Aspen Plus

Rate-Based Model of the CO2 Capture Process by

MDEA using Aspen Plus
Copyright (c) 2008-2016 by Aspen Technology, Inc. All rights reserved.

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trademarks of Aspen Technology, Inc., Bedford, MA.

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This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1

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Revision History
Version Description

2006.5 First version

V7.0 Parameters of the electrolyte NRTL model have been regressed again.
The Clarke density model parameters have been regressed again.
Reaction kinetics between CO2 and MDEA has been added.
Mass transfer coefficient method has been changed to Gerster et al.
(1958).
Interfacial area factor has been changed to 2.
V7.1 Update H2 S solubility model parameters
V7.1 CP1 Add N2 , O2 , CO and H2 to the model as Henry components
V7.2 Some mistakes in this document have been fixed:
 Remove 4 unused references
 Update the reference for kinetics in the introduction part from
Pacheco et al. (1998) to Rinker et al. (1997)
 Update the references for CO 2 solubility data from Jou et al. (1982,
1993) to Kuranov et al. (1996) and Kamps et al. (2001)
Update Henry’s constant of CO 2 in H2 O by fitting VLE data of Takenouchi
(1964), Tödheide (1963), Dodds (1956), Drummond (1981), Zawisza
(1981), Wiebe (1940) and Houghton (1957). Update Henry’s constant
of CO2 in MDEA based on the works of Wang (1992).
Update NRTL parameters between MDEA and H2 O by fitting VLE data of
Xu (1991), Voutsas (2004) and Kim (2008), excess enthalpy data of
Posey (1996), Maham (1997) and Maham (2000), and heat capacity
data of Chiu (1999), chen (2001) and Zhang (2002).
Determine DGAQFM, DHAQFM, CPAQ0 of MDEAH+ by fitting VLE data of
Kuranov (1996), Kamps (2001), Ermatchkov (2006), Jou (1982) and
Jou (1993), absorption heat data of Mathonat (1995) and Carson
(2000), heat capacity data of Weiland (1997) and speciation
concentration data of Bottinger (2008) together with the interaction
energy parameters between H2 O and (MDEAH+, HCO3 - ) and those
between MDEA and (MDEAH+, HCO3 - ).
Update interaction parameters between H2 O and (MDEAH+, HS-) and
those between MDEA and (MDEAH+, HS- ) by fitting VLE data of Kuranov
(1996), Kamps (2001) and Huang (1998).
Update figures for properties.
Calculate chemical equilibrium constants from Gibbs free energy,
Update kinetics.
Update simulation results.

Revision History 1
 Version Description

V7.3 Update the MDEA-H2 O-CO2 and MDEA-H2 O-H2 S thermodynamic model
based on the recent works of Zhang and Chen (2011).
Use ENRTL-RK method to replace ELECNRTL method; use PC-SAFT EOS
to model vapor-phase fugacity coefficient for its ability to model at high
pressure.
Update databank to PURE25.
Update the Antoine equation parameters, heat of vaporization
parameters, ideal gas heat capacity parameters and PC-SAFT
parameters for MDEA.
Update the NRTL interaction parameters between MDEA and H2 O, H2 O
and (MDEAH+, HCO3 - ), H2 O and (MDEAH+, CO3 -2 ), MDEA and (MDEAH+,
HCO3 - ), H2 O and (MDEAH+, HS- ) and those between MDEA and
(MDEAH+, HS- ).
Update the Henry’s constants of CO 2 and H2 S in H2 O and MDEA.
Update DGAQFM, DHAQFM and CPAQ0 of MDEAH+, update CPAQ0 of
HCO3 - , CO3 -2 , HS- and S-2 .
Update the Henry’s constant of CH4 in H2 O and MDEA. Update the
characteristic volume parameter of CH4 for the Brelvi-O’Connell Model.
Update the Clarke model parameter, VLCLK/1, for (MDEAH +, HCO3 - ),
(MDEAH+, CO3 -2 ) and (MDEAH+, HS- ).
Update the Jones-Dole model parameters, IONMUB, for HS- .
Add the missing MDEA parameters for transport properties in V7.2.
Add the definition of acid gas loading and amine weight fraction
convention.
Update figures for properties.
Calculate all chemical equilibrium constants from Gibbs free energy.
Update kinetics.
Add temperature estimates in the absorber specification to aid
convergence, update simulation results.
V7.3.2 Update databank to Pure 26
August Update flowsheet to Kaiserslautern Pilot Plant
2012
V8.0 Update databank to PURE27
V8.2 Update databank to PURE28.
Correct mass balance block OVERALL by adding stream MDEAMU.
Update simulation results.
V8.6 Update databank to PURE32.
Update simulation results.
V9.0 Update component lists to match the example file.
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.

