Aspen Plus

Rate-Based Model of the CO2 Capture Process by Methanol using Aspen Plus

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Contents
Introduction ............................................................................................................2 1 Components .........................................................................................................3 2 Process Description..............................................................................................4 3 Physical Properties...............................................................................................6 4 Simulation Approaches.......................................................................................15 5 Simulation Results .............................................................................................17 6 Conclusions ........................................................................................................18 References ............................................................................................................19

Contents

Introduction

This document describes an Aspen Plus rate-based model of the CO2 capture process by methanol (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. Thermophysical property models have been validated against DIPPR correlations[2] for component vapor pressure and liquid density, and literature data for vapor-liquid equilibrium from Semenova (1979)[3] and Leo(1992)[4]. Transport property models have been validated against literature data for viscosity[5-9], thermal conductivity[10-13] , surface tension[7, 14-18], and diffusivity[19]. 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

Introduction

1 Components

The following components represent the chemical species present in the process:

Table 1. Components Used in the Model

ID MEOH CO2 H2S CO N2 COS H2 CH4 Type CONV CONV CONV CONV CONV CONV CONV CONV Name METHANOL CARBON-DIOXIDE HYDROGEN-SULFIDE CARBON-MONOXIDE NITROGEN CARBONYL-SULFIDE HYDROGEN METHANE Formula CH4O CO2 H2S CO N2 COS H2 CH4

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

Table 2. Data of the Absorber from the Pilot Plant [1]

Absorber Diameter Nominal Packing Height Packing Type Packing Size Sour Gas Flow rate CO2 in Sour Gas H2S in Sour Gas Sweet Gas CO2 in Sweet Gas H2S in Sweet Gas Lean MEOH Flow rate Temperature Pressure 8.29lbmol/hr -34.7F 400psia** 0.0095 (mole fraction) 0.00037 (mole fraction) 2.17 lbmol/hr 0.2801(mole fraction) 0.00807(mole fraction)
*

0.127 m 2.2 m ceramic Intalox saddles 6.25 mm(0.25 in)

* The column was found to be too high for the experiments and no absorption was detected above certain height of the packing [1]. Liquid and gas samples were taken at the height of 1.5m from the bottom as liquid feed and gas product. Therefore, effective packing height (1.5m), is used instead of the real height (2.2m) in this simulation model. 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]

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 CO2, H2S, CO and COS have been regressed against vapor pressure and liquid density data generated from DIPPR correlations[2] for each component. For all other components, the PC-SAFT pure component parameters are taken from the work by Gross and Sadowski (2001, 2002)[20,21]. The binary parameters between CO2 and MEOH and H2S and MEOH have been regressed against vapor-liquid equilibrium data from Semenova (1979)[3] and Leu (1992)[4]. DIPPR correlation models[2] are used to calculate MEOH viscosity, thermal conductivity and surface tension, respectively; the predictions are in excellent agreement with literature data[5-18] as showed in Figures 13-15. Wilke-Chang model[22] is used for calculating the gas diffusivity in MEOH. The model quality has been justified by CO2 diffusivity data from Littel (1991)[19] as showed in Figure 16. Figures 1-16 show property predictions together with literature data.

3 Physical Properties

MEOH vapor pressure 100 Vapor pressure, bar 10 1 0.1 0.01 0.001 0.0001 0.00001 150 250 350 Temperature, K
Figure 1. MEOH vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for methanol.
Data PC-SAFT

450

550

MEOH liquid density

1000 Liquid density, kg/m3 900 800 700 600 500 400 300 150 250 350 Temperature, K
Figure 2. MEOH liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for methanol.
Data PC-SAFT

450

550

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

3 Physical Properties

H2S vapor pressure

80 Vapor pressure, bar 70 60 50 40 30 20 10 0 180 230 280

Temperature, K
Figure 5. 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 6. 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

CO vapor pressure

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

Temperature, K
Figure 7. 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 8. CO liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for CO.
Data PC-SAFT

130

10

3 Physical Properties

COS vapor pressure

60 Vapor pressure, bar 50 40 30 20 10 0 130 180 230 280 330 380

Data PC-SAFT

Temperature, K
Figure 9. COS vapor pressure. PC-SAFT is used to fit data generated from DIPPR correlation[2] for COS.

COS liquid density

1400 Liquid density, kg/m3 1300 1200 1100 1000 900 800 700 600 130 180 230 280 330 380
Data PC-SAFT

Temperature, K
Figure 10. COS liquid density. PC-SAFT is used to fit data generated from DIPPR correlation[2] for COS.

3 Physical Properties

11

Figure 11. Vapor-liquid equilibria of CO2-MEOH at three temperatures. Comparison of experimental data[3] to calculation results of PC-SAFT with adjustable binary parameter.

Figure 12. Vapor-liquid equilibria of H2S-MEOH at three temperatures. Comparison of experimental data[4] to calculation results of PC-SAFT with adjustable binary parameter.

12

3 Physical Properties

MEOH liquid viscosity 0.1

Data DIPPR

Viscosity, Pa.s

0.01

0.001

0.0001 150

200

250 Temperature, K

300

350

Figure 13. MEOH liquid viscosity. Comparison of literature data[5-9] to calculation results of DIPPR correlation model[2].

