Journal of Natural Gas Science and Engineering 31 (2016) 585e588

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Journal of Natural Gas Science and Engineering

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Feasibility study of a sulfur recovery unit containing mercaptans in

lean acid gas feed
Hamid Reza Mahdipoor*, Ashraf Dehghani Ashkezari
Department of Process and Equipment Technology Development, Research Institute of Petroleum Industry, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Acid Gas Enrichment (AGE) and Tail Gas Treatment (TGT) are conventional processes to enhance recovery
Received 1 December 2015 of sulfur in sulfur recovery plants. Depending on the presence of organic sulfur components such as
Received in revised form mercaptans and carbonyl sulfide, two configurations for AGE off-gas may be considered. Optionally, AGE
14 March 2016
off-gas can be sent to incinerator or fed to TGT section. In this paper, these two cases are investigated in
Accepted 15 March 2016
terms of technical and economical points of view. The achieved results show that although routing AGE
Available online 17 March 2016
off-gas to TGT section will increase the size and cost of TGT equipment, it can reduce the environmental
pollutants.
Keywords:
Sulfur recovery
© 2016 Elsevier B.V. All rights reserved.
Tail gas treatment
Mercaptan
AGE off-gas

1. Introduction flame in the reaction furnace. Moreover, incomplete combustion of

Claus process is usually applied for converting hydrogen sulfide
to elemental sulfur in oil and gas refineries. This process consists of
a reaction furnace, a waste heat boiler (WHB) and a series of cat-
alytic converters and condensers. In first stage, about 60% of H2S is
converted to elemental sulfur. More conversion is achievable in the
catalytic converters. Overall recovery of sulfur in the Claus process
hardly exceeds 96 percent. Unrecovered sulfur compounds
including elemental sulfur, COS, and CS2, are burned and converted
to SO2 in the Claus incinerator and then sent to atmosphere.
Nowadays, stricter environmental regulations have limited the
allowable emission of SO2. For low calorific gases from gasification
of refinery residues, SO2 emission has been limited to 800 mg/Nm3
in the EU and the USA. According to Iranian parliament law, this
value must be lower than 800 mass ppm. In both of them O2 con-
tent must be less than 3 mol% in the flue gas. Therefore, TGT section
is applied before incinerator for more processing of the Claus tail
gas and improving the overall recovery of sulfur (Zhang and Wood,
2015; Santo and Rameshni, 2014; Alaei et al., 2014; ZareNezhad,
2009; Monnery et al., 2001; Emission limit values, 2001).
On the other hand, a lean acid gas feed containing a relatively
low concentration of H2S may be incapable of producing a stable
* Corresponding author.
E-mail address: mahdipoorhr@ripi.ir (H.R. Mahdipoor).
hydrocarbons in the feed can lead to deterioration of the catalyst.
Furthermore, the amount of the byproducts such as COS will be
increased at low furnace temperatures. During decades, several
configurations for processing of lean acid gas have been presented,
including oxygen enrichment of the combustion air, acid gas bypass
around the furnace, fuel gas injection, acid gas preheating, acid gas
enrichment, etc (Selim et al., September 2013; Sames; Anonymous,
1987). The AGE section enriches the H2S content of the acid gas
stream making it practical to recover sulfur in a Claus section. Fig. 1
shows the schematic diagram of the AGE and TGT sections (Flowers
et al., 2011; Slavens and La mar, 2011; Perry et al., 2010).
As illustrated in Fig. 1, lean acid gas feed coming from gas
treatment unit, enters the bottom of the AGE amine absorber col-
umn. Lean amine enters from the top of the AGE absorber. Rich
amine from the bottom of AGE absorber after mixing with rich
amine coming from the bottom of the TGT absorber is routed to the
regenerator column (stripper) in which the absorbed acid gases are
stripped from amine solution. Then, the stripped acid gases from
the stripper overhead are sent to Claus section as rich acid gas
(purified from H2S). Lean amine from the bottom of the stripper
which contains negligible amount of H2S and CO2 is then recycled
to the AGE and TGT absorbers. When mercaptans and/or other
organic sulfur compounds such as COS are present in the feedstock,
the AGE absorber off-gas can be alternatively directed to inciner-
ator (case A) or TGT section (case B).
In the next section, a typical industrial Sulfur Recovery Unit

http://dx.doi.org/10.1016/j.jngse.2016.03.045
1875-5100/© 2016 Elsevier B.V. All rights reserved.
586 H.R. Mahdipoor, A. Dehghani Ashkezari / Journal of Natural Gas Science and Engineering 31 (2016) 585e588

Fig. 1. Schematic diagram of the AGE and TGT sections (Slavens and La mar, 2011).

