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Aspen Plus Rate-Based Model of the CO 2 Capture Process by TEA using Aspen Plus

Aspen Plus

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

Copyright (c) 2008-2014 by Aspen Technology, Inc . All rights reserved.

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This software includes NIST Standard Reference Database 103b: NIST Thermodata Engine Version 7.1

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Revision History

Version

Description

 

V7.0

First version

 

V7.1

Re-verified simulation results using Aspen Plus V7.1

 

V7.1 CP1

Add N 2 , O 2 , CO and H 2 to the model as Henry components

 

V7.2

Updated results for V7.2

 

V7.3

Update databank to PURE25. Add the definition of acid gas loading and amine weight fraction

convention.

 

V7.3.2

Update databank to PURE26

 

V8.0

Update databank to PURE27

 

Use ENRTL-RK method to replace ELECNRTL method; use PC -SAFT EOS to model vapor-phase fugacity coefficient for its ability to model at high pressure.

Update the PC-SAFT parameters, Antoine equation parameters and DIPPR heat of vaporization parameters for TEA.

Update the NRTL parameters between TEA and H 2 O, H 2 O and (TEAH + , HCO 3 - ), H 2 O and (TEAH + , CO 3 -2 ), H 2 O and (TEAH + , HS - ), H 2 O and (TEAH + , S -2 ), TEA and (TEAH + , HCO 3 - ), TEA and (TEAH + , HS - ), CO 2 and (TEAH + , HCO 3 - ) and those between H 2 S and (TEAH + , HS - ).

Update the DGAQFM, DHAQFM, CPAQ0 of TEAH + .

 

Update

the

interaction

parameters,

VLQKIJ, between PZ

and H 2 O.

Update the interaction parameters, MULIJ and MUKIJ, between TEA and H 2 O.

Update figures for properties.

 

Update kinetics.

 

Update flowsheet to Levelland Pilot Plant.

 

V8.2

Update databank to PURE28.

 

V8.6

Update databank to PURE32.

 

V10.0

Update GMENCC parameters between CO 2 and (TEAH + , HCO 3 - ), and those between CO 2 and (TEAH + , CO 3 -2 ) to match CO 2 activity coefficient.

Update simulation results.

Contents

Introduction

3

1 Components

4

2 Process Description

5

3 Physical Properties

6

4 Reactions

19

5 Simulation Approach

22

6 Simulation Results

25

7 Conclusions

26

References

27

Introduction

This file describes an Aspen Plus rate-based model of the CO 2 capture process by aqueous TEA (Triethanolamine) solution from a gas mixture of CH 4 , CO 2 , H 2 S and H 2 O. The model consists of an absorber and stripper. The pilot plant test data of a gasoline plant in Levelland [1] were used as feed conditions and unit operation block specifications in the model. Thermophysical property models and reaction kinetic models used in the simulation are based on the works of Zhang and Chen (2011) [2] , Pinsent et al. (1956) [3] and Little et al.(1990) [4] .Transport property models and model parameters have been validated against experimental data from open literature.

The model includes the following key features:

True species including ions

Unsymmetric electrolyte NRTL activity coefficient model for liquid and PC- SAFT equation of state for vapor

Activity-based reaction kinetics

Electrolyte transport property models

Rate-based model for absorber with tray

1 Components

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

Table1. Components Used in the Model

ID

Type

Name

Formula

TEA

Conventional

TRIETHANOLAMINE

C6H15NO3

H2O

Conventional

WATER

H2O

CO2

Conventional

CARBON-DIOXIDE

CO2

H2S

Conventional

HYDROGEN-SULFIDE

H2S

H3O+

Conventional

H3O+

H3O+

OH-

Conventional

OH-

OH-

HCO3-

Conventional

HCO3-

HCO3-

CO3-2

Conventional

CO3--

CO3-2

HS-

Conventional

HS-

HS-

S-2

Conventional

S--

S-2

TEAH+

Conventional

   

CH4

Conventional

METHANE

CH4

C2H6

Conventional

ETHANE

C2H6

C3H8

Conventional

PROPANE

C3H8

N2

Conventional

NITROGEN

N2

O2

Conventional

OXYGEN

O2

CO

Conventional

CARBON-MONOXIDE

CO

H2

Conventional

HYDROGEN

H2

2 Process Description

Process Description

The bulk CO 2 separation process reported by Petty and Ho (1984) for the Levelland gasoline plant [1] was carried out in two steps: CO2 is removed in absorber using aqueous TEA solution and then the CO 2 loading TEA solution is stripped to refresh the TEA solution in the stripper.

