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CORROSION CONTROL

SPECIALREPORT

Reduce CO2 in acid gas

from amine-based TGTUs
Improve furnace temperature and sulfur recovery
B. SPOONER, Amine Experts, Kemah, Texas; and F. DERAKHSHAN,
Sulphur Experts, Calgary, Alberta, Canada

Effects of CO2 on the sulfur plant. Slip is maximized

through the TGTU to prevent CO2 from re-entering the sulfur

plant. There are several reasons why it is advantageous to minimize
CO2 in the SRU feed, the most important involving the reaction
furnace temperature, carbonyl sulfide (COS) and carbon disulfide
(CS2 ) formation, and sulfur plant capacity, as outlined below.
Reaction furnace temperature. CO2 does not burn in the
reaction furnace and will, therefore, lower the furnace temperature. This will have negative effects on ammonia and aromatic
destruction, which will, in turn, have consequences for the converter beds and the overall sulfur recovery.
Maintaining reaction furnace temperature is critical in sustaining smooth and trouble-free operation of a sulfur plant. When
processing sour water stripper gas, ammonia destruction is of
primary concern, and reaction furnace temperatures of 2,250F or
higher are required to avoid ammonia salt formation and plugging
of downstream process equipment.
When processing acid gases containing aromatic hydrocarbons, reaction furnace temperatures of 1,920F or higher are
required to properly combust the benzene, toluene and xylene
(BTX) components. Incomplete combustion of these compounds
can lead to poisoning of the downstream catalyst bed. Finally, to
maintain stable flame operation, a reaction furnace temperature
of 1,700F is required.
Although some cracking can occur in the reaction furnace,
CO2 is generally considered an inert compound, and it cools the

reaction furnace flame. As seen in Fig. 1, the dilution of an acid

gas stream with increasing amounts of CO2 results in a rapid
reduction of the reaction furnace temperature.
Fig. 1 shows that, for a simple acid gas containing varying
amounts of H2S and CO2 and 1% hydrocarbons, significant
problems with maintaining the required reaction furnace temperature start to occur at very low concentrations of CO2 in the amine
acid gas (AAG). With a CO2 content of less than 5% (based
on this example), it becomes difficult to maintain the required
reaction furnace temperature for good ammonia destruction.
At a CO2 content of 30%, a breakthrough of benzene, toluene,
ethylbenzene and xylenes (BTEX) could start to occur; and with a
CO2 content of over 50%, problems with maintaining a reaction
furnace flame become pronounced.
Although not necessarily detrimental to Claus plant operation,
higher CO2 content in the acid gas will require modifications to
the operation of the reaction furnace in order to achieve and maintain the required operating temperature. Sometimes, these modifications come at a high capital investment cost or at the detriment
of the overall efficiency. These items could include the addition of
air and feed gas preheaters, oxygen enrichment, split-flow reaction
furnace designs, installation of high intensity or other specialty
burners, co-firing with fuel gas or acid gas enrichment.
COS formation. Although the chemistry inside a reaction furnace is quite complex and chaotic, one certainty is that CO2 will
2,500
2,300

Thermodynamic temperature,F
Empirical temperature,F

2,100
Temperature, F

he purpose of an amine-based tail gas treating unit

(TGTU) is to recycle any leftover sulfur components in
the tail gas of a Claus sulfur recovery unit (SRU) to the
front end of the plant, rather than incinerate them. The remaining
sulfur components are converted to hydrogen sulfide (H2S) and
removed from the gas using an amine solution.
Carbon dioxide (CO2) is also present in tail gas streams and will
be partially co-absorbed with H2S. This CO2 co-absorption should
be minimized. Any CO2 removed in the TGTU will be recycled to
the SRU front end along with the H2S, which has negative consequences for the reaction furnace and for the overall sulfur recovery.
This article discusses the effect of CO2 on sulfur plants and
how to minimize CO2 co-absorption or maximize CO2 slip
through the TGTUs amine absorber. A well-designed methyl
diethanolamine (MDEA) TGTU should be able to achieve a
minimum CO2 slip of 85%.

1,900
1,700
1,500
1,300
1,100
900
700
500
0

FIG. 1

10

20

30
40
50
60
70
80
CO2 in amine acid gas, mol% dry

90

100

Calculated adiabatic reaction furnace temperatures.

