Multiple-Mixing-Cell Method for MMP
Calculations
Kaveh Ahmadi, SPE, University of Texas at Austin, and Russell T. Johns, SPE, Pennsylvania
State University at University Park
Summary
The minimum miscibility pressure (MMP) is a key parameter gov-
erning the displacement efficiency of gasfloods. There are several
methods to determine the MMP, but the most accurate methods are
slim-tube experiments, analytical methods, and numerical-simula-
tion/cell-to-cell methods. Slim-tube experiments are important
to perform because they use actual crude oil, but they are costly
and time consuming. Analytical methods that use the method of
characteristics (MOC) are very fast and help to understand the
structure of gasfloods. MOC, however, relies on finding the unique
and correct set of key tie lines in the displacements, which can be
difficult. Slim-tube simulation methods and their simplified cell-
to-cell derivatives require tedious fluid and rock inputs, and their
MMP estimates can be clouded by dispersion.
This paper presents a simple and accurate multiple-mixing-cell
method for MMP calculations that corrects for dispersion, and is
faster and less cumbersome than 1D simulation methods. Unlike
previous mixing-cell methods, our cell-to-cell mixing model uses
a variable number of cells, and is independent of gas/oil ratio,
volume of the cells, excess oil volumes, and the amount of gas
injected. The new method only relies on robust P/T flash calcula-
tions using any cubic equation-of-state (EOS). The calculations
begin with only two cells and perform additional cell-to-cell
contacts between resulting equilibrium-phase compositions based
on equilibrium gas moving ahead of the equilibrium liquid phase.
We show for a variety of oil and gas compositions that all key
tie lines can be found to the desired accuracy, and that they are
nearly identical to those found using analytical MOC methods.
Our approach, however, is more accurate and robust than those
from MOC because we do not make approximations regarding
shocks along nontie-line paths, and the unique set of key tie lines
converges automatically.
The MMP using our mixing-cell method can be calculated in
minutes using an Excel spreadsheet and is estimated from a novel
bisection method of the minimum tie-line lengths observed in the
cells at four or five pressures. Our multiple-mixing-cell method
can calculate either the MMP or the minimum miscibility for
enrichment (MME) independent of the number of components in
the gas or oil. Our approach further supports the notion that the
MMP is independent of fractional flow because we obtain the
same key tie lines independent of how much fluid is moved from
one cell to another.
Introduction
Slim-tube experiments are traditionally used to estimate MMPs
because they capture the interaction of flow in porous media with
the phase behavior of the crude (Yellig and Metcalfe 1980). Slim-
tube experiments, however, are slow and expensive, and their MMP
estimates may not be accurate because of dispersion and the lack of
data points (Johns et al. 2002). Despite difficulties and uncertainties,
if carefully conducted, slim-tube experiments remain the industry
standard and a reliable method to estimate the MMP. Besides
slim-tube experiments, multicontact mixing-cell experiments can
Copyright © 2011 Society of Petroleum Engineers
This paper (SPE 116823) was accepted for presentation at the SPE Annual Technical
Conference and Exhibition, Denver, 21–24 September 2008, and revised for publication.
Original manuscript received for review 24 November 2009. Revised manuscript received
for review 24 January 2011. Paper peer approved 25 January 2011.
December 2011 SPE Journal
provide accurate MMP estimates for vaporizing or condensing
gasfloods. Most gasfloods, however, have features of both condens-
ing and vaporizing drives (CV), which means MMPs estimated
by single mixing-cell experiments are typically not accurate (Zick
1986; Johns et al. 1993). Other experimental MMP methods, such
as vanishing-interfacial-tension tests (Rao 1997) and rising-bubble
experiments (Christiansen and Haines 1987), are suspect because
they may not duplicate the complex interaction of phase behavior
and flow for CV drives (Jessen and Orr 2008).
Because of the drawbacks of experimental methods, compu-
tational methods for MMP estimation were developed over the
years to estimate the MMP from cubic EOSs. The assumption of
all the computational methods is that the phase behavior is accu-
rately described with a tuned EOS. For the purpose of an accurate
MMP estimation, the assumption must be especially true near the
critical region. There are primarily three computational methods:
analytical calculations with MOC, slim-tube compositional simu-
lation, and multicontact mixing-cell models. Analytical methods
for MMP estimation are based on the analytical solution of disper-
sion-free 1D flow equations (Orr 2007). Monroe et al. (1990) first
examined the analytical theory for quaternary systems and showed
that there exists a third key tie line in the displacement path, called
the crossover tie line. Orr et al. (1993) and Johns et al. (1993)
confirmed the existence of the crossover tie line for CV drives and
presented a simple geometric construction to find the key tie lines
(gas, oil, and crossover). Their geometric construction assumed
that consecutive tie lines are connected by shocks along nontie-
line paths. They demonstrated that the MMP occurs at the pressure
when any one of the three key tie lines first intersects a critical
point (becomes zero length). Johns et al. (1993) further showed that
the crossover tie line controls the development of miscibility in CV
drives and that the estimated MMP is below the MMP assuming
either a pure condensing or pure vaporizing drive.
