Regression to Experimental
PVT Data
P.L. CHRISTENSEN
Calsep A/S, Lyngby
Abstract
A procedure is presented for regression of equation of state
parameters to experimental PVT-data. The starting point is a
predictive C7+ characterization based on the available analytical
data. If the agreement between the experimental and calculated
PVT data is unsatisfactory, the first step is to critically evaluate
the analytical data. If this still does not lead to satisfactory
results, an adjustment of the equation of state volume translation
parameter is performed. This parameter is chosen because it
influences the liquid phase densities without having any influ-
ence on the phase equilibrium results. Any additional parameter
regression needed is performed by adjustment of the two most
sensitive coefficients in the expressions used to determine the
equation of state parameters. It is shown that the applied proce-
dure may be used to match experimental PVT data without hav-
ing a major influence on properties which may be derived from
an equation of state, but for which no experimental data exist for
the actual composition. Also it is shown that reasonable results
are obtained for the measured PVT properties at conditions not
used in the regression.
Introduction
The requirements to a PVT simulation program are not limited
to prediction of volumetric properties, phase fractions and satura-
tion points at reservoir conditions. PVT simulation software is
also expected to be able to predict the phase behaviour at process
plant and transport conditions. Not only saturation points and vol-
umetric properties need to be calculated but also derived proper-
ties as for example enthalpies, entropies, heat capacities, Joule-
Thomson coefficients and sound velocities. This has to do with
the frequent use of PVT simulation packages to generate the PVT
property tables needed as input to reservoir and flow simulation
programs.
Petroleum reservoir fluids consist of thousands of different
hydrocarbon constituents. The diversity in chemical structure of
the individual components increases with carbon number. It is,
therefore, unpractical to analyse for all C7+ components. A stan-
dard composition analysis most often stops at either C7+, C10+ or
C20+. In PVT simulations the C7+ fraction is usually represented
through a number of pseudo-components. Previously the detailed
composition of the plus-fraction was not given much attention
when selecting the pseudo-components. Though different in their
detailed approach, the formerly used characterization procedures
had in common that experimental PVT data were needed to be
able to assign equation of state parameters to the pseudo-
Special Edition 1999, Volume 38, No. 13 PAPER: 96-10-15
components. The applied experimental data most often originated
from PVT experiments (constant mass expansion, constant vol-
ume depletion and differential liberation) carried out at reservoir
temperature. One of the most extensive works on how to perform
a component pseudorization without estimating the composition
of the plus-fraction has been presented by Coats(1).
One reason for previously making no attempt to estimate the
detailed composition of the plus-fraction was lack of high quality
analytical data. Composition analyses to above C7+ were rare and
often the information available about the C7+ fraction was limited
to its mole fraction. New analytical techniques have made it possi-
ble to develop C7+ characterization procedures based on fairly
accurate estimations of the molar composition of the plus fraction.
For each of the estimated C7+ components, the equation of state
parameters (typically Tc, Pc and ) are estimated from empirical
correlations. The C7+ components are subsequently grouped into a
convenient number of pseudo-components and for each one, aver-
age equation of state parameters are determined. Examples of the
latter type of characterization procedures are those of Pedersen et
al.(2,3) and Whitson(4). This type of characterization procedure has
the advantage that experimental PVT data are not necessarily
needed. Experimental data may on the other hand be used after-
wards to improve the agreement between experimental and calcu-
lated data. This paper deals with the problem of selecting the most
appropriate regression parameters, i.e., the model parameters
which should be allowed to vary during a regression to experi-
mental PVT data.
Some Potential Problems with Regression
to Experimental PVT Data
The experimental PVT data available for regression will typi-
cally comprise a saturation point, gas phase compressibility fac-
tors and liquid drop out curves or liquid phase densities, all mea-
sured at reservoir temperature. In addition, gas/oil ratios will often
be available from a differential liberation and/or a separator
experiment. This means that in reality no other experimental
information than saturation points and volumetric properties are
available for regression. It is obvious that the parameters estimat-
ed will be those for which the model most closely reproduces the
measured PVT data. There is, however, no reason to believe that
these parameters are valid for other properties than those used in
the fit, and there is no reason to believe that the parameters are
valid for the properties of the fit outside the temperature and pres-
sure ranges covered in the parameter estimation. This may, for
example, lead to erroneous results when the program is used to
generate input for conditions much different from those of the
PVT experiment. These shortcomings of parameter regression in
Journal of Canadian Petroleum Technology
 FIGURE 1: The limitations of regression to experimental PVT
data.

their traditional form are illustrated in Figure 1, and are further

exemplified by Pedersen et al.(5). FIGURE 2: C7+ mole fractions versus carbon number for
experimental and adjusted plus molecular weight.

