Aspen Plus

Rate-Based Model of the CO2 Capture Process by

DIPA using Aspen Plus
Copyright (c) 2008-2014 by Aspen Technology, Inc. All rights reserved.

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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

V7.3 First version

V7.3.2 The VLE data of the DIPA-H2O binary system generated from UNIFAC
used for identifying NRTL binary parameters for the DIPA-H2O pair were
replaced by experimental VLE data of the DIPA-H2O system.
August Updated Flowsheet to model the University of Kaiserslautern Pilot Plant.
2012
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
Update the simulation results.
V8.6 Update databank to PURE32.
Update the simulation results.
V10.0 Update GMENCC parameters between CO 2 and (DIPAH+, DIPACOO- ),
and those between CO 2 and (DIPAH+, HCO3 - ) 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 ...........................................................................................................18

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

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

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

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

2 Contents
Introduction

This file describes an Aspen Plus model of the CO2 and H2S capture process by
the aqueous DIPA solution. The model consists of an absorber and stripper
with heat integration. As there appear to be no public domain industrial or
pilot plant data available for aqueous DIPA/CO2 separations, 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]. The flows, feed compositions, reboiler duty, and absorber
and stripper packed heights were adjusted so that the CO 2 recovery was close
to 80% using the HANLEY -STRUC mass transfer correlations. These variables
would need to be adjusted with the choice of different mass transfer
correlations.
Thermophysical property models are developed based on the work of Zhang
and Chen (2010) [2,3] and Aspen Technology (2011) [4]. Reaction kinetic models
are based on the works of Pinsent et al. (1956) [5] and Blauwhoff et al.
(1985)[6]. Transport property models and model parameters have been
validated against experimental data from open literature. Physical property
data for H2S is included in the properties section of this model should the user
wish to model processes which include it.
This simulation is meant to be used as a guide for modeling the CO 2 capture
process with DIPA. 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

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

DIPA Conventional DIISOPROPANOLAMINE C6H15NO2

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
DIPAH+ Conventional
DIPACOO- Conventional
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

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 DIPA
model. CO2, H2S, CH4 and C2H6 are selected as Henry components to which
Henry’s law is applied. Henry’s constants are specified for these components
with water and DIPA. 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 the infinite-dilution
condition in water, instead of in mixed solvents.
The Henry’s constant parameters for CO2, H2S, CH4 and C2H6 are obtained
from the literature or regressed from VLE data (See Table 2).

Table 2. Henry’s constants

Solute Solvent Source

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

H2 S H2 O Zhang and Chen (2010) [3]
CH4 H2 O Zhang and Chen (2010) [3]
C 2 H6 H2 O Zhang and Chen (2010) [3]
CO2 DIPA Calculation with N2 O analogy[8,9]
H2 S DIPA Regression with VLE data for the DIPA-H2 S-H2 O and
sulfolane-DIPA-H2 S-H2 O systems [10-13]
CH4 DIPA Let to be default
C 2 H6 DIPA Let to be default

PC-SAFT pure component parameters for DIPA are regressed against the
vapor pressure data generated from the Antoine equation [4] and experimental
data on liquid density[8,14]. The parameters of the ideal gas heat capacity
correlations for DIPA are then respectively obtained by fitting the
experimental liquid heat capacity data of DIPA [15]. The characteristic volume
parameters of H2O for the Brelvi-O’Connell model are taken from Brelvi and
O’Connell (1972) [16], and those of CO2 are obtained from Yan and Chen
(2010)[7]. For the other selected components, the parameters are taken from
the Aspen databank[4].

