Aspen Plus

Aspen Plus Model of the CO2 Capture Process by

DEPG
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Revision History
Version Description

V7.0 First version

V7.1 Re-verified simulation results using Aspen Plus V7.1
V7.2 Add formic acid and its PC-SAFT parameters
V7.3 Re-verified simulation results using Aspen Plus V7.3
V7.3.2 Re-verified simulation results using Aspen Plus V7.3.2
V8.2 Update the model to V8.2
V8.4 Update the model to V8.4
V8.6 Update the model to V8.6

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

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

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

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

4 Simulation Approaches.......................................................................................15

5 Simulation Results .............................................................................................18

6 Conclusions ........................................................................................................20

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

2 Contents
Introduction

This document describes an Aspen Plus model of the CO2 capture process by
the physical solvent DEPG from a gas mixture of CO, CO2, H2, H2O, N2, Ar,
CH4, NH3, and H2S from gasification of Illinois No. 6 bituminous coal[1]. The
operation data from an engineering evaluation design case by Energy
Systems Division, Argonne National Laboratory (1994)[1] are used to specify
the feed conditions and unit operation block specifications in the process
model. Since only the equilibrium stage results are available in the literature,
the process model developed here is based on the equilibrium stage
distillation model instead of the more rigorous rate-based model.
DEPG[2] is a mixture of the dimethyl ethers of polyethylene glycol with
formula CH3O(C2H4O)nCH3 where n ranges from 2 to 9. However, DEPG in this
model is represented by an Aspen Plus databank component, also called DEPG
(dimethyl ether of polyethylene glycol), with the average molecular weight of
280 - corresponding to n = 5.3. DEPG data from Coastal Chemical[3] for vapor
pressure, liquid density, heat capacity, viscosity, and thermal conductivity are
used to determine parameters in thermophysical property and transport
property models used in this work. For all other components, thermophysical
property models have been validated against DIPPR correlations[4] , which are
available in Aspen Plus, for component vapor pressure and liquid density.
Vapor-liquid equilibrium data from Xu et al. (1992)[5] between DEPG and
selected components are used to adjust binary parameters in thermophysical
property models. The designed packing information from the literature[1] is
also included in the process model, which allows rigorous rate-based
simulation to be performed.
The model includes the following key features:
 PC-SAFT equation of state model for vapor pressure, liquid density, heat
capacity, and phase equilibrium
 Transport property models
 Equilibrium distillation model for absorber with designed packing
information from the literature[1]

Introduction 3
1 Components

The following components represent the chemical species present in the

process. As already stated, DEPG in real processes is a mixture of the
dimethyl ethers of polyethylene glycol with formula CH3O(C2H4O)nCH3 where n
ranges from 2 to 9 [2] and in this model an average molecular weight of 280
corresponding to n = 5.3 is used to represent the DEPG solvent by an Aspen
Plus databank component DEPG.

Table 1. Components Used in the Model

ID Type Name Formula

DEPG CONV DIMETHYL-ETHER-POLYETHYLENE-GLYCOL DEPG

CO CONV CARBON-MONOXIDE CO
CO2 CONV CARBON-DIOXIDE CO2
H2 CONV HYDROGEN H2
H2O CONV WATER H2O
N2 CONV NITROGEN N2
AR CONV ARGON AR
CH4 CONV METHANE CH4
NH3 CONV AMMONIA H3N
H2S CONV HYDROGEN-SULFIDE H2S
HCN CONV HYDROGEN-CYANIDE CHN
COS CONV CARBONYL-SULFIDE COS
CH2O2 CONV FORMIC-ACID CH2O2

4 1 Components
2 Process Description

The flowsheet for CO2 capture by DEPG in the report by Energy Systems
Division, Argonne National Laboratory (ANL) [1] includes an absorber for CO2
absorption by DEPG at elevated pressure, flash tanks to release CO2 and
regenerate solvent at several different pressure levels, and compressors and
turbines to change pressures of streams. However, the process model
presented in this work focuses only on the absorber and the other unit
operations are not included.
The sour gas enters the bottom of the absorber, contacts with lean DEPG
solvent from the top counter-currently and leaves at the top as sweet gas,
while the solvent flows out of the absorber at the bottom as the rich solvent
with absorbed CO2 and some other gas components.
Two pressure levels for absorption were evaluated in the ANL report: 250psia
and 1000psia. For each pressure case study, the gas feeds into the absorber
is the same, but solvent flow rates and number of equilibrium stages used are
different. Typically, to achieve a certain CO2 recovery, the high pressure case
used less solvent and fewer stages. Table 2 represents some operation data:

