Académique Documents
Professionnel Documents
Culture Documents
Mines Paris/ParisTech, CEP/TEP, CNRS FRE 2861, 35 Rue Saint Honore, 77305 Fontainebleau, France
b Laboratory for Thermophysical Properties (LTP GmbH), Institute at the University of Oldenburg,
Marie-Curie-Str. 10, 26129 Oldenburg, France
Received 10 May 2006; received in revised form 4 July 2007; accepted 4 July 2007
Available online 10 July 2007
Abstract
VLE data (gas solubilities (TPx data) or complete TPxy data) were measured for the following systems:
hydrogen sulfide (H2 S) + dimethylsulfide (DMS) at 278, 293, 313, and 333 K.
H2 S + ethylmethylsulfide (EMS) at 293 and 313 K.
H2 S + carbon disulfide (CS2 ) at 273, 298, 323, and 348 K.
methane (CH4 ) + DMS at 253, 273, 293, and 313 K.
CH4 + EMS at 248, 273, 293, and 313 K.
CH4 + methylmercaptan (MM) at 243, 258, 273, 293, and 298 K.
CH4 + ethylmercaptan (EM) at 273, 293, and 313 K.
These data were used to establish new binary interaction parameters for the predictive SoaveRedlichKwong (PSRK) group contribution of
state. The extension of the PSRK parameter matrix allows now to perform reliable phase equilibrium calculations for systems with any hydrocarbons
and sulfur compounds. The mean relative deviation of PSRK compared to the experimental data for the bubble point pressures is less than 2% and
the mean absolute deviation for the vapor phase composition is 0.03 in terms of mole fraction.
2007 Elsevier B.V. All rights reserved.
Keywords: VLE measurements; H2 S; Carbonylsulfide; Dimethylsulfide; Ethylmethylsulfide; Ethylmercaptan; Methylmercaptan; Methane; Binary interaction
parameters; PSRK equation
1. Introduction
The idea of the study presented here was born while being
faced with a large demand from gas processing industry for
partition coefficients of sulfur compounds in solvents containing volatile hydrocarbons and hydrogen sulfide. Experimental
studies mainly performed by ARMINES and funded by Gas
Processors Association (GPA) in the project 876 [1,2] and after
0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.013
in the project 986 provided a large VLE database for multicomponent systems, whereas almost no data are available for the
binary subsystems with respect to the sulfur compounds. The
attempt of a correlation in order to enable at least interpolations
did not allow a reliable and consistent representation of the total
set of experimental data, because in most cases several equation
of state (EoS) binary interaction parameters had to be fitted to
VLE data of multicomponent systems, whereby the data were
available only at very limited composition.
A group contribution approach (predictive Soave
RedlichKwong: PSRK [37]) should then be applied to
compare the experimental data from GPA project 876 with
50
Fig. 1. Flow diagram of equipment. Co1: variable volume cell for component 1; Co2: variable volume cell for component 2; DAU: data acquisition unit; DDD:
digital displacement transducer; DL: degassed liquid; DT: displacement transducer; FVC: fixed volume cell; GC: gas chromatograph; LB: liquid bath; LS: liquid
sampler; LVi loading valve i; Me: methane cylinder; MS: magnetic stirrer; PP: platinum probe; N: pressurized nitrogen; PTh: high pressure pressure transducer;
PTl: low pressure pressure transducer; SD: stirring device; SM: sample monitoring; SV: home made shut off valve; TR: thermal regulator; Vi: shut off valve i; VP:
vacuum pump; VS: vapor sampler.
