Aspen Plus

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

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., Cambridge, 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. Ten Canal Park Cambridge, MA 02141-2201 USA Phone: (1) (617) 949-1000 Toll Free: (1) (888) 996-7001 Fax: (1) (617) 949-1030 URL: http://www.aspentech.com

Revision History
Version V7.0 Description First version

Revision History

Contents
Introduction ............................................................................................................5 1 Components .........................................................................................................6 2 Process Description..............................................................................................7 3 Physical Properties...............................................................................................8 4 Reactions ...........................................................................................................13 5 Simulation Approaches.......................................................................................16 6 Simulation Results .............................................................................................20 7 Conclusions ........................................................................................................22 References ............................................................................................................23

Contents

Introduction

This document describes an Aspen Plus rate-based model of the CO2 capture process by DEA (Diethanolamine) from a gas mixture of CH4, C2H6, C3H8, N2, CO2 and H2S. The model consists of an absorber and a stripper. The operation data from a natural gas treating unit at Pyote, Texas(1975)[1] were used to specify feed conditions and unit operation block specifications. Thermophysical property models and reaction kinetic models are based on the works of Aspen Technology(2007)[2] and Rinker(1996)[3]. Transport property models and model parameters have been validated against experimental data from open literature. The model presented here includes the following key features: True species including ions Electrolyte NRTL method for liquid and RK equation of state for vapor Concentration-based reaction kinetics Electrolyte transport property models Rate-based models for absorber and stripper with valve trays

Introduction

1 Components

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

Table 1. Components Used in the Model

ID H2O DEA CO2 H3O+ OHHCO3CO3-2 DEAH+ DEACOOH2S HSS-2 CH4 C2H6 C3H8 N2 Type Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Conventional Name WATER DIETHANOLAMINE CARBON-DIOXIDE H3O+ OHHCO3CO3-DEA+ DEACOOHYDROGEN-SULFIDE HSS-METHANE ETHANE PROPANE NITROGEN Formula H2O C4H11NO2-1 CO2 H3O+ OHHCO3CO3-2 C4H12NO2+ C5H10NO4H2S HSS-2 CH4 C2H6 C3H8 N2

1 Components

2 Process Description

The Pyote Unit[1] flowsheet for CO2 capture by DEA includes three absorbers and two strippers. However, only one absorber and one stripper data are reported. Table 2 represents the typical operation data:

Table 2. Data of the Pyote Unit

Absorber Diameter Tray Stripper Diameter Tray Feeds and Products Sour Gas to Absorber Lean Amine to Absorber Rich Amine to Stripper CO2 in Sour Gas H2S in Sour Gas CO2 in Sweet Gas H2S in Sweet Gas DEA solution 2.92 MM scfh 188 gpm 380 gpm 0.013(mole fraction) 0.00054(mole fraction) 150 ppm (mole fraction) 0.15 ppm (mole fraction) 28.69%(wt) 72 inch 31 66 inch 20

