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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct
R&D Center for Membrane Technology and Department of Chemical Engineering, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC
School of Chemical Engineering and Chemistry, Mapa Institute of Technology, Manila 1002, Philippines
a r t i c l e
i n f o
Article history:
Received 31 December 2009
Received in revised form 3 February 2010
Accepted 4 February 2010
Available online 10 February 2010
Keywords:
Carbon dioxide
Solubility
Blended amines
Triethanolamine
Piperazine
a b s t r a c t
In this study, a new set of data for the equilibrium solubility of carbon dioxide in the amine solvent system that consists of triethanolamine (TEA), piperazine (PZ), and water is presented. Equilibrium solubility
values were obtained at T = (313.2, 333.2, and 353.2) K and pressures up to 153 kPa using the vapourrecirculation equilibrium cell. The TEA concentrations in the considered ternary (solvent) mixture were
(2 and 3) kmol m3 and those of PZs were (0.5, 1.0, and 1.5) kmol m3. The solubility data (CO2 loading
in the amine solution) obtained were correlated as a function of CO2 partial pressure, system temperature, and amine composition via the modied KentEisenberg model. Results showed that the model
applied is generally satisfactory in representing the CO2 absorption into mixed aqueous solutions of
TEA and PZ.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
Carbon dioxide has long been identied as one of the major contributors to global warming. Thus, its removal and recovery from
industrial process streams and emissions have become vital and
the search for efcient and economical absorbents has gained signicant interests [13].
In industrial gas treating processes, aqueous alkanolamine solutions have been widely used to remove acid gases such as CO2 and
H2S, triethanolamine (TEA), a tertiary amine, being one of the rst
amines used for such application. Although it was superseded by
methyldiethanolamine (MDEA) and monoethanolamine (MEA)
[4], its application in the removal of acid gas is still recommended.
This has been proven throughout the decades as research interests
on TEA continuously increased resulting in the availability of
numerous experimental solubility data (H2S and CO2 in aqueous
ethanolamine solutions) in a wide range of temperatures, pressures, solvent compositions, and acid gas loadings [48]. The use,
however, of such solutions is subject to limitations in loading
capacity and absorption rate. Thus, the search for an effective promoter, such as piperazine (PZ), has gained recent interests in research [9].
Studies have been conducted on the effect of piperazine (PZ)
on the rate of absorption of CO2 when blended in aqueous
* Corresponding author. Tel.: +886 3 265 4109; fax: +886 3 265 4199.
E-mail address: mhli@cycu.edu.tw (M.-H. Li).
0021-9614/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2010.02.005
803
TABLE 1
Solubility of CO2 in aqueous (2.0 kmol m3) MDEA solution at T = 313.2 K.
Jou et al. [15]
This work
P CO2 =kPa
aa
P CO2 =kPa
P CO2 =kPa
P CO2 =kPa
0.184
2.38
11.2
101
0.0680
0.224
0.441
0.866
1.17
4.15
48.9
0.124
0.267
0.686
0.177
0.419
0.887
6.95
92.8
0.0440
0.74sss0
0.113
0.362
0.842
0.28
0.60
3.48
13.26
18.67
46.44
89.90
0.0580
0.0960
0.240
0.442
0.522
0.697
0.803
AAD %b = 21.7
AAD % = 2.7
AAD % = 4.1
AAD % = 9.2
804
In equation (1), P is the CO2 partial pressure in kPa and a the CO2 loading capacity in
(mol CO2 mol amine1).
After validating the methodology, the solubility data at the considered CO2
partial pressures, temperatures, and amine solvent systems compositions were
obtained by measurement. Tables 2 and 3 show the results obtained. Figures 2
to 4 show a representative trend of the general behaviour of the observed results.
From these tables and gures, it had been deduce that (1) at constant temperature and solvent (TEAPZH2O) composition, the CO2 loading (solubility) increases with increasing CO2 partial pressure, (2) at constant CO2 partial
pressure and solvent composition, the CO2 loading decreases with increasing temperature, and (3) at constant temperature and TEA concentration in the ternary
mixture, the increase in PZ concentration signicantly increases the CO2 loading
capacity of the aqueous blended amine system. Figures 2 to 4 also show that
the applied model, described in the succeeding paragraphs, satisfactorily predicts
the obtained solubility data.
