EUlIILlmA

ELSEVIER

Fluid Phase Equilibria 112 (1995) 45-61

Improving predictions of equation of state by modifying its

parameters for super critical components of hydrocarbon reservoir
fluids
A. Danesh *, D.-H. Xu, D.H. Tehrani, A.C. T o d d
Department of Petroleum Engineering, Heriot-Watt University, Riccarton, Edinburgh EH I 4 4AS, UK

Received 4 November 1994; accepted 28 April 1995

Abstract

The parameters of equations of state of van der Waals type have been generally correlated by matching the
properties of pure substances, and extended to mixtures by employing mixing rules commonly with binary
interaction parameters. It is proposed to use equilibrium data on binary systems to determine the attraction term
in equations of state (EOS) for super critical components instead of data of pure substances. The proposed
method was applied to the Peng-Robinson EOS, as an example, resulting in a significant improvement in
predicting the phase behaviour of different types of fluids. As no binary interaction parameters are required in
this method the computational requirement for flash calculations is drastically reduced for fluids with many
components. The proposed method is particularly advantageous for predicting fluid phase equilibria in
compositional reservoir simulators, where the reservoir fluid can be described with any desirable number of
components without any significant increase in computational time.
Keywonts: Theory; Equation of state; Cubic; Mixing rules; Vapour-liquid equilibria; Super critical; Hydrocarbons
1. Introduction

Cubic equations of state (EOS) are commonly used in the petroleum industry, particularly in
compositional reservoir simulators, to predict the phase behaviour and volumetric properties of
hydrocarbon reservoir fluids. These equations are based on the classical van der Waals equation, but
with more complex parameters to account for the attraction and repulsion forces between the
molecules. The parameters have been generally determined and correlated by matching measured and
predicted properties of pure substances.
The success of these semi-empirical EOS in predicting fluid properties depends to a large extent on
the type of data used to correlate their parameters. Almost all the equations which are used to predict

* C o r r e s p o n d i n g author.
0378-3812/95/$09.50 1995 Elsevier Science B.V. All rights reserved

SSD10378-3812(95)02782-3

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

46

the phase behaviour of hydrocarbon mixtures, have employed vapour pressure data of pure compounds for this purpose. For example, whereas saturation pressures of pure substances at the reduced
temperature of 0.7 were used to develop the parameters of Soave-Redlich-Kwong EOS (Soave,
1972), vapour pressure data from the normal boiling point to the critical point were used by Peng and
Robinson (1976). The experimental equilibrium data used in the development of these equations have,
therefore, been limited to conditions below the critical point of pure compounds. Only few
investigators (e.g. Kubic, 1982) have considered using data in supercritical regions.
EOS are applied to mixtures by introducing mixing rules to relate their parameters to properties and
concentrations of their constituents. The performance of EOS for mixtures is improved by introducing
binary interaction parameters in the mixing rules, expressing the interaction between pairs of
non-similar molecules. As the interaction parameters are determined by matching the predicted values
with experimental data, they should be considered primarily as fitting parameters for a particular EOS
than rigorous physical parameters. Hence, the interaction parameters for a pair of substances
developed for various EOS are generally different even with the same mixing rules.
In this work, we propose a different approach to determine the parameters of semi-empirical EOS
for phase behaviour studies of multicomponent systems, particularly for petroleum reservoir fluids.
The crux of the proposed method is to employ phase behaviour data of binary systems, instead of
those of pure substances, to determine the parameters of EOS for super critical components. The
advantages of the method are as follows:
1. Light components of reservoir fluids, particularly methane which constitutes a large fraction of
reservoir fluids, are generally at temperatures well above their critical points, where no vapour
pressure data exist to be used for developing EOS parameters. The use of binary data extends the
temperature range of relevant data, and it is only logical to expect more reliability when employing
any correlation within its correlated domain.
2. As binary data are used in correlating the parameters of EOS, the interaction between pairs of
non-similar molecules a n d / o r the deficiencies of EOS for binary systems, are taken into account
to some extent. The need for the use of binary interaction parameters is, therefore, reduced. This
would allow for a significant simplification in phase behaviour calculations resulting in a major
reduction in the computational requirement, particularly for mixtures described by a large number
of components. The reduction of time spent in flash calculations is highly desirable in compositional reservoir simulators, where many hundred thousand flashes may be performed in a study.
The proposed approach was applied in this work to the Peng-Robinson EOS, as the most widely
used equation in the industry. A large data bank of binary data was employed to revise the correlation
expressing the temperature effect on the attraction term for super critical hydrocarbon components.
The equation with the revised parameter has been used to predict the phase behaviour and volumetric
properties of a wide range of fluids. The reliability of the proposed method and the saving in
computational time for phase behaviour studies of reservoir fluids are demonstrated in this work.
2. Parameters of equation of states

