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

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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


natural gas treating units (Mokhatab and Poe, 2012).
Coal, oil compounds, and natural gas contain sulfur compounds Acid gases (carbon dioxide and hydrogen sulphide) are removed
that are inappropriate in terms of environmental and processing from gas streams with absorption by a solvent. Two general classes
issues. Some sulfur compounds such as COS, methyl-mercaptan, of solvents are used: chemical and physical solvents. The former is
ethyl-mercaptan, and dimethyl-sulfide are unstable and toxic for usually an aqueous solution of an alkanol amine, which reacts
industrial catalysts. Therefore, separation of gas impurities is chemically with the acid gases. The latter class is an organic com-
important from different viewpoints of catalyst poisoning, safety pound, which has a strong affinity for the acid gases, without a
and corrosion control, and reaching the acceptable environmental chemical reaction taking place. Chemical solvents have the ad-
pollution limit (Mokhatab and Poe, 2012). vantages of removing the acid gases to low levels at low partial
There are many methods for removing impurities from natural pressures, losses are not serious because most of the solvent is
gas, of which removing impurities with chemical solvents has been water, and hydrocarbons are almost insoluble in the solution. On
used much more than other methods (more than 95%). In this the other hand, physical solvents have the advantages of unlimited
method, solvents such as amines, carbonates, and special chemical 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.
* Corresponding author.
E-mail addresses: h.ghanbarabadi@gmail.com (H. Ghanbarabadi),
Alkanolamines are nitrogenous organic materials that result from
bkhoshandam@semnan.ac.ir (B. Khoshandam). 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 2. Simulation


