Aspen Plus

Rate-Based Model of the Acid Gas Removal

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

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

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

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

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

Aspen Technology, Inc.

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

V7.0 First version

V7.1 Update H2 S Solubility model parameters
V7.1 CP1 Add O2 , CO and H2 to the model as Henry Components
V7.2 Update 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.
Modify convergence specifications for the absorber.
Revise the simulation results.
V8.0 Update databank to PURE27.
V8.2 Update databank to PURE28.
Update the DEA-H2 O-CO2 and DEA-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 the PC-SAFT parameters for DEA.
Update the NRTL interaction parameters between DEA and H2O, H2O
and (DEAH+, HCO3 - ), H2 O and (DEAH+, DEACOO- ), DEA and (DEAH+,
HCO3 - ), DEA and (DEAH+, DEACOO- ), H2 O and (DEAH+, HS- ), DEA and
(DEAH+, HS- ) and those between H2 S and (DEAH+, HS- )
Update the Henry’s constants of CO 2 and H2 S in H2 O and DEA.
Update DGAQFM, DHAQFM and CPAQ0 of DEAH+ and DEACOO-, update
CPAQ0 of HCO3 - , CO3 -2 , HS- and S-2 .
Update the Henry’s constants of CH4 , C 2 H6 and C 3 H8 in H2 O and DEA.
Update the characteristic volume parameters of CH4 and C 2 H6 for the
Brelvi-O’Connell Model.
Update the Clarke model parameter, VLQKIJ, for DEA and H2 O,
VLCLK/1, for (DEAH+, HCO3 - ), (DEAH+, CO3 -2 ) and (DEAH+, DEACOO- ).
Update the interaction parameters of the viscosity model, MUKIJ and
MULIJ, for DEA and H2 O, the Jones-Dole model parameters, IONMUB,
for DEAH+, DEACOO- , HCO3 - and CO3 -2 .
Update figures for properties.
Calculate all chemical equilibrium constants from Gibbs free energy.
Update kinetics.
Update simulation results.
V8.6 Update databank to PURE32.

Revision History 3
 Version Description
V10.0 Update GMENCC parameters between CO 2 and (DEAH+, DEACOO- ),
CO2 and (DEAH+, HCO3 - ), and those between CO2 and (DEAH+, CO3 -2 )
to match the data of CO 2 activity coefficient.
Update simulation results.

4 Revision History
Contents
Introduction ............................................................................................................6

1 Components .........................................................................................................7

2 Process Description..............................................................................................8

3 Physical Properties...............................................................................................9

4 Reactions ...........................................................................................................17

5 Simulation Approach ..........................................................................................20

6 Simulation Results .............................................................................................24

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

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

Contents 5
Introduction

This file describes an Aspen Plus rate-based model of the acid gas removal
process by DEA (Diethanolamine) from a gas mixture of CH4, C2H6, C3H8, N2,
CO2 and H2S. The model consists of an absorber and a stripper. The
operation data from a natural gas treating unit at Pyote, Texas (1975)[1] were
used to specify feed conditions and unit operation block specifications.
Thermophysical property models are based on our recent work and the
reaction kinetic models are based on the work of Rinker et al. (1996)[2].
Transport property models and model parameters have been validated
against experimental data from open literature.
This simulation is meant to be used as a guide for modeling the acid gas
removal process with DEA. 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 valve trays

6 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

DEA Conventional DIETHANOLAMINE C4H11NO2-1

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
DEAH+ Conventional DEA+ C4H12NO2+
DEACOO- Conventional DEACOO- C5H10NO4-
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

1 Components 7
2 Process Description

The Pyote Unit[1] flowsheet for CO2 capture by DEA includes three absorbers
and two strippers. However, only data from one absorber and one stripper
are reported. Table 2 represents the typical operation data:

Table 2. Data of the Pyote Unit

Absorber

Diameter 66 inch
Tray 20
Stripper

Diameter 72 inch
Tray 31

Feeds and Products

Sour Gas to Absorber 2.92 MM scfh

Lean Amine to Absorber 188 gpm
Rich Amine to Stripper 380 gpm
CO2 in Sour Gas 0.013(mole fraction)
H2 S in Sour Gas 0.00054(mole fraction)
CO2 in Sweet Gas 150 ppm (mole fraction)
H2 S in Sweet Gas 0.17 ppm (mole fraction)
DEA solution 28.69%(wt)

8 2 Process Description
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 this rate-based DEA model. CO2, H2S, N2, O2, CO, H2, 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 DEA. 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 or regressed with the VLE data (See Table 3).
The other Henry’s constants are retrieved from the Aspen Databank.