2 Revision History
Contents
Introduction ............................................................................................................4

1 Components .........................................................................................................5

2 Physical Properties...............................................................................................6

3 Reactions ...........................................................................................................18

4 Simulation Approach ..........................................................................................21

5 Simulation Results .............................................................................................25

6 Conclusions ........................................................................................................29

References ............................................................................................................30

Contents 3
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by aqueous MDEA from a gas mixture of CO2, H2O, N2, and O2. The model
consists of an absorber and stripper with heat recovery. The feed conditions
and column specifications in the model were loosely based on a pilot plant
study of CO2 capture with MEA performed at the University of Kaiserslautern [1].
Some pilot plant data for CO2/MDEA do exist for the operation of Dome's
commercial North Caroline plant in Canada from Daviet et al. [2] but these
data are not complete enough for the preparation of a complete simulation of
the process.
Thermophysical property models and reaction kinetic models used in the
simulation are based on the works of Zhang and Chen (2011)[3, 4], Rinker et
al. (1997)[5] and Pinsent et al. (1956) [6]. Transport property models and
model parameters have been validated against experimental data from open
literature. Although the simulation does not contain H 2S, physical property
data for this component is included in the properties section of this model
should the user model wish to processes which include H 2S.
This simulation is meant to be used as a guide for modeling the CO 2 capture
process with MDEA. You may use it as a starting point for more sophisticated
models for process development, debottlenecking, and plant and equipment
design, among others.
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
 Rate-based models for columns with structured packing

4 Introduction
1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the Model

ID Type Name Formula

MDEA Conventional METHYL-DIETHANOLAMINE C5H13NO2

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
H2S Conventional HYDROGEN-SULFIDE H2S
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
HS- Conventional HS- HS-
S-2 Conventional S-- S-2
MDEAH+ Conventional MDEA+ C5H14NO2+
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2
CH4 Conventional METHANE CH4

1 Components 5
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,
respectively, in the Rate-based MDEA model. CO2, H2S, N2, O2, CO, H2 and
CH4 are selected as Henry-components to which Henry’s law is applied.
Henry’s constants are specified for these components with water and MDEA.
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 (GAMUS) of the solutes, the infinite dilution
activity coefficients will be calculated based on infinite-dilution condition in
pure water, instead of in mixed solvents.
The Henry’s constant parameters of CO2, H2S and CH4 are obtained from the
literature or regressed with the VLE data (See Table 2). The other Henry’s
constants are retrieved from the Aspen Databank.

