC) routinely to deter-
mine the aromatics content of diesel fuels. The question
asked about repeatability and reproducibility. We have
found those to be 0.7 mass % for repeatability, and 4.0 mass
% for reproducibility. The repeatability of the method in
our laboratory for a single sample over a one year period
has averaged 0.5 mass % (2x standard deviation).
We have also used a near-infrared method to determine
aromatics in diesel, and the calibration on this instrument
was achieved using D-5 186 as the primary method for
analyzing a set ofsamples. The standard error ofprediction
was 1.12 mass %. This method is very easy to use once the
calibration is established, but it is not yet an approved
ASTM method.
GARY L. HAMILTON (ABE Lummus Crest Inc.):
Concerning aromatics testing, in looking closer at diesel
fuels relative to aromatics content, you will need to look at
the individual feed components and the component blend
insofar as the amount of mono- and polynuclear aromatics
contents is concerned. Test methods such as W analysis
and HPLC can give you a good fingerprint on how those
feeds look, and how they will process in the unit. We have
found this to be extremely important when deciding on
what operating conditions need to be set. Differences in
aromatics distribution can have a significant impact on
hydrogen consumption, boiling range shift, API gain and
cetane index improvement opportunities.
QUESTION 20.
The trend for the coming decade is to reduce the
aromatics content in the diesel product. How will the
existing low pressure diesel hydrotreating process
units be able to reduce the aromatics content to the
marketable level; i.e., by building a new high pres-
sure unit, utilizing different technology, developing
new catalyst, etc.?
107
TOC/INDEX
CUNEO:
Based on technology that is currently available, there
does not seem to be a real need for high pressure hydro-
treating to reduce the level of aromatics. We believe a more
cost effective solution is to use lower pressure units with
new catalysts and new technology. Amongst these are the
SynSat process to manufacture low aromatics diesel, which
we are going to be employing at our refinery at Martinez.
ARMBRESTER:
Low pressure units (400 to 500 psig) can handle this
by using a noble metal catalyst that is relatively sulfur
tolerant and has exceptional hydrogenation activity. It will
probably be necessary to use a two-stage process, with the
first stage reducing the sulfur content of the diesel stream
to 0.05% less, followed by aromatic saturation in the
second stage. Since low space velocities may be needed to
accomplish the desired saturation, this will require addi-
tional reactor volume. The addition of a flash drum may
also be required between these two stages, to remove H2S
from the desulfurization reactor effluent, and provide
additional protection for the hydrogenation catalyst.
As mentioned previously, the saturation reactions will
consume much greater volumes of hydrogen than we
typically see in a desulfurization reactor.
TREESE:
To date, some refiners have used their hydrocrackers to
produce the low aromatics diesel. Some refiners have
revamped hydrocracking units originally designed to pro-
duce only naphtha to coproduce naphtha and low aromat-
ics diesel; in other words, take a midbarrel cut off their
towers, with about 15% to 25% aromatics. Others have
revamped their hydrocracking units to include aromatics
saturation catalysts or noble metal hydrocracking catalysts
to produce low aromatics diesel from the second stage of
the two-stage unit.
With respect to producing low aromatics from a diesel
hydrotreater, there are two options. One is to design a new
high pressure unit, and the other is to add an aromatic
saturation second stage onto an existing diesel hydrotreater.
Most people with whom we work, anticipating some
unknown aromatics specifications for the future, have
opted for the staged approach; that is, building a hydro-
treater that could later be modified to include the aromatic
saturation stage. One unit ofthis type is currently in design
by a client ofour Process Technology and Licensing Group.
Existing hydrotreaters could also be revamped to in-
clude a second stage of aromatic saturation, and we are
currently looking at revamp of a unit along those lines.
ARTHUR J. SUCHANEK (Criterion Catalyst Company L.P.):
Mr. Cuneo mentioned they were going to use the
SynSat process in Martinez to deal with aromatic satura-
tion. Since this process, now licensed by Criterion and
108 Hydrogen Processing
Lummus, was developed for aromatic saturation and de-
sulfurization, we have 14 licenses. There are only two
places in the world that are concerned about aromatics,
California and Sweden. It is very important there. We have
a number of licenses there: Beta, that we talked about last
year, has been producing 5% aromatics and 10 ppm sulfur
fuel and Scan RAP where a 50,000-barrel a day unit starts
up this month. Another unit, the Shell unit, will be
starting up in California towards the end of the year.
I continue to wonder about aromatics reduction and
aromatics levels in the fuels. I was recently chairing a
session on clean diesel development at a fuels meeting
here, and ended the session by asking the people in the
audience a question. I asked if 40 cetane is what you want
to call the environmental fuel of the future. I am not sure
that it will be. Most of the rest of the world is 45 cetane
or higher. I think cetane is the area that we should be
considering in the future. Criterion, with its partner Lum-
mus, has now developed a new process, which is a single
stage process for upgrading streams such as light cycle oil,
from 25 cetane to the order of 40 to 45 cetane in a single
stage process. It is called SynShift. The reason it is being
called Shift is because the products will be staying in the
same boiling range, but the whole product will be lighter.
ANDERS NIELSEN (Haldor Topsoe A/S):
We believe the trend for units operating in the range of
500 to 1,000 psi hydrogen partial pressure will be to
change out the catalyst in the existing unit with a catalyst
of high sulfur removal activity and, in particular, high
nitrogen removal activity. Then a new unit can be added
operating at the same pressure using a noble metal catalyst,
which is active at low temperature, where aromatics hy-
drogenation is favorable. Haldor Topsoe has provided
catalysts and design for such units, which have been in
operation almost 2 years.
QUESTION 21.
Are there any new or emerging technologies that can
significant/y improve the accuracy of the sulfur meas-
urement, which would allow the refiner to operate at
a level closer to 0.05 weight percent sulfur level in
diesel? What is your actual target sulfur level in diesel
now?
TREESE:
We generally use ASTM 4294 X-ray method to meas-
ure sulfur content in our diesel. At least in one refinery,
they are able to hold the standard deviation at 10 ppm in
the diesel sulfur range. They are targeting for 470 ppm of
sulfur in their product at that refinery.
At another refinery, we have located a benchtop X-ray
machine in the control room of the diesel hydrotreater.
The operators run it. This is not a new technology, but for
us, giving the analyzer directly to the operators is new.
TOC/INDEX
Running the analyses in the control room has significantly
improved response time, which previously could be several
hours between the time you take the sample and the time
you can react to it. Using this method, along with statis-
tical process controls, we have been able to reduce the
standard deviation of our analysis by more than 50%, so
we have been able to narrow our sulfur target even further.
ARMBRESTER:
We also use the D-4294 X-ray method, and we have
done a couple of things to try to make it as accurate as we
can in this low sulfur range. One of those is to use
calibration standards that are in the range from 0 to 0.25
wt% sulfur, and then we also use extended counting times,
which improves the sensitivity of the instrument and
allows us to run closer to the 0.05% specification. Under
these conditions, we find no bias between this method and
the EPA referee method, which is D-2622. As with any
analytical measurement near the detection limit of the
equipment, it is imperative to have skilled instrument
operators.
BOYCOTT:
We also use x-ray fluorescence testing for our sulfur
analysis. The accuracy of the test is dependent on the sulfur
level. At 0.05 wt% sulfur, its reported reproducibility is ±
0.007 wt%.
In respect to the second part of the question, our target
sulfur level is 0.045 wt% with a pipeline specification of
0.047 wt%. We hydrotreat all of our diesel stream and do
not see a great advantage in trying to operate any closer to
the pipeline specification.
CHARLES McCOY (Consultant):
What the panelists just said is interesting. I assumed we
had to operate a little further down than that to allow for
contamination in the pipeline and the distribution system,
as we did when we first started selling unleaded gasoline.
We had to allow for some lead pickup between the refinery
and the pump. Apparently the panelists are saying that is
not a problem, and we can operate as close as 0.047 wt%
against a 0.05 wt% specification.
BOYCOTT:
That is correct. We do operate to a 0.047 wt% pipeline
specification.
PORTER:
We produce to 0.047 wt% maximum sulfur specifica-
tion at our refineries. It is our understanding that allow-
ances will be made for results slightly above 0.05 in the
distribution system due to analytical reproducibility. We
will still be required to show that all refinery production
was below 0.05 wt%.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
SAYLES:
You have to demonstrate that the sulfur content of the
diesel fuel is less than 0.05 wt% and your records must
show this test is net prior to shipping. Downstream of the
refinery, the fuel can test up to 0.055 wt% sulfur and still
meet the EPA standard provided your records are intact.
QUESTION 22.
What has been the experience with using units de-
signed for high sulfur diesel to operate to low sulfur
diesel product specifications? What problems have
been associated with this approach and how have
these been minimized?
SAYLES:
Most pre-1993 high sulfur product hydrotreaters were
designed for an operating pressure of about 600 psi and a
space velocity of 2 to 3 LHSV. The product sulfur speci-
fication was designed for less than 0.5 wt%.
On these units, higher severities are required to produce
the lower sulfur product. Higher temperatures, lower
space velocities, and higher catalyst activity are needed to
achieve the low sulfur product. Catalyst activity loss due
to higher severity requires more frequent shutdowns to
regenerate or replace the catalyst. The maximum reactor
temperature is set by the teactor metallurgical limitations
for the given hydrogen partial pressure. Operation at these
severities also generates more low octane light ends which
must be reprocessed. In one location, we have used a low
pressure unit to treat diesel over the short term and
kerosene as the normal feed. In this unit a low space
velocity was used to reduce the temperature to acceptable
levels. We combined two existing units to decrease the
reactor space velocity.
TREESE:
Unocal’s Process Technology and Licensing Group has
revamped several diesel hydrotreaters to make low sulfur
diesel. In two cases, the clients were able to meet the lower
specifications just by changing the reactor internals, im-
proving liquid distribution inside the reactors. In other
cases, they have had to add parallel reactors, new larger
reactors, and the like, to increase catalyst volume.
The process variables you have to consider when you
want to lower the sulfur specification include increased
quench requirements, increased hydrogen consumption,
increased pressure drop, and the potential for color prob-
lems if you run your reactor temperatures too high.
To our knowledge, all the revamped units have been
able to achieve low sulfur diesel specifications without any
problems.
PORTER:
We have converted several units in Chevron. At Pas-
cagoula we converted a unit that was running previously
109
TOC/INDEX
a 0.15 wt% to 0.20 wt% product sulfur level. We increased
the capacity 40%, without adding an additional reactor.
We are achieving a run length of one year plus and are very
pleased with the results.
ARNOLD FEINBERG (Exxon Research & Engineering Company):
Units designed to produce high sulfur diesel cannot be
operated to make low sulfur diesel without significant
changes to the feed and/or operating conditions. Some
locations have undercut the feed to make it lighter and
hence easier to desulfurize. The main problem with this
approach is the yield loss. Other locations have come up
in temperature and reduced throughput to get a lower
space velocity. These steps reduce run length or capacity.
The generally recommended approach we utilize in Exxon
is to add reactor volume to lower the space velocity and
switch to a high activity distillate, HDS catalyst.
PAUL VANCE (Acreon Catalysts):
Operating high sulfur diesel units with conventional
catalysts at temperatures to produce low sulfur diesel
without reducing feed rate will cause a 50% to 80%
‘reduction in run lengths, due to approximately 40°F
increase in the reactor temperature. In addition, as men-
tioned, this may cause difficulties with product color.
Acreon recently introduced a high activity, high density
desulfurization catalyst, HR316, to increase the volumet-
ric desulfurization activity by about 30% over our previous
version. This catalyst allows recovering 10°F to 25°F
start-of-run temperature and helps get back some of the
cycle length.
We would also suggest dense loading catalyst as much
as possible, within pressure drop concerns, and utilizing a
graded bed.
ARTHUR J. SUCHANEK (Criterion Catalyst Company LP.):
One of the points that we have always laughed about
during NPRA screening sessions is the fact that back in
the ’70s and ’80s there was a lot of money spent on
residual upgrading projects, and the companies that were
the most successful and had the biggest payout were the
ones that did not spend any money at all. I wonder about
the similarity here, because we have invested a lot of
money on diesel processing. It is important that we make
good environmental fuels, but what I see happening now
in the diesel situation is that we are lightening up the
boiling range. We are now approaching the heavy jet fuel
that is made as Class 1 diesel in Sweden, which means we
are probably going to be processing a lot lighter materials.
Also, it is rather ironic, I think, that the people who did
not spend the money to revamp or build new units may
be sitting there processing to very low levels of sulfur
because the specified distillation PNA may change.
What I am suggesting is to be very careful to determine
what the future fuels are going to be. As we optimize these
110 Hydrogen Processing
fuels, let us make sure that we do not cut parts out of our
barrel that need to be there from a standpoint of profit-
ability and cost-effectiveness of our industry.
QUESTION 23.
Is diesel color an issue now that a dye marking system
is mandated to show the difference between low sulfur
and high sulfur diesel streams? Will diesel color
stability be an issue?
TREESE:
I would say yes, diesel color is an issue, but the dye
requirements have been changed so that they no longer
necessarily reflect a difference between low sulfur and high
sulfur diesel. That was the intent of the EPA with the blue
dye. The IRS, however, wanted all nontaxable diesel and
kerosene dyed red. Because of the possible confusion
between the blue diesel fuel and blue aviation gasoline, all
parties have now agreed that only red dye will be used in
nontaxable fuels after October 1, 1994. Therefore, both
high and low sulfur fuels will be dyed red if they are sold
for a nontaxable use.
The IRS is requiring the concentration of the red dye
to be about two times more than the petroleum industry
has traditionally used. Therefore, we are concerned that
we may no longer be able to perform simple product
quality tests, like ASTM D-1500 color, and individual
company tests designed to measure haze in the fuel which
indicate the presence of water or sediment. We are also
concerned that the high dye concentrations may decrease
the stability of the fuel, making it more susceptible to gum
and sediment formation during storage. Limited acceler-
ated stability tests by Unocal have shown this is definitely
a potential problem with these fuels.
Another problem which has been observed with these
high dye dosages is that when a clear fuel is loaded into a
truck transport following loading of a dyed fuel, the
residual fuel left in the delivery hose, or even possible dye
adsorbed into the delivery hose, will tint the entire load of
the clear fuel. Therefore, there may be a tint imparted to
a clear fuel which follows a batch of dyed fuel through a
pipeline. If the clear fuel is a Jet A shipment, and it ends
up with a tint as a result of the color, it may be refused by
the purchaser because of suspected contamination.
LAUX:
We also believe that diesel color or oxidation stability
will always be a quality issue. We run a 90-minute, 300°F
stability test, and a 16-hour 200°F stability test on all our
finished diesel blends. Though you cannot get an initial
and final ASTM color on the diesel that is dyed, you can
get blotter ratings and total insolubles, which are both
good stability indicators.
We use a specification of 7 maximum in the blotter
rating, with typical results around 2. For the hexane
TOC/INDEX
insolubles, our specification is 2.5 maximum, but we feel
that we have to react to anything over 1. We also peri-
odically check the color on the high sulfur diesel blend
prior to adding the dye.
SAYLES:
I agree with what has been said so far. One of the issues
with blue dye was that the EPA did not anticipate adding
blue dye with yellow diesel fuel which will produce green
fuel. I was glad we went to red dye since red dye and yellow
diesel makes orange fuel which should lead to other ques-
tions for consumers.
There is a proposal by the IRS on a diesel testing
method to determine the dye concentration in diesel. We
have reviewed the test method and it does not appear
difficult to perform. However, it is expensive. The equip-
ment is probably in the range of a $20,000 to $30,000
investment.
BOYCOTT:
This is a loaded question. I do not think there is any
doubt that color is an issue. The question is, is it a political
issue or a product quality issue? One of the members of
the IRS was in our refinery five days after the October 1
dye deadline to ensure that we were meeting the political
side of the dye issue.
As to product quality, the specification on our diesel
has been 2.5 maximum by ASTM D- 1500. Color bodies
may cause an exceedance of this specification without the
engine problems typically associated with fuel instability.
To quote from the applicability section of ASTM D-l500
“color is not always a reliable guide to product quality and
should not be used indiscriminately in product specifica-
tions”. As Mr. Treese has pointed out, the usefulness of
color testing is in even more doubt as a result of the new
dye requirements.
Color stability is really an attempt to qualify the stabil-
ity of a fuel and its tendency to gum filters and shellac
engines. It would seem that a direct test of gumming
tendency such as ASTM test method D-2274 (test for
oxidation stability of distillate fuel oil) would best be
applied to this. We have had some discussions with the
pipelines in our area on this issue.
The Clean Fuels Meeting earlier this week was discuss-
ing these issues in detail.
KENNETH ABRAHAMS (Star Enterprise):
Back on September 12, a member from another North-
east refining and marketing company and I had a meeting
with Pennsylvania’s Department of Motor Fuels Taxation
Enforcement Division. We were basically there to describe
refining and dying procedures to them, but one of the
topics that came up was the fact that two months before-
hand they caught a couple of truckers who had blue-dyed
diesel in their tanks and thought they had found a couple
1994 NPRA Q&A Session on Refining and Petrochemical Technology
of violators. They were dismayed to find that after they set
the clear bottles on the shelf for a couple of months, they
were no longer blue. So regarding the last part of the
question about diesel color stability being an issue, I think
if much more of this happens, the dye stability issue may
surface as well.
GARY L. HAMILTON (ABB Lummus Crest Inc.):
It is interesting to see that this issue was brought up in
this forum. The topic of color has been given considerable
attention by the Japanese for a long time. As we have
worked with refiners around the world, we find that the
Japanese have placed major emphasis on the color ofdiesel.
They usually target an ASTM color of about 0.5 maximum
for hydrotreated diesel product. They have had a number
of difficulties in meeting that specification as they try to
produce low sulfur diesel, because of the need to increase
temperatures on many of their units that are space velocity
limited. Lummus, together with Criterion, as Mr.
Suchanek pointed out, offer the SynSat hydrotreating tech-
nology. With SynSat technology, we focus on setting mild
operating conditions using high activity SynCat catalysts
to keep the temperatures down, thereby achieving 0.5
ASTM D 1500 color on the treated diesel stocks.
QUESTION 24.
In the naphtha hydrotreater, we have a two reactor
configuration unit forprocessing coker naphtha. In the
first liquid phase reactor, we are experiencing wide
fluctuations of reactor differential pressure. Does
anyone have similar experience and what corrective
steps have been taken?
D’AURIA:
Our typical design for a two reactor coker naphtha
hydrotreater is all vapor phase in both reactors. In the
example cited here, where the first reactor is designed for
liquid phase, we suspect that the swings in pressure differ-
ential are caused by formation of two phases, with the
pressure drop increasing as the vapor phase is formed. If
this is the case, then controlling the pressure and tempera-
ture of the first reactor to maintain the liquid phase would
be the solution.
CUNEO:
I agree with Mr. D’Auria. We have a two reactor system
as well for coker naphtha hydrotreating. We run the first
reactor in liquid phase and the second reactor in vapor
phase and do not experience wide fluctuations at all.
PORTER:
We have one unit that is processing coker naphtha in a
two reactor system, with the first reactor in the liquid
phase. We have not seen any pressure fluctuations.
111
TOC/INDEX
PAUL VANCE (Acreon Catalysts):
I would just say that most of our experience is on a
liquid phase first stage with an upflow configuration and
we are not aware of any units with similar symptoms.
Maybe there is channeling, or maybe the hydrogen distri-
bution grid is broken.
QUESTION 25.
How are most people handling their coker naphtha
stream, in a separate unit or as partial feed to a
reformer pretreater? What difficulties have been en-
countered with either approach?
DEATON:
Some keys to success at Clark’s Hartford refinery are to
hydrotreat the coker naphtha separately, to try to keep
coker naphtha a small percentage of the total feed to the
reformer, and to keep the coker naphtha end point below
360°F.
All of the coker naphtha goes through its own separate
hydrotreater, operating at 900 psig. Typical sulfur contents
are 800 ppm to 1,000 ppm in the feed, and 0.5 ppm in
the product. Typical nitrogen contents are 45 ppm to 60
ppm in the feed and 0.5 ppm in the product. This amount
of denitrification could not be achieved in the virgin
naphtha hydrotreater operating at 300 psig. The hydro-
treated coked naphtha is about 14% of the total feed going
to the reformer.
It is important to feed the coker naphtha to its own
separate unit because the catalyst is eventually poisoned
by silicone from coker antifoam agents after processing
about 50 barrels per pound of catalyst. Silicone poisoned
catalyst cannot be regenerated.
One other outlet is to inject the coker naphtha into the
base of the FCC riser. To upgrade the coker naphtha, it
must see the catalyst by itself, with the gas oil being
injected higher in the riser. I did this at one refinery and
saw about 25% conversion to olefins.
BOYCOTT:
Coker naphtha is processed as partial feed to our single
reactor naphtha hydrotreater. The concentration of coker
naphtha in the charge stream has increased from 10% to
15%, and subsequently to 25% as a result of two coker
expansions. At 10% the stream did not cause any undue
problems. After the first expansion, the problem was
handled chemically as discussed in Question 15. After the
second expansion, feed side fouling of the feed/effluent
train became much worse. We contracted Roddey Engi-
neering Services to assist in solving the problem.
Problems identified were:
storage of the coker naphtha in an unblanketed cone
roof tank,
112 Hydrogen Processing
reprocessing of the coker naphtha in our crude unit
(This caused activation of the gum precursors in the
reboiler of the naphtha splitter.), and
the presence of solid fines in the feed.
Actions taken to reduce fouling and increase run lengths
were:
hot coupling of 75% of the coker naphtha stream
directly to the naphtha hydrotreater,
N2 blanketing of the tank to which the remainder
of the coker naphtha is routed,
mechanical filtration of hydrotreater feed, and
coating of exchanger bundles with filming amine
prior to installation.
Antioxidant and dispersant additions were continued
although the necessity of their use is in question.
As a result of the above actions, run lengths have been
increased from 6 to 9 weeks to 6 to 9 months.
Another problem associated with high levels of coker
naphtha has been excessive reactor temperature rise. To
temper this, we have set up a recycle stream of hydro-
treated product. We adjust the rate of the recycle stream
and the volume of coker naphtha routed to the unit to
control the reactor outlet temperature.
CUNEO:
We prefer to process the coker naphtha commingled
with straight-run naphtha in the reformer pretreater. The
main reason for that is it is easier to cope with the high heat
release with the olefins, and also because we want to
monitor the silicone breakthrough into the reformer very
closely and ensure we do not poison our reforming catalyst.
PORTER:
In order to control heat release, coker naphtha is only
a partial feed to our naphtha hydrotreaters. Our typical
problems are fouling the feed/effluent exchangers due to
gum deposition and catalyst poisoning due to silicon
contamination.
TREESE:
Our experience has been that coker naphtha is proc-
essed by most refiners in a blend with other naphtha
stocks, straight-run stocks, or even FCC naphtha, or its
own hydrotreated naphtha in the recycle, as was men-
tioned before.
There are naphtha hydrotreaters that process 100%
coker naphtha. Not many that we know of are actually
processing 100% coker material, even though they were
designed for it.
The other problems with heat release, silicon poisoning
and so forth, have already been described.
There are catalysts that have been developed with a
high capacity for silicon and they have managed to extend
the cycle length of a number of hydrotreaters. In our
refineries, however, even the silica poisoning is frequently
TOC/INDEX
a determinant of run length, and my experience person-
ally and recently is that it is very easy to overdose that
silicon. It is a common practice to overdose it.
CHARLES MCCOY (Consultant):
Some refiners have tried low silicon antifoams to extend
hydrotreater catalyst life. Are those any good or have you
given up on them?
PORTER:
We tried them and did not find the performance cost
effective.
M. DEAN EDGAR (Criterion Catalyst Company L.P.):
I have heard that low silicon antifoam products are still
on the market, but are expensive. Refiners are still debating
whether the price is worth the performance they realize.
In regards to coker naphtha processing, most refiners
are treating it in a blend with straight-run naphtha. Prob-
ably 20% to 30% of the blend is coker naphtha. Many
people have been made aware of the high reactivity of
coker naphtha to oxygen. They have taken much time and
effort to run it hot to the hydrotreater and avoid storage;
but when they do have to store it, they use inert gas
blanketing and oxygen scavengers. An item that frequently
causes a problem is when they bring in the straight-run
naphtha, especially if the straight-run has been in storage
and contaminated with oxygen. This has caused trouble
with plugging and polymerization in the exchanges and
on top of the reactor, even though refiners have been very
careful in handling the coker naphtha.
BARLOW:
To add a little bit on the antifoams, we have evaluated
nonsilicon antifoams for cokers. The cost is the biggest
problem with them. Generally, it takes a lot more chemi-
cal. Some of the best efforts we have seen to reduce the
silicon to the HDS unit have been to evaluate the different
molecular weight silicon antifoams available, and then to
improve your feed system and control methods. Operator
training is another very key parameter.
KENNETH D. PETERS (UOP):
We have used a traditional single naphtha hydrotreat-
ing reactor design for units having a feed composition of
up to about 10% coker naphtha. As the percentage of
coker naphtha increases toward about ten percent, the feed
nitrogen concentration increases proportionally and in-
creased reactor pressure is needed for proper nitrogen
removal. Typical pressure increases range from 350 psig co
750 psig.
With higher coker naphtha concentrations, we have
added a second series reactor. This second reactor can be
considerably smaller since its purpose is to serve as a
cleanup reactor for breaking up recombination sulfur
1994 NPRA Q&A Session on Refining and Petrochemical Technology
compounds from the lead reactor. This second reactor
operates at lower temperature than the lead reactor, with
the inter-reactor cooling provided by combined feed ex-
change.
RAGHUNATH P. MEHROTRA (India Institute of Petroleum):
What is the cycle length difference when processing
straight-run naphtha versus coker naphtha with the
straight-run material?
BOYCOTT:
I can speak to two separate units, one being the unit
that we operate now with somewhere between 6 and 9
months run lengths, as determined by fouling of the
feed/effluent train and reactor. This unit is in fairly severe
service for a single reactor unit, with 25% to 30% coker
naphtha.
Another unit I worked on processed no coker naphtha,
and achieved in excess of two year runs as limited by
catalyst activity.
ARTHUR J. SUCHANEK (Criterion Catalyst Company L.P.):
There are a lot of cokers being built now in the world,
and one of the things people are trying to do is to find
places to treat the coker naphtha. I agree with everything
that has been said about the naphtha treater, but I see a lot
of people considering putting the coker naphtha into
distillate units. That scares me. You have very high olefin
content material entering the reactor, which will immedi-
ately react, resulting in a very large temperature differential
within the top 5% of the bed. I have not done any bed
lifting calculations recently; but I would not be surprised
that the velocity change is so significant, depending on
how much coker naphtha you have in there, that you
might even be doing some damage to the catalyst or the
seal balls on the top of the reactor. I have seen this happen
in several cases where people will use pilot plant data,
which is isothermal and absolutely meaningless when you
are talking about temperature differentials in adiabatic
systems. My suggestion would be to be very careful be-
cause you get significant vaporization with this high delta
T in distillate operations.
QUESTION 26.
How dues the concentration of hydrogen sulfide in the
recycle gas affect the performance of a distillate hy-
drotreater? In particular, how dues if affect the product
sulfur in a deep desulfurizer?
ARMBRESTER:
As part of the design process for our new diesel desul-
furizer unit, we have performed two side-by-side labora-
tory scale tests treating a mixture of diesel and light cycle
oil over a cobalt-molybdenum catalyst. One of the tests
was conducted with no H2 S in the hydrogen, and the
113
TOC/INDEX
other with 5% H2S in the hydrogen stream. When com-
paring the 5% H2S to the 0% H2S control case, we saw
about a 30% relative activity suppression on the high H2S
case. This translated into a 15°F start-of-run temperature
increase to make a 0.04% sulfur product, or about 3°F
temperature increase for each percent of H2S in the hy-
drogen. These values are very consistent with vendor
quotes ranging from 2°F to 4°F per percent H2S.
In designing the commercial unit, we estimated that
the catalyst life would be cut by about 25% to 40% on our
typical diesel feed with 1.1 wt% sulfur. Consequently, we
installed a recycle gas scrubber in this unit, but we are not
sure you could justify that expense for a unit that is
processing lower sulfur feedstocks.
BOYCOTT:
We went through a similar exercise in the design of our
diesel hydrotreater, and the results were identical. We were
looking at a very conservative estimate of three co six
months run length extensions with the installation of a
recycle gas scrubber. As a result, the recycle gas scrubber
was incorporated into the design of our new diesel treater.
CUNEO:
I do not think we would believe that the loss is quite as
severe as quoted. We did some pilot plant work which
showed that on a cobalt-molybdenum catalyst we went
from 96% desulfurization to 95% for 5% H2 S in the
recycle gas.
LAUX:
Our vendor recommends a maximum concentration
0.5 vol%, and we do agree with the loss of activity. When
we built our McKee diesel hydrotreater, we did nor install
a recycle gas scrubber because we have a fairly sweet unit,
but we provided provisions for it in the future. We control
the H2S and the purity in the recycle by purge. We purge
about one million standard cubic feet per day.
PORTER:
We typically scrub recycle gas to remove hydrogen
sulfide when the feed contains greater than 1 wt% sulfur.
When recycle gas scrubbing is lost for short periods of
time, HDS activity will typically drop 5°F to 10°F.
SAYLES:
A caution is at high recycle gas H2S contents, above
10%, recombination reaction can occur. Recombination
reactions occur when the recycle gas H2S reacts with the
liquid product forming a higher sulfur liquid.
CHARLES MCCOY (Consultant):
Mr. Armbrester, you said that you were not sure that
building a new unit with the scrubber was justified, and I
agree with you, but it can be a cost effective way of
114 Hydrogen Processing
improving the performance of an existing unit. Adding a
recycle gas scrubber may be cheaper than adding more
reactor volume.
GARY L. HAMILTON (ABB Lummus Crest Inc.):
I agree with the panel entirely. We have done a number
of studies for clients, as part of applying SynSat technology,
on removing versus not removing H2S from the recycle gas.
In all cases, it was found justifiable to put the adsorber in,
especially when your objective is deep desulfurization or
aromatics reduction. I have just a word of caution, and
maybe a word of suggestion for the future. If anybody is
leaving the adsorbers out at this time for units being
designed to make 0.05 wt% sulfur diesel, you might want
to consider leaving plot space to include an adsorber in the
future. Removal of H2S from the recycle gas is important
if it is necessary to achieve significant amounts of aromatics
saturation. In such cases, you will need to change the type
of catalyst used and revamp the unit to achieve lower levels
of H2S in the recycle gas in order to get maximum hydrogen
partial pressure for aromatics saturation.
QUESTION 27.
Does anyone have any experience with low levels of
sulfur in the feed of a naphtha hydrotreater? Did sulfur
have to be injected into the feed? What is considered
a minimum sulfur /eve/ before the hydrotreater cata-
lyst suffers from coke deposition?
CUNEO:
As a measure of precaution, we advise our units to run
with a minimum of 1,000 ppm hydrogen sulfide in the
recycle gas hydrogen. While our operating experience, in
general, is with moderate to high levels of sulfur in the
naphtha feed to the hydrotreaters, in the past we have
observed that we can strip the catalyst when we are oper-
ating in a mode that circulates sweet hydrogen, such as
during a hot hydrogen strip, or when there is a feed outage
for some other reason. For that reason we have established
this 1,000 ppm of H2S in the recycle as a minimum.
OEATON:
A colleague of mine once operated a C5/C6 light naph-
tha hydrotreater with feed sulfur levels typically in the
range of 10 ppm to 20 ppm and a recycle gas H2S level of
about 50 ppm. Sulfur injection was not needed, and
excellent desulfurization to 0.1 ppm or less was main-
tained over a four year period, with a catalyst life of 1,500
barrels per pound. Catalyst coking was not a concern and
runs between catalyst dumping and screening for pressure
drop concerns exceeded 700 barrels per pound.
LAUX:
Our Number 1 naphtha hydrotreater has once-through
reformer hydrogen with very sweet feed. Our vendor
TOC/INDEX
recommends that we keep our feed sulfur above 20 ppm.
Below that number, we think that we will see metal sulfide
reverting back to the base metal, causing higher coke
formation and poor desulfurization and denitrification.
We have nor had to do it yet, because we typically run
about 50 ppm, but we do have provisions available to
inject sulfur into the feed ro maintain the 20 ppm level.
PORTER:
Chevron has experience with feed sulfur levels a.s low as
50 ppm CO a naphtha hydrotreater. No sulfur is injected
into the feed. The catalyst does not suffer from high levels
of coke deposition.
QUESTION 28.
We have a 300 psig spare naphtha hydrotreater. Can
this unit be used to hydrotreat kerosene or FCC gaso-
line? What effects can we expect in each case?
LAUX:
A 300 lb hydrotreacer certainly can be used co treat
some amount of kerosene or FCC gasoline depending on
the catalyst type and volume. We converted a spare 340
psig naphtha hydrotreater to a diesel hydrotreater. It re-
duces 0.2 wt% sulfur diesel to about 0.03 wt% at a 1.5
liquid hourly space velocity, with a projected two year life,
using the same cobalt-molybdenum catalyst chat was in
the naphtha service.
A nickel-molybdenum catalyst would be more appro-
priate for the kerosene treating. FCC gasoline desulfuriza-
tion can also be done, but olefin saturation will occur,
reducing the octane.
SAYLES:
I agree with what he said. We actually have an operation
where we hydrotreat kerosene in a low pressure unit. We
do put some limitations on the unit. We limit the tem-
perature co 680°F. The space velocity is maintained around
1.5, and the recycle hydrogen rare is maintained at around
800 SCF per barrel.
For FCC naphtha, space velocity must be limited to
about 1.5 or less, EOR should be limited co 680°F, and
recycle hydrogen should be 800 SCFB. FCC naphtha
olefins saturation requires a significant amount of hydro-
gen, about 10 to 12 SCF hydrogen per bbl of olefin and
will reduce the octane by about 2 numbers. Air contact
with the FCC naphtha should be limited to avoid ex-
changer fouling due to gum buildup.
At low pressure the H2 consumption may reduce the
hydrogen parrial pressure below the limit required to treat
naphtha, H2 psia of about 250 psia. Outlet hydrogen
partial pressure should be calculated and the recycle gas
rare increased if the hydrogen partial pressure falls below
250 psia.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
ARMBRESTER:
We agree that the unit could be used to treat either
kerosene or FCC gasoline, and we would recommend the
cobalt-molybdenum catalyst in either case.
For the kerosene run, you would expect co see higher
start-of-run reactor temperatures at this low operating
pressure, resulting in more rapid coking and a shorter
catalyst life.
For gasoline hydrorreating, you can expect to see loss
of octane as a result of desulhrizing the gasoline, with the
magnitude of the octane loss being dependent on the
olefin and aromatic content of the untreated stream.
CUNEO:
We are currently operating a hydrotreater with an outlet
hydrogen partial pressure of 160 psig, hydrotreating heavy
FCC gasoline. The reason for doing this is to try to
minimize olefin saturation. When operating at this low
pressure, it is important to maintain high hydrogen circu-
lation, and to process feed directly from the unit to
minimize any fouling due to gum formation from oxygen
contaminants.
M. DEAN EDGAR (Criterion Catalyst Company L.P.):
We would like to rake issue with a couple of the
comments about being able to treat FCC gasoline and
have significant octane loss. The amount of octane loss is
related to how severe the FCC gasoline is treated for
desulfurization. If we are looking at reformulated gasoline,
you may need only 75% or 80% desulfurization of the
FCC gasoline.
Criterion is working in conjunction with ABB Lum-
mus Crest in this area, and we offer a catalyst and technol-
ogy that will allow you CO achieve these levels of
desulfurization at 300 psig pressure or less. You will get as
little as one number loss in road octane (R+M/2). Of
course, as has been indicated, the octane is due to olefin
saruration. However, if you are not saturating olefins to a
great extent, you do not have the problems with the high
hydrogen consumption or with the high delta T’s.
RICHARD M. GIALELLA (IFP Enterprises, Inc.):
FCC gasoline desulfurization may be carried out in a
300 psig naphtha hydrotreater. However, the design must
be carefully reviewed in terms of olefin saturation desired
and cycle length required.
IFP offers gasoline desulfurization/hydrotreating tech-
nology which utilizes an optimized set of process condi-
tions and catalysts which preferentially remove sulfur and
minimize olefins saturation.
We have licensed this technology CO a U.S. refiner in
order to meet government regulations for sulfur and ole-
fins content in reformulated gasoline.
115
TOC/INDEX
QUESTION 29.
Has anyone hydrotreated thermal/y cracked naphtha
in a unit where this stream was 100% of the feed? How
was the heat of reaction controlled? Was catalyst
fouling a problem?
DEATON:
At Clark’s Hartford refinery, we hydrotreat coker naph-
tha in its own separate hydrotreater. Stripper bottoms or
virgin naphtha is used as a diluent between 15% and 30%
of the feed to control the heat of reaction across the reactor
between 170°F and 200°F.
Typical start-of-run temperatures are 510°F inlet, with
675°F to 680°F outlet. Other key variables are 900 psi
product separator pressure; 4,700 standard cubic feet per
barrel hydrogen/hydrocarbon ratio on a fresh feed basis;
and 775 standard cubic feet per barrel hydrogen consump-
tion. Catalyst run lengths are 50 barrels per pound of
catalyst, and are limited by silicone poisoning from coker
antifoam agents. The catalyst cannot be regenerated be-
cause glass beads are formed with almost no active surface
area. Pressure drop and fouling across the exchangers and
catalyst bed are not a problem in this unit.
PORTER:
Chevron has several units which blend cracked naphtha
with saturated streams to control the heat of reaction.
Catalyst fouling is not a major problem; bed plugging is.
CHARLES MCCOY (Consultant):
Many years ago, we had a couple of units that fed 100%
thermal cracked naphtha. They had multiple radial flow
reactors in series. As Mr. Deaton described, we had a
facility to inject stripped hydrotreated naphtha between
the reactors for temperature control. We did not have a
very good injector, and it was a very tricky thing to operate.
Regarding Mr. Edgar’s earlier comment about ex-
changer fouling, we could run straight-run along with the
cracked naphtha. The straight-run came from tankage, so
it contained oxygen. The thermal cracked naphtha was fed
hot. A gas stripper removed oxygen from the straight-run
before it mixed with the thermal cracked. We had very
little exchanger fouling.
M. DEAN EDGAR (Criterion Catalyst Company L.P.):
We have had experience helping people treat 100%
visbroken naphtha and 100% coker naphtha. We find a
successful way of treating this type of naphtha is a two
stage, or two reactor type of process. We use a relatively
low temperature in the first stage or reactor to get rid of
the diolefins and some of the olefins, and to limit the
amount of heat rise there. We then use the second stage or
reactor as the typical naphtha hydrotreater reactor, to run
at the higher temperatures to remove the sulfur and nitro-
gen compounds and other contaminants.
116 Hydrogen Processing
GEORGE SMITH (Exxon Research & Engineering Company):
This is really a comment on both Questions 25 and 29.
Within Exxon, coker naphthas are handled either in
blends with virgin or as 100% feed to a separate unit.
Site-specific considerations usually dictate the choice for
each location. We have designed three coker naphtha
hydrotreaters which operate on 100% fluid or flexicoker
naphtha. Feed diolefin contents up to 10% and bromine
numbers in excess of 100 have been successfully processed.
The heat of reaction is controlled by a combination of one
or more of the following: product recycle or quench,
and/or inter-reactor heat exchangers.
Regarding the question of catalyst fouling, in general,
catalyst fouling has not been a problem in these hydro-
treaters where we process 100% coker naphtha. A low
temperature diolefin saturator is included in these designs
to prevent fouling due to diolefin polymerization. Also,
solids and oxygen must be excluded from the feed to
prevent catalyst and equipment fouling.
R. KEVIN DODDS (Acreon Catalysts):
We have seen several units, or have been involved with
several units that use a two-stage process, again with a low
temperature front end and a second stage hydrotreating.
Silica is still a problem with some of these, but you can
regenerate some of these catalysts and clean them up.
QUESTION 30.
What is the best strategy for operating residual desul-
furizers? Is if based on maximum distillate production
or catalyst life? What has been the highest distillate
yield, and at what catalyst life penalty? Is there any
problem with stability of distillates?
PORTER:
Strategies for operating residual desulfurizers will vary,
depending on your refinery situation and process configu-
ration. We generally follow four kinds of reactions:
hydrocracking conversion or residual destruction,
product desulfurization or denitrification,
Conradson carbon residue (CCR) reduction, and
metals reduction.
At Pascagoula, where the residual desulfurizer is up-
stream of a delayed coker, reduction of Conradson carbon
residue (CCR) is the controlling reaction. This allows
maximum utilization of the combined processes.
The strategy you use, the yields you get and the extent
to which you use your catalyst will likewise vary, depend-
ing on your feedstock quality and the economics of your
refinery situation.
Our experience is that catalyst fouls at a different rate
for each reaction. At severe end of run conditions, it is
possible to get acceptable conversion or CCR reduction
and, at the same time, very low denitrification. This could
cause distillate stability problems.
TOC/INDEX
TREESE:
In order to produce more distillate from a conventional
residual hydrotreater, the catalyst requires higher average
temperature or lower space velocity, or a combination of
both. There are a few residual hydrotreating catalysts
available that have a hydrocracking function incorporated
into them, and they can achieve a little bit more conver-
sion to distillate at lower temperatures than you could
otherwise get with a conventional catalyst.
In some cases, the optimum situation would be to
operate at slightly lower feed rate on the residual conver-
sion unit and higher temperature in order to convert more
of the feed to distillate.
Properties of the feedstock processed are part of the
equation. Processing of lower metals, sulfur and Conrad-
son carbon feed, will reduce the catalyst deactivation rate,
and may allow for operating the residual hydrotreater at a
higher temperature to achieve more conversion while
maintaining an acceptable catalyst life.
The penalty for making more distillates is reduced
throughput or shorter catalyst cycles. Higher hydrogen
consumption and gas make go along with the higher
conversion to distillates, which in turn reduces the recycle
gas hydrogen content and lowers the hydrogen partial
pressure so you end up with a higher catalyst deactivation
rate.
The highest conversion seen in units using conven-
tional residual hydrotreating catalysts is about 25% to
30% of the 650°F plus converted to 650°F minus material.
This is in a unit that was operated to desulfurize and
remove metals from the residual. The conversion ranged
from 10% to 12% at the start of the run, up to the 25%
to 30% at the end of the run.
Some units operate at higher end-of-run reactor tem-
peratures and some have experienced color stability prob-
lems in the heavy distillate at the end of run. It appears to
get worse as the cut point of the diesel is increased. The
problem occurs at the end of the cycle, as I said, when the
reactor temperatures are at their highest.
High conversion can also result in instability of the fuel
oil product, and this is related to asphaltene precipitation.
In extreme cases, this precipitation can occur inside the
reactors or in the heat exchangers, separators, and frac-
tionator, and it can result in serious operating problems
like high pressure drops, maldistribution within the reac-
tors, and foaming.
SAFA GEORGE (Criterion Catalyst Company L.P.):
The best approach or strategy for residual units depends
on unit objectives, unit fit into the refinery, and then the
catalyst system you select.
If the objective is to produce low sulfur fuel oil, then
the strategy is to enhance the HDS reaction to meet fuel
sulfur targets.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
If the objective is to prepare feedstock for a residual
catalytic cracker, then the strategy is to enhance reactions
for removals of metals, Conradson carbon, polynuclear
aromatic saturation to improve profitability on the resid-
ual catalytic cracker.
A third objective could be to increase distillate and/or
naphtha yields. In this case, Criterion Catalyst has devel-
oped a mild hydrocracking catalyst mainly applied for
residual services, to enhance distillate and naphtha pro-
duction. In other words, you are mild hydrocracking the
650°F to 1,000°F material into the distillate and naphtha
fractions. A 10 vol% increase in naphtha and distillate is
anticipated when applying a mild hydrocracking residual
catalyst without reduction in unit throughput.
ANDERS NIELSEN (Haldor Topsoe A/S):
We have pilot plant operations on the same residual oil
in both modes, one keeping sulfur constant, and the other
mode of going up to a temperature of around 750°F over
about a month, and then maintaining that temperature. In
our case, using a Kuwait atmospheric residual, the differ-
ence in the life is probably no more than 10% to 15%.
These were runs of 6,000 and 7,000 hours, respectively.
LINDA LORD (The Coastal Corporation):
Mr. Porter, at what pressure do you run your residual
hydrotreater? What sort of conversions have you realized
on the unit?
PORTER:
About 2,200 psi with a conversion level of about 60%.
MEHMET Y. ASIM (Akzo Nobel Catalysts):
Numerous comments have already been made regard-
ing the maximum distillate mode of operation. We want
to further emphasize that in this mode of operation at
elevated temperatures, if conversion of 1,000°F-plus ma-
terial exceeds 45% to 50%, sludge formation or asphaltene
precipitation will become a serious problem resulting in
pressure drop buildup in the effluent heat exchangers.
Therefore, residual desulfurizers should be operated below
the critical temperature to avoid sludge formation. Typi-
cally, when operating below 45% to 50% conversion of
1,000°F-plus material, there are no problems with the
stability of distillates.
QUESTION 31.
In hydrotreaters that are operating with a significant
temperature rise over the catalyst bed (WF), what
would be considered a minimum charge heater duty,
expressed as % of total heat input to the reactor, for
adequate reactor temperature control? Can recycle of
treated product be used instead?
117
TOC/INDEX
BOYCOTT:
We use a recycle stream of hydrotreated naphtha to
control the temperature rise in our naphtha hydrotreater
reactor. The question as to the percent of total heat input
that the charge heater should comprise is really a unit
specific question. Ours will run 12% to 20%. This is based
on the turndown of our heater and its burner design.
Running at 12%, we rely on the availability of hydro-
treated product as a quench material in case we receive a
slug of cracked stock.
Another approach is a feed/effluent bypass. I have seen
problems with this when it is employed without due care.
Severe thermal stresses will occur if the bypass is opened
too quickly.
I think the most important thing to stress is that both
start-up and normal operation need to be taken into
account in the design of the unit. If you size your charge
heater based on running conditions you could end up with
a charge heater that will take quite some time to start your
unit up based on required heat input.
My last point is that good operating procedures and
well trained operators are required to maintain control of
the system.
DEATON:
We operate a distillate hydrotreater with about 8%
hydrocracking, with as little as 20°F temperature rise
across the charge heater. This is about 15% of controllable
heat input to a reactor feed heat exchange system.
Recycle of treated product is not used in this system.
Exchanger bypassing, both controlled and manual, is used
to maintain minimum charge heater duty. Feed composi-
tion control is very important as the feed is a variable
mixture of diesel, LCO, and LVGO, with increases in the
percent LCO having the most effect on reactor tempera-
ture rise and heat exchange.
ARMBRESTER:
The only thing that I would add is that when you are
operating your charge heater at these very low firing rates,
it is even more important to have a reliable flame detection
and shutdown system, because the flame can be unstable
at low firing rates.
PORTER:
From a safety standpoint, we design our reactor charge
furnaces for about 40°F to 50°F temperature rise or about
10% of total heat input.
SAYLES:
I agree.
QUESTION 32.
Is anyone considering whole crude hydroprocessing
for naphthenic acid removal? What conditions would
118 Hydrogen Processing
be necessary? What inherent HDS and HDN levels
might be obtained?
LAUX:
We have not considered whole crude hydroprocessing
as an economic solution to the naphthenic acid problem
that we have in our small lube unit at Three Rivers.
As discussed earlier, in the General Processing and
Support Operations Session, the typical method of treat-
ing a naphthenic acid problem is to use the correct metal-
lurgy. For our lube crude unit and vacuum unit, the capital
cost to install that metallurgy was probably about 1% of
the total cost for a crude hydroprocessing unit. Operating
costs would also be significant for the crude hydroprocess-
ing unit.
QUESTION 33.
Several refiners have used catalyst passivation proc-
esses upon shutdown for unloading hydroprocessing
catalysts in air. What is the impact of such a procedure
on turnaround time and economics? Is regenerability
affected?
CUNEO:
We have used catalyst passivation, such as the CAT-
NAP process, a couple of times. On one application we
saved two days in shutting down the unit, which allowed
maintenance access to critical path equipment sooner than
expected. We have not yet attempted to regenerate and
reuse catalyst from this passivation process.
JAMES J. BARRY (CRI International, Inc.):
CATNAP has been applied about 80 times involving
over 250 reactors. On the issue of turnaround time, elimi-
nation of the hydrogen strip can save 12 to 24 hours in
the shutdown. Elimination of dust with CATNAP allows
the use of high capacity vacuum systems to remove the
catalyst 2 to 3 times faster than conventional vacuum
systems. With one hydrocracker, for example, we saved
about 2 days on the unloading time.
On the economics, most important is reduced turn-
around time. You save the nitrogen costs for inert entry.
Also, you require less makeup catalyst due to less catalyst
abrasion from the novel vacuum system. On shipping, the
catalysts can be classified as nonself-heating.
On regeneration, CRI has regenerated these treated
catalysts a number of times with success. The trick is to do
an inert nitrogen strip to remove the hydrocarbon.
MERLIN HOISETH (Reactor Services International, Inc.):
Passivating catalyst by cooling down the reactor with
gas oil and leaving the catalyst wet was the standard long
before a “passivation” chemical was ever introduced. Hot
hydrogen stripping followed by a nitrogen purge cool
down is not only a timesaver in not having to deal with a
TOC/INDEX
messy situation, but also enables the troubleshooting and
diagnosis ofoperating problems such as high pressure drop
or channeling.
Entering and working in a nitrogen atmosphere versus
an air atmosphere provides a safety factor for reactor
technicians. The potential for a pocket of gas in a “coked-
up” reactor is always present and thus the absence of
oxygen eliminates any explosive condition.
Whether or not to use the “passivating” chemical in the
shutdown process instead of hydrogen stripping the cata-
lyst bed of hydrocarbons before emptying should not be
determined on the basis of saving nitrogen costs. But
rather, it should be one of personnel safety considerations.
QUESTION 34.
What is the preferred presulfiding agent for hydro-
processing catalyst? For refiners who use TNPS (ter-
tiary nonyl polysulfide), what has been their
experience on performance, especially decomposi-
tion temperature?
ARMBRESTER:
Ashland’s preferred sulfiding agent is dimethyl sulfox-
ide, DMSO. This material is nontoxicand odorless, which
makes it considerably easier to handle than some of the
less expensive sulfiding agents such as dimethyl sulfide and
dimethyl disulfide. DMSO is also miscible with water,
which facilitates cleanup, but it does have a relatively high
freeze point of 65°F, so heat tracing of the tank and piping
may be necessary in cooler temperatures.
During the presulfiding operation, DMSO breaks
down to form DMS at 372°F, and the DMS subsequently
breaks down at 435°F to form H2S, which then reacts at
the catalyst metal sites to form metal sulfides.
BOYCOTT:
We typically use a presulfided catalyst in our naphtha
hydrotreater and DMDS for presulfiding on our diesel
hydrotreater.
D'AURIA:
We recommend DMDS or DMS as a sulfiding agent.
Several of our licensees have tried TMPS, but we dropped
it from our approved list because we had a couple of
instances of sulfur deposition in the injection piping and
pumps. This deposition occurred at temperatures below
50°F.
DEATON:
We use DMDS for presulfiding the hydrotreater and
hydrocracker reactors, and TNPS for presulfiding the re-
former reactors. We prefer DMDS over DMS, because
DMDS has a lower vapor pressure, is less odorous, and is
easier to pump. We park the bulk transport next to the unit,
pressurize the bulk transport to 100 psi with nitrogen, and
1994 NPRA Q&A Session on Refining and Petrochemical Technology
pressure the DMDS into our injection pumps. Although
DMDS reportedly begins to decompose at 350°E and this
is lower than the 425°F for decomposition of DMS, we
prefer to carry out presulfiding with DMDS at the same
temperature as required for DMS.
PORTER:
We use both DMDS and TMPS for sulfiding. We use
temperatures of 425°F to 450°F for decomposition.
TMPS costs about twice as much as DMDS per pound of
sulfur, but it has less odor problems.
SAYLES:
I agree.
TREESE:
Most of the agents that we are aware of have been
mentioned already. I would add that it is important to
maintain control of your injection rate and be sure that
you keep your recycle gas purity correct. Otherwise, you
begin experiencing hydrate precipitation problems in the
effluent.
At our other locations we have also used dimethyl
sulfide (DMS), carbon disulfide, and in some places where
we have it available, we use hydrogen sulfide gas. Any
agent that is convertible to H2S at relatively low tempera-
ture, say in the 300°F to 450°F range, can be controlled
to give satisfactory sulfiding results.
Often other factors, such as have been mentioned here,
are more important in the decision, such as odor or safety.
TOM CLANCY (Elf Atochem North America, Inc.):
We manufacture and sell virtually all of the presulfiding
agents for hydroprocessing catalysts, and based on use,
DMDS is far and away the preferred presulfiding agent.
However, I agree with the panel in that for each individual
application the preferred presulfiding agent will depend
upon the specific requirements of the refiner such as
handling, decomposition temperature, sulfur content,
and cost. Our research and commercial experience indi-
cate that TNPS decomposes at 320°F, DMDS at 392°F,
and DMS at 482°F.
QUESTION 35.
Are there advantages to using a radial flow reactor for
hydrotreating cracked naphthas?
PORTER:
Radial flow reactors are less sensitive to bed plugging
because material can build up in the scallops to a signifi-
cant extent before effecting pressure drop. Due to the
potential for small amounts ofchanneling, one should not
rely on a single radial flow reactor.
113
TOC/INDEX
SAYLES:
I agree that radial flow reactors do have a higher volume
to pick up scale and trash. Two reactors in parallel are
desirable for removal of one vessel while the other is in
service. We would use an active material to pack the
internals to aid in removing scale.
D'AURIA:
Radial flow reactors will maintain a low pressure drop
for a longer period of time when there is catalyst bed
fouling. However, if this fouling is occurring, it will result
in flow maldistribution across the catalyst bed. Cleaning
the foulant out from behind the scallops in a radial flow
reactor during turnaround can be a difficult and time
consuming task.
QUESTION 36.
In our reactor, the temperature reading among the bed
thermocouple showed 0 to 12°C difference, which
suggested uneven flow distribution. What kind of ac-
tion do you take for improved reactor bed flow? In
addition, how would the following action affect the
flow distribution:
increasing the reactor temperature,
recycle gas fate increase,
feed viscosity decrease, or
reactor internal (distribution tray) modification?
TREESE:
The radial uniformity of liquid and vapor flow distri-
bution in a catalyst bed depends on the efficiency of the
top liquid distribution tray, the uniformity of the bed, and
on the axial pressure drop through the bed.
The efficiency of the top distribution tray depends on
the design and layout of the individual distributors, and
on how tight and level the tray installation is.
The uniformity of the catalyst bed depends on the
radial permeability variations that exist in the bed, and
those variations can be caused by poor catalyst loading
technique, particulate accumulation in the bed, or coking
in the interstitial spaces between the particles.
If you experience significant radial temperature gradi-
ents in a single bed reactor, you should consider either
upgrading the top distributor tray, making appropriate
checks to ensure that the tray is installed correctly, and
monitoring the catalyst loading equipment and the tech-
niques used during the loading. Sometimes people abdi-
cate the loading of the catalyst to others. You really cannot
do that.
Also consider use of a graded bed configuration to take
fouling. Consider dense loading if your reactor mass ve-
locity is so low that you are not getting good distribution,
and you are getting too much trickle.
We have had some success identifying flow maldistribu-
tion by using radioactive scanning methods on-line like
120 Hydrogen Processing
Tru-Tee, although these are limited by the thickness of the
reactor wall.
I have a couple of comments on things that were
proposed here that affect increases in the reactor tempera-
ture. If the radial temperature spreads in the catalyst bed
are due to uneven liquid distribution, we would expect any
reactor temperature increase that is sufficient to fully
vaporize the reactants would be effective in reducing the
temperature spread. But if your temperature rise is not
going to fully vaporize the reactants, it is not going to help
you any on your temperature distribution, and it may even
make it worse.
As far as recycle gas rate, we do not really have any
evidence to indicate the recycle gas rate will always im-
prove the temperature distribution in a treating bed. In-
creased temperature gradients have been observed in some
units during turndown operation and we think that there
is a minimum axial pressure drop through the bed neces-
sary to prevent channeling. That is, the pressure drop helps
to distribute the reactants within the bed.
SAYLES:
A. Increasing the reaction temperature should not
effect temperature distribution provided the
quench is evenly distributed. Raising reactor tem-
peratures by reducing quench with poor distribu-
tion will increase maldistribution.
The total liquid plus gas mass flow through the
reactor should be between 2,000 to 5,000 lb/hr-sq
ft to maintain good flow distribution.
B. Increasing recycle gas can also provide the opposite
effects of higher maldistribution if the problem is
mechanical and good distribution if the flow is
below the critical mass flow.
C. For a given feedstock operation, naphtha, distillate,
VGO, etc., normal variations in feed physical
properties have not had an effect on feed distribu-
tion. High olefin, aromatics, or sulfur compared to
the normal feed can increase hydrogen consump-
tion to the point where radial maldistribution is
observed.
D. Reactor internal distributors have many configura-
tions. In general, the use of a redistribution tray
below each reactor bed and limiting the length to
bed depth ratio of between 3 to 4. Multiple bed
reactors and limiting the L/D will reduce the pos-
sibility of maldistribution.
An important consideration is the condition of the
catalyst bed. If only one bed is involved, coking or bed
pluggage is a likely cause of distribution problems. Un-
loading, screening, and reloading high fines catalyst can
eliminate distribution problems. High fines catalyst may
require replacement with fresh catalyst. Maldistribution
in each bed of multi-bed reactor is most likely a distributor
design problem. If the maldistribution occurs suddenly,
TOC/INDEX
then the catalyst may have experienced a water shot which
may destroy the catalyst integrity.
D’AURIA:
Before deciding there is flow maldistribution requiring
action to correct it, one would need to know the diameter
of the reactor - if it were 12 ft or more, 12°C radial
spread is not all that bad. As to what to do:
increasing reactor temperature will not improve liq-
uid flow distribution;
increasing recycle gas flow will improve distribution,
but only minimally;
feed viscosity will affect flow distribution minimally;
and
reactor internals modifications could help, provided
the existing internals are inadequate.
Another very important parameter is catalyst loading.
To get uniform pressure drop, and uniform flow distribu-
tion, the catalyst should be dense loaded.
DEATON:
For two phase flow reactors, proper installation and
design of liquid redistribution trays between beds is vital
in eliminating flow distribution problems and radial tem-
perature differences. Prior to revamping the liquid redis-
tribution decks in our Isomax hydrocracker, we
experienced radial temperature differences of up to 50°F,
but now the differences are down to 10°F maximum. I will
discuss the details in Question No. 50 of the hydrocrack-
ing section.
ADRIAN GRUIA (UOP):
Mr. Sayles, you talked about the 2,000 to 5,000 recom-
mended maximum flows. Are you talking about total
maximum flow or only liquid maximum flow?
SAYLES:
Total liquid plus gas flow.
PAUL VANCE (Acreon Catalysts):
I would like to reemphasize that the tray liquid levelness
is very important for uniform distribution.
Also, on turnarounds, inspect very closely the key
internals/tray components. Some of the designs have ver-
tical chimneys with what I call “piccolo holes” in the side.
If you put your flash light in there, they may look as if they
are clean, but I have seen them totally plugged off. You
really need to go down there and see that each has been
cleaned out individually, especially those farthest from the
manway.
CHARLES McCOY (Consultant):
I disagree on one point. Increasing recycle gas rate (or
gas to oil ratio) is always going to reduce delta T, whether
radial or axial, for the simple reason that the gas is thermally
1994 NPRA Q&A Session on Refining and Petrochemical Technology
inert. In fact, it will probably improve distribution as well.
Increasing recycle gas rate is going to help this problem.
TIMOTHY L. HECKEL (Unocal Process Technology):
Not to be too argumentative, but one case where in-
creasing recycle gas flow can create more of a problem is a
condition where the quench zone is either not properly
designed or not properly installed or has been damaged in
service. In that case, increasing quench requirement can
simply cool down part of the bed and not cool down the
rest of the bed and actually create a worse temperature
maldistribution problem.
Another potential is if, there is any bypassing of the
quench zone, say through a poorly sealed dump tube.
Then increasing recycle gas flow, and thus increasing
internals pressure drop, will result in increased bypassing
and more potential for a hot zone.
QUESTION 37.
Are there any new techniques to detect ma/distribution
other than bed thermometry (e.g., radioactive scan)?
TREESE:
We have had some experience in radioactive scans, like
I just mentioned on the previous question. This was with
Tru-Tec. The ability to use these methods is sometimes
limited by the thickness of the reactor walls, the size of the
reactor and the fact that it is loaded with a lot of dense
catalyst. What works well on a column is quite a bit less
effective on a reactor. But in a recent application, we could
spot density differences within the bed, and these were
later correlated and corresponded roughly to incorrect
installation of the upper distributor tray. Where we had
top entry thermowells, maintenance had cut out holes so
that the thermowells went in easily, but all the liquid also
went down the holes.
MICHAEL BOTHE (Tru-Tee):
Tru-Tee has developed a technique, called “SPECT-
SCAN”, for determining the liquid phase distribution
within refinery fixed bed reactors. The most important
piece of internal equipment for these reactors is the feed
distributor. Good distributor design is critical for maxi-
mizing catalyst life and to prevent “hot spots” from devel-
oping. The technique involves injecting an isotope into
the reactor that will stick to the catalyst in a pattern
consistent with the liquid distribution in the catalyst. The
reactor is then scanned at many points around the circum-
ference to collect data on the strength of the signal radiat-
ing from the isotope inside. The data is presented as
distribution and polar plots showing the pattern and
depth of the liquid maldistribution. Conventional nonde-
structive techniques, such as gamma scans and neutron
backscatter, are not effective for determining liquid
maldistribution in these reactors, because the thick walls
121
TOC/INDEX
and high catalyst density would require an extremely large
source that would be impractical to use. Still, gamma scans
can be used to locate and evaluate distributors, and find
the height of the catalyst bed. The source used for gamma
scanning these reactors is the same one used for Spect-
Scans. Additional tests that can be done with Spect-Scans
and gamma scans include: flow rate measurement, ex-
changer leak tests, and residence time distribution studies
of equipment located between the reactor and injection
point. Thus, it becomes very cost effective to have all three
of these procedures done on the same day to obtain the
most information needed to diagnose the problems with
your reactor.
QUESTION 38.
We have experienced plugging in the hot separator
vapor system of our gas oil hydrotreater where the
temperature range is 450°F to 600°F Injection of water
eliminates the plugging. We have not detected any
chloride in our feed. Have people observed formation
122 Hydrogen Processing
of solid ammonium chloride at these temperature lev-
els? What other water soluble solid compounds would
be causing this problem?
PORTER:
On rare occasions we have seen ammonium chloride
salts deposit in heat exchangers with bulk fluid tempera-
tures as high as 450°F. Usually it is with temperatures in
the 350°F range that we have had the most problems.
Chlorides are by far the most common salt, but we have
seen one or two plugging occurrences due to other halides.
Chlorides are introduced to the process via naphtha
reformer hydrogen, in the makeup hydrogen stream
and/or the liquid feed. It is difficult to measure the
minute levels of chloride in the feed that can cause
effluent plugging.
TREESE:
The precipitation ofammonium chloride is dependent
on the product of the partial pressures of the ammonia and
TOC/INDEX
the hydrochloric acid in the effluent system. If the feed
nitrogen is moderate to high, it only takes one or two ppm
of chloride in the recycle gas to cause the precipitation,
and that level can be reached with one ppm of chloride in
either the feed or the makeup hydrogen, as has been
alluded to by Mr. Porter.
One of our refineries has experienced ammonium chlo-
ride plugging at high salts levels. This occurred in the
temperature range that we are talking about, 450°F to
500°F, and we do not really have much information on
what other water soluble compounds might be causing
this. As mentioned, the other salt halides might potentially
be there, but chloride is more likely.
BOB RODDEY (Roddey Engineering Services, Inc.):
Ammonium chloride normally will not deposit at the
temperatures of 400°F to 600°F. I think what is happen-
ing in the exchanger that we are referring to is that there
is maldistribution in the exchanger. Hot separator vapors
often exchange heat with makeup hydrogen or recycle
gas, and the discharge temperature on the compressor can
be somewhere in the 175°F range, and so you can get to
the point where ammonium chloride will form. On the
tube side, there is obviously maldistribution in that the
flow in all the tubes is not the same. Therefore, if the flow
gets cold in some of the tubes because of a partial plug-
ging, you can get lower than the outlet temperature of the
exchanger in that one tube. I have seen that happen
before, where the outlet of the exchanger is, let us say,
500°F, yet some of the tubes in there are running at 250°F
or 300°F, certainly cold enough to deposit ammonium
chloride. That might be the problem to which the ques-
tion refers.
QUESTION 39.
In commercial hydrotreating processes for upgrading
of cracked distillates, usually a protection layer is
provided at the top of the active catalyst bed to provide
a good distribution of feed, demetalization, physical
adsorption, etc. Does this layer also hydrogenate the
diolefins?
CUNEO:
We use graded active support materials in loading of
the reactors and found that to be very beneficial in im-
proving the distribution. We also believe that active sup-
port materials would indeed start the hydrotreating
reaction sequence, including hydrogenation of diolefins.
BOYCOTT:
I would agree that if the active support material is used,
that it will promote the hydrogenation of diolefins and
olefins.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
PORTER:
I agree, but temperatures of less than 450°F are required
to prevent the diolefins from polymerizing before they get
to the catalyst.
R. KEVIN DODDS (Acreon Catalysts):
I agree that with active support at high temperature you
can start hydrogenating the diolefins before they reach the
catalyst. We have a catalyst, HR-945, that will help cut
down on the polymerization, gumming and the coking.
We believe that this catalyst with the demetalization or
active support will eliminate this problem.
ANOERS NIELSEN (Haldor Topsoe A/S):
It depends on the protection layer whether it will
hydrogenate the diolefins before they polymerize. To
hydrogenate the diolefins without plugging the layer, you
need a very careful grading by activity and size of a high
void material, such as rings.
Catalysts
QUESTION 40.
Has anyone ever identified formation of nickel car-
bony/ caused by partial combustion of spent catalyst?
(Some people have speculated about this. Has it ever
really happened?)
TREESE:
Nickel carbonyl formation has never been reported
during spent catalyst handling at our refineries or, to our
knowledge, by any of our licensees. However, the concern
over its presence is based on more than mere speculation.
Partial combustion of the warm spent catalyst on expo-
sure to air can lead to formation of carbon monoxide. The
carbon monoxide could then react with any small
amounts of metallic nickel that were formed by reduction
during the shutdown and hydrogen stripping operations.
These reactions, though, are not favored under any nor-
mal catalyst handling conditions. I would also note that
under regular shutdown conditions, they should not be
favored. Despite all this, given the extreme toxicity of
nickel carbonyl, it is advisable to take all the precautions
necessary, to completely eliminate any chance of its
presence.
BOYCOTT:
I would agree with Mr. Treese. We have never identified
the formation of nickel carbonyl, but we do take the
precautions of an inert reactor entry and testing for carbon
monoxide and carbon dioxide. The only instance I have
heard of is the instance in Texas in the 1960’s.
123
TOC/INDEX
CUNEO:
I have nothing more co add. We take the same precau-
tions, and we have never seen nickel carbonyl either.
D’AURIA:
Nickel carbonyl can be formed under conditions of
incomplete combustion in the temperature range of 300°F
co 400°F. It is an unstable compound and will decompose
outside this range. We are not aware of any documented
case where nickel carbonyl has been identified.
CHARLES MCCOY (Consultant):
A couple of years ago, a reactor on the West Coast fell
and broke off the piping. It burned initially, ofcourse. The
decision was made to allow it to continue burning for
some time rather than put the fire out because of the
concern chat oxygen could get drawn in, as Mr. Treese said,
and form carbon monoxide by partial combustion. If this
carbon monoxide somehow reached colder catalysts it
could react with the nickel and form nickel carbonyl. This
was hypothetical, but it was an extremely serious and
costly problem for the refinery involved. Nobody really
knew the answer. The panel does not have the answer
either. There has been more than one instance of the loss
of life in the refining industry because of nickel carbonyl,
not formed in this way but by purging with gas containing
carbon monoxide.
ANDERS NIELSEN (Haldor Topsoe A/S):
If any of you have a methanator in the cleanup of the
hydrogen, I would warn about getting the carbon oxides
out of that during shutdown procedure and before anyone
has any access to the methanator. There have been fatalities
with methanators and nickel carbonyl. Concerning safe
shutdown of methanators, see Allen D.W and Yen W.H.
Ammonia Plant Saf. 15, 96-101 (1973).
QUESTION 41.
Do any Eastern European companies manufacture and
market refining catalysts? Soviet patent literature is
full of catalyst items. Are Western refiners missing
out on some valuable technology? Does the panel
have any experience to report?
McLEAN:
The former Soviet Union excelled in research carried
out by centralized government-funded research institutes.
However, there was little progress in developing this into
manufacturing know how and capability, with the excep-
tion of the defense industry.
There are several catalyst manufacturing operations
which we know of, typically as part of a refinery which
produces catalyst for on-site consumption. We know this
applies to cracking, reforming, and isomerization cata-
lysts, usually one variety of each type produced per site.
124 Hydrogen Processing
What we have seen is that these operations are charac-
terized by severe raw material shortages, and do not have
the same attention to such factors as competition, quality
control, and customer satisfaction orientation that have
benefitted our own manufacturing operations. As a result,
the advances reported in the patent literature have gener-
ally not been commercially realized.
QUESTION 42.
It is apparent that ex situ presulfiding is gaining in
popularity. I understand that several units have expe-
rienced large exotherms during start-up with presul-
fided catalysts. What type of products or units have
these problems? How severe is the problem? How can
it be avoided?
LAUX:
We have used presulfided catalyst on numerous occa-
sions in our lube hydrotreater and once in a naphtha
hydrotreater as well. There has only been one instance of
a large exotherm occurring. The reactor had over a 300°F
delta T. The unit pressure also dropped rapidly at the same
time. We believe that there was too much presulfiding
chemical on this load of catalyst. It was a load that had
been sitting in storage at the vendor’s warehouse for some
time and potentially it was dosed twice. Interestingly, we
had a normal run on that load of catalyst, even after that
large exotherm.
DEATON:
Early methods of presulfiding catalysts did provide
considerable risk of high exotherms during start-up.
Exotherms are caused by the activation rate of the presul-
fiding catalyst. Very slow heat-up rates, on the order of
25°F per hour, and wet start-ups with liquid feed acting
as a heat sink, were typically employed co minimize the
risk of excessive exotherms. However, in the last two to
three years new presulfiding methods have dramatically
reduced exotherms and temperature rises of only 25°F to
50°F are usually expected, using only hydrogen as a circu-
lating medium.
On one recent start-up of our naphtha hydrotreater, an
exocherm of less than 15°F was observed. We use CRI’s
ACTICAT This product activates slowly over a tempera-
cure range of 350°F co 475°F, thus minimizing the degree
of exotherm.
STEPHEN MURFF (Eurecat U.S. Incorporated):
During the activation of hydroprocessing catalysts,
some exotherm is a natural and expected occurrence,
whether the unit is utilizing in situ sulfiding or ex situ
sulfiding. For the vast majority of the 60 million lb of
Sulficat® Process presulfided catalysts that our company
has provided, these activations have been smooth and
uneventful, with only moderate exotherms.
TOC/INDEX
In a limited number of cases, some specific catalysts
sulfided with off-site sulfiding were activated under gas
phase conditions, and have exhibited exotherms which
cause some concern. The number of these units is limited,
and very easily identified. For these specific cases, Eurecat
has addressed the concern by, first, working closely with
the refiners to design a specific start-up procedure for those
units, and, second, modifying the off-site presulfiding
process to meet the requirements of the units that are of
concern.
Since our company was the inventor of the first and
most widely utilized sulfiding process, and the first com-
pany in the industry to receive ISO 9002 certification for
our services, we are committed to continually evaluating
and improving the services we provide our customers.
QUESTION 43.
What is the industry experience with receiving pre-sul-
furized catalyst in intermediate bulk containers? Based
on experience, has the overall downtime of the unit(s)
been reduced? Are there any storage problems?
BOYCOTT:
We have been using presulfiding catalysts for a number
of years now. We had one serious incident with the mate-
rial based on lack of drying before shipment. Overall we
have been very pleased with its use. We continue to use
the presulfided catalysts successfully, and typically on a
small unit, we are seeing a 24- to 36-hour time savings. In
storage this material must be kept inert and dry.
LAUX:
We have received presulfided catalysts in steel drums,
catalyst flow bins that hold about 10 drums each, and in
supersacks. The supersack order did not quite make it to
the refinery, though. Some of the sacks melted while
traveling down the highway.
We also had odor problems in our warehouse from
those sacks that did arrive, even though they were there
for only ten hours. We do not allow supersacks of presul-
fided material now at all.
The catalyst bins save a lot of loading time and we use
them whenever possible. We estimate that we save about
36 hours on a start-up by using presulfided catalyst. Also,
we have stored presulfided catalyst for up to nine months
in steel drums without any problems.
RON FUNK (Federal Container Corporation):
Federal Container operates a rental pool of DOT and
UN approved Catalyst-Bins, otherwise known as IBCs, or
flow bins as you have referred to them, used specifically
for the storage and shipment of presulfurized catalyst. We
have provided this service for almost four years in the U.S.,
Canada, and just most recently, Europe. FCC Catalyst-
Bins hold a 12-to-1 size advantage over standard drums,
1994 NPRA Q&A Session on Refining and Petrochemical Technology
significantly reducing overall handling and loading times,
as well as eliminating packaging material waste.
BOYCOTT:
On the issue of bulk handling of presulfided catalyst, it
is critical to keep the material dry and inert. I would
concur with Mr. Funk on the use of flow bins. We have
not had a problem in the last three years.
QUESTION 44.
The concept of “cradle to grave” management of the
life cycle of catalyst has been advocated by several
catalyst manufacturers. What has been the industry
interest?
TREESE:
While cradle to grave management of catalysts is some-
what appealing, Unocal’s response has been lukewarm.
The issue is complicated by the definition of who the waste
generator is and the legal responsibilities involved in it.
The general concept has merit, and we may express inter-
est in this option in the future.
In a sense, we already recycle our catalysts and metals
here whenever possible, especially the noble metals cata-
lysts that we use for hydrocracking and reforming.
McLEAN:
This is a general question, and my answer applies to
FCC catalysts, even though I realize we are in the wrong
session here for that.
Engelhard does work with our customers to determine
the best disposition option for spent catalyst, but, again,
the ultimate responsibility for selecting and controlling
that option remains with the refiner. If the catalyst’s metals
level, activity, and physical properties are of sufficient
quality to allow the equilibrium catalyst to be used for
addition to another FCC unit, we assist in locating such
an option, either by a direct referral or in some cases
through a third party broker. We have also done significant
work in studying the use of equilibrium FCC catalysts as
feedstocks for the manufacture of both asphalt fillers and
cement.
We would be happy to share the information that we
have garnered from this with refiners and help them
arrange for their preferred options.
SAYLES:
The way we understand the cradle to grave concept is
the catalyst manufacturer accepts the responsibility to
supply you with the catalyst and you never really gain
possession. We are uncomfortable with not being in con-
trol of waste material. Instead, we prefer to take possession
of the catalyst and have control over the catalyst disposal.
We recycle all of our precious metals catalysts without
exception. With some of our hydrotreater catalysts, we
125
TOC/INDEX
have recycled the metals where the cost made sense. In
other cases, we have elected for landfills.
D'AURIA:
Cradle to grave is not an entirely new concept. UOP
has provided this service for precious metal catalysts since
the early ’50s. In addition to recovery of the precious
metal, the catalyst base is converted to commercial grade
alumina and totally recycled. Extending this service to
other catalyst lines has met with lukewarm response from
refiners. The reason is the lack of an economic driving
force. The expense of recycling has not been justified by
the value of the recovered materials.
STEPHEN PAVEL (Coastal Catalyst Technology, Inc.):
As the panelist brought spent FCCU catalyst disposal
options into this response, it is appropriate to add an
option absent from that review: demetallization and recy-
cling of spent FCCU catalyst is an option to disposal.
Off-site and on-site demetallization has been described in
the literature and NPRA papers since 1988.
Considering the cradle and the grave of the metals
in/on spent FCCU catalyst, the source of the metal con-
taminants and the ultimate recovery of those metals,
requires complete elemental analyses of the spent material
and their leachates. Metals taken from the ground in crude
oil and deposited on fresh FCCU catalyst can be recovered
using a pyrometallurgical and hydrometallurgical process,
DEMET ® , and the base material recycled for original use,
FCCU catalysis, or disposed in landfills or cement kilns.
CCTI’s DEMET process takes a portion of spent
FCCU catalyst and removes a portion of the metal con-
taminants, enabling the refiner to recycle demetallized
spent FCCU catalyst back to the FCCU, thus reducing
the solid waste from the refinery. Best Demonstrated
Available Technology (BDAT) for heavy metals is High
Temperature Metal Recovery (HTMR). Spent FCCU
catalyst contains a high percentage of silica and alumina,
which makes it unsuitable feed stock for HTMR due to
high slag formation, increased cost of processing and
reduced throughput. Demetallization removes heavy met-
als from spent FCCU catalyst. Metals are recovered by
precipitation (BDAT for metal recovery from waste-
waters), and are at concentrations acceptable for BDAT
metal reclaimers using HTMR.
Spent FCCU catalyst is not a listed RCRA waste.
Previously, some have compared spent FCCU catalyst to
another waste that had not been listed under RCRA, fly
ash; that was prior to this year’s Supreme Court ruling on
municipal solid waste incinerator fly ash. Newly listed
RCRA wastes are subject to rules such as the Land Dis-
posal Restrictions-Phase II (LDR-II) Universal Treatment
Standards (UTS) published in the Federal Register, Sep-
tember 19, 1994. The Toxicity Characteristic Leaching
Procedure (TCLP) is used to extract leachable metals for
126 Hydrogen Processing
comparison to the LDR-II UTS to determine whether or
not that waste requires treatment prior to disposal. Table
I provides metals in spent and demetallized spent FCCU
catalyst leachate from routine TCLE de-ionized water
TCLP (DI-TCLP), and a de-ionized water flush (versus
the TCLP 18-hour shake) at two temperatures.
Metals are contained in FCCU feed stock and in fresh
catalyst added to the FCCU. TCLP showed leachable
metals from fresh catalyst. Metals found in spent FCCU
catalyst leachate also include those which are deposited
from feed stock. Table II shows the TCLP leachate analyses
of fresh, spent and demetallized catalyst samples; demet-
allization was performed at a lower severity for reduction
of leachable metals prior to disposal rather than recycling.
Table II shows a low vanadium content spent catalyst can
leach above UTS limits, and less rigorous demetallization
conditions provide effective removal of metals which pre-
viously leached from spent catalyst. As demetallized spent
FCCU catalyst TCLP leachate is below the LDR-II UTS
for all fourteen metals, demetallization could be used to
reduce the leachable metals prior to secondary recycling
(cement kilns, etc.) or disposal. At the 1994 NPRA Envi-
ronmental meeting it was reported by a panelist that
cement kiln feed stocks are limited to a blend of 83 ppm
vanadium due to potential problems with refractory. Us-
ing DEMET to remove vanadium from feed stocks to
cement kilns would increase capability to process spent
FCCU catalyst.
DEMET process service is currently provided at an
off-site plant in Meraux, LA. Through a three and a half
year run from April, 1991, through September, 1994, one
refiner recycled over 8,700 tons of spent FCCU catalyst.
Adding to 1,300 tons previously processed and recycled,
that refinery has recycled over 10,000 tons of demetallized
spent FCCU catalyst. Fresh catalyst additions were re-
duced from fifteen to under six tons a day by recycling
about eight and a half tons per day; this reduction in-
creased the average age of the circulating FCCU catalyst
from 30 days to over 80 days without deterioration of the
yield performance of the unit. Although DEMET can be
utilized to pre-treat spent FCCU catalyst prior to disposal,
recycling demetallized spent FCCU catalyst has more
economic and environmental advantages.
HEROS OERGREGORIAN (Giant Refining Company):
In the old days we used to regenerate hydrotreating
catalyst. Concerning all the problems of environmental
and the life of the cycles, has anybody looked at ex situ or
in situ regeneration of the hydrotreating catalyst? Is the
technology available for that?
LAUX:
Yes. We definitely regenerate our hydrotreating cata-
lysts from our lube unit, as well as from our first reactor
TOC/INDEX

Table I. Table II.

Reduction of Spent FCCU Catalyst A Leachability By TCLP Leachability of Fresh, Spent and Demetallized
DEMETallization, Various Leachates Routine Spent FCCU Catalyst B
Demetallization for Recovery of Metals, And Recycle of Minimum Processing for Removal of Leachable Materials
Base Material to FCCU Prior to Disposal/Secondary Use

Method: Total Analysis Routine TCLP De-ionized H20 Catalyst: LDR-II Element Fresh Fresh
20:1 at 2.88 pH 20:1 DI-TCLP UTS Detect catalyst TCLP
Analysis: TCLP Limit Total Leachate
Catalyst: Spent DCAT Spent DCAT Spent DCAT
Element: ppm ppm ppm ppm
Sample: Total Total L’chate Lchate L’chate L’chate
Element: ppm ppm ppm ppm ppm ppm Antimony 2.1 0.050 bdl bdl
Arsenic 5.0 0.050 78.7 bdl
Antimony 2272 387 3.5 bdl 5.5 bdl
Barium 7.6 0.050 83.4 0.78
Arsenic 122 17 bdl bdl bdl bdl
Beryllium 0.014 0.001 3.3 0.002
Barium 247 36 1.1 1.2 0.20 0.32
Cadmium 0.19 0.01 bdl bdl
Beryllium 21 4 0.002 0.002 bdl bdl
Chromium 0.86 0.01 75.9 0.01
Cadmium 5 bdl bdl bdl bdl bdl
Lead 0.37 0.02 39.6 0.05
Chromium 97 33 0.02 0.02 bdl bdl
Mercury 0.025 0.0002 nt 0.0006
Lead 5 5 0.02 0.03 bdl bdl
Nickel 5.0 0.010 27.0 0.01
Mercury bdl bdl 0.0003 0.0004 bdl 0.0002
Selenium 0.16 0.15 bdl bdl
Nickel 5211 598 1.5 1.2 0.28 0.48
Silver 0.3 0.05 bdl bdl
Selenium bdl bdl bdl bdl bdl bdl
Thallium 0.078 0.05 bdl bdl
Silver 10 2 bdl bdl bdl bdl
Vanadium 0.23 0.02 61.3 bdl
Thallium bdl bdl bdl bdl bdl bdl
Zinc 5.3 0.005 101.1 0.537
Vanadium 2045 539 1.7 bdl 4.4 bdl
Zinc 233 119 0.555 0.532 0.106 0.090
Catalyst: Spent Spent DCAT DCAT
catalyst TCLP catalyst TCLP
Method: DI-Flush DI-Flush
Analysis: Total Leachate Total L'chate
20:1 flush 70°F 20:1 flush 212°F
Element: ppm ppm ppm ppm
Catalyst: Spent DCAT Spent DCAT Element
Sample: L'chate L'chate L’chate L'chate Symbol Antimony 685.7 0.05 201.4 bdl
Element: ppm ppm ppm ppm Arsenic 117.0 bdl 113.7 bdl
Barium 114.0 0.77 123.9 0.77
Antimony 0.951 0.042 12.05 0.090 Sb
Beryllium 0.97 bdl 0.99 bdl
Arsenic bdl bdl bdl bdl As
Cadmium bdl bdl bdl bdl
Barium 0.057 bdl 0.011 0.037 Ba
Chromium 88.1 bdl 82.9 0.01
Beryllium 0.010 0.012 0.056 0.014 Be
Lead 37.3 0.03 27.1 bdl
Cadmium bdl bdl bdl 0.005 Cd
Mercury bdl bdl bdl bdl
Chromium bdl 0.003 bdl 0.009 Cr
Nickel 2603.1 1.00 482.0 0.33
Lead bdl bdl bdl bdl Pb
Selenium bdl bdl bdl bdl
Mercury bdl bdl bdl bdl Hg
Silver bdl bdl bdl bdl
Nickel 0.282 0.219 0.356 0.270 Ni
Thallium bdl bdl bdl bdl
Selenium bdl bdl bdl bdl Se
Vanadium 1436.2 0.63 1038.5 bdl
Silver 0.005 bdl 0.005 bdl Ag
Zinc 173.5 0.63 151.9 0.54
Thallium bdl bdl bdl bdl TI
Vanadium 1.028 0.003 6.917 0.106 V Note: Other elements (Al, Ca, Co, Cu, Fe, K, Mg, Mn, MO, Na, P, Si, Sn, Ti)
Zn present in leachates, only elements in LDR-II UTS shown; Fresh = Fresh
Zinc 0.057 0.022 0.040 0.080 FCCU Catalyst; Spent = Spent FCCU Catalyst, DCAT = Demetallized
spent FCCU catalyst, L’chate = leachate; bdl = below detection limit, nt
= not tested.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 127