Handling of the Plus-fraction Prior to c4

T c = c 1 + c 2 ln MW + c 3 MW +
MW .........................................(1)
Regression
The potential problems with parameter regression may at least
to some extent be overcome by relying on a predictive C7+ charac- d3 d4
ln P c = d 1 + d 2 + +
terization procedure which has been validated against a compre- MW MW2 ................................................(2)
hensive experimental data set covering all the phase properties
and the full range of pressure and temperature of interest in the
PVT simulations to be performed. The procedure described below
is the one of Pedersen et al., but it could as well have been any m = e 1 + e 2 MW + e 3 + e 4 MW2 ..................................................(3)
other well tested predictive C7+ characterization procedure. The
procedure of Pedersen et al. is developed for the Soave-Redlich- where:
Kwong equation of state(6) with the volume translation principle
as proposed by Peneloux et al.(7). The binary interaction coeffi- 2
cients between two hydrocarbons are set equal to zero. For inter- m = 0.480 + 1.574 0.176 ......................................................(4)
actions with a non-hydrocarbon predetermined non-zero values
are used(8). and:
c1 = 1.6312 102 d1 = -1.3408 10-1 e1 = 7.4310 10-1
Estimation of the detailed composition of a plus fraction may at
c2 = 8.6052 10 d2 = 2.5019 e2 = 4.8122 10-3
first hand seem to be a difficult task, since the information avail-
c3 = 4.3475 10-1 d3 = 2.0846 102 e3 = 9.6707 10-3
able about the plus fraction from the composition analysis is usu-
ally limited to the average molecular weight and the average den- c4 = -1.8774 103 d4 = -3.9872 103 e4 = -3.7184 10-6
sity at atmospheric conditions. Fortunately, reservoir fluid compo- is in g/cm3, Tc in K and Pc in atm.
sitions are not completely random. Extensive composition analy-
ses comprising very many reservoir fluids from all over the world The coefficients in these expressions have been determined
have shown that the natural logarithm of the mole fraction of a using comprehensive experimental data comprising both gas con-
given C7+ fraction is approximately a linear function of the carbon densate and oil mixtures(3). Before performing any PVT simula-
number(9). This is illustrated with the full drawn line in Figure 2. tions, the number of components considered is reduced by lump-
The slope of the line may be determined from the mole fraction ing the C7+ components into a suitable number of pseudo-compo-
and the molecular weight of the plus fraction. Thus, it is made nents. For each pseudo-component, average values of Tc, Pc and
sure that the mole fractions of the individual carbon number frac- are calculated. Equation of state calculations based on the C7+
tions sum up to the mole fraction of the plus fraction and that the characterization procedure described above have shown that the
average molecular weight of the individual components equals procedure is not only applicable for phase equilibrium and volu-
that of the plus fraction. In a similar manner it can be made sure metric calculations but also for calculation of enthalpies,
that the average density of the individual fractions equals the den- entropies, heat capacities, sound velocities and Joule-Thomson
sity of the total plus fraction. The density, , of a given C7+ frac- coefficients(8).
tion is a measure of its aromaticity. A large density indicates a
high content of aromatic compounds and a low density a high
content of paraffinic and naphthenic compounds. By making the Analysing for Errors in the Analytical Data
correlations for Tc, Pc and functions of the density, it is ensured
that the distribution between paraffinic, naphthenic and aromatic If the deviations between the experimental and the calculated
compounds is taken into account. It is also obvious that the molec- PVT properties are found to be too large, it is generally worth to
ular weight must enter into these correlations. first investigate whether the reason for the deviations is to be
sought in the composition analysis. Potential sources of errors in
The correlations suggested by Pedersen et al.(3) are shown the composition analyses are the recombination ratio, the C 7+
below: composition and the plus molecular weight.

