ClM-90

021588 A Robust Algorithm for Determining Hydrocarbon PVT

Properties Using a Generalized EOS
A.C. Reynolds, U. of Tulsa; F.M. Guehria, U. of Tulsa;
L.G. Thompson, U. of Tulsa

Copyright 1990 Society of Petroleum Engineers

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 PETROLEUM SOCIETY OF CIM/SOCIETY OF PETROLEUM ENGINEERS PAPER NO. CIMISPE 90-100

21588 THIS IS A PREPRINT - SUBJECT TO CORRECTION

A ROBUST ALGORITHM FOR

DETERMINING HYDROCARBON PVT
PROPERTIES USING A
GENERALIZED EOS

BY
Fawzl M. Guehrla
Leslie G. Thompson
Albert C. Reynolds
Tulsa University

PUBLICATION RIGHTS RESERVED

THIS PAPER IS TO BE PRESENTED AT THE INTERNATIONAL TECHNICAL MEETING JOINTLY HOSTED BY THE
PETROLEUM SOCIETY OF CIM AND THE SOCIETY OF PETROLEUM ENGINEERS IN CALGARY, JUNE 10 TO 13,1990.
DISCUSSION OF THIS PAPER IS INVITED. SUCH DISCUSSION MAY BE PRESENTED AT THE MEETING AND WILL BE
CONSIDERED FOR PUBUCATION IN CIM AND SPE JOURNALS IF FILED IN WRITING WITH THE TECHNICAL PROGRAM
CHAIRMAN PRIOR TO THE CONCLUSION OF THE MEETING.

ABSTRACT whether the system temperature is greater or less than the

This paper presents and discU88es a complete phase
behavior package for determining PVT properties of mix-
tures of hydrocarbon and non-hydrocarbon species com-
monly encountered in the Petroleum Industry. All cal-
culations are performed using a generalized Equation
or State, which upon selection of appropriate parame-
ters, can be used to represent any of five Equations Of
State commonly employed in the Petroleum Industry; Le.,
Redlich - Kwong, Zudkevitch - Joffe - Redlich - Kwong,
Soave - Redlich - Kwong, Peng - Robinson and Schmidt _
Wenzel.
A robust algorithm, which utilizes a combination of
the modified successive substitution and Minimum Vari-
able Newton-Raphson methods, is used to calculate flash
composition and saturation points. The algorithm is opti-
mized to facilitate convergence near the critical point. The
modified successive substitution method is used to deter-
mine the number of phases present at a given pressure and
temperature. A new simple method is used to ascertain
critical temperature. The method does not require esti-
mation of the critical temperature for the specified mix-
ture. Straight forward application of a method proposed
by Baker and Luks allows the user to efficiently compute
all saturation points (Le., a bubble point and a dew point,
or, an upper dew point and a lower dew point) at a given
value of temperature. This latter unique feature enables
the user to define the two-phase envelope without having
to perform a multitude of time consuming flash calcula-
tions. Finally, results from our phase package are com-
pared to those presented previously in the literature in
order to verify the accuracy and efficiency of the compu-
tational procedure.
INTRODUCTION
Calculation of fluid properties and phase equilibria is
important as a general petroleum engineering tool. Nu-
merical computation of phase equilibria using Equations

100-1
 SfE 21588

of State is very important because laboratory analysis is GENERALIZED EOS

expensive and time consuming.
In this work, we discuss a robust phase package that
can be used to perform phase equilibria calculations based
on any of five Equations of State commonly used in the oil
1
industry; that is, the Redlich - Kwong (RK), Zudkevitch-
2
Joffe - Redlich - Kwong (ZJRK), Soave - Redlich - Kwong3
In this major section we show that all five Equations
of State considered here can be written in one generalized
form.
Notation and Mixing Rules
We consider a mixture composed of Ne hydrocarbon
and non-hydrocarbon species. Define Ai and h, as follows:

(SRK), Peng - Robinson 4 (PR) and Schmidt - Wenzel 5

(SW) Equations of State.
a, = O.. " _R2Tn.
_e_,,, i = 1,2, ... N e ; (1)
Pc"
The package is designed to enable the user to generate
a wide variety of fluid properties, such as densities, com- b,' = Ob"·RTc,, .
1= 1 , 2, .•. N c; (2)
Pc"
pressibility factors, and viscosities. Moreover, the package
where Tc", Pc", 0 .. " and Ob" are respectively the critical
offers the option of using one, or a combination of two temperature, critical pressure and van der Waals coeffi-
numerical techniques to solve the single,;tage separation cients for component i. In Eq. (1) n = 2 for the SW, PR
equations that describe the thermodynamic equilibrium of and SRK EOS's and n = 2.5 for the RK and ZJRK EOS.
fluids, depending on whether the mixtures considered are The phase m mixture parameters am and bm are de-
single phase, single phase saturated, or two phase (liquid fined as follows:
and vapor). N. N.

The first numerical technique is a special version of am =L L X"mXj,ma'J; (4)

the commonly known successive substitution method 6 • Its
two major advantages are its ability to detect the single
phase region without having to compute the saturation
pressure, and its simplicity. Unfortunately, this method
converges very slowly (or not at all) near the critical re-
gion. When the successive substitution method is converg-
ing slowly, our computer program automatically switches
to a more robust technique called the Minimum Variable
Newton Raphson (MVNR) method 7 .
The MVNR may be used exclusively provided the
phase region is known a priori. In this case, the pack-
age is capable of determining the saturation pressure P.at
and the equilibrium mole fraction composition of the phase
that develops at Poat, {X'}~~1 or {Y'}~1 where Ne is the
number of components that characterize the fluid. Given
pressure and temperature, the package also can perform
a constant composition flash calculation to determine the
liquid and vapor compositions, and the moles of liquid
and moles of vapor per mole of fluid mixture at any pres-
sure. Finally, the package uses correlations to determine
the phase viscosities s - 11 as functions of pressure, temper-
ature and phase compositions.
i=1 i=1
N.
bm = LXi,mbi' (5)
i=1
where ai,j is determined from the following relationship:
(6)
For the RK and ZJRK equations, ai =1 for 1 ~ i ~
N c ; (values of ai's used in each of the remaining Equations
of State considered are provided in Appendix A).
In Eq. (6), the term kiJ represents the "binary in-
teraction parameter" that is specific to binary mixtures
of components i and j. ki,j is assumed to be indepen-
dent of the actual mixture composition, system pressure
and system temperature and is determined from experi-
mental data on the particular i-j binary. It is used in the
description of most multicomponent mixtures-the major
assumption being that higher order interactions (e.g., be-
tween components j, k, and I for ternary systems) are
negligible. Most Equations of State developed in recent
years, and in particular those that are considered in this
work, take the binary interaction parameter into account.
While ki,i is a small number, the results obtained from an
EOS may be very sensitive to the value used for k"j 12.

