SPE

SPE 8287
APPLICATION OF THE DEVELOPED REDLICHKWONG EflUATION OF STATE
TO PREDICT THE THERMODYNAMIC PROFERTIES OF CONDENSATE GASES
by Andre Peneloux, Faculte des Sciences de Luminy, Marseille (France)
Corentin Jain and Emmanuel Behar, Institut du Petrole, Rueil Malmaison (France)
) CoII'/f'9III1979. __ 'n,.1UII of MtntnQ. Me<allurq1Ql. and _m Eno ....... 'nc.
ThIS paotr WIS oresented at tnt 54th Annual Flit TecftntClt ConterInet and e,cntbttJon of me SoCIefy of Engmeers of AIME. held HlUS Vequ. Nevaaa. Seotemoer 2326. 1979. The matenJitS suDteCtto correcnon Cy me
aumor. ro COQ'f IS resU1Ctld ta an a()stract Of nor montnln JOOWOIdS. Wnre 6200 N Centrat ExQY.. Dallas. TeQ! 75206.
ABSTRACT
A new characterization procedure for the heavy
fraction is used wi th PENG-ROBINSON (PR) and DEVELOPED
REDLICH-KWONG (RKD) equations of state to predict the
thermodynamic behavior of condensate gases. The compu-
ted properties show that RKD model can be considered
as an improvement of previous work with PR equation,
mainly for evaluating the compositions of equilibrium
phases.
INTRODUCTION
Most natural gases contain small amounts of com-
ponents heavier than n-pentane. In some cases, Signi-
ficant amounts of the hexanes and heavier components
are present in the reservoir effluent. Published
phase equilibria data have shown the dependence of
phase behavior on the chemical nature of hydrocarbons
present, mainly aromatics. In most instances, a compo-
sitional analysis of the hexanes and heavier fractions
is incomplete or unavailable, but phase equilibria
predictions still must be made fer =eservoir
ring purposes.
A new characterization procedure for the C7+
fraction is proposed in this work. The only datum
used is the average molar weight of this fraction,
which is considered to be a pseudo-binary made of a
"light" n-alkane and a "heavy" n-alkyl-benzene in
such proportions that the molar weight of their mix-
ture is equal to tha t of the C
7
+ fraction.
The compositions thus obtained are used with
different equations of state to predict the PVT cha-
racteristics and the molar compositions of the pro-
duced and residual fluids, under laboratory conditions
simulating the evolution of the reservoir effluent
during depletion, as well as the retrograde liquid-
deposi t cu rve.
A new non-cubic equation of state, called
DEVELOPED REDLICH-KWONG (RKD) has been proposed
References and illustrations at end of paper.
elsewhere for predicting high pressure liquid-vapor
equilibrium. All the above mentioned thermodynamic
properties of condensate gases determined with RKD
as well as SOAVE and PENG-ROBINSON equations of
state, are compared to laboratory data. It is thus
possible to evaluate the degree of accuracy of
different compositional models for application to
reservoir engineering calculations with natural gases.
THE DEVELOPED REDLICH-KWONG EQUATION (RKD)
A new non-cubic equation of state of the REDLICH-
KWONG type has been presented elsewhere
l
This expres-
sion was obtained from the original REDLICH-KWONG
equation of state by assuming that the attraction
parameter depends not only on temp'erature, but also
on density. The generalization of this equation by a
corresponding states correlation enables it to be
applied over wide ranges of temperature, pressure and
hydrocarbon molecular weight.
The RKD equation has the form :
RT
a (
b
b
2
)
P =--- - 1 - '( -+ 0-
. .
(1)
v - b v (v + b)
"
,,2
the parameters a, b, y and 8 are functions of tempe-
rature.
In order to use this equation in compositional
models needed to compute the thermodynami= behavior
of petroleum flUids, we established a three parameter
corresponding states correlation. We can thus repre-
sent the properties of the non- or slightly polar
components which play an important role in the petro-
leum industry knowing their cri tical parameters : T
c
'
Pc and their acentric factor'-'.
For mixtures, the averaging rules for use with
this equation of state are
2
:
b
m
= 1:: x. b. (2)
i

