SPE 93517

Tuning EOS Using Molecular Thermodynamics To Construct Asphaltene Deposition

Envelope (ADE)
M.A. Fahim, Kuwait U., and S.I. Andersen, IVC-SEP, Technical U. of Denmark

Copyright 2005, Society of Petroleum Engineers Inc.

Molecular Thermodynamics approach

This paper was prepared for presentation at the 14th SPE Middle East Oil & Gas Show and
Conference held in Bahrain International Exhibition Centre, Bahrain, 1215 March 2005.
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Abstract
The objective of this work to calculate ADE of
asphaltene from molecular thermodynamics. Aphaltenes and
resins are represented by pseudo-pure components, and all
other components in a crude oil are presented by a continuous
medium that affects attractions among asphaltene and resin
molecules. Model parameters are evaluated systematically
from average properties of asphaltenes and resins in crude oils,
and from dispersion-force properties of the oil medium. Given
the composition of the medium, and asphaltene and resin
concentrations, the molecular-thermodynamic, calculated
results for the effects of oil composition and pressure on
asphaltene precipitation are in good agreement with
experimental measurements for different reservoir fluids, for
several crude oils. The absolute average error was 9.8%
Introduction
Asphaltenes are heavy, black materials dissolved in
most petroleum. When petroleum is produced or transferred,
asphaltenes can precipitate, plugging-up equipment and
thereby shutting down operations. Every effort is made by oil
companies to avoid asphaltene precipitation because, when it
occurs, the cost of repair can be very large. It is important to
establish the conditions (temperature, pressure, composition)
which make asphaltene does not precipitate, so it requires to
have information about onset pressure to prevent the
precipitation. Because of deviation of Equation of state, it can
not used to predict the asphaltene onset pressure , the
existence of model to predict the asphaltene onset point is the
major task. This work is directed at establishing a reliable a
model based on molecular-thermodynamic theory which
corrects the deviation of EOS.

Crude oil is considered to be containing asphaltenes

and resins in continous media of other hydrocarbon.
Asphaltenes are represented by attractive spheres that can
associate with themselves. Resins are represented by attractive
sphere chains that can associate with asphaltenes, but not with
themselves. Asphaltene molecules and resin chains are
dissolved in a continuous medium that affects dispersion-force
interactions among asphaltenes and resin chains. The
Helmholtz energy of the system is given by an expression
based on random-phase-approximation theory . Statisticalassociated-fluid theory within the McMillan-Mayer
description of liquid solutions. The Helmholtz energy A
contains five contributions as given by Chapman et al , 1993
A= Aid+ Ahs + Avdw + Aassoc + Achain

(1)

Where N is the number of association cites and superscript id

stands for an ideal-gas mixture of asphaltenes and resin chains
at system temperature, volume, and molecular number
densities; hs stands for the contribution for hard-sphere
repulsion when resin chains are disconnected; vdw stands for
the contribution from van der Waals dispersion-force
attractions; assoc stands for the contribution from asphalteneasphaltene and asphaltene-resin associations; and chain stands
for the entropic contribution to A from connectivity of resin
chains
In this work only asphaltene-asphaltene and
asphaltene- resin associations will be considered assuming that
each asphaltene molecule has N identical association sites, and
each resin chain has only one association site. Asphaltene can
associate with each other, but resin chains can only associate
with asphaltenes. The Helmholtz energy due to association is
given by Chap man et al., 1990

1 x (2)

1 x
A assoc

= NX A ln x +
+ X R ln x +

2
2
RT

where XA and XR are, respectively, mole fractions of

asphaltene molecules and resin chains on a medium-free basis;
x is the fraction of association sites at asphaltene molecules
that are not bonded; x is the fraction of association sites at
resin chains that are not bonded. Fractions x and x are given

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SPE 93517

Z = ZSRK + Zassoc

by:

x = 1 + N A x + R x

x = 1 + N A x

(3)

(4)

where A , are as before the number densities of asphaltene

molecules and resin chains in the oil medium; , are
given by

= g 11hs ( 11 )[Exp (E / kT ) 1] 113

(5)