2 Journal of Canadian Petroleum Technology

 The molar composition of a reservoir fluid is obtained from
analyses of one or two gas samples and one or two oil samples.
The samples either originate from a reservoir fluid bottom hole
sample or from gas and oil samples taken from the well head sep-
arator. In either case the samples are flashed to standard condi-
tions before the composition analysis is made. The reservoir fluid
composition is afterwards obtained by combining the gas and liq-
uid phase compositions. If the assumed recombination ratio
(gas/oil ratio) is wrong, the reservoir fluid composition will be
wrong. In the PVT simulation results this type of error will espe-
cially show up in the results for saturation points and gas/oil
ratios. It is possible to correct errors in the recombination ratio by
treating this ratio as an adjustable parameter and choosing the
ratio giving the best correspondence with the experimental PVT
data. This type of composition adjustment is only to be recom-
mended with a very reliable C7+ characterization procedure. On
the other hand, as is exemplified by Pedersen et al.(5) an erroneous
gas/oil ratio cannot easily by accounted for by parameter adjust-
ments. If the recombination ratio is adjusted, it should be consid-
ered whether the adjusted or the original recombination ratios are
the more representative for the reservoir fluid. This ratio should
then be used in the simulations of the reservoir fluid.
Composition analyses to for example C20+ based on a gas chro-
matographic (GC) analyses are often seen. This type of analyses
should be used with much precaution because the retention of the
heavy components in the column is rather high and increases with
molecular weight. A GC based C7+ analysis will, therefore, often
underestimate the contents of the heavy C7+ fractions. A more
appropriate technique for analysing the C7+ fraction is a true boil-
ing point analysis. It has the further advantage that it allows deter-
mination of the density and the molecular weight of each C7+ frac-
tion. If all that is available for the C7+ fraction is a GC analysis it
is generally to be recommended not to use the analytical data for
the C7+ fraction. PVT simulation results of a higher quality can be
expected if the C7+ characterization is based on the C7+ fraction as
a whole.
While the above two sources of errors in the analytical data
have to do with bad or inappropriate analytical techniques, the last
source of error to be mentioned is more general. Using standard
analytical techniques (freezing point depression), the experimental
uncertainty on the molecular weight of the plus fraction is of the
order of 10%. Changes in the assumed plus-molecular weight of
this order of magnitude will affect the PVT simulation results sig-
nificantly, especially the saturation points. An obvious application
of this fact is to allow the plus-molecular weight to vary by up to
10% and then accept the plus molecular weight giving the best
agreement with the measured saturation point(s). The principle of
molecular weight adjustment is sketched in Figure 2 (dashed line).
When performing the adjustment of the molecular weight, the
weight composition and not the molar composition is to be kept
constant. This is because the composition obtained using standard
analytical techniques is in fact a weight composition. To convert a
weight fraction analysis to a mole fraction analysis, each weight
fraction is divided by the molecular weight of the corresponding
component/fraction followed by renormalization of the sum of the
weight fractions to one. Any errors in the assumed molecular
weights will of course result in errors in the molar composition.
Before the adjustment of the plus molecular weight, the composi-
tion is therefore recalculated to a weight composition. When the
optimum plus molecular weight has been determined, the compo-
sition is recalculated to a molar composition.
The Volume Translation Parameter as a
Regression Parameter
The extended SRK equation of state suggested by Peneloux et
al.(7) has the following form:
RT a(T)
P =
V b (V + c)(V + b + 2c)
............................................(5)
Special Edition 1999, Volume 38, No. 13
In this equation, P is the pressure, T the temperature, R the gas
constant, a and b the usual equation of state parameters and c is a
volume translation parameter. The c-parameter has the interesting
property that it influences the density without affecting the phase
equilibrium results (saturations points, phase compositions and
phase amounts). For a pure component, the molar volume calcu-
lated using the Peneloux equation equals the SRK molar volume
minus the c-parameter. For a mixture, the molar volume calculat-
ed using the Peneloux equation equals the SRK molar volume
minus the molar average of the c-parameters of each component.
For defined components the c-parameter may be found as suggest-
ed by Peneloux et al.:
R Tc
c = 0.40768 (0.29441 Z RA )
Pc .................................................(6)
where ZRA is the Racket compressibility factor, for which the
following approximation is used:
Z RA = 0.29056 0.08775 ...............................................................(7)
For C7+ pseudo components, the c-parameter may be deter-
mined as the difference in the molar volume calculated using the
SRK equation and the real molar volume. The latter volume may
be calculated from the density at standard conditions which is
available from the C7+ characterization. By determining the C7+ c-
parameters in this manner, it is implicitly assumed that the differ-
ence between the real molar volume and that calculated using the
SRK equation is constant, independent of T and P. This is not nec-
essarily the case. The c-parameter is, therefore, an appropriate
regression parameter in those cases when satisfactory phase equi-
librium results but unsatisfactory volumetric results are obtained.
Adjustments of Tc, Pc and Correlations
There may still be too large deviations between the measured
and the calculated PVT data after adjustment of the plus fraction
molecular weight and the volume translation parameter. These
deviations will rarely be found for saturation points and rarely for
densities because these quantities have been taken care of in the
initial parameter adjustments of the plus fraction molecular weight
and the volume translation parameter. Problems at this stage in the
regression procedure are most often encountered with liquid
dropout curves for gas condensate mixtures. The parameters left
for regression are Tc, Pc and of the C7+ components and the
binary interaction parameters. Pedersen et al.(5) warn against the
use of non-zero binary interaction coefficients as regression para-
meters because hydrocarbon-hydrocarbon non-zero binary inter-
action coefficients will often result in predictions of false liquid-
liquid phase splits. Also adjustments in Tc, Pc and have to be
made with much precaution. On the other hand the correlations
used for Tc, Pc and of the C7+ fractions are not, as is the case
with Tc, Pc and of the defined components, founded on funda-
mental physical considerations. They are only empirical correla-
tions which have been found to represent a large set of reservoir
fluid PVT data very well. As is exemplified in the example sec-
tion, small adjustments of one the coefficients in the correlations
for Tc and Pc [Equations (1) and (2)] can have a pronounced effect
on a liquid dropout curve without influencing the predictions of
other properties significantly. The two coefficients to be adjusted
are found by carrying out a sensitivity analysis, i.e., by determin-
ing the two coefficients for which the calculation results are most
affected by a given relative change in the value of the coefficient.
Unfortunately, it is not always possible by comparing measured
and calculated PVT data to decide whether deviations between
measured and calculated volumetric data are due to erroneous
density calculations, erroneous phase equilibrium calculations or
both. This is because the volumetric results are often presented as
relative volumes. For example, for gas condensate mixtures, the
liquid phase volume is often recorded in per cent of the saturation
3
TABLE 1: Molar compositions of North Sea oil mixture. The first composition shown is the measured one. The
second composition is after adjustment of the plus molecular weight to match the saturation point. MW stands for
molecular weight and for density at standard conditions.

