Aspen Plus

Rate-Based Model of the CO2 Capture Process by

Mixed PZ and MEA Using Aspen Plus
Copyright (c) 2008-2014 by Aspen Technology, Inc. All rights reserved.

Aspen Plus, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered
trademarks of Aspen Technology, Inc., Bedford, MA.

All other brand and product names are trademarks or registered trademarks of their respective companies.

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

This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech
proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of
AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of
the software and the application of the results obtained.

Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software
may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO
WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION,
ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE.

Aspen Technology, Inc.

20 Crosby Drive
Bedford, MA 01730
USA
Phone: (1) (781) 221-6400
Toll Free: (1) (888) 996-7100
URL: http://www.aspentech.com
Revision History
Version Description

V7.1 First version

V7.1 CP1 Add O2, CO and H2 to the model as Henry components
V7.2 Updated results for V7.2
V7.3 Update databank to PURE25.
Add missing transport properties parameters in the bkp file to be
consistent with the documentation.
Add the definition of acid gas loading and amine weight fraction
convention.
Update Figures 3b and 3c.
V7.3.2 Update databank to PURE26.
Update simulation results.
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
V8.6 Update databank to PURE32.

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 .............................................................................................23

6 Conclusions ........................................................................................................24

References ............................................................................................................25

2 Contents
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by the aqueous solutions of mixed piperazine (PZ) and monoethanolamine
(MEA). As there are no industrial or pilot plant data publicly available for this
process, a flash model is used to test the feasibility of CO2 absorption from a
gas stream containing CO2 and N2 by the aqueous solutions of mixed PZ and
MEA. Thermophysical property models and reaction kinetic models are based
on the recent works of Hilliard (2008)[1], Aspen Technology (2008)[2], Bishnoi
and Rochelle (2000, 2002)[3,4] and Hikita et al.(1977)[5]. Transport property
models and model parameters have been validated when experimental data
are available.
The model includes the following key features:
 True species including ions
 Electrolyte NRTL method for liquid and RK equation of state for vapor
 Concentration-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

ID Type Name Formula

PZ Conventional PIPERAZINE C4H10N2

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
PZH+ Conventional
PZH+2 Conventional
HPZCOO Conventional
PZCOO- Conventional
PZCOO-2 Conventional
MEA Conventional MONOETHANOLAMINE C2H7NO
MEAH+ Conventional MEA+ C2H8NO+
MEACOO- Conventional MEACOO- C3H6NO3-
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

4 1 Components
2 Physical Properties

The electrolyte NRTL method is used for liquid and RK equation of state for
vapor in this Rate-based PZ+MEA model. The phase equilibrium model
parameters were regressed against:
 CO2 solubility data in aqueous PZ solutions from Hilliard (2008)[1] and
Derks et al. (2005)[6].
 CO2 solubility data in aqueous MEA solutions from Jou et al. (1995)[7],
Maddox et al. (1987)[8], Isaacs et al. (1980)[9], Lawson and Garst
(1976)[10], Muhlbauer and Monaghan (1957)[11]
Predictions of CO2 solubility in aqueous solutions of mixed PZ and MEA based
on the phase equilibrium model parameters for the two sub-systems CO2-PZ-
H2O and CO2-MEA-H2O have been compared with the data from Hilliard
(2008)[1] in Figure 7c. The agreement is satisfactory.
CO2, N2, O2, CO and H2 are selected as Henry-components to which Henry’s
law is applied and the Henry’s constants are retrieved from Aspen Plus
databanks for these components with water and are regressed against CO2
solubility data[7-11] for CO2 with MEA. In the reactions 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 liquid molar volume model and transport property models have been
validated and model parameters regressed from literature experimental data
for the sub-system CO2-MEA-H2O. However, no data are found for the sub-
system CO2-PZ-H2O or the mixed PZ and MEA system loaded with CO2
Specifications of the transport property models 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
MEA and H2O is regressed against experimental MEA-H2O density data
from Kapadi et al. (2002) [12] and VLQKIJ between PZ and H2O is
regressed against experimental PZ-H2O density data from Arunkumar and
Syamalendu (2006)[13] and the data from Derks et al. (2005)[14].

