Journal of Natural Gas Science and Engineering 20 (2014) 16e22

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Journal of Natural Gas Science and Engineering

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

Feasibility study, simulation and economical evaluation of natural

gas sweetening processes e Part 1: A case study on a low capacity
plant in iran
Abolghasem Kazemi a, *, Mojtaba Malayeri a, Abolfazl Gharibi kharaji a, Ahmad Shariati b
a
Chemical Engineering Department, University of Isfahan, Isfahan, Iran
b
Natural Gas Engineering Department, Petroleum University of Technology, Ahwaz, Iran

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

Article history: Considering the natural gas produced from one of Iranian gas fields, a suitable alkanolamine solution is
Received 2 May 2014 selected for the sweetening of this gas. Based on the selected alkanolamine solution, the alkanolamine
Received in revised form process is simulated with Aspen hysys simulator and economically evaluated with Aspen economic
2 June 2014
analyzer. Sulfinol-M process, LO-CAT process and shell process for natural gas sweetening are also
Accepted 4 June 2014
Available online 22 June 2014
simulated and economically evaluated with the use of Aspen process economic analyzer in order to
remove H2S and CO2 from the natural gas produced in this field to meet the pipeline specifications.
According to results, the LO-CAT and the mixed amine processes are the two processes which have better
Keywords:
Natural gas
performance based on rich solution acid gas loading and thus, have lower costs related to corrosion in
CO2 facilities. With regard to the two aspects the LO-CAT process is the best process when capital and
H2S operating costs along with acid gas loading are taken into account.
Sweetening © 2014 Elsevier B.V. All rights reserved.
Simulation
Economic evaluation

1. Introduction process and sulfinol-M process. Alkalonamine solutions are the

Before transmission of natural gas through pipelines, Removal of
H2S and CO2 (acid gases) from the natural gas is desirable because
presence of these components in the pipeline can cause technical
difficulties (e.g. corrosion) (Campbell and Maddox, 1974; Datta and
Sen, 2006; Rufford et al., 2012); The maximum concentrations of
H2S and CO2 in the natural gas are restricted to 4 ppm and 2 mol%
respectively by regulations (Abdulrahman and Sebastine, 2013).
Numerous processes have been developed for the removal of these
acid gases from the natural gas in different operating conditions
and different CO2 and H2S concentrations in the sour gas (Kohl and
Nielsen, 1997; Processors, 2004; Rufford et al., 2012). Most of these
processes involve chemical and/or physical absorption of the acid
gases with a regenerable solvent (Campbell and Maddox, 1974;
Kohl and Nielsen, 1997; Processors, 2004).
In this study the natural gas produced from one of gas fields in
iran, with relatively high H2S (5 mol %) fraction and relatively low
CO2 (1.33 mol %) is considered and four of the well-developed pro-
cesses for the natural gas sweetening are simulated in order to meet
with the pipeline specifications. These processes are mixed alka-
lonamine process (mixed MDEA and DEA), shell process, LO CAT
most popular solutions for the acid gas removal from natural gas and
are commercially used for natural gas sweetening since early thirties
(Kohl and Nielsen, 1997; Processors, 2004; Rinker et al., 2000). Since
methyldiethanol amine (MDEA) solution, alongside requiring rela-
tively low energy for regeneration, is known for its high selectivity
toward H2S and addition of little amounts of primary or secondary
amines to MDEA, causes CO2 absorption rate of MDEA solution to
increase (Fouad and Berrouk, 2013; Nuchitprasittichai and
Cremaschi, 2011; Rangwala et al., 1992), The MDEA, DEA mixture
of amines is selected as a suitable alkalonamine solution for treat-
ment of those gases which have high H2S and low CO2 content.
(Fouad and Berrouk, 2013; Nuchitprasittichai and Cremaschi, 2011)
In this study, this process is simulated and economically evaluated
and compared to three other processes which can perform well in
sweetening of gases with high H2S (Elkanzi, 2009; Processors,
2004). All of the four processes are economically evaluated with
the use of Aspen process economic analyzer v8.1, and the best pro-
cess from an economical view is selected.
2. Sour gas composition

