CO2 removal with 7M monoethanolamine (MEA) Aspen Plus

model for base case

Work supported by DOE SBIR DOE Grant No. DE-FG02-06ER84625
through Trimeric Corporation
Progress report for October December, 2006
by
Sepideh Ziaii Fashami
Department of Chemical engineering
The University of Texas at Austin
February 6, 2007.

Introduction
This work focuses on the creation of an AspenPlus rate-based model of an
absorption/stripping process for 90% CO2 removal with 30 wt % aqueous
monoethanolamine. The process consists of an absorber, a stripper, a cross heat
exchanger, rich and lean solvent pumps and lean solvent cooler. The process flow sheet is
shown figure 1.
In this base case, flue gas contacts the aqueous solvent at 1 atm and 40 -50 C in
a countercurrent, packed absorber. The source of flue gas is a coal-fired plant giving 13
mol% CO2.The rich solvent is stripped by steam in a countercurrent reboiled column at
1.68-1.72 atm and 101-109C to produce pure CO2. Heat is recovered from the hot lean
solvent by cross heat exchanger with cold rich solvent. The lean solvent is typically
cooled further to approximately 40C. The temperature approach for cross heat exchanger
is 5C at the cold side.
In this work, sensitivity analysis has been performed to find the optimum lean
loading which minimizes the equivalent work of overall CO2 removal plant.

Figure1. Process flow sheet

Model Development
The absorber was modeled with Radfrac, using Rate-sep model, a rate-based model frame
work in Aspen plus. The stripper is a reboiled column with 2 equilibrium stages in which
one of the stages is the reboiler.
In the absorber the reactions involving CO2 were described with a kinetic model. In the
stripper all the reactions were set to equilibrium, due to higher operating temperature.

Thermodynamic model
The thermodynamic model was described with the Electrolyte-NRTL frame work.
Contacting an aqueous solution of MEA with a gas containing carbon dioxide, a series of
reactions occur in the liquid phase, driving the CO2 into the liquid, until equilibrium is
established.
MEACOO- + H2O

Kcarb

Ka,CO2
CO2 + 2 H2O

MEA + HCO3-

(1)

HCO3- + H3O+

(2)

CO3-- + H3O+

(3)

Ka,HCO3HCO3- + H2O

Ka, MEAH+
MEAH + H2O
MEA + H3O+
+

2 H2O

Kw

(4)

H3O+ + OH-

(5)

The equilibrium constants are temperature dependent, according to equation 6.

lnKj = A + B/T + ClnT + DT

(6)

The values of the constants in equation 6 for reactions 1 through 5 are based on Freguia
model (2003) and are reported in table 1.
Table 1. Values of fixed parameters for the CO2-MEA-H2O VLE Electrolyte-NRTL model.
Parameter

Keq,
reaction 1

Keq,
reaction 2

Keq,
reaction 3

Keq,
reaction 4

Keq,
Reaction 5

A
B
C
D

-0.52
-2545.53
0
0

231.46
-12092.1
-36.78
0

216.05
-12431.7
-35.48
0

-3.04
-7008.3
0
-0.00313

132.89
-13445.9
-22.47
0

Rate model
The rate model used in the absorber was made consistent with the Electrolyte-NRTL
thermodynamic model and the reactions were the same as in the equilibrium model,
except reactions 1 and 2 which are replaced by reversible reactions 7 and 8.
K 2 , MEA
CO2 + MEA + H 2 O

MEACOO + H 3 O +
K 1, MEA
CO2 + MEA + H 2O

MEAH + + HCO3

(7)

(8)

In previous works, bicarbonate formation was expressed by the reaction of CO2 and H2O
in the absence of MEA. But in this work, instead of that reaction, MEA catalyzed
bicarbonate formation was considered because of its higher rate constant (reaction 8).
The rates can be both expressed with a second order expression.
RCO 2 MEA = k 2, MEA[CO 2][MEA]

(9)

RCO 2 MEA = k1 , MEA[CO 2][MEA]

(10)

The rate constants k2,MEA and k1,MEA have Arrhenius expressions (equation 11).

 E
k = k 0 exp A
RT

(11)

The rate expression chosen as a starting point for the model developed in this work was
that of Hikita et al. (1977), given in equation 12. According to Blauwhoff et al. (1984)
this expression well represents the rates between 5 and 800 C; k2,MEA has units of liter/mol
s.

