Aspen Plus

Aspen Plus Model of the CO2 Capture Process by

N-methyl 2-pyrrolidone
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Revision History
Version Description

V7.0 First version

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

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

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

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

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

4 Simulation Approach ..........................................................................................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 N-methyl 2-pyrrolidone(NMP) from a gas mixture of CO,
CO2, H2, H2O, N2, Ar, CH4, NH3, and H2S from gasification of Illinois No. 6
bituminous coal[1]. Due to lack of design data for NMP, 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 the process
model. Since only the equilibrium stage results for the DEPG design case are
available in the literature and the Aspen Plus DEPG model uses equilibrium
stage simulation, the process model developed here is also based on the
equilibrium stage distillation model instead of the more rigorous rate-based.
In addition to the gases present in the design case, many other gas
components such as COS, CH3SH and so on are also included in this model for
potential needs by model users. Pure and/or binary parameters have been
determined and included in the model for these compounds.
NMP data for vapor pressure[2], liquid density[2], viscosity[3-5], thermal
conductivity[6], and surface tension[4,7] 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)[8] between propylene carbonate and selected
components and solubility ratios[9,10] of gases in propylene carbonate and in
NMP are used to estimate vapor-liquid data between NMP and gas
components and then 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.

Table 1. Components Used in the Model

ID Type Name Formula
NMP Conventional N-METHYL-2-PYRROLIDONE C5H9NO-
D2
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
C6H14 Conventional N-HEXANE C6H14-1
C7H16 Conventional N-HEPTANE C7H16-1
NO2 Conventional NITROGEN-DIOXIDE NO2
NO Conventional NITRIC-OXIDE NO
AR Conventional ARGON AR

4 1 Components
2 Process Description

In this NMP 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 NMP
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 feed 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 shows some operation data. In
this NMP model, we used the operation data of the low pressure case.

2 Process Description 5
 Table 2. Operation 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

6 2 Process Description
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)[11,12]. The PC-SAFT pure
parameters for NMP have also been regressed to fit vapor pressure and liquid
density data from DIPPR correlations[2].
No vapor-liquid equilibrium data for the gases in NMP were found to regress
the PC-SAFT binary parameters. However, Xu et al. (1992)[8] reported Henry’s
constants for CO2, H2S and SO2 with propylene carbonate and according to
Ranke and Mohr (1985)[9], CO2 solubilities in propylene carbonate and in NMP
are very similar on both the volume-solvent basis and the mole-solvent basis.
So the Henry’s constant of CO2 with propylene carbonate was used as a
starting point to regress binary parameters between CO2 and NMP. Then CO2
solubility in NMP at 25ºC and 1atm was calculated using the binary
parameters. Comparison of the calculated CO2 solubility and the literature
data[9] supplies direction to adjust the Henry’s constant data. Several
iterations were made to get suitable Henry’s constant data for CO2 with NMP,
which can give suitable binary parameters between CO2 and NMP, allowing
accurate estimation of CO2 solubility in NMP at 25ºC and 1atm. A diagram of
the process is shown in Figure 1.

3 Physical Properties 7
 CO2 Henry’s constant data[8]
with PC

Estimate CO2 Henry’s

constant with NMP

Regress kij between CO2

and NMP

Estimate CO2 solubility in

NMP at 25°C and 1atm

Match No
CO2 solubility Data[9]
in NMP?

Yes

Output CO2 Henry’s

constant and kij in NMP

Figure 1. Diagram of estimation process of PC-SAFT binary parameter for CO2

and NMP.
Once the Henry’s constant for CO2 with NMP was determined, solubility
ratios[10] of the other gases to CO2 were used to determine their Henry’s
constants with NMP, with the assumption that solubility ratios are equivalent
to Henry’s constant ratios. Then these estimated Henry’s constants served to
regress binary parameters between these gas components and NMP.
DIPPR model parameters for NMP are regressed to fit data for viscosity[3-5],
thermal conductivity[6] and surface tension[4,7].
Figures 2-16 show property predictions together with literature data.

8 3 Physical Properties
 NMP vapor pressure

1.00E+02

Vapor Presure, bar 1.00E+00 Data

PC-SAF

1.00E-02

1.00E-04

1.00E-06
0 200 400 600 800

Temperature, K

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

NMP liquid density

1200
Liquid density, kg/m3

1000

800
Data
PC-SAF

600
100 200 300 400 500 600

Temperature, K

Figure 3. NMP liquid density. PC-SAFT is used to fit data from the DIPPR
correlation[2] for NMP.

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 4. CO2 vapor pressure. PC-SAFT is used to fit data generated from the
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 5. CO2 liquid density. PC-SAFT is used to fit data generated from the
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 6. H2S vapor pressure. PC-SAFT is used to fit data generated from the
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 7. H2S liquid density. PC-SAFT is used to fit data generated from the
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 8. CO vapor pressure. PC-SAFT is used to fit data generated from the
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 9. CO liquid density. PC-SAFT is used to fit data generated from the
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 10. NH3 vapor pressure. PC-SAFT is used to fit data generated from
the 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 11. NH3 liquid density. PC-SAFT is used to fit data generated from the
DIPPR correlation[2] for NH3.