* Corresponding author. Tel.: þ98 9171492783. These four processes are designed for the purpose of sweetening
E-mail address: Abolghasemkazemi@gmail.com (A. Kazemi). of a typical gas produced in one of gas fields in iran. The natural gas

http://dx.doi.org/10.1016/j.jngse.2014.06.001
1875-5100/© 2014 Elsevier B.V. All rights reserved.
 A. Kazemi et al. / Journal of Natural Gas Science and Engineering 20 (2014) 16e22
produced from this field has H2S content of 5% and CO2 content of
1.33%. There are also light components such as CO, CO2 and N2 with
low mole fraction present in this gas. However methane with mole
fraction of 0.7203 and ethane with mole fraction of 0.1021 are the
major components in this gas. The feed gas temperature and
pressure are equal to 54  C and 24.5 bar respectively and its average
MW is 23.4.
Simulations of sulfinol-M and lo cat processes for the sweet-
ening of this gas have been carried out with the use of Aspen plus
v7.3 and for shell and amine processes Aspen hysys v7.3 and Aspen
hysys v8.1 have been used respectively.
3. An overview of the four processes
3.1. Mixed amine process
Alkalonamines are widely used for the removal of acid gases
from the natural gas. Alkalonamines are classified (based on the
number of alkyl groups which make bonds to the N atom of amino
group) to primary amines (e.g. MEA), secondary amines (e.g. DEA)
and tertiary amines (e.g. MDEA), each of which have advantages
and disadvantages (Fouad and Berrouk, 2013; Padurean et al.,
2011). Primary amines have higher reaction rates while tertiary
amines need less energy for regeneration (Mudhasakul et al., 2013).
Selection of a suitable amine solution for sweetening can affect
equipment sizing and operating costs. Methyl-diethanolamine
(MDEA) is known for its high selectivity toward H2S in presence
of CO2 and it's reaction with H2S is nearly instantaneous, while
absorption of CO2 in MDEA occurs at low rates (Fouad and Berrouk,
2013; Haimour and Sandall, 1987; Mudhasakul et al., 2013; Rufford
et al., 2012) furthermore, regeneration of tertiary amines requires
lower energy than primary and secondary amines (Yildirim et al.,
2012), so MDEA seems to be a good choice for the sweetening of
the natural gas with 5% H2S and 1.33% CO2. The previous studies
suggest that in order to increase the CO2 absorption rate of tertiary
amines (e.g. MDEA), little amounts of primary or secondary amines
(e.g. DEA) should be added to the solution (Anufrikov et al., 2007;
Nuchitprasittichai and Cremaschi, 2011) another reason of mixing
primary or secondary amines with tertiary amines is to combine
high reactivity of primary and secondary amines with low energy
requirement for regeneration of tertiary amines (Fouad and
Berrouk, 2013); Based on this information, a solution of 35mass%
MDEA and 5mass% DEA is selected for the sweetening of natural gas
with the specifications described in Section 2. MDEA can be syn-
thesized from reaction of the intermediate mono methyl ethanol-
amine and ethylene oxide, while, Mono methyl ethanolamine is
produced from the reaction of ethylene oxide and mono methyl-
amine. DEA also can be produced by reacing ethylene oxide and
ammonia (Jones et al., 2004). MDEA and DEA both are commer-
cially produced and available for purchase. These amines absorb
the acid gases through these chemical reactions (Cummings et al.,
2007; Lu et al., 2006; Nuchitprasittichai and Cremaschi, 2011):
Secondary amines: R2NH þ H2S / (R2NH)þ þ (HS)
Tertiary amines: R3N þ H2S / (R3NH)þ þ (HS)
Secondary amines: CO2 þ R2NH 4 R2NHþCOO
Tertiary amines : CO2 þ R3 N þ H2 O4R3 NHþ þ HCO
3 (4)
High pressure and low temperature favor the extent of the re-
actions while the reverse of these reactions is favored by high tem-