as follows:
Amine system (MDEA 45%wt) is used in Ilam refinery and its gas
 Primary amines such as mono ethanol amine (MEA) and di- treatment unit's feed contains high percentages of sulfur com-
glycol amine (DGA). pounds and mercaptans, dimethyl-sulfide, COS, carbon dioxide
 Secondary amines such as di-ethanol amine (DEA) and di- (CO2), and hydrogen sulfide (H2S) (De Angelis, 2012). The inlet gas
isopropanol amine (DIPA). compounds are presented in Table 1. In this research, Aspen Plus
 Tertiary amines such as tri-ethanol amine (TEA) and methyl di- software ver. 7.2 has been used with the thermodynamic model of
ethanol amine (MDEA). ELECNRTL (Shahsavand and Garmroodi, 2010; Zong and Chen,
2011; Simoni et al., 2007). The outline of the simulation is shown
Amines of the first type are stronger bases compared to those of in Fig. 1.
the second type and have higher tendencies to react with H2S and The simulation was carried out based on the removal of acidic
CO2 and form stronger bonds with acidic gases. Generally, alkalinity gases from the natural gas and controlling the dew point of the
and reactivity of the first type of amines are more than the second water and hydrocarbons in the output gas. In the simulated process,
type and those of the second type are more than the third firstly, sour gas enters the Knock Out Drum (K.O.D) to separate the
(Mokhatab and Poe, 2012; Sch€ afer et al., 2002). suspended liquid particles, water, and heavy hydrocarbons as
In addition to chemical solvents, we can use the mixture of liquid. This flow is sent to the stabilizer unit so that hydrogen
physical and chemical solvents to remove the impurities. Acid gas sulfide is absorbed to the sour water and its organic phase. The
and sulfur compound solubility is almost linear in physical solvents. output gas from the top of the K.O.D enters the absorption tower to
Mixed solvents are an attempt to combine the advantages of both contact the acid gas with amine, which is most often divided be-
types of solvents. One of the first mixed solvents to be used was tween two towers. The gas sweetening unit of Ilam refinery uses
sulfinol, a mixture of di-isopropanol amine, sulfolane (tetra- MDEA with 45%wt in two parallel towers and the saturated solvent
methylene sulfone (TMS)), and water (Jou et al., 1990). Later, di- is regenerated in two other parallel towers (Shahsavand and
isopropanol amine was replaced with methyldiethanol amine Garmroodi, 2010).
(MDEA) and the solvent was called sulfinol-M (Jou et al., 1990). By The gas enters the contactor from the bottom of a 20 tray tower
using the mixture of physical and chemical solvents, we can benefit and amine enters from the top. The lean solvent enters from the top
from its features in a wide range of pressures. Some of the problems of the tower with a temperature of 50  C higher than that of the
with using amine solvents are as follows: impurity absorption input gas and after passing through the trays, it exits from the
limitation to chemical reactions' ratios, high energy requirement bottom of the tower. The output gas will be heated due to receiving
for regeneration, lower absorption of sulfur compounds, require- amounts of the heat resulting from H2S and CO2 absorption.
ment of dimethyl-sulfide, ethyle-mercaptan, methyl-mercaptan, Therefore, it enters the treated gas cooler and its temperature de-
COS, and high wasting of such compounds. These problems can creases. The gas then enters the treated gas separator and the
be solved to some extent with alternative physical-chemical sol- solvent is separated from the gas. To facilitate this process, treated
vents such as Sulfinol-M and Sulfinol-D (Jou et al., 1990; Badawi gas water spray pump sprinkles water on to the sweet gas separator
et al., 2008). in the input line. After passing the treated gas separator, the gas
In Ilam gas refinery (one of the most important gas refineries in enters the treated gas filter separator and all types of possible
Iran), high levels of mercaptans and the lack of Merox unit in the particles, solvent, and heavy hydrocarbons are separated; the gas is
process cause great amounts of mercaptan and sulfur compounds then ready to enter the dew point control system. The separated
in raw LPG and condensates produced. In the present work, liquids in this filter and liquids from treated gas separator are sent
different variations on the process have been studied such as to the flash drum and also the sweet gas is sent to the dehydration
changing the solvent type from MDEA to MDEA þ AMP, DGA and unit to control the dew point (Fig. 1) (Shahsavand and Garmroodi,
Sulfinol-M, evaluation of alternative energy, checking out the 2010; Bolha r-Nordenkampf et al., 2004).
wasting level to remove dimethyl-sulfide, mercaptan, ethyl-
methyl-mercaptan, and COS. The simulation results showed that 3. The simulation results
the Sulfinol-M replacement has better impacts on the process
performances than the chemical solvents alone. 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,
Table 1
ethyl-mercaptan, COS, and methyl-mercaptan have been
The inlet gas compounds.
removed. A comparison between solvents used in the simulation is
Industrial data also provided. The Sulfinol-M with low flow rate shows higher
Sour gas feed to sweetening unit performance to remove the above-mentioned compounds.
Parameter
The water used to make solvents is demonstrated statistically in
Gas flow rate (kgmol/hr) 6143.94 Fig. 2. The Sulfinol-M solvent consumes minimum water to prepare,
Gas temperature ( C) 33.6 a property which has been used in this research. By adding sulfo-
Composition components lane to replace part of water, the amount of water to enter the gas
CO2 (%mole) 3.75
treating unit together with the solvent decreases. Different com-
H2S (%mole) 3.27
CH4 (%mole) 82.67 pound absorption values by different solvents versus the number of
COS (%mole) 0.0024 trays in contact towers are illustrated in Figs. 3e9. As is seen,
Methyl-Mercaptan (%mole) 0.1299 amines and the Sulfinol-M are absorbed, the performance of
Ethyl-Mercaptan (%mole) 0.0031 Sulfinol-M being more desirable.
Dimethyl-Sulfide (%mole) 0.0175
H2S reaction with amine needs no water; therefore, a decrease
H. Ghanbarabadi, B. Khoshandam / Journal of Natural Gas Science and Engineering 22 (2015) 415e420 417

Fig. 1. Simulation's schematic of Ilam refinery's treatment unit.

