Mitigating fouling in the caustic tower
Comprehensive analysis of foulants in an ethylene plant’s caustic tower led
to the identification of an effective treatment programme
HUA MO and DAVID DIXON Baker Hughes
LOWELL SYKES Westlake Vinyls
A
n ethylene plant experi-
enced severe fouling in
its caustic tower. The
degraded performance of the
caustic tower threatened ethyl-
ene production. The
progression of fouling in the
caustic tower indicated that the
treatment programme at that
time could not control the
fouling.
To reduce caustic system
fouling and extend unit run
length, extensive testing was
conducted to identify all foul-
ing mechanisms prior to
initiation of a new treatment
programme. Identification of
fouling mechanisms provides a
clear understanding of the root
causes of fouling. It also helps
to identify the right chemistries
to apply for a successful treat-
ment programme.
The Baker Hughes treatment
programme, based on the iden-
tified fouling mechanisms,
improved the performance of
the caustic tower. System
degradation dramatically
slowed and the run length was
extended. This article reviews
the ways to identify fouling
mechanisms and the impact of
modifying a treatment
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Quench
water
Weak caustic circulation
Cracked gas
from amine unit or
primary compression
Figure 1 The ethylene plant’s caustic tower
programme based upon the
identified fouling mechanisms.
Description of unit
The caustic tower in the ethyl-
ene plant is used to remove
acid gases from cracked gas. A
general flow diagram of the
caustic tower is shown in
Figure 1.
There are typically four
sections in a caustic tower:
weak section, intermediate
section, strong section and
water wash section. The caustic
solutions are circulated in the
Cracked gas to
secondary compression
WW make-up
WW circulation
WW blowdown
Fresh caustic make-up
Strong caustic circulation
Intermediate circulation
Liquid HC
Spent caustic
coalescer
To spent caustic treatment
strong and weak sections.
Boiler feed water is circulated
in the water wash section, and
the cracked gas from the
compressor feeds into the caus-
tic tower weak section. When
the cracked gas contacts caustic
solution, the acid in the
cracked gas is removed by an
acid-base reaction. Some
hydrocarbons are also captured
by caustic solution at the same
time. After the acid removal,
the cracked gas leaves the
tower overhead and feeds the
next stage of compression.
PTQ Q4 2013 1
 O O
OH–
R1CH2CH R1CHCH + R2CH2CH
Figure 2 Aldol condensation
Fouling mechanisms
Polymeric hydrocarbon precur-
sors present in the caustic
solution can form various poly-
meric materials by different
reaction mechanisms. These
polymers can deposit and
agglomerate in the caustic
column, causing fouling,
reduced throughput and
decreased tower efficiency.
There are three major organic
fouling mechanisms: aldol
condensation polymerisation,
free-radical polymerisation
and Diels-Alder reaction
polymerisation.
Aldol condensation
The aldol condensation reac-
tion mechanism is shown in
Figure 2. As an anionic reac-
tion, it only occurs in the base
condition; the condensation
reaction initiates and propa-
gates in the circulating caustic
solution. The precursors for the
aldol condensation reaction
include various aldehydes,
ketones and unsaturated esters.
The two most commonly iden-
Chain initiation
1. R–H  R• + H•
2a. M++ + R–H  M+R• + H+
2b. M++ + R–O–O–H  M+R–O–O• + H+
Chain propagation
1. R• + O2  R–O–O•
2. R–O–O• + R’–H  R–O–O–H + R’•
3. R• + C=C  R–C–C•  Growing polymer
Figure 3 Free-radical polymerisation
2 PTQ Q4 2013
O OH
R2CH2CHCHCH
R1
tified aldol condensation
precursors identified in olefin
cracked gas streams are acetal-
dehyde and vinyl acetate.
Free-radical polymerisation
The free-radical reaction mecha-
nism is shown in Figure 3. The
presence of free-radical initia-
tors, such as peroxides, may
initiate the reaction. In addition,
monomers such as styrene will
readily self-initiate free-radical
polymerisation reactions at typi-
cal caustic tower operating
temperatures. The presence of
olefins, such as conjugated
olefin, styrene and indene,
provides the monomers for
chain propagation. The polymer
chain length will depend on
temperature, stability of the initi-
ator or monomer concentration.
Diels-Alder reaction
The mechanism of a Diels-Alder
reaction is shown in Figure 4.
Diels- Alder reactions are
self-initiated reactions and may
occur at low temperatures. The
precursors for Diels-Alder reac-
Chain termination
1. R• + R’•  R–R’
2. R• + R’–O–O• +  R’–O–O–R’
R• = Reactive polymer,
monomer or oligomer
M = Metal
O O
–H2O
R2CH2CH=CCH
R1
tions are conjugated dienes,
such as cyclopentadiene
derivatives.