51
52
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xH2 Sexp
T = 278.46 K
0.29
0.63
0.98
1.42
1.88
2.38
2.90
4.22
5.35
6.17
6.90
7.48
7.96
8.34
8.76
9.33
9.65
9.88
10.08
10.25
10.39
10.54
10.68
10.77
0.29
0.62
0.97
1.40
1.86
2.36
2.88
4.19
5.32
6.12
6.83
7.38
7.84
8.21
8.60
9.15
9.46
9.68
9.87
10.04
10.19
10.34
10.49
10.58
0.00
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.03
0.05
0.07
0.10
0.12
0.14
0.16
0.18
0.19
0.20
0.20
0.20
0.20
0.20
0.19
0.19
0.0
1.5
1.7
1.5
1.3
1
0.8
0.5
0.6
0.8
1
1.3
1.5
1.6
1.8
1.9
2
2
2
2
1.9
1.9
1.8
1.7
0.0000
0.0486
0.0963
0.1517
0.2062
0.2619
0.3155
0.4382
0.5309
0.5926
0.6445
0.6834
0.7151
0.7401
0.7667
0.803
0.8239
0.8385
0.8515
0.8628
0.8729
0.8825
0.8924
0.8989
T = 293.43 K
0.54
3.68
3.85
4.02
4.24
5.04
5.42
5.88
6.44
7.21
8.13
8.80
9.61
10.55
11.83
12.85
14.13
15.47
0.54
3.44
3.60
3.77
3.98
4.76
5.13
5.59
6.14
6.92
7.85
8.54
9.38
10.35
11.69
12.74
14.07
15.45
0.00
0.24
0.25
0.26
0.27
0.29
0.29
0.30
0.30
0.29
0.27
0.26
0.23
0.20
0.14
0.10
0.06
0.02
0.0
6.6
6.5
6.4
6.2
5.7
5.4
5
4.6
4
3.4
2.9
2.4
1.9
1.2
0.8
0.4
0.1
0.0000
0.2527
0.2645
0.2769
0.2921
0.3452
0.3697
0.3986
0.4324
0.4776
0.5293
0.5658
0.6084
0.656
0.7189
0.767
0.8263
0.8874
yH2 Sexp
yH2 Scal
P%
y
0.879
0.9253
0.9559
0.968
0.9808
0.987
0.9926
0.996
0.8841
0.9336
0.9623
0.9745
0.9846
0.9902
0.9942
0.9972
0.9981
4
5.6
4.6
2.4
0.9
0.2
0.3
0.9
2
0.0052
0.0083
0.0065
0.0065
0.0038
0.0033
0.0016
0.0012
T = 313.22 K
3.03
3.52
3.51
5.88
5.99
9.05
9.33
11.87
12.21
0.6678
0.7257
0.855
0.918
0.9447
0.7146
0.8515
0.92
0.9485
0.3
1.9
3.2
2.9
0.0111
0.0035
0.002
0.0037
Pexp (bar)
Pcal (bar)
xH2 Sexp
0.1461
0.2726
0.4159
0.5222
xH2 Sexp
yH2 Sexp
yH2 Scal
P%
y
15.09
16.07
18.46
21.04
25.49
26.55
0.6174
0.6478
0.7192
0.7926
0.9143
0.9429
0.9631
0.9763
0.9838
0.9936
0.9658
0.9702
0.979
0.9862
0.9952
0.9969
2.8
2.9
3.1
2.1
0.9
0.5
0.0027
0.0027
0.0024
0.0016
T = 333.20 K
3.83
3.77
5.01
3.40
8.04
8.12
11.94
12.20
16.14
16.62
19.11
19.58
19.92
20.49
23.89
24.76
27.89
28.52
31.91
32.80
36.00
36.25
37.98
38.62
40.45
40.36
0.074
0.2378
0.3646
0.4822
0.5526
0.573
0.6639
0.7376
0.8167
0.8777
0.9184
0.9477
0.4714
0.6115
0.4097
0.7806
0.864
0.9106
0.9318
0.9555
0.9645
0.9781
0.984
0.9902
0.993
0.4671
0.78
0.8702
0.9176
0.9373
0.9422
0.9603
0.9717
0.9818
0.9883
0.9923
0.9951
1.6
1.1
2.1
2.9
2.5
2.8
3.7
2.3
2.8
0.7
1.7
0.2
0.0042
0.0005
0.0062
0.007
0.0104
0.0047
0.0073
0.0037
0.0043
0.0021
0.002
Pexp (bar)
14.68
15.61
17.90
20.61
25.27
26.67
53
Table 2
Experimental and calculated VLE data for the H2 S-EMS binary mixture
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xH2 Sexp
T = 293.23 K
0.17
0.67
1.23
1.82
2.57
3.51
4.65
5.71
6.98
8.42
9.57
10.50
11.30
11.94
12.47
12.93
13.35
13.70
