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Departamento de Ingeniera Qumica Basica, Universidad del Zulia, 4011, Maracaibo, Venezuela
Departamento de Ingeniera Qumica, Escuela Tecnica Superior de Ingeniera, Universitat de Valencia, 46100 Burjassot, Valencia,
Spain
ABSTRACT: In order to study the separation of 1-hexene and n-hexane, two solvents, 2-pentanol and ethyl-butyrate, are tested as possible entrainers for an extractive
distillation. In this way, isobaric vaporliquid equilibrium (VLE) data at 100 kPa
have been measured for the two ternary systems formed by the initial mixture and
one of the mentioned solvents: 1-hexene + n-hexane + ethyl butyrate and 1-hexene +
n-hexane + 2-pentanol. VLE data for the four constituent binary systems have also
been measured. These systems are 1-hexene + ethyl butyrate, n-hexane + ethyl butyrate,
1-hexene + 2-pentanol, and nally n-hexane + 2-pentanol. All binary systems show
moderate positive deviations from the ideal behavior and do not form an azeotrope.
The well-known local composition models Wilson, UNIQUAC, and NRTL have been
used for correlating VLE data. Prediction with the UNIFAC method has been also
obtained.
INTRODUCTION
Olens and parans have very similar boiling points and are only
separated by a few degrees in temperature. When this occurs,
conventional distillation is not a recommended technique due its
expensive cost, as a consequence of the high reux ratios and
large number of stages required for carrying out the separation. In these cases, one alternative is extractive distillation, which
uses a third component called an entrainer to alter the relative
volatility of the components to be separated. However, only a
few specic solvents allow an ecient and economical extractive
distillation process; thus, entrainer selection is a crucial step during the design stage. The choice of entrainer can be carried out
correctly with complete and accurate vaporliquid equilibrium
(VLE) data of the systems formed by the components to be
separated and the possible solvent.
The present work tackles a part of thermodynamic research on
the separation of paran and olen mixtures using dierent
solvents. In this work, the initial mixture is formed by 1-hexene
and n-hexane, and ethyl butyrate and 2-pentanol are the entrainer
candidates due to certain alcohols and esters being recommended
as entrainers for separation of hydrocarbons.1 An ideal entrainer
will increase the relative volatility considerably between the 1-hexane
and hexane and it will be very selective. Another important characteristic that makes an entrainer more suitable is that it is one of the
so-called ecofriendly solvents. In the present paper, both proposed
compounds can be considered green solvents.
In this work, we measured isobaric VLE data for the two ternary
systems 1-hexene (1) + n-hexane (2) + ethyl butyrate (3) and 1hexene (1) + n-hexane (2) + 2-pentanol (3) and four constituent
binary systems 1-hexene (1) + ethyl butyrate (3), n-hexane (2) +
ethyl butyrate (3), 1-hexene (1) + 2-pentanol (3), and n-hexane
(2) + 2-pentanol (3) at 100 kPa. In a previous paper,2 we reported
2012 American Chemical Society
VLE data for the binary system 1-hexene (1) + n-hexane (2).
Isobaric VLE data of binary hexane + 2-pentanol system was
obtained by Linek et al.3 at dierent pressures but none was
recorded at 100 kPa. However, for the other binary systems and for
the ternary systems, no VLE data have been previously published.
EXPERIMENTAL SECTION
Chemicals. The chemicals 1-hexene (99+ % mass), ethyl
butyrate (100 w 99.5, puriss. p.a.) and 2-pentanol (100 w 99)
were supplied by Sigma-Aldrich and the chemical n-hexane
(99.5+ % mass) was supplied by Fluka. Purity grade of 2-pentanol
was increased to 99.99 % after being treated in a batch multistage
rectication process in a Fischer SPALTROHR HMS-500 column.
The other reagents were used without further purication since
impurities are smaller than the detection limit of the analytical
method used. The specications of the used chemicals are summarized in Table 1.
source
initial mass
fraction
purity
purication
method
Fluka
Aldrich
Aldrich
Aldrich
0.9950
0.9900
0.9900
0.9900
none
none
none
distillation
nal mass
fraction
purity
analysis
method
0.9999
GCa
GCa
GCa
GCa
Gasliquid chromatography.
