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INTRODUCTION
Absorption of CO2 with amine-based absorbents is an
established and proven technology.1 Many solvents, such as
monoethanolamine (MEA), methyldiethanolamine (MDEA),
diethanolamine (DEA), and piperazine (PZ), have been applied
to capture CO2.24 However, this process always requires lots of
energy during solvent regeneration. Recent years, the novel
process of biphasic system DMX and lipophilic solvents were
proposed with the energy consumption of DMX system being
estimated to be 2.3 GJ/t CO2.5,6 Dimethylcyclohexylamine (DMCA),
dipropylamine (DPA), and DPA and DMCA blend, 3(methylamino)propylamine (MAPA) and DEEA blend and some
other unspecied amines in the literatures were studied for the
biphasic system.711
The previous researches have investigated CO2 absorption by
some potential biphasic solvents. The mixture of 8.75 mol %
BDA and 17.5 mol % DEEA (2 M BDA+4 M DEEA) was found
to be a potential biphasic solvent and has 46 % higher cyclic
loading, 48 % higher cyclic capacity, and 11 % higher cyclic
eciency than 30 mass % MEA. The phase separation of the
solution after CO2 absorption was due to the fast reaction rate of
CO2 with BDA and the limited solubility of DEEA in the reaction
products of BDA and CO2.1214
As one of the most important issues in evaluating a solvent,
kinetics parameters are typically derived from the experiments
based on mass transfer process, and the data of physical
diusivity and solubility of CO2 in aqueous solvents solutions are
required. However, due to the chemical reactions between CO2
and amine, these properties are not possible to be measured
directly.15 It is suggested that using N2O analogy to estimate
the aforementioned physicochemical properties, since N2O
resembles CO2 in molecular volume, conguration and electronic
structure, and it is a nonreactive gas in amine conditions,1618 as
2013 American Chemical Society
(1)
Article
EXPERIMENTAL SECTION
BDA ( 98 wt % pure) and DEEA ( 99 wt % pure) were from
Aladdin Reagent Company. The BDA and DEEA structures are
shown below.
n Nadded
=
2O
viscosity (mPas)
standard
measurement
ref
deviation
GBW13601(1203)
GBW13603(1203)
1.84
8.80
1.8388
8.793
0.07 %
0.03 %
VV PV1 PV2
R TV1z1 TV2z 2
(2)
where PV1 and PV2 are the pressure of the vessel before and after
feeding, Pa; TV1 and TV2 are the temperature of the vessel before
and after feeding, K; z1, z2 represent the compressibility factor of
gas before and after the feeding; R is universal gas constant,
8.3145 J(molK)1. The compressibility factor was calculated
using the PengRobinson equation of state.
The amount of N2O in the gas phase of the reactor ngN2O can be
calculated by
n Ng 2O =
PN2O(VR VS)
z N2ORTR
(3)
Article
Table 2. Measured N2O Solubilities (Mass Fraction w, kg/kg) in Water and 30 Mass % MEA, 293.15 to 333.15 K in This Work
T (K)
293.15
water
PN2O (kPa)
MEA
w (%)
PN2O (kPa)
111.0
0.1338
w (%)
a
298.15
303.15
150.9
123.6
0.1677
141.7
0.1219
0.1402
313.15
150.3
0.1180
155.5
0.1195
323.15
142.7
0.0952
333.15
181.7
0.0829
142.0
0.0736
(5)
n Nl 2O
VS
(6)
(7)
Article
Table 3. Densities of Aqueous BDA (x1), DEEA (x2), and BDA/DEEA Blended Solutions at (298.15, 313.15, and 333.15) K and
1 atm (1.01325105 Pa)
density, a103 (kg/m3)
10x1 (mol/mol)
T/K
032
0.1952
0.4244
298.15
313.15
333.15
0.99704
0.99222
0.98320
0.992346
0.986497
0.976433
0.988532
0.981237
0.969713
T/K
032
0.2012
