Aspen Plus

Rate-Based Model of the CO2 Capture Process by

AMP using Aspen Plus
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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 O2, CO and H2 to the model as Henry components
V7.2 Update Henry’s constant of CO2 in H2O 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 AMP based on the work of Wang et al. (1992).
Update AMP-H2O NRTL parameters by fitting VLE data of Pappa (2006),
excess enthalpy data of Mathonat (1997) and heat capacity data of
Chen (2001), Chiu (1999) and Zhang (2002).
Update DGAQFM and DHAQFM for AMP ions and H2O-(MEAH+, HCO3-)
interaction parameters by fitting solubility data of Roberts (1988),
Tontiwachwuthikul (1991), Li (1994), Seo (1992), Jane (1997) and
Kundu (2003) and heat absorption data of Arcis (2007).
Update figures for properties.
Update kinetics based on the works of Jamal (2006).
Update simulation results.
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.
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 Process Description..............................................................................................5

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

4 Reactions ...........................................................................................................14

5 Simulation Approach ..........................................................................................17

6 Simulation Results .............................................................................................21

7 Conclusions ........................................................................................................23

References ............................................................................................................24

2 Contents
Introduction

This document describes an Aspen Plus rate-based model of the CO2 capture
process by AMP (2-amino-2-methyl-1-propanol) from a gas mixture of N2 and
CO2, resulting from coal-fired power plants. The model consists of an absorber
and a stripper. The pilot plant operation data from Gabrielsen (2007)[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 Aspen Technology (2007)[2] and Jamal
et al. (2006)[3, 4]. Transport property models and model parameters have
been validated against experimental data from open literature.
H2S and its related chemistry and physical property parameters are included
in the model for completeness. However, since there is no H2S in the pilot
plant studies of Gabrielsen (2007)[1], H2S is not included in any of the streams
of the current model.
The model presented here 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
 Rate-based models for absorber and stripper with packing

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

AMP Conventional 2-AMINO-2-METHYL-1-PROPANOL C4H11NO-1

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
H2S Conventional HYDROGEN-SULFIDE H2S
AMPH+ Conventional AMP+ C4H12NO+
AMPCOO- Conventional AMPCOO- C5H11NO3-
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
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

4 1 Components
2 Process Description

The absorber and stripper data for the CO2 capture process by AMP are
reported by Gabrielsen (2007)[1]. Table 2 represents a typical set of
operation data:

Table 2. Data of the Pilot Plant

Absorber

Diameter 0.15 m
Packing Sulzer Mellapak 250Y
Packing Height 4.36 m
Stripper

Diameter 0.10 m
Packing Sulzer Mellapak 250Y
Packing Height 3.89 m

Feeds and Products

Sour Gas to Absorber 118 m3/hr

Lean Amine to Absorber 3 l/min
Rich Amine to Stripper 3 l/min
CO2 in Sour Gas 0.130 (mole fraction)
CO2 in Sweet Gas 0.098 (mole fraction)
AMP solution 2.89 mol/l