For the purpose of comparison and application, a correlation to describe the
behaviour of the data obtained from the experimental measurements is essentially
required. For acid gas solubility in various aqueous alkanolamine systems, the modied form of the original KentEisenberg model [18] seems to be the simplest and
yet has a theoretical basis that could be used [15,1922]. In this work, the model
developed by Li and Shen [12], which was also a modication of the original
KentEisenberg model [18] was applied to represent the CO2 solubility in the aqueous blended amine system of (TEA + PZ + H2O).
The chemical reactions that describe the equilibrium of the quarternary system (CO2 + TEA + PZ + H2O) with TEA denoted as R3N, are given as equations (1a)
to (5a)
T = 333.2 K
P CO2 =kPa
5.42
8.05
20.56
43.01
98.14
137.9
0.066
0.080
0.108
0.134
0.178
0.191
1.01
3.97
11.15
22.45
43.04
87.77
0.161
0.203
0.245
0.283
0.342
0.399
2.31
4.43
8.00
21.59
35.44
46.12
91.73
0.296
0.342
0.359
0.398
0.433
0.446
0.490
1.22
2.91
6.84
16.47
47.08
87.94
0.335
0.356
0.402
0.446
0.493
0.538
P CO2 =kPa
1.62
6.56
9.56
14.98
36.27
92.98
0.085
0.128
0.169
0.205
0.345
0.534
0.99
2.37
7.83
12.73
23.08
41.49
87.77
0.265
0.305
0.384
0.416
0.486
0.567
0.699
3.51
7.84
18.37
30.26
55.87
103.0
0.474
0.545
0.603
0.645
0.740
0.827
1.00
3.17
9.44
15.28
25.83
52.68
98.13
0.432
0.519
0.598
0.635
0.701
0.785
0.861
T = 353.2 K
R3 NH
;
R3 NH
PZH
;
K2
PZH
H HCO3
;
K3
CO2
K 4 H OH ;
K1
K5
2
3
4
5
H CO2
3
:
HCO3
Henrys law relating the CO2 partial pressure to the concentration of the physically dissolved CO2 in the solvent is given as
where P CO2 is the CO2 partial pressure in kPa and HCO2 is the Henrys law constant.
The mass balance equations for the reacting species are as follows:
mTEA R3 NH R3 N;
R3 NH $ H R3 N;
1a
10
PZH $ H PZ;
K3
H2 O CO2 $ H HCO3 ;
K4
H2 O $ H OH ;
K5
HCO3 $ H CO2
3 :
2a
3a
4a
11
3
where mTEA and mPZ are the molar concentrations (kmol m ) of TEA and PZ,
respectively, and a is the CO2 loading capacity of the solvent system (mol CO2 mol
amine1).
The apparent equilibrium constants, K3 to K5, mentioned in equations (4) to (6)
and the Henrys law constant for CO2, HCO2 , were modied forms (for units consistency) adapted from Kent and Eisenberg [18]. These relations are given as follows:
Equations (2) to (6) show the expressions for the apparent equilibrium constants, Ki,
as a function of molar concentrations of the species (the one in bracket) present in
their specic reactions
12
13
805
T = 333.2 K
P CO2 =kPa
P CO2 =kPa
T = 353.2 K
P CO2 =kPa
1.43
3.05
11.31
23.09
36.01
55.43
89.44
0.034
0.045
0.064
0.080
0.107
0.125
0.147
2.66
4.64
13.36
22.18
37.85
61.66
106.0
0.074
0.086
0.157
0.182
0.259
0.313
0.425
1.18
6.42
14.78
28.40
40.52
64.91
109.0
0.200
0.239
0.285
0.353
0.386
0.443
0.519
1.85
6.95
14.84
24.44
36.68
55.31
84.91
0.134
0.165
0.184
0.209
0.226
0.237
0.265
1.26
6.25
14.73
29.34
34.16
58.84
95.39
0.258
0.315
0.368
0.444
0.472
0.546
0.601
0.73
2.18
4.76
15.86
31.43
49.00
80.29
0.180
0.212
0.245
0.269
0.309
0.323
0.353
2.63
3.59
6.40
15.50
29.05
46.83
82.22
0.249
0.255
0.279
0.308
0.329
0.345
0.373
3
1.17
2.68
8.32
31.33
49.77
88.87
121.1
a
0.311
0.342
0.392
0.507
0.562
0.613
0.642
FIGURE 4. Plot of pressure against the solubility of CO2 in {aqueous (2.0 kmol m3
and 3.0 kmol m3) TEA + PZ} solution at T = 353.2 K: [j, (2.0 kmol m3) TEA; d,
TEA + (0.5 kmol m3) PZ; N, TEA + (1.0 kmol m3) PZ; ., TEA + (1.5 kmol m3)
TEA;
s,
TEA + (0.5 kmol m3)
PZ;
4,
PZ];
[h,
(3.0 kmol m3)
TEA + (1.0 kmol m3) PZ; O, TEA + (1.5 kmol m3) PZ]; and [solid lines,
3
3
(2.0 kmol m ) TEA solutions; dashed lines, (3.0 kmol m ) TEA solutions],
calculated using the modied KentEisenberg model.
