PAPER 2000-01

Minimum Miscibility
Pressure from EOS
T. Ahmed
Montana Tech of the University of Montana

This paper is to be presented at the Petroleum Society’s Canadian International Petroleum Conference 2000, Calgary, Alberta,
Canada, June 4 – 8, 2000. Discussion of this paper is invited and may be presented at the meeting if filed in writing with the technical
program chairman prior to the conclusion of the meeting. This paper and any discussion filed will be considered for publication in
Petroleum Society journals. Publication rights are reserved. This is a pre-print and subject to correction.

ABSTRACT displacement tests are commonly used to determine an

This paper presents a practical and simple procedure
for determining the Minimum Miscibility Pressure
“MMP” required for the multi-contact miscible
displacement of hydrocarbon systems by gas injection.
The methodology is based on applying the Peng and
Robinson Equation of State; in a modified form, in
conjunction with a newly introduced “Miscibility
Function”. The mathematical form of the miscibility
function is designed to provide with the necessary criteria
for predicting the required injection pressure in miscible
gas injection. The objective of this paper is to
demonstrate how this miscibility function can be used to
determine the necessary conditions required for miscible
displacement of hydrocarbon systems by gas injection.
The validity and the use of the proposed methodology are
demonstrated by matching several experimentally
measured minimum miscibility pressure values.
INTRODUCTION
The displacement efficiency of crude oil systems by
gas injection is highly pressure dependent and miscible
displacement is only achieved at pressures greater than a
certain minimum. This minimum pressure is called the
Minimum Miscibility Pressure “MMP”. Slim-Tube
MMP for a given crude oil. The minimum miscibility
pressure is defined as the pressure of which the oil
recovery vs. pressure curve (as generated from the slim-
tube test) shows a sharp change in slope, i.e. the inflection
point. This minimum miscibility pressure is a strong
function of temperature, composition of the crude oil
system, and composition of the injection gas.
To facilitate screening procedures and to gain insight
into the miscible displacement process, many correlations
relating the MMP to the physical properties of the oil and
the displacing gas have been proposed. Enick, et al1
pointed out that any correlation should: 1) account for
each parameter known to affect the MMP, i.e.
temperature, composition of the displacing and displaced
fluid; 2) be based on thermodynamic or physical
principles that affect the miscibility of fluids, and finally;
3) be directly related to the multiple contact miscibility
process.
In general, all the published miscibility correlations
can be divided into two categories; the first category deals
with predicting the minimum miscibility pressure for pure
and impure CO2; while the other category treats the
MMP’s of all other type of gases.
A) PURE AND IMPURE CO2 MMP:
It is well documented that the development of
miscibility in a CO2 - crude oil displacement process is
the result of extraction of some hydrocarbons from the oil
by dense CO2. Orr and Silva2 stated that there is
considerable evidence that the extraction of hydrocarbons
from a crude oil is strongly influenced by the density of
CO2. Improvement of extraction with the increase in CO2
density that accompanies increasing pressure accounts for
the development of miscibility. The presence of
impurities can affect the pressure required to achieve
miscible displacement.
1. Orr and Silva2: The authors developed a
methodology for determining the MMP for pure and
contaminated CO2 - crude oil systems. Orr and Silva
pointed out that the distribution of molecular sizes
present in a crude oil has a significantly larger impact
on the MMP than variations in hydrocarbon structure.
The carbon-number distributions of the crude oil
system are the only data needed to use the
correlation. They proposed the following steps:
a) From the chromatographic or the simulated
compositional distribution of the crude oil; omit
the Methane fraction “C1” and all the non-
hydrocarbon components from the oil
composition. Normalize the weight fractions
(wi) of the remaining components (C2 to C37).
b) Calculate the partition coefficient “ki” for each
component from the following equation:
Log (ki) = 0.761 - 0.04175 Ci
where Ci is the number of carbon atoms of
component i
c) Evaluate the weighted-composition parameter
“F” from:
37
F = ∑ ki wi
2
d) Calculate the density of CO2 that is required to
achieve miscibility from the following
expressions:
If the parameter F<1.467, then:
ρmmp = 1.189-0.542F ; For F<1.467
If the parameter F>1.467, then:
ρmmp = 0.42 ; For F>1.467
e) Using the available published CO2- pressure
density data, find the pressure at the given the
reservoir temperature at which the CO2 density is