2 Process Description 5
3 Physical Properties

The Electrolyte NRTL method and RK equation of state are used to compute
liquid and vapor properties, respectively, in this Rate-based AMP model. N2,
O2, CO, H2, H2S and CO2 are selected as Henry-components (solutes) to which
Henry’s law is applied. Henry’s constants are specified for these components
with water and AMP. 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.
Henry’s constant parameters of CO2 in water are regressed with the binary
VLE data[5-11], and those of CO2 in AMP are obtained from Wang et al.
(1992)[12]. The NRTL interaction parameters between CO2 and water are set
to zero, and those between AMP and H2O are determined from the regression
with binary VLE data of Pappa et al. (2006)[13], excess enthalpy data of
Mathonat et al. (1997)[14], and heat capacity data of Chen et al. (2001)[15],
Chiu et al. (1999)[16] and Zhang et al. (2002)[17].
The interaction energy parameters between H2O and (AMPH+, HCO3-),
GMELCC, are regressed using the heat of solution data of CO2 in aqueous AMP
from Arcis et al.[18] and CO2 solubility data in aqueous AMP solution. There are
extensive data available for CO2 solubility in AMP[19-27]. The data from Robert
et al. (1988)[19], Tontiwachwuthikul et al. (1991)[20], Teng et al. (1990)[21], Li
et al. (1994)[22], Seo et al. (1996)[23], Jane et al. (1997)[24] and Kundu et al.
(2003)[25] are used in the regression. The VLE data with high CO2 loading
(loading>1) are not included in the regression, so this model is applicable to
VLE from low to moderate CO2 loading. The data of Silkenbaumer et al.
(1998)[26] and Gong et al. (2001)[27] are not be regressed because these VLE
data are inconsistent with those from the other sources.
The interaction energy parameters between H2O and (AMPH+, HS-), GMELCC
and GMELCD, are regressed using H2S solubility data in aqueous AMP solution
from Roberts and Mather (1988)[19].
The dielectric constants of nonaqueous solvents are calculated by the
following expression:

1 1
 T   A  B   (1)
T C 

6 3 Physical Properties
 The parameters A, B and C for AMP are 21.04656, 8451.2 and 298.15, which
are derived from Hsieh et al.[28].
The liquid molar volume and transport property models have been updated
and their model parameters regressed from literature experimental data.
Specifications of these models include:
 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
AMP and H2O is regressed against experimental data from Henni et al.
(2003)[29]. The default values in Aspen Plus for the Clarke model
parameters of all the electrolytes, VLCLK, are used in the calculations due
to absence of density data.
 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 solvents. There are three models
available for electrolyte correction and the AMP model always uses the
Jones-Dole correction model. The three option codes for the MUL2JONS
model are set to: 1 (mixture viscosity calculated by mass-fraction
average), 1 (always use the Jones-Dole equation when parameters are
available), and 2 (use the ASPEN liquid mixture viscosity model for
solvents), respectively. The interaction parameters between AMP and H2O
in the ASPEN liquid mixture viscosity model, MUKIJ and MULIJ, are
regressed against AMP-H2O experimental viscosity data from Henni et al.
2
(2003) [29]. The Jones-Dole model parameters, IONMUB, of CO 3 and
HCO3- are regressed against K2CO3-H2O viscosity data from Pac et al.
(1984)[30] and KHCO3-H2O viscosity data from Palaty (1992)[31],
respectively. For AMPH+, this parameter is not available in the databank,
nor can it be determined from data regression because there are no
experimental viscosity data available. Therefore, its IONMUB/1 is missing
and IONMUB/2 is left to be the default value of 0.
 For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG
in Aspen Plus, is used with its two option codes being -9 (value of
exponent in the mixing rule) and 1 (electrolyte system), respectively. No
additional adjusted parameters are used in this model.
 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 calculated by mass-
fraction average).
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) for AMPH+ are regressed with VLE[19-25] and heat of
solution data[18]. DGAQFM and DHAQFM for AMPCOO- are derived from the
AMP carbamate stability constant in Jamal (2002)[32]. The value of the AMP
carbamate stability constants for AMP at 313 K has been reported to be about
0.03 L/mol[32]. This value indicates that AMP does not form a stable
carbamate and the concentration of AMPCOO- should be very small. The
values of heat capacity at infinite dilution (CPAQ0) for AMPH+ and AMPCOO-
are set to 0.

3 Physical Properties 7
 The estimation results of various transport and thermal properties are
summarized in Figures 1-10. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent AMP. Apparent
means before reaction, so for example if 1 mole of AMP 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 AMP after reacting. Weight percent of AMP
is calculated without CO2, so in the above example, it is calculated from the
mixture of 1 mole AMP and 9 moles of water. Since AMP has a molecular
weight of 89.137 and water has a molecular weight of 18.015, this is
89.137/(89.137+9*18.015) = 0.35474 or about 35 wt% AMP.