(SRU) is studied for these two cases. The recovery of sulfur is Table 1
investigated and the SRU performance is analyzed in terms of SO2 Specifications of lean acid gas feed to SRU.

emission. Then, each case is economically investigated. The ach- Property Value
ieved results from this study highlight the effect of AGE off-gas on Temperature 60  C
SRU emission. Quick estimation for a new SRU design can be ob- Pressure 1.8 bar
tained by comparing the new SRU feed stream with the considered Mole Flow 1500 kmol/h
feed in this study. Furthermore, if the unit operators take this factor Composition (mole%)
H2S 33
into account, probable flaring of AGE off-gas may take place
CO2 56.9
cautiously. CH4S 0.1
H2O 10
2. Feasibility study results

In order to investigate the effect of routing AGE off-gas to TGT (case A) or TGT section (case B). Table 2 compares the process
section on the performance of SRU, a typical industrial SRU is specifications of TGT section for case A and case B.
studied. This study is performed using the commercial simulation As shown in this table, feed flow rate of TGT section in case B is
software, Promax. Before starting the simulation, the simulator was about 38 percent more than feed flow rate of TGT section in case A.
calibrated and tuned by means of several SRU design and operating Therefore, 88 percent more Fuel Gas (FG) should be burned in the
data in Iran to achieve valid and accurate results. The SRU unit inline burner to provide the appropriate temperature for reduction
contains one Acid Gas Enrichment (AGE) absorber, two conven- reactor. For the same reason, 43 percent more circulation water is
tional Claus sections, and one Tail Gas Treatment (TGT) absorber. As needed in cooling column system to decrease the temperature of
described in the previous section, one regenerator column has been process gas stream down to proper TGT absorber feed.
used for providing amine solution for both absorbers of the AGE Malfunction of AGE and TGT columns leads to higher amounts of
and TGT sections. The mass percent of MDEA in the amine solution unabsorbed H2S in the off-gas streams as well as more SO2 emission
is set to be 30% and the amine solution is cooled to 45  C. to atmosphere. The required circulation rate of amine solution is
Furthermore, about 0.02 mol percent of H2S is supposed to be
remained in the lean amine stream. The specification of a lean acid
gas which is considered as AGE (SRU) feed, is given in Table 1. The Table 2
major portion of lean acid gas consists of CO2, while the H2S mass Process specifications of TGT section.
percent is equal to 33% which is not considered as an appropriate
Property Case A Case B
feedstock for Claus section. Moreover, this lean feed also contains
TGT Feed Flow Rate (m3/h) 42,000 58,000
0.1 mol percent of methyl mercaptan.
Inline Burner Fuel Gas Rate (kg/h) 340 640
As described before, the rich amine is routed to regenerator Cooling Column Circulation Water (lpm) 3500 5000
column, wherein the absorbed acid gases (i.e. CO2 and H2S) are Lean Amine Circulation Rate (lpm) 10,000 13 700
stripped and returned to Claus unit. Mercaptans can't be absorbed Reboiler Low Pressure Steam (tones/h) 77 93
by MDEA solution and therefore, leave the top of the AGE column. SO2 Emission in Stack (mass ppm) 1700 170
Overall Sulfur Recovery 99 99.3
The AGE absorber off gas can be alternatively directed to incinerator
 H.R. Mahdipoor, A. Dehghani Ashkezari / Journal of Natural Gas Science and Engineering 31 (2016) 585e588 587

related to permissible remained H2S in the off-gas of the AGE and Table 3
TGT absorber columns. Choosing a lower value for the flow rate of Effect of CO2 concentration on the performance of SRU.