Almost all van der Waals type EOS which have received significant attention for industrial
applications can be expressed by the following general form:
P=

RT
- v-b

a
v2+uv+w

(1)

A. Danesh et al. / Fluid Phase Equilibria 112 (199.5) 45-61

47

where P, u, T and R are the pressure, molar volume, temperature and universal gas constant
respectively; and a and b represent the molecular attraction and repulsion terms in EOS. In
2-parameter forms of the equation, u and w are related to b, whereas in a 3-parameter form u and w
are related to b and a third parameter e or some properties such as the acentric factor.
The parameters of an EOS can be presented by the following general equations:
R2Tc 2

(2)

Pc
R<

b=

<

(3)

RL
c = n c -

(4)

<

In the original van der Waals equation and some earlier two-parameter modifications, such as the
Redlich-Kwong EOS (1948), the values of g2a and ~'~b are constants and can be simply determined
by invoking the requirement of zero values of the first and second derivatives of pressure relative to
volume at the critical point. These parameters are, however, mostly component-dependent and may
vary with the temperature in more successful modifications. Correlations have, therefore, been
developed to determine these parameters by matching predicted values for pure compounds to
measured data.
The equations used in the modelling of petroleum reservoir fluids have been generally developed
by equating the calculated fugacities of saturated liquid and vapour phases. Hence, only data below
the critical conditions of pure compounds have been used in their development, whereas light
compounds such as methane in reservoir fluids are almost always at super critical conditions. The
majority of equations assume that the developed correlations below the critical temperature are also
applicable at conditions above the critical points of the mixture constituents. Zudkevitch and Joffe
(1970), however, assumed that the two parameters of the Redlich-Kwong equation remain constant
above the critical point as the equation explicitly includes the square root of temperature in the
attraction term. It is, therefore, logical to question the validity of these assumptions and to search for
an alternative approach which would include data at more relevant conditions in developing the
correlations.
To fix ideas we select the Peng-Robinson equation (PR EOS), as the most popular equation, for
our discussion and application of the proposed method. Nevertheless the concept and the method are
applicable to other semi-empirical EOS.
The PR EOS is obtained by making u = 2b, and w = - b 2 in Eq. (1),
RT

,P = -u --

a
b

u 2 + 2by

b2

(5)

and the parameters are given by,

RaTc2
el = 0 . 4 5 7 2 4 c ~

(6)

Pc

RL
b = 0.07780--

Pc

(7)

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

48

where a expresses the temperature dependency of the attraction term. Peng and Robinson (1976)
used vapour-pressure data from the normal boiling point to the critical point to determine o~ as,
2

(8)

where T~ is the reduced temperature, and m is a constant characteristic of each substance. The value
of m was correlated with the acentric factor w, and later modified to improve predictions for heavier
components (Robinson and Peng, 1978),
m = 0.3796 + 1.485w - 0.1644w 2 + 0.01667w 3

(9)