Table 3. Henry’s constants

Solute Solvent Source

CO2 H2 O Yan and Chen (2010) [3]

H2 S H2 O Regression with H2 S-H2 O VLE data[4-11]
CH4 H2 O Regression with CH4 -H2 O VLE data[12]
C 2 H6 H2 O Regression with C 2 H6 -H2 O VLE data[13]
C 3 H8 H2 O Regression with C 3 H8 -H2 O VLE data[14]
CO2 DEA Determined by N2 O analogy [15]

H2 S DEA Set to that of H2 S in H2 O

CH4 DEA Regression with CH4 -H2 O-DEA VLE data[16, 17]
C 2 H6 DEA Regression with C 2 H6 -H2 O-DEA VLE data[17]
C 3 H8 DEA Regression with C 3 H8 -H2 O-DEA VLE data[18]

The PC-SAFT parameters of DEA are regressed from the vapor pressure
data[19-24], the liquid heat capacity data[25] and the liquid density data[26-33].
Those of H2O are obtained from Gross and Sadowski (2002) [34], 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) [35], those of CO2 are
obtained from Yan and Chen (2010) [3], those of CH4 and C2H6 are regressed
with the CH4-H2O[12] and C2H6-H2O[13] binary VLE data, and those of DEA, 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-

3 Physica l Prope rties 9

 electrolyte binary parameters are defaulted to (8, -4), average values of the
parameters as reported for the electrolyte NRTL model [36]. The
nonrandomness factor is fixed at 0.2.
The NRTL interaction parameters between DEA and H2O are determined from
the regression with binary VLE data[37-39], excess enthalpy data[39-42] and heat
capacity data[25].
The interaction energy parameters between H 2O and (DEAH+, HCO3-),
GMENCC and GMENCD, those parameters between H 2O and (DEAH+,
DEACOO-), GMENCC and GMENCD, those parameters between DEA and
(DEAH+, HCO3-), GMENCC, and those parameters between DEA and (DEAH+,
DEACOO-), GMENCC, are regressed using the VLE data[43], absorption heat
data[44], heat capacity data[45] and speciation concentration data[46].
The interaction energy parameters between H 2O and (DEAH+, HS-), GMENCC
and GMENCD, those parameters between DEA and (DEAH+, HS-), GMENCC,
and those parameters between H2S and (DEAH+, HS-), GMENCC, are
regressed with the H 2S solubility data in aqueous DEA solution[47-48].
The interaction energy parameters between CO2 and (DEAH+, DEACOO-), CO2
and (DEAH+, HCO3-), and those between CO2 and (DEAH+, CO3-2), GMENCC,
are regressed using the data of CO2 activity coefficient [67].
The dielectric constants of nonaqueous solvents are calculated by the
following expression:

1 1
 T   A  B  
T C 
(1)
The parameters A, B and C for DEA in Aspen Databank are 28.01, 9277 and
273.15.
The liquid molar volume 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 of 1 to use the quadratic mixing rule for solvents.
The interaction parameter VLQKIJ for the quadratic mixing rule between
DEA and H2O is regressed against experimental density data of the DEA-
H2O system [30-31,49-56]. The Clarke model parameter VLCLK/1 is also
 
regressed for main electrolytes (DEAH+, HCO 3 ) and (DEAH+, DEACOO )
against experimental density data of the DEA-H2O-CO2 system from
Weiland (1998)[57].
 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. 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 DEA and H 2O in the Aspen liquid mixture viscosity
model, MUKIJ and MULIJ, are regressed against experimental DEA-H2O
viscosity data [49-50, 53-55, 58-59]. The Jones-Dole model parameters,
IONMUB, for DEAH+ and DEACOO- are regressed against DEA-H2O-CO2

10 3 Physical Properties
 viscosity data from Weiland (1998)[57]; that of CO 32 is regressed against
K2CO3-H2O viscosity data from Pac et al. (1984)[60]; and that of HCO3- is
regressed against KHCO3-H2O viscosity data from Palaty (1992)[61].
 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 model and the estimation
results are somewhat higher than the experimental data from Weiland
(1996)[62] (Figure 3).
 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) for DEAH+ are derived from the equilibrium constant
of DEA protonation reaction from Bower (1962) [63]. The heat capacity at
infinite dilution (CPAQ0) for DEAH+ and the DGAQFM, DHAQFM and CPAQ0
parameters for DEACOO- are regressed with the VLE data[43], absorption heat
data[44], heat capacity data[45] and speciation concentration data[46]. 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) [64], and that of
S-2 is calculated from the Criss-Cobble correlation[64] with the entropy value
from Wagman et al. (1982) [65].
The estimation results of various transport and thermophysical properties are
summarized in Figures 1-7. Note that acid gas loading is defined as the ratio
of the moles of apparent acid gas to the moles of apparent DEA. Apparent
means before reaction, so for example if 1 mole of DEA 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 DEA after reacting. Weight percent of DEA
is calculated without CO2, so in the above example, it is calculated from the
mixture of 1 mole DEA and 9 moles of water. Since DEA has a molecular
weight of 105.137 and water has a molecular weight of 18.015, this is
105.137/(105.137+9*18.015) = 0.39337 or about 39 wt% DEA.