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 RE 21588

In all cases, ki.i is taken to be zero. In the RK EOS ZJRK EOS: U = 1; W = o.

k i .} = 0 for 1 ~ i,j ~ N c • Fluid compressibility (Z - )factor is defined (based on
In Eqs (4)-(5) and throughout, Xi.m denotes the mole the Engineering Equation of Sta.te) as:
fraction of component i in phase m, m = L for liquid and PVm
m = V for vapor, but we also use Xi as the mole fraction of Zm = RT. (10)
component i in the liquid phase and 1/i as the mole fraction
The Generalized Equation of State (Eq. (7» may be recast
of component i in the vapor phase, Le., Xi.L = Xi and Xi. V
in terms of phase m fluid compressibility factor (Zm) to
= 1/i·
yield the following cubic equation:
In terms of the notation introduced in this section,
the generalized EOS can be written in the form: Z! - (Bm + 1 - U Bm) Z;'
RT ama(T,w) + (Am - UBm - UB;' + WB;') Zm
(7)
P = (v m - bm ) - (v~ + Ubmv m + Wb~) ; - (AmBm + WB;' + WB;!.) = 0; (11)
where P is the pressure in psia, T is the temperature in oR,
where U, W were defined previously, and Am, Bm are given
R is the universal gas constant, (~ 10.73 psi - It 3 lib -
by
moleOR), Vm is the specific volume (lt 3 lib - mole) and U amP
Am = R2Tn' (12.1)
and W are parameters whose values depend on the EOS
selected. The function a(T,w) is defined for each EOS in and
bmP
Appendix A. Bm = RT· (12.2)
For the SW EOS, U and W are independent of tem-
Equation (11) may be solved analytically for a max-
perature and are related to the mixture acentric factor,
imum of three real roots. In the two-phase region, with
Wmiz as follows:
m = V in Eq. (11), vapor compressibility factor Zv is
U = 1 + 3w m iz, (8.1) assumed to be the largest root; similarly, with m = L the
and smallest root of Eq. (11) is the liquid compressibility fac-
(8.2) tor. All remaining roots are without physical significance.
The fugacit" of component i in phase m, (h.m) is a
where the phase m mixture acentric factor is defined as
measure of the tendency of the component to escape from
LNe bO 7 the phase. When multiple phases coexist at equilibrium,
Wmiz = =~:..:i~~1'-eW_'_'X-'i.:....~-O..:.~7-· (9)
L...i=1 Xi.m i the fugacities of each component in each phase are also at
equilibrium. The values of Zm calculated from Eq. (11)
In Eq. (9) Wi is the acentric factor for pure component i.
are needed to evaluate the fugacities of each component in
Our phase package computes Wi using the following defin-
each phase. The relevant equation is:
ing equation 12 :
RTln ( /;,m ) = _ [v_ (~ _ RT) dVm
Wi = -1 -logPvp.r.i. PXi.m 100 aNi•m Vm
-RTlnZm, (13)
Here Pvp.r.i is the reduced pressure (P.at.ilPc.i) of satu-
rated vapor evaluated at the reduced temperature T ITc.i where Ni.m and Vm respectively denote the number of
= 0.7. The saturated vapor pressure is computed via Rei- moles of component i in phase m and the volume of phase
del's vapor equation 13. m.
U and W for the remaining Equations of State are con- The integration in Eq. (13) can be carried out in
stants (i.e., independent of Wmiz). The appropriate values the following manner: (i) evaluate the partial derivative
of these parameters are as follows: of pressure with respect to the number of moles of com-
PR EOS: U = 2; W = -1. ponent i from the EOS (Eq. (7»; (ii) integrate, and (iii)
SRK EOS: U = 1; W = o. use the cubic (Eq. (11) with the appropriate definitions
RK EOS: U = 1; W = o. of Am and Bm to obtain a generalized expression for the

100-3
 SPE 21588

He
partial fugacity of component i in the phase. The resulting
LXi = 1, (I7.2a)
expression 888umes the following generalized form: i=1

(17.2b)

Note that both of equations (I7.2a) and (I7.2b) can-

not be used because, given one, the second may be
derived by combining the given equation with Eqs.
(15) and (16).
(iv) Finally, the criterion for thermodynamic equilibrium:

h,L = h,v, (18)

Equation (14) represents the partial fugacity of com- where h,L is the fugacity of component i in the liquid
ponent i for the SW EOS. It reduces to the PR, SRK and phase at pressure p and temperature T and h,v is the
RK and ZJRK cases by setting Wi - W = 0 and by us- fugacity of component i in the vapor phase at pressure
ing the appropriate coefficients Am, Bm (Eqs. (12.1) and p and temperature T.

