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PVT modeling of reservoir uids using PC-SAFT EoS and Soave-BWR EoS
Wei Yan 1, Farhad Varzandeh 2 , Erling H. Stenby *
Center for Energy Resources Engineering (CERE), Department of Chemistry, Technical University of Denmark, DK-2800 Lyngby, Denmark
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 7 July 2014
Received in revised form 19 November 2014
Accepted 25 November 2014
Available online xxx
Cubic equations of state, such as the SoaveRedlichKwong (SRK) and the PengRobinson (PR) EoS, are
still the mostly used models in PVT modeling of reservoir uids, and almost the exclusively used models
in compositional reservoir simulations. Nevertheless, it is promising that recently developed non-cubic
EoS models, such as the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) EoS and the Soave
modied BenedictWebbRubin (Soave-BWR) EoS, may partly replace the roles of these classical cubic
models in the upstream oil industry. Here, we attempt to make a comparative study of non-cubic models
(PC-SAFT and Soave-BWR) and cubic models (SRK and PR) in several important aspects related to PVT
modeling of reservoir uids, including density description for typical pure components in reservoir
uids, description of binary VLE, prediction of multicomponent phase envelopes, and PVT calculation of
reservoir uids. Extensive data are used in the comparison and the four models are treated as equally as
possible. We adopt the method of Pedersen et al. as the framework for heptanes plus characterization and
the same correlations for estimating the critical properties for SRK, PR and Soave-BWR. For PC-SAFT, new
correlations for estimating its model parameters in heptanes plus are developed. The results reveal that
the non-cubic models are clearly advantageous in density calculation of pure components. For binary VLE
and multicomponent phase envelopes, the results are similar for the four models. For PVT prediction, the
non-cubic models show advantages in some high pressure high temperature (HPHT) uids but no clear
advantages in general, indicating the necessity for further improvement of the characterization
procedure.
2014 Elsevier B.V. All rights reserved.
Keywords:
Equation of state
Reservoir uids
C7+ characterization
PC-SAFT
Soave-BWR
1. Introduction
In the oil and gas industry, there is an obvious contrast between
the upstream and the downstream with regards to adopting newly
developed equations of state (EoS). In the downstream, these new
EoS models are usually quickly accepted while in the upstream, the
most widely used EoS models are still the cubic equations of state
(CEoS), specically the SoaveRedlichKwong (SRK) EoS [1] and
the PengRobinson (PR) EoS [2]. These two CEoSs are the most
used models in PVT modeling of reservoir uids and almost the
exclusively used models in compositional reservoir simulations.
There are many reasons for the phenomenon: in contrast to the
large variety of chemicals in the downstream, hydrocarbons are
the major components of concern in the upstream; CEOSs are
generally believed to provide enough accuracy in routine PVT
modeling; as a main user of PVT modeling results, compositional
* Corresponding author. Tel.: +45 4525 2012; fax: +45 4588 3136.
E-mail addresses: weya@kemi.dtu.dk (W. Yan), farvar@kemi.dtu.dk
(F. Varzandeh), ehst@kemi.dtu.dk (E.H. Stenby).
1
Tel.: +45 4525 2914; fax: +45 4588 2258.
2
Tel.: +45 4525 2033.
0378-3812/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2014.11.022
97
Table 1
Applicable ranges for the reference EoS models for various components.
Components
Tmin (K)
Tmax (K)
Pmax (bar)
rmax (mol/L)
Tr,min
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
63.15
216.59
187.70
90.69
90.37
85.53
134.90
143.47
177.83
182.55
216.37
219.70
243.50
247.54
263.60
113.73
112.65
119.60
278.67
178.00
2000
2000
760
625
675
650
575
600
600
600
600
600
675
700
700
575
500
550
750
700
22000
8000
1700
10000
9000
10000
2000
1000
1000
1000
1000
8000
8000
5000
7000
350
10000
10000
5000
5000
53.15
37.24
29.12
40.07
22.42
20.60
13.86
11.20
8.85
7.75
6.69
6.06
5.41
4.97
4.53
12.90
13.30
9.38
11.45
10.58
0.50
0.71
0.50
0.48
0.30
0.23
0.32
0.31
0.35
0.34
0.38
0.37
0.39
0.39
0.40
0.28
0.24
0.24
0.50
0.30
Table 2
AAD% and maximum absolute deviation in the calculated density for different EoSs within 273500 K and 02000 bar without volume transition.
Components
SRK
PR
PC-SAFT
Soave-BWR
CPA
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
2.24
4.88
3.04
1.29
2.07
3.28
5.21
7.67
10.16
12.37
14.46
16.54
18.33
18.38
21.48
4.23
5.85
7.84
8.70
11.08
7.01
21.00
16.48
16.47
19.91
20.60
20.07
22.71
23.14
20.09
22.26
24.60
26.56
26.70
29.60
21.24
26.58
21.31
15.92
17.90
9.35
5.04
7.61
8.78
8.52
7.42
5.51
3.62
3.00
3.37
4.84
7.02
9.02
9.08
12.54
6.48
5.00
3.66
3.36
2.74
13.62
13.28
9.51
12.43
11.85
12.01
12.82
13.60
14.44
11.05
13.46
16.06
18.25
18.40
21.63
13.44
18.97
13.82
6.84
8.57
3.23
1.23
0.47
1.35
2.07
1.71
1.61
1.22
1.42
1.57
1.77
2.20
2.05
2.09
2.01
2.23
1.56
1.93
0.73
1.04
4.91
20.90
6.72
6.11
5.73
3.86
8.38
15.71
6.91
5.85
6.93
7.92
8.27
9.31
10.14
6.55
8.37
8.37
3.05
4.88
0.57
0.74
0.38
0.88
0.64
1.44
1.81
1.70
1.35
1.29
1.04
0.85
0.78
2.61
0.63
2.17
2.78
3.17
1.03
0.79
2.63
3.81
3.45
4.08
4.15
4.57
3.46
4.73
3.39
3.51
3.22
3.38
3.44
4.74
2.84
4.48
4.72
5.26
3.12
1.62
3.94
3.18
1.87
2.62
3.24
4.45
5.50
2.86
2.92
3.00
3.24
3.82
4.41
5.32
5.86
3.69
2.73
2.63
5.84
14.77
35.97
6.54
10.47
8.25
17.60
19.13
8.82
9.51
10.51
11.86
13.16
14.51
15.19
7.65
7.60
8.10
Average
8.95
21.01
6.30
13.70
1.67
7.94
1.33
3.73
3.63
12.53
No CPA model parameters for i-pentane and i-hexane are available and these two components are excluded in the average for CPA.
