Fluid Phase Equilibria, 14 (1983) 209-218 209

ElsevierScience Publishers B.V.,Amsterdam-Printed inThe Netherlands

SRK-EOS CALCULATION FOR CRUDE OILS

K.S. PEDERSENl, P. THOMASSEN' and AA. FREDENSLUNDl

1
Instituttet for Kemiteknik, Danmarks Tekniske Hejskole,
DK-2800 Lyngby (Denmark)
2
Statoil, Forus, N-4001 Stavanger (Norway)

ABSTRACT
Analytical data for North Sea oils and gas condensates have
been measured.
The data include GC and TBP analyses and measure-
ments of molecular weights, specific gravities, and PNA-distribu-
tions of most TBP-fractions.
For each mixture, a few dew and bubble points have been mea-
sured, and in addition PVT-data and separator flash compositions
have been determined. These experimental results are simulated
using the SRK equation of state and a suitable characterization
procedure based on the analytical information. It is shown that
accurate predictions of the phase behavior can be achieved using
only a total of six hydrocarbon fractions. No "matching" or
"tuning" to experimental phase equilibrium or PVT data is needed.

INTRODUCTION
The aim of this work is to develop procedures for equation of
state computations of oils which contain heavy hydrocarbon frac-
tions. The development is based on analytical, PVT, and phase
equilibrium data measured by STATOIL for North Sea oils, and the
computations are based on computer programs developed by Michel-
sen (1980 and 1982). The PVT properties and phase equilibria in
this work are represented mainly by the Soave-Redlich-Kwong equa-
tion of state (Soave, 1972), although other models are used to
compute liquid-phase densities.
It is well known that calculated phase equilibria, especially
dew points, are highly sensitive to the values of the EOS para-
meters (T and w) chosen for the TBP-subfractions and to the
CfPC

0378-3812/83/$03.00 01983 ElsevierScienceF'ub1ishersB.V.

210

characterization of the TBP-residue, The latter constitutes up to

10 mole % of the total mixture and may contain hydrocarbons ran-
ging from C20 to C80. The procedure described in this work is
found to give consistently good predictions of the measured PVT
and phase equilibrium data. No matching to these data is perfor-
med. In addition, the procedures require only moderate computer
time, since only a total of six hydrocarbon fractions covering
the range from Cl to CL30 are needed to adequately describe, e.g.,
the dew and bubble points of the oils.

DATA
Data obtained from GC analysis, TBP distillation, and molecu-
lar weight determinations are put together to give the molar
__-__ com-
--_
pp_sition.
W--W- Up to C6 a complete component analysis can be made,
while the C7+ fraction is split into carbon number fractions by
TBP-distillation up to about CZO. PNA analyses, based on refrac-
tive index and density measurements (Nes and Westen, 1951) are
carried out for each fraction. Measurements of specific gravities
and molecular weights are carried out on the C7+ and ClO+ frac-
tions and on each carbon number fraction. These data are checked
for internal consistency by comparison between calculated and mea-
sured C7+ and ClO+ densities and molecular weights. In most cases,
the results agree to within 1%.
. --___--__--
Saturation pressures
-----__- of the oils are determined visually at
constant temperature in high-pressure steel vessels.
In differential liberation
__--___--___--__-___----_- experiments,
________ the reservoir fluid is
kept in a cell at the saturation point. The pressure is then re-
duced in 6-10 steps at constant temperature. At each step, all
the liberated gas is displaced, and the density of the remaining
oil is determined.
In a constant volume
---------------_-- depletion test,
___________ the reservoir fluid is al-
so kept in a cell at the saturation point. The pressure is again
reduced in steps at constant temperature, and at each level so
much gas is removed that the volume of the remaining gas and oil
mixture equals the initial volume. At each pressure, the liquid
volume is recorded.
These experiments are described in more detail in Pedersen et
al. (1982).
 211

CHARACTERIZATION PROCEDURE
The components of a reservoir fluid may be classified as fol-
lows:
Defined components
----------- __-___ for which there exists a quantitative GC ana-
lysis and for which Tc,Pc and w are known.
TBP-fractions
-----_----__- covering the true boiling point fractions between
C7 and C20, each of which contains many different components.
Careful analysis (Pedersen et al., 1982) has shown that for the
North Sea oils, the best results were obtained using the Cavett
(1964) relations for Tc and P :
C

