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Introduction
Fluid compressibility and sonic velocity are used for a wide range
of problems in the production and exploration of hydrocarbon
reservoirs. These include well testing, metering, and seismic exploration. Various methods are available for the estimation of
compressibility and sonic velocity in the single phaseboth gas
and liquid states.1 For hydrocarbon mixtures in the two-phase
state, the available methods are unreliable.
Compressibility is often defined on the basis of the thermodynamic path. For an isothermal process, the compressibility relates
volume change to pressure change at constant temperature. In an
isentropic path, the volume and pressure changes are given by
isentropic compressibility. These two compressibilities in the
single-phase state are related by2
c T c P /c V c S ,
335
V j z j n j,t RT/p j ,
V t RT
z n
j j,t
j1
/p j .
The key term in the above is ( V t / p 2 ) S,n ; the procedure for its
estimation is provided in Appendix A.
where P c is the capillary pressure, and r, the radius of the curvature of the interface.
Similar to the above, in the following, subscripts 1 and 2 denote the gas and liquid phases, respectively. The expression for V t
is
V t V 1 V 2 ,
Solution Procedure
When the interface between the gas and liquid phases is flat that
is, r in Eq. 4, ( p 1 / p 2 ) S,n1. In this case, there are (2c
1) equations and (2c1) unknowns; Eqs. A-6, A-9, and A-18
provide the unknowns. For a curved interface, the number of unknowns and the equations increase to 2(c1). The additional
relationship is provided by Eq. A-13. In this work, we use an
iterative procedure to calculate the effect of capillary pressure
variation on the isentropic compressibility and the sonic velocity.
We first assume the interface is flat, and compute the phase volume and compositions, then use Eq. A-14 to estimate the interfacial tension. The amount and the composition of the phases are
again calculated using
f 1,i T,p 1 ,n 1,1 ,n 1,2 ,...,n 1,c f 2,i T,p 2 ,n 2,1 ,n 2,2 ,...,n 2,c ,
i1, . . . ,c,
p 1 p 2 F S L ,
8
9
10
C3 at 130F both in the single phase and two phase. In Fig. 2a,
the isothermal compressibility c T and the isentropic compressibility c S are presented. The two-phase compressibilities are based on
the assumption of a flat interface between the gas and liquid
phases. Fig. 2a reveals that in the single-phase liquid, the isothermal compressibility is a factor of 2 to 4 more than the isentropic
compressibility. In the single-phase gas, the difference is less, but
it is still substantial. Close to the bubblepoint, the two-phase compressibilities are close, but as the amount of the gas phase increases, the difference between c T and c S increases. At the dew-
11
Composition
T
(F)
b
(dyn/cm)
P c,b
(psia)
Pb
(psia)
d
(dyn/cm)
P c,d
(psia)
Pd
(psia)
(psia cm/dyn)
(psia cm/dyn)
C1 /C3
C1 /C3
C1 /C3
C1 /C3
C1 /C3
C1 / n C10
C1 / n C10
C1 / n C10
C1 / n C10
C1 / n C4 / n C10
Crude
Crude
Crude
30/70
30/70
20/80
20/80
20/80
70/30
70/30
95/5
95/5
70/23.5/6.5
130
130
50
50
50
130
130
130
130
160
224.6
224.6
224.6
0.18
0.2
5.5
5.51
5.53
0.85
0.94
0.64
0.63
1.68
1.72
1.78
0
4
0
5.6
29
0
18.7
0
0.6
0
0
17.3
35.7
977.2
966.4
523.5
516.6
480.7
4,170.3
4,093.2
2,988.4
4,317.2
4,271.6
4,222.3
2.2
2
10.1
10
9.9
0
50.9
0
60
98.1
453.4
389.3
119.7
59.6
21.5
5,146.7*
5,151.3*
6.3
20
1
5
20
10
20
5
5
5
5
*Retrograde dewpoint.