98
Fig. 1. AAD% in the calculated density for different EoSs within 279500 K and 02000 bar without volume transition.
Fig. 2. Contour map of deviation in the calculated densities for methane by different EoSs: (a) SRK; (b) PR; (c) PC-SAFT; and (d) Soave-BWR. The relative deviations (%) are
labeled on the contour lines. The green and the red circles indicate the conditions for the minimum and the maximum deviations, respectively. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)
99
Table 3
AAD% and maximum absolute deviations in the calculated saturated liquid density for different EoSs without volume transition.
Components
SRK
PR
PC-SAFT
Soave-BWR
CPA
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
4.41
12.66
6.50
4.94
6.92
8.36
9.72
11.63
13.07
14.70
15.84
17.56
18.37
17.78
20.10
9.10
10.06
11.32
11.66
13.27
20.02
24.91
19.37
21.05
22.82
23.82
25.02
27.02
25.49
25.62
25.78
30.51
30.18
32.34
33.38
24.11
26.54
24.75
25.81
27.06
9.58
4.39
7.11
9.04
6.96
5.71
4.66
3.32
2.94
3.79
5.06
7.03
7.94
7.30
9.93
5.05
4.48
3.38
4.04
2.85
13.34
16.94
10.69
12.78
14.48
15.52
16.78
18.98
16.97
17.40
17.62
22.80
22.39
24.66
26.02
15.83
18.46
16.51
17.72
19.02
2.30
2.58
0.68
0.91
0.84
0.71
0.90
1.75
1.28
1.64
1.48
1.12
1.27
1.26
1.52
0.59
1.42
1.27
1.26
1.42
3.22
14.47
3.05
5.55
2.84
4.34
6.79
7.35
12.40
13.64
16.77
12.11
10.75
12.08
9.47
5.51
3.47
9.43
9.27
9.55
2.16
2.45
1.19
1.84
0.44
1.20
1.54
1.33
1.33
1.54
1.61
1.54
0.72
2.18
1.03
1.56
1.17
2.64
1.73
2.11
1.31
3.20
3.93
3.07
1.61
0.74
1.12
1.04
4.72
6.83
8.39
3.94
6.77
6.77
4.51
1.54
1.50
4.57
1.23
1.43
3.04
2.19
2.09
2.97
2.18
2.43
4.12
1.73
2.03
1.87
1.68
2.15
1.75
2.31
2.36
2.00
1.90
1.61
21.00
30.67
16.70
19.98
21.48
31.31
29.81
30.87
40.40
29.32
25.74
40.75
21.92
37.02
39.82
18.57
20.23
28.15
Average
11.90
25.78
5.73
17.74
1.31
8.60
1.56
3.41
2.25
27.99
No CPA model parameters for i-pentane and i-hexane are available and these two components are excluded in the average for CPA.
2. Model description
2.1. The PC-SAFT equation of state
The PC-SAFT EoS proposed by Gross and Sadowski [3,4] is one of
the successful modications of the original SAFT EoS [26]. Unlike
SAFT, PC-SAFT uses the mixture of hard-sphere chains as the
reference system and then introduces the dispersive attractions.
PC-SAFT is proposed to model asymmetric and highly non-ideal
systems. PC-SAFT can be expressed in terms of the reduced
~:
Helmholtz energy a
~
a
A
~ id a
~ hc a
~ disp a
~ assoc
a
NkT
(1)
Fig. 3. AAD% in the calculated saturated liquid density for different EoSs without volume transition.
100
Table 4
Trends in the temperature volume translation parameters: the parameters that are
not monotonic decreasing with temperature are marked with N while the others
are kept blank.
Components
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
SRK
N
N
N
PR
PC-SAFT
Soave-BWR
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
~ hc m a
~ hs a
~ chain m a
~ hs
a
(2)
m2 e2 s 3
z0 ln1 z3
z0 1 z3 z3 1 z3 2
z23
s ij
with zn dened by
6
2
XX
eij
xi xj mi mj
s 3ij
kT
i
j
(10)
(3)
p X
zn r xi mi dni n 2 f0; 1; 2; 3g
(8)
(7)
N
N
N
N
N
N
X
xi mi 1lnghs
ii
2
di dj
di dj
1
2z2
2z22
2
1 z3
di dj 1 z3
di dj 1 z3 2
s i s j
2
(12)
Despite the complex form of the PC-SAFT EoS, there are only three
model parameters for a non-associating component, the chain
length m, the segment diameter s and the segment energy e.
(5)
Table 5
AAD% and maximum deviations in the calculated density for different EoSs within 273500 K and 1000 bar with volume transition.
Components
SRK
PR
PC-SAFT
Soave-BWR
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
0.84
1.68
1.09
1.09
1.14
1.05
0.96
0.90
0.87
0.83
0.83
0.83
0.81
0.86
0.82
1.01
0.92
0.89
0.56
0.58
8.02
19.64
15.70
16.82
19.78
20.25
19.45
21.40
21.34
15.65
12.11
9.85
8.17
6.00
5.56
20.87
26.10
20.44
11.47
9.60
0.72
1.13
0.86
0.77
1.05
1.08
1.06
1.03
1.09
1.04
1.08
1.08
1.07
1.17
1.11
1.11
1.08
1.08
0.70
0.74
5.13
16.06
11.28
12.93
15.73
15.82
15.82
16.42
16.66
10.43
7.00
5.17
3.69
3.24
3.09
16.79
21.61
16.56
6.90
5.18
0.23
0.59
0.38
0.35
0.42
0.56
0.59
0.72
0.66
0.79
0.79
0.82
0.91
0.91
1.00
0.62
0.75
0.77
0.56
0.65
3.37
21.05
6.74
6.49
4.77
5.05
8.72
16.03
7.20
3.44
2.86
3.10
3.35
3.88
4.04
7.33
8.90
8.82
3.14
3.02
0.40
0.23
0.18
0.33
0.31
0.42
0.49
0.58
0.50
0.57
0.53
0.52
0.51
0.34
0.46
0.55
0.56
0.54
0.42
0.45
2.30
3.83
3.79
4.21
4.28
5.21
3.64
5.62
2.47
2.37
1.90
2.14
1.98
1.14
1.59
4.56
5.28
3.44
1.23
1.66
Average
0.93
15.41
1.00
11.27
0.65
6.57
0.45
3.13
101
Table 6
AAD% and maximum deviations in the calculated saturated liquid density for different EoSs with volume transition.
Components
SRK
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
AAD%
Max Dev.
