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Paper No.

01540
CORROSION 2001
Impact of Ammonium Chloride Salt Deposition on Refinery Operations

Philip R. Petersen, Ph.D., Arthur de Jong, William F. Minyard, and John L. Sigmon
Nalco/Exxon Energy Chemicals, L. P
P. O. Box 87
Sugar Land, TX 77487 - 0087

ABSTRACT

Fouling and consequent underdeposit corrosion caused by ammonium salts, especially ammonium
chloride, have serious impact on the reliability of operation of various process units. Fouling of tower
trays can result in the loss of throughput, changes in the vapor pressure and endpoints of product streams,
increased pressure drop in the tower, and corrosion of the trays. Salt deposition on heat exchanger tubes
causes a decrease in heat transfer efficiency, increased pressure drops, and corrosion. This paper will
discuss the causes of ammonium chloride fouling, methods to help prevent and/or mitigate the fouling,
and provide several case histories demonstrating the effects of using ammonium chloride dispersants to
clean existing ammonium chloride deposits and to help prevent deposition of this salt.

INTRODUCTION

Ammonium chloride salt deposition is a problem in many units when sufficient amounts of both
ammonia and hydrogen chloride are present. Solid ammonium chloride can deposit and collect on metal
surfaces and impede the flow of gases, liquids, and heat. Ammonium chloride can deposit in towers, on
distillation trays, in transfer lines, on heat exchanger surfaces, on pump strainers, etc. Wet solids and
aqueous solutions of ammonium chloride have pHs less than 5.0 and can be corrosive.

Ammonium chloride deposition is a phenomenon that occurs when the salt "precipitates" from a
vapor that contains both ammonia and hydrogen chloride. This deposition occurs when the product of the
molar partial pressures of the ammonia and hydrogen chloride is greater than the stability constant (Kd) of

Copyright
2001 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.
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the ammonium chloride at the temperature of the system. If the product of the partial pressures is lower,
or if the temperature is higher, the ammonia and hydrogen chloride will be thermodynamically more
stable than solid ammonium chloride salt and deposition would not occur (Figure 1).

The deposition of ammonium chloride is predicted from thermodynamics: If the energy of the
system is lower when the salt is not in the gas phase, the salt will form. As is usual with thermodynamic
calculations, there is no indication of how rapidly the reaction (phase change in this case) will occur. The
only legitimate calculations that can be done show that, given sufficient time, the salt will form. When the
salt first begins to condense out of the vapor phase, it will be in the form of individual molecules. Over
time, these molecules will aggregate into minuscule particles; these particles will eventually coalesce into
larger particles. During the first stages of salt agglomeration, the small salt particles will be carried along
with the hydrocarbon vapors. Being small, they will have little tendency to collect and form deposits.
Eventually the particles will become massive enough that they will no longer behave as Brownian
particles and can collect on surfaces. Corrosive solutions will form in the presence of water (Figure 2). If
there is only a short time for the base and acid to react, it is possible that salt might not deposit. Based on
experience, deposition is almost never as severe as predicted.

Source of Corrodents

Ammonia. There are several common sources of ammonia. Ammonia is still commonly used to
neutralize strong acids in the overheads of various distillation units. This ammonia can return to crude
units if the accumulator water is used as desalter wash water. If sour water condensate is used for desalter
wash water, the ammonia dissolved in the condensate will enter the crude tower after the basic sediment
and water (BS&W) water evaporates in the atmospheric furnace. Ammonia also can come into the unit
with the crude feed. In hydrotreaters and crackers, ammonia is formed from various nitrogen-containing
components in the feed.

Hydrogen Chloride . There are two common ways that hydrogen chloride can be formed in
various units. Calcium and magnesium chlorides that are left in the feed through inadequate desalting of
crude oil will form hydrogen chloride as these salts hydrolyze in the atmospheric and vacuum heat
exchangers and furnaces. The other common source of hydrogen chloride is the result of keeping
reformer catalysts active. Most reformer catalysts require a small, continuous dosage of an organic
chloride to maintain catalyst performance. Since this hydrogen chloride is always being stripped from the
catalyst, it must be continuously replaced. This hydrogen chloride can help form ammonium chloride not
only in the reformer unit but also in other units that use hydrogen from the reformer.

