Summary: In this study, the solubility of hydrogen sulfide and carbon dioxide in MDEA aqueous
solution was evaluated by special data packages of Aspen Plus (V 8.2). Comparison of modeling
results with a series of laboratory and industrial data released from 1997 to 2010 indicates the high
accuracy of PMDEA data package to prediction of acid gas solubility compared to the KEMDEA
package, especially in the range of acid gases operational concentration.
Keywords: MDEA, PMDEA data package, KEMDEA, Acid gas solubility, ELECNRTL
1. INTRODUCTION
Sour gas sweetening is one of the most important natural gas refining processes, which is done to remove acid gases such
as H2S and CO2 in order to reduce the corrosion rate, improve the gas quality, reduce the toxicity of catalysts, etc.
Alkanolamines such as MDEA, DEA and mixtures of MDEA/PZ and MDEA/DEA are used as the most common chemical
solvents for natural gas sweetening.
Prediction of H2S and CO2 solubility and examining the accuracy of such a thing is highly essential to design and
simulation of natural gas sweetening units. Because of this, Nowadays vary thermodynamic models are developed. Some of
these models modified to predict the equilibrium behavior of electrolyte solutions have been established based on two
separate methods. The first method, known as CorrelationBased approach, includes two thermodynamic packages of
Amine and APISour, which are embedded in the thermodynamic models series of Aspen HYSYS application. The
second method, known as Activity Coefficient ModelBased approach, has improved the accuracy of simulation results
than ever based on theoretical foundations and using experimental data. Meanwhile, several thermodynamic packages such
as ELECNRTL and ACID GAS are established based on the second method, which include data required for equilibrium
calculations of gas mixtures, acid gases and amine solutions.
As mention before, many studies have already been done on predicting the solubility of acid gases in amine solutions.
Deshmukh and Mather (1981) used the activity coefficients model to predict the solubility of H 2S and CO2 in amine
solutions [1]. Posey et al. (1996) used a simple model for prediction of acid gas solubility in alkanolamines [2]. Prashanth
Patil (2006) evaluated the solubility of H2S and CO2 in MDEA aqueous solution by the extended model of Kenneth
Eisenberg [3]. Huttenhuis et al. (2009) examined the Solubility of Carbon Dioxide and Hydrogen Sulfide in Aqueous
MDEA Solutions [4].Ying Zhang et al. (2011) also examined CO2 absorption in Aqueous MEA and MDEA Solutions with
electrolyte NRTL model [5, 6]. According to development of chemical process simulators in the last years, many of studies
are focused on comparison of them together. For example, a comparison of computer simulation results of reactive
distillation obtained by Aspen Plus and HYSYS software was done by Smejkalin 2002 [7]. John E. Edwards (2008) used
the combination of various equations of state and activity moles for selection of a suitable thermodynamic package for the
prediction of the enthalpy and the components distribution ratio [8]. Julio et al. (2009) did another comparison between
Aspen Plus and HYSYS for validation of their physical property data banks in ammonia synthesis process simulation [9].
Because one of the main applications of amine solutions is CO2 removal from gases, therefore the accuracy of the
absorption column simulation is very important. Hansen et al. (2011) compared the Aspen HYSYS and Aspen Plus
softwares accuracy in prediction of CO2 absorption by MEA solution [10]. Erik i in 2012 did a same work but this study
was focused on CO2 removal from exhaust gas [11]. He also compared Aspen HYSYS and Aspen Plus simulation of CO 2
absorption into MEA from atmospheric gas in the same year [12]. Major studies done in this research were focused on
Corresponding author. Tel.: +98 513 881 5100; fax: +98 513 881 6840.
Email address :fanaei@um.ac.ir.
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Cycle of Science & Industry Company, Tehran, Iran, cs.isi.pjs@gmail.com
2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
Comparison of Aspen Plus special data packages (KEMDEA and PMDEA) for prediction of H2S and CO2 solubility in
MDEA aqueous solution.