2 Process Description

3 Physical Properties

The Electrolyte NRTL method and RK equation of state are used to compute liquid and vapor properties respectively in this rate-based DEA model. The NRTL parameters were regressed against VLE data from Maddox(1987, 1989)[4,5]. CH4, C2H6, C3H8, N2, CO2 and H2S are treated as Henry-components (solutes) to which Henrys law is applied. Henrys constants are retrieved from Aspen Plus databanks for these components with water and are regressed against CO2 solubility data from Maddox(1987, 1989)[4, 5] for CO2 with DEA. In the reactions calculations, the activity coefficient basis for the Henrys components is chosen to be Aqueous. Therefore, in calculating the unsymmetric activity coefficients (GAMUS) of the solutes, the infinite dilution activity coefficients will be calculated based on infinite-dilution condition in pure water, instead of in mixed solvents. The liquid molar volume and transport property models have been updated and their model parameters regressed from literature experimental data. Specifications of these models include: For liquid molar volume, the Clarke model, called VAQCLK in Aspen Plus, is used with option code of 1 to use the quadratic mixing rule for solvents. The interaction parameter VLQKIJ for the quadratic mixing rule between DEA and H2O is regressed against experimental density data of the DEAH2O system from Maham(1994)[15]. The Clarke model parameter VLCLK/1 is also regressed for main electrolytes (DEAH+, HCO 3 ), (DEAH+, DEACOO ) and (DEAH+, CO 3 ) against experimental density data of the DEA-H2O-CO2 system from Weiland(1998)[6]. For liquid viscosity, the Jones-Dole electrolyte correction model, called MUL2JONS in Aspen Plus, is used with the mass fraction based ASPEN liquid mixture viscosity model for the solvents. The three option codes for MUL2JONS are set to: 1 (mixture viscosity weighted by mass fraction), 1 (always use Jones and Dole equation when the parameters are available), and 2 (ASPEN liquid mixture viscosity model), respectively. The interaction parameters between DEA and H2O in the ASPEN liquid mixture viscosity model, MUKIJ and MULIJ, are regressed against experimental DEA-H2O viscosity data from Oyevaar(1989)[16], Rinker(1994)[17], Hsu(1997)[18], Weiland(1998)[19], and Mandal(2003)[20]. The Jones-Dole model parameters, IONMUB, for DEAH+ and DEACOO- are regressed

3 Physical Properties

against DEA-H2O-CO2 viscosity data from Weiland(1998)[6]; that of CO 3 is regressed against K2CO3-H2O viscosity data from Pac et al.(1984)[21]; and that of HCO3- is regressed against KHCO3-H2O viscosity data from Palaty(1992)[22]. For liquid surface tension, the Onsager-Samaras model, called SIG2ONSG in Aspen Plus, is used with its option codes being -9 (exponent in mixing rule) and 1 (electrolyte system), respectively. No additional adjusted parameters are used in the surface tension model and the estimation results are somewhat higher than the experimental data from Weiland(1996)[7] (Figure 3). For thermal conductivity, the Riedel electrolyte correction model, called KL2RDL in Aspen Plus, is used. For binary diffusivity, the Nernst-Hartley model, called DL0NST in Aspen Plus, is used with option code of 1 (mixture viscosity weighted by mass fraction).

In addition to the updates to the above properties, the aqueous phase heat of formation at infinite dilution and 25C (DHAQFM) for DEAH+ and DEACOOand the heat capacity at infinite dilution (CPAQ0) for DEAH+ and DEACOO- are adjusted to fit to the literature data on heat of solution from Carson(2000)[9] and heat capacity from Weiland(1997)[8]. The estimation results of various transport and thermophysical properties are summarized in Figures 1-7:

1200

1150

EXP DEA EXP DEA EXP DEA EXP DEA EST DEA EST DEA EST DEA EST DEA

10w t% 20w t% 30w t% 40w t% 10w t% 20w t% 30w t% 40w t%

1100 Density, kg/m3

1050

1000

950

900 0 0.1 0.2 0.3 0.4 0.5 CO2 Loading, m ol/m ol

Figure 1. Liquid Density of DEA-CO2-H2O at 298.15K, experimental data from Weiland (1998)[6]

3 Physical Properties

10

Viscosity, mPaS

EXP DEA EXP DEA EXP DEA EST DEA EST DEA EST DEA 0.1 0 0.1 0.2

20w t% 30w t% 40w t% 20w t% 30w t% 40w t% 0.3 0.4 0.5

CO2 Loading, m ol/m ol

Figure 2. Liquid Viscosity of DEA-CO2-H2O at 298.15K, experimental data from Weiland (1998)[6]

100 90 80 Surface Tension, mN/m 70 60 50 40 30 20 10 0 0.00 EXP DEA EST DEA EXP DEA EST DEA EXP DEA EST DEA EXP DEA EST DEA 0.10 10w t% 10w t% 20w t% 20w t% 30w t% 30w t% 40w t% 40w t% 0.20 0.30 0.40 0.50

CO2 Loading, m ol/m ol

Figure 3. Surface tension of DEA-CO2-H2O at 298.15K, experimental data from Weiland (1996)[7]