Johns and Orr (1996) gave a procedure to calculate the MMP
for more than four components, and extended their geometric
construction to construct the first multicomponent displacement of
(ten-component) oil by CO2. They provided a general methodol-
ogy for composition-path construction for any number of oil and
gas components and showed that NC–1 key tie lines exist that the
composition path must follow. They showed that the composition
path consists of either a rarefaction wave (continuous variation) or
a shock along the nontie-line paths from each key tie line to the
next. They further stated that miscibility develops when any one of
these key tie lines becomes zero length (intersects a critical point).
The MMP calculation, therefore, was reduced to finding a series of
key tie lines from the oil to injection-gas composition whose tie-
line extensions intersect sequentially. Wang and Orr (1997) dem-
onstrated their multicomponent approach by calculating the MMP
for injection gases with more than one component. They found
the intersection points of the key tie-line extensions by applying
a Newton-Raphson scheme in compositional space. In their itera-
tion method, they also assumed that only shock jumps occur from
one key tie line to the next, which Johns et al. (1992) and Johns
and Orr (1996) speculated to be a close approximation. Jessen et
al. (1998) improved the speed of Wang and Orr’s method by the
inclusion of fugacity equations in the Newton-Raphson scheme.
Yuan and Johns (2005) recently simplified the size of the Newton-
Raphson problem and showed that it is possible to converge to the
wrong set of key tie lines, which is a potential drawback of these
analytical MOC methods.
733
 Another approach for MMP estimation is by 1D slim-tube
simulation. Determination of MMP by 1D compositional simula-
tion mimics the flow in porous media that occurs in slim-tube
experiments (Yellig and Metcalfe 1980). Fine-grid compositional
simulations, however, can suffer from numerical dispersion effects,
causing the MMP to be in error (Stalkup 1987; Johns et al. 2002).
Use of higher-order methods can reduce the effect of dispersion but
does not eliminate it, which is also true for slim-tube experiments
that have a small amount of dispersion that can cloud the MMP
estimate. The thermodynamic MMP is defined in the absence of
dispersion, so any dispersion that remains will generate some error
in the MMP estimate. Simulation is also somewhat time-consum-
ing and cumbersome to perform because multiple simulations must
be made at different pressures and with different gridblock sizes.
Relative permeability curves and viscosities must also be input and
verified for accuracy. As with slim-tube experiments, the MMP is
determined from an arbitrary bend in the recovery curve, typically
called the “knee” (Jarrell et al. 2002). Better accuracy of the MMP
is obtained by repeating the simulations for different levels of dis-
persion, and extrapolating the estimated MMP to zero dispersion.
Even this extrapolation, however, can be in error from the true MMP
(Johns et al. 2002).
There is also a variety of published mixing-cell methods to esti-
mate the MMP or MME (Hutchinson and Braun 1961; Cook et al.
1969; Metcalfe et al. 1973; Pedersen et al. 1986; Clancy et al. 1986;
Firoozabadi and Aziz 1986; Lake 1989; Jensen and Michelsen
1990; Neau et al. 1996). The basic idea in these single- and mul-
tiple-mixing-cell methods is to mix (analytically) gas and oil in
repeated contacts, resulting in new equilibrium compositions. In
the case of a vaporizing drive (lean-gas injection), the intermediate
component in the oil is vaporized into the more mobile gas phase,
and miscibility is developed when the equilibrium gas is repeatedly
mixed with fresh oil, causing the equilibrium gas composition to
move toward the oil tie line. Thus, in vaporizing drives, the tie line
that extends through the oil controls the development of miscibility.
Miscibility in vaporizing drives is developed at the leading edge of
the displacement. For a condensing gas drive (enriched-gas injec-
tion), however, the intermediate component in the gas is condensed
into the oil, and the gas tie line controls miscibility. Miscibility for
condensing drives, therefore, is developed at the trailing edge of the
displacement. These mixing-cell methods can give reliable MMPs
for either condensing or vaporizing drives. Most field displace-
ments, however, are combined CV drives, and thus MMPs from
these earlier mixing-cell methods are unreliable.