Table 2 represents the typical operation data of the process.

Table2. Data of Process

Absorber

Diameter

2.5ft

Tray

20 valve trays

Stripper

Diameter

2.5ft

Tray

one ideal stage, a condenser and a reboiler

Absorber Feed Gas

Design Gas rate CO 2 in Feed Gas

600 N m3/D 30 -60 mol%

Clean Gas

CO 2 in Clean Gas

2 -40 mol%

Acid Gas CO 2 in Acid Gas

76 -99.5 mol%

Lean Amine

Flow rate

30-105 gal/min

TEA Concentration

30-54 wt%

3 Physical Properties

The unsymmetric electrolyte NRTL property method (ENRTL-RK) and PC-SAFT equation of state are used to compute liquid and vapor properties, respectively, in the Rate-based TEA model. CO 2 , H 2 S, N 2 , O 2 , CO, H 2 , CH 4 , C 2 H 6 and C 3 H 8 are selected as Henry-components to which Henry’s law is applied. Henrys constants are specified for these components with water and TEA. In the reaction calculations, the activity coefficient basis for the Henry’s 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 Henrys constant parameters of CO 2 , H 2 S, CH 4 , C 2 H 6 and C 3 H 8 are obtained from the literature [2,5] or regressed with the VLE data (See Table 3). The other Henrys constants are retrieved from Aspen Databank.

Table3. Henrys constants

Solute

Solvent

Source

CO 2

H

2 O

Yan and Chen (2010) [5]

H

2 S

H

2 O

Regression with H 2 S-H 2 O VLE data [6-13]

CH 4

H

2 O

Regression with CH 4 -H 2 O VLE data [14]

C

2 H 6

H

2 O

Regression with C 2 H 6 -H 2 O VLE data [15]

C

3 H 8

H

2 O

Regression with C 3 H 8 -H 2 O VLE data [16]

CO 2

TEA

This work

H

2 S

TEA

Set to that of H 2 S in H 2 O

CH 4

TEA

Set to that of CH 4 in H 2 O

C

2 H 6

TEA

Set to that of C 2 H 6 in H 2 O

C

3 H 8

TEA

Set to that of C 3 H 8 in H 2 O

The PC-SAFT parameters of TEA are regressed from the vapor pressure data [17] , the liquid heat capacity data [18, 19] and the liquid density data [20-24] . Those of the other components are retrieved from the Aspen Databank.

The Antoine equation parameters of TEA are regressed from the vapor pressure data [17] . The heat of vaporization (from 300 K to 650 K) generated by PC-SAFT equation of state is used to determine the DIPPR heat of vaporization equation parameters for TEA. The ideal-gas heat capacity

correlation parameters are obtained by fitting to the liquid heat capacity

data [18, 19] .

The characteristic volume parameters of H 2 O for

VLBROC, are obtained from Brelvi and OConnell (1972) [25] , those of CO 2 are obtained from Yan and Chen (2010) [5] , those of CH 4 and C 2 H 6 are regressed with the CH 4 -H 2 O [14] and C 2 H 6 -H 2 O [15] binary VLE data, and those of TEA, H 2 S,

C 3 H 8 , N 2 , O 2 and CO are defaulted to their critical volume in the Aspen Databank.

Unless specified otherwise, all molecule-molecule binary parameters and electrolyte-electrolyte binary parameters are defaulted to zero. All molecule- electrolyte binary parameters are defaulted to (8, -4), average values of the parameters as reported for the electrolyte NRTL model [26] . The nonrandomness factor is fixed at 0.2.