2. THEORETICAL FOUNDATIONS
Using thermodynamic relations based on classical concepts of phase equilibriums is an approach resulting in the prediction
of dissolved gases distribution pattern in aqueous amine solvents. However, the use of parameters such as fugacity and
activity is close to the physical senses more than the abstract concept of chemical potential; thus, the equilibrium concept
can be summarized in Equation 1.[14]
(1)
For each component in the mixture, the fugacity equality of liquid and vapor phases resulted from thermodynamic
equilibrium provides the possibility of using distinct thermodynamic models for the phases. Therefore, the fugacity in each
phase has a different form in such a way that to predict the vapor phase fugacity coefficients, an equation of state will be
used, while an activity model is used for the liquid phase. In the following, the calculation methods of vaporliquid
equilibrium condition by equation of state and activity model in ELECNRTL thermodynamic package are discussed.
2.1
As mentioned, another method to predict the equilibrium behavior of electrolyte solutions embedded in Aspen One (V 8.2)
package is the activity coefficient modelbased approach, which is established based on calculating the activity coefficients
of the components in the liquid phase. The ELECNRTL thermodynamic package, embedded in the thermodynamic
packages series of Aspen Plus software, was studied according to the goals of this investigation. In this thermodynamic
package, the RedlichKwong equation of state (RK) was selected to calculate the fugacity coefficient of components in the
vapor phase. The general form of the RK equation of state is shown with its parameters in the following equation: [15]
(2)
But what has distinguished this thermodynamic package compared to other similar types, is the use of modified Electrolyte
NRTL model to calculate the activity coefficients of the components in the liquid phase. The model proposed by Chen et
al. [16], introduces the amount of excess Gibbs energy of the components in nonideal electrolyte solutions, including two
main parts that one is related to the local molecules and ions interactions (LI), and the other is related to LongRange IonIon Interaction (LR). It should be noted that in predicting the equilibrium behavior of electrolyte solutions, determining the
ionic components amounts is of great importance, which is usually done by defining ionization reactions with inclusion of
kinetic data or equilibrium constants.
In this model, to determine the excess Gibbs energy of immediate neighborhood ions and molecules, the NRTL equation is
used in such a way that the effective mole fraction of anionic, cationic and solvent molecules components are calculated
with assumed attraction and repulsion laws. In other words, where the central component is an anion, the solvent and
cationic components can only locate around it and vice versa [15]. Equations 3 and 4 can explain the excess Gibbs free
energy and activity coefficient value [15]:
(3)
(4)
The first term on the right side of equation (3), is the share of excess Gibbs energy related to the interaction of longrange
molecules, which is estimated by PitzerDebyeHuckel equation (Equation 5):
(5)
The second term of Equation 3, which is known as Born equation, is used in order to estimate the Gibbs energy of ion types
in their transfer from the extremely diluted mixture solvent to the extremely diluted aqueous phase, which will be
determined by equation 6:
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2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
(6)
The third term of equation (3) explains the excess Gibbs energy resulted from components interacting that have come
together, which is also known as "Local Interaction Contribution" and estimated based on NonRandom TwoLiquid
(NRTL) theory. All parameters used in the Electrolyte NRTL model can be divided into two general parts [15]:
a.
Dielectric constant of the pure solvent ( ), which is defined only for the solvent component and as the temperaturedependent parameters, and is calculated using Equation 7:
(7)
b.
Binary interaction parameters ( ) are individually defined tailored with the interactive components type in three
following sections.
b.1 Molecule  Molecule interaction parameters (nonionic components), which are defined as follows:
(8)
b.2 ElectrolyteMolecule interaction parameters, which can be calculated according to the following equations:
)
(9)
b.3 Electrolyte  electrolyte interaction parameters can be also calculated according to the following equations:
)
(10)
It should be considered that in the calculation of all the above parameters, the reference temperature was equal to 298.15 K,
and all the temperature variables are also included in terms of the absolute temperature.
