CO2 Conditioning for Transport and
Storage
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Inc., Bedford, MA.
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Contents
1 Background .......................................................................................... 3
2 Process Description ................................................................................ 3
3 Physical Properties ................................................................................. 4
4 Simulation Results ................................................................................. 7
5 Conclusion ............................................................................................ 9
References ............................................................................................... 11
2
1 Background
CO2 conditioning is the process to remove impurities and compress or liquefy CO2 to
achieve transport or storage specifications. This Aspen Plus example models the CO2
conditioning process including dehydration, compression, and catalytic oxidation. The
Cubic Plus Association (CPA) equation of state is used for the physical property
calculation. This example can be used as a starting point for more complex model
development, process design, and optimization.
2 Process Description
This example is developed for CO2 conditioning based on a design case from the work
of Bilsbak [1]. The flowsheet is shown in Figure 1.
Figure 1. CO2 conditioning flowsheet in Aspen Plus
The CO2 stream (0.8 bar and 49°C) emitted from a coal power plant using pre-
combustion capture [2] contains water, H2S, and other impurities. It must be further
processed to remove major impurities and achieve required qualities and conditions
for transportation and storage.
Most of the water is removed by compression and flashing. The solubility of water in
gaseous CO2 decreases with increasing pressures. When the gas is compressed and
cooled, water condenses and is removed from the gas in the separator drum. After
three stages of compression, the pressure of the CO2 stream increases to about 50
bar and the water concentration reduces to around 1000 ppm. However, water
solubility begins to increase between 50 and 65 bar (see the data in Figure 4);
therefore, additional drying is needed.
Further dehydration can be done by absorption using glycol solvents. Water is
absorbed by triethylene glycol (TEG) in the absorber, and its concentration is reduced
to below 50 ppm to meet the requirement for transportation. The used TEG solvent
is then regenerated in the regenerator and recirculated to the absorber. A fraction of
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CO2 is also absorbed by TEG and retrieved in the regenerator, so the gas stream from
the regenerator is sent back to the first compressor for CO2 recovery.
The other impurities, H2S, CO and H2, are removed by catalytic oxidation. The stream
from the first compressor is fed into a selective catalytic oxidizer, where most of the
H2S is removed by reacting with metal oxide catalyst (equation 1). CO, H2, and the
remaining H2S are removed by oxygen oxidation in another catalytic reactor
(equations 2 to 5).
+ = + (1)
2 + =2 (2)
2 + =2 (3)
2 +3 =2 +2 (4)
2 2 + 2 =2 3 (5)
The treated gas from the TEG absorber is finally compressed and pumped to 110 bar
for transportation.
3 Physical Properties
REFPROP [3] and GERG2008 [4] are well known property methods for gas processing,
however, they don’t support TEG for dehydration. In this work, we use the CPA
equation of state [5] throughout the model to calculate pure component and mixture
properties as well as phase equilibrium. All the pure and binary parameters are
validated and stored in the Aspen Databank.
The pure CO2 density and heat capacity are validated up to 500 bar, as shown in
Figures 2 and 3. The results of the three methods are very close and comparable to
the NIST data ([Link]
4
1.0E+03
1.0E+02
Density, kg/cum
1.0E+01
NIST, 320K CPA, 320K
REFP, 320K GERG, 320K
1.0E+00
1.0E+00 1.0E+01 1.0E+02
Pressure, bar
Figure 2. Pure CO2 density
450
400 NIST, 320K GERG, 320K
350
REFP, 320K CPA, 320K
Heat capacity,J/mol.K
300
250
200
150
100
50
0
1.0E+00 1.0E+01 1.0E+02
Pressure, bar
Figure 3. Pure CO2 heat capacity
The phase equilibria of CO2-H2O are investigated in Figures 4 and 5. CPA and
REFPROP match the experimental data [6] well while GERG2008 under-estimates the
water solubility at high pressures, where it predicts much lower CO2 solubility.
5
0.01
Data CPA
0.008
GERG REFP
H2O molefrac
0.006
0.004
0.002
0
0 50 100 150 200 250 300
Pressure, bar
Figure 4. H2O solubility in CO2-rich phase at 25 °C
0.1
CO2 molefrac
0.01
0.001
0.0001 Data CPA
GERG REFP
0.00001
0 50 100 150 200 250 300
Pressure, bar
Figure 5. CO2 solubility in aqueous phase at 25 °C
The vapor liquid equilibria of TEG-H2O and TEG-CO2 are also plotted in Figures 6 and
7 and match the experimental data well [7, 8].
6
300
280 Data
260 CPA
240
Temperature, C
220
200
180
160
140
120
100
0.6 0.7 0.8 0.9 1
TEG mole fraction
Figure 6. Vapor liquid equilibrium of TEG and Water at 1 bar
1.0E+03
1.0E+02
Total pressure, bar
1.0E+01
323K, data 323K, CPA
1.0E+00
0 0.1 0.2 data
348K, 0.3348K, CPA 0.4
373K, data 373K, CPA
1.0E-01
CO2 mole fraction
Figure 7. Vapor liquid equilibrium of TEG and CO2
4 Simulation Results
Case C1a in the literature [1] is closely simulated and the operating conditions are
chosen to be as close to those used in the literature.
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The key specifications and results of the compressors and pumps are summarized in
Tables 1-2.
