Professional Documents
Culture Documents
3225
GENERAL RESEARCH
Determination of Critical Properties and Acentric Factors of Petroleum Fractions
Using Artificial Neural Networks
Amir H. Mohammadi, Waheed Afzal, and Dominique Richon*
Mines Paris, ParisTech, CEP-TEP, CNRS FRE 2861, 35 Rue Saint Honore , 77305 Fontainebleau, France
Various correlations are available that can determine the critical properties and acentric factors of petroleum
fractions. The available methods may have low accuracy in determining these properties for heavy petroleum
fractions and may require further verification because, during the development of the original predictive
methods, the data describing the critical properties and acentric factors of heavy hydrocarbons and petroleum
fractions were not available. In this work, after a quick review of the most common correlations reported in
the literature, an alternative method based on the artificial neural network (ANN) technique is proposed to
predict the critical temperatures, critical pressures, critical volumes, and acentric factors of petroleum fractions,
especially heavy fractions, from their specific gravity and the average normal boiling-point temperature values.
Among the different neural networks reported in the literature, the feed-forward neural network method with
a modified Levenberg-Marquardt optimization algorithm is used. The model is trained and tested using the
data recommended in the literature for critical properties and acentric factors of C1-C45 petroleum fractions.
Independent data (not used in training and developing the model) are used to validate and examine the reliability
of this tool. The predictions of this model are found in acceptable agreement with the data recommended in
the literature, demonstrating the reliability of the ANN technique used in this work.
1. Introduction
Petroleum fluids are composed mainly of hydrocarbon
constituents. The behavior of these fluids is determined by their
chemical composition and the prevailing temperature and
pressure. This behavior is of a prime consideration in the
development and management of petroleum industry, affecting
all aspects of petroleum production, transportation, and processing.1 Real petroleum fluids could be composed of thousands of
components, which pose two major restrictions:1 (1) A full
description of the fluid by identifying all of its constituents may
not be possible. (2) Phase-behavior calculations for systems
defined by a large number of components are time-consuming
and particularly impractical in compositional modeling.1 An oil
or condensate is commonly described by discrete hydrocarbon
components up to C6 and the non-hydrocarbon gases, such as
N2, CO2, and H2S and hydrocarbon groups for heavier fractions.
The concentration of certain major nonparaffin constituents,
within the C6 to C9 groups, such as, benzene, toluene, cyclohexane, and xylene, may also be identified.1 The hydrocarbon
groups are generally determined according to their boiling point
temperatures by distillation and/or gas chromatography.1
The distilled hydrocarbon groups are characterized by measuring some of their properties such as the average normal
boiling-point temperature, molecular weight, and density.1 These
properties are used in generalized correlations to estimate other
properties, such as the critical temperature (Tc), critical pressure
(Pc), critical volume (Vc), and the acentric factor (), which
are required for phase-behavior modeling using equations of
state.1 These properties are normally determined from generalized correlations in terms of the average normal boiling point
* To whom correspondence should be addressed. Tel.: +(33) 1 64
69 49 65. Fax: +(33) 1 64 69 49 68. E-mail: richon@ensmp.fr.
3226
1
f(x) )
1 + e-x
where x [0,1]
(1)
number of neurons
1
2
3
2
4
4
Nk - 1
Sk,i )
(2)
j)1
Ok,i )
1
N
k-1[(w
-(j)1
k-1,j,iIk-1,j)+bk,i])
1+e
1
1 + e-Sk,i
(3)
To develop the ANN, the data sets are subdivided into three
classes: training, testing, and validation.12 After partitioning the
data sets, the training set is used to tune the parameters. All of
the synaptic weights and biases are first initialized randomly.12
The network is then trained; its synaptic weights are adjusted
by an optimization algorithm until it correctly emulates the input/
output mapping, by minimizing the average root-mean-square
error.12 The optimization method chosen in this work was the
Levenberg-Marquart algorithm4-6 along with Bayesian regularization technique, as mentioned earlier. This algorithm is
specially indicated to optimize ANNs using small learning
sample size.13-16 The testing set is used during the adjustment
of the networks synaptic weights to evaluate the algorithms
performance on the data not used for tuning and stop the tuning
Tb/K
112
185
231
261
273
301
283
309
342
337
366
390
416
439
461
482
501
520
539
557
573
586
598
612
624
637
648
659
671
681
691
701
709
719
728
737
745
753
760
768
774
782
788
796
801
807
813
821
826
AAD%d
Vc/m3kmol-1
Pc/MPa
exp.a
cal.
AD%b
exp.
cal.