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3 Physical Properties

0.6

Thermal Conductivity, Watt/m-K

0.5

0.4

0.3

0.2 DEA DEA DEA DEA 0 0.1 10w t% 20w t% 30w t% 40w t% 0.2 0.3 0.4 0.5 0.6

0.1

CO2 Loading, mol/mol

Figure 4. Liquid Thermal Conductivity of DEA-CO2-H2O at 298.15K

Figure 5. Liquid Heat Capacity of DEA-CO2-H2O at 298.15K, experimental data from Weiland (1997)[8]

3 Physical Properties

11

Figure 6. Heat of Solution of DEA-CO2-H2O at 298.15K, experimental data from Carson (2000)[9]

Figure 7. CO2 partial pressure of DEA-CO2-H2O (DEA mass fraction = 0.20), experimental data from Maddox (1989)[5]

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3 Physical Properties

4 Reactions

DEA is a secondary ethanolamine, as shown in Figure 8. It can associate with H3O+ to form DEAH+ ion and can also react with CO2 to form carbamate ion DEACOO-.

Figure 8. DEA Molecular Structure

The electrolyte solution chemistry has been represented with a CHEMISTRY model with ID of DEA, which is used as a global electrolyte calculation option in the simulation by specifying it on the Global sheet of the Properties | Specifications form. Chemical equilibrium is assumed with all the ionic reactions in the CHEMISTRY DEA. In addition, a REACTION model named DEA-REA has been created, which is used in calculations of the absorber and stripper by specifying it in the Reaction part of the absorber and stripper specifications. In DEA-REA, all reactions are assumed to be in chemical equilibrium except those of CO2 with OH- and CO2 with DEA.

A. Chemistry ID: DEA

1 2 3 4 5 6 7 Equilibrium Equilibrium Equilibrium Equilibrium Equilibrium Equilibrium Equilibrium

DEAH + + H 2 O DEA + H 3 O +
CO 2 + 2H 2 O H 3 O + + HCO 3

HCO 3 + H 2 O H 3 O + + CO 3 2 DEACOO + H 2 O DEA + HCO 3

2H 2 O H 3 O + + OH H 2 O + H 2 S HS + H 3 O + H 2 O + HS S 2 + H 3 O +

4 Reactions

13

B. Reaction ID: DEA-REA

1 2 3 4 5 6 7 8 9 Equilibrium Equilibrium Equilibrium Kinetic Kinetic Kinetic Kinetic

DEAH + + H 2 O DEA + H 3 O + 2H 2 O H 3 O + + OH
HCO 3 + H 2 O H 3 O + + CO 3 2

CO 2 + OH HCO 3
HCO 3 CO 2 + OH

DEA + CO 2 + H 2 O DEACOO - + H 3 O + DEACOO - + H 3 O + DEA + H 2 O + CO 2 H 2 O + H 2 S HS + H 3 O + H 2 O + HS S 2 + H 3 O +

Equilibrium Equilibrium

The equilibrium expressions for the reactions are taken from the work of Austgen et al.(1988)[10] and Jou et al.(1982, 1993)[11,12,13]. In addition, the power law expressions are used for the rate-controlled reactions (reactions 47 in DEA-REA) and the general power law expression is:

E 1 1 N ai n r = k (T To ) exp C i R T To i =1
Where: r = Rate of reaction; k = Pre-exponential factor; T = Absolute temperature; T0 = Reference temperature; n = Temperature exponent; E = Activation energy; R = Gas low constant; N = Number of components in the reaction; Ci = Concentration of component i;

(1)

ai = The stoichiometric number of component i in the reaction equation. If To is not specified, the reduced power law expression is used:

r = kT n exp (

E N ai ) C i RT i =1

(2)

In this work, the reduced expressions are used. In equation (2), the concentration basis is Molarity and the factor n is zero. k and E are given in Table 3. The kinetic parameters for reactions 4-7 in Table 3 are derived from the work of Rinker(1996)[3]. The DEA concentration range of the data of

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4 Reactions

Rinker is 0.25-2.8 M and the temperature range is 292-343 K, these conditions are the operating conditions of the absorber modeled in this work. The kinetic parameters for reaction 4 are taken from the work of Pinsent et al.(1956)[14] The kinetic parameters for reaction 5 are calculated by using the kinetic parameters of reaction 4 and the equilibrium constants of the reversible reactions 4 and 5.

