Technical
Paper
Solving Operational Problems in Cold
End Columns
Authors: P. Lucas, Global Technical Marketing
Manager, Petrochemical
YW Park, Technical Manager Asia
Introduction
Polymer fouling in olefin plant fractionation trains
can be a serious operating difficulty. In most
ethylene plants, the deethanizer and/or
depropanizer columns can become the primary
bottleneck for operating the plant at maximum
throughput and maximum service time.
Approximately 90% of all ethylene producers are
applying antifoulants to protect their distillation
equipment as a means to increase plant efficiency
and reliability. The untreated plants are typically
“front-end depropanizer” design with very low
bottoms temperatures or plants where “front-end
acetylene converters” have removed virtually all of
the diolefins from the fractionation train feedstocks.
Antifoulants are used by the ethylene industry
worldwide to control fractionation train column and
reboiler fouling. “Antifoulant” is a generic term for
formulation components that can include
antioxidants, antipolymerants and metal
deactivator. Polymerization inhibitors most often
provide the most effective solution to fouling.
Opportunities for antifoulant programs can be
found in most ethylene plants regardless of the type
of furnace feedstock. However, the specific
purification columns/reboilers affected and the
actual fouling potential is a direct function of the
feedstock being cracked.
When NGL’s are cracked, fouling occurs in
deethanizer and depropanizer systems.
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In general, while deethanizer column fouling is
minor, deethanizer reboiler runlengths (untreated)
can be very short (2-8 weeks). Almost all
depropanizers require treatment. Condensate
strippers may also exhibit polymer fouling.
When naphthas/gas oils are cracked, the overall
fouling potential in distillation columns/reboilers is
less than typically seen in NGL crackers.
Deethanizers generally are untreated due to
minimal fouling tendency. Depropanizers require
some form of antifoulant treatment because of high
butadiene concentration in the column bottoms,
which can form polybutadiene rubber. Debutanizers
may also require treatment if additional free
radicals are generated by heat in the column
bottoms.
While each ethylene producer may have their own
objectives and different set of benefits for a
fractionation train fouling control program, these
are the general needs expressed by ethylene
producers:
• Unplanned shutdowns or throughput restrictions
due to fouling are not acceptable.
• Antifoulant program effectiveness should be
verified today, tomorrow, regularly; then the
long-term unit goal could be reached with
confidence.
• Ethylene producers are pushing runlengths
between major turnarounds out to beyond six
years on average.
• Because of the ongoing pressure on ethylene
product margins, the cost for chemical
treatment should be no higher than what is
needed for current operating conditions, i.e., the
treatment program must be highly cost-
effective.
©2008, General Electric Company. All rights reserved.
TP1169EN.doc Sep-08
Fouling Mechanisms
The mechanisms that cause polymer fouling of
column trays, downcomers and reboilers are
peroxides, metals, and heat. These promote free
radical polymerization reactions of the feedstock
containing reactive materials such as 1,3 butadiene,
isoprene, propadiene, cyclopentadiene, etc. The
polymerization reactions are initiated by heat and
catalyzed by peroxide and metals such as iron.
A general free radical polymerization mechanism
consists of a sequence of three steps: initiation,
propagation, and termination.
Deethanizer Reboiler
In the initiation step, free radical formation is
generated by heat and/or metals coming from
impurities present in the cracked gas stream.
In the presence of oxygen, the initiator will rapidly
react to form peroxy radicals, which at elevated
temperatures will associate with the vinyl monomer
(diolefin) and generate larger free radical species.
In the absence of oxygen, the initiators form an
addition reaction with another monomer molecule
to form a new free radical. The process is repeated
hundreds of times and monomer molecules are
successively added to the propagating chain, which
continues growing the molecular weight of the
polymer. It will grow large enough to lay down on Depropanizer Reboiler
the equipment internals.
The fouling rate accelerates rapidly once solid
polymer forms on equipment surfaces. Newly
formed polymer acts as a seed for additional
branching/cross linking reactions. A reboiler
inspection is a valuable method to determine where
the polymer is forming. If thin, skin-type polymer is
found attached directly to process side tube
surfaces, polymer is being generated in the reboiler
itself. However, if moderate to large chunks of
polymer are found on the inlet tube sheet and
channel, polymer is forming on column trays,
breaking loose, and ultimately migrating into the
reboiler. Column fouling is the most severe case and
quickly necessitates antifoulant application.
Debutanizer Column

