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Aspen Plus

Rate-Based Model of the CO2 Capture Process by


MEA 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

2006.5 First version


V7.0 The parameters in the Clarke liquid volume model have been changed
due to a fix in the model implementation in V7.0.
Heat losses of the absorber and the stripper have been removed.
Flow model of the absorber has been changed to Countercurrent.
Reaction condition factor has been changed to 0.9 for both the
absorber and the stripper.
Film discretization ratio has been changed to 5 for both the absorber
and the stripper.
Interfacial area factor has been changed from 1.5 to 1.2 for
absorber.
Distillation rate has been changed from 100kg/hr to 96kg/hr for the
stripper.
Interfacial area and mass transfer coefficient correlations have been
changed from Bravo et al.(1992) to Bravo et al.(1985) for the stripper.
Interfacial area factor has been changed from 2 to 0.4 due to the
change of interfacial area correlation, to match data from U.T. Austin.
V7.1 Update CO2 solubility model to incorporate data from Jou et al. (1995)
V7.2 Correct x-axis label for Figures 11, 12 and 13, and update results to
match version V7.2.
Change the lower bound for the design spec to 0.1 to work around the
convergence issue.
The Convergence Issue part in the capture Simulation Approaches in
this document has been removed.
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 MEA based on the works of Wang (1992).
Determine DGAQFM, DHAQFM, CPAQ0 of MEAH+ and MEACOO- by fitting
VLE data of Lee (1976) and Jou (1995), absorption heat data of Kim
(2007) and heat capacity data of Weiland (1996) together with the
interaction energy parameters between H2 O and (MEAH+, HCO3 - ) and
those between H2 O and (MEAH+, MEACOO-).
Update the 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 MEA-H2 O-CO2 and MEA-H2 O-H2 S thermodynamic model in
this work.
Use ENRTL-RK method to replace ELECNRTL method, use PC-SAFT EOS
to model vapor-phase fugacity coefficient for its ability at high pressure.
Update databank to PURE25.
Update the PC-SAFT parameters for MEA.
Update the NRTL interaction parameters between MEA and H 2 O, H2 O
and (MEAH+, HCO3 - ), H2 O and (MEAH+, MEACOO- ) and those between
H2 O and (MEAH+, HS- ).
Update the Henry’s constants of CO 2 and H2 S in H2 O and MEA.
Update DGAQFM, DHAQFM and CPAQ0 of MEAH+ and MEACOO- , update
CPAQ0 of HCO3 - , CO3 -2 , HS- and S-2 .
Add CH4 , C 2 H6 and C 3 H8 in the component list. Update the Henry’s
constants of CH4 , C 2 H6 and C 3 H8 in H2 O and MEA. Update the
characteristic volume parameters of CH4 and C 2 H6 for the Brelvi-
O’Connell Model.
Update the Clarke model parameter, VLCLK/1, for (MEAH +, HCO3 - ),
(MEAH+, CO3 -2 ) and (MEAH+, MEACOO-).
Update the Jones-Dole model parameters, IONMUB, for HS- .
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.
Update simulation results.
V7.3.2 Update databank to PURE26.
Update the NRTL interaction parameters between MEA and H 2 O, H2 O
and (MEAH+, HCO3 - ) and those between H2 O and (MEAH+, MEACOO- ) .
Update DGAQFM, DHAQFM and CPAQ0 of MEAH+ and MEACOO- .
Update figures 10, 12 and 14.
Update kinetics.
Update simulation results.
August Update Flowsheet to 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.
V10.0 Update GMENCC parameters between CO 2 and (MEAH+, MEACOO-), CO2
and (MEAH+, HCO3 - ), and those between CO 2 and (MEAH+, 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 ...........................................................................................................17

4 Simulation Approach ..........................................................................................20

5 Simulation Results .............................................................................................24

6 Conclusions ........................................................................................................30

References ............................................................................................................31

Contents 3
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by aqueous MEA from a gas mixture of N 2, O2, CO2 and H2O. The model
consists of an absorber and a stripper. The case 1 operation data from a pilot
plant study at the University of Kaiserslautern (2012)[1] were used to specify
feed conditions and unit operation block specifications in the model.
Thermophysical property models are based on the work of Ying and Chen
(2011)[2] and the reaction kinetic models are based on the work of Hikita et al.
(1977)[3]. Transport property models and model parameters have been
validated against experimental data from open literature. Transport property
models and model parameters have been validated against experimental data
from open literature.
Although the pilot plant cases of University of Kaiserslautern do not contain
H2S, H2S, its related reactions and physical property model parameters are
still included in this model, considering potential demand of model users.
However, validation of transport property models for H 2S related systems is
not done due to absence of necessary experimental data.
This simulation is meant to be used as a guide for modeling the CO 2 capture
process with MEA. 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