Table 1. Specifications of compressors and pumps
Block ID Aspen Plus Block Specifications
COMP1 Compr Pressure increase 3 bar, polytropic efficiencies 0.85
COMP2 Compr Pressure increase 10 bar, polytropic efficiencies 0.85
COMP3 Compr Pressure increase 39 bar, polytropic efficiencies 0.80
COMP4 Compr Pressure increase 22 bar, polytropic efficiencies 0.70
PUMP1 Pump Pressure increase 43 bar, efficiencies 0.75
Table 2. Key results of compressors and pumps
Block ID Work, kJ/kg CO2
COMP1 132.98
COMP2 100.82
COMP3 108.22
COMP4 21.57
PUMP1 7.59
The hot stream outlet temperature is set to 22°C for all intercoolers (from COOL1 to
COOL8). The other heat exchangers are specified in Table 3. Key results are shown
in Table 4.
Table 3. Specifications of heat exchangers
Block ID Aspen Plus Block Specifications
HX1 HeatX Cold stream outlet temperature 240°C
HX2 HeatX Cold stream outlet temperature 105°C
Table 4. Key results of intercoolers and heat exchangers
Block ID Heat duty, kJ/kg CO2 Cooling water, kg H2O/kg CO2
COOL1 59.46 2.07
COOL2 221.90 7.24
COOL3 114.81 4.14
COOL4 155.99 5.17
COOL5 211.39 6.20
COOL6 20.53 0.62
COOL7 0.96 0.03
COOL8 0.96 0.03
HX1 81.11
HX2 2.46
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The TEG absorber has 5 theoretical stages and the regenerator has 10 stages,
including the condenser and reboiler. The circulation rate of solvent is set to be about
20 liters of TEG per kg of water removed. Reboiler temperature is 204°C and the
reflux ratio is 1. The key results are shown in Table 5.
Table 5. Key results of TEG dehydration
Item Results
TEG reboiler duty, kJ/kg CO2 5.10
TEG condenser duty, kJ/kg CO2 -2.47
TEG circulation rate, L TEG/ kg H2O removed 20.41
CO2 concentration in treated gas 48 ppm
The catalytic reactions are complex, and the modeling of catalytic oxidizer is
simplified. The selective oxidizer is modeled with an RStoic reactor and a separator.
H2S reacts with the FeO catalyst in the reactor with a conversion efficiency set to
99.9 %. The product FeS is then removed in the separator. The remaining H 2S, CO,
and H2 are oxidized in another catalytic oxidizer modeled as an RGibbs reactor. The
hot stream exiting the catalytic oxidizer is used to preheat the stream entering the
selective oxidizer to 240°C.
The key results of the streams in the process are shown in Table 6.
Table 6. Results of key streams
Stream ID CO2FEED OXDPROD WETGAS TOTRAN
Temperature [C] 49 281.4 22.7 22
Pressure [bar] 0.8 3.7 50.7 110
Molar Flow [kmole/h] 1192.07 1155.64 1102.3 1099.56
Mass Flow [kg/h] 50000 49440.3 48476 48381.9
Composition [molefrac]
CO2 0.9217 0.9525 0.9985 0.9994
CO 0.0003 0 0 0
H2O 0.0656 0.0470 980 ppm 48 ppm
H2 0.0072 0 0 0
H2S 0.0049 0 0 0
SO2 0 0 0 0
SO3 0 5.5 ppm 5.7 ppm 5.3 ppm
N2 0.0003 0.0003 0.0003 0.0003
5 Conclusion
This work simulates the CO2 conditioning process in preparation for CO2
transportation and storage. The CPA EOS is validated for the key pure components
and mixtures in the system and utilized for property calculation and phase equilibria
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in compression, heat exchange, and TEG dehydration. Catalytic oxidation is also
simulated with a simplified model to remove the other impurities. Further research
can improve the catalytic oxidation reactor model as needed. This example is useful
as a starting point for more sophisticated model development for CO2 conditioning.
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References
[1] Bilsbak, V. Conditioning of CO2 coming from a CO2 capture process for rransport and
storage purposes, Master Thesis, Norwegian University of Science and Technology, 2009
[2] Potential for improvement in gasification combined cycle power generation with CO2
capture, IEA Greenhouse House gas R&D programme, 2003
[3] Lemmon E.W., Huber M.L., McLinden M.O. NIST Standard Reference Database 23:
Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 8.0, National
Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg,
2007
[4] Kunz, O. and Wagner W. The GERG-2008 Wide-Range Equation of State for Natural
Gases and Other Mixtures: An Expansion of GERG-2004. J. Chem. Eng. Data, 2012, 57,
3032-3091
[5] Kontogeorgis, G. M., Voutsas, E., Yakoumis, I, & Tassios, D.P. An Equation of State for
Associating Fluids. Ind. Eng. Chem. Res., 1996, 35, 4310
[6] Spycher, N., Pruess, K., Ennis-King, J. CO2-H2O mixtures in the geological
sequestration of CO2. I. Assessment and calculaion of mutual solubilities from 12 to 100 C
and up to 600 bar, Ceochimica et Cosmochimica Acta, 2003, 67, 3015-3031
[7] Glycol-Type Gas Dehydration and Hydrate Inhibition Systems, Shell DEP [Link]-
Gen, December 1994. DEP = Design and Engineering Practice
[8] Jou, F. Y., Deshmukh, R. D., Otto, F. D., Mather, A. E. Vapor-liquid equilibria for acid
gases and lower alkanes in triethylene glycol, Fluid Phase Equilib., 1987, 36, 121-140
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