= g 12hs ( 12 )[Exp (E / kT ) 1] 123

(6)

where ghsij (ij) is the contact value of the pair correlation

function in the sphere mixture of asphaltene and resin
segments and are parameters related to the square-well
widths for the association potentials. To reduce the number of
unknown parameters, it can be assumed that they are identical
constants for associations between asphaltene and asphaltene,
and between asphaltene and resin chain.
To apply this equations to asphaltene precipitation at reservoir
conditions, it is needed first to establish a reliable method to
estimate required model parameters.
The association
contribution to pressure is given by expression

Passoc
Aassoc
=

RT
V RT

(6)

The pressure contribution from association is calculated from

equation (2) and (6) as:
1 x

Passoc
1 x
1

= N X A ln x +
+ X R ln +
RT
V
2
2

(7)

where V is the total volume, x mole fraction of asphaltene

free site, x mole fraction of resin site. The total pressure P is
given as a sum of the contributions from the SRK part and the
association part.
P = PSRK + Passoc

(8)

Where PSRK is give by :

P=

RT
a

V b V (V + b )

(9)

The total volume V, is calculated at pressure P presented by

equation (8). The compressibility factor in this case is :

(10)

This pressure and compressibility factor are also called PCPA

and ZCPA , referring to Cubic EOS plus association (CPA).
The flash calculation are carried using ZCPA. With this value of
the total volume and X mole fraction of asphaltene free site,
X mole fraction of resin site the pressure contribution from
association can be calculated from equation (7).
Experimental data for asphaltene onset ptrssures were
obtained from different literature sources Jamaluddin 2004,
Bruce and Nghiem 2004 , Burke et al 1990 , Behar et al 2003
,and Sorensen 2004. Four set of data at upper, saturation and
lower pressure with different temperature were used to the
association model by tuning the parameter (E/kT) and
ghsij. This two values can be measured
(E/kT)
experimentally by micro-Calorimeter technique developed by
Andersen et al (2004). It was found that ghsij, the contact value
of hard sphere pair has a value ranging 1.0 1.2 as reported by
Wu , 2000 and a value of 1.2 was used. If ghsij was used as
fitting parameter , it was found that it converge to a value of
about unity. The objective is to minimize the error in
calculating the onset pressure as :

P exp P calc
error =
P exp

* 100

(11)

by changing the adjustable parameters (E/kT) and (E/kT)

Discussion

For quantitative applications, molecular parameters

must be estimated independently or from a few experimental
data for the particular system of interest. The model
parameters of this model include the diameter of the
asphaltene molecule segment A and the diameter of resin
segment R , asphaltene-asphaltene association energy
(E/kT) , the asphaltene-resin association energy (E/kT) ,
the number of association sites of each asphaltene molecule N
, and the volume parameter k. Also the segment densities of
pure asphaltenes and pure resins should be known. These
properties are not readily obtained from typical asphaltene or
crude-oil
characterizations.
For
phase-equilibrium
calculations, We can use the average molecular weights and
densities for pure asphaltenes and resins. . As discussed by
Speight (1991, 1994), the average molecular weights of
asphaltenes and resin chains are about 2,000 and 800 ,
respectively. The mass density of a typical asphaltene is about
1200 kg/m3, close to that of the heaviest hydrocarbons, and the
mass density of a typical resin is about 1,000 kg/m3 Speight,
(1991) From the mass densities and molecular weights, the
number densities of pure asphaltenes and resin chains can be
calculated. Using the molecular weight of asphaltene and mass
density , the diameter of an asphaltene molecule segment lies
in a narrow range, 1.43 -1.58 nm. A value of =1.5 nm is
used in this calculation.

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SPE 93517

Because resin is a liquid at ambient conditions, its

packing fraction should be less than that of a hard-sphere solid
at the fluid solid phase transition (0.55) . it can be assumed
that the diameter of a resin segment is about 0.5 nm, and the
number of segments per chain is about 10. Table 1 shows
values of parameter used in this study.