MEA Conventional MONOETHANOLAMINE C2H7NO


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
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
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

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 this rate-based MEA model. CO2, H2S, N2, O2, CH4, C2H6, and
C3H8 are selected as Henry-components (solutes) to which Henry’s law is
applied. Henry’s constants are specified for these components with water and
MEA. 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, CH4, C2H6, and C3H8 are
obtained from the literatures 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) [4]


H2 S H2 O Regression with H2 S-H2 O VLE data[5-12]
CH4 H2 O Regression with CH4 -H2 O VLE data[13]
C 2 H6 H2 O Regression with C 2 H6 -H2 O VLE data[14]
C 3 H8 H2 O Regression with C 3 H8 -H2 O VLE data[15]
CO2 MEA Zhang and Chen (2011) [16]
H2 S MEA Set to that of H2 S in H2 O
CH4 MEA Regression with CH4 -H2 O-MDEA VLE data[17, 18]
C 2 H6 MEA Regression with C 2 H6 -H2 O-MDEA VLE data[18]
C 3 H8 MEA Regression with C 3 H8 -H2 O-MDEA VLE data[19]

The PC-SAFT parameters of MEA are regressed from the vapor pressure
data[20-23], the heat of vaporization data[24-25], the liquid heat capacity data[26-
27]
and the liquid density data[28-30]. 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 H 2O for the Brelvi-O’Connell Model,
VLBROC, are obtained from Brelvi and O’Connell (1972) [32], those of CO2 are
obtained from Yan and Chen (2010) [4], those of CH4 and C2H6 are regressed

6 2 Physical Properties
with the CH4-H2O[13] and C2H6-H2O[14] binary VLE data, and those of MEA, H2S,
C3H8, 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 MEA and H 2O are determined from
the regression with binary VLE data[23,33-37], excess enthalpy data[33, 38- 40] and
heat capacity data[27, 41, 42].
The interaction energy parameters between H 2O and (MEAH+, HCO3-),
GMENCC, and those parameters between H 2O and (MEAH+, MEACOO-),
GMENCC and GMENCD, are regressed using the VLE data[43-46], absorption
heat data[47], heat capacity data[42, 45] and speciation concentration data[48].
The interaction energy parameters between H 2O and (MEAH+, HS-), GMENCC
and GMENCD, are regressed with the H 2S solubility data in aqueous MEA
solution[49-50].
The interaction energy parameters between CO2 and (MEAH+, MEACOO-), CO2
and (MEAH+, HCO3-), and those between CO2 and (MEAH+, CO3-2), GMENCC,
are regressed using the data of CO2 activity coefficient [66],
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 MEA are 35.76, 14836.0 and 273.15, which
are derived from Dean et al. (1999) [51].
The liquid molar volume model and transport property models have been
validated and model parameters regressed from literature experimental data.
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) [52]. The Clarke model parameter VLCLK/1 is also
regressed for the main electrolyte (MEAH +, HCO3-), (MEAH+, MEACOO-)
and (MEAH+, CO3-2) against experimental MEA-H2O-CO2 density data from
Weiland (1996) [53]; that for (MEAH+, HS-) is set to that of (MEAH+,
HCO3-).
 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 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