Although many mechanisms
may co-exist in the caustic
tower, one or more reaction
mechanisms cannot signifi-
cantly contribute to the fouling.
Different caustic tower systems
will have different fouling
mechanisms. To ensure success-
ful treatment, each fouling
mechanism or combination of
fouling mechanisms must be
identified for each system.
Fouling control
Aldol inhibitor, free-radical
inhibitor and dispersant are
used to control the fouling.
Aldol inhibitor (Polyfree 305C)
The aldol inhibitor from Baker
Hughes is used to quickly
convert carbonyl in aldol to
another non-reactive functional
group. After the reaction, the
aldol condensation is
completely inhibited; there is
no side reaction of this
inhibitor.
Free-radical inhibitor
(Polyfree 300R1)
The active component in the
free- radical inhibitor reacts
Figure 4 Diels-Alder reaction
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with the free-radical, either
carbon or oxygen centred, in
the caustic tower. After the
free-radical reacts with the
free-radical inhibitor, free-radi-
cal polymerisation is inhibited.
Dispersant
Dispersant is used to disperse
foulants that could not be
inhibited by the aldol inhibitor
and free-radical inhibitor, such
as products of a Diels-Alder
reaction. Dispersant could
prevent foulant from
precipitation. The dispersed
foulant will be carried out of
the caustic tower by the spent
caustic system.
Identification of fouling
mechanism
Methodology
Fouling in the caustic tower is
influenced by two factors: the
accumulation of existing
foulant and the formation of
new foulant. The accumulation
of existing foulant can be eval-
uated and monitored with
filterable solids analysis and
soluble polymers analysis. The
potential to form new foulants
is influenced by many factors,
including reaction mechanisms,
fouling precursors, process
temperatures and initiators.
Although the existing foulant
was investigated, this article
will primarily focus on identi-
fying and controlling
foulant-forming reaction mech-
anism(s) to reduce and/or
eliminate the accumulation of
new foulant material.
Analytical results and discussion
Existing foulants
The following method is
widely used as an effective
caustic tower monitoring
programme. The test results
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Existing foulants
Filterable Soluble
solids, ppm polymer, ppm
Strong section 329 490
Weak section 1986 1895
Table 1
are shown in Table 1. Analysis
of the filterable solids is used
to measure the precipitated
foulants. The soluble polymer
analysis is used to measure the
total polymers in the caustic
tower. After the soluble poly-
mer agglomerates, it will
precipitate out of solution to
form filterable solids. The
particle size of filterable
solids can continue growing
until eventually it will stop
moving in the caustic system
and deposit in the pipeline and
exchanger, and foul the caustic
system. A high level of filtera-
ble solids and soluble polymer
indicated a high fouling rate in
the caustic tower system.
The existing foulants in this
unit were significantly higher
than those units that were
treated by Baker Hughes. The
results suggested that there is
room to improve with a treat-
ment programme.
Skim oil investigation
Condensed fouling precursors
are concentrated in the skim
oil. The concentration of these
fouling precursors influences
Functional group vs mechanism
Functional group Reaction mechanism
Carbonyl Aldol condensation
Conjugated vinyl Free-radical
monomer (styrene, polymerisation
butadiene, indene, etc) elemental analysis, spectros-
Cyclopentadiene Diels-Alder reaction
Table 2
the fouling rate. A high concen-
tration will increase the fouling
rate.
A skim oil sample was
collected from the caustic
tower. Visual examination
revealed that the sample was
very cloudy. There was an
organic layer on the top of the
sample. Spectroscopy and chro-
matography analytical results
showed that the organic layer
of skim oil contained a signifi-
cant amount of components
with aldol and vinyl functional
groups. The presence of aldol
and vinyl-type components
provides a significant amount
of precursors in both aldol
condensation and free-radical
polymerisation. This indicated
that aldol condensation and
free-radical polymerisation
were involved in the caustic
tower fouling. As a result,
free-radical polymerisation and
aldol condensation inhibitors
could be used to control foul-
ing. The results were confirmed
by the caustic tower reflux.
Deposit analysis
The skim oil analysis confirmed
that aldol condensation and
free-radical polymerisation
were involved in the fouling
reaction. To confirm the
hypothesis, a deposit was
collected from the caustic
tower. The fouling reaction
mechanism can be determined
by analysing the functional
group in the deposit. The rela-
tionship between the functional
group and reaction mechanism
is shown in Table 2.
Several instrumentation tech-
niques, such as weight loss,
copy and chromatography,
were used to identify the func-
tional group in the deposits.