The Clarke model parameter VLCLK/1 is also regressed for main

  2
electrolytes (MEAH+, HCO 3 ), (MEAH+, MEACOO ) and (MEAH+, CO 3 )
against experimental MEA-H2O-CO2 density data from Weiland (1996)[15].

2 Physical Properties 5
  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 PZ+MEA 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 MEA and H2O in the ASPEN liquid
mixture viscosity model, MUKIJ and MULIJ, are regressed against
experimental MEA-H2O viscosity data from Kapadi et al. (2002)[12] and
Wadi et al. (1995) [16]. Although Arunkumar and Syamalendu (2006)[5] and
Derks et al. (2005)[6] reported some experimental viscosity data for
aqueous PZ solutions, they are not enough to regress MUKIJ and MULIJ
between PZ and H2O due to absence of high concentration data points, so
MUKIJ and MULIJ between PZ and H2O are left to be defaulted at zero.
The Jones-Dole model parameters, IONMUB, for MEAH+, and MEACOO- are
regressed against MEA-H2O-CO2 viscosity data from Weiland (1996)[15];
that of HCO3- is regressed against KHCO3-H2O viscosity data from Palaty
(1992)[17] and that of CO32- is regressed against K2CO3-H2O viscosity data
from Pac et al. (1984)[18].
 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. Predictions for the sub-
system CO2-MEA-H2O can be in range of the experimental data from
Weiland (1996)[15], which themselves have questionable qualities due to
MEA degradation during experiments.
 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 aqueous phase heat of formation at infinite dilution and 25°C
(DHAQFM) for MEAH+ and MEACOO- are adjusted to fit to the literature
heat of solution data from Carson et al. (2000)[19] for the sub-system
CO2-MEA-H2O and DHAQFM for PZH+, PZCOO- and PZ(COO-)2 are also
adjusted to fit to the literature heat of solution data from Hilliard (2008)[1]
for the sub-system CO2-PZ-H2O. The heat of solution predictions for CO2 in
the aqueous solutions of mixed PZ and MEA are compared with literature
data from Hilliard (2008)[1] in a manner as shown by Figure 6c.
 Heat capacity at infinite dilution (CPAQ0) for MEAH+ and MEACOO- are
adjusted to fit to the literature heat capacity data from Weiland(1996)[15]
for the sub-system CO2-MEA-H2O. CAPQ0 for PZH+, PZCOO- and PZ(COO-
)2 are also adjusted to fit to the literature heat capacity data from Hilliard
(2008)[1] for the sub-system CO2-PZ-H2O. The heat capacity predictions
for CO2 in the aqueous solutions of mixed PZ and MEA are compared with
literature data from Hilliard (2008)[1] in a manner as shown by Figure 5c.
The estimation results of various transport and thermal properties are
summarized in Figures 1-7. Note that CO2 loading is defined as the ratio of

6 2 Physical Properties
 the moles of apparent CO2 to the moles of apparent amines. Apparent means
before reaction, so for example if 1 mole of PZ and 1 mole of MEA are added
to 8 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+1)
= 0.15, regardless of the forms of CO2, PZ and MEA after reacting. Weight
percent of amine is calculated without CO2, so in the above example, it is
calculated from the mixture of 1 mole of PZ, 1 mole of MEA and 8 moles of
water. Since PZ has a molecular weight of 86.139, MEA has a molecular
weight of 61.084, and water has a molecular weight of 18.015, this equals
86.139/(86.139+61.084+8*18.015) = 0.29566 or about 30 wt% PZ and
61.084/(86.139+61.084+8*18.015) = 0.20966 or about 21 wt% MEA.

1200
EXP MEA 10w t%
EXP MEA 20w t%
EXP MEA 30w t%
1150 EXP MEA 40w t%
EST MEA 10w t%
EST MEA 20w t%
EST MEA 30w t%
1100 EST MEA 40w t%
Density, kg/m3

1050

1000

950

900
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 1a. Liquid Density of MEA-CO2-H2O at 298.15K, Experimental Data

from Weiland (1996)[15]