2 Physica l Prope rties 7


between MEA and H 2O in the Aspen liquid mixture viscosity model, MUKIJ
and MULIJ, are regressed against experimental MEA-H2O viscosity data
from Kapadi et al. (2002) [52] and Wadi et al. (1995)[54]. The Jones-Dole
model parameters, IONMUB, for MEAH +, and MEACOO- are regressed
against MEA-H2O-CO2 viscosity data from Weiland (1996) [53]; that of
HCO3- is regressed against KHCO3-H2O viscosity data from Palaty
(1992)[55]; that of CO32- is regressed against K 2CO3-H2O viscosity data
from Pac et al. (1984) [56]; and that of HS- is regressed against MDEA-H2O-
H2S viscosity data from Rinker et al. (2000) [57].
 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 MEA-
H2O-CO2 system can be in the range of the experimental data from
Weiland (1996) [53], 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 Gibbs free energy and heat of formation at infinite dilution and 25°C
(DGAQFM and DHAQFM) and heat capacity at infinite dilution (CPAQ0) for
MEAH+ and MEACOO- are regressed with the VLE data[43-46], absorption heat
data[47], heat capacity data[42, 45] and speciation concentration data[48]. 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) [58], and that of
S-2 is calculated from the Criss-Cobble correlation[58] with the entropy value
from Wagman et al. (1982) [59].
The estimation results of various transport and thermal properties are
summarized in Figures 2-17. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent MEA. Apparent
means before reaction, so for example if 1 mole of MEA 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 MEA after reacting. Weight percent of MEA
is calculated without CO2, so in the above example, it is calculated from the
mixture of 1 mole MEA and 9 moles of water. Since MEA has a molecular
weight of 61.084 and water has a molecular weight of 18.015, this is
61.084/(61.084+9*18.015) = 0.27365 or about 27 wt% MEA.

8 2 Physical Properties
1200
EXP MEA 10w t%
EXP MEA 20w t%
EXP MEA 30w t%
EXP MEA 40w t%
1150 EST MEA 10w t%

3
EST MEA 20w t%
Density, kg/m EST MEA 30w t%
EST MEA 40w t%
1100

1050

1000
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading, mol CO2/mol MEA

Figure 1. Liquid Density of MEA-CO2-H 2O at 298.15K, experimental data from


Weiland (1996)[53]

1200
EST MEA 10w t%

EST MEA 20w t%


1150
3

EST MEA 30w t%


Density, kg/m

EST MEA 40w t%


1100

1050

1000
0 0.1 0.2 0.3 0.4 0.5

H2S Loading, mol H2S/mol MEA

Figure 2. Liquid Density of MEA-H2S-H 2O at 298.15K

2 Physica l Prope rties 9


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%
Viscosity,mPaS 10

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

Figure 3. Liquid Viscosity of MEA-CO2-H2O at 298.15K, experimental data


from Weiland (1996)[53]

100
EST MEA 20w t%

EST MEA 30w t%


Viscosity,mPaS

10 EST MEA 40w t%

0.1
0 0.1 0.2 0.3 0.4 0.5
H2S Loading, mol H2S/mol MEA

Figure 4. Liquid Viscosity of MEA-H 2S-H2O at 298.15K

10 2 Physical Properties
80

60

Surfac Tension, mN/m


40 EX P, M EA 10w t%
EX P, M EA 20w t%
EX P, M EA 30w t%
EX P, M EA 40w t%
20 ES T, M EA 10w t%
ES T, M EA 20w t%
ES T, M EA 30w t%
ES T, M EA 40w t%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading, mol CO2/mol MEA

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


from Weiland (1996)[53]

80

60
Surfac Tension, mN/m

40 ES T, M EA 10w t%

ES T, M EA 20w t%

20 ES T, M EA 30w t%

ES T, M EA 40w t%

0
0 0.1 0.2 0.3 0.4 0.5
H2S Loading, mol H2S/mol MEA

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

2 Physica l Prope rties 11


1
EST MEA 10w t%

Thermal Conductivity, Watt/m-K


0.8 EST MEA 20w t%
EST MEA 30w t%
EST MEA 40w t%
0.6

0.4

0.2

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

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

EST MEA 10w t%


Thermal Conductivity, Watt/m-K

0.8 EST MEA 20w t%


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

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5

H2S Loading, mol H2S/mol MEA

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

12 2 Physical Properties
4500

4000

Heat capacity, J/kg 3500

3000 EXP, 10wt% MEA


EST, 10wt% MEA
EXP, 20wt% MEA
EST, 20wt% MEA
2500 EXP, 30wt% MEA
EST, 30wt% MEA
EXP, 40wt% MEA
EST, 40wt% MEA
2000
0 0.1 0.2 0.3 0.4 0.5

CO2 loading, mol CO2/mol MEA

Figure 9. Liquid Heat Capacity of MEA-CO2-H2O at 298.15K, experimental


data from Weiland (1997) [42]