Impact of Salt Deposition on Operations

Ammonium chloride deposition causes a variety of problems. The economic penalties can be quite
large. These include costs related to off-spec products, reprocessing costs, and reduced feed rates. In cat
crackers, lower conversions and lower octane can also result. Corrosion caused by ammonium chloride
can result in scheduled or unscheduled equipment replacement and the consequent costs of a squat or
shutdown.

Plugl~ed Trays and Product Draws. As salt deposits accumulate, they can gradually plug the trays
in the cooler sections of towers of crude units, catalytic unit main fractionators, etc.. When this occurs, a
gradual increase in delta P across the top section will generally be observed. As the problem worsens,
flooding of the top trays will occur, evidenced by a rapid increase in delta P. Gamma ray scans of the top
section of the column can confirm the presence of flooding and verify the location of the problem.
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Salt deposits and associated corrosion products can cause partial or complete blockage of product
draws. Also, fouling of the top pumparound exchangers is commonly reported. This can limit the
pumparound rate and heat removal from the tower. Several refineries have reported difficulty in meeting
gasoline Reid Vapor Pressure (RVP) specifications due to fouling of some debutanizer reboiler
exchangers. Other refiners have reported difficulty in operating their stripper and C3/C4 splitter towers.

Increased Corrosion. Ammonium chloride salt deposits are hygroscopic and will absorb water at
temperatures above the calculated water dew point. Insufficient water washing or poor distribution of
water during water washing can leave damp salts on piping and exchanger surfaces. Localized water
condensation can occur due to cold top pumparound or reflux streams returning at temperatures below the
bulk water dew point temperature. The result can be very aggressive underdeposit corrosion of the tower
internals. The resulting corrosion products can add to the problem of plugged tray and product draws as
the corrosion products are dislodged by turbulence in the tower.

Loss of Fractionation. The increase in delta P resulting from salt deposition can have a negative
impact on fractionation efficiency. A symptom of tray fouling may be indicated by changes in the
distillation profiles of the product naphtha, kerosene, and jet fuel cuts.

An increase in tower pressure drop will also increase the de-superheating zone (flash zone)
pressure in the tower bottom. This then requires higher bottom temperature. Directionally, higher bottom
temperature will cause increased fouling in the main column bottoms wash circuit and increased furnace
fouling.

Prevention of Ammonium Chloride Deposition

Theoretically it is very easy to prevent the deposition of ammonium chloride: change the
operating parameters to move from somewhere above (to the right) of the temperature-dissociation
constant equilibrium curve to somewhere below (or to the left) of the curve. This could be accomplished
by lowering the product of the partial pressures of ammonia and hydrogen chloride by decreasing the
concentration of either or both of the specie - this will make Kd smaller, moving down on Figure 1. The
partial pressures of hydrogen chloride can usually be reduced with improved desalting.

Reducing the total pressure of the system will reduce the partial pressures of ammonia and
hydrogen chloride, shifting the system downward in Figure 1, reducing deposition potential.

Increasing the temperature of the system will move the calculated Kd to the left on the graph.
Some refiners have tried to drive the salts overhead by temporarily increasing the column overhead
temperature. The goal of this is to cause sublimation of the solid salt. This approach has been used with
limited, mixed success. Theoretically, the idea is sound because it can shift the system from deposition to
sublimation, moving from a region where solid ammonium chloride is the thermodynamically preferred
material to a region where ammonia and hydrogen chloride are the more stable materials. However,
thermodynamics only tells us that the phase change will occur, not when it will happen. If the salts are
covered with hydrocarbon or entrapped in corrosion products, etc., which they usually are, they cannot
equilibrate with the (hotter) vapor easily and so will sublime slowly.