2 Physica l Prope rties 5

 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 [17]. The nonrandomness factor is fixed at 0.2.
The NRTL parameters between DIPA and H 2O were regressed against
experimental VLE data[18], enthalpy of mixing data[19] and liquid heat
capacity[20].
The NRTL interaction parameters between H 2O and (DIPAH+, HCO3-) and
those between H2O and (DIPAH+, DIPACOO-) are regressed against VLE data
for the DIPA-CO2-H2O ternary system [10-12,21]. The NRTL binary parameters for
the H2O-(DIPAH+, HS-) and DIPA-(DIPAH+, HS-) pairs are regressed together
using the VLE data for the DIPA-H2S-H2O ternary system [10-12]. The NRTL
interaction parameters for the (DIPAH +, HCO3-)-(DIPAH+, HS-) pair and the
(DIPAH+, DIPACOO-)-(DIPAH+, HS-) pair are determined by the regression for
VLE of the DIPA-CO2-H2S-H2O system[10, 12].
For a detailed description of the thermodynamic model please see the article
from Zhang and Chen (2010) [2,3] for the MDEA-CO2-H2S-H2O system.
The liquid molar volume model and transport property models have been
updated and model parameters are regressed from literature data.
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
DIPA and H2O is regressed against experimental DIPA-H2O density data
from Henni et al. (2003)[14]. The Clarke model parameter VLCLK/1 for
main electrolytes (DIPAH +, HCO3-) and (DIPAH+, DIPACOO-) is regressed
against experimental density data of the DIPA-CO2-H2O system from
Dell’Era et al. (2010) [21]. VLCLK/1 for other electrolytes is left to the
default.
 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 DIPA 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 DIPA and H 2O in the ASPEN liquid mixture viscosity model, MUKIJ
and MULIJ, are regressed against experimental DIPA-H2O viscosity data
from Henni et al. (2003) [14]. The Jones-Dole model parameters, IONMUB,
of CO3-2 is regressed against K 2CO3-H2O viscosity data from Pac et al.
(1984)[22], that of HCO3- is regressed against KHCO3-H2O viscosity data
from Palaty (1992)[23], and that of HS- is regressed against MDEA-H2O-
H2S viscosity data from Rinker et al. (2000) [24]. For DIPAH+ and DIPACOO-,
IONMUB/1 are missing and IONMUB/2 are defaulted as 0.
 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. No additional adjusted
parameters are used in the surface tension.

6 2 Physical Properties
  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 transport properties, the Gibbs free
energy in aqueous phase infinite dilution at 298.15 K (DGAQFM) and the
enthalpy of formation in aqueous phase infinite dilution at 298.15 K
(DHAQFM) for DIPAH+ are calculated from the experimental chemical
equilibrium constant of the reaction DIPAH   H 2 O  DIPA  H 3 O  as
reported by Hamborg and Versteeg (2009) [25]. Likewise, DGAQFM and
DHAQFM for DIPACOO- are calculated from the experimental chemical
equilibrium constant of the reaction DIPACOO   H 2 O  DIPA  HCO 3 as
reported by Blauwhoff et al. (1985) [6]. The heat capacities in aqueous phase
at infinite dilution (CPAQ0) for DIPAH + and DIPACOO- are obtained by
assuming the aqueous phase infinite dilution heat capacity change for the
above two reactions to be zero. 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) [26], and that of S -2 is calculated from the Criss-Cobble
correlation[26] with the entropy value from Wagman et al. (1982)[7].
The estimation results of various transport and thermal properties are
summarized in Figures 1-21:

1200

1100

1000
Density, kg/m3

EXP DIPA 10.1 w t% (298.03 K)

900
EXP DIPA 11 w t% (298.22 K)
EXP DIPA 33.9 w t% (298.23 K)
800 EST 10.1 w t%
EST 11 w t%
EST 33.9 w t%
700

600
0.4 0.6 0.8 1 1.2 1.4
CO2 loading (m ol CO2/ m ol DIPA)

Figure 1. Liquid density of DIPA-CO2-H2O at around 298.15 K, experimental

data from Dell’Era et al. (2010)[21]

2 Physica l Prope rties 7

 1200

1000

800
Density, kg/m3

600

400

EST DIPA 10wt%

200 EST DIPA 20wt%
EST DIPA 30wt%
EST DIPA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/m ol DIPA)

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

0.1
EST DIPA 10wt%
EST DIPA 20wt%
EST DIPA 30wt%
EST DIPA 40wt%

0.01
Viscosity, PaS

0.001

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

Figure 3. Liquid viscosity of DIPA-CO2-H 2O at 298.15 K

8 2 Physical Properties
 0.1
EST DIPA 10wt%
EST DIPA 20wt%
EST DIPA 30wt%
EST DIPA 40wt%