3 Physica l Prope rties 11

 1200
EXP DEA 10wt%

1150 EXP DEA 20wt%

EXP DEA 30wt%
EXP DEA 40wt%
1100
Density, kg/m3

1050

1000

950

900
0 0.1 0.2 0.3 0.4 0.5
CO2 Loading, mol CO2/mol DEA

Figure 1. Liquid Density of DEA-CO2-H2O at 298.15K, experimental data from

Weiland et al. (1998)[57]

10

EXP DEA 20wt%

8 EXP DEA 30wt%

EXP DEA 40wt%
Viscosity, mPaS

0
0 0.1 0.2 0.3 0.4 0.5

CO2 Loading, mol CO2/mol DEA

Figure 2. Liquid Viscosity of DEA-CO2-H2O at 298.15K, experimental data

from Weiland et al. (1998)[57]

12 3 Physical Properties
 100

80

Surface Tension, mN/m

60

40 EXP DEA 10wt%

EXP DEA 20wt%
EXP DEA 30wt%
20
EXP DEA 40wt%

0
0.0 0.1 0.2 0.3 0.4 0.5

CO2 Loading, mol CO2/mol DEA

Figure 3. Surface tension of DEA-CO2-H2O at 298.15K, experimental data

from Weiland (1996)[62]

0.6

0.5
Thermal Conductivity, Watt/m.K

0.4

0.3

0.2
DEA 10wt%
DEA 20wt%
0.1 DEA 30wt%
DEA 40wt%

0
0 0.1 0.2 0.3 0.4 0.5
CO2 loading, mol CO2/mol DEA

Figure 4. Liquid Thermal Conductivity of DEA-CO2-H 2O at 298.15K

3 Physica l Prope rties 13

 120

100

Cp, kJ/kmol.K 80

60
10wt%, 0.02
40 20wt%, 0.04

30wt%, 0.07
20
40wt%, 0.10

0
0 0.1 0.2 0.3 0.4 0.5 0.6

CO2 loading, mol CO2/mol DEA

Figure 5. Liquid Heat Capacity of DEA-CO2-H2O at 298.15K, experimental data

from Weiland et al. (1997)[45]

100

300 K

80
350 K

400 K
Heat, kJ/mol

60

40

20

0
0 0.4 0.8 1.2 1.6
CO2 loading, mol CO2/mol DEA

Figure 6. Heat of Solution of DEA-CO2-H2O (DEA concentration is 35 wt%),

experimental data from Oscarson et al. (1995)[44]

14 3 Physical Properties
 1.0E+07

1.0E+06

1.0E+05
P_CO 2, Pa

273K, 72
298K, 72
1.0E+04
323K, 72
348K, 72
373K, 72
1.0E+03
393K, 72
413K, 72
1.0E+02
0.0 0.3 0.6 0.9 1.2 1.5

Loading, mol CO2/mol DEA

Figure 7. CO2 partial pressure of DEA-CO2-H2O (DEA concentration is 35

wt%), experimental data from Lee et al. (1972)[43]

1.0E+07

1.0E+06
H 2S Pressure, Pa

1.0E+05

1.0E+04 298 323

348 373
1.0E+03 393 298
323 348

1.0E+02 373 393

413

1.0E+01
0.0 0.3 0.6 0.9 1.2 1.5
H2S loading, mol H2S/mol DEA

3 Physica l Prope rties 15

 1.0E+07

298 323
1.0E+06 348 373
393 298

H 2S Pressure, Pa
1.0E+05 323 348
373 393
1.0E+04 413

1.0E+03

1.0E+02

1.0E+01
1.0E-04 1.0E-03 1.0E-02 1.0E-01 1.0E+00 1.0E+01
H2S loading, mol H2S/mol DEA

Figure 8. H2S partial pressure of DEA-H2S-H2O (DEA concentration is 35

wt%), experimental data from Lee et al. (1973)[47, 48].

0.05

0.04

0.03
Speciation

DEA+DEAH+

0.02 DEACOO

HCO3

0.01

0
0 0.2 0.4 0.6 0.8 1 1.2
CO2 loading, mol CO2/mol DEA

Figure 9. Speciation of DEA-H2S-H2O at 313.15 K (DEA concentration is 22

wt%), experimental data from Böttinger et al. (2008)[46].