Page 2 Technical Paper

Column fouling may result in the following process
difficulties:
1. Restricts plant production rate.
2. Requires additional reboiler energy – Steam
flow increase.
3. Loss of desirable olefins in column bottoms
product.
4. Inadequate Separation, Temperature profile
changes.
5. Instrument Problems (Lead Plugging)
6. Requires unscheduled shutdown for cleaning of
column intervals.
7. Increased waste incineration cost.
Factors Influencing Fractionation Train
Fouling
The polymerization rate and fouling potential of any
fractionation train system proceeds via a free
radical mechanism and is directly related to the
following factors:
• Diolefin Concentration - The fouling rate of the
fractionation columns increases when the
diolefin concentration in columns bottoms
increases. It can be measured by running a
Maleic Anhydride Value analysis (MAV).
• Temperature/Residence Time - As temperature
and residence time increase, the fouling rate
tracks more along a logarithmic path than a
linear function. The temperature also has a
direct bearing on the rate of free radical
formation and inhibitor consumption.
• Oxygen Content - Contamination of the
feedstock with oxygen will result in peroxide
formation which further increases fouling rate
when heated.
• Iron - Transition metals, iron and copper, also
catalyze polymerization. Iron catalyzes the
decomposition of peroxides into peroxy radicals
and can increase the rate of Diels - Alder
reactions that generate initiators.
• Inhibitor System Employed - Polymer formation
is also a function of the rate at which
propagating free radicals can be terminated.
This is why inhibitors are used. If effective, they
can reduce or virtually eliminate polymer
formation depending upon their own reaction
kinetics.
Technical Paper
The inhibitor applied must control peroxide
formation and be reactive with peroxy, heat and
metal catalyzed free radicals.
Inhibitor Components
Proprietary blends of fractionation train antifoulants
can contain one or more ingredients. The active
ingredients are usually preblended into an easy to
handle liquid product using aromatic solvents as
the diluent. Active ingredients and the solvents are
non-volatile at fractionation train operating
conditions and will move through the system to
debutanizer bottoms.
• Antioxidants - Control peroxide formation and
terminate peroxy radicals formed during
peroxide decomposition
• Antipolymerants - Control heat induced alkyl (or
carbon) free radicals hydrogen donation
• Metal Deactivators - Control iron catalyzed free
radical polymerization and iron catalyzed
peroxide decomposition
Fouling Control
Major components of a fractionation train program
include an understanding of fouling and inhibitor
mechanisms with product formulations that
specifically address these mechanisms.
GE Water and Process Technologies has developed
a combination of newly patented plus proven
technologies (OptiFrac) designed to improve
ethylene producers’ profitability and reliability.
These products are blends of free radical inhibitors,
new GE patented anti-oxidant and metal
deactivator (optional). OptiFrac reacts very
efficiently with peroxy (anti-oxidants) and alkyl
radicals (antipolymerants) to control fractionation
train fouling.
The GE technologies provide significant benefits
such as:
• Inhibit free radical polymerization – Control
fouling
• Decrease production losses - Extend tower and
reboiler runlengths
• Reduce pressure drop constraints
• Increase efficiency of heat transfer equipment
and other process equipment
Page 3
• Lower operating and maintenance costs due to The effectiveness of individual inhibitors, as well as
less frequent equipment cleaning and improved inhibitor blends, can be determined over a broad
process efficiency temperature range using this test. This allows for
• Reduce Disposal cost – Less exposure to program optimization by identifying the most
carcinogenic chemicals found in deposits cost/effective inhibitor for each temperature region.
• Improve profitability by using the most cost
effective treatment program
• Improve Reliability HEAT INDUCED GUMS
100 °C, 10ppm additive, 4 hours
These technologies were developed as a result of
research testing using the heat induced gum
method. The heat induced gum test is utilized to 160

