SPE 77382
An Efficient Tuning Strategy to Calibrate Cubic EOS for Compositional Simulation
Rafael A. Aguilar Zurita and William D. McCain, Jr.
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Annual Technical Conference and
Exhibition held in San Antonio, Texas, 29 September–2 October 2002.
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Abstract
A new strategy for preparing an equation of state (EOS) for
use in compositional simulation is presented. The strategy
consists of three major steps: extending the plus fraction and
matching the saturation pressure, grouping, and matching of
volumetric data.
The plus fraction is extended into 45 single carbon number
groups (SCN) using a gamma probability function. Then
critical pressure, critical temperature, and acentric factor are
assigned to each SCN using the best available correlations.
The laboratory measured saturation pressure of the fluid is
matched by adjusting the molecular weight of the
heaviest SCN.
The extended composition is grouped into two multiple
carbon number groups (MCN) with the intermediates grouped
into two pseudocomponents and methane as a pure
component. The nonhydrocarbon components are included as
required. The critical properties for the grouped components
are assigned with a methodology that preserves the
coefficients, a and b, of the equation of state that previously
matched the saturation pressure. The slight change in the
match of the measured saturation pressure caused by the
grouping is overcome by adjusting the critical properties of the
heaviest MCN.
Finally, volumetric data are matched using the volume
translation parameters as regression variables.
Introduction
Equations of state (EOS) are widely used in compositional
simulation and surface facility design. Volatile oils and gas
condensates require special treatment due to their near-critical
nature. Classical material balance cannot be applied to these
near-critical fluids because their molar compositions change as
the reservoir is depleted. The gas coming out of solution
releases signficant amounts of condensate at the surface
facilities. Thus, compositional simulation is necessary to
determine the best economical and technical exploitation.
However, the performance of cubic equations of state is
questionable in their predictive mode when they are applied to
petroleum mixtures. Some of the parameters of an equation of
state must be adjusted in order for the calculations to
reproduce experimental data of a reservoir fluid. This is a time
consuming and sometimes frustrating process.
Currently, engineers dealing with such fluids do not have a
clear methodology to follow to make these modifications to an
equation of state. Instead, several approaches are proposed in
the literature for tuning the EOS parameters. The process is
more of an art than a science.
Objective
The objective of this study is to introduce a new strategy
that is logical, systematic, easily applicable, suitable to any
naturally occurring petroleum fluid, and that requires the
modification of only a minimum number of EOS parameters.
Approach
The proposed strategy is based on the results of laboratory
tests of ten naturally occurring near-critical petroleum fluids.
This strategy is applicable to any cubic EOS. However, the
Peng-Robinson EOS1 (PREOS) has been used in this study
because of its popularity among researchers and engineers.
Moreover, the PREOS is claimed to be more suitable for
volumetric predictions. In this study, volume shift
parameters2,3 are used to improve the volumetric capability of
the PREOS.
Binary interaction coefficients (BIC) between hydrocarbon
components are assumed to be zero while BIC between non-
hydrocarbons and hydrocarbon components are set different
than zero.
The following steps are necessary to adjust an equation of
state so that calculations will match laboratory data:
1. Extend the measured plus fraction to SCN45
2. Assign critical properties and acentric factors to
the components of the extended composition
3. Match the saturation pressure using the
extended composition
2 R. AGUILAR ZURITA AND W. MCCAIN SPE 77382

4. Group SCN into MCN, assign critical properties m−1

and acentric factors, and preserve the match of the zSCN 45 = z plus − ∑ ζ ι . . . . . . . . . . . . . . . . . . . . . . . . . . . (5)
ι=1
saturation pressure
5. Match the volumetric data
The molecular weight of SCN45 is then calculated.
Extending the Measured Fraction to SCN45 m −1
The gamma probability function4 is used to extend the plus z plus ⋅ M plus − ∑ zi ⋅ M i
fraction into 45 single carbon number groups (SCN). This M SCN 45 = i =1
. . . . . . . . . . . . . . . . . (6)
model is useful for extending the plus fraction because it zSCN 45
preserves the measured molecular weight of the plus fraction.
Generalized physical properties—molecular weight, Whitson4 defined the Watson characterization factor, K, as
boiling temperature, and specific gravity given in Table 14— a function of molecular weight and specific gravity with the
are assigned to each SCN. following equation
The probabilistic model is a function of the molecular
weights of each SCN: K = 4.5579 ⋅ M i0.15178 ⋅ γ i−0.84573 . . . . . . . . . . . . . . . . . . . . . . (7)

p (M ) =
{
( M − η )α −1 exp − ( M − η ) / β  }
, . . . . . . . . . . . . . . . (1) Assuming a constant characterization factor, K, for each
β α Γ (α ) SCN group, the specific gravity can be calculated by solving
Equation 7 for γi.
where Γ is the gamma function and β is given by
1
−
M C7+ − η
 K  0.84573

β= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2) γi =  0.15178 
. . . . . . . . . . . . . . . . . . . . . (8)
α  4.5579 ⋅ M i 

The frequency of occurrence is calculated within SCN The value of K must be chosen so that the experimentally
molecular weight midpoints Mi and Mi-1. measured specific gravity of the plus fraction is calculated
correctly with the following equation:
Mi

fi = ∫ p ( M )dM = P ( M i ) − P ( M i −1 ) . . . . . . . . . . . . . (3) z plus ⋅ M plus

M i −1 γ plus = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (9)
m
zi ⋅ M i
∑ γi
Finally, the mole fraction, zi, of each SCN is calculated by i =1

multiplying the mole fraction of the plus fraction by the

respective cumulative frequency of occurrence of the SCN. Combining Equation 8 into Equation 9 gives

zi = z plus ⋅ fi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (4) z plus ⋅ M plus

γ plus = 1
. . . . . . . . . (10)
−
m
 4.5579 ⋅ M 0.15178
 0.84573
Three parameters define the gamma distribution: α, η, and ∑z ⋅M i i 
K
i

MC7+. The value of α affects the shape of the distribution; in i =1  
this study, it is set equal to unity, which results in an
exponential distribution. This is in accord with experimental Equation 10 can be rearranged to allow direct calculation
determination of compositions of naturally occurring of the characterization factor, K,
petroleum fluids. The parameter η is calculated as the average
−0.84573
molecular weight between the first single carbon number  ξ ⋅ γ plus 
group at which the molar extension starts and the previous K=  , . . . . . . . . . . . . . . . . . . . . . . . . (11)
SCN group. For instance, if the plus fraction is C7+, η is 90,  z plus ⋅ M plus 
the average molecular weight between SCN6 and SCN7.
Likewise, the midpoints between SCN molecular weights where the constant ξ is
given in Table 1 are used as the lower and upper limits for the
1
calculation of the frequency of occurrence of each SCN. m −