a =
';"
Z x x. (a
i
a.) l/2
(1
-
k . . ) T (3)
'-'
. . .
m
i J J
i j
2 APPLICATION OF RKD EQUATION OF STATE ro CONDENSATE GASES SPE 8287
.( 4)
y" .. E E x .
Xj (yi
y") 1/2
(1 - k
ij
) T
m
i j
1. j
..
o 1/2
<5 E E x. x. (0 " (1 - k
ij
) T
m
i j
l.
J
i
J
(5)
where
y" .. ya and a" .. aa
(6)
(b b )1/8
C
i
Cj
T
:
(7)
In equations (3) to (5), kij is a fitted binary
interaction parameter which is considered to be tem-
perature independent. It is adjusted on a consistent
set of data for a given binary system. For n-alkane
mixtures, we assume the RKD equation of state to be
predictive, that is k .... O.
1.J
APPLICATION OF AN EQUATION OF STATE TO PREDICT THE
PROPERTIES OF CONDENSATE GASES
During the course of this work, we have noticed
that if we want to represent with good accuracy the
retrograde dew points of natural gases, it is
difficult to represent equally well the liquid-deoosit
curves which have been measured either in constane-
mass or constant-volume conditions. Moreover, we con-
sider that the visual determination of the dew point
is susceptible to judgment of the operator. This means
that dew pressure values reported in PVT studies are
affected by errors which are difficult to estimate.
For these reasons we decided to use only the constant-
mass liquid-deposit curve (excluding the dew point) as
a data base for the parameters adjustment in the
method described hereafter.
We have used the SOAVE
3
, PENG-ROBINSON
4
and RKD
equations of state to perform the phase equilibrium
(flash) as well as the volumetric computations. In
all three cases, the binary interaction parameters
kij are those determined during the study of binary
systems for which experimental data have been publi-
shed
2
, excepting the one related to the heaviest
component, which is kept as an adjustable parameter
for each natural gas. Three possibilities were exami-
ned for this particular parameter; it can be rela-
tive to the interactions of the heaviest component
with
- methane only,
- methane, ethane and propane,
- all the alkanes lighter than C
6

We have noticed that the observed differences
between the results obtained while using these three
possibilities are not very important. Nevertheless,
we have retained the second one for the examples
which will be presented below.
In order to apply this calculation method to
condensate gases for which a compositional analysis
of the hexanes and heavier fraction is incomplete
or unavailable. we have defined a new procedure for
representing it. The only necessary experimental cha-
racteristic is the average molar weight of this
fraction, which is replaced by two hydrocarbons in
such proportions that the molar weight of their mix-
ture is equal to that of the heavier fraction. The
"light" hydrocarbon is chosen to be a n-alkane and
the "heavy" hydrocarbon a n-alkyl-benzene.
As an example, let us consider a natural gas
whose C7+ fraction has an average molar weight of 140,
which corresponds approximately to n-decane. It can
be replaced by a mixture of n-C
7
, n-C8 or and
a n-alkyl-benzene : Cll' C12, C13'
The two hydrocarbons selected, as well as the
interaction coefficient value kij between the hea-
viest one and the light n-alkanes Cl to C3, are those
for which the computed constant -mass liquid- deposit
curve gives the best agreement with the experimental
one (excluding the dew point). The characteristics of
the heaviest "aromatic" hydrocarbon are calculated
with the correlations proposed by ROBINSON and PENG
S
EXPERIMENTAL DATA SET, ADJUSTED PARAMETERS,
COMPUTED PROPERTIES
The data used as an experimental basis for the
parameters adjustment are the following :
- the molar composition of the condensate gas,
- the average molar weight of the heavy fraction,
- the liquid-deposit curve measured in constant-
mass conditions.
From these data, we determine the two hydrocar-
bons which represent the heavy fraction, as well as
the k .. value related to the heaviest one, in order
that average deViation between experimental and
. calculated liquid-deposit volumes is minimum.
We can then compute the other properties measu-
red during the laboratory study and compare the ob-
tained values with the experimental ones, mainly :
- the curve in constant-volume
condi tions,
- the compressibility factor Z of gas produced
during this simulated depletion,
- the cumulative volume of gas produced,
- the molar composition of this gas.
Whenever the experimental study of a natural
gas does not include the liquid-deposit curve in
constant mass condi tions, the parameters ;d.justment
is performed on the basis of representing the liquid-
deposit curve measured in constant-volume conditions.
TEST RESULTS
The experimental data set used for three conden-
sate gases tested is given in Tables 1, fourth con-
densate gas for which the liquid-deposit curve l.n
constant-mass conditions was not published has been
considered. The corresponding experimental data can
be found elsewhere
6