3. Binary interaction parameter

The application of EOS has been extended to multicomponent systems by defining mixing rules to
relate the mixture parameters to those of its constituents. Although different mixing rules have been
proposed, the classical van der Waals mixing rules, also called the random mixing rules, are the
accepted forms for reservoir hydrocarbon mixtures:
N

a= Y'~ yiYj(aiaj)
j=l

0.5

(1-kij)

(10)

i=l

b= ~., Yibi

(11)

j=l

where Yi and yj are the mole fractions of the component i and j, and kij is the binary interaction
parameter (BIP) expressing the interaction between pairs of non-similar molecules. As the interaction
parameter is determined by matching the predicted values for binary mixtures with experimental data,
it could be considered as a fitting parameter and not strictly a rigorous physical parameter.
Generalised correlations as well as tables of calculated/estimated values have been reported for
different equations. In this study we use the parameters determined by Knapp and Doting (1982), and
Robinson and Peng (1978) for PR EOS. No attempt was made to adjust the BIP in this work.
A comparative study of ten EOS (Danesh et al., 1991) concluded that the Patel and Teja equation
as modified by Valderrama (Valderrama, 1990) without any BIP was more successful in modelling
phase behaviour of reservoir hydrocarbon fluids than others with pertinent BIP. The success of the
above equation with no BIP strengthens the view that these parameters, at least for hydrocarbon
mixtures, mostly cover the deficiencies of EOS than accounting for the interaction between molecules
of different compounds. Furthermore, the above study also showed that the performance of the
relatively simple equation of state of Redlich and Kwong (1948) surpassed those of more advanced
equations when its parameters were determined by matching saturation data of pure compounds, as
suggested by Zudkevitch and Joffe (1970). An improvement to an EOS, such as employment of more

4t4

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

Table 1
Compositions and properties of synthetic multi-componentmixtures
Fluid
Mixture 1
Mixture 2
source
Danesh et al. (1991)
this work
component
mol.(%)
mol.(%)
Cl
C2

C3
nC 4

nC5
nC6
Met cycl pent
Cyc hex
nC7
Met cycl hex
Toluene
nC8
o-Xylene
nC,~
nC 1~
nC it
nC ,2
nC l ~
nC 1,1
nC 15
nCt6
nC ,7
nC ,~
nC,~
nC2o
Temperature C
Sat. Press (MPa)
Sat. Den (g cm -3)

46.80
8.77
7.44
4.01
2.56
1.77
2.25
2.20
0.46
2.36
0.72
1.02
1.79
1.66
2.73
2.37
2.04
1.77
1.53
1.34
1.15
0.99
0.87
0.75
0.65
100.0
20.28
0.541

82.05
8.95

Mixture 3
Danesh et al. (1991)
tool.(%)
69.82
13.09
ll.10
5.99

5.00

1.99

2.01

80.0
31.98
0.326

reliable values for its parameters, should therefore reduce the need to use BIP for hydrocarbon fluids
which do not contain complex compounds.
As an example, the values o f / 2 a and O b in PR EOS were determined by matching the properties
of pure saturated compounds at the prevailing temperature, similarly to the method of ZudkevitchJoffe, instead of the generalised expressions given by Eqs. (6) and (7). The equation was then used to
predict the dew point of a gas condensate identified by Mixture 3 in Table 1. The predicted dew
points by the above method without any BIP as well as those by the original PR EOS with and
without BIP are compared with experimental data in Fig. 1. Note that the predictions by the
Peng-Robinson EOS with revised values of a and b (Rev PR), but without any BIP, are very close to
those by PR EOS with binary interaction parameters, PR(kij), whilst PR without any BIP is inferior to
others. (The predictions identified by mPR in Fig. 1 will be discussed later). This example is not
given to suggest that the predicted values of PR EOS as revised above and without BIP are always to

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

50

35-

32

=~ 30~= 28o

Exp.

..........

PR(kij)

- - '

mPR

.......

Rev PR

.......

PR

r~
25-

20

10

60

80

100

120

Temperature (C)

Fig. I. Dew point pressureof Mixture3.

be similar to those of the original PR EOS with BIP, but merely to highlight the significance of the
method used to determine EOS parameters and also the contribution of BIP as a fitting parameter.