The partial pressure of hydrogen chloride can be reduced by better desalting, using caustic after the
desalter, or more careful, controlled use of organic chlorides for catalyst regeneration. Ammonia can be
controlled by sour water striper operations or reducing the nitrogen concentration of the feed to various
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hydrotreater traits. Operating temperatures and pressures are set by the types of crudes processed, product
cut point temperatures, RVPs, etc.

Unfortunately, in reality, we cannot change operating conditions very much, if at all. Deviation
from the optimum operating conditions can have a significant impact on refinery profitability. For
example, some refineries calculate the ammonium chloride dew point temperature for their atmospheric
tower overhead system, and operate at a tower top temperature and pressure sufficient to keep corrosive
ammonium chloride salts from depositing in the tower. In one 250 kbpd crude unit, increasing the tower
top temperature by 5 ° C (10 ° F) during the prime distillate fuel season would cost the refinery $500,000 in
lost profits during the season.

Removal of Ammonium Chloride Deposits

Ammonium chloride salt deposits can be removed by physical or chemical methods.

Physical methods. The most common physical solution to deposition problems is to use a water
wash, simply dissolving the ammonium chloride in water. Although outwardly this appears to be an
extremely simple solution to the problem, care must be taken to help ensure that the system will work as
desired.

Two important considerations are the use of an adequate amount of water and the uniform
distribution of this water. If there is insufficient water, all of the water might flash, leaving none to
dissolve the ammonium chloride deposits. Worse is that the ammonium chloride deposits could become
damp. Corrosion will increase when there is an electrical conductive water film present because this will
complete the corrosion cell. The calculation of the amount of water needed to assure the presence of a
liquid water phase is complex but many simplifying assumptions can be made to get a good guesstimate of
the amount of water required. All of these calculations are based on thermodynamic equilibrium of the
system, which almost certainly does not occur. As a result of the lack of equilibrium, there should be
liquid water present even when less than the theoretical amount of water is injected.

If the water is not uniformly distributed, there will be some areas that will be thoroughly washed
and others that could receive little or no water, leaving ammonium chloride deposits, possibly damp
corrosive deposits, on the equipment walls. The use of multiple injection points, injection quills, or spray
nozzles all help to provide more uniform distribution of the water wash. The farther upstream of the area
where deposition occurs, or is predicted to occur, the more likely it is that the water will be uniformly
distributed.

Water washes can be used either continuously or intermittently. A continuous water wash is
preferred whenever it is possible, especially if the amount of ammonium chloride deposited is large. With
a good, continuous water wash, all the metal surfaces are covered by liquid water. This water layer not
only dissolves any depositing ammonium chloride but also dilutes any hydrochloric acid, or other acids,
that might be condensing in the system. A continuous water wash system requires an adequate amount of
water, a large enough pump, piping, etc., and good water removal facilities.

An intermittent water wash is used for various reasons, the most common being that some of the
above listed requirements cannot be met. One of the problems with an intermittent water wash is that it
generally will leave the metal surfaces wet for some amount of time after the water is turned off. This
surface will be prone to corrosion if more ammonium chloride deposits on it while it is still damp. Also, if
the deposition of ammonium chloride is not continuous, a continuous water wash is not required.
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The quality of the wash water should be as high as practical. Dissolved and suspended solids can
be a source of underdeposit corrosion if the wash water completely flashes and there is no liquid water
remaining to redissolve/resuspend the solids. Oxygen dissolved in the water will cause severe corrosion.
Vacuum accumulator water, stripped sour water, boiler feed water, etc. are common water sources. The
water used should be free of contaminants, and oxygen. In Table 1 typical wash water quality guidelines
are given.

Steam condensate or boiler feed water (BFW) is preferred. We do not recommend recirculating
part of the sour water drained from the water boot of hydrotreater product separators because of the high
hydrogen sulfide and ammonia content of this water. Besides containing solids that can damage pumps,
the sour water contains hydrogen sulfide that can cause corrosion.

If oxygen is present in the wash water, it can accelerate corrosion. This phenomenon has been
known to cause serious problems, especially in the atmospheric tower overhead system of the crude unit.
Oxygen can enter with the water in many ways. For example, incomplete deaeration of BFW, condensate
from vacuum ejectors, or packing leaks on the injection pump are but a few ways that oxygen can
contaminate the wash water.

