Aspen Plus

Rate-Based Model of the CO2 Capture Process by

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

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

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Revision History
Version Description

V7.0 First version.

V7.1 Re-verified simulation results using Aspen Plus V7.1.
V7.1 CP1 1. Add O2, CO and H2 to the model as Henry components.
2. Update NRTL parameters in the DIPA-H2O-CO2 and/or H2S system
and Henry’s constant parameters for CO2 and H2S with DIPA.
3. Correct exponent of H2O in the kinetic reaction among DIPA, H2O
and CO2.
4. Update chemical equilibrium constant parameters for the dissociation
of HS-.
V7.2 Update results for V7.2.
V7.3 Update a 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.
Update the result for CO2 mole fraction in GASOUT.
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 ...........................................................................................................12

5 Simulation Approach ..........................................................................................15

6 Simulation Results .............................................................................................18

7 Conclusions ........................................................................................................20

References ............................................................................................................21

2 Contents
Introduction

This file describes an Aspen Plus rate-based model of the CO2 capture process
by aqueous DIPA. The model consists of an absorber. As there are no
industrial or pilot plant data available for aqueous DIPA separation processes,
the operation data for CO2 absorption by aqueous DEA from a natural gas
treating unit at Pyote, Texas (1975)[1] were used to specify feed conditions
and unit operation block specifications in the model. Thermophysical property
models and reaction kinetic models are based on the works of Aspen
Technology (2007)[2] and Blauwhoff et al. (1985)[3]. 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
 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 with tray

Introduction 3
1 Components

The following components represent the chemical species present in the

process:

Table 1. Components Used in the Model

Component ID Conventional Component name Formula

DIPA Conventional DIISOPROPANOLAMINE C6H15NO2

H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
DIPAH+ Conventional
DIPACOO- Conventional
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HCO3- Conventional HCO3- HCO3-
CO3-2 Conventional CO3-- CO3-2
H2S Conventional HYDROGEN-SULFIDE H2S
HS- Conventional HS- HS-
S-2 Conventional S-- S-2
N2 Conventional NITROGEN N2
CH4 Conventional METHANE CH4
C2H6 Conventional ETHANE C2H6
C3H8 Conventional PROPANE C3H8
O2 Conventional OXYGEN O2
CO Conventional CARBON-MONOXIDE CO
H2 Conventional HYDROGEN H2

4 1 Components
2 Process Description

The Pyote Unit[1] flowsheet for CO2 removal by DEA includes one absorber and
one stripper. However, only the absorber data are simulated in this file. Table
2 represents the typical operation data:

Table 2. Data of the Pyote Unit

Absorber
Diameter 66 inch
Tray Type Glitsch Ballast
Stages 20
Feeds
Sour Gas to Absorber 2.92 MM scfh
Lean Amine to Absorber 188 gpm
CO2 in Feed (Gas) 1.3(Vol %)
H2S in Feed (Gas) 0.054(Vol %)
DIPA solution 34(wt%)

2 Process Description 5
3 Physical Properties

The electrolyte NRTL method is used for liquid and RK equation of state for
vapor in this Rate-based DIPA model. The NRTL parameters between DIPA
and H2O were regressed against VLE data generated using UNIFAC method
and those related to electrolytes were regressed against VLE data for the
system DIPA-H2O-CO2 and/or H2S from Isaacs et al. (1977)[4,5].
N2, CH4, C2H6, C3H8, CO2 and H2S 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. Henry’s constants for CO2
and H2S with DIPA were regressed against VLE data from Isaacs et al.
(1977)[4,5] 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
updated 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
DIPA and H2O is regressed against experimental DIPA-H2O density data
from Henni et al. (2003)[6]. The Clarke model parameters VLCLK/1 are left
to the default for all electrolytes.
 For liquid viscosity, the Jones-Dole electrolyte correction model, called
MUL2JONS in Aspen Plus, is used with the mass fraction based ASPEN
liquid mixture viscosity model for the solvent. There are three models for
electrolyte correction and the DIPA model always uses the Jones-Dole
correction model. The three option codes for MUL2JONS are set to 1
(mixture viscosity weighted by mass fraction), 1 (always use Jones and
Dole equation when the parameters are available), and 2 (ASPEN liquid
mixture viscosity model), respectively. The interaction parameters
between DIPA and H2O in the ASPEN liquid mixture viscosity model, MUKIJ
and MULIJ, are regressed against experimental DIPA-H2O viscosity data
from Henni et al. (2003)[6]. The Jones-Dole model parameters, IONMUB,
of CO3-2 is regressed against K2CO3-H2O viscosity data from Pac et al.
(1984)[7]; that of HCO3- is regressed against KHCO3-H2O viscosity data
from Palaty (1992)[8] and those for DIPAH+ and DIPACOO-, IONMUB/1 are
missing and IONMUB/2 are defaulted as 0.