= 768.071e1.7134 T50-0.10834.10-2T~o +
TC

-6 3
0.3889-10 T50 -0.89213-10-2T50API + (1)

-6
0.53095.10 T50 2.API+0.32712*10 -'T 502AP12

= 2.829+0.9412~10-3T50-0.30475~10-5T502 +
&OgloPc

-8
0.15141.10 T50 3-0.20876'10-4T50API +

-7 -9
0.11048.10 T50 2API+0.1395.10 T502AP12 - (2)

-7 2
0.4827-10 T50API

and the Lee-Kesler relations (Kesler and Lee (1976)) for w:

-5.92714+6.09648/TBr+1.28862RnTBr-0.169347T~r
RnPBr
W= (3)
15.2518-15.6875/TBr -13.4721RnTBr+0.43577T&

(for TBr < 0.8)

W= -7.904+0.1352K-0.007465K2

+8.359TBr+(1.408-O.OOlO63K)/TBr (4)

(for TBr > 0.8)

In equation (1) and (2), API = 141.5/SG-131.5, where SG is the

60°F/60PF specific gravity. The critical temperature, Tc, and the
212

mid-volume boiling point of the fraction, T50, are given in OF

and Pc in psia. In equations (3) and (4) TBr is the reduced boi-
ling point, TB/Tc, and PBr is the reduced pressure, PB/Pc, where
PB is the pressure at which the boiling point, TB, has been mea-
1 /=!
sured. K is the Watson characterization factor which equals TB-“'
SG where TBis in OR and SG is as above.
The results are improved if the PNA-distribution of each boi-
ling point fraction is taken into consideration as suggested by
Erbar (1977).
TBP-Residue
--_---__--_

In case of gas condensates the molar composition of the TBP-

residue is estimated by assuming a logarithmic relationship be-
tween the molar content, zN, of a fraction and the corresponding
carbon number, CN, for CNz7:

cN = Al + Bl!Ln zN

Al and Bl are constants which are determined by a least squares

fit to the experimental TBP-data for the C7 - C20-fractions. C80
is the heaviest carbon number fraction considered and molar frac-
-6
tions below 5-10 are neglected. If the measured TBP-residue is
larger than the one calculated from the obtained Al- and Bl-values
Al and Bl are changed accordingly.
For the heavy oil systems, a different characterization proce-
dure is used.
The TBP-distillation curve is extrapolated to 100 weight%
distilled off by fitting a 5th degree polynomial to the experimen-
tal TBP-data plus the following two artificially generated data
points:

-0.2127 1.103 . sG-0.6495

T80w% = lo - T50w% (6)

= lol-083 0.7097 . sGO_6717

T1OOw% - T50w% (7)

are the temperatures in K at which 50,

T50w%' T80w% and TlOOw%
80 and 100 weight% have been distilled off. SG is the specific
gravity of the TBP-sample which roughly corresponds to the C7+ -
fraction of the total mixture.
The specific gravities of the subfractions of the TBP-residue
are obtained by assuming a logarithmic dependence of SG against
 213

carbon number. For the boiling points the values of Katz and Fi-
roozabadi (1978) are used up to C45. For gas condensates, the re-
lation

TB[K) = 97.58.MNO.3323 - ,&-04609 (8)

is used for the fractions heavier than C45. For the heavy oils,
the weight-based TBP-curve is related to carbon number fractions
assuming 6K boiling point intervals per carbon number for the
C45+ - fractions.
Reduction of the Number of Components
----------------_-_----------- ------
A total of more than 80 components is unpractical in most cal-
culations. Some of the carbon number fractions must be grouped
together. This grouping is done on a weiqht
-_-__--- basis which means
-__---__I
that each group contains approximately the same weight fraction
and that the critical properties of the subfractions are weight-
mean average values.