The NRTL interaction parameters between TEA and H 2 O are determined from the regression with binary VLE data [27] , excess enthalpy data [28] and heat capacity data [29] .

The interaction energy parameters, GMENCC, between H 2 O and (TEAH + , HCO 3 - ), H 2 O and (TEAH + , CO 3 -2 ), CO 2 and (TEAH + , HCO 3 - ), and those between TEA and (TEAH + , HCO 3 - )are regressed using the ternary VLE data [30] and CO 2 differential absorption heat data, which are calculated from an approximate form of the Gibbs-Helmholtz equation mentioned in the literature [30]

The interaction energy parameters, GMENCC, between H 2 O and (TEAH + , HS - ), H 2 O and (TEAH + , S -2 ), H 2 S and (TEAH + , HS - ), and those between TEA and (TEAH + , HS - ) are regressed with the ternary VLE data [30] .

The dielectric constants of nonaqueous solvents are calculated by the following expression:

the Brelvi-OConnell Model,

T

A B   1

1

T C

(1)

The parameters A, B and C for TEA in Aspen Databank are 29.12369, 14651 and 298.15.

The liquid molar volume model and transport property models and model parameters are adapted according to experimental data from literature. The adaptation includes:

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 TEA and H 2 O is regressed against experimental density data of the TEA- H 2 O system [31-34] . The Clarke model parameter VLCLK/1 for main

electrolytes (TEAH + , HCO

values for (MDEAH + , HCO

of ternary TEA, H 2 O and acid gas experiment data and for the similar properties between TEA and MDEA. The Clarke model parameter VLCLK/1

for (MDEAH + , HCO

experimental density data of the MDEA-H 2 O-CO 2 system from Weiland (1998) [35] , and that of (MDEAH + , HS - ) is regressed against experimental data of the MDEA-H 2 O-H 2 S system from Rinker et al. (2000) [36] .

3

3

2

), (TEAH + , CO 3 ), (MDEAH + , CO

) and (TEAH + , HS - ) is set to the ) and (MDEAH + , HS - ) for lack

2

3

) is regressed against

3

) and (MDEAH + , CO

2

3

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 solvent. There are three available models for electrolyte correction and the TEA model always uses the Jones-Dole correction model. 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 TEA and H 2 O in the ASPEN liquid mixture viscosity model, MUKIJ and MULIJ, are regressed against experimental viscosity data of the TEA-H 2 O system [31,37] . The Jones-Dole model parameter, IONMUB, for CO 3 2- is regressed against K 2 CO 3 -H 2 O viscosity data from Pac et al. (1984) [38] ; that of HCO 3 - is regressed against KHCO 3 -H 2 O viscosity data from Palaty (1992) [39] .

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. The predictions of surface tension of the TEA-H 2 O system can be in the range of the experimental data from Alvarez et al. (2003) [40] .and Vazquez (1996) [41]

For thermal conductivity, the Riedel electrolyte correction model, called KL2RDL in Aspen Plus, is used.

For binary diffusivity, the Nernst-Hartley model, called DL1NST in Aspen Plus, is used with its option code set to 1 (mixture viscosity weighted by mass fraction).

In addition to the updates with the above transport properties, the aqueous phase Gibbs free energy and heat of formation at infinite dilution and 25°C (DGAQFM and DHAQFM) and heat capacity at infinite dilution (CPAQ0) for TEAH + are regressed with VLE [30] and differential absorption heat, which are calculated from an approximate form of the Gibbs-Helmholtz equation mentioned in the literature [30] .

The CPAQ0 of HCO 3 - , CO 3 -2 and HS - are the average values of heat capacity between 298 K and 473 K taken from Criss and Cobble (1968) [42] , and that of S -2 is calculated from the Criss-Cobble correlation [42] with the entropy value from Wagman et al. (1982) [43] .