in water level has no effect on its absorption, but CO2 reaction with required. Some of the advantages of this solvent are the high ab-
amine should be in aqueous condition and water decrease will sorption capacity of Sulfolane than other physical solvents, low
decrease its absorption (Nikolic and Claessen, 2010; Wei et al., vapor pressure, and lack of its vapor enthalpy. Moreover, unlike
2010). As shown in Fig. 4, CO2 existence in Sulfinol-M is less than amine aqueous solvents, the mixture of this solvent, amine solvent,
MDEA þ AMP, MDEA, and DGA solvents, which distinguishes the and water has the capacity to remove carbonyl-sulfide (COS) and
selective absorption feature of this solvent from amine solvents other sulfide organic compounds (Figs. 8 and 9) (Zong and Chen,
(Zong and Chen, 2011; Bolha r-Nordenkampf et al., 2004). 2011; Nikolic and Claessen, 2010; Wei et al., 2010). Another prob-
Research and simulation results show that the addition of some lem with amines (DGA) is their reaction with COS and production of
amines without steric hindrance to a physical solvent will increase salts resistant to heat that increases wasting solvent while wasting
CO2 capture (Wei et al., 2010). Solvent AMP is a good instance in this of Sulfinol-M is low (Table 4) (Islam et al., 2010).
regard because it includes properties of amine type I (high capture Higher acid gas and sulfur compound absorption cause the
rate), amine type III (high capture capacity) and features such as temperature of rich solvent in the tower to increase (Fig. 10).
high loading and low corrosion rate compared with amine types I (Shahsavand and Garmroodi, 2010).
and II; by adding Solvent AMP to solvent MDEA, CO2 loading can Fig. 11 shows the output temperature of different rich solvents.
increase remarkably (Mokhatab and Poe, 2012; Wei et al., 2010). As is shown, the output solvent temperature is higher for DGA. The
The absorption process between the Sulfinol solution and contact higher temperature is due to solvent reaction with acid gases and
gas occurs via the CO2 reacting with the MDEA to form salt de- sulfur compounds. This causes the water to evaporate more and
rivatives along with the physical absorption of CO2 into the sulfo- exit the gas treating unit together with refined gas and subse-
lane section of the Sulfinol. quently the system make-up water amount will be increased.
The capacity of acid gas and sulfur compounds absorption with The reboiler heat duty of the process with different solvents is
chemical solvents is limited to chemical reaction's stoichiometry, illustrated in Fig. 12. The process using Sulfinol-M consumes low
but for physical solvents there is no such limitation and absorption energy to regenerate. The reason may be expressed as no chemical
capacity is proportional to partial pressure of acid gas. Moreover, reaction taking place between Sulfinol-M and the sulfur com-
these solvents have absorption capacity of mercaptans and other pounds. Finally, an economic justification should exist for
sulfur compounds such as COS, methyl-mercaptan, dimethyl-sul- increasing the solvent weight percentage in different processes due
fide, and ethyl-mercaptan (Figs. 5e7), while amine solvents have to affecting some parameters as the solvent recirculation flow rate
low power in absorbing mercaptans. In addition to offering lower and heat duties.
capital and operating costs as a result of the process Sulfinol-M, this
process offers additional benefits for some applications in that it 4. Conclusion
can provide an essentially complete extraction of mercaptans at the
same time as hydrogen sulphide and carbon dioxide are removed. It In this work, gas treating process simulation was carried out for
can also take out very high percentages of carbonyl sulphide. For Ilam gas refinery (in Iran) with alternative solvents such as MDEA,
instance, it is possible to clean the Shell Gasification Process gas DGA, AMP þ MDEA, and Sulfinol-M. A comparison between solvent
containing both hydrogen sulphide and carbonyl sulphide to less absorbing capacities has been carried out in this research by
than 1 ppm (Zong and Chen, 2011; Fahim et al., 2010; Shokouhi simulation using Aspen-Plus package. The impurities included acid
et al., 2013). gases, COS, methyl and ethyl mercaptans, and dimethyl-sulfide. The
Sulfolane has been found to be an excellent solvent for reactions, simulation showed that the physical-chemical solvent Sulfinol-M
particularly those in which anhydrous and polar solvents are 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-


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
Fig. 7. Dimethyl-Sulfide with Rich-Solvent of the contact. 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.

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