Table 2. Data of the Absorber

Low Pressure Case High Pressure Case

Absorber
Number of Stages 12 10
Diameter, ft 17 11
Packing Height, ft 3 3
Packing Type Pall ring Pall ring
Packing Size, mm 50 50
Sour Gas
Flow rate, lbmol/hr 17614.58 17614.58
CO2 in Sour Gas, mole fraction 0.2461 0.2461
Lean DEPG
Flow rate, lbmol/hr 23000 6900
Temperature, F 30 30
Pressure, psia 250 1000

2 Process Description 5
3 Physical Properties

The PC-SAFT equation of state model is used to calculate vapor pressure,

liquid density and phase equilibrium. The PC-SAFT pure component
parameters for CO, CO2, NH3, H2S have been regressed against vapor
pressure and liquid density generated from DIPPR correlations[4] for each
component. The PC-SAFT pure parameters for DEPG have been regressed to
fit vapor pressure and liquid density data from Coastal Chemical[3]. For all
other components, the PC-SAFT pure parameters are taken from the work by
Gross and Sadowski (2001, 2002)[6,7]. The binary parameters between CO2
and DEPG and H2S and DEPG have been regressed against vapor-liquid
equilibrium data form Xu et al. (1992)[5]. Based on solubility ratio of H2 to H2S
in DEPG at 25°C[8,9] and experimental vapor-liquid equilibrium data for H2S in
DEPG, we also estimated vapor-liquid equilibrium data for H2 in DEPG and
used these estimated data for regression of binary parameters between H2
and DEPG. In the same way, we obtained binary parameters between the
other gas components and DEPG[8,9], except for Ar because of the missing
solubility ratio of Ar.
DIPPR model parameters for DEPG are regressed to fit data from Coastal
Chemical[3] for viscosity and thermal conductivity. The Aspen ideal gas heat
capacity model parameters for DEPG are also regressed to fit liquid heat
capacity data from Coastal Chemical[3]. Finally, the dipole moment from the
DIPPR database[4] for pentaethylene glycol dimethyl ether is used for DEPG.
Figures 1-15 show property predictions together with literature data.

6 3 Physical Properties
 DEPG vapor pressure

0.1
Data

Vapor pressure, bar

0.01 PC-SAFT

0.001

0.0001

0.00001

0.000001

0.0000001
250 300 350 400 450
Temperature, K

Figure 1. DEPG vapor pressure. PC-SAFT is used to fit data from Coastal
Chemical[3].

DEPG liquid density

1200
1150 Data
Liquid density, kg/m3

1100 PC-SAFT

1050
1000
950
900
850
800
250 300 350 400 450
Temperature, K

Figure 2. DEPG liquid density. PC-SAFT is used to fit data from Coastal
Chemical[3].

3 Physical Properties 7
 CO2 vapor pressure

70
60 Data

Vapor pressure, bar

PC-SAFT
50
40
30
20
10
0
200 220 240 260 280 300 320
Temperature, K

Figure 3. CO2 vapor pressure. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for CO2.

CO2 liquid density

1300
1200
Liquid density, kg/m3

1100
1000
900
Data
800
PC-SAFT
700
600
500
200 220 240 260 280 300 320
Temperature, K

Figure 4. CO2 liquid density. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for CO2.

8 3 Physical Properties
 H2S vapor pressure

80
70

Vapor pressure, bar

Data
60
PC-SAFT
50
40
30
20
10
0
180 230 280 330 380
Temperature, K

Figure 5. H2S vapor pressure. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for H2S.

H2S liquid density

1100
1000
Liquid density, kg/m3

900
800
700
Data
600
PC-SAFT
500
400
300
180 230 280 330 380
Temperature, K

Figure 6. H2S liquid density. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for H2S.

3 Physical Properties 9
 CO vapor pressure

40
35

Vapor pressure, bar

30
Data
25
PC-SAFT
20
15
10
5
0
70 90 110 130
Temperature, K

Figure 7. CO vapor pressure. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for CO.

CO liquid density

850
800
Liquid density, kg/m3

750
700
650
600 Data
550 PC-SAFT
500
450
400
70 90 110 130
Temperature, K

Figure 8. CO liquid density. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for CO.

10 3 Physical Properties
 NH3 vapor pressure

90
80

Vapor pressure, bar

70
Data
60
PC-SAFT
50
40
30
20
10
0
200 250 300 350 400
Temperature, K

Figure 9. NH3 vapor pressure. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for NH3.

NH3 liquid density

750

700
Liquid density, kg/m3

650

600

550 Data
500 PC-SAFT

450

400
200 250 300 350 400
Temperature, K

Figure 10. NH3 liquid density. PC-SAFT is used to fit data generated from the
DIPPR correlation[4] for NH3.