4. M o d i f i c a t i o n

The above example demonstrated the value and significance of the data used to determine the
parameters of EOS. The limitation of correlating the parameters for super critical components of a
mixture using experimental data can be eliminated by employing binary data at prevailing temperatures. It is acknowledged that the parameters so obtained for a substance include various contributions
of the second component, and hence may be less reliable for that substance as a pure fluid. For
practical purposes, this is not really a limitation as although cubic EOS are developed and evaluated
for pure substances, they are hardly ever used to predict the behaviour and properties of pure systems.
The above approach is similar to the use of Henry's constant instead of pure compound's fugacity
for predicting gas solubility in liquids. The fugacity of the component in the mixture can be simply
evaluated as it is proportional to its concentration according to Henry's law, whereas it does not
provide reliable information for the compound at the pure condition. Indeed, the aforementioned
limitation has been well accepted as the price for simplicity and reliability achieved at working
conditions. A similar argument is presented in support of using binary data to determine the
parameters of EOS. In addition to expected improvement in reliability due to using more relevant
data, the need for BIP should be eliminated resulting in a major reduction of computational time as
will be shown in the next section.
Over 5,000 vapour-liquid equilibrium experimental data of binary systems containing a super
critical component with hydrocarbons ranging from C 1 to nC12(Knapp and Doting, 1982) were used
in this study. The bubble point pressure of the liquid phase and the composition of the equilibrated
vapour phase as predicted by PR EOS were matched to experimental data by adjusting the parameter
a of the super critical component. The optimum value of a for super critical hydrocarbon components
was found to be reasonably expressed by Eq. (8) replacing m with m',
m' = 1.21m

(12)

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

51

Table 2
Compositions and properties of tested real reservoir fluids

Fluid source
component

Fluid l
McCain (1990)
Mol.%

N2
CO 2
CI
C,
C~
i-C 4
nC~
i-C 5
nC 5
C~,
C7
Cs

0.16
0.91
36.47
9.67
6.95
1.44
3.93
1.44
1.41
4.33
33.29

CIo
Ctl
C ~2

MW

85
218

Fluid 2
Pedersen et al. (1989)
SG

0.666
0.852

Mol.%

52.00
3.81
2.37
0.76
0.96
0.69
0.51
2.06
2.63
2.34
2.35
29.52

MW

99.
110.
121.
221.

Fluid 3
Whitson and Torp (1983)
SG

0.749
0.758
0.779
0.852

Mol.%

MW

SG

0.31
2.37
73.19
7.80
3.55
0.71
1.45
0.64
0.68
1.09
8.21

85
184

0.666
0.816

C t3
C14
Cj5
(~ 17
Ci8
C19
C 20
C21
C22

Temperature (C) 104.44

Sat press (MPa) 18.17
Sat den (g cm -3) 0.656

93.4

137.8
46.64

MW, molecular weight; SG, specific gravity at 15.56 C. The last component of each fluid is the plus fraction.

More complex expressions could possibly be derived, but the above simple modification was found
to be adequate.

5. Results
Methane and ethane are almost always at super critical conditions in reservoir fluids. The
concentration of these components, particularly methane, cover a wide range depending on the type of
the fluid. In order to evaluate the reliability of the proposed method, different fluids covering black oil
to lean gas condensate samples were studied. The compositions and properties of the tested fluids are
given in Tables 1 and 2.

52

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

100

80'

..,,..."'''
o/"
o,o'
oOO'/

Michelsen
..........

Conventional

60'

000000

40'

."
o.."

20"
7 `
. . . . . . . . . . . . . . . .'

10

i
15

20

25

Number of Component

Fig. 2. CPU time of calculating multipleforward contact of gas Mixture 4 with oil Mixture 1 at 100.0 C and 20.79 MPa.

