Journal of Natural Gas Science and Engineering 22 (2015) 415e420

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Simulation and comparison of Sulfinol solvent performance with

Amine solvents in removing sulfur compounds and acid gases from
natural sour gas
Hassan Ghanbarabadi, Behnam Khoshandam*
Faculty of Chemical, Petroleum and Gas Engineering, Semnan University, Semnan, Iran

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

Article history: Natural gas issued from well production has to be treated to remove acid gases (CO2 and H2S) and sulfur
Received 9 August 2014 compounds so that it meets transport requirements and sale gas specifications. Two great families of
Received in revised form solvents are used for this kind of gas treatment: chemical and physical solvents. Ilam gas refinery (one of
22 December 2014
the main gas refineries in Iran) discharges high levels of mercaptans in the production of raw LPG and
Accepted 23 December 2014
condensates, and also there are problems with sulfur compounds because of the lack of Merox unit. In
Available online 30 December 2014
this research, we carry out the simulation and study of removing acid gases (CO2, H2S) and sulfur
compounds (methyl and ethyl mercaptans, dimethyl-sulfide, COS) with mixed solvent Sulfinol
Keywords:
Mercaptans
(Sulfolane þ MDEA þ H2O) and DGA, MDEA þ AMP solvents and compare it with the present solvent
Solvent MDEA. The purpose of this research is the feasibility study of utilizing Sulfinol-M solvent to replace the
Sulfinol-M aqueous amine solvent in the gas sweetening unit of Ilam gas refinery. The results of the simulation show
MDEA that more than 30e40% of mercaptans along with sour gas is absorbed with Sulfinol-M solvent of lower
Mixed solvents flow rate and a considerable 10e25% less energy is required for solvent regeneration; furthermore, very
Amine little waste of solvent is observed compared with amine solvents (MDEA þ AMP, DGA, MDEA). Many of
Absorption the process parameters are controlled more easily than amine solvents with the characteristic of the
Simulation
composition of Sulfinol-M compound and there will be energy and economic saving in different sections
Sulfolane
of mercaptan and acid gas absorption.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction solvents are used, among which amine solvents predominate in

Coal, oil compounds, and natural gas contain sulfur compounds
that are inappropriate in terms of environmental and processing
issues. Some sulfur compounds such as COS, methyl-mercaptan,
ethyl-mercaptan, and dimethyl-sulfide are unstable and toxic for
industrial catalysts. Therefore, separation of gas impurities is
important from different viewpoints of catalyst poisoning, safety
and corrosion control, and reaching the acceptable environmental
pollution limit (Mokhatab and Poe, 2012).
There are many methods for removing impurities from natural
gas, of which removing impurities with chemical solvents has been
used much more than other methods (more than 95%). In this
method, solvents such as amines, carbonates, and special chemical
* Corresponding author.
E-mail addresses: h.ghanbarabadi@gmail.com (H.
bkhoshandam@semnan.ac.ir (B. Khoshandam).
natural gas treating units (Mokhatab and Poe, 2012).
Acid gases (carbon dioxide and hydrogen sulphide) are removed
from gas streams with absorption by a solvent. Two general classes
of solvents are used: chemical and physical solvents. The former is
usually an aqueous solution of an alkanol amine, which reacts
chemically with the acid gases. The latter class is an organic com-
pound, which has a strong affinity for the acid gases, without a
chemical reaction taking place. Chemical solvents have the ad-
vantages of removing the acid gases to low levels at low partial
pressures, losses are not serious because most of the solvent is
water, and hydrocarbons are almost insoluble in the solution. On
the other hand, physical solvents have the advantages of unlimited
absorption out of stoichiometry, the regeneration of the solvent by
the pressure reduction, and ability to remove sulfur compounds
(COS and thiols) (Scha €fer et al., 2002). Amine solutions are weak
organic bases that can absorb gas impurities at room temperatures.
Ghanbarabadi),
Alkanolamines are nitrogenous organic materials that result from
compounding special organic materials with ammonia (NH3) and