FUGACITIES FROM THE SRK-EOS

When the SRK equation of state is used and the binary interac-
tion parameter is set to zero for all interactions the phase
equilibrium calculations may be greatly simplified (Michelsen and
Heidemann (1981)). In that case the fugacity coefficient, v., of
1
a component j is given by:

b.
Yncpj = $ (Z-1)-kn(Z-B ,)_ $B [2ajaj _ l&n(l+ i) (9)
aa
where A = \ract P/R2T2 and B = bP/RT (10)
2
au = (Zx.a.a.)
j 317

The Ki-values are functions of only aa and b for the liquid

_.
and vapor phases. This means that when Kij =0 for all interactions
the computation time for 20-component mixtures is reduced, typi-
cally, by a factor of 7.

SATURATION POINT CALCULATIONS

14 experimental saturation points of 12 different mixtures in-
cluding both gas condensates and heavy oils (compositions in Pe-
dersen et al., 1982) were used to try out the characterization
214

procedures. Table 1 gives the deviations and standard deviations

between experimental and calculated results using 3,6,10,20 and
40 hydrocarbon fractions. Six hydrocarbon fractions are seen to
be sufficient for accurate prediction of the saturation points.
The input necessary to construct a complete phase envelope for a
particular crude oil is shown. Note that the six hydrocarbon frac-
tions are grouped so as to contain as closely as possible equal
amounts by weight.

TABLE 1
Deviation between experimental and calculated dew and bubble
points.

3 CH- 6 CH- 10 CH- 20 CH- 40 CH-

fractions fractions fractions fractions fractions

Average -2.9 -1.9 -1.0 -1.9 -1.9

*%Dev.

Standard
Deviation 23.2 5.2 4.5 4.1 4.2

Relative
Computer 0.03 0.06 0.09 0.23 1.0
time

*%Dev _ Calculated saturation pressure--imental saturation pressure_ _loo$

Expsrimental saturation pressure

Input to phase envelope program:

Components Mole% TcW P,(MPa) u

N2 0.34 124.2 3.39 0.040

0.84 304.2 7.38 0.225
(0 co2
2 1:; 49.23
6.32 305.4
190.6 4.60 0.008
4.88 0.098
2
~( C3-C6 11.82 438.5 3.61 0.217
18.24 -609.7 2.63 0.599
=:,
9.22 ~~'750.6 1.59 1.038
1.07 1.555
 216

The influence on the predicted saturation points of setting

all binary interaction coefficients, Kij, equal to zero has been
checked. If the non-hydrocarbons constitute less than 1.5 mole%
of the total mixture, the saturation points deviate less than 1%
from the predictions with Kij +O. One of the gas condensates in-
cluded in Table 1 contains about 10 mole% non-hydrocarbons. In
that case the effect of K..=O was 6.2%.
iI

FLASH CALCULATIONS
Typical experimental and calculated separator flash results
for a gas condensate (sample No. 1 in Pedersen et al., 1982) are
presented in Table 2. Many similar results have been obtained by
the authors.

SIMULATION OF PVT EXPERIMENTS

The simulations described below involve both flash calculations
to determine equilibrium phase distributions and compositions and
computation of liquid and vapor phase densities. For the flash
calculations, the SRK equation is used as described above, where-
as different possibilities are used for the computation of the
densities of the separate phases.
Differential Liberation
--------~~~~~~L~~~-~---

Figs. 1 and 2 present results for relative and absolute liquid

volumes of a heavy oil (sample No. 13 in Pedersen et al., 1982).
In addition to the experimental values the results obtained with
four different methods for estimation of liquid volumes are given.
The SRK-equation gives the best results for the relative
_------- volumes
but the absolute
_-___--- volumes given in the form of liquid densities
are better represented by the Alani-Kennedy (AK) equation (1960)
and the Standing-Katz (SK) method (1942). The PBneloux (1982) den-
sities are found to be much too large.
Constant Volume
------------------ Depletion
------

The results of a constant volume depletion experiment on a gas

condensate (sample No. 14 in Pedersen et al., 1982) are shown
graphically in fig. 3. Also shown are the predicted liquid volu-
mes obtained using the SRK equation of state, the method of Pbne-
loux, and the Alani-Kennedy method. PBneloux's density correlation
iS a Consistent method which means that it can be used for both
gas and liquid densities. The general experience with gas conden-
216