5.1. Computational requirement

The reduction of computational time of flash calculations is an essential element in compositional
reservoir simulation. This is commonly achieved by grouping fluid components (Danesh et al., 1992)
and hence describing the fluid by a few pseudo components as the computational time decreases
sharply by reducing the number of components which leads to fewer equations to be solved. The main
draw back of the method is the lack of sufficient compositional information on produced reservoir
fluids required in the design and operation of fluid processes at the surface.
As Michelsen (1986) has shown the number of equations to be solved in flash calculations can be
reduced, to three, without additional complexity, regardless of the number of components when no
BIP is used in the mixing rules. Since our proposed approach to determine the parameters of EOS
eliminates the need for binary interaction parameter, it can significantly save the computational
requirement of compositional reservoir simulation along with the Michelsen method (see Appendix).
Fig. 2 shows the variation of the computer CPU time vs. the number of components for predicting
the equilibrium condition of a black oil (Mixture 1) when contacted with a rich gas (Mixture 3) at
100.0 C and 20.79 MPa in 4 consecutive stages simulating the injected gas advancement in a
reservoir. The number of components describing the 25 component mixture was reduced by the
grouping method proposed by Danesh et al. (1992). The figure demonstrates that the CPU time
required by the conventional method is about two orders of magnitude higher than the Michelsen's
method with no BIP when the mixture is described by 25 components Note that the computational
time decreases sharply for the conventional method when the number of components describing the
fluid decreases, whereas the reduction for the Michelsen's method is insignificant. The lack of BIP
also reduces the computational time greatly at near critical point where many iterations are generally
required. The above calculations were performed using a Newton type method to solve the equations.
Similar observations were also made using a successive substitution numerical method to solve the
equations.

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

53

16"
14"
.,/'

12

. , ' / ~i
f/e/"

I0

.,

/"

S / o

Vapour

"a~'"
/

4"

q~ ,

,"4~///t

e~

eeo o

.....

Liquid

PR(kij=.0515)
PR

O'

. .

20

40
60
Mole Fraction of N2,%

8o

100

Fig. 3. Phase envelopeof N2-C2 at -78.89 C.

5.2. Reliability
The performance of PR EOS as modified in this work, without any BIP, was compared with that of
the original form for a number of fluids. Examples of the results are presented in this report. The
volume translation concept, proposed originally by Peneloux et al. (1982), and adopted by Jhaveri and
Youngren (1988) for PR EOS was implemented in both methods to improve the predicted volumes.

Binary systems
The proposed method was evaluated for a few binary mixtures whose data were not used to modify
EOS. The modification had clearly improved the prediction of PR EOS in general. Fig. 3 shows the
phase envelope of the C 2 / N 2 system at - 7 9 . 8 9 C (Stryjek et al., 1974) indicating that the
modification is also applicable to mixtures containing nitrogen. As both PR EOS with BIP and mPR
EOS without BIP have used binary data to develop their parameters, kij in PR, and m' in mPR, they
are bound to generally give more reliable results than PR EOS without BIP.

Synthetic mixtures
The advantage of evaluating phase behaviour models using experimental data on synthetic
multi-component mixtures, with similar component distributions as those of real reservoir fluids, is
that the composition and properties of their components are more reliably known than real reservoir
fluids.
Fig. 4 is the ternary diagram of the C 1 / n C 4 / n C 1 0 mixture at 71.1 C and 20.68 MPa reported by
Reamer et al. (1949). The modified method predicted the phase envelope as reliably as the original
PR EOS with BIP and more reliably than the EOS without BIP.
The predicted dew-point pressures of the five-component synthetic gas condensate system (Mixture
3) by mPR are also shown in Fig. 1. It is quite evident that the modification significantly improved
the prediction of dew point pressures compared with those by PR EOS with and without BIP.
Fig. 5 shows predicted saturation pressures in a swelling test where a rich gas (Mixture 3) was
incrementally added to a synthetic black oil (Mixture 1) at 100.0 C. Both PR EOS with BIP and mPR

54

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

1.0"

CI
1.0

0.6
0.4
0.2

.........

