SPE 64520
Plus Fraction Characterization and PVT Data Regression for Reservoir Fluids near
Critical Conditions
Julian Y. Zuo, SPE, and Dan Zhang, DB Robinson Research Ltd.
Copyright 2000, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Asia Pacific Oil and Gas Conference and
Exhibition held in Brisbane, Australia, 16–18 October 2000.
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Abstract
PVT information of reservoir fluids is of great importance to
reservoir engineers. In order to describe phase behavior and
PVT properties using equations of state (EOS), a
characterization procedure is required for true boiling point
(TBP) and plus fractions of reservoir fluids. Although
reasonable prediction accuracy can be obtained, the EOS
parameters need to be tuned to improve the agreement
between the measured properties and the calculated results.
In this work, several characterization methods have briefly
been reviewed and the results of two widely used
characterization procedures have been compared with the
experimental data. The characterization methods can be
applied to both single and multiple sample systems. For single
sample systems, either an exponential or a three-parameter
gamma distribution function was used to split the plus fraction
into subfractions. Then the TBP fractions and split
subfractions were lumped into groups (pseudo-components)
by means of molar averaging, mass averaging, Qauss-
Laguerre quadrature or arbitrary selection. For multiple
sample systems, a method has been developed to generate the
same number of pseudo-components for each sample and the
same physical properties of each pseudo-component while the
mole fractions of pseudo-components reflect the overall
distribution of C7+ mixtures.
In addition, a regression technique has been developed to
fit the PVT data and phase behavior for single or multiple
samples of reservoir fluids. A modified Levenberg-Marquardt
nonlinear least-square algorithm has been utilized in this work.
A sensitivity analysis is performed to determine which
parameters are more sensitive. The more sensitive parameters
are then chosen as adjustable parameters to fit the
experimental PVT data. The lower and upper bounds can be
set for each adjustable parameter. Finally, regressions are
performed to match the measured saturation pressure,
volumetric and viscosity data of reservoir fluids separately or
simultaneously.
The developed characterization and regression techniques
have been tested for oils and gas condensates near critical
conditions and under ordinary conditions as well as for
multiple samples that taken from a reservoir with a strongly
compositional gradient. The results show that the implemented
methods provide a reliable and efficient tool for representing
PVT properties and phase behavior of reservoir fluids.
Introduction
Reservoir fluids are composed of thousands of different
hydrocarbons and some non-hydrocarbons, such as N2, CO2
and H2S. The components of a reservoir fluid may be
classified into three categories: (1). Defined components
whose critical temperature, critical pressure and acentric factor
(Tc, Pc and ω) are well known; (2). True boiling point (TBP)
or single carbon number (SCN) fractions whose density and
molecular weight are either measured or estimated; and (3) A
TBP residue or plus fraction which is too heavy to be
separated by use of a TBP distillation procedure.
As we know, equations of state (EOS) need critical
temperatures, critical pressures and acentric factors of
components to estimate the EOS parameters. Therefore, a
characterization procedure is required for TBP and plus
fractions of reservoir fluids.
A number of characterization procedures have been
available in the open literature. Among them, the widely used
characterization methods in the petroleum industry are those
proposed by Pedersen et al.1,2 and Whitson3-6. Pedersen et al.1
proposed a characterization procedure for TBP and plus
fractions. An exponential distribution function was applied to
split the plus fraction into subfractions. The fractions heavier
than C6 were lumped into pseudo-components with
approximately equal weight fraction of each pseudo-
component (mass averaging). Later, Pedersen et al.2 extended
this method to gas condensate mixtures and developed the
property correlations to estimate Tc, Pc and ω based on a great
number of the measured PVT data of reservoir fluids.
2 J. Y. ZUO AND D. ZHANG
Whitson3-5 proposed a characterization method for C7+
fractions. A three-parameter gamma distribution function was
used to represent the molar distribution of TBP and plus
fractions. Whitson et al.6 then extended this procedure to
multiple related equilibrium fluid systems. They used the
Gauss-Laguerre quadrature method to lump the TBP and plus
fractions into pseudo-components.
The advantage of the characterization procedures
mentioned above is that the experimental PVT data are not
necessarily required. The minimum input is the compositions
of reservoir fluids and the densities and molecular weights of
the plus fractions. However, it is well known that cubic
equations of state cannot represent phase behavior of reservoir
fluids accurately, especially for gas condensates and for near
critical reservoir fluids. As a result, the parameters in
equations of state need to be tuned to improve the
representation of PVT and physical properties of reservoir
fluids.
In this work, the results calculated by using the
characterization methods of Pedersen et al.2 and Whitson3-6
have been compared with the experimental data. In addition, a
regression technique has been developed to match PVT data
and phase behavior for single or multiple samples of reservoir
fluids. The implemented characterization and regression
techniques have been tested for oils and gas condensates near
critical conditions and under ordinary conditions as well as for
multiple samples that were taken from a reservoir with a
strong compositional gradient. Satisfactory results have been
obtained.
Characterization of TBP and Plus Fractions
Since the early 1980s, continuous distribution models have
been applied to describe the molar distribution of C7+
fractions. Cotterman et al.7 and Cotterman and Prausnitz8
applied continuous thermodynamics to compute vapor-liquid
equilibria of continuous and semicontinuous systems.
However, the gamma distribution functions were maintained