In Aspen Plus software package, several databases are available for thermodynamic calculations, which provide the
possibility of using a different set of interaction parameters of ELECNRTL model and Henry constants. Among them, three
special information packages, namely as KEMDEA (Kinetic ELECNRTL MDEA), KMDEA (Kinetic MDEA) and
PMDEA (Posey MDEA) were imbedded that each would be used tailored to a specific usage and given the limits of
experimental conditions for methyldiethanol amine solutions. The calculation basis of components activity coefficients in
the liquid phase was the Electrolyte NRTL model for all the packages, which a difference that their interaction parameters
have been recalled from different databases. The main difference between the KMDEA and KEMDEA packages is in the
equation of state so that the RK equation of state was used in the KEMDEA model, while the SYSOP15M equation of state
was used in the KMDEA model. The PMDEA model developed based on the results of Posey et al. (1997) studies has
considered two parameters of pH and electrical conductivity coefficient of the solution in estimating Henry constant
parameters in order to eliminate measurement error of acid gases solubility, especially at low solubility rates [17]. Since the
poor solubility changes can cause significant changes in pH and the value of solution electrical conductivity, thus, less error
would occur in the measurement values. Finally, by including the pH and electrical conductivity, Posey and Rochelle
provided new parameters for the calculation of Henry constants. As previously mentioned, the accuracy of estimation of
mole fraction of molecular and ionic components considered in the equations in activity models are based on the accuracy
of kinetic data and equilibrium constants of the existing chemical reactions. The Aspen Plus software package uses several
reactions for ionization of acidic components and amine solutions. Herein, the equilibrium and stoichiometric data of acidic
gases reactions in MDEA solution are presented.
Reaction 1
Reaction 4
Reaction 2
Reaction 5
Reaction 3
Reaction 6
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2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
(11)
The parameters (
) were calculated with respect to the range of laboratory temperature and pressure by
optimization methods, which have been used in the Aspen Plus software package. As previously mentioned, in this
software package, the possibility of using several special databases, namely as KEMDEA and PMDEA has been provided
for equilibrium calculations of acid gases and the MDEA. The details of these parameters in the PMDEA and KEMDEA
models are presented in Tables 1 and 2.
Table1. Parameters of the equilibrium constants of reactions in the KEMDEA model [18]
K1
K2
K3
K4
A
9.4165
231.465
216.049
132.899
B
4234.98
12092.10
12431.70
13445.90
C
0
36.7816
35.4819
22.4773
D
0
0
0
0
E
0
0
0
0
K5
214.582
12995.40
33.5471
K6
9.742
8585.47
Table2. Parameters of the equilibrium constants of reactions in the PMDEA model [19]
K1
K2
K3
K4
K5
K6
A
56.2
231.465
216.049
132.899
214.582
32
B
4044.8
12092.1
12431.7
13445.9
12995.4
3338
C
7.848
36.7816
35.4819
22.4773
33.5471
0
D
0
0
0
0
0
0
E
0
0
0
0
0
0
Amine Concentration
(wt.%)
Total pressure
(kPa)
Temperature
(K)
Partial pressure
of CO2 (kPa)
Partial pressure
of H2S (kPa)
MDEA (25.73%)
546.084386.8
313.17
533.904369.69
MDEA(46.78%)
6.211040.0
313.16
01000
MDEA(35%)
MDEA(50%)
6907010
6906990
298.15
298.15
0.2810.12
0.6214.9
0.18815.2
0.19411.3
In this study, the simulation results of an acid gasMDEA equilibrium stage (flash drum) by mentioned data packages were
compared with experimental data. The results are presented in Figures 2 to 7.
Evaluation the solubility of CO2 in the MDEA solution in absence of H2S shows that the special data package of PMDEA
compared to KEMDEA packages has a better estimation capability (Figure 1a).
The results of H2S solubility in MDEA solution in absence of CO2 indicate the lower accuracy of PMDEA package.
Assessment of results in figure 1b shows that the error has occurred in high acid gas solubility, but in the low range of
solubility, the results obtained from the data package of PMDEA have enough validity.