700
600

300

0
350

Model lower ADE

360

370

380

390

400

Temperature, K

Figure 2: Comparison of ADE obtained by molecular

thermodynamic model with experimental ( Crude E)
600

Pressure, atm

Model upper ADE

Model saturation

400
Pressure, atm

400

500
Exp saturation

Model lower ADE

100

500
Exp. lower ADE

Model upper ADE

Model saturation

200

Different crudes from different literature sources were used in

this work and comparison of calculated onset pressure by the
model with experimental values were satisfactory and the
(AAE) was about 9.8% with maximum error of 44% and
minimum error of 0.4%. the detailed result shown in table 4.
Figure 1 2 , and 3 show a comparison of calculated ADE four
samples with experimental data. Table 2 show properties of
crudes oil used in generating ADE.

Exp. upper ADE

Exp saturation

Exp. lower ADE

500
Pressure, atm

Table 1: Parameter used in the study

Parameter
Asphaltene
Resin
Density* , kg/m3
1200
1000
0.05
0.05
Volume parameter, k
Number of segments
1
10
Segment diameter, nm
1.5
0.5
* experimental value is used when available

Exp. upper ADE

Exp. upper ADE

Exp saturation

Exp. lower ADE

Model upper ADE

Model saturation

Model lower ADE

400

300

300
200

200

100
360

100
350

375

400
Temperature, K

425

450

Figure 1: Comparison of ADE obtained by molecular

thermodynamic model with experimental ( Crude F)
For calculation of mole fraction of asphaltene and volume of
the crude at different temperature and pressure flash
calculation was used. (equations 8 through 128 ) . This
equations are highly non linear and Newtons raphson was
used to solve the equations..

370

380
Temperature, K

390

400

Figure 3: Comparison of ADE obtained by molecular

thermodynamic model with experimental ( Crude S)
It is noticed that from the data presented in table 4 that the
value of asphaltene self association (E/kT) is ranging
between 3-20 and that of asphaltene-resin interacting is
ranging between 6-30. If we use an average value of 10 and 16
respectively, the model become completely predictive. Table
5 shows summary of error analysis for onset pressure
calculation when using (E/kT) and (E/kT) as fitting
parameters and when using average values Work is underway
to measure asphaltene/resin interactive energies for a broad
data base of crude oils.

Conclusion

The molecular thermodynamic model discussed here

has been tested with experimental data for a few reservoir
fluids to describe the effects of pressure and oil composition

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SPE 93517

on asphaltene precipitation. This model can be applied to

identify the operation conditions at the onset of asphaltene
precipitation, asphaltenes and resins. The parameters related to
association interactions, N , E/kT and Masph, are confined
within physically meaningful lower and upper limits of onset
pressure . However, because calculated results are often
sensitive to these parameters, and because asphaltenes and
resins in crude oils differ from one crude oil to another, in
typical cases, they must be correlated with some experimental
data for the particular crude oil of interest. It is expected if the
interactive energies are measured by micro-calorimeter , the
model will be completely predictive.

characterization most often used is to stop at C7+. The

reservoir fluid compositional analysis is usually carried out by
defining the pure hydrocarbon components (C1 - C6), nonhydrocarbons (N2 , H2S, CO2), and grouping components
heavier than heptane or decane into one components or limited
number of pseudo-components. Because EOS accuracy
depends on number and characterization of the plus-fraction,
based on molecular weight and density of C7+ fraction , this
fraction is divided into 10 or 12 pseudocomponents.,
In this study Katz (1983) method was used and the resulting
relationship can be conveniently expressed mathematically by
the following expression:

Acknowledgement

M. A. Fahim would like to thank Kuwait University

for granting him the sabbatical year 2003/2004 where he spent
part of it at Denmark Technical University.