The estimation results of various transport and thermal properties are summarized in Figures 1-19. Note that acid gas loading is defined as the ratio of the moles of apparent acid gas to the moles of apparent TEA. Apparent means before reaction, so for example if 1 mole of TEA is added to 9 moles of water, and then 0.3 moles of CO 2 is added to this mixture at sufficient pressure to dissolve all the CO 2 , then the CO 2 loading is 0.3/1 = 0.3, regardless of the forms of CO 2 and TEA after reacting. Weight percent of TEA is calculated without CO 2 , so in the above example, it is calculated from the mixture of 1 mole of TEA and 9 moles of water. Since TEA has a molecular weight of 149.19 and water has a molecular weight of 18.015, this is 149.19/(149.19+9*18.015) = 0.4792 or about 48 wt% TEA.

1400 1200 1000 800 600 EXP 1994Maham EXP 1964Tseng EST 400 200 0 0 0.2
1400
1200
1000
800
600
EXP 1994Maham
EXP 1964Tseng
EST
400
200
0
0
0.2
0.4
0.6
0.8
1
Density, kg/m 3

TEA Mass Fraction

Figure1. Liquid Density of TEA-H 2 O at 298.15K, experimental data from Maham(1994) [32] and Tseng(1964) [34]

1400 1200 1000 800 TEA 10wt% 600 TEA 20wt% TEA 30wt% TEA 40wt% 400 200
1400
1200
1000
800
TEA 10wt%
600
TEA 20wt%
TEA 30wt%
TEA 40wt%
400
200
0
0
0.2
0.4
0.6
0.8
1
CO 2 Loading, mole CO 2 /mole TEA
Density, kg/m 3

Figure2. Liquid Density of TEA-CO 2 -H 2 O at 298.15K

1400 1200 1000 800 600 TEA 10wt% TEA 20wt% TEA 30wt% 400 TEA 40wt% 200
1400
1200
1000
800
600
TEA 10wt%
TEA 20wt%
TEA 30wt%
400
TEA 40wt%
200
0
0
0.2
0.4
0.6
0.8
1
H 2 S Loading, mole H 2 S/mole TEA
Density, kg/m 3

Figure3. Liquid Density of TEA-H 2 S-H 2 O at 298.15K

1.00E+01 1.00E+00 EXP 2002Maham EST 1.00E-01 1.00E-02 1.00E-03 1.00E-04 0 0.2 0.4 0.6 0.8 1
1.00E+01
1.00E+00
EXP 2002Maham
EST
1.00E-01
1.00E-02
1.00E-03
1.00E-04
0
0.2
0.4
0.6
0.8
1
Viscosity, PaS

TEA Mass Fraction

Figure4. Liquid Viscosity of TEA-H 2 O at 298.15K, experimental data from Maham (2002) [37]

0.1 TEA 10wt% TEA 20wt% TEA 30wt% TEA 40wt% 0.01 0.001 0.0001 0 0.2 0.4
0.1
TEA 10wt%
TEA 20wt%
TEA 30wt%
TEA 40wt%
0.01
0.001
0.0001
0
0.2
0.4
0.6
0.8
1
Viscosity, PaS

CO 2 Loading, mole CO 2 /mole TEA

Figure5. Liquid Viscosity of TEA-CO 2 -H 2 O at 298.15K

Viscosity, PaS

1

0.1

0.01

0.001

0.0001

TEA 10wt%

TEA 20wt%

TEA 30wt%

TEA 40wt%

TEA 10wt% TEA 20wt% TEA 30wt% TEA 40wt%
TEA 10wt% TEA 20wt% TEA 30wt% TEA 40wt%
TEA 10wt% TEA 20wt% TEA 30wt% TEA 40wt%
0 0.2 0.4 0.6 0.8 1
0
0.2
0.4
0.6
0.8
1

H 2 S Loading, mole H 2 S/mole TEA

Figure6. Liquid Viscosity of TEA-H 2 S-H 2 O at 298.15K

8.00E-02 7.00E-02 6.00E-02 5.00E-02 4.00E-02 3.00E-02 EXP 2003Alvarez EXP 2001Vazquez 2.00E-02 EST 1.00E-02
8.00E-02
7.00E-02
6.00E-02
5.00E-02
4.00E-02
3.00E-02
EXP 2003Alvarez
EXP 2001Vazquez
2.00E-02
EST
1.00E-02
0.00E+00
0
0.2
0.4
0.6
0.8
1
TEA Mass Fraction
Surface Tension, N/m

