Aspen Plus

Rate-Based Model of the CO2 Capture Process by

TEA 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

V7.0 First version

V7.1 Re-verified simulation results using Aspen Plus V7.1
V7.1 CP1 Add N2 , O2 , CO and H2 to the model as Henry components
V7.2 Updated results for V7.2
V7.3 Update databank to PURE25.
Add the definition of acid gas loading and amine weight fraction
convention.
V7.3.2 Update databank to PURE26
V8.0 Update databank to PURE27
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 the PC-SAFT parameters, Antoine equation parameters and
DIPPR heat of vaporization parameters for TEA.
Update the NRTL parameters between TEA and H2 O, H2 O and (TEAH+,
HCO3 - ), H2 O and (TEAH+, CO3 -2 ), H2 O and (TEAH+, HS- ), H2 O and
(TEAH+, S-2 ), TEA and (TEAH+, HCO3 - ), TEA and (TEAH+, HS- ), CO2 and
(TEAH+, HCO3 - ) and those between H2 S and (TEAH+, HS- ).
Update the DGAQFM, DHAQFM, CPAQ0 of TEAH+.
Update the interaction parameters, VLQKIJ, between PZ and H2 O.
Update the interaction parameters, MULIJ and MUKIJ, between TEA and
H2 O.
Update figures for properties.
Update kinetics.
Update flowsheet to Levelland Pilot Plant.
V8.2 Update databank to PURE28.
V8.6 Update databank to PURE32.
V10.0 Update GMENCC parameters between CO 2 and (TEAH+, HCO3 - ), and
those between CO 2 and (TEAH+, CO3 -2 ) to match CO2 activity
coefficient.
Update simulation results.

Revision History 1
Contents
Introduction ............................................................................................................3

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

2 Process Description..............................................................................................5

3 Physical Properties...............................................................................................6

4 Reactions ...........................................................................................................19

5 Simulation Approach ..........................................................................................22

6 Simulation Results .............................................................................................25

7 Conclusions ........................................................................................................26

References ............................................................................................................27

2 Contents
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by aqueous TEA (Triethanolamine) solution from a gas mixture of CH 4, CO2,
H2S and H2O. The model consists of an absorber and stripper. The pilot plant
test data of a gasoline plant in Levelland [1] were used as feed conditions and
unit operation block specifications in the model. Thermophysical property
models and reaction kinetic models used in the simulation are based on the
works of Zhang and Chen (2011) [2], Pinsent et al. (1956) [3]and Little et
al.(1990)[4].Transport property models and model parameters have been
validated against experimental data from open literature.

The model includes the following key features:

 True species including ions
 Unsymmetric electrolyte NRTL activity coefficient model for liquid and PC-
SAFT equation of state for vapor
 Activity-based reaction kinetics
 Electrolyte transport property models
 Rate-based model for absorber with tray

Introduction 3
1 Components

The following components represent the chemical species present in the

process:

Table1. Components Used in the Model

ID Type Name Formula

TEA Conventional TRIETHANOLAMINE C6H15NO3

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
TEAH+ Conventional
CH4 Conventional METHANE CH4
C2H6 Conventional ETHANE C2H6
C3H8 Conventional PROPANE C3H8
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

4 1 Components
2 Process Description

Process Description
The bulk CO2 separation process reported by Petty and Ho (1984) for the
Levelland gasoline plant [1] was carried out in two steps: CO2 is removed in
absorber using aqueous TEA solution and then the CO2 loading TEA solution is
stripped to refresh the TEA solution in the stripper.
Table 2 represents the typical operation data of the process.

Table2. Data of Process

Absorber
Diameter 2.5ft
Tray 20 valve trays
Stripper
Diameter 2.5ft
Tray one ideal stage, a condenser and a reboiler
Absorber Feed Gas
Design Gas rate 600 N m3/D
CO2 in Feed Gas 30-60 mol%

Clean Gas
CO2 in Clean Gas 2-40 mol%
Acid Gas
CO2 in Acid Gas 76-99.5 mol%
Lean Amine
Flow rate 30-105 gal/min
TEA Concentration 30-54 wt%

2 Process Description 5
3 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 TEA model. CO2, H2S, N2, O2, CO, H2, CH4,
C2H6 and C3H8 are selected as Henry-components to which Henry’s law is
applied. Henry’s constants are specified for these components with water and
TEA. 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 literature[2,5] or regressed with the VLE data (See Table 3).
The other Henry’s constants are retrieved from Aspen Databank.