Table 2. Henry’s constants

Solute Solvent Source

CO2 H2 O Yan and Chen (2010) [7]

H2 S H2 O Regression with H2 S-H2 O VLE data[8-15]
CH4 H2 O Regression with CH4 -H2 O VLE data[16]
CO2 MDEA Zhang and Chen (2011) [3]
H2 S MDEA Set to that of H2 S in H2 O
CH4 MDEA Regression with CH4 -H2 O-MDEA VLE data[20]

The Antoine equation parameters of MDEA are regressed from the recently
available vapor pressure data[23-25]. The heat of vaporization (from 293 K to
473 K) generated with the regressed Antoine equation parameters through
the Clausius-Clapeyron equation are used to determine the DIPPR heat of
vaporization equation parameters for MDEA. The ideal-gas heat capacity
correlation parameters are obtained by fitting to the liquid heat capacity
data[26-28].
The PC-SAFT parameters of MDEA are regressed from the vapor pressure
data[23-25], the liquid heat capacity data[26-28] and the liquid density data[29. 30].
Those of H2O are obtained from Gross and Sadowski (2002) [31], and those of
the other components are retrieved from the Aspen Databank.
The characteristic volume parameters of H2O for the Brelvi-O’Connell Model,
VLBROC, are obtained from Brelvi and O’Connell (1972) [32], those of CO2 are

6 2 Physical Properties
 obtained from Yan and Chen (2010) [7], those of CH4 are regressed with the
CH4-H2O[16] binary VLE data, and those of MDEA, H 2S, N2, O2 and CO are
defaulted to their critical volume in the Aspen Databank.
Unless specified otherwise, all molecule-molecule binary parameters and
electrolyte-electrolyte binary parameters are defaulted to zero. All molecule-
electrolyte binary parameters are defaulted to (8, -4), average values of the
parameters as reported for the electrolyte NRTL model [33]. The
nonrandomness factor is fixed at 0.2.
The NRTL interaction parameters between MDEA and H 2O are determined
from the regression with binary VLE data[34-36], excess enthalpy data[26, 37, 38]
and heat capacity data[27, 28, 39].
The interaction energy parameters between H 2O and (MDEAH+, HCO3-), H2O
and (MDEAH+, CO3-2), and those between MDEA and (MDEAH +, HCO3-),
GMENCC, are regressed using the ternary VLE data[40-42], CO2 absorption heat
data [43, 44], ternary heat capacity data[45] and liquid phase concentration data
of MDEA-H2O-CO2 system from NMR spectrum [46].
The interaction energy parameters between H 2O and (MDEAH+, HS-) and
those between MDEA and (MDEAH +, HS-), GMENCC, are regressed with the
H2S solubility data in aqueous MDEA solution [47-49].
The interaction energy parameters between CO2 and (MDEAH+, HCO3-), and
those between CO2 and (MDEAH+, CO3-2), GMENCC, are regressed using the
data of CO2 activity coefficient[64].
The dielectric constants of nonaqueous solvents are calculated by the
following expression:

1 1
 T   A  B   (1)
T C 
The parameters A, B and C for MDEA in the Aspen Databank are 21.9957,
8992.68 and 298.15.
The liquid molar volume model and transport property models and model
parameters are adapted according to experimental data from literature. The
adaptation includes:
 For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus,
is used with option code of 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 density data of the
MDEA-H2O system from Bernal-Garcia et al. (2003) [50]. The Clarke model
parameter VLCLK/1 is also regressed for main electrolytes (MDEAH+,
HCO 3 ) and (MDEAH+, CO 32 ) against experimental density data of the
MDEA-H2O-CO2 system from Weiland (1998) [51], and that of (MDEAH +, HS-)
is regressed against experimental data of the MDEA-H2O-H2S system from
Rinker et al. (2000) [52].
 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 available
models for electrolyte correction and the 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