16 3 Physical Properties
4 Reactions

DEA is a secondary ethanolamine, as shown in Figure 10. It can associate

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

Figure 10. DEA Molecular Structure

The electrolyte solution chemistry has been represented with a CHEMISTRY

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

A. Chemistry ID: DEA-CHE

DEAH   H 2 O  DEA  H 3 O 
1 Equilibrium
CO 2  2H 2 O  H 3 O   HCO 3
2 Equilibrium
HCO 3  H 2 O  H 3 O   CO 32
3 Equilibrium
DEACOO   H 2 O  DEA  HCO 3
4 Equilibrium
2H 2 O  H 3 O   OH 
5 Equilibrium
H 2 O  H 2S  HS   H 3 O 
6 Equilibrium
H 2 O  HS   S 2  H 3 O 
7 Equilibrium

B. Reaction ID: DEA-REA

DEAH   H 2 O  DEA  H 3 O 
1 Equilibrium
2H 2 O  H 3 O   OH 
2 Equilibrium
HCO 3  H 2 O  H 3 O   CO 32
3 Equilibrium

4 Reactions 17
 CO 2  OH   HCO 3
4 Kinetic
HCO 3  CO 2  OH 
5 Kinetic
DEA  CO 2  H 2 O  DEACOO -  H 3 O 
6 Kinetic
DEACOO -  H 3 O   DEA  H 2 O  CO 2
7 Kinetic
H 2 O  H 2S  HS   H 3 O 
8 Equilibrium
H 2 O  HS   S 2  H 3 O 
9 Equilibrium
The equilibrium expressions for reactions 1-7 in DEA-CHE are calculated from
the standard Gibbs free energy change. DGAQFM, DHAQFM, and CPAQ0 of
DEAH+ and DEACOO-, which are used to calculate the standard DEAH+ and
DEACOO- 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 DEA-REA). 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 To 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 4.

18 4 Reactions
 The kinetic parameters for reaction 4 in Table 4 are derived from the work of
Pinsent et al. (1956)[66] 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. The kinetic parameters of reaction 6 in Table
4 are derived from the work of Rinker et al. (1996)[2]. The DEA concentration
range of the data of Rinker is 0.25-2.8 M and the temperature range is 292-
343 K, these conditions are the operating conditions of the absorber modeled
in this work. 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 4. Parameters k and E in Equation (2)

Reaction No. k E (cal/mol)
4 1.33e+17 13249
5 6.63e+16 25656
6 2.42e+10 5072
7 8.40e+18 9019

4 Reactions 19
5 Simulation Approach

The natural gas treating unit at Pyote[1] is simulated in this work and is
described in this section.
Simulation Flowsheet – The Pyote Unit has been modeled with the
following simulation flowsheet in Aspen Plus as shown in Figure 11.

GASOUT CO2OUT

LEANIN

ABSORBER RICHIN STRIPPER

GASIN

RICHOUT LEANOUT

Figure 11. Rate-Based DEA Simulation Flowsheet in Aspen Plus

20 5 Simulation Approach
 Unit Operations – The major unit operation models have been represented
by Aspen Plus Blocks as outlined in Table 5.

Table 5. Aspen Plus Unit Operation Blocks Used in the

Rate-Based DEA 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: Reaction ID is DEA-REA for all stages; when
calculation type is equilibrium, Holdup is used, and in this
file, Holdup=0.0001 m3 , which is intended to aid
convergence
5. Tray Type: Glitsch Ballast
6. Tray Diameter: 66 inch
7. Weir height: 0.06 m
8. Mass transfer coefficient method: Scheffe and Weiland
(1987)
9. Interfacial area method: Scheffe and Weiland (1987)
10. Interfacial area factor: 1
11. Heat transfer coefficient method: Chilton and Colburn
12. Holdup correlation: Bennett et al. (1983)
13. Holdup scale factor: 1
14. Film resistance: Discrxn for liquid film; Film for vapor
film
15. Flow model: Mixed
16. Estimates: provide temperature at stages 1 and 20. The
estimates are intended to aid convergence.

5 Simulation Approach 21
Unit Operation Aspen Plus Block Comments / Specifications
Stripper RadFrac 1. Calculation type: Rate-Based
2. 33 Stages
3. Partial vapor condenser
4. Kettle reboiler
5. Mole distillate rate: initialized at 0.028kmol/s with final
value of 0.0277kmol/s obtained by Design-Spec 1.
6. Mole reflux rates: initialized at 0.036kmol/s with final
value of 0.0363 kmol/s obtained by Design-Spec 2.
7. Top Pressure: 9.8 psig
8. Reaction: CHEMISTRY ID is DEA-CHE for all stages.
9. Design specs: Stage 1 temperature = 291.5K, Stream
LEANOUT LOADING = 0.01
10. Vary: Distillate rate, Reflux rate
11. Tray Type: Glitsch Ballast
12. Tray Diameter: 72 inch
13. Mass transfer coefficient method: Scheffe and Weiland
(1987)
14. Interfacial area method: Scheffe and Weiland (1987)
15. Interfacial area factor: 1
16. Heat transfer coefficient method: Chilton and Colburn
17. Holdup correlation: Bennett et al. (1983)
18. Film resistance: Discrxn for liquid film; Film for vapor
film
19. Flow model: Mixed
20. Estimates: provide temperature for stages 1 to 33. The
estimates are intended to aid convergence.