HYDROCARBON PROCESSING MARCH 2012

I 31

SPECIALREPORT

CORROSION CONTROL

partially crack in the furnace, resulting in the formation of CO,

COS and (indirectly, through a drop in temperature) CS2. Fig. 2
shows the impact of CO2 on COS and CS2 formation rates, using
the same simplified acid gas composition discussed previously.
As shown in Fig. 2, the increasing CO2 concentration of the
acid gas results in ever-increasing formation rates of CS2. CS2 formation has been shown to decrease with increasing temperatures,
although it is not clear if less CS2 is formed at higher operating
temperatures or if CS2 is formed and then quickly hydrolyzed.
However, the addition of CO2 cools the reaction furnace temperatures, which results in increased CS2 formation. CS2 is especially
unwanted since it binds up two sulfur molecules.
COS and CS2 formation in the reaction furnace is important
because, once formed, COS and CS2 do not participate in the modified Claus reaction. These compounds must, therefore, be converted
or hydrolyzed back to H2S downstream of the furnace, either in the
first Claus converter bed (operating at high temperatures, typically
600F to 630F) and/or utilizing special and often expensive catalyst; or they can be converted back to H2S in the TGTU hydrogenation reactor. Since amine-based TGTUs do not pick up COS and
CS2 in the absorber, any unconverted COS and CS2 will result in
increased sulfur emissions and reduced recovery efficiencies.
Overall gas capacity. In a world of low-sulfur fuels, the
demand for raising the existing processing capacity of refinery
sulfur plants is becoming increasingly important. Since CO2
flows straight through the sulfur plant and does not participate
in the Claus or modified Claus reactions, it takes up space and
reduces the amount of sulfur-bearing gases that could otherwise
be processed. A sulfur plant already operating at or slightly above
its design capacity would quickly run into trouble with an increase
in the CO2 content of the feed gas.
Apart from the issues related to furnace temperature and
increased COS and CS2 formation, operating a sulfur plant at
higher-than-design throughput would create greater operating
pressures that could result in:
Problems with air blowers not being able to deliver sufficient
air at the higher operating pressures
Heat exchangers not being able to sufficiently cool process
gases, resulting in additional sulfur vapor losses
Problems with mass velocities through condenser tubes,
resulting in liquid sulfur carryover (both of which would require
additional reducing gases in the TGTU hydrogenation bed).
To address some of the reduced capacity issues, processing
companies would have to consider technologies such as oxygen

Formation rate, % of inlet sulfur

35
COS formation rate
CS2 formation rate

30
25
20
15
10
5
0
0

FIG. 2

32

10

20
30
40
50
60
70
80
Percent CO2 in amine acid gas, mol%, dry

90

100

COS and CS2 formation as a function of CO2 content in acid

gas.

I MARCH 2012 HydrocarbonProcessing.com

enrichment or the construction of additional/larger sulfur plants,

which would have a significant impact on the operating or capital
budget of refineries.
Effects of CO2 on TGTU quench water. High CO2 tail

gas streams serve to lower the pH of the quench water, which can
decrease the strength of the protective iron sulfide (FeS) film. The
water will, therefore, be darker in color and could cause fouling
and plugging of the quench system. Ideally, the quench water has
a pH of 7 to 8; however, in plants with high CO2 levels, the pH
is typically between 6 and 7. Some plants try to correct this by
regular caustic addition to the (partly) circulating quench water.
Since a significant quantity of the quench water is not recycled,
caustic injection is, at best, a temporary solution. Regular caustic
injection can result in strong pH fluctuations that destabilize the
protective FeS film.
CO2 removal with MDEA. CO2 does not react directly with

the MDEA molecule; instead, it dissolves and reacts in the water

portion of the solution:
CO2 + H2O t H2CO3 (carbonic acid)
H2CO3 t H+ + HCO3 (bicarbonate)
H+ + R1R2R3N t R1R2R3NH+
CO2 + H2O + R1R2R3N t R1R2R3NH+ + HCO3
The reaction between CO2 and water (carbonic acid formation) is a slow step; it takes time to occur. Once the carbonic
acid is formed, however, the MDEA reacts with it quite quickly,
and the bond will not be broken again until the amine is regenerated. The removal of CO2 with a tertiary amine like MDEA is,
therefore, kinetically limited by the reaction rate in the first step.
H2S, on the other hand, reacts directly with the MDEA molecule:
H2S + R1R2R3N t R1R2R3NH+ + HS
The reaction between H2S and the amine is a very fast or
instantaneous reaction, which means that H2S removal is almost
always equilibrium-limited. Each contact stage or tray in an
absorber reaches the H2S equilibrium between gas and liquid.
The difference in chemistry between H2S and CO2 removal
is the key to understanding how H2S can be removed with a
minimum amount of CO2. The best strategy to minimize CO2
removal with MDEA is to prevent the CO2/water reaction from
occurring by:
1. Optimizing the amine temperature
2. Optimizing the amine strength
3. Optimizing the amine circulation rate
4. Optimizing the amine feed point of the absorber
5. Choosing a more selective solvente.g., formulated
MDEA or sterically hindered amine.
Amine temperature. As with most chemical reactions, the
higher the temperature, the faster the CO2 reaction takes place.
In a TGTU, lower lean amine temperature will minimize CO2
pickup because it reduces the reaction between CO2 and water. It
should be noted that high amine temperatures (above 140F) will
also slip amounts of CO2. Unfortunately, at high temperatures,
H2S will also be slipped due to equilibrium limitations. Therefore,
operating the absorber at high temperatures cannot be used as an
operating strategy.
A low absorber temperature slows down the kinetics of the
CO2 reaction. H2S removal occurs through a different mechanism