TOC/INDEX
in our hydrocrackers. We use regenerated hydrocracker
first reactor catalyst in our naphtha hydrotreaters.
BOYCOTT:
We purchase regenerated catalyst for our naphtha hy-
drotreater, and we intend to send the initial catalyst charge
from our diesel hydrotreater out for regeneration. We use
regenerated hydrocracker first reactor catalyst in our naph-
tha hydrotreaters.
CESAR TREVINO (Criterion Catalyst Company L.P.):
Cradle to grave management has different concepts. It
can be as simple as applying fresh catalyst and disposing
of the spent, or it can be as complex as what we put
together with Syncrude, which includes managing every-
thing in between, from the fresh catalyst, the disposal, the
loading, the unloading, the warehousing, the emergency
response team, and you name it. Although they do not put
their hands on the catalyst, you cannot take away the
responsibility of the catalyst from the refiner. That is
always going to be there. All we do is manage the services,
we put together contracts with companies like CRI, Cal-
tex, CRI-MET, and a few other companies. But you
cannot take away the responsibility from the refiner. It is
not for everybody, but there are some people that can really
take advantage of this.
JAY JAFFE (Gulf Chemical & Metallurgical Corp.):
It is our understanding that a select few refineries have
studied the cradle to grave approach for spent hydrotreat-
ing catalysts, and even fewer remain committed to it. The
comments we have heard from those refiners is that there
is a loss of control of identifying the costs associated with
it, and that the true cost of any one piece of the puzzle can
be disguised or hidden.
QUESTION 45.
What factors maximize a Catalyst's ability to absorb
SiO2 from coker naphtha?
CUNEO:
Silicon deposition appears to be maximized on catalysts
having high surface area and high pore volume. Our
observations have been that the maximum amount of
silicon is deposited at the top of the reactor bed. However,
near the bottom of the bed, silicon levels are very low, even
after break-through has occurred. In this type of situation,
short term relief is possible through increase in reactor
temperature.
Finally, we have observed that a higher feed concentra-
tion of silicon also increases the saturation level of the
silicon deposited on the catalyst, although it decreases the
time until break-through.
128 Hydrogen Processing
TREESE:
I would add that in addition to the catalyst surface area,
the high exposed surface area of the active alumina support
on the catalyst and high operating temperatures also help
in the adsorption.
ANOERS NIELSEN (Haldor Topsoe A/S):
We have investigated silicone deactivated catalysts with
a number of techniques, including 13C and 29Si solid state
NMR and by micro probe. We find that there is SiO2,
surface siloxane groups and silicon bound to alkyls in the
surface. We see no silicone oil, however. The micro probe
shows silicon equally distributed over the cross section of
catalyst pellets. We believe surface area, pore size, and
activity play a role. We see up to 25 wt% SiO2 in a spent
high activity catalyst.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
An area of concern I have regards the spent catalyst
dumping and the handling. Under what conditions, wet
or dry environment, is this done?
PORTER:
The advantages of dry dumping spent catalyst are: no
water disposal problems and catalyst regeneration is eas-
ier. The disadvantage is that an active spent catalyst has
to be handled and shipped with care to avoid overheating
problems.
MEHMET Y. ASIM (Akzo Nobel Catalysts):
The major characteristic is the surface area of the
catalyst, as deposition of the comparatively small silicon
atom apparently does not result in pore-mouth plugging.
In fact, there is a direct correlation between the catalyst
surface area and the silicon pickup capacity as shown in
the figure below (the silicon on the spent catalyst is
measured as SiO2):
Silica Capacity of
Hydrotreating Catalysts
TOC/INDEX
For many years, our Ketjenfine® 844 has provided the
refiner with the highest capacity for silicon pick-up for
hydrotreating coker naphtha. With a typical surface area
of 295 m2/g for the fresh catalyst, analyses of spent KF-844
have shown a capacity for picking up greater than 20% of
its own weight of SiO2.
QUESTION 46.
What has been the experience with using mild hy-
drocracking catalyst on an FCC feed hydrotreater to
achieve incremental refinery production of tow sulfur
diesel? What are the /imitations with this type of
approach?
ARMBRESTER:
Ashland has no commercial experience with this proc-
essing scheme, but we have performed laboratory testing
of mild hydrocracking of FCC feeds. These tests have
shown a 5% to 10% yield of diesel, with less than 0.05%
sulfur content. Relatively severe conditions are required,
with low liquid hourly space velocity being the most
beneficial. The minimum reactor inlet temperature ap-
pears to be around 725°F. These high severity conditions
will result in a relatively short catalyst life, and hydrogen
consumption can be expected to be high, at about 500
standard cubic feet per barrel or greater.
While this operation is helpful in increasing low sulfur
diesel production, the hydrotreater reactor temperature
that results in the optimum FCC operation may not
necessarily be the highest temperature attainable, which
could limit the amount of diesel produced. In addition,
the stripper and overhead system may require modifica-
tion to handle the increased volume of naphtha and diesel.
Mild hydrocracking of FCC feeds also results in an
improved light cycle oil product from the FCC unit,
which could then be blended into the diesel hydrotreater
feed streams although the LCO product has a lower sulfur
content, the cetane number or aromatics level may still
limit the amount of LCO that can be blended into the
diesel pool.
D'AURIA:
We have been involved in about ten mild hydrocrack-
ing projects, that were revamps of hydrotreaters, with the
unconverted material being used as FCC feedstocks. All
of these projects were driven by VGO conversion rather
than production of low sulfur diesel. The cetane of the
diesel product may limit this application, as cetane up-
grading is not great in mild hydrocracking.
The converted product generally is less than 100 ppm
sulfur, and the unconverted material to the FCC is in the
range of 0.1 wt% to 0.3 wt% sulfur.
Other limitations that must be considered when con-
verting an existing hydrotreater are the available catalyst
1994 NPRA Q&A Session on Refining and Petrochemical Technology
volume, the design pressure, and the reactor quench
capability.
SAFA GEORGE (Criterion Catalyst Company L.P.):
Mild hydrocracking catalyst systems have been devel-
oped and are in commercial operations in a number of
units to achieve incremental production of low sulfur
diesel fuel. The overall conversion is dependent on crude
type, catalyst system selected (alumina, amorphous silica
alumina or zeolite based), and operating conditions, in-
cluding liquid hourly space velocity, hydrogen partial
pressure, hydrogen availability, and operating tempera-
ture. The resulting 650°F+ conversion varies between 20%
to 50%. Mild hydrocracker limitations include desired
cycle life, hydrogen availability and FCC feed require-
ments. Benefits include production of low sulfur diesel,
with sulfur typically varying between less than 50 ppm at
start of run to less than 200 ppm at end of run, kerosene
jet stream for blending and upgrading of the FCC feed
such as the reductions in sulfur, metals, CCR, nitrogen
and polynuclear aromatics.
PANKAJ H. DESAI (Akzo Nobel Chemicals):
We have been selling mild hydrocracking catalysts for
the last several years. This application has been mainly in
Europe, where refiners are looking for incremental con-
version. As the gentleman from the panel mentioned, the
main objective is to obtain incremental VGO conversion,
and in all cases the diesel produced is indeed low in sulfur.
In the early ‘8Os, we published a paper, titled “Mild
Hydrocracking of FCC Feeds Produces Yield Benefits in
Mid-Distillates, Gasoline” (Oil & Gas Journal, July 22,
1985, page 106).
PAUL VANCE (Acreon Catalysts):
Mild hydrocracking in an FCC feed hydrotreater is
economically being done today to produce middle distil-
lates at several locations using a catalyst marketed by
Acreon. These are in both IFP licensed and non-IFP
licensed units. The incremental severity to achieve low
sulfur diesel is possible as long as feedstock and operating
conditions will allow meeting product properties. Nor-
mally cetane is a primary consideration in blending mild
hydrocrackate.
LEEN A. GERRITSEN (Akzo Nobel Chemicals B.V.):
Akzo Nobel introduced amorphous MHC catalyst in
the mid eighties. Zeolite-containing MHC catalysts were
introduced a few years ago. In addition to extra conver-
sion, the zeolite MHC catalysts give a better HDN and
a higher density reduction, resulting in improved FCC
feedstock properties. Zeolitic hydrocracking catalysts
have been loaded in amongst two other MAK-MPHC
units, a moderate pressure single stage hydroprocessing
process developed by Mobil Research and Development
129
TOC/INDEX
Corporation and licensed jointly by Mobil, Akzo Nobel,
and the M.W. Kellogg Company.
I refer to presentations given during the Akzo Nobel
Symposium in the Netherlands in June of this year.
ROY PRATT (Texaco, Inc.):
One of the problems with mild hydrocracking opera-
tions is the variation in conversion and product quality
during the run. You might want to consider Texaco’s
T-Star process that operates at constant operating condi-
tions throughout the run and produces a constant quality
product.
C. Hydrocracking
Mechanical
QUESTION 47.
What are the latest techniques for minimizing/elimi-
nating ammonium bisulfide corrosion in the hot high
pressure separator overhead cooling system (updates
to the 1975 NACE report)? Please address metallurgy,
washwater quality and rate, piping symmetry and
other factors which can impact this problem.
PORTER:
This topic was the subject of a four hour round table
discussion at the API Subcommittee on Corrosion and
Materials Meeting in Dallas on May 17, 1994. Minutes
are available from API. Presentations were made by
Amoco, ARCO, Chevron, Conoco, Exxon, Japan Energy
Corporation, Shell, and Unocal.
To summarize, we limit the use of carbon steel piping
and heat exchanger tubes to 10% maximum ammonium
bisulfide concentration and 20 fps maximum velocity. At
higher concentrations or higher stream velocity, we prefer
UNS NO8825 (trade name is Incoloy 825). Inlet piping
to air cooled heat exchangers is symmetrical, and long
radius bends are used in both inlet and outlet piping. Key
limits on washwater are 15 ppb oxygen maximum, pH
between 8 and 10, and Fe below 1 ppm. Washwater must
be at least 25% unvaporized entering the exchanger. We
prefer water injection using individual spray nozzles at
each bundle. Tube and piping inspection intervals for
plants vary according to velocity and ammonium bisulfide
concentration.
CUNEO:
The only thing I would add is that we also like to see
the annular liquid flow in the air cooler tubes.
D’AURIA:
The current UOP/Unocal design practice for hydro-
cracker effluent air coolers is as follows:
130 Hydrogen Processing
a. The metallurgy of the air cooler itself is a function
of a parameter called Kp, which is the product of
the ammonia and hydrogen sulfide concentrations
in mole percent. For Kp below 0.15, carbon steel
can be used. For Kp between 0.15 and 0.25, carbon
steel is specified, but an option for incoloy 825 is
given. For Kp between 0.25 and 0.4 incoloy 825 is
specified, but an option for carbon steel is given.
For Kp above 0.4, incoloy 825 only is specified.
b. For carbon steel, the velocity limits are 20 fps
maximum and 10 fps minimum. For incoloy 825
the velocity limits are 30 fps maximum and 10 fps
minimum.
C.
Piping upstream and downstream of the air con-
denser is fully symmetrical. We require that the
number of exchanger bundles be equal to 2n where
n is any integer. Also, the piping between the air
condenser and the separator has a maximum veloc-
ity of 20 fps. This piping is usually carbon steel. The
washwater is added upstream of the air condenser
in the main line before the split to the bundles.
d. The maximum concentration ofammonium bisul-
fide in the sour water is 8 wt%. The washwater rate
is a minimum of 5 vol% of the fresh feed rate,
higher if required to maintain the 8 wt% ammo-
nium bisulfide criteria.
e. Washwater quality should be that of de-aerated
boiler feedwater without treating chemicals or
clean condensate. We do allow 50% of the wash-
water to be stripped sour water, but it must origi-
nate from a sour water unit processing sour water
only from the hydrocracking unit.
f. UOP/Unocal are currently conducting a survey of
our licensees using Mr. Peale, the author of NACE
report. We expect to complete our analysis of the
results and report back to our licensees by the end
of the year. We then intend to provide our data to
NACE at their spring meeting in 1995.
QUESTION 48.
Doesanyone have experience with radial maldistribu-
tion which comes and goes in hydrocracker reactors?
CUNEO:
We have installed radial thermocouple systems in some
of our hydrocracker reactors which contain zeolite cata-
lyst. These were developed with GAYESCO and are avail-
able from them. We found that for the most part
individual points that are hotter or colder than the average
tend to remain that way relative to the other points, even
with increases and decreases in severity. As bed delta T is
increased, the deviation between the individual points also
increases.
TOC/INDEX
D’AURIA:
Radial maldistribution can vary due to changes in feed
or recycle rate. At low total liquid rates to the reactor there
is a greater possibility of experiencing variations of the
delta T.
TREESE:
I would add that you can see changes in process condi-
tions that will impact the radial temperature distribution,
i.e., mass velocity, degree of interbed quenching, reaction
severity, and feedstock reactivity. Small changes probably
would not do anything, but with more substantial
changes, you will see some changes in the radial profile.
In this specific instance, one thought that comes co
mind is that there might be an undetected hot spot in the
catalyst bed. Some condition may have changed that is
pulling the hot spot over closer to a temperature indicator
that is in turn being detected by the temperature indicator.
When they go back to the old condition, it pulls back into
the position it was in before.
We strongly recommend having extensive bed thermo-
couples and skin thermocouples. If the hot spot happens
to be near the wall, it can even result in failure of the reactor
vessel.
Another approach that might be considered would be
infrared imaging of the reactor to detect hot spots on the
wall.
MAJED A. INTABI (Saudi Aramco):
Variation in the radial temperature profile was noticed
in one of our hydrocrackers which operated at higher
severity, and fed with a blend of vacuum gas oils and a
heavy raffinate from a solvent extraction unit. Such behav-
ior of the radial profile seems to be caused by factors related
to operation and design that can induce channeling of flow
in the catalyst bed. Sudden operational changes and upsets
such as loss of recycle gas, feed or both, as well as other
1994 NPRA Q&A Session on Refining and Petrochemical Technology
parameters that promote localized temperature excur-
sions, play an important role in creating such behaviors in
the radial temperature profile.
SHAUN R. BOARDMAN (Criterion Catalyst Company L.P.):
I agree very strongly with Mr. Treese’s remarks, but we
have a slightly different explanation. This is primarily due
to localized overcracking and is a function of the liquid
refreshment rate at the catalyst surface. We have also been
able to successfully predict the minimum flux rates that
are associated with the onset of this sort of behavior.
QUESTION 49.
What is the necessity for neutralization of the stain-
less steel 347 H? What are the procedures used,
especially in vertical heaters?
SAYLES:
We neutralize all 300 Series stainless steels subject to
polythionic acids using a soda ash solution.
The question asked specifically about what is done with
vertical heaters. We have had a vertical heater that has been
in operation since 1974. We have never attempted a soda
ash wash due to the concerns of leaving soda ash in the
bends and not being able to purge the soda ash solution
our of the bottom of the tubes. For this particular heater,
we have maintained a nitrogen purge during down periods
and have had no operational problems.
LAUX:
Type 347-H stainless steel being stabilized is less sus-
ceptible to polythionic acid attack, but is not immune.
Operation at 800°F for extended periods of time with coke
present can sensitize even this stabilized steel.
I will not go into too much on the recommended
practice on how to neutralize it as it is covered in NACE’s
RP-01-70 in great detail.
We have not neutralized our heaters yet. We just keep
them blanketed with ammoniated nitrogen.
DEATON:
All 347 stainless steel in sulfiding service must be
neutralized with soda ash prior to allowing air to contact
the sulfided surfaces to prevent polythionic stress corro-
sion cracking.
We unload our hydrocracking catalyst under an inert
atmosphere and then spray wash the reactor internal walls
with soda ash solution under inert atmosphere prior to
exposing metal surfaces to air.
Concerning the heaters, I agree with the other two
gentlemen’s comments.
DANIEL N. MYERS (UOP):
Concerning neutralizing of stainless materials, you are
speaking of the inside of the tubes, but what is done to
131
TOC/INDEX
protect these tubes on the outside from polythionic acid
attack that would come from the fuel gas side? Typically,
the heaters would have the pilots continuing to run if there
was no inspection of the heater required. However, if you
had to go into the heater to do inspections on the 347 type
tubes, would neutralization be required, and if so, how
might that be done?
PORTER:
First of all, we do not leave fires (even pilots) operating
in a furnace during a plant shutdown. To avoid external
attack of the tubes we try to keep moisture out of the
furnace by using dehumidifiers during shutdown periods.
QUESTION 50.
At what temperature difference in any bed of a hy-
drocracking reactor is flow distribution considered to
be a problem? Have hydrocracker internals been suc-
cessfully retrofitted to improve distribution? What
was the nature of the modifications?
CUNEO:
The answer here really depends on how much of the
reactor bed can be monitored by looking radially, and also
whether the catalyst is amorphous or zeolite. If a refiner
has only two or three radial positions to monitor, you
really are not seeing very much of your bed. With the new
radial thermocouple systems that I talked about in an
earlier question, we are able to monitor much more than
we previously could. This has led to redesign of our
distributor trays.
It is important to understand that side-to-side bed
outlet temperature differences can result from a number
of different factors. These factors include things like poor
equilibration of temperature in the interbed quench zones,
or flow maldistribution that occurs within the bed so that
even if the temperatures is equilibrated, deviations still
occur at the outlet. It can also be caused by things like
improper catalyst loading, poor liquid tray distributor
design or levelness, or regions of low flow caused by
catalyst balls which have been formed by previous tem-
perature excursions, or even internal point line leaks.
D’AURIA:
As I mentioned earlier, determining what is a normal
radial temperature differential depends on the diameter of
the reactor as well as other unit specific criteria. With well
designed reactor internals and proper dense loading, radial
delta T’s of less than 10°F can be achieved. However,
higher differentials than this are not necessarily a problem.
We would consider a radial differential of 20°C or more
to be a problem.
Several of our licensees have had their reactor internals
retrofitted and they have observed improvements in the
thermal mixing as a result. The retrofits consisted of
132 Hydrogen Processing
installing a mixing tray in which all of the reactants from
the quench zone are mixed and then splashed down onto
a redistribution tray underneath.
DEATON:
We recently retrofitted our hydrocracker reactor redis-
tribution decks. Prior to the retrofit, radial temperature
differences of 40°F to 50°F were common. The hy-
drocracking industry standard is that any radial tempera-
ture difference over 20°F is a problem. Now, one and a
half years after the retrofit, maximum radial temperature
differences are only 10°F.
Our original redistribution decks were 1960’s vintage
“sandwich decks.” They were warped and the bottom
decks were plugged and full of scale. During our retrofit,
the bottom decks were completely removed and replaced
with a splash plate with drilled holes. Both the liquid and
gas downcomers of the top plate were modified by adding
weep holes and caps on the gas tubes.
The key feature of the retrofit was the installation of a
mixing box located between the quench headers and the
redistribution decks for the second and third catalyst beds.
Each mixing box sits in the middle of a solid deck plate
spanning an entire cross-sectional area of the reactor. All
the gas and liquid has to pass through a tortuous pathway
in the mixing box for optimal mixing before entering the
redistribution decks. Our retrofit was designed by UOP.
PORTER:
A 25°F radial delta T would prompt us to closely
evaluate the situation. We have successfully retrofitted
reactor internals, bringing radial maldistribution back in
line. Our retrofit is a “mixing box”, a feature from Chev-
ron’s state-of-the-art reactor design practice. Vapor and
liquid are mixed between beds and this prevents radial
maldistribution from propagating.
TREESE:
Most of my items have already been covered. With
state-of-the-art reactor internals and good catalyst loading
technique and procedures, you can get a uniform distri-
bution, or fairly uniform distribution, within about ± 5°F
within reactors. As noted, there is no generic answer to
what an allowable temperature difference should be.
I will relate one of our experiences. We made some very
simple modifications to the flow distributors in the hy-
drocracker at one of our refineries and it has definitely
improved the flow distribution and the radial temperature
spreads in that reactor.
ARTHUR R. GENTRY (The M. W. Kellogg Company):
A number of years ago, large radial temperature differ-
ences in existing hydrocracker beds provided the motiva-
tion for Mobil Research and Development Corporation
TOC/INDEX
to launch a program to develop improved hydrocracker
reactor internals for use within the Mobil system. The
development program achieved dramatic success within a
year of its inception and has continued over the ensuing
years achieving additional improvements to maintain a
performance lead in the industry.
Mobil’s reactor internals design, now called Spider
Vortex Quench Zone Technology, has been successfully
retrofitted into all three of Mobil’s domestic hydrocrackers
and into a VGO hydrotreater to convert it to a moderate
pressure hydrocracker (MPHC) operation. The design has
proven so effective that the technology is used for all new
hydroprocessing units in the Mobil system.
The newest hydrocracker in the Mobil system is the
MPHC unit in the Singapore refinery. This unit started
up in the early 1990’s and it, too, utilizes Spider Vortex
Quench Zone Technology.
Mobil has performed retrofits on numerous hydroproc-
essing reactors, hydrotreaters as well as hydrocrackers. For
a specific hydrocracker example, earlier this year Mobil
completed changeout of existing quench zone internals at
their hydrocracker at Chalmette, Louisiana. The modifi-
cations at Chalmette include the latest generation of Spi-
der Vortex Quench Zone Technology features, which
involve not only mix zone features but also Mobil’s pat-
ented redistribution system. These modifications will pay
out in less than a year, based on improving what was a 15°F
temperature difference at the inlets of the hydrocracking
beds. The payout is achieved through the ability to run
higher severity operations and through extending the run
length between catalyst regeneration or replacement.
With the original design at Chalmette, radial deltas were
running on the order of 15°F at inlets to the beds, and 25°F
to 30°F at the outlets. Since the retrofit, inlet deltas have
been less than 5°F and outlet deltas less than 10°F
Mobil presented a paper on their technology at the
NPRA Annual Meeting in 1993 (AM-93-73). Mobil’s
Spider Vortex Quench Zone Technology is available for
license as part of the MAK Hydrocracking process tech-
nology offered by the M. W. Kellogg Company.
QUESTION 51.
To minimize reactor flow ma/distribution problems, is
sock or dense loading the better technique for install-
ing the catalyst? When dense loading, how do you
know whether you have done it right?
LAUX:
Theoretically, there should be no difference between a
dense load and a sock load as far as flow distribution is
concerned. In practice, however, a dense load will often-
times be more consistent because we pay a lot more
attention to it and use better trained loaders and engineers
following the loading.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
If the loaders on the sock load do not move the sock
around sufficiently and stand on one part of the bed more
than others, local areas of low or high density can result
and this will cause maldistribution.
As far as the second part of the question, how do you
tell how well a dense loading is proceeding, it is important
to periodically stop the loading and check the bed to see
how the loading is going. There can be one of three
problems that you might see when you go down to look
at the bed. If the bed is high on the walls and low in the
middle, the loader speed is too high. The catalyst is being
thrown out to the walls and bouncing back. If the bed is
high in the middle and low at the walls, the speed is too
low. In either of these two cases, the loading density will
be a lot less and be more like a sock load.
The third problem is a bed that slopes to one side. This
normally means that the loader is not centered in the
reactor or that it is not level.
If the loading is going well, the bed should be flat within
a few inches and the inspector should not sink into the
catalyst at all. You may have some trouble getting your
loading contractor to stop the loading to do the inspec-
tion, if he is on a firm contract and you have not told him
about this inspection.
Trying to calculate the loading density as the beds are
being loaded can be done, but my experience is it is very
difficult.
PORTER:
Dense loaded catalyst is more uniform and it also has
a higher pressure drop per foot than sock loaded catalyst.
Both those factors will improve flow distribution.
Mr. Laux has given a good description of the things we
use to check that dense loading has been done properly.
TREESE:
Properly done, either technique is satisfactory. We have
traditionally sock loaded in Unocal, but that is changing
with demands for greater activity in smaller volumes, i.e.,
more activity out of the same volumes we already have.
We do the same things that Mr. Laux described, as far
as checking for proper dense loading and back checking
the density.
We are currently in our first run with dense loaded
catalyst at the hydrotreating and hydrocracking reactors
in one of our Unicrackers, and comparisons with previous
runs do not show any difference in flow distribution.
BOYCOTT:
After hundreds of hours running a Chevron COP
loader this is an issue that is near and dear to my heart. I
think Mr. Laux covered the mechanics of dense loading
and how to ensure that you are getting a proper load quite
well. I believe a key issue is the one presented by Mr.
Roddey yesterday on Platforming catalysts, and that is
133
TOC/INDEX
ownership. We need to be very careful about giving this
responsibility to a catalyst loading contractor without
supervision. You need to take ownership of your catalyst
loading, and the installation of all reactor internals.
D’AURIA:
We have a very simple answer, dense loading is better.
It gives more uniform loading density throughout the
reactor, uniform pressure drop, and ensures better flow
distribution. The dense loading has been done properly if
the bed is level and the target loading density is achieved.
QUESTION 52.
Our hydrocracker reactors were designed in the
7960’s. The thermowells for reactor catalyst bed ther-
mocouples enter the reactor from the top head. With
the limited amount of temperature indicator points,
there is no way to obtain a traverse profile in order to
evaluate distribution across the catalyst beds. Has
anyone been successful in adding more thermocou-
p/es to hydrocracker catalyst beds with such a reactor
design?
PORTER:
Chevron’s six isocracking reactors in the El Segundo,
California refinery match the description of the reactors
in this question. All six were modified, providing three
radial Flex-R thermocouples at the top and bottom of each
bed. The refinery is pleased with the results. Engineering
and installation was performed by Gay Engineering and
Sales Company of Pasadena, Texas.
TREESE:
I am not a big fan of top entry thermowells for chan-
neling reasons, but we do have them in our system, too.
We have heard of a few modifications made to. increase the
number of temperature readings in the hydrocracker reac-
tor, or hydrotreater, and the main technique I hear of is,
again, the one by Gay Engineering and Sales, which places
several TI’s in the bed using a top entry, or side entry. We
are presently trying this in one of our reactors.
CUNEO:
We agree, and use the GAYESCO design discussed
earlier.
DEATON:
Gay Engineering Company specializes in temperature
measurement systems and they designed a new thermo-
couple system for us, which doubled our temperature
points to 18, and provided up to three radial temperature
points at the same elevation. The response is immediate as
there is no heavy wall thermowell acting as a barrier. Each
thermocouple is a flexible 5/16th inch diameter mineral
134 Hydrogen Processing
insulated cable consisting of a thermocouple surrounded
by a hard pack of magnesium oxide.
In our design, all 18 flexible cables enter the reactor
through the existing original thermocouple nozzles at the
top of the reactor. As the flexible cables are lowered into
place, they are bent into the horizontal direction for radial
temperature sensing.
QUESTION 53.
What is the latest technology for detecting catalyst
level in ebultated bed reactors?
McLEAN:
I would like to acknowledge Ken Tasker of HRI for
supplying this answer. The basic level detection device
which has been in use for many years and is still used today
is based on nuclear radiation and detection devices. The
hardware has been significantly improved in this applica-
tion over the years. There have been alternative suggestions
for bed detection level, but none of them have been
commercially proven at this time.
Low-power nuclear sources, typically Cesium 137, and
gamma ray detection devices are used. The sources are
contained in a well or wells inside the reactor, and the
detectors are placed on the outside of the reactor wall
opposite the sources. The geometric orientation is de-
signed to minimize the effects of the metal thickness
through which the gamma rays need to pass and thus
improve the sensitivity of the system. Differences in
gamma ray adsorption translate directly to differences in
reactor density, which in turn are a function of the amount
of catalyst present in the catalyst/oil/vapor mixture.
What has changed over the years is the application of
these devices to cover more of the reactor height. The
ebullated bed level can now be automatically controlled
by a computer software program, which links the ebullat-
ing pump speed controller to the observed density read-
ings. In addition to bed level, the nature of the expanded
bed at different points can also be determined.
Process
QUESTION 54.
Has foaming been a problem in the cold high pressure
separator that receives the effluent from a hy-
drocracker or hydrotreater reactor?
TREESE:
Foaming in the cold high pressure separators has been
experienced in both hydrocrackers and hydrotreaters. The
problem manifests itself by instability in the level indica-
tion in the vessel, and by liquid carryover into the recycle
gas compressor suction.
TOC/INDEX
This kind of problem has been observed in some hy-
drocrackers that process high endpoint feeds at high con-
version levels. High levels of polycyclic aromatic
hydrocarbons in the effluent have been associated with
indications of foaming in the separator, but not always.
Surfactants introduced in the washwater have also been
implicated or suspected of causing the foaming. Stripped
sour water from the crude unit, a coker, or an FCCU can
contain trace levels of the surfactants.
Foaming in the high pressure cold separator has also
occurred in some hydrotreaters that treat very heavy, high
viscosity materials. Raising the separator temperatures has
been shown to reduce the foaming tendency in some cases.
Oil-water emulsions can form in the high pressure cold
separator of units processing heavy feedstocks. These
emulsions can be caused by the presence of asphaltenes or
other surface active agents in the feed. The asphaltenes can
be entrained in the crude unit or vacuum tower. The
asphaltenes are not completely converted in the reactor,
and when they mix with water in the separator an emul-
sion is the result. Cracked feeds, such as heavy coker gas
oils, that are only mildly hydrotreated can also contain
compounds that are not converted in the reactor and can
cause emulsions in the separator.
A feed/reactor effluent heat exchanger leak that allows
feed to bypass the reactors directly to the separator is
another cause of emulsions that has been experienced.
Emulsion breakers have only been occasionally shown
to be of value in reducing the severity of the problem. This
may be because the residence time in most high pressure
separators is not long enough to allow the emulsion to
separate. After the oil-water mixture is depressured across
the level control valve, it may be so well mixed that the
residence time required for separation cannot be provided
in the low pressure separator either.
The color, Conradson carbon and metals content of a
stream can be an indication of the presence of entrained
residual. For most crudes, the metals content (as the nickel
plus vanadium) and the Conradson carbon, are probably
the best indications of residual entrainment into the
VGO.
CUNEO:
I agree with Mr. Tteese that, in general, we have not
experienced foaming in hydrocrackers. In one of our
hydrocrackers, which had been extensively debottle-
necked, we did experience some severe entrainment, but
when we replaced the separator vessel for one that was
designed within our guidelines for demister mat size, the
problem went away.
On hydrotreaters, we have had some indication of
foaming from an intermediate pressure, high temperature
separator in one of the catalyst feed hydrotreaters while
processing significant quantities of residue. It was never
conclusively confirmed as foaming, however, and we did
1994 NPRA Q&A Session on Refining and Petrochemical Technology
raise separator temperature and reduced the amount of
this entrainment.
QUESTION 55.
What is industry experience with fouling of hy-
drocracker effluent air or water coolers by polynuclear
aromatics (PNA)? At what concentration of PNA’s does
the fouling occur? What feedproperties and operating
conditions lead to PNA buildup? What can be done
about it?
CUNEO:
Of our four hydrocrackers, two have a bottoms product
and have never had a problem with PNA. One of our other
hydrocrackers feeds a very heavy cycle oil from catalytic
cracking and converts everything to naphtha and lighter.
With zeolite catalyst in this unit, we have experienced
severe air cooler fouling problems. Our fourth hy-
drocracker feeds a somewhat lighter feed, and has some
signs of buildup of PNA in the recycle. We are avoiding
these problems currently by analyzing for a marker PNA,
coronene, that we can measure and purge and therefore
adjust the bottoms purge rate to a stream that is not
recycled back to the hydrocracker.
We feel that the PNA’s are made in the first stage by
condensation reactions to much large size than would be
expected to occur in the feed. The PNA’s are then too large
to enter the zeolite pores of the cracking catalyst.
D’AURIA:
Our experience is that fouling by PNA’s is unit-specific,
but, in general, it can be expected when the fractionator
bottoms exceed 100 ppm of heavy polynuclear aromatics
(HPNA’s). We measure these HPNA’s, which are 11+ rings,
by using a fluorescence spectroscopy method.
Higher reactor temperatures, greater conversion, and
heavier and more aromatic feedstocks will all lead to
increases in the rate of HPNA formation in the hy-
drocracker reactor. Once-through operation generally
does not build enough HPNA’s to foul any of the equip-
ment. In a recycle operation, dragging the fractionator
bottoms will help to mitigate this problem, but this is an
expensive proposition in that it results in lower product
yields.
UOP and Unocal have developed several proactive
PNA management techniques, which include hot separa-
tors, indirect recycle, and selective carbon adsorption. This
last technique has the advantage in that it can be retrofitted
into an existing unit without affecting any other piece of
equipment in the hydrocracker.
The first HPNA adsorption system was added as a
retrofit in 1990. That unit has been able to operate at
99.5% conversion without fouling since then. Two more
retrofits are due on stream next year, and there are two new
135
TOC/INDEX
hydrocracking units currently under construction that will
use this system right from the start.
BARLOW:
We have seen a few units where PNA buildup has been
a major problem. The comments on the amount of recycle
and the effect of recycle on PNA buildup are usually the
points where the operators get involved in trying to reduce
the overall impact. We have chemistry that, in conjunction
with recycle, can control and reduce the impact of PNA
fouling. Application of this chemistry has been proven
successful in commercial evaluations.
TREESE:
Polynuclear aromatics formation is inherent with hy-
drocracking reactions. Large polynuclear aromatic mole-
cules can precipitate and cause problems in the colder
sections of the unit.
Highly aromatic feedstock and a high feed endpoint
favor formation and the presence of HPNA’s. For a highly
aromatic FCC cycle oil, we think HPNA’s tend to form
with feed endpoint lower than with less aromatic coker gas
oil and with straight-run gas oil. The solubility of these
HPNA’s depends on the operating environment. The
solubility in a single-stage or two-stage unit first-stage
effluent, because of its high aromaticity, is two to three
times greater than in the second stage.
Controlling the PNA’s involves some combination of
the following: controlling the feed endpoint and type;
maintaining the lowest practical hydrotreater reactor tem-
perature; taking a bleed stream, if that is at all possible;
indirect recycle back to a feed vacuum tower, as
Mr. D’Auria mentioned; and/or use of proprietary HPNA
adsorption technology, like that offered by UOP.
In one of our refineries, we used to limit the PNA’s to
50 ppm maximum in the recycle oil, and now, as it turns
out, as the result of producing the CARB diesel stocks
from the unit, we no longer have the PNA problem. They
do not accumulate, because they go out with the diesel
stock. So that is one positive byproduct of CARB diesel
requirement.
PERVAIZ BADRUDDIN (Abu Dhabi National Oil Company):
We have replaced the internals of our vacuum column
with structured packing to improve the heavy vacuum gas
oil feed quality to the hydrocracker. Although we did not
see much improvement in the heptane insolubles, Con-
radson carbon residue, there was a significant change in
the color of the heavy vacuum gas oil. The color reduced
from greater than 8 prior to the revamp, to less than 3.
Since the revamp, we have observed the reduction in the
HPNA fouling in the reactor effluent air condensers. We
operate a 3-year cycle length for the hydrocracker. Prior to
the revamp, the reactor effluent air coolers were cleaned
two times in three years. Since the revamp, we have
136 Hydrogen Processing
operated for about 22 months without the need for any
cleaning in any of the banks of the reactor effluent cooler.
We have also checked the PNA content in the fractiona-
tor bottoms stream after revamp, which is around 20 ppm
to 35 ppm.
MAJED INTABI (Saudi Aramco):
PNA fouling was put under control in our two hy-
drocracking units and interim cleaning of the product
effluent condensers was no longer required during the
operating cycle. In both hydrocrackers, a portion of the
fractionator bottoms was routed through the vacuum
distillation column to bleed out the heavy PNA’s from the
indirect recycle stream. Furthermore, in the No. 2 unit
where the fouling rate was excessive, a modification from
a cold to a hot separator design was successfully imple-
mented.
QUESTION 56.
Have hydrocracker operators experienced the produc-
tion of sour naphtha? What was the source of the
sulfur H2S or mercaptans? What was done to reduce
or eliminate the problem?
DEATON:
We have not experienced mercaptan sulfur in our hy-
drocracker naphtha, but occasionally we do see traces of
H2S. This is a result of poor debutanizer operation, com-
bined with poor main fractionator operation.
We typically take 50% of the pentane production
overhead in the debutanizer to ensure complete stripping
of H2S from the bottoms product. To guard against re-
combinant mercaptan sulfur formed at temperatures
above 720°F, we place a small load of cobalt molybdenum
catalyst below the bottom bed of hydrocracking catalyst.
CUNEO:
We agree with Mr. Deaton about the solution. A layer
of nonacidic hydrotreating catalyst loaded at the bottom
can saturate olefins and dramatically reduce the recombi-
nation reactions.
LAUX:
We also have a post treat bed to eliminate the mercap-
tans, and we have seen sour naphtha production from
debutanizer problems. We have done a number of things
to correct this situation. We had column fouling caused
by chlorides and so we put an adsorbent on the feed to the
debutanizer. We have had inadequate light ends produc-
tion, causing poor operation at start of run, so we put in
a recycle loop to bring LPG back in the column to improve
the stripping section operation. We also installed a caustic
treater on the hydrocracker light straight-run at our Three
Rivers facility, and a sulfur sorber on the hydrocracked
naphtha as a final protection.
TOC/INDEX
PORTER:
We also use a layer of hydrotreating catalyst at the
bottom of the reactor.
TREESE:
We generally would use a post treat bed of hydrotreat-
ing catalyst, also. I would add that we take care in sampling
our naphtha. If we are looking for mercaptans, we will use
a cadmium sulfate wash to remove the H2S but not the
mercaptans, and then do the analysis.
Regarding the post treat bed, if you are operating at full
rate for an extended period of time and then you drop back
in rate, you have to obviously drop the temperature of the
cracking bed. When you do that, the post treat bed has
been deactivated such that its kinetics no longer match the
hydrotreating bed, and you cannot independently control
the post treat bed temperature, so the kinetic differences
can sometimes result in more mercaptan sulfur being
generated or leaking through than you want.
QUESTION 57.
When a temperature excursion occurs in a hydrocrack-
ing reactor, what is done to bring the reactor back
under control? Does any hydrocracker operator use
automatic depressuring for controlling temperature
runaways and what key elements are used to trigger
the depressuring?
TREESE:
To bring the reactor temperature back under control in
the case of an excursion, we have recommended and use
two action levels. If any reactor temperature increases by
more than 25°F above normal, the operator should pull
the feed. The heater firing and quench flow should be
adjusted to line out the reactor bed temperatures. The feed
should not be reintroduced until all the temperatures have
been lined out at the cut-in temperature.
If any reactor temperature increases by more than 50°F
above normal, the operator activates the 300 psi per
minute depressuring, and dumps the unit pressure.
The definition of a temperature excursion, along with
the proper response expected of the operators, should be
explicitly defined and well understood by the operators,
and by the management. It is not uncommon for a hy-
drocracker operator to try to turn around a runaway, rather
than pulling the feed or depressuring the unit. This cannot
be done in a real runaway. There are plenty of people who
have had to prove it to themselves first.
We have found that we have to emphasize to our own
operators that activating the depressuring system in a
runaway is required and is an acceptable action. We train
our operators to run the unit, and they do nor like to shut
it down. We teach them how to identify a runaway, and
ultimately we have to depend on their judgment of when
1994 NPRA Q&A Session on Refining and Petrochemical Technology
they have to dump the unit. They cannot be afraid of
repercussions if they activate the system.
We only depressure automatically on loss of recycle gas
flow. We are aware of some hydrocrackers that are instru-
mented to depressure automatically in case of a runaway.
LAUX:
The concept of automating the depressuring sequence
based on temperatures has some attractions. However, the
one emergency depressuring that we have done in a year
and a half of operation at Three Rivers, was before the
normal temperature excursion criteria were even reached.
The operators had a quick response and this kept the
excursion to a very mild level. We prefer to keep the
actuation in the hands of the operators for just this type
of response.
The temperature excursion occurred when an instru-
ment air failure caused a steam outage, slowing the recycle
compressor down so much that all the quench valves went
to 100% open. We knew were not going to get the boiler
back very quick, so the operators hit the 300 psi per
minute depressuring. The bed temperatures were really at
40°F instead of the 50°F normal criteria. We did reach
60°F as we were depressuring, and about 840°F on the
actual temperature itself, This was a very mild excursion
because the depressuring system was activated early. We
think the quench valve position is one of the key elements
that needs to be watched whenever considering whether
or not to depressure.
CUNEO:
We agree with the previous comments, especially the
ones by Mr. Laux, that the quick response is very impor-
tant to minimize the severity of the excursion.
Because of that, we are in the process of implementing
automated shutdown systems on hydrocracker reactor
systems with zeolite catalyst in them. These systems will
be triggered either by high absolute temperature or by high
deviation from temperature control targets.
D’AURIA:
Our procedures for dealing with a temperature excur-
sion call for immediate removal of the liquid feeds (fresh
feed and recycle), and the makeup hydrogen, along with
the start of controlled unit depressuring. The recycle gas
compressor is kept on-line at maximum rate for heat
removal. We do not advocate the use of automatic depres-
suring. We feel it is better to have such decisions in the
hands of a properly trained operating staff
DEATON:
Our first approach is to increase hydrogen quench.
Next, we would reduce reactor heater firing and activate a
board-operated bypass valve around the reactor feed/efflu-
ent heat exchange. Both of these steps remove heat from
137
TOC/INDEX
the inlet to the reactor. If the excursion continues, we
activate a board-operated bypass valve around the hydro-
gen quench control valve. Feed rate should not be reduced
unless the feed is totally removed. Reducing feed rate
usually only makes the temperature excursion worse.
When all else fails to turn around a temperature excur-
sion, we can depressure the product separator to the flare.
CHARLES MCCOY (Consultant):
In my reactor safety class, which many of your operators
have attended, I use two words that you have used a little
bit interchangeably here. We use the word “excursion” to
mean an incident in which a well-trained, alert operator
can turn around without losing the unit. The word “run-
away” is clearly the case where the unit must be dumped
to the flare. As Mr. Treese said, it is vitally important to
know the difference.
QUESTION 56.
In the past, our normal operation was to crack distil-
lates to extinction and make naphtha for Platformer
charge. With the advent of tow sulfur, tow aromatics
diesel, we can change reactor severity and send a
slip-stream of fractionator bottoms to storage as die-
sel. Do other refiners do this? Is there a problem
meeting cloud and pour point specifications?
DEATON:
We produced low sulfur diesel by this method last
winter in our two-stage Isomax hydrocracker. Normally,
we produce zero fractionator bottoms as we recycle to
extinction for 100% conversion. When we produced low
sulfur diesel, the Isomax charge composition was a very
light mixture of 45 vol% LCO, 30 vol% diesel, and 25
vol% range oil. We kept Stage 1 operation the same, but
reduced Stage 2 reactor severity by 15°F to 20°F to pro-
duce about 65 1% as fractionator bottoms, and had to
add a product cooler. The fractionator bottom sulfur
content was less than 0.01 wt% sulfur, and this allowed us
to blend up to 0.05 wt% sulfur with untreated range oil
at about 20 vol% of the final blend.
The typical quality of our blended low sulfur diesel was
145°F flash, 30 vol% aromatics, 44 calculated cetane, and
0°F to + 10°F cloud point. If we reduced Stage 2 severity
more, and produced more than 65 vol% fractionator
bottoms, then we would go off-test on cloud point, which
is set at ±14°F in the winter.
We are not currently making low sulfur diesel, and we
have replaced the range oil with light vacuum gas oil in
our hydrocracker charge mixture. Whenever we do make
low sulfur diesel again, this change in composition will
require increased severity in the Stage 2 reactor in order to
meet cloud point specification, and will also reduce the
amount of fractionator bottoms available for blending.
138 Hydrogen Processing
CUNEO:
We have periodically made diesel using a slip stream of
fractionator bottoms as a blending component. In our
particular application, this stream has a higher tail end
boiling range than the normal ASTM specification, so it
limits the amount of it that can be blended into the
finished product. That usually hits us before cloud point
and pour point.
QUESTION 59.
What are the experiences of applying feed forward
control to catalyst bed temperature control?
PORTER:
Our reactor multivariable model based predictive con-
trollers have the capability to add disturbance variables.
This has allowed us to feed forward feed temperature and
qualities to our reactor controllers. Our experience at
Pascagoula has resulted in a significant increase in catalyst
temperature profile stability and reduced risk of tempera-
ture excursions.
QUESTION 60.
What is the experience of refiners, if any, who have
changed their hydrocracker catalyst from amorphous
to zeolite type (especially those who are operating on
maximum middle distillate mode)? What is the major
modification?
D’AURIA:
There are approximately eight Unicrackers now oper-
ating with zeolite catalysts in distillate mode that were
originally designed with amorphous catalysts.
The typical areas evaluated when considering this
change are related to the reactors: the overall reactor
catalyst volume, the number of beds per reactor, the bed
lengths, the capacity for quenching, and the type of reactor
internals.
In some cases the conversion to zeolite catalyst was
made with only minor modifications, others have required
significant changes to reactor internals, even the addition
of a reactor. The required changes are very unit specific.
CUNEO:
We have converted four of our hydrocrackers from
amorphous to zeolite catalysts. The major change is that
the zeolite catalyst is much more active, which means with
any small increase in temperature you get a much larger
multiplication effect on the bed outlet temperature. So
improved temperature control is the area where we have
made most of the change.
We have also retrofitted to include the radial thermo-
couples and improved our tray distribution system as well.
Mr. D’Auria mentioned the other things inside the reactor,
like quench capacity, which are important.
TOC/INDEX
TREESE:
I will add that the first unit we converted from amor-
phous to zeolite was about 25 years ago.
TIMOTHY J. STELLY (Mobil Research & Development Corp.):
Mobil has two moderate pressure hydrocracking
(MPHC) units that were converted from amorphous to
zeolite catalyst over the last few years. These changes were
made for economic reasons. The first change was made in
the late 1980’s and the second change was made in late
1994.
The benefits may vary from company to company, but
the general benefits are the increased catalyst activity,
which translates to higher conversion or longer cycle
length, or a combination of both.
One of the units moved from about 30% conversion
and a one year catalyst cycle to two years at 45% conver-
sion. The second change is based on moving from 45% to
60% conversion at constant catalyst cycle length.
There are also some issues of product quality that you
will have to consider when you make the catalyst switch.
There are two types of unit modifications that are
required, the ones where you have to consider the heat and
material balance from the overall unit standpoint and the
changes needed around the reactors. In both of these
conversions, we made no changes in the reactors and very
minor changes in the unit. We believe that Mobil’s Spider
Vortex Quench Zone Technology effectively and eco-
nomically addressed the reactor issues.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Both the MAK Hydrocracking Process Technology and
the Spider Vortex Quench Zone Technology are available
for license.
PAUL VANCE (Acreon Catalysts):
Acreon markets a proprietary modified zeolite hy-
drocracking catalyst that was developed specifically to
approach amorphous catalyst middle distillates selectivity
while achieving higher activity and stability for longer
runs. The activity is tightly restrained by catalyst formu-
lation to minimize the potential for overcracking and to
provide dependable operation. This catalyst has several
years of refinery operating experience with excellent per-
formance and approximately 100% increase in run
length.
In converting to the zeolite, no modifications are re-
quired on this unit. However, a thorough review of design
and reactor systems is provided by our affiliate and process
licenser, IFP.
BEN GRIEB (GAYESCO and Gay Engineering and Sales Co.):
Both Questions 57 and 60 are related in that we have
seen the use of zeolites cause our clients to look for more
temperature measurement in different applications. We
have also had experience where a client went to the radial
system of thermometry specifically because they have had
some events in their reactor that they had not seen due to
their thermometry design.
139
TOC/INDEX
IV. LIGHT OIL CATALYTIC PROCESSING
A. Alkylation - Sulfuric Acid
Feed
QUESTION 1.
What level of light ends (hydrogen through ethane)
have refiners been able to tolerate in the feed to the
alkylation unit? Do refiners with feed selective hydro-
genation units have product strippers or flash separa-
tors on/y? How does this affect operations?
DEATON:
In one C4 olefin hydrogenation unit, a two-stage flash
separator system was used to remove light ends prior to
the sulfuric alkylation unit. The high pressure separator
operated at 250 lb pressure, with the separator gas going
to fuel. The low pressure separator operated at 80 lb
pressure, with the separator gas returning to the FCC wet
gas compressor for olefin and LPG recovery. Hydrogen,
methane, and ethane content of the alkylation unit feed
typically ran about 0.1, 0.15, and 0.2 vol%, respectively.
Alkylation unit operation was not noticeably affected,
except that a vent of noncondensables was maintained
from the depropanizer overhead receiver.
McLEAN:
I will address the second part of the question.
Typically, flash separators only are provided on selective
hydrogenation units upstream of a sulfuric acid alkylation
unit.
Strippers are typically provided upstream of hydroflu-
oric acid units due to their lower tolerance for feed light
ends.
The selective hydrogenation units can be designed to
minimize the hydrogen in the product, but the levels of
the other light ends are very dependent on the quality of
the makeup hydrogen.
MENEGAZ:
I agree with the previous comments. Most units can
tolerate 0.1 vol% to 0.2 vol% of ethane in the olefin feed
without venting due to the partial solubility of the ethane
in the propane product. On the other hand, hydrogen is
relatively insoluble in propane and will require venting at
around 0.05 vol% in the olefin feed. For this reason,
provisions for removing excess hydrogen are usually pro-
vided downstream of the feed selective hydrogenation unit.
With poor de-ethanizing performance, some ethylene
140 Light Oil Catalytic Processing
might also be found in the olefin feed. Ethylene will rapidly
deplete acid purity at a rate of 30.6 lb per pound of
contaminant. The sulfuric acid makeup cost at 0.1 vol% of
ethylene in butylene feed works out to about 14 cents per
barrel of alkylate.
Occasionally, inerts can be found in isobutane feed.
One refiner traced his inerts problem back to the use of
fuel gas to transfer purchased isobutane from rail cars to
storage.
One final thought is that sulfuric acid units are much
more tolerant of light ends than HF units. Light ends in
HF alkylation unit feed will cause acid loss and neutrali-
zation problems.
SAYLES:
I agree with the other comments.
DAVID S. McCAFFREY (Exxon Research & Engineering Company):
Light ends in the feed to a sulfuric acid alkylation plant
act as noncondensables, as has been said, and venting can
result in large quantities of isobutane being lost unless the
vent stream is routed to a recovery tower. We usually
recommend putting a stripper on the selective hydrogena-
tion unit product to avoid any chance of having to vent
in cases where the isobutane balance is tight. We have seen
some cases where only a flash drum is used, but then a vent
stream is usually taken in the refrigeration system.
JEAN-LUC NOCCA (IFP Enterprises, Inc.):
We know from experience that all hydrogen can be
consumed in a selective hydrogenation unit. Therefore, if
you can employ pure hydrogen there will be no light ends
going to the alkylation unit.
QUESTION 2.
Is an aerosol farmed from a sulfuric acid release? If
so, is it a safety or environmental concern?
SAYLES:
This question has great importance in determining the
Hazardous Air Pollutant (HAP) status for the Maximum
Achievable Control Technology (MACT) standards for
listing sulfuric acid. Studies have been conducted to dem-
onstrate that an aerosol is not stable and does not migrate
when using different nozzle sizes and nozzle differential
pressures (STRATCO Engineering and Technology
Newsletter, V3, 1993 and NPRA 1994 Annual Meeting
paper # AM-94-18).
TOC/INDEX
Our practical experience with small sulfuric acid leaks
confirms the research data, sulfuric acid aerosol formation
occurs over a limited distance, 20 ft to 30 ft.
The safety concern when handling concentrated sulfu-
ric acid is related to personnel, environmental, and equip-
ment protection. A release of sulfuric acid is a safety and
environmental concern since low pH can cause acid burns
to operators and can produce hazardous waste. Care must
be taken in disposing of contaminated soils, used person-
nel protective equipment and spent cleanup supplies to
ensure proper disposal. We have purchased special absorb-
ents which will contain the acid and maintain the greater
than 5,000 BTU/lb energy value required for disposal in
a cement kiln.
MENEGAZ:
We agree with the previous panelist’s response.
CUNEO:
I agree with the previous comments on not forming an
aerosol, or having a lingering aerosol. If light hydrocarbons
are released with the acid, a vapor cloud is seen accompa-
nied by an acid spray.
A key concern that was not mentioned before was SO2.
SO2 may be evolved during the release of sulfuric acid so
precautions need to be taken for the presence of SO2.
ROBERT PUSCHINSKY (Allied Signal):
In addition to SO2 involvement, in acid runaway situ-
ations, tanks, rail cars, and trucks have been known to
erupt, also emitting sulfuric acid mist and sulfur trioxide.
Of course, those emissions also occur in the spent sulfuric
acid regeneration process and are of concern from a safety
point of view. A detailed discussion of sulfuric acid release
safety and environmental concerns is published in the
“Letters to the Editor” section of the October 1994 edition
of “Today’s Refinery”.
QUESTION 3.
Are any refiners operating at low isobutane/olefins
ratio (<6)? What is the impact on alkylate quality?
What problems can occur at low ratios? Is there a
practical lower limit?
PORTER:
We operate two older alkylation units around a six
isobutane/olefin ratio, and we suffer about a two octane
number loss due to this low ratio plus inefficient mixing
in the units. The isobutane concentration of the reactor
effluent is around 65%. This is a key variable because an
increase in feed diluents even at a constant isobutane/ole-
fin ratio will lower the isobutane effluent concentration
and affect results.
So in general, you can operate at a ratio of six or maybe
a little less, but you will pay a penalty that has to be
1994 NPRA Q&A Session on Refining and Petrochemical Technology
acceptable. Below 62% isobutane in the reactor effluent,
or below a four isobutane/olefin ratio, the octane loss and
acid consumption will increase significantly.
SAYLES:
I agree with his comments.
BARLOW:
We have observed three units operating with isobutane
to olefin ratios less than 6. Two of those units operate with
mixed propylene and butylene feeds. In going from less
than 7, to a ratio of less than 6, we saw a penalty in terms
of volumetric conversion of olefins to alkylate of 5% to
10%, octane number dropped in the 0.5 to 1 .O unit range,
and acid consumption increased by 10% to 20%. The
third unit we witnessed processed an MTBE raffinate
stream with minimal or no propylene or isobutylene in
the feed, so the negative effect was less. We saw conversion
of olefins to alkylate drop by only about 5%. Acid con-
sumption increases were fairly nominal, and the octane
dropped in the 0.3 to 0.5 range.
The practical lower limit for the isobutane to olefin
ratio will be different for every refinery and is set by
equipment limitations, operating costs, gasoline pool con-
siderations and the availability of makeup isobutane. Our
experience is that most refiners try to stay above 7, but
higher iC4/olefin ratios have incremental benefits in alky-
late production, acid consumption and octane number.
LAUX:
The only comment I would add is that if you get much
below the 60% isobutane concentration in the reactor
effluent, the potential for an acid runaway increases dra-
matically.
MENEGAZ:
I would like to add that many refiners are re-examining
lower isobutane to olefin ratios to get more capacity from
their existing units. This is being driven by a stronger
demand for alkylate volume and low value for octane as a
result of the new RFG standards.
HEROS DERGREGORIAN (Giant Refining Company):
What component in the isobutane recycle is contribut-
ing towards the lower octane? Are there any particular
components or any impurity that would cause lower
octane?
PORTER:
The main contaminant in the acid recycle that contrib-
utes to a lower octane is water. As far as the hydrocarbon
streams, any increase in diluents in the feeds or iC4 recycle
will directionally lower product octane. The most com-
mon diluents are propane and n-butane.
141
TOC/INDEX
LAUX:
The lower octane results because you do not have the
isobutane reacting with the olefin. The olefin will react
with itself. It will make additional polymer and it will
make a lower octane C8 or higher, olefin.
HEROS DERGREGORIAN (Giant Refining Company):
Do propane or normal butane impurities not contrib-
ute?
LAUX:
Propane and normal butane do not react.
MENEGAZ:
At low ratios, the amount of isobutane in the reactor
effluent, rather than the isobutane/olefin ratio, becomes
the critical parameter. So you need to take into account
your propane and other diluents.
KENNETH ABRAHAMS (Star Enterprise):
For the gentleman on the floor, we run an alkylation
unit where we run basically all the normal butane in the
plant through it as well. We have to pay attention to the
isobutane/olefin ratio. The normal butane is like dead-
wood. It will cost in terms of operating expense, but not
in quality or yield penalties.
ROBERT DAVIS (R. E. Davis Chemical Corporation):
In answer to the question raised by this gentleman, the
isobutane has to go into solution and protronate in order
to enter into the reaction. The speed of this reaction is
1/200th that of the olefin preparation. Consequently, if
you lower the concentration of the isobutane, the reaction
mechanics are simply not there to get the job done. The
olefin looks for another home. The isobutane will take its
time and when it does go into solution, will continue to
142 Light Oil Catalytic Processing
make alkylate, totally ignoring everything else going
around.
The lower limit of this is strictly controlled by the
reaction rates. A 4.5 to 1 isobutane/olefin ratio will be the
bottom limit before severe polymerization. A ratio of 8 to
1 is desirable. At 10 to 1, you virtually control all but about
5% of the polymerization.
MICHAEL BERLYANT (Bayway Refining Co./Tosco Corp.):
We have run an alkylation unit at 40% excess isobu-
tanelolefin on a regular basis for many years.
Mechanical
QUESTION 4.
What experience is there with plugging of the alkyla-
tion reactor distributor?
SAYLES:
We have not experienced plugging in the alkylation
reactor. However, solid deposits on the tube side of our
STRATCO contactor have been observed. These deposits
are mainly iron sulfate, which was traced to the fresh acid.
The fresh acid contained iron sulfate as a contaminant
which settled into the contactor head. The sludge level
increased sufficiently to cause high pressure drop and a
shutdown was required to clean the bundle. After discuss-
ing the quality of our fresh acid with our supplier, exchang-
ing samples and improving our own testing procedures
through a joint quality control program, the deposit for-
mation was eliminated.
MENEGAZ:
We asked several refiners about this and they said they
have not seen this problem either on the feed nozzle or the
acid hydrocarbon distributor in the acid settler.
QUESTION 5.
How does one control the corrosion in the deisobutan-
izer (D/B) tower overhead condensers, debutanizer
overhead condensers and debutanizer reboiler?
FELTROP:
Corrosion control in these areas can be accomplished
by two methods:
Application of an oil-soluble inhibitor program is ef-
fective as long as appropriate diluent and adequate distri-
bution is utilized. Butane solubility for the inhibitor is an
important consideration for effective application.
A second approach is to ensure complete neutralization
of the reactor effluent and minimization of neutralization
products. Optimization of such a system is achieved with
an efficient acid water wash system utilizing electrostatic
TOC/INDEX
precipitation to separate the phases prior to neutralization.
This application will reduce the soluble esters as well as
the entrained acidity, resulting in very little acidity remain-
ing to be neutralized and fewer esters to be decomposed.
MENEGAZ:
I agree with the previous comments. I would like to add
that the corrosion on the DIB tower generally indicates
that sulfate esters are getting past the effluent treaters and
decomposing in the tower in the presence of heat. When
the treaters are designed and operated properly, overhead
corrosion should be minimal and two year intervals be-
tween reboiler cleaning should be expected.
Bauxite is probably the most effective treating system,
since 98% of the esters are removed and it makes for a very
dry isobutane recycle.
The two other methods are (1) caustic treating the tower
feed with a 10° to 15° Baume wash followed by a water
wash, or (2) an acid wash followed by a hot alkaline water
wash. Acid washing is more effective than caustic washing
because it removes neutral esters as well as acid esters. About
90% of the esters can be removed this way. With either
wash method, a good static mixer is essential to achieve
maximum ester removal. Pressure taps should be provided
on either side of the mixer to check performance.
I would also add that care should be taken to see that
amines are not recycled back to the contractor.
PORTER:
I agree with the previous comments, that if reactor
conditions are reasonable with proper treating of the
reactor effluent, DIB fouling is minimized and overhead
corrosion rates are low. We also watch the pH of the water
in the DIB overhead to be sure that it is above 6. We do
have one unit in our Pascagoula Refinery that uses a
filming amine most of the time in the DIB overhead
because we are not able to optimize the above conditions.
SAYLES:
Higher feed rates and on stream availability are pushing
existing units to the limits, resulting in reduced acid/hy-
drocarbon separation due to low settling times. Acid
carryover from the settlers can be caused by low acid
strength, high settler level, mechanical failure, or pressure
surges and these upsets are the source of DIB tower
overhead system corrosion. The corrosion mechanism is a
function of the acid entrainment and the water content of
the DIB feed. Monitoring pH is the most common prac-
tice with the injection of an amine for corrosion control.
We use Triethanolamine or TEA at a normal dosage rate
of 1 ppm to 10 ppm to the DIB feed. The overhead pH
target range is 7 to 7.5.
Severe acid carryover from the contactors occurs occa-
sionally which causes the overhead pH to rapidly drop
1994 NPRA Q&A Sesinn on Refining and Petrochemical Technology
below 7. When this occurs anhvdrous ammonia is injected
into the overhead in addition to the TEA to raise the pH.
BARLOW:
As previously stated, corrosion in the fractionation
section of the alkylation unit is typically caused by acid
carryover from the reaction section and/or acid and neu-
tral ester breakdown in the reboilers of the fractionation
section. The best way to control corrosion is to focus on
the reaction zone and reactor effIuent treating sections.
Maintaining suffcient iC4 /olefin ratios in the reactors,
operating with reactor temperatures below 55°F, main-
taining good mixing, and low emulsion and acid levels in
the settlers will help minimize the root causes of corrosion
in the fractionation section.
Operation of the effluent treating section at proper
mixing, levels, temperatures, and concentrations is critical
to effluent treating efficiencies. If operating conditions
dictate operation outside of those recommended, corro-
sion problems in the fractionation section can be effec-
tively controlled through the use of chemical neutralizers.
Neutralizers can be applied to the feed or reflux on the
DIB, debutanizer, or depropanizer. The neutralizer used
must be nonvolatile if applied to the DIB so that it does
not enter the reaction zone with the isobutane recycle.
Nonvolatile neutralizers will also protect the reboilers in
the fractionation section.
CUNEO:
I will add that in units with higher levels of propylene
in the olefin feed, we believe there is a higher degree of
formation of neutral esters and employ an acid wash prior
to the caustic wash to remove them so they do not decom-
pose in the DIB. We have used ammonia in the DIB as a
temporary measure to get control of the pH of the over-
head water in the case of breakthrough.
General
QUESTION 6.
Does anyone use multivariant process control
schemes to control the refrigeration compressor sys-
tem, or the DIB isobutane recycle loop in sulfuric
alkylation units?
PORTER:
The alkylation plant at one of our refineries has in-
stalled a multivariant process control scheme. Three sepa-
rate systems were installed on the DIB, debutanizer, and
the refrigeration loop. We are extremely happy with the
performance, particularly on the DIB and the debutanizer.
In the past, the DIB would take a very long time to
stabilize but now the time has been cut drastically. Also,
143
TOC/INDEX
the specifications on the streams remain steady, with
changes in feed composition.
FRANK KLEINSCHROOT (SETPOINT, Inc.):
In our systems, the compression system is maximized,
subject to compressor speed limitations or minimum re-
actor temperature. Olefin feed is maximized subject to a
maximum reactor temperature or isobutane availability. A
multivariable controller is used on the deisobutanizer to
regulate recycle, reflux, sidecut and reboiler rates to main-
tain isobutane inventories, alkylate RVP, and reactor is-
obutane to olefin ratio while avoiding propane and
n-butane accumulation in the tower.
QUESTION 7.
What measures are taken, or facilities installed, to
reduce the risk of having an explosive mixture in spent
alkytation sulfuric acid tanks? The vapor space of
these tanks contains SO2 as we// as hydrocarbon.
TREESE:
At our alkylation unit in Los Angeles, spent acid is sent
to the spent acid surge drum. The spent acid surge drum
floats on the flare through a check valve. From there, the
spent acid is pumped batchwise over to the spent sulfuric
acid storage tank located in our sulfuric acid plant, which
is nearby.
At the storage tank there is a blanket of CO2 main-
tained on the tank. We are also fortunate there is a CO2
plant associated with the acid plant. The CO 2 then is
pressure regulated and the tank top is equipped with a
conservation vent, and flame arrestor. Safeguards on the
tank include a low pressure alarm, operator surveillance of
the tank frequently (several times during the shift), and a
fuel gas backup to the CO2 blanket system in case we lose
the CO2 inventory.
PORTER:
We believe the key is to ensure that the spent acid is
degassed before going to storage. The spent acid is pre-
heated and fed to a weathering drum. The vapors released
are caustic treated and heavier hydrocarbons are skimmed
off the middle section.
SAYLES:
Our experience has been that the spent alkylation
tankage vapor space has tested below the lower explosive
limit (LEL). At one location, a blanket gas is used to
prevent oxygen buildup.
To prevent hydrocarbons from reaching the spent acid
tank, the spent acid is pumped from the acid settler to a
holding drum where the hydrocarbons are removed. The
drum is vented to the flare system and has a system to
prevent a vacuum from occurring using fuel gas to equalize
the pressure.
144 Light Oil Catalytic Processing
Spent acid tank construction is a cone roof, internally
lined and externally steam traced with insulation. The
temperature is maintained between 20°F and 60°F. The
freezing point of 98% fresh acid is about 14°F. In general,
as the acid strength is lowered the freezing point will be
reduced, although the relationship is not linear. Hydrocar-
bons entrained from the holding drum are low vapor
pressure components, which are collected in the spent
tank and removed by an oil skimming system.
Operationally, acid foaming is a cause of concern in
evaluating the potential for an “explosive” condition in the
tank. When foaming occurs, heat is generated and hydro-
carbons adsorbed in the spent acid can vaporize. To pre-
vent foaming (as well as corrosion) the spent acid strength
is kept above 90% and the acid settler level is maintained
at a sufficient level to ensure hydrocarbons will not be
entrained.
DOUGLAS J. EVANS (Petro-Canada Products):
I wonder if any of the panelists or anybody in this
audience, has noticed an upward pressure on sulfuric acid
regeneration costs and available capacity with the increas-
ing pressure on alkylate capacity? Are refiners considering
installing packaged sulfuric acid regeneration plants
within the refineries?
HIGGINS:
No comment.
B. Alkylation - Hydrofluoric Acid
Feed
QUESTION 8.
When operating an alkylation unit downstream of an
oxygenate unit, whatprocess changes have been found
helpful in reducing the light acid soluble oil (ASO)
make due to contaminants generated in the oxygenate
process? Which contaminants cause increased ASO
make? What has been your experience using desic-
cants designed to remove feed oxygenates?
ARMBRESTER:
Dimethylether (DME) is generally the cause of the light
ASO. Unlike methanol, which is quickly converted to
water in the alkylation reactor, the DME is very stable and
can usually be removed from the acid stream only by
lowering acid regenerator temperatures and discarding
good acid with the ASO-DME mixture.
The most effective way to reduce the production of
light ASO is to minimize oxygenate contamination of the
alkylation unit feed through proper control of the MTBE
process and the alkylation unit feed dryer system.
TOC/INDEX
Tight control of the methanol to isobutylene ratio in
the MTBE unit reactor feed is essential to minimize the
formation of oxygenated byproducts such as DME and to
avoid overloading the methanol recovery and oxygenate
removal sections of the MTBE unit.
At our Catlettsburg, Kentucky refinery we have in-
stalled an on-line oxygenate analyzer in the mixed C4
stream leaving the MTBE unit to detect any unusually
high concentrations of oxygenates in the feed stream to
the alkylation unit. We are also considering the addition
of an oxygenate selective molecular sieve in our alkylation
feed dryers. If the feed dryers are used as an oxygenate
guard, the routing of the dryer regenerant stream becomes
critical.
In the original design of our alkylation unit the isobu-
tane used to regenerate the dryers was sent back to the
alkylation unit feed surge drum and the water was re-
moved via two coalescors and the feed drum water boot.
If oxygenates are being absorbed in the alkylation unit feed
dryers, then the regeneration stream must be routed to a
location where the oxygenates can be recovered. Other-
wise, they will cycle up in the alkylation feed stream until
the concentration is high enough to break through the
dryer beds. We have resolved this problem by routing the
alkylation unit dryer regenerant stream back to the oxy-
genate removal section of the MTBE unit.
D’AURIA:
DME is the most common oxygenate contaminant.
Our recommended procedure for removing DME is to
adjust the acid regenerator conditions to reduce the degree
of stripping and allow the DME to exit the bottom of the
regenerator. The best way to prevent DME, or other
oxygenates, from entering the alkylation unit is to use an
ORU unit on the MTBE raffinate stream. To date 11
ORU units have been installed in this service.
MENEGAZ:
I agree with the previous comments. I would like to add
that maintaining acid purity is the key to avoiding loss of
octane and avoiding operational problems. Increased is-
obutane to olefin ratio may be effective in minimizing side
reactions.
Regarding contaminants, most refiners target 35 ppm
to 50 ppm oxygenates in the feed and remove the impurities
by molecular sieves or fractionation. Dienes, sulfur, and
nitrogen compounds also contribute to the ASO make.
Alkylation units without MTBE units upstream have
also experienced contamination problems with oxygen-
ates. These have been traced back to alcohol in purchased
isobutane or trace acetone in the FCC alkylation feed. The
acetone is thought to come from reactions with entrained
oxygen from the FCC regenerator.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
PORTER:
At one unit we added a water wash column to remove
DME. It was successful in reducing the ASO production
to a manageable level. We have not used any desiccants.
THOMAS DAVIS (CENEX):
I would like to ask Mr. Armbrester what type of analyzer
he was using, specifically what model or brand, for oxy-
genates.
ARMBRESTER:
The oxygenate analyzer we use in the MTBE unit is a
Vista Model 3100, manufactured by ABB (Asea Brown
Boveri) Process Analystics of Lewisburg, WV
Process
QUESTION 9.
Our depropanizer feed condensers plug up on the
process side about once per year. What causes this
and how can it be corrected? Has anyone eliminated
the depropanizer feed condensers and fed the de-
propanizer from the isobutane recycle stream?
LAUX:
Plugging the depropanizer feed condenser on the proc-
ess side is probably due to iron fluoride. This can be
confirmed by analyzing the foulant. If that is the problem,
the solution is to eliminate the source of the corrosion in
the isostripper overhead system. The typical source of
corrosion here is excess water in the HE This can be caused
by running the acid regenerator too hot to allow the
incoming water to go out the bottom of the regenerator,
or by a wet feed to the unit. In the UOP unit, the acid
moisture should be less than 1%. The specification is
typically higher in a Phillips unit, around 2% or a little bit
more.
Karl Fisher analysis of the incoming feeds should show
less than 25 ppm water if distillation drying is being used,
or 5 ppm or even less if molecular sieve drying is being used.
You can also analyze the depropanizer feed settler acid
boot acid for water to see if the regenerator is recycling too
much water. In our HF alkylate at Three Rivers we run the
acid regenerator overhead temperature at about 140°F to
ensure that water is rejected.
Eliminating the depropanizer feed condensers and
feeding the depropanizer from the isobutane recycle, as the
question implies, may simply move the corrosion problem
to the sidecut condensers.
MENEGAZ:
I agree that the corrosion problem is iron fluoride. At
one refinery, the corrosion stopped after a butadiene satu-
ration unit was added. This eliminated the need for internal
145
TOC/INDEX
regeneration which eliminated HF contamination in the
overhead of the isostripper.
Another refinery has the overhead condensers paired
with valving so that one exchanger can be taken off-line
for cleaning. Runs of between one and two years are
possible, but the exchangers are cleaned at least once a year
to avoid the risk of not being able to pull the bundles due
to heavy fluoride salt buildup. The tower is operated to
minimize the overhead temperature and minimize fluo-
ride content above the isobutane draw.
FELTROP:
I agree with the previous comments. I would emphasize
that appropriate root cause analysis is the way to solve this
problem. We should not be focusing unnecessarily on the
condenser section but the focus should be on prevention
of the polymerization that is occurring in this situation.
D'AURIA:
The most common source of fouling is iron fluorides,
and this can be controlled by controlling acid moisture
content. An additional source of plugging can be olefns
coming in with the saturate butane stream to the isostrip-
per, which can then polymerize and foul in the overhead.
With respect to the question of bypassing of the de-
propanizer feed condenser, this can be done with older
isostripper designs which use a vapor dome partial con-
denser on the overhead stream (i.e. no sidecut isobutane
stream). This bypassing will result in a small amount of
free acid in the isostripper recycle, however.
For modern isostrippers, using a sidecut isobutane
recycle, bypassing the depropanizer feed condenser will
only move the problem down to the sidecut stream.
Mechanical
QUESTION 10.
Has anyone used citric acid for chemically cleaning
the alkylation units? How did it compare to hydrochlo-
ric solutions?
LAUX:
I have seen a citric acid solution used for chemical
cleaning on an HF alkylation unit five years ago. The
cleaning worked very well. The degree of neutralization
was very good. Exchangers bundles that had been stuck
after previous hydrochloric cleanings came apart very
easily. There was very little residue in the columns or small
vessels. The residue that did remain in the acid settler was
washed out with a fire hose. We were able to dispose of
the cleaning solution by slowly draining it into the plant
API separator. The chemicals are more expensive, though,
but the cleaning duration is two to three days shorter than
the hydrochloric procedure because no neutralization is
146 Light Oil Catalytic Processing
required. The shorter downtime easily justified the extra
cost.
Because of this success, we tried using the same vendor
at our 1994 Three Rivers turnaround. We used a different
chemical, though, a sodium hexanate, and it was not as
successful in removing the iron fluoride from the exchang-
ers or the isostripper itself. The degree of neutralization
was very good because of procedural changes. The proce-
dure was very short, about 20 hours, and again we were
able to dispose of the solution in the API separator. The
cost was higher than the alternates, $85,000 versus
$50,000 for our single reactor and settler system, but the
procedure saved four days of downtime which, again,
justified the extra cost. We are now working with the
vendor to improve the chemical’s performance.
D'AURIA:
We have had comments back from several of our licen-
sees who have reported satisfactory results usingcitric acid.
The higher cost of citric acid is offset by reduced down-
time and lower disposal costs.
DEATON:
We used citric acid cleaning for the first time during
our last turnaround and we were very satisfied with the
results. The estimated time required for citric acid cleaning
was 60 hours less than for hydrochloric acid. However, the
cost for citric acid was 50% higher than for hydrochloric.
From a technical standpoint, citric acid compares favor-
ably to hydrochloric in several areas. Process corrosion is
far less severe, as the citric acid solution is maintained at a
near neutral pH. Process cleaning is as good, if not better,
as the risk of precipitating iron fluoride is eliminated.
Since the pH is near neutral, citric acid solutions can
be heated up to 200° F, which does a better job of removing
heavier hydrocarbons and polymers. Disposal of the spent
acid solution is less hazardous because the solution pH is
maintained near neutral. However, citric acid solutions
contain ammonia, which can create disposal problems
because of ammonia limits in waste water.
General
QUESTION 11.
Additives have been announced to further reduce the
potential hazards in the alkylation process. What has
been the experience of refiners in using such additives
in their commercial units?
D'AURIA:
Texaco and UOP have jointly developed a new HF
additive technology called “Alkad”. Allied Signal has also
participated in this work as a technology partner. The
TOC/INDEX
technology is based on the work of Dr. George A. Olah,
winner of the 1994 Nobel Prize in Chemistry.
The Alkad technology uses an additive to suppress the
HF aerosol formation in the event of a leak from the
alkylation unit. Large scale release tests with this additive
have demonstrated significant aerosol reductions. In 1992,
a trial run was conducted at Texaco’s El Dorado, Kansas
refinery. This operation demonscrated that the technology
could successfully produce alkylate, and in fact, the alkylate
quality improved both in octane and distillation.
The first commercial unit has now been installed at the
El Dorado refinery, using a UOP modular design for the
additive recovery and recycle unit. Texaco started up the
process on September 14th and their early results confirm
the alkylare octane and distillation improvements.
STANLEY LOMAX (Texaco Refinery):
As Mr. D’Auria mentioned, we started the injection of
the additive on September 14th to improve the safety of
our alkylation unit. In addition to the safety aspect, we are
now producing an alkylate that is more than one and a
half octane numbers higher than our operation prior to
September 14th. That is at the same unit feed rate and
feedstock composition. Along with that, the ASTM dis-
tillation 90% point and end point are both averaging
about 30°F lower.
HIGGINS:
Thank you. I believe a paper on this subject will be
presented at the 1995 NPRA Annual Meeting.
QUESTION 12.
What methods of HF leak detection are most commonly
used? Which methods have been most successful?
BOYCOTT:
We have recently installed a video monitoring system
in our alkylation unit. The system is comprised of five
cameras with zoom and pan capabilities. Each camera
feeds a high resolution color screen in the control room.
The units have been positioned to ensure coverage of all
HF containing equipment. We are currently evaluating
the addition of hydrocarbon detectors in key areas to
supplement the cameras.
Other technologies considered in the selection of this
system were infrared beam reflectors and wet chemistry
HF point source detectors.
CUNEO:
We currently use TV monitors, acid-indicating paint
on flanges, and well-trained operators to watch and detect
for HF leaks. We currently are evaluating a system which
will employ a perimeter open path infrared detection
system for isobutane coupled with ion mobility point HF
measurements around the acid regeneration facilities.
1994 NPRA Q&A Sesioon on Refining and Petrochemical Technology
DEATON:
This topic was discussed in January 1994 at the API HF
Alkylation Roundtable and Seminar on Safe Operation of
HF Alkylation units. Reports of success with detectors
seem to vary. Two types of detectors are used. One type is
a “point source” detector for specific ppm determinations.
These detectors are based either on electrochemical cells or
the etching of silicon-coated electronic chips.
The second type of detector is an “open path” or “line
of sight” detector. One type that uses infrared principles
is available and another type that uses laser principles is
under development. The “open path” type detectors
would be used to detect and respond to larger leaks for
activation of mitigation and isolation equipment.
ARMBRESTER:
I agree with the previous comments on the use of
acid-detecting paint and video monitoring, and we are also
investigating the use of HF point detectors that would be
installed at the locations most likely to experience a leak.
These analyzers can detect HF in the 0 to 10 ppm range.
Regarding video monitoring, we have that system in
place and we also set it up to record each one of the camera
signals so that if a leak does occur and the source of the
leak is not identified immediately, we can play back the
tape and identify the source of the leak.
QUESTION 13.
What are some of the considerations when designing
HF emission mitigation measures?
CUNEO:
Several years back, Shell installed extensive water deluge
systems around our HF alkylation unit at Odessa. Any
indication of leaks of either HF or hydrocarbon prompts
the board operator to immediately activate the deluge
button in the control room. They are given instructions
on the side of being conservative. Our people are told not
to go out and investigate a plume observed by the TV
surveillance. Activate the system first, and then investigate.
Our process hazards analysis and subsequent dispersion
modeling of potential worst-case scenarios pointed out the
need for immediate activation of the water deluge, if we
are to be effective in mitigating potential outside spread
of the release.
As commented in the previous question, we are engi-
neering the installation of an open path hydrocarbon
detection system and HF point monitors as well.
DEATON:
Our first step was to install systems for quick isolation
of equipment such as remote-operated valves and remote-
operated start/stop switches for pump motors. We are now
looking at water deluge systems, and the first step in this
process is to select credible release scenarios and to predict
147
TOC/INDEX
leakage rates. Water mitigation flow rates are usually rec-
ommended at a ratio of 40:1, that is, 40 gpm of water per
1 gpm of acid leak, for a 90% reduction in acid vapor
release.
Vapor cloud dispersion models such as HG System and
Trace can then be used to predict downwind concentra-
tions. There is a joint industry program working to im-
prove the accuracy of vapor cloud modeling methods.
Water delivery systems should be designed for quick
actuation and for effective delivery of the required water
flow rate to the acid release point. Water runoff, storage,
and neutralization also need to be part of the overall
mitigation design package.
LAUX:
Some additional items that we included were sizing for
300 micron droplets based on literature data, and install-
ing both water curtains and remote monitors to attack the
largest plausible leak scenario. Our system for the water
mitigation also includes a preneutralized water source as
well as remote actuation from the control room and the
field.
The rapid acid dump system that we are installing was
designed for a pressurized 10 minute dump to a new
dedicated vessel. The vessel sizing has double the maxi-
mum expected acid volume to allow room for the motive
fluid, and this system can also be activated both from the
control room as well as from the field.
QUESTION 14.
There have been many announcements regarding new
motor duel akylation technology that claim safety
improvements over existing sulfuric and HF technolo-
gies. What is the current status of solid catalyst aky-
lation technology? Have any commercial units been
licensed?
ARMBRESTER:
The most developed solid acid processes are in the 0.5
to 10 barrels per day pilot plant stage, with the earliest of
these processes having operated for up to two years now.
The status of each of the processes would be best stated by
the participating firms, but each was briefly discussed in
two recent articles in the Oil and Gas Journal Volume
92(34) of August 22, 1994, pages 49 to 54. The economics
of at least one solid acid process appeared to offer cost
savings over conventional sulfuric acid units. Although
several firms are seeking licensees, we are not aware of any
commercial licenses having been sold.
D’AURIA:
In parallel with our development of the Alkad HF
additive technology, UOP has maintained a long term
research and development program aimed at developing
a solid catalyst alkylation system. The system we are
148 Light Oil Catalytic Processing
developing uses a true solid phase, regenerable catalyst.
Currently we are in the process of conducting long-term
stability evaluations in our pilot plants.
Earlier this year we developed a preliminary design
package that indicated that the capital and operating costs
for this process would be very competitive with the exist-
ing liquid acid technology.
As part of our initiative to increase licensee involvement
with our development programs, we have held prelimi-
nary discussions with a few customers to provide a status
update and explore potential applications of this new
process. We expect to have a detailed engineering design
completed early next year, and, while significant technical
achievements have yet to be accomplished, our goal is to
have a full commercial package for the technology avail-
able by the end of 1995.
McLEAN:
I do not have anything to add to what the other
panelists have said.
PORTER:
Chevron is working with Chevron Research and Li-
censing on a process that is suitable to retrofit into an
existing process reactor system. We started a 10 BPD pilot
plant in January of this year to demonstrate process per-
formance.
PHILIP GEREN (Haldor Topsoe, Inc.):
In 1988, Haldor Topsoe began a program to develop a
solid catalyst alkylation process. Earlier this year the fin-
ishing touches were put on the development. The process
employs a small amount of a liquid catalyst deposited
upon the surface of a packed solid support bed.
We and our partner in commercialization, the M. W.
Kellogg Company, are now preparing a feasibility study
for a customer of ours who intends to employ the process
TOC/INDEX
in its first commercial scale application. We are not at
liberty at the moment to discuss our customer.
PETER KILNER (Catalytica):
Catalytica, Conoco and NESTE are working to com-
plete the development of our solid catalyst alkylation
process. We are planning to have the technology ready for
licensing by sometime next year. We are talking with
refining companies about the possibility of joining our
cooperation to build the first unit, and we will be disclos-
ing further details of our process at the Oil and Gas
Journals Alkylation Seminar at the end of this month.
C. Reforming
Feed
QUESTION 15.
How do sulfur species (i.e. H 2 S RSH, thiophenes)
affect the loading capacity of nickel oxide sulfur
sorbent?
BOYCOTT:
The pickup of sulfur species on a reduced nickel sulfur
sorbent is dependent on a chemisorption reaction. How-
ever, the molecular size of the sulfur species controls the
mass transfer of the molecules into and through the pores
of the material. In this way the mechanism and break-
through curve become very similar to those of a pure
sorption system, and molecule size has a direct impact on
ultimate capacity. As such H2S is the easiest species to pick
up. Thiophenic compounds have been found to give the
lowest loading. The published capacity for one of the
commercial chemisorbents is given below.
H2S greater than 10 wt%
Mercaptans 10 wt%
Disulfides 7 wt%
Thiophenes 1 wt%
D’AURIA:
The question asked about nickel oxide adsorbents. The
active adsorbent actually is reduced nickel. UOP’s nickel
adsorbent, ADS-llL, is sold in the reduced and surface
stabilized form. The ADS-l1L has a capacity for H2S and
mercaptans of about 15 wt% on the adsorbent. The
thiophene capacity is much lower, about 2 wt% on the
adsorbent. However, even when thiophenes are present
they do not appear to interfere with the adsorbent’s ability
to adsorb its full capacity for H2S and mercaptans.
MENEGAZ:
We agree with Mr. D’Auria’s comment. Sulfur pickup is
done only by the reduced nickel. Nickel oxide is ineffective
1994 NPRA Q&A Session on Refining and Petrochemical Technology
and acts as a diluent. The loading capacity is a function of
the sulfur compound type, the temperature, and the per-
cent of reduced nickel in the sorbent.
Reduced nickel will adsorb H2S to saturation at tem-
peratures above 100°F. Adsorption of mercaptans and
disulfides is low at l00°F, but increases to saturation
around 350°F. Thiophenes, particularly sterically-hin-
dered ones like benzothiophene, are only slightly ad-
sorbed. One supplier specifies the sulfur loading for
reduced and stabilized 50% nickel catalyst above 325°F,
as 10 wt% or more for hydrogen sulfide, 10% for mercap-
tans, 7% for disulfides, and 1% for thiophenes.
Users have achieved different results than what I have
just mentioned. This could be the result of upsets and
variability in the percentages of thiophenes in the naphtha
feed. To my knowledge, no one is routinely measuring
thiophene content at less than 1 ppm total sulfur.
PORTER:
We have not used nickel oxide commercially, but our
laboratory tests generally support the previous comments.
ROBERT W. MORSE (Acreon Catalysts):
The surface area of the nickel is also very important in
determining the adsorption of the sulfur. High surface area
nickel adsorbents have a higher capacity for thiophene.
QUESTION 16.
For those refiners using a sulfur guard bed on the
reformer feed, the very low concentrations across the
bed make monitoring the bed performance and opti-
mizing change-out before the bed is completely spent
very difficult. What analytical test methods or other
techniques are being used to ensure that the beds are
performing properly?
SAYLES:
Typical reformer feed specifications are 0.5 ppmw sul-
fur and 0.5 ppmw nitrogen when using bimetalliccatalysts
in semiregenerative units. A sulfur guard reactor will pro-
tect the reforming catalyst provided the inlet H2S concen-
tration to the guard bed does not cause a sulfur
breakthrough.
We have liquid feed sulfur guard reactors protecting
two different reformers. In both cases, low pressure pre-
treaters are used, less than 600 psi. During normal opera-
tion, the inlet sulfur concentration is about 140 ppb and
the outlet is 40 ppb. The cycle length can be calculated for
your absorber configuration using manufacturer supplied
sulfur absorption coefficients. We replace the sulfur guard
bed CuO reactant once per year. The normal run is 440
to 510 bbl of feed per pound CuO. The run is normally
limited by pressure drop before sulfur breakthrough.
From our experience, pretreater sulfur breakthrough
occurs after unit upsets, mainly power outages. As a rule,
149
TOC/INDEX
we replace the beds after a major upset as a protection to
the reformer catalyst even if breakthrough has not been
detected.
Another operational concern is that high levels of ab-
sorbed sulfur onto the guard bed absorbent, with contin-
ued use, could allow the sulfur to desorbe, causing a
reformer feedstock contamination problem. This means
that the observed sulfur breakthrough will occur before
the calculated breakthrough.
PORTER:
We rely on Houston Atlas sulfur analyzers. The analysis
takes care, but we believe we can get down to 0.05 ppm
accuracy. As far as detecting when a bed is spent, we believe
the most straightforward approach is to put liquid sample
taps at several elevations on the vessel to monitor the
progression of the sulfur removal through the bed.
TREESE:
I would echo what Mr. Porter has said. We use the
Houston Atlas machine. We use the thermal cracking
technique for analyzing our sulfur. In addition to the side
taps, I think it is a good idea to calculate sulfur accumu-
lated in the bed versus the bed capacity. Tracking that can
help act as a check and an early warning for when you are
about to expend a bed.
McLEAN:
The only proven methods are dependent on the ability
to analyze the low sulfur concentrations in and out, and
obviously that is difficult to do at such low levels of 0.1
ppm to 0.2 ppm, so this can be used as a rough estimate.
It helps to know the capacity of your sulfur guard adsorb-
ent. Nickel type liquid phase guard beds typically adsorb
between 10 wt% and 20 wt% sulfur and vapor phase
guards from 15% up. In the case of a vapor phase system,
only the liquid stripper bottoms need to be analyzed, since
100% of the sulfur in the recycle loop will eventually be
removed.
Accurate determination of bed removal efficiency may
require calculation after the fact, by comparing total sulfur
loading on the spent material with the total feed sulfur
from daily feed analyses.
BOYCOTT:
I would like to add a comment on the utilization of the
sorbent material. Sulfur guard beds use a chemisorption
reaction to fix the sulfur species on the bed material. The
concentration gradient through the bed is very similar to
that experienced in a pure sorption system. In the case of
sulfur chemisorption on reduced nickel, the gradient is
relatively shallow and results in rejection of 20% to 30%
of sorbent capacity as unused at breakthrough. One ap-
proach that has been used to reduce the rejection of unused
capacity is to sequentially label the drums as the bed is
150 Light Oil Catalytic Processing
dumped. Subsequent testing for sulfur levels will not only
define the breakthrough curve, but also indicate which
material may be reloaded. The reloaded material should
be installed at the top of the bed. Care must be taken to
maintain an inert environment.
Another approach would be to install two beds in series
with the required piping to alternate lead and lag posi-
tions. By alternating bed position in the train, essentially
all of the sorbent capacity could be utilized.
CUNEO:
Nothing further to add.
D’AURIA:
We have seen all three methods used to monitor sulfur
guard bed performance: calculating the sulfur loading
based on feed sulfur, monitoring the outlet sulfur, and
also analyzing the adsorbent. The most common method
is monitoring outlet sulfur. As the outlet sulfur begins
approaching 0.2 wt%, we recommend shutting down and
reloading the bed. The best analytical method for meas-
uring sulfur in the guard bed outlet stream is ASTM-
4045, which utilizes hydrogenolysis followed by
rateometric calorimetry.
DAMIAN ARCHBOLD (ChemAlert Corporation):
This spring we will be introducing a new technology
for on-line total sulfur measurements that will give you
the capability of measuring total sulfur at one ppb on-line
consistently. This is being tested now at several refineries.
The results will be available in the spring.
SONI OYEKAN (Sun Company, Inc.):
One indirect method for checking for the problems on
the sulfur bed ahead of the reactor is to check through
catalyst samplers for the level of sulfur on the catalyst in
the first reactor. With sulfur guard systems, the sulfur in
that first bed is usually much less than 0.02%. So, if you
have inefficiencies in the performance of the sulfur guard,
you will notice a rapid increase in the sulfur level in the
first reactor catalyst samples.
DOUGLAS J. EVANS (Petro-Canada Products):
I was wondering if anybody on the panel might be able
to comment on the affinity of zinc oxide, nickel oxide,
copper oxide to mercaptan removal, if any.
D’AURIA:
The affinity for mercaptan removal of the reduced
nickel adsorbent is very good. The ultimate capacity of
ADS-11L, for example, is around 15 wt% at 250°F to
350°F. Zinc oxide is used primarily for H2S removal. Its
use in reformer applications is limited by the fact that for
every mole of H2S adsorbed, a mole of water is produced.
TOC/INDEX
MENEGAZ:
We understand that the copper material picks up most
of the hydrogen sulfide and only a very limited amount of
the mercaptans.
QUESTION 17.
The benefits of removing sulfur in reformer feed has
promoted several approaches to a sulfur guard bed
system. Both a system on the liquid feed and the
recycle gas stream are possible. How does the expe-
rience on these compare and what unit aspects make
one or the other more appropriate? Have there been
any problems, difficulties, or limitations with either
approach?
McLEAN:
Liquid phase sulfur guards treat the reformer feed,
while vapor phase systems treat both the feed and the
recycle gas before they enter the reactor. A guard solely on
the recycle itself would have marginal value since it could
only take out the H2S in the gas and the catalyst would
still be exposed to all the feed sulfur on the first pass.
Acreon Catalysts markets adsorbents for both systems.
Liquid phase systems are smaller, operate at lower tem-
peratures, and are less expensive to install. They com-
monly use copper- or nickel-based adsorbents. Copper is
effective at removing H2S and mercaptans, while nickel
can also remove some thiophenes. It is also easier to change
out the adsorbent on the run with a liquid phase system.
Vapor phase systems are more expensive because they
are directly in the reformer loop and operate at higher
temperatures. They must be isolated during regeneration,
requiring some additional valving and piping. Since the
vapor phase unit treats both the feed and the recycle gas,
it is more effective in responding to upsets which may feed
a large quantity of sulfur to the unit in a short period of
time. If this upset condition exceeds the ability of the
guard to remove on the first pass, thiophenic sulfur will
convert to H2S in the reformer and will be removed on
the second pass. As a result, vapor phase units may be
preferred for reformers which are subject to such upsets,
particularly on more thiophenic feeds.
Engelhard has presented a paper at the 1989 Annual
Meeting, Paper Number AM-89-45, which compared
these options and offered an economic comparison.
MENEGAZ:
I would agree with Mr. McLean’s comments. The vapor
phase process is definitely more effective for removing
sulfur. It is also quite a bit more expensive. I have seen
figures quoted of $425,000 for installation in a 10,000
barrel per day reformer. Many of these processes are found
in conjunction with units using high-skewed plati-
num/rhenium catalysts. Such catalysts are extremely intol-
erant of sulfur and require a higher degree of sulfur removal.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
The liquid feed guard beds are relatively simple and
inexpensive. A typical installation using reduced nickel is
a small carbon steel vessel, sized for liquid-hour phase
velocity (LHSV) of 8 to 12. Normal effluent purity is less
than 0.1 ppm sulfur. There are 50 or more liquid sulfur
phase units worldwide.
Several refiners have added liquid guard beds as retrofits
to existing units with minimum capital investment. One
refiner is reported to have increased the cycle length from
8 to 23 months after adding a nickel guard bed. Experience
with sulfur adsorbents is discussed on pages 147 to 148 of
the 1992 NPRA Question and Answer Session transcripts.
PORTER:
Many years ago, we tried to remove the sulfur in the
recycle gas and did not like it for the same reason Mr.
McLean mentioned. The sulfur in the feed hit the catalyst
before the recycle guard bed could take it out. So we
invented the Chevron Sulfur Sorber process, which re-
moves sulfur from the liquid feed. We now use that on all
our reformers.
BOYCOTT:
I agree with the previous comments. I will add that we
employ a reduced nickel adsorbent on our liquid feed
stream.
D’AURIA:
The only thing I will add is that the liquid system does
have the advantage of not having any impact on the
reformer recycle gas compressor circuit, whereas the vapor
phase system will add additional pressure drop in the
recycle gas circuit.
MARK DORAN (ICI Katalco):
I agree with most of the comments from the panel.
With vapor phase sulfur guards, it is possible to place the
guard on the recycle gas at the low temperature part of the
circuit, and that may well reduce the capital cost of the
figures given by people on the panel.
A liquid feed guard will only remove sulfur from the
hydrocarbon feed to the plant. Another point in favor of
vapor phase guards is that they do not increase the hydro-
carbon inventory of the reformer unit. ICI Katalco can
provide PURASPEC™ absorbent for both vapor and liq-
uid phase applications. Liquid phase is the most common.
WILLIAM TOREK (Texaco Refining & Marketing, Inc.):
We recently loaded fresh, high nickel, catalyst in a sulfur
guard reactor on the run and experienced quite a bit of
water in the downstream reformer. Can someone com-
ment on the possibilities of water formation resulting from
the sulfur guard catalyst’s passivation agent?
151
TOC/INDEX
D'AURIA:
It is possible to form significant quantities of water if
you use an adsorbent that is sold in the oxidized state, and
then reduced in situ. UOP’s ADS-11L, however, is sold in
the reduced, surface stabilized state. We do not perform
an in situ reduction, and, hence, do not generate any water
on start-up.
RONALD E. MARRELLI (Phillips Petroleum Company):
Is the main purpose of the sulfur guard to prevent
possible upsets on the hydrotreater from upsetting the
reformer or to prevent any sulfur from getting to the
reformer? Are there additional benefits in normal opera-
tion?
PORTER:
Sulfur guard beds are useful to reduce the impact of a
process upset, but we find they have a great value in
removing the trace sulfur in normal feed.
MENEGAZ:
I know of one incident where a refiner developed a
problem with the upstream hydrotreater with a crack in
one of the feed-effluent exchangers, and consequently they
had 4 ppm to 5 ppm in their feed sulfur. They used the
vapor phase sulfur guard process and operated for approxi-
mately 18 months without shutting down or seeing any
loss of octane.
LAUX:
We have our sulfur sorber on our hydrocracker naphtha
which bypasses the naphtha hydrotreater and is fed di-
rectly to the reformer. The sulfur sorber provides protec-
tion against H 2 S from upsets in the hydrocracker
fractionation system and protection from mercaptans that
may be formed in the hydrocracker reactor at end of run
temperatures.
HEROS DERGREGORIAN (Giant Refining Company):
In regards to water formation in the nickel guard bed,
is it possibly high enough for the water to cause unbal-
anced chloride in the reformer?
D'AURIA:
We have not seen any problems with water generation
on start-up. Theoretically, if you were reducing a high
nickel content, nickel oxide material, a significant amount
of water would be generated. You would have to make sure
this water did not enter the reformer reactor section. As
stated earlier, this is not a problem with ADS-11L.
BOB RODDEY (Roddey Engineering Services, Inc.):
I have not heard anyone say anything about chloride
water balance, until the previous comment, on units that
put the sulfur guard in the reactor circuit I have had
152 Light Oil Catalytic Processing
experiences with chloride water problems when there is a
guard bed in the reactor circuit on the combined feed. It
is more difficult to maintain chloride. A serious water
upset will give a large liberation in H2S, which will in turn
nullify the economic benefit for installing the guard bed.
SONI OYEKAN (Sun Company, Inc.):
I want to address the question of whether the sulfur
guard is only for upsets. In the case of skewed metal
catalysts or unbalanced catalysts, where you have high
rhenium to platinum ratio, you get substantial benefits in
terms of performance if you operate below 0.2 ppmw
sulfur in the feed. So in order to make sure that the sulfur
is quite low in these systems, you need to have the sulfur
guard in line for that particular type of catalyst.
You could also have similar benefits for the balanced
catalysts as well, that is, balanced metals catalysts, but you
have substantial performance benefits for the skewed met-
als if you run in the range of 0.1 ppm to 0.2 ppm sulfur.
That is benefits in terms of octane barrels as well as cycle
length.
CORNELL SLADE (ACREON Catalysts):
Acreon is in a unique position because we can supply
two types of vapor phase and two types of liquid phase
sulfur guards.
For complete sulfur removal (i.e., H2S, thiophenes), we
recommend our HRD 264, vapor phase sulfur guard.
Sulfur (as H2S) can be removed by this adsorbent, up to
18% by its weight, which is up to 65 lb/ft3.
Our ZN 0406, also used in vapor phase, is a zinc-based
product and at 99 lb/ft3 is one of the most dense sulfur
guards on the market. It can pick up up to 10% of its
weight.
For liquid phase applications, the D- 1275 is the prod-
uct of choice. It can pick up up to 15% of its weight, and
weighs up to 50 lb/ft3. Nickel is the active ingredient.
Our MD 101 copper product is also for liquid phase
applications and can pick up up to 5% of its weight. The
density is 56 lb/ft3.
QUESTION 18.
What are some of the ways refiners are using N/R
analytical technology to monitor catalytic reformer
performance?
ARMBRESTER:
Ashland is using its Infratane® on-line NIR technology
to provide octane value, aromatic content, and olefin con-
tent of the reformate product from our low pressure CCR
reformer at the Catlettsburg refinery. At the present time,
the NIR analyzer reports research, motor and pump octane
numbers as operating indicators only, but we have a project
under way to establish closed-loop octane control by using
TOC/INDEX
the analyzer’s research octane signal to set the weighted
average inlet temperature on the reformer reactors.
In addition to the octane values mentioned previously,
the NIR also provides on-line analysis for total olefins,
total aromatics, benzene, toluene, total xylenes, and ethyl
benzene. These values can be used to optimize our down-
stream aromatic extraction process.
CUNEO:
We are doing work on characterizing the reformer feed
for possible consideration in feed forward control, as well
as for analyzing octane and for benzene.
D’AURIA:
The NIR technique replaces traditional lab or on-line
techniques (such as knock engines, on-line octane analyz-
ers, gas chromatographs) that introduce high maintenance
costs, slow turnaround, and yet provide limited capabili-
ties. State-of-the-art NIR analyzers measure properties of
several process streams in the reformer simultaneously on
a real-time basis. UOP recognized the importance of this
technology and recently purchased Guided Wave in order
to offer this capability to our licensees. As of this date, there
are 14 Guided Wave analyzers sold for reformer applica-
tions measuring RON, MON, RVP, benzene, or PONA.
These applications are being utilized for both feed forward
control based on PONA, or feedback control based on
octane. The data from a single NIR analyzer monitoring
the feed and reformate streams, coupled with data on
moisture, chloride and hydrogen content in the recycle gas
from other on-line analyzers, will provide the basis for
implementing advanced control strategies for the reformer.
PETER MIKKELSEN (Petro-Canada Products):
Has anyone had experience with the hand-held NIR
analyzers for operators to use for control. There are a few
of them on the market that are relatively inexpensive and
we are in fact investigating use of such a piece of equip-
ment.
Process
QUESTION 19.
In order to control the amount of benzene in future RFG
(reformulated gasoline) what are the relative advan-
tages or disadvantages to limiting precursors in re-
former feed versus removing benzene from
reformate?
DEATON:
Clark’s Blue Island refinery in Chicago will market both
RFG and conventional gasoline. First, we plan to use
precursor prefractionation to reduce the benzene content
of the total gasoline pool. The precursor product will be
1994 NPRA Q&A Session on Refining and Petrochemical Technology
about 10% of the available reformer charge and will allow
us to reduce the benzene content in reformate by about
70%, and reduce the overall gasoline pool benzene content
by 30%. In our case, this amounts to about 500 barrels
per day less benzene in the gasoline pool. Then, to allocate
benzene between RFG and conventional gasoline, we plan
to pull a side draw from the reformer stabilizer. This side
draw will remove up to 70% of the produced benzene from
the reformate product in a volume as small as 15% of the
total reformate produced. The benzene content of the side
draw will contain up to 4.5 times the normal benzene level
of 1.1 vol% in the whole reformate. The vapor side draw
will be used as blendstock for conventional gasoline.
The fractionation systems we will employ avoids the
high cost of constructing and operating a solvent extrac-
tion unit. Precursor prefractionation can be done with
minimal capital investment, but will negatively impact the
gasoline pool octane by diverting 10% of the reformer feed
as a 60 octane blendstock.
ARMBRESTER:
The advantages and disadvantages obviously depend
on each refiner’s processing configuration, as well as their
individual situation regarding RFG production and anti-
dumping considerations. If a refiner has an outlet for
benzene, either through outside sales or as an in-plant
petrochemical feedstock, then the best option may be to
maximize benzene precursors in the reformer feed and
then extract the benzene from the reformate.
If an outlet for benzene is not available, then it is
probably best to minimize the benzene precursors, primar-
ily cyclohexane and methylcyclopentane, in the reformer
feed by raising the initial boiling point of this stream.
These components would then be saturated in the C5-C6
isomerization unit, thus reducing the total benzene in the
gasoline pool. Efficient fractionation will be needed to
move the benzene precursors into the isomerization unit
feed stream without also sending an excessive amount of
C7S and benzene to the isomerization unit.
One disadvantage of this route is that it reduces the
total amount of reformer feed available, which can nega-
tively impact the refinery’s hydrogen balance. If a refiner
has neither an isomerization unit nor aromatic extraction
capability, they may be forced to minimize the benzene
precursors in the reformer feed and blend the entire light
straight run naphtha stream to gasoline.
D’AURIA:
The major source of benzene in the gasoline pool is the
catalytic reformate that typically contributes 50% to 75%
of the benzene in the gasoline pool. Two basic approaches
can reduce net benzene production: minimize its forma-
tion by removing the precursors charged to the reformer
or fractionate a benzene-rich light reformate stream for
subsequent benzene conversion or extraction. Preventing
153
TOC/INDEX
the formation of benzene rather than converting it after it
is formed makes good engineering sense. However, in
certain cases, practical and economic constraints may limit
the ability of refiners to implement this strategy.
When choosing between light reformate processing or
precursor removal for benzene reduction, refiners must
consider three variables: the level of benzene allowed in the
regulated pool, the benzene-producing tendency of the
reformer, and the overall refinery flow scheme and crude
source. If reducing benzene below 1 vol% is necessary, the
precursor removal may not be sufficient. If the reformer
operating pressure is high, the production of benzene can
occur even after precursor removal due to dealkylation of
heavier hydrocarbons. Light reformate processing may also
be necessary if the refinery flow scheme is heavily depend-
ent on the reformer as a gasoline pool component, if the
crude used is highly cyclic, or if the reformer feed comes
from a number of other process units in which accurate
control of benzene precursors is difficult. Finally, if the
refiner has a petrochemical outlet for benzene, extraction
of benzene from the reformate may be the most economical
choice for reducing the benzene content of gasoline.
McLEAN:
Engelhard presented a paper at the 1992 NPRA Annual
Meeting which addressed this question. That was paper
number AM-92-51. This answer will summarize the con-
clusions from that paper.
The primary advantage for removing benzene precur-
sors from the reformer feed is that in many cases it can be
accomplished with existing fractionation equipment and
is therefore on the surface a “no capital required” option.
It has a number of disadvantages. Valuable hydrogen
producing compounds are also removed, which of course
reduces the potential hydrogen yield from the reformer.
This front end is also low in octane and if it is routed
directly to the gasoline pool, then the reformer severity
154 Light Oil Catalytic Processing
may have to be increased to compensate, which will reduce
the overall gasoline yield. Also, benzene originally present
in the naphtha will not be removed by the fractionation.
And, finally, in some cases this may result in pool benzene
levels below allowable target limits, with the effect of
unnecessary octane and hydrogen debits.
The alternative presented in the paper was the installa-
tion of a reformate splitter and liquid phase catalytic
hydrogenation of the benzene-containing light reformate
stream. This option was evaluated for four different crude
types, with hydrogenation severity adjusted to meet pool
benzene limits while maintaining improved overall gaso-
line yield and hydrogen balance. For the cases evaluated,
significant economic rates of return for the incremental
capital involved were indicated.
PORTER:
I agree with a lot of the previous comments, that the
key decision is whether you want your refinery to make a
benzene product. At our Pascagoula refinery, we are re-
moving benzene from our reformate, but at another refin-
ery we will try to minimize benzene formation. Once you
decide whether to make a benzene product, then choosing
the right option will depend on capital costs and operating
expenses between the various alternatives.
SAYLES:
A similar question was asked in the 1990 Question and
Answer Session, question 30.
From our perspective, benzene control to produce RFG
or conventional gasoline conforming to the refiner’s 1990
baseline requires a comprehensive review of all the gasoline
pool benzene sources. Benzene sources are the FCCU
naphtha, 25% of the total; light straight run or conden-
sate, 5% of the total; coker naphtha, 5% of the total; and
reformate, 65% of the total benzene in the pool. Limiting
reformer benzene can have a significant effect and the
methods for limiting benzene are:
1. Benzene precursors boil from 180°F to 230°F in
the HSR feed. Control of the reformer feed IBP to
greater than 220°F to 230°F should remove the
benzene precursors. The increased light naphtha
yield from the CDU will lower the gasoline pool
octane/bbl. To recover the octane loss, LSR
isomerization can be used to increase the octane
from about 67 to 78 RON. The disadvantage is
shorter isomerization catalyst life and increased
isomerization hydrogen consumption due to the
saturation of benzene.
2. Another approach is removal of the benzene from
the light reformate which produces a higher octane
gasoline pool. Several commercial processes exist
to remove the benzene. However, these processes
must be carefully reviewed with respect to the
benzene NESHAP regulations, OSHA benzene
TOC/INDEX
exposure limitations, and disposition of the con-
centrated benzene naphtha produced. The RFG
regulations have strict prohibitions to limit the
outlets for these concentrated benzene streams.
3. The third approach is to limit the operating sever-
ity to minimize benzene production. The produc-
tion of benzene is a thermodynamically controlled
reaction (temperature/pressure) and a maximum
benzene concentration will be reached depending
on the operating conditions. For a semiregenera-
tion reformer, there can be a maximum possible
benzene increase of 30% above start of run. An-
other way of estimating the benzene rise is a
0.0125%/°F increase in WABT. An interesting
exception is benzene produced by a CCR unit
which shows no increase in benzene with time.
(UOP R32 fresh versus spent data, NPRA Ques-
tion and Answer Session on Refining and Petro-
chemical Technology, 1991)
At constant severity, lower reactor pressure will
reduce benzene formation by about 0.0024 wt%
benzene per 1 psi reduction in separator pressure.
Higher pressures will increase aromatics by 0.028
vol% aromatics per 1 psi decrease in separator
pressure. (Feed IBP is at 215°F; Gilsdorf, et al,
“Platforming in the Reformulate Gasoline Era”,
1992 NPRA Annual Meeting, AM-92-16)
Pressure, psig 300 50
RONC Benzene, wt% Benzene, wt%
92 0.8 0.2
96 1.0 0.3
100 1.2 0.4
TREESE:
I would, ofcourse, go with the previous comments. We,
being primarily a California refiner, have the additional
problem of trying to meet the California Air Resources
Board (CARB) Regulations, which require less than 1%
benzene in the product.
We already have dehexanizers ahead of our reformers,
so most of the precursors are already fractionated out. In
our case, we have to post-fractionate in order to meet the
CARB Regulations.
Outside California, people may be able to meet the EPA
benzene requirements with prefractionation only. Our
thought is that there may be additional fractionation
required to meet toxics targets that are upcoming.
Refinery rest runs confirmed that prefractionation
alone, in our case, was not sufficient to meet the benzene
requirements in our reformate.
HEROS DERGREGORIAN (Giant Refining Company):
My question is regarding impact of pressure on the
alkylation of high aromatics into benzene. How sensitive
1994 NPRA Q&A Session on Refining and Petrochemical Technology
is that? Are the impacts a combination due to pressure and
severity of the operation?
D'AURIA:
The reformer pressure and octane severity, in addition
to feedstock boiling range, will impact the amount of
benzene made through dealkylation of heavier compo-
nents. To illustrate this relationship, the table below shows
benzene yields from the reforming of a midcontinent
naphtha:
Benzene Yield, LV%/FF
Boiling Range RONC 50 PSIG 300 PSIG
C6-370°F 98 2.2 2.5
C6-370°F 102 2.7 3.0
C7-370°F 98 0.5 1.2
C7-370°F 102 0.6 1.5
RICHARD M. GIALELLA (IFP Enterprises Inc.):
Limiting precursors may be effective in decreasing ben-
zene in gasoline. However, it does nothing to control
benzene formed by the hydrodealkylation reaction. Also,
it may severely impact light paraffin isomerization because
of poorer feedstock. This solution may not be adequate
for reformers operating at high pressure and high severity.
Controlling benzene downstream of the reformer permits
monitoring benzene regardless of reformer feed quality
and octane of the reformate. In addition, processing
downstream of the reformer permits the decrease of ben-
zene to low levels in the gasoline pool and takes full
advantage of the complex model equations in terms of
toxics reduction, thereby allowing more aromatics ulti-
mately into the gasoline pool.
IFP offers a full set of processes which allow for the
reduction of benzene downstream of the reformer, for
example, benzene saturation using either a noble or a
non-noble metal catalyst followed by isomerization, if so
desired.
DAVID N. WATERFIELD (BP Oil London):
You will be very lucky to get below 1% benzene on a
400 lb to 500 lb reformer, even if you remove all the C6
in the feed. On a low pressure CCR you may get down to
about one-half percent.
QUESTION 20.
What methods are being used to reduce plugging and
corrosion in the catalytic reforming stabilizer?
SAYLES:
Similar questions were asked in the 1987 NPRA Ques-
tion and Answer Session, question 30 (p. 120) and in the
1989 NPRA Question and Answer Session, question 22
(p. 133).
155
TOC/INDEX
Our semiregenerative stabilizer columns have not ex-
perienced plugging problems in the overhead system.
However, corrosion byproducts in the stabilizer overhead
water boot have been detected. The areas of highest cor-
rosion are locations where the overhead vapors reach their
dew point. Normally the stabilizer offgas contains 5 ppm
to 7 ppm H2S and NH3 with trace amounts of chlorides
and water. The corrosion is due to water entrainment in
the stabilizer which hydrates a chloride salt, typically
ammonium chloride and causes localized corrosion. The
concentrations in the overhead water boot are relatively
high, 0.5 ppm to 1 ppm Fe and the water rate is very low.
Corrosion can be eliminated by keeping the tower bone
dry which is difficult while maintaining a proper
water/chloride balance in the reactors.
We believe the corrosion rate is low. However, as a
precaution, a low level of filming amine is used, 1 ppm to
5 ppm. Another approach is to use liquid phase scrubbers
to reduce chloride levels and eliminate plugging.
We have had an experience with high pressure drop on
the feed side of the stabilizer/feed effluent exchanger of
about 90 psi. The high pressure drop was believed to be
due to ammonium chloride pluggage. Condensate injec-
tion into the feed washed the ammonium chlorides from
the bundle and reduced the pressure drop to about 25 psi.
During the condensate wash, the observed stabilizer over-
head water phase ammonium concentration increased to
3,000 ppmw from the normal 5 ppmw to 7 ppmw range
and the chlorides increased to 2,500 ppmw from the
normal 5 ppmw to 7 ppmw range. (The Cl/NH3 ratios
are: observed 0.9, calculated 1.0 a good check for ammo-
nium chloride salts). A corresponding increase in the iron
content from less than 1 ppmw to less than 7 ppmw was
observed. The high concentrations existed for the duration
of the water wash and then returned to the normal.
TREESE:
Unocal has been using continuous process improve-
ment methods to prevent excursions by improving control
of the addition of our chloriding agent. That has resulted
in reduced pluggage and reduced corrosion.
FELTROP:
I agree with the previous comments on elimination of
nitrogen from the reformer feed, the effects ofammonium
chloride, and using the water wash systems. A corrosion
inhibitor can also be used to protect the overhead and
minimize corrosion products in the system. Amine injec-
tion has also been used by several refiners. If it is used, it
needs to be carefully monitored because the high molecu-
lar weight salts can deposit in the tower bottoms and
downstream equipment.
An analogous plugging problem was seen recently at a
major refiner and was treated effectively using an antifou-
lant that combined a dispersant and a metal deactivator.
156 Light Oil Catalytic Processing
This, however, is not a method that addresses the causes
of the pluggage and corrosion.
PORTER:
We control plugging in our stabilizer, by water washing
the column. This is usually done during regeneration, but
some do it on the run.
BARLOW:
Most of the fouling and corrosion problems associated
with reformer stabilizer operation are due to NH4CI depo-
sition. When a water wash in a stabilizer is not practical,
the use of a chemical solution has proven very successful.
We have seen the use of amine technology to convert the
ammonium chloride salt into a more mobile salt. In
addition to the potential for plugging, the mobile salt can
be extremely corrosive. This approach is not recom-
mended. We have been successful using detergent/disper-
sant packages to reduce salt deposition and keep the salt
in the liquid phase.
LAUX:
When we operated only a semiregenerative reformer,
we also were able to simply water wash our stabilizer at
each regeneration to solve the plugging problem. When
we started up our continuous reformer in 1991, that
option disappeared.
We have good success with injecting a salt dispersant
chemical that drops the ammonium chloride out the
bottom of the stabilizer. We have heard of severe corrosion
resulting from using these chemicals, but we did not see
any corrosion when we last inspected the stabilizer. That
inspection was done 2 years after we started using the
chemical.
BOYCOTT:
I would agree with the comments on ammonium chlo-
ride salts causing the plugging problems. The source of the
problem is in the hydrotreater providing feed pretreat to
the reformer. The breakthrough of organic nitrogen com-
pounds causes the formation of ammonia in the reformer
and subsequently ammonium chloride salts. The process-
ing of coker naphtha can worsen this problem.
Although we process up to 25% to 30% coker naphtha
in our reformer feed pretreater, we do not experience
plugging problems in the stabilizer. We believe that this is
due to careful selection of hydrotreater catalysts to elimi-
nate the nitrogen compounds in our reformer feed.
CUNEO:
We would agree with the previous comments, espe-
cially about the need to set the severity of the naphtha
hydrotreater by organic nitrogen rather than by sulfur.
We try to treat down to less than 0.2 ppm weight.
TOC/INDEX
Another potential source of ammonia is sulfiding cata-
lysts during regeneration. We recommend use of a sulfid-
ing agent, such as dimethyldisulfide as opposed to sour
hydrogen from a hydrotreater which can contain some
ammonia in the vent stream.
DEATON:
For those refiners who run coker naphtha through the
reformer, plugging problems will occur if the naphtha
contains high nitrogen content coker naphtha. At Clark’s
Hartford refinery, a 900 psi coker naphtha hydrotreater is
effective in lowering the nitrogen content from 60 ppm
down to 0.5 ppm prior to blending with virgin naphtha
fed to a typical 300 psi naphtha hydrotreater.
We have also heard that some people have installed zinc
oxide and calcium oxide adsorbent beds in the stabilizer
liquid feed line to remove chlorides. Putting these adsor-
bers in a liquid service is relatively new, and the success of
these systems is not yet available. These beds are much
more common in gas service and the results are good at
reducing offgas line fouling and corrosion.
DAVID L. SMITH (ALCOA):
To support Mr. Deaton’s comments, there are selective
adsorbents that are effective in removing chlorides from
the liquid reformates to quite low levels, to prevent the
formation of ammonium chlorides in the stabilizer trays
and to eliminate the corrosion problems.
PAUL FEARNSIDE (Nalco/Exxon Energy Chemicals):
We have seen success for certain refiners where they pay
particularly close attention to the water wash system on
the naphtha hydrotreater, particularly if the water wash is
intermittent. We have seen at those times that the feed to
the reformer becomes extremely wet, carrying the resul-
tant ammonia content with it.
HEROS DERGREGORIAN (Giant Refining Company):
We have been discussing guard beds for sulfur break-
through to reformer charge. Is anybody doing work on the
use of guard beds for a nitrogen problem? If one is proc-
essing different kinds of feedstock, and the naphtha con-
tains different levels of nitrogen compounds, I would
expect nitrogen breakthrough causing problems down-
stream. I am less concerned about chloride fouling than
on balancing the chloride level on the catalyst. I was
wondering if anybody has discovered a guard bed for
nitrogen removal.
Secondly, has anybody had experience with Alaskan
crude having a high nitrogen level in the naphtha?
SAYLES:
We periodically get Alaskan North Slope into our
refinery and have noticed a slight increase in the feed
nitrogen to the hydrotreater. We run about a 900 psi
1994 NPRA Q&A Session on Refining and Petrochemical Technology
hydrotreater and have not observed any problems with the
reformer feed nitrogen content.
KENNETH D. PETERS (UOP):
Further to Mr. Deaton’s comments, we have been speci-
fying calcium oxide/zinc oxide treaters on the feed to the
Platforming unit stabilizer column for about four years
now. We have had some success with these treaters, par-
ticularly when the feed has been heated. The colder or
ambient temperature treaters do not always seem to oper-
ate as well as the treaters that are set up to run with
preheated feed in the 200°F to 300°F range.
Regarding the ammonium chloride, the primary time
when enough ammonium chloride is formed to cause
operational problems in the Platforming equipment is
when the upstream naphtha hydrotreating unit has an
upset situation and nitrogen breakthrough occurs. The
increased feed nitrogen then accelerates the ammonium
chloride formation. Also, in units where the reformer
catalyst surface area has declined significantly, the catalyst’s
ability to retain chloride is reduced, and the recycle gas
HCI level increases as more chloride is injected to keep up
catalyst activity. This increased HCI level also contributes
to increased ammonium chloride formation.
The best method to minimize plugging and corrosion
in the stabilizer column is to minimize ammonium chlo-
ride formation with better naphtha hydrotreating opera-
tion to avoid nitrogen breakthrough and better reforming
catalyst surface area management to minimize HCI in the
recycle gas.
J. DOUGLAS PERKINS (United Catalysts, Inc.):
We find with the zinc oxide/calcium oxide chloride trap
that the amount of ammonia will severely affect the use-
fulness of this material at lower temperatures, around
100°F. The ammonium chloride coats the material. At
higher temperatures, the ammonium chloride decom-
poses, i.e., at 230°F to 250°F and higher. So at higher
temperatures it works quite well. At lower temperatures it
also works, but only if there is no ammonia in the feed.
MICHAEL BUCKO (Merichem Company):
Fiber-Film Contactor technology has been proven suc-
cessful in eliminating HCI corrosion and both ammonium
and ferric chloride plugging of column internals and the
reboiler. Several treating units are currently in operation,
most of which are in the Far East.
MARK DORAN (ICI Katalco):
Fixed beds of chloride absorbent are an attractive solu-
tion to this problem because they offer a low capital cost
project, compared to a caustic wash system for instance.
They also offer a low maintenance/operator attention re-
quirement, compared to an antifoulant injection system.
157
TOC/INDEX
PURASPEC™ absorbents are succesfully installed in such
applications.
QUESTION 21.
Does anyone have experience in the use of molecular
sieves on the recyc/e stream for drying during start-
up? How much could the dryout time be reduced? Is
there any new technology available for avoiding chlo-
ride attack on the molecular sieve? What other proce-
dures or products are being used?
LAUX:
We route our recycle gas from our semiregenerative
reformer at the Three Rivers refinery through a glycol
contractor and then two parallel molecular sieve beds when
we start up after regeneration. The dryout time is cut to
two days, which is about 50% of the dryout time without
the dryers. The molecular sieves are loaded with 3A sieve
and we have not noticed any chloride attack, but they are
only used in this service two or three times per year.
The contractor and the sieve beds are used as part of a
cryogenic gas liquids recovery unit when they are not
being used for regeneration dryout.
McLEAN:
Recycle gas dryers can significantly reduce dryout time.
Engelhard makes an adsorbent known as “Sorbead R,”
which is specifically designed for recycle gas applications.
There are three domestic applications of this material in
this service. Sorbead R is more cost effective than molecu-
lar sieves in this HCI-bearing application. For units with-
out recycle dryers, dryout time can be improved by careful
attention to draining, making sure that there are adequate
low point drains, and that these and the separator are
continuously kept moisture-free until the introduction of
feed. Ensuring that there are no dead areas during nitrogen
and hydrogen purges, and minimizing the time for chang-
ing of blinds also help.
PORTER:
We have historically used molecular sieves to improve
the dryout time. We find that we can improve dryout time
by about two to three days using them.
At the Pascagoula refinery, we put a layer of activated
alumina in front of the molecular sieve and believe this
helps co reduce chloride attack on the molecular sieve.
D’AURIA:
UOP has specified dryers on recycle gas screams in order
to reduce dryout time on start-up. The numbers quoted
by others are similar to our experience.
We offer three different adsorbent products for this
service: RDG-418, AW-500, and AW-300. The most
commonly used are RDG-418 and AW-500. The AW-500
158 Light Oil Catalytic Processing
is a more acid-resistant material, but has a slightly lower
water capacity than the RDG-418.
An alternative to using an acid-resistant sieve is to install
a nonregenerable chloride trap upstream of the drier.
These recycle gas dryers have been used since the early
1970’s, and the chloride-resistant adsorbent has been used
successfully for over a decade.
HEROS DERGREGORIAN (Giant Refining Company):
We have been using nitrogen drying successfully for
reducing the drying time approximately in half.
QUESTION 22.
What has been the industry experience with the new
high alumina/low platinum CCR reformer catalyst?
Comment on stability, activity and physical properties.
D’AURIA:
UOP’s R-132 catalyst was first put in stream in March
of 1992. This catalyst exhibits yields equivalent to our
earlier R-30 series catalyst, with improved activity and a
significant improvement in surface area retention.
In March of 1993, we commercialized a second catalyst
in this series, R-l34. This product has the same perform-
ance benefits as the R-132, but with about 23% less
platinum.
As of September of this year, there are 17 units in
operation with R-130 series catalysts, and there are an
additional seven refiners that have selected this type of
catalyst for reloads in the near future. The units have been
achieving their expected catalyst strength, surface area
retention, activity and yield performance. We have been
very happy with the commercial results.
McLEAN:
Our affiliate, Acreon Catalysts, markets several new
generation catalysts for continuous reforming, including
E-1000 and CR-201. Both offer improved ultimate life
versus older catalysts due co decreased rates of surface area
loss. This has been demonstrated commercially on both.
The CR-201 has a higher density and therefore has
been effective at increasing throughput in bottlenecked
units without experiencing any problems in circulation.
PORTER:
We have recently cried UOP R-134 and the early results
look fine.
HEROS DERGREGORIAN (Giant Refining Company):
Does this new high level of alumina have any effect on
aromatic production?
D’AURIA:
The R-130 series catalyst has essentially the same yield
pattern as R-30 series catalyst, so that at a given octane,
TOC/INDEX
the aromatic production is the same. For petrochemical
operations, the higher activity of R- 130 catalysts can be
used to increase aromatic production by increasing the
operating severity.
STEVE WILLIAMS (Star Enterprise):
Has UOP seen any increased coking with the new
R-130 series catalysts?
D’AURIA:
The R-130 series catalyst coke laydown rate is essen-
tially the same as that for the R-30 series. We have done
extensive pilot plant and commercial tests that have con-
firmed this.
QUESTION 23.
Discuss the presence of iron on reformer catalyst and
the formation of iron sulfide scale in reformer heaters
and heat exchangers. What effect do these sulfur de-
posits have on sulfate formation during regeneration?
CUNEO:
We have taken core samples from reformer reactor beds.
They typically exhibit iron contamination at the top with
rapidly decreasing concentration as the samples are taken
down into the bed. Very little iron has been found at
depths greater than 12 to 18 inches.
While the iron on the catalyst could be a source of SO2
during regeneration, a more likely source is deposits found
in the feed site of the feed effluent heat exchangers. The
SO2 is generated when oxygen passes over these deposits
and then comes into the reactors and deposits these during
regeneration. The majority of the SO2 remains in the first
reactor.
Closely monitoring the sulfate removal allows material
balancing the sulfur movement in and out of the reactors.
DEATON:
Iron sulfide scale is formed in reformer reactor feed heat
exchangers and reactor heaters during normal operations
due to trace quantities of sulfur not removed in upstream
hydrotreating units. Iron on reformer catalysts is usually
highest on the first reactor. Recent iron analysis ofcatalysts
at one of Clark’s reformers indicated iron contents of 0.36
wt% in Number 1 reactor compared to 0.22 wt% in
Number 2 reactor, 0.07 wt% in Number 3, and 0.04 wt%
in Number 4 reactor. We recommend rotating catalysts
between Number 1 and Number 4 reactors every three
years, when the catalyst is unloaded for reactor internal
inspection.
Iron sulfide scale burns to sulfur dioxide during both
the carbon burn and the oxidation step. Sulfur dioxide
reacts with the metals on the catalyst to form sulfate, which
prevents metals dispersion and causes subsequent lack of
activity. Sulfates can be removed from the catalyst during
1994 NPRA Q&A Session on Refining and Petrochemical Technology
a sulfate removal step conducted prior to the oxidation
step by circulating electrolytic hydrogen in the presence of
a high concentration of hydrochloric acid. Hydrogen sul-
fide is formed and then neutralized with a caustic wash.
However, if all the iron sulfide scale in the heat exchangers
and heaters has not been removed during the carbon burn,
sulfates will again be formed during the hotter oxidation
step and thus counteract the total effectiveness of the
sulfate removal step. We therefore recommend hydroblast-
ing the feed exchangers before the oxidation step to re-
move iron sulfide scale.
McLEAN:
I agree with what has been said before. I would add that
the activity loss is due to the effect of sulfates on the
alumina base, which adversely affects the platinum redis-
persion process. This is where the activity loss comes from.
MENEGAZ:
I agree with the previous comments also. I would add
that we also see most of the iron on the first reformer bed.
In addition, we have also seen a lot of iron sulfide scale on
the bottom of the stabilizer, suggesting we had water down
there at one time or another.
Secondary sources of scale can come from a direct
reduction of carbon steel by hydrogen sulfide at tempera-
tures below 400°F, by oxygen contamination in the naph-
tha, and by corrosion products in the regeneration
procedure.
Oxygen contamination has been traced back to storage
in unblanketed tanks, pipeline naphtha, or city water used
upstream in the naphtha hydrotreater. One refiner strips
his feed with nitrogen to remove the oxygen.
Regarding the regeneration procedure, we have no
comment except that attempting regeneration above 0.5
wt% sulfur will permanently damage the catalyst.
SAYLES:
I would like to echo the earlier comment, we have also
found iron sulfide in our stabilizer bottom, which fouled
a fired reboiler heater. The fouling required cleaning at
about an 8-year cycle.
QUESTION 24.
What are the mechanisms of platinum loss from re-
forming catalyst? How much platinum is typically lost
during the life of the catalyst?
LAUX:
Actual platinum loss from the reforming catalyst is hard
to determine because you are dealing with small concen-
trations on large volumes of catalysts over several years of
operation. The balances are not as accurate as your audi-
tors would like to think. Generally, accounting errors are
the cause of many platinum losses.
159
TOC/INDEX
The one true loss that does occur is the catalyst that falls
to the ground each time you handle it or open equipment.
This can actually be very significant. We try to lay plastic
out to catch as much of the droppings as possible, and have
picked up as much as a drum during one turnaround.
An effective platinum loss does occur as well. If you
expose your CCR catalyst to high temperatures, over
1200°F, alpha alumina can be formed. This alpha alumina
can encapsulate the platinum, making it harder to recover.
We have developed some catalyst particles that are nearly
pure alpha alumina. Based on surface areas, over 65% of
the platinum was encapsulated. The platinum refiners
reduce their recovery guarantees to about 98% when the
alpha alumina content exceeds 10%. The guarantee drops
to 97% recovery when the alpha alumina exceeds 25%.
Laboratory tests have also shown that platinum can be
leached off the catalyst during very severe oxychlorina-
tion. However, commercial units do not approach these
conditions.
McLEAN:
We do not know the mechanisms for certain, but we
do believe that the losses occur during the regeneration
and activation processes, in the presence of chlorides and
oxygen. We suspect platinum oxychlorides have a finite
vapor pressure and therefore are liberated from the catalyst
in very minute concentrations. We do see evidence of
measurable ppm levels of both platinum and rhenium in
the circulating washwater used during regeneration and
activation.
As a rule, less than 5% of the metal will be lost over the
life of a semiregenerative type catalyst, and I would agree
with what Mr. Laux said about the difficulty in balancing
such small numbers.
SAYLES:
Platinum loss is through two mechanisms:
1. Loss of catalyst fines is the major mechanism in
platinum loss. For semiregeneration units the loss
is from handling during fresh catalyst loading or
spent catalyst unloading. Our experience has been
an overall platinum recovery based on fresh plati-
num addition of about 98 wt%. For CCR units
another loss occurs in addition to loading and
unloading losses; catalyst fines are produced via
attrition. Reported attrition losses are in the range
of 0.1 wt% to 0.2 wt% fresh catalyst.
2. Platinum can be lost if extremely high tempera-
tures occur during regeneration or during unit
upsets. Platinum can form platinum crystal growth
in the temperature range of 900°F to 950°F as a
result of high sulfur at the start of the regeneration.
A sulfur removal step is needed to restore the
catalyst activity at the end of the regeneration.
160 Light Oil Catalytic Processing
ARMBRESTER:
We agree with several of the previous comments on the
mechanisms for losing platinum, both in the CCR and
the semiregenerative units. Our losses will typically aver-
age 2% to 3% over the life of the catalyst, but we will lose
more than that in the CCR units just due to attrition.
BOYCOTT:
I agree with the comments on the mobilization of
platinum as platinum oxychloride during the regeneration
step. I am not aware of a mechanism by which this
mobilization can remove the platinum from the catalyst
structure itself. We have not been able to document a loss
of platinum from our catalysts, other than physical attri-
tion and loss on recovery.
D’AURIA:
Platinum losses are, for the most part, due to fines
generation in catalyst handling. Paying attention to cata-
lyst handling is the best way to minimize loss of platinum.
While platinum volatilization is theoretically possible,
it is extremely unlikely to occur at any reforming condi-
tions, either during operation or regeneration. Our expe-
rience is that questions related to potential volatilization
of platinum usually arise as disputes over assay differences
with the catalyst reclaimer. We have not seen any signifi-
cant differences reported by our customers for catalysts
that we have reprocessed.
BOB RODDEY (Roddey Engineering Services, Inc.):
Through the years refiners’ personnel have backed off
from being involved in catalyst loading with the advent of
companies that specialize in catalyst loading. As a result,
there is some sloppy catalyst loading occurring sometimes,
and the representatives of the refinery are not there to see
it. I have seen drums of platinum catalysts on the ground
after a loading. We will be able to help anybody by
supervising the catalyst handler, and that is a good step in
minimizing platinum loss.
M. DEAN EDGAR (Criterion Catalyst Company L.P.):
Occasionally we are asked to help refiners figure out
what happens to the platinum between the time the fresh
catalyst arrives and the time the spent catalyst is sent out
for recovery. By far, the two biggest problems we find,
which the panel mentioned, are: bookkeeping, or keeping
track of the amount of removed and replaced catalyst when
the reactors are dumped and screening losses are replaced,
and the physical attrition of the catalyst during loading that
may result in losses downstream of the reactors.
Another item is support material. When the catalyst is
sent to the reclaimer, if you mix the support materials in
with the catalyst, even in small amounts, this will act as a
diluent and the percent platinum analyzed will be a lot
lower in some cases.
TOC/INDEX
One more item to consider is the analytical procedures
used by the catalyst vendor and reclaimer. We sometimes
see as much as a 10% variation in results.
QUESTION 25.
What are the pros and cons of converting a 400 psig
semiregenerative reformer to 225 psig? Please dis-
cuss yield gains, relative coking rates, compressor
and heater revamp and possible charge reduction due
to increased pressure drop.
McLEAN:
The advantage of this reduction in pressure will be a 4
vol% to 6 vol% increase in C5+ reformate yield. Hydrogen
yield will also increase between 0.4 vol% and 0.6 wt%,
and hydrogen purity in the recycle gas will increase by
more than 10 vol%.
Disadvantages are shorter cycle time and a greater
endotherm across the reactors. The net heat of reaction
may increase by up to 40%. Increased furnace duty and
increased heat exchanger surface area may be required to
meet this extra heat requirement.
At constant octane, space velocity, and hydrogen to
hydrocarbon recycle ratio, the cycle length of the lower
pressure operation will only be 40% to 50% as long. If this
is unacceptable, then feed rate can be cut, reformate octane
reduced, catalyst loading increased (if possible), or hydro-
gen to hydrocarbon ratio increased.
Catalyst loading and throughput will be directly related
to the cycle length. That is, a 50% increase in loading will
increase cycle length 50%. The hydrogen to hydrocarbon
ratio will have to be doubled to maintain the same cycle
length. Finally, octane decrease of 10 to 15 numbers may
be required to hold cycle length constant. Of course,
combinations of these variables could also be employed.
Reduced pressure at constant feed rate will significantly
increase the pressure drop. Reactor internals may have to
be changed from downflow to radial configuration in order
to conserve pressure drop. Also, new low pressure drop feed
effluent exchangers may also be required to conserve the
overall delta P with the lower pressure operation.
D’AURIA:
UOP has done many revamps of high pressure semire-
generative reformers to lower pressure operations. Every
project has its own unique constraint, but some general
guidelines can be given.
In most cases, a refiner will want to retain his current
recycle compressor, and maintain feed rate. This can usu-
ally be accommodated by allowing the H2 /HC ratio to
drop as the pressure is decreased. For a decrease in pressure
from 400 psig to 225 psig, a semiregenerative unit would
theoretically see an increase in C5+ yield in the range of 3
to 4 LV%, depending on feedstock properties and operat-
ing severity. With the decrease in pressure and H2/HC
1994 NPRA Q&A Session on Refining and Petrochemical Technology
ratio, however, the catalyst coking rate will increase by a
factor of 5 or 6.
The changes usually required for such a revamp are:
switch to a more stable catalyst,
installation of a low pressure drop vertical combined
feed exchanger,
addition of a large fourth reactor and heater, and
add a net gas compressor.
The case cited here is an extreme and may not be
practical due to the high coking rates and limits on the
capability of the recycle compressor. In this instance, the
next alternative to consider is conversion to a CCR opera-
tion. This can be accomplished easily at 225 psig with
changes similar to the SR revamp case, except that a new
reactor stack and regenerator are added, instead of a single
reactor. This conversion would provide an additional 2
LV% C5+ yield over the semiregeneration revamp (5 to 6
LV% gain total), and could cost as little as 45% of a new
CCR platforming unit. To date, 24 semiregenerative plat-
formers have converted to CCR operation, 9 of these from
a side-by-side configuration.
A third alternative would be the addition of a last
reactor and regenerator, leaving the first three reactors in
semiregeneration mode. This is sometimes referred to as a
hybrid revamp. We have found that this option has not
had a good payout because the required investment, while
lower than a CCR revamp, is significantly higher than a
semiregeneration revamp, while the yield benefit is similar.
DEATON:
A similar question regarding mechanical details was
answered during the 1993 NPRA Question and Answer
Session. Two advantages of converting a 400 psi unit to a
225 psi unit would be increased yield of about 3 vol%,
and increased hydrogen production of over 250 scf/bbl.
Four disadvantages ofconverting the unit would be, (1)
the need to regenerate catalyst about twice as often, (2) the
need to revamp the reactor feed effluent exchangers to
reduce system pressure drop, (3) the need to revamp the
recycle compressor to operate at lower suction pressure,
and (4) the need to install a booster compressor to supply
produced hydrogen to consuming units. The cost of the
revamp must be weighed against the value of the yield and
hydrogen increases. Assuming average 1993 prices and
severity of 97 to 98 octane, we estimate the value of the
yield alone to be twenty-five cents per barrel.
LEE E. TURPIN (Honeywell Profimatics):
Dropping reactor pressures has been evaluated on sev-
eral units using Profimatics’ kinetic reformer model REF-
SIM. A few general observations are: (1) a greater C5+ yield
increase is observed when dropping from 300 psig to 200
psig than from 400 psig to 300 psig, and (2) a greater C5+
yield increase is gained when dropping the last reactor than
the first reactor. Usually, incremental capital spending to
161
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reduce pressure in the last reactor, preferentially over the
first and second reactors, yields the highest return on
capital investment. The use of a kinetic model allows a
refiner to determine the economic impact of specific
mechanical changes on a unit. With this knowledge, those
modifications that provide real economic gains, on a
discounted cash flow basis, can be identified.
FRANCOIS REVEROY (Packinox, S.A.):
One of the options that has not been brought up is that
you may need to find some additional heat duty at the
charge heater, and also find some savings in pressure drop.
One of the options which is currently looked at by refiners
is to go to a plate-like feed effluent exchanger. In most
cases, the increased heat recovery will eliminate com-
pletely the need to revamp the heater, and in certain cases
where you deal with the older generations of shell and tube
exchangers, the savings in pressure drop can also be very
substantial.
JEAN-LUC NOCCA (IFP Enterprises, Inc.):
IFP has developed two processes to revamp reformers
and take full advantage of the lower pressure. The first one
is the addition of a continuous reactor and associated
regenerator in the reaction train. You can, for example, at
constant octane, decrease the pressure from 350 psi to 250
psi and increase the cycle. You can gain about 3.50 scf/bbl
in hydrogen, and 6% or 7% gain in yield.
Another option is to add the continuous reactor down-
stream of the separator, and to recontact the net hydrogen
produced with the liquid from the separator. The advan-
tage of that is that you need no revamp to your existing
reaction system. With that you can get in the range of 450
scf/bbl additional hydrogen and 8% additional liquid
yield while also increasing the cycle of the semiregenerative
reactors. The additional advantage of lowering the pres-
sure is, of course, that you will make less benzene in your
reformer and that prefractionation will in most cases be
sufficient to meet benzene requirements.
KENNETH D. PETERS (UOP):
I would like to expand a little bit on the comments from
Mr. D’Auria from the panel and Mr. Reverdy of Packinox.
The UOP Engineering Department has done numerous
revamps with a pressure reduction of this level. Currently,
we have found that the replacement of the existing com-
bined feed exchangers with a Packinox welded plate-type
heat exchanger works out well by reducing the reactor
circuit pressure drop and also reducing the load on both
the charge heater and products condenser.
Typically, the old 400 psig reformer design required a
larger charge heater than first interheater, and dropping
the pressure significantly increases both the total heat of
reaction and the first interheater load. With the addition
of a Packinox CFE, these first two heaters can be switched
162 Light Oil Catalytic Processing
in positions by simple repiping, often then allowing both
to fit the new revamp requirements. Also, remanifolding
of the reactor section heaters to increase the number of
passes can relieve a pressure drop bottleneck caused by the
pressure reduction. If needed, more tubes often can be fit
in the firebox at the same time the remanifolding is done.
A charge reduction can often be avoided by adding
catalyst to the unit. The first reactor is scrapped, the
subsequent reactors are moved up in position, and a new
larger last reactor is installed.
In the last six months, we have completed projects both
in Australia and the Russian Federation for the revamp
described above, including successful installations of a
Packinox CFE.
Mechanical
QUESTION 26.
Has anyone operating a semiregenerative reforming
unit ever experienced combustion in the heat ex-
changers downstream of the reactors during the coke
burn or subsequent steps in the regeneration? What
causes this? How can this be prevented?
LAUX:
We have not experienced the problem described. One
potential cause is residual hydrocarbons being swept off
the catalyst and accumulating in low spots. To avoid this
problem we take extra time to check all of the low spots
in the recycle loop for residual hydrocarbons and drain
these low spots while cooling down. We actually have a list
of all these low spots in our procedures.
Our inerting procedure uses two depressuring steps to
the flare header pressure, followed by repressuring to 100
psig with nitrogen. The third depressuring step goes to
vacuum before the final repressuring. We then test the
nitrogen in the recycle loop for hydrocarbon content. If it
is over l%, we depressure and repressure again until the
analysis shows less than 1%.
McLEAN:
This phenomenon can occur due to combustion of
heavy ends and sulfur compounds. The material will start
to burn only as sufficient oxygen breaks through from the
terminal reactor and temperatures are elevated to the proof
burn level.
PORTER:
Many years ago we experienced combustion in the heat
exchanger downstream of the reactors during a start-up.
At that time, the reformer operated with a lot of H2S in
the recycle gas so the exchangers were heavily fouled with
iron sulfide. We believe the combustion was caused by the
ignition of the iron sulfide.
TOC/INDEX
CUNEO:
We discussed the potential for combustion of iron
sulfide which is generally on the feed side of the reactor
feed to effluent exchangers. In addition to that, we have
occasionally found the deposits on the effluent side of the
exchanger which were identified as polynuclear aromatics.
We have used a solvent prior to regeneration to remove
these.
BOB RODDEY (Roddey Engineering Services, Inc.):
Twice during my career, we have had combustion begin
to take place in the feed effluent exchanger during the
regeneration oxidation step on a reformer . On both
occasions, it was sufficient to melt one of the tubes in the
bundle and subsequently get recycle gas bypassing back to
the suction of the compressor. When we shut down and
went in, we found that there were iron sulfide scale and
coke in the exchanger. We had gone through the precau-
tions of making sure that there was no hydrocarbon in the
recycle gas, of course, before we started. Nevertheless, it
was sufficient to start the burn and the heat liberated was
enough to burn a hole in the exchanger tubes. The solution
to the problem is not to let your heat transfer coefficient
get low before cleaning the feed effluent exchangers.
DAVID N. WATERFIELD (BP Oil London):
We had a problem on one of our units about three years
ago. It was a semiregenerative unit which had been re-
vamped to have a vertical countercurrent exchanger. The
conclusion that we came to from our investigations was
that catalyst had migrated from the last reactor through a
damaged center pipe and lodged against the baffle plates
in the exchanger. This occurred around the point where
the dew point was reached in the exchanger. We believe
that coke was built around that catalyst and it did not
ignite during the carbon burn step, but it burned very
fiercely during the oxychlorination step and did signifi-
cant damage to a number of tubes in the exchanger. This
experience shows that it is important to make sure of the
integrity of your center pipe and regularly clean your
exchangers, as some of the other answers have indicated.
QUESTION 27.
Have there been any advances in moisture analyzers
for reforming units? Does anyone use water analyzers
on both the liquid feed and the recycle gas? What has
experience been with these systems?
D’AURIA:
UOP has recently commercialized a new type of recycle
gas moisture analyzer called the “Continuous Moisture
Measurement System”, which overcomes some of the
problems experienced with some earlier analyzers in this
service. This analyzer uses a silicon-based sensor that is
much more resistant to the corrosive agents that are found
1994 NPRA Q&A Session on Refining and Petrochemical Technology
in reformer recycle gas. In addition, it has two sensors that
can provide for continuous and automatic calibration.
Another feature is the analyzer has a rapid sensor drydown
if it does become saturated by high gas moisture content.
This feature allows for accurate and timely moisture moni-
toring during times of rapid moisture change, such as
start-up after regeneration. This analyzer has been proven
in a first commercial reforming unit, and there are four
more installations planned in the near future.
It has been our practice to measure only the recycle gas
moisture on a continuous basis. We feel that the recycle
gas moisture is the most pertinent variable in the reform-
ing operation, and direct measurement of this variable is
the most straightforward way to control the unit’s water
chloride balance.
BOYCOTT:
We installed moisture analyzers on both the feed and
recycle gas streams two years ago. The units have proven
reliable. We have used them primarily for trend checking
of moisture levels, but as we are gaining experience with
the systems we are starting to put more faith in the absolute
numbers.
The systems that we have are based on an aluminum
oxide probe. We have two probes for each installation.
They have been giving us about 6-month run lengths
between recalibration. While one probe is in service the
other is sent out for recalibration.
The one weakness we have seen with the system is the
susceptibility to chloride attack during periods of high
moisture level. For this reason we block in the recycle gas
probe during catalyst regenerations. Neglecting to do so
during one regeneration caused us to destroy a probe.
PORTER:
We agree with Mr. D’Auria that the recycle gas is the
best location to measure moisture content. We do not
measure the feed on a continuous basis. We prefer Ametec
moisture analyzers on the recycle gas.
SAYLES:
Again, we concur with the previous comments and
would add that we measure the moisture only in the
recycle gas. We have had an analyzer on the recycle gas the
last seven years, with only minor maintenance. Ours is one
of the older designs, which means that during, or just
before regeneration and before start-up you have to make
sure that the analyzer is blocked in from the process
streams. Otherwise, the high moisture content will destroy
the cell.
TREESE:
I will add another vote for recycle gas stream analyzers.
We have been relatively happy with the Panametrics ana-
lyzer. They have made a number of improvements in their
163
TOC/INDEX
sensors and electronics over the years. They also perform
well at low ppm.
As a check of the on stream analyzer, we use a Shaw
portable analyzer. Shaw uses a different sensor system, so
it acts as a confirming cross check.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
I have two questions on moisture streams. What is the
best location for sampling the recycle gas, in the suction
or in the discharge of the compressor? Secondly, is there
another laboratory testing method?
CUNEO:
We typically sample recycle gas on the suction side of
the compressor and we do off-line analysis of feed mois-
ture content with Karl Fisher.
HEROS DERGREGORIAN (Giant Refining Company):
NHT stripper is where you should remove the water
which is part of the naphtha hydrotreater sulfur removal
process. From where else would water be coming in the
reformer charge? How could you guarantee that the strip-
per is operating properly besides maintaining the proper
reflux rate?
BOYCOTT:
We have noted two sources of water in our reformer
feed; improper stripper operation, and cold charge from
tankage. We use the reflux to feed ratio to control stripper
operation. As to cold charge, we are currently installing a
line to route cold charge through the stripper. We are
doing this to strip water from the stream prior to feeding
it to the reformer.
DEATON:
Our guideline for naphtha hydrotreater operation on
the stripper is that the reflux should be 25% of the unit
charge rate, and if your reflux is that rate, you are firing
enough in the reboiler to remove water.
LAUX:
One other source of water that we have seen is from
dryer malfunction on our continuous unit. We carried
water back into the unit with the catalyst from the
regenerator.
PORTER:
When feeding cold feed from tankage, we prefer to feed
it through the stabilizer to dry it out.
KENNETH D. PETERS (UOP):
In terms of evaluating the naphtha hydrotreating unit
stripper column for water removal, you really have to look
at the vapor/liquid ratio in the bottom of the column.
Even if you have a relatively high reflux ratio, the
164 Light Oil Catalytic Processing
feed/bottoms exchanger could be picking up too much
heat, and the resultant lower vapor/liquid ratio might be
too low for proper water removal. An analysis of the entire
stripper column operation is needed to determine if the
conditions are severe enough to produce a dry reforming
unit feed.
QUESTION 26.
Our reformer feed sometimes contains up to 3 ppm
organic nitrogen. We have managed to sustain this
operation with higher chloride rates. Has anyone else
had this problem? What is the experience with high
organic nitrogen in the feed?
McLEAN:
I am aware of one reformer which has operated at 6
ppm feed nitrogen in a 300 psi operation. The biggest
problem which was noted was increased compressor foul-
ing due to ammonium chloride deposition, which was
discussed in detail in a previous question.
PORTER:
We do not run any of our reformers at that level of
nitrogen for sustained periods. We would immediately try
to find the source and stop the problem.
ARMBRESTER:
When high levels of basic nitrogen are present in the
reformer feed, we would expect it to temporarily reduce
the catalyst activity by neutralizing some of the acid sites.
The primary effect of the lower catalyst activity would be
a reduction in isomerization and/or hydrocracking teac-
tions in the reformer. The catalyst activity can be main-
tained to some extent by increasing chloride addition, but
as mentioned previously, you need to be concerned with
ammonium chloride salt formation.
D’AURIA:
Our specification is less than 0.5 weight ppm nitrogen
in the reformer feed. Nitrogen will act as a temporary acid
function poison. Increasing chloride injection will help
marginally, but will also lead to greater catalyst deactiva-
tion and ammonium chloride salt formation. A 10,000
bbl/d reforming unit with only 0.5 ppm nitrogen in the
feed will produce about 2,000 lb per year of ammonium
chloride, which is going to settle out somewhere in the
cold end of the plant. Operation at higher nitrogen levels
will produce even greater quantities of salt.
RONALD E. MARRELLI (Phillips Petroleum Company):
With respect to nitrogen, I know UOP mentioned 0.5
ppm as their maximum specification. What about lower
levels of nitrogen? How low a nitrogen level can you have
and still see noticeable effects of nitrogen poisoning on the
catalyst? And are there specific nitrogen compounds that
TOC/INDEX
will give you more problem in the feed, such as chemical-
treating amines or other corrosion inhibitors that may give
you feed poisoning of your reformer catalyst?
D’AURIA:
The 0.5 ppm specification is historical, set by the lower
limit of detection of the analytical method. You should try
to operate with no detectable nitrogen in the feed. Any
amount of nitrogen coming in is going to remove chloride
from the catalyst and eventually wind up as a salt in the
cold end of the plant.
With respect to the types of nitrogen species, we have
not seen any real difference in the types. We assume that
any organic nitrogen is going to break down and form
ammonia over the platinum catalyst, and both strip chlo-
ride as well as lead to downstream plugging.
Our experience is that operating at less than 0.5 ppm
nitrogen, with our normal chloride maintenance proce-
dures, allows proper catalyst chloride balance and long run
lengths.
QUESTION 29.
We are considering the replacement of our reciprocat-
ing catalytic reformer recycle compressors with one
centrifugal recycle compressor. The maintenance
cost is quite high on the reciprocating machines and
extreme problems are experienced during catalyst
regenerations. What is the difference in operating and
maintenance cost of the reciprocating and centrifugal
machines?
SAYLES:
We have reciprocating compressors on our reformers at
two locations and a centrifugal compressor at one location.
All three units are semiregenerative reformers allowing the
opportunity for major maintenance during catalyst regen-
eration.
Our experience with the centrifugal recycle compressor
is that a major overhaul would be expected every 5 to 6
years. Only one compressor is needed due to the excellent
on stream time. With the advent of improved rotating
equipment monitoring techniques problems are detected
before significant damage can accumulate. We believe the
major mechanical overhaul cycle can be increased further.
We have not had to take an outage to conduct repairs on
the centrifugal compressor between regeneration.
For reciprocating compressors the anticipated major
mechanical overhaul cycle should be the same as the
centrifugal machines, 5 to 6 years. However, our experi-
ence has been that the reciprocating machines require
major overhauls every 3 to 4 years. If a single machine were
used, valve replacements about every three months and
other more routine problems could cause unscheduled
outages for repairs. Normally two reciprocating machines
are required to allow for routine maintenance and to
1994 NPRA Q&A Session on Refining and Petrochemical Technology
prevent unscheduled outages. A mechanical availability
analysis, taking into consideration the refinery mainte-
nance history, should be used to determine the number of
machines.
Comparing the options of reciprocating compressor
versus centrifugal compressor during a recent major capi-
tal project resulted in the selection of the reciprocating
compressor. Although the reciprocating compressor op-
tion held higher maintenance costs, the overall mainte-
nance plus capital investment is much lower than for the
centrifugal compressor.
ARMBRESTER:
Ashland operates two CCR reformers at our
Catlettsburg refinery, each of which is equipped with a
centrifugal recycle gas compressor and reciprocating net
gas compressors. In general, centrifugal compressors cost
less to maintain and have more reliability than their
reciprocating counterparts.
Our experience shows that the maintenance cost for the
reciprocating compressors is more than twice as high as
the centrifugal machines, with the centrifugal compressors
having a mean time between failures that is about three
times as long as the reciprocating compressors.
In terms of operating cost, the reciprocating compres-
sors are inherently more efficient than centrifugal com-
pressors. When operating at design conditions the
reciprocal compressors are 10% to 15% more efficient.
However, much of this efficiency advantage can be lost if
the compressor is throttled for operation at reduced flow
rates, so the centrifugal compressors offer more opera-
tional flexibility.
For semiregenerative units, we have found that the
reciprocating compressors require extensive valve work to
remove salt deposits following regeneration, while the
centrifugal machines usually do not require any additional
work related to the regeneration.
CUNEO:
I agree with the previous comments. We believe the
availability of reciprocating compressors can be worked
into the 96% to 97% reliability range with good mainte-
nance practices.
CHARLES S. McCOY (Consultant):
Also, lubricated reciprocating compressors will put
some lube oil into the system. It shows up as coke on the
first reactor catalyst where you least want to build a high
coke level. Nonlubricated compressors solve that problem,
but have a few of their own.
KENNETH D. PETERS (UOP):
Several years ago, we shifted our specification for both
the smaller reciprocating recycle gas compressors and for
the larger net gas machines away from the nonlubricated
165
TOC/INDEX
machines to synthetic-lubricated machines. We found
these synthetic lubrication packages have significantly
extended the valve life and given us a much higher reliabil-
ity with the reciprocating machines. I refer you to my
response to Question 19 on Page 83 of the 1987 NPRA
Q&A Sessions book.
MAJED A. INTABI (Saudi Aramco):
In the case of a set of reciprocating compressors, the
spare machines allow continuity of operations and on the
run maintenance. On the other hand, when problems are
encountered with the centrifugal compressor, it will have
a greater impact on operations and can result in long
duration shutdowns.
QUESTION 30.
During in situ catalyst regenerations, we have expe-
rienced salt carryover into our centrifugal compres-
sor. Some refiners wash the compressor with a weak
basic solution at some point prior to start-up but after
regeneration. We have heard that some refiners do
not wash the compressor during this downtime.
f/ease discuss the best timing for washing the com-
pressor and problems associated with this washing
operation. Why would one not wash the compressor
during this time?
DEATON:
Foaming and carryover of circulating caustic solutions
during regeneration are best minimized by maintaining
pH between 7.5 and 8. Higher pH tends to cause foaming.
To avoid spikes in pH, makeup solution strength should
be only 5 Baumt. Also, solids in solution cause foaming
and a good guideline is to flush enough to keep the specific
gravity of the solution below 1.07.
The best times to wash compressor internals are either
after the carbon burn or after the reduction step. From a
technical standpoint, the best time to wash is after the
reduction step because this would remove any salt deposits
incurred during the oxidation step. From a monetary
standpoint, many refiners prefer to wash after the carbon
burn if they are doing other maintenance between the
carbon burn and oxidation.
For many years, Clark’s Blue Island refinery did not
wash their compressor internals for fear of damaging
labyrinth seals and for fear of uneven washing off of large
deposits, which could throw the rotating element out of
balance. However, during a recent carbon burn, severe
vibration in the compressor caused us to stop in the middle
of the carbon burn and wash the compressor internals. We
followed the procedure in the UOP Operating Manual,
which consists of five washes with 2 wt% soda ash solu-
tion. The compressor was started back up with very low
vibration and very high pumping rates. We also inspected
166 Light Oil Catalytic Processing
the product separator drum and found the demister pad
to be partially dislodged, allowing caustic carryover.
CUNEO:
We have had instances where the compressor was op-
erating very smoothly on shutdown and the decision was
made not to wash, as Mr. Deaton said, and then the
compressor vibrated violently. Those kinds of situations
have been corrected in the past with water washing, so we
recommend washing compressors on shutdown if any
capacity loss or vibration has been measured. We routinely
wash after regeneration.
D’AURIA:
The decision on whether to wash the recycle compres-
sor during downtime is based on two factors. One, if you
are going to open the machine and expose it to air for some
maintenance, it should be washed. Two, it should be
washed if there is a probability of ammonium salt deposi-
tion having occurred, either during the normal operation
or during the regeneration. If either of these apply, then
we would recommend following the washing procedure,
as Mr. Deaton just outlined.
The typical reasons for not washing have been either
time constraints, or existing conditions that did not war-
rant washing; in other words, no history of ammonium
chloride deposition and no problem with nitrogen in the
feedstock. Also, some people do maintain a continuous
on-line injection of antifoulant and feel that this will
remove the likelihood of compressor fouling.
MENEGAZ:
We agree with Mr. D’Auria’s comments regarding the
timing. An excellent description of the water wash pro-
cedure can be found in the 1988 NPRA Question &
Answer Session transcript. Most refiners to whom we
talked employ a similar procedure. Most do not do a
disassembly and cleaning unless planning to service the
compressor. Most reported excellent results, provided
care was taken in thoroughly removing the water from
the system. We would also suggest washing the inlet lines
to the compressor as well.
Many refiners also wash on-line with heavy naphtha or
antifoulants to extend run lengths to three years. As with
any wash of a high speed machine, it should be started
before you have appreciable amounts of buildup on the
blades. Otherwise, you get nonuniform spalhng and vi-
bration problems.
PORTER:
We do not wash on a routine basis or every regenera-
tion, but we do it for a specific reason. Usually it is an
increase in vibrations.
TOC/INDEX
SAYLES:
We wash the centrifugal recycle compressor at every
regeneration, but by looking at the critical path we deter-
mine that our window of opportunity is while blinds are
being installed before regeneration.
CHARLES S. McCOY (Consultant):
Two of you have alluded to the case for washing before
regeneration. I remember a disastrous wreck at one refin-
ery. They did not think they had a vibration problem, but
with the generation of moisture during the regeneration,
deposits on the wheels were dislodged. Before the opera-
tors could stop the machine, serious damage was done.
HEROS DERGREGORIAN (Giant Refining Company):
How effective is the antifoulant on preventing com-
pressor fouling during operation and as well as during or
after regeneration?
D’AURIA:
We have had a number of clients report success with
the injection of antifoulant. They use a hydrotreated
naphtha or a reformate stream injected at about two pints
per million standard cubic feet of recycle gas. Once begun,
this procedure must be maintained on a continuous basis.
Intermittent injection can result in an imbalance of the
rotor due to uneven cleaning of deposits.
ANGELO FURFARO (UOP):
I want to add one point to Mr. D’Auria’s comments.
You should always start the injection on a clean ma-
chine/rotor. The machine should be clean so that starting
this injection does not cause existing deposits to come off,
which can damage the rotor blades.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Does anyone keep the compressor on-line during the
reduction step?
PORTER:
No, we shut the compressor down.
ANGELO FURFARO (UOP):
During the reduction, UOP utilizes the compressor.
Other reforming licensers may not. Others may perform
a hydrogen or hydrogen/nitrogen gas-through reduction.
Since UOP specifies use of the compressor, we would not
add any more hydrocarbon to the system while circulating
that gas than normal, so UOP would not be using the
compressor wash ar that point in time.
LAUX:
We do use our compressors to circulate hydrogen dur-
ing the reduction step.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
D. Aromatics Extraction
QUESTION 31.
What are refiners’ experiences with respect to re-
boiler corrosion in aromatic extraction p/ants using
Sulfolane as so/vent? What are the practices followed
to prevent corrosion in the reboiler?
BARLOW:
It has been our experience that corrosion in the solvent
circulation section of the sulfolane unit is generally asso-
ciated with organic acids formed by degradatiomoxida-
tion of the sulfolane solvent. Caustic and organic amines
such as morpholine have been used to neutralize these
acids and control pH. However, some processors continue
to experience problems in the reboiler sections, even while
they are using the neutralizers. The problem is generally
blamed on both continuing organic acid attack and ero-
sion due to buildup of insoluble salts in the recirculation
loop.
We would recommend use of a proper neutralizing
amine, an amine which forms a liquid salt, that you apply
in the overhead system. Also, consider evaluation of some
of the newer higher temperature organic acid neutralizers.
CUNEO:
We operate three sulfolane extraction units that predate
the current UOP design. A number of years ago we
experienced significant reboiler fouling and corrosion
problems. It was attributed to buildup across the salts in
the system resulting from the ingress of oxygen and chlo-
rides. We had to focus on source control of the oxygen
chloride in order to eliminate the problem.
D’AURIA:
There are three mechanisms for corrosion at the Sulfo-
lane extraction unit reboilers: acidic attack, erosive attack,
and chloride stress corrosion cracking. Historically, these
types of corrosion occur under different circumstances.
Acidic attack occurs when the Sulfolane solvent inven-
tory is exposed to excessive heating (greater than 350°F)
and/or oxygen; the Sulfolane solvent undergoes a thermal
decomposition, which is accelerated at higher tempera-
tures, and dramatically increased in the presence of oxy-
gen. The key to preventing acidic attack is to prevent
overheating at reboilers and prevent oxygen contamina-
tion. However, if the solvent becomes acidic, it can be
corrected through proper operation of solvent regenera-
tion facilities and effective neutralization with MEA.
(Typical desirable pH ranges are greater than 7 for circu-
lation water streams and 5 to 6 for circulating solvent;
solvent acid number should be less than 0.05 mg
KOH/g.)
Erosive attack originates from circulation of solids
(such as pipe scale, corrosion debris, polymeric byproducts
167
TOC/INDEX
of solvent decomposition and other foreign matter) which
are not properly removed from the unit. The erosive attack
typically occurs at the extractive stripper column reboiler,
due to the higher velocities involved to limit the tube skin
temperatures. The best countermeasures are effective
chemical cleaning of the extraction section prior to initial
start-up and periodically at turnarounds (if necessary), and
effective operation ofsolvent regeneration, so as to remove
the solids from the circulating solvent. UOP is studying
alternate metallurgies to improve erosion resistance in this
service.
Chloride stress corrosion cracking is caused by chloride
contamination in the feed. UOP recommends that the
feed contain less than 0.1 ppmw total chloride in order to
avoid this type of corrosion. For units which have in-
creased likelihood for chloride contamination, UOP has
begun to recommend use of Duplex 2205 metallurgy
(22% Cr, 5% Ni, 3% MO, annealed such that it is equal
parts austenitic and ferritic steel).
DEATON:
During five years associated with a sulfolane unit, I did
not experience corrosion in any of the reboilers in contact
with sulfolane. All of these reboilers were carbon steel and
they were either stab-in reboilers or kettle reboilers. All of
them used 450 psi steam and the steam was on the tube
side. The sulfolane solvent in this unit was maintained in
good condition by operating the solvent regenerator con-
tinuously and with the addition of MEA.
At another refinery, corrosion was a problem in both
the stripper reboiler and the solvent regenerator reboiler.
The predominant mode of failure was process-side corro-
sion near the steam inlet of the vertical thermosiphon
reboilers. All of these reboilers used 250 psi steam, and
steam was on the shell side. Corrosion was eliminated by
replacing the carbon steel bundles with 304 stainless steel
and by operating the solvent regenerator continuously.
168 Light Oil Catalytic Processing
Some miscellaneous failures also occurred, attributed to
erosion. A particulate filter system was added to eliminate
erosion failure.
Finally, any refiner with ongoing corrosion problems
in the sulfolane unit should be aware that air leaks into
the towers which operate under vacuum is the single
largest source of corrosion in a sulfolane unit. Large air
leaks are readily obvious because the solvent will turn red
due to iron in the solution. Small air leaks are best
detected by regularly testing the sulfolane solvent for acid
neutralization number, expressed as mg of KOH per gram
of solution.
ARMBRESTER:
We also use MEA addition to maintain a low acid
number and the guideline that we use is 0.05 mg KOH
per gram of solution, maximum.
QUESTION 32.
Are there any activity and selectivity comparisons of
the commercially available clays to minimize unde-
sirable reactions such as disproportion tran-
salkylafion? What types of clays and operating
conditions reduce these undesirable reactions in
paraxylene, cumene and BTX processes?
ARMBRESTER:
At our Catlettsburg petrochemical complex, we use
Engelhard’s F-24 clay in the clay treaters for both the
cumene unit and the sulfolane BTX unit. In the sulfolane
unit, the typical start of run temperature is 310°F and the
inlet temperature is increased as the clay ages. The typical
end of run inlet temperature is 390°F. It is critical that the
operating pressure be kept high enough to ensure that the
BTX stream remains in the liquid phase during this
operation.
Poor clay life has been a problem in these treaters as a
result of low space velocities and relatively high olefin
content, but selectivity has not been an issue.
In the cumene unit, benzene production in the clay
treater is a problem as a result of disproportionation of
cumene to benzene and di-isopropyl benzene. These
treaters are run at much lower temperatures than the BTX
clay treaters, with typical start of run inlet temperature of
80oF, because we have seen the benzene production in-
crease at higher temperatures or reduced liquid hourly
space velocity.
We have tested Engelhard’s F-44 and F-54 clays in this
treater and we were able to operate at higher temperatures,
but the clay life appeared to be shorter. At the 3.5 liquid
hourly space velocity we run, the F-24 appears to give us
the best service. If we were consistently running below 3.0
liquid hourly space velocity, one of the more selective clays
would be reconsidered.
TOC/INDEX
D’AURIA:
We have not seen any quantitative comparisons of the
various clays. For benzene or cumene treating services,
where generally there is a lower olefin content, the impact
of yield loss is not significant. Therefore, most operators
will select the highest activity clays for these services as they
typically give the longest run lengths.
For xylene service, however, where olefins can be higher,
the higher activity clays tend to have greater losses of
product due to transalkylation, unless the clay tempera-
ture can be reduced. Therefore, in these services we tend
to recommend lower activity clays such as Sud Chemie’s
Tonsil CO, in order to minimize ring loss.
E. Polymerization
QUESTION 33.
What techniques have been used other than
hydroblasting for removing catalyst from tubular
reactors?
D’AURIA:
The other catalyst unloading technique that has been
successfully used is dry drilling of the tubular reactors.
Government environmental regulations are making it
more and more difficult to dispose of the low pH, high
phosphorus water produced in the conventional hy-
droblasting.
Dry drilling, coupled with, a well designed catalyst
conveying and separation system, can provide a very clean
and efficient operation and the catalyst can then easily be
collected in super sacks and sent to disposal. As an exam-
ple, one refiner who has a tubular reactor with 160 tubes
of 2-inch ID, 30 feet long, required only eight to nine
hours from the beginning of the reactor unheading to the
completing of the reactor closure after catalyst loading
when using this dry drilling technique. Drilling times are
approximately 3 minutes per tube for the drilling itself,
and about 1.5 minutes per tube for wire brushing.
The only reported problem we have heard with dry
drilling is drill bit sticking. This can result if there are some
soft, gummy deposits encountered in the tubes. Typically,
there are three to five tubes that have these deposits, and
these are hydroblasted out after the rest of the catalyst has
been unloaded.
SAYLES:
I agree with Mr. D’Auria.
DAVID WOOD (CRI International, Inc.):
I agree with the panel comments on dry drilling for
removing catalyst from tubular reactors. I would add that
our affiliated company, Catalyst Technology, has consider-
able experience for removing catalyst from tubular reactors
1994 NPRA Q&A Session on Refining and Petrochemical Technology
with different techniques, and I would encourage anyone
who has specific problems related to this to contact Catalyst
Technology directly.
QUESTION 34.
In a chamber type reactor, high pressure drop and bed
channeling are problems that shorten catalyst run
length. What mechanical and/or process steps can be
taken to reduce these problems?
DEATON:
Catalyst manufacturers have always stressed the impor-
tance of feed moisture control. Other factors to consider
are (a) catalyst bed inlet temperature philosophy, (b) novel
catalyst loading ideas, (c) quench nozzle design, and (d)
thermowell design.
The normal practice with catalyst bed inlet tempera-
tures has been to stagger the inlet temperatures in ascend-
ing order. However, I understand that some refiners are
now experimenting with running a constant inlet tem-
perature profile, with hotter inlet temperatures on the first
three beds, in an effort to decrease the heat of reaction in
the last two beds where higher temperatures cause more
polymer formation.
In the area of novel catalyst loading ideas, one catalyst
manufacturer offers blends of catalysts and charcoal. Two
super sacks of these blends are put at the top of each
catalyst bed. This provides an inert component of similar
density and size in the top of each bed to prevent high
reaction rates, thus preventing excess polymer formation
in the top of the bed.
Quench nozzle design is important in order to provide
uniform radial temperature profile even during unit turn-
downs. I had good experience redesigning for lower charge
rates using Bete Fog nozzles.
As far as thermowell designs, the optimum setup is to
have radial temperature readings across the top and bot-
tom of each bed to help in adjusting quench rates to
minimize radial temperature differences.
D’AURIA:
We have seen refiners try both mechanical and process
steps. As Mr. Deaton just mentioned, mixing an inert
material such as charcoal in with the catalyst has been
successfully used to minimize pressure drop buildup. In
addition, refiners have sometimes short loaded the bottom
bed of catalyst in order to give them less pressure drop
buildup and prolong the catalyst life.
On the process side, the primary knob you have to turn
is proper catalyst hydration, and this is really the most
important parameter in prolonging catalyst life.
Other process variables that can prolong run length are
maintaining the proper severity ofoperation by maintain-
ing the combined feed olefin concentrations within the
recommended levels, controlling catalyst temperature
169
TOC/INDEX
profile by propet use of interbed quench, and minimizing
the reactant residence time over the catalysts. We normally
recommend a 0.9 minimum space velocity.
MENEGAZ:
I agree with Mr. D’Auria’s comments. Limiting the
temperature rise per bed to 35°F has worked well for one
refiner. If the olefin content of feed is above 30%, using
recycle diluent should be considered.
Regarding the temperatures, multiple thermocouples
are recommended since channeling makes individual tem-
perature readings unreliable.
Catalyst breakage during loading is generally not sub-
stantial enough to cause problems. In one odd case, recip-
rocating pumps caused high pressure drop by introducing
air into the process, forming coke.
SAYLES:
I would like to add that we have seen situations where
pressure drop has developed in one reactor and not in
another. We have skewed the feed rates to the individual
reactors and tried to balance the pressure drop.
We typically get 2,500 hours per catalyst load and
attribute the run length mainly to processing only C3
olefins and keeping the heavier materials out of the unit.
QUESTION 35.
Are there any other catalysts beside solid phosphoric
acid catalysts that can be used commercially for poly-
merization?
DEATON:
I am aware of two technologies licensed by IFP. These
are the Dimersol process and the Polynaphtha process.
The Dimersol process utilizes a liquid soluble nickel-
based catalyst injected into the feed at a rate of a few
hundred ppm. The reactor is a simple residence time
vessel operating at 120°F and 300 psi pressure. Heat of
reaction is controlled with a cooled pumparound system.
The reactor effluent contains catalyst and the reaction in
the effluent is stopped with the injection of caustic. The
caustic wash is usually neutralized or used in FCC flue
gas scrubbers. Propane product meets HD-5 specifica-
tions.
The polynaphtha process utilizes an acidic silica alu-
mina catalyst in a fixed bed reactor. There is no chemical
injection used to maintain catalyst activity such as in a
reformer. The process is relatively low pressure at about
150 psi pressure and reactor temperatures are less than
those in phosphoric acid catalyzed reactors. Multiple
reactors in series are used and the heat of reaction is
controlled by cooling between reactors. LPG recovered in
the fractionation column is recycled to the reactor to raise
conversion and to decrease the concentration of olefin in
170 Light Oil Catalytic Processing
the reactor inlet, and thus help dissipate the heat of
reaction.
ARMBRESTER:
Theoretically, any strong acid catalyst with the appro-
priate acid strength and distribution will be effective for
polymerization or aromatic alkylation. Several systems,
including zeolites, have been identified for this applica-
tion. However, we are not aware of any significant use of
these materials, probably due to the relatively low cost of
purchasing and disposing of the solid phosphoric acid
catalysts, and their years of effective performance.
All the alternative catalysts of which we are aware are
significantly mote expensive. The major driving force to
change may be disposal costs. If an in situ regenerable
catalyst were available, future landfill liabilities may pro-
vide incentive for their use even at a high per barrel
purchased catalyst cost.
MENEGAZ:
Except for Dimersol units, almost all polymerization
gasoline units today use solid phosphoric acid. There was
a liquid phosphoric acid process developed by Chevron,
which involves spraying the acid periodically on quartz
particles, but I do not believe anyone is using that today.
Also, Chevron had a bulk polymerization process in-
volving phosphoric acid. I do not believe that went past
the pilot plant stage.
Several suppliers are looking at zeolite-based catalysts.
Cumene synthesis is successfully being done that way. In
the past, alumina chloride and solid copper pyrophos-
phate have been tried.
ROBERT ALLSMILLER (United Catalysts, Inc.):
To follow up on Mr. Armbrester’s comment about
zeolite polymerization, our parent company, Sud-Chemie,
has developed in conjunction with a South African Com-
pany, a process using zeolites for the conversion of olefins
to diesel. This process has now been operated commer-
cially for well over a year and is available for licensing.
The comment about the cost of the catalyst is abso-
lutely correct. Zeolites do cost quite a bit more than solid
phosphoric acid catalyst but zeolite catalysts last longer.
MARK DORAN (ICI Katalco):
One of our customers using a PURASPEC™ sulfur
guard process on the liquid feed to their C5/C6 isomeriza-
tion unit has seen a significant improvement in perform-
ance of their isomerization unit. Installation of the guard
bed has increased the life of the isomerization catalyst by
800%. The increased protection to sulfur ingress offered
by the PURASPEC™ unit has also allowed more flexible
operation of the upstream hydrotreater leading to its cycle
lengths increasing more than 100%.
TOC/INDEX
F. lsomerization
QUESTION 36.
Have refiners processed defluorinated alkylation bu-
tane through a butane isomerization unit? if so what
has been the commercial experience? Has catalyst
life been affected?
PORTER:
Yes, we have processed defluorinated alkylation butane.
Fluoride, of course, is a serious poison for isomerization
catalysts, and so you need to closely monitor the operation
of the defluorinators. We consider 1 ppm fluoride the
maximum specification. Also, any residual HF in the
isomerization feed will react with the molecular sieves, and
require them to be recharged more frequently. If you are
not careful, you can have water breakthrough, which will
also poison the isomerization catalyst.
One side note is that we have had catalyst poisoning
from fluorides in purchased butane that was received in
rail cars.
LAUX:
I agree with Mr. Porter’s comments. An actual experi-
ence we had involved not changing out the KOH treater
downstream of the alumina treaters quickly enough. We
took four days to change it out instead of one. When you
are pushing your alumina lives to the end of the run, that
will allow enough fluoride to get to the molecular sieves.
This actually destroys the sieve, as Mr. Porter mentioned.
We deactivated the first reactor catalyst in one month after
poisoning the sieve in the isomerization unit.
BOYCOTT:
The feed stream to our butamer is the normal side draw
off of the alkylation unit isostripper. We operate two
defluorination alumina beds in series on this stream. The
defluorinators have provided protection against HF attack
on both the mole sieve driers and the isomerization cata-
lyst. We are getting six to nine months operation on the
lead bed.
D’AURIA:
It is common practice to treat the normal butane stream
from an HF alkylation unit prior to feeding it to a butane
isomerization unit, such as Butamer. We specify the two
bed system that Mr. Boycott just mentioned. We use a
special high purity grade of alumina, and operate at ele-
vated temperatures. Typically, this is then followed by a
KOH treater to guard against any fluoride breakthrough
and also to reduce the moisture content of the butane
stream.
Organic fluorides, if they do get through this pretreat
system, will not be removed by the Butamer feed dryers
but will convert to HF over Butamer catalyst. The HF is
1994 NPRA Q&A Session on Refining and Petrochemical Technology
a permanent poison for this catalyst. It is considered a
more severe poison than water because part of the deacti-
vation mechanism will release more water, which further
deactivates the Butamer catalyst.
HF itself will be picked up by the feed dryers but will
deactivate the sieves and lead to water breakthrough.
QUESTION 37.
What has been the experience with temperature run-
away in a butane isomerization reactor during start-
up? How do you prevent these runaways?
PORTER:
Most of our butane isomerization experience has been
with recycle hydrogen units. There have been no problems
with temperature excursions. However, one of our once
through units did have a runaway situation on restart after
a short shutdown.
It is believed the hydrocarbon was not adequately
purged from the reactor on shutdown due to the low flow
rate of hydrogen during the sweep step and the hydrocar-
bons began to crack during the outage. When the hydro-
gen flow was reestablished with the catalyst still hot, the
hydrocarbons were promptly saturated, releasing heat.
For this specific situation, the heat input to the process
should have been stopped and the catalyst cooled below
250°F using feed or recycled isomerate. Recycled isomerate
is the best choice, since it is more likely to be non-reactive.
D’AURIA:
Temperature excursions have occurred on several Bu-
tamer units. The cause of these excursions has either been
long hydrocarbon residence time in the reactor at high
reactor temperatures, or, in a couple of cases, mistakenly
charging feed with high olefin content to the unit. To
avoid excessive residence time at high temperatures, we
have revised our operating procedures so that the unit is
brought to full feed rate before raising temperature to
reaction conditions.
QUESTION 38.
What methods are being employed to reduce dryout
time in the reactor and fractionator systems at start-up
in a butane isomerization unit?
D’AURIA:
One of the time-consuming steps for the start-up of the
Butamer unit is the removal of iron oxide from the equip-
ment. Many of our customers have done chemical clean-
ing of the reactor section as well as the stabilizer section
prior to the precommissioning phase. Once the iron oxide
is removed by this chemical cleaning, the drydown proce-
dure proceeds very quickly.
171
TOC/INDEX
DEATON:
I agree with what Mr. D’Auria said. I can add that
mechanical cleaning should be followed by chemical
cleaning with solutions of citric acid until iron in solution
comes to equilibrium. If the iron scale is not removed prior
to dryout, then the dryout will be prolonged when hydro-
chloric acid used during most dryouts reacts with the iron
scale and forms moisture. Worse yet, a butane isomeriza-
tion unit started up without removal of iron scale will lead
to catalyst deactivation because of moisture generation.
QUESTION 39.
Use of a sulfur guard bed to protect sulfur sensitive
isomerization catalyst is desirable to extend unit op-
eration. What has been the industry experience with
using a sulfur guard system on isomerization unit feed?
BOYCOTT:
I was involved in the installation of a reduced nickel
sulfur guard bed on the feed stream to a pentane/hexane
isomerization unit. The unit was originally built without
a guard bed. Prior to the installation of the guard bed, the
unit was experiencing severe sulfur poisoning due to sulfur
recombination reactions in the hydrotreater. Of serious
concern in evaluating the installation of a guard bed was
the available temperature of the stream. On-site pilot plant
work indicated that the sorbent would function in the
200°F range. The success of the subsequent installation
proved this to be the case. It is important to note that the
species we were attempting to pick up was methyl-mer-
captan.
As I understand it, current pentane/hexane isomeriza-
tion unit designs incorporate a sulfur sorber guard bed.
DEATON:
For a C5/C6 feed, typical operation of a liquid phase
sulfur guard system operating at 400°F, with a liquid
hourly space velocity of about 15, is 0.2 ppm sulfur inlet,
and 0.1 ppm or less sulfur outlet. Sulfur guard catalyst life
is six to twelve months, with catalyst bed plugging limiting
run length due to coking, not sulfur saturation.
Untypical operation with sulfur levels at or above 0.3
ppm passing through the unit reduced the C5/C6 paraffin
isomerization number, by 4 to 5 numbers, requiring a
15°F lead reactor temperature increase to compensate.
ARMBRESTER:
Ashland has successfully used 13x molecular sieves in
the dryer beds for both moisture and sulfur removal in its
butane isomerization unit at our Catlettsburg refinery.
The inlet stream to the dryer beds typically contains 2
ppmw to 60 ppmw moisture, 10 ppmw to 50 ppmw sulfur
as mercaptan, 5 ppmw to 25 ppmw sulfur as disulfides,
0.5 vol% olefins, and 1 ppmw to 6 ppmw chloride. Our
172 Light Oil Catalytic Processing
outlet sulfur concentrations have been 1 ppmw or less,
with a few excursions to 2 ppmw to 5 ppmw.
The dryer beds are regenerated with dry hydrogen at
500°F on 12- to 14-hour cycles. We have required replace-
ment of these beds due to sulfur breakthrough after ap-
proximately 170 to 230 cycles.
McLEAN:
We are aware of some units that have had sulfur guard
beds installed to protect against sulfur upsets, and others
that are currently considering doing it. Most of these units
were not initially built with guard beds since the design
feedstock did not exceed the contaminant levels, but later
experience due to upsets created a situation where they
chose to add them. Both nickel- and copper-based adsor-
bents are available which are effective in removing sulfur
from isomerization unit feed.
SAYLES:
I agree with the comments.
CHARLES S. McCOY (Consultant):
Do not try to use a copper adsorbent ahead of a butamer
type catalyst. Sulfur displaces oxygen from the copper
oxide, and you can exchange a mild poison for a severe one.
McLEAN:
This should not be a problem if the copper adsorbent
is properly reduced during the start-up procedure.
QUESTION 40.
Are there any new developments in the area of a
regenerable butane isomerization catalyst?
McLEAN:
Engelhard has developed and markets through our
Acreon affiliate a regenerable butane isomerization cata-
lyst, RD-291. This is the approved catalyst for a process
which is currently licensed by IFP. This catalyst has suc-
cessfully operated in commercial applications dealing with
both refinery and field butanes.
Alumina-based isomerization catalysts are well known
to be extremely sensitive to water, sulfur, and other feed-
stock contaminants, and upsets can and will occur. With
a regenerable catalyst, the catalyst can be regenerated and
reactivated and the unit placed back on-line with a mini-
mum of downtime. Other catalysts that are nonregener-
able would need to be replaced.
ARMBRESTER:
We are aware of considerable effort in the area of
promoted sulfates or zirconias, which are reported to be
active for butane isomerization, and we understand that
Sun Refining and Marketing Company received a patent
for a catalyst of this type in 1990.
TOC/INDEX
G. Etherification
QUESTION 41.
Has anyone produced TAME (tertiary amyl methyl
ether), ETBE (ethyl tertiary butyl ether), or TAEE (ter-
tiary amyl ethyl ether) commercially, either in a unit
designed for MTBE or in a unit specially designed for
this purpose?
McLEAN:
TAME and ETBE have been and are being commer-
cially produced. I am not sure about TAEE. Maybe some-
body can comment on that.
It is my understanding that both MTBE and TAME
units are now being designed with flexibility to use either
methanol or ethanol as the alcohol source. The units for
producing the ethers are similar, but operating conditions
are different due to the thermodynamic and kinetic con-
straints. So while it may be possible to havesome flexibility
in the design, co-production is difficult.
Amylene conversion to TAME typically requires addi-
tional investment for fractionation, sulfur removal, and
selective hydrogenation of diolefins. MTBE or ETBE is
usually the first option a refiner will employ.
THOMAS F. KELLETT (CDTECH):
CDTECH does have five operating TAME units in
catalytic distillation mode, with a sixth one to start up in
December of this year. No CDTECH MTBE units have
been converted to produce TAME, although studies have
been made for that purpose.
Although TAME production requires additional in-
vestment for fractionation, as Mr. McLean has stated,
sulfur removal and selective hydrogenation of diolefins
can be accomplished very economically in the depentan-
izer with CD Hydro technology.
Several of our MTBE units have been evaluated for
conversion to ETBE production, and some of those may
be converted to do that. That conversion does not tend to
be very complicated, but there are some subtleties to it.
One unit has been specifically designed to produce MTBE
or ETBE. Two CDTECH MTBE have produced ETBE,
with one of those now operating for more than a year and
a half.
HIGGINS:
Would you comment on how long it takes to complete
a MTBE to ETBE revamp, in terms of lead time for
equipment purchases?
THOMAS F. KELLETT (CDTECH):
I would expect that the equipment purchase would be
in the drying sections that would take care of any water
associated with the recycle and water in the ETBE unit.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
We are talking probably somewhere in the neighborhood
of six months.
RICHARD M. GIALELLA (IFP Enterprises, Inc.):
Of IFP’s licensed etherification units, there are four
units which are operating for TAME production which
were specifically designed for TAME production. In addi-
tion, we have retrofitted one MTBE unit to ETBE service,
which has been operating continuously for one year in the
ETBE mode. Also, there are two units designed for MTBE
or ETBE production, which are planned to be on stream
next year.
QUESTION 42.
What is the maximum recommended concentration
level for nitriles in the feed and how effective is water
wash in achieving this level?
LAUX:
The maximum recommended levels of nitriles in the
feed to an MTBE plant is 1 ppm. At our McKee unit, the
raw feed contains about 15 ppm to 16 ppm. The water
wash we have there removes about 50% of these nitriles.
This is because the water wash system is not very well
designed. It is an old butylene Merox extractor that has
been revamped for use as a water wash, but it only has six
trays.
Also, because of fresh water availability and waste water
disposal restrictions, we limit the fresh water rate to 10
gpm for this 8,000 barrel per day system. A good design
would have 20 or more trays and a fresh water rate over
30 gpm. Such a system would have much better removals,
80% to 90%.
The effect of nitrile in the feed can be reduced by not
recycling methanol because the nitrile conversion to am-
monia per pass is very low. If you do recycle, 1 ppm in the
fresh olefin charge will concentrate up to about 5 ppm in
the reactor influent.
Since all of our MTBE from McKee is used internally,
we do not recycle the methanol and let it go out with the
product. This reduces the purity on the MTBE to about
92%, but with this, our R-1 catalyst lasts about 18 months
and our R-2 catalyst lasts about four years. We accept these
as good lives for the catalysts, with that level of nitrile in
the feed.
For our new TAME system, we also looked at a water
wash for the propionitrile in the feed. The column would
have needed 36 trays and a 35 gpm washwater rate. Instead
we are converting an old ethylene regenerable drier system
into a solid bed nitrile adsorber.
MENEGAZ:
We are aware of an MTBE unit without a water wash.
The feed has between 20 ppm and 60 ppm acetonitrile,
depending on the FCC severity. Catalyst life is about one
173
TOC/INDEX
year, and I do not know the catalyst space velocity. How-
ever, the refiner feels it is definitely more economical to
replace the catalyst than to go ahead and try to retrofit and
operate a water wash. Spent catalyst has been loaded into
the guard bed upstream of the reactor in hopes of extend-
ing the catalyst life, but it is too early to tell if that is going
to work.
PORTER:
We typically see about a 95% to 97% efficiency removal
of nitriles in our MTBE plants. At our Pascagoula refinery
MTBE plant, the total nitrogen in the feed is 100 ppm to
200 ppm, and we get it down to 2 ppm to 5 ppm in the
product.
ARMBRESTER:
I would just add that we did some testing in 1990, after
start-up of our MTBE unit. With about 5 ppm to 10 ppm
acetonitrile in the feed to the unit, we were able to treat
down to 200 parts per billion or less, if we lowered the pH
of the washwater to 6 units.
We test our reactor feed stream weekly for nitriles and
typically see less than 300 parts per billion.
CUNEO:
I agree with the previous comments, that the water
wash can be quite effective in removing the acid nitrile
down to very low concentrations.
D’AURIA:
In addition to acetonitrile, some operators are finding
propylnitrile both in their C4 streams in MTBE units, or
more commonly in the C5 fraction charged to a TAME
unit. The standard water wash technology and resin guard
beds do not offer the same protection for propylnitrile
removal as they do for acetonitrile. More aggressive water
wash systems have shown to be effective in the removal of
propylnitriles, but now we are talking about water wash
rates in the range of 60% to 90% of the feed rate.
An alternative to this would be a sieve system. UOP has
developed a nitrogen removal sieve system which can
remove both acetonitrile and propylnitrile from the eth-
er&cation feed streams.
The choice of the system to be used depends on the
refiner’s utility balance and availability of the proper re-
generants for the nitrile removal unit.
CHARLES KRUSE (Bechtel Corporation):
What is the effect of these impurities on the longevity
of the catalyst using reactive distillation processes versus
fixed bed processes.
D’AURIA:
The catalyst used in fixed bed as well as the reactive
distillation processes are basically the same, so the effect
174 Light Oil Catalytic Processing
of the nitrogen poisoning of the acidic sites on the catalyst
would be the same.
ROGER SINGER (The Purolite Company):
We have experience indicating the water wash can be
optimized, as some of the folks have mentioned, by reduc-
ing the nitrile level from optimizing variables such as the
water quality, flow rate, and pH of the water wash system.
As a precaution, to make certain all the nitriles are ac-
counted for, we also recommend that the methanol recycle
stream be checked for nitriles as well. What we are cur-
rently finding is that even if the nitrile level in the feed is
reduced to ppm levels in the water wash, we can see the
buildup from anywhere from 1 to 2 orders of magnitude
higher levels of nitriles that can accumulate in this recycle
stream.
Apart from the process optimization, we also find that
selection of a more poison-resistant catalyst can serve to
extend the catalyst life. Substantial commercial experience
in both MTBE and TAME units with one of the Purolite’s
catalysts demonstrated that both extended life with high
conversion can be achieved.
DAVID L. SMITH (ALCOA):
As a follow-up to Mr. D’Auria’s comments, there are
alumina-based selective adsorbents available that can re-
move both acetonitrile and propionitrile to levels well
below 0.5 ppm by weight.
QUESTION 43.
Has anyone with a water wash/methanol extractor
system on a MTBE or TAMEunit experienced corrosion
in the overhead section of the extractor column? How
has this been eliminated?
MENEGAZ:
We know of a TAME unit that is experiencing a six
month life on the carbon steel tubes in the extractor
overhead fin fan condenser. The refiner suspects oxygen
contamination from the well water used in the water wash.
They are looking at an alternate water source.
D’AURIA:
Corrosion problems could arise in the raffinate wash-
water system through the formation of formic acid by the
hydrolysis of methyl formate. Methyl formate can be
introduced in the methanol feed to the unit. The circulat-
ing water system gradually becomes more acidic as formic
acid builds up and this can lead to corrosion problems. We
recommend the pH of the raffinate water loop be checked
weekly and be controlled at about an 8 pH with the
addition of caustic, if necessary, to the circulating water
system.
TOC/INDEX
QUESTION 44.
Are other refiners experiencing problems associated
with catalyst migration from MTBE reactors? Is resin
shrinkage a factor? What are some of the critical
practices during catalyst loading and start-up to pre-
vent damage to catalyst and reactor internals?
D'AURIA:
Migration and shrinkage of resin catalyst in etherifica-
tion reactors is related to three parameters: (1) the metha-
nol to isobutene ratio in the reactor, (2) the amount of
fines in the resin as delivered, and (3) the design of the
reactor internals.
The methanol to isobutene ratio is generally controlled
in the range of 1.05 to 1.2, depending on the type of
feedstock. This ensures excess methanol is available in
order to keep the resin swelled.
The most critical period is during start-up. UOP’s
procedures call for loading the resin under water, then
gradually replacing the water with a methanol rinse. Two
to three reactor volumes is generally called for. On start-
up, the C4 stream is gradually introduced while always
maintaining the target methanol to isobutene ratio.
Various resin manufacturers have different methods
and quality control procedures for their resins, and we
have seen some differences in the amount of fines which
are in the resins. Some fines can migrate through the bed
and out the slot openings in the reactor outlet screen. We
are working with resin vendors to try to standardize their
size distribution.
The containment of the resin in the reactor is also
dependent on the physical design of the cross sectional
screens and baskets placed at the outlet of the reactor.
Smaller slot openings will decrease migration, but can also
introduce a more easily fouled surface.
And finally, in addition to migration from fixed bed
reactors there have been some industry reports of catalyst
1994 NPRA Q&A Session on Refining and Petrochemical Technology
losses from catalytic distillation systems. Generally, use of
a metal structured packing system, as opposed to fiber
bales, is a better insurance of catalyst containment in the
catalytic distillation section.
ARMBRESTER:
I agree with Mr. D’Auria comments, particularly the
procedures he was talking about on start-up. Immediately
after filling the reactor with butane, we will backwash the
reactor to remove any fines that are present, and then over
the first week or two of operation we typically clean our
reactor effluent filters two to three times a week. Beyond
that, we do not see much catalyst migration from the
reactor.
PORTER:
The only problems we have had with catalyst migration
have been due to screen and attachment failures, so we
view those as really design problems.
As far as catalyst loading, we do it with a sock, nothing
very special. We have not had any problems as the new
catalysts appear to be very hardy. We also use a methanol
wash during start-up, similar to what Mr. D’Auria de-
scribed.
ROGER SINGER (The Purolite Company):
From the catalyst loading point of view, we certainly
believe that if the reactors can be accommodated, prefill-
ing the reactor with water can certainly serve to minimize
any potential damage when the catalyst is loaded.
As an alternative, Purolite can also deliver catalysts in a
tanker truck in which the catalyst is introduced directly to
the reactor in a water slurry. We find this approach can
offer substantial savings in reduced downtime for loading,
savings in reduced manpower required, and savings in
elimination of the cost for disposing of the pallets and the
super sacks.
175
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V. ENVIRONMENTAL CONTROL&
ENERGYCONSERVATION