Log10 k 2, MEA = 10.99

2152
T

(12)

Also, the kinetic for amine-catalyzed bicarbonate formation was assumed equal to that of
the MDEA-catalyzed reaction provided by Little et al. (1971) (equation 13); kMDEA has
units of liter/mol s.
ln k MDEA = 21

5771
T

(13)

In addition, the backward reactions were considered for the model (equations 14 & 15).
K 2 , MEA
MEACOO + H 3O +
CO2 + MEA + H 2O

K 2 , MEA
MEAH + + HCO3
CO2 + MEA + H 2O

(14)
(15)

The parameters of rate expressions for backward reactions were calculated by

implementing equilibrium constants of related equilibrium reactions (table 1) and rate
expression parameters of forward reactions.

The concentration range of the data of Hikita is 0.015-0.18 M, much lower than the 5 M
(approximately equal to 30 wt %) used industrially and studied in this work. This is a
limitation to the validity of this model.
Aboudheir (2002) provides the best kinetic data for CO2 loaded MEA solutions at a range
of concentrations, CO2 loadings and temperatures. The data include the measured kg
(mass transfer coefficient of CO2) at temperatures (40 and 60 C) and a range of loading.
We used those data to make correction in the rate expression of reaction 7 by rising the
rate constant somehow we reached Aboudheirs kg.

For bicarbonate formation, we used equation 13 as the starting point and then changed
the exponent factor of that kinetic expression in order to adjust the composition of

bicarbonate in the liquid at the bottom of the absorber with that of the liquid stream
coming out of the absorber.
The kinetic expression defined in Aspen plus is temperature dependent according to 16.
E 1 1
r = k (T / T0 ) n exp ( )
R T T0

(16)

The values of the constants in equation 16 for reactions 7, 8, 14, 15 obtained from the
above explained methods are activity based and are reported in table 2.
Table 2. Kinetic parameters for reactions.
Parameter

Reaction
7
6e+7

Reaction
8
1.6e+4

Reaction
14
8.8e+11

Reaction
15
8e-4

36.8

36.8

E (KJ/Kmol)
T0(K)

2.2e+4
298

4.8e+4
298

-5.7e+4
298

5.7e+3
298

Sensitivity analysis
Sensitivity analysis was performed in two values of packing height of the absorber to
calculate the optimum lean loading which gives the minimum equivalent work per mole
of removed CO2.
Equivalent work for this process is expressed in equation 17.
T
+10 40
+W
W = 0.75Qreb reb
+W

richpump
leanpump
Treb +10

(17)

W = Equivalent work
Qreb = Reboiler duty
Treb = Reboiler temperature (C)
W
= Rich solvent pump work
richpump
W
=
leanpump

Lean solvent pump work

Results of sensitivity analysis are shown in figure 2. The optimum lean loadings obtained
from sensitivity analysis are 0.39 and 0.4 for 18.5 m and 22.5 m packing height

respectively. As shown in figure 2, the equivalent work for the case with 22.5 m packing
height is less, so this case is chosen for our process modeling.

Figure2. Sensitivity Analysis Results

Conclusion and future work

In this quarter, a model of CO2 absorption with 30 wt % MEA has been
successfully created in AspenPlus successfully. The rate-based calculation mode has been
chosen for absorber and the activity based rate expressions have been set for nonequilibrium reactions. Also the kinetic parameters have been calculated such that they
match Aboudheirs experimental kinetic data. Sensitivity analysis has been performed to
obtain optimum lean loading and finally a material balance table has been provided and
attached for this process.
It was found that lean loading is a factor that affects the equivalent work of the
plant significantly.

In this work, lean loading was the only one variable used for

optimization. In addition to lean loading other parameters such as stripper pressure,

packing height and cross heat exchanger temperature approach are effective too and can
be accounted for optimization.
In next quarter, another process configuration (Double matrix) will be modeled
and optimized. We are determined to implement some proper optimization techniques to
consider all the variables that are effective in optimization and also implement economic
issues to have more complete objective function.

References
Aboudheir, A. A. (2002). Kinetics, Modeling, and Simulation of Carbon Dioxide
Absorption into Highly Concentrated and Loaded Monoethanolamine Solutions.
Chemical Engineering. Regina, Saskatchewan, Canada, University of Regina.
Ph.D.: 364.
Freguia, S. (2002). Modeling of CO2 removal from Flue Gas with Monoethanolamine.
Chemical Engineering. Austin, TX, The University of Texas at Austin. M.S.E.:
183.