22 5 Simulation Approach
 Streams - Feeds to the absorber are gas stream GASIN containing CH4, C2H6,
C3H8, N2, CO2 and H2S and liquid solvent stream LEANIN containing aqueous
DEA solution with a little CO2 loaded in. Feed to the stripper is rich solvent
stream RICHIN containing aqueous DEA solution with absorbed CO 2. Feed
streams' conditions are summarized in Table 6.

Table 6. Feed specifications

Stream ID GASIN LEANIN RICHIN
Substream: MIXED
Temperature: F 72 102 212
Pressure: psig 900 900
Vapor fraction 0
Total flow 3689 kmol/hr 188 gal/min 380 gal/min
Mole-Frac Mass-Frac Mole-Frac
DEA 0 0.2869 0.063
H2O 0 0.7118 0.91
CO2 0.013 0.0012 0.026
H2S 0.00054 0.0001 0.001
CH4 0.924 0 0
C2H6 0.036 0 0
C3H8 0.016 0 0
N2 0.01 0 0

5 Simulation Approach 23
6 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are
presented in Table 7. The measured versus calculated absorber and stripper
liquid temperature profiles are presented in Figures 12 and 13, respectively.

Table 7. Key Simulation Results

Variable Measurement Rate-Based DEA Model

Absorber
CO2 mole fraction in GASOUT 150 ppm 131ppm
H2S mole fraction in GASOUT 0.17 ppm 0.45 ppm
Loading of RICHOUT, MolAcidGas/MolDEA 0.50 0.425
Stripper
Reboiler duty, lbs. steam/ gal. circ. solution 0.85 0.92

200

150
Temperature, F

100

AspenPlus: Liquid
50
AspenPlus: Vapor
Measure

0
0 5 10 15 20

Stage number

Figure 12. The Absorber Liquid Temperature Profile

24 6 Simulation Results
 250

200

Temperature, F
150

100
AspenPlus: Liquid
AspenPlus: Vapor
50 Measurement

0
0 5 10 15 20 25 30 35
Stage number

Figure 13 The Stripper Liquid Temperature Profile

6 Simulation Results 25
7 Conclusions

The rate-based DEA 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.

26 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] E.B. Rinker, S.S. Ashour, O.C. Sandall, “Kinetics and Modeling of Carbon
Dioxide Absorption into Aqueous Solutions of Diethanolamine”, Ind. Eng.
Chem. Res., 35, 1107-1114 (1996)
[3] Y. Yan, C. –C. Chen, “Thermodynamic Modeling of CO2 Solubility in
Aqueous Solutions of NaCl and Na2SO4”, J. of Supercritical Fluids, 55, 623-634
(2010)
[4] R. H. Wright, O. Maass, “The Solubility of Hydrogen Sulphide in Water
from the Vapor Pressures of the Solutions”, Can. J. Res. Sect. B. 6, 91-101
(1932).
[5] H. A. Phol, “Thermodynamics of the Hydrogen Sulfide-Water System
Relevant to the Dual Temperature Process for the Production of Heavy
Water”, J. Chem. Eng. Data. 6, 515-521 (1961)
[6] M. P. Burgess, R. P. Germann, “Physical Properties of Hydrogen Sulfide-
Water Mixtures”. AIChE J., 15, 272-275 (1969)
[7] E. C. W. Clarke, D. N. Glew, “Aqueous Nonelectrolyte Solutions. Part VIII.
Deuterium and Hydrogen Sulfides Solubilities in Deuterium Oxide and Water”.
Can. J. Chem., 49, 691-698 (1971)
[8] J. I. Lee, A. E. Mather, “Solubility of Hydrogen Sulfide in Water”. Ber.
Bunsen-Ges. Phys. Chem. 81, 1020-1023 (1977)
[9] P. C. Gillespie, G. M. Wilson, “Vapor-Liquid Equilibrium Data on Water-
Substitute Gas Components: N 2-H2O, H2-H2O, CO-H2O, H2-CO-H2O, and H2S-
H2O” GPA Research Report, No. 41, 1980.
[10] O. M. Suleimenov, R. E. Krupp. “Solubility of Hydrogen Sulfide in Pure
Water and in NaCl Solutions, from 20 to 320 °C and at Saturation Pressures”.
Geochim. Cosmochim. Acta., 58, 2433-2444 (1994)
[11] G. Kuranov, B. Rumpf, N. A. Smirnova, G. Maurer, “Solubility of Single
Gases Carbon Dioxide and Hydrogen Sulfide in Aqueous Solutions of N-
Methyldiethanolamine in the Temperature Range 313-413 K at Pressures up
to 5 MPa”, Ind. Eng. Chem. Res., 35, 1959-1966 (1996)
[12] O. L. Culberson, J. J. McKetta, “Phase Equilibria in Hydrocarbon-Water
Systems. III-The Solubility of Methane in Water at Pressures to 10000 psia”,
Trans. Am. Inst. Min. Metall. Pet. Eng., 192, 223-226 (1951)
[13] O. L. Culberson, J. J. McKetta, “Phase Equilibria in Hydrocarbon-Water
Systems. II-The Solubility of Ethane in Water at Pressures to 10000 psi”.
Trans. Am. Inst. Min. Metall. Pet. Eng., 189, 319-322 (1950)

