Rate-Based MEA Aspen Plus Model

• • • • • • • • • • • • • • • • •

Rate-Based Model of the CO2 Capture Process by MEA using Aspen Plus

Revision Date Description Author

2007-8-8 Add H2S Ying
2007-8-21 The kinetics of the CO2 and OH- reaction has Ying
been revised to be consistent with that in the
MDEA file;
the scale of the Y axis in Figure 4 has been
changed to be consistent with Figure 3;
the viscosity parameters (IONMUB) have
been revised;

2007-8-28 Change component ID MEA+ to MEAH+ Ying

Table of Contents

Introduction.................................................................................................................................................. 2

1. Components.................................................................................................................................... 3

2. Process Description....................................................................................................................... 4

3. Physical Properties ........................................................................................................................ 5

4. Reactions ........................................................................................................................................ 6

5. Simulation Approaches.................................................................................................................. 8

6. Simulation Results ....................................................................................................................... 12

7. Conclusions .................................................................................................................................. 14

References ................................................................................................................................................. 15

Aspen Plus Example Library - October 2007

Proprietary Information of AspenTech
Unauthorized duplication or distribution strictly prohibited without prior written permission i
Introduction
This file is a RateSep model of the CO2 capture process by MEA from a gas mixture of N2, O2,
CO2 and H2O. The operation data from a pilot plant at the University of Texas at Austin[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 recent works of
U.T. Austin[2,3]. Transport property models and model parameters have been validated against
experimental data from open literature.

The model includes the following key modeling 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

1. Components

The following components represent the chemical species present in the process:

Table 1. Components Used in the Model

ID Type Name Formula
H2O Conventional WATER H2O
CO2 Conventional CARBON-DIOXIDE CO2
MEA Conventional MONOETHANOLAMIN C2H7NO
E
N2 Conventional NITROGEN N2
O2 Conventional OXYGEN O2
H2S Conventional HYDROGEN-SULFIDE H2S
MEAH+ Conventional MEA+ C2H8NO+
MEACOO- Conventional MEACOO- C3H6NO3-
HCO3- Conventional HCO3- HCO3-
CO3-- Conventional CO3-- CO3-2
H3O+ Conventional H3O+ H3O+
OH- Conventional OH- OH-
HS- Conventional HS- HS-
S-- Conventional S-- S--
2. Process Description

Figure 1 is a flowsheet diagram representing the pilot plant at the University of Texas at Austin
for CO2 capture by MEA and the units are described in Table 2:

Figure 1. Simple Schematic of the CO2 Capture Pilot Plant in University of Texas, Austin (reproduced with
permission from the University of Texas at Austin)

Table 2. General Unit Operations Used in the CO2 Capture Process by MEA

Unit Purpose

Gas Mixer Mix CO2 from the Gas Accumulator with pure gas containing N2, O2
and H2O to make up feed rich flue gas for the absorber

Liquid Storage Tank Large storage of MEA solvent to buffer any unsteady state
disturbances in the system

Absorber MEA solvent contacts with flue gas in the absorber and captures CO2
from the gas.

Heater Heat the bottom flow from the absorber before it goes into the stripper

Stripper Strip CO2 from MEA solvent. It includes a partial condenser at the top
and a reboiler at the bottom.

Cooler Cool the bottom flow from the stripper before it goes into the liquid
storage tank

Gas Accumulator Large storage for CO2 from the top of the stripper to buffer any
unsteady state disturbances in the system
3. Physical Properties

Electrolyte NRTL method is used for liquid and RK equation of state for vapor in this Rate-
based MEA model. The model parameters were taken from the work of Austgen et al. (1989)[3]
and Jou et al.[4,5,6].
CO2, H2S, N2 and O2 are selected as Henry-components to which Henry’s law is applied and the
Henry’s constants are specified. Aqueous is specified as the basis for the infinite dilution activity
coefficient in the calculation of the unsymmetrical activity coefficient (GAMUS) for the solute.
With this basis, the infinite dilution activity coefficient of solute is calculated based on infinite
dilution condition in pure water.

In addition, transport property models have been updated and model parameters regressed from
literature experimental data. Specifications of the transport property models include:

1. For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus, with
quadratic mixing rule for solvent is used (the option code of VAQCLK is 1). The
interaction parameter VLQKIJ for the quadratic mixing rule between MEA and H2O is
regressed against experimental data. The Clarke model parameter VLCLK/1 is also
regressed for main electrolytes (MEAH+, HCO 3− ), (MEAH+, MEACOO − ) and (MEAH+,
CO 32− ).

2. 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 totally three models for electrolyte correction and the MEA
model always uses the Jones-Dole’s 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 MEA and
H2O in the ASPEN liquid mixture viscosity model, MUKIJ and MULIJ, are regressed
against MEA-H2O viscosity experimental data. The Jones-Dole model parameters,
IONMUB, for MEAH+, MEACOO- and HCO3- are regressed against MEA-H2O-CO2
viscosity data; and that of CO32- is regressed against K2CO3-H2O viscosity data.

3. 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.