2 Physica l Prope rties 7

 Jones and Dole equation when the parameters are available), and 2
(ASPEN liquid mixture viscosity model), respectively. The interaction
parameters between MDEA and H 2O in the ASPEN liquid mixture viscosity
model, MUKIJ and MULIJ, are regressed against experimental viscosity
data of the MDEA-H2O system from Teng et al. (1994) [53]. The Jones-Dole
model parameter, IONMUB, for MDEAH+ is regressed against MDEA-H2O-
CO2 viscosity data from Weiland et al. (1998)[51]; that of CO32- is
regressed against K 2CO3-H2O viscosity data from Pac et al. (1984) [54]; that
of HCO3- is regressed against KHCO3-H2O viscosity data from Palaty
(1992)[55]; and that of HS - is regressed against MDEA-H2O-H2S viscosity
data from Rinker et al. (2000) [52].
 For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG
in Aspen Plus, is used with its option codes being -9 (exponent in mixing
rule) and 1 (electrolyte system), respectively. The predictions of surface
tension of the MDEA-H2O-CO2 system can be in the range of the
experimental data from Weiland (1996) [56].
 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 its option code set to 1 (mixture viscosity weighted by
mass fraction).
In addition to the updates with the above transport properties, the aqueous
phase Gibbs free energy and heat of formation at infinite dilution and 25°C
(DGAQFM and DHAQFM) and heat capacity at infinite dilution (CPAQ0) for
MDEAH+ are regressed with VLE [40-42], absorption heat [43, 44], heat capacity[45]
and liquid phase concentration data[46]. 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 (1968) [57], and that of S -2 is calculated from the Criss-Cobble
correlation[57] with the entropy value from Wagman et al. (1982) [58].
The estimation results of various transport and thermal properties are
summarized in Figures 1-20. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent MDEA. Apparent
means before reaction, so for example if 1 mole of MDEA is added to 9 moles
of water, and then 0.3 moles of CO2 is added to this mixture at sufficient
pressure to dissolve all the CO2, then the CO2 loading is 0.3/1 = 0.3,
regardless of the forms of CO2 and MDEA after reacting. Weight percent of
MDEA is calculated without CO2, so in the above example, it is calculated from
the mixture of 1 mole of MDEA and 9 moles of water. Since MDEA has a
molecular weight of 119.164 and water has a molecular weight of 18.015, this
is 119.164/(119.164+9*18.015) = 0.42362 or about 42 wt% MDEA.

8 2 Physical Properties
 1200

1150

Density, kg/m 3
1100

1050
EXP MDEA 30w t%
EST MDEA 30w t%
1000 EXP MDEA 40w t%
EST MDEA 40w t%
EXP MDEA 50w t%
950 EST MDEA 50w t%
EXP MDEA 60w t%
EST MDEA 60w t%
900
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

CO2 Loading, mol CO2/mol MDEA

Figure 1. Liquid Density of MDEA-CO2-H2O at 298.15K, experimental data

from Weiland (1998)[51]

1100

1080

1060

1040
Density, kg/m 3

1020

1000 EXP MDEA 10w t%

EST MDEA 10w t%
980 EXP MDEA 20w t%
EST MDEA 20w t%
960 EXP MDEA 30w t%
EST MDEA 30w t%
940 EXP MDEA 40w t%
EST MDEA 40w t%
EXP MDEA 50w t%
920 EST MDEA 50w t%
900
0 0.1 0.2 0.3 0.4 0.5 0.6

H2S Loading, mol H2S/mol MDEA

Figure 2. Liquid Density of MDEA-H 2S-H2O at 298.15K, experimental data

from Rinker et al. (2000)[52]

2 Physica l Prope rties 9

 1000
EXP MDEA 30w t%
EST MDEA 30w t%
EXP MDEA 40w t%
EST MDEA 40w t%
EXP MDEA 50w t%
EST MDEA 50w t%
Viscosity, mPa.S 100 EXP MDEA 60w t%
EST MDEA 60w t%

10

1
0 0.1 0.2 0.3 0.4 0.5

CO2 Loading, mol CO2/mol MDEA

Figure 3. Liquid Viscosity of MDEA-CO2-H 2O at 298.15K, experimental data

from Weiland (1998)[51]

100 EXP MDEA 10w t%

EST MDEA 10w t%
EXP MDEA 20w t%
EST MDEA 20w t%
EXP MDEA 30w t%
EST MDEA 30w t%
EXP MDEA 40w t%
Viscosity, mPa.S