Attachment
(Material balance)

FLUEGAS
Phase:
Vapor
Component Mole Flow (Kmol/h)
H2O
1307.88
CO2
2623.66
MEA
0
N2
14839.06
O2
985.85
MEA+
0
MEACOOHCO3CO3-H3O+
OHHCOOComponent Mole Fraction
H2O
CO2
MEA
N2
O2
MEA+
MEACOOHCO3CO3-H3O+
OHHCOOComponent Mass Flow
(Kg/h)
H2O
CO2
MEA
N2
O2
MEA+
MEACOO-

INLETFG
Vapor

LEANIN
Liquid

PUREGAS
Vapor

RICHABS
Liquid

RICHP
Liquid

1307.88
2623.66
0
14839.06
985.85
0

218041.59
0.08
5982.01
0
0
11201.68

1103.84
262.37
0.27
14838.32
985.76
0

217085.43
1.67
2460.84
0.75
0.09
13523.33

217083.35
1.7
2463.72
0.75
0.09
13522.53

0
0
0
0
0
0

0
0
0
0
0
0

10371.56
471.18
179.28
0
0.38
0

0
0
0
0
0
0

11570.81
1669.43
141.47
0
0.14
0

11568.72
1672.26
140.7
0
0.14
0

0.07
0.13
0
0.75
0.05
0

0.07
0.13
0
0.75
0.05
0

0.89
0
0.02
0
0
0.05

0.06
0.02
0
0.86
0.06
0

0.88
0
0.01
0
0
0.05

0.88
0
0.01
0
0
0.05

0
0
0
0
0
0

0
0
0
0
0
0

0.04
0
0
0
0
0

0
0
0
0
0
0

0.05
0.01
0
0
0
0

0.05
0.01
0
0
0
0

23561.76
115466.54
0
415693.8
31545.9
0

23561.76
115466.54
0
415693.8
31545.9
0

3928078.8
3.56
365403.24
0
0
695524.67

19886.07
11546.65
16.41
415672.92
31542.98
0

3910856.4
73.66
150317.24
20.87
2.91
839678.39

3910816.8
74.89
150493.39
20.87
2.91
839629.07

1079536

1204360.6

1204143.5

HCO3CO3-H3O+
OHHCOOComponent Mass Fraction
H2O
CO2
MEA
N2
O2
MEA+
MEACOOHCO3Phase:
H3O+
OHHCOOMole Flow
Kmol/h
Mass Flow
Kg/h
Volume Flow M3/h
Temperature C
Pressure
KPa
Vapor Fraction
Liquid Fraction
Solid
Fraction
Molar
Enthalpy
J/mol
Mass
Enthalpy
J/Kg
Molar
Entropy
J/mol-K
Mass
Entropy
J/Kg-K
Molar
Density
Kmol/M3
Mass
Density
Kg/M3
Average Molecular Weight
Specific
Heat
J/Kg-K
CO3--