0.01
Viscosity, PaS

0.001

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

Figure 4. Liquid viscosity of DIPA-H2S-H 2O at 298.15 K

0.07

0.06
Surface Tension, N/m

0.05

0.04

0.03

0.02
EST DIPA 10wt%
EST DIPA 20wt%
0.01 EST DIPA 30wt%
EST DIPA 40wt%

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

Figure 5. Surface tension of DIPA-CO2-H2O at 298.15 K

2 Physica l Prope rties 9

 0.07

0.06

Surface Tension, N/m 0.05

0.04

0.03

0.02
EST DIPA 10wt%
0.01 EST DIPA 20wt%
EST DIPA 30wt%
EST DIPA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/m ol DIPA)

Figure 6. Surface tension of DIPA-H 2S-H2O at 298.15 K

0.6

0.5
Thermal Cnductivity, Watt/m-K

0.4

0.3

0.2

EST DIPA 10wt%

0.1 EST DIPA 20wt%
EST DIPA 30wt%
EST DIPA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol DIPA)

Figure 7. Liquid thermal conductivity of DIPA-CO2-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 DIPA 10wt%
EST DIPA 20wt%
0.1 EST DIPA 30wt%
EST DIPA 40wt%

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

Figure 8. Liquid thermal Conductivity of DIPA-H 2S-H 2O at 298.15 K

5000

4500

4000
Heat Capacity, J/kg-K

3500

3000

2500

2000
1500
EST DIPA 10wt%
1000
EST DIPA 20wt%
500 EST DIPA 30wt%
EST DIPA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol DIPA)

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

2 Physica l Prope rties 11

 5000

4500

4000
Heat Capacity, J/kg-K 3500

3000

2500

2000
1500
EST DIPA 10wt%
1000
EST DIPA 20wt%
500 EST DIPA 30wt%
EST DIPA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5
H2S loading (m ol H2S/m ol DIPA)

Figure 10. Liquid heat Capacity of DIPA-H 2S-H 2O at 298.15 K

-20000
Integral Heat of Solution, J/mol

-40000

-60000

-80000

-100000

-120000 EST DIPA 10wt%

EST DIPA 20wt%
-140000 EST DIPA 30wt%
EST DIPA 40wt%

-160000
0 0.1 0.2 0.3 0.4 0.5
CO2 loading (m ol CO2/ m ol DIPA)

Figure 11. Integral heat of solution of CO 2 in DIPA-H 2O at 298.15 K

12 2 Physical Properties
 0

-10000

Integral Heat of Solution, J/mol

-20000

-30000

-40000

-50000
EST DIPA 10wt%
EST DIPA 20wt%
-60000
EST DIPA 30wt%
EST DIPA 40wt%
-70000

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

Figure 12. Integral heat of solution of H 2S in DIPA-H 2O at 298.15 K

1.0E+04

1.0E+03
CO 2 partial pressure, kPa

1.0E+02

1.0E+01

1.0E+00 35 wt%DIPA, 283.15 K (ter Maat et al. 2004)

35 wt%DIPA, 298.15 K (ter Maat et al. 2004)
33 wt%DIPA, 313.15 K (Isaacs et al. 1977a)
1.0E-01 33 wt%DIPA, 313.15 K (Isaacs et al. 1977b)
33 wt%DIPA, 373.15 K (Isaacs et al. 1977a)
33 wt%DIPA, 373.15 K (Isaacs et al. 1977b)

1.0E-02
0 0.2 0.4 0.6 0.8 1 1.2
CO2 loading (m ol CO2/ m ol DIPA)

Figure 13. CO2 partial pressure of the DIPA-CO2-H2O System, experimental

data from the literature[10-12]

2 Physica l Prope rties 13

 1.0E+04

1.0E+03

Total pressure, kPa

1.0E+02

1.0E+01 EXP DIPA 10.1wt%(299.28 K)

EXP DIPA 11wt%(298.22 K)
EXP DIPA 33.9 wt%(298.23 K)

1.0E+00
0.4 0.6 0.8 1 1.2 1.4
CO2 loading (m ol CO2/ m ol DIPA)

Figure 14. Total pressure of the DIPA-CO2-H2O system at around 298.15 K,

experimental data from Dell’Era et al. (2010)[21]

0.06
EXP DIPA 10 wt%(96.2 kPa)
EXP DIPA 20 wt%(101.6 kPa)
0.05
EXP DIPA 25 wt%(101.5 kPa)
EXP DIPA 35 wt%(100.6 kPa)
0.04
CO 2 mole fraction

