Aspen Plus

Aspen Plus Model of the

CO2 Capture Process by
Propylene Carbonate
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Revision History
Version Description

V7.0 First version

V7.1 Re-verified simulation results using Aspen Plus V7.1

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

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

2 Process Description..............................................................................................6

3 Physical Properties...............................................................................................8

4 Simulation Approaches.......................................................................................17

5 Simulation Results .............................................................................................19

6 Conclusions ........................................................................................................21

References ............................................................................................................22

2 Contents
Introduction

This document describes an Aspen Plus model of the CO2 capture process by
the physical solvent propylene carbonate (PC) 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 using DEPG as solvent by Energy Systems Division, Argonne National
Laboratory (1994)[1] are used to specify the feed conditions and unit
operation block specifications in this PC process model. Since only the
equilibrium stage results for the DEPG design case 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.
Besides the gases present in the flows of the design case, many other gas
components such as COS, HCN and so on are also included in this model for a
potential need by customers, for which, pure and/or binary parameters have
been determined and included in the model.
Propylene carbonate data for vapor pressure[2], liquid density[2], viscosity[3-9],
thermal conductivity[3,10] and surface tension[11-13] 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[2] , which are available in Aspen
Plus, for component vapor pressure and liquid density. Vapor-liquid
equilibrium data from Xu et al. (1992)[14] between DEPG and selected
components and solubility ratios[15] of gases in DEPG and in propylene
carbonate are used to estimate vapor-liquid data between propylene
carbonate and gas components and then 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.

Table 1. Components Used in the Model

ID Type Name Formula
PC CONVENTIONAL PROPYLENE-CARBONATE C4H6O3-D1
CO2 CONVENTIONAL CARBON-DIOXIDE CO2
H2S CONVENTIONAL HYDROGEN-SULFIDE H2S
CO CONVENTIONAL CARBON-MONOXIDE CO
H2O CONVENTIONAL WATER H2O
CS2 CONVENTIONAL CARBON-DISULFIDE CS2
NH3 CONVENTIONAL AMMONIA H3N
N2 CONVENTIONAL NITROGEN N2
COS CONVENTIONAL CARBONYL-SULFIDE COS
O2 CONVENTIONAL OXYGEN O2
SO2 CONVENTIONAL SULFUR-DIOXIDE O2S
SO3 CONVENTIONAL SULFUR-TRIOXIDE O3S
CH3SH CONVENTIONAL METHYL-MERCAPTAN CH4S
C2H5SH CONVENTIONAL ETHYL-MERCAPTAN C2H6S-1
CH3SCH3 CONVENTIONAL DIMETHYL-SULFIDE C2H6S-2
HCN CONVENTIONAL HYDROGEN-CYANIDE CHN
H2 CONVENTIONAL HYDROGEN H2
BENZENE CONVENTIONAL BENZENE C6H6
CH4 CONVENTIONAL METHANE CH4
C2H6 CONVENTIONAL ETHANE C2H6
C2H4 CONVENTIONAL ETHYLENE C2H4
C3H8 CONVENTIONAL PROPANE C3H8
IC4H10 CONVENTIONAL ISOBUTANE C4H10-2
NC4H10 CONVENTIONAL N-BUTANE C4H10-1
C2H2 CONVENTIONAL ACETYLENE C2H2
NC5H12 CONVENTIONAL N-PENTANE C5H12-1
C6H14 CONVENTIONAL N-HEXANE C6H14-1
C7H16 CONVENTIONAL N-HEPTANE C7H16-1
C10H22 CONVENTIONAL N-DECANE C10H22-1
NO2 CONVENTIONAL NITROGEN-DIOXIDE NO2

4 1 Components
 ID Type Name Formula
NO CONVENTIONAL NITRIC-OXIDE NO
C6H12R CONVENTIONAL CYCLOHEXANE C6H12-1
NC8H18 CONVENTIONAL N-OCTANE C8H18-1
AR CONVENTIONAL ARGON AR

1 Components 5
2 Process Description

In this propylene carbonate model, we use the operation data taken from a
CO2 capture design case by DEPG reported by Energy Systems Division,
Argonne National Laboratory (ANL) [1].The reported flowsheet 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 propylene
carbonate 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.
In this propylene carbonate model, we used the operation data of the low
pressure case.

6 2 Process Description
 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 7
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 gases have been regressed against vapor pressure and liquid
density generated from DIPPR correlations[2] for each component or taken
from the work by Gross and Sadowski (2001, 2002)[16,17]. The PC-SAFT pure
parameters for propylene carbonate have been regressed to fit vapor
pressure and liquid density data from DIPPR correlations[2]. The binary
parameters between CO2 and propylene carbonate, H2S and propylene
carbonate and SO2 and propylene carbonate have been regressed against
experimental vapor-liquid equilibrium data from Xu et al. (1992)[14], which are
expressed as Henry’s constants. For the other gas components, their ratios[15]
of solubility in propylene carbonate to that of CO2 are assumed equivalent to
their Henry’s constant ratios. Thus, their Henry’s constants with propylene
carbonate are estimated and then used to regress their binary parameters.
Because no information of relative solubility of Ar and NH3 were found, their
binary parameters are missing for now.
DIPPR model parameters for propylene carbonate are regressed to fit data for
viscosity[3-9], thermal conductivity[3,10] and surface tension[11-13].
Figures 1-15 show property predictions together with literature data.