CORROSION CONTROL

H2S, ppm

400
360
320
280
240
200
160
120
80
40
0

H2S in vapor space

CO2 in vapor space
H2S higher ow
CO2 higher ow

6.0
5.9
5.8
5.7
5.6
5.5
5.4
5.3
5.2
5.1
5.0

CO2, mol%

The contact time between the CO2 and amine depends on

the internals of the absorber and the height at which the amine is
injected. In a trayed absorber, contact time on each tray is determined by the weir height and the number of trays. If packing is
used, contact time depends on the height and size of the packing.
In either case, lowering the injection point of the lean amine will
reduce the contact time and interfacial contact area between the
gas and amine, thus increasing the amount of CO2 slip.
Neither the weir height of trays nor the total height of packing is a parameter that can be adjusted during normal operation.
Changes to either require shutting down the system and performing large-scale maintenance. This is why multiple feedpoints are
built into the design of most TGTU absorbers.
It should be noted that differences exist in the selectivity of
packed and trayed towers. These differences are due to the hydraulics of the internals and the corresponding relationship with mass
transfer. A trayed tower has the liquid phase, which is highly agitated; packed towers are opposite in that the liquid flows over the
packing relatively smoothly. The gas flows are turbulent in both.
Either type of internals can result in decent CO2 slip, but the choice
between the two must be carefully considered and researched in the
design stage. Since the net liquid holdup in a packed bed (1% to
6% of tower volume) is lower than in a trayed tower (8% to 12% of
tower volume), the lower liquid hold-up can result in less interfacial
contact area and, therefore, lower CO2 absorption.
A TGTU absorber typically has three lean amine injection
points: one at the top tray or top height of packing, and two more
at successively lower intervals. Balance is achieved by injecting
at a high enough point to remove all of the H2S necessary, but
no higher. This procedure is best predicted first on a simulator,

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Tray number

4,000
3,500
3,200
2,800
2,400
2,000
1,600
1,200
800
400
0

Effect of an increase in circulation rate on H2S and CO2

removal.

H2S in vapor space

CO2 in vapor space

FIG. 4

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Tray number

6.0
5.9
5.8
5.7
5.6
5.5
5.4
5.3
5.2
5.1
5.0

CO2, mol%

FIG. 3

H2S, ppm

that is much less affected by temperature. Therefore, the amine

temperature should be kept as low as possible, although typically
not lower than the inlet gas temperature.
Since the gas is coming from the TGTU quench tower, it is saturated with water. An amine temperature lower than the gas temperature would condense water and dilute the amine solvent. It
should be noted that the normal temperature guideline for amine
systemsmaintain 5F to 10F temperature difference between
gas and amineis not applicable for amine-based TGTUs. Normal operation is to maintain the lean amine temperature at or
within 1F to 2F of the inlet gas. An ideal temperature range for
both the amine and the gas is 90F to 100F.
Amine strength. Since water is one of the reactants, the more
water there is in the absorber, the more CO2 will be absorbed into
the amine solution. MDEA can be successfully operated at up to
50% strength, with the other 50% consisting of water. Above this
strength, the viscosity of the solution becomes too high and will
negatively affect the mass transfer of H2S into the amine.
The CO2 hydrolysis should be minimized by limiting the
water content of the MDEA solution. Solvent strength should be
maintained between 45% and 50% while utilizing a proper filtration program to ensure that the viscosity of the amine does not
rise too high. Minimizing SO2 breakthrough from the Shell Claus
Offgas Treatment (SCOT) or SCOT-type cobalt-molybdenum
(CoMo) reactor will reduce the heat-stable amine salt buildup in
the system and minimize the chance of a viscosity increase due to
excess heat-stable salt formation.
Amine circulation rate. The CO2 reaction with water (to form
bicarbonate) is a kinetically limited reaction. This means that CO2
builds up at the gas/liquid interface and only reacts with the water
and amine as it slowly diffuses to the bulk of the amine solution.
In a trayed tower, higher circulation rates increase the height
of the liquid on each tray, as the weir creates a flow obstruction.
The amine stacks up against it and provides a larger surface area
for CO2 absorption. In a packed tower, greater amine flows create
higher holdup of amine into each section of packing. The more
liquid in the tower, the higher the CO2 removal will be, as there
is more gas/liquid interface for the CO2 to be absorbed. Overcirculation of the amine is the single largest contributor to poor
CO2 slip in TGTUs.
Furthermore, CO2 increases the loading of the amine, which
takes up valuable acid gas holding capacity, especially in lowpressure TGTU applications. Under certain conditions, it is possible that CO2 will force the amine to release previously absorbed
H2S. Optimizing (i.e., reducing) the amine circulation rate will
always result in a decrease in H2S and an increase in CO2 in the
treated gas, which is the goal.
In Fig. 3, the effects of circulation rate are shown. As the amine
rate is decreased from 200 gallons per minute (gpm) to 150 gpm,
the CO2 in the treated gas increases by 1,000 ppm, whereas the
H2S decreases from 45 ppm to 40 ppm.
The circulation rate should be initially targeted for a rich H2S
loading of 0.05 mol/mol, and slowly decreased with a final target
loading of 0.1 mol/mol. This should be reinforced by the use of a
reliable amine plant simulator.
Amine feedpoint into absorber. TGTU absorbers often have
multiple inlet points for the lean amine solution. Several inlet
points are normal and can be used to increase or decrease the
interfacial contact area between the gas and the amine solution.
A shorter contact time (less interfacial contact area) will result in
less CO2 absorption.