0.03

0.02

0.01

0
290 300 310 320 330 340 350 360
Tem perature, K

Figure 15. VLE of the DIPA-CO2-H2O system at around 100 kPa total pressure,
experimental data from from Dell’Era et al. (2010) [21]

14 2 Physical Properties
 1.0E+04

1.0E+03

H2 S partial pressure, kPa

1.0E+02

1.0E+01 33 wt%DIPA, 313.15 K (Isaacs et al. 1977a)

33 wt%DIPA, 313.15 K (Isaacs et al. 1977b)
33 wt%DIPA, 373.15 K (Isaacs et al. 1977a)
1.0E+00 33 wt%DIPA, 373.15 K (Isaacs et al. 1977b)
35 wt%DIPA, 283.15 K (ter Maat et al. 2004)
35 wt%DIPA, 298.15 K (ter Maat et al. 2004)
1.0E-01
0 0.5 1 1.5 2
H2S loading (m ol H2S/ m ol DIPA)

Figure 16. H 2S partial pressure of the DIPA-H2S-H 2O system, experimental

data from the literature[10-21]

1.0E+04

EXP 0.1H2S
1.0E+03
EXP 0.2 H2S
EXP 0.3 H2S
CO 2 partial pressure, kPa

EXP 0.4 H2S

1.0E+02
EXP 0.5 H2S
EXP 0.6 H2S

1.0E+01 EXP 0.7 H2S

EXP 0.8 H2S
EXP 0.9 H2S

1.0E+00 EXP 1H2S

EXP 1.1H2S
EXP 1.2 H2S

1.0E-01
0.01 0.1 1 10
CO2 loading (m ol CO2/ m ol DIPA)

Figure 17. CO2 partial pressure of the DIPA-CO2-H2S-H2O system at 313.15 K,

experimental data from Isaacs et al. (1977) [12]

2 Physica l Prope rties 15

 1.0E+04

EXP 0.1H2S
EXP 0.2 H2S
EXP 0.3 H2S
1.0E+03
EXP 0.4 H2S

CO 2 partial pressure, kPa EXP 0.5 H2S

EXP 0.6 H2S
EXP 0.7 H2S
1.0E+02
EXP 0.8 H2S
EXP 0.9 H2S
EXP 1H2S

1.0E+01

1.0E+00
0.001 0.01 0.1 1
CO2 loading (m ol CO2/ m ol DIPA)

Figure 18. CO2 partial pressure of the DIPA-CO2-H2S-H2O system at 373.15 K,

experimental data from Isaacs et al. (1977) [12]

1.0E+04

EXP 0.1CO2
1.0E+03
EXP 0.2 CO2
EXP 0.3 CO2
H2 S partial pressure, kPa

EXP 0.4 CO2

1.0E+02
EXP 0.5 CO2
EXP 0.6 CO2
EXP 0.7 CO2
1.0E+01
EXP 0.8 CO2
EXP 0.9 CO2
EXP 1CO2
1.0E+00
EXP 1.1CO2
EXP 1.2 CO2

1.0E-01
0.001 0.01 0.1 1 10
H2S loading (m ol H2S/ m ol DIPA)

Figure 19. H 2S partial pressure of the DIPA-CO2-H 2S-H2O system at 313.15 K,

experimental data from Isaacs et al. (1977) [12]

16 2 Physical Properties
 1.0E+04

1.0E+03 EXP 0.1CO2

H2 S partial pressure, kPa

EXP 0.2 CO2
EXP 0.3 CO2
EXP 0.4 CO2
1.0E+02 EXP 0.5 CO2
EXP 0.6 CO2
EXP 0.7 CO2
EXP 0.8 CO2
1.0E+01
EXP 0.9 CO2
EXP 1CO2

1.0E+00
0.001 0.01 0.1 1 10
H2S loading (m ol H2S/ m ol DIPA)

Figure 20. H 2S partial pressure of the DIPA-CO2-H 2S-H2O system at 373.15 K,

experimental data from Isaacs et al. (1977) [12]

