Aspen Plus

Rate-Based Model of the CO2 Capture Process by

MEOH using Aspen Plus
Copyright (c) 2008-2013 by Aspen Technology, Inc. All rights reserved.

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

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Revision History
Version Description

V7.0 First version

V7.1 Re-verified simulation results using Aspen Plus V7.1
V7.2 Refined PC-SAFT parameters for components. Added additional
literature data and updated plots to show comparisons to new data.
V7.3 Re-verified simulation results using Aspen Plus V7.3
V7.3.2 Include PC-SAFT binary parameters for H2O-methanol binary system
V8.2 Update the model to V8.2
V8.4 Update the model to V8.4

Revision History 1
Contents
Revision History ......................................................................................................1

Contents..................................................................................................................2

Introduction ............................................................................................................3

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

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

3 Physical Properties...............................................................................................7

4 Simulation Approach ..........................................................................................27

5 Simulation Results .............................................................................................29

6 Conclusions ........................................................................................................31

References ............................................................................................................32

2 Contents
Introduction

This document describes an Aspen Plus rate-based model of the CO2 capture
process by MEOH from a gas mixture of H2, CO2, CO, N2, CH4, H2S and COS
from gasification of Western Kentucky coal char[1]. The operation data from a
pilot scale absorber[1] are used to specify the feed conditions and unit
operation block specifications in the model.
The model includes the following key features:
PC-SAFT equation of state model for vapor pressure, liquid density and
phase equilibrium
Transport property models
Rate-based model for absorber with ceramic Intalox saddles packing
Thermophysical property models have been validated against DIPPR
correlations[2] for pure component vapor pressure and liquid density and
experimental data for liquid heat capacity[3-20, 38-66], heat of vaporization[21-37,
67-81]
, and vapor-liquid equilibrium[82-122]. Transport property models have
been validated against literature data for viscosity[123-127], thermal
conductivity[128-131], surface tension[125, 132-136], and diffusivity[137].

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

MEOH CONV METHANOL CH4O

H2O CONV WATER H2O
CO2 CONV CARBON-DIOXIDE CO2
H2S CONV HYDROGEN-SULFIDE H2S
CO CONV CARBON-MONOXIDE CO
N2 CONV NITROGEN N2
COS CONV CARBONYL-SULFIDE COS
H2 CONV HYDROGEN H2
CH4 CONV METHANE CH4

4 1 Components
2 Process Description

The flowsheet for the pilot plant[1] for CO2 capture by MEOH includes an
absorber, a flash tank, a stripper, and so on. However, only the absorber
data are reported.
The sour gas enters the bottom of the absorber, contacts with lean MEOH
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.
Table 2 presents the absorbers typical operation data.

2 Process Description 5
 Table 2. Data of the Absorber from the Pilot Plant[1]
Absorber
Diameter 0.127 m
*
Packing Height 0.45 m (1.5 ft)
Packing Type ceramic Intalox saddles
Packing Size 6.25 mm (0.25 in)
Sour Gas
Flow rate 2.17 lbmol/hr
CO2 in Sour Gas 0.2801 (mole fraction)
H2S in Sour Gas 0.00807 (mole fraction)
Sweet Gas
CO2 in Sweet Gas 0.0095 (mole fraction)
H2S in Sweet Gas 0.00037 (mole fraction)
Lean MEOH
Flow rate 8.29 lbmol/hr
Temperature -34.7 F
Pressure 400 psia**

* The nominal packing height 2.2 m (7.1 ft) of the column used in the
experiments was found to be too high and no absorption was detected above
certain height of the packing[1]. Liquid and gas samples were taken at the
height of 1.5 m (5 ft) from the bottom as liquid feed and gas product. For the
case presented in Table 2, the effective packing height 0.45 m (1.5 ft) is used
instead of the real height 2.2 m (7.1 ft) in this simulation model and this
effective height was also used in the literature model[1].
** Because pressure unit is not reported explicitly[1], it is assumed to be psia
based on the pressure data in Table II and Figure 12 of [1].