ξ = ∑ 4.5579 ⋅ M
0.84573
After applying the gamma distribution to calculate the
0.15178
i
 ⋅ zi ⋅ M i . . . . . . . . . . . . . . (12)
i =1
mole fraction of each SCN group, mole fraction of the
heaviest SCN or residue is calculated. If the plus fraction is
The value of the characterization factor, K, is used in
extended to SCN45, this fraction will be the heaviest fraction
Equation 8 to calculate the specific gravity of each SCN, thus
or residue.
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION
preserving the measured value of the specific gravity of the
plus fraction.
This procedure results in a fifty-component mixture:
SCN7 to SCN45, the intermediates (including i-butane and i-
pentane), methane, and the three nonhydrocarbon components.
Each SCN is assigned a composition, mole fraction (Equation
4 or 5), a molecular weight (Table 1 or Equation 6), and a
specific calculated gravity (Equation 8).
Figure 1 shows the extension of the plus fraction to SCN45
for Fluid 10 using this procedure. The relatively large mole
fraction assigned to SCN45 is typically observed when the
plus fraction of petroleum fluids is extended as SCN45
becomes the heaviest fraction, the residue.
Match the Saturation Pressure Using the
Extended Composition
The accuracy of the experimental data has a great
influence on the gas-liquid equilibria. The procedure for
measuring the molecular weight of the plus fraction is not
particularly accurate. A 20% experimental error is most likely
inherent to the molecular weight determination. Consequently,
it is reasonable to use the molecular weight of the plus fraction
as a tuning parameter.5,6,7,8
The molecular weights of the plus fractions of the ten fluid
samples utilized in this study were adjusted to cause the
saturation pressure (calculated with the EOS using the
extended composition) to match the experimental
saturation pressure.
The laboratory analysis measures the fluid composition in
weight fraction, while EOS calculations require the
composition in mole fraction. When the molecular weight of
any component is changed, the mole fractions must be
recalculated. Therefore, the accuracy of the molar composition
to be used in phase behavior calculations depends on the
accuracy of the determination of the molecular weight of the
plus fraction.
Once the molecular weight of the plus fraction is adjusted,
the molar composition of the mixture is recalculated. The
molecular weights of each component and the plus fraction are
needed to convert measured weight fractions into
corresponding mole fractions.
The following rationale was followed to match the
saturation pressure by adjusting the molecular weight of the
heaviest SCN. First, the apparent molecular weight of the
fluid is calculated with the following equation:
n
M a = ∑ zi M i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (13)
i =1
Then the weight fraction of each component in the fluid is
determined using the reported mole fractions.
zi M i
wi = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (14a)
Ma
3
Equations 13 and 14a show that the weight fraction of each
component in the fluid is related to the molecular weights and
mole fractions of all the other components. The weight
fractions are maintained constant, and the molar composition
is recalculated with each change in the molecular weight of
the plus fraction.
Modifying the apparent molecular weight of the fluid is
more convenient, since this has the same effect as modifying
the molecular weight of the plus fraction.
The new molar composition of all components except the
plus fraction is calculated after each adjustment of the
apparent molecular weight of the fluid.
wi M a
zi = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (14b)
Mi
Then the mole fraction of the plus fraction is calculated to
yield unity.
n −1
z plus = 1 − ∑ zi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (15)
i =1
Next, molecular weight of the plus fraction is calculated.
n −1
M a − ∑ zi M i
M plus = i =1
. . . . . . . . . . . . . . . . . . . . . . . . (16)
z plus
The new mole fraction and molecular weight of the plus
fraction are extended to SCN 45 with the gamma distribution.
The mole fraction of SCN45 is calculated with
S −1
zSCN 45 = z plus − ∑ zi . . . . . . . . . . . . . . . . . . . . . . . . . . (17)
i =1
And the molecular weight of SCN45 is then calculated.
S −1
M plus − ∑ zi M i
M SCN 45 = i =1
. . . . . . . . . . . . . . . . . . . . . (18)
z SCN 45
Finally, the EOS is used with the new molar composition
to calculate the saturation pressure. The apparent molecular
weight is changed until the calculated saturation pressure
equals the measured saturation pressure.
Figure 2 shows the calculated saturation pressure for each
adjustment of the molecular weight of the plus fraction for
Fluid 10. The measured saturation pressure is matched by
adjusting the molecular weight of the heptanes plus to 198.56
lb/lb-mol.
4 R. AGUILAR ZURITA AND W. MCCAIN
Assign Critical Properties to the Components of the
Extended Composition
Several correlations of critical temperature, Tc, critical
pressure, pc, and acentric factor, ω, for each SCN are available
in the literature. The most commonly used correlations have
been evaluated. The criterion for selecting critical property
correlations is to prefer the correlations that result in the least
adjustment of the molecular weight of the plus fraction in
matching the measured saturation pressure.
Critical pressure and critical temperature were calculated
by means of the following correlations: Riazi-Daubert,9
Twu,10 Cavett,11 Lee-Kesler,12 Riazi-Al-Hassaf,13 and
Pedersen, et al.5 The correlations of Lee-Kesler,12 Kesler-
Lee,14 Edminister,15 Pedersen, et al.,5 and Riazi-Al-Hassaf13
were used to assign acentric factors to each SCN.
The combination of Cavett correlations for critical
temperature and critical pressure with Riazi-Al-Hassaf
acentric factor correlation yielded the best results. The
adjustment of the molecular weight of the plus fraction ranges
between 0.35% and 25.7% for the ten fluids. This is
consistent with the expected experimental error.
The Cavett11 equations for calculating critical pressure and
critical temperature for each SCN are functions of the normal
boiling point and the specific gravity of each SCN.
The Riazi-Al-Hassaf13 correlation for acentric factor is
simply a function of the molecular weight assigned to
each SCN.
Figure 3 shows the critical temperature, critical pressure,
and acentric factor calculated for each SCN of the extended
composition of Fluid 10 obtained with Cavett and Riazi-Al-
Hassaf correlations. These values were used in the match of
the saturation pressure.
Table 2 shows the extent of the PVT analysis for each
fluid, the measured molecular weight of the plus fraction, the
apparent molecular weight of the total fluid, the measured
saturation pressure, reservoir temperature, and mole percent of
the C7+ fraction. Table 3 gives the saturation pressure
calculated with the extended composition and the magnitude
of the adjustment of the molecular weight of the plus fraction
required to achieve the match of the measured saturation
pressure. Table 3 also shows the altered value of mole
function of C7+.
The magnitude of the adjustment of the molecular weight
of the plus fraction required to match the measured saturation
pressure depends on the choice of equation of state, the
number of pseudocomponents representing the plus fraction,
the selection of critical property correlations, and the accuracy
of experimental data.6
Binary Interaction Coefficients. Most equations of state
allow the selection of binary interaction coefficients (BIC) for
each pair of components.16
Binary interaction coefficients between hydrocarbon
components are set to zero in this study. Binary interaction
coefficients are set nonzero for hydrocarbon to
nonhydrocarbon interactions. The binary interaction
SPE 77382
coefficients used with the Peng-Robinson equation of state
(PREOS) are displayed in Table 4.
Group SCN into MCN
Several authors4,5,17,18,19,20,21,22,23 have given recommend-
tions on procedures to group the single-carbon-number
fractions into multiple-carbon-number groups, MCN, for
simulation purposes. The reason for grouping the SCN groups
into MCN groups is to save computational time. Although the
improvement of computers and microprocessors allows more
flexibility on the number of components, the use of 47
components to represent the hydrocarbon portion of a fluid is
still impractical in compositional simulation.
In this study, the light fractions have been grouped
following the suggestions of Pedersen, et al.5 Accordingly,
methane and nonhydrocarbon components are left as pure
components, and the intermediates are grouped into two
pseudocomponents. The extended composition representing
the heptanes plus fraction is grouped into two MCN.
The fluid composition in this study is represented by eight
components or less, depending on the presence of
nonhydrocarbons. The resulting components after grouping
are H2S, CO2, N2, C1, C2-C3, C4-C6, MCN1, and MCN2.
Thus, the n components of the extended composition (n ≤ 50)
have been grouped into N pseudocomponents (N ≤ 8).
Assign Critical Properties to the MCN. Leibovici’s24
method determines the critical properties of each MCN using
the equation of state mixing rules to minimize the changes to
the grouped EOS parameters a and b which had been
calculated previously with the extended composition.
The Leibovici equations for critical temperature and
critical pressure of each MCN when the term a is a function of
temperature and includes binary interaction coefficients and b
is neither a function of temperature nor binary interaction
coefficients are
Tcm2 m m TciTcj
= ∑∑ zi z j α i (Tcm )α j (Tcm ) (1 − kij ) . . (19)
pcm i =1 j =1 pci pcj
Tcm m
T
= ∑ zi ci . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (20)
pcm i =1 pci
These equations can be combined to eliminate pcm.
However, the resulting equation cannot be solved directly for
the critical temperature of each MCN Tcm because the values
of α in Equation 19 depend on Tcm. The equation is solved
iteratively using an initial trial value of
m m TciTcj
∑∑
i =1 j =1 pci pcj
Tcm = . . . . . . . . . . . . . . . . . . . . . . . . . (21)
m
T
∑
i =1
zi ci
pci
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION 5