A. Sulfur Plant Operations
Amine Plants
QUESTION 1.
Has anyone identified ammonium polysutfide formed
in amine containing ammonia? Is oxygen required to
cause the problem?
LAUX:
Polysulfide can be formed in the amine unit if oxygen
is fed to the unit in sufficient quantities. It will show up
as a black or dark green gum that plugs instrument taps
and low point bleeders.
We identified and eliminated two sources of oxygen
and thus solved the problem. The major source was a leak
in a vacuum unit that allowed over 2% oxygen in the feed
gas. A very minor source, but one that we thought was
significant was an unblanketed condensate addition tank
that put oxygen directly into the regenerator.
concentration and pH. In the 1950’s, Dow’s Gas Condi-
tioning Group analyzed deposits found in this loop and
did confirm the presence of ammonium polysulfides.
These polysulfide liquids are typically a reddish brown
color. From chemistry considerations, an oxidant such as
oxygen would have to be present to convert the sulfide to
polysulfides. Other problems with amine quality also
point to oxygen contamination as a frequent precursor to
undesirable chemistry in amine systems.
The concentration ofammonia in the regenerator over-
head loop can be reduced by purging reflux to the sour
water system as a method of reducing problems as a result
of ammonium salts.
QUESTION 2.
We frequent/y face the problem of amine discoloration
and foaming at high H 2 S loading. What are other
refineries’ experiences in this field? How effective is
the antifoulant in this regard? What types of back-
washable amine filters are available?

MENEGAZ:
FELTROP:
At high H2 S loading, corrosion problems become a
Although this is certainly not a common problem,
much more serious problem, especially where the solvent
ammonium polysulfide may form in high pH aqueous
changes phases such as in the rich/lean exchanger or the
systems containing significant quantities of hydrogen sul-
reboiler. The amine discoloration and foaming problems
fide. I agree with Mr. Laux’s comments, particularly with
described are a good indication that the corrosion has
relation to oxygen or similar oxidants that must be present
gotten out of hand and that more problems are on the way.
to oxidize the sulfide to polysulfide. This should be con-
sidered a major portion of the problem.

BARLOW:
We generally believe that this problem is more prevalent
if there is oxygen present in the system. However, the
following proposed mechanism is theoretical, but does not
require oxygen: NH4OH + H2S + S8 -> (NH4)2Sx.

THOMAS R. BACON (Dow Chemical U.S.A.):

Ammonia absorbed in an amine system will concen-
trate in the regenerator overhead loop, vaporizing with the
acid gas overhead, absorbing in the condensed water from
the overhead condenser, returning to the regenerator with
the reflux to be flashed again to the overhead. The aqueous
ammonia reacts with the aqueous hydrosulfide to form
ammonium hydrosulfide and ammonium sulfide depend-
ing on the driving forces for those species, primarily

176 Environmental Control & Energy Conservation

TOC/INDEX
The iron sulfide particulates from the corrosion will erode
away the protective sulfide scale in the circulating system,
accelerating the problem.
As far as foaming goes, pure amines do not form stable
foams, but will do so if iron sulfide, liquid hydrocarbons,
organic acids, or amine degradation products are present.
MDEA is much more sensitive than DEA or MEA, due
to its lower surface tension and greater hydrocarbon solu-
bility. I am going to give you a short list here of house-
keeping tips we have considered.
The first is to limit the amine concentration and load-
ing to keep the corrosion manageable. Below are some
generally accepted guidelines for common amines:
Max Max Loading
Amine Conc. % (Moles Acid Gas/Mole Amine)
MEA 15 0.35
MEA w/filming inhibitor 20 0.42 (eq.)
DEA 30 0.65-0.80
MDEA 50 0.45 (cq.)
The second is to run at least 30% of the total flow
through a filter and carbon unit. For MDEA, which is
much more prone to foaming, we recommend mechanical
filtration of the entire stream. A 10 micron absolute
mechanical filter will remove most of the iron sulfide
particulate, which is mostly one micron or so. A good
setup would be a 10 micron filter on the slipstream,
followed by a carbon filtration, then a 5 micron filter.
Some refiners move to a coarser filter size when they
encounter fouling. We think this is absolutely the wrong
thing to do. It just prolongs the problem. A solids content
of 0.1% or less is acceptable.
As far as backwashable filters, we recommend the Vacco
etched disk filters giving excellent results and it can be
backwashed with high pressure steam.
Regarding the carbon filter, do not wait for the carbon
filter to spend before changing it. That is just going to
create foaming problems. If your amine has color, it has
already gone too far. A new idea here is, in addition to the
traditional foaming tests people have been using, to use a
surface tensiometer. It can give you a reliable and precise
indication of where your system is. You can purchase one
for a few thousand dollars.
An iodine number specification of 900 for carbon has
traditionally been used. We think 950 or 1,000 would
probably be better. For hydrocarbon removal, a molasses
number of 200 or better should be used. We know of some
instances where people used phosphoric acid washed carb-
on and had disastrous results with foaming and plugging,
so you want to avoid that.
As far as antifoaming agents, there are temporary solu-
tions. I think better housekeeping is the way to go. You
certainly want to keep the oxygen out of your system, and
use an antioxidant, if you need it. The reboiler temperature
1994 NPRA Q&A Session on Refining and Petrochemical Technology
should be kept below 255°F to avoid forming degradation
products.
Heat stable salts should be kept below 10% of the
amine strength.
PORTER:
We normally do not operate refinery amine systems at
very high loading. We have not seen discoloration prob-
lems just from amine loading, even where we have oper-
ated a very high loading. We have seen amine
discoloration mainly from iron sulfide corrosion prod-
ucts, and oil contamination.
We do not utilize antifoulants in amine systems.
FELTROP:
The previous comments have covered this very well. I
concur that the most frequent cause of amine discolora-
tion and foaming is the presence of finely divided iron
sulfide particles in the amine. Increased H2 S loadings
certainly do increase the corrosion rate, which may over-
load the filters with iron sulfide. An effective corrosion
control program will help prevent the formation of iron
sulfide, thus preventing the problem. Once the particles
are present, the type of filters mentioned earlier are the
solution.
The question also references antifoulants. Antifoulants
are effective in preventing the deposition of particulate
matter in exchangers. They will not prevent the problem
and as such should be viewed as an interim solution.
LAUX:
We also had a similar problem of discolored amine and
foaming, and we agree that it is basically overloading of
the amine. We were able to control the problem initially
by using a corrosion inhibitor, and then completely elimi-
nated it by switching amine to MDELA. This was on an
FCC gas stream. By rejecting the CO2 your mole loading
goes down, and you run a higher concentration, which
also reduces the mole loading.
Our filtering system is on the rich amine. It is a sock
filter, but I have also seen the etched disk filters work and
they work very well. They are also good if you have a
hydrocarbon upset in the unit.
ARMBRESTER:
We concur with many of the earlier comments. We do
use a filtering system on a slipstream of the lean amine,
where we have a particulate filter followed by carbon
filters, and then another particulate filter. The particulate
filters are backwashable bag filters manufactured by Ron-
ningen-Petter. In addition to the lean amine filtration, at
our Catlettsburg refinery we also filter the entire rich
amine stream as it returns back to the regenerator, and that
is for particulate removal only. We also use an antifoam
additive in the Catlettsburg amine system.
177
TOC/INDEX
BARLOW:
I would reinforce that high H2 S loadings and heat
stable salts can result in the conversion of the soluble
corrosion products to insoluble iron sulfide. This will
discolor the amine. We do not immediately recommend
the use of an antifoulant. We believe that you should attack
the corrosion problem either with better housekeeping,
better control of your system, such as what has already
been discussed, or the use of corrosion inhibitors at rea-
sonable levels.
DEATON:
Sometimes we do experience foaming when our FCC
and hydrocracker units are at maximum off gas rates, and
we attribute the foaming to excessive hydrocarbon carry-
over. We target to keep the amine temperature 10°F hotter
than the incoming gas, to prevent adsorbing hydrocarbons
into the amine. We also agree that at high FCC rates, LCO
sponge oil carries over into the off gas as a mist and absorbs
into the amine solution. When foaming does occur, it is
in the contactor, not the regenerator. We use antifoam on
an as-needed basis by adding one pint of antifoam into the
lean amine via a pressurized blow pot, and it takes care of
the problem within a half hour. Our amine is clean and
sediment-free so we have not had to install backwashable
filters, and we do not use antifoulants.
DAVID DWYER (Union Carbide Corporation):
Everything that has been mentioned is right on the
money. This does sound like an iron sulfide problem. Iron
is insoluble in amine solutions that are highly loaded with
H2 S and will be present as finely divided iron sulfide
particulates. These particulates will cause foaming and can
plug equipment. Also, as the solution pH approaches 9 or
less, which roughly equates to a 0.45 mole/mole loading,
the iron sulfide film that forms on vessels or piping is
destabilized and can slough off, This greatly contributes
to the problem.
In addition, solution pH can be further lowered by any
strong acids present as heat stable salts. Neutralizing these
heat stable salts will raise the solution pH and help to avoid
these problems. Solution condition must be examined
closely and care taken when attempting neutralization.
Over neutralization must be avoided. Antifoams only
serve as a temporary cure. The housekeeping tips that were
mentioned are the long term solution, i.e., reducing the
loading by raising amine concentration, increasing circu-
lation rate, switching to a solvent with a higher molecular
capacity, and heat stable salt neutralization.
MOHAMMAO AL-SHAHRANI (Saudi Aramco):
What is the typical concentration of amine that has
been used? Has DGA been used as well? Is there a reclaimer
that can be used to improve the concentration of the
amine?
178 Environmental Control & Energy Conservation
MENEGAZ:
As far as MEA, we would go with a maximum concen-
tration of 15%. If you use a filming inhibitor, you can go
up to 20%. For DEA, we recommend a maximum con-
centration of 30%, and for MDEA, a maximum concen-
tration of 50%.
LAUX:
I have seen DGA used in a refinery system like that and
it works well. You can run a concentration up around
50%. There are generally no problems with it. It does
require reclaiming, though.
DEATON:
We use MDEA, and our concentration is between 48%
and 50%. The maximum recommended loading is 0.35
molecules of H2S per molecule of amine, and our normal
maximum loading is 0.285.
MENEGAZ:
On MDEA, we think you can go to 0.45 loading which
is the equilibrium limit, but you have to be very careful on
your filtration and corrosion management.
JOHN SORIA (Global Engineering Systems, Houston, TX):
My company produces and sells a new line of catalyzed
oxygen scavengers that virtually eliminate degradation of
MDEA caused by oxygen attack.
Historically, scavengers have been used in the amine
plants with fairly disappointing results, primarily because
the products that were used were applicable to boiler
systems that run at much higher temperatures than amine
units. Those products only protected the reboiler section,
which is less than 5% of the surface area of the amine plant.
My products react instantly with oxygen at tempera-
tures as low as 80°F. What this means is that oxygen is
immediately consumed as soon as it enters the unit. The
high activity of my product also causes the formation of a
protective layer of magnetite that protects the whole sys-
tem. In one application in Houston, we went from replac-
ing filters once every day to once every three months. We
completely eliminated reclaiming. We had the luxury of
shutting down our carbon bed. Losses have been minimal
because of lower foaming tendency. We went from 90%
in compliance to 100% in compliance. The savings result-
ing from this program amount to about $300,000 and the
cost of the treatment was about $30,000.
We are also targeting quench towers and tail gas treating
systems, and we have some products that have already been
patented for those applications.
WILLIAM TOREK (Texaco Refining & Marketing, Inc.):
We had a foaming problem with the DEX system on a
delayed coker, and we traced it back to something very
simple. It turned out to be our guard filter, which is
TOC/INDEX
specified to be 100% cotton and was not. We believe we
were experiencing polyester and other materials dissolving
and becoming part of the problem. Once we respecified
and replaced the filter, the problem was resolved.
JESSE SANTOS (Dow Chemical):
I heard two different rich loading recommendations.
We have been able to use our in-house simulator program
to predict at which rich amine temperature our client
should operate their FCC offgas adsorbers and other
hydrotreater adsorbers. We do this so that they do not get
into a problem with the valve seats on the letdown valve.
That way they can extend the life of the letdown valve and
avoid excessive flashing.
DAVID STREET (Huntsman Specialty Chemicals):
I concur with the 50% recommendation on DGA.
Huntsman supplies DGA to the U.S. refinery market, and
that is typically what we limit the solution strength to.
QUESTION 3.
Operational benefits are observed by the neutraliza-
tion of heat stable salts to control corrosion in amine
units. How does using caustic to reduce heat stab/e
salts affect the corrosion mechanism in amine units?
Has a wash water system been effective in removing
acidic compounds from sour gas streams to reduce
the generation of heat stable salt in the amine? Are
laboratory data available to confirm these observa-
tions and how were the laboratory tests conducted?
PORTER:
Adding caustic to the amine solution converts amine
salts to sodium salts. In general, the sodium salts are less
corrosive, as long as the total salt content is not allowed to
get too high.
At Pascagoula we have had significant success reducing
corrosion by adding caustic to a very large amine system.
This is only first-aid because at some point you will need
to remove the salts or replace your amine. We recently
successfully treated our amine system by Union Carbide’s
UCARSEP® process. Caustic was added to convert the
amine salts to sodium salts, and the sodium salts were then
removed. This reduced the amount of amine salts in our
system down to an acceptable level. This salt removal was
cost effective compared to replacing the amine. We have
set a 15,000 ppm maximum sodium content. Going
higher than this can result in precipitation problems.
We have not tried a water wash system on sour gas.
MENEGAZ:
I agree with Mr. Porter’s comments, particularly the fact
that adding caustic is a band-aid rather than a cure.
Certainly, if you are adding caustics you can get away with
1994 NPRA Q&A Session on Refining and Petrochemical Technology
it once or twice, before you are going to have to replace
the amine.
Regarding the caustic addition, I would like to mention
that if you put too much in you will strip iron sulfide scale
and create a tremendous foaming problem.
As far as the water washing, I know several people who
have considered water washing the gas from the FCC and
coker because it contains a large portion of the organic
acids which are the precursors of the heat stable salts. I
have heard reports of 50% reduction heat in stable salts by
washing. This also removes ammonia and cyanides which
cause overhead corrosion.
ARMBRESTER:
We have used low chloride caustic to neutralize heat
stable salts in the amine system at Catlettsburg on two
separate occasions, and in each case we were able to reduce
the heat stable salt content from approximately 4 wt%
down to 0.5 wt%. We have not seen any apparent increase
in corrosion due to the presence of the neutralized prod-
uct, but as Mr. Porter mentioned, our amine makeup rate
has been sufficient to keep our ash content in the safe range
(less than 5%). In fact, the caustic neutralization tends to
aid in reducing corrosion by adjusting the solution to a
better pH range and supplying hydroxide ion for some of
the acidic compounds that would be unstable at higher
temperatures.
Water wash systems are used in our gas concentration
units to control precursors to heat stable salt formation,
and have been found to be effective in limiting the forma-
tion of heat stable salts.
The water wash is monitored for cyanide and thiocy-
anate content, which is the greatest contributor to heat
stable salt formation in our systems.
We also use ion chromatography to monitor the con-
centration of the various contaminants in the amine, to
track the accumulation of salts over time.
BARLOW:
We support the caution on the overuse of caustic. A
small amount of caustic can be used with little side effect.
At concentrations greater than 100 ppm, caustic will
convert the iron scale, forming iron hydroxide and sodium
bisulfide and you run the risk of fouling in your system.
We have recently observed that mechanism on three
MDEA systems. MDEA appears, from our experience, to
be more sensitive than DEA to sodium.
Concerning water wash, we have had the opportunity
to monitor the amine solvent composition at two refinery
locations following changes in the water wash from
stripped sour water to sour water. At each of these refin-
eries, the change in water supply resulted in increased heat
stable salt content in the amine. Salt content was deter-
mined by ion chromatography. A switch from the sour
water to the stripped sour water resulted in the resumption
179
TOC/INDEX
of lower normal heat stable salt formation rates. This is
further evidence that proper water wash can indeed reduce
the formation of heat stable salts.
DEATON:
We use Union Carbide’s UCARSOL® MDEA solvent.
We test for heat stable salts weekly. When the heat stable
salts build up to 1.5%, we add a 55-gallon drum of DHM,
which is a blend of caustic and corrosion inhibitors, and
this brings the heat stable salt content down to about 1%.
The salts get converted to ash. We send in periodic amine
samples to Union Carbide, and when the ash content
reaches 10%, remediation of the solvent will need to be
considered either by a solvent changeout or by using
Union Carbide’s UCARSEP® technology to reduce ash
levels.
We also helped ourselves during a maintenance turn-
around recently by replacing the carbon steel bundles with
304-L stainless steel in the amine reboilers, heat exchang-
ers, and overhead condensers.
DAVID BURNS (Union Carbide Corporation):
As the question implies, several benefits result from
neutralizing heat stable amine salts, and Union Carbide
concurs with the panelists’ comments that neutralization
using caustic or, where indicated, UCARSOL® Neutral-
izer DHM, is an effective means of controlling heat stable
salt problems. Not only are the effective concentration of
the solution restored and operating problems minimized,
but the potential for corrosion is substantially reduced.
Although corrosion is a complex phenomenon and
therefore a function of several variables, including hydro-
dynamic and metallurgical, heat stable amine salts can play
a significant part. Typically, they lead to generalized cor-
rosion, especially in the hot areas of the system. Although
the type and extent of corrosion is dependent on the
anions in question, (for example, thiocyanates do not seem
to be as bad as formates), in all cases when the amine salt
is formed and the amine is “inactivated” for gas treating
purposes, the pH of the solution is reduced. As a result,
the level of free acid in solution increases, albeit at ppm
levels even at high heat stable salt levels. This can contrib-
ute to corrosion particularly in the case ofmoderately weak
acids such as formic or acetic, at the low pH’s encountered
when a system has not been neutralized, and where acid
gas loadings are not negligible. Neutralization decreases
the possibility of corrosion by raising the system pH. One
reason for this is that the concentration of the free acid is
decreased.
Finally, our experience has been that sour gas water
wash systems can be very effective at reducing heat stable
salt buildup rates. We have seen 50% reductions in some
of our customers’ systems as a result of water washing. It
seems to be effective at removing acidates and formates.
Our recommendation would be to use a water wash system
180 Environmental Control & Energy Conservation
whenever possible to minimize heat stable salt buildup
rates, along with a neutralization program to counter the
effects when they do get into the system. Although this
will prolong the life of the solution quite considerably the
salts can still ultimately reach a high enough level whereby
they have to be removed. We would recommend an on-site
and on-line removal technology such as the UCARSEP®
process for this purpose.
H. T. BALL (Coastal Chemical Company, Inc.):
One of the things that you have to look for in the water
wash system is that it does remove a tremendous amount
of hydrocarbons that could cause foaming problems in the
amine unit.
For the heat stable salt removal, as has been stated, the
type of water used is very important or, in other words,
the basicity of the water that is used. The more basic the
water the more heat stable salt precursors it will remove.
We are currently running tests in cooperation with Dow
on operating a water wash system to collect data to quan-
tify how much heat stable salt is removed, depending on
the type of water used.
STEVEN FISCHER (CITGO Refining & Chemicals):
Mr. Armbrester, are you using any additives in the water
to enhance the removal of the precursors to heat stable salts?
ARMBRESTER:
As I mentioned in yesterday’s session, we add air to our
wet gas streams for in-situ production of polysulfide, but
we do not use any other additives in our water wash
system.
JOHN SORIA (Global Engineering Systems):
To clarify the point that I tried to make earlier, before
we started using this catalyzed oxygen scavenger, the rate
of amine degradation or heat stable salt increase was 2.2%
per month. After we started using this product, the rate
went down to 0.2% per month. We also tested an uncata-
lyzed oxygen scavenger similar to the ones that are being
used currently in the industry, and the rate of increase was
also about 2% per month. I believe that the small rate of
increase during the usage of our catalyzed oxygen scaven-
ger resulted because we did not have a water wash system
to take care of products that were coming in with the FCC
feed.
MO VADEKAR (CHEMTECH Consulting):
After having serviced quite a few cracked gas systems
with alkanol amines (including FCCU, coker and steam
crackers), I would fully agree with the consensus arrived
at this session on caustic addition for prevention of corro-
sion in amine units. I think, at one time, some amine
vendors used to discourage addition of caustic to amine
TOC/INDEX
systems. Caustic effectively neutralizes heat stable salts,
frees amine, and reduces corrosive potential.
As far as water wash is concerned, I believe somebody
asked a question as to where to locate the water wash. I
have seen a few amine plants where the washwater was
directly injected into the pipeline carrying FCC, coker,
and cracked gases, near the source of gas, and water was
allowed to run all through the piping, to the amine plant,
to a knockout drum in front of the amine unit, where the
water was removed. This on-line wash effectively removed
stronger acids and part of the ammonia.
Regarding earlier comments about the removal of
acidic components, such as hydrocyanic and carboxylic
acids, which add considerably to the heat stable acid load
in the amine solution, these can be removed very effec-
tively by water wash. (Liquid hydrocarbon removal is also
important in that respect.) I have seen considerable reduc-
tion in foaming and heat stable salts as a result of the water
wash.
Finally, as far as source of water is concerned, I have
seen some people use stripped sour water for water wash
in conjunction with condensate or fresh water. But make
sure that if it is fresh water, it is not hard water, but treated
water. Otherwise, you will run into severe scaling prob-
lems in the whole system.
DAVID VASQUEZ (CITGO Refining & Chemicals):
We use an MDEA system that has full flow rich filters
and we use a water wash on our coker fuel gas coming out
of the coker to remove the oxygenates which originate
from drum switches, etc. To combat this we inject an
oxygen scavenger into our amine and found this to be very
effective in reducing our heat stable salts.
We also use a caustic injection in order to maintain
below 2% heat stable salts. The problem with this is that
the ash levels can get very high. We can get as high as 7%
or 8% ash levels, and I believe the number that everybody
uses is 10% for precipitation. Once you get to that point,
caustic injection really needs to be watched very closely.
We have used UCARSEP® before and have been very
successful with it.
Finally, purging your amine regenerator through your
overhead drag stream can effectively help you remove the
thiosulfates from the circulating amine.
JOHN W. DEAN (Union Carbide Corporation):
We agree with the comments made by the panel, and
at Union Carbide we have always recognized the benefits
of neutralization and water wash. We have an extensive
amount of laboratory data to support these observations.
Most of our data is based on 14-day autoclave coupon tests
and steady-state recording parameter studies. It is very
critical when performing these tests that they be done
using accepted methodologies and be done at steady-state.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
We will be releasing several papers in various forms,
including NACE, AIChE, this year, describing the proper
techniques for obtaining accurate data. Although in the
past we have held some of these techniques to be proprie-
tary, we have concluded that because of some recent
developments, the need for good laboratory techniques is
overwhelming and we should release some of that infor-
mation to the industry.
In addition to this quantitative data, we also have quite
a lot of qualitative data utilizing sophisticated spectro-
graphic and surface analysis techniques, which over-
whelmingly support the benefits of incorporating
neutralization and water wash into a well administered
Amine Management Program.
TOM DAVIS (CENEX Refinery):
Concerning these discussions of the addition of too
much caustic, has anybody seen any harmful effects on
carbon filters from the addition of too much caustic?
HIGGINS:
No comment.
GEORGE W. BROWN (Conoco, Inc.):
In the past, we used to use caustic addition for heat
stable salt control. Now we are doing the opposite. Caustic
addition provides some benefits, but not as much as
everyone thinks. We have done enough testing in our
research and development laboratories and have shown
that it really does not do as much as we thought. Heat
stable salts are going to form; they are there. You are going
to lose them with amine losses or you are going to have to
remove them. We have used both UCARSEP® and the ion
exchange process for removing salts. We advocate removal
of the salts to keep your system noncorrosive as the best
way to control corrosion.
QUESTION 4.
What is the maximum recommended LPG to amine
ratio in a countercurrent packed tower to maintain
treating efficiency?
CUNEO:
Shell Oil has a lot of LPG treaters, and the concentra-
tion of H2S, carbonyl sulfide and mercaptan varies over a
fairly wide range. In general, our economics favor maxi-
mizing the treat that you get with amine solution. In order
to do that we run in an amine continuous phase at a
maximum loading of 11 to 1 LPG to amine. Now, if a
plant needs additional treating capacity and we have an
opportunity to use more caustic, we go to an LPG con-
tinuous phase and in that area we are able to run down as
low as 9.5 to 1.
181
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SAYLES:
In our LPG treaters, we run with an amine continuous
phase somewhere in the neighborhood of 10 to 50 gallons
per minute per barrel of LPG. The tower flow rates are 14
to 18 gallons per minute per foot square, with the normal
rates in the clean system as high as 20 gallons per minute
per foot square.
We do have carryover problems when the interphase
level controller becomes fouled.
LINDA LORD (The Coastal Corporation):
Mr. Cuneo, what was a recommended velocity in the
tower? Could you repeat that, please?
CUNEO:
We give a recommended ratio rather than an absolute
velocity. The recommended ratio when you are running
in the amine continuous phase was 11 to 1, and the
recommended ratio when you run in the LPG continuous
phase was as low as 9.5 to 1.
S. N. MATHUR (Hindustan Petroleum Corporation, Ltd.):
In a refinery normally there would be several H2 S
containing streams. There could be two options for treat-
ing. One would be to have an absorber regenerator at each
location, and pipe the H2S to the sulfur plant. The other
alternative would be to have an absorber at each H2 S
source, and a central regeneration unit. Which is the
preferred mode?
CUNEO:
In general, we prefer to have the absorbers located with
the process units, and to use a common regeneration
facility which is usually remotely located.
JESSE SANTOS (Dow Chemical):
About the LPG treaters, we have found that the LPG
amine efficiency is more a function of interfacial area,
basically final droplet size, than overall amine flow. To
minimize amine carryover to the coalescer, as a general rule
we recommend no less than one barrel per day of amine
solution flow for every ten barrels pet day of LPG flow.
HERBERT WIZIG (Merichem Company):
Merichem’s AMINEX Technology, which uses the fi-
ber-film contactor, is very flexible with respect to the LPG
to amine volumetric ratios to maintain treating efficiency.
QUESTION 5.
What corrosion levels do people see in amine regen-
erator overhead systems? How do you control high
corrosion levels, i.e., corrosion inhibitor chemicals,
purge system, metallurgy? Have corrosion inhibitor
chemicals caused foaming problems?
182 Environmental Control & Energy Conservation
BARLOW:
Although we do not see this necessarily as a common
problem, we have seen corrosion rates as high as 100 mils
per year on carbon steel metallurgy in regenerator over-
head systems. We find that system purges can be extremely
helpful. However, you run the risk of excessive amine
losses.
We have experience in several refineries where we have
reduced the corrosion rate through the use of a filming
inhibitor, some to less than 5 mils per year. Concerning
metallurgy, stainless steel has been effective. We have seen
problems with titanium hydriding.
The question asks if corrosion inhibitor chemicals
cause foaming problems. You do run the risk of causing
foaming problems, so you have to evaluate specific inhibi-
tors for the system whose surface tendencies are not to
cause foaming. Some water soluble inhibitors designed for
FCCU’s and cokers have caused foaming problems.
BOYCOTT:
The overhead system on our amine regenerator is carb-
on steel. We have had one instance of a leaking bundle in
the two years the unit has been in service. Subsequent
testing has shown that current corrosion rates are negli-
gible in this area.
I have seen both purge systems and inhibitors used
successfully to control problems in this area.
DEATON:
We have not seen any significant corrosion in the
overhead piping. As I mentioned previously, a decision was
made a few years ago to upgrade all carbon steel tube
bundles with stainless steel for improved plant reliability.
We do not use any chemical corrosion inhibitor injections
in the overhead. A practical guide is to operate the amine
regenerator to keep about 1% to 2% amine in the over-
head receiver, and this will effectively coat the overhead
system and prevent excessive corrosion.
FELTROP:
We apply the same water soluble inhibitor to the over-
head that we use in the circulating amine system. However,
adding the makeup to the overhead is not sufficient to
inhibit and control corrosion in the overhead. We do this
by installing a slipstream of circulating amine to the
overhead. Since this amine has inhibitor in it, it is a way
of including the overhead in the circulation system. Typi-
cally, we will add a slipstream of rich amine to the over-
head, which is equal to the volume of amine being
condensed in the overhead. This does not result in the loss
of amine since it is refluxed back to the stripping tower.
Many inhibitors that have been used in amine units
have contributed to foaming. The particular one that we
recommend does not foam.
TOC/INDEX
Foams are usually caused by hydrocarbons in the system
and stabilized by solids in the system. If the system is clean
and free of solids, the severity of foaming is usually much
less. This is where the right corrosion inhibitor is impor-
tant, as Mr. Barlow has mentioned. If it prevents corro-
sion, the amine will stay clean and the foaming will be
minimal. The recommended inhibitor is excellent in loos-
ening the iron sulfide deposits so that they can be removed
from the system by filters.
MENEGAZ:
Ammonia is trapped in the regenerator overhead as
ammonium bisulfide, and it is very corrosive at high con-
centrations. The cyanide acts as a catalyst for this process,
particularly in stainless steel. The cyanide can also form
hydrogen blistering. The primary control is bleeding off
the regenerator reflux water to limit the bisulfides to under
3%. Keeping ammonia out of the system by water washing
the gas from the hydrotreaters and other locations is a good
idea. We use a primary metallurgy of 304 stainless steel and
we like to keep the velocities in the overhead under 20 feet
per second, that is, in the tubes, to avoid wiping away the
bisulfide film and further aggravating corrosion.
We certainly agree with the previous comments regard-
ing the water soluble corrosion inhibitors. One thing we
would caution, as the panelists have previously men-
tioned, is to choose the right corrosion inhibitor.
The high molecular weight alcohol-based corrosion
inhibitors can cause foaming if an excessive amount is
used. The alcohol portion will oxidize to an acid which
subsequently will react with the hydrocarbons in the
system and form a fatty acid soap.
PORTER:
We use titanium tubes in the overhead condenser.
Second, we use ammonium polysulfide as an inhibitor in
the overhead system. Third, we ensure that the ammo-
nium bisulfide concentration is less than 10% in the
overhead reflux drum water.
SAYLES:
I agree. Our system is normally noncorrosive. However,
if for some reason oxygen is introduced into the system, it
becomes highly corrosive very quickly, and usually we can
trace that back to a problem upstream of the amine
regenerator.
ROBERT HLOZEK (Union Carbide Corporation):
We basically concur with what the panel has stated. We
have examined over 100 UCARSOL® units and many
more DEA units with no corrosion found in the overhead.
We realize that many of the column overheads are stainless
steel clad and the condenser bundles are stainless so that
stainless steel will certainly protect the unit from corrosion.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
We have some concerns where there is carbon steel only,
but even there, usually the iron sulfide acts as a protective
coating, which serves as a barrier to corrosion. We have,
however, noted problems where the vapor velocities and
turbulence at the top of the tower are extreme. The
turbulence and high velocities will erode the protective
coating and certainly can initiate corrosion.
The main area of concern is where the unit is removing
only CO2 and there is no H2S, as in a case of hydrogenation
units. Carbonic acid is formed upon water condensation.
This situation has forced us to do what one of the
panelists has mentioned, take a slipstream of the lean
amine from the discharge of the pump, circulate to the top
of the tower and spray the lean amine onto the areas of
concern. This technique has worked well in several cases.
Another approach in reducing corrosion is to eliminate
any water condensation on the internal walls of the strip-
per. Make sure the equipment is properly insulated and
that adequate stripping ratios are provided.
We do not use inhibitors in our solvents, and we have
also found that many of today’s corrosion inhibitors can
cause foaming problems. Not only that, in some cases
there are inhibitors that have a negative impact on the
performance of the solvent. So we recommend conducting
simple laboratory screening tests to see if the inhibitors are
compatible with the amine. We also suggest that you
contact your amine supplier for more details on which
inhibitors work and which do not work.
MO VADEKAR (CHEMTECH Consulting):
Mr. Sayles mentioned that the oxygen entry into the
amine system can cause several problems, including foam-
ing. My comment is that oxygen can be brought into the
system not only by hydrocarbon feed gas or liquid con-
taining oxygen traces, but also from fresh amine storage
tanks if not inert blanketed. Some oxygen can get through
there. The makeup water for dilution of the amine can also
contain some oxygen. My axiom for that situation is “2
ppm O2 is 2 ppm too much”, so try to get away from
oxygen!
QUESTION 6.
How are refiners controlling corrosion in sour water
stripper overhead systems?
MENEGAZ:
In a conventional sour water stripper overhead system,
titanium tubes have been used as a cost effective way to
mitigate the corrosion. The longer service life of the tita-
nium outweighs the higher initial cost over carbon steel.
Tube corrosion is most severe where the water initially
starts to condense due to acid gas corrosion. We have
modified the design configuration of the sour water strip-
per tower to include a direct contact condensing section
at the top of the stripper to replace the traditional overhead
183
TOC/INDEX
condenser reflux system. Avoiding a phase change and
having all the surfaces wetted significantly reduces the
corrosion environment and allows the use of a less expen-
sive material.
SAYLES:
Sour water stripper overhead systems are corrosive due
to an imbalance between the anions. The presence of
ammonia and CO 2 forms a highly buffered solution,
maintaining a constant pH even after acidic components
of H2S and cyanide are added. Under these conditions,
the solution can become basic, high pH. High corrosion
rates can be observed under these conditions.
We use a gunite lined vessel, 316-L stainless steel
pumps, Carpenter 7 molybdenum condenser tubes, and
concrete lined carbon steel pipes to control corrosions in
the sour water system.
FELTROP:
Corrosion in these systems can be controlled by use of
a water-soluble filming corrosion inhibitor. Application is
by small water slipstream ahead of the overhead coolers at
100 ppm, based on the volume of water in the overhead,
not on the feed to the stripper.
If the design is such that there is a reflux, the inhibitor
will return to the tower and protect the area below the reflux
entry. When the stripper has a pumparound for cooling,
inhibitor is added to the pumparound at the same concen-
tration based on the volume of water in the pumparound.
LAUX:
We control the corrosion in this overhead system
mostly by metallurgy. We have a sour water stripper with
an air-cooled top pumparound. The pumparound starts
below tray 5 and returns above tray 1. The top six trays are
316-L stainless steel and the tower itself is clad with 316
stainless. The air cooler outlet temperature is controlled at
over 160°F to make sure that ammonium bisulfide does
not deposit in the overhead line. The air cooler tubes are
titanium, but the header boxes are killed carbon steel. Our
overhead line is also 316 stainless steel, and we do not
experience any problems in this system.
ARMBRESTER:
We have experienced ongoing problems with corrosion
in our foul water stripper overhead systems, and we are
currently conducting a trial program using a filming
amine to provide corrosion protection in the pumparound
section of one of our phenolic foul water strippers. Since
this amine has a low volatility, we are not sure if it will
provide protection for the overhead system itself. How-
ever, our coupon results on the pumparound stream have
shown less than 0.5 mil/year corrosion rate, and the run
length on this tower appears to be considerably longer
than it has been in the past.
184 Environmental Control & Energy Conservation
BOYCOTT:
I agree with the previous comments, corrosion prob-
lems in this area are typically addressed with metallurgy.
However, sour water stripper overhead corrosion appears
to be very site dependant. Although our system is com-
prised totally of carbon steel we have not experienced
significant corrosion.
CUNEO:
We have a wide variety of metallurgies in our sour water
stripper overheads, all the way from carbon steel through
the austenitic stainless, alloy 20, and incoloy. Basically, the
metallurgy is specified on the basis of ammonium bisul-
fide. If people are experiencing very high corrosion rates
with these types of alloys and they suspect the ammonium
bisulfide is in the proper range, we think they should look
for cyanides. If cyanides are found, they should be ad-
dressed by the addition of ammonium polysulfide, either
in the overhead line of the sour stripper or further up-
stream in the sour water system.
DEATON:
We have a conventional tower design and the condenser
tube bundle is titanium. Our experience with carbon steel
condenser tube bundles is that they last less than six
months.
We have also upgraded our carbon steel reflux pumps
to stainless steel because of overall corrosion and frequent
seal failures. I am told that the top dome of towers with
our designs do not usually have much corrosion, but if
they do, they are lined with 304 stainless steel.
MOHAMMAO AL-SHAHRANI (Saudi Aramco):
Mr. Armbrester, you indicated that corrosion inhibitor
is added, but did not mention on-line monitoring of this
system.
ARMBRESTER:
On the one application I spoke of, we are using corro-
sion coupons and pulling those about every 30 days to
check the corrosion rate.
QUESTION 7.
What is the typical run length for a sour water stripper
(between turnarounds)? What determines the run
length?
ARMBRESTER:
At our Catlettsburg refinery, we have experienced run
lengths of approximately one year on our foul water
strippers. The end of run is usually determined by a failure
of the top packed section of the tower, failure of the
pumparound tray, or corrosion problems in the tower or
overhead system. The common failure of the top packed
TOC/INDEX
section is due to corrosion of the support grid, which
affects the pumparound rate and tower pressure drop.
We have also experienced some failures in the tower
reboilers. General corrosion in the pumparound section
of the towers is what led us to begin the filming amine trial
that I mentioned earlier.
DEATON:
I have had varying experiences at different refineries. At
one refinery, we shut down about every six months to clean
out solid deposits in the reboiler, the outlet feed exchang-
ers and outlet piping, and the trays below the feed tray.
Analysis of the tray deposits indicated the source was
hydrocarbon, but I do not know the mechanism of the
deposits or how they were formed.
At another refinery, there have been shutdowns about
once a year to repair leaking tube bundles in the reboiler
and feed bottom exchangers. These two bundles are carbon
steel and possibly they should be upgraded to stainless steel.
LAUX:
We tie our sour water stripper run length to our FCCU
turnaround cycle. It runs for three years between internal
column cleaning and inspection. The reboiler, however,
fouls out in about a year and a half, When this happens,
we shut down for one day and install a spare reboiler
bundle that we keep on hand for this purpose.
TREESE:
Our experience has been similar to Mr. Deaton’s. Typi-
cally, we try for a sour water stripper run of about two
years, but we experience a wide variation depending
mostly on the water charged to the stripper.
At our San Francisco Refinery, the strippers process
water from the coker and the Unicracker, and they are able
to get runs up to two years. At the Los Angeles refinery,
the strippers process water from hydrotreaters, Unicracker,
FCCU, tank drains, spent caustic (which I think is one of
our problems) and many other sources. The run lengths
in Los Angeles can be as short as six months.
Sour water frequently contains excessive amounts of
ammonium polysulfide from the FCCU and that seems
to reduce to deposits of sulfur in the stripper and the
exchangers. We also see corrosion in the stripper tower,
which has caused us to have to replace the towers recently.
I am aware of one stripper that processed desalter water
with a run length of about six weeks between acid washes.
QUESTION 8.
Does anyone have experience using antifoams or
emulsion breakers to reduce carryover of amine from
LPG contactors? Reference: A question on the use of
antifoams in amine systems was asked in 1993 (V
A-04). The additional information requested here is
specific to LPG treaters.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
BARLOW:
Our experience in this area, indicates that in the LPG
contactors, the major problem is excessive velocities for
the design, in which case the use of an antifoam or an
emulsion breaker is not going to be very effective. We have
had success with antifoams or emulsion breakers, surface-
active type chemistries, in reducing entrainment, espe-
cially during upset conditions. But if you have a design
problem, the chemistry is generally not very effective.
Check your design first.
B. B. PATIL (Hindustan Petroleum Corporation, Ltd.):
We use amines in our LPG treaters, and we maintain a
concentration of about 12 wt%. This emulsion formation,
causes interface level controls to malfunction, causing
amine carryover. Is there any guideline for replacing amine
from the system after a certain period? If so, what is the
time frame, and how do you dispose of this degraded
amine?
HIGGINS:
No response.
BILL GIBBONS (Union Carbide Corporation):
Several of Union Carbide’s UCARSOL® customers in
the USA and in Japan have had success using glycol-based
antifoam to break amine/LPG emulsions and reduce
amine carryover from LPG contactors. This field experi-
ence is dramatic and convincing; adding antifoam can
reduce amine carryover.
MO VAOEKAR (CHEMTECH Consulting):
The emulsion formations in these kinds of LPG amine
treating systems are caused primarily by dirty amines. If
the amine contains a surface active foaming agent, particu-
late iron sulfide, heavier hydrocarbons, etc., emulsions will
be formed at the interphase between the LPG and amine.
The interphasial layer could be as wide as a foot or so and
it will travel back and forth. In that situation, amine
carryover is a strong possibility.
As far as antifoaming emulsion breakers are concerned,
my experience has been that it is not very easy to break
those emulsions unless you keep your amine clean. And
that is the only way you are going to reduce or prevent the
formation of emulsions and the resulting problems.
TOM CLANCY (Elf Atochem North America, Inc.):
We manufacture and sell a product called MDEA-LF,
which is specifically formulated to reduce amine losses in
primary refinery amine systems. We have had success in
reducing amine carryover, particularly in LPG treaters, by
as much as 80% in a number of refineries by replacing the
existing MDEA or formulated MDEA solution via
makeup with MDEA-LE
185
TOC/INDEX
THOMAS R. BACON (Dow Chemical U.S.A.):
In my opinion, the primary causes of carryover of
amine from LPG treaters are a combination of unsteady
hydraulics caused by excessive cycling in flow and pressure
controls, excessive mixing from high velocity in the dis-
tributors, and inadequate settling time due to high veloc-
ity, exacerbated by the standard application of a level
transmitter using a 24 inch torque tube device for interface
control. Any significant rag layer will eliminate the density
difference between the phases and cause the level trans-
mitter to go blind. Any problem in instrument tuning will
cause the same. When that happens, confidence in the
process control disappears and alternate control plans are
varied and inconsistent, as are the results.
An alternate level control using a longer range differen-
tial pressure transmitter has been shown to provide more
reliable level indication over wider ranges of process upsets
and has allowed the best possible operation with the
existing tower design.
Assuming the above problems are corrected, the most
effective method of preventing amine carryover with
treated LPG or other hydrocarbon liquids is a circulating
water wash coupled to an effective coalescer in the treated
product.
HANS DIRKSE (Shell Development Company):
We have experienced some carryover of amine from our
LPG treater, and therefore changed from continuous
amine phase to continuous hydrocarbon phase. Actually,
what this did was to bring the interface down to the
bottom of the column, and from there we did not experi-
ence amine carryover.
HERBERT WIZIG (Merichem Company):
With Merichem’s AMINEX Technology, amine carry-
over with LPG is minimal, thus avoiding the need for
antifoams or emulsion breakers.
Sulfur Plants
QUESTION 9.
With multiple Claus units and low sulfur production,
is it better to run all the Claus units at low rate, or to
run some at high rates and keep one on hot standby?
CUNEO:
We feel very strongly that it is better to run all the Claus
units at low rates, as long as you are within the acceptable
operating range of the low rates, rather than having units
kept on hot standby for long periods of time. When I talk
about long periods, I am talking weeks or months.
We have had very poor experience trying to operate for
extensive periods in hot standby mode. Some of the things
that can happen are catalyst deactivation and plugging,
186 Environmental Control & Energy Conservation
resulting both from soot formation when we got too
substoichiometric in the combustion, and also sulfation
when we let oxygen slip. We have had extensive corrosion
of the equipment and a lot of risk there switching between
reducing and oxidizing conditions. We have had plugging
of drain legs and plugging problems with increased corro-
sion rates; and main burner choking. So our philosophy
is to operate both units in parallel.
DEATON:
We have two Claus units at our plant, and we recom-
mend running both at low rates rather than putting one
on hot standby. When these units are put on hot standby,
the operators struggle with plugged sulfur seal legs during
the hot standby and also when they are initially brought
back on-line.
We can turn our units down to about 25% of the
maximum design. To help do this, we have normal and
low range acid gas meters for both units. The low range
meters are 40% of the normal range meters. This provides
the operator better control in turndown situations.
ARMBRESTER:
We have parallel sulfur plants in all of our refineries and
we concur fully with Mr. Cuneo and Mr. Deaton. We
prefer to operate both units at low rates rather than to try
to keep one on hot standby. In one instance, when we did
try to keep one unit on hot standby, we found that the
sulfur legs were plugged when we tried to return the unit
to normal operation.
One other comment I would make on this issue is that
we have found it much easier to operate at those low
turndown rates since we upgraded to DCS instrumenta-
tion. We are not sure we could have done that with our
previous controls.
BOYCOTT:
When sulfur production has been reduced we have had
success with two modes of operation:
baseloading our smaller unit at a low rate and taking
all production swings with the larger unit, or
shutting the smaller unit completely down, and
maintaining it on cold standby with a positive pres-
sure nitrogen blanket.
It takes about 60 hours to bring a unit on-line from
cold standby. It is important to make sure that the unit is
tight and positive nitrogen pressure is maintained if it is
put on cold standby.
We do not attempt to maintain a unit on hot standby
due to corrosion and plugging concerns.
As to minimum production rates for sulfur plants, in
my experience it is fairly easy to get to 10% of design
capacity with no unit modifications. I have seen units run
as low as 1% of design capacity with some modifications.
TOC/INDEX
LAUX:
This debate is really somewhat site specific. It depends
upon what equipment you have and what types of phi-
losophies you want to stick with.
Soot formation on a hot standby unit typically can be
dealt with if you use a very good quality fuel gas going to
your reaction furnace, for instance, if you use propane or
natural gas. Seal leg plugging obviously is a problem. If
you have a good design for unplugging them, you can get
around that.
I have had problems running all of them in parallel
because of the amine system. If you are subject to severe
hydrocarbon carryovers, that will eventually plug up all
your running sulfur plants. As a refinery manager, at that
point you will want to know what you do without a sulfur
plant.
Generally, I think we agree that we would want to run
them in parallel, but the amine system needs to have
enough hydrocarbon surge and skimming capacity.
MENEGAZ:
We are definitely going to cast our vote for operating
at a low rate rather than trying to operate on a hot standby.
This avoids the problems with carbon laydown, sulfation
and corrosion that have been previously mentioned. A well
designed sulfur plant should operate at least at a 5 to 1
turndown. We have designed units that have operated as
low as 20 to 1.
Operation at low rates should be adjusted to avoid low
temperatures in the beds and the condenser sections. The
burner performance, the fine air trim control, the system
heat loss are all considerations that need to be looked at
for turndown operation.
PORTER:
Our experience is similar. When we tried operating in
hot standby, we found the standby unit often not ready
for reliable operation.
Several years ago, we aggressively addressed the control
problems to improve the turndown ratio for the sulfur
recovery units. The development of smart transmitters,
programmable logic controllers, distributed control sys-
tems and other control system improvements made these
improvements possible. As a result, we now operate avail-
able sulfur recovery units at low rates or shut down one
unit rather than attempt hot standby.
TREESE:
I agree with my fellow panelists, especially the problems
created by hot standby. Where we have the opportunity,
sometimes we will shut a plant completely down and leave
it down and cold but ready for immediate start-up.
I would add that, in our plants, where we are generally
using a tail gas unit, on hot standby, we experience water
1994 NPRA Q&A Session on Refining and Petrochemical Technology
balance problems. You have to figure out a way to reject
that water.
H. DAVID SLOAN (The M. W. Kellogg Company):
We would recommend that one unit be designated as
a swing unit and operate this one on pressure control, and
the other units operate on flow control. This way the
fluctuations are taken by the swing unit while maintaining
the others at steady flow. This approach can be utilized,
provided that the total flow to the swing unit does not fall
below minimum turndown.
QUESTION 10.
Are refiners keeping the sulfur plant emergency shut-
down system (ESD) completely separate from control
computers? If the ESD is in the control computer, how
is its integrity protected?
BOYCOTT:
Our emergency shutdown system is in a local PLC. This
PLC sends indication outputs to the DCS, but it does not
rely on regulatory control indications from the DCS for
shutdown response. A system bypass has been installed to
allow on-line testing of the system.
MENEGAZ:
In many refineries, the operators and engineers can
interact with the process computers on a routine basis. We
do not think this is such a good idea if you are on the SRU
ESD. Our philosophy is to design the SRU ESD as a
separate control system, apart from the DCS. We use a
programmable logic controller, hard-wired relay system,
or similar discrete electronic logic system. This protects
the ESD system from unauthorized tampering, and pro-
vides a stand-alone system dedicated to shutdown.
PORTER:
We are in the process of improving the reliability of the
ESD at several refineries. The redesign work we have
performed does not utilize the control computer. Instead,
the systems are operated through a PC based installation.
One of our refineries does utilize the distributed control
computer for the emergency shutdown system. Changes
in the programming for the shutdown system can be made
only by the control engineer. The SRU shutdown system
and its elements have no bypass provisions, they are armed
all the time.
At Pascagoula we recently completed conversion to a
distributed control system that does not include control
of the shutdown system in the computer. The computer
does monitor the status of the shutdown system and its
components. We have a reliable, PLC field mounted
shutdown system and control continues to be accom-
plished in the field.
187
TOC/INDEX
TREESE:
In general, the Unocal philosophy on emergency shut-
down systems goes along with what has been said here. We
use separate dedicated PLCs. Depending on hazard analy-
sis, it may be a dual or triple redundant PLC. If the
situation is very critical, we will carry that redundancy all
the way to the source instruments. In other words, double
or triple flow, pressure, or temperature sensors.
We will generally not put a critical shutdown on a DCS.
We may put a routine type shutdown on a DCS, but not
a critical shutdown. At one plant we did use a DCS in
place of a PLC due to the complexities of this plant. It
turned out that it was more cost effective to actually buy
a separate DCS and put the shutdown system on that
DCS. There, again, the operators were locked out from
making any changes in the emergency shutdowns.
I would add that we also regularly test our shutdown
systems with gagged valves. There are software ways of
testing it, but we still only trust it if that valve tries to close.
We gag the valves and punch the button.
LEE E. TURPIN (Honeywell Profimatics):
We encourage clients to have locally mounted shut-
down systems on individual pieces of equipment. These
are fundamental, fast-acting, first steps in emergency shut-
down systems. We do recommend the locally-mounted
emergency shutdown systems then be monitored by the
control computer for operator notification, post emer-
gency analysis, and other more complex functions, such
as secondary equipment shutdowns, unit shutdowns, and
load shedding.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
My question is regarding the high temperature on the
reaction furnace. Is it being used as an ESD input for the
entire furnace? Does it contribute?
PORTER:
We do not monitor reaction furnace temperatures at
Pascagoula.
LAUX:
We have an ammonium thiosulfate at Three Rivers and
that is a little bit different unit, but the reaction furnace is
essentially the same. We do have the high temperature set
point tied into our shutdown circuit.
BRUCE SCOTT (Consultant):
The answer to Mr. Al-Shahrani’s question is that prob-
ably 50% do have high temperature shutdowns and 50%
do not. I have seen plants with both configurations. I have
also seen people take out temperature ESD’s because they
feel they have enough time to respond to a high tempera-
ture at the source before they actually damage anything.
188 Environmental Control & Energy Conservation
DEATON:
What I have seen is a high temperature shutdown on
the exit of the first catalytic reactor, so that if you get into
a sulfur fire condition, it will shut the unit down.
QUESTION 11.
What are the factors and reasons that can create
severe vibration in the muff/e furnace of the Claus
Sulfur Recovery Unit?
BOYCOTT:
I was involved in one instance of severe vibration in the
combustion furnace of a Claus unit. This occurred during
the commissioning of an oxygen enrichment system and
was caused by flame instability. The vibration began at
approximately 28% oxygen in the enriched air stream. As
a result, the oxygen limit on the enrichment system was
set at 27% as calculated in the enriched air stream. No
further problems occurred.
MENEGAZ:
We have never had a problem like this in any of the
units we have designed. However, we are familiar with the
units he has discussed. This problem is sometimes found
in the in-line heaters in the tail gas units as well. We believe
the problem is caused by the swirling air or acid gas
inducing harmonic vibrations inside the unit.
As I mentioned, we have never had this problem, but
if we did, we might look at using stabilizer vanes or
geometry modifications to cure it using flow modeling.
QUESTION 12.
In our Claus units, we are facing frequent blockage in
the final condensers. We have 5 vol% to 72 vol%
ammonia in the feed to the Claus unit. What are the
practical limits for ammonia in the feed gas?
CUNEO:
We have had a wide variety of experience in operating
Claus plans to combust ammonia. We have done this on
units that are both built for that purpose and units that
have been revamped. We have worked with Pritchard on
this and have had very good experience.
Our sustained upper limit for ammonia has been 30%
on a combined feed basis, calculated using the sour water
stripper tops where we try to concentrate the ammonia
plus the acid gas feed. We have achieved multiyear runs
without ammonium salt plugging. Typical production of
sulfur in these type of units has been in the 75 to 100-ton
a day range.
Our plants operate in what we refer to as a front end
split or two zone thermal reactors. All of the gas from the
sour water stripper is fed to the first zone where the typical
operating temperature is 2,200°F to 2,600°F We want to
make sure that we destroy all the ammonia in that zone.
TOC/INDEX
Acid gas is fed into zone 1 if there is extra capacity
within zone 1, until it begins to affect that minimum
target temperature of 2,200°F The remainder of the acid
gas is fed into zone 2.
The idea in zone 1 is to be in a reducing atmosphere,
to minimize oxygen break-through to zone 2, and then
subsequently out of the thermal reactor. And, of course,
you have to make sure there is sufficient residence time
within zone 1.
A key upstream operating feature is to minimize the
ammonia in the amine acid gas, because a portion of that
could be fed into zone 2, which would bypass the high
temperature in zone 1. So we target via water balance for
less than 1% ammonia in the amine regenerator reflux.
Because ammonium hydrosulfide can condense out of
the Claus phase as it reaches the colder portions of the
unit, our target is to stay above 300°F until the final
condenser, to minimize potential plugging problems.
DEATON:
We process about 15% of ammonia every day with no
problems, and as Mr. Cuneo does, we split the acid gases.
We try to control the first stage of the combustion furnace
between 2,300°F and 2,400°F F, so that we get complete
destruction of the ammonia. If you do not destroy the
ammonia, you are going to get ammonia salt deposits in
the condensers.
MENEGAZ:
We concur with the previous responses. Pritchard has
designed units of up to 45% ammonium in the combined
feed without sulfate problems in the back end exchanger.
When operating on high ammonia feeds, a well de-
signed unit can get down to 275°F and still avoid plug-
ging. However, some refiners find 300°F to 315°F is
necessary to avoid problems. This reduces sulfur recovery
due to the higher sulfur vapor content in the tail gas feed.
PORTER:
The previous panelists have covered my comments. I
agree with the temperatures Mr. Cuneo gave for ammonia
destruction.
We recently operated a unit with 35% ammonia in the
SRU feed gas.
TREESE:
Provided the process is correctly controlled, we operate
consistently up to and even over 25% ammonia in the
Claus feed without significant problems. In theory and, of
course, we have heard in some practice, ammonia can be
much higher and the plant can operate that way. We get a
little nervous if it gets too high.
One of our Unocal sulfur plants had a serious problem
with plugging in the sulfur condenser tubes and demister
pads. The deposits were found to be ammonium sulfate
1994 NPRA Q&A Session on Refining and Petrochemical Technology
crystals. The ammonia concentration in that unit runs
15% to 20%. After a considerable amount of study, in-
cluding the review of some other ammonia-burning Claus
plants, we identified the probable cause as formation of
sulfur trioxide in the reaction furnace. The problem was
remedied by diverting more of the MEA acid gas to the
front burner of the two-stage combustion furnace. Again,
this is one of those furnaces, as Mr. Cuneo mentioned,
where all the sour water stripper gas goes to the front end.
The plugging problem disappeared overnight.
We saw the same problem show up a little later, and we
found that one of the in-line burners was operating with
too much excess oxygen. This, again, probably resulted in
the formation of sulfur trioxide. Even with the tiny
amount of unreacted ammonia leaking through the reac-
tion furnace, there was apparently enough ammonia to
cause the ammonium sulfate crystals to form.
MOHAMMAD AL-SHAHRANI (Saudi Aramco):
Do all the condensers have demister pads or just the
first one?
TREESE:
We have demister pads on all our condensers.
MENEGAZ:
I believe we specify them in all the condenser sections.
RANDALL HULL (BOC Gases):
As most of the panelists have said, the typical approach
is to go to split flow at the burner reaction furnace where
most of the amine gas is bypassed to some midpoint of the
reaction furnace. The only drawbacks to that system is that
you have to maintain, to a very high degree, an instrumen-
tation system to control that combustion in a split flow.
And, secondly, if you do have amine unit upsets, where
you get a hydrocarbon carryover situation, often times
those hydrocarbons will see much reduced residence time
because they are, again, being bypassed around the burner.
I might mention that on a mole basis, ammonia re-
quires about 70% more air than regular amine acid gas.
Several refiners are using high levels of oxygen, using either
our technology, Air Products, or Pritchard/Lurgi technol-
ogy. I know that one of the benefits in that operating mode
is that you generally do not have to look at a bypass. You
can put all the mixed acid gas to the burner.
ROBERT ALLEN LANNING (Dow Chemical U.S.A.):
The SulFerox process is capable of treating high H2S
high ammonia streams, such as sour water stripper off gas.
SulFerox is an iron chelate liquid redox process that con-
verts H2S directly to elemental sulfur in the sulfur range
of 1 to 20 tons per day. SulFerox is a good option for
incremental sulfur plant capacity, or to reduce ammonia
189
TOC/INDEX
in the feed to the Claus by treating the sour water stripper
streams separately.
BRUCE SCOTT (Consultant):
All the things that the panel has mentioned for com-
busting ammonia in sulfur plants work well if the amine
acid gas does not have a lot of ammonia. And this gets
back to proper operation of the amine unit, and the purge
of the regenerator reflux to keep the ammonia level down.
QUESTION 13.
What are refiners’ experiences with new Claus cata-
lysts versus alumina for increasing sulfur conversion?
How was this type of catalyst justified and under what
conditions might it be appropriate?
MENEGAZ:
The titanium dioxide-based catalysts offer superior
COS and CS 2 conversion and excellent sulfation resis-
tance. Pilot plant work by Acreon showed 98% hydrolysis
of carbon disulfide for high titanium oxide catalysts, as
compared to 65% for unpromoted alumina. This was at
650°F and 3 seconds residence time.
Unfortunately, these catalyst can cost up to ten times
as much as that of equivalent high alumina catalysts, so
their use is limited to situations where the sulfur recovery
is at a premium. Units with sulfation problems due to
direct fired reheat or faulty burners are a good application.
We have specified this catalyst in one instance to help
meet a stack emission limit of 50 ppm total sulfur, and in
another instance to achieve an overall recovery specifica-
tions of 99.3% for a Claus and CBA facility. COS and CS2
can be a large portion of the sulfur species exiting the Claus
plants. The tail gas processes like Scot, which convert these
COS and CS2 in the hydrogenation reactor, have less need
for the high performance catalyst than do the sub-dew
point tail gas processes like Sulfreen or CBA, which do not
convert them.
PORTER:
We have two small units operating with titanium oxide
catalyst in the first reactor. The units have no tail gas
treating. In order to meet tail gas stack gas requirements
for SO2, it is necessary to destroy essentially all of the COS
and CS2 in the Claus unit.
TREESE:
Unocal has been operating two Claus units at the same
refinery, with two of the newer catalysts on the market.
One is a high surface area alumina; the other is a “natu-
rally” promoted catalyst. After a two year side-by-side
comparison, we see little difference in performance. Both
are doing very well, maintaining 96% to 97% sulfur
recovery. This is with feed containing up to 60% sour
water stripper off gas. We do not think there is a significant
190 Environmental Control & Energy Conservation
difference between these two in COS and CS2 emissions
from the Claus units. Again, we fall in the category of
having hydrogenation reactors, so that mitigates some of
the COS and CS2 issues.
Based upon considerable experience with the different
catalysts, the primary factor in good performance seems
to be minimizing the process upsets and avoiding sulfur
burn-off from the catalyst during shutdowns.
Assuming these two catalysts are good examples of the
state of the art, catalyst selection for us reduces more to a
matter of price.
McLEAN:
These catalysts may be new to some U.S. refiners, but
they have been in successful operation for over 10 years in
Europe and Asia. Acreon markets several of these.
The AM catalyst is an oxygen scavenger, and this is
specifically useful to fit the needs of refiners that have a
problem with excess oxygen from the reactor furnace.
Others include CRS-21 and CRS-31, which are alumina-
titanium and titanium based catalysts, respectively. Both
of these provide excellent COS and CS2 hydrolysis with-
out the poisoning effects of sulfation, which can be expe-
rienced with Claus catalysts promoted with alkali metals.
These catalysts can be justified when the use of higher
sulfur feeds puts increased demand on the sulfur recovery
facility, but the ability to build or expand capacity is
limited. They are also useful where sulfation in the current
facility has increased to the point where it severely affects
the operation. Claus catalysts promoted with calcium
oxide or magnesium oxide are particularly susceptible to
this. These are good promoters for the hydrolysis reac-
tions, but can be severely affected by sulfate poisoning.
MICHAEL BERLYANT (Bayway Refining Co., Tosco Corp.):
We have had a lot of experience with a new type of
catalyst. We have three Claus plants with tail gas units. In
TOC/INDEX
he middle of the run, we were required by the New Jersey
Department of Environmental Protection to install con-
tinuous emissions monitor (CEM) on the tail gas unit,
and unfortunately the catalyst in the tail gas unit was
already spent so it did not perform well. We replaced the
catalyst in one of our units with a new type of Claus
catalyst, and we reduced the level of total reduced sulfur
from 600 ppm to 5 ppm in no time. So it did help us to
continue to run the refinery for almost a year.
QUESTION 14.
What are the NOx levels exiting Claus units but before
the tail gas incinerator? Are the NOx levels a function
of the NH3 fed to the Claus unit?
MENEGAZ:
We design the thermal reactor to operate in a reducing
condition where NO, and SO3 formation is not favored.
We have no reports of NO, problems with tail gas leaving
the Claus or tail gas units.
TIM ARMSTRONG (TPA, Inc.):
We design our systems with an oxidizing atmosphere
in the front chamber of the thermal reactor, and due to
the reducing atmosphere in the back part of the sulfur
recovery unit, any NOx formed when the ammonia is
combusted is reduced. We have no reports of NOx exiting
the sulfur recovery unit.
QUESTION 15.
We have two sulfur plants producing about 780
tons/day each, and have experienced a main burner
overheating problem. This has lead to a matrix block
(a compartment plate between mixing chamber and
waste heat boiler) melting down during the heating up
period. Have others experienced this? How many
temperature sensing points are in your sulfur p/ant,
and how do you monitor the main burner and matrix
block temperature?
PORTER:
We have had a similar problem. We now avoid over-
heating during heatup by injecting steam to the main
burner to quench the flame temperature.
To measure temperature we use the E2T (infrared in-
strument). A number of our units have no continuous
temperature measurement. There have been no significant
temperature related incidents recorded. All of the units
that burn ammonia have the E2T devices.
SAYLES:
We use two thermocouples at right angles to each other.
The temperatures between the two thermocouples must
agree within 25°F. The catalytic reactor bed has 9 thermo-
couples, 3 in each bed. We also use flame scanners and IR
1994 NPRA Q&A Session on Refining and Petrochemical Technology
detectors in some installations. We were concerned in-
itially about excessive maintenance with the IR detectors
due to soot on the lenses, but after over a year in operation
they have performed well.
MENEGAZ:
Overheating during the SRU heatup period is a com-
mon industry problem. The fuel gas used for the heatup
burns at a much higher temperature than the acid gas, and
unless the firing rate is held to a reasonable minimum and
moderated with a steam or inert gas injection, you can
severely damage your burner and internals. Close moni-
toring of the temperatures is essential. We use temperature
scanning of the reactor with one or two optical pyrometers
and two to four thermocouples.
ARMBRESTER:
Our experience is similar. We also have a capability to
inject either steam or nitrogen into the burner to keep the
temperatures cooler. We also use the E2T instrument for
temperature measurement, and during start-up we have a
thermocouple in the front end of the thermal reactor. That
will usually fail sometime after we have come up to normal
operation, but it is useful for monitoring the temperatures
during the early part of the start-up.
QUESTION 16.
Have refiners successfully applied oxygen enrichment
to their sulfur plants to increase sulfur capacity? How
are the safety issues of using oxygen in excess of 30
vol% being handled to ensure reliable and safe op-
eration?
DEATON:
If the oxygen content is under 30% it is referred to as
“oxygen enrichment.” Many of these units have been
installed and they provide 25% to 30% capacity increases
for sulfur production. Both of Clark’s Claus units at the
Blue Island refinery are typically maxed out and we are
working to install oxygen enrichment.
If the oxygen content is over 30%, it is referred to as
“oxygen injection.” This term is used because a special
injection nozzle is used. A concern with oxygen injection
is that it can lead to exceeding the refractory temperature
limits if the proper controls are not installed. The upper
limit for refractory is 3,000°F when you reach the soften-
ing point. And you never want to exceed 2,700°F to
2,800°F.
BOYCOTT
We successfully installed an oxygen enrichment system
on our 35 ton per day plant. We operated this system for
three years until a new facility was built. The system was
successful in increasing capacity by 25% to 30%.
191
TOC/INDEX
One point to note is that the question has to do with
safety in handling of oxygen in excess of 30% purity. The
combined air stream in our plant never exceeded 27%
oxygen. The oxygen was injected into the air line with a
Monel quill. We did not perform any burner modifica-
tions for the oxygen enrichment system.
CUNEO:
We are in the process of constructing two sulfur recov-
ery units for our Deer Park Refining Limited Partnership.
They are going to utilize the O2 combustion technology
in the Claus reactors. The especially-engineered burner
design was developed by Lurgi. The reason for bringing it
up here is that we found that this would give us a much
better capital-to-operating cost trade-off and allow us to
have lower capital cost for design of these units.
If the oxygen were physically mixed with the air, the
concentration would be about 37%. It is our under-
standing that Lurgi estimates the upper limit for oxygen
in air for their burner at around 60%. .
We are using conventional refractory and design criteria
around the furnace. We intend to limit overall reactor
temperature to less than 2,900°F.
MENEGAZ:
Pritchard is a U.S. licenser of the Lurgi technology,
which is capable up to 60% oxygen, as Mr. Cuneo men-
tioned. We think we will be taking it much higher, to
100% shortly, pending refractory considerations.
A proprietary thermal reactor burner is utilized, which
moderates the combustion temperature without the need
for gas recycle. The oxygen is burned with a part of the
acid gas in the center of an extremely hot flame core while
air is introduced around the outside of the flame combust-
ing the balance of the acid gas.
Downstream recovery of elemental sulfur is accom-
plished by conventional Claus technology, without spe-
cialized equipment or operating practices. Six Claus units
with oxygen enrichment are in operation in Europe. Six
additional units, four in Europe, two in the United States,
are currently under construction.
The oxygen enrichment offers excellent flexibility re-
garding feed rate and feed composition, while achieving
high conversion and contaminant destruction. A typical
design uses air only for normal loading, and oxygen en-
richment to double capacity. This approach offers consid-
erable capital cost savings.
Regarding safety, the oxygen flow system must be pro-
vided with interlocks to ensure an automatic shutoff in the
case of a unit upset. The oxygen flow must stop in the event
of a thermal reactor temperature or SRU shutdown, such
as loss of flame, loss of instrument air, or power failure. The
oxygen system should be purged with inert gas after auto-
matic shutoff. Operators should be provided training for
safely commissioning and operating with oxygen.
192 Environmental Control & Energy Conservation
SAYLES:
We agree with the comments that have been made.
The cost of the oxygen has a significant impact on
whether or not you choose this option. We have evaluated
oxygen enrichment for several of our installations and have
chosen to build another unit.
TROY WILSON (Air Liquide America Corporation):
(Formerly Big 3 and Liquid Air Corporation) The
question relates to the safety issues with oxygen concen-
trations above 30%. Basically with oxygen enrichment,
the concentration should be limited to 30%. When the
technology being applied is enrichment, actually adding
oxygen directly to the air piping, the safety issue is the
cleanliness of the air piping itself.
When needing concentrations above 30% oxygen, us-
ing a technology that incorporates taking oxygen-clean
piping all the way into the furnace should be considered.
There are several technologies available to safely operate
above 30% oxygen. The panel has mentioned the Lurgi
process. TPA is an engineering company that has worked
closely with Air Liquide. We have experience with a dozen
or more sulfur units using the TPA process, some of which
operate up to 50% oxygen with only minor burner modi-
fications. These units are taking the oxygen into the
furnace without any replacement of the existing burner,
which is very economical.
Another safety consideration with the oxygen enrich-
ment technology (considering low upstream pressure)
would be a fast-acting shutoff valve for the oxygen. If the
unit trips and the air blower shuts down, the valve insures
that there is not greater than 30% concentrations in that
piping. Also, to prevent impingement, a sophisticated
sparger should be considered for good mixing and a
homogeneous concentration before any elbows or instru-
mentation are introduced to the flow path. Finally, the
issue of burner vibration, as Mr. Boycott pointed out, is
always a consideration when using enrichment. Concen-
trations somewhere between 25% and 30% will typically
cause burner vibrations, depending on plant-specific con-
ditions. Air Liquid is experienced to perform engineering
and oxygen enrichment testing to determine capabilities
of the existing burner and other equipment before any
long term commitments are made by the refiner.
RANDALL HULL (BOC Gases):
There are two issues. One is the safety. We do not
recommend enriching an air stream beyond 30% in any
carbon steel air distribution system. At those high levels,
in a hydraulically limited sulfur tail gas system, as Mr. Boy-
cott mentioned, at 27% to 28% you have backed out so
much air that you have to be concerned about your flame
characteristics, your mixing performance. Beyond 30%,
you typically look at a new type of a burner, a new
technology. BOC and Air Products have technologies
TOC/INDEX
which will permit 100% oxygen use, which can give you
very large capacity increases. Other companies sell tech-
nologies for lower levels of oxygen use.
We manufacture an oxy-acid gas insert that can be used
on existing systems to go beyond 30%, typically up to the
maximum reaction furnace temperature, which has been
mentioned at 2,800°F to 3,000°F That will generally
occur in a refinery situation around 40% to 50% oxygen.
But the capacity increase is significant.
GEORGE W. BROWN (Conoco, Inc.):
We have been operating two sulfur plants with basically
cope oxygen injection or enrichment, whichever you
want, since about 1985. When we first were doing all this,
we worked pretty closely with companies like Air Liquide
and also Linde, now Praxair, on special procedures in
dealing with oxygen. With the oxygen, special care has to
be taken if you are using 1% enriched air. If you are
operating 25%, and we can operate on 60%, we treat it
the same way. Still, with oxygen enrichment you have to
take special care; all of our lines are Monel pipe. We treat
everything the same way when we are using oxygen, so we
do not get complacent.
UDAY PAREKH (Air Products and Chemicals, Inc.):
Air Products, along with the Gear, Allison & Associ-
ates, Inc., pioneered sulfur recovery unit oxygen enrich-
ment technology in 1985 at a U.S. Gulf Coast refinery.
Over the past decade, Air Products has participated in
oxygen enrichment at over 20 Claus units in the U.S. and
around the world. The oxygen enrichment levels have
varied from about 24% to over 60%. Besides the obvious
benefit of higher sulfur recovery unit capacity, refiners
have also noted better ammonia destruction, better tail gas
unit operation, and higher overall sulfur recovery.
With regard to the issue of oxygen enrichment in excess
of 30%, one method is oxygen injection into the acid gas
burner that has already been mentioned. Another method
is to use a burner with a separate oxygen pass, such as the
proprietary COPE burner. The use of such a burner would
have additional benefits of achieving better mixing and
better ammonia destruction.
And, finally, one can go up to 100% oxygen using Air
Products’ patented COPE technology that helps moderate
Claus reaction furnace temperature. Barring other limita-
tions, precautions with respect to refractory temperature,
metallurgy, cleanliness of the piping, and oxygen velocity
should allow refiners to safely use oxygen enrichment
levels well in excess of 30%.
QUESTION 17.
Some heavy oil processing systems produce high
ratios of CO2 to H2S What is the industry experience
with Claus units processing such feeds?
1994 NPRA Q&A Session on Refining and Petrochemical Technology
ARMBRESTER:
In the early 1980’s, we experienced problems with high
CO2 concentrations in our acid gas feed stream, and since
this material is inert and takes up capacity in the Claus
unit, (we were operating at our hydraulic limit). In 1985
we converted our amine system at Catlettsburg from MEA
to MDEA, which is more selective to H2S and allows more
CO2 slippage in the gas scrubbers. After the switch to
MDEA, the CO2 content of our acid gas dropped to 15%,
compared to approximately 30% while using MEA. The
reduction in acid gas volume unloaded our Claus unit and
allowed us to increase our FCC feed hydrotreating severity
or, alternatively, to process more sour crude oils.
MENEGAZ:
High CO 2 to H2 S ratios are more common in gas
processing facilities. There are many such facilities oper-
ating successfully, some with acid gas containing less than
20% H2S. Design features such as air and acid gas preheat,
supplemental fuel gas firing, oxygen enrichment, or split
flow plant configuration are used to achieve a stable burner
operation. In a refinery setting, requirements for ammonia
destruction also need to be considered.
Low purity acid gas is discussed in great detail in the
1993 Q&A transcript, on pages 147-148.
PORTER:
We have not operated at a high percentage of CO2. The
highest we have been is about 50% CO2. These units need
supplemental fuel in the main reaction furnace for ammo-
nia destruction.
TREESE:
A high ratio of CO2 to H2S usually results in a dilute
acid gas stream entering the Claus unit. Concentrations
of H2 S below 30% can be a problem for conventional
Claus technology.
193
TOC/INDEX
Unocal has two sulfur recovery units that contain 20%
and 4.5% H2S, respectively, in the acid gas streams. We
use our Selectox technology to process these streams.
Selectox is the catalytic part of the Claus plant, without
the reaction furnace. Operation of both units has been
good. We are getting 97% and 93% sulfur recovery,
respectively.
TIM ARMSTRONG (TPA, Inc.):
We have one application operating on acid gas from a
gasifier system. Utilizing Oxygen InjectionTM technology,
a feed as low as 14% H2S has been successfully processed
without split flow of feed preheat.
QUESTION 18.
What alternatives to the use of a tail gas H2S/SO 2
analyzer are there for fine (trim) adjustment of the
process air to a Claus unit?
LAUX:
If you have a Scot reactor, the temperature rise across
the reactor is an indication of the SO2 concentration in
the Claus tail gas. By watching what that temperature rise
is when the unit is operating at your desired 2 to 1 ratio,
you can establish a baseline that can be used for trim air
control when the tail gas analyzer goes out, as they always
do. The actual temperature rise will vary, depending upon
the Claus feed gas analysis. For a refinery that I worked in
that ran about 90% H2S amine feed concentration, a 35%
H2S concentration in the sour water gas, with 35% am-
monia, the temperature rise was about 40°F.
MENEGAZ:
I certainly agree that excess tail gas capacity with a Scot
unit, is very forgiving to the upstream operation. The tail
gas H2S to SO2 ratio, however, is the critical parameter for
achieving maximum sulfur recovery. We currently recom-
mend use of a UV photometric tail gas analyzer for air trim
adjustment. As Mr. Laux mentioned, these analyzers do
require frequent maintenance, and the sampling system
configuration is critical. Heat control is also important.
TREESE:
We have different approaches on this one. At three of
Unocal’s Claus units, we use tail gas hydrogenation reactor
effluent hydrogen analyzers. Since we have hydrogenation
reactors, we can do this. These are used for trim adjust-
ment of the process air to the upstream Claus section. The
trim air control loop will increase the air to the Claus
section if the hydrogen increases above a certain set point
and decreases it if the hydrogen decreases. This type of
control has been in service at our refineries for over 19
years and has proven to be very accurate and reliable.
194 Environmental Control & Energy Conservation
QUESTION 19.
What is the industry experience with using hydrogen
as a supplemental fuel source throughout the Claus
p/ant reaction train?
CUNEO:
We have had very good experience with the use of
hydrogen as supplemental fuel and even total fuel to one
of our Claus units. It is about a 60-ton-a-day unit. It is an
acid gas only unit; there is no sour water stripper tops feed.
Therefore, it is not operating in ammonia combustion
mode. The catalytic train has three auxiliary burners, three
beds, and the normal auxiliary burner firing was with acid
gas and air.
The approach which we have employed to use hydrogen
was to route the hydrogen directly into the acid gas accu-
mulator that feeds the unit. Thus, the main burner and
auxiliary burners can be used for that combustion. With
hydrogen in the acid gas header, the same controls are
utilized, without additional burner instrumentation. Only
small adjustments to meter factors have been required.
One of the main benefits gained has been the ability to
operate on start-up and shutdown with the burners at a
more substoichiometric condition because there is no
hydrocarbon to cause sooting. The unit has been operated
on 100% hydrogen for about 10 days of hot standby mode
earlier this year, and the performance was very good and
steady.
DEATON:
Several years ago, I worked on a Claus plant that could
supplement the combustion furnace with hydrogen dur-
ing periods of low acid gas rates, when the firing of the
acid gas was difficult. Hydrogen was used instead of fuel
gas because burning hydrogen is smokeless and would not
lay down soot. The hydrogen rate was controlled by a
manually-operated valve. Sometimes it was necessary to
put a controlled amount of steam into the furnace to help
carry away the heat because of the low mass for the
hydrogen. This same Claus plant had fired reheaters with
flame scanners. However, hydrogen could not be used in
the reheaters because the flame scanners would not detect
enough flame and the reheaters would shut down. Fuel gas
had to be used there.
ARMBRESTER:
We have also successfully used hydrogen as a supple-
mental fuel both in the thermal reactor and, to some
extent, in the first reactor reheater, which is the only fired
reheater we have.
We agree with the previous comments, and one thing
I would add is that if you are going to do this, you need
to use the highest purity hydrogen stream that is available,
because any hydrocarbon contamination can cause ash
deposits on your downstream reactors.
TOC/INDEX
PORTER:
We have used reformer hydrogen successfully in the
reaction furnace. We have not tried it in any reheat burn-
ers, but would have concerns if gas quality was not steady.
SAYLES:
We used hydrogen as a supplement to fuel gas for many
years in several of our sulfur units. With the advent of low
sulfur diesel, the value of the hydrogen has increased so
that practice has been stopped.
QUESTION 20.
Does anyone perform regular rejuvenations on their
Claus units? What is the timing between rejuvena-
tions? How is the unit monitored to decide when
rejuvenations should be done? What is the effective-
ness?
MENEGAZ:
Rejuvenation removes sulfur and reduces the sulfates
on the catalyst, which increases surface area and rejuve-
nates the catalyst activity. Effectiveness has been a mixed
bag, with some refiners seeing improvement on the order
of 1% to 2%, and others seeing no benefit at all. The heat
soak portion is believed to be more effective when the
catalyst is new or if the unit has been operating at reduced
rates.
Timing between rejuvenations will depend on the op-
eration. Many refiners find rejuvenations unnecessary and
can go five to six years with adequate catalyst activity. On
the other hand, we know of one refiner who was hear
soaking once a week because he had a direct fire auxiliary
burner which was allowing oxygen to get to the converter
bed. Low converter bed delta T’s and high pressure drop
indicate when to rejuvenate.
PORTER:
We perform rejuvenation on an as needed basis. Timing
can be anywhere from six weeks to one year. At Pascagoula,
on our sulfur plants without tail gas plants, we monitor
our tail gas and correlate this to sulfur recovery. If sulfur
recovery goes down we would first do a heat soak and then
consider a rejuvenation if there was no improvement.
On our plants that have Stretford tail gas plants, in-
creases on the load on the tail gas plant is used to determine
if a rejuvenation is required.
We also use catalyst exotherms to monitor the need and
effectiveness of our rejuvenations.
BOYCOTT:
My experience with rejuvenations indicates that it is
really, as indicated earlier, plant-specific. Fired interheaters
will cause higher levels of sulfation and hence the need to
rejuvenate more often. At the plants I worked on, we
monitored the bed temperature profiles and rejuvenated
1994 NPRA Q&A Session on Refining and Petrochemical Technology
as required. We would also go into a heat soak and
rejuvenation after start-up in order to reverse the effects of
sulfation and sulfur deposition in catalyst micro-pores.
Tail Gas Plants
QUESTION 21.
We have been having a problem minimizing the COS
and mercaptan concentration in the effluent gas from
our tail gas unit hydrogenation/hydrolysis reactor.
What can be done to reduce these emissions?
CUNEO:
We have had quite a bit of success in reducing the
amount of COS and metcaptan. The COS is a reaction
product because what you are trying to do in that reaction
is take CO to CO2 and hydrogen via the water gas shift
reaction. If that does not occur over an active catalyst, then
the CO can react with the H2S to form COS. We have
had good success with active catalysts such as Criterion
534 and 234.
When it comes to actually operating conditions, we
recommend a bed temperature around 600°F. One of our
associate research laboratories in Shell International had
reported that mercaptan could be formed at low bed
temperatures, around 500°F, so if you are having a prob-
lem, the first remedy would be to try and increase the
reactor temperature to around 600°F. Another possibility
is to add steam to the reactor feed to increase the driving
force for the water gas shift reaction, as we said. And then,
the other thing, of course, is always make sure the catalyst
has plenty of activity left.
ARMBRESTER:
I will add a few comments. We use 650°F as a minimum
reactor temperature on our first catalytic reactor to ensure
the destruction of COS and mercaptans. If they do get
beyond that point and into the tail gas unit, then they
should be converted to H2S in the hydrogenation reactor.
If you find COS or CS2 in the effluent from this reactor,
then the catalyst may be spent or there may not be
sufficient hydrogen available for the reaction.
Since the presence of these compounds is in proportion
to the amount of hydrocarbon in the acid gas, efforts
should be made to identify and eliminate the source of
hydrocarbon contamination.
MENEGAZ:
We agree with all the previous comments. We would
like to add that operating the thermal burner at a higher
temperature might be helpful since the carbon disulfide is
decomposed much more easily at the thermal reactor than
in the converter section.
195
TOC/INDEX
TREESE:
Most of the Unocal tail gas units rarely have a problem
with controlling trace sulfur emissions to below the maxi-
mum allowable limits. However, one of our units has a
maximum total sulfur emission limit of 65 ppmv (undi-
luted with incinerator combustion gas). For this unit, we
typically have to increase reactor temperatures as the tail
gas hydrotreating catalyst ages to keep the COS, carbon
disulfide, and mercaptan levels within acceptable limits.
After a recent restart with fresh hydrotreating catalyst,
this unit was experiencing unacceptably high COS emis-
sions. We discovered that the cause was excessive natural
gas flow to the reducing gas generator, due to an incor-
rectly calibrated flow meter. This is a very simple cause.
Once the problem was discovered and corrected, the COS
level in the reactor effluent gas decreased back to the
expected concentrations.
QUESTION 22.
Does anyone treat the Claus tail gas to less than 70
ppm H2S in order to bypass incineration or operate the
thermal oxidizer on warm standby?
TREESE:
Unocal uses the BSR/Stretford process in most of our
refineries for processing the Claus tail gas. All of our units
reduce the H2S level in the tail gas to well below 10 ppm.
We typically keep just the pilot light lit in the combustor.
If the hydrogen sulfide level ever exceeds 10 ppm, however,
we do bring the incinerator to operating temperatures and
continue to operate the combustor until the problem is
resolved.
MENEGAZ:
We agree with Mr. Treese’s approach. In today’s regula-
tory environment, allowances for SRU and TGU upsets
are tighter and you want to be operating so you can stay
in compliance at all times.
PORTER:
Our Stretford plants operate in a similar manner to that
described by Mr. Treese.
DEATON:
We also have a Stretford unit for our tail gas. The
Stretford vent to the atmosphere is always less than 10
ppm. We go to the atmosphere without incineration. This
Stretford unit was the original sulfur recovery plant in our
refinery, but when we built a Claus plant, we converted
the Stretford unit to the tail gas unit.
JAMES L. DAUGHTRY (Dow Chemical U.S.A.):
Dow Chemical offers the gas specification TG-10 sol-
vent for removal of less than 10 ppm H2S in the Scot tail
gas treaters. Our experience has seen the thermal oxidizer
196 Environmental Control & Energy Conservation
operate on warm standby while operating at less than 10
ppm H2S removal.
JAMES RONNANDER (Union Carbide Corporation):
We have several tail gas units operating on hot standby
with our UCARSOL® HS-103.
B. Environmental Control
Air
NO X and SO X Emissions
QUESTION 23.
What has been the experience with f/are pilot thermo-
coup/es which can be retracted from grade, or retract-
able from flare pilots? Does anyone have extended
on-line use with either? What has been the experience
with alternative methods of flare pilot flame proving,
other than thermocouples, i.e., optical detectors at
grade, flame rods, UV sensors, etc?
PORTER:
Flare pilot thermocouples that are retracted from grade
are not used in Chevron. At Pascagoula, for pilot proving,
we are using infrared cameras located at grade. These
cameras are manufactured by PowerTrol and have proven
to be virtually maintenance free. The PowerTrol infrared
camera outputs are recorded and annunciated if a loss of
the pilot occurs. We do have thermocouples but they are
used only for automatic reignition of the pilots if the pilot
goes out for any reason. This is a new system and we are
very pleased with the early results.
TREESE:
We really have not found anything reliable for us yet. I
do not think we have tried the infrared camera approach
that Mr. Porter mentioned. We have recently, however,
reinstalled reigniters on our Wilmington plant flares.
These reigniters spark periodically, every few minutes, to
reignite the pilots on a regular, timed basis. This has
proven to be a reasonable alternative to pilot proving.
BOYCOTT:
We have replaced both of our flares in the last two years.
Each was equipped with fixed thermocouples as opposed
to retractable thermocouples. We took extreme care to
fully protect the thermocouple wires in the vicinity of the
flare tip, and we have not had any problems with this
arrangement.
Our thermocouples are set to activate the pilot auto-ig-
nition system. Each flare is monitored by a video camera
feeding a color monitor in the control room. We did install
TOC/INDEX
one black-and-white monitor. It was totally unsuitable for
this service.
CUNEO:
We have on-line retractable thermocouples on the
ground flare at our olefins unit at Deer Park. The success
has been very good with that.
We have been using the PowerTrol IR flare camera, as
Mr. Porter mentioned. We have also used the John Zink
camera. We have even gone as far as to tie these cameras
into the control system to adjust steam flow to control
smoking.
QUESTION 24.
What is the experience with air-assisted flares?
LAUX:
We have an air-assisted flare at our propane-propylene
splitter column and underground storage facility at Mont
Belvieu, Texas. Our experience with this type of flare is to
avoid them if you can do so. Unfortunately, steam is not
available at Mont Belvieu and we are stuck with it.
Manufacturers claim air-assisted flares achieve high
efficiency smokeless combustion at low operating cost.
While this may hold true at times, we have encountered
unexpected smoking problems during low flow cases. Low
flow smoking can be corrected by supplementing the
stream with fuel gas, but this would be costly. At Mont
Belvieu, we were able to eliminate all the low flow streams
from the flare header itself. That is probably not very
practical in a typical refinery.
CUNEO:
We have one air-assisted flare on our BPA unit at Deer
Park. It was put in service in 1991, and has operated
smoothly. No one has any reports of either start-up or
operational problems. Our first inspection is scheduled for
1995, so there is no history.
Hydrocarbon Emissions
QUESTION 25.
What are the best forms of odor abatement that have
proven themselves for asphalt storage and loading
facilities?
FELTROP:
Odor abatement for asphalt facilities can be addressed
by mechanical or chemical means, depending on the odor
type.
This past summer we saw a flurry of activity at asphalt
loading facilities where H2S liberation was a problem. The
treatment was accomplished by utilizing our SX-9200 line
of proprietary H2 S scavengers. More recently, asphalt
1994 NPRA Q&A Session on Refining and Petrochemical Technology
storage facilities have also been utilizing this technology
for a combination of odor and safety concerns.
ARMBRESTER:
Ashland has been using an activated carbon canister
system on some of our asphalt storage tank vents in
terminal locations for about five years now. The system we
are using is marketed by Hoyt Corporation under the
name “Odor Miser,” and has been used on asphalt and
road oil tanks as small as 2,500 barrels and as large as
50,000 barrels, with storage temperatures up to 325°F.
The carbon canisters do require periodic inspection and
maintenance due to condensate buildup, and we have
added a condensate drain on each canister which is
drained at least weekly.
Breather vents have been installed on tanks that are
equipped with these carbon canisters to provide for vac-
uum relief in the event the canister becomes plugged.
These breather vents operate at a half ounce per square
inch of pressure.
An emergency pressure cover vent is also installed on
the tank roof manway to provide adequate pressure relief.
The emergency pressure covers are set to vent below the
tank design pressure and at a slightly higher pressure than
the breather vents so that the normal flow of vapors during
tank filling is through the carbon canister.
These devices have Teflon pallet seats for stick resis-
tance, and this system has proven to be very effective in
reducing odor complaints in these areas.
DEATON:
We came up with a different application based on the
success of odor abatement additives for asphalt loading
facilities. We understood from our chemical supplier that
these additives are special amines that bind up the H2S in
asphalt, and they will not liberate H2S. Our application
was that we had to shut down our sour water stripper for
some planned maintenance and had no place to put the
sour water except to the industrial waste treatment plant.
Our chemical supplier did field testing at our refinery
and it was determined that we could treat our unstripped
sour water with their asphalt H2S abatement additive. Our
sour water stripper was down for three days and we
controlled the H2 S levels going to the industrial waste
treatment plant.
The unstripped sour water rate was 50 gpm with total
sulfides of 12,000 ppm. Additive rate was 200 gal/day at
a cost, a very high cost, of $3,500 per day. The treated
unstripped sour water was routed to downstream of the
dissolved air flotation unit. We had no odor complaints
from the neighborhood, and we had no complaints from
the industrial waste treatment plant. Ammonia odor was
controlled by bleach addition.
197
TOC/INDEX
QUESTION 26.
Does anyone use a vapor recovery system when load-
ing marine vessels? What products do you use it with
when loading? What is your experience with your
vapor recovery system?
CUNEO:
We have four vapor recovery installations, one of which
is a carbon absorption system that was chosen by one of
our marketing terminals. The reason for that is it only
operates on gasoline and we can recover the gasoline by
compression and separation.
All the other systems are at refineries and they are
thermal oxidizers because we load a multiplicity of prod-
ucts using vapor recovery there. All of them have done well.
TREESE:
At our San Francisco refinery we recover and incinerate
vapors from the hulls of ships which are being loaded with
light hydrocarbons. We also recover any vapors from any
hulls that previously contained light hydrocarbons but
had not been washed and purged prior to loading. The
light hydrocarbons we are talking about include crude
(sometimes not so light but it has light ends), gasoline,
gasoline blend stocks, naphtha, Jet A, JP-4, and aviation
gasoline. We have operated our vapor control system
successfully for three years.
At our Los Angeles plant, we were headed in this
direction until we came up with a creative solution. We
offset the marine vessel loading emissions by buying and
destroying old cars, and as it turned out this avoided the
expenditure of several million dollars on an incinerator
system.
QUESTION 27.
What is your experience with domes on floating roof
tanks? Is the dome water tight? Do you leave the roof
drain connected on the f/oating roof? Does anyone
pressurize the dome with inert gas?
DEATON:
Many of Clark’s terminals have floating roof tanks with
domes over them. These geodesic dome roofs were manu-
factured by Conseravek and were installed about three to
four years ago at a cost of about $150,000 for a 100-k
diameter tank. Since the installation of the domes, the
terminal operators have noticed dramatic decreases in tank
water draws, which translated to large cost savings in the
disposal of the water draws. The domes prevent rain, snow,
and ice from collecting on top of the roofs and leaking into
the tank. Most of the roof drains are still connected, but
are temporarily plugged. The plugs can be removed
quickly if needed. None of these domes is pressurized.
198 Environmental Control & Energy Conservation
CUNEO:
We have half a dozen or so domes. They are water tight,
and we do not pressurize with inert gas. We have discon-
nected the drains.
TREESE:
We are pretty much along the same lines as the others.
Our roof drains are connected. We have geodesic domes
over most or all of our MTBE tanks. We keep the roof
drains connected but do not use them, and we do not
pressurize the dome.
Two extra features that were required in the Los Angeles
area by the Fire Department were fire detectors under the
domes and fixed foam injection facilities under the domes
of the tanks.
Water
Secondary Treatment
QUESTION 28.
What parameters are used to control and optimize
dissolved air flotation units?
LAUX:
At Three Rivers we have two parallel DAFs of very
different design. The Number 1 DAE performs very well,
while the Number 2 DAF performs poorly. The major
differences in the design are the detention time for Num-
ber 1 is 32 minutes; for Number 2 it is 8 minutes. The
feed to recycle ratio on Number 1 is 2 to 1, while it is 6 to
1 on Number 2.
The larger volume and better air supply provided by
the lower feed to recycle ratio in the Number 1 DAF help
it perform better. We also found that some spring loaded
check vales on the Number 2 DAF air inductors were
restricting the air flow. Flocculation improved tremen-
dously when we removed these check valves.
We also added a water spray bar to the sludge trough
to improve the floc deaeration and to make the sludge
more pumpable.
Several other factors also contribute to a DAF’s per-
formance. We inject a flocculation aid as well as sulfuric
acid for pH control to help the DAF’s performance.
Skimmer blade speed and depth below the water sur-
face need to be watched to ensure that the floc that is
formed is removed efficiently.
ARMBRESTER:
We also have two parallel dissolved air floatation units
at our Catlettsburg, Kentucky refinery. Our units use a
recycle stream of water into which the air is injected and
then that mixture is injected at the bottom of the dissolved
air floatation unit, at a pressure of approximately 40 psig.
TOC/INDEX
The recycle water rate that we use is about 25% of the
incoming feed rate to the DAF, and we use an air injection
rate of approximately 8 scf of air per 1,000 gpm of inlet
water. We perform regular sampling of the DAF inlet and
outlet water for turbidity. Typical turbidity results are 60
to 70 NTU at the inlet, and about 10 to 20 NTU at the
outlet. We also sample daily for total suspended solids and
oil and grease, and we see about 75% to 80% removal
across the DAF on both of those parameters.
In our unit, we also use a cationic polymer to enhance
the flocculation of the oil and solids.
BARLOW:
The main parameters that our Water Management
Group uses in control are recycle ratio, feed solids concen-
tration, air-to-solids ratio, and solids and hydraulic load-
ing rates. Obviously, the hydraulic or solids loading, when
they exceed design, create problems. Comments on ranges
of successful design values follow:
Hydraulic or solids loading that exceeds design will
tend to cause poor removal of solids. Typical design
values are 1.5-4.0 gpm/ft2 overflow rate, and 0.2-
5.0 lbs./ft2/hr. solids loading.
The recycle ratio determines the amount of pressur-
ized air that is introduced with the fresh feed via the
recycle stream. The recycle stream pressure is let
down from approximately 40 psig to 70 psig to
atmospheric upon introduction to the reactor. This
releases the air as tiny bubbles. The tiny bubbles
attach to oil and solids contained in the feed to the
reactor, adding buoyancy so that oil and solids are
driven to the surface and removed by skimming.
The air-to-solids ratio is an important monitoring
parameter. If this ratio is too high, small air bubbles
will coalesce and cause greater turbulence in the
reactor, which will tend to break up existing floc
particles. If the air-to-solids ratio is too low, the unit
will perform poorly with regard to floating solids.
An optimal air-to-solids ratio may be anywhere from
0.02 to 0.06, depending on the system.
QUESTION 29.
Can the panel comment on their experience with
waste waler reuse wilhin the refinery? Which streams
are reused? To which service does reused water go?
What problems are encountered?
FELTROP:
Some refiners are recycling a portion of their desalter
brine effluent as wash water makeup. This reduces the
amount of fresh water required and the volume of brine
discharged to the waste water treatment plant. It allows
for lower pH desalting, which minimizes hydrogen sulfide
levels and oil content in the desalter brine. It also improves
iron reduction and hardness removal across the desalter.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Recycling the desalter brine also saves energy because
the water is already at desalter operating temperature. For
example, recycling 4,000 bbl/day brine in 100,000
bbl/day desalter can save 210 million Btu’s per day in
energy.
Brine requires no additional treatment for recycling.
However, careful attention must be paid to the brine, salt,
and oil content to avoid compromising the desalter op-
eration.
Storm water, which is low in dissolved solids, can often
be used as cooling tower makeup without softening, re-
ducing overall softening costs and softening waste dis-
posal. Storm water can also be used as makeup to asphalt
emulsion processes if filtered to remove solids.
TREESE:
We have a number of different locations where we have
tried reusing waste water, with mixed results. In some
cases, we have sent stripped water to a cooling tower. We
have tried this a number of times, but we have ultimately
discontinued due to bug growth and other deleterious side
effects.
Another project reused stripped water in the desalter,
and that is not all that unusual.
When you have stripped or sour water that starts out
as wash water in the hydrotreater or hydrocracker and if
you can afford to segregate and strip it, it can go back to
the original unit as wash water. A blowdown stream is
necessary for solids control.
At another of our refineries, in our waste water treating
unit, some of the unit’s effluent is sent back to the front
end of the unit rather than discharged to the Bay. It is used
for filter backwash, water sprays above chambers, and
miscellaneous other uses within that water treatment unit.
That unit has a secondary bug unit.
And, finally, untreated process waste water, that is,
water in our waste water tanks, has been used to hydrotest
tanks which have undergone turnaround, but have not yet
been returned to service.
BARLOW:
The most common reuse we see of process water is in
various overhead condensates, especially in the crude and
vacuum unit, as desalter wash water. A typical problem
encountered with this method is the recycle of ammonium
chloride or amine chloride salt back to the desalter. If you
have a desalter with high BS&W carryover, these salts can
find their way back to the crude tower and lead to depo-
sition, fouling, and potential underdeposit corrosion.
Another common reuse of waste water is stripped sour
water. A lot of those have been talked about: stripped sour
water as a desalter wash water or wash water for distillation
tower overhead condenser systems.
‘In the desalters, if you are processing heavy crudes the
residual ammonia content in the stripped sour water needs
199
TOC/INDEX
to be watched very carefully. Emulsion problems in the
desalter can occur.
Other opportunities for recycle of refinery waste water
effluent exist. In many cases it is of such quality that it is
suitable for on-site reuse. The organic, metals and toxics
content have been reduced to very low levels to meet
NPDES restrictions. On the other hand, the inorganic
dissolved solids are typically significantly higher than the
refinery influent, due to evaporative concentration effects
and addition of pH control and other chemicals.
Effluent waste water could be recycled in open recircu-
lating cooling systems. Extra disinfection steps may be
necessary if you do this, so as not to create or exacerbate
microbiological fouling in the cooling systems. If you do
not have a system-wide dissolved solids removal mecha-
nism, there will be a limit on the amount of waste water
that you can recycle. You can use mathematical models of
flow rates and purge rates, and the resultant water quality
to determine acceptable flows.
Besides quality concerns, another drawback is physi-
cally getting the wastewater effluent to the cooling sys-
tems. The distance from the effluent line to the cooling
systems makes piping and pump installation costs high
enough to require good clear economic justification for a
reuse project.
Another example is the reuse of demineralizer fast rinse
water as partial cooling system makeup (less common).
The cooling system can often accept other streams such as
reverse osmosis concentrate, and boiler blowdown. In
general, the larger and more contaminant-laden the waste
stream, the less the cooling systems can accept. Normally,
boiler and cooling deposit control chemicals are incom-
patible, so that defines a boiler blowdown to cooling
system limitation.
MAJED INTABI (Saudi Aramco):
In addition to the conventional waste water reuse
schemes mentioned earlier, sanitary sewage, being the
major source of water supply to one of our inland refiner-
ies, is treated and reused as makeup for cooling water,
boiler feed water and other process requirements within
the refinery. Treatment includes air oxidation, lime treat-
ment, gravity filtration, reverse osmosis and ion exchange.
The main attention required is control of biological de-
posits and corrosion induced by the aggressive nature of
this type of water.
V. KANNIAPPAN (Madras Refineries Limited):
After treating water to the minimum requirements of
national standards, we have been using it for the fire water
system and for water washing, that is, floor washing, etc.
We are installing further treatment of this water with
tertiary treatment and reverse osmosis, and we are going
to use it for our cooling water system.
200 Environmental Control & Energy Conservation
ANANO KUMAR (Indian Oil Corporation Limited):
We also use the treated effluent in the fire water net-
work for makeup apart from in the circulating water
system. In some of our refineries, it is used as coke cutting
water in the delayed cokers.
In one of the refineries, the treated water polishing
pond attracts thousands of migratory birds during the
winter season. These birds are nesting and breeding in
these lagoons and it has become one of the points of
tourists’ interest. In fact, this refinery is also located in
proximity to the famous monument-Taj Mahal.
BHAGWAN B. PATIL (Hindustan Petroleum Corporation Ltd.):
In view of this recycle of the wash water to the cooling
tower, what is the metallurgy of the tubes, each of those
tubes? Is the metallurgy changing and if it is changing,
then what would the metallurgy be at the start?
BARLOW:
We have reviewed this question; however, the question
is too broad. The choice of ideal metallurgy will depend
on the amount and quality of the water. An answer cannot
be given without specific stream analyses.
WILLIAM MERTES (Arrowhead Industrial Water):
After installation of reverse osmosis units for boiler
makeup water, we have successfully used our reject as
cooling water makeup at a number of refinery installations.
General
QUESTION 30.
Considering the advent of “aquatic toxicity”, please
comment on the following questions:
a. Which pollutants (specific organic& inorganics, met-
als) are most likely to cause problems?
b. Are there any “screening analyses” which can be used
in lieu of or as indicators of formal aquatic toxicity
testing?
c. How is the industry coping with the discharge of rela-
tive/y “sa/ty” wastewaters to in/and (fresh) receiving
waters?
BOYCOTT:
I will speak on parts a) and b) of this question:
a. Frontier conducted extensive testing of the
WWTP effluent stream to identify toxicity prob-
lems. All of the testing pointed to a non-polar
organic compound as the prime source of our
toxicity problem. Although we were unable to
identify the specific compound we were able to
identify the appropriate treatment method, acti-
vated carbon.
b. Yes, Microtox. This is a screening method that can
be used for non-compliance monitoring of aquatic
TOC/INDEX
toxicity. The test is very fast and inexpensive. Cor-
relations have proven very good at high toxicity
levels. However, there does not appear to be a good
correlation at lower toxicity levels.
ARMBRESTER:
Our testing indicates that the presence of high concen-
trations of ammonia, as well as some amine, fluoride and
phenolic compounds may result in increased toxicity of
the effluent water. Some industrial soaps and solvents can
also lead to higher toxicity levels. Several years ago we
began screening our equipment washing materials by
checking the ratio of BOD to COD in a sample of water
that is spiked with the cleaning agent; only those with a
low BOD/COD ratio are approved for use at Catletcsburg.
We use the COD content of the treatment plant influ-
ent water as a quick “screening analysis,” since it can
indicate the presence of some of the contaminants listed
above. We also perform daily acute toxicity tests on our
effluent water, using fathead minnows. This test is rela-
tively simple to perform: we place ten fathead minnows
(approximately 10 days old) in a sample of our effluent
water and then record the number of survivors at 24 hour
intervals over a period of four days. This testing is per-
formed by the operators in our waste water treatment
plant. We publish the minnow survival data in our daily
operating reports, and find that this helps increase the
awareness level of operators throughout the plant, result-
ing in better control of the oily water systems.
I would add one caution regarding screening tests for
toxicity: we believe that toxicity indications can be very
specific to the species being tested. We also tested the
Microtox system a few years ago, and found that the
toxicity to micro-organisms, as measured by this instru-
ment, did not always correlate with the bioassay testing that
we perform as part of our discharge permit requirements.
BARLOW:
The metals that we are most often testing for are zinc,
copper, and chromium. The EPA is promoting analysis for
dissolved metals, instead of total recoverable metals. The
latter is currently required by state and federal permitting
agencies. We also look at other materials: ammonia, chlo-
rine, chlorinated compounds (including biocides), chlo-
rinated phenolics, PCBs, and dioxins.
We would support an investigation into the use of
Microrox. In some cases, correlations have been developed
beforehand with some fairly good success. However, the
cautions previously stated should not be ignored.
LAUX:
Regarding Parr a. and part b. of this question, our hands
are pretty much tied by our EPA Discharge Permit if we
are ever going to the river. There is not much else we can
change about that.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
For inland discharge, though, we have done something
rather unique. We purchased 500 acres of land in 1985
and scarred irrigating it and growing hay. We grow Coastal
Bermuda grass, which was selected specifically for its
ability to withstand salts. We have certain discharge limits
that we have to meet, but aquatic toxicity is not one of
them.
The system works very well, though there are some
different operations and maintenance problems dealing
with irrigation systems. It also actually produces some
revenue for the refinery, especially in dry seasons when hay
is scarce. Of course, you need to be able co go out and find
500 acres in the area, and proper climate is absolutely
necessary.
PORTER:
Organic pollutant problems are phenolics, organic ac-
ids including naphthenic acids and certain polyaromatic
hydrocarbons. Inorganics pollutant problems are ammo-
nia and fluoride. Metal pollutant problems are nickel and
zinc with selenium having the potential to bio-accumu-
late. We have found it very difficult to precisely identify
the specie or species that is causing the problem with test
failures.
We have utilized several rapid screening tests that give
results in hours to 1 day. We have had mixed success using
them - sometimes they correlate, but often they don’t.
Currently regulators consider surrogate tests supplemental
to formal tests.
We have also utilized short term screening tests of 1-2
days using the same test organisms that are used in the
formal toxicity testing. These tests correlate better than the
rapid screening tests.
SHIRLEY BOWLES (Texaco Refining & Marketing, Inc.):
I was wondering if anyone had any success stories in
using constructed wetlands to reduce aquatic toxicity.
PORTER:
At our refinery in Richmond, California, we have been
working since 1988 with governmental agencies to estab-
lish and demonstrate a wetlands that does tertiary treat-
ment of effluent water. Results are encouraging in that a
reduction of contaminants has been achieved.
QUESTION 31.
Have you used odor modifiers at your wastewater
treater? It so, what is your experience with them?
ARMBRESTER:
We have conducted several tests of an odor-masking
agent in the waste water treatment stream at our
Catlettsburg refinery, to determine the effect of injecting
the additive at several different points in the treatment
plant. Addition of a masking agent prior to the API
201
TOC/INDEX
separators appears to reduce the odors originating from
the separator section of the treatment plant, but does little
to improve odors from the aerated section. The masking
agent addition is kept at the lowest recommended rate, so
that the odor of the additive itself is barely detectable.
Increasing the addition rate of the masking agent does
not improve the plant odor, but does increase the odor of
the masking agent. We had the whole treatment plant
smelling like bubble gum at one point.
Addition of the masking agent prior to the aerated
section of the plant resulted in a strong odor of the
additive, with little or no improvement in the overall
odor, so this was discontinued. We are currently consid-
ering several odor-neutralizing agents that are distributed
as an atomized vapor to help improve odors from the
aerated section of the treatment plant. One temporarily
installed system appeared to improve the area odor, with-
out adding much additional odor from the neutralizing
agent itself.
We currently are considering a trial of a vaporizer
system, and are surveying other refiners to determine
whether these systems have been effective in reducing
odors from their waste water treatment facilities.
PORTER:
At one refinery, we have used the masking agent that
Mr. Armbrester referred to. Our operators called it “juicy
fruit.”
Currently we are using an odor-neutralizing com-
pound. We do not use it on an ongoing basis, but when
required during maintenance work.
QUESTION 32.
What are the refiners doing regarding control of storm
water contamination?
PORTER:
At Pascagoula we segregate the storm water from the
process water. We used raised hubs for process streams in
order to keep storm water separate. Even with diligent
housekeeping, there continues to be problems with con-
tamination in the storm water. We collect and process the
storm water runoff through our effluent treating plant.
During a heavy rainstorm we will collect the first one inch
of rain in tankage and then process it in a ratable fashion
through our effluent treating plant. Rainfall after the first
inch has little contamination and will bypass the majority
of our effluent treating system.
SAYLES:
At our refinery in Tulsa we sometimes receive over one
inch of rain too, and have a large retention facility to
control run-off. We have a process sewer system, a sanitary
sewer system, and a storm water sewer system. We have
been very fortunate in being able to keep the storm water
202 Environmental Control & Energy Conservation
sewer system uncontaminated. Not only to satisfy the
regulation but the storm water is used as cooling water
makeup.
In the Wyoming refineries, with a very low average
rainfall, storm water really has not been an issue.
LAUX:
We process the rain water that falls in the process areas
through our water treatment system. The process unit
API’s have a small oily water pump and a larger rain water
pump to handle the storm surge. The small pumps route
to the main refinery API. The large storm water pump
discharges bypass the main API and go directly to the
Waste Water Treater feed surge tank. This is a 75,000 bbl
tank which is about 5 times the daily oily waste water
production rate. The main API also has two 25,000 bbl
surge tanks in front of it that handle the initial storm
surge.
The storm water that falls in the tank farm is held in
the tank dikes until it is determined that it is clean and
then is discharged without treatment. The rain that falls
in the remaining areas of the refinery like the parking lots,
shop areas, and roads run off to drainage ditches and is
discharged with certain effluent limits.
Solid & Chemical Waste
QUESTION 33.
What technologies are refiners using to minimize
waste caustic and waste acid? Does anyone strip
spent caustic with carbon dioxide?
D'AURIA:
I am going to address the portion of the question
referring to waste caustic.
One of the things we have found very helpful recently
is to work with refiners to conduct a caustic management
survey across the whole refinery. The goal of such a survey
is to minimize the usage of fresh caustic in the refinery and
to evaluate spent caustic disposal options. As a first step,
we look at optimizing each individual unit in order to
minimize the caustic usage and the amount of spent caustic
produced. The second step is to evaluate caustic reuse
options within the refinery. The refiner conducts a refin-
ery-wide caustic balance, with the objective of integrating
caustic usage and disposal, with emphasis on identifying
opportunities to reuse spent caustic. The composition of
spent caustic streams will determine the best reuse or
disposal options. Some examples of reuse are H2S scrub-
bing with spent extraction caustic, or reuse of extraction or
sweeting caustic for crude unit overhead pH control.
The next step is to look at disposal options. In-house
options that are being utilized are incineration, neutraliza-
tion and partial oxidation. As mentioned in the question,
TOC/INDEX
some refiners are using carbon dioxide containing streams
to neutralize their spent caustic.
Once the overall refinery balance is complete, if there
is a net spent caustic stream leaving the refinery, there are
companies that will provide disposal services.
UOP recently commercialized the Caustic Free Merox
process, which requires no caustic. This process is now
available for both gasoline and kerosene sweetening, and
can be a valuable too! to help bring the refinery caustic use
into balance.
We are also currently working on a process that will
catalytically oxidize sulfitic caustic. This process will offer
the refiner an in-house solution to one of the more difficult
caustic disposal problems, caustic from H2S scrubbing.
We hope to have this process available sometime next year.
SAYLES:
Currently, we minimize the use of caustic wherever we
can. However, the caustic used in our FCC gasoline treat-
ment contains sufficient creyslic acid to allow selling to an
off-site reclaimer.
The sulfitic caustic from the light gas treatment is also
recycled to a reclaimer.
The spent caustic from scrubbing butanes produced in
the sulfuric acid alkylation unit is used for neutralization
of the acid stream from the hydrogen softeners at the
boilerhouse. The spent acid stream from the alkylation
unit is also recycled.
JIM LEHR (Star Enterprise):
Regarding the second part of that question, at our
Delaware City plant we are building a unit to strip spent
caustic with CO2, and the overhead can go to a sulfuric
acid plant or a Claus plant. We tried this in a pilot plant
and found a set of operating conditions that worked quite
well.
HERBERT WIZIG (Merichem Company):
To minimize caustic usage and the subsequent caustic
production, the following is suggested: (1) Cascade caus-
tic from LPG treating to gasoline treating for reuse; (2)
use sulfitic or phenolic caustic for crude unit pH control;
(3) use oxidative rather than extractive treating for mer-
captan removal from gasoline streams; and (4) use
air/catalyst regeneration of caustics from mercaptan ex-
traction systems.
The technologies for handling caustics at the refinery
site are either wet air oxidation, which converts the
sulfides to thiosulfates and sulfates, or neutralization with
sulfuric acid to pH 4 or pH 7. Finally, if you need an
outside source, Merichem Company has handled refiner-
ies’ sulfitic, phenolic and naphthenic caustics for the past
50 years.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
QUESTION 34.
What is the industry experience with environmental
classification of used ceramic support media, and
what is its final disposition?
BOYCOTT:
We treat support balls as a nonhazardous solid waste.
They are disposed of at an industrial waste landfill permit-
ted to handle such material. Often the balls are not
separated from the catalyst prior to its being shipped our
for disposal.
We have found that most of our catalyst can also be
disposed of as nonhazardous solid waste. Much of it does
nor fail the RCRA Subtitle C characteristic waste rests for
leachable constituents.
LAUX:
Our used ceramic support material is presently classified
as a Class II nonhazardous waste. It is dumped into an
on-site landfill. We are currently setting up to have it
recycled back to a cement manufacturer. We need to resolve
whether it needs to be regenerated first or not. We just need
to get a sample of it first and let him take a look at it.
ARMBRESTER:
We have conducted sampling and TCLP testing of the
catalyst and the support materials and have found that the
ceramic support materials have been classified as nonhaz-
ardous according co both the EPA and DOT Regulations,
even though the catalyst they were associated with has
been classified as hazardous. Therefore, we are recycling
the ceramic support material back to a company which
cleans and repackages the material for use in ocher units.
This has allowed us to substantially reduce the cost of new
support material for our reactors.
PORTER:
One of our refineries segregates support media from
spent catalyst and disposes of the support media in an
on-site landfill as a nonhazardous waste.
JOHN N. GLOVER (CRI-MET):
We recycle a large amount of spent hydrotreating cata-
lyst. When the catalyst comes in, the ceramic support is
mixed with the catalyst. If the catalyst is classified hazard-
ous, everything, support included, comes in as hazardous
waste. In the process, we take the support out of the
catalyst. We clean the support at our plant and then
transfer it over to a company called Crystaphase Products,
Inc. which recycles the support. So whether the support is
hazardous or nonhazardous, there is now a mechanism to
allow the support to be recycled and then sold back into
the industry.
One of the concerns that may arise in the future is, as
part of the Consent Decree with EDF, that hydrotreating
203
TOC/INDEX
catalysts that are being considered for hazardous waste
listing. There will be a Proposed Rulemaking on that in
August of 1995. If spent catalysts do become a listed
hazardous waste, then the support, regardless of the char-
acteristics, could also become hazardous due to the mix-
ture and derived from rule.
QUESTION 35.
How are people recycling and/or reusing spent solid
phosphoric acid catalyst?
DEATON:
Spent solid phosphoric acid catalyst can be used in
making fertilizer blends. I have recycled catalyst used in
polymerization units by this method. The catalyst cannot
contain benzene, so this method of recycle probably elimi-
nates catalysts used in the cumene process.
The spent catalyst must be dry because it is transported
in bulk to the blending facility by truck. The truck beds
are lined with plastic and a tarp is used to cover the catalyst.
Make sure you receive a certificate ofreclamation verifying
the final destination and end use of the spent catalyst.
This method of recycle was arranged through a broker,
Resource Chemical Company, in Louisville, Kentucky.
D’AURIA:
We estimate about 20% of our SPA catalyst customers
are disposing of their spent catalyst by blending it in with
fertilizers. Typically, it is blended in at about 10% of the
total fertilizer mix. The ability to reuse spent catalyst in
this way is limited by the contaminants, such as benzene,
that are on the catalyst.
Other recycling or reuse options for spent phosphoric
acid catalysts are limited both by the contaminant level,
as well as by the economics of recycle versus landfill.
QUESTION 36.
Have you seen environmental programs reduce ex-
penses and/or improve profitability through benefits
such as raw material recovery or reduced in-process-
ing losses? Do you see any otherproblems which have
not been addressed through current technologies?
BARLOW:
Our primary area of focus where we have seen environ-
mental programs reduce expenses or improve profitability
is around the desalter. The programs are focused on either
allowing the processing of greater levels of slop or reducing
or eliminating oil in the effluent brine. The elimination of
oil in the effluent brine has been tremendously successful
in terms of recovering profits related to that recovered oil,
and reducing the processing losses.
It has been our experience that improvements can be
accomplished through mechanical upgrades of the existing
204 Environmental Control & Energy Conservation
equipment, in addition to uses of different types of chemi-
cals which were discussed earlier in this Q&A meeting.
Modification of the programs around the desalter have
also been applied to minimize benzene concentration in
the brine effluent stream. This has allowed some refiners to
meet the new benzene NESHAP requirements with either
lower cost or substantially reduced capital requirements.
BOYCOTT:
We have reduced our off-site hazardous waste disposal
volumes by reclaiming oily sludges through our coker, via
the MOSC process licensed by Mobil. In 1994, we expect
to run more than 20,000 barrels of oily sludge through the
coker and recover the hydrocarbon constituents. In 1992,
off-site disposal of refinery hazardous waste was reduced
by more than 1,000 tons as a result of this process. In
addition to the obvious savings in avoided disposal costs
and our hydrocarbon recovery, the elimination of this
waste removes the liability associated with waste transport
and Superfund exposure.
FELTROP:
Although not always viewed from an environmental
standpoint, the desalters in your refinery literally form the
interface between operations and the environment. As
such, I wanted to briefly give you an idea of some of the
economics surrounding subpar desalter operation. We
have performed numerous analysis of this type to justify
desalter upgrades or new installations. From this data, one
can typify a 100M BPD crude unit can improve its
operation from 2 to l# salt per thousand barrels, 0.3% to
0.2% BS&W and 1% to 0.2% oil in effluent water and
improve profitability by a conservative $2,500 per day.
These values are certainly site specific but the point to
emphasis is that significant profit improvement is possible
with this performance improvement.
STEPHEN PAVEL (Coastal Catalyst Technology, Inc.):
The DEMET® process takes a portion of spent FCCU
catalyst and removes a portion of the metal contaminants,
enabling the refiner to recycle demetallized spent FCCU
catalyst back to the FCCU, thus reducing the solid waste
from the refinery.
DEMET processing capacity is available technology for
processing spent FCCU catalyst for others for the purpose
of recycle or treatment prior to disposal. DEMET process
service is currently provided at an off-site plant in Meraux,
LA. Through a three and a half year run from April, 1991,
to-date (i.e., through September, 1994) and continuing,
one refiner recycled over 8,700 tons of spent FCCU
catalyst. Adding the 8,700 tons to 1,300 tons previously
processed and recycled, that refinery has recycled over
10,000 tons of demetallized spent FCCU catalyst.
Although spent FCCU catalyst is not listed as a RCRA
waste, expenses are reduced and profitability improved
TOC/INDEX
through benefits of recovery of raw material, FCCU cata-
lyst, and reduced in-processing losses, FCCU catalyst
fines. Demetallized spent FCCU catalyst Toxicity Char-
acteristic Leaching Procedure leachate is below the Phase
II-Land Disposal Restrictions-Phase II Universal Treat-
ment Standards (non-wastewaters) for all 14 elements.
Although DEMET can be utilized to pretreat spent
FCCU catalyst prior to disposal, recycling demetallized
spent FCCU catalyst has more economic and environ-
mental advantages. An on-site DEMET unit was de-
scribed in a 1992 NPRA annual meeting presentation;
on-site recycling represents waste minimization by source
reduction.
Demetallized spent FCCU catalyst from an off-site
DEMET has reduced the requirements for fresh catalyst
additions and associated costs. FCCU catalyst losses have
been reduced commensurate with the reduction of fresh
catalyst additions. Spent FCCU catalyst disposal costs
have been reduced commensurate with recycling of de-
metallized catalyst. DEMET processing has removed con-
taminants known to be detrimental to product
conversion, high value product selectivities, hydrothermal
stability of the catalyst, and mechanical performance of
the FCCU. Fresh FCCU catalyst additions were reduced
from 15 to under 6 tons a day by recycling about 8.5 tons
per day; this reduction increased the average age of the
circulating FCCU catalyst from 30 days to over 80 days
without deterioration of the yield performance of the unit.
With DEMET capacity sized to reduce metals levels on
circulating catalyst, yields could be improved due to lower
metals on circulating catalyst. Over 10,000 tons of DE-
MET processing experience has shown there are substan-
tial benefits provided by solid waste reduction through
demetallizing and recycling spent FCCU catalyst. For
further information, several NPRA papers have been pre-
sented on off-site and on-site demetallization.
EARL ZICKEFOOSE (Scaltech, Inc.):
We have worked with many refineries in the Gulf Coast
area on recycling their Kand F waste both to cement kilns.
This technology is usually 30% to 60% less expensive than
incineration, and allows for recycling of the resource. This
technology especially lends itself to the processing of the
emulsions found in DAF, DNF, and MLE and the oily
tank bottoms and API bottoms.
QUESTION 37.
How are refiners handling oily Sludges? We are par-
ticularly interested in API separators, DAF units and
tan& bottoms.
TREESE:
Unocal has handled oily sludges in several ways, mostly
depending on whether the refinery is equipped with a
coker. For refineries with coker units, sludges are usually
1994 NPRA Q&A Session on Refining and Petrochemical Technology
injected into the coker for processing. For refineries with-
out a coker unit, sludges can be disposed of as-is, filter
pressed, or centrifuged. The resulting cake from either
filter pressing or centrifuging is disposed of by incineration
or landfill, depending on the hazardous characteristics of
the cake.
We have carried out filter pressings at 200 psi and
150°F. The filter cloths are coated with a filter aid to allow
ease of coke removal. The coke buildup can be sub-
sequently dried through a thermal dryer to reduce water
content, and the dried cake then disposed of by incinera-
tion or landfill, depending on the characteristics.
Centrifuging is ideal for highly emulsified sludges. The
resulting cake has a higher water content than filter press-
ing. The centrifuged cake runs 45% to 60% water versus
15% to 20% for filter pressing. Although the cake can be
dried using a thermal dryer, it still seems to end up with
more water than filter pressing.
Sludges from API separators and DAF units are RCRA-
listed hazardous wastes, and must be disposed of by incin-
eration or other approved methods if the Btu and mercury
contents are less than 5,000 Btu and greater than 100
ppm, respectively. If the cake Btu value is greater than
5,000 and mercury content is less than 100 ppm, the
material can be disposed of as fuel for cement kilns, as was
mentioned previously.
Tank bottom sludges are sampled to determine whether
the solids are hazardous waste. They can be disposed of
through landfill or incineration, depending on the char-
acteristics of the cake.
BARLOW:
I do not have much more to add on what to do with the
sludges. However, I would like to say we are aware that the
PERF Group has been looking at several technologies that
would enhance the oil, water and solids separation. We
have been exposed to technology that is being evaluated by
Unipure Corporation. It seems to show some promise.
QUESTION 36.
Can anyone provide an update on performance of
thermal desorption systems to process solid waste?
CUNEO:
There are two basic systems available for thermal
desorption. One is direct fired and the other is indirect
heated.
RCRA hazardous wastes are only processed in indirect
systems which recover the desorbed hydrocarbons. These
systems enjoy exemptions from RCRA permitting by
being recovery units. Direct fired systems cannot get these
exemptions because the desorbed products are burned and
are then considered to be incinerators. So for non-RCRA
wastes such as hydrocarbon contaminated soils, the direct
fired units can be used.
205
TOC/INDEX
There are numerous types of designs of both units in
the marketplace, some of them more successful than oth-
ers, the key factor being equipment reliability. Many of
these units are also designed to be mobile, so they can
move from one location to another, but often the mobili-
zation and demobilization costs are significant, so for
small jobs it may be more economical to transport the
material to the unit.
Direct fired units have to compete with landfill, bio-
logical, and in situ options.
ANAND KUMAR (Indian Oil Corporation Limited):
I would like to know if the panel has any experience of
using polymers or any other chemical for removal of oil
from sludge-particularly the crude oil sludge.
BARLOW:
We have used polymers and various other different
types ofchemistries to aid in the separation of oil and water
in the sludge. We also use surface-active chemistries to
condition the oil removal off the solid particles. In some
of the new processes being investigated by PERF, chemi-
cals are used to assist in these processes and in the removal
separation process.
DEATON:
On crude oil tank bottoms, you can use a cutter stock,
such as light cycle oil, heat it up to about 20°F below the
flash point of the light cycle oil, dissolve the sludge with
the hot cutter stock, and then use a centrifuging process
co separate water and solids. But oftentimes in crude tank
bottoms, there is a crystalline, wax-like material, so some-
times you have to use a wax inhibitor chemical once the
wax is dissolved so that you prevent the recrystallization
of the wax.
ANAND KUMAR (Indian Oil Corporation Limited):
In fact, we have been using this method of deoiling the
crude oil tank sludge with hot gas oil for a number of years.
Gas oil is circulated in the tank at 60° C plus. Thereafter,
it is transferred co another crude oil tank, where more fresh
crude oil is received and reprocessed in the crude distilla-
tion unit.
For reducing the deposits of sludge in the tank, what
type of mixers, tank mixers, are you using in the crude
tanks?
DEATON:
In our crude tanks, we have circulating pumps with jet
nozzles on them that return back to the tanks to keep the
tank circulated. In another plant that I worked in, we
actually had propeller-type mixers on the tanks. And in a
third refinery that I worked in, we also had propeller-type
mixers on the crude tanks.
206 Environmental Control & Energy Conservation
ANAND KUMAR (Indian Oil Corporation Limited):
Which one of the two have you found better?
DEATON:
Well, I personally prefer the one with the nozzles be-
cause if you have ever had a crude tank that has a mixer
on it and it develops a seal leak on the mixer and you have
to take the crude tank out ofservice, you would soon prefer
the pump type with the jet nozzle.
C. Energy Conservation
Process Heaters
QUESTION 39.
What has been the industry’s experience with CO trim
control for process heaters and boilers? Will future
environmental regulations restrict its use?
PORTER:
We use Chevron’s patented Automatic Combustion
exclusively as a CO trim control for process heaters. We
have had good experience with it at Pascagoula and other
locations. We have not implemented ACC on boilers.
We currently limit CO levels in most of our process
heaters co 150 ppm. If future environmental regulations
are passed mandating lower CO emissions, then the CO
constraint will be reduced accordingly.
RONALD BREDEHOFT (Kinetics Technology International Corp.):
We install a lot of automatic combustion controls in
the furnaces we build. We can design the control system
co operate with or without CO control. If you are taking
your oxygen sample from the stack, you are measuring the
flue gas and oxygen leakage into the furnace. With this
configuration you may want to use CO control.
Exchangers
QUESTION 40.
What is the preferred method for in situ heat ex-
changer Cleaning?
TREESE:
As we understand the question here, I think the pre-
ferred method for in situ heat exchanger cleaning in the
Unocal refineries is hydroblasting. Obviously, it is not
done on-line. It is done in place, but it is not on-line.
Hydroblascing requires a shutdown.
We have done some on-line cleaning of surface con-
denser tubes using plastic spheres, similar to whiffle balls,
or little plastic brushes, but I do not really have any details
on the effectiveness. I have heard it worked okay, but I
TOC/INDEX
know we continue to find a few of the little whiffle balls
here and there for a long time afterwards. It is hard to
contain them.
PORTER:
I am not sure what is meant by in situ. We have
successfully on-lined cleaned the water side of some crude
unit overhead condensers. The exchangers were back-
flushed for 1 hour with a circulating inhibited acid solu-
tion.
BOYCOTT:
I, as well, was not sure of the intent of the question.
When an exchanger is out ofservice and to be cleaned with
its bundle in place, we lance the tubes with high pressure
water wash equipment.
For on-line cleaning of cooling water exchangers we
have developed a procedure that we term a “salt blast”. The
idea behind this method is that rock salt will act as an
abrasive to help remove dirt/scale/etc. The salt is water
soluble and can be back-flushed onto the pad. The proce-
dure is as follows:
A fire hose connection is located on the cooling
water outlet piping, upstream of the block valve. A
standard backflush connection is located between
the inlet block valve and the exchanger.
A fire hose is filled with coarse rock salt. The hose is
connected to the cooling water outlet and to a fire
hydrant.
The exchanger is blocked in on supply and return,
the backflush valves are opened, and the salt is flushed
through the bundle and to the pad with firewater.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
This procedure will remove a significant amount of
debris from an exchanger even after two or three standard
backflushes.
B. B. PATIL (Hindustan Petroleum Corporation Ltd.):
In crude distillation units we go further and water wash
exchangers in the crude. The water is sent upstream of the
desalter. This can be done when the crude distillation unit
is running under turndown ratio up to 50%. We realize
some benefit from this.
KENNETH D. PETERS (UOP):
We are aware of two reforming units where the com-
bined feed exchangers have been fouled with a material
that was primarily PNA’s (polynuclear aromatics). In both
cases, the refiners successfully cleaned the exchangers in
place, using a closed-loop reformate circulation system.
Each unit had to be shutdown, and the temporary refor-
mate recirculation pump and piping was installed. This
procedure was reported to have taken about two days for
the fouling problem to be cleared up.
P. S. RAO (Indian Oil Corporation Limited):
What experience is there with on-line cleaning of con-
vection tubes in the furnace?
CUNEO:
We routinely employ conventional soot blowing and
occasionally do water washing ofconvection section tubes
on-line.
207
TOC/INDEX