6 2 Process Description
3 Physical Properties

The PC-SAFT equation of state model is used to calculate all thermophysical

properties including vapor pressure, liquid density, heat capacity, enthalpy,
and phase equilibrium. The PC-SAFT pure component parameters for CO2, H2S,
CO, and COS have been regressed against vapor pressure and liquid density
data generated from DIPPR correlations[2] for each component. For MEOH, the
PC-SAFT pure component parameters are regressed against experimental
liquid heat capacity data[3-20] and heat of vaporization data[21-37] in addition to
vapor pressure and liquid density data from DIPPR[2]. Likewise, the vapor
pressure and liquid density data of H2O generated from DIPPR correlation[2]
along with the experimental data on liquid heat capacity[38-66] and heat of
vaporization[67-81] are used to determine the PC-SAFT pure component
parameters for H2O. For all other components, the PC-SAFT pure component
parameters are taken from the work by Gross and Sadowski (2001,
2002)[138,139]. The binary parameters between the solutes CO2, H2S, CO, N2,
COS, H2, CH4 and the solvent MEOH are respectively regressed against vapor-
liquid equilibrium data from the literature[82-109]. The binary parameters
between H2O and MEOH are also regressed against vapor-liquid equilibrium
data from the literature[110-122].
The literature data of volume solubility[140-142] and solubility ratios[140] are
used to verify the binary parameters between these gas components and
MEOH.
DIPPR correlation models[2] are used to calculate MEOH viscosity, thermal
conductivity and surface tension. The predictions are in excellent agreement
with literature data[123-136] as shown in Figures 33-35.
Wilke-Chang model[143] is used to calculate the gas diffusivity in MEOH. The
model predictions are supported by CO2 diffusivity data from Littel et al.
(1991)[137] as shown in Figure 36.
Figures 1-36 show various property predictions in comparison to the available
literature data.

3 Physical Properties 7
 MEOH vapor pressure
100

10

Vapor pressure, bar

1
Data
0.1
PC-SAFT
0.01

0.001

0.0001

0.00001
150 250 350 450 550
Temperature, K

Figure 1. MEOH vapor pressure. PC-SAFT is used to fit data for methanol
generated from the DIPPR correlation[2].

MEOH liquid density

900
850
Liquid density, kg/m3

800
750
700 Data
650 PC-SAFT

600
550
500
150 250 350 450 550
Temperature, K

Figure 2. MEOH liquid density. PC-SAFT is used to fit data for methanol
generated from the DIPPR correlation[2].

8 3 Physical Properties
 MEOH liquid heat capacity
400000

Liquid heat capacity, J/kmol-K

350000
Experimental Data
300000
PC-SAFT
250000
200000
150000
100000
50000
0
150 250 350 450 550
Temperature, K

Figure 3. MEOH liquid heat capacity. PC-SAFT is used to fit experimental data
for methanol from literature[3-20].

MEOH heat of vaporization

4.50E+07
Heat of Vaporization, J/kmol

4.00E+07
3.50E+07
3.00E+07
2.50E+07 Experimental data
2.00E+07 PC-SAFT

1.50E+07
1.00E+07
150 250 350 450 550
T emperature, K

Figure 4. MEOH heat of vaporization. PC-SAFT is used to fit experimental

data for methanol from literature[21-37].

3 Physical Properties 9
 H2O vapor pressure
1.00E+08
1.00E+07

Vapor Pressure, N/sqm 1.00E+06

1.00E+05
1.00E+04
Data
1.00E+03
PC-SAFT
1.00E+02
1.00E+01
1.00E+00
250 350 450 550 650
Temperature, K

Figure 5. H2O vapor pressure. PC-SAFT is used to fit data for H2O generated
from the DIPPR correlation[2].

H2O liquid density

1100

1000
Liquid Density, kg/m3

900

800
Data
700 PC-SAFT

600

500
250 350 450 550 650
Temperature, K

Figure 6. H2O liquid density. PC-SAFT is used to fit data for H2O generated
from the DIPPR correlation[2].