(12.2)), U and W. This equation will be used throughout
the remainder of this work.
THE MODIFIED SUCCESSIVE SUBSTITUTION METHOD
The condition of thermodynamic equilibrium between
coexisting phases is described by the following mathemat-
ical equations:
We have chosen to use Eq. (18) as our criterion for
thermodynamic equilibrium since fugacities are easily ob-
tainable as functions of pressure, temperature and compo-
sition from an Equation of State.
Nghiem et al. 6 used the modified successive substi-
tution method for the SRK EOS. In our phase package,
we have successfully implemented the successive substitu-

(i) The overall material balance: tion method for all EOS's considered here. This method
may be used for detecting the single phase region or per-
L+ V = 1, (15) forming flash calculations. Its main disadvantage is that it
converges slowly (or not at all) in the neighborhood of the
where L is the moles of liquid per mole of fluid mixture critical point. Whenever this problem occurs, the program
and V is the moles of vapor per mole of fluid mixture. switches automatically to the robust MVNR (Minimum
(ii) The component material balance: Variable Newton-Raphson) method.
We now provide a brief description of the Successive
Zi = LXi + V'!Ii, (I6)
Substitution Method. Equations (15), (16), (17.1) and

where {Zi} f.; 1 is the mole fraction composition of the (17.2a) or (17.2b) can be combined to give:

initial fluid and {Xi};:;1 and {'!Ii};:;1 are the mole Z.

fraction compositions of the liquid and gas phases re- X. = -1-+-'V:-:-:-(K=-i---1--;-) , (19.1)

spectively at pressure p and temperature T. (Note

and
that Eq. (16) shows that Zi moles of component i,
when equilibrated, will be distributed as Lx. moles Ki Z •
'!I. = ---,-----,- (19.2)
of component i in the liquid phase and V'!I' moles of 1 + V(K. -1)'
component i in the vapor phase.)
where K. = '!I;/x •. The criterion for the thermodynamic
(iii) Mole fraction constraints:
equilibrium (Eq.(18)) can be rewritten as :
He
LZ, = 1, (17.1) F. = J;,L
h,v
= 1. (19.3)
.=1

100-4
 SP.E 21588

It is easy to see that the equilibrium K - values are If r(O) > 0 and r(1) < 0 solve Eq. (19.5) for V.
related to the fugacities via the following equation : (7) Update Xi and Yi from Eqs.(19.1) and (19.2) and go
to step (4)
In the single phase region, where V = 0 or V = I, the
Ki = (J;,L/ XiP) = Fi Yi • (19.4)
(J;,v /YiP) Xi
F;'s may converge to a value different than unity. Nghiem
et al. 6 suggest iterating until Eq.(20.2) is satisfied even in
A major step in the successive substitution method is single phase cases. However, in all computations we have
the solution of
done, if r(O) < 0 (or r(l) > 0) at the second iteration (i.e.,
N. N. N. z.(K- _ 1) at the first application of steps (4) and (5), then r(O) < 0
r(V) = LYi - LXi =L " =0 (19.5) (or r(1) > 0) at all subsequent iterations.
i=1 i=1 i=1 1 + V(Ki - 1)
The advantage of this procedure is that it allows us
for V. to detect the single phase region. Our phase package also
uses this technique to provide a reasonable initial guess for
Successive Substitution Algorithm
the MVNR method. In Eq. (20.2), we have normally used
First iteration 7
£ = 10- for the error tolerance.
(1) Compute initial estimate of Ki from the following
semi-theoretical equation 14: MVNR METHOD

Ki = Pe,iexp [5.37(1 + Wi) (1- ~)] (20.1)

The MVNR method was first presented by Fussel and
Yanosik 7 as a robust algorithm for solving the non-linear
P system of equations describing thermodynamic equilibrium
(2) Compute r(V = 0) and r(V = 1) from Eq. (19.5). using the RK EOS, (see Eqs.(15)-(18)). The equations
If r(O) > 0 and r(l) < 0, we have two phases and were solved either for saturation pressure and composi-
Eq. (19.5) is solved (using Newton's method) for V. tion of the forming phase or phase compositions at fixed
Otherwise, (i.e., if r(O) ::; 0 or r(l) ~ 0) we may only temperature and pressure (assuming constant feed compo-
have a single phase present; in this case, we assume a sition and that two phases exist). Since MVNR is a multi-
value of V = 0.5 and proceed with the calculation. variable Newton-Rhapson method, it requires the compu-
(3) Calculate Xi and Yi, respectively from Eqs. (19.1) and tation of partial derivatives of each phase fugacity with
(19.2). respect to pressure and phase compositions. Although
Subsequent iterations other researchers have, for simplicity, evaluated these par-
(4) Compute /i,L and J;,v from Eq.(14). Evaluate tial derivatives using numerical differentiations, they have
also suggested that improved performance of the MVNR
F, - J;,L will be obtained if these partial derivatives are eVcl.luated
, - fi,v
analytically. Our phase package employs analytical expres-
and sions for the relevant partial derivatives. These analytical
Yi
Ki = Fi-. expressions, which are given in Appendix B, were derived
Xi
from the generalized EOS (Eq. (7)) and to the best of
(5) Check for convergence using the following criterion:
our knowledge, have not been presented previously except
N. for the RK EOS7. Here, we do not repeat the details of
L (Fi - 1)2 ::; £. (20.2) the method; rather, we simply provide analytical expres-
i=1
sions for the relevant partial derivatives when a generalized
If Eq.(20.2) is satisfied stop - if not proceed to step EOS (Eq. (7)) is used to describe the phase behavior (see
(6) Appendix B).
(6) Compute r(O) and r(l) As with all methods based on Newton's iteration, the
If r(o) < 0 set V = 0, Le., single phase liquid. initial guess is critical to the success of the convergence
If r(1) > 0 set V = 1, Le., single phase vapor. of the computations. For Flash calculations, we use the