N2
CO2
H2S
CH4
C2H6
C3H8
nC4H10
nC5H12
nC6H14
nC7H16
nC8H18
nC9H20
nC10H22
nC11H24
nC12H26
iC4H10
iC5H12
iC6H14
Benzene
Toluene
4.96
9.60
4.62
5.25
4.98
5.24
5.46
5.84
5.82
6.09
6.29
6.71
6.77
6.38
6.67
5.40
5.65
5.76
7.16
6.01
20.56
23.79
18.74
21.34
22.69
23.53
24.43
26.06
23.92
23.79
23.52
28.15
27.54
29.86
30.27
23.76
26.03
23.93
24.85
25.59
3.86
5.73
2.81
3.76
3.44
3.49
3.61
3.82
3.91
3.95
4.03
4.42
4.31
4.21
4.17
3.56
3.74
3.77
4.18
3.81
15.69
19.27
14.11
16.67
18.02
18.77
19.58
21.23
18.93
18.67
18.36
23.17
22.41
24.73
25.34
18.93
21.23
19.01
20.12
20.79
0.96
1.74
0.71
0.95
1.33
1.85
2.04
2.44
2.21
2.65
2.52
2.62
2.63
2.54
2.53
2.10
2.54
2.66
1.67
1.97
4.77
14.76
3.00
5.92
2.36
3.09
5.52
6.30
11.00
12.35
15.43
10.32
9.21
10.65
8.10
3.89
2.76
7.84
8.33
8.51
0.65
0.97
2.26
2.02
0.92
1.03
1.97
2.18
2.01
2.32
2.25
2.32
1.31
0.72
1.21
2.19
2.17
2.17
1.01
2.05
1.43
2.83
4.25
2.84
1.42
1.41
1.46
1.84
3.65
5.81
7.53
2.92
5.68
5.68
3.53
1.71
1.73
2.66
1.23
1.66
Average
6.03
24.62
3.93
19.75
2.03
7.71
1.69
3.06
PR
PC-SAFT
(13)
4h 3h2
1 h2
(14)
ghs
Soave-BWR
1 h=2
1 h3
(15)
Fig. 4. AAD% in the calculated density for different EoSs within 279500 K and 1000 bar with volume transition.
102
Fig. 5. AAD% in the calculated saturated liquid density for different EoSs with volume transition.
Table 7
AAD (%) in the calculated high pressure liquid densities for heavy normal alkanes.
SRK
PR
PC-SAFT
Soave-BWR
nC7
nC9
nC11
nC13
nC17
nC20
Average
11.58
2.97
1.95
2.14
14.45
4.70
1.74
1.57
17.13
7.58
1.80
1.99
19.68
10.45
1.60
1.85
26.80
18.42
1.94
3.15
29.32
21.26
2.47
3.93
19.83
10.90
1.92
2.44
Fig. 6. Change of s for non n-alkanes with the relative difference in specic gravity SG. s 0 and SG0 are for the n-alkanes at the same boiling point temperatures.
103
Fig. 7. Change of e for non n-alkanes with the relative difference in specic gravity SG. e0 and SG0 are for the n-alkanes at the same boiling point temperatures.
P
1 Br C r2 Dr5 Er2 1 F r2 expF r2
RT r
(16)
P
1 Br C r2 Dr4 Er2 1 F r2 expF r2
RT r
(17)
P
1 Br Dr4 Er2 1 F r2 expF r2
RT r
(18)
(19)
d DT c r4c
(20)
Fig. 8. Change of m for non n-alkanes with the relative difference in specic gravity SG. m0 and SG0 are for the n-alkanes at the same boiling point temperatures.
104
Table 8
Deviations in bubble point pressures and vapor phase compositions predicted by SRK, PR, PC-SAFT and Soave-BWR (experimental data from [49,50]).
System
Temp. range
SRK
PR
PC-SAFT
Soave-BWR
COMP1
COMP2
Tmin (K)
Tmax (K)
DP/P (%)
DY1 (mol%)
DP/P (%)
DY1 (mol%)
DP/P (%)
DY1 (mol%)
DP/P (%)
DY1 (mol%)
C1
CO2
H2S
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C14
C16
C20
C24
C32
C36
153
193
130
90
110
115
344
176
183
200
223
223
244
257
321
289
305
321
343
346
301
367
283
361
378
411
444
450
444
511
423
423
583
318
433
704
371
388
343
347
11.20
15.76
1.69
5.70
3.36
5.27
9.72
5.47
13.94
10.68
13.79
13.60
10.35
15.62
18.28
14.41
12.61
9.79
20.47
27.20
3.13
4.54
0.49
0.87
1.18
0.98
4.30
1.10
0.29
0.48
0.49
0.31
0.42
0.79
11.16
16.00
1.40
6.12
3.83
6.30
9.77
6.78
15.71
11.80
15.05
15.07
11.37
16.61
18.85
15.02
11.25
15.43
16.10
23.74
3.09
4.66
0.31
0.98
1.38
1.06
4.34
0.99
0.32
0.45
0.49
0.32
0.41
1.08
8.35
14.31
2.03
4.00
3.92
5.81
10.63
6.83
10.13
8.92
12.28
12.39
10.83
12.48
19.16
14.54
14.59
16.21
12.19
2.60
2.09
3.63
0.51
0.65
1.00
0.85
3.89
0.90
0.30
0.30
0.43
0.26
0.44
0.63
11.41
15.30
1.42
3.51
3.20
3.88
9.75
3.97
5.95
11.86
10.05
14.68
17.72
26.76
17.59
21.67
18.59
15.79
3.46
5.11
0.35
0.65
1.04
0.76
3.08
1.42
0.55
0.67
0.21
0.28
1.21
4.84
N2
CO2
H2S
C1
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C16
218
228
78
111
120
255
250
278
277
311
305
322
344
311
344
463
301
344
184
290
353
394
411
377
378
444
497
344
344
411
367
703
3.97
17.53
6.97
9.60
12.33
17.04
14.41
14.70
14.47