amine can result in excessive residual H2S in the off-gas streams. On Property Case A Case B
the other hand, using a flow rate of amine more than required will Claus Feed Flow Rate (m3/h) 5100 5500
increase the size of equipment and operating costs. Therefore, an Required Combustion Air (m3/h) 11,000 11,000
optimum value should be determined for the flow rate of amine CO2 in the TGT Absorber Feed (mole%) 13 41
circulation during simulation and process design of AGE and TGT H2S to CO2 ratio in the TGT Absorber Rich Amine 1.77 0.41
H2S Concentration in Claus feed (mole%) 72 67
sections. Since the flow rate and composition of acid gas feed are
Reaction Furnace Temperature ( C) 1095 1061
alike in both cases, the required flow rate of lean amine for the AGE COS in the WHB Outlet (mole%) 0.86 1.04
column is the same in case A and case B. However, TGT absorber
needs more lean amine to absorb H2S in case B the same as H2S in
case A (Mahdipoor, 2015).
entering to the AGE absorber is alike in both investigated cases, the
Since the operating pressure of system is low, applying struc-
same AGE absorber column is needed for case A and case B.
tured packing is preferred as column internals in the AGE and TGT
Moreover, Claus feed flow rate in case A and case B is mostly the
absorbers. Generally, about 10e12 theoretical stages with tray ef-
same (see Table 3). Therefore, the size of equipment would not have
ficiency of 30% are needed. In this work, 10 and 12 theoretical stages
significant difference. Since in Claus reaction, 2 mol of H2S react
are used to simulate the TGT and AGE absorbers, respectively. AGE
with 1 mol of SO2 to produce elemental sulfur, the required flow
and TGT columns should operate such a way that absorbs more H2S
rate of combustion air is adjusted such a way that the ratio of H2S to
and less CO2. The selective absorption of H2S can be improved by
SO2 to be equal to 2 in the tail gas stream. Simply, one third of inlet
using shorter packed bed with lower residence time. However, the
H2S should be oxidized to SO2 in the reaction furnace (Mahdipoor
operating and design conditions of the AGE and TGT absorber col-
et al., 2012). Although the flow rate of Claus feed in case B is
umns are the same in both cases.
slightly more than Case A, the molar flow of H2S is the same in both
Another important parameter that can affect on the perfor-
cases (equal to 257 kmol/h), therefore, the required flow rate for
mance of the AGE and TGT absorbers is the amounts of residual H2S
combustion air is the same too.
and CO2 in the lean amine (Mahdipoor, 2015). Regenerator column
On the other hand, as indicated in Table 2, TGT feed flow rate in
(amine stripper) should operate such that the residual H2S and CO2
case B is 38 percent higher than TGT feed flow rate in case A. Hence,
in the lean amine become reasonably low to ensure appropriate
larger equipment as well as higher investment would be expectable
absorption of H2S in the AGE and TGT columns. For this reason, the
for case B. For example, reduction reactor operates at an optimum
duty of reboiler is assign such that the concentration of H2S at the
GHSV (Gas Hourly Space Velocity). GHSV is defined as reactant gas
regenerator bottom outlet becomes lower than 200 ppm, as
flow rate per reactor volume. Therefore, when the feed of TGT as
mentioned before. Generally, about 7e10 theoretical stages with
well as the feed of reduction reactor is increased, the larger volume
tray efficiency of 40%e50% are needed (Manning and Thompson,
of reactor and more investment is needed to achieve the same
1991). In this work, 7 theoretical stages are used to simulate the
conversion. A comparison between size of equipment in TGT sec-
amine regenerator. For more stripping of acid gases (H2S and CO2)
tion for case A and case B is presented in Table 4.
from rich amine solution, more duty is required in the reboiler of
Data presented in Table 5 compare the cost of equipment in TGT
regenerator. The values of residual H2S and CO2 are assumed to be
section. Equipment costs presented in this table are based on USA
the same in case A and case B. Since the required circulation rate for
in first quarter of 2003 and for other locations and times, correction
lean amine in case B is more than case A, more Low Pressure Steam
factors should be used. Sometimes only a preliminary design and
(LPS) is needed for stripping of the acid gases from the rich amine in
cost estimation are needed to evaluate the advisability of further
the regenerator.
research on a new process or a proposed plant expansion or
Although the amount of utility consumption in case B is higher
detailed design work; or a preliminary design may be needed to
than case A, SO2 emission in case B will be ten times less than SO2
establish the approximate funding for a complete design and con-
emission in case A. In fact, when AGE off-gas is routed to inciner-
struction. Because exact prices can be obtained only by direct
ator, all its sulfur compounds such as mercaptans and COS is burned
quotations from manufacturers, the analysis of cost for complete
and converted to SO2. If the amounts of sulfur compounds were
plant is beyond the scope of this work. So, to examine modifications
considerable, then the emission of SO2 to the atmosphere would be
higher than environmental regulation limits mentioned before.
Moreover, the amount of H2S which is slipped from the AGE and
TGT absorbers should be kept low enough to ensure allowable SO2 Table 4
Comparison between sizes of equipment in TGT section.
emission in stack (e.g. below 200 ppm).
Because of routing the AGE off-gas to TGT and burning more fuel Property Case A Case B
gas in the inline burner, the percentage of CO2 in the TGT absorber Quench Water Pump Rate (m /h) 3
224.1 318.3
feed stream is increased from 13 mol percent in case A to 41 mol TGT Rich Amine Pump Rate (m3/h) 121.3 301.4
percent in case B. Therefore, more CO2 will be absorbed by TGT Lean Amine Pump Rate (m3/h) 608.4 789.7
absorber in case B and consequently, H2S to CO2 ratio will decreased Reflux Pump Rate (m3/h) 35.6 41.9
Quench Column Diameter (m) 2.8 3.5
in the top of the regenerator column. The concentration of H2S in TGT Absorber Diameter (m) 2.6 3.5
Claus feed is reached 72% in case A, while the concentration of H2S Regenerator Diameter (m) 3.7 4.0
is equal to 67% in case B. The more concentration of H2S in the Claus TGT Waste Heat Boiler Surface (m2) 3408 5453
feed will result in higher temperature of reaction furnace, as well as Quench Water Trim Cooler Surface (m2) 522 746
Lean Amine Trim Cooler Surface (m2) 1753 2282
lower by-product reactions. The concentration of COS in the exiting
Lean/Rich Amine Heat Exchanger Surface (m2) 3939 5357
streams from Waste Heat Boiler (WHB) in case A and case B are Reboiler Surface (m2) 2421 2905
equal to 0.86% and 1.04%, respectively. Therefore, more reaction is Acid Gas Trim Condenser Surface (m2) 355 414
needed to hydrolyze COS to H2S in Claus hydrolyzing reactor. The Quench Water Air Cooler Baer Tube Surface (m2) 404 385
above discussion is summarized in Table 3. Lean Amine Air Cooler Baer Tube Surface (m2) 1292 1497
Acid Gas Condenser Baer Tube Surface (m2) 1345 1587
Since the specifications of lean acid gas feed and lean amine
588 H.R. Mahdipoor, A. Dehghani Ashkezari / Journal of Natural Gas Science and Engineering 31 (2016) 585e588