6 3 Physical Properties
  For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG
in Aspen Plus, is used with its option codes being -9 (exponent in mixing
rule) and 1 (electrolyte system), respectively. No additional adjusted
parameters are used in the surface tension.
 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 heat
capacity at infinite dilution (CPAQ0) for DIPAH+ and DIPACOO- are set as the
heat capacity of liquid DIPA at 298.15K, the aqueous phase heat of formation
at infinite dilution and 25°C (DHAQFM) for DIPACOO- is derived from the
difference of heat of reaction between DIPA and DEA with CO2, and the
DHFORM of DIPA and DEA and DHAQFM of DEACOO-. The difference of heat of
reaction between DIPA and DEA is obtained from Barth et al. (1986)[9] and
the DHFORM of DIPA and DEA and the DHAQFM of DEACOO- are obtained
from Aspen Plus databank. The DHAQFM for DIPAH+ is adjusted to match the
data of the heat of solution of CO2 in aqueous 30wt% DIPA solution from
Gonzalez-Barba et al.(2007)[10].
The estimation results of various transport and thermal properties are
summarized in Figures 1-8. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent DIPA. Apparent
means before reaction, so for example if 1 mole of DIPA 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 DIPA after reacting. Weight percent of
DIPA is calculated without CO2, so in the above example, it is calculated from
the mixture of 1 mole DIPA and 9 moles of water. Since DIPA has a molecular
weight of 133.191 and water has a molecular weight of 18.015, this is
133.191/(133.191+9*18.015) = 0.45100 or about 45 wt% DIPA.

3 Physical Properties 7
 1400

1200

Density, kg/m3 1000

800

600

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

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

0.1
EST DIPA 10w t%
EST DIPA 20w t%
EST DIPA 30w t%
EST DIPA 40w t%

0.01
Viscosity, PaS

0.001

0.0001
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

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

8 3 Physical Properties
 0.07

0.06

Surface Tension, N/m

0.05

0.04

0.03

0.02
EST DIPA 10w t%
0.01 EST DIPA 20w t%
EST DIPA 30w t%
EST DIPA 40w t%
0
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

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

0.6

0.5
Thermal Cnductivity, Watt/m-K

0.4

0.3

0.2

EST DIPA 10w t%

0.1 EST DIPA 20w t%
EST DIPA 30w t%
EST DIPA 40w t%
0
0 0.05 0.1 0.15 0.2 0.25
CO2 Loading

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

3 Physical Properties 9
 5000

4500

4000

Heat Capacity, J/kg-K 3500

3000

2500

2000

1500

1000 EST DIPA 10w t%

EST DIPA 20w t%
500 EST DIPA 30w t%
EST DIPA 40w t%
0
0 0.05 0.1 0.15 0.2 0.25
CO2 Loading

Figure 5. Liquid Heat Capacity of DIPA-CO2-H2O at 298.15K

-20000
Heat of Solution, J/mol

-40000

-60000

-80000

-100000

-120000
EST DIPA 10w t%
EST DIPA 20w t%
-140000 EST DIPA 30w t%
EST DIPA 40w t%
-160000
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading

Figure 6. Heat of Solution of CO2 in DIPA-H2O at 298.15K

10 3 Physical Properties
 10000
EXP 40C 1
1000 EXP 40C 2
EST 40C
100 EXP 100C 1
EXP 100C 2
Pressure, KPa 10 EST 100C
1

0.1

0.01

0.001

0.0001

0.00001

0.000001
0.001 0.01 0.1 1 10
CO2 Loading

Figure 7. CO2 Partial Pressure of DIPA-CO2-H2O (DIPA concentration = 2.5

kmol/m3), experimental data from Isaacs et al. (1977)[4]