4500

4000
Heat Capacity, J/kg

3500

3000 EST MEA10w t%


EST MEA 20w t%
2500 EST MEA 30w t%
EST MEA 40w t%

2000
0 0.1 0.2 0.3 0.4 0.5
H2S Loading, mol H2S/mol MEA

Figure 10. Liquid Heat Capacity of MEA-H 2S-H 2O at 298.15K

2 Physica l Prope rties 13


100

80

Absorption heat, kJ/mol 60 EXP, 40C


EST, 40C

40

20

0
0 0.2 0.4 0.6 0.8

CO2 loading, mol CO2/mol MEA

Figure 11. Differential Absorption Heat of CO 2 in aqueous MEA solution (MEA


mass fraction = 0.30), experimental data from Kim et al. (2007) [47]

100
Absorption heat, kJ/mol

80
ES T, 40C

60

40

20

0
0 0.2 0.4 0.6 0.8 1 1.2

H2 S loading, mol H2S/mol MEA

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


mass fraction = 0.30)

14 2 Physical Properties
100000

1000

CO 2 pressure, kPa EST, 313K


10 EST, 353K
EST, 393K
EXP, 313K
0.1
EXP, 353K
EXP, 393K

0.001
0 0.5 1 1.5

CO2 loading, mol CO2/mol MEA

Figure 13. CO2 Partial Pressure of MEA-CO2-H 2O (MEA mass fraction = 0.30),
experimental data from Jou et al. (1995)[ 43]

100000

1000
H 2S pressure, kPa

10 EST, 313K
EST, 353K
EST, 393K

0.1 EXP, 313K


EXP, 353K
EXP, 393K

0.001
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
H2S loading, mol H2S/mol MEA

Figure 14. H2S Partial Pressure of MEA-H 2S-H 2O (MEA concentration is 5 M),
experimental data from Lee et al. (1976)[50]

2 Physica l Prope rties 15


20000
EST, 298K
EST, 348K
EST, 398K
15000
EXP, 298K
Total pressure, kPa EXP, 348K
EXP, 398K
10000

5000

0
0.0E+00 5.0E-04 1.0E-03 1.5E-03 2.0E-03 2.5E-03

CH4 mole fraction

Figure 15. Total pressure of the CH 4-MEA-H2O system (MEA concentration is


3 M), experimental data from Carroll et al. (1998) [17]

10000
EST, 311K
EST, 339K
EXP, 311K
EXP, 339K
Total pressure, kPa

5000

0
5.0E-04 6.0E-04 7.0E-04 8.0E-04 9.0E-04 1.0E-03

C2H6mole fraction

Figure 16. Total pressure of the C2H 6-MEA-H2O system (MEA mole fraction is
0.0495), experimental data from Lawson et al. (1976) [18]

16 2 Physical Properties
3 Reactions

MEA is a primary ethanolamine, as shown in Figure 17. It can associate with


H+ to form an ion MEAH +, and can also react with CO2 to form a carbamate
ion MEACOO-.

Figure 17. MEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY


model with CHEMISTRY ID = 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 MEA. In addition, two
REACTION models called Absorber (used in the absorber, 303-353 K) and
Stripper (used in the stripper, 353-393 K) have been created. In
Absorber/Stripper, all reactions are assumed to be in chemical equilibrium
except those of CO2 with OH- and CO2 with MEA.

A. Chemistry ID: MEA


1 Equilibrium MEAH   H 2 O  MEA  H 3 O 
2 Equilibrium MEACOO   H 2 O  MEA  HCO 3
3 Equilibrium 2H 2 O  H 3 O   OH 
4 Equilibrium CO 2  2H 2 O  HCO 3  H 3 O 
5 Equilibrium HCO 3  H 2 O  CO 32  H 3 O 
H 2 S  H 2 O  HS   H 3 O 
6 Equilibrium
HS -  H 2 O  S 2  H 3 O 
7 Equilibrium

B. Reaction ID: Absorber/Stripper


1 Equilibrium MEAH   H 2 O  MEA  H 3 O 
2 Equilibrium 2H 2 O  H 3 O   OH 

3 Reactions 17
3 Equilibrium HCO 3  H 2 O  CO 32  H 3 O 
4 Equilibrium H 2 O  H 2 S  HS   H 3 O 
5 Equilibrium H 2 O  HS   S 2  H 3 O 
6 Kinetic CO 2  OH   HCO 3
7 Kinetic HCO 3  CO 2  OH 
8 Kinetic MEA  CO 2  H 2 O  MEACOO -  H 3 O 

9 Kinetic MEACOO -  H 3 O   MEA  H 2 O  CO 2


The equilibrium constants for reactions 1-7 in MEA are calculated from the
standard Gibbs free energy change. DGAQFM, DHAQFM, and CPAQ0 of MEAH +
and MEACOO-, which are used to calculate the standard MEAH + and MEACOO-
Gibbs free energy, are determined in this work. 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 4-
7 in Absorber/Stripper). The general power law expression is:

  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 gamma, the factor n is zero, k and E are given
in Table 3.