evaluate and develop these inhibitor products for 140

m g P olym er / 100 m l
fractionation train fouling control. This is a static 120

test where a high concentration of a diolefin is 100

80
polymerized under an inert gas pressure. Oxygen is
60
excluded from the sample as it is polymerized. Heat
40
alone at 100 - 120°C is used to generate radicals
20
and test inhibitor efficacy. The test is conducted in
0
a stainless steel reactor, which is constantly stirred Blank Inhib. 1 Inhib. 2 Inhib. 3 Inhib. 4
to avoid hot spots. The amount of polymer formed
during 4 hours is measured to evaluate the best
product compared to a blank. The inhibitor that
results in the lowest amount of polymer formed
BOMB OXYDATION TEST
during the period of heating is the best product for
a specific temperature region. This test closely Effectiveness of the New Antioxidant vs Others
simulates the polymer formed in distillation
columns. Induction Period Test 20% Isoprene / 80% Heptane @ 100 °C under 7 bar oxygen
180
167
160
Ind uct ion Per iod ( Minut es)

140 130
118
120 113
104
100 87 84
76 77
80
61
60 55
35
40
21 25
20

0
1

)
k

AO
2

2
8

:2
7

)
3

6
5

1
an

:3
4
Ao

AO
AO

:1
AO
AO

AO

AO
AO

(1
AO

(1
Bl

/A

7/
Ne

3
AO

AO

AO

AO
w

4/

2/
Ne

AO

O
/A
AO
w
Ne

Complementary to the supply of the inhibitors, GE

Water & Process Technologies has developed other
accurate and timely tools to monitor, optimize and
determine the most cost effective treatment
program. Free residual testing on the bottom of
each column, pretreatment/passivation techniques
for both column/reboilers and the Multiple
Regression Analysis software MRA/SPC are
commonly used to achieve these objectives.

Page 4 Technical Paper

In-Plant Free Residual Analyses
The purpose of these tests is to determine the “free”
or unreacted treatment residuals in fractionation
train bottoms samples. By analyzing and
measuring the unreacted residual of the
antioxidant and antipolymerant in the plant
samples, we can determine the consumption of the
chemicals in the system and optimize feedrates to
minimize fouling or to optimize treatment costs.
These analyses can be performed on samples of
deethanizer, condensate stripper, depropanizer and
debutanizer bottoms samples, although the typical
target free residual is based on the depropanizer
bottoms fluid. Two methods are available to
determine the unconsumed or unreacted free
residuals in the plant - spectrophotometric and gas
chromatography.
Analyzing fractionation train bottoms samples for
free residual antioxidant and antipolymerant is an
integral part of administering the most
cost/effective fractionation train program. The
main benefit is meaningful residual measurements
that can determine program efficacy and enable
treatment optimization to match goals and needs.
The guesswork in dosing the system daily is virtually
eliminated when inhibitor-free residuals are
measured.
During its technical assistance, the GE sales
representative can analyze for free residual
antioxidant/antipolymerant in the field using the
spectrophotometric methods and provide guidance
and recommendation in real time to optimize the
program.
It can also be determined using gas chromoto-
graphy technology. This test procedure is
preferably run at the customer’s plant by the
customer’s analytical department. Both inhibitor
component free residuals (antioxidant and alkyl free
radical scavenger) can be determined with one GC
injection of the sample. GCs with nitrogen
phosphorous detectors (NPD) are employed. Before
a customer can be given a copy of the test
procedures utilizing GC technology, they will sign a
confidential information agreement with GE Water
& Process Technologies to receive these test
procedures.
Technical Paper
Pretreatment/Passivation
During major olefin plant turnarounds, the
fractionation train columns and reboilers are
normally cleaned of old polymer formed during the
previous run. It is recommended that the newly
cleaned columns and reboilers be pretreated or
passivated before the start of the next run of the
plant. A good passivation of the columns/reboilers
coupled with an effective antipolymerant program
will assure the success of meeting the desired plant
runtime. During the run, reboiler passivation of
cleaned reboilers will extend runtime when placed
back into service.
The recommended passivation program effectively
addresses several critical issues. First, passivation
reduces the rate of polymerization at start-up by
effectively retarding seed growth and scavenging
oxygen/peroxides. Another component of the
passivation program forms a protective film on
freshly cleaned metal surfaces. This minimizes iron-
catalyzed polymerization.
The GE passivation technique allows significantly
extended equipment runlength.
MRA/SPC
Depropanizer column pressure drop and reboiler
steam chest pressure may swing or fluctuate
independently of process side fouling. Changes in
column charge rate, reflux rate, feed composition,
etc. will influence column delta P, reboiler heat duty
and steam chest pressure. Therefore, to develop a
true fouling trend, MRA should be used to model
these important operating conditions.
The MRA program is a statistical method used to
determine whenever one set of data has any
relationship or correlation to another set of data.
This program is a tool for both diagnosis and
control and has been designed to determine a
mathematical function likely to describe, with a
good correlation, the progress of a parameter in
time according to other parameters it is
subordinated to.
The "M.R.A." program allows us to:
• Normalise the behaviour of a given variable
(dependant variable) by using numerous other
variables (independent variables)
Page 5
• Predict process behaviours
• Analyse impact of process changes
• Generate control charts
• Identify key process variables
When modelling column delta P or steam chest
pressure, independent variables that can be used
include column charge, reflux and bottom flow,
temperature of column feed and bottom, overhead
and bottom pressure, column liquid level, etc.
Actual
220
Condensate Temp. °F
polymerization induced with heat, metals and
peroxides of the unsaturated hydrocarbons such as
butadiene, isoprene, and pentadiene. GE
Passivation/Pretreatment techniques were also
applied on column & reboilers to help increase the
runlength. A GE passivator, Petroflo 24Y617, and
the antioxidant/antipolymerant Petroflo 24Y618 are
currently used during each plant shutdown.
In order to optimize the program, active residual
analysis on bottom columns for each component of
the product were measured to fine tune/optimize
the dosage and minimize the product addition to
Model Normalized the system.
The active free residual analysis coupled with