14.06
14.42
14.67
14.97
15.24
15.48
15.74
0.17
0.69
1.26
1.86
2.63
3.58
4.72
5.78
7.02
8.42
9.53
10.42
11.19
11.80
12.31
12.76
13.16
13.51
13.86
14.21
14.47
14.77
15.05
15.30
15.57
0.00
0.02
0.03
0.05
0.06
0.07
0.07
0.06
0.04
0.00
0.04
0.08
0.11
0.14
0.16
0.18
0.19
0.20
0.20
0.20
0.20
0.20
0.19
0.19
0.17
0.00
2.6
2.8
2.7
2.4
2.1
1.6
1.1
0.6
0
0.4
0.8
1
1.2
1.3
1.4
1.4
1.4
1.4
1.4
1.4
1.3
1.3
1.2
1.1
0.0000
0.0483
0.0987
0.149
0.2094
0.2781
0.3546
0.4201
0.4917
0.5663
0.6223
0.6654
0.7012
0.7295
0.7525
0.7727
0.7907
0.8061
0.8215
0.8373
0.8487
0.8617
0.8743
0.8853
0.8974
T = 313.33 K
0.40
1.49
2.57
3.71
4.77
5.84
6.93
8.21
9.36
10.50
11.58
12.65
13.53
14.54
16.24
17.52
18.65
19.57
20.57
21.39
22.21
23.00
23.79
24.56
25.17
0.40
1.48
2.55
3.68
4.73
5.80
6.87
8.14
9.27
10.41
11.47
12.53
13.40
14.39
16.07
17.34
18.46
19.38
20.38
21.20
22.03
22.83
23.64
24.43
25.05
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.09
0.10
0.11
0.12
0.13
0.15
0.16
0.18
0.18
0.19
0.19
0.19
0.18
0.17
0.16
0.14
0.12
0.00
0.5
0.6
0.7
0.8
0.8
0.8
0.9
0.9
0.9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.9
0.9
0.8
0.7
0.7
0.6
0.5
0.0000
0.0653
0.1253
0.1845
0.2358
0.2852
0.3322
0.3842
0.4285
0.4705
0.5083
0.5442
0.5728
0.6044
0.6558
0.6931
0.7251
0.7508
0.7784
0.8007
0.823
0.8444
0.8658
0.8867
0.9031
Fig. 4. Pxy diagrams of the H2 S (1)CS2 (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).
54
Table 3
Experimental and calculated VLE data for the H2 S-CS2 binary mixture
xH2 Sexp
yH2 Sexp
yH2 Scal
P%
T = 273.08 K
0.17
0.17
3.45
4.01
4.87
7.47
7.26
10.33
10.33
0.0000
0.6207
1.0000
0.0000
0.9460
0.9596
0.9658
0.9821
1.0000
0.0000
0.9855
1.0000
0.0
2.8
0.0
0.0000
0.0033
0.0000
T = 298.40 K
0.49
0.49
4.23
4.68
5.11
6.07
7.10
6.13
8.69
8.20
12.27
11.52
13.09
12.92
13.79
13.64
16.05
15.97
19.34
19.28
20.24
20.24
0.1919
0.2821
0.463
0.5541
0.6038
0.7655
0.9563
1.0000
0
0.8758
0.8817
0.9043
0.9211
0.9368
0.9488
0.9722
0.9818
0.9979
1.0000
0.0000
0.926
0.9472
0.9666
0.9725
0.9753
0.9839
0.9962
1.0000
0.0
13.7
5.7
6.1
1.3
1.1
0.5
0.3
0.0
0.0000
0.0108
0.0016
0.0031
0.0021
0.0017
0.0000
T = 323.50 K
1.16
1.16
5.27
6.69
8.05
9.59
11.24
11.27
13.93
14.29
21.73
22.01
22.96
23.06
27.23
27.40
33.66
33.65
35.64
35.64
0.0000
0.2172
0.2982
0.5556
0.5957
0.7603
0.9528
1.0000
0.0000
0.7603
0.8241
0.8473
0.8808
0.9011
0.9167
0.9566
0.9714
0.9945
1.0000
0.0000
0.9012
0.9242
0.9576
0.961
0.974
0.9933
1.0000
0.0
0.3
2.6
1.3
0.4
0.6
0
0.0
0.0000
0.0001
0.0076
0.9576
0.0044
0.0026
0.0011
0.0000
T = 348.45 K
2.40
2.40
8.01
9.98
11.94
14.18
14.83
16.55
17.25
20.66
21.58
35.27
36.15
42.91
42.73
54.42
54.22
58.12
58.12
0.0000
0.1754
0.2145
0.2893
0.5953
0.7451
0.9502
1.0000
0.0000
0.5965
0.7311
0.7914
0.8285
0.857