1.0E+02
H2 S partial pressure, kPa

1.0E+01

EXP 0.05 CO2, 283.15 K

EXP 0.15 CO2, 283.15 K

1.0E+00 EXP 0.3 CO2, 283.15 K

EXP 0.05 CO2, 298.15 K

EXP 0.15 CO2, 298.15 K

EXP 0.3 CO2, 298.15 K

1.0E-01
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
H2S loading (m ol H2S/ m ol DIPA)

Figure 21. H 2S partial pressure of the DIPA-CO2-H 2S-H2O system at 283.15 K

and 298.15 K, experimental data from ter Maat et al. (2004) [10]

2 Physica l Prope rties 17

3 Reactions

DIPA is a secondary ethanolamine, as shown in Figure 22. It can associate

with H3O+ to form an ion DIPAH +, and can also react with CO2 to form a
carbamate ion DIPACOO-.

Figure 22. DIPA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with the CHEMISTRY ID = DIPA. 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 DIPA. In addition,
a kinetic REACTION model called DIPA-REA has been created. In DIPA-REA,
all reactions are assumed to be in chemical equilibrium except those of CO 2
with OH- and CO2 with DIPA.

A. Chemistry ID: DIPA

1 Equilibrium DIPAH   H 2 O  DIPA  H 3 O 
2 Equilibrium CO 2  2H 2 O  H 3 O   HCO 3
3 Equilibrium HCO 3  H 2 O  H 3 O   CO 32
4 Equilibrium DIPACOO   H 2 O  DIPA  HCO 3
5 Equilibrium 2H 2 O  H 3 O   OH 
6 Equilibrium H 2 O  H 2 S  HS   H 3 O 
7 Equilibrium H 2 O  HS   S 2  H 3 O 

B. Reaction ID: DIPA-REA

1 Equilibrium DIPAH   H 2 O  DIPA  H 3 O 
2 Equilibrium 2H 2 O  H 3 O   OH 
3 Equilibrium HCO 3  H 2 O  CO 32  H 3 O 

18 3 Reactions
 4 Kinetic CO 2  OH   HCO 3
5 Kinetic HCO 3  CO 2  OH 
6 Kinetic DIPA  CO 2  H 2 O  DIPACOO -  H 3 O 
7 Kinetic DIPACOO -  H 3 O   DIPA  CO 2  H 2 O
8 Equilibrium H 2 O  H 2 S  HS   H 3 O 
9 Equilibrium H 2 O  HS   S 2  H 3 O 
The equilibrium constants for reactions 1-7 in Chemistry DIPA are calculated
from the standard Gibbs free energy change.
The power law expressions are used for the rate-controlled reactions
(reactions 4-7 in DIPA-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:

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 4 are taken from the work of Pinsent et al.
(1956)[5], and the kinetic parameters for reaction 5 are calculated by using
the kinetic parameters of reaction 4 and the equilibrium constants of the
reversible reactions 4 and 5. The kinetic parameters for reaction 6 in Table 3
are derived from the work of Blauwhoff et al. (1985) [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.

3 Reactions 19
 Table 3. Parameters k and E in Equation (2)
Reaction No. k E , cal/mol
4 1.33E+17 13249
5 6.62E+16 25656
6 1.26E+13 9563.1
7 2.08E+25 18278

20 3 Reactions
4 Simulation Approach

The Kaiserslautern pilot plant [1] flowsheet for CO2 removal by MEA includes an
absorber, stripper, and heat integration. We have modified some of the
operating conditions to better accommodate DIPA. Table 4 represents the
operation data.
Simulation Flowsheet – Simulation Flowsheet – The process has been
modeled with the following simulation flowsheet in Aspen Plus, shown in
Figure 23.

Figure 23. DIPA simulation 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
DIPA Model
Unit Aspen Plus Block Comments / Specifications
Operation

Absorber RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: .998 bar
4. Reaction: Reaction ID is DIPA-REA for all
stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Total Height: 15.42m
8. Wash Section Height: .42m
9. Mass transfer coefficient method:
HanleyStruc (2010) [28]
10. Interfacial area method: HanleyStruc
(2010) [28]
11. Flooding Method: Wallis [29]
12. Heat transfer coefficient method: Chilton
and Colburn
13. Film resistance options: Discrxn for liquid
film; Film for vapor film
14. Flow model: VPlug
15. Estimates: provide temperature at stages
1, 12 and 20. These estimates are intended to
aid convergence.
Stripper RadFrac 1. Calculation type: Rate-Based
2. 20 Stages
3. Top Pressure: 1.999 bar
4. Reaction: Chemistry ID is DIPA for
condenser and reboiler, Reaction ID is DIPA-
REA for all other stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Height: 5.42
8. Mass transfer coefficient method:
HanleyStruc (2010) [28]
9. Interfacial area method: HanleyStruc (2010)
[28]