Stephen P. Frayne Nalco Chemical Company

MEMORANDUM A. Bruce Gilliam
Tony S. Go
Betz Process Chemicals, Inc.
Amoco Oil Company
Martin P Grosboll Lyondell Petrochemical Company
The comments contained in the transcript for the 1994 Dan Hartley D. H. Associates
NPRA Question and Answer Session on Refining and Gerald D. Henderson Ashland Petroleum Company
Petrochemical Technology, which was held October 12- William E. Heck Energy BioSystems Corporation
Peter T. Jackson UOP
14, in Washington, DC, have been edited by the panelists Mark R. Keim Costal Corporation
and conferees who commented during the Session. Patrick Laabs Star Enterprise
The Question and Answer Session on Refining and Patrick D. Lavergne Lyondell Petrochemical Company
Charles F. LeRoy Champlin Refining and Chemicals Co.
Petrochemical Technology is under the cognizance of the
Warren S. Letzsch Stone & Webster Engineering Corp.
NPRA Manufacturing Committee listed as follows: L. E. Lew Phillips Petroleum Company
Glenn C. Liolios STRATCO, INC.
NPRA MANUFACTURING COMMITTEE Charles S. McCoy McCoy Consultants, Inc.
Jeff K. Utley, Chairman Flying J Incorporated Christina McDowell Pacific Refining Company
Paul D. Fritz, Vice Chairman Pennzoil Products Company William D. Meyer Amoco Oil Company
Allen M. Burns Ethyl Corporation David R. Morris Chevron Research and Technology Co.
Alan J. Cabodi U. S. Oil & Refining Co. Brian M. Moyse Haldor Topsoe
Robert H. Douglass Farmland Industries, Inc. Kenneth A. Peccatiello Grace Davison
John M. Ehlen Koch Refining Company Roger D. Pelham Profimatics. Inc.
Fred D. Foster CITGO Petroleum Corporation Kevin R. Proops Conoco Inc.
R. J. Frazier Union Texas Petrochemicals J. B. Roddey Roddey Engineering Services
James A. Gesick Murphy Oil USA, Inc. The M. W. Kellogg Company
H. David Sloan
Ronnie D. Jackson Lion Oil Company
G. Andrew Smith INTERCAT, Inc.
A. P. Johnson Mobil Oil Corporation
Charles W. Stanger Akzo Catalysts
R. E. Kerns Diamond Shamrock, Inc.
Gary A. Stephens IFP Enterprises Texas, Inc.
Virgil R. Langford Navajo Refining Company
Phibro Energy USA, Inc. Arthur J. Suchanek Criterion Catalyst Company L.P.
Ronald W. Lewis
J. J. Lipinski Coastal Refining & Marketing Inc. Delbert F. Tolen Rocky Mountain Salvage & Equipment Co.
John D. Mackey Ultramar Inc. Terrel D. Williams Kerr-McGee Refining Corporation
James H. McCov Total Petroleum, Inc. A. Witoshkin Engelhard Corporation - S.C. Div.
Charles B. Miller Ashland Petroleum Company
William G. Miller MAPCO PETROLEUM, Inc. Attendance at the 1994 Q&A Session totaled 1,273
David R. Morris Chevron Research and Technology Co. conferees representing the petroleum refining and petro-
Jean E. Neuberger Hunt Refining Company
chemical industries, supply and service organizations, gov-
Ronald E. Pletcher CENEX
Allen C. Randle Unocal Corporation ernment and members of the press who came from 36
Kenneth Roane National Cooperative Refinery Assn. states, the District of Columbia and Puerto Rico. One
J. A. Ross Phillips Petroleum Co. hundred and seventy seven conferees came from the fol-
Donald R. Unruh Conoco Inc.
David L. Uzzell Tosco Refining Company lowing 33 countries: Abu Dhabi, Argentina, Australia,
J. E. Warn Kerr-McGee Refining Corporation Belgium, Brazil, Canada, Chile, Columbia, Denmark,
John P. Yoars Lyondell-CITGO Refining Company Ltd France, Finland, Germany, Hungary, India, Italy, Japan,
Maurice H. McBride National Petroleum Refiners Association
Terrence S. Higgins National Petroleum Refiners Association Jordan, Korea, Kuwait, Malaysia, Mexico, The Nether-
lands, Netherlands Antilles, Norway, Peru, Philippines,
Each year the Manufacturing Committee selects the Russia, Saudi Arabia, Spain, South Africa, UAE, United
panelists and appoints a Screening Committee to select the Kingdom, and Venezuela.
questions submitted by individuals and companies regard- The 13 member panel was joined by 163 conferees in
less of membership in the Association. The Screening commenting on the 234 questions during the 2 1/2 day
Committee consolidates questions, eliminates duplicates exchange of technical information on modern petroleum
and arranges the questions in the correct category and refining and petrochemical technology. The following table
sequence so that the maximum number of questions can is comparison of the attendance for the past five years:
be considered in the 2 1/2 days of sessions. This year, from
Phila- Wash-
some 571 questions submitted, 234 questions were selected delphia Denver Anaheim Dallas ington
by the panelists and the following Screening Committee 1990 1991 1992 1993 1994
Members:
No. of Member Companies 219 220 185 164 180
SCREENING COMMllTEE No. of Member Locations 347 387 465 481 410
Peter G. Andrews Conoco Inc.(retired) Member Conferees 1,125 1,226 1,245 1,191 1,158
David B. Bartholic BAR-CO Processes Joint Venture Others 152 163 127 112 115
Mike Bober Mobil Research & Development Corp. TOTAL 1,277 1,389 1,372 1,303 1,273
Carlos A. Cabrera UOP No. of Conferees Commenting 165 206 172 169 176
Robert E. Davis R. E. Davis Chemical Corporation
Francis N. Dawson, Jr. California Synfuels Research Corp.
Edward G. Ellis Exxon Research & Engineering Co. Terrence S. Higgins
Paul Fernside Nalco Chemical Company Technical Director

208 Memorandum
TOC/INDEX

PANEL BIOGRAPHIES

MICHAEL S. ARMBRESTER — Assistant Refinery Superintendent, Ashland Petroleum’s Refin-

ing and Petrochemical Complex, Catlettsburg, Kentucky He is responsible for managing all of the
operations and technical functions within the refinery. He began his career with Ashland as a
technical services engineer, and has since served in a variety ofsupervisory and managerial positions
within the refinery Operations Department. He has also served as a presenter at several FCC
technology seminars in the U.S. and Europe. He holds a Bachelor of Science degree in Chemical
Engineering from Purdue University.

R. C. “BUZZ” BARLOW — Vice President of Marketing services, Betz Process Chemicals, Inc..
The Woodlands, Texas. He began his career with Betz in 1981 after spending six years in the HPI
industry in process engineering and operations. Throughout his Betz career, he has served in several
product management and technical service positions. He holds Bachelor of Science degrees in
Biochemistry and Chemical Engineering and a Master of Science degree in Chemical Engineering
from Rice University. He is a registered Professional Engineer in the State of Texas.

WILLIAM A. BOYCOTT — Technical Manager, Frontier Refining Inc., Cheyenne, Wyoming. In

his current position, he is responsible for directing the Process, Inspection, Design, and Environ-
mental functions at the refinery. Bill joined Frontier in 1989 and has held various Operations and
Technical positions in the organization. He began his career as a Process Engineer at Irving Oil
Ltd. in Saint John, New Brunswick, Canada. He holds a Bachelor of Science degree in Chemical
Engineering from University of New Brunswick and is a registered Professional Engineer in the
Province of New Brunswick.

PAUL L. CUNEO — Director Oil Products Research Development & Technology, Shell Develop-
ment Company, Westhollow Research Center, Houston, Texas. He is responsible for managing
Shell’s research and development for both refining processes and oil products and for providing
technical support to operating refineries. He has been employed by Shell for 2.5 years in 4 refineries
and in the corporate office doing facilities planning for refineries prior to assuming his current
position. He holds a Bachelor of science degree in Chemical Engineering from the Colorado School
of Mines.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 209

TOC/INDEX

JAMES H. D’AURIA — Director of Marketing Services, Licensing Department, UOP, Des Plaines,
Illinois. He joined UOP in 1969 after receiving a Bachelor of Science degree in Chemical
Engineering from the University of Notre Dame. His prior positions with UOP include: Pilot
Plant Development Engineer, Technical Services Field Representative, Process Development
Manager of Platforming and Hydrocracking, Director of Development Services, Director of
Process Development in Research and Development. He assumed his present position in March,
1993. He holds a Bachelor of science degree in Chemical Engineering from the University of Notre
Dame.

JOHN T. DEATON — Operations Manager, Clark Refining & Marketing Refinery, Blue Island,
Illinois. Prior to joining Clark, he was operations manager at The Coastal Corporation’s refinery at
Wichita, Kansas. He also held positions as projects manager, area operations supervisor, technical
assistant to the refinery manager, shift supervisor, and technical service engineer all at Ashland Oil
Company’s refinery in Catlettsburg, Kentucky. He began his refinery career in 1974 as a process
engineer at Shell’s Deer Park, Texas, Refinery. He received a Bachelor of science degree in Chemistry
from College of William and Mary and a Master of Science degree in Chemical Engineering from
the University of Maryland.

B. W. FELTROP — Director of Industrial Technology, Petrolite Corporation, Industrial Chemicals

Division, St. Louis, Missouri. Prior to 1992, he was with Ashland Oil Company for 14 years.
During those years, he served in various capacities from technical services engineer through
operations manager at the Catlettsburg Refinery. His experiences include FCC operations, refinery
LP modeling, crude oil evaluation and analysis, environmental and safety expertise and overall
refinery operations/management experience at a 220,000 bbl/day refinery. He has a Bachelor of
Science degree in Chemical Engineering from the University of Kentucky and a Master of Business
degree Administration from Morehead State University.

210 Panel Biographies

TOC/INDEX

MICHAEL A. LAUX — Assistant Refinery Manager, Diamond Shamrock, Three Rivers , Texas.
He is responsible for all of the operations and maintenance functions and the laboratory for this
75,000 bbl/day cracking refinery. He started his career in 1975 working for Chevron at their El
Segundo, California refinery as a design engineer. He held several positions in design and process
engineering and operations before transferring to Chevron’s Southern California Pipeline Division
as the supervisor in charge ofoperations and maintenance. He joined Champlin at their Wilming-
ton, California refinery in 1985 and moved to their Corpus Christi, Texas refinery in 1989. He
again held various positions in process engineering and operations. He joined Diamond Shamrock
in 1991. He earned his Bachelor of Science degree in Chemical Engineering from the Pennsylvania
State University.

JOSEPH B. MCLEAN — Executive Technology Specialist, Engelhard Corporation, Petroleum

Catalyst Group, Houston, Texas. His responsibilities include FCC catalyst technical service and
sales support, performance projections, and development and field evaluation of new products.
He has held this position since 1991, following four years with Engelhard Research and Develop-
ment in FCC catalyst evaluation. Prior to joining Engelhard in 1987, he held positions in various
aspects of process research and development and engineering with ARCO, Research-Cottrell, and
Hydrocarbon Research, Inc. He holds a Bachelor of Science degree in Chemical Engineering from
Princeton University and a Master of Science degree in Chemical Engineering from the University
of California at Berkeley. He holds six patents and has authored numerous publications related to
fluid catalytic cracking, residual oil processing, and synthetic fuels production.

STEPHEN G. MENEGAZ — Business Development Manager, Black & Veatch Pritchard, Hous-
ton, Texas. He started his career with ARCO Product Company as a process engineer at the Lyondell
Olefins Complex, then worked seven years with the M.W. Kellogg Company in the design and
start-up ofethylene, LNG and FCC units. Just before coming to Pritchard, he was with Engelhard
Corporation in FCC technical service and sales. He received his Bachelor of Science degree in
Chemical Engineering from University of Texas at Austin.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 211

TOC/INDEX

WILLIAM J. PORTER — Manager - Operations, Chevron U.S.A. Products Company Refinery,

Pascagoula, Mississippi. He joined Chevron in 1968 as a research engineer. since then, he has had
a variety of operations and technical assignments at Chevron refineries in Richmond and El
Segundo, California. He also was the Manufacturing Manager - Aromatics Division for Chevron
Chemical Company in Houston, Texas. he received a Bachelor of Science degree in Chemical
Engineering from the University of California at Davis. In 1989, he was the first recipient of the
UC Davis College of Engineering Distinguished Alumni Award.

SCOTT M. SAYLES — Technical Manager for Sinclair Oil Corporation, Tulsa Refinery, Tulsa,
Oklahoma. His prior assignment was as the Assistant Supervisor of Operations at Star Enterprise,
Convent, Louisiana, and he also held the position of Operating Supervisor at Star Enterprise. He
was Senior Project Engineer at Texaco, Convent, Louisiana, and Project Engineer at Texaco
Research in Port Arthur, Texas. He holds a Bachelor of Science degree in Chemical Engineering
from Michigan Technological University and a Master of Science degree in Chemical Engineering
from Lamar University. He also holds fifteen U.S. patents.

STEVEN A. TREESE — Consulting Process Engineer at Unocal’s Los Angeles Refinery, Carson
Plant, Carson, California. In over twenty years with Unocal, he has seen assignments in process
engineering, operations, design, and research, as well as plant construction. His experience includes
project management, hydrocracking, hydrotreating, synthetic fuel operations, petrochemicals,
geothermal, and power generation. He holds a Bachelor of Science degree in Chemical Engineering
from Washington State University. He is a Registered Professional Engineer in California, Colo-
rado, Oregon, and Washington, member of the Chemical Engineering Industry Advisory Council
for California State Polytechnic University at Pomona, and Cochair for an AIChE One-Day
Technical Meeting.

212 Panel Biographies

TOC/INDEX
Abrahams, Kenneth, 111, 142
Adair, Scott, 96
Al-Shahrani, Mohammad, 30-31,
35, 47, 55, 89, 94, 96-98, 104,
128. 164, 167, 178, 184, 188-
189
Allsmiller, Robert, 170
Anderson, Gary, 51
Andrews, Peter G., 69, 72
Archbold, Damian, 150
Armbrester, Michael S., 9, 11-12,
15-16, 18, 21-22, 27, 29-33, 38-
41, 43, 47, 52, 54-56, 58-59, 62,
65, 69-70, 74, 77-79, 81, 83,
93-98, 101-102, 106-109, 113-
115, 118-119, 129, 144-145,
147-148, 152-153, 160, 164-
165, 168, 170, 172, 174-175,
177, 179-180, 184, 186, 191,
193-195, 197-198, 201-203
Armstrong, Timothy, 191, 194
Asim, Mehmet, l00-101, 107, 117,
128
Bacon, Thomas R., 176, 186
Badruddin, Pervaiz, 136
Ball, Thomas H., 180
Barlow, R. C., 8-10, 14-16, 19-20,
23-24, 27, 33-34, 37, 42-43, 46,
52, 57-58, 60, 62, 76, 79-80,
87-89, 94, 101-102, 104, 113,
136, 141, 143, 156, 167, 176,
178-179, 182-183, 185, 199-
201, 204-206
Barry, James, 118
Berlyant, Michael, 142, 190
Binford, Mark, 20
Boardman, Shaun, 131
Bober, Michael Jr., 70
Bothe, Michael, 121
Bowles, Shirley, 201
Boycott, William A., 10, 15, 23, 25,
27-31, 36, 43-44, 49, 51, 53, 66,
71, 83, 85-87, 89, 93-94, 98,
101-105, 109, 111-114, 118-
119, 123, 125, 128, 133, 147,
149-151, 156, 160, 163-164,
171-172, 182, 184, 186-188,
191-192, 195-196, 200, 203-
204, 207
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Index
Bredehoft, Ronald, 94, 96, 206
Brown, George, 181, 193
Brunson, Ross, 93
Bucko, Michael, 157
Burns, David, 180
Campbell, Bruce A., 34
Cavanaugh, Curt, 31
Chlapik, Kenneth, 92-93
Citarella, Vicente A., 82
Clancy, Thomas, 119, 185
Cromarty, Ben, 97
Cuneo, Paul, 8, 14, 20-21, 23, 27-
28, 31, 33, 35-37, 39-41, 47,
51-53, 55, 66, 69-70, 72, 78, 80,
84, 86-90, 92, 96, 98, 101, 106,
108, 111-112, 114-115, 118,
123-124, 128, 130, 132, 134-
138, 141, 143, 147, 150, 153,
156, 159, 163-167, 174, 181-
182, 184, 186, 188-189, 192,
194-195, 197-198, 205,207
D’Auria, James H., 12-13, 25, 28-
29, 32-37, 41, 44, 46, 50, 52-53,
59, 65-66, 68, 70-71, 78, 81-83,
86, 88, 90-91, 95, 98-101, 111,
119-121, 124, 126, 129-132,
134-138, 145-153, 155, 158-
167, 169-172, 174-175, 202,
204
Daughtry, James, 196
Davis, Kent, 63
Davis, Robert, 142
Davis, Ruth, 97
Davis, H. Thomas, 145, 181
Dean, John W., 113, 115-l16, 160,
181
Deaton, John, 10, 13, 19-20, 24,
30-31, 35, 40-41, 46, 50-51, 53,
59, 65, 72, 74, 80, 84-90, 96-97,
99, 103, 112, 114, 116, 118-
119, 121, 124, 131-132, 134,
136-138, 140, 146-147, 153,
157, 159, 161, 164, 166, 168-
170, 172, 178, 180, 182, 184-
186, 188-189, 191, 194, 196-
198, 204, 206
Dergregorian, Heros, 16, 60, 65,
70, 78, 104-106, 126, 141-142,
152, 155, 157-158, 164, 167
Desai, Pankaj H., 129
Dharia, Dilip, 83
Dirkse, Hans, 186
Dodds, Kevin, 116, 123
Doran, Mark, 151, 157, 170
Dougan, Timothy, 74
Dwyer, David, 178
Edelman, Allen M., 90
Edgar, M. Dean, 113, 115-116,
160
Elvin, Frank J., 50, 63
Evans, Douglas, 144, 150
Fearnside, Paul, 14, 25, 70, 157
Feinberg, Arnold, 110
Feltrop, B. W., 8-9, 11, 14-15, 17-
18, 20, 23-24, 26-27, 33-34, 42-
45, 52, 56, 58, 75, 79-80, 89,
103-104, 142, 146, 156, 176-
177, 182, 184, 197, 199, 204
Fischer, Steven M., 78, 180
Funk, Ronald, 125
Furfaro, Angelo, 167
Fussell, Becky, 13
Gentry, Arthur K., 132
George, Safa, 107, 117, 129
Geren, Philip, 148
Gerritsen, Leendert A., 129
Gialella, Richard, 115, 155, 173
Gibbons, Bill, 185
Glendinning, Robert, 68, 71
Glover, John, 203
Grandle, Denny, 12, 16, 42
Grieb, Benjamin, 139
Gruia, Adrian, 105, 121
Guglietta, Glenn, 59
Haley, John, 84
Hamilton, Gary, 107, 111, 114
Hartley, Dan, 29
Heckel, Timothy, 121
Higgins, Terrence S., 22, 50, 64,
144, 147, 173, 181, 185
Hlozek, Bob, 183
Hoiseth, Merlin, 118
Hull, Randall, 63, 189, 192
Humphries, Adrian, 74
Husted, Don, 38
213
TOC/INDEX
Intabi, Majed, 34, 131, 136, 166,
200
Jaffe, Jay, 128
Johnson, David, 47
Jones, Henry, 15, 94, 98
Kalota, Steven A., 67-68, 73
Kanniappan, Veerappa, 200
Keller, Ted, 13
Kellett, Thomas E, 173
Kelly, James, 15, 19, 104
Khouw, Frank, 77
Kilnet, Peter, 149
Kleinschrodt, Frank, 28-29, 31-32,
35, 37-38, 144
Kruse, Charles, 174
Kumar, Anand, 200, 206
Lacijan, Larry, 71
Lal, Ravi, 97
Lanning, Robert Allen, 189
Laux, Michael A., 12-13, 22, 24-
28, 32, 40, 52-53, 58, 60, 66, 69,
73, 76-78, 81, 84-85, 99-101,
103, 110, 114-115, 118, 124-
126, 131, 133, 136-137, 141-
142, 145-146, 148, 152, 156,
158-160, 162, 164, 167, 171,
173, 176-178, 184-185, 187-
188, 194, 197-198, 201-203
Lehan, Kathleen, 94
Lehr, James (day trip), 203
LeRoy, Charles, 39
Letzsch, Warren, 59, 61, 63
Lomax, Stanley, 147
Lord, Linda, 87, 89, 117, 182
Marrelli, Ronald, 78, 105, 152, 164
Mathur, S. N., 26, 182
Matos, Jose, 60
McCaffrey, David, 140
McCoy, Charles, 99, 102, 105, 109,
113-114, 116, 121, 124, 138,
165, 167, 172
McLean, Joseph, 23, 45, 49, 51,
53-57, 59, 6l-66, 68-71, 73, 76-
77, 82-83, 90, 95, 124-125, 134,
140, 148, 150-151, 154, 158-
162, 164, 172-173, 190
Meeker, Roon, 65
Mehrotra, Raghunath, 61, 113
Menegaz, Stephen G., 8, 13-14, 19,
23, 26, 44-45, 49, 51-55, 57, 62,
64-66, 69-74, 77, 81-83, 94,
102, 140-143, 145, 149, 151-
152, 159, 166, 170, 173-174,
176, 178-179, 183, 187-196
214
Mikkelsen, Peter, 153
Miller, Rik, 74, 82-83
Mitchell, John, 13
Morris, Lee W., 39, 72, 81
Morse, Robert, 107, 149
Murff, Stephen R., 124
Myers, Daniel N., 68, 80, 131
Nelsen, Dennis, 81
Nielsen, Anders, 92-93, 97, 100,
108, 117, 123-124, 128
Nocca, Jean-Luc, 140, 162
Oyekan, Soni, 150, 152
Parekh, Uday, 193
Patil, Bhagwan B., 77, 185, 200,
207
Pavel, Stephen K., 126,204
Pearce, John, 61
Perkin, J. Douglas, 157
Peters, Kenneth D., 27, 42, 46,
103-106, 113, 157, 162, 164
165,207
Porter, William J., 9, 12, 14-16, 19,
21, 23-24, 26, 28, 30, 32, 34-36,
39-42, 46, 49-51, 53, 56-58, 64,
70, 73, 75, 77, 79, 84, 86-87,
89-90, 92-93, 96, 99-100, 107,
109, 111-119, 122-123, 128,
130, 132-134, 137-138, 141,
143-145, 148-152, 154, 156,
158, 162-164, 166-167, 171,
174-175, 177, 179, 183, 187-
191, 193, 195-197, 201-203,
206-207
Pratt, Roy E., 130
Puschinsky, Bob, 141
Quinn, George, 65
Rao, P.S., 207
Reverdy, Francois, 162
Roddey, Bob, 105, 112, 123, 133,
152, 160,163
Romero, Sim, 89
Ronnander, James C., 94, 196
Santos, Jessie, 179, 182
Sayles, Scott M., 9, 16, 24-25, 30,
32-35, 38-39, 4l-44, 50-51, 53-
55, 58, 62-65, 67-68, 70, 73, 75,
80, 84, 99, 104-105, 109, 111,
114-115, 118-121, 125, 131,
140-144, 149, 154-155, 157,
159-160, 163, 165, 167, 169-
170, 172, 182-184, 191-192,
195, 202-203
Scheirer, Glen E., 97
Scott, Bruce, 188, 190
Subject Index
Scruggs, Darrell, 42, 92, 98
Singer, Roger M., 174-175
Slade, Cornell, 152
Sloan, H. David, 61, 187
Sloley, Andrew W., 88
Smith, David L., 157, 174
Smith, G. Andrew, 60
Smith, George A., 116
Soni, Dahp, 69, 150, 152
Soria, John, 178, 180
Stelly, Timothy J., 139
Street, David, 179
Suchanek, Arthur, 34, 47, 101, 104,
108, 110-111, 113
Tolen, Delbert, 77
Torek, William, 151, 178
Treese, Steven A., 9, 12, 16, 24, 28,
30-33, 36, 39, 41-44, 47, 61, 71,
84-87, 89, 95-96, 98-100, 102,
107-112, 117, 119-125, 128,
131-139, 144, 150, 155-156,
163, 185, 187-190, 193-194,
196, 198-l99, 205-206
Trevino, Cesar, 128
Turpin, Lee E., 35-36, 40, 161, 188
Vadekar, MO, 180, 183, 185
Valentine, Julie, 31
Vance, Paul W., 101, 110, 112, 121,
129, 139
Vasquez, David, 181
Waterfield, David N., 155, 163
Wells, Jan W., 50, 64
Williams, Stephen, 159
Wilson, Troy, 86, 192
Wizig, Herbert W., 74, 182, 186,
203
Wood, David, 37, 169
Zickefoose, Earl, 91, 205
TOC/INDEX

Index to Topics Discussed at

1994
NPRA
Q & A Sessions on Technology

The next several pages comprise an index of the tran-
script of the 1994 NPRA question-and-answer sessions on
refining and petrochemical technology.
Availability. Readers who do not have access to this
volume may obtain it by writing: NPRA, Suite 1000,
1899 L Street, N.W., Washington, DC 20036, Attention:
Publications. Price is $25.00 plus postage.
Using the Index. The index follows a hierarchal format,
which is broken down into:
1. Subjects
2. Subheadings
3. Words
Two general guides should be kept in mind by the
searcher for making the index easier to use:
The index is oriented primarily (but not entirely)
toward specific refining processes. Under each proc-
ess the entries tend to be clumped into such areas as
“charge stocks, ” “equipment” and “operation.”
Equipment which is not uniquely associated with a
specific process is entered by name under the major
subject heading “equipment.” This major subject
heading also has some sub-headings such as “main-
tenance” and “standby.”
Subjects. As noted, included in the broad subject cate-
gory are all major processing activities, such as “cracking”
and “reforming.” With a question involving hydrocrack-
ing, for example, the searcher should skip the temptation
to go directly to the body of the index and try to find
“hydrocracking” in alphabetical order. “Hydrocracking”
is a subheading of “cracking,” which governs the alpha-
betical location of the material.
Four large all-purpose subjects are “additives,” “chemi-
cals” (which can cover feedstock materials, contaminants,
or reagents, etc.), “analysis” (testing and analytical meth-
ods), and “instrumentation” (metering, monitoring, and
control).
Subheadings. Only the broadest subjects have sub-
headings. They are given their governing subject headings
on the next page and are preceded there and in the body
of the index by a dash.
An example, “sulfur and mercaptans” is the subhead
under the subject “chemicals and chemical elements and
metals.”
Words. The words, which are the highest degree of
specificity before the actual information entry, are listed
alphabetically under the subjects and/or subheadings. For
example, “riser” is a word under the subheading “cat
cracking” which is under the subject heading “cracking.”
When the index user is at the word stage, it is advisable
that several “word” entries be scanned. For example, when
searching for information concerning a riser, the words
“cat” (catalyst) and “charge stock” may also, depending on
the nature of the information needed, deserve scrutiny. On
the other hand, the words “cat regeneration” and “pollu-
tion control,” also under the subheading “cat cracking”
can, with a high degree of confidence, be ruled out as
pointing to appropriate information.
The information entry associated with the words is, of
course, the final criterion for turning to the NPRA book.
The Entry. The word and entry describe as briefly as
possible the content of the information available.
Page. The right-hand column of the index gives the page
where the information described in the entry can be found.

1994 NPRA Q&A Session on Refining and Petrochemical Technology 215

TOC/INDEX

SUBJECT HEADINGS FOR INDEX

Additives Environmental Control

-Antifoam - See Also - Foaming Equipment
Alkylation -See Also - Entries Under Individual Processes
-HF Alkylation -Failure
-Sulfuric Acid Alkylation -Maintenance
Analysis (Testing & Analytical Methods) -Operation
Asphalt Etherification
Biological Treating & Microorganisms Fires
Blending Flow
Catalysts Foaming
-See Also - Specific Processes Fouling & Deposits
-Cobalt Moly -See Also - Entries Under Individual Processes
-Fines -See Also - Coking(Fouling)
-Nickel Moly Gasoline
-Passivators -See Also - Naphtha
-Platinum
Hydrogen
-Poisons & Poisoning
Hydrogen Production
Charge Stocks
Hydrotreating
-See Also - Name of Specific Process Using Stock
Instrumentation(Metering, Monitoring & Control)
-See Also - Naphtha or Oils
Chemicals & Chemical Elements & Metals Isomerization
-See Also - Catalysts Lube Oils (As Products)
-Fluorides Mathematical Models
-Sulfur & Mercaptans & Sulfur Compounds Naphtha
Coke (Coke Production) -See Also - Gasoline
-Delayed Coking Oils
-Fluid Coking -See Also - The Names of Specific Processes
Coking (Fouling) Olefins
Combustion Promoters Polymer Unit
-See Also - Cracking Refinery Operation
Computer Control Reforming
Contaminants Safety & Industrial Hygiene
Control Shutdown
Corrosion & Equipment Problems Sludge
Cracking Start-Up
-Cat Cracking-Fluid Cat Cracking (FCC)
Sulfur Plant
-Hydtocracking
Temperature
Crude Oil Processing
Training
Deasphalting
Diesel Oils - See - Oils Treating
Distillation -See Also - Hydrotreating
Employees Turnaround
Energy Recovery & Conservation Washing

216 Subject Index

TOC/INDEX

Index
1994 NPRA Q&A Session on Refining and Petrochemical Technology
ADDITIVES Hydrotreating Running with sweet naphtha 114-94
Diesel Lubricity 33-94 Hydrotreating For 300 psig unit treating kero./FCC naphtha 115-94
-ANTIFOAM Hydrotreating O2, silicon problems with cracked naphtha 116-94
Coker & HDS Experience 113-94 Hydrotreating Catalyst life for various resid objectives 116-94
Hydrotreating Silicon antifoams 113-94 Hydrotreating Passivation during unloading cuts costs 118-94
Hydrotreating Safety, not costs, criterium for technique 119-94
ALKYLATION Hydrotreating Presulfiding 119-94
-HF ALKYLATION Hydrotreating Support material hydrogenates olefins 123-94
Acid solubles Role of MTBE plant 144-94 Hydrotreating Nickel carbonyl from spent catalyst 123-94
Acid solubles Dimethyl ether is culprit 144-94 Hydrotreating Danger of Cd when purging spent catalyst 123-94
Acid solubles Feed dryer absorb oxygenates 145-94 Hydrotreating Large exotherms with presulfided catalysts 124-94
Acid solubles Oxygenate analyzer on mixed C4 stream 145-94 Hydrotreating Presulfided in bulk 125-94
Acid solubles Water wash removes the DME precursor 145-94 Hydrotreating Presulfided saves time 125-94
Aerosol Additive to suppress 146-94 Hydrotreating Keep presulfided dry and inert 125-94
Emissions Water curtain 147-94 Hydrotreating “Cradle to grave” management has drawbacks 125-94
Feed Reduce acid solubles due to oxygenate process 144-94 Hydrotreating Regenerated catalyst is used 128-94
HF leak Rapid acid dump system 148-94 Hydrotreating Maximizing SiO2 absorption 128-94
HF leaks Various detectors in use 147-94 Management Refiner has ultimate responsibility 128-94
Maintenance Clean iron fluoride from condenser each year 146-94 Methanol Copper promoted makes more 93-94
Maintenance Citric acid vs HCI for cleaning 146-94 Methanol Copper promoted does not make more 93-94
Plus Iron fluoride causes 145-94 Mild HDC For production of low sulfur diesel 129-94
Process Status of solid catalysts 148-94 MTBE Losses from reactor 175-94
Process Solid cat. ready by end of 1995 148-94 Ni passivation Technologies for Ni 57-94
-SULFURIC ACID ALKYL4TION Ni passivation Catalyst vs. passivator 57-94
Aerosols Limited, but safety & enviro. threat 140-94 No 1 emissions Good experience 95-94
Contactor Plugging traced to fresh acid 142-94 Passivation Traps cut need for Sb 59-94
Control Multivariant scheme a success 143-94 Passivators Tin
_... 56-94
Corrosion Deisobutanizer tower 142-94 Polymerization Dry drilling tubes removes cat. 169-94
Corrosion Effuent treaters and DIB corrosion 143-94 Polymerization Problems in chamber reactor 169-94
Corrosion pH control & amine for DIB protection 143-94 Polymerization Charcoal minimizes pressure drop 169-94
Feed How much H2 through C2H6 tolerable 140-94 Polymerization Various catalysts 170-94
Feed Ethylene major contaminant 140-94 Reforming For H2 from butane 92-94
Feed Don’t vent IC4 with light ends 140-94 Reforming SMR vs. SNR cats for H2 from C4 92-94
Feed Low IC4/olefins ratio 141-94 Reforming Alkali promoted for H2 from C4 92-94
Feed IC4/olefins than six incurs penalties 141-94 Reforming Pt/Re cats. require high S removal from feed 151-94
Feed IC4/olefin ratio seven desirable 141-94 Reforming Sulfur guard enhances cat. performance 152-94
Feed RTG prompts new look at IC4/olefins ratio 141-94 Reforming High alumina, low Pt CCR cat. 158-94
Feed NC4 like “deadwood ” in feed 142-94 Reforming CCR cats: E-1000, CR-201, R-130 series 158-94
Feed 4.5/l lower limit IC4/olefin ratio 142-94 Reforming Iron sulfide on cat. 159-94
H2SO4 release Safety & enviro. concern 140-94 Reforming Rotate cat. to combat iron sulfide 159-94
H2SO4 release Dealing with contaminated soils 140-94 Reforming Pt loss; mechanisms 160-94
Hydrogenation Strippers or separators 140-94 Reforming Pt loss from fines, high temp. 160-94
Process H4O in acid recycle cuts octane 141-94 Reforming Fines major reason for Pt loss 160-94
Spent acid Preventing explosive mix in tanks 144-94 Reforming Pt loss bookkeeping 160-94
Spent acid Tank design or safety 144-94 SiO2 absorp. Can go up to 25 wt% in spent catalyst 128-94
Tail-gas unit TiO2 meets tail gas requirements 190-94
ANALYSIS (TESTING &ANALYTICAL METHODS) Va passivation Technologies for Va 56-94
Aromatics Chromatography for aromatics in diesel 107-94 Va passivation Tin, traps, in dual single particle systems 56-94
Diesel fuel Blotter ratings indicate stability 110-94 Va passivation High matrix, alumina works 56-94
Diesel fuel Dye complicates stability test 111-94 Va passivation Separate trap preferred 56-94
Gasoline On-line analyzers 28-94 Va passivation Tin better for Ni 56-94
H2O analyzer On reformer feed & recycle 163-94 Va passivation Separate trap can dilute catalyst 56-94
Reforming Analysis to check sulfur guard 150-94 Va passivation Two stage regen. enhances it 59-94
Reforming On-line NIR for octane, RVP & PONA 153-94 Va passivation Sulfur competes for trap 61-94
Reforming NIR for feed forward control Va traps Selection is complex 61-94
Instrumentation systems 153-94 ZSM-5 Effect on FCC dienes 65-94
RFG Measuring in diesel at low levels 108-94 -COBALT MOLY
Sulfur Analyzer in hydrotreater control room 108-94 Hydrotreating N2 & O2 in feed are factors 107-94
-FINES
ASPHALT MTBE Different amounts in various resins 175-94
Multi-grade Meeting new standards 35-94 -NICKEL MOLY
Hydrotreating Premium cat. guards against nitrogen 107-94
BIOLOGICAL TREATING & MICROORGANISMS -PASSIVATORS
Applications Wastes, desulfurization, ethanol production 44-94 Antimony For Ni in FCCU 57-94
Bismuth For Ni in FCCU 57-94
BLENDING Cerium Replaces antimony 58-94
Analyzers On-line types for RFG certification 27-94 Lift gas Contributes to Ni passivation 59-94
Flowmeters Types for in-line service 31-94 Ni Rarely needed at less than 800 ppm Ni 60-94
MTBE Dealing with water in MTBE 42-94 Performance Comparison Sb, Bi & Ce 59-94
RFG Instruments. control systems for RFG 28-94 Sb vs. Bi Bi more important in future 58-94
RFG Complex vs. simple model changes 32-94 -PLATINUM
Reforming Las mechanisms 160-94
CATALYSTS Reforming Cat. handling major cause of pt loss 160-94
C4 isom. Regenerable 172-94 Reforming Loss bookkeeping 160-94
Cat Cracking Cost of Na in feed 8-94 -POISONS & POISONING
Claus unit TiO2 compared with alumina cats. 190-94 H2S in H, Cuts hydrotreater run length 114-94
Claus unit TiO2 cats are costly 190-94 Hydrotreating Silica problem 112-94
Claus unit TiO2 cats resist sulfate poisoning 190-94 MTBE Nitrogen 174-94
Claus unit AM catalyst is O2 scavenger 190-94 MTBE & ETBE Poison resistant cats. 174-94
Claus unit Rejuvenation results mixed 195-94
Deact. rate FCC O2 enrichment increases rate in FCC 62-94 CHARGE STOCKS
Deactivation Diverse opinions on steam method 62-94 CGO vs. VGO As feeds for FCC & HCC units 70-94
FCC Select Catalyst offset deactivation by O2 62-94 Coker FCC slurry to coker 89-94
FCC Process 126-94 Coker Coking F, K, wastes 89-94
FCC Analyses bifore & after demetallization 126-94 Coker gas oil Better for FCC than hydrocracker 70-94
FCC olefins Role in RFG 54-94 Coker gas oil Do only partial conversion in HDC 70-94
Feed filter Spent catalyst poor choice 100-94 Coker naphtha Treating problems, solutions 112-94
Feed nozzles datalyst flow most important 81-94 Coker naphtha Problems in distillate unit 113-94
H2 reforming No penalty for running butanes 93-94 FCC feed Afterburn 66-94
H2 reforming Blanketing with nitrogen 97-94 HDC buns. Process hydrocracker btms. in FCC 78-94
HF alkylation Status of solid catalysts 148-94 Resid Various desulfurization strategies 116-94
HF alkylation Solid cat. ready by end of 1995 148-94
Hydrocracking Dense vs sock loading. 133-94 CHEMICALS & CHEMICAL ELEMENTS & METALS
Hydrocracking Evaluating dense loading job 133-94 Antimony As passivator 57-94
Hydrocracking Switching from amorphous to zeolite 138-94 Antimony Cuts FCC hydrogen output 58-94
Hydrotreating Low sulfur operation cuts run 110-94 Arsine H2S problem with guard beds 81-94

1994 NPRA Q&A Session on Refining and Petrochemical Technology 217

TOC/INDEX

Cerium Replaces antimony passivator 58-94 Sulfur .Sulfur content vs. corrosion rate 19-94
Chloride Deposits in fractionator 69-94 Sulfur plant Amine foaming, discoloration from corrosion 176-94
H2 S Problem for FCC guard beds 81-94 Sulfur plant High H2S loading causes corrosion 176-94
HCN Control by polysulfide in FCC gas plant 80-94
Metals On spent FCC cat. before/after demetallization 126-94 CRACKING
Methanol New generation catalysts 93-94 -CAT CRACKING-FLUID CAT CRACKING (FCC)
Ni Traps vs. liquid passivators 57-94 Afterburn Designs to reduce 65-94
Ni Passivator rarely needed below 800 ppm 60-94 Afterburn Spent catalyst distribution is key 65-94
Ni “New” Ni has bigger effect on FCC H2 61-94 Afterburn Water & torch oil to control 66-94
Ni carbonyl Danger from CO in purge gas, methanators 124-94 Afterburn Temperatures to 1,800oF 66-94
O2 FCC enrichment 63-94 Afterburn Promoters, low O2 & coker gas oil 66-94
O2 scavenger Hydrazine compounds for HDT feed 104-94 Afterburn Mechanical causes 66-94
Polysulfides Rates for use in gas plant washing 81-94 Afterburn Cyclone hangers set maximum temp 67-94
Propylene Arsine removal bed 81-94 Afterburn Air and coke distribution 67-94
Tin Pros & cons as passivator 57-94 Afterburn Two stage regeneration avoids problem 68-94
-FLUORIDES Afterburning Causes of 66-94
Isomerization Problems caused 171-94 Afterburning Torch oil rate & cat circulation 66-94
Isomerization Defluorinate feed with alumina beds 171-94 Analyzers On-line uses in FCC 78-94
-SULFUR & MERCAPTANS & SULFUR COMPOUNDS Antimony Reduces hydrogen output 58-94
Distribution In FCC naphtha 74-94 Arsine Removal from gases 81-94
FCC naphtha Reduction before, after, in FCC 73-94 Arsine New guard material 81-94
FCC naphtha Effect on FCC catalyst 73-94 Butadiene Riser temperature correlation 64-94
FCC naphtha Reduce gasoline S with riser recycle 74-94 Cat stripper Staged stripping system 68-94
Iron sulfide Effects on reforming cat. 159-94 Catalyst Cost of Na in feed 8-94
Reduction Ways to reduce in gasoline 73-94 Coke buildup Between refractory and metal 53-94
Coke buildup Weld hexmesh to inlet horn to reduce 53-94
COKE (COKE PRODUCTION) Coker gas oil Better cracked in FCC than HCC 70-94
-DELAYED COKING Control Advanced systems 77-94
Coke drum Drum distortion, cracking 86-94 Control Reluctance to use in react./regen. 78-94
Coke drum Correlation of cycles and distortion 86-94 Control Overlay advanced control on DCS 78-94
Coke drum Failure & thermal fatigue 86-94 Corrosion From polysultide 80-94
cutting Using untreated water 87-94 Dienes Cyclones, nozzles, coolers limit production 64-94
Decoking On-line decoking 89-94 Dienes Regenerator temperature correlation 64-94
Feedstock FCC slurry to coker 89-94 Dienes Proper catalyst reduces output 65-94
Feedstock FCC slurry from coker gas oil 90-94 Dienes ZSM-5 increases dienes and butenes 65-94
Feed-stock effect of waste on operations 91-94 Diencs Quench dilute phase to reduce 65-94
Fouling Extending run lengths 88-94 Erosion Design or operations to prevent 50-94
Fouling Steady operation key preventative 89-94 Erosion Space velocity 50-94
Fouling Desalting & antifoulants 89-94 Erosion Localized coking can cause 49-94
Fractionator Use of structured packing 87-94 Erosion Role of catalyst cyclones 51-94
Heater tube Correlation of fouling with feed 88-94 Feed Bielectric desalter for purchased resid 8-94
Process Coke fines carryover 87-94 Feed Cost of increased Na 8-94
Sludge Equipment for handling 85-94 Feed inject. Schemes for curved risers 71-94
Valves Downstream of multiport valve 85-94 Feed nozzles Improve yield in curved risers 71-94
-FLUID COKING Feed nozzles Concerns in curved riser revamps 71-94
Feedstock Effect of F, K, wastes or operations 90-94 Feed nozzles Heart of the FCC 72-94
Feed nozzles Benefits of radial type 81-94
COKING (FOULING) Feed nozzles Radials preferred design 82-94
Coker Cost of increased Na in furnace fouling 8-94 Feed nozzles Upgrade payout in months 82-94
FCC Reasons for in fractionator 74-94 Feedstock Solvent deasphahing of feed 22-94
FCC Coker gas oil culprit 74-94 Fouling Avoid coking in main fractionator 74-94
FCC Avoid with six design features 74-94 Fouling Operating conditions that cause 75-94
FCC Role of fresh feed 75-94 Fouling Slurry recycle minimizes problem 77-94
FCC Mechanical changes help prevent 75-94 Fractionator Tray salting problem 69-94
FCC Reduce bottoms temp. and residence 76-94 Fractionator Design features to avoid coking 74-94
FCC Cycle oil analyses 76-94 Gas plants Wash water rates and additives 80-94
Riser Experience 77-94 H2 prod. “New” Ni causes bigger increase 61-94
HDC btms. Process hydrocracker btms. in FCC 78-94
COMBUSTION PROMOTERS Local coke Use high matrix catalyst 53-94
Afterburn Promoter additions 66-94 Local coke Wrapping refractory prevents 53-94
Local coke Refractory in high contour areas 53-94
COMPUTER CONTROL Local coke Low start-up, upset temperature 53-94
PCs and LANs Pulling all refinery information 39-94 Local coke Weld stand offs to inlet horn 53-94
LPG dienes Function of riser temperature 64-94
CONTAMINANTS Modern design Stripper, feed inject., riser 68-94
Delayed coking Sodium 8-94 Nap. aromatics Reducing for RFG 56-94
Nap. olefins Meeting RFG standards 54-94
CONTROL Nap. olefins Seven ways to cut for RFG 54-94
Console oper. Qualifications required 38-94 Nap. olefins Hydrotreating is RFG option 54-94
Expert systems Applications and drawbacks 38-94 Nap. olefins Alkylate for RFG 54-94
Flame scanners Interference from x-raying 30-94 Nap. olefins Catalyst is option for RFG 54-94
Information Pulling together information systems 39-94 Ni & H2 Chlorides reactivate seed Ni 62-94
Maintenance Type personnel for DCS hardware, software 29-94 Ni/Sb Ratio for passivation 58-94
Model based Payout experience in closed loop system 36-94 No x Regen. conditions that reduce 83-94
Model based Support staff needed 36-94 Nox Reduce nitrogen in feedstock first 83-94
Neural Applications, drawbacks of networks 37-94 Nozzle failed Metallurgy recommended for catalyst nozzle 51-94
Process models “On-line” application of rigorous models 35-94 Nozzle oxidat. Causes 51-94
Nozzle oxidat. Ceramic solution 51-94
CORROSION & EQUlPMENT PROBLEMS O2 enrich. Increases catalyst deactivation 62-94
Alky DIB tower Ways to prevent 143-94 O2 enrich. Catalyst deactivation avoided 63-94
Amine unit Heat stable salts major corrosion agent 180-94 O2 enrich. Air, catalyst contact design 63-94
Amine unit Control corrosion in sour H2O stripper 183-94 Process Methods to control fractionator bottoms temp. 77-94
Crude overhead Modeling of neutralizers eliminates corrosion 23-94 Passivation Ni trop cuts Sb need 59-94
Crude overhead Design of system is important 24-94 Passivators Comparison of three 59-94
FCC Cause of in Naphtha pumparound 52-94 Pentadiene Quench dilute phase to reduce 65-94
FCC pumparound Ammonium chloride a cause 52-94 Pumparound Corrosion of naphtha circuit and pipe 52-94
FCC pumparound Ammonium disulfide possibility 52-94 Reactor Hot wall vs. cold wall design 49-94
FCC pumparound No problem with killed carbon’sreel 52-94 Refractory Maintenance monitoring for wear 53-94
MTBE Corrosion in extractor overhead 174-94 Refractory Four wear monitoring methods 54-94
Na & Va Effect on heater metallurgy 41-94 Sulfur Reduce in mid range naphtha with cat. 74-94
Naphth. acid Methods to control corrosion 18-94 Shutdown Four conditions for automatic 72-94
Naphth. acid Acceptable content level 19-94 Shutdown Automatic systems 72-94
Naphth. acid Monitoring corrosion 19-94 Shutdown Auto. follows manual steps 72-94
Naphth. acid Acid number correlates with crude blends 19-94 Shutdown Air blower check valve 73-94
Naphth. acid Velocity to avoid erosion/corrosion 19-94 Shutdowns Nuisance auto. in FCC 72-94
NH 4 HS Reduce corrosion from it in hydrotreater 130-94 Sidedraws Tray salting causes loss 69-94
Overhead Affect of iron sulfide solubility 22-94 Stripper Multiple steam injection works well 68-94
Overhead Problem from sulfuric acid 25-94 Stripper Important design factors 68-94
Reforming H2O wash, dispersants for stabilizer plug 155-94 Stripper Riser termination device 69-94
Reforming Nitrogen hydrotreating critical 156-94 Sulfur Undercutting is option 73-94
Sulfolane Reboiler in unit 167-94 Tray salting Indicators of problem 69-94
Sulfolane Three mechanisms cause corrosion in reboiler 167-94 Tray salting Waterwash on-line 69-94
Sulfolane Air leaks major cause of corrosion 168-94 Tray salting Some crudes cause more 70-94
Sulfur Methods to control corrosion 18-94 Tray salting Filming amine solution to problem 70-94
Sulfur Acceptable content level 19-94 Va passivation Two stage regen. a plus 59-94

218 Subject Index

TOC/INDEX

Va traps Success related to Va mobility 60-94 Water Designs, techniques for good air flotation 198-94
Va traps Sulfur competes for trap 61-94 Water reuse Streams and their reuse 199-94
Waterwash Best option 79-94 Water reuse Desalter brine for wash water 199-94
Waterwash Practices at various units 79-94 Water reuse Stripped water worked poorly in cooling 199-94
Yield Small stripper causes loss 69-94 Water reuse Unit effluent sent back to front end 199-94
-HYDROCRACKING Water reuse Condensate in desalter popular, but troublesome 199-94
cat. level Detector for level in ebullated bed reactors 134-94 Water reuse Treated sanitary sewage in cooling H2O 200-94
catalyst Evaluating dense loading job 133-94 Water reuse After treatment for cooling water 200-94
catalyst Switching from amorphous to zeolite 138-94 Water reuse Treated for coke cutting 200-94
Coker gas oil Can be poor feed 70-94
Feedstock Solvent deasphalting of feed 22-94 EQUIPMENT
Foaming In cold high pressure separators 134-94 Failure Electrostatic precipitators 84-94
Fouling Better VGO solved PNA fouling 135-94 Furnaces Use of flame scanners 30-94
Heaters Neutralization of stainless steel 131-94 Maintenance Flue gas electrostatic precipitators 84-94
Low s diesel Specs of diesel from hydrocracker 138-94 Metallurgy Response to Ni and Va in fuel oil to heater 41-94
Mild Limitation for making low sulfur diesel 129-94 Operation Flue gas electrostatic precipitators 84-94
PNA fouling in effluent air or water coolers 135-94 Precipitator Factors to keep electro. precip. on swam 84-94
PNA fouling Management techniques for retrofits 135-94 valves Types in coke drum system 85-94
Process Reaction to temperature excursions 137-94
-FAILURE
Process Making low sulfur diesel 138-94 Draft Fan H2 reformer furnace shutdown 96-94
Reactor Radial maklistribution 130-94 MAINTENANCE
Reactor Neutralization after cat. unloading 131-94 Synthetic lubed reformer recips 165-94
Compressors
Reactor flow Temp difference that indicates problem 132-94 Washing reformer compressors 166-94
Compressors
Reactor flow Mixing box improved distribution 132-94 Neutralization of stainless steel in hydrocrackers 131-94
Heaters
Reactor flow Quench zone technology improves distribution 133-94 HF alkylation Citric acid vs HCL for cleaning 146-94
Reactor flow Sock vs. dense cat loading 133-94 Reformer Recip vs. centrifugal compressors 165-94
Sour naphtha H2S stripping & cobalt moly solve problem 136-94 167-94
Reformer Compressor antifoulant
Thermocouples Adding to reactors with top entry thermowells 134-94
-OPERATION
Burners Flame scanners 94-94
CRUDE OIL PROCESSING
Vis. reduction Gravity that requires diluent 26-94
26-94 ETHERIFICATION
Vis. reduction Benefit of diluents in desalting
catalyst Losses from MTBE reactor 175-94
MTBE catalyst Load to reactor in water slurry 175-94
DEASPHALTING Nitrile effect on life 173-94
For cracking feeds 22-94 MTBE cats.
Solvent Max. nitriles 173-94
MTBE feed
MTBE feed Water wash removes nitriles 173-94
DISTILLATION
Crude oil Conditions that affect underdeposit corrosion 23-94 MTBE feed Solid bed nitrile absorber 173-94
24-94 MTBE feed Nitrogen removal efficiency is 95 to 97% 174-94
Crude oil Amine in tail water stops underdeposit corrosion
Crude oil Iron sulfide and underdeposit corrosion 24-94 Process TAME & ETBE from MTBE plant 173-94
Experience within crude and vacuum units 25-94 Process Check methanol recycle for nitrogen 174-94
Packing
Packing Experience within FCC fractionators 26-94 Revamp Time requited 173-94
Seal problems Problems from pure MTBE or in gasoline 43-94
EMPLOYEES Wet MTBE Dealing with haze potential 42-94
Console Qualifications requited 38-94
Info. sys. Giving employees access to networks 39-94 FIRES
Number Consolidation and hourly vs. salaried on board 39-94 Cone roofs Floating roofs for tanks in sour water service 40-94
Training New engineers 47-94 Reforming In effluent exchangers 162-94

ENERGY RECOVERY & CONSERVATION FLOW

Boilers CO trim control 206-94 Measurement Pulsating flow for injection pumps 27-94
Exchangers Preferred methods for in place cleaning 206-94
Exchangers PNAs removed with reformate circulation 207-94 FOAMING
Hydrocracking Effluent from reactor 134-94
ENVIRONMENTAL CONTROL
Air-flares Conflicting experience 197-94 FOULING & DEPOSITS
Antimony Toxicity problem as passivator 57-94 Alkylation Contactor fouling from fresh acid 142-94
catalysts Proposed rule to list hot cat. as hazardous 204-95 Amine Iron sulfide discolors amine 177-94
catalysts Recycle spent phosphoric acid 204-94 Claus unit NH4 salt plugging 188-94
Caustic Process to cat. oxidize sulfitic caustic 203-94 Coker Heater tube problem and feed 88-94
Caustic sulfitic caustic & cresylic acid to reclaimers 203-94 Coker Extending run lengths 88-94
Caustic/acid Minimizing waste 203-94 Coker gas oil Poses problem in FCC 70-94
Ceramic support Nonhazardous solid waste 203-94 Compressors Antifoulants for units in H2 service 104-94
Ceramic support hazardous if mixed with hazardous catalyst 203-94 Compressors Waterwash units in H2 surface 104-94
Ceramic support Cleaned & recycled 203-94 Compressors Type lubricant significant 104-94
Desalter effl. Advantage of bielectric unit 14-94 Exchangers Antifoulants for hydrotreater effluent 102-94
Desalting Bielectric units improve heavy crude effluent 15-94 FCC coke Coping with problem 53-94
Diesel Meeting California rules 33-94 HF alkylation Iron fluoride from wet HF plugs condenser 145-94
Diesel Characteristics of ultra-low sulfur fuel 33-94 HF alkylation Clean salt from condensers each year 146-94
Dome tanks Work well over floating roofs 198-94 Hydrocracker PNA in effluent air or water coolers 134-94
Econo. benefit Desalter eliminates oil in effluent 204-94 Hidrocracker PNA management techniques 135-94
Econo. benefit Run sludge through coker 204-94 Hydrocracker Better VGO solved PNA problem 135-94
Econo. benefit Pay off from desalter 204-94 Hydrotreater Waterwash exchangers for chloride 103-94
FCC Nox Regen. conditions that reduce 83-94 Hydrotreater Gum in feed exchanger 103-94
FCC Nox Reduce nitrogen in feedstock first 83-94 Hydrotreater Blanketing of charges helps 104-94
FCC Nox Cat. treat flue gas to reduce 83-94 Hydrotreater Oxygen scavengers 104-94
FCC Nox Mechanisms of formation 84-94 NH4Cl plugging in 600oF separator system 122-94
Hydrotreater
FCC Nox Reduction additives 84-94 Hydrotreater Oxygen contact with feed major cause 103-94
Flair pilots Experience with various systems 196-94 Low temp. may permit NH4CI deposit 123-94
Hydrotreater
Gasoline Effect of EPA rules on properties 33-94 Compressor antifoulant 167-94
Reformer
Nox Catalytic reduction in H2 plant 95-94 Nitrogen causes fouling 164-94
Reformer feed
Odor H2S scavengers & carbon canister for asphalt 197-94
H2O wash, dispersants for stabilizer plug 155-94
205-94 Reforming
Oily sludges Inject into coker Reforming NH4CI major cause of stabilizer plugging 156-94
Oily sludges Filter press or centrifuge 205-94
Reforming Nitrogen hydrotreating critical 156-94
Oily sludges Maybe hazardous waste 205-94
206-94 Reforming Coker naphtha can cause plugging 157-94
Sludge Materials to remove oil from sludge 157-94
Tank mixers for reducing sludge 206-94 Reforming Hydrotreater key to reducing stabilizer plugging
Sludge 70-94
205-94 Trays Some crudes cause more
Solid waste Two basic thermal desorption systems
205-94 Tray salting Problems, solutions 64-94
Solid waste One desorb system exempt from RCRA
Asphalt odor additive works in sour water 197-94 Va Problems in Benfield process 95-94
Sour water
Building unit to strip with CO2 203-94 Water inject. Points for injection on reactor outlet 105-95
Spent caustic
Preventing contamination 202-94 Water wash Be sure most water stays liquid 105-94
Storm water
Treatment 202-94 Water wash Stripping sour water cost 105-94
Storm water
Reduction in FCC naphtha 73-94 Water wash Washing essential for hydrotreaters 105-94
Sulfur
Vapor recovery Ship loading and thermal oxidizers 138-94
Vapor recovery Destruction of old cars negates need 198-94 GASOLINE
Washwater Dealing with turnaround water 43-94 Analyzers On-line types for EPA certification 27-94
Waste caustic Caustic management, options 202-94 Benzene Remove benzene precursors from reformate 153-94
Waste water Major pollutants 200-94 Enviro. regs Effect on properties 33-94
Waste water Screening test for aquatic toxicity 200-94 FCC olefins Reduce for RFG 54-94
Waste water Worst pollutants 201-94 RFG Benzene precursor prefractionation 153-94
Waste water COD & minnows for toxicity screening 201-94 RFG Ways to limit benzene 154-94
Waste water Metal, dissolved and recoverable 201-94 RFG Pressure &severity vs. benzene make 154-94
Waste water Irrigates hay field 201-94 RFG Instrument control system for making 28-94
Waste water Odor masking neutralizing trials 201-94 RFG Complex vs. simple model changes 32-94