21.66
17.91
26.68
27.52
19.02
21.15
16.32
0.71
6.05
1.76
1.43
1.41
2.67
2.18
2.67
1.66
1.61
4.54
0.11
1.06
2.74
17.51
7.48
6.85
13.19
18.88
14.70
16.85
16.51
22.55
18.05
27.06
28.50
22.28
23.44
16.11
0.56
6.24
2.05
1.68
1.48
3.18
2.29
3.10
2.02
1.73
5.08
0.13
1.13
3.50
15.73
8.12
7.87
13.03
16.83
14.85
20.01
18.73
24.47
17.81
27.39
24.53
24.15
19.41
1.50
7.25
1.96
1.91
1.77
3.83
2.44
4.74
2.96
1.83
5.48
0.17
1.06
5.42
17.43
7.63
8.03
12.57
11.14
9.58
5.57
7.14
10.71
7.09
7.77
4.48
15.39
10.41
13.49
1.45
5.67
1.99
1.32
1.46
1.91
2.58
1.34
1.01
1.49
1.86
0.09
3.41
CO2
H2S
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C13
C14
C15
C16
C19
C20
C21
C22
C24
C28
C32
C36
225
207
233
273
228
278
253
273
311
216
343
236
254
255
269
270
463
293
300
302
315
373
348
336
373
366
302
361
398
419
453
463
393
502
466
343
594
267
339
311
305
664
304
373
338
373
573
423
573
423
11.71
15.46
15.37
13.71
14.88
16.27
12.15
15.70
17.44
15.30
20.02
19.36
10.54
11.62
12.61
0.55
16.06
0.13
10.96
10.24
22.93
9.17
12.95
11.78
7.76
3.96
6.09
4.07
3.30
3.49
3.19
3.49
1.44
2.41
1.23
1.00
1.79
1.81
0.07
0.02
12.34
15.83
15.24
13.61
14.75
16.31
12.27
15.69
17.64
15.38
19.28
18.75
10.77
11.95
14.26
1.13
14.62
8.67
13.78
13.81
21.48
7.74
11.59
10.95
9.18
4.01
6.08
3.96
3.14
3.28
3.12
3.52
1.28
2.19
1.09
0.84
1.61
1.68
0.12
0.03
12.99
14.49
15.01
12.62
13.96
15.76
12.00
17.06
16.84
15.29
17.77
18.47
7.78
13.03
15.07
2.82
16.64
3.24
3.52
3.80
29.67
18.39
23.94
21.17
23.41
4.19
5.67
3.82
2.76
3.23
2.74
3.06
1.47
2.16
1.36
1.48
1.81
1.43
0.14
0.03
12.54
15.72
14.02
9.79
12.48
12.16
10.39
14.53
7.90
11.63
8.77
7.73
5.40
4.96
2.81
3.50
11.99
5.51
7.09
7.19
8.99
11.84
12.44
15.66
27.59
3.95
5.95
3.53
1.99
2.32
1.82
2.01
0.72
0.68
0.40
0.08
0.49
1.05
0.01
0.00
H2S
C2
C3
C4
iC4
C5
iC5
C6
C7
C10
C15
200
217
367
278
278
323
323
311
278
423
283
367
418
398
444
413
423
478
444
423
12.54
10.78
5.97
6.36
12.04
8.94
12.40
15.25
11.16
8.35
5.77
4.54
2.19
2.44
1.87
3.13
1.50
1.80
0.17
0.12
13.10
10.81
5.73
6.02
11.81
9.03
11.56
14.90
9.27
7.93
6.06
4.41
2.06
2.31
1.89
3.00
1.46
1.62
0.27
0.23
13.35
10.92
5.49
6.11
11.40
8.94
11.84
13.25
13.91
9.58
5.97
4.13
2.46
2.19
1.81
3.05
1.20
0.96
0.21
0.04
12.97
8.93
3.75
2.79
4.13
4.20
2.79
3.64
14.42
6.09
3.89
1.29
1.56
1.13
1.86
0.43
0.88
0.18
13.08
2.08
13.48
2.11
13.26
2.12
10.11
1.79
Average
105
Table 9
Regressed kij values for the four EOS models and their deviations in calculated bubble point pressures and vapor phase compositions (experimental data from [49,50]).
System
SRK
PR
PC-SAFT
Soave-BWR
COMP1
COMP2
kij
DP/P (%)
DY1 (mol%)
kij
DP/P (%)
DY1 (mol%)
kij
DP/P (%)
DY1 (mol%)
kij
DP/P (%)
DY1 (mol%)
C1
CO2
H2S
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C14
C16
C20
C24
C32
C36
0.0993
0.0879
0.0030
0.0180
0.0054
0.0100
0.0267
0.0213
0.0355
0.0280
0.0410
0.0449
0.0411
0.0442
0.0703
0.0586
0.0534
0.0298
0.0728
0.0868
1.99
4.09
1.55
3.77
3.06
4.26
8.84
2.36
3.77
7.45
3.97
2.68
4.29
7.11
1.43
5.34
13.00
7.20
2.96
8.87
0.78
1.80
0.45
0.76
1.13
0.89
4.02
1.00
0.20
0.43
0.36
0.24
0.31
0.65
0.0985
0.0859
0.0017
0.0188
0.0108
0.0168
0.0253
0.0270
0.0417
0.0335
0.0451
0.0485
0.0409
0.0500
0.0693
0.0561
0.0541
0.0500
0.0559
0.0763
1.94
4.29
1.35
2.77
2.75
3.78
8.94
2.24
3.90
7.54
4.15
3.03
4.30
6.88
1.35
5.39
13.61
12.83
2.86
7.25
0.75
1.69
0.32
0.79
1.28
0.87
4.07
0.81
0.17
0.36
0.35
0.28
0.26
0.86
0.0328
0.0411
0.0058
0.0034
0.0061
0.0041
0.0236
0.0121
0.0114
0.0103
0.0159
0.0151
0.0172
0.0103
0.0329
0.0189
0.0172
0.0223
0.0160
0.0040
2.31
3.95
1.47
4.30
2.90
5.27
8.71
3.28
5.58
6.56
5.93
4.85
6.51
5.88
4.96
4.11
3.69
3.99
3.25
1.07
1.30
1.66
0.39
0.70
0.93
0.80
3.39
0.77
0.17
0.29
0.35
0.29
0.33
0.79
0.0804
0.0692
0.0002
0.0024
0.0079
0.0044
0.0142
0.0076
0.0048
0.0149
0.0149
0.0184
0.0311
0.0315