Table 3. Parameters k and E in Equation (2)

Reaction No. 4 5 6 7

k
4.32e+13 2.38e+17 6480000 1.34e+17

E (cal/mol)
13249 29451 5072 11497

4 Reactions

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5 Simulation Approaches

The natural gas treating unit at Pyote[1] is simulated in this work and is described in this section. Simulation Flowsheet The Pyote Unit has been modeled with the following simulation flowsheet in Aspen Plus as shown in Figure 9.

GASOU T

CO2OU T

LEANIN ABSORBER GASIN RICHOUT LEANOUT RICHIN STRIPPER

Figure 9. Rate-Based DEA Simulation Flowsheet in Aspen Plus

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5 Simulation Approaches

Unit Operations The major unit operation models have been represented by Aspen Plus Blocks as outlined in Table 4.

Table 4. Aspen Plus Unit Operation Blocks Used in the Rate-Based MEA Model
Unit Operation Absorber Aspen Plus Block RadFrac Comments / Specifications 1. Calculation type: Rate-Based 2. 20 Stages 3. Top Pressure: 900 psig 4. Reaction: Reaction ID is DEA-REA for all stages; when calculation type is equilibrium, Holdup is used, and in this file, Holdup=0.001 m3, which is intended to aid convergence 5. Tray Type: Glitsch Ballast 6. Tray Diameter: 66 inch 7. Weir height: 0.06 m 8. Mass transfer coefficient method: Scheffe and Weiland (1987) 9. Interfacial area method: Scheffe and Weiland (1987) 10. Interfacial area factor: 0.72 11. Heat transfer coefficient method: Chilton and Colburn 12. Holdup correlation: Bennett et al. (1983) 13. Holdup scale factor: 1 14. Film resistance: Discrxn for liquid film; Film for vapor film 15. Additional discretization points for liquid film: 0.0001, 0.001, 0.01, 0.1 and 0.5 16. Flow model: Mixed 17. Estimates: provide temperature estimates for all stages. These estimates are intended to aid convergence

5 Simulation Approaches

17

Unit Operation Stripper

Aspen Plus Block RadFrac

Comments / Specifications 1. Calculation type: Rate-Based 2. 33 Stages 3. Partial vapor condenser 4. Kettle reboiler 5. Mole distillate rate: initialized at 0.03kmol/s with final value of 0.02804509kmol/s obtained by Design-Spec 1 6. Mole reflux rates: 0.04kmol/sec 7. Top Pressure: 9.8 psig 8. Reaction: Reaction ID is DEA-REA for all stages; when calculation type is equilibrium, Holdup is used, and in this file, Holdup=0.001 m3, which is intended to aid convergence. 9. Design specs: Stage 1 temperature = 291.5K 10. Vary: Distillate rate 11. Tray Type: Glitsch Ballast 12. Tray Diameter: 72 inch 13. Mass transfer coefficient method: Scheffe and Weiland (1987) 14. Interfacial area method: Scheffe and Weiland (1987) 15. Interfacial area factor: 1 16. Heat transfer coefficient method: Chilton and Colburn 17. Holdup correlation: Bennett et al. (1983) 18. Film resistance: Discxrn for liquid film; Film for vapor film 19. Additional discretization points for liquid film: 0.0001, 0.001, 0.01, 0.1 and 0.5 20. Flow model: Mixed 21. Estimates: provide temperature estimates for all stages; these estimates are intended to aid convergence

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5 Simulation Approaches

Streams - Feeds to the absorber are gas stream GASIN containing CH4, C2H6, C3H8, N2, CO2 and H2S and liquid solvent stream LEANIN containing aqueous DEA solution with few CO2 loaded in. Feed to the stripper is rich solvent stream RICHIN containing aqueous DEA solution with absorbed CO2. Feed streams conditions are summarized in Table 5.