0.4547
298.15
313.15
333.15
0.99704
0.99222
0.98320
0.993744
0.987552
0.976860
0.6965
0.985772
0.976817
0.963518
10x2 (mol/mol)
0.7875
0.990151
0.983322
0.981577
0.972648
0.968366
0.957191
10x1/10x2(mol/mol)
1.0253
1.4336
0.982813
0.972197
0.957323
0.978544
0.966791
0.950667
1.2520
1.9329
0.971858
0.959656
0.942334
0.961569
0.948632
0.930379
T/K
0.3629/1.4516
0.8749/1.7499
1.6703/2.2270
0.6799/1.0198
0.5618/0.5618
0.8712/0.9376
298.15
313.15
333.15
0.962903
0.950135
0.932259
0.948513
0.935423
0.917224
0.930513
0.917399
0.899304
0.967362
0.954889
0.937515
0.979531
0.968135
0.952165
0.973321
0.961226
0.944402
Figure 5. Densities of aqueous DEEA solutions measured and calculated by this work and compared with literature data.23,24
Table 4. Correlation Parameters, AADs, SSE, and R2 for Densities of BDA, DEEA, and BDA/DEEA Blended Solutions
k1
BDA
DEEA
BDA+DEEA
a
0.5635
0.5260
0.9686
k2
64.004
2920.0
142.11
k3
k4
k5
0.8865
0.01838
4.9035
1.495810
1.5151104
1.9634105
4
273.87
307.54
346.75
AADa
k6
0.65421
37.2233
0.11514
1.4610
1.56103
1.77103
SSEb
R2c
5
4.5910
6.76105
6.58105
0.9829
0.9889
0.9917
AAD = (1/N)i N= 1((|cal,i exp,i|)/exp,i). bSSE = i N= 1(cal,i exp,i)2. cThe squared correlation coecients.
For DEEA solutions, the deviations are less than 0.3 % when
compared with Barbas et al. and Lebrette et al. under the same
conditions,23,24 as shown in Figure 5.
The densities of the binary and ternary mixtures decrease
with increasing mole fractions of BDA and DEEA and
temperature in the mixture. The experimental density data for
the binary and ternary mixtures were tted as a function of
temperature and concentration of amine using the equation
proposed by Liu et al.,31 as shown in eq 8. The correlation
parameters were tted for lowest average absolute deviation
(AAD) using LevenbergMarquardt and Universal Global
k
k
= k1 + 2 (x BDA + k 3x DEEA ) + 42
T
T
k5
(8)
Article
Table 5. Viscosities of Aqueous BDA (x1), DEEA (x2), and BDA/DEEA Blended Solutions from (298.15 to 333.15) K and 1 atm
(1.01325105 Pa)
viscosity a (mPas)
10x1 (mol/mol)
T/K
032
0.1952
0.4244
0.6965
1.0253
1.4336
298.15
303.15
313.15
323.15
333.15
0.89
0.80
0.65
0.55
0.48
1.86
1.23
0.98
0.80
0.63
2.64
1.83
1.39
1.10
0.90
3.50
2.51
1.85
1.40
1.06
5.53
3.65
2.57
1.86
1.37
7.92
4.87
3.29
2.29
1.62
T/K
32
0.7875
1.2520
1.9329
5.57
3.61
2.42
1.72
1.24
8.00
5.75
3.76
2.60
1.87
11.61
8.05
5.27
3.69
2.53
10x2 (mol/mol)
0
298.15
303.15
313.15
323.15
333.15
0.2012
0.4547
0.89
0.80
0.65
0.55
0.48
2.16
1.40
1.12
0.94
0.75
3.62
2.34
1.66
1.32
1.03
10x1/10x2(mol/mol)
T/K
0.3629/1.4516
0.8749/1.7499
1.6703/2.2270
0.6799/1.0198
0.5618/0.5618
0.8712/0.9376
298.15
303.15
313.15
323.15
333.15
13.50
8.42
5.42
3.67
2.47
16.48
9.86
6.13
3.99
2.61
15.28
9.10
6.00
3.93
2.54
11.97
7.97
5.18
3.53
2.43
9.12
5.26
3.70
2.64
1.89
10.05
6.76
4.54
3.21
2.30
Figure 6. Viscosities of aqueous DEEA solutions measured and calculated by this work and compared with literature data.25
Table 6. Correlation Parameters, AADs, SSE, and R2 for Viscosities of BDA, DEEA, and BDA/DEEA Blended Solutions
BDA
DEEA
BDA+DEEA
a
k1
k2
k3
k4
k5
k6
AADa
SSEb
R2c
1290
4486
975.1
0.7115
2.4061
0.9854
2.0806107
1.6338106
3.3713107
4011.71
4324.48
4032.22
1.238106
1.31106
1.40106
17.178
1.1926
119.26
0.1091
0.08617
0.09759
1.8350
1.4616
13.424
0.9748
0.9919
0.9726
AAD = (1/N)i N= 1((|cal,i exp,i|)/exp,i). bSSE = i N= 1(cal,i exp,i)2. cThe squared correlation coecients.