http://dx.doi.org/10.1016/j.jngse.2014.12.024
1875-5100/© 2015 Elsevier B.V. All rights reserved.
416 H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420
are classified according to the organic groups connected to nitrogen
as follows:
 Primary amines such as mono ethanol amine (MEA) and di-
glycol amine (DGA).
 Secondary amines such as di-ethanol amine (DEA) and di-
isopropanol amine (DIPA).
 Tertiary amines such as tri-ethanol amine (TEA) and methyl di-
ethanol amine (MDEA).
Amines of the first type are stronger bases compared to those of
the second type and have higher tendencies to react with H2S and
CO2 and form stronger bonds with acidic gases. Generally, alkalinity
and reactivity of the first type of amines are more than the second
type and those of the second type are more than the third
(Mokhatab and Poe, 2012; Sch€ afer et al., 2002).
In addition to chemical solvents, we can use the mixture of
physical and chemical solvents to remove the impurities. Acid gas
and sulfur compound solubility is almost linear in physical solvents.
Mixed solvents are an attempt to combine the advantages of both
types of solvents. One of the first mixed solvents to be used was
sulfinol, a mixture of di-isopropanol amine, sulfolane (tetra-
methylene sulfone (TMS)), and water (Jou et al., 1990). Later, di-
isopropanol amine was replaced with methyldiethanol amine
(MDEA) and the solvent was called sulfinol-M (Jou et al., 1990). By
using the mixture of physical and chemical solvents, we can benefit
from its features in a wide range of pressures. Some of the problems
with using amine solvents are as follows: impurity absorption
limitation to chemical reactions' ratios, high energy requirement
for regeneration, lower absorption of sulfur compounds, require-
ment of dimethyl-sulfide, ethyle-mercaptan, methyl-mercaptan,
COS, and high wasting of such compounds. These problems can
be solved to some extent with alternative physical-chemical sol-
vents such as Sulfinol-M and Sulfinol-D (Jou et al., 1990; Badawi
et al., 2008).
In Ilam gas refinery (one of the most important gas refineries in
Iran), high levels of mercaptans and the lack of Merox unit in the
process cause great amounts of mercaptan and sulfur compounds
in raw LPG and condensates produced. In the present work,
different variations on the process have been studied such as
changing the solvent type from MDEA to MDEA þ AMP, DGA and
Sulfinol-M, evaluation of alternative energy, checking out the
wasting level to remove dimethyl-sulfide, mercaptan, ethyl-
methyl-mercaptan, and COS. The simulation results showed that
the Sulfinol-M replacement has better impacts on the process
performances than the chemical solvents alone.
Table 1
The inlet gas compounds.
Industrial data
Sour gas feed to sweetening unit
Parameter
Gas flow rate (kgmol/hr) 6143.94
Gas temperature ( C) 33.6
Composition components
CO2 (%mole) 3.75
H2S (%mole) 3.27
CH4 (%mole) 82.67
COS (%mole) 0.0024
Methyl-Mercaptan (%mole) 0.1299
Ethyl-Mercaptan (%mole) 0.0031
Dimethyl-Sulfide (%mole) 0.0175
2. Simulation
Amine system (MDEA 45%wt) is used in Ilam refinery and its gas
treatment unit's feed contains high percentages of sulfur com-
pounds and mercaptans, dimethyl-sulfide, COS, carbon dioxide
(CO2), and hydrogen sulfide (H2S) (De Angelis, 2012). The inlet gas
compounds are presented in Table 1. In this research, Aspen Plus
software ver. 7.2 has been used with the thermodynamic model of
ELECNRTL (Shahsavand and Garmroodi, 2010; Zong and Chen,
2011; Simoni et al., 2007). The outline of the simulation is shown
in Fig. 1.
The simulation was carried out based on the removal of acidic
gases from the natural gas and controlling the dew point of the
water and hydrocarbons in the output gas. In the simulated process,
firstly, sour gas enters the Knock Out Drum (K.O.D) to separate the
suspended liquid particles, water, and heavy hydrocarbons as
liquid. This flow is sent to the stabilizer unit so that hydrogen
sulfide is absorbed to the sour water and its organic phase. The
output gas from the top of the K.O.D enters the absorption tower to
contact the acid gas with amine, which is most often divided be-
tween two towers. The gas sweetening unit of Ilam refinery uses
MDEA with 45%wt in two parallel towers and the saturated solvent
is regenerated in two other parallel towers (Shahsavand and
Garmroodi, 2010).
The gas enters the contactor from the bottom of a 20 tray tower
and amine enters from the top. The lean solvent enters from the top
of the tower with a temperature of 50  C higher than that of the
input gas and after passing through the trays, it exits from the
bottom of the tower. The output gas will be heated due to receiving
amounts of the heat resulting from H2S and CO2 absorption.
Therefore, it enters the treated gas cooler and its temperature de-
creases. The gas then enters the treated gas separator and the
solvent is separated from the gas. To facilitate this process, treated
gas water spray pump sprinkles water on to the sweet gas separator
in the input line. After passing the treated gas separator, the gas
enters the treated gas filter separator and all types of possible
particles, solvent, and heavy hydrocarbons are separated; the gas is
then ready to enter the dew point control system. The separated
liquids in this filter and liquids from treated gas separator are sent
to the flash drum and also the sweet gas is sent to the dehydration
unit to control the dew point (Fig. 1) (Shahsavand and Garmroodi,
2010; Bolha r-Nordenkampf et al., 2004).
3. The simulation results
The solvents and their flow rate and concentration specifica-
tions used in the simulation are given in Table 2. The specifications
are chosen in a way that all mercaptans and sour gases are absorbed