10 3 Physical Properties
 H2O liquid heat capacity
4.00E+05

Liquid Heat Capacity, J/kmol-K

3.50E+05
Experimental Data
3.00E+05
PC-SAFT
2.50E+05
2.00E+05
1.50E+05
1.00E+05
5.00E+04
0.00E+00
200 300 400 500 600 700
Temperature, K

Figure 7. H2O liquid heat capacity. PC-SAFT is used to fit experimental data
for H2O from literature[38-66].

H2O heat of vaporiz ation

5.00E+07
4.50E+07
Heat of Vaporization, J/kmol

4.00E+07
3.50E+07
3.00E+07
2.50E+07 Experimental Data
2.00E+07 PC-SAFT
1.50E+07
1.00E+07
5.00E+06
0.00E+00
250 350 450 550 650
T emperature, K

Figure 8. H2O heat of vaporization. PC-SAFT is used to fit experimental data

for H2O from literature[67-81].

3 Physical Properties 11
 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 9. CO2 vapor pressure. PC-SAFT is used to fit data for CO2 generated
from the DIPPR correlation[2].

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 10. CO2 liquid density. PC-SAFT is used to fit data for CO2 generated
from the DIPPR correlation[2].

12 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 11. H2S vapor pressure. PC-SAFT is used to fit data for H2S generated
from the DIPPR correlation[2].

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 12. H2S liquid density. PC-SAFT is used to fit data for H2S generated
from the DIPPR correlation[2].

3 Physical Properties 13
 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 13. CO vapor pressure. PC-SAFT is used to fit data for CO generated
from the DIPPR correlation[2].

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 14. CO liquid density. PC-SAFT is used to fit data for CO generated
from the DIPPR correlation[2].

14 3 Physical Properties
 COS vapor pressure

60

Vapor pressure, bar

50
Data
40
PC-SAFT
30

20

10

0
130 180 230 280 330 380
Temperature, K

Figure 15. COS vapor pressure. PC-SAFT is used to fit data for COS
generated from the DIPPR correlation[2].

COS liquid density

1400
1300
Liquid density, kg/m3

1200
1100
1000
Data
900
PC-SAFT
800
700
600
130 180 230 280 330 380
Temperature, K

Figure 16. COS liquid density. PC-SAFT is used to fit data for COS generated
from the DIPPR correlation[2].

3 Physical Properties 15
 25 213.15 K (Schneider 1978)

213.15 K (Shenderei et al. 1959)

223.15 K (Takeeuchi et al. 1980)

20
228.15 K (Schneider 1978)

228.15 K (Shenderei et al. 1959)

230 K (Hong et al. 1988)

15
Pressure, bar
233.15 K (W eber et al. 1984)

237.15 K (Schneider 1978)

237.15 K (Shenderei et al. 1959)

10
243.15 K (Chang et al. 1985)

247.15 K (Schneider 1978)

247.15 K (Shenderei et al. 1959)

5
248.15 K (Takeeuchi et al. 1980)

248.15 K (W eber et al. 1984)

253.15 K (W eber et al. 1984)

0
258 K (Ferrell et al. 1979)
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
258.15 K (Chang et al. 1985)
CO2 Mole Fraction in Liquid Phase

Figure 17. Vapor-liquid equilibria of CO2-MEOH at the temperature from

213.15 K to 258.15 K, experimental data[82-88] used in the regression.

70

60

50
Pressure, bar

40

30 273.15 K (Chang et al. 1985)

273.15 K (Schneider 1978)
273.15 K (Takeeuchi et al. 1980)
20 273.15 K (W eber et al. 1984)
273.15 K (Krichevskii et al. 1947)
298.15 K (Chang et al. 1985)
10 298.15 k (W eber et al. 1984)
298.15 K (Brunner et al. 1987)
298.15 K ((Krichevskii et al. 1947)
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CO2 Mole Fraction in Liquid Phase

Figure 18. Vapor-liquid equilibria of CO2-MEOH at the temperature 273.15 K

and 298.15 K, experimental data[82,84,86,88,89] used in the regression.