8 3 Physical Properties
 Propylene carbonate vapor pressure

1.00E+03

1.00E+01
Vapor Presure, bar
1.00E-01

1.00E-03
Data
1.00E-05
PC-SAF
1.00E-07

1.00E-09
0 200 400 600 800 1000

Temperature, K

Figure 1. Propylene carbonate vapor pressure. PC-SAFT is used to fit data

from DIPPR correlation[2].

Propylene carbonate liquid density

1400
Liquid density, kg/m3

1200

1000

Data
800
PC-SAF

600
100 200 300 400 500 600

Temperature, K

Figure 2. Propylene carbonate liquid density. PC-SAFT is used to fit data from
DIPPR correlation[2].

3 Physical Properties 9
 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
DIPPR correlation[2] 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
DIPPR correlation[2] for CO2.

10 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
DIPPR correlation[2] 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
DIPPR correlation[2] for H2S.

3 Physical Properties 11
 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

DIPPR correlation[2] 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 DIPPR
correlation[2] for CO.

12 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
DIPPR correlation[2] 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
DIPPR correlation[2] for NH3.

3 Physical Properties 13
 VLE for CO2-Propylene carbonate

0.02

Pressure, MPa 0.015

0.01

0.005 Data
PC-SAFT

0
290 300 310 320 330 340 350

Temperature, K

Figure 11. Vapor-liquid equilibria of CO2-Propylene carbonate. Comparison of

data[14] to calculation results of PC-SAFT with adjustable binary parameter.

VLE for H2S-Propylene carbonate

0.01

Data
Pressure, MPa

PC-SAFT

0.005

0
290 300 310 320 330 340 350

Temperature, K

Figure 12. Vapor-liquid equilibria of H2S-Propylene carbonate. Comparison of

data[14] to calculation results of PC-SAFT with adjustable binary parameter.

14 3 Physical Properties
 Surface tension of Propylene Carbonate

0.06

0.05 DIPPR
Surface tension (N/m) Data
0.04

0.03

0.02

0.01

0
200 300 400 500 600
Temperature (K)

Figure 13. Propylene carbonate liquid surface tension. DIPPR correlation

model[2] is used to fit data[11-13] .

Viscosity of Propylene Carbonate

3.00E-02

2.50E-02
Viscosity (Pa.s)

2.00E-02 Data
DIPPR
1.50E-02

1.00E-02

5.00E-03

0.00E+00
200 300 400 500 600
Temperature (K)

Figure 14. Propylene carbonate liquid viscosity. DIPPR correlation model[4] is

used to fit data[3-9].

3 Physical Properties 15
 Thermal conductivity of Propylene Carbonate

0.25

Thermal conductivity (W/m.K)

0.23
Data
DIPPR
0.21

0.19

0.17

0.15

0.13
200 250 300 350 400 450 500 550
Temperature (K)

Figure 15. Propylene carbonate liquid thermal conductivity. DIPPR

correlation model[2] is used to fit data[3,10].

16 3 Physical Properties
4 Simulation Approaches

As stated in the previous sections, this propylene carbonate model uses

operation data of a DEPG design case from [1], the low pressure case. Feed
conditions, absorber configurations and operation conditions of the DEPG low
pressure case were used in this model as a base case and then solvent flow
rate is adjusted to reach the same CO2 capture amount as DEPG does.
The absorber is 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 DEPG model, which also
uses the Equilibrium calculation type because only equilibrium results are
available for comparison in [1]. 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 absorber has been modeled with the following
simulation flowsheet in Aspen Plus, shown below.

GASOUT

LEANIN

ABSORBER

GASIN

RICHOUT

Figure 16. Propylene Carbonate Process Flowsheet in Aspen Plus

4 Simulation Approaches 17
 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

Propylene Carbonate Model
Unit Operation Aspen Plus Block Comments / Specifications

ABSORBER 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

Streams – The gas feeds of the propylene carbonate model is GASIN,

containing CO, CO2, H2, H2O, N2, Ar, CH4, NH3, and H2S.
The solvent liquid feeds is LEANIN, containing propylene carbonate and a
small amount of CO2 and H2O.
Feed conditions are summarized in Table 4.