Once Tcm is known, Equation 20 gives the critical pressure, αm − 1

pcm, of the MCN. With these values of critical temperature mm = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (25b)
and critical pressure, the values of the constants for each 1 − 0.7
MCN, acm and bm, can be determined with
The larger root obtained from Equation 26a is the correct
RT 2 2 acentric factor of the MCN, ωm.
acm = 0.45724 cm
. . . . . . . . . . . . . . . . . . . . . . . . . . (22) This technique was used for grouping C2-C3 and C4-C6,
pcm as well as for the MCNs.
These procedures for grouping Tc, pc, and ω worked well.
and However, the saturation pressures calculated with the grouped
composition were slightly altered from the previously matched
RTcm values. Consequently, the EOS parameters, a and b, that
bm = 0.07780 . . . . . . . . . . . . . . . . . . . . . . . . . . . (23)
pcm previously matched the measured saturation pressure were not
preserved after regrouping.
Twu and Coon25 derived an equation to determine the
temperature dependent term, αm, for each MCN. Preserve the match of the saturation pressure. In this
section a methodology is presented that allows preservation of
the EOS parameters, a and b, of the extended composition that
m m TciTcj
∑∑ z z i j α i (T )α j (T ) (1 − kij ) previously matched the saturation pressure, considering that
i =1 j =1 pci pcj the n components of the extended composition have been
α m (T ) = . . . (24) grouped into N pseudocomponents.
Tcm2
The methodology modifies only the critical properties of
pcm the heaviest MCN group, MCN+; the critical properties of the
other MCN groups retain the values with
They proposed a simplified procedure to calculate the Leibovici’s methodology.
acentric factors for the MCN groups. The temperature In order for the match of saturation pressure to be
dependent term, αi, of each component in the MCN is preserved, the value of constant a must be the same when
computed at Tm = 0.7 Tcm. calculated with the extended composition, aextended, or the
grouped composition, agrouped, as follows:
2
   T 1/ 2  
α i (Tm ) = 1 + m 1 −  m    , . . . . . . . . . . . . . . . . (25)
 1
n n 2
   Tci    aextended = ∑∑ zi z j ( ai a j ) (1 − k ) , . . . . . . . . . . . . . (27)
   i =1 j =1
ij

where where
m = 0.37464 + 1.54226ω - 0.2699ω2 . . . . . . . . . . . . . (26)
ai = aciα i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (28)
The value of αm of the MCN is then obtained from
Equation 24. Then the acentric factor, ωm, of the MCN is R 2Tci2
obtained using Equations 25a and 26a. aci = 0.45724 . . . . . . .. . . . . . . . . . . . . . . . . . . . (29)
pci
The slope of the temperature dependence relation, mm, can
be obtained by rearrangement of the defining equation,
as follows: Combining Equations 27 through 29 results in Equation 30:

n n
αi α j
⋅ ( 1 − kij ) . . (30)
2
   T 1/ 2   aextended = 0.45724 ⋅ R 2 ⋅ ∑∑ zi ⋅ z j ⋅ Tci ⋅ Tcj ⋅ ⋅
α m (Tm ) = 1 + mm 1 −  m    . . . . . . . . . . . . . . . (25a) i =1 j =1 pci pcj
   Tcm   
  
Define a term Z with
and, finally, the acentric factor for each MCN is
calculated with αi
Z i = zi ⋅ Tci ⋅ . . . . . . . . . . . . . . . . . . . . . . . . . . . . (31)
pci
0.26992ω m2 − 1.54226ω m − ( 0.37464 + mm ) = 0 , . . . . (26a)

where
6 R. AGUILAR ZURITA AND W. MCCAIN SPE 77382

Using the definition of Equation 31 in Equation 30: In order to preserve the match of saturation, the values of
bgrouped and bextended must be the same.
n n The EOS parameter b of the fluid after grouping is
aextended = 0.45724 ⋅ R 2 ⋅ ∑∑ Ζ i ⋅ Ζ j ⋅ ( 1 − kij ) . . . . . . (32) calculated with
i =1 j = 1