in the phase equilibrium calculations. Thus it is difficult to
implement this method into compositional reservoir
simulators. As pointed out by the authors, six to ten quadrature
points (pseudo-components) are usually sufficient to
accurately describe a continuous molar distribution.
Behrens and Sandler9 used a semicontinuous
thermodynamic description to model C7+ fractions. The
Gaussian quadrature method was applied to choose an optimal
discretization of C7+ fractions. Recently, Manafi et al.10
extended continuous thermodynamics to represent phase
behavior of petroleum fluids.
As mentioned in the previous section, the widely used
characterization methods in the petroleum industry are those
proposed by Pedersen et al.1,2 and Whitson3-6. Therefore, the
two distribution functions have been utilized to split plus
fractions in this work: an exponential and a three-parameter
gamma distribution function.
SPE 64520
An Exponential Distribution Function. Pedersen et al.1,2
proposed that the molar composition of the plus fraction is
estimated by an exponential distribution function:
ln zi = A + BM i (1)
where zi and Mi stand for the mole fraction and the molecular
weight of subfraction i, respectively. Coefficients A and B are
determined from the measured or estimated weight fraction
and molecular weight of the plus fraction. The molecular
weight of a given carbon number (Ni) split subfraction can be
computed by:
M i = 14 N i − 4 (2)
Once A and B are determined, the mole fraction and
molecular weight can be attributed to each subfraction of the
plus fraction. The density (ρ) of the subfractions of the plus
fraction at atmospheric pressure are estimated by:
ρ i = C + D ln N i (3)
where coefficients C and D are determined from the measured
or estimated densities of the plus fraction and that of the last
defined or TBP (SCN) fraction. For a given plus fraction,
equations (1)-(3) guarantee that the mole fraction, molecular
weight and density are consistent with the measured or
estimated data for the plus fraction.
Once Mi and ρi are known for TBP fractions and
subfractions, the property correlations (such as Pedersen et
al.2, Winn11, Cavett12, Kesler and Lee13, Twu14, and Riazi and
Daubert15) can be used to estimate Tci, Pci and ωi.
The number of components and fractions (including
subfractions) in a mixture may be greater than 80; for instance,
the plus fraction is split up to C80. Lumping methods are
required to group the TBP fractions and split subfractions into
several pseudo-components. In the original paper of Pedersen
et al.1,2, only the mass averaging was employed. In this work,
the TBP fractions and subfractions can be lumped into pseudo-
components by means of molar averaging, mass averaging, or
arbitrary selection.
However, the characterization method of Pedersen et al.1,2
cannot be suitable for multiple sample systems because each
sample has its own coefficients A, B, C and D. In the case of a
multiple sample system, we first specify the “main” fluid
sample among multiple samples. In general, the sample that
dominates the simulation process is chosen as the main fluid
sample. The main fluid sample is then characterized using the
above characterization procedure. Based on the results of the
main fluid sample, the TBP fractions and subfractions of the
plus fraction of the remaining samples are lumped by keeping
the similar molecular weight to that of the pseudo-components
of the main fluid sample. Each pseudo-component has the
same properties as those of the main fluid sample.
SPE 64520PLUS FRACTION CHARACTERIZATION AND PVT DATA REGRESSION FOR RESERVOIR FLUIDS NEAR CRITICAL CONDITIONS
A Three-Parameter Gamma Distribution Function.
Whitson et al.3,4,5 proposed a three-parameter gamma
distribution function to describe the relation between mole
fractions (zi) and molecular weights (Mi) of TBP and plus
fractions:
M −η
(M − η )α −1 exp ÿÿ
β
p( M ) = (4)
β α Γ (α )
where Γ is the gamma function. α gives a measure of the
shape of the distribution. η is the lowest molecular weight in
the plus fraction and β stands for a normalization condition:
M Cn + − η = αβ (5)
Mcn+ is the molecular weight of the plus fraction.
The cumulative distribution function is the integral of p(x)
from η to x:
∞ yα + 1
P( x ,α ) = p(x )dx = e − y
x pressure because the correlation of Jhaveri and Youngren is
(6)
j =0 Γ (α + j + 1)
η
where y=(x-η)/β.
The mole fraction is given by:
z i = P(M i ,α ) − P(M i −1 ,α ) (7)
and the molecular weight is expressed as:
αβ
Mi = η + [P(M i ,α + 1) − P(M i −1 ,α + 1)] (8)
zi
The TBP fractions and subfractions can then be lumped
into pseudo-components by means of molar averaging, mass
averaging, Qauss-Laguerre quadrature or arbitrary selection.
The density of each pseudo-component is estimated by the
method of Whitson3,4. Once the molecular weight and density
of each pseudo-component are known, the property
correlations (such as Pedersen et al.2, Winn11, Cavett12, Kesler
and Lee13, Twu14, and Riazi and Daubert15) are applied to
estimate Tci, Pci and ωi.
For multiple sample systems, the characterization
procedure with the gamma distribution function extended by
Whitson et al.6 is used in this work.
Regression Technique
In general, cubic EOS cannot accurately predict volumetric
properties and phase behavior of reservoir fluids. Therefore,
the EOS parameters are tuned to fit the measured PVT data.
Tunable Parameters. For a given cubic EOS (such as the
PR EOS16), the tunable parameters are: critical temperature
(Tc), critical pressure (Pc), acentric factor (ω), binary
3
interaction coefficient (kij), dimensionless volume shift
parameter (Vt), and power (θ) in the binary interaction
coefficient correlation between hydrocarbons:
θ
2Vci1 / 6 Vcj1 / 6
k ij = 1 − ÿ (9)
Vci1 / 3 + Vcj1 / 3 ÿ
where Vc denotes the critical molar volume. The binary
interaction coefficient between the specified components i and
j will overwrite the value calculated by equation (9). The
dimensionless volume shift parameter is defined as:
~ c
Vi t = i (10)
bi
where c and b stand for the volume shift parameter and the
covolume of the EOS. For light components (C1-C6, N2, CO2
and H2S), Vt’s are estimated by the correlation of Jhaveri and
Youngren17, while for heavy components, Vt’s are determined
by matching density of each component at atmospheric
not applicable to heavy components.
In addition, Vt’s are also correlated by the following
