Absorption of CO2 in Aqueous Diglycolamine
Absorption of CO2 in Aqueous Diglycolamine
Absorption of CO2 in Aqueous Diglycolamine
2473
Absorption of CO2 into aqueous DGA (Diglycolamine) was performed at 25-60 C in a wetted-wall column.
The absorption data were analyzed using a rigorous model based on eddy diffusivity theory and approximations
assuming pseudo-first-order (PFO) and interface pseudo-first-order (IPFO) reactions. The PFO is a good
approximation for CO2 absorption into DGA at a CO2 loading of less than 0.2 mol/mol DGA. At CO2 loadings
greater than 0.4, instantaneous reactions are approached. The IPFO model matches the rigorous model very
well. The second-order rate constant in 65 wt % DGA at 25 C for the reaction with CO2 is four times larger
than previously published values, but 25 wt % DGA yields a rate constant which is in good agreement with
literature values. This finding suggests that the second-order rate constant is probably a function of DGA
concentration. The second-order rate constant in 65 wt % DGA increases by a factor of 5 from 0 to 0.4 mol
CO2/mol DGA. Experiments with 65 wt % DGA + glycolic acid and 65 wt % DGA + potassium formate
at 25 C and 40 C showed similar trends. The rate constant increases a factor of 2 to three in these solutions,
suggesting that the rate constant is a function of ionic strength.
1. Introduction
RCO2 ) -
(1)
k-b
R2NH+ COO- + B 9
8 R2NCOO- + BH+
k
(2)
k2[R2NH][CO2]
k-1
1+
kb[B]
(3)
RCO2 ) -k2[R2NH][CO2]
(4)
RCO2 ) -
k2
[R NH][CO2]
k-1 2
kb[B]
(5)
2474
()
DCO2 ) DCO2
0.6
(10)
2. Experimental Methods
The absorption rate of carbon dioxide was determined in the
wetted-wall column used by Bishnoi9 and others. The use of
this apparatus to provide data for CO2 absorption in DGA
solutions has been described in detail by Al-Juaied.10,20 Solution
flowed down the outside of a stainless steel tube that was 9.1
cm long with a contact area of 38.52 cm2. The column operated
at 1-8 atm with nitrogen gas rates of 4-6 standard L/min.
Loaded amine solution was recirculated at 2 cm3/s from
reservoirs with a 1 L volume. The absorption rate was determined from continuous infrared analysis of the gas leaving the
system. The reported CO2 partial pressure is the log mean
average of the gas entering and leaving the contactor. The liquidfilm mass-transfer coefficient was determined by CO2 desorption
from water and ethylene glycol mixtures. The gas film coefficient was determined by the absorption of sulfur dioxide into
sodium hydroxide solutions.9
3. Physical Properties
(11)
(12)
(13)
HN2O,DGA
HCO2,DGA )
H
HN2O,H2O CO2,H2O
(H*H ) ) (k + k + k )I
+
(9)
[DGACOO-][H3O+]
K13
(14)
[ (
Ea 1
1
R T 298.15
)]
(15)
K13 )
[DGACOO-][H3O+]
(16)
[DGA][CO2]
(8)
1
Ii ) cizi2
2
(6)
log10
Kw
R13 ) kDGA [DGA][CO2] - [DGACOO-]
K13[OH-]
(17)
where
[DGACOO-][H3O+]
[DGA][CO2]
NCO2 ) xk2,DGA[DGA]bulkDCO2
/
(PCO2,i - PCO2,i
)
HCO2
(21)
P/CO2,i is the partial pressure of CO2 that would be in equilibrium with the composition at the interface.