N
The EOS parameter a after grouping is given by bgrouped = ∑ zi bi , . . . . . . . . . . . . . . . . . . .. . . . . . . . . . (40)
i =1
N N
agrouped = 0.45724 ⋅ R 2 ⋅ ∑∑ Ζ i ⋅ Ζ j ⋅ ( 1 − kij ) . . . . . . . (33) where
i =1 j = 1

RTci
Removing terms pertaining to MCN+ from the bi = 0.07780 . . . . . . . . . . . . . . . . . . . . . . . . . . . . (41)
double summation: pci

 N −1 N −1 Thus,
agrouped = 0.45724 ⋅ R 2 ⋅  ∑ ∑ Z i ⋅ Z j ⋅ ( 1 − kij ) +
 i =1 j =1 N
Tci
bgrouped = 0.07780 ⋅ R ⋅ ∑ zi ⋅ . . . . . . . . . . . . . . . . . (42)
N −1
 pci
2 ⋅ Z MCN + ⋅ ∑ Z i ⋅ ( 1 − kMNC +⋅i ) + Z MCN
2
+  . . . . . . . . . . . . (34)
i =1

i =1 
When the heaviest fraction in Equation 42 is isolated,

Equating Equations 32 and 34, i.e., aextended = agrouped, and  N −1 T Tc 

rearranging Equation 48a and simplifying gives bgrouped = 0.07780 ⋅ R ⋅  ∑ zi ⋅ ci + z MCN + MCN +  . . . . (43)
 i =1 pci pcMCN + 
N −1

+ + 2 ⋅ Z MCN + ⋅ ∑ Z i ⋅ ( 1 − k MCN +⋅i )

2
Z MCN Introducing a correction factor, Ψb, in Equation 43 yields
1
N −1 N −1 n n
+ ∑ ∑ Z i ⋅ Z j ⋅ ( 1 − kij ) − ∑∑ Z i ⋅ Z j ⋅ ( 1 − kij ) = 0 . . (35)  N −1 T Tc 
i =1 j =1 i =1 j =1 bgrouped = 0.07780 ⋅ R ⋅  ∑ zi ⋅ ci +Ψ b ⋅ z MCN MCN  . . (44)
 i =1 pci pcMCN 
Define the following constants:
The correction factor, Ψb, only affects the ratio of the
N −1 critical temperature to the critical pressure for the heaviest
A = 2 ⋅ ∑ Z i ⋅ ( 1 − k MNC +⋅i ) . . . . . . . . . . . . . . . . . . . . . . (36) pseudocomponent MCN+.
i =1
The b parameter of the extended composition is equated to
N −1 N −1 n n
the b parameter of the grouped composition, bextended = bgrouped,
B = ∑ ∑ Z i ⋅ Z j ⋅ ( 1 − kij ) − ∑∑ Z i ⋅ Z j ⋅ ( 1 − kij ) . . . (37) resulting in
i =1 j =1 i =1 j = 1
n
Tci  N −1 T Tc 
0.07780 ⋅ R ⋅ ∑ xi ⋅ = 0.07780 ⋅ R ⋅  ∑ xi ⋅ ci +Ψ b ⋅ x MCN + ⋅ MCN +  . . (45)
When Equations 36 and 37 are combined with Equation i =1 pci  i =1 pci pcMCN + 
35, a quadratic equation in ZMCN+ is observed:
Rearrange and simplify
+ + A ⋅ Z MCN + + B = 0 . . . . . . . . . . . . . . . . . . . . . . (38)
2
Z MCN
N −1
n
Tci Tci
Solving Equation 38 will always yield two roots, one TcMCN + ∑z ⋅ p
i =1
i − ∑ zi ⋅
i =1 pci
positive and one negative. The positive root is used for the = ci
. . . . . . . . . . . . . . . . . . (46)
pcMCN + Ψb ⋅z +
next calculations. MCN