100-5

Successive Substitution method (described above) with a
large value of f ( R: 10- 3 ) in Eq. (20.2) to obtain our initial
guess for the phase compositions.
While an "upper"saturation point (bubble or dew)
will always exist for a tw<>-phase mixture, the existence of
a "lower" dew point pressure is dependent on the shape of
the tw<>-phase envelope on a p- T diagram. For all practical
purposes, petroleum engineers are only interested in min-
imum pressures in excess of a few hundred psi. Thus, we
have designed the following simple method of determining
(a) whether the "upper" saturation pressure is a bubble or
dew point pressure; and (b) whether we will encounter the
lower dew point pressure over normal operating pressures.
(This information is vital in modeling the behavior of flow
of multiple hydrocarbon components in a porous medium,
where in 8itu fluid composition varies continuously with
time.)
Assuming that a tw<>-phase region exists at the system
temperature (i.e., system temperature is to the left of the
cricondentherm on a p-T diagram), the method consists
of the following steps:
i) perform a Flash calculation (using the previously de-
scribed modified successive substitution method) at
system temperature and a very high pressure (e.g.,
10000 psi) so that we are assured of single phase fluid.
This determines the location of the system tempera-
ture relative to the mixture critical temperature: i.e.,
if V = 1, the fluid is retrograde condensate; conversely
if V = 0 the fluid is black oil.
ii) Repeat Step (i) at the lowest anticipated system pres-
sure; if 0 < V < 1, the lower dew point pressure is
of no practical significance. Otherwise (if V = 1), the
lower dew point pressure must be determined.
The initial guess for determining upper and lower sat-
uration points employs the following method due to Baker
and Luks 15 .
The phase m partial fugacity coefficient is defined as:
tP. - !;,m
I,m - PXi,m·
For a bubble point calculation, the Xi'S are known (equal
to z;'s for the overall fluid mixture in-place) and the vapor
phase composition is given by
Yi = (PtPi,LXi) = (tPi'L) Xi, 1 ~i ~ Nc
(pt/Ji,V) tPi,V
seE 21588
The dew point calculation analog of Eq.(21.2a) is
(21.2b)
The method involves the following steps:
(1) pick a low pressure (e.g., 1 psi)
(2) Compute tPi,V and tPi,L at the pressure of the new
iteration level using the composition from the old it-
eration level.
(3) Evaluate the unknown phase composition using Eq.
(21.2a) for bubble point or Eq. (21.2b) for dew point.
If L~l Xi,m < 1 then the assumed pressure is too
high, if not, the assumed pressure is lower than the
saturation pressure.
(4) Correct the pressure in accordance with step (3). Baker
and Luks 15 recommend an increment of 100 to 300 psi.
At this stage, a bisection type method may be used
to narrow the search range.
(5) Repeat steps (2) - (4) until convergence.
The resulting phase composition and pressure is then
used to start the p - X or p - Y iteration of the MVNR
method. This procedure inevitably results in an "upper"
saturation point. The "lower" dew point is obtained by
starting at the last Baker and Luks estimated "upper" sat-
uration point and modifying the criterion of step (3) above
in the following way: if Li Xi,m < 1, the guessed pressure
is less than the lower dew point pressure; otherwise, the
pressure estimate is too high.
MODEL VERIFICATION
The package has been extensively tested for each Equa-
tion of State and here, we compare our results with pub-
lished results.
Saturation points
Tables (1) - (5) compare saturation point computa-
tions from three Equations of State, (ZJRK, PR and SW
EOS).
One of the modifications made by Zudkevitch and
(21.1)
Joffe to the original RK EOS was expression of the van
der Waals coefficients Oa and Ob as functions of tempera-
ture and acentric factor. Table (1) shows the computation
of the bubble point pressure (referred to simply as pres-
sure in table (1))and the composition of the forming gas in
a methane/butane/decane system, using the ZJRK EOS.
(21.2a)
We used the same set of binary interaction parameters as
100-6

Ref. 16, i.e., ki,i = 0, except for k 1 ,2 = k 2 ,l = 0.024 and
k 2 ,3 = k 3 ,2 = 0.025 (Here, methane, butane and decane
are referred to as components 1, 2 and 3, respectively.)
For T = 160°F, using the same values for 0" and
Ob as Ref. 16, table (1) indicates that the experimental
and package results agreed within less than 3% for bubble
point pressure. The K - values computed from our pack-
age are essentially identical to those obtained by Ref. 16
and in reasonable agreement with Laboratory results. The
greatest discrepancy between computed and experimental
K - values occurs for the lighter mixture (Xl = 0.663).
To generate the T = 280°F results of Table (1), we used
the set of coefficients originally reported by Zudkevitch
and Joffe 2
; here deviations from the reported experimen-
tal values were more significant. In general, we found that
replacing the van der Waals coefficients reported in Ref.
17 by those generated by Coats 16 procedure yielded better
agreement with values of bubble point pressure obtained
experimentally.
Tables (2) and (3) show the saturation point compu-
tations using the PR and SW Equations of State, respec-
tively. As shown, results obtained from the package agree
very closely with the results of Ref. 17.
The PR EOS was used to simulate the variation of the
bubble point and dew point of a mixture containing thir-
teen hydrocarbon components plus a concentration of CO 2
ranging from 0 to 80% (See Table (4)). Table (5) shows the
results for a seventeen component mixture that includes
a fixed concentration of CO 2 plus a concentration of N2
ranging from 0 to 50%. In both cases, our phase pack-
age yields results that agree well with published data 18.
The results in column 2 of Tables (4) and (5) represent
Laboratory values.
Flash calculations
Table (6) shows results for flash calculations on a ten
component system over a range of pressure which included
the system critical point at 2810 psia and 162.2° F. The
SRK EOS was used and as expected, the SS method did
not converge near the critical region; however, the robust
MVNR predicted properties that agree closely with those
of Ref. 6. Note that Ref. 6 uses Powell's method 19 ,2o
instead of the MVNR. Equally good results were obtained
with other mixtures presented in Ref. 6.
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SPE 21588
CONCLUSIONS
The major contribution of this work is that it collects
and synthesizes all information vital to writing a robust
PVT package based on a generalized Equation of State.
We have provided analytical expressions for evaluation of
the partial derivatives used in Newton-Rhapson iteration
for Five Equations of State. Procedures for determining
saturation points (both upper and lower) at a given tem-
perature have been delineated. Further, details on a sim-
ple method (based on the Successive Substitution Solu-
tion procedure) for determining whether the system tem-
perature is above or below the mixture critical tempera-
ture (without actuallll determining the critical temperature)
were provided. We have successfully applied the succe&-
sive substitution solution procedure to all five Equations
of State discussed in this work.
In summary, this paper facilitates the design and im-
plementation of a robust commercial quality hydrocarbon
PVT phase package.
ACKNOWLEDGEMENT
Fawzi M. Guehria wishes to thank Phillips Petroleum
Company for their financial support during this study. The
authors also thank the University of Tulsa for providing
computer facilities. This research was performed under
the auspices of the University of Tulsa Petroleum Reservoir
Exploitation Projects (TUPREP).
NOMENCLATURE
am Attraction parameter in the generalized EOS for mul-
tiphase systems, Eq.(4).
ai,i mixing rule parameter, Eq.(6).
ai,m mixing rule parameter, Eq. (B2).
Am Cubic equation coefficient, Eq. (12.1).
bi Repulsion parameter of component i in the van der
Waals EOS, Eq.(2).
bi,m mixing rule parameter as defined in Eq. (Bl).
Bm Cubic equation coefficient, Eq. (12.2).
Ii,m Fugacity of component i in phase m.
Ii,L Fugacity of component i in the liquid phase.
Ii, v Fugacity of component i in the vapor phase.
Fi Ratio of fugacities, Eq. (19.3)
 aeE 21588
k parameter in the Schmidt and Wensel EOS, Eq. (A4). i Component i.
Ki K - value of component i. j Component j.
L Number of moles of liquid per mole of fluid mixture. L Liquid phase.
M Molecular weight. m phase.
Nc Number of components in a mixture. mix Mixture.
Ni,m Number of moles of component i in phase m.
r Reduced property.
P System pl'etl8Ule, pai.
&at At saturation point.
Pc Critical pressure, pai.
Transpose.
Pc,i Critical pressure of component i, pai.
VP At vapor point.
R Universalgu constant.
V Vapor phase.
T System temperature, degree Rankine.
Tc Critical temperature, degree Rankine.
Superscript
Tc,i Critical temperature of component i, degree Rankine.
• Idealgu property.
Ui,m parameter uaed in differentiation, Eq.(B3).
U parameter in the generalized EOS, Eq.(8.1).
Greek notation
Vm Specific molar volume of phase m, ItS /llnnole.
Q Equation of State parameter, Eqs. (AI), (A2), (A3).
V Volume, ItS.
V Number of moles of vapor per mole of fluid mixture.
fJ parameter in the Schmidt - Wensel EOS, Eq. (A6).
Vc Critical volume, ItS. 6i,i Kroenecker delta.