2 Physical Properties 7
 1030

1020

1010

Density, kg/m3
1000

990

980

970
EST PZ=2m LD=0.16
960 EST PZ=2m LD=0.27
950
20 40 60 80 100 120 140
Tem perature, C

Figure 1b. Liquid Density of PZ-CO2-H2O, ‘LD’ denotes CO2 loading

1200
EST PZ=2m MEA=7m LD=0.1
1150 EST PZ=2m MEA=7m LD=0.25
EST PZ=2m MEA=7m LD=0.43
1100
Density, kg/m3

1050

1000

950

900
20 40 60 80 100 120 140
Tem perature, C

Figure 1c. Liquid Density of PZ+MEA-CO2-H2O, ‘LD’ denotes CO2 loading

8 2 Physical Properties
 100
EXP MEA 20w t%
EXP MEA 30w t%
EXP MEA 40w t%
EST MEA 20w t%
EST MEA 30w t%
EST MEA 40w t%
10
Viscosity,mPaS

0.1
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading, mol/mol

Figure 2a. Liquid Viscosity of MEA-CO2-H2O at 298.15K, Experimental Data

from Weiland (1996)[15]

1
Viscosity, mPaS

EST PZ=2m LD=0.16

EST PZ=2m LD=0.27

0.1
20 40 60 80 100 120 140
Tem perature, C

Figure 2b. Liquid Viscosity of PZ-CO2-H2O, ‘LD’ denotes CO2 loading

2 Physical Properties 9
 10
EST PZ=2m MEA=7m LD=0.1
EST PZ=2m MEA=7m LD=0.25
EST PZ=2m MEA=7m LD=0.43

Viscosity, mPaS
1

0.1
20 40 60 80 100 120 140
Tem perature, C

Figure 2c. Liquid Viscosity of PZ+MEA-CO2-H2O, ‘LD’ denotes CO2 loading

0.1

0.09

0.08

0.07
Surface Tension, N/m

0.06

0.05

0.04

0.03 EXP MEA 10wt%

EXP MEA 20wt%
EXP MEA 30wt%
0.02 EXP MEA 40wt%
EST MEA 10wt%
0.01 EST MEA 20wt%
EST MEA 30wt%
EST MEA 40wt%
0
0 0.1 0.2 0.3 0.4 0.5 0.6

CO2 Loading, mol/mol

Figure 3a. Surface tension of MEA-CO2-H2O at 298.15K, Experimental Data

from Weiland (1996)[15]

10 2 Physical Properties
 0.07

0.06

Surface tension, N/m

0.05

0.04

0.03
EST, LD = 0.16
0.02 EST, LD = 0.27

0.01

0
20 40 60 80 100 120 140

Temperature, C

Figure 3b. Surface tension of PZ-CO2-H2O (PZ concentration is 2m). ‘LD’

denotes CO2 loading.

0.06

0.05
Surface tension, N/m

0.04

0.03
EST, LD = 0.1
0.02 EST, LD = 0.25
EST, LD = 0.43
0.01

0
20 40 60 80 100 120 140

Temperature, C

Figure 3c. Surface tension of PZ+MEA-CO2-H2O (PZ concentration is 2m and

MEA concentration is 7m), ‘LD’ denotes CO2 loading

2 Physical Properties 11
 1
EST MEA 10w t%
0.9 EST MEA 20w t%

Thermal Conductivity, Watt/m-K

EST MEA 30w t%
0.8
EST MEA 40w t%
0.7
0.6

0.5
0.4
0.3
0.2

0.1
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 4a. Liquid Thermal Conductivity of MEA-CO2-H2O at 298.15K

0.5

0.45
Thermol Conductivity, Watt/m-K

0.4

0.35
0.3

0.25
0.2

0.15
0.1 EST PZ=2m LD=0.16
0.05 EST PZ=2m LD=0.27

0
20 40 60 80 100 120 140
Tem perature, C

Figure 4b. Liquid Thermal Conductivity of PZ-CO2-H2O, ‘LD’ denotes CO2

loading

12 2 Physical Properties
 1
EST PZ=2m MEA=7m LD=0.1
0.9

Thermol Conductivity, Watt/m-K

EST PZ=2m MEA=7m LD=0.25
0.8
EST PZ=2m MEA=7m LD=0.43
0.7
0.6
0.5
0.4
0.3

0.2
0.1
0
20 40 60 80 100 120 140
Tem perature, C

Figure 4c. Liquid Thermal Conductivity of PZ+MEA-CO2-H2O, ‘LD’ denotes CO2

loading

4500

4000
Heat Capacity (J/kg)

3500

3000 EXP MEA 10w t%

EXP MEA 20w t%
EXP MEA 30w t%
EXP MEA 40w t%
2500 EST MEA10w t%
EST MEA 20w t%
EST MEA 30w t%
EST MEA 40w t%
2000
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 5a. Liquid Heat Capacity of MEA-CO2-H2O at 298.15K, Experimental

