Journal o f Petroleum Science and Engineering, 8 ( 1993 ) 315-328 315

Elsevier Science Publishers B.V., Amsterdam

A study on the minimum miscibility pressure for miscible

flooding systems

You-xiang Zuo, Ji-zheng Chu, Shui-lin Ke* and Tian-min Guo

University of Petroleum, Beijing, P.R. China
( Received December 30, 1991 ; revised version accepted July 16, 1992 )

ABSTRACT

Zuo, Y.-X., Chu, J.-Z., Ke, S.-L. and Guo, T.-M., 1993. A study on the minimum miscibility pressure for miscible flooding
systems. Z Pet. Sci. Eng., 8: 315-328.

The minimum miscibility pressures (MMP) of a Chinese reservoir crude oil injected with pure and impure CO2 have
been measured in a RUSKA slim tube apparatus. New correlations are proposed for CO/-flooding and lean natural gas-
flooding systems, respectively. The comparisons of the new correlations with several representative MMP correlations
available in the literature show that the new correlations give the best prediction results. Based on the cell-to-cell algorithm
proposed by Jensen and Michelsen, minimum misibility pressures for various gas-flooding processes were predicted using
an equation-of-state and a semicontinuous description of heptane-plus fraction. Satisfactory results were obtained.

Introduction when an optimum driving-gas composition is

Miscible flooding is recognized as an effec-
tive enhanced oil-recovery method. A flood is
considered miscible when there is no phase
boundary between the displacing fluid and the
displaced fluid. Light hydrocarbon gas mix-
tures, carbon dioxide, nitrogen and flue gas
mixtures are the common driving fluids. The
key parameter required for evaluating and de-
signing a miscible flood is the m i n m u m mis-
cibility pressure (MMP).
The minimum miscibility pressure depends
on reservoir temperature and the composi-
tions of reservoir oil and injection gas. It is a
common practice to measure the M M P data
using a slim tube apparatus, however, this is
time-consuming and expensive, especially
Correspondence to. Tian-min Guo, Beijing University of
Petroleum, Beijing Graduate School, P.O. Box 902,
100083 Beijing, P.R. China.
*Present address: The Shengyan Petroleum Transporta-
tion Corporation, Shengyang, China.
to be searched. Furthermore, different experi-
mental procedures and definitions of miscibil-
ity may lead to confusing results.
A reliable method for predicting the M M P
is of critical importance in the screening of po-
tential reservoirs suitable for applying the mis-
cible flooding technique. Empirical M M P cor-
relations are widely used in petroleum
industry, numerous M M P correlations for var-
ious gas-flooding processes have been re-
ported in the literature. Recently, a theoretical
approach based on an equation-of-state was
proposed by Jensen and Michelsen ( 1987 ).
The objectives of this work are:
( 1 ) Measure the M M P data for pure and im-
pure CO2-displacement of a typical
Chinese reservoir crude oil.
(2) Compare the performance of representa-
tive empirical M M P correlations cur-
rently available, and try to improve some
of the correlations.

0920-4105/93/$06.00 © 1993 Elsevier Science Publishers B.V. All rights reserved.

316 YOU-X1ANG Z U O E T AL.

(3) Test the Jensen-Michelsen M M P algo-
rithm by using different equations-of-
state and the semicontinuous description
of the heptane-plus fraction in reservoir
oils.
Experimental work
CH4 by mole). The plots of the stock tank
(S.T.) oil recovery at breakthrough point ver-
sus displacement pressure for both cases are
depicted in Figs. 1 and 2, respectively. The
pressure at the intersection point of two
straight-line sections is taken as the M M P
100

A RUSKA slim tube apparatus was used in • EXPERIMENTAL DATA

this work, the specifications of the apparatus 95 T = 358.B K
is given in Table 1.
A reservoir crude oil sampled from Jianhan
Oil Field (Mid China) is used for the CO2- 90
E
miscible flooding test, the composition of the
oil sample is given in Table 2.
The M M P experiments were performed at c~
s=.
85"

the reservoir temperature (358.8 K), by us-

ing: Case 1 - - pure CO2 (99.99 tool%); and
80-
Case 2 - - impure CO2 (93.21% CO2+6.79%

TABLE 1
75 | I i I I I ,,, I
6 18 20 22 24
Specifications of the RUSKAslim tube apparatus
PRESSURE (MPa)

Inside diameter (mm) 6.16

Fig. 1. Stock tank oil recovery (%) at breakthrough point
Outside diameter (mm) 7.94
Length (m) 18.3 versus displacement pressure (pure CO2-displacement,
Glass bead packing (mesh) 80-100 T=358.8 K).
Porosity (%) 35
I00
Permeability (darcy) 13
• EXPER[MENIAL DAIA

TABLE 2 95 1 = 358.8 K

Composition of the reservoir crude-oil sample tested

>- 90
Component Mol% >
cJ
N2 0.166 L_ ~15 .