1994 NPRA Q&A Session on Refining and Petrochemical Technology 219

TOC/INDEX

HYDROGEN Water wash Washing essential 105-94

Production Old vs. new Ni 64-94
INSTRUMENTATION
HYDROGEN PRODUCTION Alky H2SO4 Multivarient process control a success 143-94
Burners Burner management system & fuel 93-94 Desalter Microwave level sensor 10-94
Catalyst For nat. gas through butane 93-94 Desalter Capacitance & dP cells didn’t work well 16-94
Corrosion Non-heavy metal inhibitors 94-94 Desalters samplers, floats, probes, level detectors 15-94
Feedstock Process butane over SMR catalyst 92-94 Desalting Microwave probes reduce undercarry 12-94
Feedstock No design penalty for flexibility 92-94 FCC Use of on-line analyzers 78-94
Furnaces Selective catalytic reduction 95-94 Flow measures Pulsating flow 27-94
Furnaces SCR add-on difficult 96-94 Maintenance Type personnel for DCS hardware, software 29-94
Furnaces Draft fan shutdown 76-94 Process models On-line applications 35-94
Nickel carbonyl Methanators can pose danger 124-94
Nox Alternative to ammonia injection 96-94 ISOMERIZATION
Purification Automatic. control of PSA 98-94 C4 catalyst Regenerable cat. 172-94
Tubes Failure of Manaurite XM tubes 97-94 C4 feed Defluorinated alky butane 171-94
Tubes Failure protection 97-94 C4 feed 1 ppm fluoride in feed is max. 171-94
Tubes Eight years safe operations 98-94 C4 feed Residual HF in feed 171-94
Turndowns Burner operations 94-94 C4 feed Defluorination with alumina beds 171-94
C5, C6 feed Use of sulfur guard system 172-94
HYDROTREATING C5, C6 process Sulfur guard conditions, results 172-94
Aromatics Analysis for in diesel 107-94 Process Temperature runaways 171-94
Aromatics Type, distribution strongly impacts process 108-94
Cat unloading Time savings with passivation techniques 118-94 LUBE OILS (AS PRODUCT)
Catalyst Premium nickel moly for nitrogen 107-94 Analysis VI by NIR 21-94
Catalyst Cobalt moly 107-94 Dewaxing Prediction of VI 21-94
Catalyst Large exotherms with presulfided catalysts 124-94 Dewaxing Prediction of VI by NIR 21-94
Catalyst Handling presulfided in bulk 125-94 Extraction Fouling in NMP units 20-94
Catalyst Presulfided saves time 125-94 Hydrotreating In combination with solvent extraction 21-94
Catalyst Cat characteristics for high SiO2 absorption 128-94 Solvent Refine In combination with hydrotreating 21-94
Charge heater Charge heater’s percent of total duty 118-94
Corrosion Reduce NH4HS in hot, high pressure separator 130-94 MATHEMATICAL MODELS
Diesel Technology to reduce aromatics 108-94 Control Applications 35-94
Diesel Sulfur analyzer in control room 108-94
Diesel Changes need to make high into low S units 110-94 NAPHTHA
Feed Effect of oxygenates in feed 106-94 Aromatics Reduce in FCC naphtha for RFG 56-94
Feed O2 in feed requires temp. boost 107-94 Cracked Problems, solutions in hydrotreating 116-94
Feed Treating coker naphtha 112-94 FCC aromatics Poor options for RFG 55-94
Feed Two reactors for coker naphtha 113-94 FCC aromatics Reduce T90 point for RFG 55-94
Feed Coker vs. SR naphtha - cycle length 113-94 FCC yields Improved with radial feed nozzles 82-94
Feed Danger from coker naphtha in distillate unit 113-94 FCC yields Big increases from radial nozzles 82-94
Feed Running with sweet naphtha 114-94 Sulfur Ways to reduce 73-94
Feed Treating FCC gasoline at 300 psig 115-94 Sulfur Hydrotreating options for FCC naphtha 74-94
Feed Treating kerosene in 300 psig unit 115-94 Sulfur Distribution in FCC naphtha 74-94
Feed Treating 100% thermally cracked naphtha 116-94
Feed Thermal cracked naphtha needs two stage unit 116-94 OILS
Feed Support material hydrogenates olefins 123-90 Diesel fuel Measures to comply with California rules 33-94
Filtration Filters better than spent catalyst 100-94 Diesel fuel Options to avoid haze 22-94
Filtration Waxy deposits, excessive backwash 100-94 Diesel fuel Low sulfur from hydrocracker 138-94
Filtration Wax, deposits due to coldness 100-94 Diesel fuel Lubricity problems with ultra low Sulfur 33-94
Filtration Excessive backwashing and salt 101-94 Diesel fuel Lubricity test methods under study 33-94
Filtration Reactor operations without scale basket 101-94 Diesel fuel Chromatography for low aromatics content 107-94
Filtration Graded material preferred to baskets 101-94 Diesel fuel Hydrotreating technology to reduce aromatics 108-94
Filtration Trash baskets prevent pressure drop 101-94 Diesel fuel Hydrocracking employed to reduce aromatics 108-94
Filtration Trash baskets take up cat. space 101-94 Diesel fuel Methods to measure S at low levels 108-94
Filtration Baskets vs. graded beds 102-94 Diesel fuel 0.045 wt% S target 109-94
Filtration Chain trash baskets together and pull out 102-94 Diesel fuel Old hydrotreater meeting new specs 109-94
Filtration Dry ice cleaning of trash baskets 102-94 Diesel fuel Dye, low S vs. High S 110-94
Fouling Antifoulant for reactor effluent exchangers 102-94 Diesel fuel Problems from high dye 110-94
Fouling Gum in feed exchanger 103-94 Diesel fuel Blotter ratings indicate stability 110-94
Fouling Water wash effluent exchangers 103-94 Diesel fuel Dye color controversy 111-94
Fouling Feed contact with oxygen major cause 103-94 Diesel fuel Dye content test 111-94
Fouling Contact of feed with oxygen major cause 103-94 Diesel fuel Dye complicates stability test 111-94
Fouling Type lubricants significant 104-94 Diesel fuel Making low sulfur with mild hydrocracking 129-94
Gas scrubber H2S scrubbrng helps maintain HDS activity 114-94
H2S adsorber Essential for deep HDS 114-94 OLEFINS
Low sulfur Old units meeting new specs 109-94 FCC naphtha Reduce for RFG 54-94
Maldistribution Techniques to detect 121-94
Mild HDC cat. Using to produce low sulfur diesel 129-94 POLYMER UNIT
Plugging NH4CI in hot separator 122-94 catalyst Dry drilling for unloading tubular reactors 169-94
Presulfiding Agents and their performance 119-94 catalyst Problems in chamber reactor 169-94
Presulfiding Criteria for selecting presulfiding agent 119-94 catalyst Charcoal minimizes pressure drop 169-94
Presulfiding Decomposition temperature of presulfiding agent 119-94 catalyst Process variables to lengthen run 170-94
Process Effects of oxygenates in feed 106-95 catalyst Process C3 olefins only for longer runs 170-94
Process 0.045 wt% S in diesel 109-94 catalyst Various catalysts 170-94
Process Revamping units for low sulfur diesel 109-94
Process Wade pressure deltas in first reactor 111-94 REFINERY OPERATIONS
Process Treating coker naphtha 112-94 Alliances Types, benefits 44-94
Process Treat coker naphtha in reformer pretreater 112-94 Expert systems Applications and drawbacks 38-94
Process Coker naphtha problem in distillate unit 113-94 Information Access from single work station 39-94
Process Effect of H2S in hydrogen 113-94 Neural Applications, drawbacks of neural networks 37-94
Process Scrub recycle gas to avoid H2S problem 114-94
Process Treating kero. or FCC gasoline in 300 psig point 115-94 REFORMING
Process Resid HDS for low sulfur fuel oil 117-94 Catalyst High alumina, low Pt CCR cat. 158-94
Process Resid HDS for FCCU 117-94 Catalyst Iron sulfide on cat. 159-94
Process Resid HDS for higher distillate, naphtha yields 117-94 Catalyst Rotate cat. to combat iron sulfide 159-94
Process High conversion cause sludge problem 117-94 Catalyst Pt loss; mechanisms 160-94
Process Control temperature in reactor 118-94 Catalyst Pt loss from fines, high temp. 160-94
Process Problem of uneven reactor bed flow 120-94 Catalyst Cat. handling major cause of Pt loss 160-94
Process Effect of four factors on reactor bed flow 120-94 Catalyst Fines major reason for Pt loss 160-94
Process Increased recycle gas improves reactor bed flow 121-94 Catalyst Pt loss bookkeeping 160-94
Radial reactor Best for cracked naphtha 119-94 Compressors Synthetic lubed recips do well 165-94
Radial reactor Two in parallel are best for cracked naphtha 120-94 Compressors When and how to wash 166-94
Reactor Startup practices on 2.25 Cr-1 Mo units 98-94 Compressors Antifoulants 167-94
Reactor Support material hydrogenates olefins 123-90 Compressors On or off during reduction 167-94
Reactor bed Coping with uneven flow distribution 120-94 Extraction Clays for BTX, cumene processes 168-94
Reactor bed Increased recycle gas improves flow distribution 121-94 Extraction Clay activity & ofefin content 169-94
Reactors Startup guidelines 99-94 Feed Nickel oxide sulfur sorbent 149-94
Removal Comparison for S, N, O compounds 106-95 Feed Tests for sulfur guard effectiveness 149-94
Resid HDS Best operating strategies 116-94 Feed Replace sulfur guard each year 149-94
Startup 2.25 Cr-1 Mo reactors temperature & pressure 98-94 Feed Analyzer to check sulfur guard 150-94
Startup Reactor pressure, remperature guidelines 99-94 Feed Recycle sulfur sorbent after breakthrough 150-94
Startup Get whole reactor hot 99-94 Feed Methods to monitor sulfur guard 150-94
Startup Temperature, pressure cautions 100-94 Feed Catalyst indicates sulfur guard performance 150-94
Sulfur 0.045 wt% S diesel target 109-94 Feed Liquid vs. vapor phase S guards 151-94

220 Subject Index

TOC/INDEX

Feed Vapor phase sulfur guard costly 151-94 Claus units Turndown of 20 to 1 possible 187-94
Feed Water resulting from S guard 151-94 Claus units Operate one on pressure control, other on flow 187-94
Feed Primary reasons for S guard 151-94 Claus units Emergency shutdown not on computer control 187-94
Feed Sulfur guard H2O nullifies benefits 152-94 Claus units Emergency shutdown on PLC 187-94
Feed Problem of nitrogen in feed 164-94 Claus units Hi temperature destroys NH3 188-94
Feed Nitrogen increases fouling 164-94 Claus units Flame instability cause furnace vibration 188-94
Feed No detectable nitrogen is best 164-94 Claus units NH4 salt plugging in condensers 188-94
Maintenance Recip. vs. centrifugal compressors 165-94 Claus units NH3 limits in feed 189-94
Process NIR for octane, RVP PONA 153-94 Claus units SO3 from firnace involved in plugging 189-94
Process NIR for feed forward control 153-94 Claus units All condensers have demister pads 189-94
Process Benzene/RFG strategy 153-94 Claus units TiO2 compared with alumina catalysts 190-94
Process Benzene precursor removal for RFG 153-94 Claus units TiO2 improves COS & CS2 conversion 190-94
process Three benzene variable for RFG 154-94 Claus units TiO2 catalysts resist sulfation 190-94
Process Ways to limit benzene for RFG 154-94
Claus units No reports of NOx exiting unit 191-94
Process Pressure & severity vs. benzene make 155-94
Claus units Steam quench prevents burner overheating 191-94
Process 1% benzene not easy in 500 lb unit 155-94
Process Hydrotreater culprit in NH4CI fouling 154-94 Claus units Infrared instrument measures temperature 191-94
Process Coker naphtha can cause stabilizer plugging 157-94 Claus units O2 enrichment ups unit capacity 25-30% 191-94
Process Reducine recycle dryout time 158-94 Claus units O2% is enrichment; 30% is injection 191-94
Process Mol. sieves for recycle dryout 158-94 Claus units O2 injection set for 37% in new burner 192-94
Process Gas dryers reduce startup time 158-94 Claus units O2 injection to 100% with new technology 192-94
Process Mol. sieves cut startup time 158-94 Claus units O2 cost can kill enrichment scheme 192-94
Process Nitrogen used for recycle dryout 158-94 Claus units Safety factors in O2 addition schemes 192-94
Process Fire in effluent exchangers 162-94 Claus units No complacency at any level added O2 193-94
Process Avoiding fire in effluent exchangers 162-94 Claus units O2 destroys NH,, enhances tail gas operation 193-94
Process Iron sulfide sparks tire in exchangers 163-94 Claus units Amine switch solves high CO2/H2S problem 193-94
Process Moisture analyzers 163-94 Claus units Low H2S content feed successfully processed 194-94
Process H2O analyzer on recycle gas 163-94 Claus units Analyzer for process air control 194-94
Process Location of H2O analyzer 164-94 Claus units Scot reactor temp. indicates SO 2 from Claus 194-94
Process Source of H2O in feed 164-94 Claus units W tail gas analyzer for trim 194-94
Process Reflux to feed ratio controls H2O 164-94 Claus units H2 analyzers for trim 194-94
Revamp Semiregen. unit to lower pressure 161-94 Claus units Clean H2 is good fuel 194-94
Revamp Considerations for lower pressure 161-94 Claus units Flame scanner won’t detect H2 flame 194-94
Revamp Lower pressure increases yield & H2 161-94 Claus units Rejuvenation results mixed 195-94
Revamp Exchangers for lower pressure unit 162-94 DGA Works well at 50% concentration 178-94
Revamp Two process options or lower pressure units 162-94 MDEA degrade O2 scavenger eliminates degradation 178-94
Sulfolane Corrosion in reboiler 167-94 Tail gas Reducing COS, metcaptan 195-94
Sulfolane Three mechanisms cause corrosion in reboiler 167-94
Tail gas Catalyst key to COS reduction 195-94
Sulfolane No reboiler corrosion observed for 5 years 168-94 Tail gas Bed temp., steam reduce COS, mercaptan 195-94
Sulfolane Air leaks major cause of corrosion 168-94
Tail gas Stretford unit holds H2S to ppm 196-94
Sulfur Checking effectiveness of guard sorbent 150-94
Liquid vs. vapor phase guards Tail gas Combustors on warm standby 196-94
Sulfur 151-94
Sulfur S guard enhances cat. performance 152-94 Tail gas unit TiO2 meets tail gas requirements 190-94

SAFETY & INDUSTRIAL HYGIENE TEMPERATURE

Alky H2 O4 Release forms limited aerosol 140-94 Claus unit Infrared and thermocouples used 191-94
sky H2 SO4 Spent acid tanks 144-94
Claus unit Safety factor for O2 addition 192-94 TRAINING
HF alkylation Aerosol/additive to suppress 146-94 Console Qualifications required for operators 38-94
HF alkylation Water curtain for emission mitigation 147-94 Engineers Training new refinery and R&D staff 47-94
HF leaks Various detectors 147-94
Nickel carbonyl Always a threat 124-94 TREATING
Desalter Bielectric unit improves heavy crude effluent 15-94
SHUTDOWN Desalter Monitoring and controlling interface 15-94
FCC auto. Four conditions to activate 72-94 Desalter Automatic interface control 16-94
Systems parameters automatically triggers 72-94 Desalters Design, operating improvements 10-94
Desalters Probes that didn’t work well 16-94
SLUDGE Desalting Multiple stage advantages for resid on FCC charge 8-94
Desalting Reasons for removal, cost of 20-94 Desalting Multiple stage disadvantage for resid or FCC charge 8-94
Desalting Salt removed from gas oils 9-94
START-UP Desalting Performance assessment 9-94
C4 isom. Reducing dryout time at start-up 171-94 Desalting Naphthanic crude special case 9-94
Desalting 99% salt removal in two-stages 9-94
SULFUR PLANT Desalting Run length targets 9-94
Amine Foaming, discoloration mean corrosion 176-94 Salt, water, sediment goals
Desalting 9-94
Amine foaming Traced to dissolving of polyester filter 179-94 Guideline for operating results
182-94 Desalting 9-94
Amine foaming Select water soluble inhibitor carelidly
Monitoring impact on overall operation
Amine problem Housekeeping tips to solve problems Desalting 10-94
177-94
Desalting Ways to reduce oil in water effluent 10-94
Amine problem Iron sulfide is culprit 177-94
Amine problem Hydrocarbon carryover causes foaming 178-94 Desalting Coke fine problem in effluent water 10-94
Amine salts Economically removed 179-94 Desalting Polymers enhance solids removal 10-94
Amine salts Conversion to Na salt cuts corrosion 179-94 Desahing Monitors rag layer & temperature 10-94
Amine salts Type H2O for removal important 180-94 Desalting Processing heavy crudes 11-94
Amine unit Polysullide formation 176-94 Desalting Microwave probe use reduces undercarry 12-94
Amine unit O2 promotes polysulfide 176-94 Desalting Benefits of polymers for heavy crudes 14-94
Amine unit H2S reaction to polysulfide 176-94 Desalting Problem from polymer addition 14-94
Amine unit Caustic is short term corrosion cure 179-94 Desalting Conventional vs. bielectric units 14-94
Amine unit Water washing effective heat stable salts 179-94 Desalting Bielectric increase crude throughput 15-94
Amine unit Salts control with caustic & inhibitor 180-94 Desalting Eliminating residual sludge ahead of unit 16-94
Amine unit Heat stable salt major corrosion agent 180-94 Desalting Mud wash systems 16-94
Amine unit Removal of acids added H2O wash benefit 181-94 Desalting Producer to remove sludge from unit 17-94
Amine unit Inject H2O near source of gases 181-94 Desalting Sediment wash system design 17-94
Amine unit Caustic for corrosion overrated 181-94 Desalting Alternate sludge wash procedure 18-94
Amine unit LPG to amine ratio 181-94 Desalting Chloride analyzer, on stream 18-94
Amine unit Corrosion in regen. overhead 182-94 Desalting Solids removal, methods, criteria 20-94
Amine unit Inhibitor, metallurgy reduce regen. corrosion. 182-94 Desalting Reasons for removal, costs of 20-94
Amine unit Alcohol-based inhibitors can cause foaming 183-94 Desalting Common method for solids removal 290-94
Amine unit O2 causes corrosive condition in overhead 183-94 Disulfide Oil& offgas disposal options 12-94
Amine unit Sour H2O stripper corrosion 183-94 Disposal options
Disulfide oil 12-94
Amine unit NH, & CO2 in sour stripper are corrosive 183-94 Caustic carryover hydrotreater problem
Disulfide oil 13-94
Amine unit Metallurgy for sour H2O stripper 184-94
Extraction Disulfide oil, offgas disposal options 12-94
Amine unit Inhibitors for sour H2O stripper 184-94
Sweetening Carbon bed compression problems , solutions 13-94
Amine unit Use NH4HS for cyanides in sour H2O stripper 184-94
Amine unit Typical sour H2O stripper run 185-94 Sweetening Caustic free for gasoline and kerosene 203-94
Amine unit Sour H2O stripper runs: 1/2 to 3 years 185-94
Amine unit Spare reboiler extends sour H2O stripper run 185-94 TURNAROUND
Amine unit Amine carryover from LPG contactors 185-94 Cat. unloading Safety, not costs, criterium for technique 11-94
Amine unit Antifoam reduces carryover from LPG treater 185-94 Cat. unloading Passivation saves time and money 118-94
Amine unit Dirty amine foams in LPG treater 185-94 H2 plants Benfild plants 95-94
Amine unit Several process condition cause carryover 181-94 Hydrotreater Chained trash baskets pulled out quickly 102-94
Claus units Low turndown vs. hot standby 186-94 Washwater Processing, preventing waste streams 42-94
Claus units Low rate better than hot standby 186-94
Claus units Runs at 25% of max 186-94 WASHING
Claus units Cold standby also an option 186-94 FCC Gas Plant cascade options 78-94
Claus units Amine system crucial to running multiple units 187-94 FCC Washwater rates and additives 80-94

1994 NPRA Q&A Session on Refining and Petrochemical Technology 221

TOC/INDEX

References

The next several pages provide a list of references by I. ALKYLATION

subject from the publications Chemical Engineering, Whittle, David K., Lorenzo, Donald K., and Kirkman, John Q.,
Hydrocarbon Processing and Oil & Gas Iournal. The Sub- “Results of alkylation unit hazard, operability study are ana-
ject Index for the References is organized as follows. lyzed and summarized,” Oil & Gas Journal, July 10, 1989, p.
96.
I. Alkylation Novalany, S. and McClung, R.G., “Better alky from treated
II. Hydrocracking olefins,” Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989,
III. Catalytic Cracking p. 66.
IV. Hydrotreating/Hydrorefining McDonald, G.W.G., “FCC charge-stock value depends on op-
V. Reforming erational response,” Oil & Gas Journal, July 31, 1989, p. 80.
VI. Treating and Desalting Unzelman, George H., “ETHERS IN GASOLINE-I: Ethers
VII. Crude Distillation have good gasoline-blending attributes,” Oil & Gas Journal,
VIII. Petrochemical Apr. 10, 1989, p. 33.
Unzelman, George H., “ETHERS IN GASOLINE-Conclu-
IX. Delayed Coking
sion: Ethers will play larger role in octane, environmental spec
X. Environmental Controls for gasoline blends,” Oil & Gas Journal, Apr. 17, 1989, p. 44.
XI. Instrumentation, Product Blending, Davis, Brian C., “Supplying high-octane gasoline will further
and Quality Control challenge U.S. refiners,” Oil & Gas Journal, May 15, 1989, p.
XII. Miscellaneous 35.
XIII. Lube Oil and Waxes Desai, Pankaj H., and Haseltine, Robert P, “Advanced FCC
XIV. Maintenance catalyst formulations can be used co boost motor octane
XV. Piping number ofgasoline,” Oil & Gas Journal, Oct. 23, 1989, p. 68.
XVI. Furnaces & Heat Ramsey, John R., and Truesdale, Patrick B., “Blend optimization
XVII. Storage and Transfer integrated into refinery-wide strategy,” Oil & Gas Journal,
XVIII. Corrosion Mar. 19, 1990, p. 49.
XIX. Energy Conservation Corbett, Richard A., “ANNUAL REFINING REPORT: Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
XX. General
26, 1990, p.49.
XXI. Light-Oil Cat Processing
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
XXII. Isomerization Refining Survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
XXIII. Aromatics Extraction Unzelman, George H., “REFORMULATED FUELS-l: Refor-
XXIV. Visbreaking mulated gasolines will challenge product-quality mainte-
XXV. Hydrogen Production nance,” Oil & Gas Journal, Apr. 9, 1990, p. 43.
XXVI. Sulfur Plant Operations Unzelman, George H., “REFORMULATED FUELS-Conclu-
XXVII. Polymerization sion: Options to meet 1990s fuel composition rules limited,”
XXVIII. Hydrogen Oil & Gas Journal, Apr. 23, 1990, p. 91.
Corbett, Richard A., “FUELS FORTOMORROW-Tough air-
quality goals spur quest for transportation fuel changes,” Oil
& Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FORTOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal June 18, 1990, p. 52.
Corbett, Richard A., “Proposed OSHA safety regs target process
plant procedures,” Oil & Gas Journal, Aug. 20, 1990, p. 80.
Parkinson, Gerald, “HF’s future is up in the air,” Chemical
Engineering, May 1990, p. 39.
Gilman, Robert H., “Capital outlays for gasoline reformulation
can be minimized,” Oil & Gas Journal, Sept. 3, 1990, p. 44.