Data from Weiland (1996)[15]

2 Physical Properties 13
 5
EXP PZ=2m LD=0.16
EST PZ=2m LD=0.16
EXP PZ=2m LD=0.27

Heat capacity, kJ/kg.K

4.5
EST PZ=2m LD=0.27

3.5

3
20 40 60 80 100 120 140
Tem perature, C

Figure 5b. Liquid Heat Capacity of PZ-CO2-H2O, experimental data from

Hilliard (2008)[1], ‘LD’ denotes CO2 loading

5
EXP PZ=2m MEA=7m LD=0.1
EST PZ=2m MEA=7m LD=0.1
4.5 EXP PZ=2m MEA=7m LD=0.25
EST PZ=2m MEA=7m LD=0.25
Heat capacity, kJ/kg.K

EXP PZ=2m MEA=7m LD=0.43

4 EST PZ=2m MEA=7m LD=0.43

3.5

2.5

2
20 40 60 80 100 120 140
Tem perature, C

Figure 5c. Liquid Heat Capacity of PZ+MEA-CO2-H2O, Experimental Data from

Hilliard (2008)[1], ‘LD’ denotes CO2 loading

14 2 Physical Properties
 -70000 EXP MEA 10wt%
EXP MEA 20wt%
-72000
EXP MEA 30wt% 1
-74000 EXP MEA 30wt% 2

He a t o f So lu tio n , J/m o l
EST MEA 10wt%
-76000 EST MEA 20wt%
EST MEA 30wt%
-78000

-80000
-82000

-84000
-86000

-88000
-90000
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
CO 2 L o a d in g

Figure 6a. Heat of Solution of CO2 in MEA-H2O at 298.15K, Experimental Data

from Carson et al. (2000)[19]

120

100
Heat of solution, kJ/mol CO2

80

60

40 EXP m(PZ)=2.4 40C

EST m(PZ)=2.4 40C
EXP m(PZ)=2.4 80C
EST m(PZ)=2.4 80C
20
EXP m(PZ)=2.4 120C
EST m(PZ)=2.4 120C

0
0 0.1 0.2 0.3 0.4 0.5 0.6
CO2 loading

Figure 6b. Heat of Solution of CO2 in PZ-H2O , Experimental Data from Hilliard
(2008)[1]

2 Physical Properties 15
 120

Heat of solution, kJ/mol CO2

100

80

60

40 EXP PZ=2m MEA=7m 40C

EST PZ=2m MEA=7m 40C
EXP PZ=2m MEA=7m 80C
20 EST PZ=2m MEA=7m 80C
EXP PZ=2m MEA=7m 120C
EST PZ=2m MEA=7m 120C
0
0 0.2 0.4 0.6 0.8
CO2 loading

Figure 6c.. Heat of Solution of CO2 in PZ+MEA-H2O, Experimental Data from

Hilliard (2008)[1]

1000000
EXP 40C
EST 40C
100000 EXP 60C
EST 60C
10000 EXP 80C
EST 80C
EXP 100C
CO2 Pressure, kPa

1000 EST 100C

EXP 120C
100 EST 120C

10

0.1

0.01

0.001
0.001 0.01 0.1 1 10
CO2 Loading

Figure 7a. CO2 Partial Pressure of MEA-CO2-H2O (MEA Mass Fraction = 0.3),
Experimental Data from Jou et al. (1995)[7]

16 2 Physical Properties
 100
EXP m(PZ)=2.0 40C
EST m(PZ)=2.0 40C
EXP m(PZ)=2.0 60C
EST m(PZ)=2.0 60C

CO2 partial pressure, kPa

10

0.1

0.01
0.1 1
CO2 loading

Figure 7b. CO2 Partial Pressure of PZ-CO2-H2O, Experimental Data from

Hilliard (2008)[1]