210
200
existent gums determination helps GE to determine
190
180 the impact of feedstock contaminants such as
170 methanol, acetone and others on polymerization
160 rate and inhibitor requirement. During the first year
150
of the treatment, Petroflo 20Y697 was injected with
0 20 40 60 80 100 120 140
Days good results: reboiler runlengths went from 6 to 7
months. Due to the change in feedstock quality and
presence of contaminants, the program moved to
Petroflo 20Y698, a technology more concentrated in
Normalized Corrected LCL UCL peroxy-free radical inhibitor to prevent the bad
220 impact of contaminants/peroxides. Free residual
measurement was also applied on a regular basis in
Condensate Temp. °F

210
200 order to optimize the program.
190
180
170
160
Naphtachimie ethylene plant
150
0 50 100 150 120
Days 100
Residuals (ppm)

80
60
40
20
0

Case Studies & Applications Dec-99 Apr-01 Sep-02 Jan-04

Date
May-05 Oct-06 Feb-08

B residual D residual Product dosage

Case Study #1: Petroflo 20Y698 and Free Residual
Analysis Help Fractionation Train Runlengths
Improvement
Naphtachimie ethylene plant
Naphtachimie, a 740Kton French naphta cracker
owned by TOTAL Petrochemicals and INEOS was
Existent Gums Deprop.

10
bottom (mg/100ml)

9
treated by competitive alternatives to GE Water & 8
7
Process Technologies, when GE started an 6
5
4
antifouling program to increase deethanizer and 3
2
depropanizer reboilers runlength but also achieve 1
0
the best cost effective treatment program. Sep-02 Jan-04 May-05 Oct-06 Feb-08
Date
GE Water & Process Technologies selected first
Petroflo* 20Y697 to prevent free radical