expression:
~
Vi t = d 1 + d 2Vi t (11)
where d1 and d2 are two adjustable parameters (the default
values are d1=0 and d2=1).
Four viscosity models18-21 are used to calculate viscosities
of reservoir fluids. When viscosity is computed, the following
equation is employed to calculate critical temperatures in the
models of Pedersen and Fredenslund19, Aasberg-Petersen et
al.20 and Guo et al.21:
Tcivis = d ivis Tci (12)
For the Lohrenz-Bray-Clark viscosity model18, the critical
molar volume is computed by:
Vcivis = divisVci (13)
The coefficients (dvis) can be tuned to fit experimental
viscosity data. The default values are equal to unity.
PVT Properties to Be Fitted. The following measured
data may be fitted by tuning the EOS parameters: the
volumetric and physical property data from saturation
(dew/bubble point) pressure test, constant composition
expansion (CCE) test, constant volume depletion (CVD) test,
differential liberation (DL) test, separator (SPE) test, swelling
test and P-T flash test. Each lab test may be performed several
times at different temperatures for different reservoir fluid
samples.
4 J. Y. ZUO AND D. ZHANG
It should be noted that volume shift parameters do not
influence saturation pressure calculations and viscosity
coefficients do not affect saturation pressure and volumetric
data calculations. Therefore, saturation pressure data,
volumetric data and viscosity data can be fitted separately or
simultaneously.
Regression Procedure. The EOS parameter tuning is a
nonlinear minimization problem. The objective function is
expressed as:
ÿ 2
eiexp − eical (x ) ÿ
ÿ M exp
F (x ) = wi (14)
i =1 eexp ÿ
i Methods I and II with the experimental data for Mixture 4 of
where x is the vector of adjustable parameters with N (number
of adjustable parameters) dimension. Mexp, w, eexp and ecal
denote the number of experimental data points, the weighing
factor, the experimental and calculated values, respectively.
The lower bound Xmin and the upper bound Xmax are used
to scale the adjustable parameters X.
X j − X min
xj =
j
(15)
X max − X min
j j
Thus, xj always lies between zero and unity.
The goal of the EOS parameter tuning is to find the values
of adjustable parameters so that the objective function reaches
its minimum. The partial derivatives (gradients) of the
objective function, with respect to the adjustable parameters,
represent the sensitivity of the objective function to the
parameters. The parameters with larger absolute values of
gradients are more sensitive; therefore, they are good
candidates for being adjustable variables. A modified
Levenberg-Marquardt nonlinear least-square algorithm is
utilized in this work.
A typical regression procedure is as follows:
(1). Select tunable parameters (initial values are obtained
from characterization) and set lower and upper bounds for
each parameter;
(2). Input experimental data and specify a weighing factor
for each data point;
(3). Perform a sensitivity analysis and sort the tunable
parameters in decreasing order of ∂F/∂xj;
(4) Select the more sensitive parameters as adjustable
parameters and carry out a nonlinear regression.
Comparison of Two Characterization Procedures
The two characterization procedures mentioned above have
been applied to predict saturation pressures of reservoir fluids.
The Peng-Robinson EOS16 was used in all calculations. C7+
fractions were lumped into 5 pseudo-components with mass
averaging for the exponential distribution function and with
the Gaussian quadrature for the gamma distribution function,
respectively. The property correlations of Pedersen et al.1 were
employed to estimate Tc, Pc and ω of each pseudo-component.
SPE 64520
Table 1 illustrates the results predicted by the exponential
(referred to as Method I) and the gamma distribution function
(referred to as Method II). The average deviation of the
predicted saturation pressures by Method I is 4.88% and that
by Method II is 13.21%. Method I is much better than Method
II. Coats and Smart22 used the PR EOS to predict saturation
pressures for several oils and gases with an average deviation
of 14%. If we utilized Methods I and II and Coats and Smart’s
method to predict the saturation pressures for the same
systems only taken from Coats and Smart22 as shown in Table
1, the deviations are 4.9%, 6.3% and 13.6% by Methods I and
II and Coats and Smart’s method, respectively.
Fig. 1 compares the predicted saturation pressure using
Pedersen et al.1 near critical conditions. Method I predicts two
dew points and two bubble points at the four experimental
temperatures, which are consistent with the measured data.
While Method II under-predicts saturation pressures and
predicts all the bubble points at the four experimental
temperatures (all four open circles are on the left side of the
critical point), which conflicts with the experimental
observation.
Table 2 lists the predicted saturation densities by
application of Methods I and II and the measured data for
several reservoir fluids reported by Coats and Smart22. The
saturation pressures were matched by tuning the power (θ) in
Eq. (9) since pressures affect density calculations. The
deviation of the predicted densities is less than 1%.
In general, Method I gives better predictions of PVT
properties and phase behavior of reservoir fluids than Method
II.
Examples of the EOS Tuning
As mentioned above, a cubic EOS with a suitable
characterization procedure may not represent PVT properties
and phase behavior of reservoir fluids accurately. The EOS
parameters are usually tuned to fit the experimental data. This
section gives several examples of the EOS parameter tuning
for different kinds of reservoir fluids. The Peng-Robinson
EOS16 and the property (Tc, Pc and ω) correlations of Pedersen
et al.1 were employed in the following calculations.
Near Critical Gas Condensate. The composition of the near
critical gas condensate is given in Table 3. The experimental
data were measured by the laboratory of DB Robinson
Research Ltd. The original composition was analyzed to C30+.
Method I was used to characterize the TBP and plus
fractions of this near critical gas condensate. The C7+ fraction
was lumped into 15 pseudo-components with approximately
equal weight percentage of each pseudo-component. The
experimental data to be matched are the dew point, the liquid
volume percentage and the relative volume in the CCE test