Article
P/kPa
T/K
P/kPa
22.50
25.00
27.50
30.03
32.51
35.02
37.52
40.04
42.51
45.03
47.51
50.01
52.51
55.03
57.52
60.00
379.48
380.68
381.82
382.96
384.07
385.13
386.19
387.22
388.21
389.17
390.12
391.06
391.95
392.83
393.71
394.13
65.03
67.53
70.00
72.52
75.01
77.51
79.99
82.52
85.02
87.54
89.98
92.53
94.92
97.45
100.01
101.31
ln Pi0/kPa = Ai
T/K
348.97
351.83
354.39
356.76
359.00
361.08
363.04
364.86
366.66
368.24
369.87
371.44
372.86
374.31
375.67
376.95
T/K
P/kPa
T/K
P/kPa
354.47
356.60
358.86
360.81
362.76
364.38
366.00
367.49
369.03
370.52
371.77
373.05
374.33
375.51
376.68
377.81
378.95
22.55
25.05
27.47
30.03
32.55
35.08
37.56
40.03
42.51
45.07
47.54
50.02
52.58
55.03
57.48
60.03
62.45
379.97
381.01
381.96
382.90
383.88
384.79
385.64
386.56
387.35
388.19
389.00
389.76
390.55
391.31
392.07
392.26
65.05
67.58
70.03
72.56
75.05
77.59
80.03
82.58
85.01
87.55
90.09
92.52
95.02
97.55
100.03
101.38
(1)
compound
Ai
Bi
Ci
1-hexene (1)a
n-hexane (2)a
ethyl butyrate (3)
2-pentanol (3)
15.1210
12.8239
14.2846
14.1880
3433.84
2178.19
3234.24
2684.71
9.47
76.39
59.59
111.86
yP
i
xiPi0
3722
Article
T/K
x1
y1
389.91
384.16
378.87
374.16
370.93
366.17
362.24
359.78
356.05
353.79
351.38
349.22
347.45
345.55
343.80
342.17
340.51
339.04
0.027
0.069
0.112
0.160
0.198
0.256
0.318
0.351
0.426
0.468
0.525
0.573
0.630
0.679
0.735
0.804
0.851
0.905
0.133
0.300
0.433
0.535
0.603
0.686
0.749
0.779
0.825
0.850
0.876
0.896
0.916
0.931
0.943
0.960
0.970
0.984
1.224
1.225
1.227
1.185
1.167
1.155
1.123
1.128
1.087
1.084
1.064
1.060
1.036
1.032
1.016
0.992
0.995
0.992
0.991
0.988
0.983
0.987
0.979
0.977
0.973
0.981
1.002
1.006
1.017
1.029
1.026
1.045
1.119
1.132
1.193
1.059
T/K
x2
y2
391.29
388.09
380.32
375.04
371.15
366.84
364.07
359.85
357.90
355.64
353.83
352.05
350.37
349.07
347.72
346.41
345.27
344.13
343.07
342.44
0.015
0.038
0.098
0.148
0.195
0.251
0.294
0.373
0.418
0.472
0.520
0.573
0.633
0.682
0.730
0.783
0.833
0.878
0.925
0.954
0.085
0.192
0.398
0.517
0.596
0.671
0.709
0.778
0.804
0.832
0.852
0.873
0.891
0.905
0.921
0.935
0.947
0.963
0.978
0.987
1.677
1.594
1.509
1.459
1.396
1.353
1.306
1.256
1.218
1.184
1.155
1.127
1.090
1.065
1.052
1.033
1.016
1.013
1.007
1.004
0.994
0.984
0.983
0.983
0.985
0.994
1.023
1.017
1.036
1.061
1.098
1.13
1.201
1.269
1.308
1.408
1.559
1.558
1.571
1.552
x1
y1
0.017
0.032
0.056
0.100
0.125
0.150
0.215
0.282
0.344
0.395
0.456
0.515
0.577
0.628
0.681
0.734
0.789
0.841
0.895
0.949
0.983
0.140
0.268
0.395
0.568
0.626
0.678
0.778
0.834
0.873
0.892
0.910
0.923
0.933
0.940
0.947
0.953
0.958
0.961
0.971
0.983
0.994
2.136
2.323
2.179
2.058
2.006
1.939
1.854
1.731
1.628
1.559
1.468
1.395
1.314
1.255
1.206
1.155
1.104
1.062
1.030
1.005
0.992
0.999
0.963
0.969
0.939
0.983
0.974
0.973
0.992
0.968
1.010
1.041
1.099
1.181
1.267
1.383
1.536
1.796
2.300
2.686
3.368
3.639
T/K
388.05
384.92
380.13
373.28
369.17
366.41
359.50
354.51
351.19
348.56
346.34
344.39
342.90
341.85
340.71
339.87
339.14
338.40
337.71
337.00
336.63
T/K
x2
y2
389.01
384.49
377.11
369.96
365.17
359.96
355.46
352.14
350.43
348.74
347.29
346.18
345.15
344.42
343.74
343.13
342.55
342.10
341.72
341.46
0.013
0.033
0.080
0.127
0.165
0.232
0.294
0.372
0.414
0.470
0.531
0.588
0.646
0.699
0.753
0.806
0.862
0.911
0.952
0.992
0.106
0.248
0.468
0.605
0.684
0.776
0.824
0.863
0.875
0.887
0.901
0.910
0.920
0.926
0.930
0.937
0.948
0.959
0.971
0.994
2.535
2.563
2.337
2.241
2.188
2.010
1.893
1.712
1.635
1.530
1.432
1.348
1.278
1.214
1.154
1.106
1.064
1.032
1.011
1.001
1.002
1.005
0.978
1.008
1.024
0.984
1.025
1.044
1.105
1.196
1.269
1.386
1.508
1.701
2.028
2.396
2.863
3.583
4.794
6.040
(3)
Article
Figure 1. Experimental VLE data for the system 1-hexene (1) + ethyl
butyrate (3) at 100.0 kPa: , experimental data; solid line, smoothed
data using the NRTL model with the parameters given in Table 10;
dotteddashed line, predicted by UNIFAC method.