Table 5. Feed specifications

Stream ID Substream: MIXED Temperature: F Pressure: psig Total flow H2O DEA CO2 H2S CH4 C2H6 C3H8 N2 72 900 3689 kmol/hr Mole-Frac 0 0 0.013 0.00054 0.924 0.036 0.016 0.01 102 900 188 gal/min Mass-Frac 0.7118 0.2869 0.0012 0.0001 0 0 0 0 212 10 380 gal/min Mole-Frac 0.91 0.063 0.026 0.001 0 0 0 0 GASIN LEANIN RICHIN

5 Simulation Approaches

19

6 Simulation Results

The simulation was performed using Aspen Plus V7.0. Key simulation results are presented in Table 6. The measured versus calculated absorber and stripper liquid temperature profiles are presented in Figures 10 and 11, respectively.

Table 6. Key Simulation Results

Variable Absorber CO2 mole fraction in GASOUT Loading of RICHOUT, MolAcidGas/MolDEA Stripper Loading of LEANOUT, MolAcidGas/MolDEA Reboiler duty, lbs. steam/ gal. circ. solution 0.01 0.85 0.007 0.87 150 ppm 0.50 178ppm 0.42 Measurement Rate-Based DEA Model

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6 Simulation Results

200

150

Temperature, F

100

Measure 50 AspenPlus: Liquid AspenPlus: Vapor

0 0 5 10
Stage num ber

15

20

Figure 10. The Absorber Liquid Temperature Profile

250

200 Temperature, F

150

Measurement 100 AspenPlus: Liquid AspenPlus: Vapor

50 0 5 10 15 20 25 30 35 Stage number

Figure 11. The Stripper Liquid Temperature Profile

6 Simulation Results

21

7 Conclusions

The rate-based DEA model provides a rate-based rigorous simulation of the process. Key features of this rigorous simulation include electrolyte thermodynamics and solution chemistry, reaction kinetics for the liquid phase reactions, 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 DEA. You may use it as a starting point for more sophisticated models for process development, debottlenecking, plant and equipment design, among others.

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7 Conclusions

References

[1] Butwell, F. B., Perry C. R., Performance of Gas Purification Systems Utilizing DEA Solutions. Laurance Reid Gas Conditioning Conference, 1975 [2] Aspen Technology Inc., 2007 [3] Rinker E. B., Ashour S. S., Sandall O. C., Kinetics and Modeling of Carbon Dioxide Absorption into Aqueous Solutions of Diethanolamine, Ind. Eng. Chem. Res., Vol. 35, 1107 (1996) [4] Maddox R. N., Bhairl A. H., Diers J. R., Thomas P. A., Equilibrium Solubility of Carbon Dioxide or Hydrogen Sulfide in Aqueous Solutions of Monoethanolamine, Diglycolamine, Diethanolamine and Methldiethanolamine, GPA Research Report RR-104, 1987 [5] Maddox R. N., Elizondo E. M., Equilibrium Solubility of Carbon Dioxide or Hydrogen Sulfide in Aqueous Solutions of Diethanolamine at Low Partial Pressures, GPA Research Report RR-124, 1989 [6] Weiland R.H., Dingman J.C., Cronin D.B., Browning G.J., Density and viscosity of some partially carbonated aqueous alkanolamine solutions and their blends, J. Chem. Eng. Data, Vol. 43, 378 (1998) [7] Weiland R.H., Physical Properties of MEA, DEA, MDEA and MDEA-Based Blends Loaded with CO2, GPA Research Report No. 152, 1996 [8] Weiland R.H., Dingman J.C., Cronin D.B., Heat capacity of aqueous monoethanolamine, diethanolamine, N- methyldiethanolamine, and Nmethyldiethanolamine-based blends with carbon dioxide, J. Chem. Eng. Data, Vol. 42, 1004 (1997) [9] Carson J.K., Marsh K.N., Mather A.E., Enthalpy of solution of carbon dioxide in (water + monoethanolamine, or diethanolamine, or Nmethyldiethanolamine) and (water + monoethanolamine + Nmethyldiethanolamine) at T = 298.15 K, J. Chem. Thermodyn., Vol. 32, 1285 (2000) [10] Austgen D.M., Rochelle G.T., Peng X., Chen C.C., A Model of VaporLiquid Equilibria in the Aqueous Acid Gas-Alkanolamine System Using the Electrolyte-NRTL Equation, paper presented at the New Orleans AIChE meeting, March 1988 [11] Jou F. Y., Mather A. E., Otto F. D., Solubility of Hydrogen Sulfide and Carbon Dioxide in Aqueous Methyldiethanolamine Solutions, Ind. Eng. Chem. Proc. Des. Dev., Vol. 21, 539 (1982)