0.8837
0.9419
0.9752
1.0000
0.0000
0.8366
0.86
0.8891
0.9411
0.9576
0.988
1.0000
0.0
4.6
4.3
4.5
2.5
0.4
0.4
0.0
0.0000
0.5965
0.7311
0.7914
0.0082
0.003
0.0055
0.9411
0.0157
0.0128
0.0000
Pexp (bar)
Pcal (bar)
Table 4
Experimental and calculated VLE data for the CH4 -DMS binary mixture
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xCH4exp
T = 252.89 K
0.08
0.87
2.30
4.57
7.21
10.40
15.16
20.08
24.95
48.16
63.01
69.63
78.65
86.30
92.93
97.30
100.88
0.08
0.88
2.32
4.61
7.27
10.48
15.29
20.25
25.17
48.64
63.69
70.41
79.57
87.36
94.10
98.56
102.21
0.00
0.01
0.02
0.04
0.06
0.09
0.13
0.18
0.23
0.48
0.68
0.78
0.92
1.05
1.18
1.26
1.33
0.0
0.7
0.8
0.8
0.8
0.8
0.9
0.9
0.9
1.0
1.1
1.1
1.2
1.2
1.3
1.3
1.3
0.0000
0.0020
0.0055
0.0112
0.0177
0.0256
0.0373
0.0494
0.0612
0.1165
0.1503
0.1650
0.1843
0.2002
0.2136
0.2222
0.2290
T = 253.06 K
0.08
1.42
2.99
4.62
7.70
13.00
18.79
34.60
39.54
49.25
55.03
60.82
65.62
70.29
75.16
80.51
85.73
91.31
95.82
103.36
0.08
1.46
3.08
4.76
7.92
13.37
19.33
35.52
40.58
50.49
56.39
62.29
67.17
71.93
76.87
82.32
87.61
93.27
97.85
105.48
0.00
0.04
0.09
0.14
0.23
0.38
0.53
0.92
1.04
1.24
1.36
1.47
1.56
1.64
1.71
1.81
1.88
1.96
2.03
2.12
0.0
2.9
2.9
3.0
2.9
2.9
2.8
2.7
2.6
2.5
2.5
2.4
2.4
2.3
2.3
2.2
2.2
2.1
2.1
2.1
0.0000
0.0034
0.0074
0.0115
0.0193
0.0326
0.0471
0.0858
0.0977
0.1206
0.1340
0.1471
0.1578
0.1681
0.1786
0.1899
0.2006
0.2118
0.2207
0.235
T = 272.76 K
0.22
1.56
2.46
4.61
4.69
7.37
9.27
10.08
14.45
14.62
19.17
21.02
25.44
30.57
35.57
40.68
45.46
50.16
50.72
55.21
60.23
65.02
69.82
0.22
1.57
2.48
4.64
4.71
7.42
9.33
10.15
14.54
14.71
19.29
21.16
25.60
30.76
35.79
40.94
45.74
50.47
51.04
55.56
60.60
65.42
70.25
0.00
0.01
0.01
0.03
0.03
0.05
0.06
0.06
0.09
0.09
0.12
0.13
0.16
0.19
0.22
0.26
0.29
0.32
0.32
0.34
0.37
0.40
0.43
0.0
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.0000
0.0031
0.0051
0.0100
0.0102
0.0163
0.0206
0.0224
0.0323
0.0327
0.0429
0.0471
0.0569
0.0683
0.0794
0.0906
0.1010
0.1112
0.1124
0.1220
0.1327
0.1428
0.1529
Table 4 (Continued )
Pcal (bar)
diff P (bar)
P%
xCH4exp
Pexp (bar)
74.69
75.20
79.47
85.15
89.32
89.60
94.29
99.01
101.95
75.16
75.66
79.96
85.67
89.87
90.15
94.87
99.61
102.56
0.46
0.46
0.49
0.52
0.55
0.55
0.58
0.60
0.61
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.1630
0.1640
0.1728
0.1843
0.1926
0.1932
0.2025
0.2118
0.2175
74.48
79.70
84.73
89.85
95.43
100.72
T = 293.16 K
0.53
5.28
10.39
16.07
23.30
30.86
35.72
40.01
46.01
50.27
55.57
58.56
65.65
70.47
75.34
83.16
88.54
93.68
99.86
0.53
5.28
10.38
16.06
23.30
30.87
35.73
40.02
46.03
50.31
55.62
58.62
65.73
70.57
75.47
83.32
88.73
93.89
100.11
0.00
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.03
0.04
0.05
0.06
0.08
0.10
0.12
0.16
0.19
0.21