Vc,i Critical volume of component i, Its. r Function defined in Eq. (19.5)

Wi,m parameter uaed in differentiation, Eq. (B4). w Acentric factor.

W parameter in the generalized EOS, Eq. (8.2). o van der Waala coefficient, Eqa. (1), (2).

Xi Mole fraction of component i in the liquid phase. tPi,m Fugacity coefficient of component i in phase m, Eq.
Xi,m Mole fraction of component i in phase m. (21.1).

Jli Mole fraction of component i in the vapor phase. p Density, lbmole/ Its.

Zi Overall mole fraction of component. e parameter in the Schmidt - Wensel EOS, Eq. (A8).
Z Compressibility factor.
REFERENCES
Zm Compressibility factor of phase m.
Zt Compressibility factor of component i saturated liquid 1. Redlich, O. and Kwong, J.N.S.:"On the Thermody-

at P...t,i and T. namics of Solutions. V - An Equation of State. Fu-

Zi,L Compressibility factor of the liquid phase of comp<>- gacities of Gaseous Solutions," Chemical Review8, Vol.
nent i. 44 (52-63).
2. Zudkevitch, D. and Joffe, J.:"Correlation and pre-
diction of Vapor-Liquid Equilibria with the R.edlich-
Subscripts
Kwong Equation of State," AIChE Journal, Jan. 1970,
a Relative to the parameter a.
(112-119).
b Relative to the parameter b.
3. Soave, G.:"Equilibrium Constants from a Modified
c Critical property. Redlich-Kwong Equation of State," Chemical Engi-
dew At dew point. neering Science, 1972, Vol. 27, (1197-1203).