Zn = 1.38205 Z7+ e-0.25903 n

where

Z7+ = mole fraction of C7+

n = number of carbon atoms
Zn = mole fraction of pseudo-component with n
carbon atoms

Nomenclature

Aassoc
P
R
T
N
M
x
x
XA
XR
E

Association part of correction

Pressure
Gas constant
Temperature
Number of chain
Molecular weight
mole fraction of asphaltene free site
mole fraction of resin free site
mole fraction of asphaltene
mole fraction of resin
Association Energy
Mean diameter
Volume parameter
Density of asphaltne
Density of resin
Fugacity coefficient in liquid phase

iV
is

Fugacity coefficient in vapor phase

ghsij
i
z
Z
Pc
Tc

a
b

Contact of the pair correlation function

Equilibrium ratio
Feed fraction
Compressibility factor
Critical pressure
Critical pressure
Acentric factor
First SRK parameter
Second SRK parameter

iL

(I-1)

The molecular weight and density of last fraction (n+) is

calculated as follows:
n
MWn+ = [ Z7+ MW7+ - (Zn . MWi)]/Zn+
(I-2)
i=7
n
SGn+=Zn+ MWn+ /(Z7+ MW7+ / SG7+) - (Zn . MWi/Zi) (I-3)
i=7
Once the mole fraction and the molecular weight and gravity
of each subtraction are determined, critical properties and
acentric factor are calculated

Fugacity coefficient in solid phase

To use the EOS, it is required to characterize the

subtractions by estimating their critical properties, The
Pedersen et al. (1989) correlation is used to calculate critical
properties and acentric factor for the pseudo-fractions forming
heptane plus using the molecular weight (MW) and density
(SG) of the subtraction as follows:
Tc = 1.6312x102. SG+ 8.6052*101- ln(MW) + 4.3475x10.MW-1.8774x10-3/MW
(I-4)

lnPc = -1.3408x10-1 + 2.5019. SG + 2.0846x102/MW 3.9872x103/MW2

(I-5)
The acentric factor is calculated from the following equations:

Appendix

m = 0.48 + 1.574 - 0.1762

Since Petroleum fluids consist of thousands of

different hydrocarbon constituents. The diversity of the
chemical structure of the individual components increases
with carbon number; it is therefore impractical to analyze for
all the C7+ components. A standard composition analysis

(I-6)

where
m = 7.4310x10 -1 + 4.8122x10 -3 . MW +9.6707x10-3. SG 3.7184x10-6. MW2
(I-7)

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SPE 93517

where Tc is in K, Pc in atm, MW is in g/mol, and SG is in

g/cm3

Jamalddin, A.K.M. , Nighswander, J.N. SPE 80261, 2003

Katz, D., JPT, June 1983, pp. 1205-1214

Oil n gas mixture is a complicated system with

special characterization. However one can assume that there is
no heavy hydrocarbon with high molecular weight such as
asphaltene in vapor phase. The following material balance can
be written :

z i K iVL
V
=
x
1 i i V ( K VL 1) S + 1 = 1
i
n

L
i

x nS =

=
i

V (K

VL
i

zi
=1
1) S ( K iSL 1) + 1

K nSL z n
1 V + S ( K nSL 1)

(I-8)

iL
iV

K iSL =

iL
iS

Pedeson, K. S. Fredenslund, Aa., ThomassenP., 1989. Gulf

Publishing, Huston.
Sorensen , C. ; (2003) M-Sc thesis, Technecal university of
Denmark.

(I-9)

(I-10)

Speight, J. G., The Chemistry and Technology of Petroleum,

Dekker, . New York 1991.
Speight, J. G. . Arab. J. Sci. Eng., 19, 335 1994 .
Wu, J., J. M. Prausnitz, and A. Firoozabadi, AIChE J., 44,.
1188 1998 .

Where
K iVL =

Merino-Garcia , D. and Andersen , S. I (2003); 4th

international conference on petroleum Phase behaviour ,
Norway

(I-11)

Wu J. and John M. Prausnitz , A. Firoozabadi January 2000

Vol. 46, No. 1 AIChE

(I-12)

Initial values of equilibrium ration for each component in the

mixture at specified temperature and pressure can predicted
from wilsons equation as initial guess for calculation

K iVL =

iL

and

iV

Pci
T

exp 5.37(1 + i )(1 ci )

P
T

(I-13)

can be calculated from SRK - EOS and for

iS

can be evaluated from solid phase fugacity at reference point.