0.25
0.0
0.1
0.1
0.0
0.0
0.0
0.0
0.0
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.2
0.3
0.0000
0.0102
0.0210
0.0331
0.0484
0.0643
0.0744
0.0833
0.0958
0.1046
0.1155
0.1216
0.1361
0.1458
0.1557
0.1713
0.1820
0.1922
0.2044
T = 313.30 K
1.12
3.04
7.70
14.54
20.42
29.31
34.97
44.48
50.54
55.50
61.68
68.84
73.91
85.04
90.61
96.08
100.37
1.12
2.99
7.53
14.23
20.01
28.78
34.38
43.85
49.91
54.87
61.09
68.33
73.46
84.81
90.52
96.14
100.57
0.00
0.05
0.16
0.31
0.41
0.53
0.59
0.63
0.64
0.62
0.59
0.51
0.44
0.23
0.09
0.06
0.20
0.0
1.6
2.1
2.1
2.0
1.8
1.7
1.4
1.3
1.1
1.0
0.7
0.6
0.3
0.1
0.1
0.2
0.0000
0.0039
0.0133
0.0271
0.0389
0.0569
0.0683
0.0875
0.0997
0.1097
0.1221
0.1366
0.1468
0.1692
0.1805
0.1915
0.2002
T = 313.43 K
1.12
5.29
8.76
11.86
14.52
19.00
23.84
27.97
32.81
37.57
45.11
50.65
56.30
62.06
68.26
1.12
5.27
8.72
11.81
14.47
18.94
23.76
27.90
32.74
37.51
45.07
50.64
56.32
62.13
68.38
0.00
0.02
0.04
0.05
0.06
0.07
0.07
0.07
0.07
0.07
0.04
0.01
0.02
0.06
0.12
0.0
0.4
0.4
0.4
0.4
0.4
0.3
0.3
0.2
0.2
0.1
0.0
0.0
0.1
0.2
0.0000
0.0086
0.0157
0.0221
0.0275
0.0367
0.0466
0.0550
0.0649
0.0746
0.0899
0.1011
0.1125
0.1242
0.1366
Pexp (bar)
55
Pcal (bar)
diff P (bar)
P%
xCH4exp
74.66
79.94
85.05
90.24
95.90
101.28
0.18
0.24
0.31
0.39
0.48
0.56
0.2
0.3
0.4
0.4
0.5
0.6
0.1491
0.1596
0.1697
0.1799
0.1911
0.2016
Pexp (bar)
Pcal (bar)
xCH4exp
yCH4exp
yCH4cal
P%
y
T = 313.16 K
3.40
5.00
10.04
15.00
20.03
29.96
40.06
50.03
60.11
70.04
80.10
90.04
100.02
110.10
120.00
3.74
5.42
10.30
15.63
21.01
31.43
42.12
52.40
62.89
71.76
83.97
92.50
103.23
113.94
124.68
0.0055
0.0089
0.0190
0.0300
0.0410
0.0623
0.0840
0.1047
0.1258
0.1434
0.1676
0.1844
0.2054
0.2264
0.2472
0.6552
0.7502
0.8729
0.9080
0.9284
0.9463
0.9539
0.9582
0.9603
0.9615
0.9612
0.9606
0.9591
0.9572
0.9550
0.6904
0.7815
0.8776
0.9136
0.9311
0.9473
0.9548
0.9584
0.9601
0.9606
0.9602
0.9594
0.9578
0.9557
0.9531
9.9
8.4
2.6
4.2
4.9
4.9
5.1
4.7
4.6
2.5
4.8
2.7
3.2
3.5
3.9
0.0351
0.0313
0.0046
0.0056
0.0027
0.0010
0.0009
0.0001
0.0003
0.0009
0.0010
0.0012
0.0013
0.0015
0.0019
Table 5
Experimental and calculated VLE data for the CH4 -EMS binary mixture
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xCH4exp
T = 247.76 K
0.01
1.15
3.66
7.10
10.21
14.72
19.13
24.42
29.18
33.96
41.84
56.18
66.68
77.21
85.84
97.35
0.01
1.15
3.64
7.06
10.16
14.65
19.03
24.30
29.04
33.80
41.64
55.91
66.34
76.79
85.35
96.74
0.000
0.006
0.019
0.036
0.051
0.073
0.094
0.118
0.140
0.162
0.201
0.277
0.342
0.421
0.494
0.611
0.0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.6
0.6
0.0000
0.0035
0.0111
0.0215
0.0308
0.0442
0.0571
0.0725
0.0861
0.0995
0.1212
0.1590
0.1851
0.2098
0.2289
0.2527
T = 272.96 K
0.06
0.82
2.18
4.45
9.00
13.81
18.76
24.04
37.96
54.10