It is clear that eq 20 can be applied explicitly to calculate
the flux because [DGA]bulk can be calculated with the equilibrium model described in Al-Juaied and Rochelle.10,20 Equation
21 presents the problem that the concentration of DGA at the
interface, [DGA]i, is not known a priori. The diffusion of
reactants and products needs to be accounted for with mass
transfer coefficients for those species. The calculation of [DGA]i
and P/CO2,i was performed using the equilibrium model in AlJuaied and Rochelle10 and knowing also the CO2 loading at the
interface, ldgi, which can be calculated using the following
equation
ldgi )
at x )
[i] ) [i]o for all species i in solution
NCO2
+ ldgbulk
kl,prod[DGA]T
(22)
(20)
NCO2 ) xk2,DGA[DGA]iDCO2
equilibrium relationships
K18 ) ([DGAH+][OH-])/[DGA]
K18 ) [CO3)]/([HCO3-][OH-])
/
(PCO2,i - PCO2,bulk
)
HCO2
(18)
(19)
kl,prod ) kl,CO2
Dprod
DCO2
(23)
2476
T
(C)
POUT
CO2
(kPa)
flux
(106 kmol m-2 s-1)
kg
(109 kmol m-2 Pa-1 s-1)
kl
(105 m/s)
PIN
CO2
(kPa)
kG
(109 kmol m-2 Pa-1 s-1
0
0
0
0
0
0
0.109
0.112
0.234
0.228
0.390
0.391
0.115
0.117
0.236
0.242
0.384
0.387
0.104
0.106
0.253
0.257
24.3
24.7
40.4
41.0
60.6
60.7
25.9
26.2
24.0
24.0
25.1
24.8
40.2
40.6
39.3
39.4
40.0
40.0
59.2
58.8
60.1
59.9
1.57
2.26
1.36
2.04
0.59
1.23
6.11
8.29
10.35
14.03
80.43
44.92
6.05
8.26
20.93
9.77
65.87
84.07
5.17
7.22
8.54
11.56
3.05
5.61
4.34
6.84
2.55
5.42
8.78
11.55
7.51
10.04
34.31
18.15
8.78
11.43
19.92
10.61
14.07
16.80
10.96
14.19
11.55
15.39
7.34
7.38
7.56
7.60
7.45
7.48
2.30
2.31
1.70
1.69
1.04
0.89
2.33
2.34
1.53
1.51
1.01
1.00
2.31
2.30
1.61
1.62
2.53
2.52
3.30
3.38
6.20
6.35
2.81
2.68
3.77
3.73
1.67
1.65
2.74
2.84
2.87
2.89
2.49
2.48
5.13
5.07
3.97
3.90
1.97
2.99
1.92
2.91
0.92
1.93
9.91
13.23
14.95
20.17
114.6
68.56
9.82
13.11
34.54
17.32
81.33
101.9
9.94
13.38
16.26
21.73
2.27
3.04
4.13
4.42
6.40
6.56
2.18
2.08
0.93
0.92
0.54
0.52
2.19
2.04
1.42
1.74
0.24
0.22
4.52
3.84
3.13
2.83
(24)
1
1
1
) I
+ I
I
kg kg,IPFO kg,inst
(25)
Figure 1. Second-order rate constant for the reaction between CO2 and 65
wt % DGA at 40 C.
xk2[DGA]iDCO2
HCO2
(26)
kIg,inst )
1
k0l,prod
P/CO2
(27)
[CO2]*
The instantaneous coefficient depends on the partial derivative
of the equilibrium partial pressure with respect to the CO2 total
concentration. It also depends on the physical mass-transfer
coefficient of the reaction products and DGA, k0l,prod. The
derivative was obtained using the electrolyte-NRTL model
described in Al-Juaied and Rochelle;10,20 k0l,prod was obtained
using eq 23.
The error introduced by extracting the second-order rate
constant from the rate data at high loading can be estimated by
calculating the fractional resistance of the kinetic term
fraction kinetic )
kIg
I
kg,IPFO
(28)
Table 3 shows the result of the analysis done for 25, 40, and
60 C. At low loading for the three temperatures, the instan-
0.078
0.101
0.100
0.390
0.385
0.257
4.39 104
4.66 104
2.06 104
2.52 105
1.06 105
3.14 104
1.27 101
1.26 102
9.23 102
1.13 104
1.61 104
3.57 103
0.999
0.997
0.957
0.957
0.868
0.898
value
A
B
C
R
ln k2 ) A + Bldg + C/T
(29)
where A, B, and C are the fitting parameters and ldg is the CO2
loading in mol CO2/mol DGA. A limited set of data, shown in
Table 2, was regressed to minimize the computation time using
the rigorous model. This work used 38 nodes with small spacing
to achieve the desired accuracy.