AD%
exp.
cal.
AD%
exp.
cal.
AD%
0.300
0.356
0.507
0.563
0.584
0.625
0.597
0.631
0.664
0.690
0.727
0.749
0.768
0.782
0.793
0.804
0.815
0.826
0.836
0.843
0.851
0.856
0.861
0.866
0.871
0.876
0.881
0.885
0.888
0.892
0.896
0.899
0.902
0.905
0.909
0.912
0.915
0.917
0.920
0.922
0.925
0.927
0.929
0.931
0.933
0.934
0.936
0.938
0.940
190.6
305.3
369.8
408.1
425.1
460.4
433.8
469.7
507.6
509.9
547.2
574.1
603.2
626.9
649.1
670.0
688.9
708.2
727.1
743.0
758.1
770.0
781.0
793.2
803.7
814.7
824.9
834.3
844.1
853.3
861.7
869.9
877.0
885.1
893.3
901.4
906.7
914.1
920.4
926.2
931.9
937.6
943.2
949.6
954.0
956.3
964.2
969.6
973.9
190.6
305.4
369.5
408.0
422.9
459.9
435.8
469.7
509.3
509.7
546.4
574.3
602.7
626.6
648.6
669.4
688.4
707.2
725.6
742.4
757.6
769.5
780.6
793.2
804.1
815.7
825.7
835.5
845.4
854.1
862.7
871.0
877.8
886.0
893.7
901.0
907.7
914.0
919.9
926.2
931.9
937.6
942.4
948.7
952.9
957.5
962.4
968.7
972.9
0.0
0.0
0.1
0.0
0.5
0.1
0.5
0.0
0.3
0.0
0.1
0.0
0.1
0.0
0.1
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.0
0.0
0.1
0.1
0.1
0.2
0.1
0.1
0.1
0.1
0.1
0.0
0.0
0.1
0.0
0.1
0.0
0.1
0.0
0.1
0.1
0.1
0.1
0.2
0.1
0.1
0.1
4.599
4.872
4.248
3.648
3.796
3.381
3.199
3.370
3.025
3.271
3.071
2.877
2.665
2.481
2.310
2.165
2.054
1.953
1.853
1.752
1.679
1.614
1.559
1.495
1.446
1.393
1.356
1.314
1.263
1.230
1.200
1.164
1.140
1.107
1.085
1.060
1.039
1.013
0.998
0.974
0.964
0.941
0.927
0.905
0.896
0.877
0.864
0.844
0.835
4.598
4.867
4.250
3.700
3.577
3.345
3.479
3.266
3.013
3.225
3.062
2.885
2.677
2.493
2.320
2.172
2.052
1.943
1.839
1.741
1.666
1.605
1.552
1.492
1.444
1.394
1.355
1.318
1.271
1.238
1.206
1.173
1.149
1.117
1.092
1.065
1.042
1.018
1.000
0.977
0.962
0.939
0.924
0.902
0.890
0.873
0.858
0.838
0.827
0.0
0.1
0.0
1.4
5.8
1.1
8.8
3.1
0.4
1.4
0.3
0.3
0.5
0.5
0.4
0.3
0.1
0.5
0.8
0.6
0.8
0.6
0.4
0.2
0.1
0.1
0.1
0.3
0.6
0.7
0.5
0.8
0.8
0.9
0.6
0.5
0.3
0.5
0.2
0.3
0.2
0.2
0.3
0.3
0.7
0.5
0.7
0.7
1.0
0.8
0.099
0.146
0.200
0.263
0.255
0.306
0.304
0.313
0.371
0.348
0.392
0.433
0.484
0.532
0.584
0.635
0.681
0.727
0.777
0.830
0.874
0.915
0.951
0.997
1.034
1.077
1.110
1.147
1.193
1.226
1.259
1.296
1.323
1.361
1.389
1.421
1.448
1.480
1.502
1.534
1.550
1.583
1.604
1.636
1.652
1.680
1.701
1.733
1.749
0.094
0.145
0.203
0.263
0.277
0.316
0.293
0.332
0.389
0.339
0.376
0.419
0.473
0.526
0.580
0.633
0.679
0.726
0.775
0.828
0.872
0.911
0.948
0.993
1.031
1.074
1.109
1.145
1.193
1.228
1.263
1.301
1.330
1.368
1.398
1.431
1.459
1.490
1.513
1.542
1.560
1.588
1.607
1.633
1.648
1.667
1.684
1.707
1.740
5.1
0.7
1.5
0.0
8.6
3.3
3.6
6.1
4.9
2.6
4.1
3.2
2.3
1.1
0.7
0.3
