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Aspen Plus

Aspen Plus Model of the CO2 Capture Process by N-methyl 2-pyrrolidone

Copyright (c) 2008 by Aspen Technology, Inc. All rights reserved. Aspen Plus, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Burlington, MA. All other brand and product names are trademarks or registered trademarks of their respective companies. This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of the software and the application of the results obtained. Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE. Aspen Technology, Inc. 200 Wheeler Road Burlington, MA 01803-5501 USA Phone: (1) (781) 221-6400 Toll Free: (1) (888) 996-7100 URL: http://www.aspentech.com

Revision History
Version V7.0 V7.1 Description First version Re-verified simulation results using Aspen Plus V7.1

Revision History

Contents
Introduction ............................................................................................................3 1 Components .........................................................................................................4 2 Process Description..............................................................................................5 3 Physical Properties...............................................................................................7 4 Simulation Approaches.......................................................................................16 5 Simulation Results .............................................................................................19 6 Conclusions ........................................................................................................21 References ............................................................................................................22

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

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 CO2 H2S CO H2O CS2 NH3 N2 COS O2 SO2 SO3 CH3SH C2H5SH CH3SCH3 HCN H2 BENZENE CH4 C2H6 C2H4 C3H8 IC4H10 NC4H10 C2H2 C6H14 C7H16 NO2 NO AR

Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional

N-METHYL-2-PYRROLIDONE CARBON-DIOXIDE HYDROGEN-SULFIDE CARBON-MONOXIDE WATER CARBON-DISULFIDE AMMONIA NITROGEN CARBONYL-SULFIDE OXYGEN SULFUR-DIOXIDE SULFUR-TRIOXIDE METHYL-MERCAPTAN ETHYL-MERCAPTAN DIMETHYL-SULFIDE HYDROGEN-CYANIDE HYDROGEN BENZENE METHANE ETHANE ETHYLENE PROPANE ISOBUTANE N-BUTANE ACETYLENE N-HEXANE N-HEPTANE NITROGEN-DIOXIDE NITRIC-OXIDE ARGON

C5H9NO-D2 CO2 H2S CO H2O CS2 H3N N2 COS O2 O2S O3S CH4S C2H6S-1 C2H6S-2 CHN H2 C6H6 CH4 C2H6 C2H4 C3H8 C4H10-2 C4H10-1 C2H2 C6H14-1 C7H16-1 NO2 NO AR

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 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 NMP model, we used the operation data of the low pressure case.

2 Process Description

Table 2. Data of the Absorber


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

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 Henrys constants for CO2, H2S and SO2 with propylene carbonate and according to reference [9], CO2 solubility in propylene carbonate and in NMP are very similar in both the volume-solvent basis and the mole-solvent basis. So CO2 Henrys constant with propylene carbonate were used as a starting point to regress binary parameters between CO2 and NMP. Then CO2 solubility in NMP at 25C and 1atm was calculated using the binary parameters. Comparison of the calculated CO2 solubility and the literature data[9] supplies direction to adjust the Henrys constant data. Several iterations were made to get suitable Henrys 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 25C and 1atm. A diagram of the process is shown in Figure 1.

3 Physical Properties

CO2 Henrys constant data[8] with PC

Estimate CO2 Henrys constant with NMP

Regress kij between CO2 and NMP

Estimate CO2 solubility in NMP at 25C and 1atm

Match CO2 solubility Data[9] in NMP?

No

Yes Output CO2 Henrys constant and kij in NMP


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

Once Henrys constant for CO2 with NMP were figured out, solubility ratios[10] of the other gases to CO2 were used to determine their Henrys constants with NMP, with the assumption that solubility ratios are equivalent to Henrys constant ratios. Then these estimated Henrys constant 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.

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 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 DIPPR correlation[2] for NMP.

3 Physical Properties

CO2 vapor pressure 70 Vapor pressure, bar 60 50 40 30 20 10 0 200 220 240 260 280 300 320
Data PC-SAFT

Temperature, K
Figure 4. CO2 vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for CO2.