The values of the diffusion coefficients of the reactants and
products used in the initial guess are those obtained by Pacheco.7
We regressed these values using the same temperature and
viscosity dependence as obtained by Pacheco.7 The following
equations for the diffusion of reactants and products were used
in the regression
(30)
(31)
Figure 3. Effect of CO2 loading on the second-order rate constant for the
65 wt % DGA. Lines are model predictions.
2478
Figure 7. Normalized CO2 flux with 65 wt % DGA at low and high driving
force at 40 C.
Figure 5. Predicted activity coefficients for 65 wt % DGA at 313 K.
Keq )
Therefore
DGACO2
RCO2 ) kbKeq[DGA][CO2]
DGAH+COOThe rate-based activity constant can be written as a function
of CO2 loading as follows
(
(
kA ) kldg)0
)
)
DGACO2
DGAH+COO- loaded
DGACO2
DGAH+COO- unloaded
(32)
T
(K)
DGA
(mol/L)
k298
(m3kmol-1 s-1)
Ea
(kJ/mol)
278-313
298
278-298
298-318
298-333
298-313
298-333
0.015-0.032
0-0.050
0.1, 0.2
0.1-3
4.8 (50 wt %)
2.4 (25 wt %)
6.2 (65 wt %)
5923
4480
4517
3990
40.7
39.4
44.3
47.8
40.1
51.7
6663
17300
technique
stopped flow
stopped flow
stirred cell
wetted-wall column
wetted-wall column
T
(C)
POUT
CO2
(kPa)
flux
(106 kmol m-2 s-1)
kg
(109 kmol m-2 Pa-1 s-1)
kl
( 105m/s)
PIN
CO2
(kPa)
kG
(109 kmol m-2 Pa-1 s-1)
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
2.38
24.5
24.5
24.5
24.6
24.9
40.2
40.9
40.8
41.0
41.1
60.9
61.0
61.2
61.2
61.3
2.54
5.24
8.03
10.98
13.76
2.24
4.59
7.22
10.12
12.90
2.25
4.72
7.41
10.22
12.76
2.68
5.78
8.66
11.15
13.84
2.96
6.44
9.62
12.42
15.06
2.54
5.57
8.29
10.47
13.07
1.98
2.00
2.02
2.04
2.06
2.11
2.13
2.10
2.08
2.10
2.32
2.28
2.25
2.27
2.30
6.63
6.63
6.63
6.64
6.65
8.88
8.91
8.91
8.92
8.92
12.16
12.16
12.18
12.18
12.18
4.09
8.52
12.82
17.01
21.07
3.86
8.03
12.36
16.76
20.77
3.51
7.49
11.55
15.33
19.00
1.41
1.50
1.46
1.34
1.33
1.89
2.06
1.93
1.73
1.61
1.45
1.56
1.47
1.31
1.31
( (
Ea 1
1
R T 298 K
))
(33)
Figure 8. Second-order rate constant for the reaction between CO2 and
DGA at zero loading.