100
EXP MEA7m PZ2m 40C
EST MEA7m PZ2m 40C
EXP MEA7m PZ2m 60C
10
CO2 partial pressure, kPa

EST MEA7m PZ2m 60C

0.1

0.01

0.001
0.01 0.1 1
CO2 loading

Figure 7c. CO2 Partial Pressure of PZ+MEA-CO2-H2O, Experimental Data from

Hilliard (2008)[1]

2 Physical Properties 17
3 Reactions

PZ is a cyclic amine, as shown in Figure 8. It can associate with H3O+ to form

an ion PZH+, and react with CO2 to form a carbamate ion PZCOO- and a
dicarbamate ion PZ(COO-)2.

Figure 8. PZ Molecular Structure

MEA is a primary amine, as shown in Figure 9. It can associate with H3O+ to
form an ion MEAH+, and react with CO2 to form a carbamate ion MEACOO-.

Figure 9. MEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY
model with the CHEMISTRY ID = PZ-MEA. 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 PZ-MEA. In addition,
a kinetic REACTION model called R-PZ-MEA has been created, which can be
used in calculations of the absorber and stripper by specifying it in the
Reaction part of the absorber and stripper specifications. In R-PZ-REA, all
reactions are assumed to be in chemical equilibrium except those of CO2 with
OH- and CO2 with PZ, PZCOO- and MEA.

A. Chemistry ID: PZ-MEA

1 Equilibrium 2H 2 O  H 3 O   OH 
2 Equilibrium CO 2  2H 2 O  HCO 3  H 3 O 
3 Equilibrium HCO 3  H 2O  CO 32   H 3O 
4 Equilibrium PZH   H 2 O  PZ  H 3 O 

18 3 Reactions
 5 Equilibrium PZ  HCO 3-  PZCOO -  H 2 O
6 Equilibrium HPZCOO  H2O  PZCOO -  H 3 O 
7 Equilibrium 
PZCOO -  HCO 3-  PZ COO - 
2  H 2O
8 Equilibrium MEAH   H 2 O  MEA  H 3 O 
9 Equilibrium MEACOO -  H 2 O  MEA  HCO -3

B. Reaction ID: R-PZ-MEA

1 Equilibrium PZH   H 2 O  PZ  H 3 O 
2 Equilibrium 2H 2 O  H 3 O   OH 
3 Equilibrium HCO 3  H 2 O  CO 32   H 3 O 
4 Equilibrium HPZCOO  H 2 O  PZCOO   H 3 O 
5 Equilibrium MEAH   H 2 O  MEA  H 3 O 
6 Kinetic CO 2  OH   HCO 3
7 Kinetic HCO 3  CO 2  OH 
8 Kinetic PZ  CO 2  H 2 O  PZCOO -  H 3 O 
9 Kinetic PZCOO -  H 3 O   PZ  CO 2  H 2 O
10 Kinetic PZCOO -  CO 2  H 2 O  PZ (COO - ) 2  H 3 O 
11 Kinetic PZ(COO - ) 2  H 3 O   PZCOO -  CO 2  H 2 O
12 Kinetic MEA  CO 2  H 2 O  MEACOO -  H 3 O 
13 Kinetic MEACOO -  H 3 O   MEA  CO 2  H2O
The equilibrium expressions for the reactions are taken from the work of
Hilliard (2008)[1], Derks et al. (2005)[6] and Austgen et al. (1988)[20]. The
following power law expressions (reference temperature T0 not specified) are
used for the rate-controlled reactions (reactions 6-13 in R-PZ-MEA):

E N
r  kT n exp (  ) C i i
a
(1)
RT i 1
Where:
r = Rate of reaction;
k = Pre-exponential factor;
T = Absolute temperature;
n = Temperature exponent;
E = Activation energy;
R = Universal gas constant;

3 Reactions 19
 N = Number of components in the reaction;
Ci = Concentration of component i;
ai = The stoichiometric coefficient of component i in the reaction equation.
In equation (1), the concentration basis is Molarity, the factor n is zero, k
and E are given in Table 3. The kinetic parameters for reactions 6, 8, 10 and
12 are taken from the work of Pinsent et al. (1956)[21], Bishnoi and Rochelle
(2000, 2002)[3,4] and Hikita et al. (1977)[5], and the kinetic parameters for
corresponding reversible reactons 7, 9, 11 and 13 are calculated by using the
kinetic parameters and the equilibrium constants of the forward reactions 6, 8,
10 and 12.