References

Behar E., Mougin P. , and Pina A. Oil and Gas Science

Technology, Vol 58 (2003), No 6, pp 637-646
Burce F.K. , Nghiem L.X. , SPE64465, 2000
Burke, N. E., R. E. Hobbs, and S. F. Kashou J. Pet. Technol.,
42, 1440. 1990
Chapman , W., Gubbins, K., Jackson, G. and Radosz, M.
(1989); Fluid Phase Equilibria 52, 31-38
Chapman , W., Gubbins, K., Jackson, G. and Radosz, M.
(1990) ; Ind Eng Chem Res. 29, 1709-1721
Jamalddin, A.K.M. , Nighswander, J.N. SPE 87292, 2000

www.petroman.ir

SPE 93517

Table 2: Properties of crude oils used in generating ADE

Crude
E1
E2
E3
E4
F1
F2
F3
F4
K1
K2
K3
K4
K5
S1
S2
S3
S4

C7%
26.88
26.88
26.88
26.88
32.29
32.29
32.29
32.29
28.11
28.11
28.11
28.11
28.11
26.88
26.88
26.88
26.88

S.G
C7+
0.865
0.865
0.865
0.865
0.877
0.877
0.877
0.877
0.852
0.852
0.852
0.852
0.852
0.865
0.865
0.865
0.865

MWT
C7+
228.1
228.1
228.1
228.1
248.8
248.8
248.8
248.8
209.5
209.5
209.5
209.5
209.5
228.1
228.1
228.1
228.1

Asp.
Wt%
1.3
1.3
1.3
1.3
1.4
1.4
1.4
1.4
0.5
0.5
0.5
0.5
0.5
1.3
1.3
1.3
1.3

Res
Wt%
7.0
7.0
7.0
7.0
10.4
10.4
10.4
10.4
11.3
11.3
11.3
11.3
11.3
18.8
18.8
18.8
18.8

Crude
MWt
82.5
82.5
82.5
82.5
103.1
103.1
103.1
103.1
81.8
81.8
81.8
81.8
81.8
82.0
82.0
82.0
82.0

T
(K)
372.0
378.0
384.0
389.0
361.0
383.0
400.0
422.0
322.0
339.0
355.0
389.0
496.0
372.0
377.0
383.0
389.0

Pupper
(atm)
466.8
448.1
437.2
423.4
367.3
275.5
248.3
258.5
590.8
528.0
490.0
484.1
470.0
460.3
442.4
431.1
416.9

Psat
(atm)
219.1
223.0
223.0
223.0
169.8
181.3
197.4
207.3
173.7
194.7
201.4
221.1
240.1
216.3
220.5
220.0
220.9

Plow
(atm)
121.4
128.3
133.2
133.2
105.6
185.5
158.9
200.3
94.0
86.9
93.3
104.1
80.0
129.2
131.6

Res
Wt%
8.3
0.9
18.0
1.5
10.4
7.6
6.0
7.4
1.1
18.0
4.5
4.6
6.4
7.5
13.5
2.3
2.1
7.7

Crude
MWt
171.3
78.4

T
(K)
373.0
384.0
403
386.0
422.0
361.0
386.0
383.0
391.0
322.0
316.0
327.0
327.0
376.0
361.0
386.0
383.0
386.0

Pupper
(atm)
351.7
543.0
409.6
228.3
374.0
361.6
510.2
421.4
255.0
491
151.4
258.5
350.4
205.1
355.0
268.6
258.6
270.0

Psat
(atm)
198.4
284.2
133.2
272.1
289.9
205.3
225.0
160.3
149.7
65.8
82.6
200.7
286.1
116.8
169.8
126.3

Plow
(atm)
125.3
182.6
88.8
260.8
79.0
125.3
106.6
55.0
257.2
128.3
68.2

Table 3: Properties of crude oils used in testing model

Crude
A
B
C
D
H
I
J
L
M
N
O
P
Q
R
T
U
V
W

C7%
47.96
26.61
30.29
39.74
30.68
24.17
30.41
27.94
29.88
32.69
50.92
43.33
29.92
66.68
24.17
41.39
73.56
42.19

S.G
C7+
0.959
0.853
0.926
0.846
0.877
0.875
0.846
0.846
0.832
0.8772
0.852
0.832
0.833
0.902
0.875
0.874
0.860
0.874

MWT
C7+
329.0
215.9
295
223.2
248.8
368.9
204.8
205.2
209.8
239.0
210.7
208.7
213.1
281.0
368.9
245.5
230.3
245.5

Asp.
Wt%
15.8
0.5
3.5
0.9
1.4
4.6
0.5
0.3
0.5
6.1
1.0
0.9
0.5
7.8
4.6
3.3
1.5
3.3