2480
65 wt % DGA
65 wt % DGA
65 wt % DGA
65 wt % DGA + potassium formate
65 wt % DGA + potassium formate
65 wt % DGA + glycolic acid
T
(C)
ko
(m3 kmol-1 cm-2 s-1)
C
(m6 kmol-2 cm-2 s-1)
25
40
60
25
40
40
1.73 104
5.00 104
1.51 105
1.41 +104
3.84 104
8.90 104
0.674
0.674
0.674
0.730
0.230
0.510
T
(C)
POUT
CO2
(kPa)
0
0
0
0
0
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.2
0.3
0.3
0.3
0.3
0.3
0.4
0.4
0.4
0.4
0.4
39.5
39.9
39.9
39.9
39.8
39.6
39.7
39.7
39.8
39.6
40.4
40.3
40.0
39.8
39.8
39.2
39.8
39.6
39.9
40.1
39.2
39.7
39.6
39.7
39.7
0.84
1.67
2.54
3.59
4.67
0.98
1.99
3.00
4.15
5.31
1.12
2.28
3.45
4.76
6.08
1.30
2.57
4.06
5.45
6.91
1.60
3.20
4.85
6.70
8.40
flux
m-2 s-1)
(106 kmol
(109
2.49
5.72
8.71
11.3
14.1
2.50
5.58
8.61
11.3
13.9
2.50
5.58
8.61
11.3
13.9
2.15
5.31
8.01
10.7
13.1
2.56
5.84
8.95
11.5
14.3
kg
kmol m-2 Pa-1 s-1)
5.50
5.53
5.56
5.40
5.25
4.69
4.71
4.73
4.69
4.64
4.09
4.11
4.13
4.09
4.06
3.79
3.77
3.66
3.67
3.69
2.84
2.86
2.87
2.88
2.90
kl
(105 m/s)
PIN
CO2
(kPa)
kG
(109 kmol m-2 Pa-1 s-1)
4.39
4.39
4.39
4.39
4.39
3.95
3.95
3.95
3.95
3.95
3.42
3.42
3.42
3.42
3.42
2.89
2.89
2.89
2.89
2.89
2.61
2.61
2.61
2.61
2.61
1.29
2.71
4.10
5.67
7.31
1.52
3.18
4.82
6.53
8.27
1.74
3.65
5.53
7.48
9.46
1.88
3.98
6.25
8.34
10.4
2.51
5.26
7.97
10.6
13.3
4.18
5.14
5.15
4.61
4.38
3.60
4.12
4.26
3.96
3.79
3.14
3.59
3.71
3.45
3.31
2.14
2.93
2.78
2.77
2.64
2.28
2.78
2.83
2.52
2.51
solution
T
(C)
HCO2
(atm.cm3/mol-1)
(cP)
40
40
40
40
25
25
40
40
40
67500
75000
81000
90000
45981
54836
62397
72773
98396
8.5
11.7
16.7
20.5
11.3
11.3
6.7
6.7
6.7
log k ) log ko + C
(34)
T
(C)
POUT
CO2
(kPa)
flux
(106 kmol m-2 s-1)
kg
(109 kmol m-2 Pa-1 s-1)
kl
(105 m/s)
PIN
CO2
(kPa)
kG
(109 kmol m-2 Pa-1 s-1)
0
0
0
0
0
0
0
0
0
1
1
1
0
1
1
1
1
1
1
1
3
3
3
3
3
25.2
25.2
25.1
25.2
24.4
39.3
39.5
39.6
39.4
24.9
25.4
26.0
39.7
40.0
25.9
39.8
25.7
39.9
39.6
39.7
40.0
40.3
40.1
40.2
40.2
1.1
2.4
3.7
4.9
6.2
1.0
3.0
4.0
1.9
0.9
2.1
3.2
5.1
1.1
5.5
2.2
4.4
5.8
4.6
3.4
1.1
2.2
3.4
4.6
5.8
1.7
4.1
6.1
8.3
9.9
2.1
7.7
10.3
5.1
1.6
4.4
6.5
12.4
2.0
10.7
4.8
8.6
11.3
9.2
6.8
2.0
5.1
7.6
10.1
12.1
5.4
4.9
4.9
5.0
5.0
5.5
5.5
5.6
5.5
6.5
5.4
5.4
5.6
5.0
5.5
5.0
5.5
5.1
5.1
5.0
4.8
4.9
4.9
4.9
4.9
2.72
2.72
2.72
2.72
2.72
3.02
3.02
3.02
3.02
2.61
2.61
2.61
3.02
3.03
2.61
3.03
2.61
3.03
3.03
3.03
3.46
3.46
3.46
3.46
3.46
1.4
3.2
4.9
6.5
8.1
1.4
4.3
5.8
2.9
1.2
2.9
4.4
7.2
1.5
7.4
3.2
5.9
8.0
6.4
4.8
1.6
3.3
5.0
6.6
8.2
1.77
2.07
2.04
2.09
1.91
2.62
3.47
3.45
3.56
2.01
2.64
2.48
3.20
2.24
2.41
2.80
2.45
2.47
2.53
2.51
2.29
3.07
2.98
2.95
2.72
2482
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