and the liquid dropout in the CVD test. In totally, 12
parameters were tuned and the adjustable parameters before
and after tuning are given in Table 4.
SPE 64520PLUS FRACTION CHARACTERIZATION AND PVT DATA REGRESSION FOR RESERVOIR FLUIDS NEAR CRITICAL CONDITIONS
Fig. 2 shows the phase envelope of the near critical gas
condensate. The dashed and the solid lines are the saturation
(bubble/dew) point curves before and after the EOS parameter
tuning, respectively. The open circle and square represent the
critical points predicted by use of the PR EOS before and after
tuning, respectively. It can be seen that the dew point
prediction is in good agreement with the measured point
denoted by an open diamond symbol.
A comparison between the calculated results and the
experimental data of the liquid volume percentage and relative
volume as a function of pressures in the CCE test at 281.9 oF
is given in Fig. 3. The liquid volume percentage increases
steeply as pressures drop slightly near the dew point. As we
can see, the calculated results, after the EOS parameter tuning,
agree extremely well with the experimental data.
Fig. 4 shows the calculated and experimental results of the
liquid dropout in the CVD test, which are in good agreement.
Near Critical Oil. The composition of the near critical oil is
also given in Table 3. The original composition was analyzed
to C30+.
Method I was used to characterize the TBP and plus
fractions of the near critical oil. The C7+ fraction was lumped
into 6 pseudo-components in terms of mass averaging. The
experimental data to be matched are: the bubble point, the
liquid volume percentage, the oil density and the relative
volume in the CCE test, and the liquid density, the oil FVF
and the solution GOR in the DL test. The tunable parameters
before and after the EOS tuning are listed in Table 5.
Fig. 5 shows the phase envelope of the near critical oil.
The dashed and the solid lines are the saturation point
(bubble/dew) curves before and after the EOS parameter
tuning, respectively. The open circle and square represent the
critical points predicted by use of the PR EOS before and after
tuning, respectively. The bubble point prediction agrees well
with the measured data (diamond) after the EOS tuning.
A comparison between the calculated results and the
experimental data of the liquid volume percentage and relative
volume as a function of pressures in the CCE test is depicted
in Fig. 6. The liquid volume percentage decreases steeply as
pressures drop slightly near the bubble point. The calculated
results, after the EOS parameter tuning, match extremely well
with the experimental data.
Fig. 7 compares the calculated results of the liquid density
with the experimental data, as a function of pressures, in the
CCE and DL tests. The PR EOS, without tuning, somewhat
over-predicts the liquid density while the calculated results,
after the EOS tuning, are in good agreement with the
experimental data.
A comparison of the calculated results of the oil formation
volume factor (Bo, FVF) and solution GOR with the
experimental data in the DL test is shown in Fig. 8. The PR
EOS, without tuning, under-predicts the oil FVF and solution
GOR at pressures a little lower than the bubble point as the
predicted bubble point pressure is slightly higher than the
measured point. The agreement is good, between the
calculated and the experimental data, after the EOS tuning.
5
Gas Condensate. The composition of the gas condensate is
also given in Table 3. The original composition was analyzed
to C11+.
Method I was applied to characterize the TBP and plus
fractions of this gas condensate. The C7+ fraction was lumped
into 15 pseudo-components by means of mass averaging. The
experimental data to be matched are: the dew point, the liquid
volume percentage and the relative volume in the CCE test
and the liquid dropout in the CVD test. The adjustable
parameters before and after the EOS tuning are tabulated in
Table 6.
Fig. 9 shows the phase envelope of the gas condensate.
The dashed and the solid lines are the dew point curves before
and after the parameter tuning, respectively. The solid circles
represent the experimental data. The dew point calculations
are in good agreement with the measured data after the EOS
tuning. There is no critical point for this gas condensate.
A comparison between the calculated results and the
experimental data of the liquid volume percentage and relative
volume as a function of pressures in the CCE test is shown in
Fig. 10. The PR EOS without tuning (dashed curves) over-
predicts the relative volume over the pressure range, and much
over-predicts the liquid volume percentage at higher pressures,
but under-predicts it at lower pressures. The calculated results
after the parameter tuning are in good agreement with the
experimental data, especially for liquid volume percentage
around the dew point, which is usually much over-predicted
by a cubic EOS.
Multiple Samples of Riemens et al.25 Riemens et al.25
published PVT properties of two fluid samples taken from
wells producing from the same geological formation in Birba
Field. One is the oil sample and the other is the gas condensate
sample.
The method of Whitson et al.6 was employed to
characterize the C7+ fractions of the multiple samples in Birba
Field. The C7+ fractions were lumped into 3 pseudo-
components with the Gaussian quadrature method. The
experimental data to be matched are the saturation pressures
and GOR. In total, 4 parameters were tuned and the tunable
parameters before and after tuning are given in Table 7. The
calculated results are tabulated in Table 8. The calculations
after the EOS tuning are in good agreement with the measured
data.
Multiple Samples of Hoffmann et al.26 Hoffmann et al.26
reported PVT properties of two oil and gas cap fluid samples.
The method of Whitson et al.6 was used to characterize the
C7+ fractions of the multiple samples and the C7+ fractions
were lumped into 2 pseudo-components with the Gaussian
quadrature method. The experimental data to be matched are:
the saturation pressures, GOR and liquid densities. In total, 6
parameters were tuned, and the tunable parameters, before and
after the EOS tuning, are given in Table 9. The calculated
results are given in Table 10. The calculations after the EOS
tuning agree well with the measured data.
6 J. Y. ZUO AND D. ZHANG SPE 64520

