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Aspen Plus

Aspen Plus Sulfolane-MDEA Model


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Revision History
Version Description

V7.3 First version.


V7.3.2 Re-verified simulation results using Aspen Plus V7.3.2.
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
V8.6 Update databank to PURE32.
V10.0 Update GMENCC parameters between CO 2 and (MDEAH+, HCO3 - ), and
those between CO 2 and (MDEAH+, CO3 -2 ) to match the data of CO 2
activity coefficient.
Update simulation results.

Revision History 1
Contents
Revision History ......................................................................................................1

Contents..................................................................................................................2

Introduction ............................................................................................................3

1 Components .........................................................................................................4

2 Physical Properties...............................................................................................5

3 Reactions ...........................................................................................................16

4 Simulation Approach ..........................................................................................19

5 Simulation Results .............................................................................................21

6 Conclusions ........................................................................................................22

References ............................................................................................................23

2 Contents
Introduction

This file describes an Aspen Plus model of the CO2 and H2S capture process by
mixed solvent composed of sulfolane, MDEA and water. As process simulation
is not within the scope of current phase of this work, we only give a single
stage flash model to simulate the CO2 and H2S absorption by aqueous
sulfolane-MDEA solution. Thermophysical property models are developed
based on the work of Zhang and Chen (2010) [1,2] and Aspen Technology
(2011)[3]. Reaction kinetic models are based on the works of and Rinker et al.
(1997)[4] and Pinsent et al. (1956) [5]. Transport property models and model
parameters have been validated against experimental data from open
literature.
The model includes the following key features:
 True species including ions
 Unsymmetric electrolyte NRTL activity coefficient model for liquid and PC-
SAFT equation of state for vapor
 Activity-based reaction kinetics
 Electrolyte transport property models

Introduction 3
1 Components

The following components represent the chemical species present in the


process:

Table 1. Components Used in the Model


Component ID Conventional Component name Formula

SULFOLAN Conventional SULFOLANE C4H8O2S


MDEA Conventional METHYL-DIETHANOLAMINE C5H13NO2
H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
MDEAH+ Conventional MDEA+ C5H14NO2+
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
H2S Conventional HYDROGEN-SULFIDE H2S
HS- Conventional HS- HS-
S-2 Conventional S-- S-2
CH4 Conventional METHANE CH4
C2H6 Conventional ETHANE C2H6
C3H8 Conventional PROPANE C3H8
C4H10 Conventional N-BUTANE C4H10-1

4 1 Components
2 Physical Properties

The unsymmetric electrolyte NRTL property method (ENRTL-RK) and PC-SAFT


equation of state are used to compute liquid and vapor properties in the
sulfolane-MDEA model. CO2, H2S, CH4, C2H6, C3H8 and C4H10 are selected as
Henry-components to which Henry’s law is applied. Henry’s constants are
specified for these components with water, MDEA and sulfolane. In the
reaction calculations, the activity coefficient basis for the Henry’s components
is chosen to be Aqueous. Therefore, in calculating the unsymmetric activity
coefficients of the solutes, the infinite dilution activity coefficients will be
calculated based on infinite-dilution condition in water, instead of in mixed
solvents.
The Henry’s constant parameters for CO2, H2S, CH4, C2H6, C3H8 and C4H10 are
obtained from the literatures or regressed with the VLE data (See Table 2).

Table 2. Henry’s constants


Solute Solvent Source

CO2 H2 O Yan and Chen (2010) [6]