Measured Composition MW Adjusted Composition

MW MW
Component Mole % (g/mole) (g/cm3) Mole % (g/mole) (g/cm3)

N2 0.34 0.34
CO2 0.84 0.84
C1 49.23 49.45
C2 6.32 6.35
C3 4.46 4.48
iC4 0.86 0.86
nC4 2.18 2.19
iC5 0.93 0.93
nC5 1.33 1.34
C6 2.06 2.07
C7 3.33 90. 0.6888 3.34 90. 0.6888
C8 4.06 99. 0.7395 4.08 99. 0.7395
C9 2.76 106. 0.7518 2.77 106. 0.7518
C10+ 21.30 289. 0.8904 20.95 295.1 0.8904

point volume at the same temperature. In those cases a three para-
meter regression is recommended with the volume translation
parameter and the two most sensitive coefficients of the Tc, Pc and
correlations as the three regression parameters.
Summary of the Suggested Regression
Procedure
The step wise regression procedure described above is summa-
rized below. The only source of errors in the analytical data is
assumed to be the plus molecular weight. Errors in the recombina-
tion ratio or the C7+ composition may for a single composition be
handled as described above, but in general this type of errors
should instead be handled by improving the analytical techniques.
1. Make regression to the experimental saturation point(s). The
plus molecular weight is allowed to vary by up to 10%.
2. Evaluate whether the deviations between experimental and
calculated data indicate deficiencies in density predictions. If
so, regression to volumetric data is performed and the vol-
ume translation parameter of the C7+ components is allowed
to vary by 100% (same per cent for all C7+ components).
3. Determine the two most sensitive coefficients in Equations
(1) (3). These are the two with the largest impact on the
calculation results.
4. Perform parameter regression using the two coefficients
determined under step 3 above, (max. adjustment 20%). If
the volume translation parameter was not used as regression
parameter under step 2 above, it is included as a regression
parameter at this stage.
Any of the above steps may be omitted if it is concluded that
adjustments of that/those particular parameter(s) will not signifi-
cantly improve the simulation results. If, for example, the density
predictions are satisfactory, there is no reason to include step two.
Examples on Suggested Regression
Technique
The use of the above described regression technique is exem-
plified below for three reservoir fluids. For all three fluids the
characterization procedure of Pedersen et al. is used and twelve
C 7+ pseudo-components are used to represent the total C 7+-
fraction.
Oil Mixture
Table 1 shows the molar composition of a North Sea oil mix-
ture(8). The saturation point of the mixture has been measured as
274.5 bar at 93.3 C. The calculation results without any parame-
ter adjustment is 271.2 bar, i.e., 1.2% too low. In Tables 2 and 3
are shown gas/oil ratio and liquid density results from a differen-
tial liberation experiment at 93.3 C. Also shown in Tables 2 and
3 are the calculation results [marked with (1)] obtained based on a
fully predictive C7+ characterization. It is seen that the calculated
gas/oil ratios as well as the liquid phase densities are somewhat
higher than those measured.

TABLE 2: Measured and calculated gas/oil ratios (in std. m3/std. m3) obtained from a differential liberation experi-
ment at 93.3 C on mixture of Table 1. (1) is using unmodified parameters, (2) is using plus molecular weight cor-
rected composition and (3) is using plus molecular weight corrected composition and a corrected volume transla-
tion parameter.

Pressure (bar) Exp. GOR Calc. GOR (1) % Dev. Calc. GOR (2) % Dev. Calc. GOR (3) % Dev.

274.5 175.8 182.6 3.9 182.7 3.9 176.6 0.5

227.0 138.3 146.7 6.1 144.7 4.6 139.9 1.2
193.7 119.1 122.6 2.9 121.1 1.7 117.1 -1.7
148.1 91.8 93.1 1.4 92.0 0.2 88.9 -3.2
109.9 69.5 70.6 1.6 69.9 0.6 67.5 -2.9
70.6 47.5 49.1 3.4 48.7 2.5 47.1 -0.8
31.4 25.4 28.2 11.0 28.0 10.2 27.0 8.0

CalculatedResult - ExperimentalResult
%Dev. = C 100
ExperimentalResult

4 Journal of Canadian Petroleum Technology

TABLE 3: Measured and calculated liquid phase densities, , (in g/cm3) obtained from differential liberation exper-
iment at 93.3 C on the oil mixture of Table 1. (1) is using unmodified parameters, (2) is using plus molecular
weight corrected composition and (3) is using plus molecular weight corrected composition and a corrected vol-
ume translation parameter.

Pressure (bar) Exp. Calc. (1) % Dev. Calc. (2) % Dev. Calc. (3) % Dev.

274.5 0.660 0.679 2.9 0.679 2.9 0.664 0.6

227.0 0.680 0.698 2.7 0.700 2.9 0.683 0.4
193.7 0.693 0.713 2.9 0.715 3.1 0.697 0.6
148.1 0.711 0.734 3.2 0.736 3.5 0.716 0.7
109.9 0.727 0.752 3.4 0.753 3.6 0.733 0.8
70.6 0.742 0.771 3.9 0.772 4.0 0.750 1.1
31.4 0.759 0.792 4.3 0.792 4.3 0.769 1.3
1.0 0.814 0.823 1.1 0.824 1.2 0.797 -2.1

%Dev. is defined in Table 2.