109.8
99.3
103.0
84.4
76.0
86.8
122.4
126.0
110.8
84.2
202.4
109.6
123.2
193.7
125.2

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A
B
C
D
E1
E2
E3
E4
E5
F1
F2
F3
F4
H
I
J
K1
K2
K3
K4
K5
L
M
N
O
P
Q
R

Crude

T
(K)
373.0
384.0
403.0
386.0
372.0
378.0
383.0
389.0
361.0
361.0
386.0
400.0
422.0
422.0
361.0
386.0
322.0
339.0
355.0
389.0
496.0
383.0
391.0
322.0
316.0
327.0
327.0
376.0

PEXP
(atm)
351.0
543.0
450.0
228.0
466.0
448.0
437.0
423.0
364.0
367.0
275.0
248.0
258.0
374.0
361.0
510.0
590.0
528.0
490.0
484.0
470.0
421.0
255.0
491.0
151.0
258.0
350.0
205.0

PSRK
(atm)
555.0
331.0
490.0
170.0
493.0
475.0
454.0
440.0
430.0
404.0
304.0
271.0
300.0
347.0
379.0
550.0
275.0
258.0
256.0
247.0
296.0
428.0
192.0
620.0
190.0
288.0
375.0
178.0

3500
3500
2500
3500
2000
2000
2000
2000
2000
2200
2200
2200
2200
3500
2500
3500
3900
3900
3900
3900
3900
2350
3500
2800
2700
3000
2500
2500

Masp

900
850
900
850
800
800
800
800
800
850
850
850
850
820
800
830
830
830
830
830
830
800
850
850
820
800
800
820

MRes

17.0
20.0
9.0
20.0
10.0
9.0
9.0
9.0
15.0
15.0
15.0
13.0
17.0
11.0
10.0
11.0
3.0
3.0
4.0
4.0
3.0
10.0
12.0
9.0
10.0
13.0
10.0
9.0

(E/kT)

25.0
30.0
11.0
25.0
17.0
15.0
13.0
15.0
17.0
17.0
17.0
15.0
19.0
13.0
12.0
12.0
25.0
28.0
30.0
26.0
25.0
12.0
15.0
11.0
11.0
17.0
12.0
11.0

(E/kT)

0.00202
0.00089
0.15012
0.00100
0.10443
0.16594
0.17414
0.16602
0.00836
0.00857
0.00814
0.02317
0.00330
0.04934
0.09384
0.04947
0.88830
0.88845
0.77038
0.77574
0.89051
0.09651
0.03056
0.14243
0.09064
0.01947
0.09407
0.15017

Table 4: Calculation result of different crude for molecular Thermodynamic method

3.2E-06
5.0E-08
0.07497
0.00001
0.00036
0.00167
0.01062
0.00167
0.00359
0.00389
0.00419
0.00833
0.00124
0.02331
0.04552
0.06076
0.00000
0.00000
0.00000
0.00000
0.00000
0.04701
0.00519
0.07089
0.11058
0.00129
0.04542
0.07495

0.00322
0.00040
0.00330
0.00060
0.00087
0.00087
0.00087
0.00087
0.00300
0.00100
0.00100
0.00100
0.00100
0.00100
0.00035
0.00030
0.00035
0.00035
0.00035
0.00035
0.00035
0.00030
0.00040
0.01280
0.00550
0.00066
0.00034
0.00550

XA

0.00756
0.00090
0.01410
0.00150
0.00526
0.00526
0.00526
0.00526
0.00410
0.01040
0.01040
0.01040
0.01040
0.01040
0.01130
0.00180
0.01130
0.01130
0.01130
0.01130
0.01130
0.00240
0.00110
0.03390
0.00750
0.00460
0.00640
0.00750