CO2 0.166
CH 4 17.195 c

C2H6 5.892 a~" 80 "

C3H8 4.528
iC4HIo 0.892
nC4Hjo 1.441 75
iCsHj2 1.053
HCsHI2 0.650
C6 0.206 7 [7 I I I ; I I I
20 22 22 2t6 28 30
C~ 67.811
PRESSURE (MPa)
X 100.000
Fig. 2. Stock tank oil recovery (%) at breakthrough point
Properties of C~--fraction: molecular weight = 282; specific versus displacement pressure (impure CO2-displace-
gravity = 0.8446 ment, T=358.8 K).
MINIMUM MISCIBILITY PRESSURE FOR MISCIBLE FLOODING SYSTEMS 317

/ fig weight of injection gas; and ]/=constant,

EXPERIMENIAL DATA =0.285.
c~i is a constant, when the content of impur-
8U" ities in CO2 (}'2) is less than 10 mol%, and 300
K < T< 410 K.
For pure CO2, a i = 18.9; for (CO2+N2),
~- 6 [~
oti=lO.5[1.8+lOOOY2/(T-Tci)]; for (CO2
+CH4), t~i=lO.5[1.8+lOOY2/(T-Tci)];
and I is the characterization index of oil, which
~ a0
=:
is determined as a function of API gravity and
molecular weight of oil:
20. I=Cll +C21M+C31M2+C41M3
+ (C12 + C 2 2 M ) A P I + CI3API 2 (2)
0
.0
J
O.2
I
0.4
I
8.6
p
0.8
I
1 .0 1
where: CII= - 11.7300; C21 =0.06313;
P.V. CO 2 INJECIED
C31=-- 1.954× 10-4; C12=0.1362; C22=
1.138× 10-5; C41=2.502× 10-7; and C13=
Fig. 3. Cumulative stock tank oil recovery (%) versus pore
volume (%) pure CO2, injected at 20.0 MPa and 358.8 - 7.2220X 10 -3.
K. The authors have tested the Johnson-Pollin
(J-P) correlation on the prediction of the
(20.61 MPa for pure CO2-displacement and MMP of several pure CO2-displacement sys-
25.79 MPa for impure CO2-displacement are tems, and found that the predicted MMPs are
thus determined). consistently too low (typical results are given
A typical S.T. oil-recovery curve plotted in Table 3).
against pore volume (PV) of pure CO2 in- For improving its accuracy in predicting the
jected at 20.0 MPa and 358.8 K is shown in MMP for pure CO2-displacement systems, two
Fig. 3. compositional parameters, the mole fractions
of the light (CH4-1- N2) and intermediate
Study on the M M P correlations for common (CO2+H2S+C2H6 through C4Hlo) compo-
driving gases nents in reservoir oil are introduced into the
J-P correlation.
The new MMP correlation (MJP) for pure
Pure COe-displacement CO2-displacement proposed by the authors is
of the following form:
The original Johnson-Pollin ( 1981 ) corre- Pmmp = 7 . 3 7 + 6 . 8 9 5 × 1 0 - 3 X
lation for CO2-displacement is in the following
form (with units changed to SI units): [ 18.9 ( T - 304.2) +I(AIM-44.01 )2] X

Pmmp--Pci =0.006939ai ( T - Tci) ] (3)

+ I(flM-Mi) 2
where: Pmmp=minimum miscibility pres-
sure (MPa); Pci = critical pressure of injection
gas (MPa); Tci=critical tempeature of injec-
tion gas (K); T= reservoir temperature (K);
M = molecular weight of oil; Mi = molecular
(1) where the minimum miscibility pressure,
Pmmp, is in MPa; M is the average molecular
weight of the heptane-plus fraction in oil; X.t
and Xin t a r e mole fractions of light and inter-
mediate components in oil, respectively; T is
reservoir temperature in K; Al, A2, and A3 are
regressed constants, and are equal to 0.16853,
318 YOU-XIANG ZUO ET AL.

TABLE 3

Comparison of the results of MMPprediction by various correlations" for pure CO2-displacement systems

Temp. Exp. Relative deviation ** of predicted MMP (%) Data

(K ) MMP source
(MPa) New J-P Glaso Alston Cronq- Cronq- PRI- 1 PRI-2
1 2

305.4 6.89 7.03 16.58 -18.88 -10.57 -7.26 - 15.73 -9.37 0.69 a
313.7 8.28 -0.15 17.43 -13.97 -8.40 -14.55 -11.59 -7.82 -12.74 a
330.4 11.72 -2.93 23.15 -1.67 0.07 -16.64 -0.10 -4.10 -16.53 a
338.8 13.45 -0.91 20.75 2.96 -7.00 - 16.98 3.53 -5.00 - 15.28 a
373.2 25.27 -2.59 36.66 -39.53 -35.89 -20.20 2.76 5.26 18.15 b
344.2 15.52 0.14 20.12 4.99 3.54 -25.22 0.70 0.43 -6.77 c
316.0 10.62 12.29 29.21 5.90 5.28 -3.56 5.80 12.09 6.02 d
314.2 8.10 -17.77 11.53 -25.15 -57.72 -68.49 -37.90 -11.23 -16.92 e
316.0 10.34 7.99 27.64 3.20 -6.27 - 15.26 -0.83 9.75 3.51 f
312.6 13.79 35.12 47.66 31.19 23.39 23.46 30.05 36.69 34.63 f
313.2 12.40 27.60 39.79 22.99 14.43 11.14 20.34 28.75 25.91 g
316.0 8.90 -10.26 20.90 -15.08 -44.86 -54.36 -26.90 -4.18 -11.38 g
305.4 8.00 4.92 6.18 -2.29 2.14 15.83 2.93 5.72 14.39 h
327.6 10.99 -6.31 4.90 -3.61 10.50 -0.63 5.73 -5.58 -18.24 i
359.2 20.61 -1.17 -66.81 -16.70 -92.82 -61.28 -44.64 5.18 7.67 j