3 Physical Properties 11
 VLE for CO2-DEPG

0.9 Data
PC-SAFT
Pressure, psia

0.8

0.7

0.6

0.5
50 70 90 110 130 150
Temperature, F

Figure 11. Vapor-liquid equilibria of CO2-DEPG. Comparison of experimental

data[5] to calculation results of PC-SAFT with adjustable binary parameters.

VLE for H2S-DEPG

0.15

0.13 Data
PC-SAFT
Pressure, psia

0.11

0.09

0.07

0.05
50 70 90 110 130 150
Temperature, F

Figure 12. Vapor-liquid equilibria of H2S-DEPG. Comparison of experimental

data[5] to calculation results of PC-SAFT with adjustable binary parameters.

12 3 Physical Properties
 DEPG liquid heat capacity

750000
Heat capacity, J/kmol-K
Data
DIPPR

650000

550000
250 300 350 400 450
Temperature, K

Figure 13. DEPG liquid heat capacity. The Aspen ideal gas heat capacity
model is used to fit data from Coastal Chemical[3].

DEPG liquid viscosity

0.1
Data
DIPPR
Viscosity, Pa.s

0.01

0.001

0.0001
200 250 300 350 400 450
Temperature, K

Figure 14. DEPG liquid viscosity. The DIPPR correlation model[4] is used to fit
data from Coastal Chemical[3].

3 Physical Properties 13
 DEPG liquid thermal conductivity

0.21
Data

Thermal conductivity, W/m-K

DIPPR
0.19

0.17

0.15

0.13
200 250 300 350 400 450
Temperature, K

Figure 15. DEPG liquid thermal conductivity. The DIPPR correlation model[4]
is used to fit data from Coastal Chemical[3].

14 3 Physical Properties
4 Simulation Approaches

The high pressure case and the low pressure case are included in the process
model as two separate absorber columns. The absorbers are modeled with
the Equilibrium calculation type instead of the more rigorous rate-based
calculation type because the design cases from [1] were based on equilibrium
stage calculations. This allows us to make meaningful comparison between
our model and the literature. However, we included designed packing
information from the literature in the model so that the rate-based calculation
type can be used. In addition, as shown above, transport properties, which
are crucial for rate-based calculations, have also been validated. Therefore,
this model is ready for rate-based calculations, in which correlations and scale
factors of interfacial area, mass transfer coefficient, heat transfer coefficient,
liquid holdup and so on can be selected and adjusted. You can also select the
film resistance types and flow models to be used.
Simulation Flowsheet – The absorbers for the two cases have been
modeled with the simulation flowsheet in Aspen Plus shown in Figure 16, in
which ABSORB-H is the absorber for the high pressure case and ABSORB-L is
the absorber for the low pressure case.

GASOUT-L GASOUT-H

LEAN-L LEAN-H
ABSORB-L ABSORB-H

GASIN-L GASIN-H

RICH-L RICH-H

Figure 16. DEPG Process Flowsheet in Aspen Plus

4 Simulation Approaches 15
 Unit Operations – Major unit operations in this model have been
represented by Aspen Plus blocks as outlined in Table 3.

Table 3. Aspen Plus Unit Operation Blocks Used in the

DEPG Model
Unit Operation Aspen Plus Block Comments / Specifications

ABSORB-H RadFrac The absorber for the high pressure case with the following
settings:
1. Calculation type: Equilibrium stage
2. Number of stages: 10
3. Top Pressure: 1000psia
4. Column diameter: 11ft
5. Packing Type: Pall ring
6. Packing Size: 50mm(2in)
7. Packing Height per stage: 3ft
ABSORB-L RadFrac The absorber for the low pressure case with the following
settings:
1. Calculation type: Equilibrium stage
2. Number of stages: 12
3. Top Pressure: 250psia
4. Column diameter: 17ft
5. Packing Type: Pall ring
6. Packing Size: 50mm(2in)
7. Packing Height per stage: 3ft

16 4 Simulation Approaches
 Streams – The gas feeds of the DEPG model are GASIN-H for the high
pressure absorber ABSOR-H and GASIN-L for the low pressure absorber
ABSORB-L, both containing CO, CO2, H2, H2O, N2, Ar, CH4, NH3, and H2S.
The solvent liquid feeds are LEAN-H for the high pressure absorber ABSORB-H
and LEAN-L for the low pressure absorber ABSORB-L, both containing DEPG
and a small amount of CO2 and H2O.
Feed conditions are summarized in Table 4.