H2 S H2 O Zhang and Chen (2010) [2]
CH4 H2 O Zhang and Chen (2010) [2]
C 2 H6 H2 O Zhang and Chen (2010) [2]
C 3 H8 H2 O Zhang and Chen (2010) [2]
C 4 H10 H2 O Zhang and Chen (2010) [2]
CO2 MDEA Zhang and Chen (2010)[1]
H2 S MDEA Set to that of H2 S in H2 O
CH4 MDEA Zhang and Chen (2010) [2]
C 2 H6 MDEA Zhang and Chen (2010) [2]
C 3 H8 MDEA Zhang and Chen (2010) [2]
C 4 H10 MDEA Zhang and Chen (2010) [2]
CO2 Sulfolane Regression with CO 2 -sulfolane VLE data[7-11]
H2 S Sulfolane Regression with H2 S-sulfolane VLE data[7-10]
CH4 Sulfolane Regression with CH4 -sulfolane VLE data[7]
C 2 H6 Sulfolane Regression with C 2 H6 -sulfolane VLE data[7]
C 3 H8 Sulfolane Set to that of C 3 H8 in H2 O
C 4 H10 Sulfolane Set to that of C 4 H10 in H2 O

2 Physica l Prope rties 5


The Antoine equation parameters, DIPPR heat of vaporization equation
parameters, ideal gas heat capacity correlation parameters and PC-SAFT pure
component parameters for MDEA are taken from the work of Zhang and Chen
(2010)[1].
The parameters of the ideal gas heat capacity correlations for sulfolane are
obtained by fitting the liquid heat capacity data of sulfolane generated from
DIPPR correlation[3]. In addition, dielectric constants of solvent sulfolane are
regressed against the dielectric constant data[12-16]. The characteristic volume
parameters of H2O for the Brelvi-O’Connell model are taken from Brelvi and
O’Connell (1972) [17]; those of CO2 are obtained from Yan and Chen (2010) [6];
those of CH4 and C2H6 are obtained from Zhang and Chen (2010) [2]. For the
other selected components, the parameters are taken from Aspen databank[3].
Unless specified otherwise, the binary interaction parameters for all molecule-
molecule pairs and electrolyte-electrolyte pairs are defaulted to be zero. All
molecule-electrolyte binary parameters are defaulted to (8, -4), average
values of these parameters [18]. The nonrandomness factor is fixed at 0.2.
The NRTL interaction parameters between MDEA and H 2O are taken from the
work of Zhang and Chen (2010) [1], which are determined from the regression
with binary VLE data[19-21], excess enthalpy data[22-24] and heat capacity
data[25-27]. The NRTL parameters for the sulfolane-H2O binary are identified by
fitting the experimental VLE data[14,28-30] and excess enthalpy data[14,28,29] of
the sulfolane-H2O system. The NRTL binary parameters for sulfolane-CO2 and
sulfolane-H2S systems are respectively regressed against the experimental
solubility data[7-11] of CO2 and H2S in sulfolane solvent.
The interaction parameters (GMENCC) between H2O and (MDEAH+, HCO3-),
H2O and (MDEAH+, CO3-2), and those between MDEA and (MDEAH +, HCO3-),
are regressed using the ternary VLE data[31-33], CO2 absorption heat data[34, 35],
ternary heat capacity data[36] and liquid phase concentration data of MDEA-
H2O-CO2 system from NMR spectrum [37].
The interaction parameters (GMENCC) between H2O and (MDEAH+, HS-) and
those between MDEA and (MDEAH +, HS-), are regressed with the solubility
data of H2S in aqueous MDEA solution[38-40].
For a detailed description of the thermodynamic model for MDEA-CO2-H2S-
H2O system, please see the article from Zhang and Chen (2010) [1,2].
The NRTL interaction parameters between sulfolane and (MDEAH+, HCO3-)
and between sulfolane and (MDEAH+, CO3-2) are then identified by fitting VLE
data for the sulfolane-MDEA-CO2-H2O quaternary system [41]. The NRTL binary
parameters for the sulfolane-(MDEAH+, HS-) pair are regressed using the VLE
data for the sulfolane-MDEA-H2S-H2O quaternary system [41].
The liquid molar volume model and transport property models and model
parameters have been updated according to experimental data from the
literature. Specifications include:
 For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus,
is used with option code 1 to use the quadratic mixing rule for solvents.
The interaction parameter VLQKIJ for the quadratic mixing rule between
MDEA and H2O is regressed against experimental MDEA-H2O density data
from Berbal-Garcia et al. (2003)[42]. The interaction parameter VLQKIJ