Table 3. Parameters k and E in Equation (1)

Reaction No. k E , cal/mol
6 4.32e+13 13249
7 2.38e+17 29451
8 4.14e+10 8038.3
9 9.47e+20 15333
10 3.62e+10 8038.3
11 3.46e+20 17958
12 9.77e+10 9855.8
13 2.80e+20 17230

20 3 Reactions
4 Simulation Approach

As we are unable to find industrial or pilot plant data publicly available for CO2
capture process by aqueous solutions of mixed PZ and MEA, we use a single
stage equilibrium model (flash calculations) to simulate the CO2 absorption
from a gas stream of CO2 and N2 by mixed PZ and MEA.
Simulation Flowsheet – In the following simulation flowsheet in Aspen Plus
(Figure 10), CO2 is absorbed by mixed PZ and MEA from a mixture of CO2 and
N2 in an absorber.

GASOUT

LEANIN
ABSOR BER

GASIN

RIC HOUT

Figure 10. PZ+MEA Simulation Flowsheet in Aspen Plus

4 Simulation Approach 21
 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

mixed PZ and MEA Model
Unit Aspen Plus Block Comments / Specifications
Operation
Flash Flash2 1. Temperature is set at 40 °C
2. Pressure is set at 1 atm

Streams - Feeds to the absorber are gas stream GASIN containing N2 and
CO2 and liquid solvent stream LEANIN containing aqueous PZ and MEA
solution loaded with some CO2. Feed conditions are summarized in Table 5.

Table 5. Feed specifications

Stream ID GASIN LEANIN

Substream: MIXED
Temperature: °F 60 80
Pressure: atm 1 1
Flow rate mole/hr mole/hr
H2O 0 71000
PZ 0 1000
MEA 0 3000
CO2 3000 300
N2 27000 0

Prop-Sets – Prop-Set XAPP is used to report apparent mole fraction of CO2,

PZ, MEA, H2O and N2 in liquid streams.

22 4 Simulation Approach
5 Simulation Results

The simulation has been run successfully in Aspen Plus. Key simulation results
are presented in Table 6. Here the RICHOUT and LEANOUT compositions are
the mole fraction of apparent components.

Table 6. Key Simulation Results

Stream ID GASOUT RICHOUT

Substream: MIXED
Temperature: °C 40 40
Pressure: psig 0 0
Total flow 29897mol/hr 72903 mol/hr
Mole-Frac Mole-Frac
H2O 0.070 0.914
PZ 0 0.013
MEA 0 0.040
CO2 0.027 0.033
N2 0.903 0

5 Simulation Results 23
6 Conclusions

The Rate-Based PZ+MEA model provides a simple simulation of the CO2

capture process by aqueous solutions of mixed PZ and MEA with rigorous
electrolyte thermodynamics and solution chemistry and reaction kinetics for
the liquid phase reactions.
The model is meant to be used as a guide for modeling the CO2 capture
process with mixed PZ and MEA. Users may use it as a starting point for more
sophisticated models for process development, debottlenecking, plant and
equipment design, among others. Further validation of this PZ+MEA model
will be done when industrial or pilot plant data become available.