Oil 2 of Coats and Smart22. Coats and Smart22 reported PVT Nomenclature
properties of the very volatile Oil 2. In the previous section, A = coefficient in Eq. (1)
we utilized Method I with 5 pseudo-components for B = coefficient in Eq. (1)
representing the C7+ fraction. The predicted bubble point b = covolume of the PR EOS, ft3/lb mole
pressure was 3879.9 psia, which is considerably below the C = coefficient in Eq. (3)
measured 4474.7 psia. After the power (θ) in Eq. (9) was c = volume shift parameter, ft3/lb mole
adjusted to match the observed bubble point pressure, Oil 2 D = coefficient in Eq. (3)
behaves as a gas condensate at the reservoir temperature of Dev% = (1/Mexp)Σj|1-ecal/eexp|j×100
176 OF. This is obviously discrepant with the experimental dvis = viscosity coefficient in Eqs. (12) and (13)
observation. d1 = coefficient in Eq. (11)
Therefore, we applied two pseudo-components to represent d2 = coefficient in Eq. (11)
the C7+ fraction. The predicted bubble point pressure is closer e = property
to the measured value. Then power (θ) in Eq. (9) was tuned to F(x) = objective function
match the observed bubble point pressure. In this case, Oil 2 kij = binary interaction coefficient
behaves as oil at the reservoir temperature of 176 OF. Next, the M = molecular weight, lb/lb mole
EOS was employed to predict PVT properties of Oil 2. The Mexp = number of data points
overall relative deviation is 1.93%. Satisfactory results were Mi = molecular weight of species i, lb/lb mole
obtained. N = number of adjustable parameters
This example indicates that the number of pseudo- Ni = carbon number of species i
components chosen in the characterization of TBP and plus P = pressure, psi
fractions is sometimes crucial. The number of pseudo- P(x, α) = cumulative distribution function, defined in Eq. (6)
components may result in an incorrect representation of the p(x) = distribution or probability density function
reservoir fluid, especially for reservoir fluid in the vicinity of Pc = critical pressure, psi
the critical point. Usually, 2-6 pseudo-components for oil and Tc = critical temperature, oF
10-15 pseudo-components for gas condensate are sufficient to Vc = molar critical volume, ft3/lb mole
represent C7+ fractions. Vt = dimensionless volume shift parameter
w = weighing factor
Other Systems of Coats and Smart22. In addition, we x = integral variable in Eq. (6)
compared Method I with the method of Coats and Smart22. In x, X = adjustable parameter
our calculations, C7+ fractions were lumped into 5 pseudo- y = (x-η)/β
components. Only power (θ) in Eq. (9) was tuned to match zi = mole fraction of species i
saturation pressures. The other properties were predicted by α = parameter of the gamma distribution function
the PR EOS. The overall deviation of the predicted PVT β= parameter of the gamma distribution function
properties using Method I for Gas 4, Gas 5, Oil 3, Oil 4, Oil 6 η = lowest molecular weight in the plus fraction
and Oil 7 is around 3%, which is comparable to the results θ = power in the binary interaction coefficient
regressed by Coats and Smart22. correlation between hydrocarbons, in Eq. (9)
ρ = density, lb/ft3
Conclusions ω = acentric factor
In this work, several characterization methods have briefly
been reviewed and the results obtained by using two widely Superscripts
used characterization procedures have been compared with the cal = calculated value
experimental data. The characterization method of Pedersen et exp = experimental value
al.2 usually gives better predictions than that of Whitson et max = maximum value (upper bound)
al.5,6 without the EOS beong tuned. min = minimum value (lower bound)
In addition, a regression technique has been developed to
fit PVT data and phase behavior for single or multiple samples Subscripts
of reservoir fluids. The implemented characterization and c = value at critical conditions
regression techniques have been tested for oils and gas i,j = species i, j
condensates at near critical conditions and under ordinary s = value at saturation conditions
conditions as well as for multiple samples. The results indicate
that the implemented methods provide a reliable and efficient
tool for representing PVT properties and phase behavior of References
reservoir fluids. 1. Pedersen, K.S., Thomassen, P. and Fredenslund, Aa.:
“Characterization of Gas Condensate Mixtures,” Presented in
Chorn, L.G. and Mansoori, G.A.: C7+ Fraction
Characterization, Taylor & Francis New York Inc., New York
SPE 64520PLUS FRACTION CHARACTERIZATION AND PVT DATA REGRESSION FOR RESERVOIR FLUIDS NEAR CRITICAL CONDITIONS 7