6 2 Physical Properties
between sulfolane and H 2O is validated by experimental sulfolane-H2O
density data from the literature[14,30,43-52]. The Clarke model parameter
VLCLK/1 is also regressed for main electrolytes (MDEAH+, HCO 3 ) and
(MDEAH+, CO3-2 ) against experimental density data of the MDEA-H2O-CO2
system from Weiland et al. (1998)[53], and that for (MDEAH +, HS-) is
regressed against experimental data of the MDEA-H2O-H2S system from
Rinker et al. (2000) [54]. The Clarke model parameters VLCLK/1 are left to
the default for other electrolytes.
 For liquid viscosity, the Jones-Dole electrolyte correction model, called
MUL2JONS in Aspen Plus, is used with the mass fraction based ASPEN
liquid mixture viscosity model for the solvent. There are three models for
electrolyte correction and the sulfolane-MDEA model always uses the
Jones-Dole correction model. The three option codes for MUL2JONS are
set to 1 (mixture viscosity weighted by mass fraction), 1 (always use
Jones and Dole equation when the parameters are available), and 2
(ASPEN liquid mixture viscosity model), respectively. The interaction
parameters between MDEA and H2O in the ASPEN liquid mixture viscosity
model, MUKIJ and MULIJ, are regressed against experimental MDEA-H2O
viscosity data from Teng et al. (1994)[55]. MUKIJ and MULIJ for sulfolane-
H2O binary are regressed against experimental sulfolane-H2O viscosity
data from the literature[14,43-51,56]. The Jones-Dole model parameter,
IONMUB, for MDEAH+ is regressed against MDEA-H2O-CO2 viscosity data
from Weiland et al. (1998)[53], that of CO3-2 is regressed against K2CO3-
H2O viscosity data from Pac et al. (1984)[57], that of HCO3- is regressed
against KHCO3-H2O viscosity data from Palaty (1992)[58] and that of HS - is
regressed against MDEA-H2O-H2S viscosity data from Rinker et al.
(2000)[54].
 For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG
in Aspen Plus, is used with its option codes set to -9 (exponent in mixing
rule) and 1 (electrolyte system). The predictions of surface tension of the
MDEA-H2O-CO2 system can be in the range of the experimental data from
Weiland (1996)[59]. No additional adjusted parameters are used in the
surface tension model.
 For thermal conductivity, the Riedel electrolyte correction model, called
KL2RDL in Aspen Plus, is used.
 For binary diffusivity, the Nernst-Hartley model, called DL1NST in Aspen
Plus, is used with option code of 1 (mixture viscosity weighted by mass
fraction).

In addition to the updates with the above liquid volume and transport
properties, the aqueous phase Gibbs free energy (DGAQFM) and enthalpy
(DHAQFM) of formation at infinite dilution at 298.15 K and the heat capacity
at infinite dilution (CPAQ0) for MDEAH+ are regressed with VLE[31-33], heat of
absorption[34,35], heat capacity[36] and liquid phase concentration data[37]. The
CPAQ0 of HCO3-, CO3-2 and HS- are the average values of heat capacity
between 298 K and 473 K taken from Criss and Cobble (1964)[60], and that of
S-2 is calculated from the Criss-Cobble correlation[60] with the entropy value
from Wagman et al. (1982) [61].
As the estimation results of various transport and thermal properties for the
MDEA-CO2/H2S-H2O ternary system have been summarized in the Aspen

2 Physica l Prope rties 7


documentation[62], only the transport and thermal properties for the sulfolane-
MDEA-CO2/H2S-H2O quaternary system will be presented here.