The first parameter adjustment made is of the assumed molecu-
lar weight of the C10+ fraction. By increasing it from 289 to 295.1
(~ 1.2%) the calculated saturation point at 93.3 C is changed
from 271.2 bar to 274.5 bar, i.e., agreement is obtained with the
measured saturation point. A new differential liberation simula-
tion is performed. It gives the gas/oil and liquid density results
shown in Tables 2 and 3 [marked with (2)]. A comparison of the
results obtained with the unmodified and the modified plus molec-
ular weight reveals that the agreement with the experimental
gas/oil ratios has been slightly improved whereas the liquid densi-
ties are almost unchanged.
The second adjustment made is of the volume translation para-
meters of the C7+ components. They are all decreased by 75%
(i.e., to 25% of the original value). The resulting calculation
results for gas/oil ratios and liquid densities are shown in Tables 2
and 3 [marked with (3)]. It is seen that a very good correspon-
dence with the experimental results is obtained.
It is unlikely that the calculation results can be much further
improved by continuing the regression with the coefficients in the
Tc, Pc and correlations. The regression is, therefore, stopped at
this stage. Plots of the experimental and calculated results are
shown in Figures 3 and 4.
As is mentioned above, it is essential that a parameter regres-
sion does not have too much influence on properties not included
in the regression and not too much influence on properties includ-
ed in the regression at conditions not covered in the regression.
An evaluation of the regression performed in this case does not
give any reasons for concern. By comparing the molar composi-
tions in Table 1 before and after the plus molecular weight adjust-
ment, it is seen that they are almost identical. It seems unlikely
that the small adjustment performed should give rise to great devi-
ations in any phase properties.
The adjustment in the volume translation parameter may on the
other hand appear to be quite dramatic. It should, however, be rec-
ognized that the volume translation parameter represents an
adjustment as compared with the SRK equation. By setting the
volume translation parameter to zero, the results will be identical
to those obtained with the SRK equation of state. The results of
the regression can therefore be seen as an indication that the ini-
tially assumed correction of the SRK equation was too large for
the C7+ components (the correction for the defined components is
unchanged). The optimum correction was only 25% of that initial-
ly assumed. By treating the volume translation parameter in this
manner it seems very unlikely that the performed regression
should lead to unrealistic results at reservoir conditions or for
properties not covered by the regression.
Light Gas Condensate
Table 4 shows the molar composition of a North Sea gas con-
densate mixture [mixture one of Pedersen et al.(3)]. At 96.6 C the
saturation point of this mixture has been measured as 282 bar. The
liquid volumes of the mixture at 96.6 C in per cent of the satura-
tion point volume (from a constant mass experiment), are shown
in Table 5. Using the standard C7+ characterization procedure
described above the saturation pressure at 96.6 C is calculated as

FIGURE 3: Experimental and calculated GORs (std. m3 / std. m3) FIGURE 4: Experimental and calculated liquid densities (g/cm3)
for mixture of Table 1 at 93.3 C. for mixture of Table 1 at 93.3 C.

Special Edition 1999, Volume 38, No. 13 5

 FIGURE 5: Experimental and calculated liquid drop out curves FIGURE 6: Experimental and calculated liquid drop out curves
for mixture of Table 6 at 136.1 C. for mixture of Table 4 at 96.6 C.

263.3 bar, i.e., 6.6% too low. The calculated liquid volumes at the
experimental pressures are shown in Table 5 [marked with (1)]. It
is seen that the liquid volumes are generally lower than those
measured.
The first adjustment made is of the assumed molecular weight
of the C10+ fraction. By increasing it from 167. to 176.9 (~ 5.9%)
the calculated saturation point at 96.6 C is changed from 263.3
bar to 282.0 bar, i.e., agreement is obtained with the measured sat-
uration point. A new constant mass expansion simulation is per-
formed. It gives the liquid volume results marked by (2) in Table
4. A comparison of the results obtained with the unmodified and
the modified plus molecular weight reveals that the agreement
with the experimental liquid volumes has generally been
improved, but the liquid volumes at the lower pressures are slight-
ly too high whereas the liquid volumes at the higher pressures are
slightly too low.
Errors in the calculated liquid volumes can originate from
errors in the calculated liquid phase densities, from errors in the
phase equilibrium calculations or from a combination of these two
factors. Phase equilibrium calculations at pressures below approx-
imately 100 bar can in general be performed very accurately if the
mixture is not near critical at these conditions. In the actual case it
is, therefore, unlikely that there should be major deviations
between the measured and the calculated gas and liquid phase
mole fractions below approximately 100 bar. The deviation
between the measured and the calculated liquid phase volumes at
pressures below 100 bar must, therefore, be expected to be due to
inaccuracies in the liquid phase density calculations. This can be
corrected by adjusting the volume translation parameter. In Table
5 are shown the results [marked with (3)] of adjusting the volume
translation parameter to 40% of its original value.
Finally, a regression is performed where the two most sensitive
coefficients in the Tc, Pc and correlations are allowed to vary.
This only leads to marginal improvements in the liquid volumes
as compared with the results already obtained and it is therefore
decided to let the coefficients in the Tc, Pc and correlations be
unchanged.
Plots of the experimental and calculated liquid volume per
cents are shown in Figure 5. The parameters modified for this
mixture are the same as those modified for the oil. Using the same
arguments as for the oil, it can be concluded that the performed
regression is unlikely to lead to unrealistic results for properties or
at conditions not covered in the regression.