3 Physical Properties 13
 VLE for CO2-NMP

0.015

Pressure, MPa
0.01

0.005
Data
PC-SAFT

0
290 300 310 320 330 340 350

Temperature, K

Figure 12. Vapor-liquid equilibria of CO2-NMP. Comparison of estimated data

to calculation results of PC-SAFT with an adjustable binary parameter.

VLE for H2S-NMP

0.005

Data
Pressure, MPa

PC-SAFT

0
290 300 310 320 330 340 350

Temperature, K

Figure 13. Vapor-liquid equilibria of H2S-NMP. Comparison of estimated data

to calculation results of PC-SAFT with an adjustable binary parameter.

14 3 Physical Properties
 Surface tension of NMP

0.06

0.05 DIPPR
Surface tension (N/m) Data
0.04

0.03

0.02

0.01

0
200 300 400 500 600 700
Temperature (K)

Figure 14. NMP liquid surface tension. The DIPPR correlation model[4] is used
to fit data[4,7].

Viscosity of NMP

0.005
0.0045
DIPPR
0.004
Data
0.0035
Viscosity (Pa.s)

0.003
0.0025
0.002
0.0015
0.001
0.0005
0
200 300 400 500 600
Temperature (K)

Figure 15. NMP liquid viscosity. The DIPPR correlation model[4] is used to fit
data[3-5].

3 Physical Properties 15
 Thermal conductivity of NMP

0.15

Thermal conductivity (W/m.K)

0.14
DIPPR
Data
0.13

0.12

0.11

0.1

0.09
200 300 400 500
Temperature (K)

Figure 16. NMP liquid thermal conductivity. The DIPPR correlation model[4] is
used to fit data[6].

16 3 Physical Properties
4 Simulation Approach

As stated in the previous sections, this NMP 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 the solvent flow rate was adjusted
to reach the same amount of CO2 captured as occurs with DEPG.
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 a
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 packing design
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.

GASOU T

LEANIN

ABSORBER

GASIN

RIC HOUT

Figure 17. NMP Process Flowsheet in Aspen Plus

4 Simulation Approach 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

NMP 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 feed of the NMP model is GASIN, containing CO, CO2, H2,
H2O, N2, Ar, CH4, NH3, and H2S.
The solvent liquid feed is LEANIN, containing NMP 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
NMP 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 Approach
5 Simulation Results

The simulation was performed using Aspen Plus with the absorber calculation
type set to Equilibrium. Key simulation results are presented in Figures 18
and 19, together with the simulation results of the DEPG model using
operation data from the low pressure case.
As shown by Figures 18 and 19, with the same flow rate (23000lbmol/hr) and
temperature (30F) for the solvent fed to the absorber, DEPG (squares in
Figures 18 and 19) has a much higher removal capacity than NMP (solid lines
in Figures 18 and 19). To achieve a similar CO2 removal to DEPG, the NMP
flow rate should be increased to about 50700lbmol/hr (dashed lines in Figures
18 and 19), which is about 2.2 times the DEPG flowrate.
According to Table 1 in reference [9], at 25ºC, CO2 solubility is
0.485ft3/gallon DEPG and 0.477ft3/gallon propylene carbonate. At 25ºC,
specific gravity is 1030kg/m3 for DEPG, whose molecular weight is 280, and
1027kg/m3 for propylene carbonate, whose molecular weight is 99. In a mole-
solvent basis, CO2 solubility in DEPG is about 2.9 times the solubility in
propylene carbonate at 25ºC

1
2
3
4
Stage Number

5
6
7
8 DEPG 23000 30F
9
NMP 23000 30F
10
NMP 50700 30F
11
12
0 5 10 15 20 25 30 35 40 45 50 55 60 65

Temperature, F

Figure 18. Absorber Temperature Profile

5 Simulation Results 19
 1
2
3
4

Stage Number
5
6
7
8 DEPG 23000 30F
9
NMP 23000 30F
10
11 NMP 50700 30F

12
0 0.05 0.1 0.15 0.2 0.25 0.3

CO2 Mole Fraction

Figure 19. Absorber Vapor Phase CO2 Composition Profile

20 5 Simulation Results
6 Conclusions

The NMP model provides an equilibrium stage simulation of the process and
validated 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 NMP. Users 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 Divison, Argonne National Laboratory (1994)
[2] DIPPR® 801 database, BYU-Thermophysical Properties Laboratory (2007)
[3] V.A. Granzhan, O.G. Kirillova, "Physico-Chemical Analysis of the System
n-Methyl-alpha-Pyrrolidone-Methanol," J. Appl. Chem. USSR, 43, 1898 (1970).
[4] M-Pyrol Handbook, GAF Corporation, New York (1972)
[5] J.A. Riddick, W.B. Bunger, "Organic Solvents: Physical Properties and
Methods of Purification, 3rd ed., " Wiley Interscience, New York (1970)
[6] 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)
[7] S. Sugden, "The Variation of Surface Tension with Temperature and Some
Related Functions," J. Chem. Soc. (London, Transactions), 125, 32 (1924)
[8] 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)
[9] 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)
[10] 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.)
[11] 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)
[12] J. Gross, G. Sadowski, “Application of the Perturbed-Chain SAFT
Equation of State to Associating Systems”, Ind. Eng. Chem. Res., 41, 5510-
5515 (2002)

22 References