Article
(x
(x
+ k 2x DEEA )
+ k 2x DEEA)2
= 1 + k1 BDA
+ k 3 BDA
T
T2
k
exp 4 + 52 + k6(x BDA + k 2x DEEA )2
T
(9)
Article
Table 7. Solubility of N2O (Mass Fraction w, kg/kg) in Aqueous BDA (x1), DEEA (x2), and BDA/DEEA Blended Solutions at
(298.15, 313.15, and 333.15) K
10x1 (mol/mol)
0
0.1952
T/K
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
298.15
313.15
333.15
150.90
150.30
181.70
0.1677
0.1180
0.0829
129.80
152.98
146.43
0.1468
0.1111
0.0882
133.50
145.50
146.50
0.2012
0.6965
w/%
PN2O/kPa
0.1358
143.20
0.1009
166.02
0.0868
145.00
10x2 (mol/mol)
0.4547
T/K
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
298.15
313.15
333.15
150.90
150.30
181.70
0.1677
0.1180
0.0829
133.10
156.60
170.19
0.1281
0.1130
0.1104
158.10
154.39
142.15
0.3629/1.4516
0.4244
0.8749/1.7499
1.0253
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
0.1143
0.1001
0.0863
143.20
166.02
145.00
0.1030
0.1053
0.0791
155.40
138.81
158.00
0.1039
0.0831
0.0827
0.7875
w/%
PN2O/kPa
0.1566
131.70
0.1196
140.97
0.1025
141.63
10x1/10x2(mol/mol)
1.6703/2.2270
1.4336
1.2520
1.9329
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
0.1385
0.1273
0.1141
128.80
130.94
139.49
0.1638
0.1513
0.1501
125.40
124.68
114.77
0.1962
0.1797
0.1457
0.6799/1.0198
0.5618/0.5618
0.8712/0.9376
T/K
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
PN2O/kPa
w/%
298.15
313.15
333.15
126.30
107.40
135.00
0.1798
0.1343
0.1513
122.10
117.50
127.80
0.2022
0.1748
0.1765
115.90
107.40
119.70
0.2628
0.2077
0.1993
140.40
151.10
132.40
0.1548
0.1572
0.1282
141.20
150.30
135.20
0.1281
0.1255
0.1065
152.40
145.90
142.00
0.1788
0.1530
0.1360
Notes
CONCLUSION
Densities, viscosities, and solubilities of N2O in BDA, DEEA, and
BDA/DEEA aqueous solutions were measured with the amine
concentration of (1.9514.3 mol %) BDA, (2.0119.3 mol %)
DEEA, and (3.6316.7 mol %) BDA + (2.6222.2 mol %)
DEEA. The densities and N2O solubilities were measured at
(298.15, 313.15, and 333.15) K, whereas the viscosities were
obtained at (298.15, 303.15, 313.15, 323.15, and 333.15) K. The
measurement results agreed well with the literature data.
The densities and viscosities of the binary and ternary mixtures
were correlated by two semiempirical correlations in the literature.
The correlated results are in good agreement with the experimental
and literature data within the range of temperature and amine
concentration in this work. The N2O solubility in BDA solution
increases with the increasing BDA concentration, whereas that in
DEEA solution decreases with the increasing DEEA concentration.
The N2O solubility in BDA/DEEA mixture decreases with the
increasing DEEA concentration in the mixture.
REFERENCES
AUTHOR INFORMATION
Corresponding Author
*E-mail: wangshuj@tsinghua.edu.cn.
Funding
Financial support from Chinese MOST project Key Technology Research and Development on Advanced Coal Conversion
and Power Generation (2010DFA72730) is greatly appreciated.
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Article