AAD (%) 9.15 25.95 13.87 21.53 23.66 13.97 10.08 13.92

* Cronq-l--Cronquist (1977); Cronq-2--Cronquist (1978); Glasff---Glaso (1985); PRI-I and PRI-2--Petroleum Recovery
Institute (Lee, 1979)
*° Relative deviation is defined as: Rel. Dev. (%) = (Pexp-PcJP~xp) X 100.
Data sources: (a) Metcalfe ( 1980); (b) Husodo et al. ( 1985 ); (c) Graue and Zana ( 1981 ); (d) Gardner et al. ( 1981 ); (e)
Sebastian et al. ( 1985); ( f ) Rathmell and Stalkup ( 1971 ); (g) Spence and Watkins ( 1981 ); (h) DOE Final Report ( 1981 ); (i)
Dicharry et al. ( 1974); (j) This work.

0.13471 and 0.43945, respectively; the char- Impure C02-displacement

acterization index I of oil is calculated from
Eq. 2.
The new MMP correlation gives an average
absolute deviation (AAD) of 6.79% in the pre-
diction of MMP for six pure CO2-displace-
ment systems not entering into the parameter
regression. Table 3 tabulates the results of
MMP calculations for 15 pure CO2-displace-
ment systems. Eight correlations (Glaso, 1985;
Alston et al., 1985; Cronquist, 1977, 1978;
Johnson-Pollin, 1981; Petroleum Recovery
Institute, PRI-1 and PRI-2, 1979; and Eq. 3)
were used for comparison.
The calculation results indicate that the new
correlation established in this work gives the
best MMP predictions.
For impure CO2-displacement systems, the
original J-P correlation is restricted to low
concentrations ( < 10 tool%) of impurities
(CH4 and N2 ) in CO2.
Sebastian et al. (1985) proposed a correla-
tion for impure CO2-displacement in the fol-
lowing form:
pim p ----romp
romp __ppure X F i m p (4)
where Fim p i s a correction factor to the MMP
calculated for pure CO2-displacement
(ppur~ ~ and correlated as follows"
--romp.,,
Fimp - - 1 . 0 - - 0 . 0 2 1 3 ( T ~ m - 3 0 4 . 2 )
+2.51 × 10-4(Zcm - 3 0 4 . 2 ) 2 - 2 . 3 5 X 10 -7
× (T~m - 3 0 4 . 2 ) 3 (5)
MINIMUM MISCIBILITY PRESSUREFOR MISCIBLEFLOODING SYSTEMS 319

where Tcmis the molar average critical tem-
perature of the driving gas:
Tcm=ZX, Tc,
i relation which is in the same form as Eq. 4, but
X, and Tc~ denote the mole fraction and crit-
ical temperature (K) of component i in the in-
jection gas, respectively.
The M M P correlation for impure CO2-dis-
placement developed by Kovarik ( 1985 ) is in
the following form (with units changed to SI
units):
pimp
romp ~--
0.2831 [ (548-- 1.8T~m) + 144.1Ppure
* --mmp j1
where Pmmpis in MPa; Tom is in K, and cal-
culated from Eq. 6.
(6) Alston et al. (1985) proposed a M M P cor-
the correction factor F~mp is correlated as fol-
lows (with units changed to SI units ):
Fimp = ( 4 8 " 7 8 / T c w ) 94"38/7b* (8)
T~w=~ W, T~,-273.2 (9)
/
where Tow is in K; Wi and T. denote the
(7) weight fraction and critical temperature (K)

TABLE 4

Comparison of the results of MMP prediction by various impure CO2 MMP-correlations (:]/L~/Ppureco2 based on experimental
values )

Temp. Inj. gas Exp. Rel. dev. of predicted MMP (%) Data
(K ) comps. MMP source
(tool%) (MPa) Sebastian Kovarik Alston

358.8 93.2CO2 + 6.8C1 25.790 5.68 4.38 9.12 This work

313.7 90CO2 + 10Cl 11.073 -4.75 27.79 -8.70 [a]
313.7 80CO2+20C~ 14.873 - 10.08 33.82 -6.69 [a]
330.4 90CO2 + 1OCt 15.341 - 2.06 24.71 - 6.63 [a ]
330.4 80CO2 + 20Ct 18.617 1.77 25.43 5.6 l [a ]
322.0 90CO2+ 10C2 9.998 10.06 10.98 4.24 [b]
322.0 90CO2 + 10C3 9.308 3.23 - 15.84 - 4.55 [b ]
322.0 80CO2 + 20C3 7.929 6.19 - 43.09 - 3.34 [b ]
338.8 90CO2 + 10C2 13.032 2.91 3.66 - 2.53 [b ]
338.8 90CO2+ 10C3 11.032 6.15 -7.12 3.91 [b]
338.8 80CO2+20C2 12.873 3.91 4.46 -6.53 [b]
338.8 80CO2 + 20C3 10.494 -2.14 -33.91 - 10.93 [b]
314.2 90CO2 + 10C~ 10.79I -4.30 29.54 -8.26 [c]
314.2 81CO2+ 19C~ 12.514 2.22 53.06 4.40 [c]
314.2 72CO2 + 28C~ 15.031 4.51 61.88 35.99 [c ]
314.2 45C02 + 27C~ + 28C3 10.480 0.53 37.93 - 41.03 [c ]
314.2 92C02 + 8N2 11.653 - 5.80 32.47 15.32 [c]
344.2 Gas ~zl * 15.169 15.53 22.12 12.04 [d]
344.2 Gas =2* 22.064 12.83 22.21 70.18 [d ]