0.3
0.1
0.3
0.2
0.2
0.4
0.3
0.4
0.3
0.3
0.1
0.2
0.0
0.2
0.3
0.4
0.5
0.5
0.6
0.7
0.8
0.7
0.7
0.5
0.6
0.3
0.2
0.2
0.2
0.8
1.0
1.5
0.5
1.3
0.012
0.100
0.152
0.177
0.200
0.228
0.196
0.252
0.301
0.251
0.280
0.312
0.352
0.389
0.429
0.467
0.501
0.536
0.571
0.610
0.643
0.672
0.698
0.732
0.759
0.789
0.815
0.841
0.874
0.897
0.944
0.968
0.985
1.008
1.026
1.046
1.063
1.082
1.095
1.114
1.124
1.142
1.154
1.172
1.181
1.195
1.207
1.224
1.232
0.012
0.100
0.146
0.187
0.198
0.228
0.210
0.242
0.286
0.249
0.278
0.311
0.353
0.392
0.433
0.472
0.506
0.540
0.576
0.614
0.646
0.675
0.701
0.733
0.761
0.791
0.816
0.842
0.876
0.900
0.925
0.951
0.971
0.998
1.019
1.041
1.061
1.081
1.097
1.117
1.129
1.148
1.161
1.178
1.188
1.201
1.212
1.227
1.235
0.0
0.0
3.9
5.6
1.0
0.0
7.1
4.0
5.0
0.8
0.7
0.3
0.3
0.8
0.9
1.1
1.0
0.7
0.9
0.7
0.5
0.4
0.4
0.1
0.3
0.3
0.1
0.1
0.2
0.3
2.0
1.8
1.4
1.0
0.7
0.5
0.2
0.1
0.2
0.3
0.4
0.5
0.6
0.5
0.6
0.5
0.4
0.2
0.2
1.0
a (Pseudo-)experimental data have been reported by Danesh.1 b AD ) (|(experimental value - calculated value)/experimental value|). c These values
have been used for testing. The rest of data have been used for training. d AAD ) ((1/M)Mi ) 1|(experimental value - calculated value)/experimental
value|), where M represents number of (pseudo-)experimental points.
values are less than 2.5 K for the critical temperatures, less than
0.3 MPa for the critical pressures, less than 0.03 m3kmol-1
for the critical volumes, and 0.02 for the acentric factors,
reconfirming that the ANN method results are quite acceptable.
The data on normal paraffins were then used for validation.
It should be mentioned that the use of this model, which has
been deVeloped for SCN groups, for normal paraffins may be
conserVatiVe, however, as can be seen in Table 3, acceptable
results have been obtained. Table 3 shows the absolute deviations and average absolute deviations between the pseudoexperimental1 and predicted data. As can be observed, the
AADs% equal to 1, 8, 2.7, and 3 were obtained for the critical
temperatures, critical pressures, critical volumes, and acentric
factors, respectively, which are relatively acceptable. Figures
3228
Tb/K
n-heptane
371.58
n-octane
398.83
n-nonane
423.97
n-docane
447.30
n-undecene
469.08
n-dodecane
489.47
n-tridecane
508.62
n-tetradecane
526.73
n-pentadecane
543.83
n-hexadecane
560.01
n-heptadecane
575.30
n-octadecane
589.86
n-nonadecane
603.05
n-eicosane
616.93
n-heicosane
629.70
n-docosane
641.80
n-tricosane
653.40
n-tetracosane
664.40
AAD%d
Vc/m3kmol-1
Pc/MPa
exp.b
pred.
AD%c
exp.
pred.
AD%
exp.
pred.
AD%
exp.
pred.