10000
EXP 40C 1
EXP 40C 2
EST 40C
1000 EXP 100C 1
EXP 100C 2
EST 100C
Pressure, KPa

100

10

0.1
0.001 0.01 0.1 1 10
H2S Loading

Figure 8. H2S Partial Pressure of DIPA-H2S-H2O (DIPA concentration = 2.5

kmol/m3), experimental data from Isaacs et al. (1977)[4]

3 Physical Properties 11
4 Reactions

DIPA is a secondary ethanolamine, as shown in Figure 9. It can associate with

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

Figure 9. DIPA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY

model with the CHEMISTRY ID = DIPA. This CHEMISTRY ID is used as the
global electrolyte calculation option in the simulation by specifying it on the
Global sheet of the Properties | Specifications form. Chemical equilibrium
is assumed with all the ionic reactions in the CHEMISTRY DIPA. In addition, a
kinetic REACTION model called DIPA-REA has been created, which is used in
calculations of the absorber by specifying it in the Reaction part of the
absorber specifications. In DIPA-REA, all reactions are assumed to be in
chemical equilibrium except those of CO2 with OH- and CO2 with DIPA.

A. Chemistry ID: DIPA

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

B. Reaction ID: DIPA-REA

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

12 4 Reactions
 3 Equilibrium HCO 3  H 2 O  CO 32   H 3 O 
4 Kinetic CO 2  OH   HCO 3
5 Kinetic HCO 3  CO 2  OH 
6 Kinetic DIPA  CO 2  H 2 O  DIPACOO -  H 3 O 
7 Kinetic DIPACOO -  H 3 O   DIPA  CO 2  H 2 O
8 Equilibrium H 2 O  H 2S  HS   H 3 O 
9 Equilibrium H 2 O  HS   S 2   H 3 O 
The equilibrium expression in Chemistry DIPA for reaction 1 is taken from the
work of Barth et al. (1986)[9], and that for reaction 4 is taken from the work
of Blauwhoff et al. (1985)[3], the others are taken from the work of Austgen et
al. (1988)[11]. The power law expressions (T0 not specified) are used for the
rate-controlled reactions (reactions 4-7 in DIPA-REA):

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;
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 6-7 in Table
3 are derived from the work of Blauwhoff et al. (1985)[3]. The kinetic
parameters for reaction 4 are taken from the work of Pinsent et al. (1956)[12] ,
and the kinetic parameters for reaction 5 are calculated by using the kinetic
parameters of reaction 4 and the equilibrium constants of the reversible
reactions 4 and 5.

4 Reactions 13
 Table 3. Parameters k and E in Equation (1)
Reaction No. k E , cal/mol
4 4.32e+13 13249
5 2.38e+17 29451
6 4.09e+9 9563.1
7 2.16e+19 15021

14 4 Reactions
5 Simulation Approach

The absorber of the natural gas treating unit at Pyote[1] is simulated in the
simulation.
Simulation Flowsheet – The absorber has been modeled with the following
simulation flowsheet in Aspen Plus, shown in Figure 10.

GASOU T

LEANIN

ABSORBER

GASIN

R IC HOUT

Figure 10. Rate-Based DIPA Simulation Flowsheet in Aspen Plus

5 Simulation Approach 15
 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 DIPA Model
Unit Operation Aspen Plus Block Comments / Specifications

Absorber RadFrac 1. Calculation type: Rate-Based

2. 20 Stages
3. Top Pressure: 900 psig
4. Reaction condition factor: 0.9
5. Film discretization ratio: 5
6. Heater Cooler: Heat loss is ignored for the absorber
7. Reaction: Reaction ID is DIPA-REA for all stages; when
calculation type is equilibrium stages, Holdup is 0.08 m3 for
all stages, which is close to the value calculated by Holdup
correlation in rate-based run mode
8. Tray Type: Glitsch Ballast
9. Tray Diameter: 66 inch
10. Weir Height: 0.06 m
11. Mass transfer coefficient method: Scheffe and
Weiland(1987)
12. Interfacial area method: : Scheffe and Weiland(1987)
13. Interfacial area factor: 1
14. Heat transfer coefficient method: Chilton and Colburn
15. Holdup correlation: Bennett et al. (1983)
16. Holdup scale factor: 1
17. Film resistance: Discrxn for liquid film; Film for vapor
film
18. Additional discretization points for liquid film: 5
17. Flow model: Mixed
18. Estimates: provide temperature estimates for all stages.
These estimates are intended to aid convergence

16 5 Simulation Approach
 Streams - Feeds to the absorber are GASIN containing CH4, C2H6, C3H8, N2,
CO2 and H2S and LEANIN containing aqueous DIPA solution with few CO2
loaded in. Feed conditions are summarized in Table 5.