AAD'" (%) 5.51 26.02 13.69

*Composition (mol%) of Gas ~1: 95.016CO> 0.081N2, 4.892C1, 0.009C> 0.002C>

Composition (mol%) of Gas ¢t2: 85.757CO> 9.658N> 4.563C1, 0.014C2, 0.004C3, 0.003iC4.0.001iCs.
**AAD is defined as:

N~PlPexp-- Peal]
AAD(%) = 1/Np)... - - X 100
j ] Pexp [j

Np--number of data points.

Data source: (a) Cronquist (1977); (b) Cronquist (1978); (c) Sebastian et al. (1985): (d) Alston et al. (1985).
320 YOU-XIANG ZUO ET AL.

TABLE 5

S u m m a r y o f impure CO2 M M P prediction results (MMPvure co2 based on calculated values )"

Correction AAD, %
factor
correlation New J-P Glaso Alston Cronq- 1 Cronq-2 PRI- 1 PRI-2

Sebastian 10.68 19.32 12.64 27.50 34.71 16.13 10.94 17.07

Kovarik 29.09 27.30 31.58 39.78 45.45 34.17 29.42 33.08
Alston 37.76 36.16 39.79 56.60 65.71 45.39 36.22 41.96

* S y s t e m s tested are the s a m e with Table 4.

TABLE 6

Comparison of the M M P predictions by various correlations for pure N2-displacement systems"

Temp, Exp. Rel. dev. o f predicted M M P (%) Data

(K ) MMP source
(MPa) Glaso- 1 Glaso-2 Firoozabadi-Aziz Hudgins

406.2 41.49 14.31 2.14 -3.12 21.22 a

333.2 44.00 31.31 - 0.66 2.07 25.52 a
366.2 45.50 28.28 - 1.91 1.89 26.98 a
364.2 32.00 2.81 -0.20 0.85 9.10 a
410.4 61.02 45.70 1.66 6.58 - 0.64 b
380.4 58.61 40.74 - 8.78 3.45 - 4.59 b
422.1 62.05 47.61 5.66 7.91 0.98 b
410.4 46.20 28.27 - 3.33 - 15.75 0.64 b
380.4 44.13 21.29 - 16.67 - 19.85 -2.56 b
422.1 47.23 31.16 2.03 - 13.62 2.36 b
410.2 34.34 3.47 3.66 - 44.17 - 0.59 b
380.4 33.44 -3.89 - 10.13 -45.77 -2.69 b
422.1 35.16 7.54 10.16 -41.49 1.58 b

/L4D (%) 23.57 5.15 15.89 7.65

" Glaso- l - - G l a s o ( 1985 ); G l a s o - 2 - - G l a s o ( 1987 ); F i r o o z a b a d i - A z i z ( 1986 ); H u d g i n s - - H u d g i n s et al. ( 1987 )

Data sources: (a) Glaso ( 1987); ( b ) H u d g i n s et al. ( 1 9 8 7 ) .

of component i in the injection gas, ment obtained by several correlations. The Se-
respectively. bastian's correlation with ~rnmp
ppure calculated
The comparison of the relative deviations in from the new correlation (MJP) gives the best
M M P prediction by using the above men- predictions.
tioned correlations is listed in Table 4.
pure
Experimental values are used for Pmmp. The
superiority of Sebastian's correlation over Pure N2-displacement
other correlations compared is obvious. In the
absence of experimental M M P data for pure Based on the examination of the represent-
COz-displacement, ppure
--rnmp can be evaluated ative M M P correlations for pure N2-displace-
from various correlations mentioned in the ment reported in the literature, the Glaso
previous section. Table 5 lists the results of (1987) and Hudgins et al. (1987) correla-
M M P prediction for impure CO2-displace- tions are recommended.
MINIMUM MISCIBILITY PRESSURE FOR MISCIBLEFLOODING SYSTEMS 321

TABLE 7

Comparison of the M M P predictions by various correlations for lean hydrocarbongas-displacement systems

Temp. Exp. Composition of Rel. dev. of predicted MMP (%) Data

(K ) MMP driving gas source
(MPa) New Kuo Glaso* Firoozabadi-Aziz

328.8 26.75 65%C~ + 35%C3 -9.24 -2.40 22.11 - 136.25 a

328.8 25.17 62.4%C~ + 37.6%C3 -4.39 -1.48 24.47 -151.08 a
328.8 18.96 54.3%C j + 45.7%C3 3.51 - 6.16 25.04 -233.32 a
349.8 16.55 Gas #1 10.36 8.94 20.08 - 146.04 a
369.8 18.48 Gas #1 17.92 5.35 14.21 - 125.29 a
365.4 39.30 Gas # 2 -2.63 24.94 -8.00 - 18.11 b
352.0 47.22 Gas # 3 3.80 19.80 - 1.03 3.80 b
372.0 35.85 Gas#4 5.44 1.32 -9.12 6.75 b
380.4 41.37 Gas#5 -0.19 -36.13 -157.70 -0.19 c
366.5 39.99 Gas # 6 3.30 14.76 - 33.03 3.30 c
444.3 33.10 100% C~ -2.04 -216.70 -319.19 -2.04 c
423.8 43.44 100% C~ -2.17 -163.59 -163.49 -2.17 c

AAD (%) 5.42 41.80 66.45 69.03

" Glaso (1985).