SPECIALREPORT

Simulated acid gas removal tray-by-tray in a TGTU

absorber.
HYDROCARBON PROCESSING MARCH 2012

I 33

SPECIALREPORT

CORROSION CONTROL

as shown in Fig. 4. Using this type of chart, it is apparent where

appropriate injection points into the absorber exist, depending on
the required H2S specification.
If possible, the amine injection should be lowered by one
feedpoint, and the treated gas H2S content should be measured.
If it is acceptable and simulations agree, the amine injection can
be lowered to another feedpoint. The main concern here is the
H2S content of the treated gas.

By lowering the H2S lean loading, the H2S in the treated

gas will also drop. This could enable the lean amine to be introduced into a lower feedpoint in the absorber, thus increasing the
CO2 slip, as described above. Normally, however, the aim of the
improved regeneration is to obtain a lower H2S level in the treated
gas. TGTUs are, therefore, often designed with more trays in the
regenerator than what is normally seen in amine units; this allows
for deep H2S stripping. HP

Choosing a more selective solvent. The use of an amine

with high selectivity can engender a number of benefits for the

TGTU, as discussed in the following two options.
Hindered amine. The most selective solvent for TGTU applications is a hindered amine, which is normally a secondary amine
with a bulky group that hinders the direct reaction with CO2.
These molecules combine the low CO2 reaction rate of a tertiary
amine with the base strength of a secondary amine. The high
base strength is particularly useful at the low pressure of a TGTU
absorber because it makes it possible to have a significantly higher
rich amine loading than with MDEA. The higher loading allows
for a reduction in amine circulation rate, which further improves
the selectivity.
Formulated MDEA. Enhanced MDEA formulations for
TGTUs have been available for 25 years. These are normally the
solvents that contain pH suppressants such as phosphoric acid.
The reduction in pH allows for easier and deeper regeneration
of the amine, especially for H2S. The same effect of improved
regeneration is achieved in MDEA solutions containing between
0.5 wt% and 1.0 wt% heat-stable salts.

34

I MARCH 2012 HydrocarbonProcessing.com

Ben Spooner, a senior process engineer, has been working

in the amine industry as an operator and engineer since 1998. He
joined Amine Experts in 2003 and has worked in over 25 countries
and on hundreds of amine systems, providing expert assistance and
advice regarding plant operations, troubleshooting, optimization
and operator training. Mr. Spooner is one of the primary speakers at Amine Experts
world-recognized Amine Treating Seminar, which has been presented in dozens of
locations around the globe. He holds a BSc degree in petroleum engineering from
the University of Alberta.

Farsin Derakhshan is a professional engineer with over 16

years of experience. He joined Sulphur Experts in 1996, initially
working out of the German office, and since then he has been
directly involved in all aspects of Sulphur Experts process engineering consulting work. Now residing in Canada, Mr. Derakhshan is
an experienced and well-traveled sulfur plant engineer, providing expert advice and
consulting services to clients around the world. His specialty areas include sulfur plant
troubleshooting and process optimization. Mr. Derakhshan is also Sulphur Experts
regional engineer for Europe and the Middle East. He is technically responsible for all
projects in those regions, and he is also a guest speaker at the internationally recognized Sulphur Recovery seminars. He holds a BSc degree in mechanical engineering
from the University of Calgary.

Select 159 at www.HydrocarbonProcessing.com/RS