Figure7. Surface tension of TEA-H 2 O at 298.15K, experimental data from Alvarez (2003) [40] and Vazquez(2001) [41]

0.1 0.09 0.08 0.07 0.06 0.05 0.04 TEA 10wt% TEA 20wt% 0.03 TEA 30wt% TEA
0.1
0.09
0.08
0.07
0.06
0.05
0.04
TEA 10wt%
TEA 20wt%
0.03
TEA 30wt%
TEA 40wt%
0.02
0.01
0
0
0.2
0.4
0.6
0.8
1
CO 2 Loading, mole CO 2 /mole TEA
Surface Tension, N/m

Figure8. Surface tension of TEA-CO 2 -H 2 O at 298.15K

0.1 0.09 0.08 0.07 0.06 0.05 0.04 TEA 10wt% 0.03 TEA 20wt% TEA 30wt% 0.02
0.1
0.09
0.08
0.07
0.06
0.05
0.04
TEA 10wt%
0.03
TEA 20wt%
TEA 30wt%
0.02
TEA 40wt%
0.01
0
0
0.2
0.4
0.6
0.8
1
Surface Tension, N/m

H 2 S Loading, mole H 2 S/mole TEA

Figure9. Surface tension of TEA-H 2 S-H 2 O at 298.15K

0.3 0.25 EST 0.2 0.15 0.1 0.05 0 0 0.2 0.4 0.6 0.8 1 TEA
0.3
0.25
EST
0.2
0.15
0.1
0.05
0
0
0.2
0.4
0.6
0.8
1
TEA Mass Fraction
Thermal Conductivity, Watt/m-K

Figure10. Liquid Thermal Conductivity of TEA-H 2 O at 298.15K

0.6 0.5 0.4 0.3 0.2 TEA 10wt% TEA 20wt% TEA 30wt% 0.1 TEA 40wt% 0
0.6
0.5
0.4
0.3
0.2
TEA 10wt%
TEA 20wt%
TEA 30wt%
0.1
TEA 40wt%
0
0
0.2
0.4
0.6
0.8
1
CO 2 Loading, mole CO 2 /mole TEA
Thermal Conductivity, Watt/m-K

Figure11. Liquid Thermal Conductivity of TEA-CO 2 -H 2 O at 298.15K

0.6 0.5 0.4 0.3 0.2 TEA 10wt% TEA 20wt% 0.1 TEA 30wt% TEA 40wt% 0
0.6
0.5
0.4
0.3
0.2
TEA 10wt%
TEA 20wt%
0.1
TEA 30wt%
TEA 40wt%
0
0
0.2
0.4
0.6
0.8
1
Thermal Conductivity, Watt/m-K

H 2 S Loading, mole H 2 S/mole TEA

Figure12. Liquid Thermal Conductivity of TEA-H 2 S-H 2 O at 298.15K

350 300 250 EXP 1999Chiu 200 EST 150 100 50 0 0 0.2 0.4 0.6
350
300
250
EXP 1999Chiu
200
EST
150
100
50
0
0
0.2
0.4
0.6
0.8
1
Heat Capacity, J/mol-K

TEA Mass Fraction

Figure13. Liquid Heat Capacity of TEA-H 2 O at 298.15K, experimental data from Chiu (1999) [29]

120 100 80 60 TEA 10wt% 40 TEA 20wt% TEA 30wt% 20 TEA 40wt% 0
120
100
80
60
TEA 10wt%
40
TEA 20wt%
TEA 30wt%
20
TEA 40wt%
0
0
0.2
0.4
0.6
0.8
1
CO 2 Loading, mole CO 2 /mole TEA
Heat Capacity, J/mol-K