equal to the required ρmmp . This pressure is set
equal to MMP.
A detailed description of Orr and Silva method and its
extension is given in reference 2.
2. Extrapolated Vapor Pressure (EVP) Method. Orr and
Jensen3 suggested that the vapor pressure curve of
CO2 could be extrapolated and set equal to the
minimum miscibility pressure for low temperature
reservoirs (T<120oF). This Extrapolated Vapor
Pressure (EVP) is conveniently expressed in an
equation form by Newittelal4 , as:
 2015 
EVP = 14.7 exp 10.91 −
 255.372 + 0.5556T 
With the extrapolated vapor pressure EVP as
expressed in psia and the temperature T in oF.
Researchers in the Petroleum Recovery Institute31
suggest equating the MMP with the vapor pressure of
CO2 when the system temperature below the critical
temperature “Tc” of CO2. For reservoir temperatures
greater than Tc ; they proposed the following expression
for estimating the MMP for pure CO2:
MMP = 1071.82893 10b
With the coefficient “b” as defined by:
b = [2.772-(1519/T)]
Where MMP is in psia and T in oR.
3. Yellig and Metcalfe5: From their experimental study,
the authors proposed a correlation for predicting the
CO2 MMP’s that uses the temperature “T” as the only
correlating parameter. The proposed expression is
given below:
MMP=1833.7217+2.2518055T+.01800674T2-103949.93/T
Yellig and Metcalfe pointed out that if the bubble
point pressure of the oil is greater than the predicted
MMP, then the CO2 MMP is set equal to the bubble point
pressure.
4. Alston et al6: The authors presented an empirically
derived correlation for estimating the MMP’s for
pure or impure CO2-Oil systems. Alston and co-
workers used the temperature T, molecular weight of
the pentane-plus of the oil MC5+, the mole fraction of
the oil intermediate components (C2-C5, CO2, and
H2S), and the mole fraction of volatile (C1 and N2) oil
components as the correlating parameters for
developing an expression for estimating the MMP for
pure CO2 - oil systems. The proposed correlation is
given by:
MMP = 0.000878 T1.06 [MC5+]1.78 [Xvol/Xint]0.136 Where yi is the mole fraction of component i in the
injected gas. To give a better fit to their data, the authors
Where: adjusted Tc of H2S from 212 to 125oF.
MC5+= molecular weight of oil pentane and heavier 5. National Petroleum Council (NPC): The NPC
fractions. proposed an empirical correlation that provides
Xint = mole fraction of intermediate oil components rough estimates of the pure CO2 MMP’s. The
(C2-C4, CO2, and H2S) correlation uses the API gravity and the temperature
as the correlating parameters as shown below:
Xvol = mole fraction of the volatile (i.e. C1 and N2) oil
components.
T = system temperature in oF. Gravity MMP 8
o
Contamination of CO2 by C1 or N2 has been shown to ( API) (psi)
adversely affect the MMP. Conversely, the addition of C2, <27 4,000 1
C3, C4, or H2S to CO2 has been shown to have the effect
27 to 30 3,000
of lowering the MMP. To account for the effects of the
presence of contaminants in the injected CO2, Alston and >30 1,200
co-workers correlated impure CO2 MMP with the 1
weighted-average pseudo-critical temperature “Tcm” of
the injected gas and the pure CO2 MMP by the following
expression: Reservoir Temperature Correction
T Additional Pressure
MMPimp = MMP [87.8 / Tcm ]168.893 / Tcm ( F)o
(psi)
<120 0
With : 120 to 150 +200
150 to 200 +350
Tcm = [Σ wi Tci] - 459.7 200 to 250 +500
Where:
MMP = Pure CO2 MMP 6. Enick-Holder-Morsi1: Enick and co-authors
presented a set of working graphs for estimating the
wi = Weight fraction of component i in the injection gas MMP for CO2-crude oil systems. The graphs are
Tci = Pseudocritical temperature of the injection gas, oF. divided into four categories:
Ti . = Critical temperature of component i in the injection • Pure CO2-Stock Tank oil MMP prediction
gas, oR. graph
The critical temperatures used in the above • Three correction graphs to account for CO2
expressions are the True Critical Temperature except impurities
those of H2S and C2. The authors assigned a uniform
value of 585oR for both components. • Two graphs that are designed to account for
CO2 gaseous components
Sebastian et al7 proposed a similar corrective step that
adjusts the pure CO2 MMP by an amount related to the • A correction graph to account for the
mole average critical temperature “Tcm” as follows: temperature dependency of CO2 impurities
and live-oil gases
MMPimp = [C] MMP The authors reported an average reported predicted
MMP/actual MMP ratio of 1.09; with a standard deviation
Where the correction parameter C is given by: of 19%
7. Croquist32: The author proposed an empirical
equation that was generated from regression fit on 58
C = 1.0 -A [0.0213 - 2.51x10-4 A + 2.35 A2]
data points. Croquist characterizes the miscibility
pressure as a function of T, molecular weight of the
With
oil pentanes-plus fraction, and the mole percentage of
A = [Tcm – 87.89]/1.8 methane and nitrogen. The correlation has the
Tcm = Σ yi Tci following form:

A
MMP=15.988 T
With:
A = 0.744206+0.0011038 MC5+ + 0.0015279 Ycl
Where:
T = Reservoir temperature, 0F
Ycl = sum of the mole% of methane and nitrogen
B) Lean-Gas and Nitrogen Miscibility
Correlations:
High pressure Lean gases and N2 injection have been
successfully used as displacing fluids for EOR projects
and also widely used in gas cycling and pressure
maintenance. Firoozabadi and Aziz8 documented the
successful use of Lean gas and N2 as high-pressure
miscible gas injection in several oil fields.
1. Firoozabadi and Aziz: The authors proposed a
generalized correlation that can predict MMP for N2
and Lean gases. They used the concentration of oil
intermediate components, temperature, and the
molecular weight of C7+ as the correlating
parameters. The authors define the intermediates as
C2 - C5, CO2, and H2S components. The correlation
has the following form:
MMP = 9433 - 188x103 F + 1430x103 F2
with
F = I/(Mc7+ T2.5)
where
I = concentration of intermediates , i.e. C2-C4, CO2, and
H2S, mol%
T = temperature, oF
Mc7+ = molecular weight of C7+
2. Hudgins - Liave - Chung9: The authors performed a
comprehensive laboratory study of N2 miscible
flooding for enhanced recovery of light crude oil.
They stated that the reservoir fluid composition,
especially the amounts of C1 through C5 fractions, is
the major determining factor for miscibility. For pure
N2, the authors proposed the following expression:
MMP = 5568 e-R1 + 3641 e -R2
With:
R1 = 792.06 [C2 - C5]/W
R2 = 2.158x106 [C1]5.632/W
where:
W = Mc7+ T0.25
T = temperature, oF
C1 = mole fraction of methane
C2 - C5 = mole fraction of C2 -C5
3. Glaso10: The author investigated the effect of
reservoir fluid composition, displacement velocity,
column length of the slim-tube, and temperature on
slim-tube oil recovery with N2. Glaso used Mc7+, T in
o
F, and the mole percent methane and intermediates
(C2 - C6) in his correlation. He proposed the
following relationships:
For API<40
MMP = 80.14 + 35.35 H + 0.76 H2
where:
H = M C0.788+ T 0.11 / [(C2 − 6 ) 0.64 (C1 ) 0.33 ]
For API>40
MMP = -648.5 + 2619.5 H - 1347.6 H2
where:
H = M C0.748+ / [T 0.25 (C2 − C6 ) 0.12 (C1 ) 0.42 ]
EQUATION OF STATE APPROACH
11,12
The usefulness of the PREOS has been tested with
limited success in predicting the phase behavior and
MMP's of simulated reservoir fluids. Firoozabadi and
8
Aziz compared the PREOS prediction results with
available experimental data and concluded that the EOS
in general overestimates the MMP. Lee and Reitzel13
observed a similar trend and attributed the deviation to
inaccuracies in establishing critical points and to a lack of
suitable data to fine tuning the PREOS. Creek and
Sheffield14 investigated the formation of a CO2 rich
second “liquid phase in mixtures of CO and Permian
2
Basin reservoir fluids. The authors stated that they were
unable to adjust the parameters of the EOS to match the
experimentally generated phase envelope. They
attributed that to the inability of cubic equations of state
to model the behavior of molecules like CO . A modified
2
version of the Redlich-Kwong equation of state (RKEOS)
has reportedly been used successfully to model the phase
behavior of complex hydrocarbon systems. The original RTc
RKEOS has the following form. b=( )ΩbT = constant ⋅ ΩbT ............................ (9)
Pc
RT a It should be pointed out that equations 2 and 3 can be
P= − ............................... (1)
Vm − b T V m (V m + b) used to produce identical values of coefficients “a and b”
as those calculated from equations 8 and 9 by adjusting
the critical properties, i.e. Tc and Pc, of carbon dioxide, as
Where the system temperature changes. The following
relationships correlate the adjusted critical pressure (p*c)
R 2 Tc2 .5 and critical temperature (T*c) with the unadjusted critical
a = Ωa ........................................................... (2) properties of CO2 and EOS parameters Ω’s:
Pc
1 / 1.5
Ω   Ω aT   Ωb 
p =  b
∗
     p c ............ (10)
RT c
 Ω bT   Ω a   Ω bT 
b = Ωb c ................................................................ (3)
Pc