18 3 Reactions
Note that Absorber and Stripper share all kinetic parameters except those
of reaction 9. The kinetic parameters for reaction 6 (forward reaction) are
taken from the work of Pinsent et al. (1956) [60] , and the kinetic parameters
for reaction 7 (reverse reaction) are calculated by using equation 4 with the
kinetic parameters of reaction 6 and the equilibrium constants of the
reversible reactions 6 and 7:

k af
k ra  (4)
a
K eq

k af = Rate constant of the forward reaction, mole gamma basis;

k ra = Rate constant of the forward reaction, mole gamma basis;


a
k eq = Equilibrium constant, mole gamma basis.

The kinetic parameters of reaction 8 in Table 3 are derived from the work of
Hikita et al. (1977) [3] and the kinetic parameters of reaction 9 are calculated
by using the kinetic parameters of reaction 8 and the equilibrium constants of
the reversible reactions 8 and 9. Two sets of linear approximation (respect to
1/T) for the equilibrium constants (calculated from the Gibbs free energy
change) are used for Absorber and Stripper, respectively. One is the linear
approximation of the equilibrium constant for the temperature from 303 to
353 K (for the absorber) and the other is the linear approximation for the
temperature from 353 to 393 K (for the stripper). Two sets of kinetic
parameters of reaction 9 for Absorber and Stripper are obtained using
equation 4, as listed in Table 3.

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 3.02e+14 9855.8
9 (Absorber) 5.52e+23 16518
9 (Stripper) 6.50e+27 22782

3 Reactions 19
4 Simulation Approach

The current flowsheet closely simulates case 1 of the pilot plant cited in Notz,
Mangalapally, and Hasse (2012) [1] which incorporates an absorption and
stripping column, heat exchange between the two columns, and water and
amine recycles. The operating conditions of this plant were chosen to be as
close to those used in case 1 as possible. Where data necessary for the
simulation were not reported reasonable estimates for these missing data
were made.
An amine makeup stream and a water makeup stream were not present in
the pilot plant, but were added to the simulation to maintain mass balance
and to aid convergence.
Simulation Flowsheet - The process has been modeled with the following
simulation flowsheet in Aspen Plus, shown in Figure 18.

Figure 18. Rate-Based MEA 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.

20 4 Simulation Approach
Table 4. Aspen Plus Unit Operation Blocks Used in the
Rate-Based MEA Model
Unit Aspen Comments / Specifications
Operation Plus Block

Absorber RadFrac 1. Calculation type: Rate-Based


2. 20 Stages
3. Top Pressure: .97708 bar
4. Reaction: Reaction ID is ABSORBER for all stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Total Height: 4.62m
8. Wash Section Height: .42m
9. Absorber Section Height: 4.2m
10. WATEROUT Flowrate: 28.53 kg/hr
11. Mass transfer coefficient method: Bravo (1985)[61]
12. Interfacial area method: Bravo (1985)[61]
13. Flooding method: Wallis [62]

14. Heat transfer coefficient method: Chilton and


Colburn
15. Film resistance options: Discrxn for liquid film;
Film for vapor film
16. Flow model: VPlug
17. Estimates: provide temperature at stages 1, 12,
and 20. These estimates are intended to aid
convergence.