Data sources: (a) Kuo ( 1985); (b) Glaso ( 1985); (c) Firoozabadi and Aziz (1986).
Compositions of Gas # l - G a s # 6 (tool%):
Gas # 1 - - 0 . 4 5 % C O 2 + 0.26%N2+ 52.88%Ci + 19.43%C2 + 13.11%C3 + 3.02%iC4 + 4.68%nC4 + 1.66%iC5 + 1.5 l%nC5 +
3.ooo/ocg- .
Gas #2--0.76%CO2+0.50%N2+72.04%C~ + 12.41%C2+8.60%C3+ 1.19%iC4+2.55%nC4 +0.58%iC5+0.65%nC5+0.35%C6
+ 0.37%C + .
Gas # 3 - - 1 . 3 5 % C O 2 + 1.40%N2+ 82.17%C~ +8.42%C2+4.53%C3+0.49%iC4+0.95%nC4+0.19%iCs+0.18%nCs+0.16%C6 +
0.16C ¢ .
Gas #4--0.76%C02+0.29%N2+73.05%C~+13.95%C2+8.17%C3+0.77%iC4+ 1.89%nC4 + 0.29%iC5 + 0.33%nC~ +
0.24%C6 + 0.26%C + .
Gas #5--2.48%N2 + 87.83%C~ + 7.50%C2 + 1.91%C3 + 0.26%C4
Gas # 6 - - 1.05%CO2 + 83.21%Cj + 8.81%C2 + 4.11%C3 + 1.40%C4.

Glaso (198 7) correlation with:

R1 = 792.06X25/(MT °25 ) (13)
emmp : 7 2 5 . 0 - 3 . 8 5 X - 9.22 Y+ 0.63 T
and:
(for S G > 0 . 8 0 1 7 ) (10)
emmp = 878.0- 9.17X- 1.71 Y - 1 . 2 5 T R2 = 2 . 1 5 8 × 1 0 6 X 1 5 6 3 2 / ( M T °'25) (14)

(for S G < 0.807)
where emmp is M M P in bar; T is reservoir
temperature in ° C; X and Y are mole percents
of methane and the intermediate fraction
(C2H6-C6HI4) in oil, respectively; and SG is
the specific gravity ofoil.
Hudgins et al. (198 7) correlation
emmp : 5568 exp( - R 1 ) + 3641 e x p ( - R e )
( 11 ) where Prnmpis MMP in psi; XI and X25 are
mole fractions of CH4 and the intermediate
components (CO2, H2S and C 2 H 6 - C 5 H I 2 ) in
oil, respectively; M is the average molecular
weight of heptane-plus fraction in oil; and T is
reservoir temperature in ° F.
Table 6 summarizes the results of the M M P
prediction for pure N2-displacement obtained
by four correlations. The Glaso (1987) and
Hudgins et al. correlations show better agree-
(12) ment with the experimental data.
322 VOU-XlAN6ZVOEVAL.

Lean hydrocarbon gas-displacement M M P prediction based on equations-of-state

A brief description of the Jensen-Michelsen

Firoozabadi and Aziz ( 1986 ) developed the
method
following correlation for predicting the MMP
of lean hydrocarbon gas-displacement:
The MMP prediction methods based on the
Pmmp =9433-- 188X 103 [(X2s/(MT°25)] limiting tie-line concept were proposed by Luks
et al. (1987), Hagoort and Dumore (1985),
+1430>(103 [X2s/(MT°25)] 2 (15)
Kuo (1985) and Jensen and Michelsen
(1987 ). These procedures are not suitable for
where Pmmp is MMP in psi; T is reservoir
multicomponent mixtures. For the latter, Jen-
temperature in °F; Xzs and M have the same
sen and Michelsen proposed an algorithm for
meaning in Eq. 13.
simulating the multi-contact process.
Because the Firoozabadi-Aziz (F-A) cor-
The miscibility process for a vaporizing gas-
relation was developed from the experimental
drive can be simulated through continuous ad-
data for lean hydrocarbon gas-drive (contain-
dition of reservoir oil at constant pressure and
ing more than 80 mol% methane), and the
temperature to a cell initially containing the
composition of the driving gas does not enter
injection gas. This experiment is schemati-
into the correlation, it produces large errors
cally illustrated in Fig. 4. The starting point is
when the methane content in the driving gas is
a cell filled with injection gas; reservoir oil is
significantly lower than 80%.
continuously added to this cell and equili-
By introducing two additional variables, the
brated with the gas. The oil, not dissolved in
mole percent of methane and the average mo-
the gas phase, is removed continuously from
lecular weight of the intermediate components
the cell. At some later stage, if no further oil is
(C2H6-C4Ht0) in the driving gas, the follow- formed in the cell, miscibility has been
ing modified F-A correlation (MFA) is pro-
achieved.
posed by the authors: To simulate a condensing gas-drive, the cell
F-A ( f o r X I >__80mo1%) is initially filled with the original reservoir oil.
emmp=emmp (16)
Injection gas is added continuously at con-
F-A AI A2 stant pressure and temperature, and the gas not
Pmmp=Pmmp X (Xl /Mint) (17)
(for XI < 80 mol% ) dissolved in the oil phase is continuously re-
moved. At some later stage, when all the added
where Pmmp is MMP in psi; pF~p is MMP gas enters the oil phase in the cell, miscibility
calculated from the F-A correlation, Eq. 15;
X~ is the mole percent of CH4 in driving gas; P l l
Mint is the average molecular weight of inter-
mediate components (C2H6-C4HIo) in driv-
ing gas; A I and A2 are regressed constants
(A1 = 2.6040 and A2 = 3.0746).
Table 7 lists the results of MMP prediction
for the lean hydrocarbon gas-displacement ob-
tained by four correlations. Significant im-
provement in MMP prediction is observed by
using the new correlation (MFA) proposed in Fig. 4. Diagram of multi-contact miscibility process
this work. simulation.
M I N I M U M M I S C I B I L I T Y P R E S S U R E F O R MISCIBLE F L O O D I N G S Y S T E M S 323