0.0425
0.0441
0.0405
0.0110
0.0866
0.0400
1.97
3.93
1.41
2.99
2.62
4.19
8.72
3.05
5.71
9.25
5.17
6.64
7.06
12.22
5.89
9.60
11.42
12.80
12.89
0.84
1.66
0.36
0.65
1.01
0.78
3.16
1.25
0.43
0.58
0.26
0.24
0.82
1.51
N2
CO2
H2S
C1
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C16
0.0196
0.1802
0.0307
0.0392
0.0838
0.1021
0.0974
0.0962
0.0934
0.1496
0.1402
0.1834
0.1896
0.1079
0.1612
0.2504
2.27
5.20
2.34
4.17
8.55
4.64
4.95
4.42
4.59
7.11
8.16
4.75
2.58
5.32
8.35
5.05
0.70
1.42
1.27
0.71
0.67
1.40
2.22
1.52
0.96
1.57
2.18
0.10
1.02
0.0067
0.1852
0.0326
0.0504
0.0944
0.1065
0.1037
0.1022
0.1000
0.1548
0.1419
0.1821
0.1885
0.1172
0.1654
0.2110
2.61
5.51
2.13
4.04
8.56
4.41
4.71
4.14
4.58
6.26
6.90
4.31
2.35
4.97
8.40
3.02
0.70
1.27
1.15
0.54
0.50
1.23
1.78
1.50
0.80
1.21
2.08
0.10
0.77
0.0046
0.1082
0.0258
0.0472
0.0669
0.0734
0.0711
0.0727
0.0665
0.0853
0.0751
0.0877
0.0852
0.0540
0.0683
0.0921
2.93
9.76
2.12
3.30
8.04
4.72
4.46
4.09
4.97
5.03
5.91
4.46
2.48
6.39
8.06
1.77
1.47
1.15
1.14
0.48
0.32
1.21
1.64
1.64
0.99
0.75
1.88
0.15
0.35
0.0163
0.1041
0.0246
0.0333
0.0447
0.0361
0.0341
0.0148
0.0145
0.0280
0.0086
0.0143
0.0048
0.0414
0.0180
0.0778
2.55
9.07
2.09
2.69
7.86
3.47
3.90
3.16
4.30
5.26
5.85
4.74
3.80
4.64
10.46
7.82
1.61
1.48
1.14
0.84
0.81
1.44
3.14
1.08
0.98
1.74
1.92
0.08
1.80
CO2
H2S
C2
C3
iC4
C4
iC5
C5
C6
C7
C8
C9
C10
C12
C13
C14
C15
C16
C19
C20
C21
C22
C24
C28
C32
C36
0.1014
0.1315
0.1443
0.1269
0.1395
0.1321
0.1274
0.1320
0.1096
0.1238
0.1151
0.1237
0.1019
0.0953
0.1086
0.1084
0.1178
0.1113
0.1051
0.1011
0.0936
0.0560
0.0421
0.0284
0.0145
1.25
2.46
3.12
2.62
3.13
3.15
4.37
4.59
4.93
6.31
1.86
4.72
1.50
3.23
1.51
0.79
4.08
2.19
3.12
3.35
5.70
5.66
9.10
9.79
6.88
0.99
2.17
0.83
1.05
1.20
1.26
1.45
0.56
1.23
0.12
0.11
0.58
0.53
0.06
0.02
0.0999
0.1272
0.1372
0.1181
0.1315
0.1219
0.1198
0.1236
0.0977
0.1155
0.1054
0.1115
0.0948
0.0967
0.0959
0.0979
0.1028
0.0978
0.0912
0.0875
0.0791
0.0333
0.0307
0.0154
0.0264
1.34
2.48
3.15
2.37
2.95
2.83
3.99
4.43
5.09
6.57
1.75
4.07
1.09
2.52
1.27
0.85
4.13
2.64
3.43
3.51
6.03
7.70
9.19
10.21
6.91
0.97
2.13
0.89
1.16
1.29
1.35
1.49
0.64
1.38
0.10
0.26
0.68
0.59
0.10
0.03
0.0627
0.0662
0.0751
0.0631
0.0672
0.0671
0.0665
0.0726
0.0527
0.0699
0.0600
0.0662
0.0687
0.0725
0.0718
0.0700
0.0599
0.0625
0.0612
0.0590
0.0561
0.0517
0.0497
0.0471
0.0424
1.16
2.76
2.98
2.23
2.79
1.65
3.60
3.63
6.21
6.90
1.96
4.25
0.58
3.21
3.58
1.27
5.51
4.50
4.87
4.80
4.82
3.36
3.83
4.33
2.90
0.87
2.47
0.55
0.89
1.08
1.01
1.01
0.61
1.11
0.15
0.09
0.55
0.24
0.06
0.05
0.0733
0.0937
0.0802
0.0602
0.0675
0.0550
0.0541
0.0538
0.0209
0.0389
0.0205
0.0177
0.0219
0.0179
0.0049
0.0103
0.0113
0.0071
0.0060
0.0086
0.0018
0.0293
0.0205
0.0305
0.0567
1.53
2.48
3.07
1.90
2.52
1.53
3.64
3.18
6.57
5.52
2.43
5.45
0.98
2.52
2.54
1.43
11.38
4.69
6.05
5.43
9.15
15.89
11.39
11.12
11.19
0.88
2.11
0.53
0.76
1.14
0.57
0.67
0.50
0.68
0.16
0.03
0.53
0.88
0.02
0.00
H2S
C2
C3
C4
iC4
C5
iC5
C6
C7
C10
C15
0.0870
0.0838
0.0979
0.0594
0.0692
0.0781
0.0691
0.0790
0.0447
0.0067
1.26
1.87
1.85
2.34
2.84
3.93
2.18
5.04
3.94
7.88
1.27
1.82
1.44
1.63
1.66
1.93
0.60
1.08
0.19
0.13
0.0834
0.0791
0.0894
0.0542
0.0625
0.0707
0.0599
0.0691
0.0352
0.0110
1.37
1.88
1.86
2.11
2.50
3.96
2.07
4.60
3.75
8.22
1.56
1.81
1.47
1.69
1.73
2.00
0.73
1.19
0.27
0.21
0.0581
0.0538
0.0504
0.0384
0.0454
0.0474
0.0404
0.0475
0.0387
0.0287
1.31
2.09
1.83
1.99
1.69
3.24
3.06
4.57
3.28
3.48
1.37
1.59
0.70
1.10
1.26
1.56
0.39
0.85
0.15
0.10
0.0605
0.0486
0.0364
0.0160
0.0152
0.0182
0.0016
0.0043
0.0336
0.0000
1.51
1.95
1.84
1.97
1.50
3.38
2.73
3.65
4.31
1.62
1.73
0.87
1.29
1.22
1.47
0.44
0.90
0.13
4.41
1.01
4.38
1.00
3.96
0.87
5.30
0.99
Average
106
Table 10
Statistics for the four EoS models in binary VLE calculation: sensitivities and average
kij.