16 3 Physical Properties
 1000

248.15 K (Yorizane et al. 1969)

253.15 K (Preus s et al. 1990)

258.15 K (Yorizane et al. 1969)

100
263.15 K (Short et al. 1983)

273.15 K (Yorizane et al. 1969)

273.15 K (Preus s et al. 1990)

Pressure, bar

293.15 K (Preus s et al. 1990)

10 298.15 K (Short et al. 1983)

298.15 K (Fis cher et al. 2002)

323.15 K (Preus s et al. 1990)

343.15 K (Preus s et al. 1990)

1 348.15 K (Leu et al. 1992)

363.15 K (Preus s et al. 1990)

393.15 K (Preus s et al. 1990)

398.15 K (Leu et al. 1992)

0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
H2S Mole Fraction in Liquid Phase

Figure 19. Vapor-liquid equilibria of H2S-MEOH at the temperature from

248.15 K to 398.15 K, experimental data[90-94] used in the regression.

10000

298 K (Tonner et al. 1983)

298.15 K (Brunner et al. 1987)

298.15 K (Krichevs kii et al. 1937)

323 K (Tonner et al. 1983)

1000
323.15 K (Brunner et al. 1987)
Pressure, bar

363.15 K (Krichevs kii et al. 1937)

373.15 K (Brunner et al. 1987)

398.15 K (Brunner et al. 1987)

100 413.15 K (Krichevs kii et al. 1937)

423.15 K (Brunner et al. 1987)

448.15 K (Brunner et al. 1987)

473.15 K (Brunner et al. 1987)

498.75 K (Brunner et al. 1987)

10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
CO Mole Fraction in Liquid Phase

Figure 20. Vapor-liquid equilibria of CO-MEOH at the temperature from 298 K

to 498.75 K, experimental data[89, 95,96] used in the regression.

3 Physical Properties 17
 350
223.15 K (W eber et al. 1984)

225 K (W eber et al. 1984)

300
240 K (Zeck 1984)

248.15 K (W eber et al. 1984)

250 250 K (W eber et al. 1984)

Pressure, bar 260 K (Zeck 1984)

200 273.15 K (W eber et al. 1984)

273.15 K (Krichevskii et al. 1947)

275 K (W eber et al. 1984)

150
300 K (W eber et al. 1984)

100

50

0
0 0.01 0.02 0.03 0.04 0.05
N2 Mole Fraction in Liquid Phase

Figure 21. Vapor-liquid equilibria of N2-MEOH at the temperature from

223.15 K to 300 K, experimental data[86,97,98] used in the regression.

10000

1000

298.15 K (Brunner et al. 1987)

Pressure, bar

298.15 K (Krichevskii et al. 1947)

100 298.15 K (Brass et al. 1982)

298.15 K (Krichevskii et al. 1951)
323.15 K (Brunner et al. 1987)
323.15 K (Krichevskii et al. 1947)
348.15 K (Brunner et al. 1987)
10
348.15 K (Krichevskii et al. 1947)
373.15 K (Brunner et al. 1987)

1
0 0.05 0.1 0.15 0.2 0.25
N2 Mole Fraction in Liquid Phase

Figure 22. Vapor-liquid equilibria of N2-MEOH at the temperature from

298.15 K to 373.15 K, experimental data[89,98-100] used in the regression.

18 3 Physical Properties
 3.00E-04

2.80E-04

2.60E-04

N2 Mole Fraction in Liquid Phase

2.40E-04
1 atm (Melzer 1990)
2.20E-04 1 atm (Kretschmer et al. 1946)
1 atm (PC-SAFT)
2.00E-04

1.80E-04

1.60E-04

1.40E-04

1.20E-04

1.00E-04
200 220 240 260 280 300 320 340
T emperature, K

Figure 23. Vapor-liquid equilibria of N2-MEOH at 1 atm total pressure,

experimental data[101,102] used in the regression.