(1989) 137. 22. Coats, K.H. and Smart, G.T.: “Application of a Regression-
2. Pedersen, K.S., Fredenslund, Aa. and Thomassen, P.: Based EOS PVT Program to Laboratory Data,” SPE Reservoir
Properties of Oils and Natural Gases, Gulf Publishing Co., Eng. (May 1986) 277.
Houston, Texas (1989). 23. Agarwal, R.K., Li, Y.-K. and Nghiem, L.: “A Regression
3. Whitson, C.H.: “Characterizing Hydrocarbon Plus Fractions,” Technique with Dynamic Parameter Selection for Phase-
Soc. Pet. Eng. J. (August 1983) 683. Behavior Matching,” SPE Reservoir Eng. (February 1990) 115.
4. Whitson, C.H.: “Effect of C7+ Properties on Equation of State 24. Christesen, P.L.: “Regression to Experimental PVT Data,” J.
Predictions,” Soc. Pet. Eng. J. (December 1984) 685. Can. Pet. Tech. (1999) 38, 1.
5. Whitson, C.H., Anderson, T.F. and Soreide, I.: “Application of 25. Riemens, W.G., Shulte, A.M. and de Jong, L.N.J.: “Birba Field
the Gamma Distribution Model to Molecular Weight and PVT Variations Along the Hydrocarbon Colum and
Boiling Point Data for Petroleum Fractions,” Chem. Eng. Confirmatory Field Tests,” J. Pet. Tech. (January 1988) 83.
Comm. (1990) 96, 259. 26. Hoffmann, A.E., Crump, J.S. and Hocott, C.R.: “Equilibrium
6. Whitson, C.H., Anderson, T.F. and Soreide, I.: “C7+ Constants for a Gas-Condensate System,” Pet. Trans. AIME
Characterization of Related Equilibrium Fluids Using the (1953) 198, 1.
Gamma Distribution,” Presented in Chorn, L.G. and Mansoori,
G.A.: C7+ Fraction Characterization, Taylor & Francis New
York Inc., New York (1989) 35. SI Metric Conversion Factors
7. Cotterman, R.L., Bender, R. and Prausnitz, J.M.: “Phase o
Equilibria for Mixtures Including Very Many Components
F (oF+459.67)/1.8 =K
Development and Application of Continuous Thermodynamics psi x 6.894 757 E+00 = kPa
for Chemical Process Design,” Ind. Eng. Chem. Proc. Des. Dev. lb/ft3 x 1.601 846 E+01 = kg/m3
(1985) 24, 194. scf/stb x 1.781 073 E+00 = std m3/st m3
8. Cotterman, R.L. and Prausnitz, J.M.: “Flash Calculations for *Conversion factor is exact
Continuous or semicontinuous Mixtures Using an Equation of
State,” Ind. Eng. Chem. Proc. Des. Dev. (1985) 24, 434.
9. Behrens, R.A. and Sandler, S.I.: “The Use of Semicontinuous
Description to Model the C7+ Fraction in Equation of State
Calculations,” SPE Reservoir Eng. (August 1988) 1041.
10. Manafi, H., Mansoori, G.A. and Ghotbi, S.: “Phase Behavior
Prediction of Petroleum Fluids with Minimum Characterization
Data,” J. Pet. Sci. Eng. (1999) 22, 67.
11. Winn, F.W.: “Physical Properties by Nomogram,” Pet. Refiner
(1957) 36, 157.
12. Cavett, R.H.: “Physical Data for Distillation Calculation,
Vapor-Liquid Equilibria,” Presented at the 27th Midyear
Meeting, API Division of Refining, San Francisco, CA, May
15, 1964.
13. Kesler, M.G. and Lee, B.I.: “Improve Prediction of Enthalpy of
Fractions,” Hydrocarbon Processing (1976) 55, 153.
14. Twu, C.H.: “An internally Consistent Correlation for Predicting
the Critical Properties and Molecular Weights of Petroleum and
Coal-Tar Liquids,” Fluid Phase Equilibria (1984) 16, 137.
15. Riazi, M.R. and Daubert, T.E.: “Prediction of the Composition
of Petroleum Fractions,” Ind. Eng. Chem. Process Des. Dev.
(1980) 19, 289.
16. Peng, D.-Y. and Robinson, D.B.: “A New Two-Constant
Equation of State,” Ind. Eng. Chem. Fundam. (1976) 15, 59.
17. Jhaveri, B.S. and Youngren, G.K.: “Three Parameter
Modification of the Peng-Robinson Equation of State to
Improve Volumetric Predictions,” SPE Reservoir Eng. (August
1988) 1033.
18. Lohrenz, J., Bray, B.G. and Clark, C.R.: “Calculating
Viscosities of Reservoir Fluids from Their Compositions,” J.
Petr. Tech. (October 1964) 1171.
19. Pedersen, K. S. and Fredenslund, Aa.: “An Improved
Corresponding States Model for the Prediction of Oil and Gas
Viscosities and Thermal Conductivities,” Chem. Eng. Sci.
(1987) 42, 182.
20. Aasberg-Petersen, K., Knudsen, K. and Fredenslund, Aa.:
“Prediction of the Viscosities of Hydrocarbon Mixtures,” Fluid
Phase Equilibria (1991) 70, 293.
21. Guo, X.-Q., Wang, L.-S., Rong, S.-X. and Guo, T.-M.:
“Viscosity Models Based on Equations of State for
Hydrocarbon Liquids and Gases,” Fluid Phase Equilibria
(1997) 139,405.
8 J. Y. ZUO AND D. ZHANG SPE 64520