58.82
0.06
0.78
2.07
4.23
8.56
13.17
17.95
23.09
36.78
52.99
57.81
0.00
0.04
0.11
0.23
0.44
0.64
0.81
0.96
1.18
1.11
1.02
0.0
5.0
5.2
5.1
4.9
4.6
4.3
4.0
3.1
2.1
1.7
0.0000
0.0019
0.0054
0.0111
0.0226
0.0347
0.0471
0.0603
0.0947
0.1339
0.1452
56
Table 5 (Continued )
Pcal (bar)
diff P (bar)
P%
xCH4exp
73.79
80.01
84.90
99.08
108.44
116.32
73.29
79.83
85.03
100.32
110.65
119.47
0.50
0.18
0.12
1.24
2.21
3.15
0.7
0.2
0.1
1.3
2.0
2.7
0.1805
0.1949
0.2061
0.2380
0.2586
0.2756
T = 293.41 K
0.17
1.79
3.15
5.08
11.71
16.46
21.03
27.84
32.93
38.57
44.12
48.65
53.80
59.17
63.98
68.73
74.00
79.96
86.56
92.14
97.79
103.42
0.17
1.74
3.06
4.94
11.41
16.06
20.55
27.27
32.31
37.92
43.46
48.01
53.18
58.61
63.47
68.32
73.69
79.81
86.62
92.40
98.29
104.18
0.00
0.05
0.09
0.14
0.30
0.40
0.48
0.57
0.62
0.65
0.66
0.65
0.62
0.57
0.50
0.42
0.31
0.15
0.06
0.26
0.50
0.76
0.0
2.6
2.7
2.7
2.6
2.4
2.3
2.0
1.9
1.7
1.5
1.3
1.2
1.0
0.8
0.6
0.4
0.2
0.1
0.3
0.5
0.7
0.0000
0.0039
0.0072
0.0119
0.0278
0.0391
0.0500
0.0660
0.0780
0.0911
0.1039
0.1143
0.1260
0.1382
0.1490
0.1596
0.1712
0.1843
0.1987
0.2107
0.2228
0.2347
T = 313.35 K
0.40
3.79
8.82
16.94
20.73
26.19
30.07
34.84
39.75
46.67
51.18
54.99
61.41
67.00
71.37
75.45
82.44
87.67
91.30
96.43
99.57
104.08
0.40
3.62
8.44
16.24
19.90
25.21
28.99
33.67
38.50
45.35
49.84
53.65
60.11
65.76
70.20
74.37
81.55
86.96
90.73
96.09
99.39
104.15
0.00
0.16
0.39
0.70
0.83
0.98
1.08
1.18
1.25
1.32
1.34
1.34
1.31
1.25
1.17
1.08
0.89
0.71
0.57
0.34
0.18
0.07
0.0
4.3
4.4
4.1
4.0
3.8
3.6
3.4
3.2
2.8
2.6
2.4
2.1
1.9
1.6
1.4
1.1
0.8
0.6
0.3
0.2
0.1
0.0000
0.0077
0.0191
0.0374
0.0459
0.0581
0.0668
0.0774
0.0883
0.1037
0.1136
0.1220
0.1361
0.1483
0.1578
0.1666
0.1818
0.1930
0.2008
0.2118
0.2186
0.2282
Pexp (bar)
Table 6
Experimental and calculated VLE data for the CH4 -MM binary mixture
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xCH4exp
T = 243.19 K
0.20
0.98
3.00
6.23
10.74
16.29
20.46
26.06
32.07
37.33
43.61
47.77
58.90
65.36
70.15
75.62
81.95
0.20
0.95
2.88
5.99
10.35
15.78
19.89
25.46
31.50
36.84
43.30
47.63
59.40
66.37
71.64
77.74
84.94
0.00
0.04
0.12
0.24
0.38
0.51
0.57
0.60
0.57
0.49
0.31
0.15
0.49
1.02
1.49
2.12
2.99
0.0
3.5
4.0
3.9
3.6
3.1
2.8
2.3
1.8
1.3
0.7
0.3
0.8
1.6
2.1
2.8
3.6
0.0000
0.0014
0.0050
0.0107
0.0187
0.0285
0.0358
0.0456
0.0561
0.0651
0.0757
0.0826
0.1007
0.1107
0.1180
0.1260
0.1349
T = 258.00 K
0.42
1.59
3.68
7.32
11.71
16.25
20.45
40.91
45.31
61.89
69.02
75.10
80.37
0.42
1.50
3.42
6.81
10.94
15.27
19.34
39.94
44.56
62.71
70.92
78.14
84.58
0.00
0.10
0.26
0.51
0.77
0.98
1.11
0.97
0.75
0.82
1.90
3.04
4.21
0.0
6.0
7.0
7.0
6.6
6.0
5.4
2.4
1.7
1.3
2.7
4.0
5.2
0.0000
0.0019
0.0053
0.0112
0.0183
0.0258
0.0326
0.0661
0.0733
0.1002
0.1115
0.1211
0.1292