12

233.2 K (Oscarson et al. 1987)

10 253.2 K (Oscarson et al. 1987)
253.15 K (Kiryanova et al. 1967)
273.2 K (Oscarson et al. 1987)
273.15 k (Kiryanova et al. 1967)
8
293.2 K (Oscarson et al. 1987)
Pressure, bar

293.15 K (Kiryanova et al. 1967)

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
COS Mole Fraction in Liquid Phase

Figure 24. Vapor-liquid equilibria of COS-MEOH at the temperature from

233.2 K to 293.2 K, experimental data[103,104] used in the regression.

3 Physical Properties 19
 45

40

293 K (Choudhary et al. 1986)

35
308 K (Choudhary et al. 1986)

30 318 K (Choudhary et al. 1986)

Pressure, bar 328 K (Choudhary et al. 1986)
25

20

15

10

0
0 0.001 0.002 0.003 0.004 0.005 0.006 0.007
H2 Mole Fraction in Liquid Phase

Figure 25. Vapor-liquid equilibria of H2-MEOH at the temperature from 293 K

to 328 K, experimental data[105] used in the regression.

291 K (Wainwright et al. 1987)

2000 294.15 K (Krichevs kii et al. 1937)
297.55 K (Michels et al. 1953)
298.15 K (Brunner et al. 1987)
298.15 K (Krichevs kii et al. 1951)
1500 322.55 K (Michels et al. 1953)
323.15 K (Brunner et al. 1987)
Pressure,bar

363.15 K (Krichevs kii et al. 1937)

373.15 K (Brunner et al. 1987)
1000 413.15 K ( (Krichevs kii et al. 1937)

500

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0.22
H2 Mole Fraction in Liquid Phase

Figure 26. Vapor-liquid equilibria of H2-MEOH at the temperature from 291 K

to 413.15 K, experimental data[89,96,100,106,107] used in the regression.

20 3 Physical Properties
 600

200 K (Hong et al. 1987)

500 220 K (Hong et al. 1987)
250 K (Hong et al. 1987)
273.15 K (Hong et al. 1987)
400
290 K (Hong et al. 1987)
Pressure, bar
310 K (Hong et al. 1987)
300 330 K (Hong et al. 1987)

200

100

0
0 0.05 0.1 0.15 0.2 0.25 0.3
CH4 Mole Fraction in Liquid Phase

Figure 27. Vapor-liquid equilibria of CH4-MEOH at the temperature from 200

K to 330 K, experimental data[108] used in the regression.

140
298.15 K (Yarym et al. 1985)
120 313.15 K (Yarym et al. 1985)
338.15 K (Yarym et al. 1985)
100
Pressure,bar

80

60

40

20

0
0 0.02 0.04 0.06 0.08 0.1 0.12
CH4 Mole Fraction in Liquid Phase

Figure 28. Vapor-liquid equilibria of CH4-MEOH at the temperature from

298.15 K to 338.15 K, experimental data[109] used in the regression.

3 Physical Properties 21
 10 273.15 K (Pierotti et al. 1959)

283.15 K (Pierotti et al. 1959)

292.35 K (Pierotti et al. 1959)

298.14 K (Kooner et al. 1980)

1 298.15 K (Pierotti et al. 1959)

298.15 K (Bader et al. 1996)

298.15 K (Hall et al. 1979)

Total Pressure, bar

308.15 K (McGlas han et al. 1976)

0.1 313.15 K (Pierotti et al. 1959)

318.15 K (Yao et al. 1999)

323.15 K (Kurihara et al. 1995)

323.15 K (McGlas han et al. 1976)

0.01 328.15 K (Kurihara et al. 1995)

333.15 (Kurihara et al. 1995)

333.15 K (Lee et al. 2000)

333.15 K (Pierotti et al. 1959)

0.001 338.15 K (McGlas han et al. 1976)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 338.15 K (Nagatani et al. 2000)

Methanol Mole Fraction in Liquid Phase

Figure 29. Vapor-liquid equilibrium of H2O-methanol at the temperature from

273.15 K to 338.15 K, experimental data[110-118] used in the regression.

10
Total Pressure, bar

1
343.15 K (Nagatani et al. 2000)
353.15 K (Bao et al. 1995)
353.15 K (Pierotti et al. 1959)
373.1 K (Albert et al. 1996)
373.15 K (Bao et al. 1995)
388.15 K (Bao et al. 1995)
403.15 K (Bao et al. 1995)
0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Methanol Mole Fraction in Liquid Phase