MEOH liquid thermal conductivity Thermal conductivity, W/m-K 0.25

0.2
Data DIPPR

0.15 200

250

300 Temperature, K

350

400

Figure 14. MEOH liquid thermal conductivity. Comparison of literature data[10-13] to calculation results of DIPPR correlation model[2].

3 Physical Properties

13

MEOH surface tension

0.1

Surface tension, N/M

0.01

0.001

Data DIPPR

0.0001 250 300 350 400 Temperature, K 450 500 550

Figure 15. MEOH liquid surface tension. Comparison of literature data[7,14-18] to calculation results of DIPPR correlation model[2].

Diffusivity of CO2 in MEOH

8 Data Diffusivity (m2/s)*E9 6 Wilke-Chang

0 250 275 300 Temperature, K 325 350

Figure 16. CO2 diffusivity in MEOH. Comparison of experimental data[19] to calculation results of Wilke-Chang model[22].

14

3 Physical Properties

4 Simulation Approaches

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 17.

GASOUT

LEANIN ABSORBER

GASIN

RICHOUT

Figure 17. Rate-Based MEOH Flowsheet in Aspen Plus

4 Simulation Approaches

15

Unit Operations - The unit operation in this model has been represented by an Aspen Plus Block as outlined in Table 3.

Table 3. Aspen Plus Unit Operation Blocks Used in the Rate-Based MEOH Model
Unit Operation Absorber Aspen Plus Block RadFrac Comments / Specifications 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: 1.5m* 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: Mixed

* The column was found to be too high for the experiments and no absorption was detected above certain height of the packing[1]. Liquid and gas samples were taken at the height of 1.5m from the bottom as liquid feed and gas product. Therefore, effective packing height(1.5m), is used instead of the real height(2.2m) in this simulation model. 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 4.

Table 4. Feed specification

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

16

4 Simulation Approaches

5 Simulation Results

The simulation was performed using Aspen Plus version 2006.5. Key simulation results are presented in Table 5 and Figure 18. 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 18.

Table 5. Key Simulation Results

Measurement CO2 mole fraction in GASOUT H2S mole fraction in GASOUT Temperature of RICHOUT, F 0.95% 0.037% 0.7 Rate-Based MEOH model 1.235% 0.0008% 2.65

1.5 1.35 1.2 Packing Height, m 1.05 0.9 0.75 0.6 0.45 0.3 0.15

Literature Data ASPEN RateSep ASPEN Equilibrium Stages

0 -45 -40 -35 -30 -25 -20 -15 -10 -5 Tem perature, F

10 15

Figure 18. Absorber Liquid Temperature Profile

5 Simulation Results

17

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, rate-based multi-stage simulation with Aspen Rate-Based Distillation which incorporates heat and mass transfer correlations accounting for columns specifics and hydraulics. The model is meant to be used as a guide for modeling the CO2 capture process with MEOH. Users may use it as a starting point for more sophisticated models for process development, debottlenecking, plant and equipment design, among others.

18

6 Conclusions

References

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References

19

[13] Mukhamedzyanov, I.Kh.; Mukhamedzyanov, G.Kh.; Usmanov, A.G., "Thermal Conductivity of Liquid Saturated Monobasic Alcohols at Pressures Below 2500 Bars, " Proc. of Kazan Chem. Tech. Inst. of S.W. Kirov, 44, 57 (1971). [14] Kaye, G.W.C.; Laby, T.H., "Tables of Physical and Chemical Constants, 14th ed., " Longman Group, Limited, London (1973). [15] Vargaftik, N.B., "Tables on the Thermophysical Properties of Liquids and Gases, 2nd ed., " Halsted Press, New York (1975). [16] Jasper, J.J., "The Surface Tension of Pure Liquid Compounds, " J Phys Chem Ref Data, 1, 4, 841-1009 (1972). [17] Riddick, J.A.; Bunger, W.B., "Organic Solvents: Physical Properties and Methods of Purification, 3rd ed., " Wiley Interscience, New York (1970). [18] Won, Y.S.; Chung, D.K.; Mills, A.F., "Density, Viscosity, Surface Tension, and Carbon Dioxide Solubility and Diffusitivity of Methanol, Ethanol, Acqueous Propanol, and Acqueous Ethylene Glycol at 25 C, " J. Chem. Eng., 26, 2, 140 (1981). [19] Littel, R.J.; Versteeg,G.F.; van Swaaij,W.P.M., Physical absorption into nonaqueous solutions in a stirred cell reactor, Chem. Eng. Sci., 46, 33083313 (1991). [20] Gross, J.; Sadowski, G., Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules, Ind. Eng. Chem. Res., 40, 1244-1260 (2001). [21] Gross, J.; Sadowski, G., Application of the Perturbed-Chain SAFT Equation of State to Associating Systems, Ind. Eng. Chem. Res., 41, 55105515 (2002). [22] Reid, R.C.; Prausnitz, J.M.; Poling, B.E., The Properties of Gases and Liquids, 4th ed.; McGraw-Hill: New York (1987).

20

References