337
m/s. At the dewpoint, the sonic velocity increases from 190 to 240
m/s. The capillary pressure dampens the change of the sonic velocity at the dewpoint.
The compressibility and the sonic velocity for the second
C1 /C3 system are plotted in Fig. 3. For this system, the composition is 20% C1 and 80% C3, and the temperature is 50F. Fig. 3a
reveals that the isentropic compressibility varies much less than
the isothermal compressibility in the two-phase region. The effect
of capillary pressure on c T is shown in Fig. 3b; on the bubblepoint
side the effect is small. However, on the dewpoint side, capillarity
reduces the difference between the single- and two-phase compressibilities. Table 1 provides the saturation pressures and P c for
this system. Note that on the dewpoint side, P c is larger than on
the bubblepoint side due to the pressure effect. Fig. 3c shows the
effect of P c on the c S ; there is no decrease in c S as the fluid
enters the single-phase gas. Fig. 3d shows the sonic velocity for
the C1 /C3 system; the trends are similar to Fig. 2d.
C1 nC10. Two different mixtures of C1 /nC10 were studied; one
has a bubblepoint at high pressures and the other has a retrograde
dewpoint.
Fig. 4 shows the compressibility and the sonic velocity for the
mixture of 70% C1 and 30% nC10 at 160F. Fig. 4a shows that in
the two-phase region close to the bubblepoint, c T and c S are different by a factor of 3. Unlike the c T where there is a sharp
increase, cS increases much less when the fluid enters the two
phase. Figs. 4b and 4c show that the effect of capillarity on the
two-phase compressibility is negligible in the pressure range of
the plot. Note that similar to the C1 /C3 system, the bubblepoint
pressure decreases due to capillary pressure see also Table 1.
Fig. 4d depicts the sonic velocity which has a trend similar to the
C1 /C3 system. Capillarity increases the sonic velocity for the system of Fig. 4, but not appreciably.
338
Fig. 5 shows the compressibility and sonic velocity for a mixture of 95% C1 and 5% nC10 . As was pointed out earlier, this
system has a retrograde dewpoint of 5,146.7 psia. At the dewpoint, c T increases while c S decreases. This behavior is different
from the bubblepoint systems which were presented in Figs. 2
through 4. As a result, we observe a significant difference between
c T and c S a factor of 20. Note that for this system, the change
for c S at the dewpoint is more than for c T . The effect of capillary
pressure on c T and c S is not very pronounced results not shown
due to low P c 0.6 psi. It is interesting to note that the capillary
pressure increases the dewpoint pressure see Table 1. The sonic
velocity is plotted in Fig. 5b; it increases in the two phase. This
behavior is in contrast to the sonic velocity of water-air and watersteam mixtures. Fig. 5b also shows that the sonic velocity decreases initially due to the P c effect.
sonic velocity
defined in Eq. B-4
defined in Eq. B-3
total number of components
isentropic compressibility
isothermal compressibility
heat capacity at constant pressure
heat capacity at constant volume
mass density of phase j ( j1,2)
fugacity of component i in phase j
molecular weight of phase j ( j1,2)
vector of overall mole numbers
339
z /n
j
i1
z j / p j T,n j p j / p 2 S,n
c
1. Batzle, M. and Wang, Z.: Seismic Properties of Pore Fluids, Geophysics 1992 57, No. 11, 1396.
2. Firoozabadi, A.: Thermodynamics of Hydrocarbon Reservoirs,
McGraw-Hill Book Co. Inc., New York City 1999.
3. Firoozabadi, A. et al.: EOS Predictions of Compressibility and
Phase Behavior in Systems Containing Water, Hydrocarbons, and
CO2, SPERE May 1988 673.
4. Kieffer, S.W.: Sound Speed in Liquid-Gas Mixtures: Water-Air and
Water-Steam, J. Geophys. Res. 1977 82, No. 20, 2895.
5. Michaelides, E.E. and Zissis, K.L.: Velocity of Sound in Two-Phase
Mixtures, Int. J. Heat Fluid Flow 1983 4, No. 2, 79.