EST MDEA 40w t%

EXP MDEA 50w t%
EST MDEA 50w t%
10

1
0 0.1 0.2 0.3 0.4 0.5 0.6

H2S Loading, mol H2S/mol MDEA

Figure 4. Liquid Viscosity of MDEA-H 2S-H 2O at 298.15K, experimental data

from Rinker et al. (2000)[52]

10 2 Physical Properties
 0.08

0.06

Surface Tension, N/m

0.04
EXP MDEA 30w t%
EST MDEA 30w t%
EXP MDEA 40w t%
EST MDEA 40w t%
0.02 EXP MDEA 50w t%
EST MDEA 50w t%
EXP MDEA 60w t%
EST MDEA 60w t%

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

CO2 Loading, mol CO2/mol MDEA

Figure 5. Surface tension of MDEA-CO2-H 2O at 298.15K, experimental data

from Weiland (1996)[56]

0.08

0.06
Surface Tension, N/m

0.04

EST MDEA 30w t%

0.02 EST MDEA 40w t%

EST MDEA 50w t%
EST MDEA 60w t%
0
0 0.1 0.2 0.3 0.4 0.5 0.6

H2S Loading, mol H2S/mol MDEA

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

2 Physica l Prope rties 11

 0.4

Thermal Conductivity, Watt/m-K

0.3

0.2

EST MDEA 30w t%

0.1 EST MDEA 40w t%
EST MDEA 50w t%
EST MDea 60w t%

0
0 0.1 0.2 0.3 0.4 0.5

CO2 Loading, mol CO2/mol MDEA

Figure 7. Liquid Thermal Conductivity of MDEA-CO2-H2O at 298.15K

0.4
Thermal Conductivity, Watt/m-K

0.3

0.2

EST MDEA 30w t%

0.1 EST MDEA 40w t%
EST MDEA 50w t%
EST MDea 60w t%

0
0 0.1 0.2 0.3 0.4 0.5

H2S Loading, mol H2S/mol MDEA

Figure 8. Liquid Thermal Conductivity of MDEA-H 2S-H2O at 298.15K

12 2 Physical Properties
 140

120

Heat capacity, kJ/kmol.K

100

80

30w t% M D EA , EX P
60 30w t% M D EA , ES T
40w t% M D EA , EX P
40 40w t% M D EA , ES T
50w t% M D EA , EX P
50w t% M D EA , ES T
20 60w t% M D EA , EX P
60w t% M D EA , ES T

0
0 0.2 0.4 0.6 0.8

CO2 loading, mol CO2/mol MDEA

Figure 9. Liquid Heat Capacity of MDEA-CO2-H 2O at 298.15K, experimental

data from Weiland (1997)[45]

120

100
Heat capacity, kJ/kmol.K

80

60
30w t% M D EA , ES T
40 40w t% M D EA , ES T
50w t% M D EA , ES T
20
60w t% M D EA , ES T

0
0 0.1 0.2 0.3 0.4 0.5

H2S loading, mol H2S/mol MDEA

Figure 10. Liquid Heat Capacity of MDEA- H2S-H2O at 298.15K

2 Physica l Prope rties 13

 70

60

Absorption heat, kJ/mol

50

40

30 313K , EX P
313K , ES T
20 353K , EX P
353K , ES T
10 393K , EX P
393K , ES T
0
0 0.5 1 1.5

CO2 loading, mol CO2/ mol MDEA

Figure 11. Integral CO2 absorption heat in aqueous MDEA solution (MDEA
mass fraction = 0.30), experimental data from Mathonat (1995) [43]

50

40
Absorption heat, kJ/mol

30

20
300K, EXP
300K, EST
350K, EXP
10 350K, EST
400K, EXP
400K, EST
0
0 0.5 1 1.5 2 2.5

H2S loading, mole H2S/mole MDEA

Figure 12. Differential H 2S absorption heat in aqueous MDEA solution (MDEA

mass fraction = 0.30), experimental data from Oscarson and Izatt (1990) [59]