4. For thermal conductivity, the Riedel electrolyte correction model, called KL2RDL in
Aspen Plus, is used.

5. For binary diffusivity, the Nernst-Hartley model, called DL0NST 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 heat of
formation at infinite dilution and 25°C (DHAQFM) and heat capacity at infinite dilution
(CPAQ0) for MEAH+ and MEACOO- are adjusted to fit to the literature heat of solution and
heat capacity data.

4. Reactions

The electrolyte solution chemistry has been modeled with a CHEMISTRY model and the
CHEMISTRY ID is MEA. Chemical equilibrium is assumed with all the ionic reactions in the
CHEMISTRY MEA. In addition, a kinetic REACTION model named MEA-REA has been
created. In MEA-REA, all reactions are assumed to be in chemical equilibrium except the
reactions of CO2 with OH- and the reactions of CO2 with MEA.

A. Chemistry ID: MEA

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 32−
4 Equilibrium MEAH + + H 2 O ↔ MEA + H 3 O +
5 Equilibrium MEACOO − + H 2 O ↔ MEA + HCO 3−
6 Equilibrium H 2 O + H 2 S ↔ HS − + H 3 O +
7 Equilibrium H 2 O + HS − ↔ S 2− + H 3 O +

B. Reaction ID: MEA-REA

1 EQUIL MEAH + + H 2 O ↔ MEA + H 3 O +
2 EQUIL 2H 2 O ↔ H 3 O + + OH −
3 EQUIL HCO 3− + H 2 O ↔ H 3 O + + CO 32−
4 EQUIL H 2 O + H 2 S ↔ HS − + H 3 O +
5 EQUIL H 2 O + HS − ↔ S 2− + H 3 O +
6 KINETIC CO 2 + OH − ↔ HCO 3−
7 KINETIC HCO 3− ↔ CO 2 + OH −
8 KINETIC MEA + CO 2 + H 2 O ↔ MEACOO - + H 3 O +
9 KINETIC MEACOO- + H 3 O + ↔ MEA + H 2 O + CO 2

The equilibrium expressions for the reactions are taken from the work of Austgen et al.[3] and Jou
et al.[4,5,6]. In addition, the power law expressions (T0 not specified) are used for the rate-
controlled reactions (reactions 6-9 in MEA-REA):

E N ai
r = kT n exp ( − )∏ C i (1)
RT i =1

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 taken from the work of Freguia
and Rochelle[2]. The kinetic parameters for reaction 8 are taken from the work of Pinsent et al.[7] ,
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.

Table 3. Parameters k and E in Equation 1

Reaction No. k E , cal/mol
6 4.32e+13 13249
7 2.38e+17 29451
8 1170000 1797.1
9 1.93e+14 7471.7
5. Simulation Approaches

Case 47 of the UT-Austin pilot plant[1] is used in this file.

Simulation Flowsheet – The U.T. Austin pilot plant shown in Figure 1 has been modeled with
the following simulation flowsheet in Aspen Plus, shown in Figure 2.

PUREGAS

PUMP

RICHOUT CO2OUT

TOHEATER
LEANIN

ABSORBER STRIPPER

FLUEGAS
RICHIN
LEANOUT

HEATER

Figure 2. Rate-Based MEA Simulation Flowsheet in Aspen Plus

Unit Operations - Major unit operations in this model have been represented by Aspen Plus
Blocks as outlined in Table 4.

Table 4. Aspen Plus Unit Operation Blocks Used in the Rate-Based MEA Model
Unit Operation Aspen Plus Block Comments / Specifications
Absorber RateSep 1. Calculation type: Rate-Based
2. 20 Stages
3. Top Pressure: 1atm
4. Heater Cooler: Heat loss is specified for the absorber
5. Reaction: Reaction ID is MEA-REA for all stages;
when calculation type is equilibrium, Holdup is used, and
in this file, Holdup=0.0075 cum, which is close to the
value calculated by Holdup correlation
6. Packing Type: IMTP, 1.5-IN, METAL
7. Packing height: 6.1m and Section diameter: 0.427m
8. Mass transfer coefficient method: Onda et al (1968)
9. Interfacial area method: Onda et al (1968)
10. Interfacial area factor: 1.5
11. Heat transfer coefficient method: Chilton and
Colburn
12. Holdup correlation: Stichlmair et al. (1989)
13. Film resistance: Discrxn for liquid film; film for
vapor film
14. Additional discretization points for liquid film: 0.1,
0.2, 0.3, 0.4 and 0.5
15. Flow model: Mixed
16. Estimates: Generate estimates for temperature, liquid
& vapor mole flows, and liquid & vapor component mole
fractions for all stages. These estimates are intended to
aid convergence
Unit Operation Aspen Plus Block Comments / Specifications
Stripper RateSep 1. Calculation type: Rate-Based
2. 20 Stages
3. Partial vapor condenser
4. Kettle reboiler
5. Mass reflux ratio: 0.969
6. Bottom rates: 2226.38kg/hr
7. Top Pressure: 10 psi and column pressure drop is 1.66
in-water.
8. Heater Cooler: Heat loss is specified for the stripper.
9. Reaction: Reaction ID is MEA-REA for all stages;
when calculation type is equilibrium, Holdup is used, and
in this file, Holdup=0.0075 cum, which is close to the
value calculated by the holdup correlation.
10. Packing Type: FLEXIPAC 1Y, STELL
11. Packing height: 6.1m
12. Section Diameter: 0.427m
13. Mass transfer coefficient method: Bravo et al (1992)
14. Interfacial area method: Bravo et al (1992)
15. Interfacial area factor: 2
16. Heat transfer coefficient method: Chilton and
Colburn
17. Holdup correlation: Bravo et al. (1992)
18. Film resistance: Discxrn for both liquid film; film for
vapor film
19. Additional discretization points for liquid film: 0.1,
0.2, 0.3, 0.4 and 0.5
20. Flow model: Mixed
21. Estimates: Generate estimates for stages for
temperature, liquid and vapor mole flows, liquid and
vapor component mole fractions, these estimates are
intended to aid convergence
Pump PUMP Increase pressure of the rich out stream from bottom of
the absorber by 20 psia
Heater HEATER Heat rich out stream from bottom of the absorber to
178.13ºF
Streams - Feeds to the absorber are FLUEGAS containing N2, O2, CO2 and H2O and LEANIN
containing aqueous MEA solution. Feed conditions are summarized in Table 5.