during the process and, indeed, energy consumption minimizes
(Fahim et al., 2010). The simulation results are presented in Table 3.
As can be observed, most compounds including dimethyl-sulfide,
ethyl-mercaptan, COS, and methyl-mercaptan have been
removed. A comparison between solvents used in the simulation is
also provided. The Sulfinol-M with low flow rate shows higher
performance to remove the above-mentioned compounds.
The water used to make solvents is demonstrated statistically in
Fig. 2. The Sulfinol-M solvent consumes minimum water to prepare,
a property which has been used in this research. By adding sulfo-
lane to replace part of water, the amount of water to enter the gas
treating unit together with the solvent decreases. Different com-
pound absorption values by different solvents versus the number of
trays in contact towers are illustrated in Figs. 3e9. As is seen,
amines and the Sulfinol-M are absorbed, the performance of
Sulfinol-M being more desirable.
H2S reaction with amine needs no water; therefore, a decrease
 H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420
Fig. 1. Simulation's schematic of Ilam refinery's treatment unit.
in water level has no effect on its absorption, but CO2 reaction with
amine should be in aqueous condition and water decrease will
decrease its absorption (Nikolic and Claessen, 2010; Wei et al.,
2010). As shown in Fig. 4, CO2 existence in Sulfinol-M is less than
MDEA þ AMP, MDEA, and DGA solvents, which distinguishes the
selective absorption feature of this solvent from amine solvents
(Zong and Chen, 2011; Bolha r-Nordenkampf et al., 2004).
Research and simulation results show that the addition of some
amines without steric hindrance to a physical solvent will increase
CO2 capture (Wei et al., 2010). Solvent AMP is a good instance in this
regard because it includes properties of amine type I (high capture
rate), amine type III (high capture capacity) and features such as
high loading and low corrosion rate compared with amine types I
and II; by adding Solvent AMP to solvent MDEA, CO2 loading can
increase remarkably (Mokhatab and Poe, 2012; Wei et al., 2010).
The absorption process between the Sulfinol solution and contact
gas occurs via the CO2 reacting with the MDEA to form salt de-
rivatives along with the physical absorption of CO2 into the sulfo-
lane section of the Sulfinol.
The capacity of acid gas and sulfur compounds absorption with
chemical solvents is limited to chemical reaction's stoichiometry,
but for physical solvents there is no such limitation and absorption
capacity is proportional to partial pressure of acid gas. Moreover,
these solvents have absorption capacity of mercaptans and other
sulfur compounds such as COS, methyl-mercaptan, dimethyl-sul-
fide, and ethyl-mercaptan (Figs. 5e7), while amine solvents have
low power in absorbing mercaptans. In addition to offering lower
capital and operating costs as a result of the process Sulfinol-M, this
process offers additional benefits for some applications in that it
can provide an essentially complete extraction of mercaptans at the
same time as hydrogen sulphide and carbon dioxide are removed. It
can also take out very high percentages of carbonyl sulphide. For
instance, it is possible to clean the Shell Gasification Process gas
containing both hydrogen sulphide and carbonyl sulphide to less
than 1 ppm (Zong and Chen, 2011; Fahim et al., 2010; Shokouhi
et al., 2013).
Sulfolane has been found to be an excellent solvent for reactions,
particularly those in which anhydrous and polar solvents are
417
required. Some of the advantages of this solvent are the high ab-
sorption capacity of Sulfolane than other physical solvents, low
vapor pressure, and lack of its vapor enthalpy. Moreover, unlike
amine aqueous solvents, the mixture of this solvent, amine solvent,
and water has the capacity to remove carbonyl-sulfide (COS) and
other sulfide organic compounds (Figs. 8 and 9) (Zong and Chen,
2011; Nikolic and Claessen, 2010; Wei et al., 2010). Another prob-
lem with amines (DGA) is their reaction with COS and production of
salts resistant to heat that increases wasting solvent while wasting
of Sulfinol-M is low (Table 4) (Islam et al., 2010).
Higher acid gas and sulfur compound absorption cause the
temperature of rich solvent in the tower to increase (Fig. 10).
(Shahsavand and Garmroodi, 2010).
Fig. 11 shows the output temperature of different rich solvents.
As is shown, the output solvent temperature is higher for DGA. The
higher temperature is due to solvent reaction with acid gases and
sulfur compounds. This causes the water to evaporate more and
exit the gas treating unit together with refined gas and subse-
quently the system make-up water amount will be increased.
The reboiler heat duty of the process with different solvents is
illustrated in Fig. 12. The process using Sulfinol-M consumes low
energy to regenerate. The reason may be expressed as no chemical
reaction taking place between Sulfinol-M and the sulfur com-
pounds. Finally, an economic justification should exist for
increasing the solvent weight percentage in different processes due
to affecting some parameters as the solvent recirculation flow rate
and heat duties.
4. Conclusion
In this work, gas treating process simulation was carried out for
Ilam gas refinery (in Iran) with alternative solvents such as MDEA,
DGA, AMP þ MDEA, and Sulfinol-M. A comparison between solvent
absorbing capacities has been carried out in this research by
simulation using Aspen-Plus package. The impurities included acid
gases, COS, methyl and ethyl mercaptans, and dimethyl-sulfide. The
simulation showed that the physical-chemical solvent Sulfinol-M
has a better ability, as compared with chemical solvents, to
418 H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420