Figure 30. Vapor-liquid equilibrium of H2O-methanol at the temperature from

343.15 K to 403.15 K, experimental data[110, 118-120] used in the regression.

22 3 Physical Properties
 10

x=0.00005 (Christensen 1998)

x=0.00006 (Christensen 1998)

x=0.00005 Est.
1
Total Pressure, bar

0.1

0.01
320 330 340 350 360 370 380 390
Te mpe rature , K

Figure 31. Vapor-liquid equilibrium of H2O-methanol at 0.00005 and 0.00006

mole fraction of methanol in the liquid phase, experimental data[121] used in
the regression.

380

370
1 bar (Khalfaoui et al. 1997)

1 bar Est.
Temperature, K

360

350

340

330
0 0.2 0.4 0.6 0.8 1
M e thanol M ole Fraction in Liquid Phase

Figure 32. Vapor-liquid equilibrium of H2O-methanol at 1 bar total pressure,

experimental data[122] used in the regression.

3 Physical Properties 23
 MEOH liquid viscosity

0.1
Data
DIPPR
Viscosity, Pa.s
0.01

0.001

0.0001
150 200 250 300 350
Temperature, K

Figure 33. MEOH liquid viscosity. Comparison of literature data[123-127] to

calculation results of the DIPPR correlation model[2].

MEOH liquid thermal conductivity

0.25
Thermal conductivity, W/m-K

0.2

Data
DIPPR

0.15
200 250 300 350 400
Temperature, K

Figure 34. MEOH liquid thermal conductivity. Comparison of literature

data[128-131] to calculation results of the DIPPR correlation model[2].

24 3 Physical Properties
 MEOH surface tension

0.1

Surface tension, N/M

0.01

0.001 Data
DIPPR

0.0001
250 300 350 400 450 500 550
Temperature, K

Figure 35. MEOH liquid surface tension. Comparison of literature

data[125,132-136] to calculation results of the DIPPR correlation model[2].

Diffusivity of CO2 in MEOH

Data
Diffusivity (m2/s)*E9

6 Wilke-Chang

0
250 275 300 325 350
Temperature, K

Figure 36. CO2 diffusivity in MEOH. Comparison of experimental data[137] to

calculation results of the Wilke-Chang model[143].

Table 3 presents additional comparisons of published gas solubility data in

methanol[140-142] with the predictions of PC-SAFT. As the solubility data is
reported in volume units by Burr and Lyddon[142], we convert the mole-

3 Physical Properties 25
 fraction-based solubility predicted with PC-SAFT into the result in volume
units. The required molar volume for gases is predicted with PC-SAFT at 0 C
temperature and 1 atm pressure while the molar volume of methanol is
estimated at -25 C and the specified pressure.

Table 3. Solubilities of Selected Gases in Methanol (-25C)

in Volume Gas/Volume Solvent
[140-142] [142]
Gas Specified Pressure Data P-R Polar This Model
CO2 1 atm 13.46 13.24 12.91
*
H2 1 atm 0.073 0.069 0.062
*
CO 1 atm 0.269 0.135 0.239
CH4 1 atm 0.686* 0.727 0.775
*
COS 1 atm 52.75 56.76 56.89
**
H2S 2 atm 147 172.3 167.9
* Data are calculated from 13.46[140] and solubility ratio relative to CO2 of
each gas [140] by Burr and Lyddon[142].
** Data at -25C and 2 atm from Rousseau et al. (1981)[141]
The solubilities of various gases in methanol relative to that of CO2 at -25C
have been reported in the literature[140] but the pressure is not specified. We
report the predicted solubility ratio relative to CO2 at 1 atm in Table 4.

Table 4. Relative Solubilities of Gases in Methanol at -

25C
Gas Data Relative to CO2[140] This Model (relative to CO2)
H2 0.0054 0.0048
N2 0.012 0.012
CO 0.02 0.0185
CH4 0.051 0.060
CO2 1.0 1.0
COS 3.92 4.41
H2S 7.06 5.14

26 3 Physical Properties
4 Simulation Approach

Run 35I of the pilot absorber[1] is used in this work.