100-8

4. Peng, Ding-Yu and Robinson, D.B.:"A New Two -
Constant Equation of State," Ind. Eng. Chern. Fund.
(1976) 59--64.
5. Schmidt, G. and Wenzel, H.:"A Modified Van Der
Waals Type Equation of State," Chern. Eng. Science,
Vol. 35, 1503-1512.
6. Nghiem, L.X., Aziz, K. and Li, Y.K.:"A Robust Iter-
ative Method for Flash Calculations Using the Soave-
Redlich-Kwong or the Peng-Robinson Equation of
State," SPEJ, June 1983,521-530.
7. Fussell, D.D. and Yanosik, J.L.:"An Iterative Sequence
for phase-Equilibria Calculations Incorporating the
Redlich-Kwong Equation of State," SPEJ, June 1978,
173-182.
8. Lohrenz, J., Bray, B.G. and Clark, C.R.:"Caiculating
Viscosities of Reservoir Fluids From Their Composi-
tions," JPT, Oct. 1964,1171-1176.
9. J088i, J.A., Stiel, L.!. and Thodos, G.:"The Viscosity
of pure Substances in the Dense Gaseous and Liquid
phases," AIChE Journal, March 1962, Vol. 8, No.1,
59-62.
10. Heming, F. and Zipperer, L. :" Calculation of the Vis-
cosity of Technical Gas Mixtures from the Viscosity of
Individual Gases," Gas u. Wasserfach, (1936) 79, No.
39,69.
11. Stiel, L. I. and Thodos, George,:" The Viscosity of
Nonpolar Gases at Normal pressure," AICHE J., (1962)
8,59.
12. Modell, M. and Reid, R.: Thermodynamics and
its applications, Prentice Hall (2ed.), Prentice Hall,
Inc. (1983), pp. 151, 189.
13. Reid, R.C., Prausnitz, J.M. and Sherwood, T.K.: The
properties 0/ Gases and Liquids, 3rd Edition Mc-Graw
Hill 1977, New -York.
14. Wilson, G.:"A Modified Redlich-Kwong Equation of
State, Application to General physical Data Calcula-
tions," paper 15C presented at the 1968 AIChE Na-
tional Meeting, Cleveland, OH, May 4-7.
15. Baker, Lee E. and Luks, K. D., :" Critical point and
Saturation pressure Calculations for Multipoint sys-
tems," SPEJ 1980, 15-24.
16. Coats, Keith H.: An Equation of State Compositional
Model," SPEJ, October 1980, 363-376.
100-9
SPE 21588
17. Firoozabadi, Abbas: Reservoir - Fluid phase Be-
havior and Volumetric prediction With Equation of
State., JPT, April 1988,397-406.
18. Hong, C.: "Lumped-Component Characterization of
Crude Oils for Compositional Simulation," SPE DOE
10691 241-245
19. Powell, M. J. D.:"A Hybrid Method for Nonlinear
Equations," Numerical Methods for Nonlinear
Algebraic Equations, T. Rabinowitz (ed.), Gordon
and Breach, London (1970).
20. Powell, M. J. D.:"A Fortran Subroutine for Solving
Systems of Nonlinear Algebraic Equations," Numer-
ical Methods for Nonlinear Algebraic Equa-
tions, T. Rabinowitz (ed.), Gordon and Breach, Lon-
don (1970).
21. Yarborough, Lyman: "Applications of A Generalized
Equation Of State to Petroleum Fluids," in: Equa-
tions 0/ State in Engineering, Advances in Chemistry
Series, 182 K. C. Chao and Robert L. Robinson, ed.,
American Chemical Society, Washington, DC, (1979),
385-435.
ApPENDIX A
EOS PARAMETERS
Here we present expressions for the parameters a, 0 4
and Ob for the EOS's discussed in this work.
Redlich Kwong EOS
The function a is given by
1
a= Vf' (AI)
with
04 = 0.4274802327
and
Ob = 0.08664035
Zudkevitch Joffe Redlich Kwong EOS
The function a is the same as Eq.(Al). Zudkevitch
and Joffe developed a method of computing 0 4 ,; and Ob,;
for each component i at a given temperature using the com-
ponent's vapor pressure, saturated liquid density and Ly-
ckman's fugacity coefficient14. An extensive application of
the RK EOS to reservoir fluids was made by Yarborough21.
He used the Zudkevitch - Joffe RK EOS (ZJRK) with 0 4 ,;
and Ob,; as functions of reduced temperature and acentric
 seE 21588

factor12 and with binary interaction parameter developed is solved for Pi. H an iterative method (such as Newton -
for the cases in hand. Raphson) is used to solve this cubic, then an initial guess
Soave Redlich Kwong EOS is provided via:
Here Q is given by:

Q = [1 + (0.48508 + 1.55171w - 0.15613w 2 ) (1 - "ITr) r'

(A2)
Pe,i = 0.25989 - 0.0217wi + 0.00375wl-

The smallest root of Eq. (A6) is used to compute an

(A 7)

where Tr = T ITe • intermediary parameter e.,i as follows:

Here, n.. and n~ are the same as for the RK EOS
Peng Robinson (PR) (A8)
In this case:
Finally, n ..,i and n~,i are given by the following ex-
Q = [1 + (0.37464 + 1.5422&1 - 0.26992w 2 ) (1- vIT.)] ~ pressions :
(A3) n.. ,i = [1 - e.,i (1 - P.,i)]s; (A9)
with
n.. = 0.45724 and
(A10)
and
n~ = 0.00778 APPENDIX B
Schmidt Wensel EVALUATION OF PARTIAL DERIVATIVES
The function Q is given by We present the derivatives of the partial fugacities
with respect to the various variables for each iteration. We
(A4) will perform the differentiation on the generalized fugacity
equation that applies to all presented Equations of State
where
with the appropriate parameters.
k" if W::; 0.4; First define the following,
k - k2 , if W ~ 0.55;
- { ( ... -o... }) k
0.111 2
+ (0.1I11-...
0.111
}) k .
b otherwise

with
kl = ko + (;0) (5Tr - 3ko - 1) 2
a;,m
N.
= L X I,mP(l- ki,l) n .. ,in .. ,IQiQI (Te,iT.,,)"
1=1
A~ (P.,iP.,I) Tn
k2 = ko + 0.71 (Tr - 0.779)2 (B2)
ko = {0.465 + 1.347w - 0.528w 2 ; if W ::; 0.3671; where m = Liquid or Vapor;
0.5361 + 0.9593w; if W > 0.3671
and

Q = 1.0 - (0.4774 + 1.328w) InTr ; T> T.. (A5)

Here Tr is the reduced temperature and w is the acentric

factor of the component considered.
The method used by Schmidt and Wenzel II to evaluate
n .. ,i (Wi) and nb,i (Wi) is now described. For each given
value of Wi, the cubic

(A6) p - x or p - " iteration

100-10
 seE 21588

We will develop the derivative of the partial fugacity

with respect to pressure for component i in phase m.
~ [In (2Zm + UBm + Bm';U2 - 4W)] =
ap 2Zm + U B"; - Bm ';U2 - 4W

ah,m -f.
ap - ',m p {I 2
aZm
ap
+ aBm (U + v'U2 - 4W)
ap
2Zm + U Bm + Bm ';U2 - 4W
a 1 a
+ ap [bi,m (Zm - 1)]- Zm _ Bm ap (Zm - Bm) 2 aZm + aBm (U _ v'U2 _ 4W)
ap ap . (Bll)
+~ [Ui min (2Zm + UBm + Bm';U2 - 4W)] 2Zm + UBm - Bm';U2 - 4W '
ap' 2Zm + U Bm - Bm ';U2 - 4W

+ --ap
aWi,m}
, (BS)
(BI2)
where,
a [bi,m (Zm - 1)]
ap
= bi,m aaZm
p
(B6)

and (BI3)
aZm aZm aAm aZ aBm
- - = - - - - + -m
--- (B7)
ap aAm ap aBm ap .
Differentiating the cubic equation with respect to Am aA", Am
--=-;
and Bm, we get ap p