with 1 / 1.5
 Ω   Ωb 
T ∗
c =  aT    Tc ............................. (11)
Ω a = 0.42748 ............................................................ (4)  Ω a   Ω bT 

The authors also proposed a more systematic approach

Ωb = 0.08664 ............................................................ (5)
Significant improvements in the RKEOS have been
made by making the parameters Ωa and Ωb functions of
temperature for each component. Zudevitch and Joffe15
allowed Ωa and Ωb to vary with temperature below the
critical temperature, determining their values from the
saturation pressure, saturated liquid density, and Fugacity
coefficient. Yarborough15 applied the Zudkevitch and
Joffe method and expressed Ωa and Ωb in a dimensionless
form as functions only of reduced temperature and
Acentric factor. Turek et al.17 adopted Yaborough’s
approach and extended the temperature-dependent
parameters Ωa and Ωb of CO2 to temperatures above the
CO2 critical temperature, to give:
for representing the behavior of CO2-hydrocarbon
mixtures. A second interaction coefficient “Dii” for CO2-
hydrocarbon binaries was introduced by modifying the
mixing rule for the parameter “b” to give:
1 n n
bmix = Σ Σ x x (b b )(1 + Dij ) .......................... (12)
2 i =1 j =1 i j i j
These newly introduced interaction coefficients were
assumed to be a cubic function of the hydrocarbon
Acentric factor. The investigators concluded that with the
above-recommended modifications, the RKEOS is
capable of predicting the complex phase equilibrium
found in CO2-hydrocarbon systems.