TABLE 4: Molar compositions of light North Sea gas condensate mixture. The first composition shown is the
measured one. The second composition is after adjustment of the plus molecular weight to match the saturation
point. MW stands for molecular weight and for density at standard conditions.

Measured Composition MW Adjusted Composition

MW MW
Component Mole % (g/mole) (g/cm3) Mole % (g/mole) (g/cm3)

N2 0.85 0.85
CO2 0.65 0.65
C1 83.58 83.63
C2 5.95 5.95
C3 2.91 2.91
iC4 0.45 0.45
nC4 1.11 1.11
iC5 0.36 0.36
nC5 0.48 0.48
C6 0.60 0.60
C7 0.80 95. 0.7243 0.80 95. 0.7243
C8 0.76 103. 0.7476 0.76 103. 0.7476
C9 0.47 116. 0.7764 0.47 116. 0.7764
C10+ 1.03 167. 0.8120 0.97 176.9 0.8120

6 Journal of Canadian Petroleum Technology

TABLE 5: Measured and calculated liquid volumes for mixture of table 4 in percent of saturation point volume.
The results are for a constant mass experiment at 96.6 C. (1) is using unmodified parameters, (2) is using plus
molecular weight corrected composition and (3) is using plus molecular weight corrected composition and a cor-
rected volume translation parameter.

P (bar) Liq % (exp) Liq % (calc) (1) Dev. Liq % (calc) (2) Dev. Liq % (calc) (3) Dev.

280.0 0.00 0.00 0.00 0.00 0.00 0.00 0.00

261.5 0.22 0.00 -0.22 0.78 0.58 0.81 -0.59
197.0 2.95 2.99 0.04 3.39 0.44 3.53 -0.58
160.0 4.28 4.07 -0.21 4.37 0.09 4.57 -0.29
152.0 4.42 4.22 -0.20 4.51 0.09 4.72 -0.30
135.5 4.77 4.45 -0.32 4.73 -0.04 4.96 -0.19
120.5 5.05 4.57 -0.48 4.85 -0.20 5.09 0.04
101.0 5.09 4.61 -0.58 4.88 -0.21 5.13 0.04
90.0 5.10 4.57 -0.53 4.84 -0.26 5.10 0.00
71.5 4.95 4.41 -0.54 4.67 -0.28 4.93 -0.02
51.5 4.55 4.01 -0.54 4.30 -0.25 4.57 0.02

TABLE 6: Molar compositions of heavy North Sea gas condensate mixture. The first composition shown is the
measured one. The second composition is after adjustment of the plus molecular weight to match the saturation
point. MW stands for molecular weight and for density at standard conditions.

Measured Composition MW Adjusted Composition

MW MW
Component Mole % (g/mole) (g/cm3) Mole % (g/mole) (g/cm3)

N2 0.42 0.42
CO2 2.98 2.99
C1 66.36 66.54
C2 8.44 8.46
C3 5.12 5.13
iC4 1.04 1.04
nC4 2.35 2.36
iC5 0.84 0.84
nC5 1.12 1.12
C6 1.36 1.36
C7 2.14 93 0.743 2.15 93. 0.743
C8 2.20 107. 0.753 2.21 107. 0.753
C9 1.43 120. 0.776 1.43 120. 0.776
C10+ 4.20 226. 0.848 3.94 241.4 0.848