Page 6 Technical Paper

After three months implementation, guidance of the After 16 months operation, the unit is still running
product injection was linked with the methanol with no presence of fouling and the nitrogen
concentration in the propylene finished product. content in the feed to C4/C5 reactor has been
Runlengths were increased from 6 to 13 months on significantly reduced involving reactor runlength
deethanizer, and from 6 to 10 months on increase.
depropanizer.
This is another good example where GE completed
This application, which has been running the customer objectives by diagnosing; monitoring
successfully for 10 years, is a good example of and implementing the right technology.
success, results of combination of inhibitor,
passivation techniques, residual analysis and TVK2 Ethylene plant - Hungary
technical assistance. Reboiler T3161/2
10000

Case Study #2: GE Treatment Program on 9000

Reboiler Steam flow (Kg/h)

Deethanizer and Depropanizer Improves 8000

Reliability and Efficiency of the Plant 7000

An antifoulant GE treatment program has been 6000

used on the ethylene fractionation train of a Eastern 5000

ethylene plant for 4 years to prevent 4000

1 21 41 61 81 101 121 141 161 181 201 221 241 261 281 301 321 341 361
polymerization on the columns, reboilers and Date of run (15/05/06 to 10/06/07) - still running
maintain plant efficiency and reliability. The plant is Y Y Calc
processing low quality naphta, AGO with high
nitrogen content and LPG. Despite the treatment,
the plant experienced short runlength (1 to 6
TVK2 Ethylene plant - Hungary
months) on the deethanizer reboilers involving loss Reboiler T3161/2
in maintenance but also from time to time some 12000

nitrogen spike above the specification on the feed 10000

going to the C4/C5 hydrogenation reactor. Request
Reboiler Steam flow (Kg/h)

8000
from the plant was to improve runlength and
reduce the nitrogen content in the system. 6000

4000
After a complete diagnosis, GE suspected that the
high fouling was due to oxygen/peroxide 2000

contamination on the deethanizer and 0

depropanizer system. 1 21 41 61 81 101 121 141 161 181 201 221 241 261 281 301 321 341 361
Date of run (15/05/06 to 10/06/07) - still running

In order to improve both runlength of the

deethanizer and C4/C5 reactor, GE implemented
newly developed technologies with low nitrogen
content replacing the previous inhibitor program
and the volume of catalyst was increased. The new
program, combination of alkyl, peroxy free radicals
inhibitors and new GE patented anti-oxidant, was
initiated and implemented in 2006.
This technology is particularly suited to plants which
experience feedstock contamination with
oxygenates involving big decrease in runlength.
Case Study #3: GE Antifouling Program
Eliminated Debutanizer Fouling and Reduced
Treatment Cost by 50% at PTT Chem I4 in
Thailand
In August 2001, 6 months before the scheduled turn
around, PTT Chem I4 ethylene plant in Thailand
(former TOC) had to shut down the plant due to the
high pressure drop in the debutanizer.

GE Water & Process Technologies performs a The debutanizer was opened and severe fouling
technical assistance including the monitoring of the was observed at the upper trays although an
reboilers steam flow with the MRA/SPC. antifouling program had been used in the HP

[Figure 1]
Technical Paper Page 7
depropanizer and the LP depropanizer. The foulant was observed in the debutanizer (figure 3 & 4). The
was sheet-type rubbery polymers (figure 1). HP depropanizer was not opened.

Figure 1 Figure 3 - LP Depropanizer

GE Water & Process Technologies was invited to

review the existing antifouling program and
concluded the need of antioxidants and additional
injection point.
Petroflo 20Y698 and monitoring tools were
recommended and tried.
The trends of pressure drop, reboiler steam
consumption and 20Y98 residuals were monitored
and the Petroflo 20Y698 injection rate was
optimized based on this monitoring result. Figure 4 - Debutanizer

It was proved that GE Water & Process
Technologies chemical and monitoring tools were
effective by showing no fouling with 50% less
treatment cost in the debutanizer after 3 year
operation (figure 2).
Reboiler runlengths of HP & LP depropanizers are
more than 1,000 days and those of debutanizers
are more than 650 days.

Figure 2

The HP and the LP depropanizers were not opened

this time.
The GE treatment program continued and the LP
depropanizer (5 year operation) and the
debutanizer (2 year operation) were opened in
February 2007. Only a small amount of polymer
was found at the bottom of the LP depropanizer,
which was easily removed by hand, and no fouling

Page 8 Technical Paper