TcMCN + Z MCN + Finally, the critical pressure and critical temperature of the
= . . . . . . . . . . . . . . . . . . . (39) MCN+, which will preserve the saturation pressure match, are
(p )
1/ 2
cMCN +
zMCN + ⋅ α MCN + calculated using Equations 39 and 46.
Define a term C as the reciprocal of the right-hand side of
αMCN+ in Equation 39 is the acentric factor obtained from Equation 46, as follows:
the Twu and Coon method.
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION
Ψb ⋅z
C= MCN
. . . . . . . . . . . . . . . . . . . . . (47)
n
Tci N −1 Tci
∑ z i ⋅ − ∑i p
pci i =1
z ⋅
i =1 ci
Thus, Equation 46 becomes
pcMCN = C ⋅ TcMCN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (46a)
Combining Equations 46a and Equation 39 yields
TcMCN + Z MCN +
= . . . . . . . . . (48)
( )
1/ 2
C ⋅ Tc MCN + C ⋅ Tc MCN + z MCN + ⋅ α MCN +
Finally, the critical temperature of MCN+ is calculated by
rearranging Equation 48 as
2
 Z ⋅ C  occurring petroleum fluids that were studied.
TcMCN =  MCN  . . . . . . . . . . . . . . . . . . . . . (48a)
 z MCN ⋅ α MCN 
The critical pressure of MCN+ is then calculated using the
critical temperature from Equation 48a with Equation 46a.
The optimum correction factor, Ψb, is found by iteration to
rematch the saturation pressure. The correction factor, Ψb,
modifies the ratio of the critical properties of MCN+ by less
than 5% of the values calculated with Leibovici’s method for
each of the fluids studied. The introduction of this correction
factor always yields a perfect match of the saturation pressure.
The saturation pressure for Fluid 10 was calculated using
eight different grouping schemes. The measured dewpoint
pressure for Fluid 10 was 6024.7 psia. Table 5 shows the
correction factor and the calculated saturation pressure for
each grouping scheme. The match of the saturation pressure is
excellent. The grouping schemes were obtained by grouping
the SCN groups in the two MCN. The intention of this table is
to show that the correction factor, Ψb, is very efficient to
maintain the match of the saturation pressure, regardless of the
grouping scheme. Consequently, the grouping scheme
becomes trivial when matching the saturation pressure.
Unfortunately, grouping schemes 1 and 2 predicted
bubblepoint pressures.
EFFECT OF GROUPING
The grouping scheme has a strong influence on the
calculated critical point of the fluid. The critical point for
Fluid 10 was calculated with the PREOS using the same
grouping schemes given in Table 5. The resulting critical
points are tabulated in Table 6. The calculated critical
temperature and critical pressure of the fluid change
significantly with each grouping scheme.
Figure 4 shows how the calculated critical point shifts
when different grouping schemes are selected for Fluid 10, a
retrograde gas. Also observed is that the prediction of fluid
7
type using the PREOS for Fluid 10 changes from dewpoint
gas to bubblepoint oil as a consequence of the grouping
scheme. The grouping schemes that yielded a calculated
bubble point instead of a dew point were the equal-weight and
equal-mol scheme, two popular techniques.
The location of the critical point determines the
distribution of the isovolume lines (saturation lines) in the
two-phase region of the resulting phase diagram. Therefore,
the grouping scheme is very important when laboratory
volumetric data are being matched.
RECOMMENDED GROUPING SCHEME
The best grouping scheme was achieved by grouping the
C7+ fraction into two MCN groups. The weight fraction of the
C7+ was distributed in different proportions between the two
MCN groups to find the distribution that (after regession, to be
discussed later) gave minimum deviation between the
calculated results and the experimental data. Table 7 gives the
optimum grouping schemes for each of the ten naturally
When the results are plotted, as shown in Figure 5, a trend
can be observed in the mole fraction assigned to MCN2,
depending on the mole fraction of heptanes plus in the fluid
(after the saturation pressure has been matched). Larger mole
fractions are assigned to MCN2, the heaviest fraction, for
volatile oils than those for retrograde gases.
The following correlation has been established to
determine the correct mole fraction that has to be assigned to
MCN2 in order to get a good match of volumetric data. The
statistical correlation coefficient, R2, of this correlation
is 0.990.
0.028686608
zMCN 2 = . . . . . . . . . . . . . (49)
1 + 335.91986 ⋅ e−56.345274⋅ zC 7 +
The mole fraction of MCN1 is consequently the difference
between the heptanes plus mole fraction and the mole fraction
of MCN2 calculated with Equation 49.
zMCN 1 = zC 7 + − zMCN 2 . . . . . . . . . . . . . . . . . . . . . . . . . . (50)
Although excellent results are obtained with only two
MCN groups and the proposed MCN composition correlation,
in some cases, splitting MCN1 into two groups may improve
the match of volumetric data.
In the event that there is not a satisfactory agreement with
the laboratory data, the MCN1 group may be split into two
MCN groups: MCN1a and MCN1b, where MCN1a is the
lighter of the two pseudocomponents. For volatile oils,
approximately 60% of the former MCN1 mole fraction should
be assigned to the MCN1b group and 40% to MCN1a. For
retrograde gases only 5% of the former MCN1 mole fraction
should be assigned to MCN1b, and the remaining 95% has to
be assigned to MCN1a. For both cases, the mole fraction of
MCN2 is held constant.
8 R. AGUILAR ZURITA AND W. MCCAIN
The values of MCN1 of Fluid 1 and Fluid 10 (volatile oil
and retrograde gas, respectively) have been split into values of
MCN1a and MCN1b, as shown in Table 8. The match of the
laboratory data improved with the new grouping scheme for
these particular fluids. However, the other eight fluids splitting
MCN1 into two MCN did not show further improvement of
the match.
MATCHING PVT DATA
In the previous sections the problem of how to prepare the
equation of state for simulation has been addressed. The plus
fraction has been extended, the measured saturation pressure
has been matched, the extended composition has been grouped
into pseudocomponents, and the critical properties and
acentric factors of the pseudocomponents have been assigned.
At this point, the equation of state is ready to simulate the
laboratory experiments. This is the most important step; if the
selected EOS can reproduce the volumetric data, then it is
ready to be used in compositional simulation.
However, an equation of state is expected to fail to
accurately reproduce the measured PVT data because of its
deficiency in calculating liquid density. Thus, volume
translation parameters are introduced in the PREOS to correct
this deficiency.
VOLUME TRANSLATION PARAMETER
Peneloux2 demonstrated that the introduction of volume
shift parameters in cubic equations of state, like the PREOS,
does not affect the vapor-liquid equilibria calculations and
therefore does not affect the original gas-liquid equilibria
capability of the equation of state. Yet these volume
translation parameters improve the volumetric capability of
the equations of state.
These volume translation parameters are, in fact,
correction terms applied to the molar volume calculated with
the equation of state.
m
vL = vLEOS − ∑ xi ⋅ ci . . . . . . . . . . . . . . . . . . . . . . . . . . . (51)
i =1
m temperature and critical pressure and the Riazi-Al-
vv = vvEOS − ∑ yi ⋅ ci . . . . . . . . . . . . . . . . . . . . . . . . . . . (52)
i =1
vLEOS and vvEOS are the EOS-calculated liquid and vapor
molar volumes, respectively, and ci is the volume translation
parameter of each component. Jheveri and Youngren3 wrote ci
as a dimonesionless ratio as
si = ci / bi, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (53)
where bi is the equation of state constant given in Equation 23.
The only regression variables used to match the volumetric
data are these volume translation parameters.
Initial trial values are taken from Table 9 for the pure
components and from
SPE 77382
si = 1 − A0 / M A1 , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (54)
where the values of A0 and A1 may be found in Table 10.
These initial values yield close agreement with
experimental data. However, using the volume shift
parameters of all components as regression variables further
improves the match of volumetric data.
The prediction of volumetric data after using the volume
translation parameters as regression variables is shown in
Figures 6–11 for Fluid 10. It can be observed that regression
on the volume translations parameters is sufficient to match
the laboratory data. The matches of calculated results and
experimental data work equally as well for the other
nine fluids.
The ten fluids used in this study had different geographical
origins and the laboratory measurements were from various
service companies, yet the experimental data have been
matched satisfactorily for every fluid.
The good agreement with experimental data, despite the
diversity of the fluids, is a clear indication that the proposed
strategy for preparing an equation of state for use in
compositional simulation is robust and accurate.
CONCLUSIONS
A new tuning strategy is proposed in this study that is
applicable to any naturally occurring petroleum fluid. This
tuning strategy is simple and requires the modification of only
one parameter in each step of the fluid characterization, i.e.,
matching the saturation pressure, grouping, and matching
volumetric data. In this research PVT data of ten naturally
occurring petroleum fluids have been studied. From this
experience the following conclusions can be drawn:
1. Adjusting only the molecular weight of the plus
fraction is sufficient to obtain a perfect match of the
saturation pressure. This adjustment falls within the
experimental error expected in the measurement of
molecular weight. Thus, changing the molecular
weight of the plus fraction is logical and acceptable.
2. Calculating critical properties of each SCN after
splitting with Cavett’s equation for critical
Hassaf equation for acentric factor resulted in the
smallest modification of the molecular weight of the
plus fraction required to match the measured
saturation pressure.
3. Setting the binary interaction coefficients to zero for
hydrocarbon-to-hydrocarbon interactions and nonzero
for nonhydrocarbon-to-hydrocarbon interactions
reduces the computational time and gives excellent
results.
4. Grouping the light fractions as suggested by Pedersen,
et al., along with two MCN groups representing the
C7+ fraction saves computational time and yields
excellent results.
5. Assigning the mole fraction of the heaviest fraction,
MCN2, with Equation 49 results in good agreement
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION 9