TABLE 1 COMPARISON OF THE PREDICTED SATURATION

PRESSURES WITH EXPERIMENTAL DATA USING TWO TABLE 3 COMPOSITIONS OF RESERVOIR FLUIDS
CHARACTERIZATION PROCEDURES
Near Critical Gas Near Critical Oil Gas Condensate
Sample T Exp. Method I Dev Method II Dev CO2 1.812 1.013 0.68
O
F psia psia % psia % N2 0.000 0.613 3.43
Mix 11 205.88 4090.0 3703.0 9.46 3753.0 8.24 C1 76.96 55.850 76.11
Mix 2 1 246.02 5772.5 5350.7 7.31 3085.0 46.56 C2 7.172 12.858 9.07
Mix 3 1 289.40 6526.7 6065.1 7.07 3643.2 44.18 C3 2.853 6.704 2.71
Mix 4 1 287.96 5665.2 5662.6 0.05 5078.6 10.35 C4 1.333 5.009 1.30
Mix 4 1 303.98 5666.3 5667.0 0.01 5065.8 10.60 C5 0.285 2.883 0.56
Mix 4 1 325.94 5594.1 5655.5 1.10 5030.9 10.07 C6 0.187 1.893 0.43
Mix 4 1 338.00 5568.0 5640.7 1.31 5003.4 10.14 C7+ 9.398 13.177 5.71
Mix 5 1 281.00 4787.7 4764.4 0.49 4402.5 8.05
Oil 122 180.00 2534.7 2459.4 2.97 2464.6 2.77
Oil 2 22 176.00 4474.7 3879.9 13.29 3709.8 17.09
Oil 3 22 179.00 2611.7 2652.9 1.58 2566.1 1.75
Oil 4 22 250.00 2561.7 2435.6 4.92 2416.3 5.68
Oil 6 22 234.00 2760.7 2563.4 7.15 2531.7 8.29
Oil 7 22 131.00 1708.7 1674.7 1.99 1674.9 1.98
Gas 2 22 190.00 4464.7 4426.0 0.87 4172.8 6.54
TABLE 4 TUNED PARAMETERS FOR THE NEAR CRITICAL GAS
Gas 4 22 240.00 3374.7 3651.4 8.20 3520.7 4.33 CONDENSATE
Gas 5 22 267.00 4856.7 4770.8 1.77 4637.2 4.52
Mix 12 311.00 5627.5 5019.1 10.81 3416.1 39.30 Parameter Initial Value Final Value
Mix 2 2 199.04 3885.6 3810.9 1.92 1912.8 50.77 θ 0.0000 -0.1089
Mix 3 2 160.88 3466.4 3406.0 1.74 3438.4 0.81 d1 0.0000 -0.1062
Mix 4 2 285.80 4935.6 4795.0 2.85 4614.7 6.50 d2 1.0000 1.023975
Mix 9 2 180.50 4075.6 3969.9 2.59 3935.3 3.44 Tc of Pseudo 2, oF 686.066 719.186
Mix 5 2 264.20 6729.8 6187.8 8.05 3942.0 41.42 Tc of Pseudo 3, oF 726.782 759.362
Mix 6 2 199.94 3981.3 3697.8 7.12 3721.4 6.53 Tc of Pseudo 5, oF 809.258 865.436
Mix 7 2 200.12 3839.2 3399.0 11.47 3310.1 13.78 Tc of Pseudo 6, oF 831.956 897.404
Mix 8 2 200.12 3839.2 3536.2 7.89 3758.9 2.09 Tc of Pseudo 7, oF 850.658 905.72
Mix 10 2 89.96 6712.4 5969.3 11.07 6645.5 1.00 Tc of Pseudo 8, oF 869.576 915.17
Mix 10 2 154.04 5824.7 5601.7 3.83 6191.5 6.30 Tc of Pseudo 12, oF 1014.332 1004.36
Mix 10 2 257.72 4401.9 4453.6 1.17 4929.7 11.99 Tc of Pseudo 13, oF 1072.814 1005.656
Mix 10 2 336.92 3330.1 3123.1 6.22 3699.7 11.10 Tc of Pseudo 15, oF 1479.668 1478.75
Overall 4.88 13.21

TABLE 2 COMPARISON OF THE PREDICTED SATURATION TABLE 5 TUNED PARAMETERS FOR THE NEAR CRITICAL OIL
DENSITIES WITH EXPERIMENTAL DATA USING TWO Parameter Initial Value Final Value
CHARACTERIZATION PROCEDURES
θ 0.0000 0.00416
Sample T Exp. Method I Dev. Method II Dev. d1 0.0000 -0.06377
O
F lb/ft2 lb/ft2 % lb/ft2 % d2 1.0000 0.659552
Oil 122 180 47.96 47.86 0.21 47.77 0.40 Tc of Pseudo 1, oF 550.544 515.516
Oil 222 176 33.01 33.48 1.40 33.30 0.88 Tc of Pseudo 2, oF 621.986 591.746
Oil 322 179 44.17 44.05 0.27 44.70 1.20 Tc of Pseudo 3, oF 696.398 660.182
Oil 422 250 40.34 40.20 0.35 40.09 0.62 Tc of Pseudo 4, oF 802.706 764.600
Oil 622 234 38.01 38.39 0.99 38.26 0.66 Tc of Pseudo 5, oF 923.576 898.304
Oil 722 131 44.48 44.37 0.25 44.31 0.38 Tc of Pseudo 6, oF 1199.930 1184.936
Gas 222 190 29.54 29.54 0.00 29.89 1.18 Vt of Pseudo 1 -0.00855 -0.02335
Gas 522 267 19.15 18.72 2.30 18.80 1.83 Vt of Pseudo 4 0.01922 -0.01835
Overall 0.72 0.89
SPE 64520PLUS FRACTION CHARACTERIZATION AND PVT DATA REGRESSION FOR RESERVOIR FLUIDS NEAR CRITICAL CONDITIONS 9

TABLE 6 TUNED PARAMETERS FOR THE GAS CONDENSATE TABLE 9 TUNED PARAMETERS FOR THE FLUID SAMPLES OF
HOFFMANN ET AL.23
Parameter Initial Value Final Value
θ 0.0000 0.2948 Parameter Initial Value Final Value
Tc of Pseudo 1, oF 511.815 545.612 θ 0.0000 -0.36257
Tc of Pseudo 2, oF 553.686 601.974 d1 0.0000 -0.26879
Tc of Pseudo 4, oF 628.384 685.46 d2 1.0000 0.933407
Tc of Pseudo 5, oF 686.409 752.328 Pc of Pseudo 1, psi 345.687 366.338
Tc of Pseudo 7, oF 763.062 801.021 Tc of Pseudo 1, oF 722.184 670.476
Tc of Pseudo 8, oF 809.261 825.462 Vt of Pseudo 2 -0.5709 -0.2000
Tc of Pseudo 9, oF 852.614 834.408
Tc of Pseudo 10, oF 893.716 868.25
Tc of Pseudo 11, oF 941.954 887.274
Tc of Pseudo 12, oF 1005.816 913.537
Tc of Pseudo 13, oF 1075.751 922.45
Tc of Pseudo 14, oF 1169.195 935.357
Tc of Pseudo 15, oF 1384.106 1274.4 TABLE 10 RESULTS FOR THE FLUID SAMPLES OF HOFFMANN
Pc of Pseudo 11, psi 202.15 181.98 ET AL.26
Pc of Pseudo 12, psi 194.22 174.046
Oil Gas
Pc of Pseudo 13, psi 188.025 174.35
Property Exp. Before After Exp. Before After
Pc of Pseudo 14, psi 182.724 168.665
Pc of Pseudo 15, psi 177.794 181.24 Ps, psia 3837 4236 3854 3839.7 4650.3 3825.5
GOR, scf/stb 910 947 869
FVF, scf/stb 1.475 1.466 1.430
ρs,lb/ft3 40.98 44.09 39.81
ρs,lb/ft3 40.80 45.05 40.75
TABLE 7 TUNED PARAMETERS FOR THE RESERVOIR FLUID ρs,lb/ft3 40.81 46.23 41.87
SAMPLES OF RIEMENS ET AL.25 ρs,lb/ft3 42.15 47.44 42.97
ρs,lb/ft3 44.69 48.72 44.08
Parameter Initial Value Final Value
ρs,lb/ft3 45.00 50.16 45.25
θ 0.0000 0.01888
Dev, % 5.04 2.68 12.20 1.40
Tc of Pseudo 3, oF 1272.93 1291.38
d1 0.0000 -0.3437
d2 1.0000 -1.4500