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2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
1.5
KEMDEA
PMDEA
1.4
KEMDEA
PMDEA
1.2
1.4
1.3
1.2
1.1
1
0.9
0.8
0.8
0.9
1.1
1.2
1.3
1.4
1
0.8
0.6
0.4
0.2
0
1.5
0.2
0.4
0.6
0.8
1.2
1.4
Since in sweetening processes, both H2S and CO2 components are usually present in the sour gas stream, thus, investigating
the estimating ability of their interaction effect on solubility by thermodynamic packages is of utmost importance.

The modeling results presented in Figs. 2 to 5 demonstrate the ability to predict the H2S and CO2 solubility simultaneously
in the MDEA solution by PMDEA and KEMDEA packages in low acid gas loading values. However, the increasing this
parameter (loading), will reduce the accuracy of solubility modeling by KEMDEA package compared to PMDEA.

The results of H2S and CO2 solubility in MDEA solution indicate the lower accuracy of KEMDEA package in wide range
of acid gas loading compared to PMDEA (Figs. 2 and 3).
Figs.4 and 5 show that the accuracy of H2S solubility prediction by PMDEA data package was found to decrease with
increasing MDEA concentration. However, for high MDEA concentration values, this data package (PMDEA) also has
high accuracy in predicting CO2 solubility.
T=298.15K, PH2S=0.18815.2 kpa
KEMDEA
0.35
PMDEA
0.6
0.5
KEMDEA
0.3
0.25
0.4
0.3
0.2
0.15
0.2
0.1
0.1
0.05
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.05
0.1
0.15
0.2
0.25
0.3
0.35
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2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
0.4
KEMDEA
PMDEA
0.35
PMDEA
KEMDEA
0.6
0.5
0.3
0.4
0.25
0.3
0.2
0.15
0.2
0.1
0.1
0.05
0
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.1
0.2
0.3
0.4
0.5
0.6
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2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
GEx
Ix
k'
K
M
p
Qe
r
R
T
V
x
y
z'
'
ij
BB'
ca,B, B,ca
ca', ca'' , c'a,c''a
Subscripts
a
B
i,j,k
t
Anion component
Solvent component
Cation component
Species i,j,k
Total
Superscripts
Born
lc
PDH
ref
w
Born equation (related to transfer of ionic species from the infinite dilution state in a mixed
solvent to the infinite dilution state in aqueous phase)
LongRange
PitzerDebyeHuckel (represent the longrange interaction contribution)
Reference state property
Water
6. REFERENCES
Ruchi Deshmukh, A.E ., Mather, A mathematical model for equilibrium solubility of hydrogen sulfide and carbon
dioxide in aqueous alkanolamine solutions, Journal of Chemical Engineering Science, vol. 36, pp. 355362, 1981.
2. Mark Posey, K.G ., Tapperson, G.T .,Rochelle, A simple model for prediction of acid gas solubilities in
alkanolamines, Journal of Gas Separation and Purification, vol. 1, pp. 181186, 1996.
3. Prashant Patil, Z ., Malik, M., Jobson, Prediction of CO2 and H2S Solubility in aqueous MDEA solutions using an
extended Kent and Eisenberg model, Institution of Chemical Engineers Symposium Series, vol. 152, pp. 498510,
2006.
4. Patrick Huttenhuis, N.J., Agrawal, G.F., Versteeg, Solubility of Carbon Dioxide and Hydrogen Sulfide in Aqueous
NMethyldiethanolamine Solutions, Journal of Industrial and Engineering Chemistry, vol. 48, pp. 40514059, 2009.
5. Ying Zhang, H ., Que, C.C ., Chen, Thermodynamic modeling for CO2 absorption in Aqueous MEA Solution with
electrolyte NRTL model, Journal of Fuel and Energy Abstracts, vol. 311, pp. 6775, 2011.
6. Ying Zhang, C.C ., Chen, Thermodynamic modeling for CO2 absorption in Aqueous MDEA Solution with electrolyte
NRTL model, Journal of Industrial and Engineering Chemistry, vol. 50, pp. 163175, 2011.