Simulation Flowsheet The pilot absorber has been modeled with the
following simulation flowsheet in Aspen Plus as shown in Figure 37.

GASOUT

LEANIN
ABSORBER

GASIN

RICHOUT

Figure 37. Rate-Based MEOH Flowsheet in Aspen Plus

4 Simulation Approach 27
 Unit Operations - The unit operation in this model has been represented by
an Aspen Plus block as outlined in Table 5.

Table 5. Aspen Plus Unit Operation Block Used in the

Rate-Based MEOH Model
Unit Operation Aspen Plus Block Comments / Specifications

Absorber RadFrac 1. Calculation type: Rate-Based

2. Number of Stages: 10
3. Top Pressure: 400psia
4. Packing: 6.25mm (0.25in) ceramic Intalox saddles
5. Packing Height: 0.45m* (1.5ft)
6. Mass transfer coefficient method: Onda (1968)
7. Interfacial area method: Onda (1968)
8. Interfacial area factor: 1
9. Film resistance option: Film for liquid and vapor
10. Flow model: Countercurrent

* The nominal packing height 2.2 m (7.1 ft) of the column used in the
experiments was found to be too high and no absorption was detected above
certain height of the packing[1]. Liquid and gas samples were taken at the
height of 1.5 m (5 ft) from the bottom as liquid feed and gas product. For the
case presented in Table 2, the effective packing height 0.45 m (1.5 ft) is used
instead of the real height 2.2 m (7.1 ft) in this simulation model and this
effective height was also used in the literature model[1].
Streams - Feeds to the Rate-Based MEOH model are gas stream GASIN
containing H2, CO2, CO, N2, CH4, H2S, and COS and liquid solvent stream
LEANIN containing pure MEOH solvent. Feed conditions are summarized in
Table 6.

Table 6. Feed specification

Stream ID GASIN LEANIN
Substream: MIXED
Temperature: F 53.9 -34.7
Pressure: psia 400 400
Mole-flow: lbmol/hr
MEOH 0 8.29
CO2 0.608109 0.0
H2S 0.01752 0.0
CO 0.438551 0.0
N2 0.340854 0.0
COS 0.000977 0.0
H2 0.720569 0.0
CH4 0.043421 0.0
HCN 0 0

28 4 Simulation Approach
5 Simulation Results

The simulation was performed using Aspen Plus V8.4. Key simulation results
are presented in Table 7 and Figure 38. To illustrate the effectiveness of the
rate-based approach, simulation results for the absorber using the equilibrium
stage calculation type are also shown in Figure 38.

Table 7. Key Simulation Results

Measurement Rate-Based MEOH model
Temperature of RICHOUT, F 0.7 -3.4
CO2 mole percents in GASOUT 0.95 4.67
H2S mole percents in GASOUT 0.037 0.015
CO mole percents in GASOUT 27.85 26.61
N2 mole percents in GASOUT 23.23 21.01
COS mole percents in GASOUT 0.003 0.0018
H2 mole percents in GASOUT 45.50 45.30
CH4 mole percents in GASOUT 2.44 2.39

5 Simulation Results 29
 1.5

Data
1.2
RateSep

Packing Height, ft
Equilibrium Stages

0.9

0.6

0.3

0
-45 -35 -25 -15 -5 5 15
Te mpe rature , F

Figure 38. Absorber Liquid Temperature Profile

30 5 Simulation Results
6 Conclusions

The Rate-Based MEOH model provides a rate-based rigorous simulation of the

process. Key features of this rigorous simulation include the PC-SAFT
equation of state model for vapor pressure, liquid density, and phase
equilibrium; rigorous transport property modeling; and rate-based multi-
stage simulation with Aspen Rate-Based Distillation which incorporates heat
and mass transfer correlations accounting for column specifics and hydraulics.
The model is meant to be used as a guide for modeling the CO2 capture
process with MEOH. You may use it as a starting point for more sophisticated
models for process development, debottlenecking, and plant and equipment
design, among other purposes.

6 Conclusions 31
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