TABLE 8 RESULTS FOR THE RESERVOIR FLUID SAMPLES OF

RIEMENS ET AL.25
Birba-2 Birba South-1
Property Exp. Before After Exp. Before After
Ps, psia 6883 6610 6883 6844 6568 6844
ρs, lb/ft3 41.89 42.13 41.30 30.59 27.02 25.90
GOR, scf/stb 1465 1521 1465 6176 7894 6176
FVF, scf/stb 1.65 1.65 1.63 4.80 3.94
Dev, % 2.09 0.66 14.50 5.11
10 J. Y. ZUO AND D. ZHANG SPE 64520

6000 80 5
Exp.
After Tuning
5000
Before Tuning 4
60 Exp. (Vr)

Relative Volume
Vliquid/Vtotal %
4000 After Tuning (Vr)
Pressure, psia

Before Tuning (Vr) 3

3000 40

Exp. (Pedersen et al.) 2

2000 Method I
20
CP (Method I) 1
1000 Method II
CP (Method II)
0 0
0 0 2000 4000 6000 8000 10000
-150 50 250 450 650 850
Pressure, psia
Temperature, F

Fig. 1—Comparison of the Predicted Saturation Pressures Fig. 3—Liquid Volume Percentage and Relative Volume as
1 a Function of Pressure in the CCE Test for the Near
with the Experimental Data for Mixture 4 of Pedersen et al. o
Near Critical Conditions. Critical Gas Condensate at 281.9 F.

10000 60

8000
Liquid Dropout % in CVD

40
Pressure, psia

6000

4000
Exp. Dew Point 20 Exp.
CP (Before Tuning) After Tuning
CP (After Tuning) Before Tuning
2000
Before Tuning
After Tuning
0
0
0 2000 4000 6000 8000 10000
-400 -200 0 200 400 600 800 1000
Temperature, F Pressure, psia

Fig. 2—Phase Envelope of the Near Critical Gas

Condensate. Fig. 4—Liquid Dropout as a Function of Pressure in the
o
CVD Test for the Near Critical Gas Condensate at 281.9 F.
SPE 64520PLUS FRACTION CHARACTERIZATION AND PVT DATA REGRESSION FOR RESERVOIR FLUIDS NEAR CRITICAL CONDITIONS 11

5000 0.7 0.8

Exp.
Before Tuning
4000

Liquid Density(CCE), g/cc

After Tuning 0.6

Liquid Density(DL), g/cc

0.6 Exp. (DL)
Pressure, psia

3000 Before Tuning (DL)

After Tuning (DL) 0.4

Exp. BP
2000
CP (Before Tuning) 0.5
CP (After Tuning) 0.2
1000 Before Tuning
After Tuning
0.4 0
0 0 2000 4000 6000 8000 10000
-300 0 300 600 900 Pressure, psia
Temperature, F

Fig. 7—Liquid Density as a Function of Pressure in the

Fig. 5—Phase Envelope of the Near Critical Oil. o
CCE and DL Tests for the Near Critical Oil at 231 F.

100 4 8000 5
Exp.
Exp. Before Tuning
80 Before Tuning After Tuning 4
3 6000
After Tuning Exp. (Bo)
Solution GOR, scf/stb

Oil FVF(Bo), bbl/stbbl

Relative Volume
Vliquid/Vtotal %

Exp. (Vr) Before Tuning (Bo)

60 Before Tuning (Vr) 3
After Tuning (Bo)
After Tuning (Vr) 2 4000
40 2

1 2000
20 1

0 0 0 0
0 2000 4000 6000 8000 10000 0 1000 2000 3000 4000 5000
Pressure, psia Pressure, psia

Fig. 6—Liquid Volume Percentage and Relative Volume as Fig. 8—Solution GOR and Oil Formation Volume Factor as
a Function of Pressure in the CCE Test for the Near a Function of Pressure in the DL Test for the Near Critical
o o
Critical Oil at 231 F. Oil at 231 F.
12 J. Y. ZUO AND D. ZHANG SPE 64520

10000

8000
Pressure, psia

6000

4000
After Tuning
Before Tuning
Exp.
2000

0
0 200 400 600 800
Temperature, F

Fig. 9—Phase Envelope of the Gas Condensate.

30 2.5
After Tuning (Vol.%)
Before Tuning (Vol.%)
Exp. (Vol.%)
2.0
After Tuning (Rel. Vol.)
Before Tuning (Rel. Vol.)
20
Relative Volume
Liquid Volume%

Exp. (Rel. Vol.)

1.5

1.0
10

0.5

0 0.0
2000 4000 6000 8000 10000
Pressure, psia

Fig. 10—Liquid Volume Percentage and Relative Volume

as a Function of Pressure in the CCE Test for the Gas
o
Condensate at 270.5 F.