1400

1200

1000
Density, kg/m3

800

600

400
EST AMP 10w t%
200 EST AMP 20w t%
EST AMP 30w t%
EST AMP 40w t%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 1. Liquid Density of AMP-CO2-H2O at 298.15K

8 3 Physical Properties
 0.1

0.01
Viscosity, PaS

0.001

EST AMP 10w t%

EST AMP 20w t%
EST AMP 30w t%
EST AMP 40w t%
0.0001
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 2. Liquid Viscosity of AMP-CO2-H2O at 298.15K

0.06

0.05
Surface Tension, N/m

0.04

0.03

0.02

0.01 EST AMP 10w t%

EST AMP 20w t%
EST AMP 30w t%
EST AMP 40w t%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 3. Surface tension of AMP-CO2-H2O at 298.15K

3 Physical Properties 9
 0.6

Thermal Conductivity, Watt/m-K

0.5

0.4

0.3

0.2

EST AMP 10w t%

0.1 EST AMP 20w t%
EST AMP 30w t%
EST AMP 40w t%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

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

250

200
Heat capacity, J/mol.K

150

100
AMP 0.2, EXP AMP 0.4, EXP
AMP 0.6, EXP AMP 0.8, EXP
50 AMP 0.2, EST AMP 0.4, EST
AMP 0.6, EST AMP 0.8, EST

0
300 310 320 330 340 350 360

Temperature, K

Figure 5. Liquid Heat Capacity of AMP-H2O, experimental data from Chen et

al. (2001)[15]

10 3 Physical Properties
 -2500

-2000

Excess enthalpy, J/mol -1500

EXP
-1000
EST

-500

0
0.00 0.20 0.40 0.60 0.80 1.00
H2O m ole fraction

Figure 6. Excess enthalpy of AMP-H2O at 308.15K, experimental data from

Mathonat et al. (1997)[14]

90

80
H eat o f ab so rp tio n ,kJ/m o lC O 2

70

60

50

40

30
0 .2 5 M p a ,E X P 0 .5 1 M p a ,E X P
20 2 .1 9 M p a ,E X P 5 .1 0 M p a ,E X P
0 .2 5 M p a ,E S T 0 .5 1 M p a ,E S T
10
2 .1 9 M P a ,E S T 5 .1 0 M p a ,E S T
0
0 0.5 1 1.5 2 2.5
C O 2 lo ad in g

Figure 7. Integral Heat of Solution of CO2 in aqueous solution of AMP 30 wt %

at 322.5K, experimental data from Arcis et al. (2007)[18]

3 Physical Properties 11
 440

420

400

Temperature, K 380

360
66.7kPa, EST 80kPa, EST
340
101.3kPa, EST 66.7kPa, EXP
320
80kPa, EXP 101.3kPa, EXP

300
0 0.2 0.4 0.6 0.8 1
X-Y of AMP

Figure 8. VLE of AMP-H2O, experimental data from Pappa et al. (2006)[13]

100000 313K ,ES T

333K ,ES T
353K ,ES T
313K ,Tontiw achw uthikul
10000 313K ,R oberts
333K ,Tontiw achw uthikul
353K ,Tontiw achw uthikul
C O 2 p artialp ressu re,kP a

1000

100

10

0.1

0.01
0 0.2 0.4 0.6 0.8 1 1.2
C O 2 lo ad in g

Figure 9. CO2 Partial Pressure of AMP-CO2-H2O (AMP concentration = 3M),

experimental data from Roberts et al (1988)[19] and Tontiwachwuthikul et al.
(1991)[20]

12 3 Physical Properties
 10000

1000

Pressure, KPa 100

10

1 EXP 313K
EST 313K
EXP 373K
EST 373K
0.1
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
H2S Loading

Figure 10. H2S Partial Pressure of AMP-H2S-H2O (AMP concentration = 2M),

experimental data from Roberts and Mather (1988)[19]

3 Physical Properties 13
4 Reactions

AMP is a hindered primary amine, as shown in Figure 11. It can associate with
H3O+ to form AMPH+ and can also react with CO2 to form unstable carbamate,
which easily reacts with other species in the solution, ending with AMPH+.