222 References
TOC/INDEX
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Albright, L.F., “MODERN ALKYLATION - 1: Alkylation will
be key process in reformulated gasoline era,” Oil & Gas
Journal Nov. 12, 1990, p. 79.
Albright, L F., “MODERN ALKYLATION - Conclusion:
H2S04, HF processes compared, and new technologies re-
vealed,” Oil & Gas Journal, Nov. 26, 1990, p. 70.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal
Dec. 31, 1990, p. 84.
“NPRA Q&A - 2: HF alkylation drawn process, safety ques-
tions,” Oil & Gas Journal, June 24, 1991, p. 48.
“Alkylation unit scheduled for Ufa refinery,” Oil& Gas Journal,
Sept. 2, 1991, p. 24.
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
Hoffman, H.L., “Refining catalyst market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 1991, p. 37.
Lerner, H. and Citarella, VA., “Improve alkylation efficiency,”
Hydrocarbon Processing, Vol. 70, No. 11, Nov. 1991, p. 89.
“Alkylation of MTBE raffinate increases octane, unloads alky
unit,” Oil & Gas Journal, Nov. 18, 1991, p. 99.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal Dec. 23, 1991, p. 39.
“Group pursuing new alkylation process,” Oil & Gas Journal,
Feb. 10, 1992, p. 40.
“H2SO4 alkylation shows promise for upgrading gasoline pen-
tenes,” Oil & Gas Journal, Feb. 17, 1992, p. 72.
“Refiners discuss HF alkylation process and issues,” Oil & Gas
Journal, Apr. 6, 1992, p. 67.
“Refiners look at H2SO4 alkylation, catalytic reforming,” Oil &
Gas Journal, Apr. 27, 1992, p. 45,
Chang, E.J. and Lelby, S.M., “Ethers help gasoline quality,”
Hydrocarbon Processing, Feb. 19 92, p. 41.
Nierlich, E, “Oligomerize for better gasoline,” Hydrocarbon
Processing, Feb. 1992, p. 45.
Abraham, O.C. and Prescott, G.F., “Make isobutylene from
TBA,” Hydrocarbon Processing, Feb. 1992, p. 51.
Chaput, G., et al., “Pretreat alkylation feed,” Hydrocarbon Proc-
essing, Sept. 1992, p. 51.
Scott, B., “Identify alkylation hazards,” Hydrocarbon Processing,
Vol. 71, No. 10, Oct. 1992, p. 77.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
“New processes and catalysts solve problems of feed contami-
nants,” Oil & Gas Journal, Oct. 12, 1992, p. 51.
Sloley, Andrew W. and Golden, Scott W., “Analysis key to
correcting debutanizer design flaws,” Oil & Gas Journal Feb.
8, 1993, p. 50.
“New HF alky unit key to Navajo’s $50-million expansion,” Oil
& Gas Journal, June 14, 1993, p. 42.
Jezak, A., “C5 alkylate: a superior blending component,” Hydro-
carbon Processing, Vol. 73, No. 02, Feb. 1994, p. 47.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Spanish refinery starts up HF alky unit,” Oil & Gas Journal,
Nov. 22, 1993, p. 77.
“NPRA Q&A: Refiners focus on FCC, hydroprocessing, and
alkylation catalysts,” Oil & Gas Journal Mar. 28, 1994, p. 41.
“U.S. refiners must increase alkylation capacity to meet de-
mand,” Oil & Gas Journal Aug. 22, 1994, p. 49.
Rhodes, Anne K., “Searches for new alkylation catalysts, proc-
esses forge ahead,” Oil & Gas Journal, Aug. 22, 1994, p. 52.
Rhodes, Anne K., “New process schemes, retrofits, fine tune
alkylation capabilities,” Oil & Gas Journal, Aug. 22, 1994, p.
56.
Sheckler, John C., Ross, Larry J., and Comey, Kenneth R. III,
“New process additive reduces HF cloud-forming potential,”
Oil & Gas Journal Aug. 22, 1994, p. 60.
II. HYDROCRACKING
Powell, Robert T, “Kinetic hydrocracker model helps engineers
predict yields, targets, operations,” Oil & Gas Journal, Jan. 9,
1989, p. 61.
Corbett, Richard A., “Modern hydrocracking is the key to
upgrading processes,” Oil & Gas Journal, June 26, 1989, p.
42.
Court, A.L. and Smith, W.H., “Canada’s first heavy oil upgrader
complex on stream,” Oil & Gas Journal, June 26, 1989, p. 46.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Adams, C.T., et al., “Hydroprocess catalyst selection,” Hydrocar-
bon Processing, Vol. 68, No. 09, Sept. 1989, p. 57.
Nash, Richard M., “REFINING/GAS PROCESSING RE-
PORT: Process conditions and catalyst for low-aromatics
diesel studies,” Oil & Gas Journal, May 29, 1989, p. 47.
Aalund, Leo R., “Expanded Mongstad refinery has major export
role,” Oil & Gas Journal, Mar. 12, 1990, p. 33.
Corbett, Richard A., “ANNUAL REFINING REPORT: Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
26, 1990, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
refining survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
Suchanek, Arthur J., “Catalytic routes to low-aromatics diesel
look promising,” Oil & Gas Journal, May 7, 1990, p. 109.
Shaffer, Arthur G., Jr., and Hemler, Charles L., “Seven years of
operation prove RCC capability,” Oil & Gas Journal, May 28,
1990, p. 62.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Bucheim, Gerrit M., “Ways to deal with wet H2S cracking
revealed by study,” Oil & Gas Journal, July 9, 1990, p. 92.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
“Acoustic tests during cooldown find cracks in reactors at Gulf
Coast refinery,” Oil & Gas Journal June 17, 1991, p. 47.
“Annual refining survey” Oil & Gas Journal, Mar. 18, 1991, p.
84.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY:
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
223
TOC/INDEX
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal Dec. 23, 1991, p. 39.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
“Texas refinery gets two reactors,” Oil & Gas Journal, Dec. 7,
1992, p. 30.
Ladeur, Peter and Bijwaard, Harry, “Shell plans $2.2-billion
renovation of Dutch refinery,” Oil & Gas Journal, Apr. 26,
1993, p. 64.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal Oct. 11, 1993, p. 44.
Farina, G.L. and Fontana, M., “Cogeneration refinery for total
residue destruction,” Hydrocarbon Processing, Vol. 72, No. 11,
Nov. 1993, p. 52.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 100 c.
Sloan, H.D., “Refinery expansion/upgrading means lighter,
quality products,” Hydrocarbon Processing, Vol. 72, No. 01,
Jan. 1994, p. 82.
“Russian refinery update to employ Isocracking unit,” Oil & Gas
Journal, Mar. 21, 1994, p. 48.
III. CATALYTIC CRACKING
Humphries, Adrian and Wilcox, Jack R., “Zeolite components
and matrix composition determine FCC catalyst perform-
ance,” Oil & Gas Journal, Feb. 6, 1989, p. 40.
Key-worth, Donald A., Reid, Terry A., Kreider, Keith R., and
Yatsu, Carolyn A., “FCC LPG olefinicity and branching
enhanced by octane catalysts,” Oil & Gas Journal May 29,
1989, p. 56.
McDonald, G.W.G., “FCC charge stock value depends on
operational response,” Oil & Gas Journal, July 31, 1989, p.
80.
Christie, David A. and Holden, David G., “Fluid cat cracking
units’ advanced control can achieve benefits in six areas,” Oil
& Gas Journal Sept. 25, 1989, p. 104.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal Oct. 2, 1989, p. 49.
Desai, Pankaj H. and Haseltine, Robert I?, “Advanced FCC
catalyst formulations can be used to boost motor octane
number ofgasoline,” Oil & Gas Journal, Oct. 23, 1989, p. 68.
Bartholomew, Karl D. and Soudek, Ales, “LP accuracy is im-
proved by incorporating FCC simulation data,” Oil & Gas
Journal, Oct. 30, 1989, p. 57.
Rhemann, H., et al., “On-line FCCU advanced control and
optimization,” Hydrocarbon Processing, Vol. 68, No. 06, June
1989, p. 64.
Adams, C.T., et al., “Hydroprocess catalyst selection,” Hydrocar-
bon Processing, Vol. 68, No. 09, Sept. 1989, p. 57.
Carter, G.D.L. and McElhiney, G., “FCC catalyst selection,”
Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989, p. 63.
Washimi, K. and Limmer, H., “New unit to thermal crack
resid,” Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989, p.
69.
Elvin, F.J., “Catalyst demetallized for reuse,” Hydrocarbon Proc-
essing, Vol. 68, No. 10, Oct. 1989, p. 71.
224 References
Brown, Gordon W., “Direct measurement of FCC fluidizability
helps spot problems,” Oil & Gas Journal, Jan. 15, 1990, p. 46.
Aalund, Leo R., “Expanded Mongstad refinery has major export
role,” Oil & Gas Journal Mar. 12, 1990, p. 33.
“Innovative improvements highlight FCC’s past and future,” Oil
& Gas Journal, Jan. 8, 1990, p. 33.
Parkinson, Gerald, Johnson, Eric, “Designer catalysts are all the
rage,” Chemical Engineering, Sept. 1989, p. 30.
Avidan, Amos, Krambeck, Frederick J., Owen, Hartley, and
Schipper, Paul H., ‘ANNUAL REFINING REPORT: FCC
closed-cyclone system eliminates post-riser cracking,” Oil &
Gas Journal, Mar. 26, 1990, p. 56.
Yatsu, Carolyn A., and Keyworth, Donald A., “ANNUAL RE-
FINING REPORT Modified MAT and GC help predict
FCC gasoline quality,” Oil & Gas Journal, Mar. 26, 1990, p.
64.
Thrash, Lou Ann, “ANNUAL REFINING REPORT Annual
refining survey,” Oil & Gas Journal Mar. 26, 1990, p. 77.
Unzelman, George H., “REFORMULATED FUELS- 1: Refor-
mulated gasolines will challenge product-quality mainte-
nance,” Oil & Gas Journal, Apr. 9, 1990, p. 43.
Weeks, Simon A., and Dumbill, Peter, “Method speeds FCC
catalyst attrition resistance determinations,” Oil & Gas Jour-
nal, Apr. 16, 1990, p. 38.
Unzelman, George H., “REFORMULATED FUELS-Conclu-
sion: Options to meet 1990s fuel composition rules limited,”
Oil & Gas Journal, Apr. 23, 1990, p. 91.
Heite, Richard S., English, A.R., and Smith, G. Andrew, “Bis-
muth nickel passivation effective in FCCU,” Oil&Gas Jour-
nal, June 4, 1990, p. 81.
Nieskens, Mart J.P.C., Khouw, Frank H.H., Barley, Martin
J.H., and Roebschlaeger, Karl-Heinz W., “Shell’s resid FCC
technology reflects evolutionary development,” Oil & Gas
Journal, June 11, 1990, p. 37.
Corbett, Richard A., “FUELS FOR TOMORROW-Tough air-
quality goals spur quest for transportation fuel changes,” Oil
&Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal, June 18, 1990, p. 52.
Bucheim, Gerrit M., “Ways to deal with wet HzS cracking
revealed by study,” Oil & Gas Journal, July 9, 1990, p. 92.
Gilman, Robert H., “Capital outlays for gasoline reformulation
can be minimized,” Oil & Gas Journal, Sept. 3, 1990, p. 44.
Stokes, G.M., Wear, C.C., Suarez, W., and Young, G.W., “Re-
formulated gasoline will change FCC operations and cata-
lysts,” Oil & Gas Journal, July 2, 1990, p. 58.
Alkemade, U., Cartlidge, S., and Thompson, J.M., “WORLD-
WIDE CATALYST REPORT: Improved alumina sol FCC
catalysts meet challenges of the 1990s,” Oil & Gas Journal,
Oct. I, 1990, p. 52.
Upson, L.L., Lawson, R.J., Cormier, W.E., and Baard, F.J.,
“WORLDWIDE CATALYST REPORT: Matrix, sieve,
binder developments improve FCC catalysts,” Oil & Gas
Journal Oct. 1, 1990, p. 64.
Lovink, H.J., “Siberian catalyst research center works at world
class level,” Oil & Gas Journal, Dec. 31, 1990, p. 119.
TOC/INDEX
Hoek, A., Huizinga, T., Esener, A.A., Maxwell, I.E., Stork, W.,
van de Meerakker, EJ., and Sy, O., “New catalyst improves
heavy feedstock hydrocracking,” Oil & Gas Journal Apr. 22,
1991, p. 77.
Elvin, F.J. and Pavel, SK., “Metals removal of FCC catalyst
operating in refinery,” Oil & Gas Journal, July 22, 199 1, p. 94.
“Additives play important role in FCC development,” Oil & Gas
Journal Sept. 23, 1991, p. 50.
Strong, R.C., Majestic, V.K., and Wilhelm, S.M., “FCC COR-
ROSION - 1: Basic steps lead to successful FCC corrosion
control,” Oil & Gas Journal Sept. 30, 199 1, p. 8 1.
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
Hayward, C.M.T. and Winkler, W.S., “FCC: Matrix/zeolite
interactions,” Hydrocarbon Processing, Vol. 69, No. 02, Feb.
1990, p. 55.
Soudek, M. and Lacatena, J.J., “Crack isobutane for isobuty-
lene,” Hydrocarbon Processing, Vol. 69, No. 05, May 1990, p.
73.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Santner, C.R., “Rare earth and matrix activity effects in resid
FCC cat,” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990,
p. 75.
Strong, R.C., Majestic, V.K., and Wilhelm, S.M., “FCC COR-
ROSION - Conclusion: Basic corrosion control methods
solve varied problems,” Oil&Gas Journal, Oct. 7, 1991, p.
86.
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY:
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Hoffman, H.L., “Refining catalysr market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 199 1, p. 37.
Sadeghbeigi, R., “Estimating hydrogen of FCC coke,” Hydro-
carbon Processing, Vol. 70, No. 02, Feb. 1991, p. 38.
McLean, J.B. and Moorehead, E.L., “Steaming affects FCC
catalyst,” Hydrocarbon Processing, Vol. 70, No. 02, Feb. 199 1,
p. 41.
Humphries, A., et al., “Catalyst helps reformulation,” Hydrocar-
bon Processing, Vol. 70, No. 04, Apr. 1991, p. 69.
Jazayeri, B., “Optimize FCC riser design,” Hydrocarbon Process-
ing, Vol. 70, No. 05, May 1991, p. 93.
Letzsch, W.S., et al., “Passivate nickel in FCC feeds,” Hydrocar-
bon Processing, Vol. 70, No. 06, June 1991, p. 89.
Golden, SW. and Martin, G.R., “Improve HVGO quality and
cutpoint,” Hydrocarbon Processing, Vol. 70, No. 11, Nov.
1991, p. 69.
Johnson, TE., “Improve regenerator heat removal,” Hydrocar-
bon Processing, Vol. 70, No. 11, Nov. 1991, p. 55.
Krishna, A.S., et al., “Additives improve FCC process,” Hydro-
carbon Processing, Vol. 70, No. 11, Nov. 1991, p. 59.
O’Connor, P., et al., “Improve resid processing,” Hydrocarbon
Processing, Vol. 70, No. 11, Nov. 1991, p. 76.
Sloan, H.D., “Process heavier crude blends,” Hydrocarbon Proc-
essing, Nov. 1991, p. 99.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Rhodes, Anne K., “Survey shows over 1,000 refining catalysts,”
Oil & Gas Journal, October 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
Schmitt, Rodolphe, “FCC catalyst find three safe reuse outlet in
Europe,” Oil & Gas Journal, Nov. 18, 1991, p. 101.
Rowlands, Gareth, Konuk, Aydin, and Kleinschrodt, Frank,
“FCCU advanced controls increase feed rate and column
stability,” Oil & Gas JoumaL Nov. 25, 199 1, p. 64.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 199 1, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil 8 Gas
Journal Dec. 23, 1991, p. 39.
McDonald, G.W.G., “Upgrading FCC VRU can yield attractive
payoff,” Oil & Gas Journal Jan. 27, 1992, p. 79.
“Presulfiding, FCC olefins focus of catalyst sessions,” Oif & Gas
Journal, Mar. 16, 1992, p. 37.
“UOP to end operations in FCC catalyst manufacture,” Oil &
Gas JournaL Mar. 23, 1992, p. 46.
Leiby, Susan, “FCC catalyst technologies expand limits of proc-
ess capability,” Oil & Gas Journal, Mar. 23, 1992, p. 49.
Eriksson, Per-Olaf, Tomlins, Aric, and Dash, Sachindra,
“FCCU advanced control system achieves 2-month payout,”
Oil & Gas Journal, Mar. 23, 1992, p. 62.
Brahn, Michael G., “Olefin recovery from FCC offgas can pay
off,” Oil & Gas Joumal Apr. 20, 1992, p. 94.
Perez de Haro, Juan, Berlanga Gonzales, Aantonio J., Schroder,
Nina, and Stenberg, Olle, “O2 enrichment increases FCC
operating flexibility,” Oil & Gas Joumal May 11, 1992, p. 40.
Reichle, A.D., “Fluid catalytic cracking hits 50 year mark on the
run,” Oil & Gas Journal May 18, 1992, p. 41.
Aalund, Leo, “Human element key to FCC success,” Oil & Gas
Journal, May 18, 1992, p. 46.
Murphy, James R., “Evolutionary design changes mark FCC
process, ” Oil & Gas Joumal May 18, 1992, p. 49.
Avidan, Amos A., “FCC is far from being a mature technology,”
Oil & Gas Journal, May 18, 1992, p. 59.
Murcia, Alvaro A., “Numerous changes mark FCC technology
advance,” Oil & Gas Journal May 18, 1992, p. 68.
Rajagopalan, K. and Habib, H.P., Jr., “Understand FCC matrix
technology,” Hydrocarbon Processing, Sept. 1992, p. 43.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
Campos, Mario Cesar M.M., and Rodrigues, Paulo Sergio B.,
“Practical control strategy eliminates FCCU compressor surge
problems,” Oil & Gas Journal, Jan. 11, 1993, p. 29.
Sarrazin, Patrick, Cameron, Charles J., Barthel, Yves, and Mor-
rison, M. Edward, “Processes prevent detrimental effects from
As and Hg in feedstocks,” Oil & Gas Journal, Jan. 25, 1993,
p. 86.
“NPRA Q&A-2: Catalytic cracking receives heavy attention
at Q&A meeting,” Oil & Gas Journal, Apr. 19, 1993, p. 48.
Golden, Scott W., Martin, Gary R., and Schmidt, Karl D.,
“Field data, new design correct faulty FCC tower revamp,”
Oil & Gas Journal, 1993.
Goelzer, Alan R., Ram, Sanjeev, Hernandez-Robinson, Agustin,
Chin, Arthur A., Harandi, Mohsen N., and Smith, C. Morris,
“Refiners have several options for reducing gasoline benzene,”
Oil & Gas Journal, Sept. 13, 1993, p. 63.
225
TOC/INDEX
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Sarathy, ER. and Suffridge, G.S., “Erherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 89.
Sarathy, P.R. and Suffridge, G.S., “Etherify field butanes, Part
2,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Golden, S.W., et al., “FCC main fractionator revamps,” Hydro-
carbon Processing, Vol. 72, No. 03, March 1993, p. 77.
Lin, T.D.V., “FCCU advanced control and optimization,” Hy-
drocarbon Processing, Vol. 72, No. 04, Apr. 1993, p. 107.
Wong, RF., “Increasing FCC regenerator catalyst level,” Hydro-
carbon Processing, Vol. 72, No. 11, Nov. 1993, p. 59.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 100C.
Sloan, H.D., “Refinery expansion/upgrading means lighter,
quality products,” Hydrocarbon Processing, Vol. 73, No. 01,
Jan. 1994, p. 82C.
Radigan, M.J., “How to select a continuous emission monitor-
ing system,” Hydrocarbon Processing, Vol. 73, No. 02, Feb.
1994, p. 73.
Dziewulski, T.A., “Tune-up your FCCU expander,” Hydrocar-
bon Processing, Vol. 73, No. 08, Aug. 1994, p. 144.
Murphy, Martin A., “Analysis, calculation techniques predict
FCC erosion and fluidization,” Oil & Gas Journal, Feb. 21,
1994, p. 54.
“NPRA Q&A: Refiners focus on FCC, hydroprocessing, and
alkylation catalysts,” Oil & Gas Journal, Mar. 28, 1994, p. 41.
“NPRA Q&A: Re finers exchange experiences on FCC prob-
lems, coking operations,” Oil & Gas Journal, May 2, 1994, p.
110.
Dougan, Timothy J., Alkemade, Ulrich, Lakhanpal, Balbir, and
Boock, Lori T, “New vanadium trap proven in commercial
trials,” Oil & Gas Journal Sept. 26, 1994, p. 81.
I. HYDROTREATING AND HYDROREFINING
Nash, Richard M., “Process conditions and catalyst for low-aro-
matics diesel studied,” Oil & Gas Journal, May 29, 1989, p.
47.
Christman, Robert D., Plesko, Ronald W., and Donahue, Mi-
chael, and Wilson, Robert E., “Tests show DMSO effective
for HDS, HDN catalyst sulfiding,” Oil & Gas Journal, Sept.
18, 1989, p. 90.
“Panel gives hydrotreating guides, ” Hydrocarbon Processing, Vol.
68, No. 03, Mar. 1989, p. 113.
Adams, C.T., ec al., “Hydroprocess catalyst selection,” Hydrocar-
bon Processing, Vol. 68, No. 09, Sept. 1989, p. 57.
Novalany, S. and McClung, R.G., “Better alky from treated
olefins,” Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989,
p. 66.
Parkinson, Gerald, Johnson, Eric, “Designer catalysts are all the
rage,” Chemical Engineering, Sept. 1989, p. 30.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
226 References
“European emission, fuel quality regs tighten,” Oil & Gas Jour-
nal, Dec. 18, 1990, p. 41.
Suchanek, Arthur J., “Catalytic routes to low-aromatics diesel
look promising,” Oil & Gas Journal May 7, 1990, p. 109.
Hohnholt, John E, Shifflet, Woodrow K., and Suchanek, Arthur
K., “REFINING/GAS PROCESSING REPORT: Higher
severity hydroconversion hikes diesel and distillate yields at
Valero,” Oil & Gas Journal, May 28, 1990, p. 72.
Corbert, Richard A., “FUELS FOR TOMORROW - Tough
air-quality goals spur quest for transportation fuel changes,”
Oil & Gas Journal June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW - Fuel
reformulation, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW - New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal, June 18, 1990, p. 52.
Kahn, H.U., Mungali, M.M., Agrawal, K.M., and Joshi, G.C.,
“Graphical method simplifies diesel cloud point determina-
tions,” Oil & Gas Journal Sept. 24, 1990, p. 98.
Smith, Fritz A., and Bortz, Robert W., “Applications vary for
dewaxing process over 10-year span,” Oil & Gas Journal, Aug.
13, 1990, p. 51.
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
Eastwood, D. and Van de Venne, H., “Revamp distillate desul-
furizers,” Hydrocarbon Processing, Vol. 69, No. 05, May 1990,
p. 63.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Hoffman, H.L., “Refining catalyst market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 1991, p. 37.
“Hydrotreating unit installed in Texaco’s Wales refinery,” Oil &
Gas Journal Apr. 22, 1991, p. 36.
LeRoy, C.E, Hanshaw, M.J., Fischer, S.M., Malik, T., and
Kooiman R., “HYDROTREATING OPTIMIZATION - 1:
Refiner conducts full scale VGO hydrotreating study,” Oil &
Gas Journal, May 27, 1991, p. 49.
LeRoy, CE, Hanshaw, M.J., Fischer, S.M., Malik, T., and
Kooiman R., “HYDROTREATING OPTIMIZATION -
Conclusion: Optimization of catalyst system reaps economic
benefits,” Oil & Gas Journal, June 3, 1991, p. 87.
“Annual refining survey,” Oil & Gas Journal Mar. 18, 1991, p.
84.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY:
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
Plantenga, Frans L., Inoue, Yoshimasa, and Torihara, Naoyuki,
“Specialized guard-bed technology can improve resid unit
operation,” Oil & Gas Journal, Oct. 21, 1991, p. 74.
“Ashland refinery starts up two sulfur units,” Oil & Gas Journal,
Oct. 28, 1991, p. 95.
“End seen for high sulfur fuel oil in Europe,” Oil & Gas Journal,
Dec. 2, 1991, p. 21.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
TOC/INDEX
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
“Single and dual stage hydrotreating can up diesel cetane,” Oil
& Gas Journal Aug. 17, 1992, p. 88.
Desai, PH., et al., “Enhance gasoline yield and quality,” Hydro-
carbon Processing, Vol. 71, No. 11, Nov. 1992, p. 51.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Cooper, B.H., et al., “Hydrotreating catalysts for diesel aromat-
ics saturation,” Hydrocarbon Processing, Vol. 72, No. 06, June
1993, p. 83.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal Oct. 12, 1992, p. 41.
“New processes and catalysts solve problems of feed contami-
nants,” Oil & Gas Journal, Oct. 12, 1992, p. 51.
“Process passivates spent catalyst to allow unloading under air,”
Oil & Gas Journal, Oct. 12, 1992, p. 56.
“NPRA Q&A-1: Experience exchanged on complex effects of
catalysts,” Oil & Gas Journal, Feb. 22, 1993, p. 45.
Simonsen, Knut A., O’Keefe, Luke F., and Fong, W. Francis,
“Changing fire formulations will boost hydrogen demand,”
Oil & Gas Journal, Mar. 22, 1993, p. 45.
Toman, Jerry J., and Beckman, Robert F., “Visbreaker hardware
has alternate uses in low-sulfur fuel era,” Oil & Gas Journal,
Mar. 22, 1993, p. 66.
“Ashland refinery units take shape,” Oil & Gas Journal, Apr. 19,
1993, p. 20.
“NPRA Q&A: Hydroprocessing key issue in ‘low sulfur’ era,”
Oil & Gas Journal, July 26, 1993, p. 88.
Booth, Martin and Wolveridge, Peter E., “Severe hydrotreating
of diesel can cause fuel-injector pump failure,” Oil & Gas
Journal, Aug. 16, 1993, p. 71.
Gorra, Filippo, Scribano, Giorgio, Christensen, Preben, An-
dersen, Karin Vibeke, and Corsaro, Osvaldo Gaetano, “New
catalyst, improved presulfiding result in 4-year hydrotreater
run,” Oil & Gas Journal, Aug. 23, 1993, p. 39.
“Oklahoma hydrotreater nearly finished,” Oil & Gas Journal,
Sept. 13, 1993, p. 36.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Farina, G.L. and Fontana, M., “Cogeneration refinery for total
residue destruction,” Hydrocarbon Processing, Vol. 72, No. 11,
Nov. 1993, p. 52.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 100C.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
“Conoco’s new Ponca City hydrotreater jumps low sulfur diesel
output,” Oil & Gas Journal, Nov. 8, 1993, p. 34.
Rhodes, Anne K., “Lyondell, Citgo join for heavy oil upgrade
project at Houston refinery,” Oil & Gas Journal, Mar. 21,
1994, p. 60.
“NPR4 Q&A: Refiners focus on FCC, hydroprocessing, and
alkylation catalysts,” Oil & Gas Journal Mar. 28, 1994, p. 41.
“BP preparing for hydrofiner at Grangemouth,” Oil & Gas
Journal, May 2, 1994, p. 138.
“Oxygenate carry-over may cause overheating in naphtha hydro-
treaters,” Oil & Gas Journal, Sept. 12, 1994, p. 93.
1994 NPR4 Q&A Session on Refining and Petrochemical Technology
V. REFORMING
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Aalund, Leo R., “Expanded Mongstad refinery has major export
role,” Oil & Gas Journal, Mar. 12, 1990, p. 33.
Ramsey, John R., and Truesdale, Patrick B., “Blend optimization
integrated into refinery-wide strategy,” Oil & Gas Journal,
Mar. 19, 1990, p. 40.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
refining survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
Unzelman, George H., “REFORMULATED FUELS-l: Refor-
mulated gasolines will challenge product-quality mainte-
nance,” Oil & Gas Journal, Apr. 9, 1990, p. 43.
Unzelman, George H., “REFORMULATED FUELS-Conclu-
sion: Options to meet 1990s fuel composition rules limited,”
Oil & Gas Journal, Apr. 23, 1990, p. 91.
Corbett, Richard A., “FUELS FORTOMORROW-Tough air-
quality goals spur quest for transportation fuel changes,” Oil
& Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal, June 18, 1990, p. 52.
Gilman, Robert H., “Capital outlays for gasoline reformulation
can be minimized,” Oil & Gas Journal, Sept. 3, 1990, p. 44.
McClung, R.G., “Reformer operation improved by feed sulfur
removal,” Oil & Gas Journal, Oct. 8, 1990, p. 98.
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
“Gas Process Handbook ‘90,” Hydrocarbon Processing, Vol. 69,
No. 04, Apr. 1990, p. 69.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Santner, C.R., “Rare earth and matrix activity effects on resid
FCC cat,” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990,
p. 75.
“Acoustic tests during cooldown find cracks in reactors at Gulf
Coast refinery,” Oil & Gas Journal, June 17, 1991, p. 47.
Hoffman, H.L., “Refining catalyst market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 1991, p. 37.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY:
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal Oct. 14, 1991, p. 46.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
“Japanese refinery starts up UOP Platforming unit,” Oil&Gas
Journal Apr. 27, 1992, p. 32.
“Refiners look at H2SO4 alkylation, catalytic reforming,” Oil &
Gas Journal Apr. 27, 1992, p. 45.
Hennico, Alphonse, Mank, Larry, Mansuy, Christophe, and
Smith, D.H., “Texas reformer designed for two-step expan-
sion,” Oil & Gas Journal, June 8, 1992, p. 54,
227
TOC/INDEX
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Baade, W.E, et al., “Generate hydrogen for reformulated gaso-
line and clean diesel,” Hydrocarbon Processing, Vol. 72, No. 01,
Jan. 1993, p. 77.
Ladebeck, J., “Improve methanol synthesis,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, March 1993, p. 89.
Liers, J,, et al., “Reforming using erionite catalysts,” Hydrocar-
bon Processing, Vol. 72, No. 08, Aug. 1993, p. 165.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 4 1.
Simonsen, Knut A., O’Keefe, Luke F., and Fong, W. Francis,
“Changing fuel formulations will boost hydrogen demand,”
Oil & Gas Journal, Mar. 22, 1993, p. 45.
“Ashland refinery units take shape,” Oil & Gas Journal, Apr. 19,
1993, p. 20.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Christensen, T.S. and Primdahl, I.I., “Improve syngas produc-
tion using autothermal reforming,” Hydrocarbon Processing,
Vol. 73, No. 03, Mar. 1994, p. 39.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Jeanneret, J.J., et aI., “New strategies maximize para-xylene
production,” Hydrocarbon Processing, Vol. 73, No. 06, June
1994, p. 43.
Ancheyta-Juarez, Jorge, and Aguilar-Rodriguez, Enrique, “New
model accurately predicts reformate composition,” Oil & Gas
Journal Jan. 31, 1994, p. 93.
Ragsdale, Ralph, “U.S. refiners choosing variety of routes to
produce clean fuels,” Oil & Gas Journal, Mar. 21, 1994, p. 5 1.
Aguilar-Rodriguez, Enrique, and Ancheyta-Juarez, Jorge, “New
process model proves accurate in tests on catalytic reformer,”
Oil & Gas Journal, July 25, 1994, p. 80.
VI. TREATING AND DESALTING
Pitsinigos, VD. and Lygeros, A.I., “Predicting H2S-MEA equi-
librium,” Hydrocarbon Processing, Vol. 68, No. 04, Apr. 1989,
p. 43.
Vervalin, C.H., “Bioremediation on the move,” Hydrocarbon
Processing, Vol. 68, No. 08, Aug. 1989, p. 50.
Isla, M.A., et al., “Improvingsour water strippers,” Hydrocarbon
Processing, Vol. 68, No. 08, Aug. 1989, p. 65.
Elvin, EJ., “Catalyst demetallized for reuse,” Hydrocarbon Proc-
essing, Vol. 68, No. 10, Oct. 1989, p. 71.
Chiu, C.H., “Advances in gas separation,” Hydrocarbon Process-
ing, Vol. 69, No. 01, Jan. 1990, p. 69.
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
Smith, R.S., “Gas dehydration process upgraded,” Hydrocarbon
Processing, Vol. 69, No. 02, Feb. 1990, p. 75.
“Gas Process Handbook ‘90,” Hydrocarbon Processing, Vol. 69,
No. 04, Apr. 1990, p. 69.
Eastwood, D. and Van de Venne, H., “Revamp distillate desul-
furizers,” Hydrocarbon Processing, Vol. 69, No. 05, May 1990,
p. 63.
Talavera, PG., “Selecting gas/liquid separators,” Hydrocarbon
Processing, Vol. 69, No. 06, June 1990, p. 81.
228 References
Frank, B.E., “Canadian natural gas exports: Positioning for the
1990s,” Hydrocarbon Processing, Vol. 69, No. 09, Sept. 1990,
p. 136C.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Cooley, D.F., “Strip SO2 from acid treated soil,” Hydrocarbon
Processing, Vol. 69, No. 12, Dec. 1990, p. 85.
Hoffman, H.L., “Refining catalyst market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 1991, p. 37.
Motiee, M., “Estimate possibility of hydrates,” Hydrocarbon
Processing, Vol. 70, No. 07, July 1991, p. 98.
Yamanlar, S., et al., “Control hydrate formation,” Hydrocarbon
Processing, Vol. 70, No. 09, Sept. 1991, p. 155.
Dillion, E.T., “Triazines sweeten gas easier,” Hydrocarbon Proc-
essing, Vol. 70, No. 12, Dec. 199 1, p. 65.
Duke, R.B., “Water content test for EOR crude simulates
desalter,” Oil & Gas Journal, Feb. 25, 1991, p. 40.
Minikkinen, Ari, Larue, Joseph Y.M., Patel, Suru, and Levier,
Jean-Francois, “Methanol gas-treating scheme offers econom-
ics, versatility,” Oil & Gas Journal, June 1, 1992, p. 65.
Desai, PH., et al., “Enhance gasoline yield and quality,” Hydro-
carbon Processing, Vol. 71, No. 11, Nov. 1992, p. 51.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Felten, J.R., et al., “Residual fuels in a clean-fuels environment,”
Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p. 82B.
Cooper, B.H., et al., “Hydrotreating catalysts for diesel aromat-
ics saturation,” Hydrocarbon Processing, Vol. 72, No. 06, June
1993, p. 83.
“Filtration method efficiently desalts crude in commercial test,”
Oil & Gas Journal, May 17, 1993, p. 59.
Farina, G.L. and Fontana, M., “Cogeneration refinery for total
residue destruction,” Hydrocarbon Processing, Vol. 72, No. 11,
Nov. 1993, p. 52.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 100C.
Monticello, D.J., “Biocatalytic desulfurization,” Hydrocarbon
Processing, Vol. 73, No. 02, Feb. 1994, p. 39.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Stewart, E.J. and Lanning, R.A., “Reduce amine plant solvent
losses, Part 1,” Hydrocarbon Processing, Vol. 73, No. 05, May
1994, p. 67.
Stewart, E.J. and Lanning, R.A., “Reduce amine plant solvent
losses, Part 2,” Hydrocarbon Processing, Vol. 73, No. 06, June
1994, p. 51.
“NPRA Q&A: Auxiliary equipment, corrosion focus of refiner
meeting,” Oil & Gas Journal, Apr. 4, 1994, p. 62.
VII. CRUDE DISTILLATION
“Upgrading process can be used upstream or down,” Oil & Gas
Journal, Jan 23, 1989, p. 55.
Al-Besharah, Jasem M., Akashah, Saed A., and Mumford, C.J.,
“Binary mixture viscosities-Conclusion: Binary mixtures of
petroleum products and mixtures based of base oils exam-
ined,” Oil & Gas Journal, Mar. 6, 1989, p. 50.
Corbett, Richard A., “Canada’s heavy oil, bitumen upgrading
activity is growing,” Oil & Gas Journal, June 26, 1989, p. 33.
TOC/INDEX
Corbetr, Richard A., “Modern hydrocracking is the key to
upgrading processes,” Oil & Gas Journal, June 26, 1989, p.
42.
Al-Besharah, Jasem M., Akashah, Saed A., and Mumford, C.J.,
“Binary mixrure viscosities - 1: Viscosities of binary crude oil
mixtures correlated,” Oil & Gas journal, Feb. 20, 1989, p. 35.
Corbett, Richard A., “Oseberg premium crude is in produc-
tion,” Oil & Gas Journal, July 24, 1989, p. 56.
Court, A.L. and Smith, W.H., “Canada’s first heavy oil upgrader
complex on stream,” Oil & Gas Journal, June 26, 1989, p. 46.
West, Karen I., Hankinson, R.W., and Downer, Lionel, “Petro-
leum Measurement Tables of 1980 reaffirmed,” Oil & Gas
Journal, Aug. 7, 1989, p. 63.
Du, Pham Quang, “Highly parafhnic Vietnamese crudes char-
acterized,” Oil & Gas Journal, Nov. 6, 1989, p. 39.
Vatcha, S.R., “How efficient can distillation be?,” Hydrocarbon
Processing, Vol. 68, No. 01, Jan. 1989, p. 65.
Chen, G.K. and Chuang, K.T., “Recent developments in distil-
lation,” Hydrocarbon Processing, Vol. 68, No. 02, Feb. 1989,
p. 37.
Harrison, Mark E., France, John J., “Troubleshooting distilla-
tion columns - Part 1: Technique and tools,” Chemical Engi-
neering, Mar. 1989, p. 116.
Harrison, Mark E., France, John J., “Troubleshooting distilla-
tion columns - Part 3: Trayed columns,” Chemical Engineering,
May 1989, p. 126.
Harrison, Mark E., France, John J., “Troubleshooting distilla-
tion columns - Part 4: Auxiliary equipment,” Chemical Engi-
neering, June 1989, p. 130.
Trigueros, David, Coronado-Velasco, Cristina, and Gomez-Mu-
noz, Alejandro, “Synthesize simple distillation the thermody-
namic way,” Chemical Engineering, Aug. 1989, p. 129.
Corbett, Richard A., “Important Norwegian crude assays up-
dated,” Oil & Gas Journal, Mar. 12, 1990, p. 37.
Corbett, Richard A., “ANNUAL REFINING REPORT: Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
26, 1990, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
Refining Survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
Coker, A.K., “Program provides short-cut distillation tower
calculations,” Oil & Gas Journal, June 25, 1990, p. 33.
Corbett, Richard A., “GUIDE TO WORLD EXPORT
CRUDES: Brent blend, North Sea benchmark, assayed,” Oil
& Gas Journal, June 25, 1990, p. 38.
Du, Pham Quang, “Detailed assays conducted on Vietnamese
crude oils,” Oil & Gas Journal, July 16, 1990, p. 58.
Bird, Graham, Limb, David, and Pandit, Alok, “Flowsheet
simulation models crude distillation and ammonia produc-
tion,” Oil & Gas Journal July 23, 1990, p. 43.
Lee, C., “Enhance gas oil from crude,” Hydrocarbon Processing,
Vol. 69, No. 05, May 1990, p. 69.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Furgang, S.R., “State-of-the-art refinery training,” Hydrocarbon
Processing, Vol. 69, No. 12, Dec. 1990, p. 89.
Manriquez, L., Moreno, A., and Anaya, C.G., “EXPORT
CRUDES FOR THE ’90s: Assays for important Mexican
crudes updated,” Oil & Gas Journal, Mar. 4, 1991, p. 41.
“EXPORT CRUDES FOR THE ’90s: Alba is first heavy North
Sea crude,” Oil & Gas Journal, May 27, 1991, p. 94.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“EXPORT CRUDES FOR THE ’90s: Commingled crude
from the Brent and Ninian streams assayed,” Oil & Gas
Journal, July 8, 1991, p. 46.
Rhodes, A.K., “EXPORT CRUDES FOR THE ’90s: Assay of
Forties stream updated,” Oil & Gas Journal, July 15, 1991, p.
53.
Bruening, I.M.R.d.A., “Crude oil polarity measures quality,
products behavior,” Oil & Gas Journal, Aug. 5, 1991, p. 38.
Lieberman, N.P and Lieberman, E.T., “Design, installation
pitfalls appear in vac tower retrofit,” Oil & Gas Journal Aug.
26, 1991, p. 57.
Rhodes, Anne K., “EXPORT CRUDES FOR THE ’90s: Char-
acteristics of North Sea’s Flotra crude updated,” Oil & Gas
Journal, Sept. 2, 1991, p. 90.
Swain, E.J., “U.S. crude slate gets heavier, higher in sulfur,” Oil
& Gas Journal, Sept. 9, 1991, p. 59.
Rhodes, Anne K., “EXPORT CRUDES FOR THE ’90s: North
Sea Emerald crude oil assayed,” Oil & Gas Journal, Sept. 16,
1991, p. 84.
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Parrott, K.S., “Better crude oil sample systems,” Hydrocarbon
Processing, Vol. 70, No. 03, Mar. 1991, p. 63.
Hewer, T.C., Jr., and Kister, H.Z., “Solve process column prob-
lems, Part 1,” Hydrocarbon Processing, Vol. 70, No. 05, May
1991, p. 89.
Hower, TC. Jr., and Kister, H.Z., “Solve process column prob-
lems, Part 2,” Hydrocarbon Processing, Vol. 70, No. 06, June
1991, p. 83.
Ashcroft, S.J., et al., “Find shrinkage of spiked crudes,” Hydro-
carbon Processing, Vol. 70, No. 10, Oct. 1991, p. 109.
Golden, S.W. and Martin, G.R., “Improve HVGO quality and
cutpoint,” Hydrocarbon Processing, Vol. 70, No. 11, Nov.
1991, p. 69.
Sloan, H.D., “Process heavier crude blends,” Hydrocarbon Proc-
essing, Vol. 70, No. 11, Nov. 1991, p. 99.
Rhodes, Anne K., “U.K. North Sea’s Kittiwake crude assayed,”
Oil & Gas Journal Oct. 28, 1991, p. 55.
Rhodes, Anne K., “Two important Saudi crudes assayed,” Oil
& Gas Journal, Dec. 2, 199 1, p. 64.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
Rhodes, Anne K., “East Zeit Mix and Dulang crudes assayed,”
Oil & Gas Journal, Mar. 2, 1992, p. 46.
“Koch to construct sour crude unit at Corpus Christi,” Oil &
Gas & Journal, Mar. 2, 1992, p. 56.
Rhodes, Anne K., “Four California OCS crudes assayed,” Oil &
Gas Journal, Mar. 30, 1992, p. 67.
Rhodes, Anne K., “Malaysian, Canadian, Saudi crudes assayed,”
Oil & Gas Journal Apr. 27, 1992, p. 44.
“Tyumen due U.S. topping unit,” Oil & Gas Journal June 15,
1992, p. 25.
“Lyondell plans to hike heavy crude runs at Houston,” Oil &
Gas Journal, July 20, 1992, p. 41.
Rhodes, Anne K., “Assays of two Saudi crudes updated,” Oil &
Gas Journal, Sept. 28, 1992, p. 91.
229
TOC/INDEX
Jamialahmadi, Mohamad, and Muller-Steinhagen, Hans,
“Computer program designs packed columns,” Oil & Gas
Journal, Aug. 31, 1992, p. 33.
Golden Scott W., and Sloley, Andrew W., ‘Simple methods solve
vacuum column programs using plant data,” Oil & Gas
Journal, Sept. 14, 1992, p. 74.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing Vol.
71, No. 11, Nov. 1992, p. 133.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 89.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Part
2,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Golden, S.W., et al., “FCC main fractionator revamps,” Hydro-
carbon Processing, Vol. 72, No. 03, March 1993, p. 77.
Fair, J.R., “How to design baffle tray columns,” Hydrocarbon
Processing, Vol. 72, No. 05, May 1993, p. 75.
Roberts, D.A., et al., “Recover additional distillate from vacuum
residue,” Hydrocarbon Processing, Vol. 72, No. 07, July 1993,
p. 75.
Golden, SW., et al., “Troubleshoot vacuum columns with
low-capital methods,” Hydrocarbon Processing, Vol. 72, No.
07, July 1993, p. 81.
Lieberman, Norman I? and Lieberman, Elizabeth T., “Inade-
quate inspection cause of flawed vac tower revamp,” Oil & Gas
Journal, Dec. 14, 1992, p. 33.
Rhodes, Anne K., “EXPORT CRUDES FOR THE ’90s: Papua
New Guinea’s first commercial crude assayed,” Oil & Gas
Journal, Feb. 15, 1993, p. 73.
Toman, Jerry J., and Beckman, Robert F., “Visbreaker hardware
has alternate uses in low-sulfur fuel era,” Oil & Gas Journal,
Mar. 22, 1993, p. 66.
French, Eddie C., “New inhibitor reduces crude-unit corrosion
problems at lower pH,” Oil & Gas Journal, May 24, 1993, p.
45.
Lieberman, Norman I?, “Four steps solve crude-tower overhead
corrosion problems,” Oil & Gas Journal, July 5, 1993, p. 47.
Rhodes, Anne K., “GUIDE TO WORLD CRUDES: Two light,
sweet C.I.S. crudes assayed,” Oil & Gas Journal, Sept. 6, 1993,
p. 82.
Campagne, W. v. L., “Use Ponchon-Savarit in your process
simulation, Part 1,” Hydrocarbon Processing, Vol. 72, No. 09,
Sept. 1993, p. 41.
Visigalli, R., et al., “Predict AGO quality,” Hydrocarbon Process-
ing, Vol. 72, No. 09, Sept. 1993, p. 47.
Liebert, T.C., “Distillation feed preheat-is it energy efficient?,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 37.
Campagne, W. v. L., “Use Ponchon-Savarit in your process
simulation, Part 2,” Hydrocarbon Processing, Vol. 72, No. 10,
Oct. 1993, p. 63.
Cassata, J.R., et al., “Modeling of tower relief dynamics, Part 1,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 71.
Farina, G. L. and Fontana, M., “Cogeneration refinery for total
residue destruction,” Hydrocarbon Processing, Vol. 72, No. 11,
Nov. 1993, p. 52.
Golden, S.W., et al., “Revamping FCC main fractionator energy
systems,” Hydrocarbon Processing, Vol. 72, No. 11, Nov. 1993,
p. 43.
230 References
Cassata, J.R., et al., “Modeling of tower reliefdynamics, Part 2,”
Hydrocarbon Processing, Vol. 72, No. 11, Nov. 1993, p. 69.
Capps, R.W. and Thompson, J.R., “Statistical safety factors
reduce overdesign,” Hydrocarbon Processing, Vol. 72, No. 11,
Nov. 1993, p. 77.
Miquel, J. and Castells, E, “Easy characterization of petroleum
fractions, Part 1,” Hydrocarbon Processing, Vol. 72, No. 12,
Dec. 1993, p. 101.
Miquel, J. and Castells, F., “Easy characterization of petroleum
fractions, Part 2,” Hydrocarbon Processing, Vol. 73, No. 01, Jan.
1994, p. 99.
Ghoshal, PC. and Mukhopadhyay, S., “Improve glycol dehydra-
tion unit efficiency,” Hydrocarbon Processing, Vol. 73, No. 03,
Mar. 1994, p. 75.
Rhodes, Anne K., “Northwest Australia’s Saladin crude assayed,”
Oil & Gas Journal, Oct. 18, 1993, p. 50.
Rhodes, Anne K., “Lyondell, Citgo join for heavy oil upgrade
project at Houston refinery,” Oil & Gas Journal, Mar. 21,
1994, p. 60.
Rhodes, Anne K., “Two offshore Australian crudes assayed,” Oil
& Gas Journal, May 9, 1994, p. 76.
Rhodes, Anne K., “Yemen’s light, sweet Alif crude assayed,” Oil
& Gas Journal, May 23, 1994, p. 78.
Rhodes, Anne K., “Benchmark West Texas Intermediate crude
assayed,” Oil & Gas Journal, Aug. 15, 1994, p. 88.
Rhodes, Anne K., “Danish North Sea crude assayed,” Oil&Gas
Journal, Sept. 12, 1994, p. 91.
VIII. PETROCHEMICAL
Sardar, Hashim, Allen, S.U.Li, and Gendler, Jeffrey L., “Ther-
mal hydrodealkylation adapted to heavy aromatics feeds,” Oil
& Gas Journal, Mar. 20, 1989, p. 91.
Otto, K.W., “Olefin capacity surge will tighten feedstock sup-
plies,” Oil & Gas Journal, July 3, 1989, p. 35.
Han, S., Shihabi, D.S., Absil, R.P.L., Huang, Y.Y., Leiby, SM.,
Marler, D.O. and McWilliams, J.P., “ZSM-5 catalyst devel-
oped for toluene disproportionarion,” Oil&Gas Journal Aug.
21, 1989, p, 84.
Inkrott, Kenneth E., Scinta, James, and Smith, Paul D., “Poly-
olefin catalyst manufacturing,” Oil & Gas Journal, Oct. 16,
1989, p. 49.
Shannahan, N., “‘Ammonia loop modernization,” Hydrocarbon
Processing, Vol. 68, No. 01, Jan. 1989, p. 60.
Emmrich, G. and Lackner, K., “Recover butene-1 or -2 easier,”
Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989, p. 71.
Barton, J., “Pinch technology improves olefin heat recovery,”
Hydrocarbon Processing, Vol. 68, No. 02, Feb. 1989, p. 47.
Schultheisz, D.J. and Sommerfeld, J.T., “More interest in batch
simulation,” Hydrocarbon Processing, Vol. 68, No. 06, June
1989, p. 73.
Parkinson, Gerald, Johnson, Eric, “Designer catalysts are all the
rage,” Chemical Engineering, Sept. 1989, p. 30.
Ahmad, I., et al., “Epoxies from maleic anhydride,” Hydrocarbon
Processing, Vol. 68, No. 02, Feb. 1989, p. 51.
Michel, S., “Cost to make CO or H2 + CO,” Hydrocarbon
Processing, Vol. 68, No. 04, Apr. 1989, p. 37.
Yaws, C.L., et al., “Critical properties of chemicals,” Hydrocar-
bon Processing, Vol. 68, No. 07, July 1989, p. 61,
TOC/INDEX
Doolan, PC. and Pujado, ER., “Make aromatics from LPG,”
Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989, p. 72.
“Petrochemical Handbook ‘89,” Hydrocarbon Processing, Vol.
68, No. 11, Nov. 1989, p. 85.
Irving-Monshaw, Susan, and Johnson, Eric, “Ethylene’s riding
high,” Chemical Engineering, May 1989, p. 35.
Toomey, Joseph E., Jr., and Yu, Jimmy C., “Making organic
chemicals via electrochemical processing,” Chemical Engineer-
ing, June 1989, p. 140.
Johnson, Eric and Chowdhury, Jay, “New menu for MMA
plants,” Chemical Engineering, Mar. 1990, p. 35.
Corbett, Richard A., “ANNUAL PETROCHEMICAL RE-
PORT: Derivative demand pushes ethylene capacity up,” Oil
& Gas Journal, Sept. 4, 1989, p. 53.
Han, S., Shihabi, D.S., Absil, R.P.L., Huang, Y.Y., Leiby, SM.,
Marler, D.O. and McWilliams, J.P., “ZSM-5 catalyst devel-
oped for toluene disproportionation,” Oil & Gas Journal Aug.
21, 1989, p. 84.
Barton, Jan, “Method improves pyrolysis TLE operation,” Oil
& Gas Journal, Jan. 29, 1990, p. 81.
Morrison, T.A. and Laflamme, D., “Advanced controls improve
performance of two-shell dual-pressure column,” Oil & Gas
Journal, May 14, 1990, p. 60.
Coker, A.K., “Program provides short-cut distillation tower
calculations,” Oil & Gas Journal, June 25, 1990, p. 33.
Lieberman, Norman I?, “Diagnosis key to flooding problem
solution,” Oil & Gas Journal, July 16, 1990, p. 62.
Corbett, Richard A., “Proposed OSHA safety regs target process
plant procedures,” Oil & Gas Journal, Aug. 20, 1990, p. 80.
Krembs, John A. and Connolly, James M., “Analysis shows
process industry accident losses rising,” Oil & Gas Journal,
Aug. 27, 1990, p. 40.
Corbett, Richard A., “ANNUAL PETROCHEMICAL RE-
PORT: World ethylene capacity still growing,” Oil & Gas
Journal, Sept. 10, 1990, p. 49.
Lee, A.K.K. and Aitani, A.M., “ANNUAL PETROCHEMI-
CAL REPORT Saudi ethylene plants move toward more feed
flexibility,” Oil & Gas Journal, Sept. 10, 1990, p. 60.
Field, S., “Ethylene profitability trends,” Hydrocarbon Processing,
Vol. 69. No. 03, Mar. 1990, p. 47.
LeBlanc, J.R. and Rovner, J.M., “Remote gas conversion in
worldscale methanol plant,” Hydrocarbon Processing, Vol. 69,
No. 03, Mar. 1990, p. 51.
Carstensen, J.H., et al., “New developments in shift catalysts for
ammonia,” Hydrocarbon Processing, Vol. 69, No. 03, Mar.
1990, p. 57.
Harris, N. and Tuck, M.W., “Butanediol via maleic anhydride,”
Hydrocarbon Processing, Vol. 69, No. 05, May 1990, p. 79.
Di Cintio, R., et al., “Improve ethylene’s demethanizer,” Hydro-
carbon Processing, Vol. 69, No. 12, Dec. 1990, p. 65.
“Methanol supplies could be pinched by mid-1990s,” Oil&Gas
Journal Sept. 17, 1990, p. 82.
“Dewitt study sees growth for polypropylene in 1990s,” Oil &
Gas Journal, Sept. 17, 1990, p. 27.
“Petrochemical recycling to pick up speed,” Oil & Gas Journal,
Oct. 1, 1990, p. 35.
“Phillips 66 Co. restoring Houston petrochem capacity,” Oil &
Gas Journal, Oct. 8, 1990, p. 42.
“Special efforts required to rebuild Hoechst Celanese Pampa
plant,” Oil & Gas Journal Oct. 8, 1990, p. 100.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT Petrochemicals,” Oil & Gas Journal, Oct. 15, 1990, p.
65.
“Westlake’s Louisiana ethylene project past halfway mark,” Oil
& Gas Journal, Oct 29, 1990, p. 31.
Aalund, L.R., “Exxon HDPE train uses Mitsui process,” Oil &
Gas Journal, Dec. 10, 1990, p. 22.
“Shell Berre steam cracker blast causes cited,” Oil & Gas Journal,
Dec. 17, 1990, p. 24.
“Sabic details outlook for key petrochemicals,” Oil & Gas Jour-
nal Jan. 28, 1991.
“Pdvsa, ENI plan Venezuelan methanol plant,” Oil & Gas
Journal, Mar. 18, 1991, p. 135.
“MTBE demand to soar if methanol available,” Oil & Gas
Journal Mar. 25, 1991.
“Iran pushing petrochemical industry growth,” Oil&Gas Jour-
nal, Mar. 25, 1991, p. 29.
“China targets doubling of ethylene capacity by 2000,” Oil &
Gas Journal, Apr. I, 1991, p. 26.
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT Petrochemicals,” Oil & Gas Journal, Apr. 15, 1991, p.
69.
“Chinese downstream projects move forward,” Oil & Gas Jour-
nal, Apr. 29, 1991, p. 40.
Graham, J.F., “ISO QUALITY SYSTEM - Conclusion: Texas
petrochemical plant gets certification,” Oil & Gas Journal,
May 13, 1991, p. 48.
Taylor, M.A., “Ethylene plant steam strips waste water to recover
benzene,” Oil & Gas Journal, May 27, 1991, p. 62.
“Union Texas eyes ethylene plant project,” Oil & Gas Journal,
June 17, 1991, p. 19.
Halle, R.T., and Vadekar, M., “Rust catalyzed ethylene hydro-
genation causes temperature runaway,” Oil & Gas Journal,
June 17, 1991, p. 33.
“UOP acquires acetylene conversion process,” Oil & Gas Jour-
nal June 17, 1991, p. 46.
“Demand for methanol will strain capacity,” Oil & Gas Journal,
Aug. 19, 1991, p. 28.
“Polyolefins operating rate seen staying at less than 90%,” Oil
& Gas Journal, Sept. 30, 1991, p. 38.
“Beijing’s Sinopec adding plants in expansion program,” Oil &
Gas Journal, Oct. 14, 1991, p. 26.
Burns, K.G., et al., “Chemicals increase ethylene plant effi-
ciency,” Hydrocarbon Processing, Vol. 70, No. 01, Jan. 1991,
p. 83.
Sundaram, K.M., et al., “Sty rene plant simulation and optimi-
zation,” Hydrocarbon Processing, Vol. 70, No. 01, Jan. 1991,
p. 93.
Hummel, H.K., et al., “Optimization of EB plant by constraint
control,” Hydrocarbon Processing, Vol. 70, No. 03, Mar. 1991,
p. 67.
“Petrochemical handbook ‘91,” Hydrocarbon Processing, Vol. 70,
No. 03, Mar. 1991, p. 121.
Ibn Salamah, I.A., “Saudi petrochemicals outlook,” Hydrocar-
bon Processing, Vol. 70, No. 05, May 1991, p. 50C.
Brown, R.E. and Lee, EM., “Way to purify cyclohexane,”
Hydrocarbon Processing, Vol. 70, No. 05, May 1991, p. 83.
Di Cintio, R., etal., “Separate ethylene efftciently,” Hydrocarbon
Processing, Vol. 70, No. 07, July 1991, p. 83.
231
TOC/INDEX
Al-Morished, M.H. and Lamb, M.Y., “Synthesize styrene,”
Hydrocarbon Processing, Vol. 70, No. 08, Aug. 1991, p. 125.
Brockwell, H.L., et al., “Sythesize ethers,” Hydrocarbon Process-
ing, Vol. 70, No. 09, Sept. 1991, p. 133.
Fulmer, J.W. and Graf, K.C., “Distill acetone in tower packing,”
Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991, p. 87.
Abraham, O.C. and Chapman, G.L., “Hydrogenate benzene,”
Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991, p. 95.
Armstrong, E.H., “Define olefins competition,” Hydrocarbon
Processing, Vol. 70, No. 10, Oct. 1991, p. 116C.
Gosling, CD., et al., “Upgrade LPG to BTX products,” Hydro-
carbon Processing, Vol. 70, No. 12, Dec. 1991, p. 69.
Schneider, R.V., “Choose optimum syngas route,” Hydrocarbon
Processing, Vol. 71, No. 3, Mar. 1992, p. 51.
Resetarits, M.R., “Trays inhibit foaming,” Hydrocarbon Process-
ing, Vol. 71, No. 3, Mar. 1992, p. 61.
Lee, J. and Wang, C.C., “Dehydrogenate cyclohexanol,” Hydro-
carbon Processing, Vol. 71, No. 3, Mar. 1992, p. 67.
Giacobbe, F.G., et al., “Increase hydrogen production,” Hydro-
carbon Processing, Vol. 71, No. 3, Mar. 1992, p. 69.
Farina, G.L. and Supp, E., “Produce syngas for methanol,”
Hydrocarbon Processing, Vol. 71, No. 3, Mar. 1992, p. 77.
Hausch, G.W., et al., “Structured packing at high pressure,”
Hydrocarbon Processing, Vol. 71, No. 4, Apr. 1992, p. 67.
Turpin, L.E., “Cut benzene out of reformate,” Hydrocarbon
Processing, Vol. 71, No. 6, June 1992, p. 81.
Amorelli, A.A., et al., “Estimate feedstock processability,” Hy-
drocarbon Processing, June 1992, p. 93.
Wagner, E.S. and Fromet, G.F., “Steam reforming analyzed,”
Hydrocarbon Processing, Vol. 71, No. 7, July 1992, p. 69.
“Petrochem health, safety training at issue,” Oil&Gas Journal,
Oct. 21, 1991, p. 41.
“WORLDWIDE CONSTRUCTION REPORT: Petrochemi-
cals,” Oil & Gas Journal, Oct. 28, 199 1, p. 65.
“Statoil outlines MTBE development program,” Oil & Gas
Journal, Nov. 25, 1991, p. 37.
“MTBE key to Total’s octane campaign,” Oil & Gas Journal,
Dec. 16, 1991, p. 35.
“Shell plans MTBE units,” Oil & Gas Journal, Dec. 16, 1991,
p. 35.
“Two petrochemical plants scheduled at Venezuelan sites,” Oil
& Gas Journal, Jan. 13, 1992, p. 17.
Albano, John V., Olszewski, Edward E, and Fukushima, Toshi-
yuki, “Gas turbine integration reduces ethylene plant’s energy
needs,” Oil & Gas Journal Feb. 10, 1992, p. 55.
“S. Korean petchem exports to soar,” Oil & Gas Journal, Mar.
30, 1992, p. 23.
Upchurch, James Alan, “Big Texas C3 splitter unites feedstock
suppliers with users,” Oil & Gas Journal Mar. 30, 1992, p. 58.
Udengaard, Niels R., Bak Hansen, Jens-Henrick, Hanson,
David C., and Stal, Joseph A., “Sulfur passivated reforming
process lowers syngas H2/CO ratio,” Oil & Gas Journal, Mar.
9, 1992, p. 62.
“Thai petrochemical boom on track,” Oil & Gas Journal Mar.
16, 1992, p. 29.
“India approves big petchem project,” Oil & Gas Journal, Apr.
6, 1992, p. 42.
“Taiwanese companies expanding petrochemical investment,”
Oil & Gas Journal, Apr. 13, 1992, p. 30.
232 References
“Polyolefins handling plant nears start-up,” Oil & Gas Journal,
Apr. 13, 1992, p. 52.
Brahn, Michael G., “Olefin recovery from FCC offgas can pay
off,” Oil & Gas Journal, Apr. 20. 1992, p. 94.
“China schedules construction of polypropylene unit,” Oil &
Gas Journal Apr. 27, 1992, p. 29.
“New process produces alternative oxygenate from propylene,”
Oil & Gas Journal, May 25, 1992, p. 39.
“BP-Enichem venture to dominate European polystyrene mar-
ket,” Oil & Gas Journal, June 8, 1992, p. 36.
“S. Korea moving up petrochem list,” Oil & Gas Journal, June
15, 1992, p. 17.
“MTBE plant planned at Mont Belvieu,” Oil & Gas Journal,
June 15, 1992, p. 32.
“Cleaning up gasoline will increase refinery hydrogen demand,”
Oil & Gas Journal, July 27, 1992, p. 92.
Summers, Daniel R., Coleman, Steven T., and Venner, Ronald
M., “Ethylene fractionator revamp results in 25% capacity
increase,” Oil & Gas Journal Aug. 10, 1992, p. 52.
“Beijing project to use Texaco technology,” Oil & Gas Journal,
Aug. 17, 1992, p. 103.
“DOE to help fund methanol production project,” Oil & Gas
Journal, Sept. 7, 1992, p. 31.
Rhodes, Anne K., “U.S. refiners choose variety of routes to
MTBE,” Oil&Gas Journal, Sept. 7, 1992, p. 36.
“Novacor slates petrochem expansions, upgrades,” Oil & Gas
Journal Sept. 14, 1992, p. 36.
“Shell, Montedison to form polyolefins joint venture,” Oil &
Gas Journal, Sept. 28, 1992, p. 32.
“Petrochem industry expends North American MTBE capac-
ity,” Oil & Gas Journal, Oct. 5, 1992, p. 34.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Tomlinson, T.R., “Produce more LPG,” Hydrocarbon Processing,
Vol. 71, No. 12, Dec. 1992, p. 75.
Baas, J. and Warner, R., “How much ‘life’ is left in your olefin
unit?,” Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992,
p. 81.
Sarathy, P.R. and Suffridge, G.S., “Etherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 0 1, Jan. 1993, p. 89.
Tagoe, C., et al., “Are there contaminants in your feedstream?,”
Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 117.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Part 2,”
Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Lian, H.Y., et al., “Vibration effects of two-phase cross flow on
heat exchangers,” Hydrocarbon Processing, Vol. 72, No. 03,
March 1993, p. 53.
Gorra, Filippo, Breckenridge, Lee L., Guy, Wayne M., and
Sailor, Robert A., “Selective toluene disproportionation proc-
ess proven at Italian refinery,” Oil & Gas Journal, Oct. 12,
1992, p. 60.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Petrochemicals,” Oil & Gas Journal, Oct. 26, p. 102.
“IFP offers three new process technologies,” Oil & Gas Journal
Nov. 23, p. 36.
Sarrazin, Patrick, Cameron, Charles J., Barthel, Yves, and Mor-
rison, M. Edward, “Processes prevent detrimental effects from
TOC/INDEX
As and Hg in feedstocks,” Oil & Gas Journal, Jan. 25, 1993,
p. 86.
“Methanol plant design choices affect operations, costs, other
equipment,” Oil & Gas Journal, Mar. 29, 1993, p. 53.
“New two-stage process converts butadiene to ethylbenzene,”
Oil & Gas Journal, Mar. 29, 1993, p. 58.
“Korean company starts up first ARS-based ethylene unit,” Oil
& Gas Journal, Mar. 29, 1993, p. 60.
“Plans advance for Chinese ammonia unit,” Oil & Gas Journal
Apr. 5, 1993, p. 32.
Bell, Laura, “WORLDWIDE CONSTRUCTION SURVEY-
Petrochemicals,” Oil & Gas Journal, Apr. 12, 1993, p. 70.
“Phillips ready to license process for production of fuel ethers,”
Oil & Gas Journal, Apr. 19, 1993, p. 24.
“Petrochemical complex due in Kuwait,” Oil & Gas Journal July
5, 1993, p. 23.
“Taiwan’s sixth naphtha cracker gets green light,” Oil & Gas
Journal, July 12, 1993, p. 34.
Rhodes, Anne K., “Texas plant will use new process to copro-
duce propylene oxide, MTBE,” Oil & Gas Journal, Aug. 30,
1993, p. 82.
Goelzer, Alan R., Ram, Sanjeev, Hernandez-Robinson, Agustin,
Chin, Arthur A., Harandi, Mohsen N., and Smith, C. Morris,
“Refiners have several options for reducing gasoline benzene,”
Oil & Gas Journal, Sept. 13, 1993, p. 63.
Higgins, Thomas, Thorn, James, “Solvents: Know your op-
tions,” Chemical Engineering, Mar. 1994, p. 92.
Christensen, TS. and Primdahl, II., “Improve syngas produc-
tion using autothermal reforming,” Hydrocarbon Processing,
Vol. 73, No. 03, Mar. 1994, p. 39.
Sedriks, W., “Understanding the petrochemical cycle, Part 1,”
Hydrocarbon Processing, Vol. 73, No. 03, Mar. 1994, p. 49.
Montagna, A.A. and Floyd, J.C., “Single-sited catalysis leads
next polyolefin generation,” Hydrocarbon Processing, Vol. 73,
No. 03, Mar. 1994, p. 57.
Sedriks, W., “Understanding the petrochemical cycle, Part 2,”
Hydrocarbon Processing, Vol. 73, No. 04, Apr. 1994, p. 45.
Sanchezllanes, Teresa, Perez, Ana Lilia, Martinez, Martha P.,
Aguilar-Rodriguez, Enrique, and de1 Rosal, Rodolfo, “Simple
rules help select best hydrocarbon distillation scheme,” OiI &
Gas Journal, Oct. 18, 1993, p. 50.
“Quantum to shut down three LDPE units,” Oil & Gas Journal,
Nov. 29, 1993, p. 29.
“Lyondell advances petrochemical operations,” Oil & Gas Jour-
nal Dec. 6, 1993, p. 20.
Myers, Philip E., “OSHA confined-space reg interpreted for
storage tank operations,” Oil & Gas Journal, Feb. 14, 1994, p.
84.
“Ammonia plant in Indonesia tops own world mark,” Oil & Gas
Journal, Feb. 28, 1994, p. 30.
“Dow starts up new ethyleneamines plant,” Oil & Gas Journal,
Mar. 7, 1994, p. 81.
“Toral slates two ETBE units at its French refineries,” Oil &Gas
Journal, Mar. 14, 1994, p. 28.
“Shell Nederland plans petrochem units,” Oil & Gas Journal,
Mar. 21, 1994, p. 48.
“Nigerian petrochemical project aims to start production by
midyear,” Oil & Gas Journal, Apr. 4, 1994, p. 81.
“Naphtha cracker starts up in Taiwan,” Oil & Gas Journal, Apr.
4, 1994, p. 83.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Singapore petrochem contracts let,” Oil & Gas Journal Apr.
25, 1994, p. 32.
Rhodes, Anne K., “World ethylene capacity tops 71 million
mtly,” Oil & Gas Journal, Apr. 25, 1994, p. 35.
“Ethylene survey,” Oil & Gas Journal Apr. 25, 1994, p. 40.
“Industry analysts focus on U.S., Asian, Latin American mar-
kets,” Oil & Gas Journal, Apr. 25, 1994, p. 45.
“Argentine polybutenes producer installing dehydro unit,” Oil
& Gas Journal Apr. 25, 1994, p. 50.
“China’s Campaign For Petrochem Self-Sufficiency,” Oil & Gas
Journal May 9, 1994, p. 43.
“Polystyrene Weak Link In China’s Burgeoning Petrochem In-
dustry,” Oil & Gas Journal, May 9, 1994, p. 52.
“New additive retards coke formation in ethylene furnace
tubes,” Oil & Gas Journal May 9, 1994, p. 73.
“FINA polypropylene plant due expansion,” Oil & Gas Journal,
July 11, 1994, p. 29.
“Refinery, petrochemical plant injuries decline,” Oil & Gas
Journal, July 25, 1994, p. 102.
“New ammonia plant starts up at complex in E. Java, Indone-
sia,” Oil & Gas Journal, July 25, 1994, p. 114.
Rhodes, Anne K., “New integrated methanol/NH3 plant starts
up in Oklahoma,” Oil & Gas Journal, Aug. 8, 1994, p. 65.
“Borealis to finish polyethylene plant,” Oil & Gas Journal, Sept.
12, 1994, p. 106.
IX. DELAYED COKING
Lieberman, Norman I?, “Frequently asked questions on coke
quality answered,” Oil & Gas Journal, Mar. 27, 1989, p. 67.
Nagy, Anthony J. and Antalffy, Leslie l?, “Head operating
mechanism improves delayed coker safety, efftciency,” Oil &
Gas Journal, May 29, 1989, p. 77.
Acciarri, Jerry A. and Stockman, Gordon H., “Demand for
superhuman needle cokes on upswing,” Oil & Gas Journal,
Dec. 25, 1989, p. 118.
Lieberman, Norman P., “Causes of shorter delayed coker heater
runs reported,” Oil & Gas Journal, Feb. 12, 1990, p. 49.
Corbett, Richard A., ‘ANNUAL REFINING REPORT: Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
26, 1990, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT Annual
Refining Survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Elliot, J.D., “Design, operation factors can up coker liquid
yields,” Oil & Gas Journal Feb. 4, 1991, p. 41.
Swain, E.J., “REFINERY COKE - 1: Major growth in coke
production takes place,” Oil & Gas Journal, May 6, 1991, p.
100.
Swain, E.J., “REFINERY COKE - Conclusion: Power, cement
industries shape coke future,” Oil & Gas Journal, May 20,
1991.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
Dymond, R.E., “World markets for petroleum coke,” Hydrocar-
bon Processing, Vol. 70, No. 09, Sept. 1991, p. 162C.
233
TOC/INDEX
Adams, W.V., “Assure delayed coking safety,” Hydrocarbon PYOC-
essing, Mar. 1992, p. 109.
Thorpe, Wilson A. and Sivaraman, Srini, “Simple techniques
reduce coke inventory, sales measurement errors,” Oil & Gas
Journal, Jan. 18, 1993, p. 44.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 73, No. 12, Dec.
1993, p. 1ooc.
Sloan, H.D., “Refinery expansion/upgrading means lighter,
quality products,” Hydrocarbon Processing, Vol. 73, No. 01,
Jan. 1994, p. 82C.
Bansal, B.B., et al., “I mprove your coking process,” Hydrocarbon
Processing, Vol. 73, No. 02, Feb. 1994, p. 63.
“Latest coker designs increase liquid yields, reduce emissions,”
Oil & Gas Journal, Nov. 8, 1993, p. 82.
“Bonner & Moore sees gain in U.S. delayed coking capacity,”
Oil & Gas Journal, Dec. 27, 1993, p. 30.
Rhodes, Anne K., “Lyondell, Citgo join for heavy oil upgrade
project at Houston refinery,” Oil & Gas Journal, Mar. 21,
1994, p. 60.
“NPRA Q&A: Refiners exchange experiences on FCC prob-
lems, coking operations,” Oil & Gas Journal May 2, 1994, p.
110.
“Oman, India team up for proposed fertilizer plant,” Oil & Gas
Journal, Aug. 15, 1994, p. 33.
“DOE: New process cuts ethanol cost,” Oil & Gas Journal, Aug.
15, 1993, p. 48.
X. ENVIRONMENTAL CONTROLS
Concawe, “Survey reveals Europe’s refinery waste disposal meth-
ods, amounts, and costs,” Oil & Gas Journal, Aug. 28, 1989,
p. 53.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Tzikas, Stephen A., “Save money on drum-quality waste dis-
posal,” Chemical Engineering, Feb. 1989, p. 118.
Parkinson, Gerald, “Surging interest in leakproof pumps,”
Chemical Engineering, June 1989, p. 30.
Hopper, David R., “Cleaning up contaminated waste sites,”
Chemical Engineering, Aug. 1989, p. 94.
Parkinson, Gerald, and Johnson, Eric, “Designer catalysts are all
the rage,” Chemical Engineering, Sept. 1989, p. 30.
Anderson, P.H. and McInnes, R.G., “Guidelines for SARA
compliance,” Hydrocarbon Processing, Vol. 68, No. 01, Jan.
1989, p. 77.
Schultz, D.L., “The communication side of environmental
control,” Hydrocarbon Processing, Vol. 68, No. 04, Apr. 1989,
p. 63.
Vervalin, C.H., “Loss prevention information resources,” Hy-
drocarbon Processing, Vol. 68, No. 06, June 1989, p. 80.
Baybutt, P,, “Communicating risk, step by step,” Hydrocarbon
Processing, Vol. 68, No. 06, June 1989, p. 85.
Jacobs, H.C., “Improve process safety reviews,” Hydrocarbon
Processing, Vol. 68, No. 07, July 1989, p. 66.
Iaquaniello, G., et al., “Rotary kiln incineration control strate-
gies,” Hydrocarbon Processing, Vol. 68, No. 08, Aug. 1989, p.
39.
Wimberley, W.E, “To dispose of waste wisely...,” Hydrocarbon
Processing, Vol. 68, No. 08, Aug. 1989, p. 45.
234 References
Isla, M.A., et al., “Improving sour water strippers,” Hydrocarbon
Processing, Vol. 68, No. 08, Aug. 1989, p. 65.
Roberts, R.H., “Design plants for safety,” Hydrocarbon Process-
ing, Vol. 68, No. 09, Sept. 1989, p. 92.
Stacklin, CA., “Expert-control accident mitigation (Part 1),”
Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p. 83.
Mackenzie, John, “Hydrogen peroxide without accidents,”
Chemical Engineering, June 1990, p. 84.
Scacklin, CA., “Expert-contol accident mitigation (Part 2),”
Hydrocarbon Processing, Vol. 68, No. 11, Nov. 1989, p. 71.
Parkinson, Gerald, “HF’s future is up in the air,” Chemical
Engineering, May 1990, p. 39.
Vatavuk, William M., “Pricing equipment for air-pollution
control,” Chemical Engineering, May 1990, p. 126.
Hill, Joel, “Controlling emissions from marine loading opera-
tions,” Chemical Engineering, May 1990, p. 133.
Gallant, R.W., “Highly toxic liquids: Teaching operators to
handle them,” Chemical Engineering, Apr. 1990, p. 116.
Grossel, Stanley S., “Highly toxic liquids: Moving them around
the plant,” Chemical Engineering, Apr. 1990, p. 110.
“SARA goes public,” Chemical Engineering, Mar. 1990, p. 30.
Lucks, John O., “Dispose hazardous wastes safely,” Chemical
Engineering, Mar. 1990, p. 141.
Monshaw, Susan, “New zip in activated carbon,” Chemical
Engineering, Feb. 1990, p. 43.
Arniella, Elio F. and Blythe, Leslie J., “Solidifying traps hazard-
ous wastes,” Chemical Engineering, Feb. 1990, p. 92.
Parkinson, Gerald, “Petroleum refiners clean up their act,”
Chemical Engineering, Jan. 1990, p. 30.
Vaientin, Fred H., “Making chemical-process plants odor: Free,”
Chemical Engineering, Jan. 1990, p. 112.
Melamed, Dennis, “Fixing superfund,” Chemical Engineering,
Nov. 1989, p. 30.
Unzelman, George H., “ETHERS IN GASOLINE-1 : Ethers
have good gasoline-blending attributes,” Oil & Gas Journal,
Apr. 10, 1989, p. 33.
Nougayrede, J. and Voirin, R., “Liquid catalyst efficiently re-
moves H2S,” Oil & Gas Journal July 17, 1989, p. 65.
Nash, Richard M., “REFINING/GAS PROCESSING RE-
PORT: Process conditions and catalyst for low-aromatics
diesel studies,” Oil & Gas Journal, May 29, 1989, p. 47.
DeRoocker, A., Buonocuore, V., Martin, D.E., Marvillet, J.,
Ooms, A.C., Sibra, P., Williams, P.J. and Brandt, J., “Survey
reveals Europe’s refinery-waste disposal methods, amounts,
and costs,” Oil & Gas Journal, Aug. 28, 1989, p. 53.
deWit, Johannes, “Brittle fracture of old storage tanks can be
prevented,” Oil & Gas Journal, Feb. 19, 1990, p. 40.
Corbett, Richard A., “ENVIRONMENT & SAFETY RE-
PORT: Refiners, petrochem plants focus on new waste chal-
lenges,” Oil & Gas Journal Mar. 5, 1990, p. 33.
Unzelman, George H., “REFORMULATED FUELS-1 : Refor-
mulated gasolines will challenge product-quality mainte-
nance,” Oil & Gas Journal, Apr. 9, 1990, p. 43.
Unzelman, George H., “REFORMULATED FUELS-Conclu-
sion: Options to meet 1990s fuel composition rules limited,”
Oil & Gas Journal, Apr. 23, 1990, p. 91.
Suchanek, Arthur J., “Catalytic routes to low-aromatics diesel
look promising,” Oil & Gas Journal, May 7, 1990, p. 109.
TOC/INDEX
Corbett, Richard A., “FUELS FOR TOMORROW-Tough air-
quality goals spur quest for transportation fuel changes,” Oil
& Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal June 18, 1990, p. 52.
Gilman, Robert H., “Capital outlays for gasoline reformulation
can be minimized,” Oil & Gas Journal, Sept. 3, 1990, p. 44.
Finch, R.N. and Serth, R.W., “Model air emissions better,”
Hydrocarbon Processing, Vol. 69, No. 01, Jan. 1990, p. 75.
Anon (Conoco), “Rescue team learns the ropes,” Hydrocarbon
Processing, Vol. 69, No. 01, Jan. 1990, p. 81.
Li, K.Y. and Hsiao, K.J., “VOC stippers: how many trays?,”
Hydrocarbon Processing, Vol. 69, No. 02, Feb. 1990, p. 79.
Nelson, K.E., “Use these ideas co cut waste,” Hydrocarbon
Processing, Vol. 69, No. 03, Mar. 1990, p. 93.
Berglund, R.L. and Snyder, G.E., “Minimize waste during
design,” Hydrocarbon Processing, Vol. 69, No. 04, Apr. 1990,
p. 39.
“Gas Process Handbook ‘90,” Hydrocarbon Processing, Vol. 69,
No. 04, Apt. 1990, p. 69.
Kuhlke, W.C., “Recycle your plastic waste,” Hydrocarbon Proc-
essing, Vol. 69, No. 05, May 1990, p. 89.
Hoare, M.C., “Worldwide options for butane,” Hydrocarbon
Processing, Vol. 69, No. 05, May 1990, p. 116B.
Van Zele, R.L., and Diener, R., “On the road to HF mitigation,
Part 1,” Hydrocarbon Processing, Vol. 69, No. 06, June 1990,
p. 92.
Piel, W.J. and Thomas, R.X., “Oxygenates for reformulated
gasoline,” Hydrocarbon Processing, Vol. 69, No. 07, July 1990,
p. 68.
Van Zele, R.L. and Diener, R., “On the road to HF mitigation,
Part 2,” Hydrocarbon Processing, Vol. 69, No. 07, July 1990,
p. 77.
Early II, W.F. and Eidson, M.A., “Design for zero releases,”
Hydrocarbon Processing, Vol. 69, No. 08, Aug. 1990, p. 47.
Hethcoat, H.G., “Minimize refinery waste,” Hydrocarbon Proc-
essing, Vol. 69, No. 08, Aug. 1990, p. 51.
Steinmeyer, D., “Learn from energy conservation,” Hydrocarbon
Processing, Vol. 69, No. 08, Aug. 1990, p. 57.
Vervalin, C.H., “To incinerate waste...,” Hydrocarbon Processing,
Vol. 69, No. 08, Aug. 1990, p. 61.
Lorenz, W.T., “Where the money is going,” Hydrocarbon Proc-
essing, Vol. 69, No. 08, Aug. 1990, p. 65.
Anon, “EC seeks gasoline emission control,” Hydrocarbon Proc-
essing, Vol. 69, No. 09, Sept. 1990, p. 43.
Wade, D.E., “Manage for process safety,” Hydrocarbon Process-
ing, Vol. 69, No. 09, Sept. 1990, p. 44.
Brown, R.A. and Cartwright, R.T., “Biotreat sludges and soils,”
Hydrocarbon Processing, Vol. 69, No. 10, Oct. 1990, p. 93.
Early II, W.F., et al., “ARCHIE evaluates hazard incidents,”
Hydrocarbon Processing, Vol. 69, No. 11, Nov. 1990, p. 69.
DiBona, C.J., “The environment dominates industry’s atten-
tion,” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p.
49.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Wilson, J.L., “Theme for ‘91 could be ‘The Future is Now’,”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 51.
Beach, R.C., “California, a pacesetter for HPI environmental
future,” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990,
p. 52.
McGraw, L., “Brand new decade brings the same old crisis,”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 53.
Drew, E.H., “Strategies for leadership: a challenge in the 1990s,”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 57.
Tevis, P, “Environmental issues: An E/C’s perspective,” Hydro-
carbon Processing, Vol. 69, No. 12, Dec. 1990, p. 58.
Cooley, D.E, “Strip SO2 from acid treated soil,” Hydrocarbon
Processing, Vol. 69, No. 12, Dec. 1990, p. 85.
Poche, L.R., Derby, R.E., and Wagner, D.R., “Solvent extraction
of refinery wastes rates EPA BDAT,” Oil & Gas Journal, Jan.
7, 1991, p. 73.
“Advanced filter system part of oily groundwater cleanup,” Oil
& Gas Journal, Jan. 14, 1991, p. 59.
“ARCO cites S. California clean air milestone,” Oil & Gas
Journal, Feb. 4, 1991, p. 63.
Brown, G.W., Roderick, D., and Nastri, A., “Dry scrubber
reduces SO;! in calciner flue gas,” Oil & Gas Journal, Feb. 18,
1991, p. 41.
“Landfill closure cell completed at refinery,” Oil&Gas Journal,
Apr. 1, 1991, p. 66.
Yaws, C.L. and Pan, Xiang, “New correlation calculates reliable
paraffin solubiliries,” Oil & Gas Journal Apr. 8, 1991, p. 79.
“Sun outlines R&M environmental initiatives,” Oil & Gas
Journal, May 13, 1991, p. 70.
Taylor, M.A., “Ethylene plant steam strips waste water to recover
benzene,” Oil & Gas Journal May 27, 1991, p. 62.
Spicer, G.W. and Woodward, C., “H2S control keeps gas from
big offshore field on spec,” Oil & Gas Journal, May 27, 1991,
p. 76.
“Fina halts emission releases at Port Arthur plant,” Oil & Gas
Journal, June 24, 1991, p. 31.
Nyman, G.B.G. and Tokerud, A., “Seawater scrubbing removes
SO2 from refinery flue gases,” Oil & Gas Journal July 1, 1991,
p. 52.
Taylor, N.A., Hugill, J.A., van Kessel, M.M., and Verburg,
R.P.J., “Gas-desulfurization plant handles wide range ofsour
gas compositions,” Oil & Gas Journal Aug. 19, 1991, p. 57.
de Filippi, R. and Markiewicz, J., “Propane extraction treats
refinery wastes to BDAT standards,” Oil & Gas Journal, Sept.
9, 1991, p. 52.
Yaws, C.L., Pan, X., and Piper, D.G., Jr., “New correlation
accurately calculates naphthene water solubilities,” Oil & Gas
Journal, Sept. 16, 1991, p. 86.
McInnes, Robert, Jelinek, Steven and Putsche, Victoria, “Cut-
ting toxic organics - Part 1,” Chemical Engineering, Sept. 1990,
p. 108.
McInnes, Robert, Jameson, Kevin and Austin, Dorothy, “Scrub-
bing toxic inorganics - Part 2,” Chemical Engineering, Sept.
1990, p. 116.
McInnes, Robert and Van Royen, Ross, “Desulfurizing fluegases
- Part 3,” Chemical Engineering, Sept. 1990, p. 124,
McInnes, Robert and Van Wormer, Mary B., “Cleaning up NOx
emissions - Part 4,” Chemical Engineering, Sept. 1990, p. 130.
Kirby, G.N. and Firtel, J., “Wastewater systems: Materials of
contruction,” Chemical Engineering, Oct. 1990, p. 166.
235
TOC/INDEX
Gurvitch, Martin M. and Lowenstein, Jack G., “Waste disposal
in pilot plants,” Chemical Engineering, Dec. 1990, p. 108.
Derks, Robert, “Be safe - eliminate PCBs from transformers,”
Chemical Engineering, Jan. 199 1, p. 133.
Helishom, Elyse D., “Removing VOCs from contaminated
water - Part 1,” Chemical Engineering, Feb. 1991, p. 120.
Helishom, Elyse D., “Removing VOCs from contaminated
water - Part 2,” Chemical Engineering, March 1991, p. 152.
Adams, William V, “Sealing off fugitive emissions,” Chemical
Engineering, May 1991, p. 189.
Heumann, William L., “Cyclone separators a family affair,”
Chemical Engineering, June 1991, p. 118.
Li, K.Y. and Hsiao, K.J., “How to optimize an air stripper,”
Chemical Engineering, July 1991, p. 114.
Berglund, R.L. and Lawson, C.T., “Preventing pollution in the
CPI - Part 1,” Chemical Engineering, Sept. 1991, p. 120.
Benforado, D.M., Ridlehoover, G. and Gores, M.D., “Pollution
prevention: One firm’s experience - Part 2,” Chemical Engi-
neering, Sept. 1991, p. 130.
Pojasek, Robert B., “For pollution prevention: Be descriptive,
not prescriptive,” Chemical Engineering, Sept. 1991, p. 136.
Couch, Robert O., “A guide to multiple-pipe containment,”
Chemical Engineering, Sept. 1991, p. 158.
Bosworth, Michael A., “Dilute-phase pneumatic conveying:
Instrument selection guide,” Chemical Engineering, Sept.
1991, p. 166.
Van Valkenburgh, Gary, “Storing hazardous wastes safely,”
Chemical Engineering, Sept. 1991, p. 203.
Stucker, Thomas, “Tracking ever-shrinking emissions,” Chemi-
cal Engineering, Oct. 1991, p. 90.
McGowan, Thomas and Ross, Richard, “Hazardous waste in-
cineration is going mobile,” Chemical Engineering, Oct. 1991,
p. 114.
Campbell, D. and Foundos, A., “Chromatographs meet envi-
ronmental needs,” Hydrocarbon Processing, Vol. 70, No. 02,
Feb. 1991, p. 63.
Matson, L., “Improve secondary containment,” Hydrocarbon
Processing, Vol. 70, No. 03, Mar. 199 1, p. 73.
Leite, O.C., “Smokeless, efficient, nontoxic flaring,” Hydrocar-
bon Processing, Vol. 70, No. 03, Mar. 1991, p. 77.
Singh, B., “Selecting nonasbestos sheet gasketing,” Hydrocarbon
Processing, Vol. 70, No. 04, Apr. 1991, p. 79.
Hyland, R.P., “Environment and maintenance: strategies for the
1990s,” Hydrocarbon Processing, Vol. 70, No. 05, May 1991,
p. 113.
Ross, L.L., “CWRT pushes waste reduction,” Hydrocarbon Proc-
essing, Vol. 70, No. 05, May 1991, p. 121.
Aalbersberg, H.G., “Health, safety, environment: a preconstruc-
tion focus,” Hydrocarbon Processing, Vol. 70, No. 06, June
1991, p. 34B.
Norman, M.E., “Refinery primary sludge listing,” Hydrocarbon
Processing, Vol. 70, No. 08, Aug. 1991, p. 53.
Daggett, J. and Brown, R., “Control compliance costs,” Hydro-
carbon Processing, Vol. 70, No. 08, Aug. 1991, p. 61.
Shelby, SE., et al., “Meet new NPDES permit limits,” Hydro-
carbon Processing, Vol. 70, No. 08, Aug. 1991, p. 67.
Alkhatib, E.A. and Thiem, L.T., “Wastewater oil removal
evaluted,” Hydrocarbon Processing, Vol. 70, No. 08, Aug. 1991,
p. 77.
236 References
Hanson, T.P., et al., “How Shell reduced waste,” Hydrocarbon
Processing, Vol. 70, No. 08, Aug. 1991, p. 83.
Fogman, C.B. and Brummer, T.A., “Ammonia storage for NOx
control,” Hydrocarbon Processing, Vol. 70, No. 08, Aug. 1991,
p. 120.
Newman, S.A., “Sour water design by charts, Part 1,” Hydrocar-
bon Processing, Vol. 70, No. 09, Sept. 1991, p. 145.
Kelly, W.J., “Oversights and mythology in a HAZOP program,”
Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991, p. 114.
Newman, S.A., “Sour water design by charts, Part 3,” Hydrocar-
bon Processing, Vol. 70, No. 11, Nov. 1991, p. 139.
Ruzzo, W.P., Prepare for stormwater regulations,” Hydrocarbon
Processing, Vol. 70, No. 12, Dec. 1991, p. 105.
Kurla, Matthew L. and Jones, Stephen C., “Air pollution per-
mits,” Chemical Engineering, Nov. 1991, p. 225.
Sundin, David, “New options in transformer oils,” Chemical
Engineering, Dec. 1991, p. 125.
Hartung, Robert, Marturana, David, “Water treatment: Invest
in quality program,” Chemical Engineering, Jan. 1992, p. 98.
Princiotta, Frank, “Inside EPA research,” Chemical Engineering,
Mar. 1992, p. 153.
Kobylinski, E.A. and Hunter, G.L., “Wastewater: Part I,”
Chemical Engineering, June 1992, p. 74.
Seton, Waldermar, Fitterer, Richard S. and Harris, Thomas,
“Step up to the challenge: Hazmat storage,” Chemical Engi-
neering, June 1992, p. 118.
Kuryla, Matthew and Yahay, Stephen C., “New safety rules add
to plant managers’ worries, ” Chemical Engineering, June 1992,
p. 153.
Sober, Ronald E and Paul, Dibyendu, “Less-subjective odor
assessment,” Chemical Engineering, Sept. 1992, p. 130.
Ozog, Henry and Stickles R., Peter, “What to do about process
safety audits,” Chemical Engineering, Sept. 1992, p. 173.
Newman, S.A., “Sour water design by charts,” Hydrocarbon
Processing, Vol. 70, No. 11, Nov. 1991, p. 131.
Ruzzo, W.P., “Prepare for stormwater regulations,” Hydrocarbon
Processing, Dec. 1991, p. 105.
Egan, B., “Environment action game plan,” Hydrocarbon Proc-
essing, Jan. 1992, p. 99.
Reynolds, B.E., “Clean gasoline via VRDS/RFCC,” Hydrocar-
bon Processing, Apr. 1992, p. 43.
Jones, D.W., “Lessons from HAZOP experience,” Hydrocarbon
Processing, Apr. 1992, p. 77.
Graham, J.F., “Understand ISO 9000’s application and require-
ments,” Hydrocarbon Processing, May 1992, p. 83.
Rock, K., “TAME: technology merits,” Hydrocarbon Processing,
May 1992, p. 86.
Davis, B.C., “Adventures in Clean Air Act amendments and
implementation,” Hydrocarbon Processing, May 1992, p. 91.
Menon, K.R. and Mink, B.H., “Residue conversion options for
European refineries,” Hydrocarbon Processing, May 1992, p.
100-i.
Hall, J.R., “Cleaner products: a refining challenge,” Hydrocar-
bon Processing, May 1992, p. 100-c.
Crowley, E.D. and Hart, D.G., “Minimize fugitive emissions,”
Hydrocarbon Processing, July 1992, p. 93.
Sarmanian, S., “Improve regulatory compliance,” Hydrocarbon
Processing, Aug. 1992, p. 56.
Gardner, J.F., “Control emissions from valves,” Hydrocarbon
Processing, Aug. 1992, p. 49.
TOC/INDEX
Kunz, R.G., “Control NOx from furnaces,” Hydrocarbon Proc-
essing, Aug. 1992, p. 57.
Oolman, T., “Biotreat oily refinery wastes,” Hydrocarbon Proc-
essing, Aug. 1992.
Freiman, J.p and Hill, J., “Use dispersion modeling update,”
Hydrocarbon Processing, Aug. 1992, p. 73.
Frayne, S.P., “Minimize plant wastewater,” Hydrocarbon Process-
ing, Aug. 1992, p. 79.
Frank, L.D., “Lower plant noise with lagging,” Hydrocarbon
Processing, Aug. 1992, p. 83.
McCluer, P.E. and Whirtle, D.K., “Lessons learned from HA-
ZOP reviews,” Hydrocarbon Processing, Aug. 1992, p. 140-d.
Hyland, R.E and Moore, J.F., “Beyond environmental and safety
compliance,” Hydrocarbon Processing, Sept. 1992, p. 82-c.
Mak, H.Y., “Amine unit converted to MDEA,” Hydrocarbon
Processing, Oct. 1992.
Diepolder, P., “Is zero discharge realistic?,” Hydrocarbon Process-
ing, Vol. 71, No. 10, Oct. 1992, p. 129.
Scott, B., “Identify alkylation hazards,” Hydrocarbon Processing,
Vol. 71, No. 10, Oct. 1992, p. 77.
Reddi, S.V., “Thermal insulation safety, Part 1,” Hydrocarbon
Processing, Vol. 71, No. 10, Oct. 1992, p. 122-C.
Reddi, S.V., “Thermal insulation safety, Part 2,” Hydrocarbon
Processing, Vol. 71, No. 11, Nov. 1992, p. 100-c.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY
Surveyshowsover 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
“Environmental costs close Wyoming refinery,” Oil&Gas Jour-
nal Oct. 21, 1991, p. 41.
“French refiners grappling with new octane specs, environ-
mental rules,” Oil & Gas Journal, Nov. 18, 1991, p. 23.
“Union Carbide claims 99% effectiveness for flue gas scrubber,”
Oil & Gas Journal, Nov. 18, 1991, p. 118.
“Alternative auto fuels pose cost or technical challenge,” Oil &
Gas Journal Dec. 9, 1991, p. 57.
Rhodes, Anne K., “Recentand pending regulations push refiners
to the limit,” Oil & Gas Journal, Dec. 16, 1991, p. 39.
“Industry hits California reformulation move,” Oil & Gas Jour-
nal, Dec. 23, 1991, p. 26.
“NRC: Smog control off mark,” Oil & Gas Journal, Jan. 6, 1992,
p. 40.
“U.S. refiners scramble to meet reformulated gasoline man-
date,” Oil & Gas Journal, Jan. 27, 1992, p. 21.
“Group pursuing new alkylation process,” Oil & Gas Journal,
Feb. 10, 1992, p. 40.
Nasato, Elmo, Goar, B. Gene, and Boorsboom, J., “Canadian
retrofit meets stiffer sulfur recovery regularions,” Oil & Gas
Journal, Feb. 10, 1992, p. 61.
“CERA: Refiners can cope with CAA requirements,” Oil & Gas
Journal, Feb. 17, 1992, p. 27.
“Lyondell to produce gasoline from used lubricating oil,” Oil &
Gas Journal, Feb. 17, 1992, p. 27.
“EPA postpones effective date for benzene reduction rule,” Oil
& Gas Journal Mar. 2, 1992, p. 25,
de Wind, Menno, Heinerman, J.J.L.(Hans), Lee, Seek Leong,
Plantenga, Frans, Johnson, Chris C., and Woodward, Debbie
C., “Au quality and economics spur use of presulfided cata-
lysts,” Oil & Gas Journal, Feb. 24, 1992, p. 49.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Chevron details Port Arthur revamp,” Oil & Gas Journal, Mar.
16, 1992, p. 30.
“Environmental regulatory vise squeezing U.S. refiners,” Oil &
Gas Journal Apr. 13, 1992, p. 21.
“Cogen plant first to use new high-temperature de-NO, proc-
ess,” Oil & Gas Journal, Apr. 13, 1992, p. 53.
“U.S. refiners lament lack of final CAA rules,” Oil & Gas Journal,
May 25, 1992, p. 26.
“New process proudces alternative oxygenate from propylene,”
Oil & Gas Journal, May 25, 1992, p. 39.
Norman, Michael E., Kapoor, Sunil, Smalley, G. Allan, Jr., and
Daniel, Bruce M., “U.S. regs cause refiners to rethink waste-
water systems,” Oil & Gas Journal, June 1, 1992, p. 54.
“Chevron’s ‘clean’ diesel gets California nod; Unocal mostly opts
out of state’s diesel market,” Oil & Gas Journal June 8, 1992,
p. 30.
“Mobil refineries reduce wastes,” Oil & Gas Journal, June 15,
1992, p. 29.
Norman, Michael E., Kapoor, Sunil, Smalley, G. Allan, Jr., and
Daniel, Bruce M., “Hazardous waste regs affect refinery waste-
water schemes,” Oil & Gas Journal, June 15, 1992, p. 45.
Norman, Michael E., Kapoor, Sunil, Smalley, G. Allan, Jr., and
Daniel, Bruce M., “Wastewater planning helps meet antici-
pated changes in regulations,” Oil & Gas Journal, June 29,
1992, p. 63.
“EPA moves to ease industrial air pollution rules,” Oil & Gas
Journal July 6, 1992, p. 26.
Lemanski, John, “Automated compressor-packing system meets
California emissions reg,” Oil & Gas Journal, July 6, 1992, p.
71.
“Oxygenates to hike gasoline price,” Oil & Gas Journal Aug. 3,
1992, p. 28.
“Ontario to stiffen water pollution rules,” Oil & Gas Journal,
Aug. 31, 1992, p. 27.
“Ashland beats target in program to cut emissions,” Oil & Gas
Journal, Sept. 7, 1992, p. 33.
Rhodes, Anne K., “U.S. refiners choose variety of routes to
MTBE,” Oil & Gas Journal, Sept. 7, 1992, p. 36.
Eble, Karen S., and Feathers, Jennifer, “Characterization of
streams first step in reuse scheme,” Oil & Gas Journal, Sept.
21, 1992, p. 87.
“Two-step process treats variety of waste water streams,” Oil &
Gas Journal, Sept. 28, 1992, p. 84.
“Petrochem industry expands North American MTBE capac-
ity,” Oil & Gas Journal, Oct. 5, 1992, p. 34,
Eble, Karen S., and Feathers, Jennifer, “Water reuse optimiza-
tion requires knowledge of cleanup methods,” Oil & Gas
Journal, Oct. 5, 1992, p. 83.
Harris, Graham E., Fuchs, Michael R., and Holcombe, Larry J.,
“A guide to environmental testing,” Chemical Engineering,
Nov. 1992, p. 98.
Garg, Ashutosh, “Trimming NOx from furnaces,” Chemical
Engineering, Nov. 1992, p. 122.
Kroupa, Ralph, “Selecting valves for tough conditions,” Chemi-
cal Engineering, Feb. 1993, p. 74.
Spock, Thomas, “Control fugitive emissions from valves,”
Chemical Engineering, Feb. 1993, p, 82.
Colannino, Joseph, “Low-cost techniques reduce boiler NOx,”
Chemical Engineering, Feb. 1993, p. 100.
237
TOC/INDEX
McGowan, Thomas E., Lipinski, George E. and Santoleri,
Joseph J., “New rules affect the handling of waste fuels,”
Chemical Engineering, Mar. 1993, p. 122.
Kotcher, Raymond L., “Turn a permitting challenge into an
opportunity,” Chemical Engineering, Mar. 1993, p. 157.
Lin, Sheng H. and Yeh, Kuo L., “Looking to treat wastewater?
Try ozone,” Chemical Engineering, May 1993, p. 112.
Blair, Hugo, “The Environmental pluses ofdiaphragm pumps,”
Chemical Engineering, May 1993, p. 118.
Stubblefield, Fred, Jr., “Get topnotch performance from jack-
eted pipes,” Chemical Engineering, June 1993, p. 110.
Jespersen, Chris, Jerger, Douglas and Exner, Jurgen, “Bioreme-
diation tackles hazwaste,” Chemical Engineering, June 1993,
p. 116.
Fruci, Leonard, “Valves put a plug on emissions,” Chemical
Engineering, June 1993, p. 139.
Anspach, Kenneth, “Insuring against environmental risks,”
Chemical Engineering, June 1993, p. 145.
Crowley, E.D., “Stemming leaks with spiral-wound gaskets,”
Chemical Engineering, July 1993, p. 139.
Kuryla, Matthew, “TSCA traps for the unwary plant manager,”
Chemical Engineering, Sept. 1993, p. 161.
Diepolder, P., “Is ‘zero discharge’ realistic?,” Hydrocarbon Proc-
essing, Vol. 71, No. 10, Oct. 1992, p. 129.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Higgins, T.S., “U.S. refiners will make tough decisions in 1993,”
Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p. 33.
Luding, W., “Europe’s harried refiners face regulatory chal-
lenge,” Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992,
p. 34.
Lenz, L.J., “Global harmonization is chemical indusrry focus,”
Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p. 36.
Tejml, E.L., “Commodity petrochemicals look to an uncertain
1993,” Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992,
p. 41.
Sutton, M., “HPI’s gas processors expect growing demand,”
Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p. 44.
Evans, R.E., “Environmental technology can be cost effective,”
Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p. 47.
Petchonka, J., et al., “How CAA impacts polymer processing,”
Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 95.
Sadhukhan, l? and Bradford, M., “Fluidized bed incineration:
improved waste disposal method,” Hydrocarbon Processing,
Vol. 72, No. 03, March 1993, p. 61.
Hanisch, J.L., et al., “How to prepare a successful operating
permit,” Hydrocarbon Processing, Vol. 72, No. 04, Apr. 1993,
p. 95.
Quernemoen, B.L., “When is part substitution okay?,” Hydro-
carbon Processing, Vol. 72, No. 05, May 1993, p. 101.
Felten, J.R., et al., “Residual fuels in a clean-fuels environment,”
Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p. 82-B.
Gallupe, W., “Retrofit methods reduce valves’ fugitive emis-
sions,” Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p.
97.
Capps, R.W., et al., “Reduce oil and grease content in wastewa-
ter,” Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p.
102.
238
Loftus, D., et al., “Partnership programs can solve environ-
mental waste problems,” Hydrocarbon Processing, Vol. 72, No.
07, July 1993, p. 90.
Portal, G.M.A., “Europe’s refiners face new horizons,” Hydro-
carbon Processing, Vol. 72, No. 07, July 1993, p. 92-C.
Cindric, D.T., ec al., “Reduce crude unit pollution with these
technologies,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 45.
Agar, G., et al., “Energy absorption probes control oily-water
discharges,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 55.
Callahan, B. and McCaw, EA., “Risk assessment alleviates envi-
ronmental liabilities,” Hydrocarbon Processing,Vol. 72, No. 08,
Aug. 1993, p. 61.
Anon, “Environmental Processes ‘93,” Hydrocarbon Processing,
Vol. 72, No. 08, Aug. 1993, p. 67.
Bergmann, E.P, “Approximate risk assessment prioritizes reme-
dial decisions,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 111.
Robinson, J.E., “Underground storage tank: removal vs. aban-
donment,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 149.
Rhodes, Anne K., “Suppl iers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
Fusselman, Deborah and Liposher, Dan, “Several technologies
available to cut refinery NOx,” Oil & Gas Journal, Nov. 2,
1992, p. 45.
Abrishamian, Ramin, Kabrick, Randolph, and Swett, Geoffrey,
“Two on site treatment methods reduce sludge waste quanti-
ties,” Oil & Gas Journal, Nov. 2, 1992, p. 51.
Broussard-Welther, Patricia, “Thermal desorption meets BDAT
standards at Louisiana refinery,” Oil & Gas Journal, Nov. 2,
1992, p. 58.
“Bioremediation system treats contaminated soils in Canadian
winter,” Oil & Gas Journal, Nov. 2, 1992, p. 68.
Cunha-Leite, Olavo, “FLARE SYSTEMS-Design alterna-
tives, components key to optimum flares,” Oil & Gas Journal,
Nov. 23, 1992, p. 70.
“New technology reduces SOx emissions,” Oil & Gas Journal,
Nov. 30, 1992, p. 54.
Cunha-Leite, Olavo, “FLARE SYSTEMS-Safety, noise, and
emissions elements round out flare guidelines,” Oil & Gas
Journal, Dec. 7, p. 68.
“EPA issues clarification on rule governing benzene emissions,”
Oil & Gas Journal, Jan. 18, 1993, p. 24.
“Tests show limits on oxygen content to be unwarranted,” Oil
& Gas Journal, Jan. 18, 1993, p. 46.
“W. European refiners face tough environmental rules,” Oil &
Gas Journal, Jan. 25, 1993, p. 29.
“Big upgrade slated at Shell’s Pernis refinery,” Oil & Gas Journal,
Jan. 25, 1993, p. 40.
“NPRA Q&A—1: Experience exchanged on complex effects of
catalysts,” Oil & Gas Journal, Feb. 22, 1993, p. 45.
“Diesel fuel quality is improving in most European countries,”
Oil & Gas Journal Mar. 8, 1993, p. 54.
“Oxygenated fuel cuts emissions, EPA data show,” Oil & Gas
Journal Mar. 22, 1993, p. 32.
“California approves Texaco diesel,” Oil & Gas Journal Mar. 22,
1993, p. 34.
References
TOC/INDEX
“U.S. refiners face record stacks of laws and regulations,” Oil & Grover, R. and Gomaa, H.M., “Proven technologies manage
Gas Journal, Mar. 29, 1993, p. 32.
“Italian refiners’ environmental spending to soar in 1990s,” Oil
& Gas Journal, Apr. 5, 1993, p. 19.
True, Warren R., “GLYCOL-REBOILER EMISSIONS-l:
Federal, state efforts force reexamination of glycol-reboiler
emissions,” Oil & Gas Journal, May 17, 1993, p. 28.
True, Warren R., “GLYCOL-REBOILER EMISSIONS-2:
Glycol mass-balance method scores high for estimating
BTEX, VOC emissions,” Oil & Gas Journal, May 31, 1993,
p. 54.
Myers, Philip E. and Ferry, Robert L., “Tables simplify deluge
of U.S. storage tank regulations,” Oil & Gas Journal June 7,
1993, p. 46.
True, Warren R., “GLYCOL-REBOILER EMISSIONS-
Conclusion: PC program estimates BTEX, VOC emissions,”
Oil & Gas JoumaI, June 14, 1993, p. 36.
Rhodes, Anne K., “Recommissioned German refinery ready ro
meet tough fuels, emissions specs,” Oil & Gas Journal, Aug.
9, 1993, p. 29.
“Glycol reboiler emissions control process tested,” Oil & Gas
Journal, Aug. 23, 1993, p. 44.
“Witco: new diesel grade meers California specs,” Oil & Gas
Journal Aug. 30, 1993, p. 24.
“Ash1 an d produces low sulfur diesel for highway use,” Oil&Gas
Journal, Sept. 20, 1993, p. 42.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Sweetland, Kirk, “Dealing with lead in the workplace,” Cbemi-
cal Engineering, Dec. 1993, p. 127.
Morelli, Janis A., “Performing environmental audits,” Chemical
Engineering, Feb. 1994, p. 104.
Giffin, Gary L., “Keeping a lid on volatile liquids,” Chemical
Engineering, Feb. 1994, p. 147.
Higgins, Thomas and Thorn, James, “Solvents: Know your
options,” Chemical Engineering, Mar. 1994, p. 92.
Gorry, Matthew, Arnin, Pradeep and Richardson, D. Wayne,
“Take the guesswork our of demineralization design,” Chemi-
cal Engineering, Mar. 1994, p. 112.
La Russo, Anthony, “Audit your environmental contractors,”
Chemical Engineering, Mar. 1994, p. 149.
Leahy, Maureen C. and Brown, Richard A., “Bioremediation:
Optimizing results,” Chemical Engineering, May 1994, p. 108.
Boyes, Walt, Jean, Randall, “Loo at your process non-invasively,” Gomaa, H. and Allawi, A., “Minimize air-toxic emissions,”
Chemical Engineering, June 1994, p. 84
Blattner, J. Wray and Bramble, Gary M., “Avoiding criminal
liabilities,” Chemical Engineering, June 1994, p. 127.
Cartwrighc, Peter, “Pollution prevention drives membrane tech-
nologies,” Chemical Engineering, Sept. 1994, p. 84.
Barber, Terry A., and Miller, Brian D., “Pervaporation technol-
ogy: Fundamentals and environmental applications,” Chemi-
cal Engineering, Sept. 1994, p. 88.
Simmons, Vicki, et al., “Membrane systems offer a new way to
recover volatile organic air pollutants,” Chemical Engineering,
Sept. 1994. p. 92.
Wagschal, JoAnna J., “Do not let a crisis catch you off guard,”
Chemical Engineering, Sept. 1994, p. 159.
Martinson, B., “How to set up an environmental audit pro-
gram,” Hydrocarbon Processing, Vol. 72, No. 09, Sept. 1993,
p. 55.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
olefin plant’s spent caustic,” Hydrocarbon Processing, Vol. 72,
No. 09, Sept. 1993, p. 61.
Hill, J. and Brush, P., “Performing capital projects in ozone
nonattainment areas,” Hydrocarbon Processing, Vol. 72, No.
09, Sept. 1993, p. 76C.
Miller, M. and Jackson, R., “New valve packing technology
extends service life,” Hydrocarbon Processing, Vol. 72, No. 10,
Oct. 1993, p. 105.
Riddle, A.L., “Recognize and advertise environmental success,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 139.
Goldblatt, M., “How to justify water conservation projects,”
Hydrocarbon Processing, Vol. 72, No. 12, Dec. 1993, p. 65.
Chieu, J. and Foster, S., “Improve storm water management for
refineries, Part 1,” Hydrocarbon Processing, Vol. 72, No. 12,
Dec. 1993, p. 73.
Capps, R.W., et al., “Design more flexibility into wastewater
treatment,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 81.
Radigan, M.J., “How to select a continuous emission monicor-
ing system,” Hydrocarbon Processing, Vol. 73, No. 02, Feb.
1994, p. 73.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Sokic, M.I., “Life-cycle model assesses petrochemical technol-
ogy,” Hydrocarbon Processing, Vol. 73, No. 07, July 1994, p.
77.
Morgan, D.J. and Swett, G.H., “Simplify remedial decisions by
using risk-based management,” Hydrocarbon Processing, Vol.
73, No. 08, Aug. 1994, p. 37.
Davis, M., “ Use advanced methods to treat wastewater,” Hydro-
carbon Processing, Vol. 73, No. 08, Aug. 1994, p. 43.
King, G.P. and Sinauskas, D., “Does the HON apply to your
facility?,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994,
p. 47.
Anon, “Environmental Processes ‘94,” Hydrocarbon Processing,
Vol. 73, No. 08, Aug. 1994, p. 51.
Radecki, PI?, et al., “Build pollution prevention into system
design,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994,
p. 55.
Vivona, M.A., “Audit environmental processes using life cycle
costs,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p.
115.
Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p. 121.
Johnson, J.E., Tzap, Stephen J., Kelley, Robert E., and Laczko,
Lawrence P., “H2S IN EOR-Gas processing for CO2 EOR
involves sulfur removal,” Oil & Gas Journal, Nov. 15, 1993,
p. 61.
“Stepwise approach selects most effective remediation alterna-
tive,” Oil & Gas Journal Nov. 15, 1993, p. 68.
Johnson, J.E., Tzap, Stephen J., Kelley, Robert E., and Laczko,
Lawrence r), “H2S IN EOR-Options narrowed to Claus or
redox processes,” Oil & Gas Journal Nov. 22, 1993, p. 70.
Rhodes, Anne K., “Technology, efficient operation key elements
in environmental strategy,” Oil & Gas Journal, Nov. 29, 1993,
p. 39.
Frayne, Srephen P, “Refinery operating experiences reveal com-
mon steam-stripper problems,” Oil & Gas Journal, Nov. 29,
1993, p. 50.
239
TOC/INDEX
Fewel, Kenneth J., and Conroy, John H., “Design guidelines for
NH3 injection grids optimize SCR Nox removal,” Oil & Gas
Journal Nov. 29, 1993, p. 56.
Davis, Gregory B., Goss, Michael L., Schoemann, Pete, and
Tyler, Susan S., “Crude oil tank-cleaning process recovers oil,
reduces hazardous wastes,” Oil & Gas Journal Dec. 13, 1993,
p. 35.
Rasmussen, George P., “New desorption process treats refinery
K and F wastes in demo trial,” Oil & Gas Journal, Jan. 10,
1994, p. 48.
“Dutch refinery remediating contaminated soils on site,” Oil &
Gas Journal, Feb. 7, 1994, p. 62.
“Gulf Coast plant slated to process, recycle wastes,” Oil & Gas
Journal Mar. 7, 1994, p. 37.
“Russian refiner tests new one-stage H2S removal process,” Oil
& Gas Journal, Mar. 7, 1994, p. 81.
AL-Tell, Nasser, and Lueders, Richard, “Texas refiner starts up
new waste water treatment plant,” Oil & Gas Journal, Mar.
21, 1994, p. 72.
Portz, Bruce, “Compression upgrade at Texas plant hits emis-
sions targets,” Oil & Gas Journal, Apr. 11, 1994, p. 55.
Aalund, L.R., “Hawaii offers challenge and opportunity to
refiner,” Oil & Gas Journal, May 30, 1994, p. 43.
Aalund, L.R., “Danube refinery operates under complex air
regulations,” Oil & Gas Journal, May 30, 1994, p. 50.
Rhodes, Anne K., “Employee participation key to meeting
environmental goals,” Oil & Gas Journal May 30, 1994, p.
60.
Rhodes, Anne K., “Public, agencies key players in L.A. refiner’s
program,” Oil & Gas Journal May 30, 1994, p. 64.
“Emissions fine imposed at Philadelphia refinery,” Oil & Gas
Journal, June 13, 1994, p. 36.
“Shell inaugurates U.K. water treatment plant,” Oil & Gas
Journal July 25, 1994, p. 113.
“Study sparks German call for benzene reduction in Euroopean
gasoline,” Oil & Gas Journal, Aug. 1, 1994, p. 25.
Rhodes, Anne K., “New process effectively recovers oil from
refinery waste streams,” Oil & Gas Journal Aug. 15, 1994, p.
92.
Yaws, Carl L., Bu, Li, and Nijhawan, Sachin, “New correlation
accurately calculates water solubilities of aromatics,” Oil &
Gas Journal, Aug. 29, 1994, p. 80.
Law, Denny, “New MDEA design in gas plant improves sweet-
ening, reduces CO2,” Oil & Gas Journal Aug. 29, 1994, p.
83.
XI. INSTRUMENTATION, PRODUCT
BLENDING, AND QUALITY CONTROL
Cadmus, Richard H. and Woolsey, Melvin D., “Expert systems
complement refinery information systems,” Oil & Gas Jour-
nal, Jan. 9, 1989, p. 50.
Goodpaster, Ross and Kennedy, J. Patrick, “Software commu-
nications integrated into refinery system,” Oil & Gas Journal
Jan. 16, 1989, p. 53.
Reif, David R., “Standardized field bus would improve inte-
grated computer system communications,” Oil & Gas Journal
Feb. 13, 1989, p. 42.
240 References
Gomez, Jose Vicente, “Correlations allow calculation of density
of petroleum fractions,” Oil & Gas Journal, Mar. 27, 1989, p.
66.
Unzelman, George H., “Ethers in gasoline - 1: Ethers have good
gasoline blending attributes,” Oil & Gas Journal, Apr. 10,
1989, p. 33.
Unzelman, George H., “Ethers in gasoline - Conclusion: Ethers
will play a larger role in octane, environmental specs for
gasoline blends,” Oil & Gas Journal, Apr. 17, 1989, p. 44.
Gibbs, Lewis M., “Additives boost gasoline quality,” Oil & Gas
Journal, Apr. 24, 1989, p. 60.
Nash, Richard M., “Process conditions and catalysr for low-aro-
matics diesel studied,” Oil & Gas Journal, May 29, 1989, p.
47.
Christie, David A. and Holden, David G., “Fluid cat cracking
units’ advanced control can achieve benefits in six areas,” Oil
& Gas Journal, Sept. 25, 1989, p. 104.
Bartholomew, Karl D. and Soudek, Ales, “LP accuracy is im-
proved by incorporating FCC simulation data,” Oil & Gas
Journal, Oct. 30, 1989, p. 57.
Mather, T.W. and Garner, H.E., “Implementing CIM in an
existing facility,” Hydrocarbon Processing, Vol. 68, No. 01, Jan.
1989, p. 43.
Mullins, T.E. and Shorland, M., “Predict asphalt performance,”
Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989, p. 67.
Kulkarni, B.D. and Deshpande, EB., “New method for solving
equations impacts process control,” Hydrocarbon Processing,
Vol. 68, No. 03, Mar. 1989, p. 97.
Kennedy, J.P., “Real-time refinery optimization (Part l),” Hy-
drocarbon Processing, Vol. 68, No. 04, Apr. 1989, p. 57.
Kennedy, J,P., “Real-time refinery optimization (Parr 2),” Hy-
drocarbon Processing, Vol. 68, No. 05, May 1989, p. 57.
“Advanced Process Control Handbook IV,” Hydrocarbon Proc-
essing, Vol. 68, No. 03, Mar. 1989, p. 35.
Lawrence, P.J., “Data reconciliation: Getting better informa-
tion,” Hydrocarbon Processing, Vol. 68, No. 06, June 1989, p.
55.
Ayral, T.E., “On-line expert system for process control,” Hydro-
carbon Processing, Vol. 68, No. 06, June 1989, p. 61.
Rhemann, H., et al., “On-line FCCU advanced control and
optimization,” Hydrocarbon Processing, Vol. 68, No. 06, June
1989, p. 64.
Chawla, V.K., et al., “New digital control algorithm applied to
SISO systems,” Hydrocarbon Processing, Vol. 68, No. 10, Oct.
1989, p. 59.
Yaws, CL. and Yang, H.C., “To estimate vapor pressure easily,”
Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p. 65.
Stacklin, C.A., “Expert-control accident mitigation (Part 1),”
Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p. 83.
“Panel discusses control systems upgrading,” Hydrocarbon Proc-
essing, Vol. 68, No. 10, Nov. 1989, p. 63.
Stacklin, C.A., “Expert-control accident mitigation (Part 2),”
Hydrocarbon Processing, Vol. 68, No. 11, Nov. 1989, p. 71.
Hazlewood, Eric, “Getting the noise out,” Chemical Engineer-
ing, Nov. 21, 1988, p. 105.
Roper, D.L., “Select the right vacuum gage,” Chemical Engineer-
ing, Mar. 1989, p. 125.
Snyder, Dale R., “Understanding distributed control,” Chemical
Engineering, May 1989, p. 87.
TOC/INDEX
Funk, John C. and McAllister, Larry, “Controlling continuous
processes with DCS,” Chemical Engineering, May 1989, p. 90.
Modell, Donald J,, “DCS for batch process control,” Chemical
Engineering, May 1989, p. 97.
Condon, Bejamin T., “Engineering workstations improve pro-
ductivity,” Chemical Engineering, May 1989, p. 104.
May, Donald L. and Koontz, Donald W., “Planning cuts the
cost of retrofitting controls,” Chemical Engineering, Oct.
1989, p. 181.
Mei, Kenneth W., “Automaric tankgauges can be use for custody
transfer,” Oil & Gas Journal, Nov. 13, 1989, p. 81.
Piel, William “EthersJ., will play key role in ‘clean’ gasoline
blends,” Oil & Gas Journal, Dec. 4, 1989, p. 39.
Brown, Gordon W., “Direct measurement of FCC fluidizability
helps spot problems,” Oil & Gas Journal, Jan. 15, 1990, p. 46.
Lindsay, Scott and Palladino, David, “Advanced ion chroma-
tograph detects low MEA levels,” Oil & Gas Journal, Jan 22,
1990, p. 50.
Sivaraman, S., “Guidelines help select storage tank calibration
method,” Oil & Gas Journal, Feb. 5, 1990, p. 41.
Touchstone, Terrell, Blackwell, Derek E., Carter, Grady E., and
Kramer, Jolene K., “Expert system trains, advises process
operators,” Feb. 12, 1990, p. 41.
Ramsey, John R., and Truesdale, Patrick B., “Blend optimization
integrated into refinery-wide strategy,” Oil & Gas Journal,
Mar. 19, 1990, p. 49.
Yatsu, Carolyn A., and Keyworth, Donald A., “ANNUAL RE-
FINING REPORT: Modified MAT and GC help predict
FCC gasoline quality,” Oil & Gas Journal, Mar. 26, 1990, p.
64.
Unzelman, George H., “REFORMULATED FUELS-1: Refor-
mulated gasolines will challenge product-quality mainte-
nance,” Oil & Gas Journal, Apr. 9, 1990, p. 43.
Weeks, Simon A., and Dumbill, Peter, “Method speeds FCC
catalyst attrition resistance determinations,” Oil & Gas Jour-
nal, Apr. 16, 1990, p. 38.
Sivaraman, S., “Field tests prove radar tank gauge accuracy,” Oil
& Gas Journal, Apr. 23, 1990, p. 89.
Unzelman, George H., “REFORMULATED FUELS-Conclu-
sion: Options to meet 1990s fuel composition rules limited,”
Oil & Gas Journal, Apr. 23, 1990, p. 91.
Berto, Frank J., “Hydrostatic tank gauges accurately measure
mass, volume, and level,” Oil & Gas Journal, May 14, 1990,
p. 57.
Morrison, T.A. and Laflamme, D., “Advanced controls improve
performance of two-shell dual-pressure column”, Oil & Gas
Journal, May 14, 1990, p. 60.
“Field trials to provide experience for field-bus standardization,”
Oil & Gas Journal., July 16, 1990, p. 64.
Gilman, Robert H., “Capital outlays for gasoline reformulation
can be minimized,” Oil & Gas Journal Sept. 3, 1990, p. 44.
Palluzi, Richard and Porcelli, Joseph J., “Timely temperature
control of stirred reactors,” Chemical Engineering, Aug. 1990,
p. 143.
Grover, Paul, “Infrared can warn of an impending disaster,”
Chemical Engineering, July 1990, p. 141.
Monshaw, Susan, “Quality advice: Listen to your customers,”
Chemical Engineering, June 1990, p. 27.
Lewis, Clifford W., “Measure remote temperatures efficiently,”
Chemical Engineering, May 1990, p. 114.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Ginesi, Donald, “Electronic transmitter: Key operating tool,”
Chemical Engineering, Apr. 1990, p. 201.
Parkinson, Gerald, “Petroleum refiners clean up their act,”
Chemical Engineering, Jan. 1990, p. 30.
Egol, Len, “Desktop products for process control,” Chemical
Engineering, Dec. 1990, p. 157.
Egol, Len, “What’s new in networking and data acquisition,”
Chemical Engineering, Nov. 1989, p. 269.
Schmer, L.D. and Goodman, M.A., “Using ultrasonics to in-
spect bellows and towers,” Hydrocarbon Processing, Vol. 69,
No. 01, Jan 1990, p. 61.
Mabe, W.J. and Mulholland, R.A., “Variable high-speed motors
optimizesealless pumps,” Hydrocarbon Processing, Vol. 69, No.
02, Feb. 1990, p. 71.
Staroselsky, N. and Carter, D., “Protecting multicase compres-
sors,” Hydrocarbon Processing, Vol. 69, No. 03, Mar. 1990, p.
85.
Breeman, D.J., “Backflush column removes GC sample water,”
Hydrocarbon Processing, Vol. 69, No. 03, Mar. 1990, p. 90.
Poche’, H., “Fiber optics: characteristics and applications,” Hy-
drocarbon Processing, Vol. 69, No. 05, May 1990, p. 85.
Sullivan, T.L., “Refinery-wide blending control and optimiza-
tion,” Hydrocarbon Processing, Vol. 69, No. 05, May 1990, p.
93.
Stanton, B.D., “Using historical data to justify controls,” Hydro-
carbon Processing, Vol. 69, No. 06, June 1990, p. 57.
Conley, R.C. and Ayral, T.E., “Choosing and using advanced
control consultants,” Hydrocarbon Processing, Vol. 69, No. 06,
June 1990, p. 63.
Aronson, C.R. and White, D.C., “Implementacing advanced
controls with new DCSs,” Hydrocarbon Processing, Vol. 69,
No. 06, June 1990, p. 69.
Witt, S.D. and Waggoner, R.C., “Tuning parameters for non-
PID three-mode controllers,” Hydrocarbon Processing, Vol. 69,
No. 06, June 1990, p. 74.
Serridge, M., “Berter machinery monitoring,” Hydrocarbon
Processing, Vol. 69, No. 07, July 1990, p. 53.
Sivasubramanian, R. and Penrod, W.V., “Computer control for
third world: fantasy or reality?,” Hydrocarbon Processing, Vol.
69, No. 08, Aug. 1990, p. 84C.
Campos, M.C.M.M. and Rodrigues, P.S.B., “Program finds
centrifugal compressor operating point,” Hydrocarbon Process-
ing, Vol. 69, No. 09, Sept. 1990, p. 47.
“Advanced Process Control Handbook V,” Hydrocarbon Process-
ing, Vol. 69, No. 09, Sept. 1990, p. 51.
Oser, M.G., “Implementing programmable safety shutdown
systems,” Hydrocarbon Processing, Vol. 69, No. 10, Oct. 1990,
p. 83.
Brambilla, A., et al., “Robust tuning of conventional control-
lers,” Hydrocarbon Processing, Vol. 69, No. 11, Nov. 1990, p.
53.
Weideruh, E. and Strobl, U., “Program evaluates radial com-
pressors, ” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990,
p. 71.
Bloch, H.P., “Laser optics accurately measure running shaft
alignment,” Oil Gas Journal, Nov. 5, 1990, p. 42.
Khan, H.U. and Mungali, M.M., Agrawal, K.M. and Joshi,
G.C., “Graphical method simplifies diesel cloud point deter-
minations,” Oil & Gas Journal Sept. 24, 1990, p. 98.
241
TOC/INDEX
Coker, A.K., “Equilibrium flash calculations quickly computed
on PC,” Oil & Gas Journal, Jan. 14, 1991, p. 55.
Hollrah, D.P. and Burns, A.M., “MMT increases octane while
reducing emissions,” Oil & Gas Journal, Mar. 11, 1991, p.86.
Serpemen, Y., Wenzel, EW., and Huebel, A., “MODERN
FUEL BLENDING - 1: Blending technology key to making
new gasolines,” Oil & Gas Journal, Mar. 18, 1991, p. 62.
Serpemen, Y., Wenzel, F.W., and Huebel, A., “MODERN
FUEL BLENDING - Conclusion: Diesel blending system
cuts quality giveaway,” Oil & Gas Journal, Apr. 1, 1991, p.54.
Schindler, G. and Lamprecht, J., “ISO QUALITY SYTEMS -
1: E&P companies, suppliers move to international stand-
ards,” Oil & Gas Journal, May 6, 1991, p. 92.
Graham, J.F., “ISO QUALITY STYSTEM -Conclusion: Texas
petrochemical planr gets certifcation,” Oil & Gas Journal
May 13, 1991, p. 48.
“Acoustic tests during cooldown find cracks in reactors at Gulf
Coast refinery,” Oil & Gas Journal, June 17, 1991, p. 47.
“Ethyl renews request for HiTEC 3000 approval by EPA,” Oil
& Gas Journal, July 22, I99 1, p. 37.
Khan, H.U., Mungali, M.M., Agrawal, K.M., and Joshi, G.C.,
“Graphical correlation calculates diesel properties from
known values,” Oil & Gas Journal, Sept. 23, 1991, p. 47.
“MTBE: ARCO Chemical’s No. 1 performer,” Oil & Gas Jour-
nal, Oct. 15, 1990, p. 40.
Unzelman, G.H., “OXYGENATES FOR THE FUTURE - 1:
U.S. Clean Air Act expands role for oxygenates,” Oil & Gas
Journal, Apr. 15, 1991, p. 44.
“GM mounts push for reformulated Fuel now,” Oil & Gas
Journal, Mar. 25, 1991, p. 28.
Unzelman, G.H., “OXYGENATES FOR THE FUTURE -
Conclusion: Oxygenate/hydrocarbon shift will rewrite gaso-
line recipes,” Apr. 29, 1991, p. 62.
“More MTBE, TAME plants due U.S.,” Oil & Gas Journal, Apr.
29, 1991, p. 40.
“Coastal Chem breaks ground on MTBE plant,” Oil & Gas
Journal, May 6, 1991, p. 30.
“Tenneco building Houston area MTBE plant,” Oil & Gas
Journal, May 20, 1991, p. 25.
“Mobil, Chemvest study Saudi MTBE plant,” Oil & Gas Jour-
nal, May 20, 1991, p. 27.
“More U.S. oxygenates projects scheduled,” Oil & Gas Journal,
May 27, 1991, p. 32.
Scherr, R.C., Smalley, G.A., Jr., and Norman, M.E., “REFIN-
ING IN THE ’90s - 1: Clean Air Act complicates refinery
planning,” Oil & Gas Journal May 27, 1991, p. 68.
“UOP develops new oxygenates process,” Oil & Gas Journal,
June 3, 1991, p. 30.
“Way clear for reformulated gasoline rule,” Oil & Gas Journal,
Aug. 26, 1991, p. 37.
“Exxon U.S.A. plans three MTBE plants,” Oil & Gas Journal,
Sept. 16, 1991, p. 34.
del Valle El Cid, J.L., “Multiply savings using field multiplex-
ers,” Chemical Engineering, Sept. 1990, p. 164.
Tyson, George K. and Willis, Reid S., “Successful online chemi-
cal analysis,” Chemical Engineering, Dec. 1990, p. 67.
Shinskey, F.G., “Putting controllers to the test,” Chemical Engi-
neering, Dec. 1990, p. 96.
Boteler, Jack E. and Lapus, Benjamin V., “Meter flow with a
pump,” Chemical Engineering, Jan. 1991, p. 96.
242 References
Ginesi, Donald, “Choices abound in flow measurement,”
Chemical Engineering, Apr. 1991, p. 88.
Ginesi, Donald, “A raft of flowmeters on tap,” Chemical Engi-
neering, May 1991, p. 146.
Ottino, Charles, “Designing and laying our a control room,”
Chemical Engineering, Sept. 1991, p. 174.
Hall, G.F., “GC-directed control improves refining,” Hydrocar-
bon Processing, Vol. 70, No. 02, Feb. 1991, p. 47.
Gokhale, N.D., et al., “Advanced control ofnonlinear processes,
Part 1,” Hydrocarbon Processing, Vol. 70, No. 04, Apr. 1991,
p. 75.
Gardner, J.F., “Selecting valves for reduced emissions,” Hydro-
carbon Processing, Vol. 70, No. 08, Aug. 1991, p. 87.
Secterlund, R.B., “Selecting process piping materials,” Hydrocar-
bon Processing, Vol. 70, No. 08, Aug. 1991, p. 93.
Miles, M.E., “Valve and piping safety factors,” Hydrocarbon
Processing, Vol. 70, No. 08, Aug. 1991, p. 103.
Black, P. and Junier, R., “Precise valve position control improves
efficiency,” Hydrocarbon Processing, Vol. 70, No. 08, Aug.
1991, p. 109.
“Advanced Process Control Handbook VI,” Hydrocarbon Proc-
essing, Vol. 70, No. 09, Sept. 1991, p. 51.
Dronoff, A. and Hammann, M., “Improve return on advanced
controls,” Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991,
p. 112.
Porter, Ted, “Upgrading control systems and the bottom line,”
Chemical Engineering, Jan. 1992, p. 137.
Petersen, Kent, “Testingsensors for accuracy and speed,” Chemi-
cal Engineering, Feb. 1992, p. 131.
Bhatt, Siddharth, “Process control ties into business: Part I,”
Chemical Engineering, May 1992, p, 90.
Mehra, Chetan, “The business link,” Chemical Engineering, May
1992, p. 96.
Bell, R. Michael, “Find the hidden errors in batch flow meter-
ing,” Chemical Engineering, May 1992, p. 128.
May, Donald L. and Payne, John Thurman, “Validate process
data automarically,” Chemical Engineering June 1992, p. 112.
Kowalczyk, Stan W., “Root out the silent effects of electrical
noise,” Chemical Engineering, June 1992, p. 145.
Roughton, James E., “Logging plant data without pencil and
paper,” Chemcial Engineering, July 1992, p. 137.
Brown, Nigel P. and Heywood, Nigel I., “The right instrumen-
tation for slurries,” Chemical Engineering, Sept. 1992, p. 107.
Hasselbaum, Robert, “Keeping tabs from afar,” Chemical Engi-
neering, Oct. 1992, p. 148.
Rohan, Thomas H., “Troubleshoot with quality-improvement
methods,” Chemical Engineering, Oct. 1992, p. 161.
Tu, F.C.U., “On-line process identification for SMPC,” Hydro-
carbon Processing, Vol. 70, No. 11, Nov. 1991, p. 115.
Chatha, A., “Fieldbus begins new era in process control,” Hy-
drocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 59.
Senyard, C.P., “Control consulrants address user questions,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 81.
Elliott, J.D., “Maximize distillate liquid production,” Hydrocar-
bon Processing, Vol. 71, No. 01, Jan. 1992, p. 75.
Zhaohul, C. and Xinlu, E, “Use NMR spsectroscopy for on-line
gasoline analysis,” Hydrocarbon Processing, Vol. 71, No. 01,
Jan. 1992, p. 94.
TOC/INDEX
Daneman, H.L., “Improve thermocouple temperature measure-
ment,” Hydrocarbon Processing, Vol. 71, No. 02, Feb. 1992, p.
100.
Yeager, R.L. and Davis, T.R., “Reduce process variation with
real-time SPC,” Hydrocarbon Processing, Vol. 71, No. 03, Mar.
1992, p. 89.
Barreth, R., and Pankoff, “Training DCS operators,” Hydrocar-
bon Processing, Vol. 71, No. 03, Mar. 1992, p. 95.
Berkowittz, I?, “On-line optimal control improves gas process-
ing,” Hydrocarbon Processing Vol. 71, No. 04, Apr. 1992, p.
71.
Conley, R.C. and Clerrico, A.T., “Select and implement a
plantwide imformation system,” Hydrocarbon Processing, Vol.
71, No. 05, May 1992, p. 47.
Stout, J.B., “Develop a strategic automation plan,” Hydrocarbon
Processing, Vol. 71, No. 05, May 1992, p. 57.
Latour, P.R., “Quantify quality control’s intangible benefits,”
Hydrocarbon Processing, Vol. 71, No. 05, May 1992, p. 61..
Kennedy, J.P., “Integrate real-time data with decision support,”
Hydrocarbon Processing, Vol. 71, No. 05, May 1992, p. 69.
Gonzalez-Jeanne, P., “Statistical analysis updates on-line predic-
tive models,” Hydrocarbon Processing, Vol. 71, No. 05, May
1992, p. 75.
Wheatcroft, C., “Present and future refinery information sys-
tems,” Hydrocarbon Processing, Vol. 71, No. 05, May 1992, p.
101.
Ayral, T.E. and Melville, S.J., “Conduct a process control tech-
nology audit,” Hy drocarbon Processing, Vol. 71, No. 06, June
1992, p. 43.
King, M.J., “How to lose money with advanced controls,”
Hydrocarbon Processing, Vol. 71, No. 06, June 1992, p. 47.
Devlin, J.F., “Fluid coker benefits from advanced control,”
Hydrocarbon Processing, Vol. 71, No. 06, June 1992, p. 55.
Fatora, EC., “Successful closed loop and real-time operation,”
Hydrocarbon Processing, Vol. 71, No. 06, June 1992, p. 65.
“On-line quality control for changing setpoints,” Hydrocarbon
Processing, Vol. 71, No. 06, June 1992, p. 75.
Kinm, W.H., “Improve process measurements with a least
squares filter,” Hydrocarbon Processing, Vol. 71, No. 08, Aug.
1992, p. 143.
“Advanced Process Control Handbook VII,” Hydrocarbon Proc-
essing, Vol. 71, No. 09, Sept. 1992, p. 99.
Friedman, Y.Z., “Avoid advanced control project mistakes,”
Hydrocarbon Processing, Vol. 71, No. 11, Oct. 1992, p. 115.
Rowlands, Gareth, Konuk, Aydin, and Kleinschrodt, Frank,
“FCCU advanced controls increase feed rate and column
stability,” Oil & Gas Journal, Nov. 25, 1992, p. 64.
“Auto-oil research finds no immediate benefits in use of gaso-
line-methanol blend,” Oil & Gas Journal, Feb. 24, 1992, p.
46.
Eriksson, Per-Olaf, Tomlins, Aric, and Dash, Sachindra,
“FCCU advanced control system achieves 2-month payout,”
Oil & Gas Journal Mar. 23, 1992, p. 62.
Muller, Alwin, “New method produces accurate octane blend-
ing values,” Oil & Gas Journal, Mar. 23, 1992, p. 80.
Morris, William E., “Simple calculation predicts hydrocarbon
loss from gasoline blends,” Oil & Gas Journal, June 22, 1992,
p. 68.
Gomez, Jose Vicente, “New correlation predicts density of pe-
troleum fractions,” Oil & Gas Journal, July 13, 1992, p. 49.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Amoco producing improved premium for Midwest market,”
Oil & Gas Journal, Sept. 21, 1992, p. 38.
Liptak Bela G., “Level measurement with problem liquids,”
Chemical Engineering, Mar. 1993, p. 130.
Crandall, John A., “How to specify, design and maintain on-line
process analyzers,” Chemical Engineering, Apr. 1993, p. 94.
Hodgson, Steve and Holden, David, “Scaling new heights in
plant automation,” Chemical Engineering, July 1993, p. 103.
Harris, Graham E., Fuchs, Michael R. and Holcombe, Larry J.,
“A guide to environmental testing,” Chemical Engineering,
Nov. 1992, p. 99.
Friedman, Y.Z., “Avoid advanced control project mistakes,”
Hydrocarbon Processing, Vol. 71, No. 10, Oct. 1992, p. 115.
Catena, D., Dietz, J.T and Traubert, T.D., “Create intelligent
P&IDS,” Hydrocarbon Processing, Vol. 71, No. 11, Nov. 1992,
p. 65.
Korchinski, W.J., et al., “FCCU advanced control in a DCS,”
Hydrocarbon Processing, Vol. 71, No. 11, Nov. 1992, p. 73.
Beckman, L.V., “Optimum proof testing of programmable
safety systems,” Hydrocarbon Processing, Vol. 71, No. 11, Nov.
1992, p. 87.
Pakianathan, M.J., “P only or P+I in one controller,” Hydrocar-
bon Processing, Vol. 71, No. 12, Dec. 1992, p. 93.
Dailey, W.V., “Improve process analyzer availability,” Hydrocar-
bon Processing, Vol. 72, No. 01, Jan. 1993, p. 69.
Gruhn, P., “Safety system performance terms: clearing up the
confusion,” Hydrocarbon Processing, Vol. 72, No. 02, Feb.
1993, p. 63.
Beckman, L.V., “Selecting redundant microprocessor-based sys-
tems,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p.
71.
Kobyakov, A.I., “Include heuristics in protection systems,” Hy-
drocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 79.
Golden, S.W., et al., “FCC main fractionator revamps,” Hydro-
carbon Processing, Vol. 72, No. 03, March 1993, p. 77.
Haq, I., “Improve machinery vibration data,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, March 1993, p. 94.
Forsell, K.A., “Protect motors with solid-state overloads,” Hy-
drocarbon Processing, Vol. 72, No. 03, March 1993, p. 100.
Zecter, M.S. and Politzer, B.A., “On-line octane control with
NIR analyzers,” Hydrocarbon Processing, Vol. 72, No. 03,
March 1993, p. 103.
Dollar, R., et al., “Consider adaptive multivariable predictive
controllers,” Hydrocarbon Processing, Vol. 72, No. 03, March
1993, p. 109.
Berkowitz, EN., et al., “On-line optimal NGL recovery in lean
oil plants,” Hydrocarbon Processing, Vol. 72, No. 04, Apr.
1993, p. 55.
Fleming, G. and Dupuis, G.E., “Hydrogen membrane recovery
estimates,” Hydrocarbon Processing, Vol. 72, No. 04, Apr.
1993, p. 61.
Lin, T.D.V., “FCCU advanced control and optimization,” Hy-
drocarbon Processing, Vol. 72, No. 04, Apr. 1993, p. 107.
Kopple, L.B., “Information system master planning,” Hydrocar-
bon Processing, Vol. 72, No. 05, May 1993, p. 45.
Yoshimura, J.S., “Computer integrated manufacturing/process-
ing in the HPI,” Hydrocarbon Processing, Vol. 72, No. 05, May
1993, p. 65.
243
TOC/INDEX
Haskins, D.E., “How to justify small-refinery info/control sys-
tem modernization,” Hydrocarbon Processing, Vol. 72, No. 05,
May 1993, p. 69.
Coonan, T. and Strobhar, D., “Manage plant modernization
projects ‘humanistically’,” Hydrocarbon Processing, Vol. 72,
No. 05, May 1993, p. 55.
Quernemoen, B.L., “When is part substitution okay?,” Hydro-
carbon Processing, Vol. 72, No. 05, May 1993, p. 101.
Hussain, M.S., “Improve planetary gear vibration analysis,”
Hydrocarbon Processing, Vol. 72, No. 05, May 1993, p. 105.
Lines, B., et al., “Polyethylene reactor modeling and control
design,” Hydrocarbon Processing, Vol. 72, No. 06, June 1993,
p. 119.
Dragoo, R.E. and Letendre, R., “Manage costs in real time,”
Hydrocarbon Processing, Vol. 72, No. 07, July 1993, p. 41.
Stoll, K.E., et al., “Simplify fuzzy controller implementation,”
Hydrocarbon Processing, Vol. 72, No. 07, July 1993, p. 49.
King, M.J. and Evans, H.N., “Assessing your competitors’ ap-
plication of CIM/CIP,” Hydrocarbon Processing, Vol. 72, No.
07, July 1993, p. 57.
Roberson, C.G., et al., “Benefits of standardized advanced con-
trols,” Hydrocarbon Processing, Vol. 72, No. 07, July 1993, p.
63.
Pelham, R.O., “Process optimization in the HPI,” Hydrocarbon
Processing, Vol. 72, No. 07, July 1993, p. 69.
Agar, G., et al., “Energy absorption probes control oily-water
discharges,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 55.
Singh, B., et al., “Heavy oil viscosity range from one test,”
Hydrocarbon Processing, Vol. 72, No. 08, Aug. 1993, p. 157.
Jaisinghani, R., et al., “Delayed coker fractionator advanced
control,” Hydrocarbon Processing, Vol. 72, No. 08, Aug. 1993,
p. 173.
Chou, Kelley, Clay, Roger M., Gamez, Jorge I?, Berkowitz, P.N.,
and Papadopoulos, M.N., “Multivariable control system in-
stalled at ARCO West Texas gas plant,” Oil & Gas Journal,
Nov. 16, 1992, p. 53.
Mullally, Michael J. and Goens, Kathleen D., “Changing opera-
tions prompt major gas plant automation,” Oil & Gas Journal,
Dec. 28, 1992, p. 90.
White, John and Hall, Fred, “Gasoline blending optimization
cuts use of expensive components,” Oil & Gas Journal, Nov.
9, p. 81.
“Ashland cites savings in measuring octane,” Oil & Gas Journal,
Nov. 23, 1992, p. 23.
Lubeck, Axe1 J. and Cook, Robert D., “Bromine number should
replace FIA in gasoline olefins testing,” Oil & Gas Journal.
Dec. 28, 1992, p. 86.
Edalat, M., Bozar-Jomehri, R.B., and Mansoori, G.A., “Gener-
alized equation predicts vapor pressure of hydrocarbons,” Oil
& Gas Journal, Feb. 1, 1993, p. 39.
King, Myke, “OIL MOVEMENTS-l: Automarion of oil
movement systems prevents mistakes, saves money,” Oil &
Gas Journal, Mar. 22, 1993, p. 76.
King, Myke, “OIL MOVEMENTS-Conclusion: Integrating
oil movement and data systems beefs project benefits,” Oil &
Gas Journal, Apr. 12, 1993, p. 52.
DiFoggio, Rocco, Sadhukhan, Maya, and Rant, Martha L.,
“Near-infrared techniques for octane analysis have limita-
tions,” Oil & Gas Journal, May 3, 1993, p. 87.
244 References
Riazi, Mohammad-Reza and Mansoori, G. Ali, “Simple equa-
tion of state accurately predicts hydrocarbon densities,” Oil &
Gas Journal, July 12, 1993, p. 108.
“EPA to require addition of dye to higher-sulfur diesel fuel,” Oil
& Gas Journal, Aug. 2, 1993, p. 76.
Aulich, Ted R., He, Xinming, and Knudson, Curtis L., “Gaso-
line sampling technique crucial to ensuring Rvp compliance,”
Oil & Gas Journal, Oct. 4, 1993, p. 30.
Smithline, Herb, “Practical guidelines for temperature measure-
ment.” Chemical Engineering, Dec. 1993, p. 78.
Lewis, Clifford W., “Accuracy in temperature measurements,”
Chemical Engineering, Dec. 1993, p. 85.
Anderson, Jim, et al., “Getting the most from advanced process
control,” Chemical Engineering, Mar. 1994, p. 78.
McPherson, Lori, “Understanding ORP systems,” Chemical
Engineering, Mar. 1994, p. 143.
Ziegler, J.G. and Connell, J.R., “For optimum control: Modify
the process, not the controls-Part I,” Chemical Engineering,
May 1994, p. 132.
McCracken, Philip G., “Technical audits and crucial clues,”
Chemical Engineering, May 1994, p. 161.
Boyes, Walt, “Look at your process non-invasively,” Chemical
Engineering, June 1994, p. 84.
Ziegler, J.G. and Connell, J.R., “For optimum control: Modify
your process-Part 2,” Chemical Engineering, July 1994, p. 107.
Wilson, David H., “Automate bulk-solids delivery with feed-
back control,” Chemical Engineering, Aug. 1994, p. 87.
Brenner, Raul, “Nuclear radiation sees it all,” Chemical Engineer-
ing, Aug. 1994, p. 118.
Book, Neil, Sitton, Oliver, et al., “The road to a common Byte,”
Chemical Engineering, Sept. 1994, p. 98.
Visigalli, R., et al., “Predict AGO quality,” Hydrocarbon Process-
ing, Vol. 72, No. 09, Sept. 1993, p, 47.
Anon, “Advanced process control strategies ‘93,” Hydrocarbon
Processing, Vol. 72, No. 09, Sept. 1993, p. 77.
Wadi, I., “Take an integrated approach to refinery automation,”
Hydrocarbon Processing, Vol. 72, No. 09, Sept. 1993, p. 155.
Leibovici, CE, et al., “I mprove prediction with data reconcili-
ation,” Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p.
79.
Hall, J. and Verne, T, “RCU optimization in a DCS gives fast
payback,” Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993,
p. 85.
Valleur, M., “Integrate offsites management with information
systems,” Hydrocarbon Processing, Vol. 72, No. 11, Nov. 1993,
p. 63.
Pugh, T., et al., “Improve heat exchanger leak detection,” Hy-
drocarbon Processing, Vol. 72, No. 11, Nov. 1993, p. 85.
Christie, D.A., “Improve plant performance with automation
studies,” Hydrocarbon Processing, Vol. 72, No. 11, Nov. 1993,
p. 103.
Early, EL., Jr., and Miller, J., “Fieldbus: How a worldwide
standard will benefit the HPI,” Hydrocarbon Processing, Vol.
72, No. 12, Dec. 1993, p. 107.
Wittliff, M., et al., “Improve plant reliability with information
systems,” Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994,
p. 63.
Page, E.A. and Berggren, J.C., “Improve predictive maintenance
with HFE monitoring,” Hydrocarbon Processing, Vol. 73, No.
01, Jan. 1994, p. 69.
TOC/INDEX
Faust, E., “Pressure calibration standards: How accurate should
they be?,” Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994,
p. 79.
Lang, G.A., “NIRs monitor critical gasoline parameters,” Hy-
drocarbon Processing, Vol. 73, No. 02, Feb. 1994, p. 69.
Radigan, M.J., “How to select a continuous emission monitor-
ing system,” Hydrocarbon Processing, Vol. 73, No. 02, Feb.
1974, p. 73.
Jiskoot, R.J.J., “Improve natural gas sampling techniques,” Hy-
drocarbon Processing, Vol. 73, No. 02, Feb. 1994, p. 77.
Moon, J., “Monitor fluid density accurately,” Hydrocarbon Proc-
essing, Vol. 73, No. 02, Feb. 1994, p. 87.
Friedman, Y.Z., “Model-based control of crude product quali-
ties,” Hydrocarbon Processing, Vol. 73, No. 02, Feb. 1994, p.
97.
Albers, J.E., “Data reconciliation with unmeasured variables,”
Hydrocarbon Processing, Vol. 73, No. 03, Mar. 1994, p. 65.
Morgan, S.W., et al., “Improve process training with dynamic
simulation,” Hydrocarbon Processing, Vol. 73, No. 04, Apr.
1794, p. 51.
Treiber, S., et al., “Optimize control of natural gas plants,”
Hydrocarbon Processing, Vol. 73, No. 04, Apr. 1994, p. 63.
Iscovici, R.S., “Kinetic model solves visbreaker constraint con-
trol problem,” Hydrocarbon Processing, Vol. 73, No. 05, May
1994, p. 109.
Edwards, L.A. and Kipper, J.P., “Computerization: problems
and solutions,” Hydrocarbon Processing, Vol. 73, No. 06, June
1974, p. 57.
Cunningham, D.B., “Adaptive control of sulfur recovery units,”
Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p. 147.
Gill, Milton R., Sisk, Linden B., Warren, Wayne E, and Simp-
son, Terry W., “PLC/PC monitoring, control systems a boon
for smaller NGL plants,” Oil & Gas Journal, Nov. 1, 1993, p.
62.
Wentworth, Craign E., “Guidelines useful for incorporating
DCS in existing process plant,” Oil & Gas Journal, Nov. 29,
1793, p. 74.
Khan, H.U., Dilawar, S.V.K., Nautiyal, S.E, and Srivastava, S.P.,
“New methods determine pour point more accurately than
ASTM D-77,” Oil & Gas Journal, Nov. 1, 1993, p. 74.
Bayard, Pete, “Improved, integrated yield-accounting system
saves time and money,” Oil & Gas Journal, Nov. 22, 1993, p.
67.
Rhodes, Anne K., “U.S. reformulated gasoline rule complex,
confusing,” Oil & Gas Journal, Jan. 17, 1994, p. 16.
“When a refinery stops making JP-4,” Oil & Gas Journal, Jan.
17, 1994, p. 17.
Morris, William E., Smith, William E., and Snee, Ronald D.,
“Interaction blending equations enhance reformulated gaso-
line profitability,” Oil & Gas Journal, Jan. 17, 1994, p. 54.
“California refiners’ RFG worries compounded by dual rules,”
Oil & Gas Journal Jan. 24, 1974, p. 17.
“GPM Gas Corp. brings New Mexico plant on line,” Oil & Gas
Journal, Jan. 24, 1994, p. 41.
Lee, Anthony L., Feldkirchner, Harlan L., Gamez, Jorge I?, and
Meyer, Howard S., “Membrane process for CO2 removal
tested at Texas plant,” Oil & Gas Journal, Jan. 31, 1994, p. 70.
“Meters to answer needs for low cost EFM, energy measure-
ment,” Oil & Gas Journal, Mar. 7, 1974, p. 47.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Trosper, Robert L., Stubbs, Robert G., and Carver, Darrell,
“New Mexico gas plant operator automates field control,” Oil
& Gas Journal Mar. 7, 1794, p. 54.
Stark, Stephen T., and Heuer, Richard D., “Testing paves way
for electronic flow monitoring system,” Oil & Gas Journal,
Mar. 7, 1994, p. 58.
“European diesel fuel quality continues to improve,” Oil & Gas
Journal, Mar. 14, 1994, p. 68.
Poynter, Wesley G., and Barrios, Roy J., “Coulometric Karl
Fischer titration simplifies water content testing,” Oil & Gas
Journal, Apr. 11, 1994, p. 53.
Semwal, Prem B., and Varshney, Ram G., “New pour point
correlations improve economics of distillate blending,” Oil &
Gas Journal, June 6, 1994, p. 89.
“New correlations predict diesel cold-flow properties accu-
rately,” Oil & Gas Journal June 20, 1994, p. 51.
Welch, William T., Bain, Michael L., Maggard, Steven M., and
May, Jack M., “Experience leads to accurate design of NIR
gasoline anlaysis systems,” Oil & Gas Journal, June-27, 774,
p. 48.
XII. MISCELLANEOUS
“Nelson-Farrar cost indexes,” Oil & Gas Journal, Oct. 7, 771,
p. 91; Nov. 4, 1991, p. 75; Dec. 2, 1971, p. 57; Jan. 6, 772,
p. 73; Feb. 3, 1992, p. 50; Mar. 2, 1991, p. 45; Apr. 6, 1972,
p. 61; May 4, 1992, p. 130; June 1, 1972, p. 78; July 6, 1772,
p. 83-84; Aug. 3, 1992, p. 61; Sept. 7, 1992, p. 48; Oct. 5,
1992, p. 82.
“Nelson-Farrar Quarterly Costimating,” Oil & Gas Journal,
Oct. 7, 1791, p. 72; Jan. 6, 1772, p. 82; Apr. 6, 1992, p. 62;
July 6, 1992, p. 84; Oct. 5, 1992, p. 86.
Rhodes, Anne K., ‘Survey shows over 1,000 refining catalysts,”
Oil & Gas Journal, Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
“Fixed-bed reactor successful in fuels from coal synthesis,” Oil
& Gas Journal, Jan. 20, 1772, p. 53.
de Wind, Menno, Heinerman, J.J.L. (Hans), Lee, Seek Leong,
Plantenga, Frans, Johnson, Chris C., and Woodward, Debbie
C., “Air quality and economics spur use of presulfided cata-
lysts,” Oil & Gas Journal, Feb. 24, 1992, p. 49.
“Presulfiding, FCC olefins focus of catalyst sessions,” Oil & Gas
Journal, Mar. 16, 1992, p. 37.
Leiby, Susan, “FCC catalyst technologies expland limits of
process capability,” Oil & Gas Journal Mar. 23, 1992, p. 49.
Koch, Pierre, “Simple program calculates partial liquid vol-
umes,” Oil & Gas Journal, Apr. 13, 1992, p. 54.
“Texaco presses projects for gasification process,” Oil & Gas
Journal, July 6, 1772, p. 38.
Jamialahmadi, Mohamad, and Muller-Steinhagen, Hans,
“Computer program designs packed columns,” Oil & Gas
Journal, Aug. 31, 1972, p. 33.
Jenkins, John H., “LP modeling pieces together reformulation
puzzle,” Oil & Gas Journal, Nov. 16, 1772, p. 41.
Holm, Peter, “Offshore TEG dehydration unit performance
exceeds design,” Oil & Gas Journal, Jan. 25, 1993, p. 96.
Sloley, Andrew W. and Golden, Scott W., “Analysis key to
correcting debutanizer design flaws,” Oil & Gas Journal, Feb.
8, 1993, p. 50.
245
TOC/INDEX
Mani, Karthik C., Matthews, Michael A., and Haynes, Henry
W., Jr., “Continuous’ approach optimizes vapor-liquid equi-
librium calculations,” Oil & Gas Journal, Feb. 15, 1993, p. 76.
England, Ed and George, Spencer, “Idle plant key to quick
completion of tough gas-treating project,” Oil & Gas Journal,
Mar. 15, 1993, p. 57.
Richardson, Kenneth W. and Taibi, Frank D., “Louisiana joint
venture starts up coke-fueled cogen plant,” Oil & Gas Journal,
Apr. 5, 1993, p. 38.
Coker, A.K., “Computer program enhances guidelines for gas-
liquid separator designs,” Oil & Gas Journal, May 10, 1993,
p. 55.
Mehra, Yuv R., Wood, Glenn C., and Ross, Michael M., “Non-
cryogenic N2-rejection process gets Hugoton field test,” Oil
& Gas Journal, May 24, 1993, p. 62.
“Italian refinery plans cogen unit,” Oil & Gas Journal May 31,
1993, p. 78.
Sasson, Richard and Pate, Robin, “Retraying and revamp double
big LPG fractionator’s capacity,” Oil & Gas Journal, Aug. 2,
1993, p. 71.
Connell, David E., Horth, Paul, and Powell, R.H.W., “Analysis
sets optimum C3 recovery for N. Sea gas terminal,” Oil & Gas
Journal, Oct. 4, 1993, p. 74.
XIII. LUBE OIL & WAXES
Smith, Fritz A., and Bortz, Robert W., “Applications vary for
dewaxing process over 1O-year span,” Oil & Gas Journal, Aug.
13, 1970, p. 51.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
“Lube oil catalysts go commercial,” Oil & Gas Journal, Apr. 8,
1991, p. 81.
Brinkman, D.W., “Large grassroots lube rerefinery in opera-
tion,” Oil & Gas Journal, Aug. 17, 1991, p. 60.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
“Lyondell to produce gasoline from used lubricating oil,” Oil &
Gas Journal Feb. 17, 1992, p. 27.
“BP to make lubes in Vietnam,” Oil & Gas Journal, Mar. 2,
1992, p. 29.
“Conoco schedules consolidation of U.S. lubricants,” Oil & Gas
Journal May 11, 1992, p. 26.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
Rhodes, Anne K., “Refinery operating variables key to enhanced
lube oil quality,” Oil & Gas Journal, Jan. 4, 1993, p. 45.
“New extraction-based re-refining process saves money,” Oil &
Gas Journal, May 30, 1994, p. 87.
XIV. MAINTENANCE
Lieberman, Norman P. and Golden, Scott W., “Foaming is
leading cause of tower flooding,” Oil & Gas Journal Aug. 14,
1989, p. 45.
Cat-y, John B. and Liss, Jerome B., “Automated system monitors
refinery pipe corrosion,” Oil & Gas Journal, Sept. 11, 1989,
p. 37.
246 References
Gaylord, ED., “Solving reed frequency vibration problems,”
Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989, p. 50.
Fisher, L., “Operational speed balancing: Should you be doing
it?,” Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989, p. 55.
Misra, L.N., “Unique repair method saved rotor shafts,” Hydro-
carbon Processing, Vol. 68, No. 02, Feb. 1989, p. 54.
Goyal, O.P., “Guidelines on rotating equipment,” Hydrocarbon
Processing, Vol. 68, No. 10, Oct. 1989, p. 39.
Fischbach, M.J., “Dry seal applications in centrifugal compres-
sors,” Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p.
47.
Sheppard, Walter Lee, “Inspection-key to quality masonry
lining,” Chemical Engineering, Mar. 1989, p. 191.
Fijas, David F., “Getting top performance from heat exchang-
ers,” Chemical Engineering, Dec. 1989 p. 141.
Sattler, Frank J., “Improving quality through non-destructive
testing,” Chemical Engineering, Apr. 1989, p. 116.
Kent, George R., “Troubleshooting rotating equipment. Con-
fessions of a service engineer, Part II,” Chemical Engineering,
Apr. 1787, p. 163.
Condon, Benjamin T., “Engineering workstations improve pro-
ductivity,” Chemical Engineering, May 1989, p. 104.
Sattler, Frank J., “Finding surface defects with non-destructive
testing,” Chemical Engineering, July 1989 p. 125.
Sattler, Frank J., “Finding defects with nonde-
structive testing,” Chemical Engineering, Sept. 1989, p. 161.
Egol, Len, “Save dollars on maintenance management,” Chemi-
cal Engineering, June 1990, p. 157.
Ginesi, Donald, “Electronic transmitter: Key operating tool,”
Chemical Engineering, Apr. 1990, p. 201.
Finn, Gavin A. and Reinschmidt, Kenneth F., “Expert systems
in operation and maintenance,” Chemical Engineering, Feb
1790, p. 131.
Sattler, Frank J., “Improving plant maintenance via nondestruc-
tive testing,” Chemical Engineering, Dec. 1989, p. 115.
Sattler, Frank J., “Nondestructive testing via optical and acous-
tical methods,” Chemical Engineering, Nov. 1989 p. 171.
Brown, Gordon W., “Direct measurement of FCC fluidizability
helps spot problems,” Oil & Gas Journal, Jan. 15, 1990, p. 46.
Lieberman, Norman P., “Causes of shorter delayed coker heater
runs reported,” Oil & Gas Journal, Feb. 12, 1990, p. 47.
deWit, Johannes, “Brittle fracture of old storage tanks can be
prevented,” Oil & Gas Journal, Feb. 19, 1990, p. 40.
Heite, Richard S., English, A.R., and Smith G. Andrew, “Bis-
muth nickel passivation effective in FCCU,” Oil & Gas Jour-
nal, June 4, 1990, p. 81.
Bucheim, Gerrit M., “Ways to deal with wet H2S cracking
revealed by study,” Oil & Gas Journal, July 7, 1990, p. 72.
Lieberman, Norman P., “Diagnosis key to flooding problem
solution,” Oil & Gas Journal, July 16, 1990, p. 62.
Bloch, Heinz P. and Carroll, Joseph R., “Preventive maintenance
can be more effective than predictive programs,” Oil & Gas
Journal, July 30, 1990, p. 81.
Archuletta, Jim, Bitler, Bruce, Binford, Mark, and Modi, John,
“Cooperative corrosion control and treatment program proves
effective,” Oil & Gas Journal, Aug. 6, 1990, p. 60.
Corbett, Richard A., “Proposed OSHA safety regs target process
plant procedures,” Oil & Gas Journal Aug. 20, 1970, p. 80.
TOC/INDEX
Krembs, John A. and Connolly, James M., “Analysis shows
process industry accident losses rising,” Oil & Gas Journal,
Aug. 27, 1990, p. 40.
Godse, A.G., “Rotating equipment shop testing,” Hydrocarbon
Processing, Vol. 69, No. 01, Jan. 1990, p. 47.
Prescott, M., “HPRT developments improve payout,” Hydro-
carbon Processing, Vol. 67, No. 01, Jan. 1990, p. 53.
Sohal, H.S. and McClister, W.J., “Hydro-cutting speeds main-
tenanceand retrofitting,” Hydrocarbon Processing, Vol. 69, No.
01, Jan. 1990, p. 65.
Goyal, O.P., “Guidelines on fluid flow systems,” Hydrocarbon
Processing, Vol. 69, No. 04, Apr. 1990, p. 47.
Shull, W.W. and Church, M.L., “Improve pump efficiency,”
Hydrocarbon Processing, Vol. 69, No. 07, July 1990, p. 43.
Maten, S., “Rotors in magnetic bearings require field balancing,”
Hydrocarbon Processing, Vol. 67, No. 07, July 1990, p. 47.
Garbers, A.W.F. and Wash, A.K., “Preventing cavitation in high
energy centrifugal pumps,” Hydrocarbon Processing, Vol. 67,
No. 07, July 1990, p. 48.
Serridge, M., “Better machinery monitoring,” Hydrocarbon
Processing, Vol. 67, No. 07, July 1990, p. 53.
Doolin, J.H., “Pump baseplate design and installation,” Hydro-
carbon Processing, Vol. 69, No. 07, July 1990, p. 57.
Casado, E., “Model optimizes exchanger cleaning,” Hydrocarbon
Processing, Vol. 69, No. 08, Aug. 1990, p. 71.
Leite, O.C., “Structural design of stacks,” Hydrocarbon Process-
ing, Vol. 67, No. 11, Nov. 1990, p. 64.
Bloch, H.P., “Laser optics accurately measure running shaft
alignment,” Oil & Gas Journal, Nov. 5, 1990, p. 42.
“NPRA MAINTENANCE Q&A—1 : Rotary machinery main-
tenance is key process plant activity,” Oil & Gas Journal, Dec.
17, 1990, p. 47.
Lieberman, N.P. and Lieberman, E.T., “Design, installation
pitfalls appear in vac tower retrofit,” Oil & Gas Journal, Aug.
26, 1991 p. 57.
Sivaraman, S., “Field tests prove radar tank gauge accuracy,” Oil
& Gas Journal, Apr. 23, 1990, p. 87.
Sivaraman, S. and Wallace, R.I., “Vessel experience factor issues
clarified,” Oil & Gas Journal, Oct. 15, 1990, p. 44.
Rangel, E.K. and Lindsay, J.D., “System provides secondary
containment for above ground storage tanks,” Oil & Gas
Journal, Oct. 29, 1990, p. 33.
Tamimi, A., “Explosion hazards in crude, distillate storage tanks
assessed,” Oil & Gas Journal, Nov. 19, 1990, p. 53.
“ARCO spells out cause of Channelview blast,” Oil & Gas
Journal, Jan. 14, 1991 p. 22.
Trenchard, A.J., Bull, V., and King, M.J., “Port study solves
refinery shipping bottleneck,” Oil & Gas Journal Jan. 21,
1991, p. 29.
Ludlam, R., “Automatic system drains tank water without prod-
uct loss,” Oil & Gas Journal, July 15, 1991, p. 64.
Berto, EJ., “Gauging data pose question on stability of reference
gauge heights,” Oil & Gas Journal, July 29, 1991 p. 78.
“Refiners receive antispill orders,” Oil & Gas Journal, Sept. 23,
1991, p. 14.
Sattler, Frank J., “Nondestructive testing methods can aid plant
operation,” Chemical Engineering, Oct. 1990, p. 177.
Sattler, Frank J., “Success in managing nondestructive testing,”
Chemical Engineering, Feb. 1991, p. 126.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Ramakrishna, P., “How often to clean an evaporator,” Chemical
Engineering, July 1991, p. 143.
Nasr Ali, “Extending the life of magnetic-drive pumps,” Chemi-
cal Engineering, Oct. 1991, p. 157.
Bloch, H.P., “Use laser optics for on-stream alignment verifica-
tion,” Hydrocarbon Processing, Vol. 70, No. 01, Jan. 1991, p.
71.
Shull, W.W. and Church, M.L., “Field performance test: key to
pump savings,” Hydrocarbon Processing, Vol. 70, No. 01, Jan.
1991, p. 77.
Misra, L.N., “Emergency steam turbine rotor repair,” Hydrocar-
bon Processing, Vol. 70, No. 05, May 1991, p. 126.
Granere, V.R., “Understand torsional vibration,” Hydrocarbon
Processing, Vol. 70, No. 07, July 1991, p. 53.
Gresh, M.T., “On-line cleaning restores compressor perform-
ance,” Hydrocarbon Processing, Vol. 70, No. 07, July 1991,
p. 65.
Croix, R. and Suarez, S., “Monitor cooling tower and cooler
fans,” Hydrocarbon Processing, Vol. 70, No. 07, July 1991,
p. 71.
Dube, J.C., et al., “Reciprocating compressor bottle sizing,”
Hydrocarbon Processing, Vol. 70, No. 07, July 1991, p. 79.
Godse, A.G., “Implement machinery predictive maintenance,”
Hydrocarbon Processing, Vol. 70, No. 09, Sept. 1991, p. 163.
Myers, Phillips, “Keeping above-ground storage tanks in top
shape,” Chemical Engineering, Apr. 1992, p. 161.
Ojala, Russell, “Keep ejectors online,” Chemical Engineering,
May 1992, p. 114.
Kowalczyk, Stan W., “Root out the silent effects of electrical
noise,” Chemical Engineering, June 1992, p. 145.
Pless, Lowell, Bowman, John D., “Scanning columns with
gamma rays,” Chemical Engineering, Aug. 1992, p. 127.
Hasselbaum, Robert, “Keeping tabs from afar,” Chemical Engi-
neering, Oct. 1992, p. 148.
Ray, J., “Fast-track retrofitting,” Hydrocarbon Processing, Vol. 71,
No. 01, Jan. 1992, p. 45.
Petersen, P.R., “Improve corrosion control by computer simula-
tion,” Hydrocarbon Processing, Vol. 71, No. 01, Jan. 1992, p.
50.
Gresh, M.T., “Troubleshooting compressor performance,” Hy-
drocarbon Processing, Vol. 71, No. 01, Jan. 1992, p. 57.
Pennington, J., “In formation key to on-line leak sealing,” Hy-
drocarbon Processing, Vol. 71, No. 01, Jan. 1992, p. 63.
Gandy, T. and Bailey, J.. “Reduce costs with acoustic emission
cool-down monitoring,” Hydrocarbon Processing, Vol. 71, No.
01, Jan. 1992, p. 66.
Chiu, C.H. and Murray, K.L., “Retrofit baseload LNG plants,”
Hydrocarbon Processing, Vol. 71, No. 01, Jan. 1992, p. 69.
Junier, R. and Purvis, H., “Ceramic valves lower FCCU main-
tenance costs,” Hydrocarbon Processing, Vol. 71, No. 01, Jan.
1992, p. 72.
Lester, L. et al., “Building a world class maintenance organiza-
tion,” Hydrocarbon Processing, Vol. 71, No. 02, Feb. 1992, p.
98-c.
Granere, VR., “Torsional vibration: Are your measurements
accurate?,” Hydrocarbon Processing, Vol. 71, No. 04, Apr.
1992, p. 71.
“Nelson-Farrar cost indexes,” Oil & Gas Journal, Oct. 7, 1991,
p. 91; Nov. 4, 1991, p. 75; Dec. 2, 1991, p. 57; Jan. 6, 1992,
p. 73; Feb. 3, 1992, p. 50; Mar. 2, 1991, p. 45; Apr. 6, 1992,
247
TOC/INDEX
p. 61; May 4, 1992, p. 130; J une 1, 1992, p. 78; July 6, 1992,
p. 83-84; Aug. 3, 1992, p. 61; Sept. 7, 1992, p, 48; Oct. 5,
1992, p. 82.
“OSHA levies fine on Citgo,” Oil & Gas Journal, Sept. 9, 1991,
p. 36.
“Nelson-Farrar Quarterly Costimating,” Oil & Gas Journal,
Oct. 7, 1991, p. 92; Jan. 6, 1992, p. 82; Apr. 6, 1992, p. 62;
July 6, 1992, p. 84; Oct. 5, 1992, p. 86.
Strong, Russell C., Majestic, Veronica K., and Wilhelm, Mark
S., “Basic steps lead to successful FCC corrosion control,” Oil
& Gas Joumal, Sept. 30, 1991 p. 81.
Strong, Russell C., Majestic, Veronica K., and Wilhelm, Mark
S., “Basic corrosion control methods solve varied problems,”
Oil & Gas Journal, Oct. 7, 1991, p. 86.
“Petrochem health, safety training at issue,” Oil & Gas Journal,
Oct. 21, 1991, p. 41.
de Wit, Johannes, “Safe jack up method permits repairs of tank
bottoms and foundations,” Oil & Gas Journal, Nov. 4, 1991,
p. 76.
Ferguson, K.R., and Stutheit, A.G., “Weld overlay chosen for
corrosion repair at Texas CO2 plant,” Oil & Gas Journal, Dec.
2, 1991, p. 54.
Ferguson, K.R., and Stutheit, A.G., “Unusual weld overlay
project stressed quality, safety,” Oil & Gas Journal, Jan. 6,
1992, p. 69.
Ferguson, K.R., and Stutheit, A.G., “Extensive testing ensures
success of unusual weld-overlay project,” Oil & Gas Journal
Jan. 13, 1992, p. 39.
“Survey updates amine stress corrosion cracking data,” Oil &
Gas Journal, Jan. 13, 1992, p. 42.
Hassan, Hassan M.K., “Sequential lifting of tank shell used to
repair floors,” Oil & Gas Journal, Feb. 3, 1992, p. 33.
“Kuwaiti refinery repairs eyed,” Oil & Gas Journal, Mar. 9, 1992,
p. 31.
“Refiners discuss HF alkylation process and issues,” Oil & Gas
Journal, Apr. 6, 1992, p. 67.
Bellomo, P.J., “OSHA safety regulations calls for step-by-step
approach,” Oil & Gas Journal, June 1, 1992, p. 49.
Bloch, Heinz, “Bearing seals ward off failures,” Chemical Engi-
neering, Mar. 1993, p. 149.
Heckman, Andrew T., “Vibration monitoring yields big bene-
fits,” Chemical Engineering, May 1993, p. 126.
Thibault, Larry, “Takin gcare of enclosed gear drives,” Chemical
Engineering, May 1993, p. 145.
Andrews, Robert and Weber, Paul, “High pressure operations:
Part 1: Upkeep of equipment,” Chemical Engineering, Sept.
1993, p. 98.
Sheppard, B., “Determine bearing inner race defect length,”
Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p. 101.
Kotnour, T.J., “Manage your time wisely,” Hydrocarbon Process-
ing, Vol. 71, No. 12, Dec. 1992, p. 114.
Pradhan, S., “Apply reliability centered maintenance to sealless
pumps,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993,
p. 43.
Singh, B., “Specifying clad CRA piping,” Hydrocarbon Process-
ing, Vol. 72, No. 01, Jan. 1993, p. 51.
Peterson, J.R. and Davidse, G.J., “Consider pump cast refrac-
tory for critical linings,” Hydrocarbon Processing, Vol. 72, No.
01, Jan. 1993, p. 55.
248 References
Nelson, W.E., “Improve relief valve reliability,” Hydrocarbon
Processing, Vol. 72, No. 0 1, Jan. 1993, p. 57.
Dailey, W.V., “Improve process analyzer availability,” Hydrocar-
bon Processing, Vol. 72, No. 01, Jan. 1993, p. 69.
Gamboa, R., “Consider insulation reliability,” Hydrocarbon
Processing, Vol. 72, No. 01, Jan. 1993, p. 73.
Thorman, G.O. and Unruh, C., “Use a simple color code for
maintenance priorities,” Hydrocarbon Processing, Vol. 72, No.
02, Feb. 1993, p. 116-D.
Haq, I., “Improve machinery vibration data,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, March 1993, p. 74.
Forsell, K.A., “Protect motors with solid-state overloads,” Hy-
drocarbon Processing, Vol. 72, No. 03, March 1993, p. 100.
Karassik, I.J., “When to maintain centrifugal pumps,” Hydro-
carbon Processing, Vol. 72, No. 04, Apr. 1993, p. 101.
Hussain, M.S., “Improve planetary gear vibration analysis,”
Hydrocarbon Processing, Vol. 72, No. 05, May 1993, p. 105.
Woollatt, D., “Factors affecting reciprocating compressor per-
formance,” Hydrocarbon Processing, Vol. 72, No. 06, June
1993, p. 57.
Leonard, S.C., “Improve maintenance reliability,” Hydrocarbon
Processing, Vol. 72, No. 08, Aug. 1993, p. 162-C.
El Sherif, A.H., “Monitor lube-oil quality in service,” Hydrocar-
bon Processing, Vol. 72, No. 08, Aug. 1993, p. 171.
“Process passivates spent catalyst to allow unloading under air,”
Oil & Gas Journal, Oct. 12, 1992, p. 56.
“Nelson-Farrar Cost Index,” Oil & Gas Journal, Nov. 2, 1992,
p. 79; Dec. 7, 1992, p. 74; Jan. 4, 1993, p. 38; Feb. 1, 1993,
p. 44; Mar. 1, 1993, p. 70; Apr. 5, 1993, p. 62; May 3, 1993,
p. 76; June 7, 1793, p. 36; July 5, 1993, p. 50; Aug. 2, 1993,
p. 78.
“Nelson-Farrar Quarterly Costimating,” Oil & Gas Journal, Jan.
4, 1993, p. 52; Apr. 5, 1993, p. 64.
“NPRA MAINTENANCE Q&%-Refiners focus on mainte-
nance inspection and analysis techniques,” Oil & Gas Journal,
Oct. 26, 1992, p. 86.
Lieberman, Norman P. and Lieberman, Elizabeth T., “Inade-
quate inspection cause offlawed vac tower revamp,” Oil& Gas
Journal, Dec. 14, 1992, p. 33.
Campos, Mario Cesar M.M., and Rodrigues, Paulo Sergio B.,
“Practical control strategy eliminates FCCU compressor surge
problems,” Oil & Gas Journal, Jan. 11, 1993, p. 29.
“New cat converter design for compressors cuts service time,”
Oil & Gas Journal, Apr. 17, 1793, p. 53.
Hingoraney, Rajan, “Putting expert systems to work,” Chemical
Engineering, Jan. 1994, p. 121.
Clark, Ed and Littlefield, David, “Maximize centrifugal pump
reliability,” Chemical Engineering, Feb. 1994, p. 90.
Petersen, David G., “Capacitance: Redefining maintenance,”
Chemical Engineering, Aug. 1974, p, 78.
Pradhan, S., “Maintenance strategies for greater availability,”
Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994, p. 37.
Ward, K.A., “Retrofitting older turbomachinery with vibration
monitors,” Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994,
p. 47.
Rayner, R.E., “Better metallurgy for process equipment,” Hy-
drocarbon Processing, Vol. 73, No. 01, Jan. 1994, p. 53.
Wittliff, M., et al., “Improve plant reliability with information
systems,” Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994,
p. 63.
TOC/INDEX
Page, E.A. and Berggren, J.C., “Improve predictive maintenance
with HFE monitoring,” Hydrocarbon Processing, Vol. 73, No.
01, Jan. 1994, p. 69.
Young, L.A. and Key, W.E., “Select the right seal barrier fluid,”
Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1994, p. 74.
Faust, E., “Pressure calibration standards: How accurate should
they be?,” Hydrocarbon Processing, Vol. 73, No. 01, Jan. 1794,
p. 79.
Roy, G.K., “Improve FCCU expander reliability,” Hydrocarbon
Processing, Vol. 73, No. 03, Mar. 1974, p. 67.
El Sherif, A.H., “Analyze bearing problems by ball path inspec-
tion,” Hydrocarbon Processing, Vol. 73, No. 04, Apr. 1994, p.
120.
McGuiness, N., “Specifying and applying metal-seated ball
valves,” Hydrocarbon Processing, Vol. 73, No. 07, July 1994, p.
48.
King, G.P. and Sinauskas, D., “Does the HON apply to your
facility?,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994,
p. 47.
Gomaa, H. and Allawi, A., “Minimize air-toxic emissions,”
Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1974, p. 121.
“NPRA MAINTENANCE Q&A: Engineers discuss mainte-
nance programs, procedures at meeting,” Oil & Gas Journal,
Jan. 24, 1994, p. 42.
Myers, Philip E., “OSHA confined-space reg interpreted for
storage tank operations,” Oil & Gas Journal, Feb. 14, 1994, p.
84.
Murphy, Martin A., “Analysis, calculation techniques predict
FCC erosion and fluidization,” Oil & Gas Journal, Feb. 21,
1994, p. 54.
“Gas turbine unit pushes past 300,000 hr of service,” Oil & Gas
Journal Feb. 28, 1994, p. 47.
Van Way, Chris, “Plant replacement key to Louisiana field
revival,” Oil & Gas Journal, Mar. 28, 1994, p. 58.
Ricketts, Richard, “Survey points to practices that reduce refin-
ery maintenance spending,” Oil & Gas Journal, July 4, 1994,
p. 37.
Deley, Stephen J., and Graf, Kenneth, “Random packing debot-
tlenecks refinery de-ethanizing stripper,” Oil & Gas Journal,
Aug. 1, 1994, p. 39.
XV PIPING
Cary, John B. and Liss, Jerome B., “Automated system monitors
refinery pipe corrosion,” Oil & Gas Journal, Sept. 11, 1989,
p. 37.
Gaylord, ED., “Solving reed frequency vibration problems,”
Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989 p. 50.
Fisher, L., “Operational speed balancing: Should you be doing
it?,” Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989, p. 55.
Misra, L.N., “Unique repair method saved rotor shafts,” Hydro-
carbon Processing, Vol. 68, No. 02, Feb. 1989 p. 54.
Sandberg, C., “Heat tracing: steam or electric?,” Hydrocarbon
Processing, Vol. 68, No. 03, Mar. 1989, p. 107.
McGuiness, W.N., “Strainers for equipment protection,” Hy-
drocarbon Processing, Vol. 68, No. 05, May 1989, p. 53.
Goyal, O.P., “Guidelines on rotating equipment,” Hydrocarbon
Processing, Vol. 68, No. 10, Oct. 1989, p. 37.
Simiskey, EL. and Faulkner, CR., “Better reliefsystems design,”
Hydrocarbon Processing, Vol. 68, No. 05, May 1989, p. 63.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Godse, A.G., “Predict compressor performance at new condi-
tions,” Hydrocarbon Processing, Vol. 68, No. 06, June 1989, p.
77.
Cassolato, B.M., “Holzer analysis using spreadsheet macros,”
Hydrocarbon Processing, Vol. 68, No. 08, Aug. 1989, p. 55.
Shah, B.V., “Solving fluid flow problems with spreadsheets,”
Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989, p. 85.
Fischbach, M.J., “Dry seal applications in centrifugal compres-
sors,” Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989 p.
47.
Bauer, F., ‘Valve pocket losses in reciprocating compressors,”
Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p. 55.
Wyss, Stephen E., “How to organize pipe tie-ins for revamp
projects,” Chemical Engineering, Feb. 1989 p. 107.
Smith, Byron D., “Sizing the economic pipe,” Chemical Engi-
neering, Sept. 1989, p. 201.
Britt, Frank, “Stainless steel vs. fiberglass pipe,” Chemical Engi-
neering, Feb. 1990, p. 105.
Hunt, Jack, “Joining thermoplastic pipe,” Chemical Engineering,
Feb. 1990, p. 110.
Strauss, B.M., “Use replication to evaluate high temperature
creep,” Hydrocarbon Processing, Vol. 68, No. 10, Oct. 1989, p.
77.
Archuletta, Jim, Bitler, Bruce, Binford, Mark, and Modi, John,
“Cooperative corrosion control and treatment program proves
effective,” Oil & Gas Journal Aug. 6, 1990, p. 60.
Bucheim, Gerrit M., “Ways to deal with wet H2S cracking
revealed by study,” Oil & Gas Journal, July 9, 1990, p. 92.
Corbett, Richard A., “Proposed OSHA safety regs target process
plant procedures,” Oil & Gas Journal, Aug. 20, 1990, p. 80.
McGuiness, W.N., “Block-type ball valve considerations,” Hy-
drocarbon Processing, Vol. 69, No. 03, Mar. 1990, p. 101.
Wenger, J.L., “Add piping to recover more NGL,” Hydrocarbon
Processing, Vol. 69, No. 08, Aug. 1990, p. 67.
Soliman, R.H. and Collier, P.B., “Pressure drop in slurry lines,”
Hydrocarbon Processing, Vol. 67, No. 11, Nov. 1990, p. 60.
Bhasin, Vinod C., “Actuator selection,” Chemical Engineering,
Nov. 1990, p. 140.
Lewis, Sidney A., “Take the stress out of strainer selection,”
Chemical Engineering, June 1991, p. 110.
Anderson, Vaughn R., “Quarter-turn valves: Choose the right
one,” Chemical Engineering, July 1991, p. 78.
Hotchkiss, C., Jr., “The long arm of valve control,” Chemical
Engineering, Aug. 1991, p. 104.
Couch, Robert O., “A guide to multiple-pipe containment,”
Chemical Engineering, Sept. 1991, p. 158.
Peterson, D.J., “Better piping and expansion joint design,”
Hydrocarbon Processing, Vol. 70, No. 01, Jan. 1991, p. 89.
Singh, B., “Specifying high nickel alloy piping,” Hydrocarbon
Processing, Vol. 70, No. 11, Nov. 1991, p. 109.
Alspach, W.J. and Maurer, G., “Consider digital valves,” Hydro-
carbon Processing, Vol. 70, No. 12, Dec. 1991, p. 101.
Cagle, Larry L., “Fiberglass pipe’s fringe benefit,” Chemical
Engineering, Nov. 1991, p. 170.
Ridey, Michael, “Relieving over-pressure,” Chemical Engineer-
ing, Dec. 1991, p. 98.
Grumstrup, Bruce, “Shut out leaks with bellows seal valves,”
Chemical Engineering, Apr. 1992, p. 124,
Brown, Nigel P. and Heywood, Nigel I., “The right instrumen-
tation for slurries,” Chemical Engineering, Sept. 1992, p. 106.
249
TOC/INDEX
Wong, W.J., “PRV sizing for exchanger tube rupture,” Hydro-
carbon Processing, Vol. 71, No. 02, Feb. 1992, p. 59.
Escoe, A.K., “Maximum allowable pressure for nozzle open-
ings,” Hydrocarbon Processing, Vol. 71, No. 05, May 1992, p.
95.
Hassan, H.M.K., “Code check floating tank roofs,” Hydrocar-
bon Processing, Vol. 71, No. 10, Oct. 1992.
“Flow improver eliminates bottleneck in refinery transfer pip-
ing,” Oil & Gas Journal, Jan. 20, 1992, p. 47.
Lindley, Nancy L. and Lloyd, Joe C., “Piping systems: How
installation costs stack up,” Chemical Engineering, Jan. 1993,
p. 94.
Kroupa, Ralph, “Selecting valves for tough conditions,” Chemi-
cal Engineering, Feb. 1993, p. 74.
Spock, Thomas, “Control fugitive emissions from valves,”
Chemical Engineering, Feb. 1993, p. 82.
Stubblefield, Fred, Jr., “Get topnotch performance from jack-
eted pipes,” Chemical Engineering, June 1993, p. 110.
Fruci, Leonard, “Valves put a plug on emissions,” Chemical
Engineering, June 1993, p. 139.
Henthorn, Greg and Lednicky, Randy, “Sealing tips for plastic-
lined pipe,” Chemical Engineering, Nov. 1992, p. 142.
Hartman, Richard R., “Piping design: One phase at a time-Part
I,” Chemical Engineering, Oct. 1993, p. 82.
Morran, Don, “How to design stressless steam lines-Part II,”
Chemical Engineering, Oct. 1994, p. 88.
Higoraney, Rajan, “Putting expert systems to work,” Chemical
Engineering, Jan. 1994, p. 121.
Clark, Ed and Littlefield, David, “Maximize centrifugal pump
reliability,” Chemical Engineering, Feb. 1994, p. 90.
Patel, M.R. and Mehta, B.P.S., “Optimize thermal insulation,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 51.
Yu, EC., “Calculate optimum pipe size for vapor,” Hydrocarbon
Processing, Vol. 73, No. 05, May 1994, p. 79.
Sloane, B.A., “Select pipe size based on payback,” Hydrocarbon
Processing, Vol. 73, No. 07, July 1994, p. 55.
King, G.P. and Sinauskas, D., “Does the HON apply to your
facility?,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994,
p. 47.
Gomaa, H. and Allawi, A., “Minimize air-toxic emissions,”
Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p. 121.
Murphy, Martin A., “Analysis, calculation techniques predict
FCC erosion and fluidization,” Oil & Gas Journal, Feb. 21,
1994, p. 54.
XVI. FURNACES & HEAT EXCHANGERS
AI-Najjar, Hazim S.H. and Pauls, G. Abdul-Ahad, “Equation
calculates properties of saturated steam,” Oil & Gas Journal,
Sept. 4, 1989, p. 86.
Ganapathy, V., “Cold end corrosion: causes and cures,” Hydro-
carbon Processing, Vol. 68, No. 01, Jan. 1989, p. 57.
Barton, J., “Pinch technology improves olefin heat recovery,”
Hydrocarbon Processing, Vol. 68, No. 02, Feb. 1989, p. 47.
Lee, K.L., et al., “Refinery heat integration using pinch technol-
ogy,” Hydrocarbon Processing, Vol. 68, No. 04, Apr. 1989, p.
49.
Ganapathy, V, “Basic program computes boiler and heater
efficiencies,” Hydrocarbon Processing, Vol. 68, No. 05, May
1989, p. 69.
250 References
Ranade, S.M., et al., “Impact of utility costs on pinch designs,”
Hydrocarbon Processing, Vol. 68, No. 07, July 1989, p. 37.
Garg, A., “Better burner specifications,” Hydrocarbon Processing,
Vol. 68, No. 08, Aug. 1989, p. 71.
Ranade, SM., et al., ‘Know marginal utility costs,” Hydrocarbon
Processing, Vol. 68, No. 09, Sept. 1989, p. 81.
Klaren, D.G. and Bailie, R.E., “Consider nonfouling fluidized
bed exchangers,” Hydrocarbon Processing, Vol. 68, No. 07, July
1989, p. 48.
Goyal, O.P., “New approaches solve difficult exchanger prob-
lems,” Hydrocarbon Processing, Vol. 68, No. 11, Nov. 1989, p.
53.
Parkinson, Gerald, “Heat transfer perks up with new fluids,”
Chemical Engineering, Feb. 1989, p. 39.
Green, Richard L., Larsen, Alvin H., and Pauls, Allen C., “The
heat-transfer fluid spectrum,” Chemical Engineering, Feb.
1989, p. 90.
Bowman, Jeff and Turton, Richard, “Quick design and evalu-
ation: Heat exchangers,” Chemical Engineering, July 1990, p.
92.
Glavic, Peter, Kravanja, Zdravko and Homsak, Marko, “Putting
the pinch on reactors,” Chemical Engineering, June 1990, p.
106.
Deacon, Walter T., “Quality steam, not steam quality, delivers
maximum heat,” Chemical Engineering, June 1990, p. 141.
Echols, J.T. and Mayne, S.T., “Cooling-water cleanup by
ozone,” Chemical Engineering, May 1990, p. 163.
Ganapathy, V., “Win more energy from hot gases,” Chemical
Engineering, Mar. 1990, p. 102.
Tuthill, Arthur H., “The right metal for heat exchanger tubes,”
Chemical Engineering, Jan. 1990, p. 120.
Haas, John H., “Steam traps: Key to process heating,” Chemical
Engineering, Jan. 1990, p. 151.
Fijas, David E, “Getting top performance from heat exchang-
ers,” Chemical Engineering, Dec. 1989 p. 141.
Garg, A., “How to boost the performance of fired heaters,”
Chemical Engineering, Nov. 1989, p. 239.
Barton, Jan, “Method improves pyrolysis TLE operation,” Oil
& Gas Journal Jan. 29, 1990, p. 81.
Lieberman, Norman P., “Causes of shorter delayed coker heater
runs reported,” Oil & Gas Journal, Feb. 12, 1990, p. 49.
Smith, K., “Refractory heat dry considerations,” Hydrocarbon
Processing, Vol. 67, No. 01, Jan. 1990, p. 57.
Ganapathy, V, “Simplify HRSG performance evaluation,” Hy-
drocarbon Processing, Vol. 69, No. 03, Mar. 1990, p. 77.
Yaws, C.L., et al., “Predict enthalpy of vaporization,” Hydrocar-
bon Processing, Vol. 69, No. 06, June 1990, p. 87.
Ganapathy, V., “Evaluate extended surface exchangers carefully,”
Hydrocarbon Processing, Vol. 67, No. 10, Oct. 1990, p. 65.
Trom, L., “Consider plate and spiral heat exchangers,” Hydro-
carbon Processing, Vol. 69, No. 10, Oct. 1990, p. 75.
Foreman, J.M., “Pre-reformer aids syngas units,” Hydrocarbon
Processing, Vol. 69, No. 12, Dec. 1990, p. 34B.
Rao, K.R., et al., “Design options reduce exchanger cost,”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 81.
Garg, Ashutosh, Ghosh, H., “Make every Btu count,” Chemical
Engineering, Oct. 1990, p. 217.
Armer, Albert, “Operating steam-heated exchangers at high
downturn,” Chemical Engineering, Dec. 1990, p. 131.
TOC/INDEX
Hernandez-Guerrero, A. and Macias-Machin, A., “How to de-
sign bayonet heat exchangers,” Chemical Engineering, Apr.
1991, p. 122.
Mart, Tony and Verhappen, Ian, “Improving fuel efficiency with
statistics,” Chemical Engineering, June 1991, p. 143.
Burley, James R., “Don’t overlook compact heat exchangers,”
Chemical Engineering, Aug. 1991, p. 90.
Rossiter, A.P., et al., “Pinch technology identifies process im-
provements,” Hydrocarbon Processing, Vol. 70, No. 01, Jan.
1991, p. 63.
Schad, M., et al., “How nuclear reactors can supply heat for the
HPI,” Hydrocarbon Processing, Vol. 70, No. 03, Mar. 1991, p.
120C.
Nieh, CD. and Zhang, M.X., “Natural frequencies of ex-
changer U-tubes,” Hydrocarbon Processing, Vol. 70, No. 05,
May 1991, p. 97.
Dotiwalla, K.K., “Process heating systems: Steam or thermal
fluid?,” Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991,
p. 67.
Gross, P.G., “Prevent exchanger waterlogging,” Hydrocarbon
Processing, Vol. 70, No. 10, Oct. 1991, p. 73.
Miller, U.R., “Stress analysis and design ofexchanger expansion
joints,” Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991,
p. 93.
Crisi, Giovanni S., “Buying heat exchangers,” Chemical Engi-
neering, Feb. 1992, p. 74.
Ghosh, H., “Improve your fired heaters,” Chemical Engineering,
Mar. 1992, p. 116.
Plants, Chester A., “Evaluate heat-exchanger performance-
Part 1,” Chemical Engineering, June 1992, p. 100.
Burd, Vladimir, “Squeezing clean energy from boilers and heat-
ers,” Chemical Engineering, Mar. 1992, p. 145.
Plants, Chester A., “Evaluate heat-exchanger performance-
Part 2,” Chemical Engineering, June 1992, p. 104.
Rubin, Frank L., “Heat transfer topics often overlooked,”
Chemical Engineering, Aug. 1992, p. 74.
Fehr, M., “Make the boiler part of the team,” Hydrocarbon
Processing, Vol. 70 No. 11, Nov. 1991, p. 131.
Steinmeyer, D.E., “Optimum delta p and delta t in heat ex-
change,” Hydrocarbon Processing, Vol. 71, No. 04, Apr. 1992,
p. 53.
Love, D.L., “No hassle reboiler selection,” Hydrocarbon Process-
ing, Vol. 71, No. 10, Oct. 1992, p. 41.
Ganapathy V, “Fouling-the silent heat transfer thief,” Hydro-
carbon Processing, Vol. 71, No. 10, Oct. 1992, p. 49.
Steinmeyer, D., “Save energy, without entropy,” Hydrocarbon
Processing, Vol. 71, No. 10, Oct. 1992, p. 55.
O’Donnell, J., “Improve seawater cooling with titanium finned
tubes,” Hydrocarbon Processing, Vol. 71, No. 10, Oct. 1992,
p. 61.
Sloane, B.A., “Maximize your energy savings with proper insu-
lation size,” Hydrocarbon Processing, Vol. 71, No. 10, Oct.
1992, p. 67.
Ancheyta, Jorge, Nares, Ruben, Moreno, Abel, and Anaya,
Carlos G., “New algorithm simplifies heat-exchanger calcula-
tions,” Oil & Gas Journal Dec. 16, 1991, p. 70.
AIbano, John V., Olszewski, Edward F., and Fukushima, Toshi-
yuki, “Gas turbine integration reduces ethylene plant’s energy
needs,” Oil & Gas Journal, Feb. 10, 1992, p. 55.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Richardson, Kenneth W. and Taibi, Frank D., “Louisiana joint
venture starts up coke-fueled cogen plant,” Oil & Gas Journal,
Apr. 5, 1993, p. 38.
Reddi, S.V., “Thermal insulation safety,” Hydrocarbon Process-
ing, Vol. 71, No. 10, Oct. 1992, p. 122-c.
Ganapathy, V., “Effective use of heat-recovery steam gener-
ators,” Chemical Engineering, Jan. 1993, p. 102.
Ganapathy, V., “Recovering heat when generating power,”
Chemical Engineering, Feb. 1993, p. 74.
McGowan, Thomas E, Lipinski, George E. and Santoleri,
Joseph J., “New rules affect the handling of waste fuels,”
Chemical Engineering, Mar. 1993, p. 122.
Bayer, John and Trumpfheller, Gary, “Specification tips to maxi-
mize heat transfer,” Chemical Engineering, May 1993, p. 90.
Garg, Ashutosh, “Trimming NO, from furnaces,” Chemical
Engineering, Nov. 1992, p. 122.
Kerner, Jeff, “Sizing plate heat exchangers,” Chemical Engineer-
ing, Nov. 1993, p. 177.
Finn, Adrian, “Enhance gas processing with reflux heat-ex-
changers,” Chemical Engineering, May 1994, p. 142.
Hall, Stephen G. and Morgan, Steve W., “Heat exchanger
databases accelerate process design & costing,” Chemical En-
gineering, July 1994, p. 139.
Brandstatter, A.L. and Sawatzki, Howard, “Hot tips to rejuve-
nate old boilers,” Chemical Engineering, Sept. 1994, p. 153.
Campagne, W.v.L., “Use Ponchon-Savarit in your process simu-
lation, Part 1,” Hydrocarbon Processing, Vol. 72, No. 09, Sept.
1993, p. 41.
Liebert, T.C., “Distillation feed preheat-is it energy efficient?,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 37.
Ganapathy, V., “BASIC program calculates flue gas energy
balance,” Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993,
p. 47.
Patel, M.R. and Mehta, B.P.S., “Optimize thermal insulation,”
Hydrocarbon Processing, Vol. 72, No. 10, Oct. 1993, p. 51.
Hellander, J.C. and Bryant, G.B., “Use ceramic coatings to
improve efficiency of gas-fired furn,” Hydrocarbon Processing,
Vol. 72, No. 10, Oct. 1993, p. 59.
Campagne, W.v.L., “Use Ponchon-Savarit in your process simu-
lation, Part 2,” Hydrocarbon Processing, Vol. 72, No. 10, Oct.
1993, p. 63.
Golden, S.W., et al., “Revamping FCC main fractionator energy
systems,” Hydrocarbon Processing, Vol. 72, No. 11, Nov. 1993,
p. 43.
Pugh, T., et al., “Improve heat exchanger leak detection,” Hy-
drocarbon Processing, Vol. 72, No. 11, Nov. 1993, p. 85.
Goldblatt, M., “How to justify water conservation projects,”
Hydrocarbon Processing, Vol. 72, No. 12, Dec. 1993, p. 65.
Christensen, T.S. and Primdahl, I.I., “Improve syngas produc-
tion using autothermal reforming,” Hydrocarbon Processing,
Vol. 73, No. 03, Mar. 1994, p. 39.
Anon, “Gas Processes ‘74,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Tindall, B.M. and King, D.L., “Designing steam reformers for
hydrogen production,” Hydrocarbon Processing, Vol. 73, No.
07, July 1994, p. 69.
Wojdon, W. and George, M., “How to replace CFC refriger-
ants,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p.
107.
251
TOC/INDEX
Gomaa, H. and Allawi, A., “Minimize air-toxic emissions,”
Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994, p. 121.
Ganapathy, V., “Understand boiler performance charac-
teristics,” Hydrocarbon Processing, Vol. 73, No. 08, Aug. 1994,
p. 131.
Kals, W., ‘Air-cooled heat exchangers: conventional and uncon-
ventional,” Hydrocarbon Processing, Vol. 73, No. 08, Aug.
1994, p. 138.
Burger, R., “Select the right cooling tower fill,” Hydrocarbon
Processing, Vol. 73, No. 08, Aug. 1994, p. 141.
Yaws, Carl L., Lin, Xiaoyan, Bu, Li, and Nijhawan, Sachin,
“New equation calculates thermal conductivities of C1-C4
gases,” Oil & Gas Journal, Apr. 18, 1994, p. 43.
XVII. STORAGE & TRANSFER
Berto, Frank J., “Methods for volume measurement using tank
gauging devices can be error prone,” Oil & Gas Journal, Mar.
13, 1989, p. 57.
Edvardsson, Olle, “Radar used to measure tank hydrocarbon
liquid level,” Oil & Gas Journal, Jan. 2, 1989, p. 39.
Sivaraman, S. and Hampton, B.J., “Guidelines set for recalibra-
tion of storage tanks,” Oil & Gas Journal, June 12, 1989, p.
46.
Watkins, Don L., Jr., “Plagued by pumping problems? Consider
the flexible-impeller pump, ” Chemical Engineering, Jan. 1989,
p. 94.
Kent, George R., “Troubleshooting rotating equipment - Con-
fessions of a service engineer, Part II,” Chemical Engineering,
Apr. 1989, p. 163.
Wong, Wing Y., “Safer relief-valve sizing,” Chemical Engineer-
ing, May 1989, p. 137.
Parkinson, Gerald, “Surging interest in leakproof pumps,”
Chemical Engineering, June 1989, p. 31.
Lahr, Paul T., “Better standards, better pumps,” Chemical Engi-
neering, July 1989, p. 96.
Lapina, Ronald P., “Compressor performance: key things to
remember,” Chemical Engineering, Aug. 1989, p. 122.
Miller, John E., “Bucking up reciprocating pump performance,”
Chemical Engineering, Sept. 1989, p. 149.
Parkinson, Gerald, “Compressor choices expand,” Chemical
Engineering, Oct. 1989, p. 47.
McCaul, Colin, “Keep the wear out of pump wear rings,”
Chemical Engineering, Oct. 1989, p. 149.
Mei, Kenneth W., “Automatic tank gauges can be use for custody
transfer,” Oil & Gas Journal, Nov. 13, 1989, p. 81.
Sivaraman, S., “Guidelines help select storage tank calibration
method,” Oil & Gas Journal Feb. 5, 1990, p. 41.
Berto, Frank J., “Hydrostatic tank gauges accurately measure
mass, volume, and level,” Oil & Gas Journal, May 14, 1990,
p. 57.
Doolin, J.H. and Teasdale, Leslie M., “Sealless magnetic-drive
pumps: Stronger than ever,” Chemical Engineering, Aug. 1990,
p. 112.
Mills, David, “Keeping pneumatic delivery up to speed,” Chemi-
cal Engineering, June 1990, p. 93.
Hill, Joel, “Controlling emissions from marine loading opera-
tions,” Chemical Engineering, May 1990, p. 133.
252 References
Mills, David, “Troubleshooting pneumatic conveying: Part 2:
Major systems and their key components,” Chemical Engineer-
ing, July 1990, p. 101.
Lapina, Ronald P., “Compressor performance: How changes in
inlet conditions affect efficiency,” Chemical Engineering, July
1990, p. 110.
Margus, Edward, “Choosing thermoplastic pumps,” Chemical
Engineering, July 1991, p. 106.
Bosworth, Michael A., “Dilute-Phase Pneumatic Conveying:
Instrument selection guide,” Chemical Engineering, Sept.
1991, p. 166.
Van Valkenburgh, Gary, “Storing hazardous wastes safely,”
Chemical Engineering, Sept. 1991, p. 203.
Nasr Ali, “Extending the life of magnetic-drive pumps,” Chemi-
cal Engineering, Oct. 1991, p. 159.
Mills, David, “Troubleshooting pneumatic conveying: Part 3:
Problems from the outside,” Chemical Engineering, Sept.
1990, p. 157.
Doolin, James, Kawohl, Rudolf, et al., “Pumping difficult flu-
ids,” Chemical Engineering, Dec. 1991, p. 67.
Bloch, Heinz P. and Noack, Pierre W., “Screw compressors,”
Chemical Engineering, Feb. 1992, p. 100.
Myers, Phillip, “Keeping above-ground storage tanks in top
shape,” Chemical Engineering, Apr. 1992, p. 161.
Geyer, Wayne, “Bringing storage tanks to the surface,” Chemical
Engineering, July 1992, p. 94.
Clark, Michael A., “Fluoropolymer linings: The low-cost advan-
tage,” Chemical Engineering, Aug. 1992, p. 106.
Darby, Ron, Mun, Robert and Boger, David V, “Predict friction
loss in slurry pipes,” Chemical Engineering, Sept. 1992, p. 116.
Spivey, Marty, “Intermediate bulk containers,” Chemical Engi-
neering, Sept. 1992, p. 145.
Adams, W.V, “Controlling fugitive emissions from mechanical
seals,” Hydrocarbon Processing, Vol. 71, No. 03, March 1992,
p. 99.
Hallam, J.L., “Commissioning compressors with gas seals,”
Hydrocarbon Processing, Vol. 71, No. 07, July 1992, p. 41.
Schmidt, W.A., “Rerate driver shafts using thermal analogy,”
Hydrocarbon Processing, Vol. 71, No. 07, July 1992, p. 49.
Clark, D. and Abbott, C., “Improve slurry pump life,” Hydro-
carbon Processing, Vol. 71, No. 07, July 1992, p. 53.
Scheithe, W., “Better bearing vibration analysis,” Hydrocarbon
Processing, Vol. 71, No. 07, July 1992, p. 57.
Wiederuh, E. and Meinhart, D., “Isothermal compressors for
process gas,” Hydrocarbon Processing, Vol. 71, No. 09, Sept.
1992, p. 58.
Wong, RF., “Troubleshooting rotating equipment,” Hydrocar-
bon Processing, Vol. 71, No. 10, Oct. 1992, p. 123.
de Wit, Johannes, “Safe jack up method permits repairs of tank
bottoms and foundations,” Oil & Gas Journal, Nov. 4, 1991,
p. 76.
“Flow improver eliminates bottleneck in refinery transfer pip-
ing,” Oil & Gas Journal, Jan. 20, 1992, p. 47.
Hassan, Hassan M.K., “Sequential lifting of tank shell used to
repair floors,” Oil & Gas Journal, Feb. 3, 1992, p. 33.
Koch, Pierre, “Simple program calculates partial liquid vol-
umes,” Oil & Gas Journal, Apr. 13, 1992, p. 54.
Mei, Kenneth W., “Accurate, automatic temperature measure-
ments reduces tank volume errors,” Oil & Gas Journal, July
20, 1992, p. 105.
TOC/INDEX
Vandell, Craig and Foerg, Wolfgang, “The pluses of positive
displacement,” Chemical Engineering, Jan. 1993, p. 74.
Sumbry, Louis C. and Bogner, Ben R., “Lining tank bottoms to
extend service life,” Chemical Engineering, Jan. 1993, p. 131.
Blair, Hugo, “The environmental pluses ofdiaphragm pumps,”
Chemical Engineering, May 1993, p. 118.
Fruci, Leonard, “Pipeless plants boost batch processing,” Chemi-
cal Engineering, June 1993, p. 102.
Birgenheler, David B., Butzbach, Thomas L., et al., “Designing
steam-jet vacuum systems,” Chemical Engineering, July 1993,
p. 116.
Thorpe, Wilson A. and Sivaraman, Srini, “Simple techniques
reduce coke inventory, sales measurement errors,” Oil & Gas
Journal, Jan. 18, 1993, p. 44.
King, Myke, “OIL MOVEMENTS-l: Automation of oil
movement systems prevents mistakes, saves money,” Oil &
Gas Journal Mar. 22, 1993, p. 76.
King, Myke, “OIL MOVEMENTS-Conclusion: Integrating
oil movement and data systems beefs project benefits,” Oil &
Gas Journal, Apr. 12, 1993, p. 52.
Sivaraman, Srini and Wallace, Richard I., “New tank calibration
method could be wave of the future,” Oil & Gas Journal, Oct.
19, 1992, p. 81.
Chen, C.C., “Cope with dissolved gases in pump calculations,”
Chemical Engineering, Oct. 1993, p. 106.
Bittermann, Hans-Jurgen, “Avoid downtime in centrifugal
pumps,” Chemical ngineering, Oct. 1993, p. 145.
Vetter, Gerhard, Schlucker, Eberhard, et al., “Know your dia-
phragm pump internals,” Chemical Engineering, Nov. 1993,
p. 130.
Clark, Ed and Littlefield, David, “Maximize centrihtgal pump
reliability,” Chemical Engineering, Feb. 1994, p. 90.
Giffin, Gary L, “Keeping a lid on volatile liquids,” Chemical
Engineering, Feb. 1994, p. 78.
Carson, John W., “Characterize bulk solids to ensure smooth
flow,” Chemical Engineering, Apr. 1994, p. 78.
Yedidiah, Shmariahu, “Recirculation sheds its villainous image,”
Chemical Engineering, July 1994, p. 118.
Wilson, David H., “Automate bulk-solids delivery with feed-
back control,” Chemical Engineering, Aug. 1994, p. 87.
Buxton, L. Willian and Henthorn, Gregory V, “Get the most
out of plastic lined pipe,” Chemical Engineering, Sept. 1994,
p. 133.
Myers, Philip E., “OSHA confined-space reg interpreted for
storage tank operations,” Oil & Gas Journal, Feb. 14, 1994, p.
84.
True, Warren R., “GRI plays critical role in U.S. gas measure-
ment research,” Oil & Gas Journal Mar. 7, 1994, p. 45.
“Meters to answer needs for low cost EFM, energy measure-
ment,” Oil & Gas Journal, Mar. 7, 1994, p. 49.
Trosper, Robert L., Stubbs, Robert G., and Carver, Darrell,
“New Mexico gas plant operator automates field control,” Oil
& Gas Journal, Mar. 7, 1994, p. 54.
Stark, Stephen T., and Heuer, Richard D., “Testing paves way
for electronic flow monitoring system,” Oil & Gas Journal,
Mar. 7, 1994, p. 58.
“China Facing Revamp of Outmoded Crude Tanker Terminal
System,” Oil & Gas Journal May 9, 1994, p. 54.
Aalund, L.R., “Hawaii offers challenge and opportunity to
refiner,” Oil & Gas Journal, May 30, 1994, p. 43.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“‘Cascaded’ pilot regulators help reduce LPG loss in hor
weather,” Oil & Gas Journal, Aug. 8, 1994, p. 63.
XVIII. CORROSION
Powell, James T., Rue, James R., and Mansuri, Mehdi M.,
“Corrosion control program maximizes crude unit reliability,”
Oil & Gas Journal, Mar. 20, 1989, p. 60.
Richert, J.P., Bagdasarian, A.J., and Shargay, C.A., “Extent of
stress corrosion cracking in amine plants revealed by survey,”
Oil & Gas Journal, June 5, 1989, p. 45.
Gary, John B. and Liss, Jerome B., “Automated system monitors
refinery pipe corrosion,” Oil & Gas Journal, Sept. 11, 1989,
p. 37.
Sheppard, Walter Lee, Jr., “Inspection: key to quality masonry
linings,” Chemical Engineering, Mar. 1989, p. 191.
Irving-Monshaw, Susan, “Non-chromates vie for a cooling water
niche,” Chemical Engineering, Sept. 1989, p. 59.
Ganapathy, V., “Cold end corrosion: causes and cures,” Hydro-
carbon Processing, Vol. 68, No. 01, Jan. 1989, p. 57.
Tuthill, Arthur H., “The right metal for heat exchanger tubes,”
Chemical Engineering, Jan. 1990, p. 120.
Bucheim, Gerrit M., “Ways to deal with wet H2S cracking
revealed by study,” Oil & Gas Journal July 9, 1990, p. 92.
Archuletta, Jim, Bitler, Bruce, Binford, Mark, and Modi, John,
“Cooperative corrosion control and treatment program proves
effective,” Oil & Gas Journal, Aug. 6, 1990, p. 60.
Christie, David A. and Holden, David G., “Fluid cat cracking
units’ advanced control can achieve benefits in six areas,” Oil
& Gas Journal, Sept. 25, 1989, p. 104.
Lowder, Roger, “Gas turbine operates on catalytic reformer
offgas,” Oil & Gas Journal, Oct. 9, 1989, p. 82.
Barton, Jan, “Method improves pyrolysis TLE operation,” Oil
& Gas Journal, Jan. 29, 1990, p. 81.
Lieberman, Norman I?, “Causes of shorter delayed coker heater
runs reported,” Oil & Gas Journal Feb. 12, 1990, p. 49.
Morrison, T.A. and Laflamme, D., “Advanced controls improve
performance of two-shell dual-pressure column”, Oil & Gas
Journal, May 14, 1990, p. 60.
Bird, Graham, Limb, David, and Pandit, Alok, “Flowsheet
simulation models crude distillation and ammonia produc-
tion,” Oil & Gas Journal, July 23, 1990, p. 43.
Buchheim, G.M., “Ways to deal with wet H2S cracking revealed
by study,” Oil & Gas Journal, July 9, 1990, p. 92.
Archuletta, J., Bitler, B., Binford, M., and Modi, J., “Coopera-
tive corrosion control and treatment program proves effec-
tive,” Oil & Gas Journal, Aug. 6, 1990, p. 60.
Strong, R.C., Majestic, V.K., and Wilhelm, S.M., “FCC COR-
ROSION—1: Basic steps lead to successful FCC corrosion
control,” Oil & Gas Journal, Sept. 30, 1991, p. 81.
Strong, R.C., Majestic, V.K., and Wilhelm, SM., “FCC COR-
ROSION-Conclusion: Basic corrosion control methods
solve varied problems,” Oil & Gas Journal Oct. 7, 1991, p.
86.
“Survey updates amine stress corrosion cracking,” Oil & Gas
Journal, Jan. 13, 1992, p. 42.
Whitecraft, Paul K., “High-tech steels to the rescue,” Chemical
Engineering, Jan. 1992, p. 116.
Clark, Michael A., “Fluoropolymer linings: The low-cost advan-
tage,” Chemical Engineering, Aug. 1992, p. 107.
253
TOC/INDEX
Pollock, Warren L., “What’s hot in metal alloys,” Chemical
Engineering, Oct. 1992, p. 78.
Puyear, Robert B., “Pick the right material for process hard-
ware,” Chemical Engineering, Oct. 1992, p. 90.
Pollock, Warren L., “Baffled by how alloys are labeled?,” Chemi-
cal Engineering, Oct. 1992, p. 169.
Dotiwalla, K.K., “Save energy with absorption chillers,” Hydro-
carbon Processing, Vol. 71, No. 02, Feb. 1992, p. 112.
Foscante, Raymond E., “Tailoring the optimum system,”
Chemical Engineering, Oct. 1990, p. 92.
Jones, M.E., “Lining up to resist corrosion,” Chemical Engineer-
ing, Oct. 1990, p. 104.
Kirby, G.N. and Firtel, J., “Wastewater systems: Material of
construction,” Chemical Engineering, Oct. 1990, p. 166.
Imbalzano, J.E, Washburn, D.N. and Mehta, PM., “Permeation
and stress cracking of fluoropolymers,” Chemical Engineering,
Jan. 1991, p. 105.
Stanislow, Lawrence, J. and Sheppard, Walter L., “Glass:
Stronger, lighter, more durable,” Chemical Engineering, Feb.
1991, p. 153.
Paciej, Richard, “How to foil the curse of corrosive gases,”
Chemical Engineering, May 1991, p. 158.
Scott, B., “Identify alkylation hazards,” Hydrocarbon Processing,
Vol. 71, No. 10, Oct. 1992, p. 77.
Reddi, S.V., “Thermal insulation safety, Part 1,” Hydrocarbon
Processing, Vol. 71, No. 10, Oct. 1992, p. 122-C.
Reddi, S.V., “Thermal insulation safety, Part 2,” Hydrocarbon
Processing, Vol. 71, No. 11, Nov. 1992, p. 100-C.
Schwinn, V. and Streisselberger, A., “Avoid H2S corrosion in
refinery vessels,” Hydrocarbon Processing, Vol. 72, No. 01, Jan.
1993, p. 103.
DuPart, M.S., et al., “Understanding corrosion in alkanolamine
gas treating plants, Part 1,” Hydrocarbon Processing, Vol. 72,
No. 04, Apr. 1993, p. 75.
DuPart, M.S., et al., “Understanding corrosion in alkanolamine
gas treating plants, Part 2,” Hydrocarbon Processing, Vol. 72,
No. 05, May 1993, p. 89.
Gallaher, Dale M. and Malhoney, Michael J., “MOBILE BAY-
1: New technologies used in development of sour Fairway
gas,” Oil & Gas Journal, Feb. 22, 1993, p, 57.
Gallaher, DaleM. and Malhoney, Michael J., “MOBILE BAY-
Conclusion: Fairway sour gas development proves new mate-
rials, monitoring,” Oil & Gas Journal, Mar. 1, 1993, p. 76.
French, Eddie C., “New inhibitor reduces crude-unit corrosion
problems at lower pH,” Oil & Gas Journal, May 24, 1993, p.
45.
Lieberman, Norman P., “Four steps solve crude-tower overhead
corrosion problems,” Oil & Gas Journal, July 5, 1993, p. 47.
Priest, David, “Measuring corrosion rates fast,” Chemical Engi-
neering, Nov. 1992, p. 169.
Sumbry, Louis C. and Bogner, Ben R., “Lining tank bottoms to
extend service life,” Chemical Engineering, Jan. 1993, p. 131.
Miller, W.A., “How to choose a fluoropolymer,” Chemical En-
gineering, Apr. 1993, p. 163.
Buxton, L. William, “Get the most out of plastic lined pipe,”
Chemical Engineering, Sept. 1994, p. 133.
Kohley, Bill, “Consider plastic spray nozzles,” Chemical Engi-
neering, Apr. 1994, p. 147.
254
Brown, R.L., Jr., and Wines, T.H., “Improve suspended water
removal from fuels,” Hydrocarbon Processing, Vol. 72, No. 12,
Dec. 1993, p. 95.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Wu, Yiing-Mei, “Calculations estimate process stream deposi-
tions,” Oil & Gas Journal, Jan. 3, 1994, p. 38.
Babaian-Kibala, Elizabeth, “Phosphate ester inhibitors solve
naphthenic acid corrosion problems,” Oil & Gas Journal, Feb.
28, 1994, p. 31.
“NPRA Q & A: Auxiliary equipment, corrosion focus of refiner
meeting,” Oil & Gas Journal, Apr. 4, 1994, p. 62.
“Study scheduled on fouling of refinery units,” Oil & Gas
Journal, May 23, 1994, p. 41.
XIX. ENERGY CONSERVATION
Raab, F.E., “New Exxon gas plant design couples NGL recovery
with cogeneration,” Oil & Gas Journal, June 19, 1989, p. 40.
Lowder, Roger, “Gas turbine operates on catalytic reformer off
gas,” Oil & Gas Journal, Oct. 9, 1989, p. 82.
Vatcha, S.R., “How efficient can distillation be?,” Hydrocarbon
Processing, Vol. 68, No. 01, Jan. 1989, p. 65.
Cooper, D., “Do you value steam correctly?,” Hydrocarbon
Processing, Vol. 68, No. 07, July 1989, p. 44.
Vervalin, C.H., “Energy information resources,” Hydrocarbon
Processing, Vol. 68, No. 11, Nov. 1989, p. 119.
Melamed, Dennis, Johnson, Eric and Chowdhury, Jayadev,
“Energy prices will rise in the 1990s,” Chemical Engineering,
Sept. 1989, p. 55.
Glavic, Peter, Kravanja, Zdravko and Homsak, Marko, “Putting
the pinch on reactors,” Chemical Engineering, June 1990, p.
106.
Ganapathy, V., “Win more energy from hot gases,” Chemical
Engineering, Mar. 1990, p. 102.
Haas, John H., “Steam traps: Key to process heating,” Chemical
Engineering, Jan. 1990, p. 151.
Sudhakar, B. and Rao, B.K.B., “India’s energy options: the latest
review,” Hydrocarbon Processing, Vol. 69, No. 04, Apr. 1990,
p. 116C.
Misra, L.N., “Innovative generator/motor repair,” Hydrocarbon
Processing, Vol. 69, No. 06, June 1990, p. 139.
Siegell, J.H., “Plant energy conservation,” Hydrocarbon Process-
ing, Vol. 69, No. 10, Oct. 1990, p. 59.
Ranade, S.M. and Chao, Y.T., “Industrial heat pumps: Where
and when?,” Hydrocarbon Processing, Vol. 69, No. 10, Oct.
1990, p. 71.
Western, E.R., and Nass, D.W., “Cogeneration improves ther-
mal EOR efficiency,” Oil & Gas Journal Oct. 15, 1990, p. 41.
Ganapathy, V., “Evaluate deaerator steam requirements
quickly,” Hydrocarbon Processing, Vol. 70, No. 02, Feb. 1991,
p. 59.
Siegell, J.H., “Analyzing process energy efficiency,” Hydrocarbon
Processing, Vol. 70, No. 03, Mar. 1991, p. 55.
Tripathi, P. and Shukla, D., “Environmentally responsible en-
ergy management,” Hydrocarbon Processing, Vol. 70, No. 10,
Oct. 1991, p. 45.
Szeto, E., “Prevent insulation from put-king,” Hydrocarbon Proc-
essing, Vol. 70, No. 10, Oct. 1991, p. 51.
References
TOC/INDEX
Ganapathy, V., “Maximize steam generation gas turbine
HRSGs,” Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991,
p. 57.
Irwin, W., “Avoid common mistakes when insulating piping,”
Hydrocarbon Processing, Vol. 70, No. 10, Oct. 1991, p. 64.
Albano, John V., Olszewski, Edward E, and Fukushima, Toshi-
yuki, “Gas turbine integration reduces ethylene plant’s energy
needs,” Oil & Gas Journal, Feb. 10, 1992, p. 55.
Newman, S.A., “Sour water design by charts, Pt. 2,” Hydrocar-
bon Processing, Vol. 70, No. 10, Oct. 1991, p. 101.
Macek, Stanley J., “Putting a lid on evaporation costs,” Chemical
Engineering, Dec. 1992, p. 139.
Ganapathy, V., “Effective use of heat-recovery steam gener-
ators,” Chemical Engineering, Jan. 1993, p. 102.
Ganapathy, V., “Recovering heat when generating power,”
Chemical Engineering, Feb. 1993, p. 94.
Burger, Robert, “Cooling towers: The often over-looked profit
center,” Chemical Engineering, May 1993, p. 100.
Nutter, Darin, Britton, Angela and Heffington, Warren, “Con-
serve energy to cut operating costs,” Chemical Engineering,
Sept. 1993, p. 126.
Hahn, Glenn E., “Get the most out of steam,” Chemical Engi-
neering, Jan. 1994, p. 80.
Power, Robert B., “Pump up your energy savings,” Chemical
Engineering, Feb. 1994, p. 120.
Nelson, Kenneth E., “A practical guide to energy accounting,”
Chemical Engineering, Sept. 1994, p. 122.
Wellons, Michael C., Sapre, Ajit V., Chang, Arthur I., and Laird,
T.L., “On-line power plant optimization improves Texas re-
finer’s bottom line,” Oil & Gas Journal, May 16, 1994, p. 53.
XX. GENERAL
Corbett, Richard A., “Capacity rise reflects return to better times
for U.S. refiners,” Oil & Gas Journal, Mar. 20, 1989, p. 49.
Gwyn, Debra A., “Annual U.S. refining survey,” Oil & Gas
Journal Mar. 20, 1989, p. 68.
Davis, Brian C., “Supplying high-octane gasoline will further
challenge U.S. refiners,” Oil & Gas Journal, May 15, 1989, p.
35.
“Study targets refiners, surplus normal butane,” Oil & Gas
Journal, May 8, 1989, p. 42.
Sears, George F., “Nomogram estimates competitive fuel prices,”
Oil & Gas Journal, May 8, 1989, p.41.
Hermes, Robert A., “High utilization, tight supply will maintain
strong refining margins in U.S.,” Oil & Gas Journal, June 19,
1989, p. 44.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Olujic, Barko, “Explicit solution is developed for vapor pressure
equation,” Oil & Gas Journal, Nov. 6, 1989, p. 46.
Furgang, S.R., “Train better by computer,” Hydrocarbon Process-
ing, Vol. 68, No. 01, Jan. 1989, p. 86.
Contino, A.V., “Process engineering management (Part l),”
Hydrocarbon Processing, Vol. 68, No. 02, Feb. 1989, p. 56.
Contino, A.V., “Process engineering management (Part 2),”
Hydrocarbon Processing, Vol. 68, No. 03, Mar. 1989, p. 121.
Torell, C.A., “Fast-track contracting can save time and money,”
Hydrocarbon Processing, Vol. 68, No. 04, Apr. 1989, p. 68.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Munisteri, J.G. and Chevriere, J.P., “E/Cs: Be ready for the
1990s” Hydrocarbon Processing, Vol. 68, No. 05, May 1989,
p. 37.
Hoffman, H.L. and Riddle, L., “Spending tied to construction,”
Hydrocarbon Processing, Vol. 68, No. 05, May 1989, p. 42.
Provost, R.D. and Lipscomb, R.S., “Partnering: A case study,”
Hydrocarbon Processing, Vol. 68, No. 05, May 1989, p. 48.
Vervalin, C.H., “Construction information resources,” Hydro-
carbon Processing, Vol. 68, No. 05, May 1989, p. 51.
Kennedy, R.D., “Ready for America’s funeral?,” Hydrocarbon
Processing, Vol. 68, No. 06, June 1989, p. 93.
Frohman, M., “Improve group problem-solving,” Hydrocarbon
Processing, Vol. 68, No. 07, July 1989, p. 77.
Woodruff, D.M., “Tools for better management (Part l),” Hy-
drocarbon Processing, Vol. 68, No. 08, Aug. 1989, p. 74.
Woodruff, D.M., “Tools for better management (Part 2),” Hy-
drocarbon Processing, Vol. 68, No. 09, Sept. 1989, p. 103.
Kent, George R., “Troubleshooting vibration problems. Con-
fessions of a service engineer, Part I,” Chemical Engineering,
Feb. 1989, p. 145.
Harrison, Mark E. and France, John J., “Distillation column
troubleshooting,” Chemical Engineering, Apr. 1989, p. 121.
Harrison, Mark E. and France, John J., “Troubleshooting distil-
lation columns - Part 3: Trayed columns,” Chemical Engineer-
ing, May 1989, p. 126.
Wong, Wing Y., “Safer relief-valve sizing,” Chemical Engineer-
ing, May 1989, p. 137.
Harrison, Mark E. and France, John J., “Troubleshooting distil-
lation columns - Part 4: Auxiliary equipment,” Chemical
Engineering, June 1989, p. 130.
Kent, George R., “Troubleshooting equipment vibration. Con-
fessions of a service engineer, Part III,” Chemical Engineering,
July 1989, p. 171.
Trigueros, David, Coronado-Velasco, Cristina, and Gomez-Mu-
noz, Alejandro, “Synthesize simple distillation the thermody-
namic way,” Chemical Engineering, Aug. 1989, p. 129.
Barnicki, Scott D. and Davis, James E, “Designing sieve-tray
columns,” Chemical Engineering, Nov. 1989, p. 202.
Barnicki, Scott D. and Davis, James E, “Designing sieve-tray
columns,” Chemical Engineering, Oct. 1989, p. 140.
Corbett, Richard A., “ENVIRONMENT & SAFETY RE-
PORT: Refiners, petrochem plants focus on new waste chaI-
lenges,” Oil & Gas Journal, Mar. 5, 1990, p. 33.
True, Warren R., “ENVIRONMENT & SAFETY REPORT
Clean Air Act and PCB cleanup hold attention of processors,
pipelines,” Oil & Gas Journal, Mar. 5, 1990, p. 38.
Aalund, Leo R., “Expanded Mongstad refinery has major export
role,” Oil & Gas Journal Mar. 12, 1990, p. 33.
Corbett, Richard A., “ANNUAL REFINING REPORT Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
26, 1990, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT Annual
Refining Survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
“WORLDWIDE CONSTRUCTION: Refineries,” Oil & Gas
Journal, Apr. 16, 1990, p. 53.
“WORLDWIDE CONSTRUCTION: Petrochemicals,” Oil
& Gas Journal, Apr. 16, 1990, p. 60.
“WORLDWIDE CONSTRUCTION: Gas Processing,” Oil &
Gas Journal, Apr. 16, 1990, p. 72.
255
TOC/INDEX
“WORLDWIDE CONSTRUCTION: Related Fuels,” Oil &
Gas Journal, Apr. 16, 1990, p. 74.
Corbett, Richard A., “FUELS FOR TOMORROW-Tough air-
quality goals spur quest for transportation fuel changes,” Oil
& Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal June 18, 1990, p. 52.
True, Warren R., “GAS PROCESSING REPORT Worldwide
gas-processing growth slows,” Oil & Gas Journal July 9, 1990,
p. 41.
Thrash, Lou Ann, “GAS PROCESSING REPORT: World
sulfur derived from oil, gas production,” Oil & Gas Journal
July 9, 1990, p. 87.
Thrash, Lou Ann, “GAS PROCESSING REPORT: Worldwide
gas processing,” Oil & Gas Journal, July 9, 1990, p. 55.
Beck, Robert J., “Crude price slump tempers midyear outlook,”
Oil & Gas Journal, July 30, 1990, p. 49.
Corbett, Richard A., ‘ANNUAL PETROCHEMICAL RE-
PORT World ethylene capacity still growing,” Oil & Gas
Journal, Sept. 10, 1990, p. 49.
Pascarella, P. and Frohman, M.A., “The purpose-driven organi-
zation, Part 1,” Hydrocarbon Processing, Vol. 69, No. 02, Feb.
1990, p. 83.
Pujado, P.R. and Vora, B.V., “Make C3-C4 olefins selectively,”
Hydrocarbon Processing, Vol. 69, No. 03, Mar. 1990, p. 65.
Desensy, M.G., ‘Chemical industry faces growth, challenges in
‘92,” Hydrocarbon Processing, Vol. 69, No. 03, Mar. 1990, p.
132C.
Kerridge, A.E., “For quality, define requirements,” Hydrocarbon
Processing, Vol. 69, No. 04, Apr. 1990, p. 103.
Wilson, J.W., “1992 will impact U.S. refiners,” Hydrocarbon
Processing, Vol. 69, No. 05, May 1990, p. 55.
Kerridge, A.E., “Be a ‘winning’ project manager,” Hydrocarbon
Processing, Vol. 69, No. 05, May 1990, p. 99.
Raudsepp, E., “Flexibility can lead to success,” Hydrocarbon
Processing, Vol. 69, No. 05, May 1990, p. 113.
Watters, P.R., “New partnerships emerge in LPG and petro-
chemicals trade,” Hydrocarbon Processing, Vol. 69, No. 06,
June 1990, p. 100B.
Grosboll, MP., “Succeed, with organized chaos,” Hydrocarbon
Processing, Vol. 69, No. 06, June 1990, p. 141.
Raudsepp, E., “Should I change jobs?,” Hydrocarbon Processing,
Vol. 69, No. 07, July 1990, p. 87.
Vervalin, C.H., “Creative problem solving revisited,” Hydrocar-
bon Processing, Vol. 69, No. 08, Aug. 1990, p. 87.
Brown, D.J., “Quality improvement: buzzword or revolution?,”
Hydrocarbon Processing, Vol. 69, No. 09, Sept. 1990, p. 123.
Marcos-Giacoman, E., “Mexican oil industry gears up for new
economic environment,” Hydrocarbon Processing, Vol. 69, No.
10, Oct. 1990, p. 50C.
Wilson, J.L., “Theme for ‘91 could be ‘The Future is Now’,”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 51.
Raudsepp, E., “Are you assertive enough?,” Hydrocarbon Process-
ing, Vol. 69, No. 10, Oct. 1990, p. 107.
Kavanagh, J.T., “Managing construction resources,” Hydrocar-
bon Processing, Vol. 69, No. 11, Nov. 1990, p. 34C.
256 References
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Drew, E.H., “Strategies for leadership: a challenge in the 1990s”
Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990, p. 57.
Weismantel, G.E., “Quality is a major focus next year and
beyond,” Hydrocarbon Processing, Vol. 69, No. 12, Dec. 1990,
p. 60.
“HPI spending for 1991,” Hydrocarbon Processing, Vol. 69, No.
12, Dec. 1990, p. 97.
“GAO: Reformulation threatens small refiners,” Oil & Gas
Journal, July 2, 1990, p. 34.
Williams, B., “Reformulated fuels set the stage for U.S. supply
pinch, price spikes,” Oil & Gas Journal July 9, 1990, p. 21.
“Ashland starts up MTBE unit,” Oil & Gas Journal, Aug. 13,
1990, p. 32.
Corbett, R.A., “WORLDWIDE CATALYST REPORT: New
catalyst designs meet environmental challenges of the 1990s,”
Oil & Gas Journal, Oct. 1, 1990, p. 49.
“Catalysts available from East Germany,” Oil & Gas Journal,
Oct. 15, 1990, p. 54.
Aalund, L.R., “East German refiners face risky future,” Oil &
Gas Journal, Oct. 15, 1990, p. 52.
“MTBE: ARCO Chemical’s No. 1 performer,” Oil & Gas Jour-
nal, Oct. 15, 1990, p. 40.
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT Refiners,” Oil & Gas Journal Oct. 15, 1990, p. 57.
“Temporary mat system supports heavy vessels,” Oil & Gas
Journal, Oct. 22, 1990, p. 80.
Aalund, L.R., “Major East German plants enter EEC refining
network,” Oil & Gas Journal, Dec. 24, 1990, p. 30.
“WORLDWIDE REPORT Worldwide Refining,” Oil & Gas
Journal, Dec. 31, 1990, p. 84.
“U.S. kerosine jet fuel consumption soars,” Oil & Gas Journal
Dec. 31, 1990, p. 23.
Ozog, H. and Stickles, RP., “Process hazard management docu-
ments, practices compared,” Oil & Gas Journal, Jan. 28, 1991,
p. 86.
“Indian revamps strategy for refining capacity expansion,” Oil
& Gas Journal, Feb. 11, 1991, p. 32.
“Shortfall looms as strike cripples Brazilian refineries,” Oil &
Gas Journal, Mar. 11, 1991, p. 40.
“Chevron revises Richmond refinery project,” Oil & Gas Jour-
nal Mar. 18, 1991, p. 44.
Aalund, L.R., “ANNUAL REFINING REPORT: U.S. refining
industry has powerful configuration,” Oil & Gas Journal, Mar.
18, 1991, p. 57.
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84.
“Chevron settles fire safety case with OSHA,” Oil & Gas Journal,
Mar. 25, 1991, p. 32.
“Esso Thai refinery project, divestiture okayed,” Oil & Gas
Journal Mar. 25, 1991, p. 32.
“GM mounts push for reformulated fuel now,” Oil & Gas
Journal, Mar. 25, 1991, p. 28.
“Mobil to add units at Singapore refinery,” Oil & Gas Journal,
Apr. 1, 1991, p. 42.
“Western closes purchase of Amoco plant,” Oil & Gas Journal,
Apr. 8, 1991, p. 91.
TOC/INDEX
Yepsen, G. and Witoshkin, T., “Refiners have options to deal
with reformulated gasoline,” Oil & Gas Journal, Apr. 8, 1991,
p. 68.
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT: Refineries,” Oil & Gas Journal, Apr. 15, 1991, p. 62.
Unzelman, G.H., “OXYGENATES FOR THE FUTURE-l:
U.S. Clean Air Act expands role for oxygenates,” Oil & Gas
Journal, Apr. 15, 1991, p. 44.
Unzelman, G.H., “OXYGENATES FOR THE FUTURE-
Conclusion: Oxygenate/hydrocarbon shift will rewrite gaso-
line recipes,” Apr. 29, 1991, p. 62.
“BP outlines U.S. refinery spending plans,” Oil & Gas Journal,
Apr. 29, 1991, p. 30.
“More MTBE, TAME plants due U.S.,” Oil & Gas Journal, Apr.
29, 1991, p. 40.
“Coastal Chem breaks ground on MTBE plant,” Oil & Gas
Journal, May 6, 1991, p. 30.
“Tenneco building Houston area MTBE plant,” Oil & Gas
Journal May 20, 1991, p. 25.
“Mobil, Chemvest study Saudi MTBE plant,” Oil & Gas Jour-
nal May 20, 1991, p. 27.
“Saudis eye Japan R&M joint venture,” Oil & Gas Journal, May
20, 1991, p. 27.
“More U.S. oxygenates projects scheduled,” Oil & Gas Journal,
May 27, 1991, p. 32.
“India to hike refining capacity,” Oil & Gas Journal, May 27,
1991, p. 112.
Scherr, R.C., Smalley, G.A., Jr., and Norman, M.E., “REFIN-
ING IN THE ‘9Os-1: Clean Air Act complicates refinery
planning,” Oil & Gas Journal May 27, 1991, p. 68.
“UOP develops new oxygenates process,” Oil & Gas Journal,
June 3, 1991, p. 30.
“Saudi, Japanese refining additions eyed,” Oil & Gas Journal
June 10, 1991, p. 18.
“Refiners may meet CAA requirements if...,” Oil & Gas Journal,
June 10, 1991, p. 26.
“Ways sought to improve E. Europe refineries,” Oil & Gas
Journal June 10, 1991, p. 27.
Scherr, R.C., Smalley, G.A., Jr. and Norman, M.E., “REFIN-
ING IN THE ’90s-Conclusion: Clean air amendments put
big burden on refinery planning,” Oil & Gas Journal, June 10,
1991, p. 35.
“EPA outlines reformulated gasoline regs,” Oil & Gas Journal,
June 17, 1991, p. 20.
“European refiners press sulfur campaign,” Oil & Gas Journal,
June 24, 1991, p. 26.
“Flexible new process converts aromatics in variety of diesel
feedstocks,” Oil & Gas Journal, July 1, 1991, p. 55.
“ARC0 claims advance in gasoline formula,” Oil & Gas Journal,
July 22, 1991, p. 37.
“German refinery to undergo large revamp,” Oil & Gas Journal,
Aug. 5, 1991, p. 30.
Vielvoye, R., “WATCHING THE WORLD: Pacific Rim proc-
essing,” Oil & Gas Journal, Aug. 12, 1991, p. 38.
Crow, l?, “WATCHING WASHINGTON: ‘Reg-neg’ gasoline
standards,” Oil & Gas Journal, Aug. 12, 1991, p. 44.
“Upgrade adds three units at Corpus plant,” Oil & Gas Journal,
Aug. 12, 1991, p. 96.
“New short contact time processes upgrade residual oils and
heavy crudes,” Oil & Gas Journal, Aug. 12, 1991, p. 79.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Saudis poised for huge refining upgrade,” Oil & Gas Journal
Aug. 19, 1991, p. 32.
“Asia-Pacific area shows big gains in processing,” Oil & Gas
Journal, Aug. 26, 1991, p. 17.
“Way clear for reformulated gasoline rule,” Oil & Gas Journal,
Aug. 26, 1991, p. 37.
“OSHA levies fine on Citgo,” Oil & Gas Journal, Sept. 9,1991,
p. 37.
“Exxon U.S.A. plans three MTBE plants,” Oil & Gas Journal,
Sept. 16, 1991, p. 34.
“Soviets avert accident at Ufa refinery,” Oil & Gas Journal, Sept.
30, 1991, p. 38.
“Malaysia to expand refining, LNG capacity,” Oil & Gas Journal
Oct.7, 1991, p. 111.
“Elf group will speed study for Shanghai area refinery,” Oil &
Gas Journal, Oct. 14, 1991, p. 27.
“EPA actions target OxyChem, Olin, Texaco,” Oil & Gas Jour-
nal Oct. 14, 1991, p. 36.
Rhodes, A.K., “WORLDWIDE CATALYST SURVEY: Survey
shows over 1,000 refining catalysts,” Oil & Gas Journal Oct.
14, 1991, p. 43.
Yanagi, Tak, “Inside a trayed distillation column,” Chemical
Engineering, Nov. 1990, p. 120.
Burger, Robert, “CoIder cooling water pays off,” Chemical En-
gineering, Mar. 1991, p. 177.
Godbey, Thomas, “Brace your plant against a dust explosion,”
Chemical Engineering, Apr. 1991, p. 130.
Simpson, L.L., “Estimate two-phase flow in safety devices,”
Chemical Engineering, Aug. 1991, p. 98.
Chatrathi, Kris, “Explosion-isolation systems,” Chemical Engi-
neering, Oct. 1991, p. 134.
Richardson, T., “Learn from the Phillips explosion,” Hydrocar-
bon Processing, Vol. 70, No. 03, Mar. 1991, p. 83.
Schuler, G.H.M., “Will Middle East oil continue to supply your
refinery?,” Hydrocarbon Processing, Vol. 70, No. 07, July 1991,
p. 50C.
Spranza, EG., “Will terrorists hit your plant?,” Hydrocarbon
Processing, Vol. 70, No. 07, July 1991, p. 102.
Karnik, J.L., “Refiners in Western Europe face emission reduc-
tions,” Hydrocarbon Processing, Vol. 70, No. 08, Aug. 1991, p.
50E.
Tarbutton, A. and Salazar, M., "Aglobal panorama of the natural
gas industry,” Hydrocarbon Processing, Vol. 70, No. 11, Nov.
1991, p. 146C.
Jones, R.L., “U.S. refiners will face a year of challenge,” Hydro-
carbon Processing, Vol. 70, No. 12, Dec. 1991, p. 47.
Portal, G.M.A., “What the new year holds for European refin-
ers,” Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p.
49.
Lenz, A.]., “Chemical industry output ‘to grow 5% in ‘92’,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 50.
Tucker, R.L., “For E/Cs the ‘92 message is ‘change with the
times’,” Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991,
p. 52.
Early II, W.F., “Wed regulatory compliance to long-term busi-
ness goals,” Hydrocarbon Processing, Vol. 70, No. 12, Dec.
1991, p. 54.
Finley, H.F., “Productivitygrowth in the U.S. refining industry,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 55.
257
TOC/INDEX
Robinson, R.I., “A major restructuring has started, or will,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 57.
Riley, K.G., “Petroleum refiners face major strategic decisions,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 58.
Chatha, A., “Fieldbus begins a new era in process control,”
Hydrocarbon Processing, Vol. 70, No. 12, Dec. 1991, p. 59.
Hearn, Graham, “Coping with electrostatic hazards,” Chemical
Engineering, Nov. 1991, p. 188.
Bechman, Lawrence V, “How reliable is your safety system?,”
Chemical Engineering, Jan. 1992, p. 109.
Olson, Kevin R., “How to remove fouling solids cooling water,”
Chemical Engineering, May 1992, p. 155.
Turner, J., “Accessing and manipulating simulation data in
spreadsheets,” Hydrocarbon Processing, Vol. 70, No. 11, Nov.
1991, p. 123.
Yaws, C.L., “Calculate liquid heat capacity,” Hydrocarbon Proc-
essing, Vol. 70, No. 12, Dec. 1991, p. 73.
Finley, H.F., “Productivity growth in U. S. refining industry,”
Hydrocarbon Processing, 1992, p. 74-c.
“Gas process handbook ‘92,” Hydrocarbon Processing, 1992, p.
83.
Wadsworth, EA. and Villalanti, D.C., “Pinpoint hydrocarbon
types,” Hydrocarbon Processing, Vol. 71, No. 05, May 1992, p.
109.
Gallun, S.E., et al., “Use open equations for better models,”
Hydrocarbon Processing, Vol. 71, No. 07, July 1992, p. 78.
Bergmann, E.P., et al., “Risk management success calls for some
hard decisions,” Hydrocarbon Processing, Vol. 71, No. 08, Aug.
1992, p. 45.
Eley, C., “Compliance audit checklist for hazardous chemicals,”
Hydrocarbon Processing, Vol. 71, No. 08, Aug. 1992, p. 97.
Mallett, R., “Rate your risk management plans,” Hydrocarbon
Processing, Vol. 71, No. 08, Aug. 1992, p. 111.
Wong, E.W., et al., “Produce high purity VCM product,”
Hydrocarbon Processing, Vol. 71, No. 08, Aug. 1992, p. 129.
Vasquez, J.J., et al., “How to estimate Rvp of blends,” Hydrocar-
bon Processing, Vol. 71, No. 08, Aug. 1992, p. 135.
Spranza, EG., “Plant security checklist,” Hydrocarbon Processing,
Vol. 71, No. 09, Sept. 1992, p. 71.
Philley, J., “Investigate incidents with MRC,” Hydrocarbon Proc-
essing, Vol. 71, No. 09, Sept. 1992, p. 77.
“Nelson Farrar cost indexes,” Oil & Gas Journal Oct. 7, 1991,
p. 91; Nov. 4, 1991, p. 75; Dec. 2, 1991, p. 57; Jan. 6, 1992,
p. 73; Feb. 3, 1992, p. 50; Mar. 2, 1991, p. 45; Apr. 6, 1992,
p. 61; May 4, 1992, p. 130; June 1, 1992, p. 78; July 6, 1992,
p. 83-84; Aug. 3, 1992, p. 61; Sept. 7, 1992, p. 48; Oct. 5,
1992, p. 82.
“Nelson-Farrar Quarterly Costimating,” Oil & Gas Journal
Oct. 7, 1991, p. 92; Jan. 6, 1992, p. 82; Apr. 6, 1992, p. 62;
July 6, 1992, p. 84; Oct. 5, 1992, p. 86.
Rhodes, Anne K., “Survey shows over 1,000 refining catalysts,”
Oil & Gas Journal, Oct. 14, 1992, p. 43.
Rhodes, Anne K., “Worldwide catalyst survey,” Oil & Gas
Journal, Oct. 14, 1991, p. 46.
Rhodes, Anne K., “U.K. North Sea’s Kittiwake crude assayed,”
Oil & Gas Journal, Oct. 28, 1991, p. 55.
“Worldwide Construction Report: Refineries,” Oil & Gas Jour-
nal, Oct. 28, 1991, p. 56.
“Malaysian upgrade delayed,” Oil & Gas Journal, Nov. 11, 1991,
p. 24.
258 References
“Long delayed Soviet refinery starts up,” Oil & Gas Journal, Nov.
18, 1991, p. 30.
“End seen for high sulfur fuel oil in Europe,” Oil & Gas Journal,
Dec. 2, 1991, p. 21.
Manah, Kambiz, “Simple refining complexity calculation tracks
regional trends,” Oil & Gas Journal, Dec. 2, 1991, p. 62.
Rhodes, Anne K., “Two important Saudi crudes assayed,” Oil
& Gas Journal, Dec. 2, 1991, p. 64.
“Samarec outlines $4 billion upgrading plans,” Oil & Gas
Journal, Dec. 9, 1991, p. 73.
“Europeans vying for German refinery,” Oil & Gas Journal, Dec.
16, 1991, p. 21.
“Corpoven plans refinery in E. Venezuela,” Oil & Gas Journal,
Dec. 16, 1991, p. 35.
Rhodes, Anne K., “Recent and pending regulations push refiners
to the limit,” Oil & Gas Journal Dec. 16, 1991, p. 39.
“Plans changed for Bahrain refinery project,” Oil & Gas Journal,
Dec. 23, 1991, p. 18.
“Unocal completes purchase of part of Shell refinery,” Oil & Gas
Journal, Dec. 23, 1991, p. 26.
“Industry hits California reformulation move,” Oil & Gas Jour-
nal, Dec. 23, 1991, p. 26.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
Tanasescu, Dumitru, “Romanian refining industry assesses re-
structuring,” Oil & Gas Journal, Dec. 30, 1991, p. 89.
“Esso Thailand schedules project to almost triple refinery capac-
ity,” Oil & Gas Journal, Jan. 13, 1992, p. 21.
“SBA plans to jump small refinery definition to 75,000 b/d
capacity,” Oil & Gas Journal, Jan. 20, 1992, p. 32.
“Elf group to buy German downstream assets,” Oil & Gas
Journal, Jan. 27, 1992, p. 28.
“Amoco to seek buyer for refinery in Salt Lake City,” Oil & Gas
Journal, Jan. 27, 1992, p. 30.
“Unease among Japanese refiners,” Oil & Gas Journal, Jan. 27,
1992, p. 38.
“Caltex signs pact to build Thailand’s fifth refinery,” Oil & Gas
Journal, Jan. 27, 1992, p. 40.
“Petro-Canada to cut refining capacity,” Oil & Gas Journal, Feb.
3, 1992, p. 22.
“CIS to get more refining technologies,” Oil & Gas Journal Feb.
3, 1992, p. 24.
“Seven projects scheduled at Ashland refinery,” Oil & Gas
Journal, Feb. 10, 1992, p. 38.
“CERA: Refiners can cope with CAA requirements,” Oil & Gas
Journal, Feb. 17, 1992, p. 27.
“CIS refining faces tough year,” Oil & Gas Journal, Feb. 17, p,
40.
“BP to make lubes in Vietnam,” Oil & Gas Journal, Mar. 2,
1992, p. 29.
“Sinopec outlines progress,” Oil & Gas Journal, Mar. 2, 1992,
p. 30.
“Statoil to expand Danish plant,” Oil & Gas Journal, Mar. 2,
1992, p. 32.
Rhodes, Anne K., “East Zeit Mix and Dulang crudes assayed,”
Oil & Gas Journal, Mar. 2, 1992, p. 46.
“Kuwaiti refinery repairs eyed,” Oil & Gas Journal Mar.9, 1992,
p. 31.
TOC/INDEX
“California a dangerous pattern for action on emissions reduc-
tion,” Oil & Gas Journal Mar. 16, 1992, p. 24.
“Chevron details Port Arthur revamp,” Oil & Gas Journal, Mar.
16, 1992, p. 30.
“New NPRA chairman sees more rationalization among U.S.
refiners,” Oil & Gas Journal, Mar. 30, 1992, p. 32.
Rhodes, Anne K., “Four California OCS crudes assayed,” Oil &
Gas Journal, Mar. 30, 1992, p. 67.
“Chevron drops methanol auto fuels program,” Oil & Gas
Journal, Apr. 6, 1992, p. 34.
“Environmental regulatory vise squeezing U.S. refiners,” Oil &
Gas Journal, Apr. 13, 1992, p. 21.
“Multibillion dollar upgrade ahead for Canadian refiners,” Oil
& Gas Journal, Apr. 13, 1992, p. 22.
“Fire hits two Houston area downstream complexes,” Oil & Gas
Journal, Apr. 13, 1992, p. 35.
“Pdvsa earmarks $3.2 billion for two refinery projects,” Oil &
Gas Journal, Apr. 13, 1992, p. 40.
“Japanese firms to hike deep conversion,” Oil & Gas Journal,
Apr. 13, 1992, p. 40.
“Chem Systems study outlines U.S. refiners strategic options,”
Oil & Gas Journal, Apr. 20, 1992, p. 32.
Rhodes, Anne K., “Malaysian, Canadian, Saudi crudes assayed,”
Oil & Gas Journal, Apr. 27, 1992, p. 44.
Duncan, Norman E., “Conversion index helps refiner assess
relative profitability,” Oil & Gas Journal, May 4, 1992, p. 108.
“Coastal unit eyes move into Romania,” Oil & Gas Journal, May
11, 1992, p. 23.
“Conoco schedules consolidation of U.S. lubricants,” Oil & Gas
Journal, May 11, 1992, p. 26.
“Philippines’ downstream sector poised for growth,” Oil & Gas
Journal, May 11, 1992, p. 28,
“C.I.S.-U.S. venture to offer process services,” Oil & Gas Jour-
nal, May 11, 1992, p. 31.
“Canadian R&M restructuring to pay dividends,” Oil & Gas
Journal, May 25, 1992, p. 18.
“Thai, Aussie refining contracts let,” Oil & Gas Journal, May 25,
1992, p. 21.
“U.S. refiners lament lack of final CAA rules,” Oil & Gas Journal
May 25, 1992, p. 26.
“Mobil refineries set plant records for 1991,” Oil & Gas Journal
June 1, 1992, p. 46.
Bellomo, P.J., “OSHA safety regulation calls for step-by-step
approach,” Oil & Gas Journal June 1, 1991, p. 49.
“Chevron’s ‘clean’ diesel gets California nod; Unocal mostly opts
out of state’s diesel market,” Oil & Gas Journal, June 8, 1992,
p. 30.
“Gasoline reformulation to roil petrochem markets,” Oil & Gas
Journal, June 8, 1992, p. 32.
“Russian refining reflects old ways,” Oil& Gas Journal, June 15,
1992, p. 24.
“Amoco to retain Utah refinery,” Oil & Gas Journal, June 22,
1992, p. 30.
“Agreement near on upgrader overrun,” Oil & Gas Journal July
13, 1992, p. 19.
Gomez, Jose Vicente, “New correlation predicts density of pe-
troleum fractions,” Oil & Gas Journal, July 13, 1992, p. 49.
“Singapore refiners in midst of huge construction campaign,”
Oil & Gas Journal, July 20, 1992, p. 23.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
“Lyondell plans to hike heavy crude runs at Houston,” Oil &
Gas Journal July 20, 1992, p. 41.
“Corpus Christi refinery due new units,” Oil & Gas Journal, July
27, 1992, p. 55.
“Problems persist for French refining sector,” Oil& Gas Journal,
July 27, 1992, p. 107.
“Pdvsa buys more downstream assets,” Oil & Gas Journal Aug.
3, 1992, p. 24.
“Oxygenates to hike gasoline price,” Oil & Gas Journal, Aug. 3,
1992, p. 28.
“Elf group buys E. German R&M assets,” Oil & Gas Journal,
Aug. 3, 1992, p. 31.
“Mobil’s Aussie refinery revamp okayed,” Oil & Gas Journal,
Aug. 17, 1992, p. 36.
“Chevron plans revamp of Richmond refinery,” Oil & Gas
Journal Aug. 17, 1992, p. 39.
“Fish agrees to settle citations issued by OSHA,” Oil & Gas
Journal, Aug. 17, 1992, p. 42.
“Two new units cut refinery costs at Puertollano,” Oil & Gas
Journal, Aug. 24, 1992, p. 21.
Collinge, J. Alan, “Auditing reduces accidents by eliminating
unsafe practices,” Oil & Gas Journal, Aug. 24, 1992, p. 38.
“Ashland outlines $261 million in refinery unit construction,”
Oil & Gas Journal, Aug. 31, 1992, p. 20.
“Pemex to acquire interest in Shell Texas refinery,” Oil & Gas
Journal, Aug. 31, 1992, p. 28.
Jamialahmadi, Mohamad and Muller-Steinhagen, Hans, “Com-
puter program designs packed columns,” Oil & Gas Journal,
Aug. 31, 1992, p. 33.
“Mothballed Canadian refineries marked for reuse,” Oil &Gas
Journal, Sept. 14, 1992, p. 42.
“Star agrees to spill settlement,” Oil & Gas Journal, Sept. 14,
1992, p. 47.
“India beckons participants in burgeoning refining sector,” Oil
& Gas Journal, Sept. 21, 1992, p. 25.
“Amoco producing improved premium for Midwest market,”
Oil & Gas Journal, Sept. 21, 1992, p. 38.
“National oil companies’ presence to hike U.S. refining compe-
tition,” Oil & Gas Journal Sept 21, 1992, p. 40.
Rhodes, Anne K., “Assays of rwo Saudi crudes updated,” Oil &
Gas Journal, Sept 28, 1992, p. 91.
“Petrochem industry expands North American MTBE capac-
ity,” Oil & Gas Journal Oct. 5, 1992, p. 34.
Humphrey, Jimmy L. and Seibert, A. Frank, “New horizons in
distillation,” Chemical Engineering, Dec. 1992, p. 86.
Mak, H.Y., “Gas plant converts amine unit to MDEA-based
solvent,” Hydrocarbon Processing, Vol. 71, No. 10, Oct. 1992,
p. 91.
Reddi, S.V., “Thermal insulation safety, Part 1,” Hydrocarbon
Processing, Vol. 71, No. 10, Oct. 1992, p. 122-C.
Shah, G.C., “Improve activated carbon bed absorber opera-
tions,” Hydrocarbon Processing, Vol. 71, No. 11, Nov. 1992, p.
61.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Catena, D., Dietz, J.T and Traubert, T.D., “Create intelligent
P&IDS,” Hydrocarbon Processing, Vol. 71, No. 11, Nov. 1992,
p. 65.
259
TOC/INDEX
Stippick, J.A., “How to check welding procedures without
becoming an expert,” Hydrocarbon Processing, Vol. 71, No. 11,
Nov. 1992, p. 93.
Reddi, S.V., “Thermal insulation safety, Part 2,” Hydrocarbon
Processing, Vol. 71, No. 11, Nov. 1992, p. 100-C.
McMarlin, R.M. and Gerrish, R.W., “Can your ‘noncombusti-
ble’ insulation burn?,” Hydrocarbon Processing, Vol. 71, No.
11, Nov. 1992, p. 101.
Baas, J. and Warner, R., “How much ‘life’ is left in your olefin
unit?,” Hydrocarbon Processing, Vol. 71, No. 12, Dec. 1992, p.
81.
Wong, W.Y., “Capacity credit calculation method for exchanger
tube rupture,” Hydrocarbon Processing, Vol. 71, No. 12, Dec.
1992, p. 89.
Sarathy, P.R. and Suffridge, G.S., “Etherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 89.
Tagoe, C., et al., “Are there contaminants in your feedstream?,”
Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 117.
Zoller, L. and Esping, J., “Use ‘What-If’ method for process
hazard analysis,” Hydrocarbon Processing, Vol. 72, No. 01, Jan.
1993, p. 132-B.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Part
2,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Gruhn, P., “Safety system performance terms: clearing up the
confusion,” Hydrocarbon Processing, Vol. 72, No. 02, Feb.
1993, p. 63.
Beckman, L.V., “Selecting redundant microprocessor-based sys-
tems,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p.
71.
Kobyakov, A.I., “Include heuristics in protection systems,” Hy-
drocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 79.
Bishop, K. and Knittel, T., “Do you have the ‘right’ flame
’
arrester In service?, ” Hydrocarbon Processing, Vol. 72, No. 02,
Feb. 1993, p. 99.
Golden, S.W., et al., “FCC main fractionator revamps,” Hydro-
carbon Processing, Vol. 72, No. 03, Mar. 1993, p. 77.
Forsell, K.A., “Protect motors with solid-state overloads,” Hy-
drocarbon Processing, Vol. 72, No. 03, Mar. 1993, p. 100.
Aitani, A.M., “Sour natural gas drying,” Hydrocarbon Processing,
Vol. 72, No. 04, Apr. 1993, p. 67.
Fair, J.R., “How to design baffle tray columns,” Hydrocarbon
Processing, Vol. 72, No. 05, May 1993, p. 75.
GoyaI, R.K., “FMEA, the alternative process hazard method,”
Hydrocarbon Processing, Vol. 72, No. 05, May 1993, p. 95.
Kletz, T.A., “Organizations have no memory when it comes to
safety,” Hydrocarbon Processing, Vol. 72, No. 06, June 1993,
p. 88.
Gallupe, W., “Retrofit methods reduce valves’ fugitive emis-
sions,” Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p.
97.
Roberts, D.A., et al., “Recover additional distillate from vacuum
residue,” Hydrocarbon Processing, Vol. 72, No. 07, July 1993,
p. 75.
Golden, S.W., et al., “Troubleshoot vacuum columns with
low-capital methods,” Hydrocarbon Processing, Vol. 72, No.
07, July 1993, p. 81.
260 References
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07, July 1993, p. 90.
Cindric, D.T., et al., “Reduce crude unit pollution with these
technologies,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 45.
Agar, G., et al., “Energy absorption probes control oily-water
discharges,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 55.
Bergmann, E.P., “Approximate risk assessment prioritizes reme-
dial decisions,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 111.
McSween, T.E., “Improve your safety program with a behavioral
approach,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 119.
Dougan, K.W. and Reilly, M.C., “Quantitative reliability meth-
ods improve plant uptime,” Hydrocarbon Processing, Vol. 72,
No. 08, Aug. 1993, p. 131.
Robinson, J.E., “Underground storage tank: Removal vs. aban-
donment,” Hydrocarbon Processing, Vol. 72, No. 08, Aug.
1993, p. 149.
Bearrow, M.E., “How to shop for a PSM consultant,” Hydrocar-
bon Processing, Vol. 72, No. 07, July 1993, p. 95.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal Oct. 12, 1992, p. 41.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Gas Processing,” Oil & Gas Journal, Oct. 26, 1992,
p. 114.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Sulfur,” Oil & Gas Journal Oct. 26, 1992, p. 77.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Refineries,” Oil & Gas Journal, Oct. 26, 1992, p. 91.
“Nelson-Farrar Cost Index,” Oil & Gas Journal, Nov. 2, 1992,
p. 79; Dec. 7, 1992, p. 74; Jan. 4, 1993, p. 38; Feb. 1, 1993,
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Rhodes, Anne K., “WORLDWIDE REFINING REPORT-
Worldwide refiners make big move into modernization,” Oil
& Gas Journal Dec. 21, 1992, p. 41.
Bell, Laura, “WORLDWIDE REFINING REPORT-Refin-
ing survey,” Oil & Gas Journal Dec. 21, 1992, p. 52.
“Shell starts up two projects at Essex refinery,” Oil & Gas Journal,
Dec. 21, 1992, p. 31.
“Texaco preparing to bring parts of Wilmington refinery back
on stream,” Oil & Gas Journal, Oct. 26, 1992, p. 29.
“Big upgrade slated at Shell’s Pernis refinery,” Oil & Gas Journal
Jan. 25, 1993, p. 40.
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Journal, Feb. 8, 1993, p. 81.
Rhodes, Anne K., “EXPORT CRUDES FOR THE ’90s: Papua
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Swain, Edward J., “U.S. refiners face declining crude quality,
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TOC/INDEX
“Shell, Pemex team up in refining venture,” Oil & Gas Journal,
Mar. 8, 1993, p. 25.
“Two Refineries Running Crude: Third to restart by September,”
Oil & Gas Journal, Mar. 15, 1993, p. 48.
King, Myke, “OIL MOVEMENTS—1: Automation of oil
movement systems prevents mistakes, saves money,” Oil &
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“Coastal to idle Kansas refineries,” Oil & Gas Journal, Mar. 22,
1993, p. 32.
Bell, Laura, “WORLDWIDE CONSTRUCTION SUR-
VEY-Refining,” Oil & Gas Journal Apr. 12, 1993, p. 55.
Bell, Laura, “WORLDWIDE CONSTRUCTION SUR-
VEY-Sulfur,” Oil & Gas Journal, Apr. 12, 1993, p. 78.
Bell, Laura, “WORLDWIDE CONSTRUCTION SUR-
VEY-Gas Processing,” Oil & Gas Journal Apr. 12, 1993, p.
79.
King, Myke, “OIL MOVEMENTS-Conclusion: Integrating
oil movement and data systems beefs project benefits,” Oil &
Gas Journal, Apr. 12, 1993, p. 52.
“Ashland refinery units take shape,” Oil & Gas Journal Apr. 19,
1993, p. 20.
Ladeur, Peter and Bijwaard, Harry, “Shell plans $2.2-billion
renovation of Dutch refinery,” Oil & Gas Journal, Apr. 26,
1993, p. 64.
“World refining outlook seen positive,” Oil & Gas Journal, Apr.
26, 1993, p. 94.
“Asia-Pacific region’s oil demand growth strains refining capac-
ity,” Oil & Gas Journal, May 10, 1993, p. 36.
“China expands refining sector to handle booming oil demand,”
Oil & Gas Journal, May 10, 1993, p. 40.
“Lyondell, Citgo join for refinery project,” Oil & Gas Journal
May 17, 1993, p. 23
Aalund, L.R., “Saudi Master Refining Program Takes Shape,”
Oil & Gas Journal June 21, 1993, p. 39.
Dahl, Carol and Garcia, Wolfgang J., “Reformulated gasoline
more profitable in Venezuela than in U.S.,” Oil & Gas Journal,
June 21, 1993, p. 72.
“Contracts let for German refinery units,” Oil & Gas Journal,
June 21, 1993, p. 35.
“NPRA establishes ‘International Workshop’ at maintenance
meeting,” Oil & Gas Journal, June 28, 1993, p. 70.
True, Warren R., “Maxus starts up Texas Panhandle gas plant,”
Oil & Gas Journal, June 28, 1993, p. 68.
“Houston refinery upgrade is a firm deal,” Oil & Gas Journal,
July 12, 1993, p. 29.
True, Warren R., “World gas processing, sulfur-recovery capaci-
ties still growing,” Oil & Gas Journal, July 12, 1993, p. 41.
“Worldwide gas processing survey,” Oil & Gas Journal, July 12,
1993, p. 55.
“World sulfur survey,” Oil & Gas Journal, July 12, 1993, p.93.
“Big upgrade starts at Shell’s Deer Park refinery,” Oil & Gas
Journal July 19, 1993, p. 28.
Sweeney, Brian N.C., “Rising costs call for new European
refining strategies,” Oil & Gas Journal, July 19, 1993, p. 30.
“French, U.S. companies merge catalyst lines,” Oil & Gas Jour-
nal, Aug. 2, 1993, p. 76.
Rhodes, Anne K., “Recommissioned German refinery ready to
meet tough fuels, emissions specs,” Oil & Gas Journal, Aug.
9, 1993, p. 29.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Aalund, L.R., “STATE OIL COMPANIES: Saudi Arabia,” Oil
& Gas Journal Aug. 16, 1993, p. 38.
Williams, Bob, “STATE OIL COMPANIES: Mexico,” Oil &
Gas Journal Aug. 16, 1993, p. 55.
Knott, David, “STATE OIL COMPANIES: Kuwait,” Oil &
Gas Journal, Aug. 16, 1993, p. 66.
Moritis, Guntis, “STATE OIL COMPANIES: Indonesia,” Oil
& Gas Journal, Aug. 16, 1993, p. 68.
Rhodes, Anne K., “GUIDE TO WORLD CRUDES: Two light,
sweet C.I.S. crudes assayed,” Oil & Gas Journal, Sept. 6, 1993,
p. 82.
“California refiners beat diesel fuel deadline,” Oil & Gas Journal,
Sept. 13, 1993, p. 33.
“NPC: U.S. refiners can meet environmental regulations,
but...,” Oil & Gas Journal, Sept. 13, 1993, p. 34.
“French refiners face shakeout with soaring costs, downturn,”
Oil & Gas Journal, Sept. 20, 1993, p. 25.
“Chevron schedules refinery outlays,” Oil & Gas Journal, Sept.
20, 1993, p. 40.
“Kuwaiti refinery back on stream,” Oil & Gas Journal, Sept. 27,
1993, p. 40.
“Supplying low sulfur diesel no great hurdle for U.S. refiners,”
Oil & Gas Journal Oct. 4, 1993, p. 29.
“Catalyst suppliers further consolidate business units,” Oil &
Gas Journal, Oct. 11, 1993, p. 41.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Jones, Jerry, Asher, William, et al., “Keep pilot plants on the fast
track-Part I,” Chemical Engineering, Nov. 1993, p. 98.
Lo, Francis and Oakes, Donald, “Leep from piot to full-scale
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Bartholomew, Calvin H. and Hecker, William C., “Catalytic
reactor design,” Chemical Engineering, June 1994, p. 70.
DeSilva, Francis, “The ion exchange deal,” Chemical Engineer-
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Martinson, B., “How to set up an environmental audit pro-
gram,” Hydrocarbon Processing, Vol. 72, No. 09, Sept. 1993,
p. 55.
Hill, J. and Brush, P., “Performing capital projects in ozone
nonattainment areas,” Hydrocarbon Processing, Vol. 72, No.
09, Sept. 1993, p. 76C.
Funk, G.L., “Systems integration: What is it and why do it?,”
Hydrocarbon Processing, Vol. 72, No. 09, Sept. 1993, p. 151.
Goodale, J.G., “Improve productivity through effective team-
work,” Hydrocarbon Processing, Vol. 72, No. 09, Sept. 1993,
p. 173.
Love, R.A., “Attain ISO-9000 certification,” Hydrocarbon Proc-
essing, Vol. 72, No. 10, Oct. 1993, p. 82B.
Ganger, J.J. and Bearrow, M.E., “How to prioritize process
hazard analyses,” Hydrocarbon Processing, Vol. 72, No. 10,
Oct. 1993, p. 95.
Schneider, D.F., “How to calculate purge gas volumes,” Hydro-
carbon Processing, Vol. 72, No. 11, Nov. 1993, p. 89.
Doane, R.C., “Rate pumps for viscous crudes quickly,” Hydro-
carbon Processing, Vol. 72, No. 11, Nov. 1993, p. 94.
Lichtblau, J.H., “Forecasting oil trends: mirror or telescope?,”
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261
TOC/INDEX
Vervalin, C.H., “Views from 1993 ECC conference,” Hydrocar-
bon Processing, Vol. 72, No. 12, Dec. 1993, p. 41.
Abbott, K.W., “TQM can improve project control,” Hydrocar-
bon Processing, Vol. 72, No. 12, Dec. 1993, p. 44.
Kerridge, A.E., “Project-manage the owner/client,” Hydrocar-
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Duty, J.M., et al., “New realities of modular construction,”
Hydrocarbon Processing, Vol. 72, No. 12, Dec. 1993, p. 57.
Winston, R.E., “Rapid method for capital investment deci-
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Chieu, J. and Foster, S., “Improve storm water management for
refineries, Part 2,” Hydrocarbon Processing, Vol. 73, No. 01,
Jan. 1994, p. 83.
Bruce, S.R., “Who’s leading your process safety efforts?,” Hydro-
carbon Processing, Vol. 73, No. 01, Jan. 1994, p. 89.
Foo, K.W., “Size steam tracers quickly, Part 1,” Hydrocarbon
Processing, Vol. 73, No. 01, Jan. 1994, p. 93.
Boutte, ED., et al., “Optimize project execution, Part 1,” Hy-
drocarbon Processing, Vol. 73, No. 01, Jan. 1994, p. 116.
Foo, K.W., “Size steam tracers quickly, Part 2,” Hydrocarbon
Processing, Vol. 73, No. 02, Feb. 1994, p. 91.
Mehall, J.R., “State of worldwide refining,” Hydrocarbon Proc-
essing, Vol. 73, No. 02, Feb. 1994, p. 96A.
Carroll, J.J., “Converting amine concentrations,” Hydrocarbon
Processing, Vol. 73, No. 03, Mar. 1994, p. 91.
Kerridge, A.E., “Risk management: a project manager’s view,”
Hydrocarbon Processing, Vol. 73, No. 03, Mar. 1994, p. 100C.
Kerridge, A.E., “Project managers should know how to ‘manage’
the contract, Part 1,” Hydrocarbon Processing, Vol. 73, No. 03,
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Derr, K.T., “Oil and its critics: The facts and the future,”
Hydrocarbon Processing, Vol. 73, No. 04, Apr. 1994, p. 136G.
Kerridge, A.E., “Project managers should know how to ‘manage’
the contract, Part 2,” Hydrocarbon Processing, Vol. 73, No. 04,
Apr. 1994, p. 141.
Vervalin, C.H., “A view of ACHEMA ‘94 conference,” Hydro-
carbon Processing, Vol. 73, No. 05, May 1994, p. 47.
Peterson, EM. and Johnson, J.E., “What’s ahead for propylene
supply?,” Hydrocarbon Processing, Vol. 73, No. 05, May 1994,
p. 61.
Rothman, S.N., “Asian petrochemicals: What impact?,” Hydro-
carbon Processing, Vol. 73, No. 05, May 1994, p. 64.
Crocco, J.R., “The global outlook for methanol,” Hydrocarbon
Processing, Vol. 73, No. 05, May 1994, p. 66C.
Thomas, J.H., “MTBE: Its impact and promise,” Hydrocarbon
Processing, Vol. 73, No. 05, May 1994, p. 66G.
Houston, J.H., “Detergents: The scene is changing,” Hydrocar-
bon Processing, Vol. 73, No. 05, May 1994, p. 66U.
Wallace, S.J. and Hunter, B.L., “Optimize facility-siting evalu-
ations,” Hydrocarbon Processing, Vol. 73, No. 05, May 1994,
p. 85.
Fesharaki, F., “Oil prices in a new light,” Hydrocarbon Processing,
Vol. 73, No. 05, May 1994, p. 143.
Wu, K. and Dorian, J.P., “China’s petrochemical outlook,”
Hydrocarbon Processing, Vol. 73, No. 06, June 1994, p. 50B.
Olstead, C.E., et al., “Objectives Matrix: A practitioner’s per-
spective,” Hydrocarbon Processing, Vol. 73, No. 06, June 1994,
p. 161.
262
Coker, A.K., “Selecting and sizing process compressors,” Hydro-
carbon Processing, Vol. 73, No. 07, July 1994, p. 39.
Nasr, A., “Sealless pumps: Limitations and developments,” Hy-
drocarbon Processing, Vol. 73, No. 07, July 1994, p. 63.
Fusaro, P.C., “Asia Pacific refining: What’s next?,” Hydroocarbon
Processing, Vol. 73, No. 07, July 1994, p. 66C.
Ranade, S.M., “Improve sizing for relief valves,” Hydrocarbon
Processing, Vol. 73, No. 07, July 1994, p. 83.
Molad, C., “New way to swap engineering data,” Hydrocarbon
Processing, Vol. 73, No. 07, July 1994, p. 109.
Kerridge, A.E., “A project manager’s approach to quality man-
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1994, p. 156C.
Vervalin, C.H., “When you look for employment...,” Hydrocar-
bon Processing, Vol. 73, No. 08, Aug. 1994, p. 163.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Refineries,” Oil & Gas Journal, Oct. 18, 1993, p. 59;
Apr. 11, 1994, p. 65.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Petrochemicals,” Oil & Gas Journal, Oct. 18, 1993,
p.71;Apr. 11, 1994, p.78.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Sulfur,” Oil & Gas Journal, Oct. 18, 1993, p. 84;
Apr. 11, 1994, p. 89.
Bell, Laura, “WORLDWIDE CONSTRUCTION RE-
PORT-Gas processing,” Oil & Gas Journal Oct. 18, 1993,
p. 86; Apr. 11, 1994, p. 91.
Rhodes, Anne K., “Northwest Australia’s Saladin crude as-
sayed,” Oil & Gas Journal Oct. 18, 1993, p. 50.
Sanchezllanes, Teresa, Perez, Ana Lilia, Martinez, Martha P.,
Aguilar-Rodriguez, Enrique, and del Rosal, Rodolfo, “Simple
rules help select best hydrocarbon distillation scheme,” Oil &
Gas Journal, Oct. 18, 1993, p. 50.
“Nelson-Farrar Cost Indexes,” Oil & Gas Journal; Oct. 18, 1993,
p. 55; Nov. 1, 1993, p. 75; Dec. 6, 1993, p. 54; Jan. 3, 1994,
p. 47; Feb. 7, 1994, p. 61; Mar. 7, 1994, p. 82; Apr. 4, 1994,
p. 49; May 2, 1994, p. 108; June 6, 1994, p. 92; July 4, 1994,
p. 4 1; Aug. 1, 1994, p. 51; Sept. 5, 1994, p. 103; Oct. 3, 1994,
p. 61.
“Quarterly Costimating: Equipment costs rise moderately,” Oil
& Gas Journal, Oct. 18, 1993, p. 56; Jan. 3, 1994, p. 48; Apr.
4, 1994, p. 60; July 4, 1994, p. 58; Oct. 3, 1994, p. 62.
Rhodes, Anne K., “World crude capacity stays flat while conver-
sion capability rises again,” Oil & Gas Journal, Dec. 20, 1993,
p. 37.
Bell, Laura, “WORLDWIDE REFINING REPORT,” Oil &
Gas Journal, Dec. 20, 1993, p. 46.
“Survey of engineers, managers rates European E&C compa-
nies,” Oil & Gas Journal, Jan. 10, 1994, p. 57,
Myers, Philip E., “OSHA confined-space reg interpreted for
storage tank operations,” Oil & Gas Journal, Feb. 14, 1994, p.
84.
“Turnaround progresses at Conoco refinery,” Oil & Gas Journal,
Mar. 28, 1994, p. 36.
Van Way, Chris, “Plant replacement key to Louisiana field
revival,” Oil & Gas Journal Mar. 28, 1994, p. 58.
“Russian refineries tap western technology,” Oil & Gas Journal,
Apr. 25, 1994, p. 24.
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TOC/INDEX
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Rhodes, Anne K., “Two offshore Australian crudes assayed,” Oil
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Dosher, John R., and Carney, Jack T., “Sulfur increase seen
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Rhodes, Anne K., “Yemen’s light, sweet Alif crude assayed,” Oil
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new gasoline,” Oil & Gas Journal, July 11, 1994, p. 63.
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profits,” Oil & Gas Journal, July 18, 1994, p. 50.
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Crum, Fred S., and Dyer, James K., “Novel C3-recovery scheme
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Deley, Stephen J., and Graf, Kenneth, “Random packing debot-
tlenecks refinery de-ethanizing stripper,” Oil & Gas Journal,
Aug. 1, 1994, p. 39.
“‘Cascaded’ pilot regulators help reduce LPG loss in hot
weather,” Oil & Gas Journal, Aug. 8, 1994, p. 63.
Rhodes, Anne K., “Benchmark West Texas Intermediate crude
assayed,” Oil & Gas Journal, Aug. 15, 1994, p. 88.
Yaws, Carl L., Bu, Li, and Nijhawan, Sachin, “New correlation
accurately calculates water solubilities of aromatics,” Oil &
Gas Journal, Aug. 29, 1994, p. 80.
“Re-refiner fluidizes tank residue using portable mixer,” Oil &
Gas Journal Sept. 5, 1994, p. 104.
Rhodes, Anne K., “Danish North Sea crude assayed,” Oil & Gas
Journal Sept. 12, 1994, p. VI.
XXI. LIGHT-OIL CAT PROCESSING
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Desai, PH., et al., “Enhance gasoline yield and quality,” Hydro-
carbon Processing, Vol. 71, No. 11, Nov. 1992, p. 51.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 89.
Sarathy, P.R. and Suffridge, G.S., “Etherify field butanes, Part
2,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Ludwig, G.H., “Industrial hydrogenation of aldehydes,” Hydro-
carbon Processing, Vol. 72, No. 03, March 1993, p. 67.
Ladebeck, J., “Improve methanol synthesis,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, Match 1993, p. 89.
Cooper, B.H., et al., “Hydtotreating catalysts for diesel aromat-
ics saturation,” Hydrocarbon Processing, Vol. 72, No. 06, June
1993, p. 83.
Liers, J., et al., “Reforming using erionite catalysts,” Hydrocar-
bon Processing, Vol. 72, No. 08, Aug. 1993, p. 165.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
“New high conversion etherification process tested and pat-
ented,” Oil & Gas Journal, Dec. 27, 1993, p. 98.
Ragsdale, Ralph, “U.S. refiners choosing variety of routes to
produce clean fuels,” Oil & Gas Journal, Mar. 21, 1994, p. 51.
“Processing, compliance options can reduce cost of producing
new gasoline,” Oil & Gas Journal, July 11, 1994, p. 63.
XXII. ISOMERIZATION
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal Oct. 2, 1989, p. 49.
Ramsey, John R., and Truesdale, Patrick B., “Blend optimization
integrated into refinery-wide strategy,” Oil & Gas Journal
Mar. 19, 1990, p. 49.
Corbett, Richard A., “ANNUAL REFINING REPORT: Con-
version gains reflect healthy margins,” Oil & Gas Journal, Mar.
26, 1990, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
Refining Survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
Corbett, Richard A., “FUELS FOR TOMORROW-Tough air-
quality goals spur quest for transportation Fuel changes,” Oil
& Gas Journal, June 18, 1990, p. 33.
Corbett, Richard A., “FUELS FOR TOMORROW-Fuel refor-
mulations, alternatives cover broad spectrum,” Oil & Gas
Journal, June 18, 1990, p. 42.
Corbett, Richard A., “FUELS FOR TOMORROW-New and
modified processes and catalysts needed for new fuels,” Oil &
Gas Journal, June 18, 1990, p. 52.
Hoffman, H.L., “Catalyst market estimated,” Hydrocarbon Proc-
essing, Vol. 69, No. 02, Feb. 1990, p. 53.
Amigues, P., et al., “Propylene from ethylene and butene-2,”
Hydrocarbon Processing, Vol. 69, No. 10, Oct. 1990, p. 79.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
11, Nov. 1990, p. 83.
Haizmann, R.S., Lowry, D.R., and Schiferli, W.J., “Isomeriza-
tion with separation/recycle brings big octane boost,” Oil &
Gas Journal, Dec. 3, 1990, p. 66.
263
TOC/INDEX
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Hoffman, H.L., “Refining catalyst market ‘91,” Hydrocarbon
Processing, Vol. 70, No. 02, Feb. 1991, p. 37.
Monfils, J.J., et al., “Upgrade isobucane to isobutylene,” Hydro-
carbon Processing, Vol. 71, No. 02, Feb. 1992, p. 47.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal Dec. 23, 1991, p. 39.
“Lyondell develops one step isobutylene process,” Oil & Gas
Journal, Mar. 23, 1992, p. 42.
Anon, “Refining Handbook ‘92,” Hydrocarbon Processing, Vol.
71, No. 11, Nov. 1992, p. 133.
Sarathy, P.R. and Suffridge, G.S., “Etherify field butanes, Part
1,” Hydrocarbon Processing, Vol. 72, No. 01, Jan. 1993, p. 89.
Sarathy, ER. and Suffridge, G.S., “Etherify field butanes, Parr
2,” Hydrocarbon Processing, Vol. 72, No. 02, Feb. 1993, p. 43.
Pescarollo, E., et al., “Etherify light gasolines,” Hydrocarbon
Processing, Vol. 72, No. 02, Feb. 1993, p. 53.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts, Oct. 12, 1992, p. 41.
John, Thomas P. and Thomas, Stephen P., “Texas plant first to
isomerize n-butylenes to isobutylene,” Oil & Gas Journal, May
24, 1993, p. 54.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal: Oct. 11, 1993, p. 44.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Ragsdale, Ralph, “U.S. refiners choosing variety of routes to
produce clean fuels,” Oil & Gas Journal, Mar. 21, 1994, p. 51.
“Processing, compliance options can reduce cost of producing
new gasoline,” Oil & Gas Journal July 11, 1994, p. 63.
XXIII. AROMATICS EXTRACTION
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
Refining Survey,” Oil & Gas Journal Mar. 26, 1990, p. 77.
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal,
Oct. 14, 1991, p. 43.
Rhodes, Anne K., “Supphers introduce more than 120 new
refining catalysts, Oct. 12, 1992, p. 41.
Goelzer, Alan R., Ram, Sanjeev, Hernandez-Robinson, Agustin,
Chin, Arthur A., Harandi, Mohsen N., and Smith, C. Morris,
264 References
“Refiners have several options for reducing gasoline benzene,”
Oil & Gas Journal, Sept. 13, 1993, p. 63.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal Oct. 11, 1993, p. 44.
Ragsdale, Ralph, “U.S. refiners choosing variety of routes to
produce clean fuels,” Oil & Gas Journal, Mar. 21, 1994, p. 51.
Sloley, Andrew W., and Kolmetz, Karl, “Texas refiner expands
aromatics capacity 20% with staged revamp,” Oil & Gas
Journal, Mar. 28, 1994, p. 61.
Tsai, Tseng-Chang, Hu, Hsin-Chung, Tsai, Kun-Yung, and
Jeng, Fu-Sou, “Improved calculations increased toluene con-
version at Taiwan refinery,” Oil & Gas Journal June 13, 1994,
p. 115.
XXIV. VISBREAKING
Mullins, T.E. and Shorland, M., “Predict asphalt performance,”
Hydrocarbon Processing, Vol. 68, No. 01, Jan. 1989. p. 67.
Washimi, K. and Limmer, H., “New unit to thermal crack
resid,” Hydrocarbon Processing, Vol. 68, No. 09, Sept. 1989, p.
69.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal
Dec. 31, 1990, p. 84.
Wood, J.R. and Marino, C.K., “Design improvements increase
run length,” Oil & Gas Journal, Feb. 25, 1991, p. 42.
Castellanos, J., Cano, J.L., de1 Rosal, R., Briones, V.M. and
Mancilla, R.L., “Kinetic model predicts visbreaker yields,” Oil
& Gas Journal Mar. 18, 1991, p. 76.
“Annual refining survey,” Oil & Gas Journal, Mar. 18, 1991, p.
84.
Rhodes, Anne K., “Worldwide refining capacity at 75 millon
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal Dec. 23, 1991, p. 39.
Toman, Jerry J., and Beckman, Robert F., “Visbreaker hardware
has alternate uses in low-sulfur fuel era,” Oil & Gas Journal,
Mar. 22, 1993, p. 66.
Iscovici, R.S., “Kinetic model solves visbreaker constraint con-
trol problem,” Hydrocarbon Processing, Vol. 73, No. 05, May
1994, p. 109.
XXV. HYDROGEN PRODUCTION
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal Oct. 2, 1989, p. 49.
Thrash, Lou Ann, “ANNUAL REFINING REPORT: Annual
refining survey,” Oil & Gas Journal, Mar. 26, 1990, p. 77.
Srivastava, R.D., et al., “Catalysts for Fischer-Tropsch,” Hydro-
carbon Processing, Vol. 69, No. 02, Feb. 1990, p. 59.
“Gas Process Handbook ‘90,” Hydrocarbon Processing, Vol. 69,
No. 04, Apr. 1990, p. 69.
“Annual refining survey,” Oil & Gas Journal Mar. 18, 1991, p.
84.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal,
Dec. 31, 1990, p. 84.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY:
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal
Oct. 14, 1991, p. 43.
Shaver, K.G., et al., “Membranes recover hydrogen,” Hydrocar-
bon Processing, Vol. 70, No. 06, June 1991, p. 77.
TOC/INDEX
Johansen, T., “Trends in hydrogen plant design,” Hydrocarbon
Processing, Vol. 71, No. 08, Aug. 1992, p. 119.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal, Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
“Cleaning up gasoline will increase refinery hydrogen demand,”
Oil & Gas Journal, July 27, 1992, p. 92.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal Oct. 12, 1992, p. 41.
Simonsen, Knut A., O’Keefe, Luke F., and Fong, W. Francis,
“Changing fuel formulations will boost hydrogen demand,”
Oil & Gas Journal, Mar. 22, 1993, p. 45.
Ladeur, Peter and Bijwaard, Harry, “Shell plans $2.2-billion
renovation of Dutch retinery,” Oil & Gas Journal, Apr. 26,
1993, p. 64.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Baade, W.F., et al., “Generate hydrogen for reformulated gaso-
line and clean diesel,” Hydrocarbon Processing, Vol. 72, No. 01,
Jan. 1993, p. 77.
Ladebeck, J., “Improve methanol synthesis,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, March 1993, p. 89.
Fleming, G.K. and Dupuis, G.E., “Hydrogen membrane recov-
ery estimates,” Hydrocarbon Processing, Vol. 72, No. 04, Apr.
1993, p. 61.
Felten, J.R., et al., “Residual Fuels in a clean-fuels environment,”
Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p. 82-b.
“Hydrogen recovery from fuel gas can help meet refinery
demand,” Oil & Gas Journal, Mar. 22, 1993, p. 60.
Schulman, B.L., et al., “Bottom-of-the-barrel upgrading moves
aggressively,” Hydrocarbon Processing, Vol. 72, No. 12, Dec.
1993, p. 100c.
Christensen, T.S. and Primdahl, I.I., “Improve syngas produc-
tion using autothermal reforming,” Hydrocarbon Processing,
Vol. 73, No. 03, Mar. 1994, p. 39.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No.
04, Apr. 1994, p. 67.
Babik, Anton, and Kurt, Josef, “Slovakian refiner operating new
hybrid hydrogen-production process,” Oil & Gas Journal,
Mar. 21, 1994, p. 66.
Patel, Nitin M., Davis, Ruth A., Eaton, Norm, Carlson, Daniel
L., Kessler, Fred, and Khurana, Vinay, “‘Across-the-fence’
hydrogen plant starts up at California refinery,” Oil & Gas
Journal Oct. 3, 1994, p. 54.
XXVI. SULFUR PLANT OPERATIONS
Kimtantas, Charles L., “Here are ways to increase sulfur proc-
essing capability,” Oil & Gas Journal May 22, 1989.
Nougayrede, J. and Voirin, R., “Liquid catalyst efficiently re-
moves H2S from liquid sulfur,” Oil & Gas Journal July 17,
1989, p. 65.
Heisel, M.P. and Marold, F.J., “Tests indicate sulfur recovery
process improves on Claus unit performance,” Oil & Gas
Journal, Aug. 14, 1989, p. 37.
Corbett, Richard A., “Catalyst industry consolidates catalysts,
companies,” Oil & Gas Journal Oct. 2, 1989, p. 49.
Lagas, J.A., et al., “Claus process gets extra boost,” Hydrocarbon
Processing, Vol. 68, No. 04, Apr. 1989, p. 40.
1994 NPRA Q&A Session on Refining and Petrochemical Technology
Luinstra, E.A. and d’Haene, P.E., “Catalyst added to Claus
furnace reduces sulfur losses,” Hydrocarbon Processing, Vol. 68,
No. 07, July 1989, p. 53.
Reif, D.R., “Sulfur unit control in a DCS,” Hydrocarbon Proc-
essing, Vol. 68, No. 08, Aug. 1989, p. 61.
Samuels, Alvin, “H2S removal system shows promise over iron
sponge, ” Oil & Gas Journal, Feb. 5, 1990, p. 44.
True, Warren R., “GAS PROCESSING REPORT: Worldwide
gas-processing growth slows,” Oil & Gas Journal, July 9, 1990,
p. 41.
Thrash, Lou Ann, “GAS PROCESSING REPORT: World
sulfur derived from oil, gas production,” Oil & Gas Journal,
July 9, 1990, p. 87.
“Gas Process Handbook ‘90,” Hydrocarbon Processing, Vol. 69,
No. 04, Apr. 1990, p. 69.
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT Sulfur,” Oil & Gas Journal, Oct. 15, 1990, p. 75.
Thrash, L.A., “WORLDWIDE CONSTRUCTION RE-
PORT: Sulfur,” Oil & Gas Journal, Apr. 15, 1991, p. 79.
Thrash, L.A., “World sulfur derived from oil, gas production,”
Oil & Gas Journal. July 22, 1991, p. 85.
“AnnuaI refining survey,” Oil & Gas Journal (Mar. 18, 1991, p.
84.
“WORLDWIDE REPORT - Refining,” Oil & Gas Journal
Dec. 31, 1990, p. 84.
Thrash, Lou Ann, “GAS PROCESSING REPORT Worldwide
gas processing,” Oil & Gas Journal, July 9, 1990, p. 55.
Rhodes, Anne K., “WORLDWIDE CATALYST SURVEY
Survey shows over 1,000 refining catalysts,” Oil & Gas Journal
Oct. 14, 1991, p. 43.
Chou, J.S., et al., “Mercaptans affect Claus units,” Hydrocarbon
Processing, Vol. 70, No. 04, Apr. 1991, p. 39.
Simek, I.O., “Sulfur unit circulates catalyst,” Hydrocarbon Proc-
essing, Vol. 70, No. 04, Apr. 1991, p. 45.
Hardison, L.C. and Ramshaw, D.E., “H2S to S: Process im-
proved,” Hydrocarbon Processing, Jan. 1992, p. 89.
Heisel, MP. and Marold, EJ., “How new tail gas treater increases
Claus unit throughput,” Hydrocarbon Processing, Vol. 71, No.
03, March 1992, p. 83.
“Worldwide Construction Report: Sulfur,” Oil & Gas Journal,
Oct. 28, 1991, p. 77.
“Ashland refinery starts up two sulfur units,” Oil & Gas Journal,
Oct. 28, 1991, p. 95.
Nasaco, Elmo, Gear, B. Gene, and Boorsboom, J., “Canadian
retrofit meets stiffer sulfur recovery regulations,” Oil & Gas
Journal Feb. 10, 1992, p. 61.
Bell, Laura, “World sulfur production,” Oil & Gas Journal, July
20, 1992, p. 96.
Rhodes, Anne K., “Worldwide refining capacity at 75 million
b/d level,” Oil & Gas Journal Dec. 23, 1991, p. 33.
Thrash, Lou Ann, “Worldwide Refining Report,” Oil & Gas
Journal, Dec. 23, 1991, p. 39.
Ladebeck, J., “Improve methanol synthesis,” Hydrocarbon Proc-
essing, Vol. 72, No. 03, March 1993, p. 89.
Aitani, A.M., “Sour natural gas drying,” Hydrocarbon Processing,
Vol. 72, No. 04, Apr. 1993, p. 67.
Felten, J.R., et al., “Residual fuels in a clean-fuels environment,”
Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p. 82-B.
Rhodes, Anne K., “Suppliers Introduce more than 120 new
refining catalysts,” Oil & Gas Journal Oct. 12, 1992, p. 41.
265
TOC/INDEX