14 2 Physical Properties
 1.E+05

1.E+03

CO2 pressure, kPa 1.E+01

313K ,EX P
313K , EX P
1.E-01 353K , EX P
373K , EX P
393K ,EX P
393K , EX P
313K , ES T
1.E-03 353K , ES T
373K , ES T
393K , ES T

1.E-05
0.0001 0.001 0.01 0.1 1 10

CO2 loading, mol CO2/mol MDEA

Figure 13. VLE of MDEA-CO2-H 2O (MDEA mass fraction is around 0.50). Empty
symbols represent experimental data from Jou et al. (1982) [47] and full
symbols represent experimental data from Ermatchkov et al. (2006) [42]

1.E+04

1.E+03
H2 S pressure, kPa

1.E+02

1.E+01
313K, EXP
313K, EXP
343K, EXP
1.E+00 373K, EXP
393K, EXP
313K, EST
1.E-01 343K, EST
373K, EST
393K, EST
1.E-02
0.001 0.01 0.1 1 10

H2S loading, mol H2S/mol MDEA

Figure 14. VLE of MDEA-H 2S-H 2O (MDEA mass fraction is around 0.50). Empty
symbols represent experimental data from Jou et al. (1982) [47] and full
symbols represent experimental data from ter Maat et al. (2004) [49]

2 Physica l Prope rties 15

 1.E+04

1.E+03

CO2 pressure, kPa

1.E+02

0.1, EXP
0.1, EST
0.3, EXP
1.E+01 0.3, EST
0.5, EXP
0.5, EST
0.8, EXP
0.8, EST
1.E+00
0 0.2 0.4 0.6 0.8

CO2 loading, molo CO2/mole MDEA

Figure 15. CO2 partial pressure of the MDEA-CO2-H 2S-H2O system (MDEA
mass fraction is around 0.50) with various H 2S loading (H 2S loading from 0.1
to 0.8), experimental data from Dicko et al. (2010) [60]

1.E+04

1.E+03
H2 S pressure, kPa

1.E+02
0.09, EXP
0.05, EST
0.31, EXP
0.31, EST
1.E+01
0.51, EXP
0.51, EST
0.71, EXP
0.71, EST
1.E+00
0 0.2 0.4 0.6 0.8 1

H2S loading, mole H2S/mole MDEA

Figure 16. H2S partial pressure of the MDEA-CO2-H 2S-H2O system (MDEA
mass fraction is around 0.50) with various CO2 loading from 0.09 to 0.71,
experimental data from Dicko et al. (2010)[60]

16 2 Physical Properties
 16000 298K, EXP
313K, EXP
343K, EXP
348K, EXP
373K, EXP
12000 403K, EXP
298K, EST

Total pressure, kPa

313K, EST
343K, EST
348K, EST
373K, EST
8000 403K, EST

4000

0
0 0.001 0.002 0.003 0.004

CH4 mole fraction

Figure 17. Total pressure of the CH 4-MDEA-H2O system (MDEA concentration

is 3 M), experimental data from Jou et al. (1998) [20]

2 Physica l Prope rties 17

3 Reactions

MDEA is a tertiary ethanolamine, as shown below in Figure 21. It can

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

Figure 21. MDEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with 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
REACTION model called MDEA-REA has been created. In MDEA-REA, all
reactions are assumed to be in chemical equilibrium except that of CO 2 with
OH- and CO2 with MDEA.

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  H 3 O   HCO 3
4 Equilibrium HCO 3  H 2 O  H 3 O   CO 32
5 Equilibrium H 2 S  H 2 O  HS   H 3 O 
6 Equilibrium HS -  H 2 O  S 2  H 3 O 

B. Reaction ID: MDEA-REA

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

18 3 Reactions
 2 Equilibrium 2H 2 O  H 3 O   OH 

3 Equilibrium HCO 3  H 2 O  H 3 O   CO 32

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 (2011) [3]. 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.
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
(2)
 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:

E N
r  kT n exp   xi  i  i
a
(3)
 RT  i 1
In this work, the reduced expression is used. In equation (3), the
concentration basis is mole fraction, the factor n is zero, k and E are given
in Table 3.