Heavy Gas Condensate
Table 6 shows the molar composition of a heavy North Sea gas
condensate mixture. At 136.1 C, the saturation point of this mix-
ture has been measured to 386.4 bar. The liquid volumes of the
mixture at 136.1 C in per cent of the saturation point volume
(from a constant mass expansion experiment) are shown in Table
7. Using the standard C7+ characterization procedure described
above the saturation pressure at 136.1 C is calculated to 360.7
bar, i.e., 6.7% too low. The calculated liquid volumes at the
experimental pressures are shown in Table 7 [marked with (1)]. It
is seen that the calculated liquid volumes are generally lower than
those measured.
The first adjustment made is of the assumed plus molecular
weight. By increasing the assumed C10+ molecular weight from
226 to 241.4 (~ 6.8%) the calculated saturation point at 93.3 C is
changed from 360.7 bar to 386.4 bar, i.e., agreement is obtained
with the measured saturation point. A constant mass expansion
simulation is performed. It gives the liquid volume results marked
by (2) in Table 7. A comparison of the results obtained with the
unmodified and the modified plus molecular weight reveals that
the agreement with the experimental liquid volumes has generally
been much improved but the liquid volumes are still slightly too
low.
The constant mass expansion data do not comprise any results
for pressures below 100 bar, i.e., it is not obvious whether the
deviations between the measured and calculated liquid volumes
are due to errors in the liquid density calculations, in the phase
equilibrium calculations or both. A three parameter regression is,
therefore, performed, where the three parameters are the volume
translation parameter, the parameter c2 in Equation (1) and the
parameter d2 in Equation (2). The two latter parameters were cho-
sen because they were the most sensitive coefficients in the Tc, Pc
and correlations with respect to the constant mass expansion
liquid volumes. The optimum parameters were found to be C7+
volume translation parameters 42% higher than those determined
from the standard condition densities, a c2 coefficient of 88.817
(i.e., 3.2% above the standard value) and a d 2 coefficient of
2.4450 (i.e., 2.6% above the standard value). The resulting liquid
volumes at 136.1 C are shown in Table 7 [marked with (3)]. It is
seen that the agreement with the experimental results is very
good. Plots of the experimental and calculated liquid volume frac-
tions are shown in Figure 6.
For this mixture it is less obvious than for the two preceding
mixtures that the adjustment will not have a major influence on
calculation results at other conditions or for other properties than
those of the experiment. As the calculation results obtained with
an equation of state are unique functions of the molar composi-
tion, it is interesting to consider what changes have been made in
the values of Tc, Pc, and and the binary interactions parameters,
as a result of the regression. The molecular weight adjusted com-
position is used as the starting point, i.e., the one matching the
experimental saturation point. During the regression no adjust-
ments have been made in the binary interaction coefficients and
no adjustments in the pure component acentric factors. In Table 8
are shown the values of Tc and Pc for the C7+ pseudo components
before and after the regression. It is seen that the maximum
change in Tc is 2.4% and the maximum change in Pc 5.2%, i.e.,
the changes are quite moderate. The changes in the C7+ volume

Special Edition 1999, Volume 38, No. 13 7

TABLE 7: Measured and calculated liquid volumes for mixture of Table 6 in percent of saturation point volume.
The results are for a constant mass experiment at 136.1 C. (1) is using unmodified parameters, (2) is using plus
molecular weight corrected composition and (3) is using plus molecular weight corrected composition and a cor-
rected volume translation parameter.

P (bar) Liq % (exp) Liq % (calc) (1) Dev. Liq % (calc) (2) Dev. Liq % (calc) (3) Dev.

386.4 0.00 0.00 0.00 0.00 0.00 0.00 0.00

384.2 0.30 0.00 -0.30 0.45 0.15 0.51 0.21
381.6 1.01 0.00 -1.01 1.07 0.06 1.60 0.59
376.6 3.21 0.00 -3.21 2.27 -0.94 3.65 0.44
366.7 8.99 0.00 -8.99 4.78 -4.21 7.73 1.26
349.5 16.99 4.55 -12.44 9.50 -7.49 14.51 -2.48
326.4 23.02 13.82 -9.20 15.99 -7.03 21.94 -1.08
292.0 27.74 23.65 -4.09 23.50 -4.24 28.38 0.64
244.4 30.46 28.88 -1.58 28.37 -2.09 31.26 0.80
190.1 31.18 29.43 -1.75 29.30 -1.88 30.80 -0.38
141.1 30.25 27.93 -2.32 28.08 -2.17 28.88 -1.37

TABLE 8: Tcs and Pcs of the C7+ fractions of the characterized gas condensate mixture of Table 6 before and
after regression of the coefficients c2 and d2 of Equations. (1) and (2).

Tc (K) Pc (bar)
C7+-Pseudo Before After Before After
-Component Regression Regression % Dev Regression Regression % Dev

C7 531.5 544.1 2.4 33.73 32.33 -4.2

C8 553.9 566.9 2.4 28.88 27.65 -4.3
C9 575.1 588.4 2.3 26.60 25.44 -4.4
C10 602.0 615.8 2.3 23.16 22.14 -4.4
C12 634.3 648.6 2.3 20.13 19.22 -4.5
C14 665.5 680.3 2.2 17.98 17.15 -4.6
C17 695.3 710.4 2.2 16.47 15.70 -4.7
C19 724.5 740.0 2.1 15.47 14.73 -4.8
C22 758.5 774.5 2.1 14.59 13.88 -4.9
C25 794.3 810.6 2.1 13.94 13.26 -4.9
C31 846.8 863.7 2.0 13.30 12.63 -5.0
C42 963.5 981.5 1.9 12.71 12.05 -5.2
% Dev. is defined in Table 2.

TABLE 9: Measured and calculated liquid mole fractions and gas/oil ratios (std. m3/ m3) by a flash of the mixture
in Table 6 to 37.5 C K and 41.7 bar. (1) is using unmodified parameters, (2) is using plus molecular weight cor-
rected composition and (3) is using plus molecular weight, volume translation parameter and c2 and d2 corrected
data.

Exp Calc (1) % Dev. Calc (2) % Dev. Calc. (3) %Dev.