Simonsen, Knut A., O’Keefe, Luke F., and Fong, W. Francis, Jeanneret, J.J., et al., “New srrategies maximize para-xylene
“Changing fuel formulations will boost hydrogen demand,” production,” Hydrocarbon Processing, Vol. 73, No. 06, June
Oil & Gas Journal Mar. 22, 1993, p. 45. 1994, p. 43.
Rhodes, Anne K., “Suppl iers introduce more than 120 new Tindall, B.M. and King, D.L., “Designing steam reformers for
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41. hydrogen production,” Hydrocarbon Processing, Vol. 73, No.
Judd, Bill, “Mercaptan removal rate exceeds 99% at Canadian 07, July 1994, p. 69.
gas plant,” Oil & Gas Journal, Aug. 16, 1993, p. 81.
“Process for H2S removal from low-volume gas streams tested,” XXVIII. HYDROGEN
Oil & Gas Journal, Sept. 13, 1993, p. 70. Corbett, Richard A., “Catalyst industry consolidates catalysts,
Schendel, Ronald, “SO2-generation process can double refinery companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
Claus unit capacity,” Oil & Gas Journal Sept. 27, 1993, p. 63. “Texaco, Carbide form hydrogen plant venture,” Oil & Gas
“OGJ international refining-catalyst compilation,” Oil & Gas Journal Mar. 30, 1992, p. 28.
Journal, Oct. 11, 1993, p. 44. “Cleaning up gasoline will increase refinery hydrogen demand,”
Sloan, H.D., “Refinery expansion/upgrading means lighter, Oil & Gas Journal, July 27, 1992, p. 92.
quality products,” Hydrocarbon Processing, Vol. 73, No. 01, “Praxair extending hydrogen pipeline in Southeast Texas,” Oil
Jan. 1994, p. 82C. & Gas Journal, Aug. 24, 1992, p, 26.
Anon, “Gas Processes ‘94,” Hydrocarbon Processing, Vol. 73, No. Baade, W.E, et al., “Generate hydrogen for reformulated gaso-
04, Apr. 1994, p. 67. line and clean diesel,” Hydrocarbon Processing, Vol. 72, No. 01,
Johnson, J.E., Tzap, Stephen J., Kelley, Robert E., and Laczko, Jan. 1993, p. 77.
Lawrence P., “H2S IN EOR-Options narrowed to Claus or Ladebeck, J., “Improve methanol synthesis,” Hydrocarbon Proc-
redox processes,” Oil & Gas Journal, Nov. 22, 1993, p. 70. essing, Vol. 72, No. 03, March 1993, p. 89.
Nasato, Elmo, MacDougall, R. Steve, and Lagas, Jan. A., “New Fleming, G.K. and Dupuis G.E., “Hydrogen membrane recov-
catalyst improves sulfur recovery at Canadian plant,” Oil & ery estimates,” Hydrocarbon Processing, Vol. 72, No. 04, Apr.
Gas Journal Feb. 28, 1994, p. 45. 1993, p. 61.
“Russian refiner tests new one-stage HzS removal process,” Oil Felten, J.R., et al., “Residual fuels in a clean-fuels environment,”
& Gas Journal Mar. 7, 1994, p. 81. Hydrocarbon Processing, Vol. 72, No. 06, June 1993, p. 82-B.
Rhodes, Anne K., “Lyondell, Citgo join for heavy oil upgrade Simonsen, Knut A., O’Keefe, Luke F., and Fong, W. Francis,
project at Houston refinery,” Oil & Gas Journal, Mar. 21, “Changing fuel formulations will boost hydrogen demand,”
1994, p. 60. Oil & Gas Journal Mar. 22, 1993, p. 45.
“NPRA Q&A Auxiliary equipment, corrosion focus of refiner “Hydrogen recovery from fuel gas can help meet refinery de-
meeting,” Oil & Gas Journal, Apr. 4, 1994, p. 62. mand,” Oil & Gas Journal, Mar. 22, 1993, p. 60.
Babik, Anton, and Kurt, Josef, “Slovakian refiner operating new
hybrid hydrogen-production process,” Oil & Gas Journal
XXVII. POLYMERIZATION Mar. 21, 1994, p. 66.
Patel, Nitin M., Davis, Ruth A., Eaton, Norm, Carlson, Daniel
Corbett, Richard A., “Catalyst industry consolidates catalysts
L., Kessler, Fred, and Khurana, Vinay, “‘Across-the-fence’
companies,” Oil & Gas Journal, Oct. 2, 1989, p. 49.
hydrogen plant starts up at California refinery,” Oil & Gas
Hennico, A., et al., “Butene-1 is made from ethylene,” Hydro-
Journal Oct. 3, 1994, p. 54.
carbon Processing, Vol. 69, No. 03, Mar. 1990, p. 73.
Amigues, P., et al., “Propylene from ethylene and butene-2,”
Hydrocarbon Processing, Vol. 69, No. 10, Oct. 1990, p. 79.
“Refining Handbook ‘90,” Hydrocarbon Processing, Vol. 69, No.
c
11, Nov. 1990, p. 83.
Roffel, B. and Chin, EA., “Fuzzy control of a polymerization
reactor,” Hydrocarbon Processing, Vol. 70, No. 06, June 1991,
p. 47.
Rhodes, Anne K., “Suppliers introduce more than 120 new
refining catalysts,” Oil & Gas Journal, Oct. 12, 1992, p. 41.
“OGJ international refining-catalyst compilation,” Oil & Gas
Journal, Oct. 11, 1993, p. 44.
Sedriks, W., “Understanding the petrochemical cycle, Part 1,”
Hydrocarbon Processing, Vol. 73, No. 03, Mar. 1994, p. 49.
Montagna, A.A. and Floyd, J.C., “Single-sited catalysis leads
next polyolefin generation,” Hydrocarbon Processing, Vol. 73,
No. 03, Mar. 1994, p. 57.
Sedriks, W., “Understanding the petrochemical cycle, Part 2,”
Hydrocarbon Processing, Vol. 73, No. 04, Apr. 1994, p. 45.
Kuhlke, W.C., “World polymers market outlook,” Hydrocarbon
Processing, Vol. 73, No. 05, May 1994, p. 57.

266 References
TOC/INDEX

1994 NPRA Q & A Session on Refining and Petrochemical Technology

Registration List

NAME COMPANY LOCATION

Abbas, Abdul Karim . . . . . . Kuwait National Petroleum Company Safat, Kuwait
Abbott, James . . . . . . . . . . The Lubrizol Corporation . . . . . . Wickliffe, OH
Abdo, Suheil . . . . . . . . . . Unocal Corporation . . . . . . . . . . Brea, CA
Abrahams, Kenneth . . . . . . . Star Enterprise . . . . . . . . . . . . Delaware City, DE
Ache, W. . . . . . . . . . . . . Shell Catalyst Ventures Inc. . . . . . . Houston, TX
Ackelson, Donald B. . . . . . . Unocal Corporation . . . . . . . . . . Brea, CA
Ackman, Rich . . . . . . . . . . Union Carbide Corporation . . . . . Houston, TX
Acosta, Alfredo . . . . . . . . . Grace Davison . . . . . . . . . . . . Caracas, Venezuela
Adair, Scott . . . . . . . . . . . KTI Corporation . . . . . . . . . . . San Dimas, CA
Adams, John . . . . . . . . . . CDTech . . . . . . . . . . . . . . . . Pasadena, TX
Adler, Kevin . . . . . . . . . . . Octane Week . . . . . . . . . . . . . Arlington, VA
Agar, Joram . . . . . . . . . . . Agar Corporation, Inc. . . . . . . . . Houston, TX
Aichele, Mike . . . . . . . . . . Koch Engineering Company, Inc. . . . Tulsa, OK
Akinyemi, Gerald . . . . . . . . Mobil Oil Corporation . . . . . . . . Torrance, CA
Al-Abdul’Al, Ah . . . . . . . . . Aramco Services Company . . . . . . New Castle, DE
Al-Aradi, Salman . . . . . . . . Saudi Aramco . . . . . . . . . . . . . Hammersmith, UK
AI-Homaidi, Khalid . . . . . . . Kuwait National Petroleum Company Shuaiba, Kuwait
Al-Mutairi, Mohammad . . . . Kuwait National Petroleum Company Safat, Kuwait
Al-QaIlaf, Ahmad H. . . . . . . Kuwait National Petroleum Company Ahmadi, Kuwait
Al-Shahrani, Mohammad . . . . Saudi Aramco . . . . . . . . . . . . . London, UK
Al Shayban, Mohsin . . . . . . Saudi Aramco . . . . . . . . . . . . . Ras Tanura, Saudi Arabia
Albers, Edwin . . . . . . . . . . CMP-Cativco International . . . . . . ‘Baltimore, MD
Albert, Brian . . . . . . . . . . Koch Engineering Company, Inc. . . . Wichita, KS
Albertson, Michael . . . . . . . ICI Katalco . . . . . . . . . . . . . . Oakbrook Terrace, IL
Alello, Stephen . . . . . . . . . Allied Signal Inc. . . . . . . . . . . . Baton Rouge, LA
Ahbuyog, Roland0 . . . . . . . Caltex Philippines, Inc. . . . . . . . . Batangas, Phillippines
Aliev, Alexandr . . . . . . . . . Oil Processing Factory . . . . . . . . Yaroslavl, Russia
Allen, Frank . . . . . . . . . . . Conoco Inc. . . . . . . . . . . . . . . Ponca City, OK
Allinson, Paul . . . . . . . . . . YPE SA DPTO Refmeria La Plats . . Buenos Aires, Argentina
Allsmiller, Robert . . . . . . . . United Catalysts Inc. . . . . . . . . . Louisville, KY
Alvarado, Jorge . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . Minatitlan, Mexico
Alvarez, Jorge L. . . . . . . . . . Discovery Aluminas . . . . . . . . . . Baton Rouge, LA
Alvarez, Lorrie . . . . . . . . . Micro Motion, Inc. . . . . . . . . . . Houston, TX
Aman, Gary B. . . . . . . . . . NaIco/Exxon Energy Chemicals Co. . Houston, TX
Ambarbar, Om . . . . . . . . . The Coastal Corporation . . . . . . . Houston, TX
Anand, Mahesh . . . . . . . . . Unocal Corporation . . . . . . . . . . Brea, CA
Anderson, Gary . . . . . . . . . Corhart . . . . . . . . . . . . . . . . Salt Lake City, UT
Andrews, Mark . . . . . . . . . BOC Gases . . . . . . . . . . . . . . Guildford, UK
Andrews, Peter G. . . . . . . . . Consultant . . . . . . . . . . . . . . Houston, TX
Aoyama, Kazuo . . . . . . . . . Exxon Research & Engineering Co. . . Florham Park, NJ
Arana, Rodolfo . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . Mexico City, Mexico
Archbold, Damian . . . . . . . ChemAlert Corporation . . . . . . . Scottsdale, AZ
Arends, Simon . . . . . . . . . Crown Central Petroleum Corporation Houston, TX
Arens, Hermann . . . . . . . . Wintershall AG, Germany . . . . . . Lingen/Ems, Germany
Armbrester, Michael S. . . . . . Ashland Petroleum Company . . . . . Ashland, KY
Armendinger, Robert . . . . . . Stone & Webster Engineering Corp. . Houston, TX
Armstrong, Tim . . . . . . . . . TPA, Inc. . . . . . . . . . . . . . . . Dallas, TX
Arnot, John . . . . . . . . . . . Chevron U.S.A. Products Company . Richmond, CA
Arrand, Rob . . . . . . . . . . Nalco Canada . . . . . . . . . . . . . Edmonton, Alberta

1994 NPRA Q&A Session on Refining and Petrochemical Technology 267

TOC/INDEX

NAME COMPANY LOCATION

Arrighi, Jeri . . . . . . . . . . . . . . . . . .
Arrighi, Kevin. . . . . . . . . . . . . . . . .
Arthur, David H. . . . . . . . . . . . . . . .
Arthur, Dick . . . . . . . . . . . . . . . . .
Artuso, Bruce J. . . . . . . . . . . . . . . . .
Aru, Guido W. . . . . . . . . . . . . . . . .
Asim, Mehmet Y. . . . . . . . . . . . . . . .
Assad, John . . . . . . . . . . . . . . . . . .
Athearn, Frank . . . . . . . . . . . . . . . .
Aubrey, Morton . . . . . . . . . . . . . . . .
Avery, Clifford . . . . . . . . . . . . . . . .
Azuara, Jaime . . . . . . . . . . . . . . . . .
Baade, William E . . . . . . . . . . . . . . .
Babikov, Anatoli . . . . . . . . . . . . . . .
Backhouse, David . . . . . . . . . . . . . . .
Bacon, Thomas R. . . . . . . . . . . . . . .
Badruddin, Pervaiz . . . . . . . . . . . . . .
Baher, Heskel . . . . . . . . . . . . . . . . .
Bailey, D. M. . . . . . . . . . . . . . . . . .
Bailey, Thomas . . . . . . . . . . . . . . . .
Bain, Douglas . . . . . . . . . . . . . . . . .
Baker, Charles . . . . . . . . . . . . . . . . .
BalaIe, Emanuel . . . . . . . . . . . . . . . .
Ball, H. T. . . . . . . . . . . . . . . . . . . .
Balsamo, Phil . . . . . . . . . . . . . . . . .
Bamon, Layton M. . . . . . . . . . . . . . .
Banchs, Jaime . . . . . . . . . . . . . . . . .
Bantanidis, Dimitris . . . . . . . . . . . . .
Barden, Jon . . . . . . . . . . . . . . . . . .
Barlow, R. C. . . . . . . . . . . . . . . . . .
Barnett, Jack W. . . . . . . . . . . . . . . . .
Barnhart, Ted . . . . . . . . . . . . . . . . .
Barrett, Andy . . . . . . . . . . . . . . . . .
Barry, J. J. . . . . . . . . . . . . . . . . . . .
Barry, Michael . . . . . . . . . . . . . . . .
Barsby, Chris . . . . . . . . . . . . . . . . .
Bartek, Robert . . . . . . . . . . . . . . . .
Bartholomew, Karl D. . . . . . . . . . . . .
Bartsch, Helmut . . . . . . . . . . . . . . .
Beardemphl, Scott . . . . . . . . . . . . . .
Beaton, William . . . . . . . . . . . . . . .
Beatty, Joseph . . . . . . . . . . . . . . . . .
Becker, Myron . . . . . . . . . . . . . . . .
Bedell, Richard . . . . . . . . . . . . . . . .
Behm, Duane. . . . . . . . . . . . . . . . .
Belcher, Jack . . . . . . . . . . . . . . . . .
Benchecroun, Nagib . . . . . . . . . . . . .
Benjamin, Kevin . . . . . . . . . . . . . . .
Bennett, Diane . . . . . . . . . . . . . . . .
Benson, Bernard A. . . . . . . . . . . . . . .
Bergeron, Daniel . . . . . . . . . . . . . . .
Berg, John . . . . . . . . . . . . . . . . . .
Berlyant, Michael . . . . . . . . . . . . . . .
Berman, David P. . . . . . . . . . . . . . . .
Bermudez, Oscar . . . . . . . . . . . . . . .
Berrios, Miguel . . . . . . . . . . . . . . . .
Bertram, Rick . . . . . . . . . . . . . . . . . .
Berzins, Valdis . . . . . . . . . . . . . . . .
UOP . . . . . . . . . . . . . . . . . Houston, TX
ALCOA . . . . . . . . . . . . . . . Houston, TX
Gulf Chemical & Metallurgical Corp. Freeport, TX
The M. W. Kellogg Company. . . . . Houston, TX
Exxon Research & Engineering Co. . . Florham Park, NJ
INTERCAT, Inc. . . . . . . . . . . . Lafayette, CO
Akzo Nobel . . . . . . . . . . . . . . Houston, TX
Coastal Chemical Company, Inc. . . . Baton Rouge, LA
Atlas Copco Comptec Inc. . . . . . . Noorheesville, NY
Dow Chemical U.S.A. . . . . . . . . Houston, TX
Akzo Nobel . . . . . . . . . . . . . . Houston, TX
PEMEX-Refinacion . . . . . . . . . . Mexico City, Mexico
Air Products and Chemicals, Inc. . . . Allentown, PA
Russian Trade Development Co., Inc. . Los Angeles, CA
Husky Oil . . . . . . . . . . . . . . . Lloydminster, SK
Dow Chemical U.S.A. . . . . . . . . Freeport, TX
Abu Dhabi National Oil Company . . Abu Dhabi, UAE
Koch Engineering Company, Inc. . . . New York, NY
Phillips Petroleum Company . . . . . Bartlesville, OK
BOC Gases . . . . . . . . . . . . . . Murray Hill, NJ
Grace Dearborn . . . . . . . . . . . . Lake Zurich, IL
Mobil Research & Development Corp. Paulsboro, NJ
Sun Refining and Marketing Company Linwood, PA
Coastal Chemical Company, Inc. . . . Houston, TX
Betz Process Chemicals, Inc. . . . . . Chicago, IL
Engelhard Corporation . . . . . . . . Sutton, UK
Gulf Chemical & Metallurgical Corp. Ponce, PR
Dow Chemical U.S.A. . . . . . . . . Rheinmuenster, Germany
BP Oil Company . . . . . . . . . . . Belle Chasse, LA
Betz Process Chemicals, Inc. . . . . . The Woodlands, TX
General Chemical Corporation . . . . Parsippany, NJ
Grace Davison . . . . . . . . . . . . Baltimore, MD
Criterion Catalyst Company L.P. . . . Houston, TX
CRI International Inc. . . . . . . . . Houston, TX
Praxair, Inc. . . . . . . . . . . . . . . San Ramon, CA
Catalyst Recovery Canada Ltd. . . . . Edmonton, Alberta
Marathon Oil Company . . . . . . . Littleton, CO
The Pace Consultants Inc. . . . . . . Houston, TX
Wintershall AG, Germany . . . . . . Lingen/Ems, Germany
Navajo Refining Company . . . . . . Artesia, NM
Amoco Oil Company . . . . . . . . . Chicago, IL
Grace Dearborn . . . . . . . . . . . . Lake Zurich, IL
Consumer’s Coop Refinery Ltd. . . . . Regina, Saskatchewan
Marathon Oil Company . . . . . . . Garyville, LA
CENEX. . . . . . . . . . . . . . . . Laurel, MT
Octane Week . . . . . . . . . . . . . Washington, DC
IFP. . . . . . . . . . . . . . . . . . Rueil Malmaison, France
ALCOA . . . . . . . . . . . . . . . Houston, TX
Nalco/Exxon Energy Chemicals Co. . Sugar Land, TX
The Pritchard Corporation . . . . . . Overland Park, KS
Pennzoil Products Company . . . . . Houston, TX
CENEX . . . . . . . . . . . . . . . . Laurel, MT
Bayway Refining Co./Tosco Corp. . . Bayway, NJ
Akzo Nobel . . . . . . . . . . . . . . Owings Mills, MD
PEMEX-IMP . . . . . . . . . . . . . Mexico City, Mexico
Caribbean Petroleum Corp. . . . . . . San Juan, PR
Unocal Corporation . . . . . . . . . . Brea, CA
Criterion Catalyst Company L.P. . . . Houston, TX

268 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Bettinger, John . . . . .
Betz, Gary . . . . . . .
Bieber, Scott A. . . . . .
Bierig, James L. . . . . .
Binford, Mark . . . .
Bingham, E Emmett . .
Bingham, Gwendelyn . .
Birnbaum, Rick . . . . .
Bishop, Robert . . . . .
Black, J. Larry . . . . .
Black, John . . . . . . .
Blew, Bruce . . . . . . .
Boardman, Shaun L. . .
Bober, Mike . . . . . . .
Bochow, Carl . . . . . .
Boczar, Edward . . . . .
Bogert, David . . . . . .
Bolduc, Bruce . . . . . .
Bolivar, Eduardo . . . .
Bolliger, James . . . . .
Bolton, Anthony P. . . .
Bonilla, Jorge . . . . . .
Bonnet, Fred . . . . . .
Boone, Rick . . . . . . .
Borgard, Bradley . . . .
Bostick,Thomas . . . .
Bothe, Michael . . . . .
Boucher, Richard . . . .
Bourdeau, Roland. . . .
Bourdon, John . . . .
Bovo, Edward . . . . . .
Bowles, Shirley . . . . .
Bowman, Elaine . . . .
Boycott, William . . . .
Boydstun, R. Les . . .
Bozza, Robert . . . . . .
Brabston, Diane. . . . .
Bracken, Paul . . . . . .
Brady, Dan . . . . . . .
Brahn, Michael . . . . .
Brandenberger, Sandie .
Branham, Russell . . . .
Bredehoft, Ronald . . .
Breidigan, Brian . . . . .
Brewer, Dale . . . . . .
Bricker, John . . . . . .
Brigham, Brent . . . . .
Brodwater, Barry . . . .
Brown, George W. . .
Brown, John . . . . . .
Brown, Robert . . . . .
Brown, Robert . . . . .
Brown, Robert L. . . . .
Brown, William . . . .
Bruch, Herb . . . . .
Brunson, Ross . . . . . .
Bryson, M. Charles . . .
Bucko, Mike . . . . . .
BP Oil Company . . . . . . . . . . . . . . . . Belle Chasse, LA
Koch Refining Company . . . . . . . . . . . . St. Paul, MN
ChemLink . . . . . . . . . . . . . . . . . . . Houston, TX
UOP . . . . . . . . . . . . . . . . . . . . . . Irvine, CA
Betz Process Chemicals, Inc. . . . . . . . . . . The Woodlands, TX
Unocal Corporation . . . . . . . . . . . . . . . Brea, CA
Star Enterprise . . . . . . . . . . . . . . . . . Convent, LA
Union Carbide Corporation . . . . . . . . . . Danbury, CT
Stone & Webster Engineering Corp. . . . . . . Houston, TX
Merichem Company . . . . . . . . . . . . . . Houston, TX
Akzo Catalysts . . . . . . . . . . . . . . . . . Allison Park, PA
Mobil Oil Corporation . . . . . . . . . . . . . Chalmette, LA
Criterion Catalyst Company L.P. . . . . . . . . Fareham, UK
Mobil Research & Development Corp. . . . . . Princeton, NJ
Howe-Baker Engineers, Inc. . . . . . . . . . . Tyler, TX
Exxon Chemical Company . . . . . . . . . . . Benicia, CA
Engelhard Corporation . . . . . . . . . . . . . Houston, TX
BOC Gases . . . . . . . . . . . . . . . . . . . Murray Hill, NJ
United Catalysts Inc. . . . . . . . . . . . . . . Spring, TX
CITGO Refining & Chemicals . . . . . . . . . Corpus Christi, TX
PQ Zeolites B .V. . . . . . . . . . . . . . . . . Leiden, Netherlands
Stone & Webster Engineering Corp. . . . . . . Houston, TX
Bonnet & Co. . . . . . . . . . . . . . . . . . . Norwalk, CT
Clark Refining & Marketing, Inc. . . . . . . . Hartford, IL
ChemLink . . . . . . . . . . . . . . . . . . . Houston, TX
Akzo Nobel . . . . . . . . . . . . . . . . . . . Tulsa, OK
Tru-Tee . . . . . . . . . . . . . . . . . . . . . Newark, DE
Ultramar Canada Inc. . . . . . . . . . . . . . . Levis, Quebec
ALCOA . . . . . . . . . . . . . . . . . . . . . Pittsburgh, PA
The Pritchard Corporation . . . . . . . . . . . Overland Park, KS
Engelhard Corporation . . . . . . . . . . . . . Houston, TX
Texaco Refining & Marketing Inc. . . . . . . . El Dorado, KS
Nalco/Exxon Energy Chemicals Co. . . . . . . Sugar Land, TX
Frontier Refining, Inc. . . . . . . . . . . . . . Cheyenne, WY
Betz Process Chemicals, Inc. . . . . . . . . . . The Woodlands, TX
Acreon Catalysts . . . . . . . . . . . . . . . . Houston, TX
STRATCO, INC. . . . . . . . . . . . . . . . . Leawood, KS
Stone & Webster Canada Limited . . . . . . . Toronto, Ontario
Exxon Research & Engineering Co. . . . . . . . Florham Park, NJ
Stone & Webster Engineering Corp. . . . . . . Houston, TX
Conoco Inc. . . . . . . . . . . . . . . . . . . . Ponca City, OK
Ashland Petroleum Company . . . . . . . . . . Ashland, KY
Kinetics Technology Int’l Corp. . . . . . . . . . San Dimas, CA
ALCOA . . . . . . . . . . . . . . . . . . . . . Pittsburgh, PA
Micro Motion, Inc. . . . . . . . . . . . . . . . San Antonio, TX
Petrolice Corporation . . . . . . . . . . . . . . St. Louis, MO
U. S. Oil & Refining Company . . . . . . . . . Tacoma, WA
Mobil Oil Corporation . . . . . . . . . . . . . Torrance, CA
Conoco Inc. . . . . . . . . . . . . . . . . . . . Westlake, LA
Petrolite Corporation . . . . . . . . . . . . . . St. Louis, MO
United Catalysts Inc. . . . . . . . . . . . . . . Louisville, KY
ChemLink . . . . . . . . . . . . . . . . . . . Mt. Laurel, NJ
Pall Corporation . . . . . . . . . . . . . . . . East Hills, NY
ChemLink . . . . . . . . . . . . . . . . . . . Concord, CA
Fuel Reformulation . . . . . . . . . . . . . . . Arlington, VA
United Catalysts Inc. . . . . . . . . . . . . . . Truckee, CA
Pittsburgh Applied Research Corp. . . . . . . . Pittsburgh, PA
Merichem Company . . . . . . . . . . . . . . Houston, TX

1994 NPRA Q&A Session on Refining and Petrochemical Technology 269

TOC/INDEX

NAME COMPANY LOCATION

Burger, John . . . . . . . . . . . . . . . . . Atlantic Richfield Company . . . . . . . . Anaheim, CA
Burgio, Karin . . . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . Iselin, NJ
Buringrud, Daniel . . . . . . . . . . . . . . Micro Motion, Inc. . . . . . . . . . . . . . Vacaville, CA
Burns, David . . . . . . . . . . . . . . . . . Union Carbide Chemicals & Plastics . . . . Houston, TX
Bussey, Karl . . . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . Houston, TX
Butz, Tom . . . . . . . . . . . . . . . . . . . Fina Oil and Chemical Company . . . . . . Port Arthur, TX
Buziuk, Frank . . . . . . . . . . . . . . . . . Chevron Research &Technology Co. . . . . Richmond, CA
Bybee, Dean J. . . . . . . . . . . . . . . . . Ford, Bacon & Davis, Inc. . . . . . . . . . Salt Lake City, UT
Byrne, Richard . . . . . . . . . . . . . . . . Airco Gases Div/The BOC Group, Inc. . . . Murray Hill, NJ
Caballero, Roberto . . . . . . . . . . . . . . Akzo Nobel Chemicals, Inc. . . . . . . . . Houston, TX
Cabrera, Carlos . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Cadena, Alvaro . . . . . . . . . . . . . . . . Graham Manufacturing Co. . . . . . . . . Batavia, NY
Camacho, Enrique . . . . . . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . . . . Mexico City, Mexico
Campagna, Robert J. . . . . . . . . . . . . . Refining Process Services, Inc. . . . . . . . Pittsburgh, PA
Campbell, Bruce . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . Houston, TX
Campbell, Roger . . . . . . . . . . . . . . . TPA, Inc. . . . . . . . . . . . . . . . . . . Dallas, TX
Campbell, Tim . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Cannon, Fred . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Carlisle, Edwin . . . . . . . . . . . . . . . . Eurecat U.S. Incorporated . . . . . . . . . Pasadena, TX
Carls, William . . . . . . . . . . . . . . . . Akzo Catalysts . . . . . . . . . . . . . . . Long Beach, CA
Cartwright, Colin . . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . Middlesex, UK
Case, James . . . . . . . . . . . . . . . . . . The Pritchard Corporation . . . . . . . . . Overland Park, KS
Casey, M. M. . . . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . Houston, TX
Casmore, Johnny . . . . . . . . . . . . . . . Mobil Oil Corporation . . . . . . . . . . . Beaumont, TX
Cassidy, Robert . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Houston, TX
Castillo, Rick . . . . . . . . . . . . . . . . . The Coastal Corporation . . . . . . . . . . Houston, TX
Catchpole, Steve . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . Billingham, UK
Cathcart, Norman . . . . . . . . . . . . . . Pall Advanced Separation Systems. . . . . . Cortland, NY
Cavanaugh, Curt . . . . . . . . . . . . . . . The Coastal Corporation . . . . . . . . . . Houston, TX
Cavanaugh, T. A. . . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . Florham Park, NJ
Cavanna, Agostino . . . . . . . . . . . . . . Agip Petroli . . . . . . . . . . . . . . . . . Rome, Italy
Chaaraoui, Ali . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . Sarnia, Ontario
Chambers, Andrew . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . London, UK
Champion, G. L. . . . . . . . . . . . . . . . ChemLink . . . . . . . . . . . . . . . . . Houston, TX
Chapin, Lark E. . . . . . . . . . . . . . . . . Stone &Webster Engineering Corp. . . . . Houston, TX
Chavez, John . . . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . Iselin, NJ
Cherman, Algerd . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . Houston, TX
Chinai, Hatish . . . . . . . . . . . . . . . . The Lubrizol Corporation . . . . . . . . . Wickliffe, OH
Chlapik, Ken . . . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
Christensen, Jon . . . . . . . . . . . . . . . Sinclair Oil Corporation . . . . . . . . . . Evansville, WY
Christman, Robert D. . . . . . . . . . . . . Pittsburgh Applied Research Corp. . . . . . Pittsburgh, PA
Ciancio, Donald J. . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
Cieraszynski, Mike . . . . . . . . . . . . . . Ashland Petroleum Company . . . . . . . . Ashland, KY
Citarella, Vicente A. . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . Florham Park, NJ
Clancy, Tom . . . . . . . . . . . . . . . . . Elf Atochem North America, Inc. . . . . . . Philadelphia, PA
Clarke, R. G. . . . . . . . . . . . . . . . . . Jacobs Engineering Group Inc. . . . . . . . Houston, TX
Clark, Michael . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Houston, TX
Clark, Norman . . . . . . . . . . . . . . . . Indian Refining . . . . . . . . . . . . . . . Lawrenceville, IL
Clark, Patrick A. . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . Fountain Valley, CA
Clayton, Jim . . . . . . . . . . . . . . . . . Koch Industries/John Zink . . . . . . . . . Tulsa, OK
Cleary, Jay D. . . . . . . . . . . . . . . . . . Total Petroleum, Inc. . . . . . . . . . . . . Commerce City, CO
Clegg, Steve . . . . . . . . . . . . . . . . . . ACS Industies - Catrep . . . . . . . . . . . Walnut Creek, CA
Clements, James . . . . . . . . . . . . . . . ALCOA . . . . . . . . . . . . . . . . . . . Irvine, CA
Coburn, Julie K. . . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . Washington, DC
Collins, Tom . . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . Houston, TX
Colston, A. . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Houston, TX
Convery, Laurence J. . . . . . . . . . . . . . ABB Lummus Crest Inc. . . . . . . . . . . Bloomfield, NJ
Cook, John D. . . . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . Houston, TX

270 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Cook, Joseph . . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . . . . . . . . . Houston, TX
Corcoran, Thomas . . . . . . . . . . . . . . Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Metairie, LA
Corcuera, Francisco . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Mexico City, Mexico
Coser, Richard J. . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . . . . . . Minnetonka, MN
Coulson, Richard . . . . . . . . . . . . . . . Elf Atochem North America, Inc. . . . . . . . . . . . Atascocita, TX
Cox, Trent . . . . . . . . . . . . . . . . . . Bechtel Corporation . . . . . . . . . . . . . . . . . Houston, TX
Crawford, Mark. . . . . . . . . . . . . . . . Lion Oil Company . . . . . . . . . . . . . . . . . . El Dorado, AR
Cressman, Paul . . . . . . . . . . . . . . . . Petro-Canada Products . . . . . . . . . . . . . . . . Oakville, Ontario
Critchfield, James . . . . . . . . . . . . . . . Huntsman Chemical Company . . . . . . . . . . . . Houston, TX
Cromarty, Ben . . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Billingham, UK
Cross, W. J. . . . . . . . . . . . . . . . . . . TEK Associates, Inc. . . . . . . . . . . . . . . . . . Media, PA
Cruz, Ruben . . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Cuneo, Paul L. . . . . . . . . . . . . . . . . Shell Development Company . . . . . . . . . . . . . Houston, TX
Cunningham, Frank . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Cupps, Stephen . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . . . . Chicago, IL
Cusick, Charles . . . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . . . . Marcus Hook, PA
D’Auria, James H. . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Dallhoff, Robert A. . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . . . . . . Houston, TX
Darling, Howard . . . . . . . . . . . . . . . NPRA - Retired . . . . . . . . . . . . . . . . . . . . Fairfax, VA
Daughtry, James L. . . . . . . . . . . . . . . Dow U.S.A. . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Davey, Steven . . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Davis, Earl . . . . . . . . . . . . . . . . . . Litwin Engineers & Constructors . . . . . . . . . . . Houston, TX
Davis, Edgar . . . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . . . . Borger, TX
Davis, Kent . . . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Davison, Richard L. . . . . . . . . . . . . . . Amoco Oil Company . . . . . . . . . . . . . . . . . Naperville, IL
Davis, Robert . . . . . . . . . . . . . . . . . R. E. Davis Chemical Corporation . . . . . . . . . . Oak Brook, IL
Davis, Ruth . . . . . . . . . . . . . . . . . . Air Products and Chemicals, Inc. . . . . . . . . . . . Allentown, PA
Davis, Tom . . . . . . . . . . . . . . . . . . CENEX . . . . . . . . . . . . . . . . . . . . . . . . Laurel, MT
De Cain, Thomas . . . . . . . . . . . . . . . Rollins Site Services . . . . . . . . . . . . . . . . . . Wilmington, DE
De Capite, Augie . . . . . . . . . . . . . . . L. A. Salomon Inc. . . . . . . . . . . . . . . . . . . Severna Park, MD
De La Fuente, Emiliano . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
De La Torriente, Paloma . . . . . . . . . . . Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
De Paul, Maria . . . . . . . . . . . . . . . . 21st Century Fuels . . . . . . . . . . . . . . . . . . Rosslyn, VA
Dean, John W. . . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Bound Brook, NJ
DeArmon, Ray . . . . . . . . . . . . . . . . General Valve Company . . . . . . . . . . . . . . . Broken Arrow, OK
Deaton, John . . . . . . . . . . . . . . . . . Clark Refining & Marketing, Inc. . . . . . . . . . . Blue Island, IL
DeCorte, Michael . . . . . . . . . . . . . . . Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Boulder, CO
Decou, Mark . . . . . . . . . . . . . . . . . Koch Engineering Company, Inc. . . . . . . . . . . . Wichita, KS
Deering, William . . . . . . . . . . . . . . . Gulf Chemical & Metallurgical Corp. . . . . . . . . Freeport, TX
Dees, James . . . . . . . . . . . . . . . . . . Exxon Chemical Company . . . . . . . . . . . . . . Beaumont, TX
Del Bosque, Oscar . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Corpus Christi, TX
Del Mundo, Javier . . . . . . . . . . . . . . Caltex Philippines, Inc. . . . . . . . . . . . . . . . . Manila, Philippines
Delgado, Alberto . . . . . . . . . . . . . . . Maraven Inversiones CA . . . . . . . . . . . . . . . Caracas, Venezuela
Delgado, Eddie . . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Demmel, Edward J. . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Newport Beach, CA
Denham, Earl E . . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Denk, Lawrence . . . . . . . . . . . . . . . Stone &Webster Engineering Corp. . . . . . . . . . Houston, TX
Dennis, Geoffrey . . . . . . . . . . . . . . . Colt Engineering Corp. . . . . . . . . . . . . . . . . Calgary, Alberta
Dergregorian, Heros . . . . . . . . . . . . . Giant Refining Company . . . . . . . . . . . . . . . Gallup, NM
Desai, Pankaj H. . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
DeSantis, David . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Iselin, NJ
Develasco, Despina . . . . . . . . . . . . . . Di-Chem De Venezuela . . . . . . . . . . . . . . . . Caracas, Venezuela
DeVelasco, Ruben . . . . . . . . . . . . . . . NaIco/Exxon Energy Chemicals Co. . . . . . . . . . Tulsa, OK
Dewitz, Thomas S. . . . . . . . . . . . . . . Shell Oil Company . . . . . . . . . . . . . . . . . . Houston, TX
Dhatia, Dilip . . . . . . . . . . . . . . . . . Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Dibble, John . . . . . . . . . . . . . . . . . Aminetech, Inc. . . . . . . . . . . . . . . . . . . . . Putnam Valley, NY
DiCamillo, David . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Dickey, Raymond . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Houston, TX