DESCRIPTION OF THE PROPOSED

Ω aT = f (T ), , T 〉 (Tc ) CO2 ............................. (6) METHOD
The main objective of this research is to develop a
practical and generalized approach for determining the
ΩbT = f (T ) , T 〉 (Tc ) CO2 .............................. (7) minimum miscibility pressure required for multi-
component miscible displacement of crude oil systems by
These temperature-dependent parameters were hydrocarbon gases, CO2 and Nitrogen. Two identified
assumed to be quadratic functions of temperature. problems are the focus of this research. These are:
Substituting the above expressions in equation (2) and • Selection of the appropriate EOS and modification of
(3), gives: the selected expression to account for the complex
phase behavior of CO2 - crude oil systems.
• Finding a mathematical expression (miscibility
R 2 Tc2 .5 function) that can be used to describe the required
a=( )Ω aT = constant ⋅ Ω aT ........................ (8)
Pc miscibility conditions in terms of injection pressure
and overall composition.
Selection of EOS
Ahmed’s modifications of the Peng and Robinson
equation of state were adopted in this study. Briefly,
Ahmed18 suggested that the inadequacy of the predictive
capability of PREOS lies with the improper procedure for
calculating the characterization parameters “a, b, and α“
for the C7+. The author devised an approach for
determining these parameters from the measured
molecular weigh and specific gravity of the heptanes-plus
fraction. The author concluded that the proposed version
of the PREOS has a significant ability to predict the PVT
properties of complex hydrocarbon mixtures.
With the apparent success of the modified Redlich-
Kwong EOS in describing the volumetric behavior CO2-
crude oil systems, it was decided to implement Turek, et
al17 recommendations and further modify the PREOS.
The Peng and Robinson EOS parameters a, b, and α
for CO2 were optimized to match the experimental
saturated liquid densities and saturation pressure data of
carbon dioxide as reported by Bukalvich and Altunin19.
The parameters were essentially correlated with the
temperature T; to give:
α = 1 ............................................................................ (13)
a = 1.7639581E4 - 21.150287 T .................................. (14)
b = 0.45713317 - 1.1260406E-4 T............................... (15)
Where T is the temperature in oF. The mixing rules as
expressed by equation (10) also introduced into the
PREOS. The binary interaction coefficients Dij between
CO2 and all other components were optimized to match
several published MMP data as determined from slim-
tube displacement tests. Results indicate the strong
dependency of Dij on the temperature as well as the
physical characteristics of the hydrocarbon system. The
following relationships are proposed:
a) Set Dij between CO2 and all other components,
excluding the plus-fraction, as:
DCO2 − components = 0.131 + 0.00004T ..................... (16)
b) Determine the characterization coefficient “F” of the
Crude Oil System from the following expression:
Log ( Pc / 14.7) 1 1
F =[ ]( − ) ............................ (17)
1 1 Tb T
− hydrocarbon mixture approaches the critical point.
Tb Tc
Where:
Tb = boiling point temperature of crude oil system, oR
Tc = critical temperature of the crude oil system, oR
pc = critical pressure of the crude oil system, psia
T = system temperature in oR
c) Calculate the binary interaction coefficient between
CO2 and the plus-fraction from the following
expression:
3
DCO2 −C 7 + = Σ (d i F i ) + d 4 / F ............................ (18)
i −0
Table 1 gives values of d0 through d4.
Equation 18 signifies the influence of oil composition
on MMP for CO2-hydrocarbon systems.
Miscibility Function
Studies of phase behavior of mixtures of CO2 and
crude oil at miscible conditions have been on single-
contact experiments using windowed equilibrium cells
that permit observations of phase distribution with the cell
as a function of pressure at constant temperature20. The
data from experimental work by different investigators on
numerous hydrocarbon-CO2 systems show extremely
complex phase behavior. Metcalfe and Yarborough21
recognized the complexities involved in studying the
mechanism of miscibility development. The investigators
concluded that the mechanisms by which multiple-contact
miscibility develops between CO2 and oil are controlled
by the temperature-dependent phase behavior. At lower
temperatures, the mechanism and is analogous to the
“condensing gas” mechanism. At higher temperatures,
the mechanism is analogous to the “vaporizing gas”
mechanism of hydrocarbon miscible flooding.
Several schemes for predicting MMP based on the
equation of state approach have been proposed.
Benmekki and Mansoori21 applied the PREOS with
different mixing rules that were joined with a newly
formulated expression for the unlike three-body
interactions between the injection gas and the reservoir
fluid. Hagoort and Dumore22 used upward pressure
increments to locate the MMP taking advantage through
extrapolation of the fact the K-values will approach unity
as the limiting coincident tie line is approached.
The scheme proposed in this study is based on the fact
that the MMP for a solvent-oil mixture is generally
considered to correspond to the critical point at which the