SRK
Average sensitivity in DP/P (%)
Average sensitivity in DY1 (mol%)
jkij j
PR
PC-SAFT
Soave-BWR
m mv
109
1.4
115
12.6
231
22.5
161
17.2
0.086
0.082
0.048
0.031
(29)
X
xi Z ci T ci =Pci
i
Z cm X
xi T ci =Pci
e ET c r2c
(21)
f F r2c
(22)
Pcm
(23)
T cm
S3
(24)
s
S2
mm
S3
S1
(25)
XX
T ci T cj
xi xj 1 kij p1 mi 1 mj
Pci Pcj
i
j
s
XX
T ci T cj
S2
xi xj 1 kij
mm
Pci Pcj i j
i
j
S3
(26)
(27)
X T ci
xi
Pci
i
(28)
Table 11
Interaction parameters for CH4C7+, N2C7+, CO2C7+, and H2SC7+ for SRK, PR, PCSAFT and Soave-BWR.
EoS
N2C7+
CO2C7+
H2SC7+
CH4C7+
SRK
PR
PC-SAFT
Soave-BWR
0.1079
0.1172
0.0540
0.0414
0.1237
0.1115
0.0662
0.0103
0.0447
0.0352
0.0387
0.0000
0.0510
0.0522
0.0103
0.0441
(30)
(31)
Table 12
An overview of the phase envelopes tested in this study.
Gas
Source
C1
C6+
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
[52]
[52]
[52]
[52]
[52]
[53]
[53]
[53]
[53]
[53]
[55]
[55]
[55]
[55]
[55]
[55]
[56]
[56]
[57]
[57]
[57]
[57]
[57]
[58]
[59]
[60]
[60]
[61]
[62]
[62]
98.94
90.42
96.62
88.19
83.35
89.96
88.76
86.48
96.47
89.00
91.00
81.40
95.90
95.00
94.50
94.30
69.11
84.45
93.51
84.28
96.61
94.09
93.60
81.18
85.13
81.00
60.00
90.99
82.32
82.05
0.04
0.01
0.03
0.16
0.09
0.00
0.00
0.00
0.00
0.00
0.00
2.30
0.00
0.00
0.00
0.27
0.11
0.05
0.00
0.00
0.00
0.00
0.00
0.00
0.00
5.00
9.00
0.00
1.98
1.99
Remark
Group II: nC7, nC9, nC11, nC13, nC17 and nC20.For the components
in Group I, high accuracy reference EoS models [31] can be used to
generate smooth and evenly spaced synthetic density data. We
have compared these EoS models for uid density over a wide
temperature and pressure range and saturated liquid density.
The comparison in this group covers light as well as heavy
components. For the components in Group II,liquid density data up
to extremely high pressures [32] are available for model
evaluation. The components in this group are relatively heavier
than those in Group II whereas it should be noted that nC7, nC9 and
nC11 appear in both groups. The method for density comparison is
inspired by the study of de Hemptinne and Ungerer [33] where
they evaluated ve equations of state for the determination of
volumetric properties of pure hydrocarbon components. In
addition to using different models in the comparison here, we
also update the reference equations of state and include more
components. The saturated liquid densities are also included in the
comparison.
107
Fig. 9. Phase envelopes for Gas 5 with (a) zero kijs and (b) the optimal kijs.
108
Fig. 10. Phase envelopes for Gas 6 with (a) zero kijs and (b) the optimal kijs.
109
Fig. 11. Phase envelopes for Gas 10 with (a) zero kijs and (b) the optimal kijs.
110
translation parameter is monotonically decreasing with temperature, the problem of crossing isotherms will not happen;
otherwise, it will. It can be seen that for SRK and PR, the trends
are ne for most hydrocarbons. CO2 and H2S give the problematic
trends for all the four models. For Soave-BWR and PC-SAFT, the
trends are problematic with many hydrocarbons. But on the other
hand, Soave-BWR and PC-SAFT already give very accurate density
results and the translation is not really necessary. It is possible to
force the volume translation parameter to follow a certain trend
while minimizing the density calculation deviation but no such
effort is made here.
The results with temperature dependent volume translation
are presented in Tables 5 and 6 and Figs. 4 and 5. For uid density
over a wide temperature and pressure range, the temperaturedependent volume translation greatly improves the results for
SRK and PR but the effect for Soave-BWR and PC-SAFT is modest,
which is not surprising since the room for further improvement is
very small. However, it should be noted that the maximum
absolute deviations for SRK and PR are much larger than those for
PC-SAFT and Soave-BWR, showing again the importance of the
functional form of an EoS. For saturated liquid density, the
improvement is obvious for SRK and modest for PR; for SoaveBWR and PC-SAFT, the results actually become slightly worse.
Compared to Soave-BWR and PC-SAFT, SRK and PR give larger
deviations in saturated liquid density even with temperature
dependent volume translation. This is because volume translation
simply shifts the Pv isotherm but does not change its slope. If the
improvement of density is focused on one region (high pressures
in this case), there is no guarantee that density in other regions can
be improved to a similar extent. Temperature dependent volume
translation can be designed to match the saturated liquid density
but this usually leads to the problem of crossing Pv isotherms
[39]. In short, if we want accurate density description over a wide
temperature and pressure range, Soave-BWR and PC-SAFT are
better than SRK an PR even if temperature dependent volume
translation is applied to the latter two.
Fig. 12. Phase envelopes for Gas 11 with (a) zero kijs and (b) the optimal kijs.
111
Fig. 13. Phase envelopes for Gas 17 with (a) zero kijs and (b) the optimal kijs.
112
and v are replaced by the Twu correlations [43] for Tc and Pc and
the LeeKesler/KeslerLee correlations [44,45] for v. The same set
of correlations is used in the method of Whitson et al. The reason
for not using the original correlations proposed by Pedersen et al.
[40], which are developed by tting PVT data directly, is that our
experiences show they are poor in reproducing the critical
properties of individual heavy hydrocarbon components in C7+.
The Twu correlations and the LeeKesler/KeslerLee correlations,
in contrast, give a much better estimate.
4.2. Characterization for PC-SAFT
Characterization for PC-SAFT also adopts the rst and the third
steps in the method of Pedersen et al. The second step, estimation
of model parameters, has to be replaced by a set of newly
developed correlations for the PC-SAFT model parameters m, s and
e. Correlations for the PC-SAFT model parameters for n-alkanes or
other hydrocarbons of a certain homologous series are available in
Fig. 14. Phase envelopes for Gas 18 with (a) zero kijs and (b) the optimal kijs.
113
Fig. 15. Phase envelopes for Gas 22 with (a) zero kijs and (b) the optimal kijs.