Table3. Henry’s constants

Solute Solvent Source

CO2 H2 O Yan and Chen (2010) [5]

H2 S H2 O Regression with H2 S-H2 O VLE data[6-13]
CH4 H2 O Regression with CH4 -H2 O VLE data[14]
C 2 H6 H2 O Regression with C 2 H6 -H2 O VLE data[15]
C 3 H8 H2 O Regression with C 3 H8 -H2 O VLE data[16]
CO2 TEA This work
H2 S TEA Set to that of H2 S in H2 O
CH4 TEA Set to that of CH4 in H2 O
C 2 H6 TEA Set to that of C 2 H6 in H2 O
C 3 H8 TEA Set to that of C 3 H8 in H2 O

The PC-SAFT parameters of TEA are regressed from the vapor pressure
data[17], the liquid heat capacity data[18, 19] and the liquid density data[20-24].
Those of the other components are retrieved from the Aspen Databank.
The Antoine equation parameters of TEA are regressed from the vapor
pressure data[17]. The heat of vaporization (from 300 K to 650 K) generated
by PC-SAFT equation of state is used to determine the DIPPR heat of
vaporization equation parameters for TEA. The ideal-gas heat capacity

6 3 Physical Properties
 correlation parameters are obtained by fitting to the liquid heat capacity
data[18, 19].
The characteristic volume parameters of H 2O for the Brelvi-O’Connell Model,
VLBROC, are obtained from Brelvi and O’Connell (1972) [25], those of CO2 are
obtained from Yan and Chen (2010) [5], those of CH4 and C2H6 are regressed
with the CH4-H2O[14] and C2H6-H2O[15] binary VLE data, and those of TEA, 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 [26]. The
nonrandomness factor is fixed at 0.2.
The NRTL interaction parameters between TEA and H2O are determined from
the regression with binary VLE data[27], excess enthalpy data[28] and heat
capacity data[29].
The interaction energy parameters, GMENCC, between H2O and (TEAH+,
HCO3-), H2O and (TEAH+, CO3-2), CO2 and (TEAH+, HCO3-), and those between
TEA and (TEAH+, HCO3-)are regressed using the ternary VLE data[30] and CO2
differential absorption heat data, which are calculated from an approximate
form of the Gibbs-Helmholtz equation mentioned in the literature[30]
The interaction energy parameters, GMENCC, between H2O and (TEAH+, HS-),
H2O and (TEAH+, S-2), H2S and (TEAH+, HS-), and those between TEA and
(TEAH+, HS-) are regressed with the ternary VLE data[30].
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 TEA in Aspen Databank are 29.12369, 14651
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
TEA and H2O is regressed against experimental density data of the TEA-
H2O system [31-34]. The Clarke model parameter VLCLK/1 for main
 2
electrolytes (TEAH+, HCO 3 ), (TEAH+, CO 3 ) and (TEAH+, HS-) is set to the
 2
values for (MDEAH+, HCO 3 ), (MDEAH+, CO 3 ) and (MDEAH+, HS-) for lack
of ternary TEA, H2O and acid gas experiment data and for the similar
properties between TEA and MDEA. The Clarke model parameter VLCLK/1
 2
for (MDEAH+, HCO 3 ) and (MDEAH+, CO 3 ) is regressed against
experimental density data of the MDEA-H2O-CO2 system from Weiland
(1998)[35], and that of (MDEAH +, HS-) is regressed against experimental
data of the MDEA-H2O-H2S system from Rinker et al. (2000) [36].

3 Physica l Prope rties 7

  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 TEA 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 TEA and H2O in the ASPEN liquid mixture viscosity
model, MUKIJ and MULIJ, are regressed against experimental viscosity
data of the TEA-H2O system [31,37]. The Jones-Dole model parameter,
IONMUB, for CO32- is regressed against K2CO3-H2O viscosity data from Pac
et al. (1984)[38]; that of HCO3- is regressed against KHCO3-H2O viscosity
data from Palaty (1992)[39].
 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 TEA-H2O system can be in the range of the experimental
data from Alvarez et al. (2003)[40].and Vazquez (1996)[41]
 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
TEAH+ are regressed with VLE[30] and differential absorption heat, which are
calculated from an approximate form of the Gibbs-Helmholtz equation
mentioned in the literature[30].
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) [42], and that of
S-2 is calculated from the Criss-Cobble correlation[42] with the entropy value
from Wagman et al. (1982) [43].
The estimation results of various transport and thermal properties are
summarized in Figures 1-19. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent TEA. Apparent
means before reaction, so for example if 1 mole of TEA 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 TEA after reacting. Weight percent of TEA
is calculated without CO2, so in the above example, it is calculated from the
mixture of 1 mole of TEA and 9 moles of water. Since TEA has a molecular
weight of 149.19 and water has a molecular weight of 18.015, this is
149.19/(149.19+9*18.015) = 0.4792 or about 48 wt% TEA.