Figure14. Liquid Heat Capacity of TEA-CO 2 -H 2 O at 298.15K

120 100 80 60 TEA 10wt% TEA 20wt% 40 TEA 30wt% TEA 40wt% 20 0
120
100
80
60
TEA 10wt%
TEA 20wt%
40
TEA 30wt%
TEA 40wt%
20
0
0
0.2
0.4
0.6
0.8
1
H 2 S Loading, mole H 2 S/mole TEA
Heat Capacity, J/mol-K

Figure15. Liquid Heat Capacity of TEA- H 2 S-H 2 O at 298.15K

Heat of Solution, kJ/mol

60

50

40

30

20

10

0

  ESP 1985JOU   TEA 10wt%   TEA 20wt% TEA 30wt% TEA 40wt% 0 0.2
  ESP 1985JOU   TEA 10wt%   TEA 20wt% TEA 30wt% TEA 40wt% 0 0.2
 

ESP 1985JOU

 
  TEA 10wt%

TEA 10wt%

 

TEA 20wt%

TEA 30wt%

TEA 40wt%

0

0.2

0.4

0.6

0.8

1

CO 2 Loading, mole CO 2 /mole TEA

Figure16. Differential CO 2 absorption heat in aqueous TEA solution at 298.15K, experimental data from Jou (1985) [30] without TEA concentration and temperature specification

45 40 35 30 25 20 15 ESP 1985JOU TEA 10wt% 10 TEA 20wt% TEA
45
40
35
30
25
20
15
ESP 1985JOU
TEA 10wt%
10
TEA 20wt%
TEA 30wt%
5
TEA 40wt%
0
0
0.2
0.4
0.6
0.8
1
Heat of Solution, kJ/mol

H 2 S Loading, mole H 2 S/mole TEA

Figure17. Differential H 2 S absorption heat in aqueous T EA solution, experimental data from Jou (1985) [30] without TEA concentration and temperature specification

10000000 298K,EXP 298K,EST 323K,EXP 1000000 323K, EST 348K,EXP 348K,EST 100000 373K,EXP 373K,EST 10000
10000000
298K,EXP
298K,EST
323K,EXP
1000000
323K, EST
348K,EXP
348K,EST
100000
373K,EXP
373K,EST
10000
398K,EXP
398k, EST
1000
100
10
0.0001
0.001
0.01
0.1
1
10
CO 2 Pressure, Pa

CO 2 Loading, mole CO 2 /mole TEA

Figure18. CO 2 partial pressure of the TEA-CO 2 -H 2 O system (TEA concentration is around 2M) with various CO 2 loading, experimental data from Jou et al. (1985) [30]

10000000 298K,EXP 298K, EST 323K,EXP 1000000 323K,EST 348K,EXP 348K,EST 100000 373K,EXP 373K,EST 398K,EXP
10000000
298K,EXP
298K, EST
323K,EXP
1000000
323K,EST
348K,EXP
348K,EST
100000
373K,EXP
373K,EST
398K,EXP
398K,EST
10000
1000
100
10
0.001
0.01
0.1
1
10
H 2 S Pressure, Pa

H 2 S Loading, mole H 2 S/mole TEA

Figure19. H 2 S partial pressure of the TEA-H 2 S-H 2 O system (TEA concentration is around 2M) with various H 2 S loading, experimental data from Jou et al. (1985) [30]

4 Reactions

TEA is a tertiary ethanolamine, as shown below in Figure 20. It can associate with H + to form TEAH + but cannot react with CO 2 to produce carbamate as primary or secondary ethanolamines can.

produce carbamate as primary or secondary ethanolamines can. Figure20. TEA Molecular Structure The electrolyte solution

Figure20. TEA Molecular Structure

The electrolyte solution chemistry has been modeled with a CHEMISTRY model with CHEMISTRY ID = TEA. This CHEMISTRY ID is used as the 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 TEA. In addition, a REACTION model called TEA-REA has been created. In TEA-REA, all reactions are assumed to be in chemical equilibrium except those of CO 2 with OH - and CO 2 with TEA.