with PVT data after regression is performed for GREEK

volatile oils and gas condensates. α = Shape constant in the gamma distribution
6. Splitting MCN1 into MCN1a and MCN1b may α( ) = Temperature-dependent equation-of-state parameter
improve the match of volumetric data. Approximately β = Gamma distribution parameter given by Equation 2
60% and 5% of the former MCN1 mole fraction γ = Specific gravity, 60/60
should be assigned to the MCN1b pseudocomponent Γ = Gamma distribution
for volatile oils and retrograde gases, respectively. η = Gamma distribution parameter
7. Properly distributing the SCN into the two MCN
ω = Acentric factor
groups is of vital importance because the grouping
Ωa = Equation-of-state constant
scheme has a strong influence on the calculated
critical locus. Thus, the grouping scheme affects the Ωb = Equation-of-state constant
performance of regression on volumetric data. ξ = Constant defined in Equation 12
8. Holding the matched saturation pressure after ψb = Correction factor, dimensionless
regrouping is not a problem if the proposed correction
factor is introduced into Leibovici’s methodology for SUBSCRIPTS
calculating the critical properties of the MCN groups. grouped = Grouped composition
9. Using the volume translation parameters as regression extended = Extended composition
variables to match volumetric data from CCE, CVD plus = Plus fraction
and DL experiments is sufficient to yield excellent C7+ = Heptanes plus
results, provided that the suggested grouping scheme MCN+ = Heaviest MCN
for the SCN is applied. SCN45 = Single carbon number group 45
i = Component i
NOMENCLATURE j = Component j
a = Temperature-dependent equation-of-state parameter m = MCN group
A = Constant defined in Equation 36
ac = Equation-of-state constant independent SUPERSCRIPTS
of temperature EOS = Equation of state
b = Equation-of-state parameter
B = Constant defined in Equation 37 ABBREVIATIONS
C = Constant defined in Equation 47 SCN Single carbon number group
fi = Cumulative frequency of occurrence for component i MCN Multiple carbon number group
K = Watson characterization factor PREOS Peng-Robinson Equation-of-state
kij = Binary interaction coefficient between components i CCE Constant composition expansion
and j CVD Constant volume depletion
m = Number of components in MCN H2S Hydrogen sulfide
M = Molecular weight, lb/lb-mol CO2 Carbon dioxide
Ma = Apparent molecular weight, lb/lb-mol N2 Nitrogen
Mplus = Molecular weight of plus fraction, lb/lb-mol C1 Methane
n = Number of components C2 Ethane
N = Total number of components after grouping C3 Propane
p ( ) = Probability density function iC4 Isobutane
psat = Saturation pressure, psia nC4 Normal butane
pc = Critical pressure, psia iC5 Isopentane
R = Universal gas constant (10.73146 psia-cu.ft/°R-lbm nC5 Normal pentane
mol) C6 Hexane
s = Volume shift parameter. C7+ Heptanes plus
T = Temperature, °R C10+ Decanes plus
Tb = Normal boiling temperature, °R C11+ Undecanes plus
Tc = Critical temperature, °R C20+ Eicosanes plus
Tr = Reduced temperature C30+ Triacontanes plus
wi = Weight fraction of component i
zi = Mole fraction of component i
Zi = Constant defined for each component by Equation 31
10 R. AGUILAR ZURITA AND W. MCCAIN SPE 77382

References 18. Chorn, L.G., and Mansoori, A. (eds.): “C7+ Fraction

1. Peng, D.Y., and Robinson, D.B.: “A New Two Constant Characterization”, Taylor and Francis, New York (1989).
Equation of State,” Ind. Eng. Chem. Fundam. (1976) Vol. 19. Neau, E., and Jaubert, J.N.: “Characterization of Heavy
15, No. 1, 59–64. Oils,” Ind. Eng. Chem. Res. (1993) Vol. 32, 1196–1203.
2. Peneloux, A., and Rauzy, E.: “A Consistent Correction 20. Shariati, A., Peters, C.J., and Moshfeghian, M.: “A
for Redlich-Kwong-Soave Volumes,” Fluid Phase Systematic Approach to Characterize Gas Condensates
Equilibria (1982) Vol. 8, 7–23. and Light Petroleum Fractions,” Fluid Phase Equilibria
3. Jheveri, B.S., and Youngren, G.K.: “Three-Parameter (1999) Vol. 154, 165–179.
Modification of the Peng-Robinson Equation of State to 21. Manafi, H., Mansoori, G.A., and Ghotbi, S.: “Phase
Improve Volumetric Predictions,” SPERE (August 1982) Behavior Prediction of Petroleum Fluids with Minimum
Vol. 8, 7–23. Characterization Data,” J. Pet. Sci. Eng. (1999),
4. Whitson, C.H.: “Characterizing Hydrocarbon Plus Vol. 22, 67–93.
Fractions,” Soc. Pet. Eng. J. (August 1983), 683–693. 22. Avaullee, L., Trassy, E., Neau, E., and Jaubert, J.N.:
5. Pedersen, K.S., Thomassen, P., and Fredenslund, A.: “Thermodynamic Modeling for Petroleum Fluids I.
Properties of Oils and Natural Gases, Contributions in Equation of State and Group Contribution for The
Petroleum Geology and Engineering, Gulf Publishing Estimation of Thermodynamic Parameters of Heavy
Co., Houston (1989) Vol. 5. Hydrocarbons,” Fluid Phase Equilibria (1997)
6. Thomassen, P., Pedersen, K.S., and Fredenslund, A.: Vol. 139, 155–170.
“Adjustment of C7+ Molecular Weights in the 23. Danesh, A., Xu, D., and Todd, C.: “A Grouping Method
Characterization of Petroleum Mixtures Containing to Optimize Oil Description for Compositional Simulation
Heavy Hydrocarbons,” paper SPE 16036 available from of Gas-Injection Processes,” SPERE (August 1992)
SPE, Richardson, TX. 343–348.
7. Guo, T.M., and Du, L.: “New Three-Parameter Cubic 24. Leibovici, C.F.: “A Consistent Procedure for the
Equation of State for Reservoir Fluids: Part 3— Estimation of Properties Associated to Lumped Systems,”
Application to Gas Condensates,” paper SPE 19374 Fluid Phase Equilibria (1993) Vol. 87, 189–197.
available from SPE, Richardson, TX. 25. Twu, C.H., and Coon, J.E.: “An Internally Consistent
8. Wang, P.: “Prediction of Phase Behavior for Gas Approach for Determining the Properties of Lumped
Condensate,” paper SPE 19503 available from SPE, Components Using a Cubic Equation of State,” Fluid
Richardson, TX. Phase Equilibria (1996) Vol. 117, 233–240.
9. Riazi, M.R., and Daubert, T.E.: “Simplify Property
Predictions,” Hydro. Proc. (March 1980) 115–116.
10. 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) Vol. 16, 137–150.
11. Cavett, R.H.: “Physical Data for Distillation
Calculations—Vapor-Liquid Equilibrium,” Proc., 27th
Annual Meeting, API, Dallas (1962) 351–66.
12. Lee, B.I., and Kesler, M.G.: “A Generalized
Thermodynamic Correlation Based on Three-Parameter
Corresponding State,” AIChE J. (1975) Vol. 21, 510–515.
13. Raizi, M.R., and Al-Hassaf, T.A.: “Physical Properties of
Heavy Petroleum Fractions and Crude Oils,” Fluid Phase
Equilibria (1996), Vol. 117, 217–224.
14. Kesler, M.G., and Lee, B.I.: “Improve Prediction of
Enthalpy of Fractions,” Hydro. Proc. (March 1976) Vol.
55, 153–158.
15. Edminister, W.C.: “Applied Hydrocarbon
Thermodynamics, Part 4: Compressibility Factors and
Equations of State,” Pet. Ref. (April 1958)
Vol. 37, 173–175.
16. McCain, W.D., Jr.: The Properties of Petroleum Fluids,
2nd ed., PennWell Books, Tulsa (1990).
17. Wu, R.S., and Fish, R.M.: “C7+ Characterization for
Fluid Properties Predictions,” JCPT (July 1989),
112–117.
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION 11