N-alkanes properties have been attributed to
cuts from c4 to the residue C
n
+.
GAS GN 750
The molar composition of gas GN 750 appears in
Table l-A ; the c
7
+ fraction is considered here as
I
SPE 8287
A. PENELOUX, C. JAIN and E. BEHAR 3
the pseudo-binary :
- n-cg, molar fraction 0.0182,
- arc. C19' molar fraction 0.0060 ;
k
ij
(RKD) 0.09, k
ij
(PR) 0.07.
These parameters were found by fi tting the can-
puted liquid-deposit curve in constant-mass condi'tions
to the measured one given in Table l-A. It is interes-
ting to notice that the use of ei ther RKD or PENG-
equations of state leads to the same pseudo-
for the C
7
+ fraction of this gas, and that
the interaction coefficient values given above,
the two thermodynamic models show the same average
deviation from experimental data (ll.4 \).
The liquid-deposit curves computed with RKD and
PR equations of state, in constant-mass as well as
constant-volume conditions are compared on Figure 1
to the experimental data. It appears that there is a
. good agreement on the whole, apart in the vicinity of
the dew point. Taking this fact into consideration,
we can conclude that the cumulative volume of gas
computed by Simulating the laboratory deple-
tion loS lon excellent agreement wi th the measured
values as shown on Figure 2.
GAS GN 776
For gas GN 776 whose molar composition appears
in Table l-B, the c
7
+ fraction is considered as the
pseudo-binary :
- n-C8' molar fraction 0.0153,
- arc c
l3
' molar fraction 0.0088
k
ij
(RKD) 0.03, k
ij
(PR) - 0.05
As for GN 750, the same pseudo-binary is found to
represent the C7+ fraction by fitting the liquid-
deposit curve in constant-mass conditions, with an ave-
rage deviation of 8.7 , for PR model and 10.5 , for
the RICD one. Using SOAVE equation of state, the mini-
mum deviation was found to be 57.8 ,. This can be
expected as it is well known that this equation leads
to highly erroneous calculated liquid phase volumetric
properties.
On Figure 3, the computed compressibility factor
Z of gas produced is compared with experimental data.
It appears that there is a good agreement between the
results obtained with RKD model, while the agreement
is only fair with those of PR model. These two equa-
tions of state lead however to molar compositions of
gas produced which are almost identical as can be
seen on Figure 4, and which are on the whole in good
agreement with the measured ones. The computed cumu-
lative volume of gas produced is also the same for
the two models, and would fit exactly the experimen-
tal data if the calculated dew point is corrected in
order to coincide with the observed one.
GAS GN 777
The analysis of gas GN 777 was performed upto
and the obtained molar composition is given in
Table l-C. The heavy fraction is considered as the
pseudo-binary :
- n-c
lO
' molar fraction 0.0099,
- aro. molar fraction 0.0013
k
ij
( ) '"' 0.00
These parameters were found by fitting the compu-
ted liquid-deposit curve in cons tant-mass condi tions
with RKD model to the measured one given in Table l-C.
The use of PR model leads to
- n-c
10
' molar fraction 0.0098,
- aro. C
20
' molar fraction 0.0014
k
ij
(PR) .. 0.01
In the first case, the average deviation is 5.9 ,
and in the second 4.9 ,.
The liquid-deposit volume and the compressibility
factor of the gas produced during the laboratory simu-
lated depletion are given in Table 2, as well as the
corresponding values calculated with the two equations
of state. It appears that in the case of this gas for
which the maximum amount of liquid-deposi t is very
small, both models lead to a relatively good agreement
with experimental data
GAS PAZANAN 10
The molar composition of this gas and its measu-
red degletion behavior were published by FlROOZABADI
and ar. It contains 0.0310 molar fraction of heptanes
plus whose molecular weight is 132. By fitting the
computed liquid-deposit curve in constant-volume
conditions with RKD model to the experimental one, we
consider the heavy fraction as the pseudo-binary
- n-C
S
' molar fraction 0.0297,
- aro. C
38
, molar fraction 0.0013
k
ij
(RKD) a 0.00
We see on Figure 5 that our resul ts are closer
f;oem the measured data than those obtained wi th PR
equation of state in the work quoted
6
. Figure 6 shows
that both models lead to compressibili ty factor values
for the gas produced which are only in fair agreement
with tr.ose experimentally determined. As noted above,
we see on Figure 7 that the computed volume of gas
produced would fit exactly the measured data if the
calculated dew point is corrected in order to coincide