Figure 11. AMP Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

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

A. Chemistry ID: AMP

1 Equilibrium 2H 2 O  H 3 O   OH 
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 AMPH   H 2 O  AMP  H 3 O 
5 Equilibrium AMPCOO   H 2 O  AMP  HCO 3
6 Equilibrium H 2 O  H 2S  HS   H 3 O 
7 Equilibrium H 2 O  HS   S 2  H 3 O 

B. Reaction ID: AMP-REA

1 Equilibrium AMPH   H 2 O  AMP  H 3 O 

14 4 Reactions
 2 Equilibrium 2H 2 O  H 3 O   OH 
3 Equilibrium HCO 3  H 2 O  H 3 O   CO 32
4 Kinetic CO 2  OH   HCO 3
5 Kinetic HCO 3  CO 2  OH 
6 Kinetic AMP  CO 2  H 2 O  AMPCOO   H 3 O 
7 Kinetic AMPCOO   H 3 O   AMP  CO 2  H 2 O
8 Equilibrium H 2 O  H 2S  HS   H 3 O 
9 Equilibrium H 2 O  HS   S 2  H 3 O 
The equilibrium constants for the reactions 1-5 in AMP are calculated from
the standard Gibbs free energy change. DGAQFM. DHAQFM and CPAQ0 of
AMPH+ and AMPCOO-, which are used to calculate the standard AMPH+ and
AMPCOO- Gibbs free energy, are determined in this work. The DGAQFM (or
DGFM), DHAQFM (or DHFM) and CPAQ0 (or CPIG) parameters of the other
components can be obtained from the databank of Aspen Plus. The
equilibrium constants for reactions 6-7 in AMP are obtained from Austgen et
al. (1988) [33].
The power law expressions are used for the rate-controlled reactions
(reactions 4-7 in AMP-REA). The general power law expression is:

  E  1 1  N
r  k T T0  exp     C 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;
Ci = Concentration of component i;
ai = The stoichiometric coefficient of components i in the reaction equation.
If T0 is not specified, the reduced power law expression is used:

E N
r  kT n exp (  ) C i i
a
(3)
RT i 1

4 Reactions 15
 In this work, the reduced expression is used. In equation (3), the
concentration basis is Molarity, the factor n is zero, k and E are given in
Table 3.
The kinetic parameters for reaction 4 are taken from the work of Pinsent et al.
(1956)[34]. 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. Note that a second order reaction rate
expression for reaction 6 is used to represent the reaction rate of AMP and
CO2, which is a simplification of the expression in Jamal et al. (2006)[3, 4]. The
kinetic parameters for reaction 6 in Table 3 are those of “ k1 ” in Jamal et al.
[3, 4]
(2006) . “ k1 ” is the forward rate constant for the zwitterion formation.

AMP  CO 2 
k1
AMP  COO  (4)

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.

Table 3. Parameters k and E in Equation (2)

Reaction No. k E (cal/mol)
4 4.32e+13 13249
5 2.38e+17 29451
6 1.00e+9 8202
7 1.52e+20 12693

16 4 Reactions
5 Simulation Approach

Studies of CO2 absorption into AMP solution in a pilot plant using structured
packing in both absorber and stripper have been carried out at the Norwegian
University of Science and Technology and SINTEF (2007)[1]. Experimental
data for eleven runs were collected. The largest gas phase concentration
range of CO2 before and after absorption was observed in Run 7 - 12.93%-vol
in the sour gas before absorption and 9.83%-vol in the sweetened gas after
absorption. The experimental data from this run are used in the simulation
described in this report.
Simulation Flowsheet – The pilot plant unit has been modeled with the
following simulation flowsheet in Aspen Plus, shown in Figure 12.