3 Reactions 19
 The kinetic parameters for reaction 6 in Table 3 are derived from the work of
Pinsent et al. (1956) [6]. 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) [5] 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 (3)

Reaction No. k E , cal/mol
6 1.33e+17 13249
7 6.63e+16 25656
8 6.85e+10 9029
9 6.62e+17 22131

20 3 Reactions
4 Simulation Approach

The current process is based on the flowsheet for University of

Kaiserslautern’s pilot plant [1] for CO2 capture by MEA which includes an
absorber and a stripper as well as heat integration. We have modified the
flowsheet to accommodate MDEA. Table 4 represents the typical operation
data.
Simulation Flowsheet – The flowsheet for the pilot plant in Notz,
Mangalapally, and Hasse[1] is used for this simulation, as seen in figure 22.

Figure 22. Rate-Based MDEA Flowsheet in Aspen Plus

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

4 Simulation Approach 21
 Table 4. Aspen Plus Unit Operation Blocks Used in the
Rate-Based MDEA Model
Unit Aspen Plus Block Comments / Specifications
Operation

Absorber RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: .98369 bar
4. Reaction: Reaction ID is MDEA-REA
for all stages
5. Packing Type: FLEXIPAC® 700Y
6. Diameter: .2m
7. Height: 20.42m
8. Wash Section Height: .42m
9. Mass transfer coefficient method:
HanleyStruc (2010) [61]
10. Interfacial area method:
HanleyStruc (2010) [61]
11. Flooding Method: Wallis [62]
12. Heat transfer coefficient method:
Chilton and Colburn
13. Film resistance options: Discrxn
for liquid film; Film for vapor film
14. Flow model: Mixed
15. Estimates: provide temperature at
stages 1, 4, 8, 12, 16 and 20. These
estimates are intended to aid
convergence.

22 4 Simulation Approach
 Unit Aspen Plus Block Comments / Specifications
Operation

Stripper RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: 2 bar
4. Reaction: Chemistry ID is MDEA for
Condenser and Reboiler and MDEA-
REA for all other stages
5. Packing Type: FLEXIPAC® 700Y
6. Diameter: .125m
7. Height: 3.42m
8. Mass transfer coefficient method:
HanleyStruc (2010) [61]
9. Interfacial area method:
HanleyStruc (2010) [61]
10. Flooding Method: Wallis[62]
11. Heat transfer coefficient method:
Chilton and Colburn
12. Film resistance options: Discrxn
for liquid film; Film for vapor film
13. Flow model: Mixed
14. Estimates: provide temperature at
feed. These estimates are intended to
aid convergence.
HX1 HeatX 1. Calculation Type: Shortcut
2. Hot Inlet – Cold Outlet Temperature
Difference: 6 C
3. Hot Side Outlet Pressure: 2bar
HX2 Heater 1. Outlet Temperature: 50C
2. Outlet Pressure: 2bar

FLEXIPAC® is a registered trademark of Koch-Glitsch, LP

Streams - Feeds to the absorber are gas stream FLUEGAS containing H2O,
CO2, N2 and O2; and liquid solvent stream LEANIN containing aqueous MDEA
solution loaded with some CO2. Feed conditions are summarized in Table 5.