FIGURE 2. Plot of pressure against the solubility of CO2 in aqueous (2.0 kmol m3)
TEA solution at the considered temperatures: (j, 313.2 K; d, 333.2 K; N, 353.2 K),
this work; and lines, calculated using the modied KentEisenberg model.
3
14
15
In this work, the apparent equilibrium constants, K1 and K2, for the main amine
reactions, equations (1a) and (2a), were assumed to be dependent on temperature
(T), CO2 loading (a), and amine compositions (mTEA and mPZ). Applying the least-
806
squares t to the equilibrium solubility values obtained for CO2 in aqueous blended
amine system of (TEA + PZ), K1 and K2 were determined to give the following
expressions as in equations (16) and (17), respectively:
17
FIGURE 5. Plot of the predicted (the predicated values are calculated by the
modied KentEisenberg model) partial pressure against the measured partial
pressure for CO2 in {aqueous (2.0 kmol m3) TEA + PZ} solutions: d,
(2.0 kmol m3) TEA; s, TEA + (0.5 kmol m3) PZ; j, TEA + (1.0 kmol m3) PZ;
h, TEA + (1.5 kmol m3) PZ.
The constants presented in Eqs. (16) and (17) were regressed from the experimental
solubility results of CO2 in aqueous system of (TEA + PZ) obtained in this work, which
has a total of 163 data points. The constants satisfactorily represent the experimental
solubility results as shown by an acceptable overall AAD of 18.9%. Aside from gures
2 to 4, such a satisfactory result is also shown in gure 5, which contains the plot of
the comparison between the predicted and measured partial pressure of CO2 in the
considered aqueous blended amine system of (TEA + PZ).
PCO2 / kPa
4000
3000
2000
1000
0.0
0.2
0.4
0.6
0.8
-1
FIGURE 6. Plot of pressure against the solubility of CO2 in aqueous (2.0 kmol m3)
TEA solution to compare data: T = (j, 313.2 K; d, 333.2 K; N, 353.2 K), this work;
(h, 273.2 K; s, 298.2 K; 4, 323.2 K; O, 348.2 K), Mason and Dodge [5]; and lines,
calculated using the modied KentEisenberg model.
FIGURE 8. Plot of pressure against the solubility of CO2 to compare solubility for
various solvent systems at T = 313.2 K: j, aqueous (2.0 kmol m3)
TEA + (1.5 kmol m3) PZ solution, this work; h, [Emim][BF4], reference [23]; (O,
[Emim][MDEGSO4]; ., [Bmim][PF6]), reference [24]; (4, [Emim][triate]; },
[Bmim][BF4]), reference [25]; (s, [Emim][EtSO4]; /, [Bmim][triate]), reference
[26].
4. Conclusions
A new set of results for the equilibrium solubility of CO2 in the
aqueous blended amine system of (TEA + PZ) at T = (313.2, 333.2,
and 353.2) K, and pressures up to 153 kPa have been determined.
The equilibrium solubility values of CO2 were obtained via measurements in a vapour-recirculation equilibrium cell for TEA and
PZ concentrations of (2 and 3) kmol m3 and (0.5, 1.0, and
1.5) kmol m3, respectively. A modied KentEisenberg model
satisfactory correlated the measured equilibrium loading (solubility)/partial pressure pairs at different temperatures and amine
concentration levels, as shown by an acceptable AAD of 18.9% for
a total of 163 data points. The model applied was also proven to
be applicable over a wider range of conditions as it represented
well the available data from the literature and systematically al-
807
JCT 10-2