8 3 Physical Properties
 1400

1200

Density, kg/m3 1000

800

600 EXP 1994Maham

EXP 1964Tseng
400 EST

200

0
0 0.2 0.4 0.6 0.8 1
TEA Mass Fraction

Figure1. Liquid Density of TEA-H2O at 298.15K, experimental data from

Maham(1994)[32] and Tseng(1964)[34]

1400

1200

1000
Density, kg/m3

800
TEA 10wt%
600 TEA 20wt%
TEA 30wt%
400 TEA 40wt%

200

0
0 0.2 0.4 0.6 0.8 1
CO2 Loading, mole CO 2/mole TEA

Figure2. Liquid Density of TEA-CO2-H 2O at 298.15K

3 Physica l Prope rties 9

 1400

1200

1000

Density, kg/m3 800

600 TEA 10wt%

TEA 20wt%
400 TEA 30wt%
TEA 40wt%
200

0
0 0.2 0.4 0.6 0.8 1
H2S Loading, mole H2S/mole TEA

Figure3. Liquid Density of TEA-H2S-H2O at 298.15K

1.00E+01

1.00E+00

EXP 2002Maham
Viscosity, PaS

1.00E-01 EST

1.00E-02

1.00E-03

1.00E-04
0 0.2 0.4 0.6 0.8 1
TEA Mass Fraction

Figure4. Liquid Viscosity of TEA-H2O at 298.15K, experimental data from

Maham (2002)[37]

10 3 Physical Properties
 0.1
TEA 10wt%
TEA 20wt%
TEA 30wt%
TEA 40wt%
0.01
Viscosity, PaS

0.001

0.0001
0 0.2 0.4 0.6 0.8 1

CO 2 Loading, mole CO 2/mole TEA

Figure5. Liquid Viscosity of TEA-CO2-H2O at 298.15K

1 TEA 10wt%
TEA 20wt%
TEA 30wt%
TEA 40wt%
0.1
Viscosity, PaS

0.01

0.001

0.0001
0 0.2 0.4 0.6 0.8 1

H2S Loading, mole H2S/mole TEA

Figure6. Liquid Viscosity of TEA-H2S-H2O at 298.15K

3 Physica l Prope rties 11

 8.00E-02
7.00E-02

Surface Tension, N/m

6.00E-02
5.00E-02
4.00E-02
3.00E-02 EXP 2003Alvarez
EXP 2001Vazquez
2.00E-02
EST
1.00E-02
0.00E+00
0 0.2 0.4 0.6 0.8 1
TEA Mass Fraction

Figure7. Surface tension of TEA-H2O at 298.15K, experimental data from

Alvarez (2003)[40] and Vazquez(2001) [41]

0.1
0.09
0.08
0.07
Surface Tension, N/m

0.06
0.05
0.04 TEA 10wt%
TEA 20wt%
0.03 TEA 30wt%
0.02 TEA 40wt%
0.01
0
0 0.2 0.4 0.6 0.8 1
CO2 Loading, mole CO2/mole TEA

Figure8. Surface tension of TEA-CO2-H2O at 298.15K

12 3 Physical Properties
 0.1
0.09
0.08
0.07

Surface Tension, N/m

0.06
0.05
0.04
TEA 10wt%
0.03 TEA 20wt%
TEA 30wt%
0.02
TEA 40wt%
0.01
0
0 0.2 0.4 0.6 0.8 1
H2S Loading, mole H2S/mole TEA