PR(kij)

' .....

0.0
nC 10

0.2

',,

0.4

0.6

0.8

1.0
nC4

Fig. 4. Ternary diagram of C 1 - n C 4 - n C 10 at 71.1 C and 20.68 MPa.

predicted nearly the same saturation pressures for the system and much closer to the measured value
than PR EOS without BIP. Methane was injected into a near critical volatile oil at 100.0 C to
simulate gas injection into a reservoir by multiple contact tests (Danesh et al., 1991). The average
absolute deviations of predicted saturation pressures of the above test by mPR, PR with BIP and
without BIP were respectively 3%, 5%, and 11%, with deviations equal to 2%, 3% and 2% in
saturation densities.

Reservoirfluids
In this study the critical properties of pseudo-components of real reservoir fluids were estimated by
using the Twu (1984) correlation The acentric factors were calculated by the Lee and Kesler (1975)
correlation. For the literature data where the fluid heavy end was reported only as a C 7+ fraction, the
gamma distribution function was used to describe the heavy end, as proposed by Whitson (1983), and

28'

26'

g,
-

....~,......

24'

22"

"~ 20"
18
|6

,-"

0.00

0.25

0.50

0.75

.....

PR(kij)

--"

PR

1.00

1.25

1.50

InjectedCraaOilMole Ratio
Fig. 5. Bubble point pressure of oil Mixture I and added gas Mixture 4 in swelling test at I00.0 C.

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

55

200'
o Exp.
E.

"~

150'

1~

100'

mPR

/-//

- - " PR

10

p~,/

14

16

18

12

20

Pressure, MPa
Fig. 6. Solution gas/oil ratio of black oil (Fluid 1) in differential liberation test at 104.44 C.

split it into a number of pseudo-components, up to C20. Due to lack of proper binary interaction
parameters for pseudo-components, the modified equation (mPR) was compared only with PR EOS
without BIP for real reservoir fluids. The compositions and properties of reservoir fluids tested in this
study are given in Table 2.
Fig. 6 shows the measured and predicted solution gas/oil ratio of a black oil (Fluid 1) determined
by the differential liberation test as reported by McCain (1990). The measured bubble point pressure
at 104.4 C was 18.17 MPa, compared with 15.65 MPa ( - 13.9%) predicted by the original PR EOS
and 17.24 MPa ( - 5 . 1 % ) predicted by mPR. The measured (Pedersen et al., 1989) and predicted
liquid mole fractions of a more volatile oil (Fluid 2) during a constant composition expansion test at
93.4 C are given in Fig. 7. All the reported results for oil systems show that the modification
improved the prediction of PR EOS.
Fluid 3 is a North Sea rich gas-condensate reported by Whitson and Torp (1983). The measured
and predicted results of a constant volume depletion test at 137.8 C are shown in Fig. 8. The original
1.0'
o

Exp.

0.9'

//
/////~

mPR

--"

0.8

'~ 0,7

PR

/4

j / /

/J

//

0.6
0.5
0.4

10
15
Pressure, MPa

20

25

Fig. 7. Liquid fraction of volatile oil (Fluid 2) in constant composition expansion test at 93.4 C.

A. Danesh et al. // Fluid Phase Equilibria 112 (1995) 45-61

56

lOO

80PR

$
~

40-

"""%'

~ 2o I
0

DewPoint

10

20

30

40

50

Pressure,MPa

Fig. 8. Cumulative gas production of gas condensate (Fluid 3) in constant volume depletion test at 137.8 C.
PR E O S significantly under predicted the dew-point pressure whereas the m P R prediction m a t c h e d
the m e a s u r e d value o f 46.7 MPa. T h e modification also i m p r o v e d predictions o f the gas compressibility factor, c u m u l a t i v e gas production and produced gas composition.