Re fere nces 27
 [14] A. Chapoy, S. Mokraoui, A. Valtz, D. Richon, A. H. Mohammadi, B.
Tohidi, “Solubility measurement and modeling for the system propane-water
from 277.62 to 368.16 K”. Fluid Phase Equilib., 226, 213-220 (2004)
[15] Y. W. Wang, S. Xu, F. D. Otto, A. E. Mather, “Solubility of N 2O in
alkanolamines and in mixed solvents”, The Chemical Engineering Journal, 48,
31-40 (1992)
[16] J. D. Lawson, A. W. Garst, “Hydrocarbon Gas Solubility in Sweetening
Solutions: Methane and Ethane in Aqueous Monoethanolamine and
Diethanolamine”, J. Chem. Eng. Data, 21, 30-32 (1976)
[17] J. J. Carroll, F. Y. Jou, A. E. Mather, F. D. Otto, “The Solubility of
Methane in Aqueous Solutions of Monoethanolamine, Diethanolamine and
Triethanolamine”, Can. J. Chem. Eng., 76, 945-951 (1998),
[18] F. Y. Jou, H. J. Ng, J. E. Critchfield, A. E. Mather, “Solubility of propane
in aqueous alkanolamine solutions”, Fluid Phase Equilib., 194-197, 825-830
(2002),
[19] R. A. McDonald, S. A. Shrader, D. R. Stull, “Vapor Pressures and
Freezing Points of 30 Organics”, J. Chem. Eng. Data, 4, 311 (1959)
[20] S. M. Danov, N. B. Matin, R. V. Efremov, K. K. Slashchinina, “Vapour
pressures of ethanolamines”, Russ. J. Phys. Chem., 43, 401 (1969)
[21] T. E. Daubert, J. W. Jalowka, V. Goren, “Vapor pressure of 22 pure
industrial chemicals”, AIChE Symp. Ser., 83(256), 128-156 (1987)
[22] M.Abedinzadegan Abdi, A. Meisen, “Vapor Pressure Measurements of
Bis(hydroxyethyl)piperazine and Tris(hydroxyethyl)ethylenediamine”, J.
Chem. Eng. Data, 43 133-137 (1998)
[23] S. Horstmann, P. Mougin, F. Lecomte, K. Fischer, J. Gmehling, “Phase
Equilibrium and Excess Enthalpy Data for the System Methanol + 2,2?-
Diethanolamine + Water”, J. Chem. Eng. Data, 47, 1496-1501 (2002)
[24] K. Klepacova, P. J. G. Huttenhuis, P. W. J. Derks, G. F. Versteeg, “Vapor
Pressures of Several Commercially Used Alkanolamines”, J. Chem. Eng. Data,
56, 2242-2248 (2011)
[25] L. –F. Chiu, H. –F. Liu, M. –H. Li, “Heat Capacity of Alkanolamines by
Differential Scanning Calorimetry”, J. Chem. Eng. Data, 44, 631-636 (1999
)
[26] E. Z. Kuss, “High Pressure Measurements III. The Viscosity and
Compressibility of Fluids”, Angew. Phys., 7, 372-378 (1955)
[27] F. Murrieta-Guevara, A. Trejo Rodriguez, “Liquid Density as a Function of
Temperature for Five Organic Solvents”, J. Chem. Eng. Data, 29, 204-206
(1984)
[28] R. M. DiGuilio, R. J. Lee, S. T. Schaeffer, L. L. Brasher, A. S. Teja,
“Densities and viscosities of the ethanolamines”, J. Chem. Eng. Data, 37,
239-242 (1992)
[29] F. Murrieta-Guevara, E. Rebolledo-Libreros, A. Trejo, “Gas solubility of
hydrogen sulfide and carbon dioxide in mixtures of sulfolane with
diethanolamine at different temperatures”, Fluid Phase Equilib., 95, 163-174
(1994)