References

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[12] Jou F. Y., Carroll J. J., Mather A. E., Otto F. D., Solubility of Mixtures of Hydrogen Sulfide And Carbon Dioxide in Aqueous N-Methyldiethanolamine Solutions, J. Chem. Eng. Data, Vol. 38, 75 (1993) [13] Jou F. Y., Carroll J. J., Mather A. E., Otto F. D., The Solubility of Carbon Dioxide and Hydrogen Sulfide in a 35 wt% Aqueous Solution of Methyldiethanolamine, Can. J. Chem. Eng., Vol. 71, 264 (1993) [14] Pinsent B. R., Pearson L., Roughton F. J. W., The Kinetics of Combination of Carbon Dioxide with Hydroxide Ions, Trans. Faraday Soc., Vol. 52, 1512 (1956) [15] Maham, Y., Teng, T. T., Hepler, L. G., Mather, A. E., Densities, excess molar volumes, and partial molar volumes for binary mixtures ofwater with monoethanolamine, diethanolamine, and triethanolamine from 25 to 80C, J. Solution Chem., Vol. 23, Issue. 2, 195(1994) [16] Oyevaar, M. H., Morsinkhof, R. W. J., Westerterp, K. R., Density, Viscosity, Solubility, and Diffusivity of Diethanolamine in Aqueous Ethlyene Glycol at 298K, J. Chem. Eng. Data., Vol. 34, Issue. 1, 77(1989) [17] Rinker, E.B., Oleschager, D.W., Colussi, A. T., Henry, K. R., Sandall, O. C., Viscosity, Density, and Surface Tension of Binary Mixtures of Water and N-Methyldiethanolamine and Water and Diethanolamine and Tertiary Mixtures of These Amines with Water over the Temperature Range 20-100C , J. Chem. Eng. Data., Vol. 39, Issue. 2, 392(1994) [18] Hsu, C.H., Li, M. H., Viscosities of aqueous blended amines, J. Chem. Eng. Data., Vol. 42, Issue. 4, 714(1997) [19] Weiland, R. H., Dingman, J. C., Cronin, D. B., Browning, G. J., Density and viscosity of some partially carbonated aqueous alkanoamine solutions and their blends, J. Chem. Eng. Data., Vol. 43, Issue. 3, 378(1998) [20] Mandal, B. P., Kundu, M., Bandyopadhyay, S. S., Density and viscosity of aqueous solutions of (N-methyldiethanolamine + monoethanolamine), (Nmethyldiethanolamine + diethanolamine), (2-amino-2-methyl-1-propanol + monoethanolamine), and (2-amino-2-methyl-1-propanol + diethanolamine), J. Chem. Eng. Data., Vol. 48, Issue. 3, 703(2003) [21] Pac, J. S., Maksimova, I. N., Glushenko, L. V., Viscosity of Alkali Salt Solutions and Comparative Calculation Method, J. Appl. Chem. USSR, Vol. 57, 846 (1984) [22] Palaty, Z., Viscosity of diluted aqueous K2CO3/KHCO3 solutions, Collect. Czech. Chem. Commun., Vol. 57, Issue. 9, 1879(1992)

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References