GASOUT CO2OU T

LEANIN

ABSORBER RIC HIN STRIPPER

GASIN

RICHOUT LEANOUT

Figure 12. Rate-Based AMP Simulation Flowsheet in Aspen Plus

5 Simulation Approach 17
 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

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

Absorber RadFrac 1. Calculation type: Rate-Based

2. 11 Stages
3. Top Pressure: 1 atm
4. Reaction: Reaction ID is AMP-REA for all stages; when
calculation type is equilibrium, Holdup is used, and in this
file, Holdup=1.0e-5 kmol for convergence
5. Packing: 250Y STANDARD MELLAPAK by Sulzer
6. Section Diameter: 0.15 m
7. Mass transfer coefficient method: Bravo et al. (1985)
8. Interfacial area method: Bravo et al. (1985)
9. Interfacial area factor: 1
10. Heat transfer coefficient method: Chilton and Colburn
11. Holdup correlation: Bravo et al. (1992)
12. Holdup scale factor: 1
13. Film resistance: Discrxn for liquid film; Film for vapor
film
14. Additional discretization points for liquid film: 5
15. Flow model: Mixed

18 5 Simulation Approach
Unit Operation Aspen Plus Block Comments / Specifications

Stripper RadFrac 1. Calculation type: Rate-Based

2. 9 Stages
3. Partial vapor condenser
4. Kettle reboiler
5. Mass distillate rate: 0.0018 kg/sec
6. Mass reflux ratio: initialized at 0.3 with final value of
0.308 obtained by Design-Spec 1.
7. Top pressure: 1.95 bar, Column pressure drop: 0.02 bar
8. Reaction: Chemistry ID is AMP for stages 1 and 9,
Reaction ID is AMP-REA for stages 2-8; when calculation
type is equilibrium, Holdup is used, and in this file,
Holdup=0.00015 m3 for convergence.
9. Design specs: Stage 1 temperature = 292.15 K
10. Vary: Reflux ratio
11. Packing: 250Y STANDARD MELLAPAK by Sulzer
12. Section Diameter: 0.1 m
13. Mass transfer coefficient method: Bravo et al. (1985)
14. Interfacial area method: Bravo et al. (1985)
15. Interfacial area factor: 1
16. Heat transfer coefficient method: Chilton and Colburn
17. Holdup correlation: Bravo et al. (1992)
18. Holdup scale factor: 1
19. Film resistance options: Discxrn for liquid film; Film for
vapor film
20. Additional discretization points for liquid film: 5
21. Flow model: Mixed

5 Simulation Approach 19
 Streams - Feeds to the absorber are gas stream GASIN containing N2, CO2
and H2O and liquid lean solvent stream LEANIN containing aqueous AMP
solution. Feed to the stripper is rich solvent stream RICHIN containing
aqueous AMP solution with absorbed CO2. Feed streams conditions are
summarized in Table 5.

Table 5. Feed specifications

Stream ID GASIN LEANIN RICHIN
Substream: MIXED
Temperature: C 41 41 99
Pressure 1 atm 1 atm 1.96 bar
Total flow 118 m3/h 3 l/m 3 l/m
Mole-Frac Mole-Conc, mol/l Mole-Conc, mol/l
AMP 0 2.89 2.89
H2O 0.078 solvent solvent
CO2 0.129 0.4913 1.327
N2 0.793 0 0

20 5 Simulation Approach
6 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 6. The measured versus calculated absorber and stripper
liquid temperature profiles are presented in Figures 11 and 12, respectively.

Table 6. Key Simulation Results

Variable Measurement Rate-Based AMP Model

Absorber
CO2 mole fraction in GASOUT 0.0983 0.1013
Loading of RICHOUT, MolAcidGas/MolAMP 0.46 0.42
Stripper
Loading of LEANOUT, MolAcidGas/MolAMP 0.17 0.18
Reboiler duty, kW 7.6 7.7
As shown by Figures 13 and 14, the calculated temperature profiles in both
absorber and stripper match the measured values very well.