0
0
0
0
0

0
0
0
0
0

28750.31
10758.37
0
6.51
0

0
0
0
0
0

101864.88
8489.93
0
2.39
0

102037.39
8443.75
0
2.39
0

0.04
0.2
0
0.71
0.05
0

0.04
0.2
0
0.71
0.05
0

0.64
0
0.06
0
0
0.11

0.04
0.02
0
0.87
0.07
0

0.63
0
0.02
0
0
0.14

0.63
0
0.02
0
0
0.14

0
0

0
0

0.18
0

0
0

0.19
0.02

0.19
0.02

FLUEGAS
Vapor
0
0
0
19756.44
586267.92
460070.64
40
111.67
1
0

INLETFG
Vapor
0
0
0
19756.44
586267.92
460070.64
40
111.67
1
0

0
0
0
246247.77
6108062.4
6288.79
40
105
0
1

PUREGAS
Vapor
0
0
0
17190.55
478665
436696.92
40.2
102.48
1
0

RICHABS
Liquid
0
0
0
246453.95
6215666.4
6532.26
50.83
111.67
0
1

0
0
0
246453.98
6215666.4
6531.82
51
594.67
0
1

-67820.06

-67820.06

-21095.98

-2285445

-2285445

-305047.3
12298040

-757631.2

-308761.5
12242530

-308741.7
12241750

4.86

4.86

-302.08

2.96

-315.45

-315.4

163.92

163.92

-12178.27

106.33

-12507.76

-12505.77

0.04

0.04

39.16

0.04

37.73

37.73

1.27
29.67

1.27
29.67

971.26
24.8

1.1
27.84

951.53
25.22

951.6
25.22

1034.51
0

1034.51
0

3212.92
0

1064.2
0

3132.4
0

3131.99
0

10

LEANIN
Liquid

RICHP
Liquid

RICHF
Phase:
Liquid
Component Mole Flow (Kmol/h)
H2O
217082.41
CO2
1.71
MEA
2464.94
N2
0.75
O2
0.09
MEA+
13522.28
MEACOOHCO3CO3-H3O+
OHHCOOComponent Mole Fraction
H2O
CO2
MEA
N2
O2
MEA+
MEACOOHCO3CO3-H3O+
OHHCOOComponent Mass Flow
(Kg/h)
H2O
CO2
MEA
N2
O2
MEA+

RICHHX
Liquid

LEANOUT
Liquid

LEANP
Liquid

LEANHX
Liquid

LEAN
Liquid

216310.61
165.53
3672.38
0.75
0.09
13250.47

214717.39
56.57
6891.12
0
0
10987.87

214715.66
57.26
6894.35
0
0
10987.06

215274.99
0.43
6132.87
0
0
11132.33

215361.21
0.08
5983.27
0
0
11195.23

11567.75
1673.46
140.47
0
0.14
0

10632.12
2553.26
32.47
0
0.15
0

9673.82
1261.7
26.03
0
0.29
0

9671.41
1263.56
25.9
0
0.29
0

10287.62
615.81
114.27
0
0.36
0

10374.32
466.8
176.86
0
0.38
0

0.88
0
0.01
0
0
0.05

0.88
0
0.01
0
0
0.05

0.88
0
0.03
0
0
0.05

0.88
0
0.03
0
0
0.05

0.88
0
0.03
0
0
0.05

0.88
0
0.02
0
0
0.05

0.05
0.01
0
0
0
0

0.04
0.01
0
0
0
0

0.04
0.01
0
0
0
0

0.04
0.01
0
0
0
0

0.04
0
0
0
0
0

0.04
0
0
0
0
0

3910798.8
75.39
150567.98
20.87
2.91
839613.59

3896895.6
7285.06
224322.51
20.87
2.91
822736.79

3868192.8
2489.66
420935.04
0
0
682249.31

3868164
2519.87
421132.32
0
0
682198.55

3878240.4
19.11
374618.52
0
0
691218.71

3879792
3.5
365480.28
0
0
695123.99

11

MEACOOHCO3CO3-H3O+
OHHCOOComponent Mass Fraction
H2O
CO2
MEA
N2
O2
MEA+
MEACOOHCO3CO3--

Phase:
H3O+
OHHCOOMole Flow
Kmol/h
Mass Flow
Kg/h
Volume Flow M3/h
Temperature C
Pressure
KPa
Vapor Fraction
Liquid Fraction
Solid
Fraction
Molar
Enthalpy
J/mol
Mass
Enthalpy
J/Kg
Molar
Entropy
J/mol-K
Mass
Entropy
J/Kg-K
Molar
Density
Kmol/M3
Mass
Density
Kg/M3
Average Molecular Weight
Specific
Heat
J/Kg-K