6. Nguyen, D.L., Winter, E.R.F., and Greiner, M.: Sonic Velocity in
Two-Phase Systems, Int. J. Multiphase Flow 1981 7, 311.
7. Wang, Z., Nur, A.M., and Batzle, M.L.: Acoustic Velocities in Petroleum Oils, JPT February 1990 192; Trans., AIME, 289.
8. Katz, D.L. et al.: Handbook of Natural Gas Engineering, McGrawHill Book Co. Inc., New York City 1959.
9. Firoozabadi, A. et al.: Surface Tension of Reservoir Crude-Oil/Gas
Systems Recognizing the Asphalt in the Heavy Fraction, SPERE
February 1988 265.
10. Peng, D.Y. and Robinson, D.B.: A New Two-Constant Equation of
State, Ind. Eng. Chem. Fundam. 1976 15, No. 1, 59.
11. Weinaugh, C.F. and Katz, D.L.: Surface Tension of MethanePropane Mixtures, Ind. Eng. Chem. 1943 35, 239.
Appendix ACalculation of V t p 2 S ,n
From Eq. 7, one obtains
2
z /p n
j
j,t
/ p 2 S,n n j,t /p j
j1
/ p 2 S,n,
A-3
z j n j,t /p j T/ p 2 S,n .
n j,t / p 2 S,n
n
i1
j,i
/ p 2 S,n ,
j1, 2.
A-4
Note that ( n j,i / p 2 ) S,n also appeared in Eq. A-3. Eqs. A-1, A-2,
and A-4 define the 2(c1) unknowns that are required to calculate ( V t / p 2 ) S,n . These unknowns are: ( p 1 / p 2 ) S,n ,
( n j,i / p 2 ) S,n and ( T/ p 2 ) S,n , which are obtained from the following equations based on material balance, equilibrium criteria,
entropy constraint, and capillary pressure relationship.
Material Balance. The component material balance provides
n i n 1,i n 2,i i1,...,c,
A-5
i1,...,c.
A-6
A-7
i1,...,c,
where f is the fugacity. The differential form of the above equation is df 1,i df 2,i . Fugacity of each component in a given phase
is a function of temperature, phase pressure, and moles in the
phase. Therefore,
df j,i f j,i / T p j ,n j dT f j,i / p j T,n j dp j
where ( z j / T) p j ,n j , ( z j / p j ) T,n j , and ( z j / n j,i ) T, p j ,n j,k coefficients can be calculated from an equation of state EOS. In this
work we use the Peng-Robinson10 PR EOS. Note that once
( T/ p 2 ) S,n , ( p 1 / p 2 ) S,n , and ( n j,i / p 2 ) S,n are estimated,
then ( z j / p 2 ) S,n will be established, as will be shown shortly.
References
j1
j1, 2,
Acknowledgments
This study was initiated while one of the authors A.F. was a
visiting professor at the U. of Texas, Austin, in the Fall of 1996.
The help of graduate student Ganesh Narayanaswamy of the U. of
Texas, Austin, in the initial stage of the work is appreciated.
340
z /n
i1
V t / p 2 S,nRT
A-2
j1,2,
z j / p 2 S,n z j / T p j ,n j T/ p 2 S,n j
gas phase
liquid phase
bubblepoint index
dewpoint index
component index
phase index
component index
component index
total
where n j (n j,1 ,...,n j,c ); n j,i is the number of moles of component i in phase j, and n j,k n(n j,1 ,...,n j,k ,...,n j,c ) and ki. By
dividing Eq. A-2 by p 2 at constant n and S,
Subscripts
1
2
b
d
i
j
k
l
t
A-1
k1
j,i
/ n j,k T, p j ,n j ,l dn j,k ,
j1, 2,
i1,...,c,
A-8
where n j,l (n j,1 ,...,n j,l ,...,n j,c ) and lk. Dividing Eq. A-8 by
p 2 , keeping S and n constant, and using the criterion of equilibrium, one obtains
f 1,i / T p 1 ,n1 f 2,i / T p 2 ,n2 T/ p 2 S,n
f 1,i / p 1 T,n1 p 1 / p 2 S,n f 2,i / p 2 T,n2
k1
k1
2,i
i1,...,c.