with the observed one. Finally, Figure 8 and Table 3
show that the molar compositions computed with RICD
equation of state are in good agreement with the expe-
rimental behavior, while the agreement is only fair
with the results obtained by FIROOZABADI and al.
using PR equation.
CONCLUSIONS
A new simple characterization procedure for the
heavy fraction (usually C
7
+) leads to encouraging
results in predicting phase and volumetric behavior
of condensate gases with PENG-ROBINSON as well as
DEVELOPED REDLICH-KWONG equations of state. The compu-
ted properties show that RKD model can be considered
as an improvement of previous work using PR equation,
mainly for evaluating the compositions of equilibrium
phases.
NOMENCLATURE
a energy parameter in RKD equation of state
b covolume parameter in RKD equation of state
k binary interaction energy parameter
P absolute pressure
R perfect gases constant
T absolute temperature
x molar fraction
4
APPLICATION OF RKD EQUATION OF STATE ro CONDENSATE GASES
v molar volume
y energy parameter in RKD equation of state
o energy parameter in RKD.equation of state
L binary interaction volumetric parameter
Subscripts
c critical property
i, j property of components l., J
ij binary interaction property
m mixture property
ACKNOWLEDGMENTZ
Andre PENELOUX acknowledges financial support
of Delegation Generale a la Recherche Scientifique
et Technique.
REFERENCES
1. BEHAR, E., SIMONET, R., and PENELOUX, A. :
"A new non-cubic REDLICH-KWONG based equation
of state", submitted for publication in Fluid
Phase Equilibria
2 B E H A 1 ~ , E., SIMONET, R., and PENELOUX, A. :
"Application of the DEVELOPED REDLICH-KWONG
equation of state to mixtures", to be submitted
for publication in Fluid Phase Equilibria
3. SOAVE, G. : "Equilibrium constants from a modi-
fied REDLICH-KWONG equation of state",
Chem. Eng. ScL, v. 27, pp. 1197-1203, (1972)
4. PENG, D.-Y. and ROBINSON, D.B. : "A new two-
constant equation of state",
Ind. Eng. Chem., Fundam., v. 15, pp. 59-64,
(1976)
5. ROBINSON, D.S., and PENG, D.-Y. : "The characte-
rization of the heptanes and heavier fractions
for the GPA PENG-ROBINSON programs", GPA, Tulsa
(1978), Research Report RR-28.
6. FIROOZABADI, A., HEKIM, Y., and KATZ, D.L. :
"Reservoir depletion calculations for gas conden-
sates using extended analyses in the PENG-
ROBINSON equation of state",
Can. J. Chem. Eng., v. 56, pp. 610-615, (1978)
SPE 8287
TABLE 1-A
EXPERIMENTAL DATA SET FOR GAS GN 750
MOLAR COMPOSITION
s s s ~ ~ ~ ~
0.7502 0.0967 0.0367 0.0196 0.0108 0.0082 0.0242
Averaqe molar weight of C
7
+ fraction : 161
LIQUID-DEPOSIT CURVE INCONSTANT-MASS CONDITIONS AT RESERVOIR TEMPERATURE
(392.15 K)
Pressure, bar
Volume, cc/mol
Pressure, bar
Volume, cc/mol
350.8 321.0 290.1 266.9 251.4 221.1 201.8
0.09 0.53 1.24 1.83 2.26 3.06 3.57
181.0 165.5 144.7 121.0 104.7 91.9 85.5
3.91 4.14 4.45 4.62 4.69 4.66 4.63
TABLE 1-B
EXPERIMENTAL DATA SET FOR GAS GN 776
.'-tOLAR COl1POSITIOiY
C
2
C
3
C
4
C
5
C
6
C
7
+
0.0521 0.0019 0.7759 0.0790 0.0316 0.0187 0.0101 0.0066 0.0241
Average molar weight of C
7
+ fraction: 137
LIQUID-DEPOSIT CURVE INCONSTANT-MASS CONDITIONS AT RESERVOIR TEMPERATURE
(363.15 K)
Pressure, bar
Volume, cc/mol
286.2 266.1 236.3 206.7 182.1 162.6 146.8
0.30 0.87 1.92 2.96 3.77 4.24 4.41
Pressure, bar 131.9 112.6
Volume, cc/mol 4.61 4.79
TABLE 1-C
EXPERIMENTAL DATA SET FOR GAS GN 777
MOLAR COMPOSITION
N2 CO
2
C
l
C
2
C
3
C
4
C
s
C
6
C
7
C
s
C
9
+
0.0082 0.0325 0.7766 0.0843 0.0411 0.0221 0.0110 0.0070 0.00320.0028 0.0112
Average molar weight of C
9
+ fraction : 159
LIQUID-DEPOSIT CURVE IN CONSTANT-MASS CONDITIONS AT RESERVOIR TEMPERATURE
(403.75 K)
Pressure, bar
Volume, cc/mol
209.9
0.02
176.3
0.43
153.2
0.74
117.9
1.18
103.5 89.6
1.30 1.37
TABLE 2
COMPARISON OF CALCULATED AND EXPERIMENTAL
DEPLETION BEHAVIOR OF GN 777 AT 403.75 K
EXPERIMENTAL RKD
Dew point pressure (bar) 219 206
Liquid voll.lllle (ee/mol)
193 bar 0.13 0.22
147 bar 0.46 0.58
117 bar 0.63 0.69
88 bar 0.68 0.72
70 bar 0.66 0.71
49 bar 0.62 0.66
Gas eompressibili ty faetor z
219 bar 0.885 0.899
193 bar 0.884 0.887
147 bar 0.889 0.879
117 bar 0.898 0.883
88 bar 0.913 0.897
70 bar 0.921 0.911
49 bar 0.938 0.931
TABr,E 3
PHASE COMPOSITION BEHAVIOR OF
PAZANAN 10 AT 355.40 K
235 bar
180 bar
125 bar
84 bar
49 bar
EXPERIMENTAL
C
7
+in gas phase (mol. %)
2.59
2.01
1.47
1.21
1.20
RKD
2.99
2.18
1.41
1.02
0.90
Residual liquid phase (mol. %)
0.82
0.01
15.64
3.62
79.91
0.92
0.01
17.50
3.80
77.77
PR
204
0.19
0.55
0.67
0.72
0.71
0.67
0.887
0.876
0.875
0.884
0.901
0.916
0.936
2.51
1.67
1.09
0.84
0.81
N
a:
g
u
<t
.....
>-