Table 5. Feed specification

Stream ID FLUEGAS LEANIN
Substream: MIXED
Temperature: C 75 50
Pressure: bar 1 2
Total flow 72 kg/hr 499.68 kg/hr
Mass-Frac Mass-Frac
MDEA 0 0.401
H2O 0.071 0.595
CO2 0.085 0.0041

4 Simulation Approach 23
 Stream ID FLUEGAS LEANIN
N2 0.743 0
O2 0.101 0
CO2 Loading n/a .028 mol CO2 /mol MDEA

Balance Blocks – The water makeup stream flowrate was determined using
a standard balance block. The inlet stream was FLUEGAS and the water
makeup stream for the water balance. The outlet streams were GASOUT,
CO2OUT, and COND.
Because the amine can be lost in the stream COND in an ionized form,
makeup amine was calculated using a design specification block. The total
amine in COND was calculated using the WAPP property set for the total flow
of amine in all speciated forms. Amine was also lost through CO2OUT and
GASOUT.
Prop-Sets - A Prop-Set, XAPP, has been created to report apparent mole
fraction of H2O, CO2 and MDEA in liquid streams to facilitate calculations of
CO2 loading of the streams. The Prop-Set MLLOAD was implemented to
display the CO2 loading of the amine, defined as the ratio of the apparent
mole fractions of CO2 and MDEA.

24 4 Simulation Approach
5 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 6 and Figures 23 - 28.

Table 6. Key Simulation Results

Variable Rate-Based MDEA Model

CO2 mole fraction in GASOUT .0174

CO2 Recovery 69%
Loading of RICHOUT, molCO2/molMDEA 0.085
Stripper Reboiler Duty 6.75 kW
Specific Energy Requirement of the Reboiler 5.75 MJ/kgCO2
Excluding Heat Losses
Makeup Water 2.028 kg/hr
Makeup MDEA 0.0027 kg/hr
Heat Recovery Exchanger Duty 29.36 kW

In this simulation the stripper operates at below 10% of predicted capacity.

The performance of public domain mass transfer correlations for predicting
column operation in this regime are untested.

5 Simulation Results 25
 80

Hanley&Chen, L

70 Hanley&Chen, V

Temperature, C

60

50

40
0 5 10 15 20 25

Packing height from top, m

Figure 23. Absorber Temperature Profiles

120

Hanley&Chen, L
118
Hanley&Chen, V
Temperature, C

116

114

112

110
0 0.5 1 1.5 2 2.5 3 3.5

Packing height from top, m

Figure 24. Stripper Temperature Profiles

26 5 Simulation Results
 0.10

CO2 loading, mol CO2/mol amine

0.08

0.06

0.04

0.02
Hanley&Chen

0.00
0 5 10 15 20 25

Packing height from top, m

Figure 25. Absorber CO 2 Liquid Loading Profile

0.10
CO2 loading, mol CO2/mol amine

0.08

0.06

0.04

0.02
Hanley&Chen

0.00
0 0.5 1 1.5 2 2.5 3 3.5

Packing height from top, m

Figure 26. Stripper CO 2 Liquid Loading Profile

5 Simulation Results 27
 0.015

CO2 mass fraction

0.010

0.005

Hanley&Chen

0.000
0 5 10 15 20 25

Packing height from top, m

Figure 27. Absorber CO2 Liquid Concentration Profile

0.015
CO2 mass fraction

0.010

0.005

Hanley&Chen

0.000
0 0.5 1 1.5 2 2.5 3 3.5

Packing height from top, m

Figure 28. Stripper CO 2 Liquid Concentration Profile

The Hanleystruc (2010) correlation [61] is used to calculate the mass transfer
coefficient and interfacial area in the simulation. The Bravo (1985)
correlation[63] is an alternative for the mass transfer calculation. The results
will be changed if the Bravo (1985) correlation is applied.

28 5 Simulation Results
6 Conclusions

The Rate-Based MDEA model provides a rate-based rigorous simulation of the

process. Key features of this rigorous simulation include electrolyte
thermodynamics and solution chemistry, reaction kinetics for the liquid phase
reactions, rigorous transport property modeling, rate-based multi-stage
simulation with Aspen Rate-Based Distillation which incorporates heat and
mass transfer correlations accounting for columns specifics and hydraulics.

6 Conc lusions 29
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