(32)
114
m0 e0
6:90845MW0 139:30870
k
(33)
m0 s 30 1:71638MW0 19:19189
(34)
The above equations differ slightly from those in [28,46] due to the
difference in the selected n-alkanes and temperature ranges. In the
second step, the properties of the SCN component is estimated by
using the difference in specic gravity SG SG0 as the perturbation
parameter, where SG0 is the specic gravity of the n-alkane
calculated by Soaves correlation [48]:
SG0 1:8T b 1=3 11:7372 3:336 103 T b 976:3T 1
b
1
3:257 105 T 2
b
(35)
Establishing simple but accurate correlations between the difference in m, e and s and the difference in SG is far from a simple task.
No general trends with sufciently small scattering can be found
between m m0 , e e0 =k, or s s 0 and DSG SG SG0 .
However, it seems that s =s 0 varies in a relatively narrow range,
as indicated in Fig. 6. Therefore, as a rst approximation, it is
assumed that:
s s0
(36)
e e0 1:2357DSG 1
(37)
With Eqs. (36) and (37) as constraints, the m values for other
hydrocarbons in DIPPR are retted. The new m values are shown in
Fig. 8 and the following correlation is suggested:
Fig. 16. Phase envelopes for Gas 24 with (a) zero kijs and (b) the optimal kijs.
m m0 1:3192DSG 1:8218DSG 1
2
(38)
Eqs. (37) and (38) provide the basis for determining the nal
correlations for e and m. In the nal step, the coefcients in these
two expressions are further tuned to t the vapor pressures and
saturated liquid densities for all the 318 other hydrocarbons.
Different weights have been assigned to different chemical classes
in these hydrocarbons: cyclohydrocarbons and aromatics are set to
5, iso-alkanes to 2, and other unsaturated hydrocarbons to 1. The
nal correlations are suggested for e and m:
e e0 1:1303391DSG 1
(39)
m m0 1:0460471DSG2 1:6209973DSG 1
(40)
and s is still calculated by Eq. (36). It should be noted that Eq. (40)
has a minimum value at DSG 0:7748204. To keep the monotonicity, the ratio of m/m0 will be xed at this minimum for DSG
larger than that. We can also assume that e and m are functions of
both DSG and SG and develop the following set of correlations:
e e0
115
0:59822690
0:55100489
DSG 1
SG
m0
1 2:6934054 0:57209122
DSG
SG
(41)
(42)
Fig. 17. Phase envelopes for Gas 25 with (a) zero kijs and (b) the optimal kijs.
116
Fig. 18. Phase envelopes for Gas 26 with (a) zero kijs and (b) the optimal kijs.
117
Fig. 19. Phase envelopes for Gas 27 with (a) zero kijs and (b) the optimal kijs.
118
Sensitivity in
DP=Poptimal DP=Pdefault
DP
j
j
P
kij;optimal kij;default
DY1optimal DY1default
j
Sensitivity in DY1 j
kij;optimal kij;default
(43)
(44)
In Table 10, the sensitivities for DP/P (%) and DY1 (mol%) averaged
for all the binary pairs are reported. For both bubble point pressure
and vapor phase composition, SRK and PR are less sensitive to kij
than PC-SAFT and Soave-BWR. According to the average sensitivities, if we change kij by 0.01, SRK and PR will give around 1% change
in DP/P (%), as compared with 2.3% for PC-SAFT and 1.6% for SoaveBWR. This indicates that PC-SAFT is roughly twice as sensitive as
SRK and PR, and Soave-BWR is around 50% more sensitive than SRK
and PR. It should be mentioned that the change of DP/P with kij is
not linear and its slope is in principle different at different kij
values. But these average sensitivities calculated using Eqs. (43)
and (44) still provide a rough sensitivity index for these models.
The relatively high sensitivities for PC-SAFT and Soave-BWR can
become a disadvantage when applying them to ill-dened uids
since a more sensitive model is more vulnerable to the uncertainty
in parameters, such as kij.
Finally, in order to apply the four models to PVT calculation, we
need to generalize the kij values for components above C7+. Table 11
gives the generalized kij values for N2C7+, CO2C7+, H2SC7+, and
CH4C7+. They are generated based on the optimal kij values with
heavy components up to C20 in Table 9. The kij values in Table 11 are
either calculated by averaging the kij values from C7 to C20 or set to
the value for a certain binary pair. There is some arbitrariness in
this process. In principle, we can tune the kij values within a certain
Fig. 20. Phase envelopes for Gas 28 with (a) zero kijs and (b) the optimal kijs.
119
(6) Predictions for Gases 12, 15 and 16 from source [55] show very
(2)
(3)
(4)
(5)
Table 13
An overview of the reservoir uid systems tested.
Fluid no.
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
Fluid
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
C1 (%)
C7+ (%)
T range (K)
49
50
50
50
32
32
23
24
46
54
27
36
31
32
45
41
42
39
23
42
36
35
40
75
64
63
63
28
39
22
33
48
47
47
45
31
31
40
44
48
61
44
46
29
21
43
34
37
35
50
54
55
51
73
54
54
34
31
6
12
11
11
68
54
57
66
25
27
29
26
366.45
337.25
337.85
337.25
346.15
333.15
374.85
372.05
387.35
388.15
394.25
383.15
393.15
393.15
322.65
344.95
346.05
346.15
329.75
319.55
339.85
427.6
418.1
323.15469.15
423.15455.15
423.15460.15
323.15460.15
345.93
318.15
331.15
329.15
303.25417.85
394.25
373.75
299.85394.25
120
Table 14
Summary of AAD(%) in predicted saturation pressures and reservoir uid densities (single phase densities and liquid densities in the two-phase region).