(BS) (BIS)

and Note that the following equations would be needed only

(BQ) for the SW EOS since Wi - W = 0 for the other cues.

where aWi,m = ___1_....., a (Z B)

ap (Zm _ Bm)2 ap m - m

x' = Z! (1- U) - (2WB m - 2UBm - U) Z'" X [3(Wi - w)

U2 - 4W "N.
b?·7
%L bo.T
]
+ (3W B! + 2W Bm + A",), ~"=1 .. ,m"
X (2Zm + UZm + 2WBm + UBm)
and 1 )3(Wi-W) b?·7 ]
- [( 1 - Zm _ B
m
U2 - 4W "N. .L bO.7
~"=l"' .. ,m "
y' = 3Z! - 2 (Bm + 1 - U Bm) Zm az
x [(U + 2) a; + (2W + U) aB ]
apm . (BI6)
+ (WB;' - UB;' - UBm + Am).

Note that U and W are functions of composition and All the equations derived above define the variation

not of pressure 80 that they are not affected by this differ- of the partial fugacity of both phases with respect to pres-
entiation process. sure, which appears in the Jacobian matrices of both the
p- % and the p - 11 iterations. The partial derivative of
~
ap
[u. ',m
In (2Zm + UBm + Bm';U2 - 4W)] _
2Zm + UBm - Bm';U2 - 4W -
the partial fugacity of vapor with respect to the gas mole
fraction composition which appears in the p - % iteration

Ui m~ [In (2Zm + UBm + Bm';U2 - 4W)] Jacobian is the same as the one developed below for the
'ap 2Zm + UBm - Bm';U2 - 4W L- % iteration.

+ In (2Zm + U Bm + Bm ';U2 - 4W) aUi,m. (BIO)

L- % iteration
2Zm + UBm - Bm';U2 - 4W ap

100-11
 RE 21588

ah,v Recalling that U = 1 + 3w, and that

-",-
v'll;
= h,v { -61 a
i ,j + !> [bi,v (Zv -
v'll;
1)]
'II;

1 a W . -
"Ne
L-,i=1 Wi%i f In
bo
"
.r
m,z - "",Ne 0.7 '
Z
v -
B a (Zv - Bv)
v 'II; ~i=1 Zi,mbi

a
+- [ U'V In (2ZV + UBv + BV";U2 - 4W)] then
a'll;" 2Zv + U Bv - Bv";U2 - 4W
au _
-3 [b
or "N.
; . ( W,. ~i=1 'IIi bO.
i
r "Ne
- ~i=1 WiYi bo.
2 '
i )
r 1
(BI7)
a'll; ("Ne
L.J,=1 '1
y.bo.r )
(B2S)
a a~
- [b iV (Zv -1)J
a'll; ,
=- (Zv -1)b· v b· v +b·v-·
"" "a'll; ,
Again, we have
aw au
(BlS) (B26)
a'll; = - a'll;'
where
ab· v
-"-
a'll;
= -b·vb·
' " ,v .
(BI9)
~ [. In (2Zv + UBv + BV";U2 - 4W)] _
Here Zv is a function of Av, Bv, U and W, which in turn a'll; u"m 2Zv + UBv - BV";U2 - 4W -
are all functions of the composition. Thus
u. ~ [In (2Zv + UBv + BV";U2 - 4W)]
az v v az aAv v az aBv az au az aw ',m a'll; 2Zv + UBv - BV";U2 - 4W
-a'll;- =- - -- + - - - - + - -v - - + - -v - -
aAv a'll; aBv a'll; au a'll; away;
(B20) + In (2ZV + U Bv + BV";U2 - 4W) (B27) aUi,m j
azv azv . 2Zv + UBv - BV";U2 - 4W a'll;
aA and aBv are given by Eqs.(BS) and (B9) re-
spectivel';..
aBv Oh,jpTc,j
a'll; = Tpc,j j
(B21) ~ [In (2Zv + UBv + BV";U2 - 4W)] =
a'll; 2Zv + UBv - BV";U2 - 4W
aA N.
a ~ = 2p E '11,(1 - k;,I)
Oo,jOo,IQ;QI (Tc,jTc,,)" .
(Pc,jPc,l) T" '
v
1 {az
.... 2-- + ( U + VU2 - 4W ) --
aBv
'II, 1=1 yay; a'll;
(B22)
UBU_2BW]
Now, the following expr_ions are only needed for the +Bv au + 8¥i ~
SW EOS. They are obtained from the cubic equation 4W
[ a'll; ";U2 -

- - + (v
U+U2 -4W ) --
v
- 2az aBv
azv X" a'll; ay;
(B23)
au = Y"' au UBU - 2BW]}
+Bv - - ~ ~ .
where [ a'll; ";U2 - 4W '
(B2S)
X" = - Bv Z~ + (2B~ + Bv) Zv - (B~ + B~ ) ,
where
and Y = 2Zv + UBv + Bv";U2 - 4W.
aWi v
aUi v .
X" = 3Z~ - 2 (Bv +1- U Bv ) Zv Finally, To evaluate
v'll;
~
and ~, we will need to
v'll;
+ (W B~ - U B~ - U Bv + Av) . apply the product rule to the derivatives of the parameters
developed and to the following,
Since U + W = 1 (see Eqs.(S.I) and(S.2)), then

azv azv
(B24)
aw au
+ (1 - ki,;)
Oa,iOa,;QiQ; (Tc,iTc,; r p2 ] . (B29)
(Pc,iPc,;) T"

100-12
 SPE 21588

=~ [(1 - ki .)
All these expressiona allow us to find aa"'v for the
IIi aai,L
ax; AL oJ
L- % and the P - II iterationa. now we will evaluate aa/;,L
needed for the L - % and the p - % iterationa. We remind
the reader that here the %i is one of the iteration variables
%i
- ~ [(1-
AL
kl .)
oJ

and thus the differentiation is slightly different. as,L aAL

- AL a%j' (B35)