Table 2
The solvents and their flow rate and concentration specifications.

Solvents

Parameter MDEA Sulfinol- DGA MDEA þ AMP

M
Flow rate (kgmol/hr) 8378.997 4704.171 8096.499 6103.493
Solvent MDEA Sulfolane MDEA DGA MDEA AMP
concentration
(Mass Fraction Wt
%)
45 41.00406 45 26.54278 45 15

Table 3
The simulation results of gas treatment unit by Aspen Plus.

Parameter Solvents

MDEA Sulfinol- DGA MDEA þ AMP

M

Outlet gas flow rate (kg mol/hr) 5561.535 5362.174 5628.688 5562.476 Fig. 3. Comparison of Hydrogen sulphide absorption.
Outlet Solvent aqueous (kgmol/ 8935.967 5480.493 8359.815 6430.853
hr)
Outlet gas temperature ( C) 50.20 65.30 50.16 50.14
CO2 Outlet gas composition 0.00001 0.026 2.6931e-6 5.07e-06
(mole)
H2S Outlet gas composition 3.048e-6 2.69e-6 2.62e-6 2.99e-06
(mole)
CH4 Outlet gas composition 0.8875 0.97 0.899 0.909703
(mole)
COS Outlet gas composition 0.000028 1.8e-7 1.20794e- 2.09e-06
(mole) 6
Methyl-Mercaptan Outlet gas 0.001260 trace 3.784e-7 4.50e-07
composition (mole)
Ethyl-Mercaptan Outlet gas 0.000032 trace 4.410e-9 4.77e-09
composition (mole)
Dimethyl-Sulfide Outlet gas 0.000177 trace 2.353e-8 2.52e-08
composition (mole)

Fig. 4. Carbon dioxide with gas treating of the contact.

Fig. 2. Comparing water chart with input solvent to contact.

absorb different types of impurities such as acid gases, COS, methyl-

mercaptan, ethyl-mercaptan, dimethyl-sulfide from natural gas
with lower flow rate. The results indicate a reduction of methyl-
mercaptan from 382.83 kg/hr together with input sour gas to the
treatment unit to 3.73e-11 kg/hr, 0.1025 kg/hr, 0.07 kg/hr, and
4.502e-07 kg/hr for Sulfinol-M, DGA, MDEA, and MDEA þ AMP
solvent, respectively. Also, a reduction of ethyl-mercaptan has been
reported from 11.09 kg/hr together with input sour gas to treatment Fig. 5. Methyl-mercaptan in Rich-Solvent of the contact.
unit to trace values of 1.1e-18 kg/hr, 0.00153 kg/hr, 0.0012 kg/hr,
and 4.77e-09 kg/hr for Sulfinol-M, DGA, MDEA, and MDEA þ AMP,
 H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420 419

Fig. 6. Ethyl-Mercaptan with Rich-Solvent of the contact.

Fig. 9. COS with Rich-Solvent of the contact.

Table 4
Comparing wasting Solvent.