1994 NPRA Q&A Session on Refining and Petrochemical Technology 271 I

TOC/INDEX

NAME COMPANY LOCATION

Diede, Troy . . . . . . . . . . . . . . . . . . Koch Refining Company . . . . . . . . . . . . . . . St. Paul, MN
Dincher, Tim . . . . . . . . . . . . . . . . . Witco Corporation . . . . . . . . . . . . . . . . . . Bradford, PA
Dirkse, Hans . . . . . . . . . . . . . . . . . Shell Oil Company . . . . . . . . . . . . . . . . . . Norco, LA
Dirksen, Feike . . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Amersfoort, Netherlands
Dixon, Peter . . . . . . . . . . . . . . . . . Christenson Engineering Corp. . . . . . . . . . . . . Bellingham, WA
Dodds, R. Kevin . . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . . . . . . Houston, TX
Dohar, Richard . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Pittsburgh, PA
Dominguez, Jose . . . . . . . . . . . . . . . Bayway Refining Co./Tosco Corp. . . . . . . . . . . Bayway, NJ
Donahue, Michael D. . . . . . . . . . . . . . GAYLORD CHEMICAL . . . . . . . . . . . . . . Houston, TX
Donahue, Patrick J. . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . San Francisco, CA
Doran, Mark . . . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Billingham, UK
Dougan, Timothy . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Dougherty, Richard . . . . . . . . . . . . . . Mobil Research & Development Corp. . . . . . . . . Paulsboro, NJ
Dover, Jerry D. . . . . . . . . . . . . . . . . Zeolyst International . . . . . . . . . . . . . . . . . Berwyn, PA
Doyle, Patrick . . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Lake Zurich, IL
Dtewry, Alison . . . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Dreyfuss, Corey . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Duchene, David D. . . . . . . . . . . . . . . LL & E Company. . . . . . . . . . . . . . . . . . . Saraland, AL
Dufresne, Pierre . . . . . . . . . . . . . . . . Eurecat SA . . . . . . . . . . . . . . . . . . . . . . La Voulte, France
Dumas, Chris . . . . . . . . . . . . . . . . . Buckman Laboratories, Inc. . . . . . . . . . . . . . . Memphis, TN
Dunn, Robert O. . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . . . . Bartlesville, OK
Dusek, Allen . . . . . . . . . . . . . . . . . Phibro Energy USA, Inc. . . . . . . . . . . . . . . . Houston, TX
Dutcher, Dale . . . . . . . . . . . . . . . . . Gay Engineering and Sales Co. . . . . . . . . . . . . Pasadena, TX
Dwyer, Dave . . . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Danbury, CT
Dwyet, Jon . . . . . . . . . . . . . . . . . . Nalco/Exxon Energy Chemicals Co. . . . . . . . . . Pleasant Hill, CA
Eccles, Richard M. . . . . . . . . . . . . . . Princeton Process Engineers . . . . . . . . . . . . . . East Orleans, MA
Economides, Nicholas . . . . . . . . . . . . Unocal . . . . . . . . . . . . . . . . . . . . . . . . Los Angeles, CA
Edelman, AIlan M. . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . . . . . . Florham Park, NJ
Edgar, M. Dean . . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Edmunds, John . . . . . . . . . . . . . . . . Phibro Energy USA, Inc. . . . . . . . . . . . . . . . Krotz Springs, LA
Ehrbright, Dale . . . . . . . . . . . . . . . . Chevron U.S.A. Products Company . . . . . . . . . Richmond, CA
Elefante, Domenico . . . . . . . . . . . . . . Praoil Agip Petroli Group . . . . . . . . . . . . . . . Gela, Italy
Elgin, Michael . . . . . . . . . . . . . . . . Amoco Oil Company . . . . . . . . . . . . . . . . . Texas City, TX
Elliott, John E . . . . . . . . . . . . . . . . Betz Process Chemicals, Inc. . . . . . . . . . . . . . The Woodlands, TX
Ellis, Paul J. . . . . . . . . . . . . . . . . . . Great Lakes Carbon Corporation . . . . . . . . . . . Port Arthur, TX
Elvin, Frank . . . . . . . . . . . . . . . . . . Coastal Catalyst Technology, Inc. . . . . . . . . . . . Houston, TX
England, John W. . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Victoria, Australia
Evans, Doug J. . . . . . . . . . . . . . . . . Petro-Canada . . . . . . . . . . . . . . . . . . . . . Calgary, Alberta
Evans, Martin . . . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . W. Hartford, CT
Everett, Gary L. . . . . . . . . . . . . . . . . Lyondell Petrochemical Company . . . . . . . . . . Channelview, TX
Everitt, David . . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Mississauga, Ontario
Eymard, Frank . . . . . . . . . . . . . . . . Placid Refining Company . . . . . . . . . . . . . . . Baton Rouge, LA
Ezhov, Valeriy V. . . . . . . . . . . . . . . . Institute Omskneftechim . . . . . . . . . . . . . . . Omsk, Russia
Farah, George G. . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Farley, Chesley . . . . . . . . . . . . . . . . Marathon Oil Company . . . . . . . . . . . . . . . Texas City, TX
Farshid, Darush . . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Fatora, Frank . . . . . . . . . . . . . . . . . Lyondell-CITGO Refining Co. Ltd. . . . . . . . . . Houston, TX
Faucher, Jean-Yves . . . . . . . . . . . . . . Ultramat Canada Inc. . . . . . . . . . . . . . . . . . Levis, Quebec
Fearnside, Paul . . . . . . . . . . . . . . . . NaIco/Exxon Energy Chemicals Co. . . . . . . . . . Sugar Land, TX
Feinberg, Arnold . . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . . . . . . Florham Park, NJ
Feistel, Gerald . . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . . . . Chicago, IL
Felmlee, Tom . . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . . . . St. Louis, MO
Feltrop, Bill . . . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . . . . St. Louis, MO
Ferguson, Larry . . . . . . . . . . . . . . . . Elf Atochem North America, Inc. . . . . . . . . . . . Kansas City, MO
Fernandez, Ricardo . . . . . . . . . . . . . . YPF SA DPTO Refineria La Plata . . . . . . . . . . Buenos Aires, Argentina
Fettis, Michael . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Fields, John D. . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . . . . Chicago, IL
Finelt, Daniel R. . . . . . . . . . . . . . . . Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Ponca City, OK

272 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Fischer, David . . . . .
Fischer, Steven . . . .
Fisher, Paul W. . . . .
Fitt, Jeffrey . . . . . .
Fleming, Brad . . . . .
Fleming, William . . .
Fletcher, Ray P. . . . .
Fletcher, Robert . . . .
Foley, Richard . . . . .
Forand, Daniel . . . .
Foster, James E. . . . .
Foster, Marlo . . . . .
Frampton, Jerry D. . .
France, John J. . . . .
Frantz, William J. . . .
Frayne, Stephen . . . .
Frazier, Michael . .
Frazier, R. J. . . . . . .
Frederickson, Lewis . .
Freeze, John G. . . . .
French, Millard . . . .
Fritsche, Ray . . . . .
Frye, Robert A. . . . .
Fugera, William . . . .
Fullelove, Richard . . .
Fumoso, Richard . . .
Funatsu, Shuichi . . .
Funk, Ron . . , . . .
Furfaro, Angelo . . . .
Furr, Celeste . . . . .
Fussell, Becky . . . . .
Gabrysch, Fabian . . .
Gale, Sidney . . . . .
Gallogly, Robert . . .
Ganster, Alan . . . . .
Garbarino, Richard . .
Garber, Howard . . . .
Garcia, Ernesto . . . .
Garrett, Glenn . . . .
Garrett, Jack . . . . .
Gary, Ewy . . . . . . .
Garzon, Claudio A. . .
Gdula, Lowell . . . . .
Gebhard, Thomas J. .
Gentile, Craig . . . . .
Gentry, Arthur K. . . .
Gentry, Joseph . . . .
George, Safa . . . . .
Geren, Philip . . . . .
Gerritsen, L. A. . . . .
Gerveshi, Luan . . . .
Gheloum, Mustafa A. A
GiaIella, Richard M. .
Gibbons, Bill . . . . .
Gibson, Michael C. . .
Giglotto, Joseph M. . .
Gilbert, Maureen . . .
Giles, Kevin . . , . . .
Petrolite Corporation . . . . . . . . . . . . St. Louis, MO
CITGO Refining & Chemicals . . . . . . . Corpus Christi, TX
Tricat, Inc. . . . . . . . . . . . . . . . . . Houston, TX
BP Oil Company . . . . . . . . . . . . . . Cleveland, OH
Glitsch, Inc. . . . . . . . . . . . . . . . . . Dallas, TX
CITGO Asphalt Refining Co. . . . . . . . Paulsboro, NJ
Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Grace Davison . . . . . . . . . . . . . . . Houston, TX
Zeolyst International . . . . . . . . . . . . Houston, TX
Shell Canada Products Limited . . . . . . . Montreal, Quebec
General Chemical Corporation . . . . . . . Parsippany, NJ
U&E Petroleum Marketing, Inc. . . . . . . Saraland, AL
PETROFAC, Inc. . . . . . . . . . . . . . . Tyler, TX
Nutter Engineering . . . . . . . . . . . . . Baton Rouge, LA
PQ Corporation . . . . . . . . . . . . . . Savannah, GA
NaIco Chemical Company . . . . . . . . . Sugar Land, TX
Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Union Texas Petrochemicals . . . . . . . . . Geismar, LA
Chevron Research &Technology Co. . . . . Richmond, CA
TheJohnG.FreezeCo. . . . . . . . . . . . Seabrook, TX
Chevron Corporation . . . . . . . . . . . . Pascagoula, MS
Chevron General Acomics . . . . . . . . . . San Diego, CA
ALCOA . . . . . . . . . . . . . . . . . . . Vidalia, LA
ChemLink . . . . . . . . . . . . . . . . . Santa Ana, CA
Stone &Webster Engineering Corp. . . . . Houston, TX
Lotepro Corporation . . . . . . . . . . . . Houston, TX
JGC Corporation . . . . . . . . . . . . . . Yokohama, Japan
Federal Container Canada . . . . . . . . . St. Catharines, Ontario
UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Fuel Reformulation . . . . . . . . . . . . . Arlington, VA
Fina Oil and Chemical Company . . . . . . Port Arthur, TX
Mobil Oil Corporation . . . . . . . . . . . Beaumont, TX
Caltex Services Corporation . . . . . . . . . Dallas, TX
Engelhard Corporation . . . . . . . . . . . Oak Park, IL
Stone & Webster Engineering Corp. . . . . Houston, TX
Bechtel Corporation . . . . . . . . . . . . Los Angeles, CA
The Lubrizol Corporation . . . . . . . . . Houston, TX
Petroleos Mexicanos . . . . . . . . . . . . . Mexico City, Mexico
Engelhard Corporation . . . . . . . . . . . Houston, TX
Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Bechtel Corporation . . . . . . . . . . . . Houston, TX
UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Tesoro Alaska Petroleum Company . . . . . Kenai, AK
Amoco Oil Company . . . . . . . . . . . . Whiting, IN
The Purolite Company . . . . . . . . . . . The Woodlands, TX
The M. W. Kellogg Company. . . . . . . . Houston, TX
Glitsch Technology Corp. . . . . . . . . . . Houston, TX
Criterion Catalyst Company L.P. . . . . . . Houston, TX
Haldor Topsoe, Inc. . . . . . . . . . . . . . Houston, TX
Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Engelhard Corporation . . . . . . . . . . . Iselin, NJ
Kuwait National Petroleum Company . . . Ahmadi, Kuwait
IFP Enterprises Inc. . . . . . . . . . . . . . New York, NY
Union Carbide Corporation . . . . . . . . Houston, TX
Nalco/Exxon Energy Chemicals Co. . . . . Sugar Land, TX
Hunt Refining Company . . . . . . . . . . Tuscaloosa, AL
The M. W. Kellogg Company. . . . . . . . Houston, TX
Barnes & Click, Inc. . . . . . . . . . . . . Dallas, TX

1994 NPRA Q&A Session on Refining and Petrochemical Technology 273

TOC/INDEX

NAME COMPANY LOCATION

Gilliam, A. Bruce . . . . . . . . . . . . . . . Betz Process Chemicals, Inc. . . . . . . . . . . The Woodlands, TX
Gillis, Brenda A. . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . . . Houston, TX
Gilmore, P. Tom . . . . . . . . . . . . . . . Kinetics Technology Int’l Corp. . . . . . . . . . Concord, CA
Gilmore, Richard . . . . . . . . . . . . . . . Betz Water Management Group . . . . . . . . Huntington Beach, CA
Gilson, E. Frank . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . Bartlesville, OK
Girardier, Frederic . . . . . . . . . . . . . . Eurecat S.A. . . . . . . . . . . . . . . . . . . . La Voulte, France
Gish, Ron. . . . . . . . . . . . . . . . . . . TPA, Inc. . . . . . . . . . . . . . . . . . . . . Dallas, TX
Giuricich, Nicholas . . . . . . . . . . . . . . Emtrol Corporation . . . . . . . . . . . . . . . Hauppauge, NY
Giuricich, Robert . . . . . . . . . . . . . . . Emtrol Corporation . . . . . . . . . . . . . . . Hauppauge, NY
Glasford, James W. . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . Houston, TX
Glass, Jim . . . . . . . . . . . . . . . . . . . Stone & Webster Engineering Corp. . . . . . . Houston, TX
Glendinning, Robert . . . . . . . . . . . . . ABB Lummus Crest Inc. . . . . . . . . . . . . Houston, TX
Glover, John N. . . . . . . . . . . . . . . . . CRI-MET . . . . . . . . . . . . . . . . . . . Houston, TX
Godwin, Roy . . . . . . . . . . . . . . . . . Gulf Chemical & Metallurgical Corp. . . . . . Freeport, TX
Goebel, Kenneth . . . . . . . . . . . . . . . The M. W. Kellogg Company . . . . . . . . . . Houston, TX
Goerlich, R. W. . . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . . . Houston, TX
Goglietta, Glenn . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . Baltimore, MD
Golden, Terry . . . . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . Marcus Hook, PA
Goliaszewski, Alan . . . . . . . . . . . . . . Betz Process Chemicals, Inc. . . . . . . . . . . The Woodlands, TX
Gomez, Leopoldo . . . . . . . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . . . . . . Mexico City, Mexico
Gonzalez, Horacio . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . Houston, TX
Gonzalez, Rene G. . . . . . . . . . . . . . . Fuel Reformulation . . . . . . . . . . . . . . . Washington, DC
Gooch, George . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . . . . . . Houston, TX
Goolsbee, Andy C. . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . Houston, TX
Gornik, Sieg A. . . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . Bartlesville, OK
Gorra, Filippo . . . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . Milan, Italy
Gosling, Keith . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . Chicago, IL
Gossard, Richard . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . Georgetown, CO
Go, Tony . . . . . . . . . . . . . . . . . . . Amoco Oil Company . . . . . . . . . . . . . . Texas City, TX
Gowdy, Hugh . . . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . Brea, CA
Goytisolo, Jorge . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . Baltimore, MD
Grabinski, Charles . . . . . . . . . . . . . . Clark Refining & Marketing, Inc. . . . . . . . Blue Island, IL
Graf, Ken . . . . . . . . . . . . . . . . . . . Norton Chemical Process Products . . . . . . . Akron, OH
Graham, Richard N. . . . . . . . . . . . . . ALCOA . . . . . . . . . . . . . . . . . . . . . Vidalia, LA
Graham, S. Diane. . . . . . . . . . . . . . . STRATCO, INC. . . . . . . . . . . . . . . . . Leawood, KS
Gramata, Tom . . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . Rodeo, CA
Grandle, Denny . . . . . . . . . . . . . . . . Agar Corporation, Inc. . . . . . . . . . . . . . Houston, TX
Graney, Thomas . . . . . . . . . . . . . . . Murphy Oil USA, Inc. . . . . . . . . . . . . . El Dorado, AR
Granniss, Lee . . . . . . . . . . . . . . . . . ABB Lummus Crest Inc. . . . . . . . . . . . . Houston, TX
Grant, Christoper S. . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . Sunbury, UK
Grant, P. E. . . . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . Chicago, IL
Gravley, Mark L. . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . Bartlesville, OK
Gray, David . . . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . . . . . . Houston, TX
Gray, Gary E. . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Gray, Richard . . . . . . . . . . . . . . . . . Frontier Refining, Inc. . . . . . . . . . . . . . Cheyenne, WY
Graziani, Ken . . . . . . . . . . . . . . . . . Mobil Oil Corporation . . . . . . . . . . . . . Fairfax, VA
Greaves, Judy . . . . . . . . . . . . . . . . . Norton Chemical Process Products . . . . . . . Akron, OH
Grenek, Michael D. . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . Houston, TX
Greenbank, Dennis . . . . . . . . . . . . . . Mobil Oil Corporation . . . . . . . . . . . . . Beaumont, TX
Gregory, Richard A. . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . Bound Brook, NJ
Gregory, William . . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . . . Florham Park, NJ
Gretschel, Mike . . . . . . . . . . . . . . . . Gulf Chemical & Metallurgical Corp. . . . . . Freeport, TX
Grieb, Ben . . . . . . . . . . . . . . . . . . GAYESCO . . . . . . . . . . . . . . . . . . . Larkspur, CA
Grifftths, Clive . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . Warrington, UK
Grosboll, Martin P. . . . . . . . . . . . . . . Jacobs Engineering Group Inc. . . . . . . . . . Houston, TX
Gruia, Adrian . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Guercio, Vincent . . . . . . . . . . . . . . . CY Monitor . . . . . . . . . . . . . . . . . . . Montclair, NJ
Guerrero, Benjamin . . . . . . . . . . . . . . PEMEX-Refinacion . . . . . . . . . . . . . . . Salamanca, Mexico

274 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Gunardson, Harold H. .
Gunter, Paul . . . . . .
Gutierra, Luis P. . . .
Habib,Thomas . . . . .
Hachmuth, Henry K. .
Hackett, James . . . .
Haelsig, Claus-Peter . . .
Haley, John . . . . . . .
Hallada, Calvin . . . . .
Hallauer, Greg . . . . .
Hallen, Ted . . . . . . .
Halliday, Jack R. . . . .
Halliwell, Kelvin . . . .
Hamilton, Don . . . . .
Hamilton, Gary L. . . .
Hamilton, Jeff . . . . .
Hammen, Douglass . . .
Hammons, Anne . . . .
Hanke, Tom . . . . . .
Hannerup-Nielsen, Peter
Hanower, Lee . . . . .
Hansen, Don . . . . . .
Hansen, Wendy L. . . .
Hanson, Daryl . . . . .
Hanson, Larry . . . . .
Harper, Kirk . . . . . .
Harrell, Jack B. . . . . .
Harrington, Michael J. .
Harris, Dan P. . . . . . .
Harris, Ernie . . . . . .
Hartley, Dan . . . . . .
Hartman, Edward . . . .
Harvey, Craig . . . . . .
Haseltine, Robert . . . .
Hastings, Thomas W. . .
Haugseth, Paul . . . . .
Hausberger, Arthur . .
Haveman, John . . . . .
Hawkins, Gerard . . . .
Hayashi, Akihiro . . . .
Haydel, Marvin C. . . .
Hayes, Ronald W. . . . .
Hazama,Takanori . . .
Heath, James . . . . . .
Heckel,TimothyL. . . .
Heck, William E. . . . .
Heinrich, Gerard . . . .
Hekkert, Erik . . . . . .
Heller, Fred . . . . . . .
Henderson, Gerald . . .
Henderson, Jody . . . .
Hendricks, Jim . . . . .
Henke, Kevin . . . . . .
Henriquez, Joseph A.R. .
Hereth, Mark . . . . . .
Hernandez, Rick . . . .
Herskovits, Lily . . . . .
Hibble, Pierre . . . . . .
Air Products and Chemicals, Inc. . . Allentown, PA
Criterion Catalyst Company L.P. . . Houston, TX
Lagoven . . . . . . . . . . . . . . . Amuay, Venezuela
Grace Davison . . . . . . . . . . . Columbia, MD
Phillips Petroleum Company . . . . Bartlesville, OK
Vista Chemical Company . . . . . . Houston, TX
Fluor Daniel BV . . . . . . . . . . Haarlem, Netherlands
Grace Davison . . . . . . . . . . . Baltimore, MD
Cyprus-Climax . . . . . . . . . . . Ypsilanti, MI
Micro Motion, Inc. . . . . . . . . . Boulder, CO
Unocal Corporation . . . . . . . . . Brea, CA
Petrolice Corporation . . . . . . . . Houston, TX
Criterion Catalyst Company L.P. . . Fareham, UK
Union Carbide Corporation . . . . Long Beach, CA
ABB Lummus Crest Inc. . . . . . . Bloomfield, NJ
The Pace Consultants Inc. . . . . . Houston, TX
Akzo Nobel . . . . . . . . . . . . . Houston, TX
The M. W. Kellogg Company. . . . Houston, TX
Conoco Inc. . . . . . . . . . . . . . Ponca City, OK
Haldor Topsoe A/S . . . . . . . . . Copenhagen, Denmark
Eurecat U.S. Incorporated . . . . . Closter, NJ
Koch Engineering Company, Inc. . . Wichita, KS
Engelhard Corporation . . . . . . . Iselin, NJ
Glitsch, Inc. . . . . . . . . . . . . . Dallas, TX
Tosco Refining Company . . . . . . Martinez, CA
Mobil Oil Corporation . . . . . . . Joliet, IL
ChemLink . . . . . . . . . . . . . Houston, TX
Crosfield Catalysts . . . . . . . . . Warrington, UK
Mobil Oil Corporation . . . . . . . Beaumont, TX
Petrolite Corporation . . . . . . . . St. Louis, MO
Haverly Systems, Inc. . . . . . . . . Summit, NJ
Glitsch, Inc. . . . . . . . . . . . . . Dallas, TX
Unocal Corporation . . . . . . . . . Alta Loma, CA
Akzo Nobel . . . . . . . . . . . . . Houston, TX
PQ Corporation . . . . . . . . . . Berwyn, PA
Powerine Oil Company . . . . . . . Santa Fe Springs, CA
United Catalysts Inc. . . . . . . . . Louisville, KY
Micro Motion, Inc. . . . . . . . . . Stafford, TX
ICI Katalco . . . . . . . . . . . . . Oakbrook Terrace,.IL
Mitsubishi Oil Company, Ltd. . . . Kawasaki, Japan
Wink Engineering . . . . . . . . . New Orleans, LA
Sun Company, Inc. . . . . . . . . . Philadelphia, PA
Cosmo Oil of U.S.A., Inc. . . . . . Sakaide, Japan
Fuel Reformulation . . . . . . . . . Los Angeles, CA
Unocal Corporation . . . . . . . . . Brea, CA
Energy BioSystems Corporation . . The Woodlands, TX
Institut Francais du Petrole . . . . . Malmaison, France
Energy BioSystems Corporation . . The Woodlands, TX
The Lubrizol Corporation . . . . . Wickliffe, OH
Ashland Petroleum Company . . . . Ashland, KY
The Lubrizol Corporation . . . . . Houston, TX
Buckman Labs . . . . . . . . . . . Beaumont, TX
Koch Refining Company . . . . . . St. Paul, MN
Refineria Isla (Curacao) S.A. . . . . Curacao, Neth. Antilles
The Hartford Steam Boiler I & I Co. Hartford, CT
The M. W. Kellogg Company. . . . Houston, TX
U.S. EPA . . . . . . . . . . . . . . San Francisco, CA
Stone &Webster . . . . . . . . . . Milton Keynes, UK

1994 NPRA Q&A Session on Refining and Petrochemical Technology 275

TOC/INDEX

NAME COMPANY LOCATION

Hickman, Gerald . . . . . . . . . . . . . . . KBC Advanced Technologies, Inc. . . . . . . . . . . Metairie, LA
Higgins, Richard . . . . . . . . . . . . . . . Shell Oil Company . . . . . . . . . . . . . . . . . . Norco, LA
Higgins, Terrence S. . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Hiller, Les A. . . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . . . . Houston, TX
Hillier, William J. . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Hlozek, Robert . . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Hoeffner, Barry . . . . . . . . . . . . . . . . ChemLink . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Hofer, Kevin . . . . . . . . . . . . . . . . . Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Hoge, Kenneth D. . . . . . . . . . . . . . . The C. W. Nofsinger Company . . . . . . . . . . . . Kansas City, MO
Hoh, Patrick . . . . . . . . . . . . . . . . . IFP Enterprises Inc. . . . . . . . . . . . . . . . . . . New York, NY
Hoiseth, Merlin . . . . . . . . . . . . . . . . Reactor Services International Inc. . . . . . . . . . . Alvin, TX
Holbrook, David . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Holdsworth, John C. . . . . . . . . . . . . . Foster Wheeler Energy Limited . . . . . . . . . . . . Berkshire, UK
Holmstrom, Charles . . . . . . . . . . . . . Betz Water Management Group . . . . . . . . . . . The Woodlands, TX
Hooper, James D. . . . . . . . . . . . . . . . Foster Wheeler USA Corporation . . . . . . . . . . . Clinton, NJ
Horsey, James E . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . . . . . . . . . Houston, TX
Hoselton, Richard . . . . . . . . . . . . . . Clark Refining and Marketing . . . . . . . . . . . . Blue Island, IL
Hostetter, Edward . . . . . . . . . . . . . . . Federal Container Corporation . . . . . . . . . . . . Houston, TX
Housenga, Brad . . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
Hufnagle, Jerry J. . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Hughes, Gary . . . . . . . . . . . . . . . . . Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Ponca City, OK
Hull, Randall . . . . . . . . . . . . . . . . . BOC Gases . . . . . . . . . . . . . . . . . . . . . . Murray Hill, NJ
Humeid, Munir Abd . . . . . . . . . . . . . Jordan Petroleum Refinery . . . . . . . . . . . . . . Amman, Jordan
Humphrey, David . . . . . . . . . . . . . . . Koch Refining Company . . . . . . . . . . . . . . . St. Paul, MN
Humphries, Adrian . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Hunderuk, Dmytro . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . . . . Marcus Hook, PA
Hunter, Michael G. . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Hurst, Joyce M. . . . . . . . . . . . . . . . . CRI-MET . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Husted, Don . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Hutchison, John D. . . . . . . . . . . . . . . LaRoche Chemicals, Inc. . . . . . . . . . . . . . . . Baton Rouge, LA
Imhoff, Scott . . . . . . . . . . . . . . . . . STRATCO, INC. . . . . . . . . . . . . . . . . . . . Leawood, KS
Ims, Pete . . . . . . . . . . . . . . . . . . . Koch Refining Company . . . . . . . . . . . . . . . St. Paul, MN
Ingraham, L. S. . . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Intabi, Majed . . . . . . . . . . . . . . . . . Aramco . . . . . . . . . . . . . . . . . . . . . . . . Riyadh, Saudi Arabia
Iqbal, Rashid . . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Iriarte, Juan . . . . . . . . . . . . . . . . . . YPF SA DPTO Refineria La Plata . . . . . . . . . . Buenos Aires, Argentina
Irons, James . . . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Philadelphia, PA
Irwin, R. Bruce . . . . . . . . . . . . . . . . Exxon Chemical Company . . . . . . . . . . . . . . Houston, TX
Izarraraz, Alicia . . . . . . . . . . . . . . . . ARCO Products Company . . . . . . . . . . . . . . Carson, CA
Jack Doug Conoco Inc. . . . . Ponca City, OK
Jackow, Francois ................................. Air Liquide America . Corporation
............................ Houston, TX
Jackson, Ron . . . . . . . . . . . . . . . . . Litwin Engineers & Constructors . . . . . . . . . . . Houston, TX
Jacobs, Terry . . . . . . . . . . . . . . . . . Western Unichem . . . . . . . . . . . . . . . . . . . Hobbs, NM
Jaffe, Jay. . . . . . . . . . . . . . . . . . . . Gulf Chemical & Metallurgical Corp. . . . . . . . . Freeport, TX
Jakubowicz, Edward . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Bensalem, PA
Jameson, Dan . . . . . . . . . . . . . . . . . LaGloria Oil and Gas Company . . . . . . . . . . . Tyler, TX
Jenkins, Jerry . . . . . . . . . . . . . . . . . Farmland Industries, Inc. . . . . . . . . . . . . . . . Coffeyville, KS
Jenkins, Robert I. . . . . . . . . . . . . . . . Imperial Oil Limited . . . . . . . . . . . . . . . . . Toronto, Ontario
Jennings, Jim . . . . . . . . . . . . . . . . . Consumer’s Coop Refinery Ltd. . . . . . . . . . . . . Regina, Saskatchewan
Jennings, Randy . . . . . . . . . . . . . . . Star Enterprise . . . . . . . . . . . . . . . . . . . . Delaware City, DE
Jerus, Paul . . . . . . . . . . . . . . . . . . . United Catalysts Inc. . . . . . . . . . . . . . . . . . Louisville, KY
Jesus, Edward . . . . . . . . . . . . . . . . . Refineria Isla (Curazao) S.A. . . . . . . . . . . . . . Curacao, Neth. Antilles
Jezak, Anne . . . . . . . . . . . . . . . . . . STRATCO, INC. . . . . . . . . . . . . . . . . . . . Leawood, KS
Jinks, Charles D. . . . . . . . . . . . . . . . TPA, Inc. . . . . . . . . . . . . . . . . . . . . . . . Dallas, TX
Jody, Linda . . . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
John, Mark W. . . . . . . . . . . . . . . . . Energy BioSystems Corporation . . . . . . . . . . . The Woodlands, TX
Johnson, Axel R. . . . . . . . . . . . . . . . Stone &Webster Engineering Corp. . . . . . . . . . Houston, TX
Johnson, Brian H. . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL

276 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Johnson, Chris C. . . . . . Akzo Nobel . . . . . . . . . . . . . Houston, TX
Johnson, Craig . . . . . . Clark Refining & Marketing, Inc. . Blue Island, IL
Johnson, David M. . . . . Chevron U.S.A. Products Company Port Arthur, TX
Johnson, E. Kenneth . . . Morrison Knudsen . . . . . . . . . Cleveland, OH
Johnson, Paul S. . . . . . Shell Development Company . . . . Houston, TX
Jokubaitis, Linas . . . . . The Lubrizol Corporation . . . . . Wickhffe, OH
Jones, Anthony . . . . . . Total Petroleum, Inc. . . . . . . . . Denver, CO
Jones, Carol . . . . . . . . Lyondell-CITGO Refining Co. Ltd. Houston, TX
Jones, David . . . . . . . GAYLORDCHEMICAL . . . . . Houston, TX
Jones, Gerwyn . . . . . . Belco Technologies Corp. . . . . . . Parsippany, NJ
Jones, Henry . . . . . . . Howe-Baker Engineers, Inc. . . . . Tyler, TX
Joseph, Joe . . . . . . . . Amoco Oil Company . . . . . . . . Naperville, IL
Joyal, Cheryl Lynn M. .. Amoco Oil Company . . . . . . . . Yorktown, VA
Joyce, Lee . . . . . . . . . CITGO Petroleum Corporation . . Lake Charles, LA
Juno, Edward E . . . . . . Pennzoil Products Company . . . . Houston, TX
Juracek, John . . . . . . . Grace Davison . . . . . . . . . . . Baltimore, MD
Kakehi, Kiyoshi . . . . . . INTERCAT, Inc. . . . . . . . . . . Tokyo, Japan
Kalota, Steven A. . . . . . The M. W. Kellogg Company. . . . Houston, TX
Kameyama, Kenji . . . . . Tohoku Oil Co., Ltd. . . . . . . . . Sendai, Japan
Kamienski, Paul . . . . . . Exxon Research & Engineering Co. . Florham Park, NJ
Kanniappan, V. . . . . . . Madras Refineries Limited . . . . . Madras, India
Kantor, Laszlo . . . . . . . Hungarian Oil and Gas Co. . . . . . Szazhalombatta, Hungary
Kapoor, Akhilesh . . . . . BOCGases . . . . . . . . . . . . . Murray Hill, NJ
Kasbaum, John . . . . . . Akzo Nobel . . . . . . . . . . . . . Houston, TX
Kataoka, Norihito . . . . . Mitsubishi Oil Company, Ltd. . . . Hoffman Estates, IL
Katdare, Vidya . . . . . . Koch Refining Company . . . . . . Wichita, KS
Kayagawa, Mikio . . . . . Exxon Research & Engineering Co. . Florham Park, NJ
Keefer, Pamela . . . . . . STRATCO, INC. . . . . . . . . . . Leawood, KS
Keller, Ted . . . . . . . . Ultramar Inc. . . . . . . . . . . . . Long Beach, CA
Kellett, Thomas . . . . CDTech . . . . . . . . . . . . . . . Houston, TX
Kelly, James . . . . . . . . CITGO Refining & Chemicals . . . Corpus Christi, TX
Kelly, Peter E. . . . . . . . Jacobs Engineering Group Inc. . . . Houston, TX
Kemock, Robert W. . . . . Grace Dearborn . . . . . . . . . . . Lake Zurich, IL
Kenichi, Hayashi . . . . . Showa Shell Sekiyu K.K. . . . . . . Tokyo, Japan
Kenney,Thomas . . . . . Huntsman Corporation . . . . . . . Houston, TX
Kepler, Larry . . . . . . . UOP . . . . . . . . . . . . . . . . Des Plaines, IL
Kessler, Randy . . . . . . Kinetics Technology Int’l Corp. . . . San Dimas, CA
Keys, Kent . . . . . . . . United Catalysts Inc. . . . . . . . . Louisville, KY
Khouw, E H. H. . . . . . Shell Int’l Petroleum Mij. B .V. . . . The Hague, Netherlands
Kibble, Alan . . . . . . . Mobil Oil Corporation . . . . . . . Fairfax, VA
Kickirillo, Rosy . . . . . . Stone & Webster Engineering Corp. Houston, TX
Kidder, Rudolph . . . . . The M. W. Kellogg Company. . , . Houston, TX
Killackey, Terry . . . . . . UOP . . . . . . . . . . . . . . . . Houston, TX
Kilner, Peter . . . . . . . . Catalytica . . . . . . . . . . . . . . Mountain View, CA
Kilroy, James . . . . . . . UOP . . . . . . . . . . . . . . . . Houston, TX
Kim, Byung Chul . . . . . Yukong Limited . . . . . . . . . . . Ulsan, Korea
Kim, Young-Mi . . . . . . The UNO-VEN Company . . . . . Lemont, IL
King, Chad . . . . . . . . Bloomfield Refining Co. . . . . . . Bloomfield, NM
King, David . . . . . . . . Howe-Baker Engineers, Inc. . . . . Tyler, TX
Kingston, Doug . . . . . . Petrolite Corporation . . . . . . . . Oakville, Ontario
King, Thomas D. . . . . . Haldor Topsoe, Inc. . . . . . . . . . Houston, TX
Kinnear, Scott . . . . . . . STRATCO, INC. . . . . . . . . . . Leawood, KS
Kirina, Vera . . . . . . . . Evroasia-Bunter . . . . . . . . . . . Novorossiysk, Russia
Kissel, Robert S. . . . . . UOP . . . . . . . . . . . . . . . . Houston, TX
Kit, Daniel . . . . . . . . Grace Davison . . . . . . . . . . . London, Ontario
Kivi, Jouni . . . . . . . . Neste Oy . . . . . . . . . . . . . . Porvoo, Finland
Kleinschrodt, Frank . . . . SETPOINT, Inc. . . . . . . . . . . Houston, TX
Kliesch, Howard . . . . . Honeywell Profimatics . . . . . . . Thousand Oaks, CA

1994 NPRA Q&A Session on Refining and Petrochemical Technology 277

TOC/INDEX

NAME COMPANY LOCATION

Klimek, Scott . . . . . . . . . . . . . . . . .
Knickerbocker, Bryan . . . . . . . . . . . . .
Knight, Robert . . . . . . . . . . . . . . . .
Knipp, John . . . . . . . . . . . . . . . . . .
Kohler, Robert . . . . . . . . . . . . . . . .
Kohut, Hersh . . . . . . . . . . . . . . . . .
Koichi, Tanaka . . . . . . . . . . . . . . . .
Kolb, Norman . . . . . . . . . . . . . . . .
Kology, Tom . . . . . . . . . . . . . . . . .
Kooiman, Randall . . . . . . . . . . . . . .
Korsfur, Bjorn . . . . . . . . . . . . . . . . .
Koryagina, Lioubov . . . . . . . . . . . . . .
Kouri, Jan . . . . . . . . . . . . . . . . . . .
Kovar, Thomas . . . . . . . . . . . . . . . .
Kovski, Alan . . . . . . . . . . . . . . . . .
Kowalczyk, Dennis . . . . . . . . . . . . . .
Kozak, Fred . . . . . . . . . . . . . . . . . .
Kramer, David C. . . . . . . . . . . . . . . .
Krasnykh, Vladimir V. . . . . . . . . . . . .
Kreitz, Roy . . . . . . . . . . . . . . . . . .
Kremer, Lawrence . . . . . . . . . . . . . . .
Krenzke, David . . . . . . . . . . . . . . . .
Krikorian, Krik . . . . . . . . . . . . . . . .
Krishna, Ashok . . . . . . . . . . . . . . . .
Krishna&, Gautham . . . . . . . . . . . . .
Krivtchenko, Evgeniy V. . . . . . . . . . . .
Kroeger, John . . . . . . . . . . . . . . . . .
Krueding, Arthur . . . . . . . . . . . . . . .
Kruger, Christiaan . . . . . . . . . . . . . .
Krukiel, James . . . . . . . . . . . . . . . .
Kruse, Charles . . . . . . . . . . . . . . . .
Kuchcinski, Gary . . . . . . . . . . . . . . .
Kuehler, Chris . . . . . . . . . . . . . . . .
Kuhel, Anthony . . . . . . . . . . . . . . . .
Kumagae, Shuji . . . . . . . . . . . . . . . .
Kumat, Anand . . . . . . . . . . . . . . . .
Kunes, Michelle A. . . . . . . . . . . . . . .
Kurumado, Hiroshi . . . . . . . . . . . . . .
Kutsche, Ronald A. . . . . . . . . . . . . . .
Kwasniewski, Vincent . . . . . . . . . . . . .
Kyshkin, Valeriy . . . . . . . . . . . . . . . .
La Russo, Anthony C. . . . . . . . . . . . .
Laabs, Patrick . . . . . . . . . . . . . . . . .
Lacijan, Larry . . . . . . . . . . . . . . . . .
Lal, Ravi . . . . . . . . . . . . . . . . . . .
Lamb, Scott . . . . . . . . . . . . . . . . . .
Lamm, Art . . . . . . . . . . . . . . . . . .
Lamourelle, AIain . . . . . . . . . . . . . . .
Langan, James . . . . . . . . . . . . . . . .
Lang, Jeff . . . . . . . . . . . . . . . . . . .
Lannen, Tom . . . . . . . . . . . . . . . . .
Lanning, Robert Allen . . . . . . . . . . . .
Larranga, Cesar . . . . . . . . . . . . . . . .
Larson, Robert . . . . . . . . . . . . . . . .
Larson, William . . . . . . . . . . . . . . . .
Lasater, Allen . . . . . . . . . . . . . . . . .
Latosinsky, Betty M. . . . . . . . . . . . . .
Laux, Michael A. . . . . . . . . . . . . . . .
United Catalysts Inc. . . . . . . . . . . . . . . . . . Louisville, KY
Mobil Oil Corporation . . . . . . . . . . . . . . . . Beaumont, TX
Pennzoil Products Company . . . . . . . . . . . . . Houston, TX
LaRoche Chemicals, Inc. . . . . . . . . . . . . . . . Baton Rouge, LA
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Houston, TX
ARC0 Products Company . . . . . . . . . . . . . . Carson, CA
Kurita Water Industries Ltd. . . . . . . . . . . . . . Tokyo, Japan
The IPC Company . . . . . . . . . . . . . . . . . . Houston, TX
Mobil Oil Corporation . . . . . . . . . . . . . . . . Fairfax, VA
Murphy Oil USA, Inc. . . . . . . . . . . . . . . . . Superior, WI
Statoil A/S . . . . . . . . . . . . . . . . . . . . . . Mongstad, Norway
Enterprise Polymer-Conteyner . . . . . . . . . . . . Moscow, Russia
International Catalyst, Inc. . . . . . . . . . . . . . . Friendswood, TX
YPF SA DPTO Refineria LA Plata . . . . . . . . . . Buenos Aires, Argentina
The Oil Daily . . . . . . . . . . . . . . . . . . . . . Washington, DC
Refining Process Services, Inc. . . . . . . . . . . . . Pittsburgh, PA
Witco Corporation . . . . . . . . . . . . . . . . . . Greenwich, CT
Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Institute Omskneftechim . . . . . . . . . . . . . . . Omsk, Russia
Lyondell-CITGO Refining Co. Ltd. . . . . . . . . . Houston, TX
ChemLink . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
KBC Advanced Technologies, Inc. . . . . . . . . . . Weybridge, UK
Chevron U.S.A. Products Company . . . . . . . . . El Segundo, CA
Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Oil Processing Factory . . . . . . . . . . . . . . . . Moscow, Russia
General Chemical Corporation . . . . . . . . . . . . Parsippany, NJ
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
NATREF . . . . . . . . . . . . . . . . . . . . . . . Natref, South Africa
Lyondell-CITGO Refining Co. Ltd. . . . . . . . . . Houston, TX
Bechtel Corporation . . . . . . . . . . . . . . . . . Houston, TX
Amoco Oil Company . . . . . . . . . . . . . . . . . Texas City, TX
Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
BP Oil Company . . . . . . . . . . . . . . . . . . . Belle Chasse, LA
Caltex Services Corporation . . . . . . . . . . . . . . Irving, TX
Indian Oil Corporation Limited . . . . . . . . . . . Bihar, India
Pittsburgh Applied Research Corp. . . . . . . . . . . Pittsburgh, PA
Hakuto Company, Ltd. . . . . . . . . . . . . . . . . Tokyo, Japan
Betz Process Chemicals, Inc. . . . . . . . . . . . . . The Woodlands, TX
Amoco Oil Company . . . . . . . . . . . . . . . . . Naperville, IL
Interpreter. . . . . . . . . . . . . . . . . . . . . . . Los Angeles, CA
CRI-MET . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Star Enterprise . . . . . . . . . . . . . . . . . . . . Delaware City, DE
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Kinetics Technology Int’l Corp. . . . . . . . . . . . . San Dimas, CA
Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Petrolite Corporation . . . . . . . . . . . . . . . . . Ranch0 Dominguez, CA
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
ABB Lummus Crest Inc. . . . . . . . . . . . . . . . Bloomfield, NJ
Calumet Lubricants Company . . . . . . . . . . . . Princeton, LA
Petrolite Corporation . . . . . . . . . . . . . . . . . St. Louis, MO
Dow Chemical U.S.A. . . . . . . . . . . . . . . . . Houston, TX
SAIMSA . . . . . . . . . . . . . . . . . . . . . . . Mexico City, Mexico
INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Glen Arm, MD
Stone &Webster Engineering Corp. . . . . . . . . . Houston, TX
Koch Refining Company . . . . . . . . . . . . . . . Wichita, KS
Novacor Chemicals Ltd. . . . . . . . . . . . . . . . Sarnia, Ontario
Diamond Shamrock, Inc. . . . . . . . . . . . . . . . Three Rivers, TX

278 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Lawrence, Peter . . .
Learman, Robert J. .
Le, Binh . . . . . .
LeBlanc, Thomas C.
Ledden, Richard A. .
Lee, Cliff . . . . . .
Lee, Young . . . . .
Lehan, Kathleen . .
Lehr, James . . .
Leiker, Wayne A. . .
Lemmon, Chaz . . .
Lerch, Dave . . . . .
LeRoy, Charles E . .
Letzsch, Warren S. .
Lewandowski, Roy A.
Liike, Thomas . . . .
Liles, Mike . . . . .
Limmex, Kimberly .
Lin, Karl . . . . . .
Link, John . . . . .
Liolios, Glenn . . . .
Lipinski, John J. . .
Lippert, Regis B. . .
Lippert, Robin . . .
Litvinov, Pave1 . . .
Liu, David . . . . .
Llanos, Zenon . . .
Lloyd, Rick . . . . .
Locke, Gary . . . . .
Locke, Tim . _ . . .
Lockett, William . .
Lockwood, James . .
Lomax, Stanley . . .
Long, Alec . . . . .
Long, James K. . . .
Long, Stephen . .
Longoria, Roland . .
Longtin, Doug . . .
Lopez, Linda L. . . .
Lord, Linda . . . . .
Love, Scott . . . . .
Lowe, Ed . . . . . .
Lucadamo, Al . . . .
Lucero, Bernardo . .
Luc, Geoffrey . . . .
Ludolph, Robert A. .
Luedemann, Thomas
Lu, Robert . . . . .
Lynch, Kelly Zachgo
Lynne, Laura . . . .
Lyons, James C. . . .
Mackey, Terry D. . .
MacRunnels, Zachary
Madden, James J. . .
Mader, Martin . . .
Mabarajh, Edward .
Maiden, James A. .
Malmberg, Doris . .
Morrison Knudsen . . . . . . . . . . . . Cleveland, OH
Dow Chemical U.S.A. . . . . . . . . . . Houston, TX
Merichem Company . . . . . . . . . . . Houston, TX
LaRoche Chemicals, Inc. . . . . . . . . . Baton Rouge, LA
Betz Process Chemicals, Inc. . . . . . . . The Woodlands, TX
KBC Advanced Technologies, Inc. . . . . Parsippany, NJ
Serck Baker, Inc. . . . . . . . . . . . . . Houston, TX
The Dow Chemical Company . . . . . . Walnut Creek, CA
Star Enterprise . . . . . . . . . . . . . . Delaware City, DE
CITGO Petroleum Corporation . . . . . Lake Charles, LA
Tosco Refining Company . . . . . . . . . Martinez, CA
Witco Corporation . . . . . . . . . . . . Bradford, PA
CITGO Petroleum Corporation . . . . . Corpus Christi, TX
Stone & Webster Engineering Corp. . . . Houston, TX
Nalco/Exxon Energy Chemicals Co. . . . Chicago, IL
Coastal Chemical Company, Inc. . . . . . Novi, MI
Mobil Oil Corporation . . . . . . . . . . Beaumont, TX
Koch Refining Company . . . . . . . . . St. Paul, MN
ALCOA . . . . . . . . . . . . . . . . . . Houston, TX
ChemLink . . . . . . . . . . . . . . . . Houston, TX
STRATCO, INC. . . . . . . . . . . . . . Leawood, KS
Coastal Refining & Marketing, Inc. . . . . Houston, TX
INTERCAT, Inc. . . . . . . . . . . . . . Sea Girt, NJ
INTERCAT, Inc. . . . . . . . . . . . . . Sea Girt, NJ
Russian Trade Development Co., Inc. . . . Los Angeles, CA
UOP . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Gulf Chemical & Metallurgical Corp. . . Freeport, TX
Chemlink . . . . . . . . . . . . . . . . . St. John, IN
Amerada Hess Corporation . . . . . . . . Woodbridge, NJ
Koch Industries/John Zink . . . . . . . . Tulsa, OK
Encon Associates, Inc. . . . . . . . . . . . Far Hills, NJ
Petrolite Corporation . . . . . . . . . . . St. Louis, MO
Texaco Refining & Marketing Inc. . . . . El Dorado, KS
Crown Central Petroleum Corporation . . Houston, TX
Nalco/Exxon Energy Chemicals Co. . . . Sugar Land, TX
Stone & Webster Engineering Corp. . . . Houston, TX
Koch Refining Company . . . . . . . . . Corpus Christi, TX
Grace Dearborn . . . . . . . . . . . . . . Pasadena, TX
Akzo Nobel . . . . . . . . . . . . . . . . Houston, TX
The Coastal Corporation . . . . . . . . . Houston, TX
Koch Industries/John Zink . . . . . . . . Tulsa, OK
TPA, Inc. . . . . . . . . . . . . . . . . . Dallas, TX
Gulf Publishing Company . . . . . . . . Summit, NJ
Norton Chemical Process Products . . . . Houston, TX
Ultramar Canada Inc. . . . . . . . . . . . Levis, Quebec
Sun Company, Inc. . . . . . . . . . . . . Marcus Hook, PA
Vista Chemical Company . . . . . . . . . Houston, TX
Stone & Webster Engineering Corp. . . . Houston, TX
Kerr-McGee . . . . . . . . . . . . . . . . Oklahoma City, OK
Glitsch, Inc. . . . . . . . . . . . . . . . . Baton Rouge, LA
ARCO Chemical Company . . . . . . . . Houston, TX
MK-Ferguson . . . . . . . . . . . . . . . Cleveland, OH
Cherokee Sanford Group . . . . . . . . . Raleigh, NC
Betz Water Management Group . . . . . Trevose, PA
Sun Company, Inc. . . . . . . . . . . . . Philadelphia, PA
Travis Chemicals Inc. . . . . . . . . . . . Calgary, Alberta
INTERCAT, Inc. . . . . . . . . . . . . . Princeton, NJ
NPRA . . . . . . . . . . . . . . . . . . . Washington, DC

1994 NPRA Q&A Session on Refining and Petrochemical Technology 279

TOC/INDEX

NAME COMPANY LOCATION

Maloy, Phillip . . . . . . . . . . . . . . . .
Manley, Fred . . . . . . . . . . . . . . . .
Manthos, George J. . . . . . . . . . . . . .
Maple, Ralph . . . . . . . . . . . . . . . .
Marcotte, Carl . . . . . . . . . . . . . . .
Mariani, Richard A. . . . . . . . . . . . . .
Markle, Rick . . . . . . . . . . . . . . . .
Marks, Chad L. . . . . . . . . . . . . . . .
Markum, Roy . . . . . . . . . . . . . . . .
Marler, David . . . . . . . . . . . . . . . .
Marple, Charles . . . . . . . . . . . . . . .
Marrelli, Ronald E. . . . . . . . . . . . . .
Marshall, Don . . . . . . . . . . . . . . .
Martin, Robert B. . . . . . . . . . . . . . .
Martin, Tim . . . . . . . . . . . . . . . .
Masak, Tom . . . . . . . . . . . . . . . . .
Masias, Guido . . . . . . . . . . . . . . .
Masters, Ken . . . . . . . . . . . . . . . .
Mathews, Richard . . . . . . . . . . . . . .
Mathisen, Melvin . . . . . . . . . . . . . .
Mathur, S. N. . . . . . . . . . . . . . . . .
Mathur, Steve S. . . . . . . . . . . . . . . .
Matos, Jose . . . . . . . . . . . . . . . . .
Matsui, Yukinori . . . . . . . . . . . . . .
Matsumoto, Kokichi . . . . . . . . . . . .
Matsuo, Hiroshi . . . . . . . . . . . . . .
Matsushita, Takashi . . . . . . . . . . . . .
Mattenson, Kirsten . . . . . . . . . . . . .
Matthews, Bruce . . . . . . . . . . . . . .
Maury, Jon . . . . . . . . . . . . . . . . .
MC Colgan, Mary Beth . . . . . . . . . . .
McArthur, Dennis P. . . . . . . . . . . . .
McBride, William . . . . . . . . . . . . . .
McCaffrey, David S. . . . . . . . . . . . .
McClure, Doug . . . . . . . . . . . . . . .
McCoy, Charles S. . . . . . . . . . . . . .
McCulloch, Donald C. . . . . . . . . . . .
McDaniel, J. Gary . . . . . . . . . . . . .
McDaniel, Norman K. . . . . . . . . . . .
McDonald, Christopher . . . . . . . . . .
McDowell, Bob . . . . . . . . . . . . . . .
McFarlane, Philip . . . . . . . . . . . . . .
McFarlin, Henry . . . . . . . . . . . . . .
McGovern, Stephen . . . . . . . . . . . . .
McHugh, Terence J. . . . . . . . . . . . . .
McKay, Dwight L. . . . . . . . . . . . . .
McKinney, Jack . . . . . . . . . . . . . . .
McLaren, Theron . . . . . . . . . . . . . .
McLean, Joseph B. . . . . . . . . . . . . .
Meakim, John T. . . . . . . . . . . . . . .
Meche, Billy . . . . . . . . . . . . . . . .
Meeker, Roon . . . . . . . . . . . . . . . .
Mehrotra, Raghunath P. . . . . . . . . . . .
Memmott, Vincent . . . . . . . . . . . . .
Mendakis, George . . . . . . . . . . . . .
Menda, Pedro . . . . . . . . . . . . . . .
Menegaz, Stephen G. . . . . . . . . . . . .
Menon, Raghu . . . . . . . . . . . . . . .
. Grace Dearborn . . . . . . . . . . . . . . . . . . . . Lake Zurich, IL
. Fisher-Rosemount . . . . . . . . . . . . . . . . . . . Atlanta, GA
. Jacobs Engineering Group Inc. . . . . . . . . . . . . Houston, TX
. Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
. Ultramar Canada Inc. . . . . . . . . . . . . . . . . . Levis, Quebec
. UOP . . . . . . . . . . . . . . . . . . . . . . . . . Tarrytown, NY
. Betz Process Chemicals, Inc. . . . . . . . . . . . . . The Woodlands, TX
. ALCOA . . . . . . . . . . . . . . . . . . . . . . . . Vidalia, LA
. Fuel Reformulation . . . . . . . . . . . . . . . . . . Houston, TX
. The Foxboro Company . . . . . . . . . . . . . . . . Houston, TX
. Sun Refining and Marketing Company . . . . . . . . Philadelphia, PA
. Phillips Petroleum Company . . . . . . . . . . . . . Bartlesville, OK
. Consultant . . . . . . . . . . . . . . . . . . . . . . Boston, MA
. Petrolite Corporation . . . . . . . . . . . . . . . . . Houston, TX
. Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
. Engelhard Corporation . . . . . . . . . . . . . . . . Markham, Ontario
. Petroleos Del Peru S.A. . . . . . . . . . . . . . . . . Lima, Peru
. STRATCO, INC. . . . . . . . . . . . . . . . . . . . Leawood, KS
. Grace Davison . . . . . . . . . . . . . . . . . . . . Houston, TX
. Encon Associates, Inc. . . . . . . . . . . . . . . . . . Far Hills, NJ
. Hindustan Petroleum Corporation Ltd. . . . . . . . . Bombay, India
. Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
. Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
. Hakuto Company, Ltd. . . . . . . . . . . . . . . . . Tokyo, Japan
. Cosmo Oil of U.S.A., Inc. . . . . . . . . . . . . . . Sakaide, Japan
. Nikki-Universal . . . . . . . . . . . . . . . . . . . . Tokyo, Japan
. Idemitsu Kosan Co., Ltd . . . . . . . . . . . . . . . Houston, TX
. CITGO Petroleum Corporation . . . . . . . . . . . Lake Charles, LA
. ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
. Federal Container Corporation . . . . . . . . . . . . Houston, TX
. United Catalysts Inc. . . . . . . . . . . . . . . . . . Louisville, KY
. Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
. Bechtel Corporation . . . . . . . . . . . . . . . . . Houston, TX
. Exxon Research & Engineering Co. . . . . . . . . . . Florham Park, NJ
. Diamond Shamrock, Inc. . . . . . . . . . . . . . . . Mont Belviev, TX
. Consultant . . . . . . . . . . . . . . . . . . . . . . Orinda, CA
. Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
. Contract Materials Processing . . . . . . . . . . . . . Baltimore, MD
. Amoco Oil Company-Retired . . . . . . . . . . . . . League City, TX
. Grace Dearborn . . . . . . . . . . . . . . . . . . . . Denver, CO
. Engelhard Corporation . . . . . . . . . . . . . . . . Iselin, NJ
. Norton Chemical Process Products . . . . . . . . . . Houston, TX
. Nalco/Exxon Energy Chemicals Co. . . . . . . . . . Sugar Land, TX
. Mobil Research & Development Corp. . . . . . . . . Paulsboro, NJ
. Discovery Aluminas . . . . . . . . . . . . . . . . . . Houston, TX
. Phillips Petroleum Company . . . . . . . . . . . . . Bartlesville, OK
. Comae Chemical Company. . . . . . . . . . . . . . Houston, TX
. ABB Randall Corporation . . . . . . . . . . . . . . Houston, TX
. Engelhard Corporation . . . . . . . . . . . . . . . . Houston, TX
. ChemLink . . . . . . . . . . . . . . . . . . . . . . Houston, TX
. Mobil Oil Corporation . . . . . . . . . . . . . . . . Beaumont, TX
. YPF SA DPTO Refineria La Plata . . . . . . . . . . Buenos Aires, Argentina
. Indian Institute of Petroleum . . . . . . . . . . . . . Dehradun, India
. Flying J Inc. . . . . . . . . . . . . . . . . . . . . . . North Salt Lake, UT
. ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Billingham, UK
. Petroleos Del Peru S.A. . . . . . . . . . . . . . . . . Lima, Peru
. The Pritchard Corporation . . . . . . . . . . . . . . Houston, TX
. The BOC Group . . . . . . . . . . . . . . . . . . . Murray Hill, NJ

280 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Mercado, Miguel A. . . . . . . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . . . . Mexico City, Mexico
Mertes, William . . . . . . . . . . . . . . . . Arrowhead Industrial Water . . . . . . . . . Lincolnshire, IL
Mettee, Elizabeth W. . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . Baltimore, MD
Metzger, Thomas . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . St. Louis, MO
Meyers, Kenneth . . . . . . . . . . . . . . . Ashland Petroleum Company . . . . . . . . Ashland, KY
Maa, Jorge . . . . . . . . . . . . . . . . . . Eurecat U.S. Incorporated . . . . . . . . . Mexico City, Mexico
Michelini, Eugene . . . . . . . . . . . . . . Sun Company, Inc. . . . . . . . . . . . . . Philadelphia, PA
Mielke, Joel . . . . . . . . . . . . . . . . . . Koch Refining Company . . . . . . . . . . St. Paul, MN
Mijares, Gerardo . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . Houston, TX
Mikkelsen, Peter . . . . . . . . . . . . . . . Petro-Canada Products . . . . . . . . . . . Mississauga, Ontario
Millensifer, Tom A. . . . . . . . . . . . . . . Powmet, Inc. . . . . . . . . . . . . . . . . Littleton, CO
Miller, David J. . . . . . . . . . . . . . . . . ARCO Chemical Company . . . . . . . . . Newtown Square, PA
Miller, Harvey S. . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . Long Beach, CA
Miller, James E. . . . . . . . . . . . . . . . . CITGO Petroleum Corporation . . . . . . Lake Charles, LA
Miller, Jeff . . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Miller, John E. . . . . . . . . . . . . . . . . Tosco Refining Company . . . . . . . . . . Ferndale, WA
Miller, Missy . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . Houston, TX
Miller, R. Michael . . . . . . . . . . . . . . . ChemLink . . . . . . . . . . . . . . . . . Mt. Laurel, NJ
Miller, Richard . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . Stafford, TX
Miller, Rik . . . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . Houston, TX
Miranda, Ron E. . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . Bartlesville, OK
Miro, Pedro . . . . . . . . . . . . . . . . . . Cepsa . . . . . . . . . . . . . . . . . . . . Madrid, Spain
Mitchell, Earl J. . . . . . . . . . . . . . . . . Jacobs Engineering Group Inc. . . . . . . . Houston, TX
Mitchell, John . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . Houston, TX
Mitchell, Richard . . . . . . . . . . . . . . . Sun Company, Inc. . . . . . . . . . . . . . Marcus Hook, PA
Mok, William . . . . . . . . . . . . . . . . . BHP Petroleum . . . . . . . . . . . . . . . Kapolei, HI
Monroe, W. D. . . . . . . . . . . . . . . . . Atlas Copco Comptec Inc. . . . . . . . . . Kingwood, TX
Moore, Albert B. . . . . . . . . . . . . . . . Buckman Laboratories, Inc. . . . . . . . . . Memphis, TN
Moore, Andy . . . . . . . . . . . . . . . . TPA,Inc. . . . . . . . . . . . . . . . . . . Dallas, TX
Moore, Carroll . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Moore, Frank . . . . . . . . . . . . . . . . . Norton Chemical Process Products . . . . . Akron, OH
Moore, Howard E . . . . . . . . . . . . . . Ashland Petroleum Company . . . . . . . . Ashland, KY
Moore, Richard 0. . . . . . . . . . . . . . . Chevron Research &Technology Co. . . . . Richmond, CA
Morales, Jose . . . . . . . . . . . . . . . . . Sun Refining and Marketing Company . . . Toledo, OH
Morash, David . . . . . . . . . . . . . . . . Rocky Mountain Salvage & Equipment . . Friday Harbor, WA
Mordhorst, Donald . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Morelli, David . . . . . . . . . . . . . . . . Federal Container Corporation . . . . . . . Houston, TX
Morgan, Barry . . . . . . . . . . . . . . . . Chevron International Oil Co. . . . . . . . San Francisco, CA
Morgan, John A. . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . Bartlesville, OK
Morgan, Lynda . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . St. Louis, MO
Morris, David . . . . . . . . . . . . . . . . . Chevron Research &Technology Co. . . . . Richmond, CA
Morris, Lee . . . . . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . Houston, TX
Morrison, M. Edward . . . . . . . . . . . . . IFP Enterprises Inc. . . . . . . . . . . . . . Houston, TX
Morse, Robert W. . . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . Iselin, NJ
Motohashi, Yoshihisa . . . . . . . . . . . . . Mitsubishi Oil Company, Ltd. . . . . . . . Kurashiki, Japan
Mountainland, David . . . . . . . . . . . . . Hydrocarbon Research Inc. . . . . . . . . . Princeton, NJ
Moyse, Brian . . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . . . . Houston, TX
Muha, George . . . . . . . . . . . . . . . . Middough Associates Inc. . . . . . . . . . . Cleveland, OH
Mulraney, Donald D. . . . . . . . . . . . . . Stone &Webster Engineering Corp. . . . . Houston, TX
Murff, Stephen . . . . . . . . . . . . . . . . Eurecat U.S. Incorporated . . . . . . . . . Pasadena, TX
Murphy, George . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . Liverpool, UK
Murthy, A.K. . . . . . . . . . . . . . . . . . BOC Gases . . . . . . . . . . . . . . . . . Murray Hill, NJ
Musgrave, Jonathan . . . . . . . . . . . . . . Chevron International Oil Co. . . . . . . . San Francisco, CA
Myers, Daniel N. . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Naeger, Dennis P. . . . . . . . . . . . . . . . Betz Process Chemicals, Inc. . . . . . . . . The Woodlands, TX
Nagel, Jeff. . . . . . . . . . . . . . . . . . . Energy BioSystems Corporation . . . . . . The Woodlands, TX
Nakamura, David . . . . . . . . . . . . . . . Hydrocarbon Processing . . . . . . . . . . Houston, TX
Nash, Richard M. . . . . . . . . . . . . . . . Shell Development Company . . . . . . . . Houston, TX

1994 NPRA Q&A Session on Refining and Petrochemical Technology 281

TOC/INDEX

NAME COMPANY LOCATION

Nassar, Emile . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Natarajan, Raju . . . . . . . . . . . . . . . . Hydro-Chem . . . . . . . . . . . . . . . . . . . . . Canton, GA
Nedanovich, Don . . . . . . . . . . . . . . . Walk, Haydel & Associates, Inc. . . . . . . . . . . . New Orleans, LA
Nedderman, Theodore J. . . . . . . . . . . . Shell Oil Company . . . . . . . . . . . . . . . . . . Houston, TX
Neighbors, John . . . . . . . . . . . . . . . ABB Randall Corporation . . . . . . . . . . . . . . Houston, TX
Nelsen, Dennis . . . . . . . . . . . . . . . . Western Unichem . . . . . . . . . . . . . . . . . . . Houston, TX
Nelson, Andrew . . . . . . . . . . . . . . . . Morrison Knudsen . . . . . . . . . . . . . . . . . . Cleveland, OH
Nelson, Douglas . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Neudorfer, Hans . . . . . . . . . . . . . . . Petrox S.A. . . . . . . . . . . . . . . . . . . . . . . Talcahuano, Chile
Neuman, Daniel J. . . . . . . . . . . . . . . Tricat, Inc. . . . . . . . . . . . . . . . . . . . . . . Owings Mills, MD
Neuman, Pamela K. . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Newell, Dennis . . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Houston, TX
Niccum, Phillip . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Nicholas, David . . . . . . . . . . . . . . . . Air Products and Chemicals, Inc. . . . . . . . . . . . Allentown, PA
Nicholson, David S. . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . . . . Warrington, UK
Nielsen, Andets . . . . . . . . . . . . . . . . Haldor Topsoe A/S . . . . . . . . . . . . . . . . . . Lyngby, Denmark
Nielsen, Lillian . . . . . . . . . . . . . . . . Today’s Refinery . . . . . . . . . . . . . . . . . . . . Chappaqua, NY
Nocca, Jean-Luc . . . . . . . . . . . . . . . IFP Enterprises, Inc. . . . . . . . . . . . . . . . . . Houston, TX
Norman, William S. . . . . . . . . . . . . . Discovery Aluminas . . . . . . . . . . . . . . . . . . Houston, TX
Northup, Aldrich H. . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Norton, Paul . . . . . . . . . . . . . . . . . Sun Company, Inc. . . . . . . . . . . . . . . . . . . Linwood, PA
Novak, John . . . . . . . . . . . . . . . . . LaRoche Chemicals, Inc. . . . . . . . . . . . . . . . Baton Rouge, LA
Novak, Kirk R. . . . . . . . . . . . . . . . . Tricat, Inc. . . . . . . . . . . . . . . . . . . . . . . Orange, CA
Novak, William J. . . . . . . . . . . . . . . . Acreon Catalysts . . . . . . . . . . . . . . . . . . . Houston, TX
Nozemack, Richard . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Numabe, Hiroshi . . . . . . . . . . . . . . . Cosmo Oil of U.S.A., Inc. . . . . . . . . . . . . . . Tokyo, Japan
Nunnelee, Don . . . . . . . . . . . . . . . . MAPCO PETROLEUM Inc. . . . . . . . . . . . . . Memphis, TN
O’Neill, Brenden . . . . . . . . . . . . . . . Koch Industries, Inc. . . . . . . . . . . . . . . . . . Corpus Christi, TX
Obluda, Gerard . . . . . . . . . . . . . . . . Mobil Oil Corporation . . . . . . . . . . . . . . . . Chalmette, LA
Ojeda, William . . . . . . . . . . . . . . . . Petroleos Del Peru S.A. . . . . . . . . . . . . . . . . Lima, Peru
Olesen, John A. . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Houston, TX
Olesky, Philip J. . . . . . . . . . . . . . . . . LaRoche Chemicals, Inc. . . . . . . . . . . . . . . . Baton Rouge, LA
Ollech, John . . . . . . . . . . . . . . . . . Buckman Laboratories, Inc. . . . . . . . . . . . . . . Memphis, TN
Olsen, Charles W. . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . . . . . . . . . Chicago, IL
Olson, Frank M. . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Houston, TX
Orr, Allan . . . . . . . . . . . . . . . . . . . Gulf Chemical & Metallurgical Corp. . . . . . . . . Freeport, TX
Osborn, Keith . . . . . . . . . . . . . . . . Farmland Industries, Inc. . . . . . . . . . . . . . . . Coffeyville, KS
Overshiner, Jody . . . . . . . . . . . . . . . Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Lake Charles, LA
Owen, Hartley . . . . . . . . . . . . . . . . Mobil Annuitant . . . . . . . . . . . . . . . . . . . Worton, MD
Oyekan, Soni . . . . . . . . . . . . . . . . . Sun Company, Inc. . . . . . . . . . . . . . . . . . . Marcus Hook, PA
Paggini, Alberto . . . . . . . . . . . . . . . . Snamprogetti S.p.A. . . . . . . . . . . . . . . . . . . Milan, Italy
Pair, Benson . . . . . . . . . . . . . . . . . . The M. W. Kellogg Company . . . . . . . . . . . . . Houston, TX
Paloumbis, Stephen . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Worms, Germany
Pannucci, Joseph A. . . . . . . . . . . . . . . Nalco Chemical Company . . . . . . . . . . . . . . Naperville, IL
Pantoja, Guillermo . . . . . . . . . . . . . . Petroleos Mexicanos . . . . . . . . . . . . . . . . . . Mexico City, Mexico
Paradis, Stephen . . . . . . . . . . . . . . . Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Parekh, Uday . . . . . . . . . . . . . . . . . Air Products and Chemicals, Inc. . . . . . . . . . . . Allentown, PA
Paris, Don . . . . . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . . . . . . Florham Park, NJ
Parker, James H. . . . . . . . . . . . . . . . Koch Industries/John Zink . . . . . . . . . . . . . . Tulsa, OK
Paspek, Steve . . . . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . . . . Cleveland, OH
Patel, Mabesh . . . . . . . . . . . . . . . . . Koch Refining Company . . . . . . . . . . . . . . . Corpus Christi, TX
Patel, Raj . . . . . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Patek Rasik . . . . . . . . . . . . . . . . . . Kinetics Technology Int’l Corp. . . . . . . . . . . . . San Dimas, CA
Patil, Bhagwan . . . . . . . . . . . . . . . . Hindustan Petroleum Corporation Ltd. . . . . . . . . Bombay, India
Patterson, Eliza . . . . . . . . . . . . . . . . Eurobusiness . . . . . . . . . . . . . . . . . . . . . London, UK
Patterson, Lewis . . . . . . . . . . . . . . . . ALCOA . . . . . . . . . . . . . . . . . . . . . . . . Pittsburgh, PA
Patton, Gary R . . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . . . . Bartlesville, OK
Paules, Jeffrey . . . . . . . . . . . . . . . . . Philbro Energy, USA, Inc. . . . . . . . . . . . . . . . Texas City, TX

282 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Pavel, Stephen . . . . . . . . . . . . . . . . Coastal Catalyst Technology, Inc. . . . Houston, TX
Pawelkowski, Stephen . . . . . . . . . . . . . Total Petroleum, Inc. . . . . . . . . . Alma, MI
Pawloski, John . . . . . . . . . . . . . . . . Terra Laboratories . . . . . . . . . . . Houston, TX
Pearce, John . . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . Houston, TX
Peccatiello, Kenneth . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . Houston, TX
Pedersen, Peter . . . . . . . . . . . . . . . . Haldor Topsoe, Inc. . . . . . . . . . . Houston, TX
Peer, Roger . . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . Des Plaines, IL
Pena, Joel . . . . . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . Houston, TX
Penman, Brian R. . . . . . . . . . . . . . . . Nalco Chemical Company . . . . . . Napa, CA
Pennels, Mark E. . . . . . . . . . . . . . . . Rocky Mountain Salvage & Equipment Golden, CO
Percy, Sam . . . . . . . . . . . . . . . . . . Today’s Refinery . . . . . . . . . . . . Chappaqua, NY
Perger, Jozsef . . . . . . . . . . . . . . . . . Hungarian Oil and Gas Co. . . . . . . Budapest, Hungary
Perkins, J. Douglas . . . . . . . . . . . . . . United Catalysts Inc. . . . . . . . . . Louisville, KY
Pesek, Chris . . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . Houston, TX
Peterman, Raymond . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . Chicago, IL
Petersen, John . . . . . . . . . . . . . . . . . ChemLink . . . . . . . . . . . . . . Corpus Christi, TX
Peters, Kenneth D. . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . Des Plaines, IL
Peterson, Mark . . . . . . . . . . . . . . . . Unocal Corporation . . . . . . . . . . Brea, CA
Petty, Randall . . . . . . . . . . . . . . . . . Texaco Reserach & Development . . . Port Arthur, TX
Pfile, Martyn E. . . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . Bartlesville, OK
Phansalkar, Sunil . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . Houston, TX
Piccari, Joseph . . . . . . . . . . . . . . . . Allied Signal Inc. . . . . . . . . . . . Morristown, NJ
Piekos, Frank . . . . . . . . . . . . . . . . . Nalco Chemical Company . . . . . . Sugar Land, TX
Pieper, Ronald . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . Houston, TX
Pierce, Eric R. . . . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . Reisterstown, MD
Pierce, Gerald K. . . . . . . . . . . . . . . . TPA, Inc. . . . . . . . . . . . . . . . Dallas, TX
Pinkerton, John . . . . . . . . . . . . . . . . Unipure Corporation . . . . . . . . . Houston, TX
Piper, Edwin M. . . . . . . . . . . . . . . . Stone & Webster Engineering Corp. . Denver, CO
Pitzer, Jeff . . . . . . . . . . . . . . . . . . . ARCO Products Company . . . . . . Carson, CA
Poddar, Syamal . . . . . . . . . . . . . . . . Bechtel Corporation . . . . . . . . . Houston, TX
Poffenbarger, Gary . . . . . . . . . . . . . . Conoco . . . . . . . . . . . . . . . . Houston, TX
Pogontcheff, Craig . . . . . . . . . . . . . . Imperial Oil Limited . . . . . . . . . Edmonton, Alberta
Poindexter, Jimmy . . . . . . . . . . . . . . Western Unichem . . . . . . . . . . . The Woodlands, TX
Pontiff, Steve D. . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . Houston, TX
Poon, Jim . . . . . . . . . . . . . . . . . . . Bechtel Corporation . . . . . . . . . San Francisco, CA
Porter, William J. . . . . . . . . . . . . . . . Chevron U.S.A. Products Company . Pascagoula, MS
Potscavage, William . . . . . . . . . . . . . . ChemLink . . . . . . . . . . . . . . Houston, TX
Potter, Frederick . . . . . . . . . . . . . . . Fuel Reformulation . . . . . . . . . . Arlington, VA
Powell, Joseph . . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . Houston, TX
Poynor, Paul . . . . . . . . . . . . . . . . . Conoco . . . . . . . . . . . . . . . . Ponca City, OK
Poythress, R. Paul . . . . . . . . . . . . . . . Betz process Chemicals, Inc. . . . . . The Woodlands, TX
Prahin, Lawrence . . . . . . . . . . . . . . . Nalco Chemical Company . . . . . . Sugar Land, TX
Prasad, A. M. . . . . . . . . . . . . . . . . . Centre for High Technology . . . . . New Delhi, India
Pratt, Roy . . . . . . . . . . . . . . . . . . . Texaco, Inc. . . . . . . . . . . . . . . Port Arthur, TX
Pritchett, Jerry . . . . . . . . . . . . . . . . Dow Chemical U.S.A. . . . . . . . . Houston, TX
Pritzel, Wayne . . . . . . . . . . . . . . . . . The UNO-VEN Company . . . . . . Lemont, IL
Prohaska, Eileen . . . . . . . . . . . . . . . STRATCO, INC. . . . . . . . . . . . Leawood, KS
Propst, James . . . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . Houston, TX
Puerto, Juan . . . . . . . . . . . . . . . . . . Stone & Webster . . . . . . . . . . . Houston, TX
Puschinsky, Bob . . . . . . . . . . . . . . . . AlliedSignal Inc. . . . . . . . . . . . . Seabrook, TX
Pusty, Thomas . . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . Chicago, IL
Quigley, Robert P. . . . . . . . . . . . . . . . Crosfield Catalysts . . . . . . . . . . Chicago, IL
Quinn, Douglas . . . . . . . . . . . . . . . . Shell Canada Limited . . . . . . . . . Edmonton, Alberta
Quinn, George P. . . . . . . . . . . . . . . . Amoco Oil Company . . . . . . . . . Chicago, IL
Ragsdale, Ralph . . . . . . . . . . . . . . . . Bechtel Corporation . . . . . . . . . Houston, TX
Rabeem, R. Abdul . . . . . . . . . . . . . . Madras Refineries Limited . . . . . . Madras, India
Rahlwes, William . . . . . . . . . . . . . . . Phillips Petroleum Company . . . . . Lake Jackson, TX
Rahmat, A. Hadi . . . . . . . . . . . . . . . Petronas Penapisan . . . . . . . . . . Melaka, Malaysia

1994 NPRA Q&A Session on Rejning and Petrochemical Technology 283

TOC/INDEX

NAME COMPANY LOCATION

Rajagopalan, Kuppuswamy R. . . . . . . . .
Ramachandran, Ram . . . . . . . . . . . . .
Rao,P.S. . . . . . . . . . . . . . . . . . . .
Rasmussen, Henrik . . . . . . . . . . . . . .
Ready, Ken . . . . . . . . . . . . . . . . . .
Reder, William . . . . . . . . . . . . . . . .
Reeves, Jerry L. . . . . . . . . . . . . . . . .
Reitz, Robert . . . . . . . . . . . . . . . . .
Remsen, Charles . . . . . . . . . . . . . . .
Resnick, Steve . . . . . . . . . . . . . . . . .
Rettenmaier, Albert C. . . . . . . . . . . . .
Reverdy, Francois . . . . . . . . . . . . . . .
Rhead, Richard . . . . . . . . . . . . . . . .
Rhodes, Anne . . . . . . . . . . . . . . . . .
Riedl, Joe . . . . . . . . . . . . . . . . . . .
Rieg, Edwin . . . . . . . . . . . . . . . . . .
Ries, Chris . . . . . . . . . . . . . . . . . .
Riggs, Lane . . . . . . . . . . . . . . . . . .
Rightmyer, Joseph A. . . . . . . . . . . . . .
Riley, Mark . . . . . . . . . . . . . . . . . .
Rios, Richard . . . . . . . . . . . . . . . . .
Roberts, C. David. . . . . . . . . . . . . . .
Robertson, Duane . . . . . . . . . . . . . .
Roddey, Bob . . . . . . . . . . . . . . . . .
Rodgers, James M. . . . . . . . . . . . . . .
Rogers, James A. . . . . . . . . . . . . . . .
Rojas, Edgardo . . . . . . . . . . . . . . . .
Rolandelli, Carlos . . . . . . . . . . . . . . .
Roman, John A. . . . . . . . . . . . . . . . .
Romero, Sim . . . . . . . . . . . . . . . . .
Ronnander, James . . . . . . . . . . . . . . .
Rosenthal, Joel W. . . . . . . . . . . . . . .
Rose, Ted . . . . . . . . . . . . . . . . . . .
Ross, Joseph . . . . . . . . . . . . . . . . . .
Rosso, J. P. . . . . . . . . . . . . . . . . . .
Roth, Jim . . . . . . . . . . . . . . . . . . .
Rowe, Alan . . . . . . . . . . . . . . . . . .
Rowe, Katherine . . . . . . . . . . . . . . .
Roy, Michel . . . . . . . . . . . . . . . . . .
Rudder, J. K. . . . . . . . . . . . . . . . . .
Ruiz, Oswaldo R. . . . . . . . . . . . . . . .
Rukovena, Frank . . . . . . . . . . . . . . .
Ruth, Ray . . . . . . . . . . . . . . . . . . .
Ryan, Charles . . . . . . . . . . . . . . . . .
Ryan, Joe . . . . . . . . . . . . . . . . . . .
Sachs, Michael . . . . . . . . . . . . . . . .
Sackett, P. S. . . . . . . . . . . . . . . . . .
Said, Hussain . . . . . . . . . . . . . . . . .
Sakaguchi, Takeo . . . . . . . . . . . . . . .
Salazar, Franklin G. . . . . . . . . . . . . . .
Salbilla, Dennis . . . . . . . . . . . . . . . .
Samaie, Lee . . . . . . . . . . . . . . . . . .
Sams, David A. . . . . . . . . . . . . . . . .
Sanchez, Maria Nilda . . . . . . . . . . . . .
Santamaria-Diaz, Saul . . . . . . . . . . . .
Santner, Chris . . . . . . . . . . . . . . . . .
Santos, Gerald E . . . . . . . . . . . . . . .
Santos, Jesse . . . . . . . . . . . . . . . . . .
Grace Davison . . . . . . . . . . . . . . . . . . . . Columbia, MD
The BOC Group . . . . . . . . . . . . . . . . . . . Murray Hill, NJ
Indian Oil Corporation Limited . . . . . . . . . . . Gujarat, India
Haldor Topsoe, Inc. . . . . . . . . . . . . . . . . . . Houston, TX
Coastal Mobile Refining Company . . . . . . . . . . Mobile, AL
Clark Refining & Marketing, Inc. . . . . . . . . . . Blue Island, IL
Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Betz Water Management Group . . . . . . . . . . . Trevose, PA
Bechtel Corporation . . . . . . . . . . . . . . . . . Houston, TX
Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Stafford, TX
The Pritchard Corporation . . . . . . . . . . . . . . Overland Park, KS
Packinox, S.A. . . . . . . . . . . . . . . . . . . . . . Baltimore, MD
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Oil & Gas Journal . . . . . . . . . . . . . . . . . . Houston, TX
Texaco Refining & Marketing Inc. . . . . . . . . . . El Dorado, KS
Koch Engineering Company, Inc. . . . . . . . . . . Wichita, KS
BOC Gases . . . . . . . . . . . . . . . . . . . . . . Murray Hill, NJ
Diamond Shamrock, Inc. . . . . . . . . . . . . . . . Sunray, TX
Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Sun Company, Inc. . . . . . . . . . . . . . . . . . . Oregon, OH
The Lubrizol Corporation . . . . . . . . . . . . . . Wickliffe, OH
Sun Company, Inc. . . . . . . . . . . . . . . . . . . Tulsa, OK
Roddey Engineering Services, Inc. . . . . . . . . . . Shreveport, LA
Catalyst Recovery of LA, Inc. . . . . . . . . . . . . . Houston, TX
Koch Engineering Company, Inc. . . . . . . . . . . . Wichita, KS
ENAP . . . . . . . . . . . . . . . . . . . . . . . . . New York, NY
Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Ashland Petroleum Company . . . . . . . . . . . . . Ashland, KY
BP Oil Company . . . . . . . . . . . . . . . . . . . Cleveland, OH
Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Nalco/Exxon Energy Chemicals Co. . . . . . . . . . Sugar Land, TX
Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Gemini Industries Inc. . . . . . . . . . . . . . . . . Santa Ana, CA
Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Ponca City, OK
Coastal Catalyst Technology, Inc. . . . . . . . . . . . Houston, TX
Norton Chemical Process Products . . . . . . . . . . Akron, OH
Petro-Canada Products . . . . . . . . . . . . . . . . Montreal, Quebec
Lion Oil Company . . . . . . . . . . . . . . . . . . El Dorado, AR
INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Cartagena, Colombia
Norton Chemical Process Products . . . . . . . . . . Akron, OH
Scaltech Inc. . . . . . . . . . . . . . . . . . . . . . Houston, TX
Chevron U.S.A. Products Company . . . . . . . . . Port Arthur, TX
CENEX . . . . . . . . . . . . . . . . . . . . . . . . Laurel, MT
Belgian Refining Corporation N .V. . . . . . . . . . . Antwerp, Belgium
Shell Chemical Company . . . . . . . . . . . . . . . Houston, TX
Kuwait National Petroleum Company . . . . . . . . Shuaiba, Kuwait
TOA Oil Company, Ltd. . . . . . . . . . . . . . . . Kanagawa, Japan
Engelhard Corporation . . . . . . . . . . . . . . . . Houston, TX
Akzo Catalysts . . . . . . . . . . . . . . . . . . . . Houston, TX
Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Grace Davison . . . . . . . . . . . . . . . . . . . . San Francisco, CA
CRI International Inc. . . . . . . . . . . . . . . . . Houston, TX
Ecopetrol . . . . . . . . . . . . . . . . . . . . . . . Bogota, Columbia
The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Corpus Christi, TX
Dow Chemical U.S.A. . . . . . . . . . . . . . . . . White Plains, NY

284 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Sappington, Jim Koch Industries, Inc. Wichita, KS
Sarli, Michael S. Mobil Research & Development Corp. Princeton, NJ
Sarubbi, Frank Huntsman Corporation Houston, TX
Sayles, Scott Sinclair Oil Corporation Tulsa, OK
Schaffer, Shannon Oxy-Fuel News Arlington, VA
Scharre, Mark D. Phillips Petroleum Company Bartlesville, OK
Schaub, Charles Crown Central Petroleum Corporation Houston, TX
Scheirer, Glen Exxon Research & Engineering Co Florham Park, NJ
Scherzer, Julius Unocal Corporation Brea, CA
Schilling, George Texaco, Inc. Houston, TX
Schimbor, R. E CRI International Inc Houston, TX
Schmidt, Mike R Akzo Nobel Houston, TX
Schmitz, Anthony Emtrol Corporation Hauppauge, NY
Schoemann, Alexander . . . . . . . . . . . . Nalco/Exxon Energy Chemicals Co. . . . . . . . . . Sugar Land, TX
Schoenbeck, Lynne E. . . . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Scholte, G. . . . . . . . . . . . . . . . . . Kuwait Petroleum Europort B.V. . . . . . . . . . . . Europort, Netherlands
Schowe, Edwin W. . . . . . . . . . . . . Nalco/Exxon Energy Chemicals Co. . . . . . . . . . Portage, IN
Schrepfer, M. W. . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Schroer, Anthon . . . . . . . . . . . . . . . Zeolyst International . . . . . . . . . . . . . . . . . Houston, TX
Schulman, Bernard L. . . . . . . . . . . . . . SFA Pacific, Inc. . . . . . . . . . . . . . . . . . . . . Englewood, CO
Schwandt, Scott. . . . . . . . . . . . . . . . Coastal Chemical Company, Inc. . . . . . . . . . . . Houston, TX
Scolari, Oscar . . . . . . . . . . . . . . . . SAIMSA . . . . . . . . . . . . . . . . . . . . . . . Mexico City, Mexico
Scott, Bradley J. . . . . . . . . . . . . . . . . Marathon Oil Company . . . . . . . . . . . . . . . Robinson, IL
Scott, Bruce . . . . . . . . . . . . . . . . . . Consultant . . . . . . . . . . . . . . . . . . . . . . San Rafael, CA
Scott, Charles . . . . . . . . . . . . . . . . . OXY USA, Inc. . . . . . . . . . . . . . . . . . . . . Tulsa, OK
Scotti, Louis . . . . . . . . . . . . . . . . . ABB Lummus Crest Inc. . . . . . . . . . . . . . . . Bloomfield, NJ
Scruggs, Darrell . . . . . . . . . . . . . . . Kinetics Technology Int’l Corp. . . . . . . . . . . . . San Dimas, CA
Scuorzo, Linda . . . . . . . . . . . . . . . . Exxon Research & Engineering Co. . . . . . . . . . . Florham Park, NJ
Seamans, James . . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . . . . . . The Woodlands, TX
Seek, Karl . . . . . . . . . . . . . . . . . . Clark Refining & Marketing, Inc. . . . . . . . . . . Hartford, IL
Seidel, Richard J. . . . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . . . . Houston, TX
Senez, Richard . . . . . . . . . . . . . . . . Shell Canada Limited . . . . . . . . . . . . . . . . . Ft. Saskatchewan, Alberta
Serdiuk, Fedor . . . . . . . . . . . . . . . . Petro Chemical Company . . . . . . . . . . . . . . . Angarsk, Russia
Shah, Laht S. . . . . . . . . . . . . . . . . . Texaco, Inc. . . . . . . . . . . . . . . . . . . . . . . Bellaire, TX
Shah, Pankaj P. . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Sharp, Curtis . . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Shaver, August . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Worms, Germany
Shearer, Bruce . . . . . . . . . . . . . . . . . Betz Industrial . . . . . . . . . . . . . . . . . . . . Baton Rouge, LA
Sheckler, John C. . . . . . . . . . . . . . . . UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Shields, Grant . . . . . . . . . . . . . . . KTI Chemicals, Inc. . . . . . . . . . . . . . . . . . San Dimas, CA
Shiflett, W. K. . . . . . . . . . . . . . . . . . Criterion Catalyst Company L.E . . . . . . . . . . . Edmonton, Alberta
Shoemaker, Larry W. . . . . . . . . . . . . . Phillips Petroleum Company . . . . . . . . . . . . . Bartlesville, OK
Shortt, Mark W. . . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Shufelt, Robert C. . . . . . . . . . . . . . . Sun Company, Inc. . . . . . . . . . . . . . . . . . . Philadelphia, PA
Sigan, Jack A. . . . . . . . . . . . . . . . . . INTERCAT, Inc. . . . . . . . . . . . . . . . . . . . Hoffman Estates, IL
Simmons, Frank . . . . . . . . . . . . . . . LaGloria Oil and Gas Company . . . . . . . . . . . Tyler, TX
Simonton, William . . . . . . . . . . . . . Petrolite Corporation . . . . . . . . . . . . . . . . . Houston, TX
Simpson, Jeremy . . . . . . . . . . . . . . . ChemLink-ChemServe . . . . . . . . . . . . . . . Chloorkop, South Africa
Singer, Roger . . . . . . . . . . . . . . . . . The Purolite Company . . . . . . . . . . . . . . . . Bala Cynwyd, PA
Sinnard, Judith . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Siravo, Michael . . . . . . . . . . . . . . . . Star Enterprise . . . . . . . . . . . . . . . . . . . . Delaware City, DE
Siwek, Janusz . . . . . . . . . . . . . . . . . Coastal Catalyst Technology, Inc. . . . . . . . . . . Houston, TX
Skeds, Jon . . . . . . . . . . . . . . . . . . . The Pro-Quip Corporation Tulsa, OK
Skripek, Milan . . . . . . . . . . . . . . . . Unocal Corporation Brea, CA
Slade, Cornell . . . . . . . . . . . . . . . . . Acreon Catalysts Houston, TX
Sleeman, Mark . . . . . . . . . . . . . . . . Reactor Services International Inc. Griffith, IN
Slemp, Brian . . . . . . . . . . . . . . . . . The UNO-VEN Company . Lemont, IL
Sloan, H. David . . . . . . . . . . . . . . . The M. W. Kellogg Company. Houston, TX

1994 NPRA Q&A Session on Refining and Petrochemical Technology 285

TOC/INDEX

NAME COMPANY LOCATION

Sloley, Andrew . . . . . . . . . . . . . . .
Smith, Arnold R. . . . . . . . . . . . . . .
Smith, Bill . . . . . . . . . . . . . . . . .
Smith, David L. . . . . . . . . . . . . . . .
Smith, G. Andrew . . . . . . . . . . . . .
Smith, George . . . . . . . . . . . . . . .
Smith, Gordon . . . . . . . . . . . . . . .
Smith, Mark . . . . . . . . . . . . . . . .
Smith, Norman F. . . . . . . . . . . . . . .
Smith, Scot K. . . . . . . . . . . . . . . .
Smith, Strom . . . . . . . . . . . . . . . .
Smyth, Sean. . . . . . . . . . . . . . . . .
Snedeker, Paul . . . . . . . . . . . . . . .
Snell, Kenneth . . . . . . . . . . . . . . .
Snyder, Michael . . . . . . . . . . . . . . .
Soanes, Victoria . . . . . . . . . . . . . . .
Soni, Dalip S. . . . . . . . . . . . . . . . .
Sopko, Thomas . . . . . . . . . . . . . . .
Soria, John . . . . . . . . . . . . . . . . .
Sourp, Thierry . . . . . . . . . . . . . . .
Spardel, Steven . . . . . . . . . . . . . . .
Spatz, David . . . . . . . . . . . . . . . . .
Speir, Robert . . . . . . . . . . . . . . . .
Spidle, Ted . . . . . . . . . . . . . . . . .
Spoerle, E Steven . . . . . . . . . . . . . .
Sprouse, Randall . . . . . . . . . . . . . .
Stamires, Dennis . . . . . . . . . . . . . .
Stanger, Charles W. . . . . . . . . . . . . .
Staub, Jennifer . . . . . . . . . . . . . . .
Stegelman, Albert . . . . . . . . . . . . . .
Steinsland, Olav . . . . . . . . . . . . . .
Stelly, Timothy . . . . . . . . . . . . . . .
Stephen, Dennis . . . . . . . . . . . . . .
Stephens, Gary . . . . . . . . . . . . . . .
Stergios, George . . . . . . . . . . . . . . .
Stewart, Sandra . . . . . . . . . . . . . . .
Stirling, Stann P. . . . . . . . . . . . . . .
Stockl, D.J . . . . . . . . . . . . . . . . . .
Street, David . . . . . . . . . . . . . . . .
Stringer, Phil . . . . . . . . . . . . . . . .
Stuart, Henry V. . . . . . . . . . . . . . .
Stull, Peter . . . . . . . . . . . . . . . . .
Suara, Felipe J. . . . . . . . . . . . . . . .
Subramaniam, Mahadevan . . . . . . . . .
Suchanek, Arthur J. . . . . . . . . . . . . .
Sugawa, Roy . . . . . . . . . . . . . . . .
Sukhon, Ahmad Saleh . . . . . . . . . . .
Summers, Steve . . . . . . . . . . . . . . .
Sumrok, Bradley . . . . . . . . . . . . . .
Sutley, John . . . . . . . . . . . . . . . . .
Svoboda, LaNell . . . . . . . . . . . . . .
Sweezey, Alan . . . . . . . . . . . . . . . .
Tacchi, Kenneth . . . . . . . . . . . . . .
Talbot, Louis A. . . . . . . . . . . . . . . .
Tanaka, Yuji . . . . . . . . . . . . . . . . .
Tang, Alice . . . . . . . . . . . . . . . . .
Tankiwala, Moiz . . . . . . . . . . . . . .
Tarantino, William . . . . . . . . . . . . .
Glitsch, Inc. . . . . . . . . . . . . . . . . . . . . . Dallas, TX
Fluor Daniel, Inc. . . . . . . . . . . . . . . . . . . Irvine, CA
Betz Water Management Group . . . . . . . . . . The Woodlands, TX
ALCOA . . . . . . . . . . . . . . . . . . . . . . . San Ramon, CA
INTERCAT, Inc. . . . . . . . . . . . . . . . . . . Missouri City, TX
Exxon Research & Engineering Co. . . . . . . . . . Florham Park, NJ
General Valve Company . . . . . . . . . . . . . . Brookshire, TX
CITGO Petroleum Corporation . . . . . . . . . . Lake Charles, LA
ChemLink . . . . . . . . . . . . . . . . . . . . . Houston, TX
Koch Industries/John Zink . . . . . . . . . . . . . Tulsa, OK
Advanced Petrogas Systems, Inc. . . . . . . . . . . Houston, TX
Mobil Oil Corporation . . . . . . . . . . . . . . . Torrance, CA
Coastal Refining & Marketing, Inc. . . . . . . . . . Corpus Christi, TX
Pennzoil Products Company . . . . . . . . . . . . Houston, TX
ChemLink . . . . . . . . . . . . . . . . . . . . . Santa Ana, CA
Coastal Chemical Company, Inc. . . . . . . . . . . Berlin, NJ
ABB Lummus Crest Inc. . . . . . . . . . . . . . . Houston, TX
Lubrizol Corporation . . . . . . . . . . . . . . . . Wickhffe, OH
Crown Central Petroleum Corporation . . . . . . . Houston, TX
Packinox, S.A. . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Glitsch, Inc. . . . . . . . . . . . . . . . . . . . . . Houston, TX
Chevron International Oil Co. . . . . . . . . . . . San Francisco, CA
U.S. Dept. of Energy . . . . . . . . . . . . . . . . Washington, DC
Middough Associates Inc. . . . . . . . . . . . . . . Cleveland, OH
Betz Water Management Group . . . . . . . . . . Trevose, PA
Chevron Research & Technology Co. . . . . . . . . Richmond, CA
Akzo Nobel . . . . . . . . . . . . . . . . . . . . . Los Angeles, CA
Akzo Nobel . . . . . . . . . . . . . . . . . . . . . Houston, TX
NPRA . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Phillips Petroleum - Retired . . . . . . . . . . . . . Borger, TX
Statoil A/S . . . . . . . . . . . . . . . . . . . . . Mongstad, Norway
Mobil Research & Development Corp. . . . . . . . Princeton, NJ
Conoco Inc. . . . . . . . . . . . . . . . . . . . . . Westlake, LA
IFP Enterprises Texas, Inc. . . . . . . . . . . . . . Houston, TX
Stone &Webster . . . . . . . . . . . . . . . . . . Milton Keynes, UK
Nalco/Exxon Energy Chemicals Co. . . . . . . . . Sugar Land, TX
Koch Engineering Company, Inc. . . . . . . . . . . Houston, TX
Mobil Oil Corporation . . . . . . . . . . . . . . . Joliet, IL
Huntsman Specialty Chemicals . . . . . . . . . . . Houston, TX
BOC Gases . . . . . . . . . . . . . . . . . . . . . Morden, UK
Grace Davison . . . . . . . . . . . . . . . . . . . Baltimore, MD
ARCO Products Company . . . . . . . . . . . . . Anaheim, CA
Merichem Company . . . . . . . . . . . . . . . . Houston, TX
Fluor Daniel, Inc. . . . . . . . . . . . . . . . . . . Sugar Land, TX
Criterion Catalyst Company L.P . . . . . . . . . . Houston, TX
ChemLink/BPCI . . . . . . . . . . . . . . . . . . Houston, TX
Jordan Petroleum Refinery . . . . . . . . . . . . . Amman, Jordan
Petrolire Corporation . . . . . . . . . . . . . . . . Houston, TX
Union Carbide Corporation . . . . . . . . . . . . Houston, TX
Nalco/Exxon Energy Chemicals Co. . . . . . . . . Sugar Land, TX
Glitsch, Inc. . . . . . . . . . . . . . . . . . . . . . Houston, TX
Engelhard Corporation . . . . . . . . . . . . . . . Houston, TX
ChemLink . . . . . . . . . . . . . . . . . . . . . Houston, TX
Total Petroleum, Inc. . . . . . . . . . . . . . . . . Alma, MI
Cosmo Oil of U.S.A., Inc. . . . . . . . . . . . . . New York, NY
Unocal Corporation . . . . . . . . . . . . . . . . . Brea, CA
Hindustan Petroleum Corporation Ltd. . . . . . . . Pradesh, India
ChemLink . . . . . . . . . . . . . . . . . . . . . Mt. Laurel, NJ

286 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Tarka, R. J. . . . . . . . . . . . . . . . . . .
Tavares, Marcos . . . . . . . . . . . . . . . .
Tchistov, Igor E . . . . . . . . . . . . . . . .
Tedesco, John . . . . . . . . . . . . . . . . .
Tenney, Edwin . . . . . . . . . . . . . . . .
Thaver, Nithianathan . . . . . . . . . . . . .
Theriault, Bert . . . . . . . . . . . . . . . .
Thiel, Phillip G. . . . . . . . . . . . . . . .
Thomas, Danny . . . . . . . . . . . . . . .
Thomas, Kenneth . . . . . . . . . . . . . . .
Thompson, Charles H. . . . . . . . . . . . .
Thompson, William M. . . . . . . . . . . .
Tinetti, Brian P. . . . . . . . . . . . . . . . .
Tippect, Tom . . . . . . . . . . . . . . . . .
Titone, Jasper . . . . . . . . . . . . . . . . .
Toberman, Richard . . . . . . . . . . . . . .
Tobin, Geoffrey . . . . . . . . . . . . . . . .
Tokerud, Pamela . . . . . . . . . . . . . . .
Tolen, Delbert . . . . . . . . . . . . . . . .
Tollefsen, Gerald . . . . . . . . . . . . . . .
Tong, Chung . . . . . . . . . . . . . . . . .
Torek, William . . . . . . . . . . . . . . . .
Tortorici, Francesco . . . . . . . . . . . . . .
Toyoda, Futoshi . . . . . . . . . . . . . . . .
Traylor, Richard . . . . . . . . . . . . . . . .
Treece, Mike . . . . . . . . . . . . . . . . .
Treese, Steven A. . . . . . . . . . . . . . . .
Trenga, Frank J. . . . . . . . . . . . . . . . .
Trent, Robert . . . . . . . . . . . . . . . . .
Trevino, Cesar . . . . . . . . . . . . . . . .
Treybig, Michael . . . . . . . . . . . . . . .
Tronchin, Amilton . . . . . . . . . . . . . .
Trout, Stanley . . . . . . . . . . . . . . . . .
Tryjankowski, Damian A. . . . . . . . . . . .
Tullock, Larry D. . . . . . . . . . . . . . . .
Tunnell, Duke . . . . . . . . . . . . . . . .
Turpin, Lee E. . . . . . . . . . . . . . . . . .
Udvari, Emery J. . . . . . . . . . . . . . . .
Ulmer, David . . . . . . . . . . . . . . . . .
Unzelman, George . . . . . . . . . . . . . .
Urbancic, Michael . . . . . . . . . . . . . .
Usher, Michael . . . . . . . . . . . . . . . .
Utley, Jeff K. . . . . . . . . . . . . . . . . .
Vadekar, MO . . . . . . . . . . . . . . . . .
Vadovic, Charles . . . . . . . . . . . . . . .
Valdes, Carlos . . . . . . . . . . . . . . . . .
Valentine, Julie . . . . . . . . . . . . . . . .
Van Der Steen, Arie . . . . . . . . . . . . . .
Vance, Paul . . . . . . . . . . . . . . . . . .
Vande Ven, John . . . . . . . . . . . . . . .
Varadi, Tom . . . . . . . . . . . . . . . . . .
Varghese, P. I. . . . . . . . . . . . . . . . . .
Varraveto, Dominic . . . . . . . . . . . . . .
Vasquez, David . . . . . . . . . . . . . . . .
Vauk, Dennis . . . . . . . . . . . . . . . . .
Vazquez, Ramiro G. . . . . . . . . . . . . . .
Veldman, Ray . . . . . . . . . . . . . . . . .
Vella, Phil . . . . . . . . . . . . . . . . . . .
Catalyst Recovery of LA, Inc. . . . . . . . . . . . . . Houston, TX
Fabrica Carioca De Catalisadores . . . . . . . . . . . Rio De Janeiro, Brazil
Institute Bash-Giproneftechim . . . . . . . . . . . . Ufa, Russia
Betz Water Management Group . . . . . . . . . . . The Woodlands, TX
GE Environmental Services, Inc. . . . . . . . . . . . Lebanon, PA
Mobil Oil Corporation . . . . . . . . . . . . . . . . Joliet, II
Catalyst Recovery Canada Ltd. . . . . . . . . . . . . Edmonton, Alberta
Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Ashland Petroleum Company . . . . . . . . . . . . . Ashland, KY
Hunt Refining Company . . . . . . . . . . . . . . . Tuscaloosa, AL
Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Commerce City, CO
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Petrolire Corporation . . . . . . . . . . . . . . . . . St. Louis, MO
Rollins Environmental Services, Inc. . . . . . . . . . Deer Park, TX
Foster Wheeler . . . . . . . . . . . . . . . . . . . . Reading, Be&s, UK
Koch Engineering Company, Inc. . . . . . . . . . . . Wichita, KS
Rocky Mountain Salvage & Equipment . . . . . . . Grand Junction, CO
Calumet Lubricants Company . . . . . . . . . . . . Princeton, LA
Litwin Engineers & Constructors . . . . . . . . . . . Houston, TX
Texaco Refining & Marketing Inc. . . . . . . . . . . Bakersfield, CA
Praoil Agip Petroli Group . . . . . . . . . . . . . . . . Priolo, Italy
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Sinclair Oil Corporation . . . . . . . . . . . . . . . Sinclair, WY
Petrolite Corporation . . . . . . . . . . . . . . . . . Baton Rouge, LA
Unocal Corporation . . . . . . . . . . . . . . . . . . Carson, CA
Elf Atochem North America, Inc. . . . . . . . . . . . Philadelphia, PA
United Catalyst - Zeochem . . . . . . . . . . . . . . Louisville, KY
Criterion Canalyst Company L.P. . . . . . . . . . . . Houston, TX
Shell Oil Company . . . . . . . . . . . . . . . . . . Houston, TX
Grace Dearborn . . . . . . . . . . . . . . . . . . . . Sao Paula, Brazil
Molycorp Inc. . . . . . . . . . . . . . . . . . . . . . White Plains, NY
Mobil Research & Development Corp. . . . . . . . . Princeton, NJ
Ashland Petroleum Company . . . . . . . . . . . . . Ashland, KY
TPA, Inc. . . . . . . . . . . . . . . . . . . . . . . . Dallas, TX
Honeywell Profimatics . . . . . . . . . . . . . . . . Thousand Oaks, CA
Grace Davison . . . . . . . . . . . . . . . . . . . . Denver, CO
Acreon Catalysts . . . . . . . . . . . . . . . . . . . Houston, TX
Fuel Reformulation . . . . . . . . . . . . . . . . . . Arlington, VA
United Catalysts Inc. . . . . . . . . . . . . . . . . . Louisville, KY
ElfAtochem North America, Inc. . . . . . . . . . . . Philadelphia, PA
Flying J Inc. . . . . . . . . . . . . . . . . . . . . . . North Salt Lake, UT
CHEMTECH Consulting . . . . . . . . . . . . . . Sarnia, Ontario
Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Pasadena, TX
PEMEX-IMP . . . . . . . . . . . . . . . . . . . . . Mexico City, Mexico
Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Boulder, CO
Fabrica Carioca De Catalisadores . . . . . . . . . . . Rio De Janeiro, Brazil
Acreon Catalysts . . . . . . . . . . . . . . . . . . . Houston, TX
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Metichem Company . . . . . . . . . . . . . . . . . Houston, TX
Abu Dhabi National Oil Company . . . . . . . . . . Ruwais, Abu Dhabi
The Pritchard Corporation . . . . . . . . . . . . . . Overland Park, KS
CITGO Refining & Chemicals . . . . . . . . . . . . Corpus Christi, TX
Unocal Process Technology . . . . . . . . . . . . . . Brea, CA
Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Coastal Chemical Company, Inc. . . . . . . . . . . . Houston, TX
Carus Chemical Company . . . . . . . . . . . . . . Ottawa, IL

1994 NPRA Q&A Session on Refining and Petrochemical Technology 287

TOC/INDEX

NAME COMPANY LOCATION

Venner, Ronald . . . . . . . . . . . . . . . .
Verachtert, Thomas A. . . . . . . . . . . . .
Verdin, Jose . . . . . . . . . . . . . . . . . .
Vergara, Jose . . . . . . . . . . . . . . . . .
Vickers, Anthony . . . . . . . . . . . . . . .
Victory, Randall . . . . . . . . . . . . . . . .
Villanueva, Ricardo . . . . . . . . . . . . . .
Villio, Robert C. . . . . . . . . . . . . . . .
Viscontini, Sal . . . . . . . . . . . . . . . .
Vogus, Charles . . . . . . . . . . . . . . . .
Wagner, David . . . . . . . . . . . . . . . .
Wagner, Paul . . . . . . . . . . . . . . . . .
Waldron, Terry R. . . . . . . . . . . . . . . .
Walker, Donald K. . . . . . . . . . . . . . .
Walker, Hugh B. . . . . . . . . . . . . . . .
Walker, John E. . . . . . . . . . . . . . . . .
Wallace, Carrie . . . . . . . . . . . . . . . .
Wallendorf, William H. . . . . . . . . . . . .
Walther, Greg . . . . . . . . . . . . . . . . .
Walther, Mike . . . . . . . . . . . . . . . . .
Ward, John W. . . . . . . . . . . . . . . . .
Ward, John W. . . . . . . . . . . . . . . . .
Wardle, Philip . . . . . . . . . . . . . . . . .
Waterfield, David N. . . . . . . . . . . . . .
Watson, David . . . . . . . . . . . . . . . .
Watters, Gordon . . . . . . . . . . . . . . .
Wear, Charles C. . . . . . . . . . . . . . . .
Weise, Mark . . . . . . . . . . . . . . . . .
Weiss, Ronald . . . . . . . . . . . . . . . . .
Welch, J. G. . . . . . . . . . . . . . . . . . .
Welker, Thomas . . . . . . . . . . . . . . . .
Wellmann, Edward E . . . . . . . . . . . . .
Wells, Jan W. . . . . . . . . . . . . . . . . .
Wen, C. J. . . . . . . . . . . . . . . . . . . .
Wenzel, Fritz W. . . . . . . . . . . . . . . .
West, Michael . . . . . . . . . . . . . . . . .
Whelchel, Paul . . . . . . . . . . . . . . . .
White, Brian . . . . . . . . . . . . . . . . .
Whitlock, C. W. . . . . . . . . . . . . . . .
Wbitson, Ray W. . . . . . . . . . . . . . . .
Wbittington, Lloyd K. . . . . . . . . . . . .
Wick, James P. . . . . . . . . . . . . . . . .
Wieliczko, Thomas B. . . . . . . . . . . . .
Wieser, Stephen L. . . . . . . . . . . . . . .
Wilburn, Randall . . . . . . . . . . . . . . .
Wilcox, Jack R. . . . . . . . . . . . . . . . .
Wildenberg, Wendy. . . . . . . . . . . . . .
Wilder, Brenette . . . . . . . . . . . . . . .
Williams, Billy . . . . . . . . . . . . . . . .
Williams, James E. . . . . . . . . . . . . . .
Williams, Rufus . . . . . . . . . . . . . . . .
Williams, Russell . . . . . . . . . . . . . . .
Williams, Stephen . . . . . . . . . . . . . .
Williamson, Joel . . . . . . . . . . . . . . .
Wilmer, Jeff. . . . . . . . . . . . . . . . . .
Wilson, Jerome . . . . . . . . . . . . . . . .
Wilson, Roy. . . . . . . . . . . . . . . . . .
Wilson, Troy . . . . . . . . . . . . . . . . .
ABB Lummus Crest Inc. . . . . . . . . . . . . . . . Bloomfield, NJ
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
Solomon Associates Inc. . . . . . . . . . . . . . . . . Dallas, TX
Petrox S.A. . . . . . . . . . . . . . . . . . . . . . . Talcahuano, Chile
UOP . . . . . . . . . . . . . . . . . . . . . . . . . Des Plaines, IL
ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Houston, TX
ENAP . . . . . . . . . . . . . . . . . . . . . . . . . New York, NY
BP Oil Company . . . . . . . . . . . . . . . . . . . Belle Chasse, LA
Mobil Research & Development Corp. . . . . . . . . Pennington, NJ
Pennzoil Products Company . . . . . . . . . . . . . Karns City, PA
STRATCO, INC. . . . . . . . . . . . . . . . . . . . Leawood, KS
Petrolite Corporation . . . . . . . . . . . . . . . . . Eddystone, PA
Mobil Oil Corporation . . . . . . . . . . . . . . . . Beaumont, TX
Petro-Canada Products . . . . . . . . . . . . . . . . Edmonton, Alberta
ALCOA . . . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Criterion Catalyst Company L.P. . . . . . . . . . . . Azusa, CA
ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Coastal Refining & Marketing, Inc. . . . . . . . . . . Corpus Christi, TX
Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Unocal Corporation . . . . . . . . . . . . . . . . . . Brea, CA
Haldor Topsoe, Inc. . . . . . . . . . . . . . . . . . . Houston, TX
Grace Dearborn . . . . . . . . . . . . . . . . . . . . Cheshire, UK
BP Oil Company . . . . . . . . . . . . . . . . . . . Sunbury-on-Thames, UK
Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Grace Davison . . . . . . . . . . . . . . . . . . . . Baltimore, MD
BOC Gases . . . . . . . . . . . . . . . . . . . . . . Murray Hill, NJ
Mobil Research & Development Corp. . . . . . . . . Princeton, NJ
CRI International Inc. . . . . . . . . . . . . . . . . Houston, TX
Welker Engineering Company . . . . . . . . . . . . Sugar Land, TX
ICI Tracerco . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Phillips 66 Company . . . . . . . . . . . . . . . . . Bartlesville, OK
Shell Oil Company . . . . . . . . . . . . . . . . . . Houston, TX
VEBA OEL Technologie GmbH . . . . . . . . . . . Gelsenkirchen, Germany
Texaco Refining & Marketing Inc. . . . . . . . . . . El Dorado, KS
Stone & Webster Engineering Corp. . . . . . . . . . Houston, TX
Sunoco . . . . . . . . . . . . . . . . . . . . . . . . Sarnia, Canada
Betz Process Chemicals, Inc. . . . . . . . . . . . . . The Woodlands, TX
NPRA - Retired . . . . . . . . . . . . . . . . . . . . Arlington, VA
ChemCat Corporation . . . . . . . . . . . . . . . . Kenner, LA
Marathon Oil Company . . . . . . . . . . . . . . . Findlay, OH
Grace Davison . . . . . . . . . . . . . . . . . . . . Cherry Hill, NJ
Grace Davison . . . . . . . . . . . . . . . . . . . . Chicago, IL
Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Ponca City, OK
Refining Process Services, Inc. . . . . . . . . . . . . Pittsburgh, PA
Koch Refining Company . . . . . . . . . . . . . . . St. Paul, MN
STRATCO, INC. . . . . . . . . . . . . . . . . . . . Leawood, KS
Chevron U.S.A. Products Company . . . . . . . . . Richmond, CA
Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Praxair, Inc. . . . . . . . . . . . . . . . . . . . . . . Houston, TX
MAPCO PETROLEUM Inc. . . . . . . . . . . . . . Memphis, TN
Star Enterprise . . . . . . . . . . . . . . . . . . . . Delaware City, DE
Norton Chemical Process Products . . . . . . . . . . Akron, OH
Micro Motion, Inc. . . . . . . . . . . . . . . . . . . Beaumont, TX
Eurecat U.S. Incorporated . . . . . . . . . . . . . . Pasadena, TX
Betz Prochem Europe . . . . . . . . . . . . . . . . . Winsford, UK
Air Liquide America Corporation . . . . . . . . . . . Countryside, IL

288 Registration List

TOC/INDEX

NAME COMPANY LOCATION

Wiltrout, Carl S. . . . . . . . . . . . . . . . Phibro Energy USA, Inc. . . . . . . . . . . . . . . . Texas City, TX
Wimberly, Mark O. . . . . . . . . . . . . . . Union Carbide Corporation . . . . . . . . . . . . . Houston, TX
Windham, Michael . . . . . . . . . . . . . . Chevron U.S.A. Products Company . . . . . . . . . Pascagoula, MS
Windholz, Otto . . . . . . . . . . . . . . . . Serck Baker, Inc. . . . . . . . . . . . . . . . . . . . Houston, TX
Winkler, Steven . . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Iselin, NJ
Winslett, Dave . . . . . . . . . . . . . . . . Petrolice Corporation . . . . . . . . . . . . . . . . . St. Louis, MO
Winslow, Craig . . . . . . . . . . . . . . . . Grace Dearborn . . . . . . . . . . . . . . . . . . . . Lake Zurich, IL
Winslow, Phil . . . . . . . . . . . . . . . . . Chevron Research & Technology Co. . . . . . . . . . Richmond, CA
Wiseman, Steve . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Witoshkin, Anatol . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Iselin, NJ
Wizig, Herb . . . . . . . . . . . . . . . . . . Merichem Company . . . . . . . . . . . . . . . . . Houston, TX
Wohlschlegel, Eric . . . . . . . . . . . . . . NPRA . . . . . . . . . . . . . . . . . . . . . . . . . Washington, DC
Wolke, Mark . . . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Wood, Dave . . . . . . . . . . . . . . . . . CRI International Inc. . . . . . . . . . . . . . . . . Houston,TX
Woodland, Brent . . . . . . . . . . . . . . . Conoco Inc. . . . . . . . . . . . . . . . . . . . . . . Ponca City, OK
Woods, Robert P. . . . . . . . . . . . . . . . Criterion Catalyst Company L.P. . . . . . . . . . . . Houston, TX
Woodward, Debbie . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Wrench, Richard . . . . . . . . . . . . . . . The M. W. Kellogg Company. . . . . . . . . . . . . Houston, TX
Wright, Dave . . . . . . . . . . . . . . . . . ENGEN Refinery . . . . . . . . . . . . . . . . . . . Durban, South Africa
Wu, Kuang . . . . . . . . . . . . . . . . . . Glitsch, Inc. . . . . . . . . . . . . . . . . . . . . . . Dallas, TX
Yarnamoto, Kazuyoshi . . . . . . . . . . . . Showa Shell Sekiyu K.K. . . . . . . . . . . . . . . . Tokyo, Japan
Yanazume, Ei . . . . . . . . . . . . . . . . . Grace Davison . . . . . . . . . . . . . . . . . . . . Tokyo, Japan
Yefremov, Nikolai . . . . . . . . . . . . . . . ABB Lummus Crest Inc. . . . . . . . . . . . . . . . Bloomfield, NJ
Yepsen, Gary L. . . . . . . . . . . . . . . . . Engelhard Corporation . . . . . . . . . . . . . . . . Iselin, NJ
Ying, Lincoln . . . . . . . . . . . . . . . . . Elf Atochem North America, Inc. . . . . . . . . . . . Philadelphia, PA
Yoars, John P. . . . . . . . . . . . . . . . . . Lyondell-CITGO Refining Co. Ltd. . . . . . . . . . Houston, TX
Yoshida, Jiro . . . . . . . . . . . . . . . . . JGC (USA), Inc. . . . . . . . . . . . . . . . . . . . Houston, TX
Youngblood, Scott . . . . . . . . . . . . . . Elf Atochem North America, Inc. . . . . . . . . . . . Houston, TX
Youssef, Sam . . . . . . . . . . . . . . . . . ICI Katalco . . . . . . . . . . . . . . . . . . . . . . Oakbrook Terrace, IL
Yung, K. Y. . . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Zacher, Michael . . . . . . . . . . . . . . . . BP Oil Company . . . . . . . . . . . . . . . . . . . Cleveland, OH
Zagnoli, David . . . . . . . . . . . . . . . . Air Products and Chemicals, Inc. . . . . . . . . . . . Allentown, PA
Zahedani, Maryam . . . . . . . . . . . . . . Buckman Laboratories, Inc. . . . . . . . . . . . . . . Houston, TX
Zeillmann, Louie E. . . . . . . . . . . . . . . GAYLORD CHEMICAL . . . . . . . . . . . . . . Slidell, LA
Zelonis, Randy . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Edison, NJ
Zickefoose, Earl . . . . . . . . . . . . . . . . Scaltech Inc. . . . . . . . . . . . . . . . . . . . . . Houston, TX
Zoller, John . . . . . . . . . . . . . . . . . . Akzo Nobel . . . . . . . . . . . . . . . . . . . . . . Houston, TX
Zyskowski, Mark . . . . . . . . . . . . . . . Petrolite Industrial Chemicals . . . . . . . . . . . . . Mississauga, Ontario

1994 NPRA Q&A Session on Refining and Petrochemical Technology 289

TOC/INDEX

Notes
TOC/INDEX

Notes
TOC/INDEX

Notes