T = 272.98 K
0.80
1.89
4.77
7.86
11.52
14.66
19.40
24.56
30.16
35.58
40.60
45.71
50.41
54.89
60.32
65.18
69.92
75.16
0.80
1.85
4.62
7.61
11.18
14.26
18.96
24.13
29.81
35.39
40.61
46.01
51.03
55.88
61.85
67.27
72.63
78.66
0.00
0.05
0.15
0.25
0.34
0.40
0.44
0.43
0.35
0.19
0.02
0.30
0.62
0.99
1.53
2.09
2.71
3.50
0.0
2.4
3.2
3.2
3.0
2.7
2.3
1.8
1.2
0.5
0.0
0.7
1.2
1.8
2.5
3.2
3.9
4.7
0.0000
0.0018
0.0064
0.0114
0.0173
0.0224
0.0301
0.0384
0.0475
0.0563
0.0645
0.0728
0.0804
0.0877
0.0965
0.1043
0.1119
0.1203
T = 293.35 K
1.70
5.96
9.65
13.66
19.27
24.49
31.74
36.07
40.81
45.96
1.70
5.81
9.40
13.33
18.88
24.10
31.47
35.93
40.87
46.30
0.00
0.15
0.26
0.34
0.39
0.38
0.27
0.14
0.06
0.34
0.0
2.5
2.6
2.5
2.0
1.6
0.8
0.4
0.1
0.7
0.0000
0.0066
0.0124
0.0186
0.0275
0.0357
0.0472
0.0541
0.0616
0.0699
Pcal (bar)
diff P (bar)
P%
xCH4exp
51.36
65.12
70.76
78.78
84.00
0.66
1.82
2.43
3.41
4.13
1.3
2.9
3.6
4.5
5.2
0.0775
0.0978
0.1060
0.1175
0.1248
2.00
2.89
3.59
4.36
4.92
7.53
10.90
20.80
34.71
51.23
71.36
0.00
0.03
0.05
0.07
0.09
0.15
0.20
0.13
0.46
1.91
4.76
0.0
1.0
1.4
1.6
1.8
1.9
1.8
0.6
1.3
3.9
7.1
0.0000
0.0014
0.0025
0.0038
0.0047
0.0088
0.0142
0.0298
0.0515
0.0766
0.1062
Fig. 5. Pxy diagrams of the CH4 (1)DMS (2) binary system at different
temperatures. Solid line: correlation using PSRK (Unifac).
Fig. 6. Pxy diagrams of the CH4 (1)EMS (2) binary system at different
temperatures. Solid line: correlation using PSRK (Unifac).
57
Table 7
Experimental and calculated VLE data for the CH4 -EM binary mixture
Pexp (bar)
Pcal (bar)
diff P (bar)
P%
xCH4exp
T = 272.94 K
0.25
0.92
2.20
5.53
7.80
10.25
15.37
20.04
25.20
29.73
35.36
40.17
64.65
69.66
74.39
89.62
93.59
97.44
103.70
107.05
0.25
0.94
2.24
5.63
7.94
10.43
15.62
20.33
25.54
30.09
35.72
40.51
64.70
69.59
74.20
88.91
92.73
96.40
102.36
105.53
0.00
0.01
0.04
0.10
0.14
0.18
0.25
0.30
0.33
0.35
0.36
0.35
0.05
0.06
0.19
0.70
0.87
1.04
1.34
1.52
0.0
1.5
1.8
1.8
1.8
1.7
1.6
1.5
1.3
1.2
1.0
0.9
0.1
0.1
0.3
0.8
0.9
1.1
1.3
1.4
0.0000
0.0017
0.0049
0.0132
0.0188
0.0248
0.0373
0.0484
0.0607
0.0712
0.0841
0.0950
0.1476
0.1578
0.1673
0.1965
0.2039
0.2109
0.2220
0.2278
T = 293.36 K
0.59
1.13
2.34
13.97
18.23
25.63
29.74
35.17
42.44
47.72
54.44
61.04
65.05
70.27
74.67
79.51
85.02
90.92
95.40
100.06
107.45
0.59
1.07
2.15
12.61
16.50
23.35
27.20
32.33
39.30
44.44
51.06
57.66
61.72
67.07
71.63
76.70
82.55
88.91
93.82
98.97
107.30
0.00
0.06
0.20
1.36
1.73
2.28
2.54
2.84
3.14
3.28
3.38
3.38
3.33
3.20
3.04
2.81
2.47
2.00
1.58
1.09
0.15
0.0
5.5
8.4
9.8
9.5
8.9
8.6
8.1
7.4
6.9
6.2
5.5
5.1
4.6
4.1
3.5
2.9
2.2
1.7
1.1
0.1
0.0000
0.0011
0.0036
0.0274
0.0362
0.0514
0.0599
0.0712
0.0862
0.0972
0.1112
0.1249
0.1333
0.1442
0.1534
0.1635
0.1750
0.1874
0.1968
0.2065