A. Chemistry ID: TEA

1

2

3

4

5

6

Equilibrium

Equilibrium

Equilibrium

Equilibrium

Equilibrium

Equilibrium

H O TEA H O H O H O O

TEAH

2

O   H O

CO 2H

HCO

OH

H O

3

2

2

2

-

3

2H O

2

3

O H O   O HS S

2

2

2

2

3

H

3

3

H

HS S   H H

3

HCO

CO

2

3

3

B. Reaction ID: TEA-REA

1

Equilibrium

TEAH

H O TEA H O

2

3

2

3

4

5

Equilibrium

Equilibrium

Equilibrium

Equilibrium

6 Kinetic

7 Kinetic

8

Kinetic

9

Kinetic

2H HCO HS H S O   H H H O O H O O S HS H OH   O H H O O CO

2

2

-

3

2

2

2

3

2

3

3

3

2

3

CO

 

OH

-

HCO

3

 

2

HCO

3

CO

2

OH

TEA TEAH CO HCO H O   TEA TEAH CO   HCO H O

2

2

-

3

2

2

-

3

The equilibrium constants for reactions 1-6 in TEA are calculated from the standard Gibbs free energy change. DGAQFM. DHAQFM and CPAQ0 of TEAH + , which are used to calculate the standard TEAH + Gibbs free energy, are obtained in this work. The DGAQFM (or DGFORM), DHAQFM (or DHFORM) and CPAQ0 (or CPIG) parameters of the other components can be obtained from the databank of Aspen Plus.

Power law expressions are used for the rate-controlled reactions (reactions 6- 9 in TEA-REA):

  1   r k T T   E   
1  
r
k T T
 E    1
n
exp
0
 R
T T
0
Where:
r
= Rate of reaction;
k
= Pre-exponential factor;
T
= Absolute temperature;

N

i 1

x

i

i

a

i

T 0 = Reference temperature;

(2)

n

= Temperature exponent;

E

= Activation energy;

R

= Universal gas constant;

N

= Number of components in the reaction;

x i = Mole fraction of component i;

γ i = Activity coefficient of component i;

a i = The stoichiometric coefficient of component i in the reaction equation.

If T 0 is not specified, the reduced power law expression is used:

r

k T

n

exp

 E

RT

N

i

1

x

i

i

a

i

(3)

In this work, the reduced expression is used. In equation (3), the concentration basis is mole fraction, the factor n is zero, k and E are given in Table 4.

The kinetic parameters for reaction 6 in Table 4 are derived from the work of Pinsent et al. (1956) [3] . The kinetic parameters for reaction 7 are calculated by using the kinetic parameters of reaction 6 and the equilibrium constants of the reversible reactions 6 and 7. The kinetic parameters for reaction 8 are taken from the work of Little et al.(1990) [4] and the kinetic parameters for reaction 9 are calculated by using the kinetic parameters of reaction 8 and the equilibrium constants of the reversible reactions 8 and 9.

Table4. Parameters k and E in Equation (3)

Reaction No.

k

E , cal/mol

6

1.33e+17

13249

7

6.63e+16

25656

8

2.02e+11

8837

9

5.02e+18

22288

5 Simulation Approach

Run 18 pilot test of the Levelland gasoline plant [1] is used in the simulation.

Simulation Flowsheet The absorber and stripper have been modeled with the following simulation flowsheet in Aspen Plus, shown in Figure 21.

CLEANGAS ABSORBER LEANIN ACIDGAS FEEDGAS STRIPPER RICH LEANOUT PUMP
CLEANGAS
ABSORBER
LEANIN
ACIDGAS
FEEDGAS
STRIPPER
RICH
LEANOUT
PUMP
LEANIN ACIDGAS FEEDGAS STRIPPER RICH LEANOUT PUMP COOLER H2OSUPP TEASUPP Figure21. Rate- Based TEA Flowsheet

COOLER

H2OSUPP TEASUPP
H2OSUPP
TEASUPP
STRIPPER RICH LEANOUT PUMP COOLER H2OSUPP TEASUPP Figure21. Rate- Based TEA Flowsheet in Aspen Plus 22

Figure21. Rate- Based TEA Flowsheet in Aspen Plus

Unit Operations - Major unit operations in this model have been represented by Aspen Plus blocks as outlined in Table 5.