Table 4. Feed specification

Stream ID GASIN LEANIN
Substream: MIXED
Temperature: F 68.13 30
Pressure:psia 248 250
Mole-flow: lbmol/hr
PC 0 23000
CO 77.37 0.0
CO2 4335.99 395.00
H2 5611.86 0.0
H2O 61.91 2.25
N2 7306.65 0.0
AR 88.6 0.0
CH4 128.77 0.0
NH3 2.99 0.0
H2S 0.4 0.0

18 4 Simulation Approaches
5 Simulation Results

The simulation was performed using Aspen Plus V7.1 with the absorber
calculation type set to Equilibrium. Key simulation results are presented in
Figure 17 and 18, together with the simulation results of the DEPG model
using the low pressure case operation data.
As shown by Figure 17 and 18, with the same flow rate (23000lbmol/hr) and
temperature (30F) for the fed solvent to the absorber, DEPG (Squares in
Figure 17 and 18) has a much higher remove capacity than propylene
carbonate (Solid line in Figure 17 and 18) with similar temperature increase.
To achieve a similar CO2 removal to what DEPG does, propylene carbonate
flow rate should be increased to about 60700lbmol/hr (Dashed Lines in Figure
17 and 18), which is about 2.6 times of DEPG’s flow rate.
According to Table 1 in reference [15], at 25°C, CO2 solubility is
0.485ft3/gallonDEPG and 0.455ft3/gallon propylene carbonate. At 25°C
specific gravity is 1030kg/m3 for DEPG, whose molecular weight is 280, and
1195kg/m3 for propylene carbonate, whose molecular weight is 102. If
transformed to a mole-solvent base, CO2 solubility in DEPG is about 3.5 times
of the solubility in propylene carbonate at 25°C.

5 Simulation Results 19
 1
2
3
4
S t age Number 5
6
7
8 DEPG 23000 30F
9 PC 23000 30F
10
PC 60700 30F
11
12
0 5 10 15 20 25 30 35 40 45 50 55 60 65
Temperat ure, F

Figure 17. Absorber Temperature Profile

1
2
3
4
S t age Number

5
6
7
8 DEPG 23000 30F
9
PC 23000 30F
10
11 PC 60700 30F
12
0 0.05 0.1 0.15 0.2 0.25 0.3
CO2 Mole Frac t ion

Figure 18. Absorber Vapor Phase CO2 Composition Profile

20 5 Simulation Results
6 Conclusions

The propylene carbonate 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 propylene carbonate. You may use it as a starting point for
more sophisticated models for process development, debottlenecking, plant
and equipment design, among others.

6 Conclusions 21
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 Division, Argonne National Laboratory (1994)
[2] DIPPR® 801 database, BYU-Thermophysical Properties Laboratory (2007)
[3] Ethylene Carbonate, Propylene Carbonate, Texaco Chemical Company,
Texaco, Inc. (1982)
[4] G. Moumouzias, G. Ritzoulis, "Viscosities and Densities for Propylene
Carbonate + Toluene at 15, 20, 25, 30 and 35 C" J. Chem. Eng. Data, 37,
482-483 (1992)
[5] P.K. Muhuri, D.K. Hazra, "Density and Viscosity for Propylene Carbonate +
1,2-Dimethoxyethane at 298.15, 308.15, and 318.15 K" J. Chem. Eng. Data,
39, 375 (1994)
[6] B.B. Tanganov, M.M. Baldanov, M.V. Mokhosev, "Multiple Regressions of
the Physicochemical Characteristics of the Nonaqueous Solvents on an
Expanded Parameter Basis," Russ. J. Phys. Chem., 66, 786 (1992)
[7] M. Salomon, "Conductance of Solutions of Lithium
Bis(Trifluoromethanesulfone)imide in Water, Propylene Carbonate, Acetonitrile
and Methyl Formate at 25 C, " J. Sol. Chem., 22, 715 (1993)
[8] J.M. Sullivan, D.C. Hanson, R. Keller, "Diffusion Coefficients in Propylene
Carbonate, Dimethyl Formamide, Acetonitrile, and Methyl Formate, " J.
Electrochem. Soc., 117, 779 (1970)
[9] Harris, U.S. Atomic Energy Comm. UCRL-8381, 6 (1958)
[10] A. Missenard, "Conductivite Thermique des Solides, Liquides, Gaz et de
Leurs Melanges, " Editions Eyrolles, Paris, 5 (1965); Also see Missenard, A.,
Comptes Rendus, 260, 5521 (1965)
[11] S. Sugden, "The Variation of Surface Tension with Temperature and
Some Related Functions," J. Chem. Soc. (London, Transactions), 125, 32
(1924)
[12] J.A. Riddick, W.B. Bunger, T.K. Sakano, "Organic Solvents: Physical
Properties and Methods of Purification, 4th ed.," Wiley Interscience, New York
(1986)

22 References
 [13] M.K. Bernett, W.A. Zismann, "Relation of Wettability by Aqueous
Solutions to the Surface Constitution of Low-Energy Solids," J. Phys. Chem.,
63, 1241 (1959)
[14] 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)
[15] 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.)
[16] 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)
[17] J. Gross, G. Sadowski, “Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems”, Ind. Eng. Chem. Res., 41, 5510-
5515 (2002)

References 23