Figure9. Surface tension of TEA-H2S-H2O at 298.15K

0.3
Thermal Conductivity, Watt/m-K

0.25 EST

0.2

0.15

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1
TEA Mass Fraction

Figure10. Liquid Thermal Conductivity of TEA-H2O at 298.15K

3 Physica l Prope rties 13

 0.6

0.5

Thermal Conductivity, Watt/m-K

0.4

0.3

0.2 TEA 10wt%

TEA 20wt%
TEA 30wt%
0.1 TEA 40wt%

0
0 0.2 0.4 0.6 0.8 1
CO2 Loading, mole CO 2/mole TEA

Figure11. Liquid Thermal Conductivity of TEA-CO2-H2O at 298.15K

0.6

0.5
Thermal Conductivity, Watt/m-K

0.4

0.3

0.2
TEA 10wt%
TEA 20wt%
0.1 TEA 30wt%
TEA 40wt%
0
0 0.2 0.4 0.6 0.8 1
H2S Loading, mole H2S/mole TEA

Figure12. Liquid Thermal Conductivity of TEA-H2S-H2O at 298.15K

14 3 Physical Properties
 350

300

Heat Capacity, J/mol-K

250
EXP 1999Chiu
200 EST

150

100

50

0
0 0.2 0.4 0.6 0.8 1
TEA Mass Fraction

Figure13. Liquid Heat Capacity of TEA-H 2O at 298.15K, experimental data

from Chiu (1999)[29]
120

100
Heat Capacity, J/mol-K

80

60

40 TEA 10wt%
TEA 20wt%
TEA 30wt%
20 TEA 40wt%

0
0 0.2 0.4 0.6 0.8 1
CO2 Loading, mole CO 2/mole TEA

Figure14. Liquid Heat Capacity of TEA-CO2-H2O at 298.15K

3 Physica l Prope rties 15

 120

100

Heat Capacity, J/mol-K

80

60
TEA 10wt%
40 TEA 20wt%
TEA 30wt%
TEA 40wt%
20

0
0 0.2 0.4 0.6 0.8 1
H2S Loading, mole H2S/mole TEA

Figure15. Liquid Heat Capacity of TEA- H 2S-H2O at 298.15K

60

50
Heat of Solution, kJ/mol

40

30

20 ESP 1985JOU
TEA 10wt%
TEA 20wt%
10 TEA 30wt%
TEA 40wt%

0
0 0.2 0.4 0.6 0.8 1
CO2 Loading, mole CO2 /mole TEA

Figure16. Differential CO2 absorption heat in aqueous TEA solution at 298.15K,

experimental data from Jou (1985)[30] without TEA concentration and
temperature specification

16 3 Physical Properties
 45

40

35
Heat of Solution, kJ/mol 30

25

20

15 ESP 1985JOU
TEA 10wt%
10 TEA 20wt%
TEA 30wt%
5 TEA 40wt%

0
0 0.2 0.4 0.6 0.8 1
H2S Loading, mole H2S/mole TEA

Figure17. Differential H 2S absorption heat in aqueous TEA solution,

experimental data from Jou (1985)[30] without TEA concentration and
temperature specification

10000000 298K,EXP
298K,EST
323K,EXP
1000000 323K, EST
348K,EXP
100000 348K,EST
373K,EXP
CO 2 Pressure, Pa

373K,EST
10000 398K,EXP
398k, EST

1000

100

10
0.0001 0.001 0.01 0.1 1 10
CO2 Loading, mole CO 2/mole TEA

Figure18. CO2 partial pressure of the TEA-CO2-H2O system (TEA

concentration is around 2M) with various CO2 loading, experimental data
from Jou et al. (1985)[30]

3 Physica l Prope rties 17

 10000000 298K,EXP
298K, EST
323K,EXP
1000000 323K,EST
348K,EXP
348K,EST
100000 373K,EXP
373K,EST
H2S Pressure, Pa
398K,EXP
10000 398K,EST

1000

100

10
0.001 0.01 0.1 1 10
H2S Loading, mole H2S/mole TEA

Figure19. H2S partial pressure of the TEA-H2S-H 2O system (TEA

concentration is around 2M) with various H2S loading, experimental data
from Jou et al. (1985)[30]

18 3 Physical Properties
4 Reactions

TEA is a tertiary ethanolamine, as shown below in Figure 20. It can associate

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

Figure20. TEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

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

A. Chemistry ID: TEA

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

B. Reaction ID: TEA-REA

1 Equilibrium TEAH   H 2 O  TEA  H 3O 

4 Reactions 19
 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 TEA  CO 2  H 2 O  TEAH   HCO 3-
9 Kinetic TEAH   HCO 3-  TEA  CO 2  H 2 O
The equilibrium constants for reactions 1-6 in TEA are calculated from the
standard Gibbs free energy change. DGAQFM. DHAQFM and CPAQ0 of TEAH+,
which are used to calculate the standard TEAH+ Gibbs free energy, are
obtained 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 6-
9 in TEA-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 4.

20 4 Reactions
 The kinetic parameters for reaction 6 in Table 4 are derived from the work of
Pinsent et al. (1956)[3]. 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 Little et al.(1990) [4] and the kinetic parameters for
reaction 9 are calculated by using the kinetic parameters of reaction 8 and
the equilibrium constants of the reversible reactions 8 and 9.