The quantity of water needed to quench the process is a function of the temperature, pressure, and
water vapor partial pressure at the proposed injection point. The ability to handle this increased water
load is a problem that has been overlooked at times. For units running at or above design rates, the
accumulator probably will not have the required residence time to adequately separate the larger amount
of water from the hydrocarbon whether the water wash is continuous or intermittent. This results in
hydrocarbon in the water and consequent handling problems of the water stream. Equally troublesome is
the presence of entrained water, and the ammonium chloride and other materials that are dissolved in the
water, in the hydrocarbon stream. This water can be corrosive and, if it evaporates at some point during
subsequent processing of the hydrocarbon stream, it will deposit the dissolved solids, possibly causing
fouling or corrosion.

The proper design and layout of the water-injection nozzle is essential to minimize corrosion or
impingement near the injection point. The injected water and the process fluid must have an opportunity
to thoroughly mix before the water comes in contact with the piping walls. To do this, it is recommended
that the water injection be made through an extended nozzle so that the water enters the middle of the
flowing stream.

Chemical methods. Conventional (classic) acids are sources of hydrogen ions (H+; more correctly
H30+); bases are sources of hydroxide ions (OH'). When a conventional acid and base react, generally but
not always in the presence of liquid water, a salt will form; water will be formed as a product of the
reaction:

NaOH + HC1 --) NaC1 + H20 (1)

There are other definitions of acids and bases. The Lowry and Bronstead definition is that an acid
is a proton donor, the same as the conventional definition. However, they define a base as a proton
acceptor. The hydroxide ion is a proton acceptor. In the process of accepting a proton, the hydroxide ion
is neutralized and forms water:
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H+ + OH .--> I-/20 (2)

The most general definition of acid and base is the Lewis definition I. A Lewis base is an electron
pair donor; a Lewis acid is an electron pair acceptor. Again, hydroxide is a base because it can donate its
pair of electrons to a (Lewis) acid such as a proton that will accept the electron pair.

The Lewis base concept explains why ammonia and amines are bases: They have a lone pair of
electrons that can be used for bonding to other atoms. When the nitrogen donates ("gives away") its lone
pair of electrons, the nitrogen acquires a positive charge and whatever atom, molecule or positively
charged ion that receives the electron pair will become negatively charged or will be neutralized

H/N., '4" H
'"H H/N'
H J "'
H

/ N
#
n t ~ R , " ',, #
~ ,,, R~

The strength of acids vary from strong (essentially completely dissociated into H+ ions and the
corresponding negative ions), such as hydrochloric acid, to weak (only partially dissociated) such as
hydrofluoric acid and organic acids. Hydroxide formers also range from strong (sodium hydroxide) to
weak (iron and aluminum hydroxides).

If the salt of a strong acid and a weak base is reacted with a stronger base, the weaker base will be
displaced from the salt forming a new salt (the salt of the strong acid and stronger base) and liberating the
free, weaker base.

W B * H C 1 + SB -9, S B * H C I + WB (3)

Where: WB = weaker base

HC1 = hydrogen chloride
SB = stronger base
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Ammonium chloride is the salt of a strong acid (hydrogen chloride) and a weak base (ammonia).
If ammonium chloride is put into contact with a base that is stronger than ammonia, a reaction will occur
that displaces the ammonia from the salt, replacing it with the stronger base:

NH3*HC1 + SB --) SB*HC1 +NH3 (4)

(NH4CI is represented as NH3 * HC1 to show the resemblance between the ammonia and
neutralizing amine salts.)

If a weaker base is added to the salt of a stronger base, there is no reaction possible. The salt of the
stronger base remains unchanged.

There are many organic amines that are stronger bases than ammonia. Methoxypropylamine
(MOPA), ethylenediamine (EDA), and monoethanolamine (MEA) are only a few of the common amines
that can be used to remove ammonium chloride from equipment 2. One very important thought to bear in
mind when using this approach is that we are replacing one salt with another. Of the amines mentioned
above, MOPA and MEA have salts that are liquid at common operating conditions and so will not present
the solids fouling problems of ammonium chloride.