A-9
V 1 V 2 / p 2 S,nV 2 V 1 / p 2 S,n
.
V 1 V 2 2
Vj
j1
2 S,n0.
A-10
j1
ln V j / n j,i RT
S /n
k1
/ p 2 S,n 0.
S j n j,t R ln
A-11
The
coefficients
( S j / T) p j ,n j ,
( S j / p j ) T,n j ,
and
( S j / n j,k ) T,p j ,n j,l can be estimated from the expression of the
phase entropy derived in Appendix B.
Capillary Pressure Effect. According to Eq. 4, if and r stay
constant as p 2 changes, ( p 1 / p 2 ) S,n1. However, with change
in p 2 , the temperature and the composition of the phases may
change. The curvature also may change. One may express the
capillary pressure in porous media as
P c p 1 p 2 F S L ,
A-12
where S L represents the liquid saturation. Then,
p 1 / p 2 S,n1F S L / p 2 S,n F/ p 2 S,n .
P x
i1
2,i 2
/M 2 x 1,i 1 /M 1 .
A-14
In Eq. A-14, x 2,i and x 1,i are mole fractions of component i in the
liquid and gas phases, respectively, and and M represent the
density and the molecular weight; P i is the parachor of component i.
A more useful form of Eq. A-14 is
c
1/4
P n
i1
2,i
/V 2 n 1,i /V 1 .
A-15
/ p 2 S,n4 3/4
P n
i1
2,i
n
i1
B-1
o
j,i s i T .
z j B j da j T /dT z j 1& B j
ln
zj
2&b j
z j 1& B j
i1
x j,i ln
zj
x s 0 T .
x j,i p j i1 j,i j
B-2
a j
B-3
x
i1 k1
j,i x j,k a ik
B-4
In Eqs. B-3 and B-4 b j and a ik are the parameters of the PR-EOS.
A-13
Kieffer neglected the last two terms on the right side of Eq. A-13
in her work.4 The interfacial tension between the gas and liquid
phases in a mixture can be represented by the Weinaugh-Katz
model,11
1/4
n j,t R
p j / T V j ,n j dV j R
n j,i
Vj
i1
c
S /p
j
A-18
S/ p 2 S,n
A-17
Since S L V 2 /(V 1 V 2 ),
S L / p 2 S,n
/V 22 V 2 / p 2 S,n
n 1,i /V 21 V 1 / p 1 S,n
n 2,i / p 2 S,n /V 2 n 1,i / P 2 S,n /V 1 .
A-16
A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures
E02
E00
mN
C
K
kPa
SPEREE
Abbas Firoozabadi is Senior Scientist and Director at the Reservoir Engineering Research Inst. (RERI) in Palo Alto, California.
e-mail: AF@rerinst.org. He has taught previously at Stanford U.
and the U. of Texas at Austin. His research interests include
equilibrium, non-equilibrium, and irreversible thermodynamics,
multiphase flow in fractured and layered permeable media,
and tidal-force-influenced pressure transients for the estimation of key parameters of fractured reservoirs. Firoozabadi
holds a BS degree from the Abadan Inst. of Technology, Iran,
and MS and PhD degrees from the Illinois Inst. of Technology,
Chicago, all in gas engineering. He has served on various SPE
Committees. Huanquan Pan is a software developer at Incyte Genomics in Palo Alto, California. Previously, he was a
scientist with the Reservoir Engineering Research Inst. (RERI),
where he worked on the modeling of asphaltene and wax
precipitation and the development of efficient phaseequilibrium algorithms for compositional reservoir simulation.
Pan holds a PhD degree in chemical engineering from Zhejiang U. in Hangzhou, China.
SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000
341