TABLE 1. GENERALIZED SCN PHYSICAL PROPERTIES4 TABLE 3. CALCULATED SATURATION PRESSURE WITH
EXTENDED COMPOSITION
Normal Boiling- C7+, Variation,
Specific Molecular
SCN point Temperature, Fluid Ma Mplus PSat, psia
Gravity, 60/60 weight, lb/lb-mol mol% Mplus%
°R
1 56.6098 351.4 9120.4 13.92 10.63
6 607 0.690 84
2 51.0389 278.6 4671.0 15.04 6.43
7 658 0.727 96
3 54.9462 496.4 7461.0 15.00 19.62
8 702 0.749 107
4 51.7552 207.7 4389.9 12.73 13.48
9 748 0.768 121
5 45.4058 136.5 3324.5 5.22 2.63
10 791 0.782 134
6 32.4254 202.2 5040.1 7.12 3.30
11 829 0.793 147
7 31.2384 150.3 4535.9 6.44 1.54
12 867 0.804 161
8 30.8837 538.4 7523.6 6.11 3.68
13 901 0.815 175
9 32.3306 125.6 3442.7 7.29 –10.26
14 936 0.826 190
15 971 0.836 206 10 37.3500 198.6 6024.6 8.11 25.67
16 1002 0.843 222
17 1032 0.851 237 TABLE 4. BINARY INTERACTION COEFFICIENTS FOR THE
18 1055 0.856 251 PREOS4
19 1077 0.861 263 Component H2S CO2 N2 Hydrocarbon
20 1101 0.866 275
21 1124 0.871 291 H2S 0.000 0.096 0.176 0.050
22 1146 0.876 300 CO2 0.096 0.000 –0.012 0.100
23 1167 0.881 312
24 1187 0.885 324 N2 0.176 –0.012 0.000 0.100
25 1207 0.888 337 Hydrocarbon 0.050 0.100 0.100 0.000
26 1226 0.892 349
27 1244 0.896 360
28 1262 0.899 372 TABLE 5. CORRECTION FACTOR AND CALCULATED
29 1277 0.902 382 SATURATION PRESSURE FOR FLUID 10
30 1294 0.905 394 Grouping MCN1 MCN2
Pdew ,
31 1310 0.909 404
Scheme
mole
weight%
mole
weight%
Ψb psia
32 1326 0.912 415 % %
33 1341 0.915 426 1* 3.61 11.51 4.50 31.63 1.04582 6024.7
34 1355 0.917 437 2** 5.87 22.83 2.24 20.31 1.03703 6025.0
35 1368 0.920 445 3 6.37 26.10 1.74 17.04 1.03798 6024.6
36 1382 0.922 456 4 6.89 29.94 1.22 13.20 1.03868 6024.7
37 1394 0.925 464 5 7.41 34.36 0.71 8.78 1.04157 6024.6
38 1407 0.927 475 6 7.69 37.23 0.43 5.91 1.04225 6024.7
7 7.89 39.63 0.22 3.51 1.04125 6025.0
39 1419 0.929 484
8 7.97 40.68 0.15 2.46 1.03778 6025.0
40 1432 0.931 495
41 1442 0.933 502 *Equal mol
42 1453 0.934 512 **Equal weight
43 1464 0.936 521
44 1477 0.938 531 TABLE 6. LOCATION OF CRITICAL POINTS
45 1487 0.940 539 OF FLUID 10 CALCULATED WITH
DIFFERENT GROUPING SCHEMES
TABLE 2. LABORATORY DATA Grouping Scheme Tc, °F Pc, psia
Satura- 1* 313.1 6105.8
Analysis PSat, TRes, C7+,
Fluid Mplus Ma tion
Extent psia °F mol% 2** 271.0 6076.9
Point
1 C10+ 317.6 56.034 Bubble 9120.0 197 14.8 3 249.2 5995.8
2 C11+ 262.0 50.793 Bubble 4674.7 267 15.4
3 C20+ 415.0 54.520 Bubble 7451.7 190 15.6 4 225.3 5864.8
4 C7+ 183.0 50.880 Bubble 4359.7 276 14.2 5 172.6 5422.7
5 C7+ 133.0 45.405 Dew 3324.7 208 5.35
6 C10+ 195.7 32.385 Dew 5040.0 229 7.23 6 120.2 4765.3
7 C7+ 148.0 31.207 Dew 4535.7 275 6.53 7 69.8 3848.0
8 C30+ 519.3 30.880 Dew 7523.7 298 6.12
9 C7+ 140.0 32.574 Dew 3442.7 200 6.59 8 59.1 3738.7
10 C7+ 158.0 36.587 Dew 6024.7 256 9.99 *Equal mol
**Equal weight
12 R. AGUILAR ZURITA AND W. MCCAIN SPE 77382