has been obtained. As compared with the real
flow process in the reservoir, the cell fluid re-
flects the situation right at the gas front.
Following Jensen and Michelsen ( 1987 ), the
vaporizing gas-drive is described by a set of
differential mass-balances and algebraic equi-
librium relations in the following form:
d v g = ( f - o i ) dt i = 1 , 2 ..... N
(oJO)Ol~=(u,/V)f)~ i = 1, 2, ..., N
0=~, Og
I Four
V = ~ v,
l 1976), VPT (Valderrama, 1990) and the
where V and vi stand for total moles and the
moles of component i in the gas phase, respec-
tively; f denotes the moles of component i in
the feed oil; O and oi stand for the total moles
and moles of component i in the removed oil,
respectively. Integration of Eq. 18 over time-
step At gives:
suits in a single-phase solution, miscibility has
been achieved. If, on the other hand, the end
results are constant compositions, miscibility
can not be obtained at the given conditions.
By performing simulation calculations under a
series of pressures, the MMP is determined as
the lowest pressure at which miscibility is
achieved.
(18)
(19) Equations-of-state tested
(20)
equations-of-state: (EOS)-SRK
(Soave, 1972), PR (Peng and Robinson,
(21)
modified Kumar-Starling (MKS) equation-
of-state (Chu et al., 1991 ) have been tested, as
comparable predictions were obtained, only
the results from SRK and MKS-EOS are re-
ported in this paper.
Since the MKS-EOS was recently developed
by our group (Chu, et al., 1991 ), it is briefly
introduced as follows:

v~( t + At) = v~( t) + f A t - f '+~' o~dt,

RT
P'v-bl
a
(v+b2)(v+b3)
[ l , V-bl
i = 1 , 2 ..... N (22)
(24)
Assuming constant feed rate, using the trap-
where
ezoidal rule for the integration of Eq. 22, the
following expression is derived: a=RT(A3 -As)re (25)
v~(t+At) = vi(t) + f A t - [oi(t) bl =A 1vc (26)
+o,(t+zlt)],~t/2 i = 1, 2, ...,N (23) b2 ={ [A3 + (A~ +4AI )° 5l/2}vc (27)

Equations 19-23 give a set of 2 N + 2 alge- b3 = { [A3 - (A 3z + 4AI )0.5]/2}vc (28)

braic equations, the unknowns being the val-
ues of the variables at t+LIt. The compositions d= [Az/RT-AI (A3 - A s - 1 ) ]vc/(A3 - A s )
of the first equilibrated phases ( t = 0) are cal- (29)
culated from phase equilibrium relations. The
amount of the gas (V) in cell at t = 0 can be A1 =0.262524 (30)
chosen freely. Adding da moles of reservoir oil A2, A3 and A5 are functions of reciprocal re-
to a gas at equilibrium results in db moles of duced temperature Tr and orientation param-
oil to be removed, the initial relative flow rate eter 7, Vcis the critical molar volume.
of oil, db/da, can be determined by applying For mixtures, the mixing rules used are:
the equilibrium relations. Successive solution
with a chosen time-step At simulates the mis- a=~,i ~ xixj(aiaj)(1-ka) (31)
cibility process. Ifa time-step at some stage re-
324 YOU-XIANG ZUO ET AL.

rameter, a, is the slope of the distribution

bk=~ xibki ( k = 1, 2, 3) (32)
curve, which depends on the molecular weight
of the heavy fraction.
d = ~i xidi (33) The carbon number Cn is related to the av-
erage molecular weight (M) approximately by:
The detailed description of the MKS-EOS is C~=(M+4)/14 (36)
contained in the original article.
The slope of the distribution curve is then
The Application of the semi-continuous determined from the following equation:
distribution function to describe the Cz+-
fraction 1 C A+~(B-A)e-"tr]
"- L -J (37)
Following Behrens and Sandier (1986), a The property of a mixture can be expressed as:
truncated exponential-decay distribution
function is chosen in this work: H= D(I)e-~ldI (38)
F ( I ) =e-~1 e -p (A<I<B<~) (34)
by transformation of variables it becomes:
Parameter ~: and the boundary values of
parameter I (A and B) in Eq. 45 can be set eas-
H= D(Z)e-ZdZ (39)
ily. The parameter p is determined from the
normalization condition:
where:
yA'F(I)dI=xa (35) I=o~Z+A (40)

where xd is the mole fraction of the oil de- c=(B-A)a (41)

scribed by the distribution function. The start- By applying the Gaussian quadrature
ing point of the distribution (A) is C7. The method to Eq. 50 yields:
second parameter, the upper cutoff (B) can be
chosen from C50 to infinity, the exact choice of H=• D(Zi)W, (42)
I
the upper cutoff is not critical. The third pa-