10. Flooding Method: Wallis [29]

11. Heat transfer coefficient method: Chilton
and Colburn
12. Film resistance options: Discrxn for liquid
film; Film for vapor film
13. Flow model: VPlug
14. Estimates: provide temperature at stages
1, 12 and 20. These estimates are intended to
aid convergence.

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

HX1 HeatX 1. Calculation Type: Shortcut

2. Hot Inlet – Cold Outlet Temperature
Difference: 5 C
3. Cold Side Outlet Pressure: 2.4bar

HX2 Heater 1. Outlet Temperature: 50 C

2. Outlet Pressure: 2bar
3. Valid Phases: Liquid Only

HX3 Heater 1. Outlet Temperature: 44 C

2. Outlet Pressure: 1.01bar
3. Valid Phases: Liquid Only

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

Streams - Feeds to the absorber are FLUEGAS containing H2O, CO2, N2 and
O2 and LEANIN containing aqueous DIPA solution. Feed conditions are
summarized in Table 5.

Table 5. Feed specifications

Stream ID FLUEGAS LEANIN
Substream: MIXED
Temperature: C 50 50
Pressure: bar 1.029 2
Total flow 76.1 kg/hr 197.7 kg/hr
Mass-Frac Mass-Frac
DIPA 0 0.405
H2O 0.061 0.591
CO2 0.081 0.004
N2 0.737 0
O2 0.121 0
CO2 Loading n/a .029 mol CO2 /mol DIPA

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 DIPA in liquid streams to facilitate calculations of
acid gas loadings of the streams. The Prop-Set MLLOAD was implemented to

4 Simulation Approach 23
 display the CO2 loading of the amine, defined as the ratio of the apparent
mole fractions of CO2 and DIPA.

24 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

Variable Rate-Based DIPA Model

CO2 mole fraction in GASOUT .0049

CO2 Recovery 90.4%
Loading of RICHOUT, molCO2/molDIPA 0.238
Stripper Reboiler Duty 7 kW
Specific Energy Requirement of the Reboiler 4.526 MJ/kgCO2
Excluding Heat Losses
Makeup Water 3.91 kg/hr
Makeup DIPA <0.001 kg/hr
Heat Recovery Exchanger Duty 14.8 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
 65

Temperature, C
55

45
Hanley&Chen, L

Hanley&Chen, V

35
0 4 8 12 16

Packing height from top, m

Figure 24. The Absorber Temperature Profiles

125

120
Temperature, C

115

110 Hanley&Chen, L

Hanley&Chen, V

105
0 1 2 3 4 5 6

Packing height from top, m

Figure 25. The Stripper Temperature Profiles

26 5 Simulation Results
 0.25

CO2 loading, mol CO2/mole amine

0.20

0.15

0.10

0.05
Hanley&Chen

0.00
0 4 8 12 16

Packing height from top, m

Figure 26. Absorber CO 2 Liquid Loading

0.25
CO2 loading, mole CO2/mol amine

0.20

0.15

0.10

0.05
Hanley&Chen

0.00
0 1 2 3 4 5 6

Packing height from top, m

Figure 27. Stripper CO 2 Liquid Loading

5 Simulation Results 27
 0.035

0.030

0.025
CO2 mass fraction
0.020

0.015

0.010

Hanley&Chen
0.005

0.000
0 4 8 12 16

Packing height from top, m

Figure 28. Absorber CO 2 Liquid Concentration Profile

0.035

0.030

0.025
CO2 mass fraction

0.020

0.015

0.010

0.005 Hanley&Chen

0.000
0 1 2 3 4 5 6

Packing height from top, m

Figure 29. Stripper CO 2 Liquid Concentration Profile

The Hanleystruc (2010) correlation [28] is used to calculate the mass transfer
coefficient and interfacial area in the simulation. The Bravo (1985)
correlation[30] 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 DIPA 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.

6 Conc lusions 29
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