Saturation pressure
Fluid 1
Fluid 2
Fluid 3
Fluid 4
Fluid 5
Fluid 6
Fluid 7
Fluid 8
Fluid 9
Fluid 10
Fluid 11
Fluid 12
Fluid 13
Fluid 14
Fluid 15
Fluid 16
Fluid 17
Fluid 18
Fluid 19
Fluid 20
Fluid 21
Fluid 22
Fluid 23
Fluid 24
Fluid 25
Fluid 26
Fluid 27
Fluid 28
Fluid 29
Fluid 30
Fluid 31
Fluid 32
Fluid 33
Fluid 34
Fluid 35
Average
Density
SRK
PR
PC-SAFT
Soave-BWR
SRK
PR
PC-SAFT
Soave-BWR
3.84
7.71
5.22
3.98
2.71
3.97
1.17
15.41
10.58
8.46
5.67
0.00
11.50
7.87
0.43
4.91
9.46
1.22
0.05
1.83
4.43
5.62
6.92
7.58
5.84
8.82
10.49
21.74
7.25
16.14
19.88
8.93
1.03
5.41
5.23
6.89
6.35
10.73
8.54
7.95
0.71
0.16
2.94
16.89
12.49
10.93
7.05
1.34
12.22
8.66
5.35
0.52
4.56
2.57
3.97
3.29
0.31
5.94
7.75
2.30
0.37
3.00
4.93
16.36
1.63
11.85
12.17
10.99
2.88
7.55
7.84
6.37
6.14
0.11
0.54
2.08
0.14
3.14
6.03
1.88
11.67
17.84
9.45
8.66
0.58
5.72
10.30
5.17
10.47
3.26
6.39
12.28
4.85
0.90
0.37
17.62
20.18
22.05
27.41
18.18
16.07
28.74
24.32
22.61
21.68
14.29
25.41
11.04
6.25
9.00
8.29
10.69
3.59
13.65
3.91
11.92
1.43
9.56
1.12
5.04
7.34
2.97
20.99
9.18
5.58
10.33
12.76
21.55
9.72
3.30
3.34
9.26
8.09
11.38
15.30
0.28
17.72
0.88
10.73
7.03
7.51
0.60
10.64
8.31
13.25
13.51
14.11
13.85
13.32
11.94
19.18
16.72
13.91
11.02
12.60
15.40
11.62
10.53
9.90
7.66
7.45
11.02
9.45
12.48
11.77
9.51
11.39
8.60
12.84
1.97
18.58
14.02
13.11
15.56
12.21
3.26
3.42
4.11
3.89
2.93
1.65
9.82
7.07
4.37
1.52
2.53
5.68
1.44
0.26
0.53
3.22
3.60
0.70
1.12
2.56
1.84
1.01
1.34
1.99
2.61
9.33
9.63
4.53
3.36
6.07
3.51
2.56
1.14
1.65
1.39
1.41
2.44
3.18
0.37
3.50
7.21
1.92
0.87
3.92
2.93
3.53
4.35
6.31
4.30
3.75
2.83
3.97
4.51
0.74
5.29
3.32
8.61
2.01
4.99
3.50
1.99
3.28
2.09
3.23
4.27
6.07
4.01
10.93
3.75
0.84
3.63
2.66
1.82
3.49
9.13
11.82
13.27
11.99
14.49
11.42
12.00
2.12
1.37
19.57
18.62
13.96
11.98
26.12
8.86
3.49
2.57
4.75
8.14
Figs. 21 and 22 show the results for two HPHT oils. For Fluid
22 at 427.6 K, PC-SAFT and Soave-BWR give the closest prediction
of the bubble point pressure while SRK and PR under predict the
bubble point pressure slightly. PC-SAFT, Soave-BWR and PR all give
the closest density prediction while SRK under predicts the
densities. For Fluid 23 at 418.1 K, the similar results are observed.
Soave-BWR and PC-SAFT again give the closest prediction of the
bubble point pressure. SRK and PR under predict the bubble point
pressure and SRK under predicts the liquid densities. Although PCSAFT and Soave-BWR gives excellent prediction for these two HPHT
oils, their predictions for other uids are not always better than
SRK and PR.
The most challenging systems for PC-SAFT and Soave-BWR are
the gas condensate systems, including Fluids 2427Fluid 27 is a
near critical system, showing gas condensate behavior at the high
temperatures and volatile oil behavior at the low temperatures.
PC-SAFT actually gives a pretty good prediction, similar to that of
PR, for the compressibility factors of Fluid 24 at high pressure
single phase regions (Fig. 23). However, the saturation pressures
predicted by PC-SAFT and Soave-BWR for those four uids are
actually poorer (Table 14 and Fig. 24(a)).
On Average, PC-SAFT and PR give the smallest deviations in
density, while PC-SAFT is slightly better than PR, and SRK is the
poorest in density prediction and undershoots the densities for
almost all the uids. The advantage of PC-SAFT in density modeling
seems to be somewhat kept with the newly developed characterization method. The densities tested here are mainly liquid
densities of oils and PR happens to predict reasonable liquid
density if the hydrocarbons are not too heavy (Table 14).
The accuracy in saturation pressure prediction is not signicantly different for PR and SRK. PR performs a bit better than the
other three while PC-SAFT seems to be the worst in saturation
pressure prediction. In contrast to the best performance for the
densities of well-dened components, Soave-BWR is much poorer
than PC-SAFT and PR for the liquid densities of reservoir uids,
although it is still better than SRK. The poor performance of SoaveBWR may be due to the fact that its density calculation is highly
121
Fig. 23. Gas phase compressibility of Fluid 24 at different temperatures: (a) 323 K; (b) 373 K; and (c) 469 K.
122
Fig. 24. Phase envelopes for Fluid 24 using characterization (a) without matching the boiling points for SCN components and (b) with matching the boiling points for SCN
components.
Table 15
Summary of the deviations for the various properties studied in this work.
Properties
SRK
PR
PC-SAFT Soave-BWR
Pure compounds
Densitya (%)
0.93 1.00
Saturated liquid densitya (%)
6.03
3.93
Densityb (%)
8.95
6.30
Saturated liquid densityb (%)
11.90
5.73
Liquid density for heavy n-alkanesb (%) 19.83 10.90
0.65
2.03
1.67
1.31
1.92
0.45
1.69
1.33
1.56
2.44
Binary mixturesc
Bubble point pressure (%)
Vapour phase composition (mol%)
3.96
0.87
5.30
0.99
Reservoir uids
Saturation pressure (%)
Densityb (%)
a
b
c
4.41
1.01
6.89
12.21
4.38
1.00
6.37 11.04
3.51
3.28
8.31
8.14
its maximum absolute deviations are still much higher than those
of PC-SAFT and Soave-BWR (see Table 5). PC-SAFT and Soave-BWR
are advantageous for density calculation, similar to SRK and PR for
binary VLE but poorer in saturation pressures of reservoir uids.
The power of cubic models lies in their simplicity and lower
computation time with respect to non-cubic models. PVT modeling
is the focus of this study and the computation speed issues will be
addressed in our subsequent paper.
7. Conclusions
A comprehensive evaluation of PC-SAFT and Soave-BWR, in
comparison with SRK and PR, has been made with regards to their
potential in PVT modeling of reservoir uids. Both PC-SAFT and
Soave-BWR are much better than SRK and PR in density calculation
of the well-dened light and heavy components in reservoir uids
over a wide temperature and pressure range, which forms a major
123
Acknowledgement
This study was carried out under the NextOil project funded by
the Danish National Advanced Technology Foundation, Maersk Oil
and DONG Energy.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.uid.2014.11.022.
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[2]
[3]
[4]
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124