1200

1000

800
Density, kg/m3

600

400
EST Sulfolane 5wt%+MDEA 5wt%
200 EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 1. Liquid density of sulfolane-MDEA-CO2-H2O at 298.15 K

1200

1000

800
Density, kg/m3

600

400
EST Sulfolane 5wt%+MDEA 5wt%
200 EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/m ol MDEA)

Figure 2. Liquid density of sulfolane-MDEA-H2S-H2O at 298.15 K

8 2 Physical Properties
0.01

Viscosity, PaS

0.001

EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%

0.0001
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 3. Liquid viscosity of sulfolane-MDEA-CO2-H2O at 298.15 K

0.01
Viscosity, PaS

0.001

EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%

0.0001
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 4. Liquid viscosity of sulfolane-MDEA-H2S-H2O at 298.15 K

2 Physica l Prope rties 9


0.08

0.07

0.06
Surface Tension, N/m
0.05

0.04

0.03

0.02 EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
0.01 EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%

0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 5. Surface tension of sulfolane-MDEA-CO2-H 2O at 298.15 K

0.08

0.07

0.06
Surface Tension, N/m

0.05

0.04

0.03

0.02 EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
0.01 EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%

0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 6. Surface tension of sulfolane-MDEA-H 2S-H 2O at 298.15 K

10 2 Physical Properties
0.6

0.5

Thermal Cnductivity, Watt/m-K


0.4

0.3

0.2

EST Sulfolane 5wt%+MDEA 5wt%


0.1 EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 7. Liquid thermal conductivity of sulfolane-MDEA-CO2-H 2O at 298.15 K

0.6

0.5
Thermal Cnductivity, Watt/m-K

0.4

0.3

0.2

EST Sulfolane 5wt%+MDEA 5wt%


0.1 EST Sulfolane 10wt%+MDEA 10wt%
EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 8. Liquid thermal conductivity of sulfolane-MDEA-H 2S-H 2O at 298.15 K

2 Physica l Prope rties 11


5000

4500

4000
Heat Capacity, J/kg-K 3500

3000

2500

2000

1500

1000 EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
500 EST Sulfolane 15wt%+MDEA 15wt%
EST Sufolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 9. Liquid heat capacity of sulfolane-MDEA-CO2-H2O at 298.15 K

5000

4500

4000
Heat Capacity, J/kg-K

3500

3000

2500

2000

1500
1000 EST Sulfolane 5wt%+MDEA 5wt%
EST Sulfolane 10wt%+MDEA 10wt%
500 EST Sulfolane 15wt%+MDEA 15wt%
EST Sufolane 20wt%+MDEA 20wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 10. Liquid heat capacity of sulfolane-MDEA-H 2S-H 2O at 298.15 K

12 2 Physical Properties
0

-20000

Integral Heat of Solution, J/mol


-40000

-60000

-80000

-100000

-120000 EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
-140000 EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%
-160000
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol MDEA)

Figure 11. Integral heat of solution of CO 2 in sulfolane-MDEA-H2O at 298.15 K

-10000
Integral Heat of Solution, J/mol

-20000

-30000

-40000

-50000

-60000 EST Sulfolane 5wt%+MDEA 5wt%


EST Sulfolane 10wt%+MDEA 10wt%
-70000 EST Sulfolane 15wt%+MDEA 15wt%
EST Sulfolane 20wt%+MDEA 20wt%

-80000
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 12. Integral heat of solution of H 2S in sulfolane-MDEA-H2O at 298.15 K

2 Physica l Prope rties 13


1.0E+04

1.0E+03

CO 2 partial pressure, kPa


1.0E+02

EXP 313.15 K
1.0E+01
EXP 373.15 K

1.0E+00

1.0E-01
0 0.5 1 1.5 2
CO2 loading (m ol CO2/ m ol MDEA)

Figure 13. CO2 partial pressure of the sulfolane-MDEA-CO2-H 2O system at


313.15 K and 373.15 K, experimental data from Macgregor and Mather
(1991)[41]

1.0E+04

1.0E+03
H2 S partial pressure, kPa

1.0E+02

1.0E+01
EXP 313.15 K
EXP 373.15 K

1.0E+00

1.0E-01
0 0.5 1 1.5 2 2.5
H2S loading (m ol H2S/ m ol MDEA)

Figure 14. H 2S partial pressure of the sulfolane-MDEA-H2S-H2O system at


313.15 K and 373.15 K, experimental data from Macgregor and Mather (1991)
[41]

14 2 Physical Properties
1.0E+05

Predicted gas partial pressure, kPa


1.0E+04

1.0E+03

EXP CO2 pressure (313.15 K)