CO2 liquid density


1300 Liquid density, kg/m3 1200 1100 1000 900 800 700 600 500 200 220 240 260 280 300 320
Data PC-SAFT

Temperature, K
Figure 5. 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 Vapor pressure, bar 70 60 50 40 30 20 10 0 180 230 280


Temperature, K
Figure 6. H2S vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for H2S.
Data PC-SAFT

330

380

H2S liquid density


1100 Liquid density, kg/m3 1000 900 800 700 600 500 400 300 180 230 280 Temperature, K
Figure 7. H2S liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for H2S.
Data PC-SAFT

330

380

3 Physical Properties

11

CO vapor pressure

40 Vapor pressure, bar 35 30 25 20 15 10 5 0 70 90 110


Temperature, K
Figure 8. CO vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for CO.
Data PC-SAFT

130

CO liquid density
850 Liquid density, kg/m3 800 750 700 650 600 550 500 450 400 70 90 110 Temperature, K
Figure 9. CO liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for CO.
Data PC-SAFT

130

12

3 Physical Properties

NH3 vapor pressure

90 80 70 60 50 40 30 20 10 0 200

Vapor pressure, bar

Data PC-SAFT

250

300
Temperature, K

350

400

Figure 10. NH3 vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for NH3.

NH3 liquid density


750 Liquid density, kg/m3 700 650 600 550 500 450 400 200 250 300 Temperature, K
Figure 11. NH3 liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for NH3.
Data PC-SAFT

350

400

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 adjustable binary parameter.

VLE for H2S-NMP


0.005 Data PC-SAFT

Pressure, MPa
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 adjustable binary parameter.

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3 Physical Properties

Surface tension of NMP


0.06 0.05 Surface tension (N/m) 0.04 0.03 0.02 0.01 0 200 DIPPR Data

300

400

500

600

700

Temperature (K)

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

Viscosity of NMP
0.005 0.0045 0.004 Viscosity (Pa.s) 0.0035 0.003 0.0025 0.002 0.0015 0.001 0.0005 0 200 300 400 Temperature (K) 500 600 DIPPR Data

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

3 Physical Properties

15

Thermal conductivity of NMP 0.15 0.14 0.13 0.12 0.11 0.1 0.09 200 300 400 500 Temperature (K)
Figure 16. NMP liquid thermal conductivity. DIPPR correlation model[4] is used to fit data[6].
DIPPR Data

16

Thermal conductivity (W/m.K)

3 Physical Properties

4 Simulation Approaches

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 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 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.
GASOUT

LEANIN ABSORBER GASIN

RICHOUT

Figure 17. NMP Process Flowsheet in Aspen Plus

4 Simulation Approaches

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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 ABSORBER Aspen Plus Block RadFrac Comments / Specifications 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 NMP model is GASIN, containing CO, CO2, H2, H2O, N2, Ar, CH4, NH3, and H2S. The solvent liquid feeds 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 Substream: MIXED Temperature: F Pressure:psia Mole-flow: lbmol/hr NMP CO CO2 H2 H2O N2 AR CH4 NH3 H2S 0 77.37 4335.99 5611.86 61.91 7306.65 88.6 128.77 2.99 0.4 23000 0.0 395.00 0.0 2.25 0.0 0.0 0.0 0.0 0.0 68.13 248 30 250 GASIN LEANIN

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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 18 and 19, together with the simulation results of the DEPG model using the low pressure case operation data. As shown by Figures 18 and 19, with the same flow rate (23000lbmol/hr) and temperature (30F) for the fed solvent to the absorber, DEPG (Squares in Figures 18 and 19) has a much higher remove capacity than NMP (Solid lines in Figures 18 and 19). To achieve a similar CO2 removal to what DEPG does, NMP flow rate should be increased to about 50700lbmol/hr (Dashed Lines in Figures 18 and 19), which is about 2.2 times of DEPG flowrate. According to Table 1 in reference [9], at 25C, CO2 solubility is 0.485ft3/gallon DEPG and 0.477ft3/gallon propylene carbonate. At 25C, specific gravity is 1030kg/m3 for DEPG, whose molecular weight is 280, and 1027kg/m3 for propylene carbonate, whose molecular weight is 99. If transformed to a mole-solvent base, CO2 solubility in DEPG is about 2.9 times of the solubility in propylene carbonate at 25C
1 2 3 Sta g e N u mb e r 4 5 6 7 8 9 10 11 12 0 5 10 15 20 25 30 35 40 45 50 55 60 65 Te m p e ra tu re , F
DEPG 23000 30F NMP 23000 30F NMP 50700 30F

Figure 18. Absorber Temperature Profile

5 Simulation Results

19

1 2 3 4 Stage Number 5 6 7 8 9 10 11 12 0 0.05 0.1 0.15 0.2 0.25 0.3 CO 2 Mole F r ac tion DEPG 23000 30F NMP 23000 30F NMP 50700 30F

Figure 19. Absorber Vapor Phase CO2 Composition Profile

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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

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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, 569573 (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, 55105515 (2002)

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References