120

100
As pen, Liquid
As pen, Vapor
80
Meas ured
Temperature, C

60

40

20

0
0 1 2 3 4 5
Height f rom Bottom, m

6 Simulation Results 21
 Figure 13. The Absorber Liquid Temperature Profile

140

120

Temperarture, C 100

80

60 As penPlus , Liquid

As penPlus , Vapor
40
Meas ured
20

0
0 1 2 3 4 5
Height f rom Bottom, m

Figure 14. The Stripper Liquid Temperature Profile

22 6 Simulation Results
7 Conclusions

The Rate-Based AMP 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 CO2 capture
process with AMP. Users may use it as a starting point for more sophisticated
models for process development, debottlenecking, plant and equipment
design, among others.

7 Conclusions 23
References

[1] J. Gabrielsen, “CO2 Capture from Coal Fired Power Plants”, PhD thesis,
Chemical Engineering, Technical University of Denmark, 2007
[2] Aspen Technology Inc., 2007
[3] A. Jamal, A. Meisen, C. J. Lim, “Kinetics of carbon dioxide absorption and
desorption in aqueous alkanolamine solutions using a novel hemispherical
contactor – I. Experimental apparatus and mathematical modeling”, Chem.
Eng. Sci., 61, 6571-6589 (2006)
[4] A. Jamal, A. Meisen, C. J. Lim, “Kinetics of carbon dioxide absorption and
desorption in aqueous alkanolamine solutions using a novel hemispherical
contactor – II. Experimental results and parameter estimation”, Chem. Eng.
Sci., 61, 6590-6603 (2006)
[5] S. Takenouchi and G.C. Kennedy, “The binary system H2O–CO2 at high
temperatures and pressures”. Am. J. Sci., 262, 1055–1074 (1964)
[6] K. Tödheide and E.U. Franck, Zeitschrift fur physikalische chemie neue
folge, BD. 37, S.387-401 (1963)
[7] W.S. Dodds, L.F. Stutzman and B.J. Sollami, "Carbon dioxide solubility in
water", industrial and engineering chemistry, 1 (1), 92-95 (1956)
[8] S.E. Drummond, “Boiling and mixing of hydrothermal fluids: chemical
effects on mineral precipitation”, Ph.D. Thesis, Pennsylvania State University,
(1981)
[9] A. Zawisza and B. Malesiska, “Solubility of carbon dioxide in liquid water
and of water in gaseous carbon dioxide in the range 0.2-5 Mpa and at
temperature up to 473K", J. Chem. Eng. Data, 26, 388-391 (1981)
[10] R. Wiebe and V.L. Gaddy, “The solubility of carbon dioxide in water at
various temperatures from 12 to 40 ◦C and at pressures to 500 atm”, J. Am.
Chem. Soc., 62, 815–817 (1940)
[11] G. Houghton, A.M. Mclean, and P.D. Ritchie, "Compressibility, fugacity,
and water-solubility of carbon dioxide in the region 0-36 atm and 0-100 C",
Chemical engineering science, 6, 132-137 (1957)
[12] Y. W. Wang, S. Xu, F. D. Otto, A. E. Mather, “Solubility of N2O in
Alkanolamines and in Mixed Solvents”, Chem. Eng. J. 48, 31-40 (1992)