Table 3
Comparison of predicted and experimental dew point pressures for Starling's gas condensates
Fluid
Fluid 4 at 101.11 C
Fluid 4 at 121.11 C
Fluid 5 at 93.89 C

Experiment 1

Dew point pressure (MPa)

26.17
24.24
26.49

Original

This work

SBWR

21.00
22.10
22.59

24.58
23.88
24.38

25.61
23.55
> 35.27

Table 4
Comparison of predicted and experimental liquid/gas ratios for Starling's gas condensates
Pressure (MPa)

Fluid 4 at 101.11 C

Fluid 4 at 121.11 C
Fluid 5 at 93.89 C

13.89
10.45
7.00
3.55
13.89
8.72
20.10
17.34
13.89
10.45
7.00
3.55

liquid/gas yields (m3/std m 3 X 106)

Experimental

Original

This work

SBWR

880.33
877.52
822.96
648.58
672.20
711.02
51.19
69.75
87.75
95.63
95.06
84.94

1213.99
1068.62
903.88
688.49
894.51
763.03
33.98
62.99
87.01
99.64
102.13
92.20

1164.21
1038.55
889.00
684.21
874.11
750.35
48.84
71.44
90.61
100.82
102.36
92.25

1056.96
990.02
872.46
673.33
830.83
755.46
63.56
77.63
90.56
98.44
97.31
83.81

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

57

The compositional analysis of two gas condensate fluids (Fluids 4 and 5) as reported by Starling
(1966) are given in Table 2. As no information on the specific gravity and molecular weight of the
single carbon groups were provided, the physical properties of relevant normal paraffin hydrocarbons
were used in this study. This also allowed a comparison with the Starling model--the modified
Benedict-Webb-Rubin (SBWR) EOS with 11 parameters. The predicted and measured dew point
pressures and liquid yields for the two fluids at various temperatures are given in Tables 3 and 4
respectively. The average absolute deviations between experimental and predicted dew-point pressures by mPR, PR, and SBWR EOS are respectively 5.17%, 14.42% and 12.69% with 12.77%,
17.12% and 11.03% deviations in predicted liquid yields. It should be noted that Starling used
measured equilibrium ratios of the these fluids to determine parameters of SBWR EOS prior to
making the above predictions. The equilibrium ratios at different pressures predicted by mPR also
agreed more closely with the experimental data than those by the original PR EOS. The above results
clearly indicate the improvement in PR EOS due to the modification. Using the generalised single
carbon properties (Katz and Firoozabadi, 1978) instead of normal alkane values for the above fluids
resulted to the same conclusion.

6. Conclusions
The proposed method which uses equilibrium data on binary systems to determine the attraction
term in EOS for super critical components can improve the prediction of the phase behaviour of fluids
containing these components. As binary data are used to develop the parameters of EOS, the equation
can be used without any binary interaction parameters for simple fluid mixtures such as hydrocarbon
reservoir fluids. This would lead to a simple set of equations for flash calculations where only three
equations need to be solved simultaneously regardless of the number of components of the mixture.
The proposed method is particularly advantageous for predicting fluid phase equilibria in compositional reservoir simulators, where many hundred thousands of equilibrium flashes may be performed
in simulation of a large reservoir. As it uses data in supercritical regions to determine the parameters
of EOS, the method may well also lead to more reliable results in supercritical extractions.
The proposed method was applied to the Peng-Robinson EOS as an example. A simple
modification of the correlation relating the attraction term to the temperature was found to be
adequate to describe the behaviour of super critical components of binary systems. The modified
equation was evaluated for different types of fluids and was found to be superior to the original EOS
without binary interaction parameters, and comparable, and in most cases more reliable, than the
equation with binary interaction parameters. A reduction in computational time by more than one
order of magnitude was achieved for mixtures described by many components using the simplified
flash algorithm developed by Michelsen without binary interaction parameters as suggested in the
proposed modification. The method is applicable to any semi-empirical cubic equation of state.