Liq. Frc. 0.191 0.201 5.2 0.197 3.1 0.191 0.0

GOR 706.2 660.8 -6.4 664.3 -5.9 693.3 -1.8

%Dev. is defined in Table 2.

translation parameters are, on the other hand, quite significant, but
again it should remembered that the volume translation parameter
is a correction parameter to the SRK equation, and modifications
of this order of magnitude will only have a minor influence on the
liquid volumes and not influence the phase equilibrium results at
all.
While it is unlikely that the very moderate adjustments per-
formed will have a significant influence on a single phase proper-
ty, it is less obvious that the phase equilibrium results will not be
influenced. In fact, the regression results indicate that the phase
equilibrium results at 136.1 C are influenced considerably. It is,
therefore, interesting to compare experimental and calculated
phase equilibrium results at other conditions than those of the
regression. For the actual mixture experimental P/T flash results
exist for P = 41.7 bar and T = 37.5 C. A summary of these results
is given in Table 9. It is seen that the regression has improved the
calculation results for the liquid mole fraction as well as for the
gas/oil ratio. This is a strong indication that the regression per-
formed is physically sound.
Conclusion
A procedure is presented for optimizing equation of state para-
meters against experimental PVT data. The procedure is based on
a predictive C7+ characterization. It is shown that it is possible to
almost perfectly match experimental PVT data without loosing the
predictive ability at conditions or for properties not covered by the
regression. This is accomplished by a step wise regression proce-
dure, first critically evaluating the composition data, and secondly
adjusting the volume translation parameter to match experimental
phase densities. For many mixtures these adjustments will be suf-
ficient to obtain satisfactory PVT simulation results. For mixtures
for which this is not the case, small adjustments in two of the
coefficients of the Tc, Pc and correlations will usually give the
desired agreement between experimental and calculated PVT data.
NOMENCLATURE
a = Equation of state parameter
b = Equation of state parameter

8 Journal of Canadian Petroleum Technology

C7+ = Hydrocarbons with 7 and more carbon atoms
c = Volume translation parameter defined in Equation Authors Biography
(6)
calc = Calculated Peter Christensen is senior engineer with Calsep A/S. He holds a
c1-c4 = Coefficients in Tc correlation defined in Equation Ph.D. degree from the Department of Chemical Engineering at the
(1) Technical University of Denmark. Until June 1998 he held a posi-
d1-d4 = Coefficients in Pc correlation defined in Equation (2) tion as Associate Professor at the Department of Applied
exp = Experimental Chemistry at the Technical University of Denmark. In the eighties
e1-e4 = Coefficients in correlation defined in Equation (3) he worked for the Ris National Research Centre engaged in PVT
GC = Gas chromatographic and reservoir simulation.
GOR = Gas/oil ratio
MW = Molecular weight
m = Function of acentric factor defined in Equation (4)
P = Pressure
PVT = Pressure-Volume-Temperature
R = Universal gas constant
SRK = Soave-Redlich-Kwong
T = Temperature
V = Molar volume
Z = Compressibility factor

Subscripts
c = Critical property
RA = Racket

Greek symbols
= Acentric factor
= Liquid density

REFERENCES
1. COATS, K.H., Simulation of Gas Condensate Reservoir
Performance; SPE paper No. 10512, presented at the Sixth SPE
Symposium on Reservoir Simulation of the Society of the Petroleum
Engineers of AIME, New Orleans, LA, January 31 February 3,
1982.
2. PEDERSEN, K.S., THOMASSEN, P., and FREDENSLUND, A.,
Thermodynamics of Petroleum Mixtures Containing Heavy
Hydrocarbons. 3. Efficient Flash Calculation Procedures Using the
SRK Equation of State; Ind. Eng. Chem. Process Des. Dev. 24, pp.
948-954, 1985.
3. PEDERSEN, K.S., THOMASSEN, P., and FREDENSLUND, A.,
Characterization of Gas Condensate Mixtures; Advances in
Thermodynamics 1, pp. 137-152, 1989a.
4. WHITSON, C.H., Characterizing Hydrocarbon Plus Fractions; SPE
Journal 23, pp. 683-694, 1983.
5. PEDERSEN, K.S., THOMASSEN, P., and FREDENSLUND, A.,
On the Dangers of Tuning Equation of State Parameters; Chem. Eng.
Sci. 43, pp. 269-278, 1988.
6. SOAVE, G., Equilibrium Constants from a Modified Redlich-
Kwong Equation of State; Chem. Eng. Sci. 27, pp. 1197-1203, 1972.
7. PENELOUX, A., RAUZY, E., and FRZE, R., A Consistent
Correction for Redlich-Kwong-Soave Volumes; Fluid Phase
Equilibria 8, pp. 7-23, 1982.
8. PEDERSEN, K.S., FREDENSLUND, A., and THOMASSEN, P.,
Properties of Oils and Gas Condensate Mixtures; Gulf Publishing
Company, Houston, 1989b.
9. PEDERSEN, K.S., BLILIE, A.L., and MEISINGSET, K.K., PVT
Calculations on Petroleum Reservoir Fluids Using Measured and
Estimated Compositional Data for the Plus Fraction; I&EC Research
31, pp. 1378-1384, 1992.

ProvenanceOriginal unsolicited manuscript, Regression to

Experimental PVT Data, (96-10-15). Abstract submitted for
review July 17, 1996; editorial comments sent to the author(s)
October 19, 1997; revised manuscript received February 24, 1998;
paper approved for pre-press March 13, 1998; final approval
November 8, 1999.M

Special Edition 1999, Volume 38, No. 13 9