28 References
 [30] J. Aguila-Hernandez, R. Gomez-Quintana, F. Murrieta-Guevara, A.
Romero-Martinez, A. Trejo, “Liquid Density of Aqueous Blended
Alkanolamines and N-Methylpyrrolidone as a Function of Concentration and
Temperature”, J. Chem. Eng. Data, 46, 861-867 (2001)
[31] E. Alvarez, D. Gomez-Diaz, M. D. La Rubia, J. M. Navaza, “Densities and
Viscosities of Aqueous Ternary Mixtures of 2-(Methylamino)ethanol and 2-
(Ethylamino)ethanol with Diethanolamine, Triethanolamine, N-
Methyldiethanolamine, or 2-Amino-1-methyl-1-propanol from 298.15 to
323.15 K”, J. Chem. Eng. Data, 51, 955-962 (2006)
[32] J. Aguila-Hernandez, A. Trejo, B. E. Garcia-Flores, R. Molnar,
“Viscometric and volumetric behaviour of binary mixtures of sulfolane and N-
methylpyrrolidone with monoethanolamine and diethanolamine in the range
303-373 K”, Fluid Phase Equilib., 267, 172-180 (2008)
[33] E. Alvarez, F. Cerdeira, D. Gomez-Diaz, J. M. Navaza, “Density, Speed of
Sound, Isentropic Compressibility, and Excess Volume of Binary Mixtures of
1-Amino-2-propanol or 3-Amino-1-propanol with 2-Amino-2-methyl-1-
propanol, Diethanolamine, or Triethanolamine from (293.15 to 323.15) K”, J.
Chem. Eng. Data, 55, 2567-2575 (2010)
[34] J. Gross, G. Sadowski, “Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems”. Ind. Eng. Chem. Res., 41, 5510-
5515 (2002)
[35] S. W. Brelvi, J. P. O’Connell, “Corresponding States Correlations for
Liquid Compressibility and Partial Molar Volumes of Gases at Infinite Dilution
in Liquids”, AIChE J., 18, 1239-1243 (1972)
[36] C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, “Local Composition Model
for Excess Gibbs Energy of Electrolyte Systems. Part I: Single Solvent, Single
Completely Dissociated Electrolyte Systems”. AIChE J., 28, 588-596 (1982)
[37] Z. Cai, R. Xie, Z. Wu, “Binary Isobaric Vapor-Liquid Equilibria of
Ethanolamines + Water”, J. Chem. Eng. Data, 41, 1101-1103 (1996)
[38] W. V. Wilding, L. C. Wilson, G. M. Wilson, “Experimental Results for
Phase Equilibria and Pure Component Properties”, DIPPR DATA Series No. 1,
6-23 (1991)
[39] S. Horstmann, P. Mougin, F. Lecomte, K. Fischer, J. Gmehling, “Phase
Equilibrium and Excess Enthalpy Data for the System Methanol + 2,2?-
Diethanolamine + Water”, J. Chem. Eng. Data, 47, 1496-1501 (2002)
[40] Y. Maham, A. E. Mather, L. G. Hepler, “Excess Molar Enthalpies of (Water
+ Alkanolamine) Systems and Some Thermodynamic Calculations”, J. Chem.
Eng. Data, 42, 988-992 (1997)
[41] M. Mundhwa, A. Henni, “Molar excess enthalpy oHE mP for various
{alkanolamine (1) + water (2)} systems at T = (298.15, 313.15, and 323.15)
K”, J. Chem. Thermodyn., 39, 1439-1451 (2007)
[42] Y. Maham, A. E. Mather, C. Mathonat, “Excess properties of
(alkyldiethanolamine + H2O) mixtures at temperatures from (298.15 to
338.15) K”, J. Chem. Thermodyn., 32, 229-236 (2000)
[43] J. I. Lee, F. D. Otto, A. E. Mather, “Solubility of Carbon Dioxide in
Aqueous Diethanolamine”, J. Chem. Eng. Data, 17, 465-468 (1972)