TABLE 7. OPTIMUM GROUPING SCHEMES

Fig. 2 Match of saturation pressure for Fluid 10
6100
MCN1, MCN2, Matched
Fluid
mol% mol% Ψb Pdew , psia 6000 saturation
5900 pressure
1 11.31 2.61 1.0336 9120.0
2 12.08 2.96 1.0308 4674.7 5800

Dewpoint pressure, psia

3 12.63 2.37 1.0407 7451.6 5700
4 10.51 2.22 1.0381 4390.2 5600
5 5.11 0.11 1.0705 3324.7
5500
6 6.83 0.29 1.0547 5039.8
7 6.32 0.12 1.0683 4535.6 5400 Measured
8 5.73 0.38 1.0742 7523.3 5300 Mplus
9 6.75 0.54 1.0467 3442.7 5200
10 7.40 0.71 1.0423 6024.6
5100

5000
TABLE 8. SPLIT OF MCN1 150 160 170 180 190 200 210
Plus fraction molecular weight, lb/lb-mol
MCN1a, MCN1b, MCN2,
Fluid
mol% mol% mol%
1 4.52 6.79 2.61
Fig. 3 Critical properties assigned to each SCN of Fluid 10
10 7.03 0.37 0.71
2500.00 2.0000

Critical temperature, °R
TABLE 9. VOLUME TRANSLATION PARAMETERS Critical pressure, psia 1.8000
FOR PURE COMPONENTS Acentric factor

Critical temperature, °R
Components si 2000.00 1.6000

H2S –0.1288
1.4000
C02 –0.0817
N2 –0.1927 1500.00 1.2000

Acentric factor
C1 –0.1595 1.0000

TABLE 10. VOLUME TRANSLATION PARAMETERS 1000.00 0.8000

FOR PSEUDOCOMPONENTS
Critical pressure, psia

Molecular weight of 0.6000

A0 A1
pseudocomponent
M<90 1.4 0.0685 500.00 0.4000

M≥90 2.5 0.20

0.2000

Fig. 1 Calculated mole fraction for each SCN of extended 0.00 0.0000

composition of Fluid 10 0 10 20
SCN
30 40 50

0.0100

Fig. 4 Effect of different grouping schemes on the critical

locus of Fluid 10
8000
SCN mole fraction (logarithm scale)

3 2 1
4
6000
5
Fluid critical pressure, psia

6
0.0010

8 7
4000

2000

Critical point of the mixture

Reservoir temperature

0.0001 0
0 10 20 30 40 50 0 50 100 150 200 250 300 350
Fluid
Fluidcritical
criticaltemperature,
temperature,F°F
SCN
SPE 77382 AN EFFICIENT TUNING STRATEGY TO CALIBRATE CUBIC EOS FOR COMPOSITIONAL SIMULATION 13

Fig. 5 Grouping scheme of the ten fluids studied Fig. 8 Gas compressibility factors from CVD for Fluid 10
1.8

Calculated
1.6
Data
1.4

z-factor
1.2

1.0

0.8

0.6
0 1000 2000 3000 4000 5000 6000 7000
Pressure, psig
Fig. 6 Gas compressibility factors from CCE for Fluid 10
1.7
Fig. 9 Liquid volume from CVD for Fluid 10
Calculated
1.5 0.4
Data Calculated
1.3 Data
0.3
Liquid saturation, fraction
Z-factor

1.1

0.9 0.2

0.7
0.1

0.5
4000 4500 5000 5500 6000 6500 7000 7500 8000
Pressure, psig 0
0 1000 2000 3000 4000 5000 6000 7000
Pressure, psig

Fig. 7 Relative volumes from CCE for Fluid 10

5.0 Fig. 10 Gas recovery from CVD experiment for Fluid 10
Calculated 1
4.0 Calculated
Data
Relative volume, ratio

0.8 Data
3.0
Recovery, fraction

0.6
2.0

0.4
1.0

0.2
0.0
0 1000 2000 3000 4000 5000 6000 7000 8000
Pressure, psig
0
0 1000 2000 3000 4000 5000 6000 7000
Pressure, psig
14 R. AGUILAR ZURITA AND W. MCCAIN SPE 77382

Fig. 11 Two-phase compressibility factors from CVD for 9. Reduce the number of components by grouping them
Fluid 10 into pseudocomponents.
1.4
a. Group the intermediate fractions as follows: C1,
C2-C3, C4-C6.
Calculated b. Add the non-hydrocarbon components as
Data required.
c. Group the heptanes plus fraction into two multiple
1.0
2-phase z-factor

carbon number groups: MCN1 and MCN2.

d. Assign the mole fractions to MCN2 and MCN1
using Equations 49 and 50.
10. Calculate critical temperature and critical pressure of
0.6
each pseudocomponent with Equations 21 and 20.
11. Calculate the acentric factor of each pseudocomponent
with Equations 25, 26, 25a, 25b, and 26a.
12. Preserve the match of the saturation pressure by
0.2
0 1000 2000 3000 4000 5000 6000 7000
adjusting the critical temperature and critical pressure
Pressure. psig of the heaviest MCN, MCN2, with Equations 47, 48
and 46a.
Appendix 13. Match the volumetric data by regressing on the
The following steps should be followed to apply the volume shift parameters of each component of the
proposed tuning strategy: grouped composition. Initial values are taken from
Table 9 or calculated with Equation 54.
1. Use the gamma distribution with α =1 to extended the
plus fraction using equations 1 to 4
2. Assign molecular weights and normal boiling points
to the SCN from Table 1.
3. Calculate mole fraction and molecular weight of the
heaviest SCN with equations 5 and 6 respectively.
4. Calculate the Watson characterization factor with
Equations 11 and 12 to honor the measured specific
gravity of the plus fraction.
5. Calculate the specific gravity of each SCN using
Equation 8.
6. Assign critical pressure, critical temperature, and
acentric factor with the Cavett and Riazi-Al-Hassaf
equations.
7. Calculate the saturation pressure of the fluid using the
extended composition.
8. Adjust the molecular weight of the plus fraction until
the match of the saturation pressure is achieved. After
each adjustment of the apparent molecular weight, the
molar composition of the fluid is recalculated
following these steps:
a. Calculate the weight fraction of each component
with Equation 14a. Hold the composition in
weight fraction constant throughout the
calculations.
b. Calculate the mole fraction of each pure
component in the fluid with Equation 14b.
c. Calculate the mole fraction of the plus fraction
with Equation 15.
d. Calculate the molecular weight of the plus
fraction with Equation 16.
e. Extend the plus fraction and assign critical
properties to each SCN as explained in steps
1 to 7.