24 6 Conclusions
References

[1] M.D. Hilliard, "A Predictive Thermodynamic Model for an Aqueous Blend of
Potassium Carbonate, Piperazine, and Monoethanolamine for Carbon Dioxide
Capture from Flue Gas", Ph.D. Dissertation, University of Texas at Austin,
2008
[2] Aspen Technology Inc., 2008
[3] S. Bishnoi, G. Rochelle, “Absorption of Carbon Dioxide into Aqueous
Piperazine: Reaction Kinetics, Mass Transfer and Solubility”, Chemical
Engineering Science, 55, 5531-5543 (2000)
[4] S. Bishnoi, G. Rochelle, “Absorption of Carbon Dioxide into Aqueous
Piperazine/Methyldiethanolamine”, AIChE Journal, 48, 2788-2799 (2002)
[5] H. Hikita, S. Asai, H. Ishikawa, M. Honda, “The Kinetics of Reactions of
Carbon Dioxide with Monoethanolamine, Diethanolamine, and
Triethanolamine by a Rapid Mixing Method”, Chem. Eng. J., 13, 7-12 (1977).
[6] P.W.J. Derks, H.B.S. Dijkstra, J.A. Hogendoorn, G.F. Versteeg, "Solubility
of Carbon Dioxide in Aqueous Piperazine Solutions", AIChE Journal, 51, 2311-
2327 (2005)
[7] F.-Y. Jou, A.E. Mather, F.D. Otto, " The Solubility of CO2 in a 30 Mass
Percent Monoethanolamine Solution", Can. J. Chem. Eng., 3, 140-147 (1995)
[8] R.N. Maddox, A.H. Bhairi, J.R. Diers, P.A. Thomas, “Equilibrium Solubility
of Carbon Dioxide or Hydrogen Sulfide in Aqueous Solutions of
Monoethanolamine, Diglycolamine, Diethanolamine and
Methyldiethanolamine”, GPA Research Report No. 104, 1987
[9] E.E. Isaacs, F.D. Otto, A.E. Mather, "Solubility of Mixtures of H2S and CO2
in a Monoethanolamine Solution at Low Partial Pressures", J. Chem. Eng. Data,
25, 118-120 (1980)
[10] J.D. Lawson, A.W. Garst, "Gas Sweetening Data: Equilibrium Solubility of
Hydrogen Sulfide and Carbon Dioxide in Aqueous Monoethanolamine and
Aqueous Diethanolamine Solutions", J. Chem. Eng. Data, 21, 20-30 (1976)
[11] H.G. Muhlbauer, P.R. Monaghan, "Sweetening Natural Gas With
Ethanolamine Solutions", Oil Gas J. 55(17), 139 (1957)
[12] U.R. Kapadi, D.G. Hundiwale, N.B. Patil, M.K. Lande, Fluid Phase
Equilibria, 201, 335-341 (2002)

References 25
 [13] S. Arunkumar, S.B. Syamalendu, "Density and Viscosity of Aqueous
Solutions of Piperazine and (2-Amino-2-methyl-1-propanol + Piperazine) from
298 to 333 K ", J. Chem. Eng. Data, 51, 467- 470(2006)
[14] P.W.J. Derks, K.J. Hogendoorn, G.F. Versteeg, "Solubility of N2O in and
density, viscosity, and surface tension of aqueous piperazine solutions", J.
Chem. Eng. Data, 50, 1947-1950(2005)
[15] R.H. Weiland, “Physical Properties of MEA, DEA, MDEA and MDEA-Based
Blends Loaded with CO2”, GPA Research Report No. 152, August 1996
[16] R.K. Wadi, P. Saxena, "Molar Conductivity of Alkali-Halides in
Ethanolamine and Water Plus Ethanolamine at 298.15 K", Indian J. Chem.
Sect. A, 34, 273 (1995)
[17] Z. Palaty, “Viscosity of diluted aqueous K2CO3/KHCO3 solutions”, Collect.
Czech. Chem. Commun., 57, 1879 (1992)
[18] J.S. Pac, I.N. Maksimova, L.V. Glushenko, ”Viscosity of Alkali Salt
Solutions and Comparative Calculation Method”, J. Appl. Chem. USSR, 57,
846 (1984)
[19] J.K Carson, K.N. Marsh, A.E. Mather, “Enthalpy of solution of carbon
dioxide in (water + monoethanolamine, or diethanolamine, or N-
methyldiethanolamine) and (water + monoethanolamine + N-
methyldiethanolamine) at T = 298.15 K”, J. Chem. Thermodyn. 32, 1285-
1296 (2000)
[20] D.M. Austgen, G.T. Rochelle, X. Peng, and C.-C. Chen, "A Model of
Vapor-Liquid Equilibria in the Aqueous Acid Gas-Alkanolamine System Using
the Electrolyte-NRTL Equation," Paper presented at the New Orleans AIChE
Meeting, March 1988
[21] B.R. Pinsent, L. Pearson, F.J.W. Roughton, “The Kinetics of Combination
of Carbon Dioxide with Hydroxide Ions”, Trans. Faraday Soc., 52, 1512-1520
(1956)

26 References