TABLE 8

Binary interaction coefficient (k~) matrix for MKS-EOS

j~ki CO2 N2 CI C2 C3 iC4 FIC4 iC5 nC5 C6 C7+

CO2 0.0000
N2 -0.0920 0.0000
Cj 0.1042 0.0520 0.0000
C2 0.1320 0.0910 0.0117 0.0000
C3 0.1462 0.1058 0.0433 -0.0193 0.0000
iC4 0.1325 0.1061 0.0488 0.0018 -0.0025 0.0000
nC4 0.1473 0.0957 0.0538 0.0490 0.0447 -0.0002 0.0000
iC5 0.1354 0.0772 0.0426 0.0183 0.0218 0.0025 0.0025 0.0000
nC5 0.1534 0.0456 0.0426 0.0183 0.0256 0.0025 0.0025 0.0000 0.0000
C6 0.1423 0.0783 0.0646 0.0010 0.0449 0.0434 0.0434 0.0100 0.0000 0.0000
C~ 0.1000 0.0000 0.0200 0.0150 0.0010 0.0050 0.0050 0.0000 0.0000 0.0000 0.000

• k~js for pseudocomponent pairs are set to zero.

MINIMUM MISCIBILITY PRESSURE FOR MISCIBLE FLOODING SYSTEMS 325

TABLE 9

M M P prediction results for pure COz-displacement based on J e n s e n - M i c h e l s e n algorithm using MKS and SRK-EOS

Temp. Exp. Rel. dev. (%) Data

(K ) MMP source
(MPa) MKS SRK

358.8 20.61 3.12 3.87 This work

305.4 6.89 5.49 7.21 a
313.7 8.28 3.43 8.31 a
330.4 11.72 10.33 6.83 a
338.8 13.45 24.10 21.95 a
373.2 25.27 -5.83 -5.78 b
344.2 15.52 -2.35 -3.72 c
316.0 10.62 -8.70 -8.55 d
314.2 8.10 17.72 20.93 e
316.0 10.34 -7.79 -5.13 f
312.6 13.79 -26.78 -26.73 f
313.2 12.40 - 20.99 - 22.91 g
316.0 8.96 12.82 14.70 g
327.6 10.99 5.52 10.73 h

A A D (%) 11.07 11.95

Data sources: (a) Metcalfe ( 1980); ( b ) Husodo et al. ( 1985); (c) Graue and Zana ( 1981 ); ( d ) G a r d n e r et al. ( 1981 ); (e)
Sebastian et al. ( 1985 ); ( f ) Rathmell and Stalkup ( 1971 ); (g) Spence and Watkins ( 1981 ); ( h ) Dicharry et al. ( 1974 ).

where Z and W are integration points and

W= 0.00292 + 0.0477 C, (49)
weights, respectively.
The carbon number of the pseudocompo- ?=0.017808+0.04655Cn (50)
nents in oil phase is given by:
where the correlations for vc and y were es-
C,,i=ZJa+A (43) tablished from the pure component data by the
authors, the other correlations were proposed
and the corresponding mole fraction is de-
by Willman and Teja ( 1987 a,b).
termined as:
x, = W~Xd (44) Results and discussion
Critical properties of the lumped pseudo-
components are required for applying the In all the calculations performed in this
equation-of-state. In this work, the following work, the binary interaction coefficients (k 0)
generalized correlations are used for estimat- were set to zero for SRK-EOS, whereas, non-
ing the critical properties of pseudo- zero k~js were used for MKS-EOS, the k,fval-
components: ues determined for MKS-EOS are listed in Ta-
ble 8.
Tb = 306.83 + 21.732C, - 0 . 1 5 9 1 C ] Table 9 shows the results of M M P predic-
- 0.00406 C 3 (45) tion for pure CO2-displacement obtained by
MKS and SRK-EOS. Comparable results are
T c = T b [ l + ( 1 . 2 5 1 2 7 + O . 1 3 7 2 4 C , ) -I] (46) observed, but it should be noted that the
(2.33761 + 8.16448C,) liquid-phase densities predicted differ
Pc - (0.87315 + 0.54285 C, )2 (47) appreciably.
Similar comparison for impure CO2-dis-
Vc= 25.724+ 57.454Cn (48) placement is shown in Table 10. The MKS-
326 YOU-XIANG ZUO ET AL.