Another chemical way of removing ammonium chloride deposits is by using an ammonium

chloride dispersant. Dispersants can act in a variety of ways, from neutralizing charges on the surface of
the solid ammonium chloride to disrupting the crystal matrix to chemically displacing the ammonia from
the crystal matrix. We have tested a wide range of products for their efficacy in preventing and/or
removing ammonium chloride deposits. In the lab, precipitation of ammonium chloride in the presence of
a dispersant indicates the ability of the dispersant to prevent the formation of deposits. If finely dispersed
ammonium chloride is formed and then the dispersant is added to the suspension, a qualitative indication
of the ability of the dispersant to remove existing ammonium chloride is obtained. As shown in Figure 3,
some chemicals have great ability to prevent the deposition of ammonium chloride.

The ammonium chloride dispersants can be used in two ways: as a continuous prophylactic
treatment to prevent the deposition of ammonium chloride or, at higher treat rates to remove existing
deposits.

In cases where there is a chronic tendency to deposit salts, salt dispersant additives can be used on
a continuous basis to maintain clean conditions in the unit. When used in this manner, salts are removed
from the system as they form, before they can deposit. In a relative clean system, an additive dosage of 8
- 15 ppm is normally applied to keep salts from building up.

The larger amount of surface-active material injected into the column or vapor lines can cause
several short-term side effects. Because the dispersants are surface active, they can loosen all deposits,
such as iron sulfide, not just ammonium chloride. All of the loosened materials must go somewhere;
typically they move down the tower or into the accumulator. In either event, they bring a lot of garbage
into the streams that are treated. This can throw the streams off spec during the duration of the treatment.
Also, because these dispersants are usually used at the 10 - 500 ppm levels, they can have adverse effects
on the Water Solubility I n d e x - Modified (WSIM; ASTM D3948) of the streams that they are added to or
come in contact with, typically the kero and jet streams. Typically, these streams are run to tankage and
reprocessed when the deposits are removed and unit process parameters return to normal. These process
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parameters range from normalized delta P measurements, heat transfer measurements or recycle gas
flowrates, etc

A chemical dispersant program can be implemented when a water wash system is not feasible due
to system design, the lack of available wash water, the wash water quality, or if the ammonium chloride
deposition point is upstream of the water wash injection point. Also, if the water wash injection point is a
location that is very hot (upstream of all exchangers) it may require large quantities of wash water. Large
quantities of wash water can negatively affect the heat exchange capacity of the feed/effluent exchangers.

CASE HISTORIES

Case History 1 - Atmospheric Unit

A refinery in the United States changed from running heavy crudes to a lighter slate in order to
make more gasoline. Simultaneous with this change in crude slate, they increased their throughput to
about 12% greater than nameplate capacity. Shortly after these changes, the refinery began experiencing
substantial pressure increase due to the fouling on the top six trays in the tower.

The customer was having problems because of increased overhead pressure, which adversely
affected their product specifications because the cut points of the products were changed. Also, because
of the fouling, they could not maintain the desired increase in throughput.

The foulant was determined to be primarily ammonium chloride based on samples collected from
the top pumparound pump strainer. We proposed the use of one of our ammonium chloride dispersant
products to remove the foulant. In pre-treatment planning meetings, the effect of the product on WSIM
was discussed and the customer decided to send the naphtha and jet streams to a storage tank while the
tower was being treated. The cost of blending the off spec product and the amount of storage available
were factors used in determining the number of days that our dispersant could be used

To optimize the program for this unit, it was decided to initially inject our chemical into the top
pumparound. After 12 hours of the chemical injection, additional chemical was injected into the reflux
return line. After the cleaning was completed, the tower pressures returned to normal.

To estimate when tower cleanings should take place, we and the customer developed a program
based on a variety of process parameters, including tower top pressure and changes in the pressure,
overhead rates, the concentration of ammonia and chloride in the accumulator water, etc. Using this
program allowed a proactive method of addressing the fouling problems and keeping the tower clean.
Rigorous exchanger heat transfer modeling can also be an extremely useful tool.