A1a
A2a
0.1643
0.4726
1.0054
1.2294
0.0120
0.0845
0.3577
0.4009
A3a
100AAD yib
AAD
Pc/kPa
0.0610
0.0941
0.625
0.529
0.872
0.270
0.635
0.176
0.539
0.837
The parameters of these models have been determined minimizing the following objective function (OF)
3724
Article
Table 10. Parameters and Correlation Statistics for Dierent GE Models for the Ternary Systems 1-Hexene (1) + n-Hexane (2) +
Solvent (3)
model
Wilsonc
NRTL
UNIQUACf
UNIFACg
Wilsonc
Aij
Aji
system i + j
Jmol1
Jmol1
1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1 + 2 + 3e
1 + 2d
1+3
2+3
1+2+3
171.69
200.90
30.68
1+3
2+3
1 + 2 + 3e
1+3
2+3
1 + 2 + 3e
1+3
2+3
1 + 2 + 3e
1+3
2+3
1+2+3
NRTL
UNIQUACf
UNIFAC
154.16
549.21
1992.99
78.87
188.21
625.83
343.44
15.18
4933.42
5239.21
2457.76
2644.33
bubble point
ij
Ethylbutyrate (3)
131.00
502.90
1744.60
195.66
148.65
237.06
0.2
0.3
0.3
88.58
380.77
201.10
2-Pentanol (3)
4984.29
5618.24
682.15
260.36
1042.08
1024.92
0.3
0.3
ARDTa/%
100AADy1b
0.056
0.191
0.054
0.218
0.056
0.190
0.054
0.217
0.056
0.189
0.054
0.225
0.062
0.230
0.518
0.290
0.115
0.651
0.138
0.136
0.164
0.151
0.270
0.258
0.132
0.242
0.225
1.395
0.970
1.051
0.885
0.473
0.116
0.654
0.473
0.116
0.653
0.486
0.072
0.752
0.487
0.338
0.951
0.341
0.897
0.368
1.141
0.879
100AADy2b
0.571
0.254
0.578
0.254
0.582
0.259
1.002
0.357
0.295
0.585
0.331
0.599
0.292
0.597
0.484
0.841
a
Average relative deviation in temperature. bAverage absolute in vapor phase composition. cMolar liquid volumes of pure components have been
estimated with the Rackett equation.11 dReference 2. eTernary estimation from binary parameters. fVolume and surface parameters from DECHEMA.12
g
Calculations based on UNIFAC.9,10
OF =
T expt T calc
i
i
expt
calc
y
y
+
|
i
i
Tiexpt
100
i=1
(4)
D=
(5)
3725
Article
x1
x2
y1
y2
382.56
365.54
353.97
345.33
337.54
339.34
342.39
345.34
349.26
352.96
357.80
363.28
373.80
364.85
357.52
352.65
349.17
345.36
340.59
338.70
340.72
343.66
346.23
350.02
353.71
361.02
353.67
349.98
346.66
343.31
339.31
341.56
344.66
347.70
352.46
347.60
344.86
340.33
342.67
347.64
342.52
342.37
0.046
0.224
0.424
0.643
0.912
0.807
0.702
0.600
0.486
0.392
0.294
0.199
0.087
0.104
0.203
0.305
0.398
0.506
0.676
0.739
0.585
0.490
0.411
0.301
0.200
0.056
0.108
0.210
0.306
0.420
0.553
0.395
0.293
0.213
0.057
0.105
0.198
0.357
0.195
0.050
0.102
0.051
0.045
0.043
0.050
0.051
0.051
0.097
0.096
0.094
0.097
0.102