AD%
0.688
0.707
0.722
0.734
0.745
0.753
0.762
0.763
0.772
0.777
0.780
0.782
0.787
0.792
0.795
0.798
0.800
0.803
540
569
595
618
639
658
675
693
708
723
736
747
758
768
782
792
801
810
543
573
599
623
644
664
683
699
715
730
743
756
767
780
791
801
810
819
0.6
0.7
0.7
0.8
0.8
0.9
1.2
0.9
1.0
1.0
1.0
1.2
1.2
1.6
1.2
1.1
1.1
1.1
1.0
2.740
2.490
2.290
2.110
1.949
1.820
1.680
1.570
1.480
1.400
1.340
1.270
1.210
1.160
1.147
1.101
1.059
1.019
2.780
2.564
2.371
2.202
2.054
1.923
1.815
1.701
1.623
1.545
1.471
1.404
1.353
1.303
1.254
1.209
1.167
1.128
1.5
3.0
3.5
4.4
5.4
5.7
8.0
8.3
9.7
10.4
9.8
10.6
11.8
12.3
9.3
9.8
10.2
10.7
8.0
0.428
0.486
0.544
0.600
0.659
0.716
0.775
0.830
0.889
0.944
1.000
1.060
1.120
1.170
1.198
1.253
1.307
1.362
0.447
0.507
0.567
0.627
0.685
0.743
0.797
0.862
0.911
0.966
1.024
1.081
1.127
1.176
1.227
1.275
1.323
1.368
4.4
4.3
4.2
4.5
3.9
3.8
2.8
3.9
2.5
2.3
2.4
2.0
0.6
0.5
2.4
1.8
1.2
0.4
2.7
0.350
0.400
0.444
0.492
0.530
0.576
0.617
0.643
0.686
0.717
0.770
0.811
0.852
0.907
0.922
0.955
0.989
1.019
0.332
0.378
0.423
0.467
0.510
0.553
0.592
0.640
0.675
0.714
0.756
0.797
0.830
0.864
0.900
0.934
0.967
0.999
5.1
5.5
4.7
5.1
3.8
4.0
4.1
0.5
1.6
0.4
1.8
1.7
2.6
4.7
2.4
2.2
2.2
2.0
3.0
a All of the values have been used for validation. b (Pseudo-)experimental data have been reported by Danesh.1 c AD ) (|(experimental value - predicted
value)/experimental value|). d AAD ) ((1/M)Mi ) 1 |(experimental value - predicted value)/experimental value|), where M represents number of
(pseudo-) experimental points.
be seen, the maximum differences between the pseudoexperimental1 and predicted values are 13 K for the critical
temperatures, 0.15 MPa for the critical pressures, less than 0.035
m3kmol-1 for the critical volumes, and less than 0.05 for the
acentric factors. It should be mentioned that although the
maximum difference between the pseudo-experimental1 and
predicted critical temperatures seems relatively high (13 K), it
can be considered acceptable due to uncertainty in estimating
critical temperatures of heavy hydrocarbons.
Figures 10 -13 show the estimated values of the critical
temperatures, critical pressures, critical volumes, and acentric
factors, respectively, for SCNs from C6 to C50. As can be seen,
the ANN model correctly determines the critical properties
and acentric factors of the SCNs for the practical applications
ranges (C1 to C50), even for SCNs not used in training the model
(i.e., C45 to C50). At high SCNs, the values of the critical
properties and the acentric factors become weak functions of
the SCNs and approach special values. As the petroleum
fractions heavier than C30 have more asphaltenic nature17,18
3230
fractions properties, and its application to very wide boilingpoint range fractions, such as C7+ is not recommended.
4. Conclusions
) a [exp(b1 + c2 + d 1 2)] 1e 2f
where a-f are constants for each property, which are given in
Table A.1.
A.4. Twu Correlations. The method initially correlates the
properties of normal paraffins as the reference. The calculated
values are then adjusted for petroleum fractions using the
difference between the specific gravity of the hydrocarbon
Tc
Tc
Pc
Pc
(Vc/M)
(Vc/M)
M
Tb
2
S
S
S
S
S
M S
Tb S
M S
1
Tb
M
Tb
M
Tb
a
10.6443
554.4
6 162 000
45 203
0.0006233
0.01206
581.96
6.77856
b
-0.00051747
-0.00013478
-0.004725
-0.0018078
-0.0014679
-0.002657
0.00054308
0.00377406
c
-0.54 444
-0.61 641
-4.8014
-0.3084
-0.26404
0.5287
-9.53384
2.984036
d
0.00035995
0.0
0.0031939
0.0
0.001095
0.0026012
0.00111056
-0.00425288
e
0.81067
0.2998
-0.4844
-0.8063
0.7506
0.20378
0.97476
0.401673
fT ) ST [-0.362456/Tb1/2 + (0.0398285 -
Tb - 0.284376 10
2
-10
(4)
-7
f
0.53691
1.0555
4.0846
1.6015
-1.2028
-1.3036
6.51274
-1.58256
Tb +
3
0.959468 10 /(Tb/100)13]-1
2
) 1 - Tb/Tcp
0.948125/Tb1/2)ST]
ST ) exp[5 (SP - S)] - 1
Critical Volume:
SM ) exp[5(Sp - S)] - 1
Acknowledgment
Waheed Afzal wishes to thank the Higher Education Commission of Pakistan for financial support.
Mp ) Tb/(10.44 - 0.0052Tb)
3232