7. List of symbols
a, b, c
K

EOS parameters
equilibrium ratio

58
kij
!
m,m
P
R
T
u

V
x

Y
Z

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

binary interaction parameter between components i and j

component dependence factor of the temperature coefficient in EOS
pressure
gas constant
temperature
molar volume
vapour phase molar fraction
mole fractions in liquid phase
mole fractions
mole fractions in feed

Greek letters
ce
temperature dependent in EOS
o9
acentric factor
g2
parameters of EOS
~b
fugacity coefficient
Subscripts
C
critical
F
feed
i,j
component i,j
L
liquid phase
r
reduced property
V
vapour phase

Acknowledgements
The authors wish to thank K. Bell, K. Malcolm and A. Reid for performing the experiments. This
study was part of a research project sponsored by the UK Department of Trade and Industry, Bow
Valley Petroleum, British Gas Exploration and Prod. Ltd., BP Exploration Operating Company Ltd.,
Chevron Petroleum (UK) Ltd., Conoco (UK) Ltd., Elf (UK) Ltd., Elf Enterprise, Marathon International (GB) Ltd., Mobil (North Sea) Ltd., Phillips Petroleum Co. (UK) Ltd., Texaco Britain Ltd., and
Total Oil Marine Plc which is gratefully acknowledged.

Appendix A

Michelsen's Flash calculation method

Let one mole of the feed be flashed at pressure P and temperature T into V moles of vapour and
(1 - V) moles of liquid. The material balance for the component i in the mixture is
z~=Vyi+(1-V)x

i i = 1 , 2 ..... N

(A1)

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

59

where z~, Yi and x i are mole fractions of the component i in the feed, vapour and liquid phases
respectively, and
Y'~ ( y , - x ~ ) = 0

(A2)

The equilibrium condition is given by

K~=--=

i = 1 , 2 .... N

(A3)

where K is the equilibrium ratio and ~b is the fugacity coefficient determined by the use of EOS.
The above 2N + 1 equations can be reduced to three equations as follows, when all binary
interaction parameters are equal to zero.
Eq. (10) is converted to
a=

Y', Y'~ y i Y j ( a i a j )

--

i=lj=l

Y',Yia{/2

=(a') 2

(A4)

i=l

where a ,i = a ii/2 and ~ Ni= 1 Y i a i,

Substituting the above in Eq. (5), the fugacity coefficient can be expressed as
In cbi = qo + q]a'i

(A5)

q2bi

where q0, q~, q2 depend on a', b, T and P only;

qo=-

In - ~ ( v - b
a

v~(bRT)

q' =

Of
_

q2 = -~

RT

+ Gql

If Eq. (AI) is multiplied by a'i, then

= V E y,.'i + (1 - V) E x,a',

or

(l

V)aL

(A6)

b F = Vb v + (1 - V ) b e

(A7)

a'F= Va v +

--

and similarly

Hence, for a set of a'v and b v, the parameters for the liquid phase can be determined from
a'F - Va v
~l~ =

1 -- V

b~-

'bE =

Vb v

1 -- V

(A8)

60

A. Danesh et al. / Fluid Phase Equilibria 112 (1995) 45-61

Substituting the K value in Eq. (A1), we obtain:

xi=

Zi
1 4- V ( K i -

1)'Yi=

Zi g i
1 -t- V ( K i -

1)

(A9)

The computational procedure, as suggested by Michelsen, which involves only the three independent variables a v, b v and V is as follows:
1. At the given T and P, evaluate the a'i and b i for each component and calculate a'F and b F.
Estimate the values of a v, b v and V.
2. Calculate aL and b L from Eq. (A8) and evaluate the fi L and fi v and the K values from Eq. (A5)
and (A3). Calculate x i and Yi from Eq. (A9).
3. Evaluate check functions
el = E ( Y i - x i )

e2 = E ( yia'i
e3=

a'v )

~,(yibi-bv)

If the above values are all less than a given tolerance, the phase distribution at equilibrium has been
determined. If not, perform an iterative correction of a'v, b v and V, then return to step (2).

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