Table5. Aspen Plus Unit Operation Blocks Used in the Rate-Based TEA Model

Unit Operation

Aspen Plus Block

Comments / Specifications

 

Absorber

RadFrac

1. Calculation type: Rate-Based

 

2. 20 Stages

3. Top Pressure: 495 psia

4. Reaction: Reaction ID is TEA- REA for all stages; when

calculation type is equilibrium, Holdup is used, and in this

file, Holdup=0.023 m 3 , which is close to the scaled calculated by Holdup correlation

value

5.

Tray Type: Nutter Float Valve

6.

Tray Diameter: 2.5 ft

7.

Number of valves per active area: 139.92/m 2

9.

Mass transfer coefficient method: Scheffe and Weiland

(1987)

 

10.

Interfacial area method: Scheffe and Weiland (1987)

11.

Interfacial area factor: 1

12.

Heat transfer coefficient method: Chilton and Colburn

13.

Holdup correlation: Bennett et al. (1983)

14.

Holdup scale factor: 1

15.

Film resistance: Discrxn for liquid film; Film for vapor

film

16.

Additional discretization points for liquid film: 5

17.

Flow model: Mixed

18.

Estimates: Provide temperature estimates for stages 1 to

20, these estimates are intended to aid convergence

Stripper

RadFrac

1. Calculation type: Equilibrium

 

2. 3 Stages: Partial-Vapor condenser

3. Kettle reboiler

4. Distillate rate: 353 mol/min

5. Mole reflux ratio: initialized at 0.1124 with the final value

of 0.112379 obtained by Design-Spec 1

 

6.

Design Specs: CO 2 loading of the stream LEANOUT is set

to 0.19

 

7. Vary: reflux ratio is set to adjusted variable

8. Reaction: Chemistry ID is TEA for all stages

Pump

Pump

Raise the pressure of stream LEANOUT from the stripper bottom to 495 psia

Cooler

Heater

Low the stream LEANIN temperature to 150 F

 

Streams - Feeds to the absorber are gas stream FEEDGAS containing CH 4 , C 2 H 6 , C 3 H 8 and CO 2 , liquid solvent stream LEANIN containing aqueous TEA solution loaded with some CO 2 recycled from stripper and supplement streams, and H2OSUPP and TEASUPP, which supplement H 2 O and TEA escaping from stripper and absorber overhead. Feed conditions are summarized in Table 6.

Table6. Feed specification

Stream ID

FEEDGAS

LEANIN

Substream: MIXED

Temperature K

308.15

338.71

Pressure psia

495

495

Total Flow Rate

mol/min

gal/min

862.151

69.6

Mole-Frac

H2O

0

0.866662

CO2

0.472

0.0212893

TEA

0

0.112049

CH4

0.4224

0

C2H6

0.0528

0

C3H8

0.0528

0

Prop-Sets - Prop-Sets, XAPP and ML-LOAD, have been created to report apparent mole fractions and CO 2 loading of the streams.

6 Simulation Results

The simulation was performed using Aspen Plus. Key simulation results are presented in Table 7 and Figure 23. Figure 23 only displays the simulation absorber liquid temperature profile, since no pilot plant temperature data is available.

Table7. Key Simulation Results

 

Measurement

Rate-Based TEA model

CO 2 mole fraction in CLEANGAS

14.00%

23 .95 %

360 358 356 354 352 350 348 346 344 342 340 338 0 1 2
360
358
356
354
352
350
348
346
344
342
340
338
0 1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21
Temperature/K

Stage

Figure23. Absorber Liquid Temperature Profile

7 Conclusions

The Rate-Based TEA 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 CO 2 capture process with TEA. You may use it as a starting point for more s ophisticated models for process development, debottlenecking, plant and equipment design, among others.

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