4 Simulation Approach 21
Unit Aspen Comments / Specifications
Operation Plus Block

Stripper RadFrac 1. Calculation type: Rate-Based


2. 20 Stages
3. Top Pressure: 1.999 bar
4. Reaction: Chemistry ID is MEA for condenser and
reboiler, and the Reaction ID is STRIPPER for all other
stages
5. Packing Type: FLEXIPAC® 250Y
6. Diameter: .125m
7. Total Height: 2.92m
8. Wash Section Height: 0.42 m
9. Stripper Section Height: 2.5 m
10. Distillate Rate: 6.93 kg/hr
11. Reboiler Duty: 7.05 kW
12. Condenser Temperature: 18 C
13. Mass transfer coefficient method: Bravo (1985)[61]
14. Interfacial area method: Bravo (1985)[61]
15: Flooding method: Wallis [62]
16. Heat transfer coefficient method: Chilton and
Colburn
17. Film resistance options: Discrxn for liquid film;
Film for vapor film
18. Flow model: VPlug
19. Estimates: provide temperature at stage 20. This
estimate is intended to aid convergence.
HX1 HeatX 1. Calculation Type: Shortcut
2. Hot Inlet – Cold Outlet Temperature Difference:
5.27 C
3. Cold Side Outlet Pressure: 2.9bar
4. Valid Phases: Vapor-Liquid both sides

HX2 Heater 1. Outlet Temperature: 112.85 C (set to match


experimental data for inlet temperature for stripper
caused by heat losses after heat recovery exchanger)
2. Outlet Pressure: 2.9bar
3. Valid Phases: Vapor - Liquid

HX3 Heater 1. Outlet Temperature: 40 C


2. Outlet Pressure: 2 bar
3. Valid Phases: Vapor - Liquid

Pump Pump 1. Discharge Pressure: 2.9bar

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

22 4 Simulation Approach
Streams – Major inlet and outlet streams and properties are summarized in
Table 5. The streams LEANIN, LEANOUT and WATERIN are tear streams in the
simulation. Initial guesses for LEANIN and WATERIN were taken from the
experimental data and shown in Table 5.

Table 5. Major Experimental Stream Properties


Stream ID FLUEGAS LEANIN RICHOUT CO2OUT COND WATERIN WATEROUT

Temperature: C 48.01 40.01 51.66 18.27 16.02 43.87 47.70


Pressure: mbar 1004.49 2000 1065.05 2000 ~1000 ~1000 ~1000
Total flow: kg/hr 72 201.3 208.3 4.46 2.47 30.75 28.53
Mass Fraction
MEA 0 0.275 0.267 0 0 0.0031 0.003
H2O 0.071 0.674 0.663 0.004 1.0 0.9954 0.995
CO2 0.085 0.051 0.070 0.994 0 0 0
N2 0.743 0 0 0 0 0 0
O2 0.101 0 0 0 0 0 0
Molar CO2 -- 0.254 0.365 -- -- -- --
Loading

Balance Blocks –The water makeup stream flowrate was determined using a
standard balance block. The inlet stream was FLUEGAS and the water makeup
stream, WATERMU, was introduced for the water balance. The outlet streams
were GASOUT, CO2OUT, and S7.
The MEA makeup stream flowrate was determined using another standard
balance block. The MEA makeup stream, MEAMU, was introduced for the MEA
balance. The outlet streams were GASOUT, CO2OUT, and S7.
Prop-Sets - A Prop-Set, XAPP, has been created to report apparent mole
fraction of CO2 and MEA in liquid 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 MEA.

4 Simulation Approach 23
5 Simulation Results

All simulations were performed using Aspen Plus. Initially, calculations for the
absorber were carried out with the Bravo (1985)[61]/Bravo (1985), Bravo
(1992)[63]/Bravo (1992), the Billet and Schultes (1993) [64]/Billet and Schultes
(1993), and the HanleyStruc (2010)[65]/Stichlmair (1989) mass transfer/liquid
holdup correlations available in Aspen Plus. The VPLUG flow model was used
for all packed sections.
Figure 19 shows the comparison of the absorber temperature profile with
those computed with the correlations listed above. Each simulation was run
with the same conditions on the feed streams as well as the same
specifications on the absorber. The predictions of the Bravo (1985)/Bravo
(1985) and the HanleyStruc (2010)/ Stichlmair (1989) mass transfer/liquid
holdup correlations match the experimental profiles much more closely than
do the profiles generated from the other two correlations. Further, the Bravo
(1985)/Bravo(1985) correlation set gave a CO2 removal of 79.1%, the Bravo
(1992)/Bravo (1992) yielded a CO2 removal of 33.4%; the Billet and Schultes
(1993)/Billet and Schultes (1993) yielded a CO2 removal of 49.5%; and the
HanleyStruc (2010)/Stichlmair (1989) gave a CO2 removal of 88.7%. The
experimental removal was reported to be 76.1%. To match the ~76% CO2
removal with the Hanleystruc (2010)/Stichlmair (1989) correlation set, the
interfacial area factor needs to be adjusted down to 0.6. Based on the close
matches of the Bravo (1985)/Bravo (1985) absorber temperature profile and
CO2 removal predictions with the experimental measurements, this
correlation set with the default interfacial area factor of unity was used to
generate and report all subsequent results.