Table 5 applicable for current feed. However, if the feedstock changes

Comparison between equipment costs in TGT section (1000$). during operation at future and the amounts of mercaptan de-
Property Case A Case B creases, operators can rout the AGE off-gas to incinerator and save
Quench Water Pump 29 33
operating costs.
TGT Rich Amine Pump 23 30
Lean Amine Pump 42 48
Reflux Pump 18.5 19 3. Conclusions
Quench Column 772 919
TGT Absorber 853 1094
Regenerator 1845 1902
Acid Gas Enrichment (AGE) and Tail Gas Treatment (TGT) are
TGT Waste Heat Boiler 3645 6852 conventional processes to enhance recovery of sulfur in sulfur re-
Quench Water Trim Cooler 378 564 covery plants. Depending on the presence of organic sulfur com-
Lean Amine Trim Cooler 1557 2157 ponents such as mercaptans and carbonyl sulfide, two
Lean/Rich Amine Heat Exchanger 4418 6634
configurations for AGE off-gas may be considered, routing to
Reboiler 3903 4909
Acid Gas Trim Condenser 260 298 incinerator or TGT section. A typical industrial Sulfur Recovery Unit
Quench Water Air Cooler 322 316 (SRU) was studied to analyze these two cases. The results show that
Lean Amine Air Cooler 512 543 routing AGE off-gas to TGT section increases the size and required
Acid Gas Condenser 520 556
investment for TGT equipment, and has not considerable effect on
Total 19,097.5 26,874
AGE and Claus sections. Although this option can reduce the
environmental pollutants and increase overall recovery of sulfur,
the final decision will depend on the environmental regulations,
of the process flow sheet or to find optimal values of key process and the amount of organic sulfur components in the SRU feedstock.
variables, it seems that an approximate analysis of cost is enough.
As stated before, since the main purpose of this work was the
comparison of results for case A and case B, using the correction References
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