PTQ Q4 2013 3

a 4.0
y = 0.0158x – 642.7
3.5
Caustic tower DP
3.0
2.5
2.0
22/1/12 1/2/12
b 10
y = 0.0076x – 305.68
Caustic tower DP
5 inhibitors, caustic reflux was
0 inhibitor is effective, the
2/5/12 10/7/12
Figure 5a Before treatment 5b After treatment
The results showed that more
than one reaction mechanism
had contributed to fouling in
the caustic tower. The majority
of the deposit was organic
components such as cyclopenta-
diene derivatives, styrene
derivatives, carbonyl deriva-
tives and other oxygenate
species. The cyclopentadiene
derivatives indicated the pres-
ence of a Diels-Alder reaction.
The styrene derivatives and
oxygenated species indicated
the presence of free-radical
polymerisation. The carbonyl
derivatives indicated the pres-
ence of aldol condensation.
Another effect of the deposit is
4 PTQ Q4 2013
Flow corrected DP
Linear (flow corrected DP)
21/2/12 12/3/12 1/4/12 11/4/12
Date
Flow corrected DP
Linear (flow corrected DP)
18/10/12 26/1/13 6/5/13 14/8/13
Date
that it could absorb some
monomers, such as styrene and
indene. The organic compo-
nent, which was absorbed in
the deposits, could contribute
Caustic sample reflux test results
Chemical Percentage
additives inhibition, %*
Blank n/a
Polyfree 300R1 additive 18.9
Polyfree 305C additive 27.9
Polyfree 300R1/
Polyfree 305C additive 81.5
*Percentage Inhibition (%)= [(Foulants with
additive) – (Foulant without additives)]/
Foulant without additives x 100
Table 3
to free-radical polymerisation
as the chain propagation
reagent.
Caustic reflux test
The stream and deposit analy-
ses indicated that both aldol
condensation and free-radical
polymerisation were involved
in the caustic fouling. Baker
Hughes’ Polyfree programme
was recommended, including a
free-radical inhibitor and aldol
condensation inhibitor to
inhibit the polymerisation reac-
tion. An additional Polyfree
dispersant was recommended
to remove the foulants formed
by other reactions, such as a
Diels-Alder reaction.
To test the efficiency of the
used. The samples from the
caustic tower were spiked with
antifoulants and refluxed. After
the reflux, the foulants that
formed were measured. If the
amount of foulant with inhibi-
tors will be lower than that
without any inhibitors. The test
results are shown in Table 3.
The reflux results showed
that both the Polyfree 300R1
and Polyfree 305C additives
could significantly decrease the
polymer formation. This
confirmed that free-radical
polymerisation and aldol
condensation contributed to
caustic tower fouling. The
combination of Polyfree 300R1
and Polyfree 305C additives
showed the best performance.
Treatment results
Based on the test results,
Polyfree 305C, Polyfree 300R1
and Polyfree 350C additives
were recommended to the
unit’s operators. The process
information in Figures 5a and
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5b shows the effect the new
chemical treatment programme
had on the unit.
The performance of the caus-
tic tower was measured by the
tower differential pressure (∆P).
∆P increased dramatically
before the treatment. The slope
was 0.0158. When the Baker
Hughes programme was
applied to substitute the previ-
ous treatment programme, the
tower’s ∆P did not climb signif-
icantly. The ∆P fouling rate was
0.0076, indicating about a 50%
fouling reduction. The field test
result showed that fouling was
successfully controlled in the
caustic tower. In addition, the
run length of the caustic tower
has been extended. It is still
performing well at the time of
writing. This successful treat-
ment indicated that the Baker
Hughes proprietary caustic
system analysis mode, which
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includes foulant analysis, a
caustic reflux test and skim oil
analysis, can be used to mini-
mise caustic tower fouling.
Conclusion
In this article, the fouling
mechanism of a caustic tower
was identified. The results
showed that free-radical
polymerisation and aldol
condensation were involved in
the caustic tower fouling.
Based on the analyses, a
successful chemical treatment
programme was recommended
to the customer. Field test data
indicated that the fouling was
controlled and the run length
of the tower was extended.
Acknowledgement
The authors wish to extend their
gratitude to the analytical group at Baker
Hughes Incorporated for their help in
providing the analysis work. We also wish
to express our appreciation to Westlake
unit personnel for their collaboration on
this project.
POLYFREE is a trademark of Baker Hughes
Incorporated.
Hua Mo is a Senior Chemist with Baker
Hughes. He holds a PhD in organic
chemistry from Rice University.
David Dixon is a Field Support
Technologist with Baker Hughes. He
holds a BS in toxicology from Northeast
Louisiana University.
Lowell Sykes is the Process Engineering
Supervisor for Westlake Vinyls Calvert
City, Kentucky, Ethylene Plant. He holds
a BS in chemical engineering from Purdue
University and an MBA from Murray
State University.
LINKS
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categories:
Corrosion/Fouling Control
Process Chemicals
Petrochemicals
PTQ Q4 2013 5