K-Values for all components converges to unity. The
following function (Miscibility Function) is found to
provide an accurate miscibility criteria as the solvent-
 n identical stock-tank oil properties and exists at a slightly
FM = − Σ [ Zi ( Ki − 1) / Ki ] .................................... (19)
i =1
Where FM is the miscibility function.
The above expression shows that as the overall
composition Zi changes by gas injection and reaches the
critical composition; the function is monotonically
decreasing and approaching zero or a negative value. The
specific steps of applying the miscibility function are
outlined below.
Step 1. Select a convenient reference volume (e.g. one-
barrel) of the crude oil with a specified initial
composition and temperature.
Step 2. Combine an incremental volume of the injection
gas with the crude oil system and determine the
overall composition “Zi”.
Step 3. Calculate the bubble point pressure “Pb” by
applying the modified PREOS.
Step 4. Determine the swollen volume and the
corresponding total number of moles at Pb.
Step 5. Remove the excess volume and readjust the
remaining number of moles for the reference
volume.
Step 6. Evaluate the miscibility function Fm using the
calculated K-values and the overall composition
at the bubble point pressure.
Step 7. If the value of the miscibility function is small,
then the calculated Pb is approximately equal to
the MMP. Otherwise, repeat steps 2 through 7.
RESULTS AND DISCUSSION
Results of the study were obtained by applying the
modified Peng-Robinson EOS as outlined in this research
and in references 18 and 23. Numerous crude oil systems
with detailed experimental data were used in validating
the proposed correction. To demonstrate the application
of the Miscibility Function, four hydrocarbon systems are
used to illustrate the predictive capability of the proposed
methodology.
Rathmell-Stalkup-Hassinger24 Miscibility Data. Two
crude oil systems (Oil-A and Oil-B) were used by the
authors to conduct a laboratory investigation of miscible
displacement by CO2. Crude oil A exists at a relatively
low temperature of 109oF with a bubble point pressure of
860 psi. The experimental MMP was recorded as 1500
psi from a slim-tube test. The proposed methodology was
applied and the values of miscibility function were
recorded as a function of volume gas injected and
resulting bubble-point pressure. Figure 1 illustrates the
characteristic shape of the miscibility function and the
corresponding calculated saturation pressures. The model
predicts an excellent match value of 1493 psi as the
miscibility function approaches zero. Crude Oil B,
although not from the same reservoir as Oil A, has nearly
different temperature of 103F. Rathmell and his co-
authors reported a MMP of 2015 psi as compared with a
predicted value of 1999 psi as shown in Figure 2.
Glaso10 and Metcalfe-Yarborough21 Miscibility Data.
The variation of the miscibility function and its
characteristic shape as a function of saturation pressure
and mole % of gas injected is further demonstrated in
Figures 3 and 4. The two figures show the smoothness
behavior of the miscibility function when applied to
predict the actual MMP data of Glaso10 lean gas- crude oil
system and Metcalfe-Yarborough21 CO2- Crude oil
system. Glaso’s Slim-Tube test data shows an
experimental MMP of 6900 psi for lean gas injection at
174 oF. The proposed methodology shows a predicted
MMP of 6916 psi. Figure 3 documents the behavior of the
miscibility function as it monotonically decreasing and
approaching zero at the lean gas MMP. Metcalfe and
Yarborough experimental Slim-Tube test results show a
pure CO2 injection has achieved miscibility of 1204 psi at
105 oF. When applied, the proposed methodology
produced a predicted value of 1209 psi, as shown in
Figure 4. The overall accuracy of the proposed
methodology to predict the MMP’s for a variety of
injection gases was further tested against those obtained
from experimental data. Table 2 documents this
comparison and shows the performance and predictive
capability of the miscibility function. The methodology11
reproduces the experimental data with an absolute
average error of only 3.4%.
CONCLUSIONS
1. A new methodology for determining the MMP from
equations of state has been outlined. The method is
simple to implement with equation of state.
2. Improved correlations for calculating the
characterization parameters “a, b, and α” for CO2 are
presented.
3. The proposed methodology is capable of predicting
accurate MMP’s for CO2 and other gases with an
absolute average error of 3.4%.
ACKNOWLEDGEMENTS
This research has been supported by the U.S.
Department of Energy (DOE/EPSCoR) and is greatly
appreciated
1
The computer model can be obtained from:
Tarek Ahmed, Ph.D., P.E.
Union Pacific Resources Professor
Petroleum Department, Head
Montana Tech of The University of Montana
Butte, MT 59701 (USA)
E-mail: TAhmed@mtech.edu
Phone: (406) 496-4259
NOMENCLATURE 13. Creek, J.L. and Sheffield, J.M.: “Phase Behavior,
Fluid Properties, & Displacement Characteristics of
Vm = Molal volume, cu ft/lb-mole Permian Basin Reservoir Fluid-CO2 Systems,”
Dij = Binary interaction coefficient in mixing rule SPE/DOE 20188, SPE/DOE 7th Symposium on EOR
for parameter b. held in Tulsa, OK., April 22-25, 1990.