1.0E+02 EXP CO2 pressure (373.15 K)
EXP H2S pressure (313.15 K)
EXP H2S pressure (373.15 K)

1.0E+01
1.0E+01 1.0E+02 1.0E+03 1.0E+04 1.0E+05
Experim ental gas partial pressure, kPa

Figure 15. CO2 or H 2S partial pressure of the sulfolane-MDEA-CO2-H 2S-H 2O


system at 313.15 K and 373.15 K, experimental data from Macgregor and
Mather (1991)[41]

2 Physica l Prope rties 15


3 Reactions

MDEA is a tertiary ethanolamine, as shown below in Figure 16. It can


associate with H + to form MDEAH+ but cannot react with CO2 to produce
carbamate as primary or secondary ethanolamines can.

Figure 16. MDEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY


model with the CHEMISTRY ID = MDEA. This CHEMISTRY ID is used as the
global electrolyte calculation option in the simulation by specifying it on the
Global sheet of the Properties | Specifications form. Chemical equilibrium
is assumed with all the ionic reactions in the CHEMISTRY MDEA. In addition,
a kinetic REACTION model called MDEA-REA has been created. In MDEA-
REA, all reactions are assumed to be in chemical equilibrium except those of
CO2 with OH- and CO2 with MDEA. As sulfolane serves as a physical solvent in
sulfolane-MDEA-H2O mixed solvent, the chemistry and kinetics in aqueous
sulfolane-MDEA solution are regarded as the same as in aqueous MDEA
solution.

A. Chemistry ID: MDEA


1 Equilibrium MDEAH   H 2 O  MDEA  H 3 O 

2 Equilibrium 2H 2 O  H 3 O   OH 
3 Equilibrium CO 2  2H 2 O  HCO 3  H 3 O 
4 Equilibrium HCO 3-  H 2 O  CO 32  H 3 O 
5 Equilibrium H 2 S  H 2 O  HS   H 3 O 

6 Equilibrium HS -  H 2 O  S 2  H 3 O 

16 3 Reactions
B. Reaction ID: MDEA-REA
1 Equilibrium MDEAH   H 2 O  MDEA  H 3 O 
2 Equilibrium 2H 2 O  H 3 O   OH 
3 Equilibrium HCO 3-  H 2 O  CO 32  H 3 O 
4 Equilibrium H 2 S  H 2 O  HS   H 3 O 
5 Equilibrium HS -  H 2 O  S 2  H 3 O 

6 Kinetic CO 2  OH -  HCO 3
7 Kinetic HCO 3  CO 2  OH 
8 Kinetic MDEA  CO 2  H 2 O  MDEAH   HCO 3-
9 Kinetic MDEAH   HCO 3-  MDEA  CO 2  H 2 O

The equilibrium constants for reactions 1-6 in MDEA are calculated from the
standard Gibbs free energy change. DGAQFM, DHAQFM and CPAQ0 of
MDEAH+, which are used to calculate the standard MDEAH+ Gibbs free energy,
are obtained from Zhang and Chen (2010) [1]. The DGAQFM (or DGFORM),
DHAQFM (or DHFORM) and CPAQ0 (or CPIG) parameters of the other
components can be obtained from the databank of Aspen Plus[3].
The power law expressions are used for the rate-controlled reactions
(reactions 6-9 in MDEA-REA):

  E  1 1  N
r  k T T0  exp     xi  i  i
n a
(1)
 R  T T0  i 1

Where:
r = Rate of reaction;
k = Pre-exponential factor;
T = Absolute temperature;
T0 = Reference temperature;
n = Temperature exponent;
E = Activation energy;
R = Universal gas constant;
N = Number of components in the reaction;
xi = Mole fraction of component i;
γi = Activity coefficient of component i;
ai = The stoichiometric coefficient of component i in the reaction equation.
If T0 is not specified, the reduced power law expression is used:

3 Reactions 17
E N
r  kT n exp   xi  i  i
a
(2)
 RT  i 1
In this work, the reduced expression is used. In equation (2), the factor n is
zero, and k and E are given in Table 3.
The kinetic parameters for reaction 6 in Table 3 are taken from the work of
Pinsent et al. (1956)[5]. The kinetic parameters for reaction 7 are calculated
by using the kinetic parameters of reaction 6 and the equilibrium constants of
the reversible reactions 6 and 7. The kinetic parameters for reaction 8 are
taken from the work of Rinker et al. (1997)[4] and the kinetic parameters for
reaction 9 are calculated by using the kinetic parameters of reaction 8 and
the equilibrium constants of the reversible reactions 8 and 9.

Table 3. Parameters k and E in Equation (2)


Reaction No. k E , cal/mol
6 1.33E+17 13249
7 6.62E+16 25656
8 6.85E+10 9029
9 6.62E+17 22131

18 3 Reactions
4 Simulation Approach

Process simulation is not within the scope of current phase of this work so we
decided to use a single stage flash model to simulate the CO 2 and H2S
absorption by the mixed solvent sulfolane-MDEA-H2O.
Simulation Flowsheet – The absorber has been modeled with the
simulation flowsheet in Aspen Plus shown in Figure 17. CO2 and H2S in stream
GASIN are absorbed by the mixed solvent (40 wt% sulfolane + 40 wt% MDEA
+ 20 wt% H2O) in stream LEANIN in a FLASH2 block.

Figure 17. Sulfolane-MDEA Simulation Flowsheet in Aspen Plus

4 Simulation Approach 19
Unit Operations - Major unit operations in this model have been represented
by Aspen Plus blocks as outlined in Table 4.

Table 4. Aspen Plus Unit Operation Blocks Used in the


Sulfolane-MDEA Model
Unit Operation Aspen Plus Block Comments / Specifications

Absorber Flash2 1. Temperature is set at 313.15 K


2. Pressure is set at 50 atm.

Streams - Feeds to the absorber are GASIN containing CO2 and H2S and
LEANIN containing aqueous sulfolane-MDEA solution. Feed conditions are
summarized in Table 5.

Table 5. Feed specifications


Stream ID GASIN LEANIN
Substream: MIXED
Temperature: k 313.15 313.15
Pressure: atm 50 50
Total flow 0.2 kmol/sec 1 kmol/sec
Mole-Frac
SULFOLANE 0 0.0812
MDEA 0 0.0561
H2O 0 0.8627
CO2 0.5 0
H2S 0.5 0

Prop-Sets - A Prop-Set, XAPP, has been created to report apparent mole


fraction of H2S, CO2, sulfolane and MDEA in liquid streams to facilitate
calculations of acid gas loadings of the streams.

20 4 Simulation Approach
5 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 6.

Table 6. Key Simulation Results


Stream ID GASOUT RICHOUT

Temperature: K 313.15 313.15


Pressure: atm 50 50
Total flow, kmol/sec 0.0818 1.090
Component flow, kmol/sec
SULFOLANE 2.12E-7 0.0812
MDEA 1.41E-10 7.25E-4
H2O 1.41E-4 0.834
CO2 0.0539 0.0178
H2S 0.0278 0.0454
MDEA+ 0.0 0.0554
HCO3- 0.0 0.0282
CO3-2 0.0 2.03E-4
HS- 0.0 0.0268
S2- 0.0 1.53E-6

5 Simulation Results 21
6 Conclusions

The sulfolane-MDEA model provides a thermodynamic basis for rigorous


simulation of acid gas removal process. Key features of this model include
electrolyte thermodynamics and solution chemistry, reaction kinetics for the
liquid phase reactions and rigorous transport property modeling.
The model is meant to be used as a guide for modeling the CO 2 capture
process with aqueous sulfolane-MDEA solution. You may use it as a starting
point for more sophisticated models for process development,
debottlenecking, plant and equipment design, among other uses. Further
validation of this sulfolane-MDEA model will be done when industrial or pilot
plant data become available.

22 6 Conclusions
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Re fere nces 27

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