Table4. Parameters k and E in Equation (3)

Reaction No. k E , cal/mol
6 1.33e+17 13249
7 6.63e+16 25656
8 2.02e+11 8837
9 5.02e+18 22288

4 Reactions 21
5 Simulation Approach

Run 18 pilot test of the Levelland gasoline plant[1] is used in the simulation.
Simulation Flowsheet – The absorber and stripper have been modeled with
the following simulation flowsheet in Aspen Plus, shown in Figure 21.

CLEANGAS
ABSORBER

LEANIN ACIDGAS

COOLER

FEEDGAS
STRIPPER
RICH

H2OSUPP

TEASUPP

LEANOUT

PUMP

Figure21. Rate-Based TEA Flowsheet in Aspen Plus

22 5 Simulation Approach
 Unit Operations - Major unit operations in this model have been represented
by Aspen Plus blocks as outlined in Table 5.

Table5. Aspen Plus Unit Operation Blocks Used in the

Rate-Based TEA Model
Unit Operation Aspen Plus Block Comments / Specifications

Absorber RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: 495 psia
4. Reaction: Reaction ID is TEA-REA for all stages; when
calculation type is equilibrium, Holdup is used, and in this
file, Holdup=0.023 m3 , which is close to the scaled value
calculated by Holdup correlation
5. Tray Type: Nutter Float Valve
6. Tray Diameter: 2.5 ft
7. Number of valves per active area: 139.92/m2
9. Mass transfer coefficient method: Scheffe and Weiland
(1987)
10. Interfacial area method: Scheffe and Weiland (1987)
11. Interfacial area factor: 1
12. Heat transfer coefficient method: Chilton and Colburn
13. Holdup correlation: Bennett et al. (1983)
14. Holdup scale factor: 1
15. Film resistance: Discrxn for liquid film; Film for vapor
film
16. Additional discretization points for liquid film: 5
17. Flow model: Mixed
18. Estimates: Provide temperature estimates for stages 1 to
20, these estimates are intended to aid convergence
Stripper RadFrac 1. Calculation type: Equilibrium
2. 3 Stages: Partial-Vapor condenser
3. Kettle reboiler
4. Distillate rate: 353 mol/min
5. Mole reflux ratio: initialized at 0.1124 with the final value
of 0.112379 obtained by Design-Spec 1
6. Design Specs: CO 2 loading of the stream LEANOUT is set
to 0.19
7. Vary: reflux ratio is set to adjusted variable
8. Reaction: Chemistry ID is TEA for all stages
Pump Pump Raise the pressure of stream LEANOUT from the stripper
bottom to 495 psia
Cooler Heater Low the stream LEANIN temperature to 150 F

5 Simulation Approach 23
 Streams - Feeds to the absorber are gas stream FEEDGAS containing CH 4,
C2H6, C3H8 and CO2 , liquid solvent stream LEANIN containing aqueous TEA
solution loaded with some CO2 recycled from stripper and supplement
streams, and H2OSUPP and TEASUPP, which supplement H 2O and TEA
escaping from stripper and absorber overhead. Feed conditions are
summarized in Table 6.

Table6. Feed specification

Stream ID FEEDGAS LEANIN

Substream: MIXED
Temperature K 308.15 338.71
Pressure psia 495 495
Total Flow Rate mol/min gal/min
862.151 69.6
Mole-Frac
H2O 0 0.866662
CO2 0.472 0.0212893
TEA 0 0.112049
CH4 0.4224 0
C2H6 0.0528 0
C3H8 0.0528 0

Prop-Sets - Prop-Sets, XAPP and ML-LOAD, have been created to report

apparent mole fractions and CO2 loading of the streams.

24 5 Simulation Approach
6 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 7 and Figure 23. Figure 23 only displays the simulation
absorber liquid temperature profile, since no pilot plant temperature data is
available.

Table7. Key Simulation Results

Measurement Rate-Based TEA model

CO2 mole fraction in CLEANGAS 14.00% 23.95%

360
358
356
354
352
Temperature/K

350
348
346
344
342
340
338
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Stage

Figure23. Absorber Liquid Temperature Profile

6 Simulation Results 25
7 Conclusions

The Rate-Based TEA 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.
The model is meant to be used as a guide for modeling the CO 2 capture
process with TEA. You may use it as a starting point for more sophisticated
models for process development, debottlenecking, plant and equipment
design, among others.

26 7 Conclusions
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