perature and low pressure (Fouad and Berrouk, 2013). Also (Ebenezer,
2005) suggests that the absorber of amine sweetening plant should
17
operate at high temperatures and low pressures and the regeneration
column to operate at high temperatures and low pressures.
Several studies have been carried out for the purpose of simu-
lation of amine sweetening units with Hysys process simulator
(Kumar et al., 2014). One of the reasons is that this simulator is
benefited from a powerful fluid property package (amine package)
suitable for the simulation of amine sweetening units. Aspen hysys
v8.1 is used for the simulation of this process. A screenshot of the
simulation flow sheet is shown in Fig. 1 (Aspenone-examples,
2013).
3.2. Sulfinol-M process
As suggested by Hiller et al. (2006) Sulfinol process is suitable
for the sweetening of gases having a summation of partial pressures
of H2S and CO2 higher than 1 bar (Hiller et al., 2006). In the natural
gas of interest (described in Section 2), the summation of partial
pressures of H2S and CO2 is calculated to be 1.4904 bar so the sul-
finol process could be a good choice for the sweetening of this gas.
In the Sulfinol-M process the acid gas removal from the natural gas
is carried out with the use of Sulfinol-M solution which consists of
water, sulfolane and MDEA (methyl-diethanolamine). Sulfolane is a
polar organic compound which has potential for absorbing acid
gases (H2S and CO2) (Jou et al., 1990), it is synthesized by reacting
sulfur dioxide gas and butadiene to produce the intermediate
product 3-sulfolene and then the reaction of 3-sulfolene with
hydrogen gas to sulfolane and this chemical is commercially pro-
duced and available for purchase (Stewart and Minnear, 2010). The
sulfinol-M solution is mainly used for the selective absorption of
H2S from the natural gas in presence of CO2 (Nasir, 1990). Sulfinol-
M solution is a physical e chemical solution in which, sulfolane is
responsible for the physical absorption and MDEA for chemical
absorption through reactions (1e4) (D.L. Nikolic, 2009; Kohl and
Nielsen, 1997; Processors, 2004) by simultaneously utilizing phys-
ical and chemical solvents, the sulfinol-M process is benefited by
advantages of the both solvents which are the high solvent capacity
of physical solvents and high purity of sweetened gas of chemical
solvents (Kunkel, 1971; Nikolic).
Aspen plus v7.3 was used for simulation of this process and a
screenshot of the simulation is shown in Fig. 2. ELECNRTL model is
used for the simulation of this process.
3.3. Chelated iron (LO CAT) process
The LO CAT process uses ferric iron solution for the removal of
H2S, the use of Fe(III) as a regenerable oxidant for the removal of
H2S from gases began at 1830 with introduction of Fe2O3 (Kohl and
Nielsen, 1997). The gas sweetening with the use of chelated iron
solution is an economical and environmentally clean process and
the solution in this process is not toxic (Kohl and Nielsen, 1997; Yu
et al., 2014). The technology of using iron evolved to homogenous
redox catalysts using Fe(EDTA) (Thompson, 1980). EDTA is an
abbreviation for Ethylene Diamine Tetra Acetic which is available
(1) for purchase. H2S absorbed in the solution is oxidized by ferric ion
and is then converted to elemental sulfur (Kohl and Nielsen, 1997);
(2)
2Fe3þ þ HS )/ 2Fe2þ þ S þ Hþ (5)
(3)
1
2Fe2þ þ O þH2 O)/2Fe3þ þ20H (6)
2 2
Simulation of this process is carried out with the use of Aspen
plus v7.3. The simulation flow sheet is shown in Fig. 3. Because of
the ionic nature of the absorption reactions, the ELECNRTL model
has been used for the simulation of this process.
18 A. Kazemi et al. / Journal of Natural Gas Science and Engineering 20 (2014) 16e22

Fig. 1. A screenshot of process flow diagram of the mixed amine process.