TABLE 10

Prediction results of the M M P for impure CO2 displacement based on Jensen-Michelsen algorithm using MKS and SRK-EOS

Temp. Exp. Composition of Rel. dev. (%) Data

(K ) MMP driving gas source
(MPa) (Mol%) MKS SRK

358.8 25.79 93.21%CO2 + 6.79%C~ 10.01 - 13.83 This

Work
313.7 11.07 90.0%COz + 10.0%C~ - 2.19 19.50 a
313.7 14.87 80%CO2 + 20.0%C~ - 8.11 19.74 a
330.4 15.34 90.0%CO2 + 10.0%C~ - 1.81 8.76 a
330.4 18.62 80.0%CO2 + 20.0%C, - 6.67 13.42 a
338.8 13.03 90.0%CO2 + 10.0%Cz 20.74 25.83 a
344.2 15.17 Gas #1 7.25 11.87 b
344.2 22.06 Gas # 2 8.61 17.18 b
314.2 10.79 90.0%CO2 + 10.0%C, 10.60 31.42 c
314.2 12.51 81.0%CO2+ 19%C, 13.78 47.69 c
314.2 15.03 72.0%COz + 28.0%Cj 10.37 54.43 c
314.2 11.65 92.0%COz + 8.0%Nz 32.62 48.52 c
327.6 32.07 Gas # 3 -49.58 - 46.13 d
327.6 33.79 Gas#4 -29.50 - 18.17 d

A A D (%) 15.13 26.89

Compositions of Gas # 1 - G a s # 4 (Mol%):

Gas # 1--95.02%CO2 + 0.081 N2 + 4.89%Cj + 0.009%C2 + 0.002%C3.
Gas #2--85.76%CO2 + 9.66%N2 + 4.56%C~ + 0.014%C2 + 0.004%C3 + 0.003%iC4 + 0.001%iC5.
Gas #3--95.03%CO2 + 0.18%N2 +4.78%C1 +0.01%C2.
Gas #4---85.32%CO2 + 9.67%N2 + 4.99%Cj + 0.01%C2.
Data sources: (a) Metcalfe ( 1980); (b) Graue and Zana ( 1981 ); (c) Sebastian et al. ( 1985); (d) Frimoding ( 1983 ).

TABLE 11

M M P prediction results for the lean hydrocarbon gas-displacement s y s t e m s b y using Jensen-Michelsen algorithm and SRK-
EOS"

System Composition of driving gas (Mol%) Temp. Exp. M M P Cald. M M P Rel. dev.
no. (K) (MPa) (MPa) (%)

1 83.2%C1 + 8.8%C2 + 4.11%C3+ 1.4%C4+ 1.05%CO2 366.48 39.99 44.10 - 10.28

2 2.48%N2 + 87.83%C~ + 7.5%C2 + 1.91%C3 + 0.26%C4 380.37 41.37 48.40 - 16.99
3 100% Cj 444.26 33.10 37.50 - 11.73
4 100% Ci 378.71 43.44 46.80 -7.73

AAD (%) 11.68

" Data source: Firoozabadi and Aziz (1986).

EOS gives better M M P predictions than SRK-
EOS.
Typical M M P prediction results for lean hy-
drocarbon-gas displacement systems based on
SRK-EOS are listed in Table 11. Over-predic-
tions are observed for the tested systems.
Table 12 tabulates the typical results of
M M P prediction for pure N2-displacement
systems based on the SRK-EOS. Significant
larger deviations are observed as compared
with other gas-driving systems examined.
The comparison of the M M P prediction re-
sults for pure and impure CO: listed in Tables
3-4, and Tables 9-10 indicates that, the Jen-
MINIMUM MISCIBILITY PRESSURE FOR MISCIBLE FLOODING SYSTEMS
TABLE 12
MMP prediction results for pure N2-displacement systems base on Jensen-Michelsen algorithm and SRK-EOS
Temp. Exp. M M P Cald. M M P
(K) (MPa) (MPa)
406.2 41.49 52.24
410.4 61.02 52.13
380.4 58.61 53.36
410.4 34.34 44.87
422.1 35.17 43.30
AAD (%)
sen-Michelsen algorithm using the equation-
of-state approach is capable to give compara-
ble, or even better, M M P predictions than
those based on the best empirical correlations.
However, as pointed out by Jensen and Mich-
elsen (1987), the exact relation between the
M M P determined by a slim tube experiment,
and the calculated M M P based on the pro-
posed algorithm is not clear.
Conclusions
Experimental M M P data for a Chinese res-
ervoir crude oil injected with pure and impure
CO2 were determined. Based on the M M P data
reported in the literature and measured in our
laboratory, a study on the existing M M P cor-
relations has been performed. The Johnson-
PoUin correlation and the Firoozabadi-Aziz
correlation were modified by the authors for
pure COz- and lean hydrocarbon gas-displace-
ment systems, respectively. Sebastian's correc-
tion factor method and Glaso's correlation are
recommended for impure CO2- and pure N2-
displacement systems. The cell-to-cell algo-
rithm recently proposed by Jensen and Mich-
elsen, as coupled with equations-of-state (SRK
and MKS) and the semicontinuous descrip-
tion of the heptane-plus fraction in oil, have
been successfully applied to predict the M M P
of various gas-displacement systems, compa-
rable or better predictions were obtained as
compared with empirical M M P correlations,
327
Rel. dev. Data
(%) source
-25.91 Glaso (1987)
14.56 Husodo et al. (1985)
8.95 Husodo et al. (1985)
-30.66 Husodo et al. ( 1985 )
-23.12 Husodo et al. ( 1985 )
20.64
but the equation-of-state approach has the ad-
vantage of thermodynamic consistency be-
tween M M P and PFT calculations.
Acknowledgement
Financial support received from the China
National PetroleumCorporation is gratefully
acknowledged.
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