Makeup-solvent

C4H8O2S MDEA (Sulfinol- MDEA DGA MDEA

M) (MDEA þ AMP)

Mole Flow (kmol/ 6.31E- 4.33E-03 5.09E- 200 6.81E-05

hr) 03 05

respectively. Similar results were obtained for absorbing dimethyl-

Fig. 7. Dimethyl-Sulfide with Rich-Solvent of the contact.
sulfide, which showed that Sulfinol-M is a better solvent for
removing different natural gas impurities. Some of the advantages
of physical solvents are as follows: the absorption of impurities is
not limited by stoichiometric coefficients, the regeneration of the
solvent can be carried out easily by reduction of pressure, and they
have a good ability to remove sulfur compounds (COS); the results,
indeed, showed the absorption of COS from 88.33 kg/hr to
0.0581 kg/hr by the Sulfinol-M solvent. This process has many
advantages over conventional treating systems. Sulfinol-M shows
better absorption properties when varying its components such as
sulfolane, MDEA, and H2O. Using different composition percentages

Fig. 8. COS with gas treating of the contact.

Fig. 10. Temperature changes in contact.

420 H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420

for Sulfinol-M gives a reduction in solvent circulation of about

35e50% and energy saving of 10e25%. The present process can use
smaller equipment because of the non-foaming specification of the
solvent and, indeed, it has a low corrosion rate in comparison with
other processes.

References

Badawi, H.M., Fo €rner, W., El Ali, B., et al., 2008. Ring inversion, structural stability
and vibrational assignments of sulfolane c-C4H8SO2 and 3-sulfolene c-C4H6SO2.
Spectrochim. Acta, Part A: Mol. Biomol. Spectrosc. 70, 983e990.
Bolhar-Nordenkampf, M., Friedl, Anton, Koss, Ulrich, et al., 2004. Modelling selec-
tive H2S absorption and desorption in an aqueous MDEA-solution using a rate-
based non-equilibrium approach. Chem. Eng. Process: Process Intens. 43,
701e715.
De Angelis, A., 2012. Natural gas removal of hydrogen sulphide and mercaptans.
Fig. 11. The temperature of the output rich solvent of the contact. Appl. Catal. B: Environ. 113e114, 37e42.
Fahim, M.A., Alsahhaf, T.A., Elkilani, A., 2010. Acid Gas Processing and Mercaptans
Removal. Fundam. Pet. Ref. 377e402.
Islam, M.S., Yusoff, R., Ali, B.S., 2010. Degradation studies of amines and alkanol-
amines during CO2 absorption and stripping system. Eng. e-Trans. 5, 97e109.
Jou, F.Y., Deshmukh, R.D., Otto, F.D., et al., 1990. Solubility of H2S, CO2, CH4 and C2H6
in sulfolane at elevated pressures. Fluid. Phase. Equilib. 56, 313e324.
Mokhatab, S., Poe, W.A., 2012. Natural Gas Sweetening. In: Handbook of Natural Gas
Transmission Processing, pp. 253e290.
Nikolic, D., Claessen, M., 2010. Sulfinol-x for Acid Gas Removal: a Solution for LNG
Production from Contaminated Gas. Shell Global Solutions International BV,
Amsterdam, the Netherlands.
€
Schafer, B., Mather, A.E., Marsh, K.N., 2002. Enthalpies of solution of carbon dioxide
in mixed solvents. Fluid. Phase. Equilib. 194e197, 929e935.
Shahsavand, A., Garmroodi, A., 2010. Simulation of khangiran gas treating units for
various cooling scenarios. J. Nat. Gas Sci. Eng. 2, 277e283.
Shokouhi, M., Jalili, A.H., Mohammadian, A.H., et al., 2013. Heat capacity, thermal
conductivity and thermal diffusivity of aqueous sulfolane solutions. Thermo-
chim. Acta 560, 63e70.
Simoni, D., Lin, Y., Brennecke, J., et al., 2007. Modeling Liquid-liquid Equilibrium of
Ionic Liquid Systems with NRTL, Electrolyte-nrtl, and UNIQUAC. Department of
Chemical and Biomolecular Engineering University of Notre Dame, Notre Dame,
IN 46556, USA.
Wei, C., Soriano, A., Yang, Z., et al., 2010. Solubility of carbon dioxide in the solvent
system. (2-amino-2-methyl-1-propanol þ sulfolane þ water). Fluid Phase
Equilibr. 291, 195e200.
Zong, L., Chen, C., 2011. Thermodynamic modeling of CO2 and H2S solubilities in
aqueous DIPA solution, aqueous sulfolane-DIPA solution, and aqueous
Fig. 12. The comparison of heating load of the reboiler in regenerator. sulfolane-MDEA solution with electrolyte NRTL model. Fluid. Phase. Equilib.
306, 190e203.