Every 4-6 months this refiner used the dispersant to reduce the fouling to acceptable levels. This
application was used for two years. During a subsequent turn around, some mechanical problems with the
trays were found and corrected and the chemical program was discontinued.

Case History 2 - Fluidized Catalytic Cracking Unit (FCCU)

A US refiner began having trouble operating the FCC at full capacity due to problems in the main
fractionator. Flooding was suspected as the root cause of the problem due to fouling and/or tray damage.
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Gamma scans were run to determine the location and, if possible, the cause of the flooding. The
main column was scanned from Tray 1 down to Tray 14. The scans indicated that the top two trays were
flooded, probably due to fouling (Figure 4). The refiner also had concerns about the integrity of the trays.

We implemented a chemical cleaning of the tower. A sample of foulant was collected from one of
the pump suction filters, and was analyzed as mostly ammonium chloride. A chemical cleaning procedure
was proposed and one of our ammonium chloride dispersants was recommended and delivered.

The ammonium chloride dispersant was added to the top reflux return to the tower. The chemical
addition was increased every eight hours for the first day, and maintained at a high dosage for three days.
During the washing, the light cycle oil (LCO) was sent to slops to avoid contamination of finished product
tanks.

Progress of the treatment was measured by sampling the LCO and washing the samples with water
and the conductivity of the water was then measured. Solids content of the LCO was measured and its
appearance noted. At the beginning of the cleaning procedure, the LCO was bright in color with no solids
present. During the first day, the conductivity increased dramatically, and dark red solids appeared. On
about the third day, the color of the solids changed to gray and green, and eventually the LCO began to
clear. The conductivity of the wash water decreased on the third day.

After three days, the inspection company gamma-scanned the upper section of the column again.
The scan revealed that all the trays were in place and holding adequate liquid levels (Figure 5).

Following the application of the chemical treatment, the operation of the FCCU returned to normal
at full operating rate. The operators were able to increase the reflux rate and to achieve better end point on
the heavy naphtha. Most importantly, the application of our salt dispersant avoided a costly shutdown of
the FCC unit to clean and inspect the tower.

Case History 3 - Hydrodesulfurization Unit (HDS)

A naphtha HDS unit experienced three corrosion failures in a time frame of six months on the effluent
side of the heat exchanger train. A water wash of 30 gpm was injected into the location shown in Figure 6,
just upstream of heat exchanger E. This bundle, about seven years old, failed. Exchangers E and F were
taken out of service, resulting in the configuration shown in Figure 7. A typical temperature profile is shown
also. During the time that the water wash was injected upstream of exchanger C at 30 gpm (location 1), the C
bundle failed within four months. The tubes were replaced, the water wash rate increased to 60 gpm, and the
C bundle failed again almost three months later.

The cause of the first failure of bundle in exchanger E is not known but, since the failed bundle was
about seven years old, the failure may have been a long time in coming and not totally unexpected.

A filming amine corrosion inhibitor and an ammonium chloride dispersant was being applied
upstream of location 1 (Figure 6). From the metallurgical analysis it was found that 60% of the internal
surface appeared to have had negligible corrosion. This was attributed to the f i l l e r and dispersant addition,
and/or iron sulfide protective deposits. The fact that all of the tube inner surfaces were not completely
protected is probably due to maldistribution of the inhibitor package

The leaks were attributed directly to accelerated galvanic corrosion, whose source was in the
fabrication of the electrical resistance welding (ERW) process. In the fabrication of heat exchanger tubes
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using ERW, the steel starts out as a flat sheet and is rolled through dies to form a complete circle. The tubing
is then welded by short-circuiting both ends of the sheet, creating a high heat zone. The fusing of the two
ends of the sheet can result in fusion line gaps, different metallurgy in the Heat Affected Zone (HAZ) and in
the welded area. It is good practice to post-weld heat treat after welding, so that these metallurgical
differences are removed.