di = Coefficients of equation 18 14. Creek, J.L. and Sheffield, J.M.: “Phase Behavior,
Fluid Properties, & Displacement Characteristics of
F = Characterization Factor Permian Basin Reservoir Fluid-CO2 Systems,”
Fm = Miscibility Function SPE/DOE 7th Symposium on EOR held in Tulsa, OK,
April 22-25, 1990.
MMP = Minimum Miscibility Function
15. Zudkevitch, D. and Joffe, J.: “Correlation and
zI = Overall Mole Fraction
Prediction of Vapor-Liquid Equilibria with the
kI = Equilibrium Ratio RKEOS,” AICHE J. (1970) Vol. 16, p. 112-119.
16. Yarborough, L.: “Application of a Generalized EOS
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Thermodynamic Correlation for the MMP in CO2
Flooding of Petroleum Reservoirs,” SPERE (Feb. 17. Turek, E.A., Metcalfe, R., Yarborough, L. and
1988), 81-92. Robinson, R.: “Phase Equilibria in CO2 -Multi-
component Hydrocarbon Systems,” SPE 9231, 55th
2. Orr, F.M. and Silva, M.K.: “Effect of Oil Annual Technical Conference and Exhibition of the
Composition on MMP-Part 2: Correlation,” SPERE
SPE, held in Dallas, TX, Sept. 21-24, 1980.
(Nov. 1987), 479-492.
18. Ahmed, Tarek: “A Practical Equation of State,”
3. Orr, F.M. and Jensen, C.M.: “Interpretation of
SPERE, (Feb. 1991), 137-146.
Pressure-Composition Phase Diagram for
CO2/Crude-Oil Systems,” SPEJ (Oct. 1986), 485- 19. Vukalovich, M.P. and Altunin, V.V.:
497. “Thermophysical Properties of Carbon Dioxide,”
Collet’s Ltd., London (1968), 243-263.
4. Newitt, D.M. et al: “Carbon Dioxide,”
Thermodynamic Functions of Gases, Vol. 1, F. 20. Goodrich, J.: “Review and Analysis of Past and
Din(ed.), Butterworths, London, 102-134. Ongoing CO2 Injection Field Tests,” SPE 8832,
SPE-DOE Symposium on Improved Oil recovery,
5. Yellig, W.F. and Metcalfe, R.S.: “Determination and
Tulsa, OK, April 20-23, 1980.
Prediction of CO2 Minimum Miscibility Pressures,”
JPT (Jan. 1980) 160-168. 21. Metcalfe, R.S. and Yarborough, L.: “The Effect of
Phase Equilibrium on the CO2 Displacement
6. Alston, R.B.; Kokolis, G.P.; James, C.F.: “CO2
Mechanism,” SPEJ, (Aug. 1979) 19-29.
Minimum Miscibility Pressure: A Correlation for
Impure CO2 Streams and Live Oil Systems,” SPEJ 22. Hagoort, J. and Dumore, J.: “Determination of
(Apr. 1985), 268-274. Minimum Miscibility Pressures with an EOS,” Proc.
European Meeting on Improved Oil Recovery, Rome
7. Sebastian, H.M.; Wenger, R.S.; Renner, T.A.:
(Apr. 16-18) 1985, 61-66.
“Correlation of Minimum Miscibility Pressure for
Impure CO2 Streams,” JPT (Nov. 1985), 2076-2082. 23. Ahmed, Tarek: “Prediction of CO2 Minimum
Miscibility Pressure,” SPE Paper #027032.
8. Firoozabadi, A. And Aziz, K.: “Analysis and
Correlation of Nitrogen and Lean Gas Miscibility 24. Rathmell, J., Stalkup, F.; and Hassinger, R.: “A
Pressure,” SPERE (Aug. 1986), 100-110. Laboratory Investigation of Miscible Displacement
by CO2,” SPE 3483, the 46th Annual Fall Meeting of
9. Hudgins, D.A.; Liave, F.; and Chung, F.: “Nitrogen
the SPE, New Orleans, LA, Oct. 3-6, 1971.
Miscible Displacement of Light Crude Oil: A
Laboratory Study,” SPERE (Feb. 1990), 100-106. 25. Spence, A. and Watkins, R.: “ The Effect of
Microscopic Core Heterogeneity on Miscible Flood
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With Nitrogen,” SPERE (Feb. 1990), 61-68. Fall Meeting of the SPE, Dallas, TX, Sept. 21-24,
11. Benmekki, E. and Mansoori, G.A.: “MMP 1980.
Prediction with Equations of State,” SPERE (May 26. Metcalfe, R.S.: “Effects of Impurities on Minimum
1988), 559-564. Miscibility Pressures and Minimum Enrichment
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Dioxide/Water/Hydrocarbon Phase Behavior 9230, the SPE 55th Annual Technical conference,
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1986), 61-72.
27. Chaback, J.: “Discussion of Vapor-Density
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TABLE 1. COEFFICIENTS OF EQUATION 18
Coefficients With Tuning* Without
Tuning
d0 -1.4969406 -0.024244087
d1 -2.4001227 -0.017046265
d2 -1.3808140 -0.0186-70702
d3 -0.27716854 -0.017987031
d4 -.15676286 0.0010391798
*Tuning EOS to match the bubble point pressure.