XR

Passoc
(atm)
-131.0
19.4
-26.1
19.1
-14.0
-10.7
-8.4
-10.4
-54.4
-25.8
-21.8
-16.3
-26.6
19.7
-8.6
-5.5
51.4
57.2
61.6
53.2
56.0
-3.5
6.3
-115.6
-33.1
-14.8
-6.1
26.0

Pcalc
(atm)
424.0
350.4
463.9
189.1
479.0
464.3
445.6
429.6
375.6
378.2
282.2
254.7
273.4
366.7
370.4
544.5
326.4
315.2
317.6
300.2
352.0
431.5
198.3
504.4
156.9
273.2
368.9
204.0

-20.8
35.5
-3.1
17.1
-2.8
-3.6
-2.0
-1.6
-3.2
-3.1
-2.6
-2.7
-6.0
2.0
-2.6
-6.8
44.7
40.3
35.2
38.0
25.1
-2.5
22.3
-2.7
-3.9
-5.9
-5.4
0.5

%ErrA

-41.7
37.9
1.2
22.4
-3.0
-3.2
-1.0
-1.1
-10.5
-4.5
-4.3
-2.6
-9.7
0.7
-0.1
-6.6
49.2
46.7
43.6
44.1
31.4
-3.0
22.8
10.3
-0.5
-7.3
-3.9
-5.4

%ErrB

-58.1
39.0
-8.9
25.4
-5.8
-6.0
-3.9
-4.0
-18.1
-10.1
-10.5
-9.3
-16.3
7.2
-5.0
-7.8
53.4
51.1
47.8
49.0
37.0
-1.7
24.7
-26.3
-25.8
-11.6
-7.1
13.2

%ErrC

SPE 93517
7

www.petroman.ir

T
(K)
372.0
377.0
383.0
389.0
361.0
386.0
383.0
386.0
X

0.13799
0.13833
0.35540
0.82803
0.00085
0.00744
0.15255
0.05819

(E/kT)

13.0
11.0
9.0
6.0
25.0
17.0
11.0
13.0

www.petroman.ir
AAE
MAX
MIN

(E/kT) and (E/kT)

11.8%
49%
0.48%

9.8%
44%
0.2%

Average

0.00985
0.06833
0.20191
0.68614
0.00001
0.00337
0.07670
0.02752

(E/kT) and (E/kT)

Variable

Table 5 : Comparison of error in onset pressure for different cases:

PSRK
MRes (E/kT)
Masp
(atm)
S1
423.0 3000
820
9.0
S2
420.0 3000
820
9.0
S3
416.0 3000
820
7.0
S4
413.0 3000
820
4.0
T
558.0 3500
800
20.0
U
317.0 3000
850
15.0
V
266.0 2400
800
9.0
W
300.0 2500
800
11.0
* A using variable value of (E/kT) and (E/kT)
B using average value of (E/kT) and (E/kT)
* C using EOS with no tuning

Crude

PEXP
(atm)
460.0
442.0
431.0
416.0
355.0
268.0
258.0
270.0

Table 4: Calculation result of different crude for molecular Thermodynamic method (Continue)

0.01880
0.01880
0.01880
0.01880
0.01350
0.00230
0.00210
0.00770

XR

Passoc
(atm)
24.1
15.9
7.4
1.2
-144.0
-42.2
-5.8
-22.3

SRK
No corection or tuning
19.2%
58.1%
0.72%

0.00090
0.00090
0.00090
0.00090
0.00320
0.00230
0.00110
0.00230

XA

Pcalc
(atm)
447.1
435.9
423.4
414.2
414.0
274.8
260.2
277.7

2.8
1.4
1.8
0.4
-16.6
-2.5
-0.9
-2.9

%ErrA

0.1
-3.1
-4.2
-7.1
-42.0
-10.5
0.3
-2.5

%ErrB

8.0
5.0
3.5
0.7
-57.2
-18.3
-3.1
-11.1

%ErrC

8
SPE 93517