0.097
0.104
0.090
0.198
0.208
0.209
0.206
0.204
0.199
0.206
0.305
0.295
0.301
0.289
0.296
0.298
0.397
0.403
0.396
0.399
0.401
0.499
0.490
0.478
0.495
0.609
0.601
0.600
0.701
0.674
0.821
0.895
0.175
0.563
0.762
0.865
0.945
0.884
0.851
0.813
0.755
0.692
0.611
0.473
0.261
0.246
0.407
0.523
0.613
0.680
0.767
0.793
0.664
0.616
0.556
0.471
0.349
0.126
0.184
0.312
0.415
0.511
0.604
0.460
0.377
0.287
0.098
0.145
0.252
0.402
0.237
0.068
0.123
0.061
0.174
0.116
0.091
0.068
0.047
0.096
0.107
0.119
0.143
0.171
0.197
0.248
0.279
0.475
0.409
0.340
0.292
0.251
0.203
0.194
0.309
0.333
0.378
0.423
0.506
0.640
0.662
0.576
0.505
0.442
0.383
0.512
0.567
0.630
0.770
0.777
0.694
0.584
0.732
0.856
0.854
0.921
1.126
1.109
1.071
1.020
0.989
0.990
1.001
1.028
1.054
1.082
1.118
1.110
1.084
1.062
1.087
1.060
1.048
1.019
0.988
0.989
0.985
1.001
1.000
1.040
1.048
1.114
1.024
0.988
0.991
0.979
0.989
0.986
0.995
0.956
1.068
0.982
0.979
0.989
0.996
0.966
0.993
0.989
1.384
1.417
1.282
1.191
1.035
1.053
1.084
1.130
1.179
1.213
1.294
1.323
1.342
1.281
1.262
1.187
1.137
1.098
1.046
1.021
1.034
1.058
1.093
1.146
1.212
1.261
1.183
1.121
1.097
1.048
1.017
1.022
1.053
1.101
1.140
1.069
1.045
1.005
1.007
1.062
1.007
1.001
0.985
1.031
0.986
1.068
1.438
1.288
1.138
1.084
1.027
0.991
0.970
1.017
1.006
0.964
0.970
1.044
1.011
1.159
1.411
1.499
1.435
1.235
1.080
1.055
1.025
0.995
1.109
1.183
1.244
1.370
1.749
1.494
1.292
1.196
1.098
1.219
1.335
1.934
1.613
1.229
1.627
1.826
u(T) = 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(x2) = u(y1) = u(y2) =
0.001.
Dmax =
(xia + xib) 1
xia
i=1
(xia + xib) P
i=1
N
1
1
1
+
+ x
yia
xib
yib
N
+ 2 |ln b ln ia|x
i=1
(6)
Figure 7. Boiling isotherms (K) for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa calculated with NRTL
model with the parameters given in Table 10.
Article
Figure 8. Boiling isotherms (K) for the ternary system 1-hexene (1) +
n-hexane (2) + 2-pentanol (3) at 100.0 kPa calculated with NRTL
model with the parameters given in Table 10.
Solvent Eects. The solvent eects in the VLE of the mixture 1-hexene + n-hexane will be discussed taking into account
two aspects: analysis of the residue curve map,15 and changes in
relative volatility. Furthermore, both solvents will be compared
with each other in order to recommend the most suitable
entrainer for the separation of the mixture 1-hexene + n-hexane
by extractive distillation.