Fig. 2. A screenshot of process flow diagram of the sulfinol-M process.

Fig. 3. A screenshot of process flow diagram of the Lo-cat process.

A typical molar ratio of iron in the solution to H2S in the feed gas
is 4:1 (Kohl and Nielsen, 1997). This ratio is applied for determi-
nation of concentration of iron in the solution. The regeneration of
the solution is carried out with the use of air at the regeneration
column's pressure. The regeneration reaction usually occurs in a
packed or spray bed (Yang et al., 2002).
Efficiency of hydrogen sulfide removal of this process is close to
100%.(Kohl and Nielsen, 1997). In this process no heating or cooling
of the solution in circulation is needed (Kohl and Nielsen, 1997;
Processors, 2004).
3.4. Shell paques process
The development of shell e paques technology by shell and
paques companies, was originally for treatment of natural gas,
synthesis gas and the tail gases of the clause process. This process
 A. Kazemi et al. / Journal of Natural Gas Science and Engineering 20 (2014) 16e22
uses the same technology as thiopaq technology, which is used for
treatment of high pressure sour gases (up to 1300 psig) in oil, gas
and petrochemical industries (Benschop et al., 2002). This process
is suitable for H2S range of 100 ppmv to very high H2S concentra-
tions and pressure range of 1e75 bar and complete removal of H2S
can be achieved in this process (Benschop et al., 2002). In the shell
process the absorption of acid gases is carried out with the use of
caustic solution which contains caustic soda, water and sulfur
bacteria (Processors, 2004). Sodium hydroxide solutions are
commercially available for purchase. The solution contacts the sour
gas in the absorber column and the caustic soda (NaOH) absorbs
H2S, the rich solution goes to a bioreactor in which the solution is
aerated and H2S is converted to elemental sulfur (Processors, 2004).
The reaction of absorption of H2S is (Sherbaniuk et al., 2003):
NaOH / Naþ þ OH
H2S þ OH / HS þ H2O
It can be concluded from reactions (7) and (8) that absorption of
H2S consumes the OH ion (and thus caustic solution). And the re-
action occurring in the bioreactor producing the consumed OH is:
1 1
HS þ O2 / S8 þOH
2 8
Existence of micro-organisms in the bioreactor increases the
rate of reaction (9), in which hydroxyl ion is reproduced. The
reproduced OH ion can absorb another H2S molecule in the
absorber. Absorption rate of CO2 is low and this solution selectively
absorbs H2S from the natural gas. Based on reaching pipeline
specifications for the sweet natural gas, simulation of this process is
carried out using Aspen hysys v7.3. The PRSV property package has
been used in this simulation and a screenshot of simulation flow
sheet is shown in Fig. 4.
4. Results and discussion
4.1. Economic evaluation of the four processes
The economic evaluation for all of the four processes is carried
out with use of Aspen process economic analyzer 8.1.
Fig. 4. A screenshot of process flow diagram of shell process.
19
One of the most important parameters in the acid gas removal
units is the flow rate (gpm) of the solution in circulation and the
project costs are strong functions of solution in circulation. As re-
ported by (Chan and Tontiwachwuthi, 1996) 70% of the investment
of a plant is directly related to this parameter. The reason of this
influence is that the solution circulation rate affects the size of fa-
cilities like absorber, piping and regenerator (Chan and
Tontiwachwuthikul, 1996). After completing the simulation for
the four processes, this parameter is extracted from the simulators
and the results are shown in Fig. 5.
Thus, based on the data extracted from the simulators, the shell
process needs the lowest solution flow rate for acid gas removal (in
order to meet pipeline specifications). The Sulfinol-M and mixed
amine processes also need lower solution flow rates than the LO
CAT process. The difference between the needed flow rate of shell
(7) process and the other three processes is significant, while the
needed flow rate of solution for mixed amine, sulfinol-M and LO
(8) CAT processes are relatively close. High solution flow rate causes
the plant to require larger equipment and thus causes the costs of
the plant to increase, on the other hand the rich solution acid gas
concentration will decrease due to high flow rate of the solution
and thus the corrosion rate will decrease at the pipes and equip-
ment. Based on this information, a process cannot be chosen only
based on the solution flow rate.
(9)
Another important operating parameter in the acid gas removal
unit is the solution loading which is defined as the number of moles
of acid gas removed from the natural gas to the number of the moles
of the material which is used for the purpose of absorption. The
loading describes the capability of 1 mol of the solvent in absorbing
the acid gases. When the acid gas loading is high, the corrosion rate in
facilities would be high too, so in accordance to Fig. 6 the shell process
has the worst performance when corrosion is taken into account. And
the best process in this case is the mixed amine process, while per-
formance of the LO CAT process is well too. Of course this parameter
shouldn't be taken into account separated from the solution flow rate,
because as the rich amine acid gas loading increases, the solution
flow rate needed (for a specific feed gas) decreases, thus the unit
would have higher costs related to corrosion in facilities while lower
fixed and operating costs related to solution flow rate.
The operating costs of the processes are extracted from the
Aspen process economic analyzer v8.1 for four different flow rates
of the sour gas and the results are shown in Fig. 7. The main
20 A. Kazemi et al. / Journal of Natural Gas Science and Engineering 20 (2014) 16e22