Other areas of the tube had similar pitting, which was not centered on the ERW and eventually could
have caused failures. Chlorides were less than 0.5% in the internal deposit, suggesting that hydrochloric acid
and ammonium chlorides were not significant corrodents. However, during clean up, the chlorides being
more soluble than the sulfides, might have been washed out. Chlorides cannot be discounted as a corrodent.
Ammonium chlorides and hydrochloric acid would also cause corrosion at the operating temperatures and
pressures especially in the absence of enough free water.

After-the-fact calculations showed that about 60 gpm are required to help ensure the presence of water
in the liquid phase. The result of adding too little water was a decrease of the pH of the small amount of
residual water near the injection point, causing increased localized corrosion in the exchanger bundle and a
failure in under three months.

The water wash rate was increased to 60 gpm after the exchanger was replaced but the injection
facility was still a tee in the line. Because the tee does not provide good dispersion of the wash water, there
probably was localized channeling of the water, leaving parts of the exchanger relatively dry and susceptible
to ammonium chloride salt deposition and consequent under deposit corrosion. As the filmer and/or iron
sulfide protective deposits did not fully protect the internal surfaces either the action was to make use of an
injection quill to deliver the chemical into the process stream.

CONCLUSIONS

Fouling and corrosion caused by the deposition of ammonium chloride can be lessened and/or prevented
by both physical and chemical means. When properly applied, water washing has been shown to be a
very effective method to mitigate problems caused by ammonium chloride deposition. Lab and field data
have shown that ammonium chloride dispersants can effectively prevent the deposition of ammonium
chloride and also remove existing deposits of ammonium chloride if the dispersants reach the deposits.
This requires properly designed injection facilities and good distribution of the dispersants to allow them
to contact the deposits.

REFERENCES

1. Van Nostrand's Scientific Encyclopedia, Fifth Edition, D. M. Considine, ed. (New York: Van
Nostrand Reinhold Co., 1976), p. 23.

2. J. V. Quagliano, Chemistry, Second Edition (Englewood Cliffs, N. J.: Prentis-Hall, Inc., 1965), p. 480.

3. A. I. Vogel, A Text-book of Quantitative Inorganic Analysis Including Elementary Instrumental

Analysis (New York: John Wiley and Sons, Inc., 1951), p. 254.
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TABLE 1
WATER WASH QUALITY GUIDELINES

Chloride < 5 ppm

Iron < 2 ppm
Calcium < 0.5 p p m
Copper < 0.05 p p m
Total Dissolved Solids < 10 p p m
Total Hardness < 1
H y d r o g e n sulfide < 100 p p m
Ammonia < 100 p p m
Dissolved o x y g e n < 20 ppb
PH 7 - 9

c o n c e n t r a t i o n in partial NH= ÷ HCI

K d = [ N H 3] [ H C l ] pressure of each specie

P extremely small particle

very small particle

P
(< smoke size)
log K d
NH/
liquid water Cl" Cl"
i

I/T
Figure 1 - Salt deposition calculation. Figure 2 - Salt deposition.

PercentAmmoniumChlorideDispersed
Dispersant A
)0%

r5%

;0%

P.5%

0%
0 I0 20 30 40 50
Thne ( r ~ )

Figure 3 - A m m o n i u m chloride dispersancy

test results.
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-t----+ t00o 1~

I I
I I
I I

I I
I I
I I
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Figure 4 - G a m m a scan of fouled fractionator Figure 5 - G a m m a scan of fractionator three

showing flooding o f the top trays. days after the start o f the cleaning. Top trays
are holding normal liquid level.

479 ° F
Water wash - 30 gpm
498°F Waterwash- 30gpm
334 ° F 28~ F
571" F
1¢ 558°F 361oF 1

~.
,q,
,

7~ 13~F 39°F 256°~ 7"~D329°F

489°
402 ° F 312° F 216 ° F
j 138°F
indicates other wmer wmh injection points
421°F 266OF

Figure 6 - HDS feed/effluent exchanger train - Figure 7 - HDS feed/effluent exchanger train -
designed operation. temporary operation.