In Figure 9 and Figure 10, residue curves simulated by Aspen
properties v7.3 using the NRTL model with the experimental
VT/K
x1
x2
y1
y2
377.02
353.23
344.42
340.56
337.17
338.06
339.45
340.99
342.96
345.32
348.90
352.35
353.65
358.48
351.95
346.86
343.90
341.54
340.04
338.36
338.03
339.63
341.43
343.70
345.72
349.55
350.51
345.42
342.75
341.03
338.80
339.96
341.63
343.07
346.69
343.53
341.97
339.86
340.95
343.40
341.54
341.40
0.044
0.252
0.454
0.646
0.900
0.794
0.696
0.590
0.487
0.392
0.305
0.225
0.209
0.111
0.127
0.247
0.364
0.493
0.580
0.711
0.727
0.540
0.434
0.318
0.235
0.138
0.098
0.176
0.295
0.382
0.546
0.399
0.293
0.210
0.051
0.103
0.203
0.344
0.208
0.057
0.104
0.056
0.038
0.052
0.064
0.059
0.054
0.106
0.102
0.100
0.096
0.099
0.100
0.095
0.092
0.127
0.240
0.226
0.207
0.205
0.210
0.200
0.211
0.316
0.297
0.289
0.291
0.281
0.288
0.383
0.387
0.411
0.405
0.498
0.491
0.491
0.488
0.613
0.600
0.599
0.696
0.698
0.798
0.895
0.267
0.691
0.804
0.868
0.930
0.866
0.842
0.812
0.774
0.730
0.671
0.591
0.569
0.368
0.303
0.474
0.601
0.677
0.719
0.775
0.775
0.627
0.577
0.496
0.417
0.289
0.228
0.301
0.423
0.483
0.593
0.460
0.376
0.299
0.093
0.146
0.265
0.385
0.246
0.079
0.128
0.066
0.250
0.160
0.118
0.079
0.051
0.104
0.114
0.131
0.149
0.183
0.220
0.258
0.256
0.433
0.569
0.420
0.322
0.264
0.234
0.193
0.199
0.330
0.363
0.424
0.493
0.584
0.657
0.615
0.509
0.466
0.384
0.503
0.566
0.634
0.809
0.787
0.683
0.585
0.714
0.854
0.834
0.906
2.035
1.668
1.379
1.172
0.998
1.025
1.090
1.185
1.291
1.413
1.508
1.637
1.638
1.753
1.503
1.394
1.305
1.163
1.098
1.015
1.003
1.041
1.130
1.240
1.331
1.410
1.525
1.294
1.172
1.087
0.998
1.023
1.084
1.153
1.331
1.133
1.092
0.997
1.020
1.112
1.043
1.003
2.654
2.211
1.691
1.374
1.073
1.085
1.185
1.327
1.484
1.652
1.778
1.998
1.977
2.135
1.763
1.590
1.448
1.284
1.161
1.057
1.044
1.101
1.222
1.373
1.497
1.650
1.763
1.430
1.265
1.147
1.025
1.055
1.146
1.231
1.425
1.207
1.120
1.023
1.040
1.155
1.041
1.013
0.892
0.970
1.114
1.501
4.118
2.853
1.926
1.502
1.366
1.125
1.016
1.047
1.112
0.937
0.973
1.229
1.267
1.553
1.920
3.366
3.996
2.617
1.783
1.451
1.226
1.175
0.963
1.249
1.599
2.011
4.300
3.098
2.125
1.650
1.310
1.698
2.055
4.565
3.418
1.982
3.089
4.588
u(T)= 0.02 K, u(p) = 0.1 kPa, and u(x1) = u(x2) = u(y1) = u(y2) =
0.001.
Figure 9. Residue curve map for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa simulated by Aspen split
using the NRTL model with the parameters given in Table 10.
Article
CONCLUSIONS
In order to study the 1-hexene + n-hexane separation process,
two solvents, ethyl butyrate and 2-pentanol have been proposed
as possible entrainers in an extractive distillation process. Hence,
consistent VLE data at 100.0 kPa have been determined for the
binary systems formed by 1-hexene (1) or n-hexane (2) with each
proposed solvent. Also the two ternary systems constituted by
the initial binary mixture and the solvent have been measured.
Wilson, NRTL, and UNIQUAC models correlated well the binary
systems and yielded good estimation for the ternary system,
without any remarkable dierence.
From the results, it is observed that both solvents decrease the
relative volatility of 1-hexene to n-hexane, ethyl butyrate even
inverts this relative volatility for high compositions of this solvent.
So, these solvents are not good entrainers for extractive distillation
to separate 1-hexene from n-hexane.
Figure 10. Residue curve map for the ternary system 1-hexene (1) +
n-hexane (2) + ethyl butyrate (3) at 100.0 kPa simulated by Aspen split
using the NRTL model with the parameters given in Table 10.
12S
solvent
x3 = 0.0
x3 = 0.7
x3 = 0.8
ethyl butyrate
2-pentanol
1.177
1.177
0.995
1.045
0.986
1.038
AUTHOR INFORMATION
Corresponding Author
REFERENCES
Figure 11. VLE data plotted on a solvent-free basis for the system
1-hexene (1) + n-hexane (2) + solvent (3) at 100.0 kPa. Continuous
line4 for x3 = 0.00: Dashed line for x3 = 0.70, calculated using the NRTL
model with the parameters given in Table 10: , ethyl butyrate; --,
2-pentanol.
Article
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