Gas condensate at separator conditions, 6.3 MPa atm and 324.3 K.

camp.
Cbnpcsition
Tbtal
Mixture
T Separator
Ccmncsitions
A
Plash
Calc. T *
%Dev. 1
[mJle% 1
G3.S Liquid G3.5 Liquid G3.5 Liquid
[Irole% 1 [nole% 1 ble% 1 [m>le%l

0.71 0.75 0.17 0.75 0.06 0

3
Cl2
8.64
70.86
8.96
74.28
3.68
16.73
8.97
74.36
3.66
17.04
0.1
0.1
-0.5
1.9
c2 8.53 8.62 7.14 8.62 7.12 0.0 -0.3
c3 4.95 4.70 8.88 4.66 9.39 -0.9 5.7
I-C4 0.75 0.65 2.26 0.65 2.35 0.0 4.0
N-C4 1.25 1.04 4.76 1.01 4.91 -2.0 3.2
I-C5 0.41 0.28 2.46 0.27 2.50 - 1.6
N-C5 0.40 0.25 2.74 0.25 2.76 0.7
C6 0.46 0.20 4.51 0.19 4.63 2.7
c7 0.61 0.17 7.44 0.15 7.75 4.2
C& 0.71 0.10 10.30 0.09 10.26 -0.4
c9 0.39 6.61 0.02 6.05 -8.5
c10+ 1.33 - 22.32 0.01 21.52 -3.6
A-

*_%Dev = Calculated result - Experimental result

* 100%
Kxparimentalresult

(Only stated if experimental mole% > 0.5)

Moles liquid per mole total mixture:
Separator: 0.596
Calculation: 0.611
%Dev.: 2.5%
217
218

sate liquid densities is that the method of PBneloux is slightly

superior to the SRK equation and as good as the liquid density
correlations of Alani-Kennedy and Standing-Katz.

CONCLUSION
Precise and complete phase equilibrium and PVT-data on North
Sea oils have resulted in a procedure, based on the SRK equation
of state, which may be used to accurately predict the phase be-
havior of petroleum mixtures ranging from gas condensates to
heavy oils. Using the Cavett-relations for the critical tempera-
tures and pressures of the C7+ -fractions and the Lee-Kesler-rela-
tions for the acentric factors, six hydrocarbon fractions are suf-
ficient to represent the mixtures. For gas condensate systems, the
most suitable method for determination of liquid densities seems
to be the procedure of P&eloux, while for heavy oils the liquid
density correlations by Alani-Kennedy or Standing-Katz are to be
recommended.

REFERENCES
Alani, H.G., and H.T. Kennedy 1960. Petroleum Transactions, AIME
219, 288
Cavett, R.H., 1964, May 15. Physical Data for Distillation Calcu-
lations-Vapor-liquid Equilibria, 27th Midyear Meeting, API
Division of Refining
Erbar, J-H., 1977. Research Report 13, GPA, Tulsa, Okla.
Katz, D.L., and A. Firoozabadi 1978. Journal of Petroleum Techno-
logy, z, 1649
Kesler, M.G., and B-1. Lee, 1976. Hydrocarbon Proc. 55, 153
Michelsen, M.L., 1980. Fluid Phase Equilibria 4, 1
Michelsen, M.L., and R.A. Heidemann, 1981. AIChE Journal 27, 521
Michelsen, M-L., 1982. Fluid Phase Equlibria 2, 1
Nes, K. van, and H.A. van Westens, 1951. Aspects of the Constitu-
tion of Mineral Oils, Elsevier, New York
Pedersen, K.S., P. Thomassen and Aa. Fredenslund, 1982.Ind.Eng.
Chem., Process Des.Dev., in press
PBneloux, A., and R. Freze 1982. Fluid Phase Equilibria 8, 7
Soave, G., 1972. Chem.Eng.Sci. 27, 1197
Standing, M-B., and D.L. Katz 1942. Transactions-American Inst.
of Mining and Metallurgical Engineers 146, 159