Re fere nces 29
 [44] J. L. Oscarson, X. Chen, R. M. IzattA “Thermodynamically Consistent
Model for the Prediction of Solubilities and Enthalpies of Solution of Acid
Gases in Aqueous Alkanolamine Solutions”, GPA Research Report, RR-130,
1995
[45] R. H. Weiland, J. C. Dingman, D. B. Cronin, “Heat capacity of aqueous
monoethanolamine, diethanolamine, N-methyldiethanolamine, and N-
methyldiethanolamine-based blends with carbon dioxide”, J. Chem. Eng.
Data, 42, 1004-1006 (1997)
[46] W. Böttinger, M. Maiwald, H. Hasse, “Online NMR spectroscopic study of
species distribution in MEA-H2O-CO2 and DEA-H2O-CO2”, Fluid Phase
Equilibria, 263, 131-143 (2008)
[47] J. I. Lee, F. D. Otto, A. E. Mather, “Partial Pressures of Hydrogen Sulfide
over Aqueous Diethanolamine Solutions”, J. Chem. Eng. Data, 18, 420-420
(1973)
[48] J. I. Lee, F. D. Otto, A. E. Mather, “Solubility of Hydrogen Sulfide in
Aqueous Diethanolamine Solutions at High Pressures”, J. Chem. Eng. Data,
18, 71-73 (1973)
[49] F. I. Chowdhury, S. Akhtar, M. A. Saleh, “Densities and excess molar
volumes of aqueous solutions of some diethanolamines”, Phys. Chem. Liq.,
47, 638-652 (2009)
[50] E. B. Rinker, D. W. Oelschlager, A. T. Colussi, K. R. Henry, O. C. Sandall,
Viscosity, “Density, and Surface Tension of Binary Mixtures of Water and N-
Methyldiethanolamine and Water and Diethanolamine and Tertiary Mixtures of
These Amines with Water over the Temperature Range 20-100.degree.C”, J.
Chem. Eng. Data, 39, 392-395 (1994)
[51] B. Hawrylak, S. E. Burke, R. Palepu, “Partial Molar and Excess Volumes
and Adiabatic Compressibilities of Binary Mixtures of Ethanolamines with
Water”, J. Solution Chem., 29, 575-594 (2000)
[52] Y. Maham, T. T. Teng, L. G. Hepler, A. E. Mather, “Densities, Excess
Molar Volumes, and Partial Molar Volumes for Binary Mixtures of Water with
Monoethanolamine, Diethanolamine, and Triethanolamine from 25-80ºC”, J.
Solution Chem., 23, 195-205 (1994)
[53] A. G. Leibush, E. D. Shorina, “Physical chemical properties of ethanol
amines”, Zh. Prikl. Khim. (Moscow), 20, 69-76 (1947)
[54] M. H. Oyevaar, R. W. J. Morssinkhof, K. R. Westerterp, “Density,
viscosity, solubility, and diffusivity of carbon dioxide an nitrous oxide in
solutions of diethanolamine in aqueous ethylene glycol at 298 K”, J. Chem.
Eng. Data, 34, 77-82 (1989)
[55] Mandal, B. P.; Kundu, M.; Bandyopadhyay, S. S. J. “Density and
Viscosity of Aqueous Solutions of (N-Methyldiethanolamine +
Monoethanolamine), (N-Methyldiethanolamine + Diethanolamine), (2-Amino-
2-methyl-1-propanol + Monoethanolamine), and (2-Amino-2-methyl-1-
propanol + Diethanolamine)”, Chem. Eng. Data, 2003, 48, 703-707
[56] Y. –M. Tseng, A. R. Thompson, “Densities and refractive indices of
aqueous monoethanolamine, diethanolamine, triethanolamine”, J. Chem. Eng.
Data, 9, 264-267 (1964)

30 References
 [57] R. –H. Weiland, J. C. Dingman, D. B. Cronin, G. J. Browning, “Density
and viscosity of some partially carbonated aqueous alkanolamine solutions
and their blends”, J. Chem. Eng. Data, 43, 378-382 (1998)
[58] T. T., Teng, Y. Maham, L. G. Hepler, A. E. Mather, “Viscosity of Aqueous
Solutions of N-Methyldiethanolamine and of Diethanolamine”, J. Chem. Eng.
Data, 39, 290-293 (1994)
[59] C. Hsu, M. –H. Li, “Viscosities of Aqueous Blended Amines”, J. Chem.
Eng. Data, 42, 714-720 (1997)
[60] 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)
[61] Z. Palaty, “Viscosity of diluted aqueous K 2CO3/KHCO3 solutions”, Collect.
Czech. Chem. Commun., 57, 1879 (1992)
[62] R.H. Weiland, “Physical Properties of MEA, DEA, MDEA and MDEA-Based
Blends Loaded with CO2”, GPA Research Report, No. 152, 1996
[63] V. E. Bower, R. A. Robinson, R. G. Bates, “Acidic Dissociation Constant
and Related Thermodynamic Quantities for Diethanolammonium Ion in Water
From 0 to 50 C”, J. Res. Natl. Bur. Stand., 66A, 71-75 (1962),
[64] C. M. Criss, J. W. Cobble, “The Thermodynamic Properties of High
Temperature Aqueous Solutions. V. The Calculation of Ionic Heat Capacities
up to 200º. Entropies and Heat Capacities above 200º”. J. Amer. Chem. Soc.,
86, 5390-5393 (1964)
[65] D.D. Wagman, W.H. Evans, V.B. Parker, R.H. Schumm, I. Halow, S.M.
Bailey, K.L. Churney, R.L. Nuttall, “The NBS tables of chemical
thermodynamic properties – Selected values for inorganic and C1 and C2
organic substances in SI units”. Journal of Physical and Chemical Reference
Data, 11 (Supplement No. 2), 1-392 (1982)
[66] 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)
[67] G. J. Browning, R. H. Weiland, “Physical Solubility of Carbon Dioxide in
Aqueous Alkanolamines via Nitrous Oxide Analogy”, J. Chem. Eng. Data, 39,
817-822 (1994)

Re fere nces 31