24 References
 [13] G.D. Pappa, C. Anastasi, E.C. Voutsas, “Measurement and
Thermodynamic Modeling of the Phase Equilibrium of Aqueous 2-Amino-2-
Methyl-1-Propanol Solutions”, Fluid Phase Equilibria, 243, 193-197 (2006)
[14] C. Mathonat, Y. Maham, A. E. Mather, L. G. Hepler, “Excess Molar
Enthalpies of (Water + Monoalkanolamine) Mixtures at 298.15K and 308.15K”,
J. Chem. Eng. Data, 42, 993-995(1997)
[15] Y. J. Chen, M. H. Li, “Heat Capacity of Aqueous Mixtures of
Monoethanolamine with 2-Amino-2-Methy-1-Propanol”, J. Chem. Eng. Data,
46, 102-106(2001)
[16] L. F. Chiu, M. H. Li, “Heat Capacity of Alkanolamine Aqueous Solutions”,
J. Chem. Eng. Data, 44, 1396-1401(1999)
[17] K. Zhang, B. Hawrylak, R. Palepu, P. R. Tremaine, “Thermodynamics of
Aqueous Amines: Excess Molar Heat Capacities, Volume, and Expansibilities of
(water + Methyldiethanolamine (MDEA)) and (Water + 2-Amino-2-Methyl-1-
Propanol (AMP))”, J. Chem. Thermodyn., 34, 679-710(2002)
[18] Arcis, H. Rodier L. Coxam, J. –Y., “Enthalpy of Solution of CO2 in
Aqueous Solutions of 2-Amino-2Methyl-1-Propanol”, J. Chem.
Thermodynamics, 39, 878-887 (2007)
[19] B.E. Roberts, A.E. Mather, “Solubility of CO2 and H2S in a Hindered
Amine Solution”, Chem. Eng. Comm., 64, 105-111 (1988)
[20] P. Tontiwachwuthikul, A. Meisen, C. J. Lim, “Solubility of CO2 in 2-Amino-
2-Methyl-1-Propanol Solutions”, J. Chem. Eng. Data, 36, 130-133 (1991)
[21] G. L. Gong, X. Y. Wang, Z. B. Zhang, “Solubilities of CO2 in Biomimetic
and Other Absorbents”, Hugong Xuebao, 52, 349-353 (2001)
[22] M. H. Li, B. C. Chang, “solubilities of Carbon Dioxide in Water +
Monoethanolamine + 2-Amino-2-Methyl-1-Propanol”, J. Chem. Eng. Data, 39,
448-452 (1994)
[23] D. J. Seo, W. H. Hong, “Solubilities of Carbon Dioxide in Aqueous
Mixtures of Diethanolamine and 2-Amino-2-Methyl-1-Propanol”, J. Chem. Eng.
Data, 41, 258-260 (1992)
[24] I. S. Jane, M. H. Li, “Solubilities of Mixtures of Carbon Dioxide and
Hydrogen Sulfide in Water + Diethanolamine + 2-Amino-2-Methyl-1-
Propanol”, J. Chem. Eng. Data, 42, 98-105 (1997)
[25] M. Kundu, B.P. Mandal, S. Bandyopadhyay, “Vapor-Liquid Equilibrium of
CO2 in Aqueous Solutions of 2-Amino-2-Methyl-1-Propanol”, J. Chem. Eng.
Data, Vol. 48, 789 (2003)
[26] D. Silkenbaeumer, B. Rumpf, R. N. Lichtenthaler, “Solubility of Carbon
Dioxide in Aqueous Solutions of 2-Amino-2-Methyl-1-Propanol and N-
Methyldiethanolamine and Their Mixtures in the Temperature Range from 313
to 353K and Pressures up to 2.7 MPa”, Ind. Eng. Chem. Res., 37, 3133-3141
(1998)
[27] G. L. Gong, X. Y. Wang, Z. B. Zhang, “Solubilities of CO2 in Biomimetic
and Other Absorbents”, Hugong Xuebao, 52, 349-353 (2001)
[28] C. J. Hsieh, J. M. Chen, M. H. Li, “Dielectric Constants of Aqueous
Diisopropanolamine, Diethanolamine, N-Methyldiethanolamine,

References 25
 Triethanolamine, and 2-Amino-2-Methyl-1-Propanol Solutions”, J. Chem. Eng.
Data, 52, 619-623 (2007)
[29] A. Henni, J.J. Hromek, P. Tontiwachwuthikul, A. Chakma, “Volumetric
Properties and Viscosities for Aqueous AMP Solutions from 25 C to 70 C”, J.
Chem. Eng. Data, 48, 551-556 (2003)
[30] 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)
[31] Z. Palaty, “Viscosity of diluted aqueous K2CO3/KHCO3 solutions”,
Collect. Czech. Chem. Commun., 57, 9, 1879 (1992)
[32] A. Jamal, “Absorption and desorption of CO2 and CO in alkanolamine
systems”, Ph.D. Thesis, University of British Columbia, Vancouver, B.C.,
(2002)
[33] 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)
[34] 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