A comparison of key simulation results with the measurements is given in


Table 6. The measured versus calculated absorber and stripper temperature
profiles are presented in Figures 23 and 24, respectively.

24 5 Simulation Results
Table 6. Key Simulation Results
Variable Measurement Rate-Based Model

CO2 loading of LEANIN, molCO2 /molMEA 0.262 0.254


CO2 loading of RICHOUT, 0.387 0.365
molCO2 /molMEA
CO2 removal, % 76.1 72.6
Specific Energy Requirement of the 5.01 5.72
Reboiler Excluding Heat Losses,
MJ/kgCO2
Makeup Water, kg/hr 1.95 2.22
Makeup MEA, kg/hr n/a 0.007
Stripper Reboiler Heat Duty Excluding 6.47 7.05
Heat Losses, kW
Heat Recovery Exchanger Duty, kW 13.52 12.62

Figures 20 through 26 further demonstrate that rate-based modeling with the


Bravo (1985)/Bravo (1985) mass transfer/liquid holdup correlations can
reproduce quite accurately the experimentally measured temperature profiles
in both the absorber and the stripper, the CO2 weight fraction profiles in both
columns, as well as the CO2 and water partial pressure profiles in both
columns.

70

65

60
Temperature, C

55

50
Experimental
45 Hanley
Bravo1985
40 Bravo1992
Billet&Schultes
35
0 1 2 3 4 5

Packing height from top, m

Figure 19. Absorber Liquid Temperature Profile: Comparison of Simulation


Predictions Using Different Mass Transfer Models with Data [1, 61, 63-65]

5 Simulation Results 25
0.08

0.07
CO2 mass fraction

0.06

Experimental
0.05 Hanley
Bravo1985

0.04
0 0.5 1 1.5 2 2.5 3

Packing height from top, m

Figure 20. Stripper CO 2 Mass Fraction Profile: Comparison of Simulation


Predictions Using Different Mass Transfer Models with Data [1, 61, 65]

70

65

60
Temperature, C

55

50
Experimental

45 Bravo1985, L

40 Bravo1985, V

35
0 1 2 3 4 5

Packing height from top, m

Figure 21. The Absorber Temperature Profiles Using Bravo (1985) Mass
Transfer Correlations[1, 61]

26 5 Simulation Results
120

118 Experimental
Bravo1985, L
Temperature, C

116 Bravo1985, V

114

112

110
0 0.5 1 1.5 2 2.5 3

Packing height from top, m

Figure 22. The Stripper Temperature Profiles Using Bravo (1985) Mass
Transfer Correlations[1, 61]

0.09

0.08
CO2 mass fraction

0.07

0.06

Experimental
0.05
Bravo1985

0.04
0 1 2 3 4 5

Packing height from top, m

Figure 23. The Absorber CO 2 Liquid Concentration Profile[1] Using Bravo


(1985) Mass Transfer Correlations [1, 61]

5 Simulation Results 27
0.08

0.07
CO2 mass fraction

0.06

Experimental
0.05
Bravo1985

0.04
0 0.5 1 1.5 2 2.5 3

Packing height from top, m

Figure 24. The Stripper CO 2 Liquid Concentration Profile[1] Using Bravo (1985)
Mass Transfer Correlations[1, 61]

250

200
Partial pressure, mbar

150 CO2, experimental


H2O, experimental

100 CO2, simulation


H2O, simulation

50

0
0 1 2 3 4 5

Packing height from top, m

Figure 25. The Absorber Partial Pressure Profiles [1] Using Bravo (1985) Mass
Transfer Correlations[1, 61]

28 5 Simulation Results
2000

Partial pressure, mbar


1500

CO2, experimental
H2O, experimental
1000 CO2, simulation
H2O, simulation

500

0
0 0.5 1 1.5 2 2.5 3

Packing height from top, m

Figure 26. The Stripper Partial Pressure Profiles [1] Using Bravo (1985) Mass
Transfer Correlations[1, 61]

5 Simulation Results 29
6 Conclusions

The Rate-Based MEA 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.

30 6 Conclusions
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