0.2221
T = 313.41 K
1.21
2.51
6.85
10.32
15.19
20.49
26.34
31.46
36.78
41.46
45.85
50.65
56.17
62.00
66.53
70.58
75.03
82.72
89.41
96.94
103.37
1.21
2.43
6.50
9.77
14.37
19.41
24.99
29.91
35.05
39.59
43.87
48.57
54.01
59.79
64.30
68.37
72.85
80.64
87.49
95.24
101.95
0.00
0.08
0.35
0.56
0.82
1.09
1.35
1.55
1.74
1.87
1.98
2.08
2.16
2.21
2.23
2.22
2.19
2.08
1.93
1.69
1.42
0.0
3.3
5.1
5.4
5.4
5.3
5.1
4.9
4.7
4.5
4.3
4.1
3.8
3.6
3.3
3.1
2.9
2.5
2.2
1.7
1.4
0.0000
0.0027
0.0117
0.0188
0.0289
0.0398
0.0518
0.0622
0.0731
0.0826
0.0915
0.1013
0.1124
0.1242
0.1333
0.1414
0.1503
0.1657
0.1791
0.1940
0.2068
58
Fig. 7. Pxy diagrams of the CH4 (1)MM (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).
Fig. 10. Experimental Henrys constants of CH4 in ethylmethylsulfide vs. temperature and prediction using PSRK (solid line).
Fig. 8. Pxy diagrams of the CH4 (1)EM (2) binary system at different temperatures. Solid line: correlation using PSRK (Unifac).
Fig. 11. Experimental Henrys constants of CH4 in methylmercaptan vs. temperature and prediction using PSRK (solid line).
Fig. 9. Experimental Henrys constants of CH4 in dimethylsulfide vs. temperature and prediction using PSRK (solid line).
Fig. 12. Experimental Henrys constants of CH4 in ethylmercaptan vs. temperature and prediction using PSRK (solid line).
H (bar)
CH4 MM
243.19
272.98
293.35
298.23
348.11
257.99
538.5
597.1
619.0
614.0
665.6
591.7
CH4 EM
252.93
272.94
293.27
313.41
411.6
391.6
476.6
471.9
CH4 DMS
252.89
253.06
272.81
293.16
313.29
313.43
CH4 MS
247.76
272.96
293.41
313.35
390.6
3820
429.4
458.7
484.3
475.2
321.3
384.9
407.3
434.3
59
Acknowledgement
The financial support of Gas Processors Association is gratefully acknowledged.
References
[1] A Valtz, J. Schwartzentruber, D. Richon, H. Renon, Gas Processors Association Research Report (RR-135), Tulsa, Oklahoma, Project 876, February
1994.
[2] A Valtz, P. Guilbot, D. Richon, Gas Processors Association Research Report
(RR-162), Tulsa, Oklahoma, Project 876, September 1998.
[3] T. Holderbaum, J. Gmehling, Fluid Phase Equilib. 70 (1991) 251265.
[4] K. Fischer, J. Gmehling, Fluid Phase Equilib. 121 (1996) 185206.
[5] J. Gmehling, J. Li, K. Fischer, Fluid Phase Equilib. 141 (1997) 113
127.
[7] S. Horstmann, K. Fischer, J. Gmehling, Fluid Phase Equilib. 167 (2000)
173186.
[8] P. Guilbot, P. Theveneau, A. Baba-Ahmed, S. Horstmann, K. Fischer, D.
Richon, Fluid Phase Equilib. 170 (2000) 193202.
[9] S. Laugier, D. Richon, Rev. Sci. Instrum. 57 (1986) 469472.
[10] U. Setzmann, W. Wagner, J. Phys. Chem. Ref. Data 20 (6) (1991)
10611151.
[11] P. Guilbot, A. Valtz, H. Legendre, D. Richon, Analysis 28 (2000) 426
431.
[12] K. Fischer, M. Wilken, J. Chem. Thermodyn. 33 (2001) 12851308.