All these expressiona do apply to the V - II iteration,

ah,L _ f,.
a%i - ',L
{~{-1' if i=
%i 6iJ, if i:f= 1
I} provided we replace V by L.' %; by II; and vice-versa.

a 1 a
+-a [bi,L (Zv -1)]- Z B a (Zv - Bv)
~ v- v ~
a
+- [
"iL
In (2Zv + UBv + Bvy=U"'2----4W=)]
a%i ' 2Zv + UBv - BV';U2 - 4W
+ aWi'L}. (B30)
a%i

The differentiation process of the equation above is

exactly the same as for :h,v
IIi,V
except for the following mod-
ificationa due to the fact that %i is an iteration variable:

The deviation factors derivatives are the same as those

aBv aAv au aas L .
evaluated above. - a ' - a ' -a and -a' are modified
%i %; %; %;
as
aB L _ nb,jpTcJ nb,lpTcJ.
(B32)
ax; - TPcJ TPcJ '

(B33)

100-13
 SPE 21588

TABLE 1

Comparison of calculated and experimental results for the Gd n- G./ n - G10

Zudkevitch - Joffe - Redlich - Kwong EOS

T Xi Preaaure (paia) K-Value

(OF) Lab. Ref. 15 Package Lab. Ref. 15 Package
280 0.203 1000 1019.7 995 3.813 3.773 3.736
0.346 0.613 0.637 0.656
0.451 0.032 0.031 0.032
280 0.402 2000 1970.5 1912 1.861 1.867 1.850
0.370 0.605 0.613 0.629
0.228 0.122 0.099 0.103
280 0.575 3000 2997.6 2915 1.459 1.475 1.470
0.179 0.631 0.635 0.645
0.246 0.193 0.156 0.157
160 0.253 1000 972.7 976 3.174 3.173 3.173
0.661 0.297 0.297 0.297
0.086 0.013 0.008 0.008
160 0.459 2000 1950.9 1960 1.854 1.862 1.861
0.390 0.367 0.361 0.362
0.151 0.039 0.028 0.028
160 0.663 3000 3128.2 3143 1.213 1.254 1.252
0.229 0.703 0.633 0.636
0.108 0.330 0.218 0.221

TABLE 2

Comparison of calculated and experimental result. for the G1 / n- G./ n- G10

Peng - Robinaon EOS

T Xi Preaaure (paia) K-Value

(OF) Lab. Ref. 18 Package Lab. Ref. 18 Package
280 0.203 1000 1009 1009 3.813 3.800 3.800
0.346 0.613 0.615 0.615
0.451 0.032 0.035 0.035
280 0.402 2000 1940 1941 1.861 1.844 1.844
0.370 0.605 0.625 0.625
0.228 0.122 0.119 0.119
280 0.575 3000 2999 3000 1.459 1.460 1.462
0.179 0.631 0.639 0.639
0.246 0.193 0.180 0.181
160 0.253 1000 952 954 3.174 3.130 3.126
0.001 0.297 0.313 0.315
0.086 0.013 0.009 0.009
160 0.459 2000 1937 1940 1.854 1.850 1.848
0.390 0.367 0.374 0.376
0.151 0.039 0.034 0.034
160 0.663 3000 3113 3117 1.213 1.247 1.245
0.229 0.703 0.643 0.646
0.108 0.330 0.241 0.244

100-14
"

SPE 21588

TABLE 3

Compari80n of calculated and experimental r ... ulta for the Cd n- C,/ n - C IO

Schmidt - Wensel EOS

T Xi Pressure (peia) K-Value

(OF) Lab. Ref. 18 Package Lab. Ref. 18 Package
280 0.203 1000 1012 1012 3.813 3.850 3.851
0.346 0.613 0.587 0.587
0.451 0.032 0.033 0.033
280 0.402 2000 1927 1928 1.861 1.873 1.873
0.370 0.605 0.600 0.600
0.228 0.122 0.109 0.109
280 0.575 3000 2955 2957 1.459 1.479 1.479
0.179 0.631 0.608 0.609
0.246 0.193 0.165 0.166
160 0.253 1000 951 952 3.174 3.155 3.152
0.661 0.297 0.304 0~305
0.086 0.013 0.006 0.007
160 0.459 2000 1940 1943 1.854 1.867 1.866
0.390 0.367 0.355 0.357
0.151 0.039 0.028 0.029
160 0.663 3000 3105 3109 1.213 1.263 1.261
0.229 0.703 0.611 0.614
0.108 0.330 0.211 0.214

TABLE 4
Computation of Saturation Point. for CO2 / C1 - C 1H
Penc - Robiuon EOS

Properiy Refennu 20 Package

Bubble Point
h,.ia)
with 0% CO2 UIU 1653
20% 1860 1857
40% 2088 2085
60% 2228 2234
65% 2637 2630

D_ Point
(peia)
with 60% CO2 2113 2110
65% 2487 2485
70% 3868 2865
75% 3182 3179
80% 3769 3773

100-15
 SPE 21588

TABLE 5
Calculation of Saturation Points for N, - CO, / C 1 - C l 6+
Peng - Robinaon EOS

Property Reference 20 Package

Bubble Point
(paia)
with 0% N, 3990 3993
5% 4742 4745
10% 5603 5606
15% 66(M 6608
20% 7787 7790
25% 9217 9221

Dew Point
(paia)
with 0% N, 3565 3567
10% 4080 4081
20% 4644 4646
30% 5259 5260
40% 5921 5924
50% 6609 6612

TABLE 6
Flash Calculatiou for 15 CompOlleM Oil
N, -CO, / C 1 - CT+
Soave - Recllida - Kwong EOS

Pressure V V
(paia) Ref. 6 Pacbce

4950 0.0116 0.0000

4925 0.1144 0.1150
4900 0.1770 0.1775
4875 0.2206 0.2218
4825 0.2536 0.2M3
4800 0.3016 0.3025
4750 0.3358 0.3364
4700 0.3623 0.3627
4650 0.3838 0.3844
4600 0.4019 0.4025
4550 0.4175 0.4181
4500 0.4313 0.4320

100-16