Table 5. Feed specifications

Stream ID FLUEGAS LEANIN
Substream: MIXED
Temperature: F 138.61 104.31
Pressure: psig 0.29 10
Total flow 290.38 cuft/min 2311.3 kg/hr
Mole-Frac
H2O 0.016 7.042
CO2 0.1841 0.281
MEA 0 1
N2 0.7528 0
O2 0.0471 0
MEAH+ 0 0
MEACOO- 0 0
HCO3- 0 0
CO3-- 0 0
H3O+ 0 0
OH- 0 0
6. Simulation Results
The simulation was performed using Aspen Plus version 2006.5. Key simulation results are
presented in Table 6. The measure versus calculated absorber and stripper liquid temperature
profiles are presented in Figures 3 and 4, respectively.

Table 6. Key Simulation Results

Variable Measurement Rate-Based MEA Model
CO2 loading of LEANIN, MolCO2/MolMEA 0.281 0.281
CO2 loading of RICHIN, MolCO2/MolMEA 0.539 0.479
CO2 loading of LEANOUT, MolCO2/MolMEA 0.286 0.286
CO2 removal level, % 69 67.3
CO2 Stripping, kg/hr 92 98.2

170

160

150
Temperature, F

140

130

120 Measurement

AspenPlus: Liquid
110

100
-1 1 3 5 7 9
Height from bottom , m

Figure 3. The Absorber Liquid Temperature Profile

 230

220

210
Temperature, F

200

190

Measurement
180
AspenPlus: Liquid

170

160
-1 1 3 5 7 9
Height from bottom, m

Figure 4. The Stripper Liquid Temperature Profile

7. Conclusions

The Rate-Based MEA model provides a rate-based rigorous simulation of the process. Key
features of this rigorous simulation include electrolyte thermodynamics and solution chemistry,
reaction kinetics for the liquid phase reactions, rigorous transport property modeling, rate-based
multi-stage simulation with RateSep 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 MEA.
Users may use it as a starting point for more sophisticated models for process development,
debottlenecking, plant and equipment design, among others.
References

[1] Dugas, R.E. Pilot Plant Study of Carbon Dioxide Capture by Aqueous
Monoethanolamine. Master thesis, Chemical Engineering, University of Texas at
Austin, 2006
[2] Freguia, S., Rochelle G.T., “Modeling of CO2 Capture by Aqueous
Monoethanolamine”, AIChE Journal, Vol. 49, 1676-1686 (2003).
[3] Austgen D.M., Rochelle G.T., Peng X., Chen C. C., “Model of Vapor-Liquid
Equilibria for Aqueous Acid Gas-Alkanolamine Systems Using the Electrolyte-NRTL
Equation”, Ind. Eng. Chem. Res., Vol. 28, 1060-1073 (1989).
[4] Jou F. Y., Mather A. E., Otto F. D., “Solubility of Hydrogen Sulfide and Carbon
Dioxide in Aqueous Methyldiethanolamine Solutions”, Ind. Eng. Chem. Proc. Des.
Dev., Vol. 21, 539(1982)
[5] Jou F. Y., Carroll J. J., Mather A. E., Otto F. D., “Solubility of Mixtures of Hydrogen
Sulfide And Carbon Dioxide in Aqueous N-Methyldiethanolamine Solutions”, J.
Chem. Eng. Data, Vol. 38, 75(1993)
[6] Jou F. Y., Carroll J. J., Mather A. E., Otto F. D., “The Solubility of Carbon Dioxide
and Hydrogen Sulfide in a 35 wt% Aqueous Solution of Methyldiethanolamine”, Can.
J. Chem. Eng., Vol. 71, 264(1993)
[7] Pinsent B. R., Pearson L., Roughton F. J. W., “The Kinetics of Combination of
Carbon Dioxide with Hydroxide Ions”, Trans. Faraday Soc., Vol. 52, 1512(1956)