4
EXPERIMENTAL
--...........
.....
.....
....
"' ...
...
"\
PRo
R.K.O.
CONSTANT _VOLUME /'l..
CONDITIONS \
100
\ I
\
\ \
200
PRESSURE,BAR
I
\ I
\
\
\
\
Fig. 1. Liquid-deposit curves
for gas GN 750 at 392.15 K
\ I
I I
II
1\
II
"
"
\

1.oo,..------------------------------,
0.95

,
\
EXPERIMENTAL
___ P.R.
_R.K.O.
/
I
/
I
::iQ90
as
\
\
\
/
/
/
/
en
en
w
a:
0-
S
0.85
\ .

.
/
,/
......
/
/
/
/
I
/
/

PRESSURE,BAR
Fig. 3. Compressibility factor of gas produced
for GN 776 at 363.15 K


'\ .

EXPERIMENTAL
PR.
R.K.O.





80
75
70
1
t
e
0-

0
u
a:
10 <t
-'
0

9
8
7
6
0
PRESSURE. BAR
Fig. 2. Cumulative volume of gas produced
for GN 750 at 392.15 K
o 0 0

0
'"
0 0
0 o 0
C
l
o EXPERIMENTAL
___ PR.
_R.KD.


C
z






C3+


-----



0


100 300
Fig. 4. Molar composition of gas produced
forGN 776 at 363.15 K

40
20
..

....

EXPERIMENTAL
"
,
,
,
,
..
,
\
\
\
\
_ R.K.D.
___
100 200
PRESSURE, BAR
Fig. 5. liquid-deposit curve
for Pazanan gas at 355.40 K
(constant-volume conditions)
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
\
300

o
UJ
75
o
o
a::
a..
(/')

u..
o
UJ 50
:E

-1

UJ
>

:5
:E 25

u
EXPERIMENTAL
_ R.K.D.
___
\
,
,
,
,.
,
,
\
\
,
\
,.
\
\
\
\
\
\
\
\
,.
\
\
\
\
\
'\
'\
'\ ..
'\
'\
'\
'\
,

PRESSURE, BAR
Fig_ 7. Cumulative volume of gas produced
for Pazanan 10 at 355.40 K

N
a::
g
u
0.90
>-

::i
as
in
(/')
UJ
g:
0.85
u
\
\
\
\
\
\
\

,
,


EXPERIMENTAL
_R.K.D.
___ PR!I
0.80
0
'----'-----,..l..oo----..i-----
2
..J.
0
-
0
-----'-----30'-0......i
80
75
70
8
7
6
PRESSURE,8AR
Fig. 6. Compressibility factor of gas produced
for Pazanan 10 at 355.40 K
.. EXPERIMENTAL
RXD.
'00
PRESSURE, BAR
Fig. 8. Molal composition of gas produced
for Pazanan 10 at 355.40 K

300