1204042.7
102110.54
8429.35
0
2.39
0

1106656.9
155794.07
1948.48
0
2.54
0

1006910.6
76986.18
1562.17
0
4.86
0

1006659.4
77099.51
1554.43
0
4.86
0

1070798
37575.22
6857.44
0
6.19
0

1079822.5
28483.35
10613.67
0
6.41
0

0.63
0
0.02
0
0
0.14

0.63
0
0.04
0
0
0.13

0.64
0
0.07
0
0
0.11

0.64
0
0.07
0
0
0.11

0.64
0
0.06
0
0
0.11

0.64
0
0.06
0
0
0.11

0.19
0.02
0

0.18
0.03
0

0.17
0.01
0

0.17
0.01
0

0.18
0.01
0

0.18
0
0

RICHF
Liquid

RICHHX
Liquid

LEANP
Liquid

LEANHX
Liquid

LEAN
Liquid

0
0
0
246617.82
6215666.4
6708.17
103.9
387.72
0
1

LEANOUT
Liquid
0
0
0
243614.81
6059332.8
6483.15
109
172
0
1

0
0
0
246453.98
6215666.4
6532.1
51.07
525.72
0
1

0
0
0
243615.49
6059332.8
6482.85
109.14
586
0
1

0
0
0
243558.68
6059332.8
6282.14
56.07
448
0
1

0
0
0
243558.18
6059325.6
6239.45
40
379
0
1

-308737.2
12241570

-304160.8
12068130

-299482.8
12040670

-299464.9
12039990

-303960.9
12217900

-305262.7
12270210

-315.38

-296.37

-282.04

-282

-298.86

-303.67

-12504.79

-11759.06

-11339.47

-11337.86

-12013

-12206.2

37.73

36.76

37.58

37.58

38.77

39.04

951.56
25.22

926.58
25.2

934.63
24.87

934.67
24.87

964.53
24.88

971.13
24.88

3132.26

3282.4

3384.29

3383.98

3240.38

3205.03

12

PCO2
Phase:
Vapor
Component Mole Flow (Kmol/h)
H2O
2891.04
CO2
2365.26
MEA
2.16
N2
0.75
O2
0.09
MEA+
0
MEACOO0
HCO30
CO3-0
H3O+
0
OH0
HCOO0
Component Mole Fraction
H2O
0.55
CO2
0.45
MEA
0
N2
0
O2
0
MEA+
0
MEACOO0
HCO30
CO3-0
H3O+
0
OH0
HCOO0
Component Mass Flow
(Kg/h)
H2O
52082.93
CO2
104094.65
MEA
132.2
N2
20.87
O2
2.91
MEA+
0

CO2COND
Mixed

H2OCOND
Liquid

2888.89
2363.1
0
0.75
0.09
2.16
0
2.16
0
0
0
0

2767.94
1.72
0
0
0
2.16
0
2.16
0
0
0
0

120.95
2361.45
0
0.74
0.09
0
0
0
0
0
0
0

0.55
0.45
0
0
0
0
0
0
0
0
0
0

1
0
0
0
0
0
0
0
0
0
0
0

0.05
0.95
0
0
0
0
0
0
0
0
0
0

52044.08
103999.68
0.17
20.87
2.91
134.04

49865.26
75.62
0.17
0
0
134.04

2178.96
103926.89
0
20.87
2.91
0

13

CO2
Vapor

MEACOOHCO3CO3-H3O+
OHHCOOComponent Mass Fraction
H2O
CO2
MEA
N2
O2
MEA+
EACOOHCO3CO3--

Phase:
H3O+
OHHCOOMole Flow
Kmol/h
Mass Flow
Kg/h
Volume Flow M3/h
Temperature C
Pressure
KPa
Vapor Fraction
Liquid Fraction
Solid
Fraction
Molar
Enthalpy
J/mol
Mass
Enthalpy
J/Kg
Molar
Entropy
J/mol-K
Mass
Entropy
J/Kg-K
Molar
Density
Kmol/M3
Mass
Density
Kg/M3
Average Molecular Weight
Specific
Heat
J/Kg-K

0
0
0
0
0
0

0.29
131.5
0.03
0
0
0

0.29
131.5
0.03
0
0
0

0
0
0
0
0
0

0.33
0.67
0
0
0
0
0
0
0

0.33
0.67
0
0
0
0
0
0
0

1
0
0
0
0
0
0
0
0

0.02
0.98
0
0
0
0
0
0
0

PCO2
Vapor
0
0
0
5259.3
156333.56
96728.26
101.47
168
1
0

CO2COND
Mixed
0
0
0
5257.14
156333.56
41684.94
40
154.2
0.47
0.53

H2OCOND
Liquid
0
0
0
2773.98
50206.9
56.65
40
154.2
0
1

-307286.5
10337590

-332529.3

-285129.6

-385479.9

-11182210

-15753690

-9019510

-13.54

-84.74

-161

0.46

-455.44

-2849.68

-8896.22

10.85

0.05

0.13

54.77

0.06

1.62
29.73

3.75
29.74

991.22
18.1

2.55
42.74

1256.84

1938.18

4152.64

890.55

14

CO2
Vapor
0
0
0
2483.24
106129.62
41635.48
40
154.2
1
0

Lost MEA:
2.43
148.61

Kmol/h
kg/h

Make up MEA:
0.3331626 Kmol/h

Required Water to mix with lean stream:

2687
Kmol/h
48407.24
kg/h

15