7. Q., Smejkal, M., Soos, Comparison of computer simulation of reactive distillation using ASPEN Plus and HYSYS
software, Journal of Chemical Engineering and Processing, vol. 41, pp. 413418, 2002.
8. J.E.,Edwards, Process Modelling Selection of Thermodynamic Methods, UK ChemCAD Seminar 2000,Available at:
www.pidesign.co.uk.
9. Alexandre Julio, Comparison of Chemical Process Simulators: Aspen vs. HYSYS, Master Thesis, IST, 2008.
10. E.,Hansen, Aspen HYSYS and Aspen Plus simulation programs for CO 2 absorption, Master's thesis, Telemark
University College, Faculty of Technology, 2011.
1.
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Cycle of Science & Industry Company, Tehran, Iran, cs.isi.pjs@gmail.com
2nd International Conference Of Oil, Gas And Petrochemical, December 18, 2014
11. i, L.E., Removal of CO2 from exhaust gas, Melaaen. M.C., revision of Ph.D. Dissertation Telemark University
College Faculty of Technolo at porsgrumm, Norway, 2012.
12. Lars Eric i, Comparison of Aspen HYSYS and Aspen Plus simulation of CO2 absorption into MEA from
atmospheric gas, Journal of Energy procedia, vol. 23, pp. 360369, 2012.
13. Optimize the entire gas process with acid gas cleaning. Available at: http://www.Aspentech .com/ products/V8releashprior,August 2013.
14. Prausnitz, J.M., Lichtenthaler, R.N., Azevedo, E.G., Molecular thermodynamics of fluidphase equilbria, Third
edition, Prentice Hall, 1998.
15. ASPEN Physical Property system, Physical Property Methods and Models, chap.11.1.
16. Chau Chyun Chen, H.I. Britt, J.F Boston, and L.B. Evans, LocalComposition Model for Excess Gibbs Energy of
Electrolyte Systems, AIChE Journal, vol. 28, p. 588,1982.
17. Mark Leon Posey, G.T., Rochelle, A Thermodynamic Model of MethyldiethanolamineCO2H2SWater,Industrial &
Engineering Chemistry Research, vol. 36, pp. 39443953, 1997.
18. David Austgen, G.T., Rochelle, C.C., Chen, Model of vaporliquid equilibria for aqueous acid gasalkanolamine
systems. 2. Representation of hydrogen sulfide and carbon dioxide solubility in aqueous MDEA and carbon dioxide
solubility in aqueous mixtures of MDEA with MEA or DEA, Industrial & Engineering Chemistry Research, vol. 30,
pp 543555,1991.
19. Even Solbraa, Equilibrium and nonequilibrium thermodynamics of natural gas processing, Ph.D. thesis, Norwegian
University of Science and Technology, 2002.
20. Reda SidiBoumedine, S., Horstmann, K., Fischer, E., Provost, W., Furst, J., Gmehling, Experimental determination
of carbon dioxide solubility data in aqueous alkanolamine solutions, Fluid Phase Equilibria, vol. 218, pp. 8594,
2004.
21. Reda SidiBoumedine, S., Horstmann, K., Fischer, E., Provost, W., Furst, J., Gmehling, Experimental determination
of hydrogen sulfide solubility data in aqueous alkanolamine solutions, Fluid Phase Equilibria, vol. 218, pp. 149155,
2004.
7. AUTHOR DETAILS
M. Vahidi Ferdowsi (vahidi@ksbco.ir) is a research engineer and head of KSB research company. He is
member of gas processing research and technology group at Ferdowsi University of Mashhad, Iran. He
holds BS from Azad Islamic University and MS from Semnan University.
M.A Fanaei (fanaei@um.ac.ir) is the assistant professor of chemical engineering at Ferdowsi University of
Mashhad, Iran. He is member of Iranian Association of Chemical Engineers (IACHE), Energy Optimization
Research Centre and head of gas processing research and technology group. Fanaei was dean of process
control lab and head of chemical engineering department at Ferdowsi University. He holds BS degree in
chemical engineering from Petroleum University of Technology and holds MS and PHD degrees from
Sharif University.
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