Table 5. Feed specifications

Stream ID GASIN LEANIN
Substream: MIXED
Temperature: F 72 102
Pressure: psig 900 900
Total flow 3689 kmol/hr 1856 kmol/hr
Mole-Frac
H2O 0.0 0.9347
CO2 0.013 0.0006
DIPA 0 0.0646
H2S 0.00054 0.0001
CH4 0.924 0
C2H6 0.036 0
C3H8 0.016 0
N2 0.01 0
Prop-Sets - A Prop-Set, XAPP, has been created to report apparent mole
fraction of H2S, CO2 and DIPA in liquid streams to facilitate calculations of acid
gas loadings of the streams.

5 Simulation Approach 17
6 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 6. The measured versus calculated absorber liquid
temperature profiles are presented in Figures 11, respectively. The measured
data are from the natural gas treating unit at Pyote using aqueous DEA as the
solvent.

Table 6. Key Simulation Results

Rate-Based DIPA Rate-Based DEA
Variable Measurement
Model Model
CO2 mole fraction in 150 ppm 2199ppm 152ppm
GASOUT
Loading of RICHOUT, 0.50 0.35 0.42
MolAcidGas/MolDIPA

160

140
Temperature, F

120

100

Experimental
Rate-Based DIPA Model
80
Rate-Based DEA Model

60
0 5 10 15 20
Stage Num ber

Figure 11. The Absorber Liquid Temperature Profile (Mixed flow model)

18 6 Simulation Results
 We can see from Table 6 and Figure 11 that at the same operating conditions,
DIPA absorbs less CO2 than DEA, which is consistent with the fact that the
reaction rate of DIPA with CO2 is slower than that of DEA.

6 Simulation Results 19
7 Conclusions

The Rate-Based DIPA 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 DIPA. You 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 DIPA model will be done
when industrial or pilot plant data become available.

20 7 Conclusions
References

[1] F.B. Butwell, C.R. Perry, “Performance of Gas Purification Systems

Utilizing DEA Solutions”, Laurance Reid Gas Conditioning Conference, 1975
[2] Aspen Technology Inc., 2007
[3] P.M.M. Blauwhoff, B. Kamphuis, W.P.M. Wan Swaaij, K.R. Westerterp,
“Absorber Design in sour Natural Gas Treatment Plants: Impact of Process
Variables on Operation and Economics”, Chem. Eng. Process., 19, 1 (1985)
[4] E.E. Isaacs, F.D. Otto, A.E. Mather, “Solubility of Hydrogen Sulfide and
Carbon Dioxide in an Aqueous Diisopropanolamine Solution”, Journal of
Chemical and Engineering Data, 22, 71-73(1977)
[5] E.E. Isaacs, F.D. Otto, A.E. Mather, “The Solubility of Mixtures of Carbon
Dioxide and Hydrogen Sulfide in an Aqueous DIPA Solution”, The Canadian
Journal of Chemical Engineering, 55, 210-212(1977)
[6] A. Henni, J.J. Hromek, P. Tontiwachwuthikul, A. Chakma, “Volumetric
Properties and Viscosities for Aqueous Diisopropanolamine Solutions from
25°C to 70°C”, J. Chem. Eng. Data., 48, 1062-1067(2003)
[7] 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)
[8] Z. Palaty, “Viscosity of diluted aqueous K2CO3/KHCO3 solutions”, Collect.
Czech. Chem. Commun., 57, 1879(1992)
[9] D. Barth, C. Tonder, J.-J. Delpuech, "Stopped-Flow Investigations of the
Reaction Kinetics of Carbon Dioxide with Some Primary and Secondary
Alkanolamines in Aqueous Solutions", International Journal of Chemical
Kinetics, 18, 445-457 (1986)
[10] M.L. Gonzalez-Barba, L. Spagnuolo, “Corrosion Mitigation Strategies for
Amine Gas Treating Plants”, Corrosion Management in Gas Processing
Facilities Seminar, Bahrain, Nov 28, 2007
[11] D.M. Austgen, G.T. Rochelle, X. Peng, 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
[12] 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)

References 21