Table 4. Feed specification

Stream ID GASIN-H LEAN-H GASIN-L LEAN-L
Substream: MIXED
Temperature: F 68.17 30 68.13 30
Pressure:psia 998 1000 248 250
Mole-flow: lbmol/hr
DEPG 0 6900 0 23000
CO 77.37 0.0 77.37 0.0
CO2 4335.99 115.55 4335.99 395.00
H2 5611.86 0.0 5611.86 0.0
H2O 61.91 0.07 61.91 2.25
N2 7306.65 0.0 7306.65 0.0
AR 88.6 0.0 88.6 0.0
CH4 128.77 0.0 128.77 0.0
NH3 2.99 0.0 2.99 0.0
H2S 0.4 0.0 0.4 0.0
HCN 0.0 0.0 0.0 0.0
COS 0.0 0.0 0.0 0.0
CH2O2 0.0 0.0 0.0 0.0

4 Simulation Approaches 17
5 Simulation Results

The simulation was performed using Aspen Plus with the absorbers'
calculation type set to Equilibrium. Key simulation results are presented in
Table 5 and 6 and Figure 17 and 18, together with available design data from
the report of the Energy Systems Division, Argonne National Laboratory[1] .
A problem was found in the literature that their calculation was based on
improper solubility ratios of the gas components in DEPG solvent, in which
N2:H2 is 0, while UOP reported a ratio of 1.5[2] and this model reports a ratio
of about 3.8. As a result, this model gives less CO2 absorption than that
reported in the literature. In addition, the temperature of the rich solvent
from the bottom of the absorbers is also lower in our simulation.

Table 5. Key Simulation Results for the High Pressure

Case
Literature This model
CO2 mole fraction in GASOUT-H 0.01619 0.050
Temperature of RICH-H, F 83.82 60.4

Table 6. Key Simulation Results for the Low Pressure Case

Literature This model
CO2 mole fraction in GASOUT-L 0.01629 0.036
Temperature of RICH-L, F 46.68 42.1

18 5 Simulation Results
 1
2

3
4

Stage Number 5
6
7
8
ABSORB-H
9
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Temperature, F

Figure 17. Absorber Temperature Profile for the High Pressure Case

1
2
3
4
Stage Number

5
6
7
8
9
10
ABSORB-L
11
12
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Temperature, F

Figure 18. Absorber Temperature Profile for the Low Pressure Case

5 Simulation Results 19
6 Conclusions

The DEPG model provides an equilibrium stage simulation of the process and
validated transport property models which allow rigorous rate-based
simulation. Key features of this model include the PC-SAFT equation of state
model for vapor pressure, liquid density, and phase equilibrium; rigorous
transport property modeling; equilibrium stage simulation with RadFrac; and
packing information from the literature[1].
The model is meant to be used as a guide for modeling the CO2 capture
process with DEPG. Users may use it as a starting point for more
sophisticated models for process development, debottlenecking, plant and
equipment design, among others.

20 6 Conclusions
References

[1] R.D. Doctor, J.C. Molburg, P.R. Thimmapuram, G.F. Berry, C.D. Livengood,
“Gasification Combined Cycle: Carbon Dioxide Recovery, Transport, and
Disposal”, Energy System Divison, Argonne National Laboratory (1994)
[2] D.J. Kubek, E. Polla, F.P. Wilcher, “Purification and Recovery Options for
Gasification,” Gasification Technologies Conference, San Francisco (1996)
[3] Coastal AGR Solvent Bulletin, Coastal Chemical Co., L.L. C
[4] DIPPR® 801 database, BYU-Thermophysical Properties Laboratory (2007).
[5] Y. Xu, R.P. Schutte, L.G. Helper, “Solubilities of Carbon Dioxide, Hydrogen
Sulfide and Sulfur Dioxide in Physical Solvents,” Can. J. Chem. Eng., 70, 569-
573 (1992)
[6] J. Gross, G. Sadowski, “Perturbed-Chain SAFT: An Equation of State
Based on a Perturbation Theory for Chain Molecules,” Ind. Eng. Chem. Res.,
40, 1244-1260 (2001)
[7] J. Gross, G. Sadowski, “Application of the Perturbed-Chain SAFT Equation
of State to Associating Systems”, Ind. Eng. Chem. Res., 41, 5510-5515 (2002)
[8] G. Ranke, V. H. Mohr, “The Rectisol Wash: New Developments in Acid Gas
Removal from Synthesis Gas,” from Acid and Sour Gas Treating Processes,
Stephen A. Newman, ed., Gulf Publishing Company, Houston, 80-111 (1985)
[9] R. Epps, “Processing of Landfill Gas for Commercial Applications: the
SELEXOL Solvent Process,” Union Carbide Chemicals & Plastics Technology
Corporation, June, 1992. (Prepared for Presentation at ECO WORLD ’92, June
15, 1992, Washington D. C.)

References 21