Fig. 5. Required solution flow rate (gpm) in order to meet pipeline specifications for different sour gas flow rates.

Fig. 6. Rich solution loading for different processes at different sour gas flow rates.

operating costs for sweetening units are the costs related to the
energy consumed in the reboilers of the regeneration columns (or
production of open steam), pumps and heaters.
As indicated in Fig. 7, in this case study, the best process for acid
gas removal based on the total annual operating costs is the LO CAT
process, the shell and the sulfinol-M processes also have lower
operating costs than the mixed amine process.
The total capital costs of the four processes are extracted from
ASPEN process economic analyzer v8.1 and the results are shown in
Fig. 8.
As shown in Fig. 8 based on total capital costs, the LO CAT
process is the best process for the removal of acid gases from the
sour natural gas described in Section 2. The sulfinol-M has the
highest capital costs among the four processes and mixed amine

Fig. 7. Annual operating costs (US$/year) for different processes at different sour gas flow rates.
 A. Kazemi et al. / Journal of Natural Gas Science and Engineering 20 (2014) 16e22
Fig. 8. Total capital costs (US$) for different processes at different sour gas flow rates.
and shell processes have lower capital costs than Sulfinol-M pro-
cess and higher than LO CAT process.
To choose one of the four processes, not only capital and oper-
ating costs, but also costs related to high corrosion rate for the
processes should be taken into account. As shown in Figs. 7 and 8,
the LO CAT process has the best economic performance for this feed
at developmental sour gas flow rates (5-20 MMSCFD). Also from
Fig. 6 it is clear that the LO CAT and the mixed amine processes are
the two processes which have better performance based on rich
solution acid gas loading and thus, have lower costs related to
corrosion in facilities. With regard to the two aspects, it seems that
the LO CAT process is the best process when capital and operating
costs along with acid gas loading are taken into account. As indi-
cated in Figs. 5e8, the simulation and economic evaluation of the
four processes have been carried out for low (developmental) sour
gas flow rates. However the large flow rates of sour natural gas for
industrial applications can be the topic of the future studies.
5. Conclusions
For the purpose of sweetening of the natural gas with relatively
high H2S content 5 mol% and low CO2 content 1.33 mol% with the
conditions described in Section 2, a suitable alkalonamine solution
is selected and then the process of sweetening with the use of
alkalonamines is simulated and economically evaluated; three
other processes which are also suitable for the sweetening of nat-
ural gas of this type are simulated and economically evaluated and
then compared to the alkalonamine process. It has been revealed
that in this case, the LO CAT process is more economical than the
alkalonamine process which is the most popular process for the
purpose of natural gas sweetening.
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