TABLE 2. Comparison of Experimental and

Predicted MMP’s
Reference T,oF Injection Gas, % MMP Deviation
CO2 N2 C1 Others Exp. Pred. (%)
8 340 0 0 100 0 4800 4808 0.17
8 200 1.05 0 83.21 15.74 5800 5790 -0.17
8 225 0 2.68 87.83 9.69 6000 6740 12.30
8 303 0 0 100 0 6300 6387 1.38
7 106 100 0 0 0 1175 1331 13.28
7 106 90 0 10 0 1565 1527 -2.43
7 106 81 0 19 0 1815 1808 -0.38
7 106 92 8 0 0 1690 1794 6.15
7 106 81 19 0 0 2815 2794 -0.74
7 106 45 0 27 28 1520 1464 -3.68
7 106 72 0 28 0 2180 2108 3.30
10 198 0.76 0.50 72.04 26.70 5800 5778 -0.38
10 174 1.35 1.40 82.17 15.08 6900 6916 0.23
10 210 0.76 0.29 73.05 25.90 5100 5353 4.96
21 105 100 0 0 0 1204 1211 0.58
21 135 100 0 0 0 1697 1632 -3.83
21 120 100 0 0 0 1595 1399 -12.47
21 150 100 0 0 0 1944 1836 -5.55
24 109 100 0 0 0 1500 1493 -0.46
24 103 100 0 0 0 2000 1999 0.0
25 104 100 0 0 0 1799 1733 -3.66
25 109 100 0 0 0 1300 1364 4.92
26 105 100 0 0 0 1209 1211 0.16
26 135 100 0 0 0 1697 1632 -3.83
26 120 100 0 0 0 1595 1399 -12.28
26 150 100 0 0 0 1944 1836 -5.55
27 220 100 0 0 0 3190 3079 -3.48
27 170 100 0 6 0 3000 2997 -.10
27 130 100 0 0 0 1708 1709 0
27 178 100 0 0 0 2315 2199 -5.01
28 160 95.02 .08 4.89 0.01 2100 2080 -.95
28 160 85.76 4.07 0.34 9.83 3150 3144 0
29 217.4 .52 1.02 85.61 12.85 4902 5025 2.51
29 215.6 .52 1.02 85.61 12.85 5076 4858 -4.29
29 222.8 .52 1.02 85.61 12.85 5497 5489 -.15
1∆1=3.4
 70000.00 1800

Miscibility Function
60000.00
1600

Pressure, psi
50000.00
40000.00 1400
30000.00 1200
20000.00
1000
10000.00
0.00 800
0 20 40 60 80 100

% CO2 in Mixture

Figure 1- Rathmel-Stalkup-Hassinger Crude Oil A

Miscibility Function

10000 2200
9000

Pressure, psi
8000 2000
7000
6000
5000 1800
4000
3000 1600
2000
1000
0 1400
0 20 40 60 80
% CO2 in Mixture

Figure 2- Rathmel-Stalkup-Hassinger Crude Oil B

8000 80
Pressure, psi

7000 60
Miscibility
Function

6000
40
5000
4000 20

3000 0
0 20 40 60 80
% Injection Gas in Mixture

Figure 3- Glaso's Lean Gas-Crude Oil

System
 140000 1400
120000

Pressure, psu
1200
Miscibility
100000

Function
80000 1000
60000 800
40000
600
20000
0 400
0 20 40 60 80
% CO2 in Mixutre

Figure 4- Metcalfe's Crude Oil System