Jaubert et al. (1998a, b) developed mixing-cell algorithms that
are similar to that of Metcalfe et al. (1973) in that they transfer
specified amounts of gas and excess oil from cell to cell without
solving the flow equations. These methods attempt to account
for all displacement mechanisms including CV drive, but, like
1D simulation, they can be affected by dispersion. To reduce the
effect of dispersion, recovery factors at 1.2 PVI are determined for
a fixed pressure and fixed number of cells. The number of cells is
changed, and the calculation of recovery factor at the same pressure
is repeated. A plot of the recovery factor vs. 1 / N , where N is the
number of cells, gives the estimated recovery factor at zero disper-
sion for that pressure. A graph of the estimated zero-dispersion
recovery factor is then made for several pressures, an extrapolation
of which to near 100% recovery gives the pressure correspond-
ing to the MMP. Zhao et al. (2006a, b) present a more complex
multiple-mixing-cell method, where they include fractional flow
to determine transfer amounts. They find key tie lines by graphing
the tie-line lengths along profiles of their fixed-cell model. Like
Jaubert et al., their approach is susceptible to dispersion, although
this is difficult to evaluate because they do not give example MMP
calculations. The tie-line length is calculated with
Nc
TL = ∑ (x i − yi )2 , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
i =1
where Nc is the number of components and xi and yi are liquid
and gas equilibrium compositions, respectively. Zick also has an
unpublished method that appears to be similar to Jaubert et al.
734
and Zhao et al., although the details of this method are unknown
(MMPz manual 2002).
In this paper, we present a simple, practical, and robust multiple-
mixing-cell method to determine the MMP for systems with any
number of components. Our mixing-cell method differs from the
previous ones in that we start with two cells, and increase them until
the desired accuracy in the key tie lines is obtained. That is, we keep
all contacts as the method proceeds. We then determine the MMP
based on the pressure at which the first key tie-line length becomes
zero. In the first section, we describe our mixing-cell algorithm in
detail, and show that we can capture all key tie lines of the dis-
placement to any accuracy desired. Subsequent sections show that
in practice, the MMP is determined not by finding all of the key tie
lines, but by tracking only the shortest one. Several example MMP
calculations are given and compared to analytical MOC calculations
and slim-tube experiments, showing good agreement.
MOC
MOC methods for MMP estimation are well documented in the
literature (Yuan and Johns 2005). They rely on finding the key tie
lines that bound the composition paths in a 1D displacement. These
key tie lines are found such that each key tie line when extended
out of the two-phase region must intersect two neighboring key tie
lines. As pressure is increased (or enrichment is increased), the key
tie lines are determined until one of them first intersects a critical
point. The MMP, therefore, is the pressure at which the first key
tie line becomes zero length.
We use the PennPVT Excel spreadsheet (2010) to calculate
the MMP based on a cubic EOS. This code is ideal to calculate
MMPs for pure-component gases because it carefully finds all
key tie lines starting with a well-defined and known solution. The
detailed procedure is as follows:
1. Set the reservoir temperature and the EOS parameters. Define
a starting pressure, say 500 psia.
2. Approximate the oil and gas by a three-component system,
where the components are the injection component and the two
heaviest components in the oil. The oil molar composition must
sum to 1.0, which is accomplished by normalizing the mole frac-
tions contained in the real system for these three components. This
solution is known because there are only two key tie lines, one that
extends through the gas (gas tie line) and one that extends through
the oil (oil tie line). We first check that a two-phase region exists
between the gas component and the heaviest component. If not,
the starting pressure is lowered and Step 2 is repeated.
3. Add small mole fraction increments of the next-heaviest
component in the real oil to the system, increasing the dimension-
ality of the problem (making a quaternary system from a ternary
system, for example). The new oil composition is normalized to
sum to 1.0 based on the original mole fractions for these com-
ponents, and the current mole fraction of the component that is
being added. We take small increments in the mole fraction until
the original mole fraction in the real oil for that component is
obtained, and we check as we proceed that the key tie lines found
are consistent with the previous ones. We locate the key tie lines for
each small increment based on the geometric construction outlined
in Yuan and Johns (2005) and the Li and Johns (2007) method for
performing a flash calculation where overall compositions can be
negative. From the Li and Johns (2007) approach, we check how
many tie lines intersect the point in negative composition space,
and if there is more than one, we select the key tie line that is
nearest the previous one.
4. Repeat Step 3 for the next-heaviest component in the oil,
adding another crossover key tie line until all components in the
oil have been added. We check as we proceed that all key tie lines
can be found. If not, the starting pressure exceeds the MMP, and
the pressure must be lowered. Once all components are complete,
we have found the key tie lines at the starting pressure (500 psia
in this example).
5. Increase the pressure in small increments, and find all key tie
lines using the geometric construction. This assumes that shocks
occur from one key tie line to the next. We compare the length
of the key tie lines found in the previous pressure step to check
December 2011 SPE Journal
 G O 1st Contact
G XY O for MMP calculation based on a novel extrapolation technique is
2nd Contact
G XY XY O 3rd Contact
G XY XY XY O 4th Contact
… 3. Mix the resulting equilibrium liquid(s) (x) with equilibrium
G XY X Y ... ... X Y XY O N th Contact
Condensing Condensing/ Vaporizing
Miscibility Vaporizing Miscibility
Miscibility
Fig. 1—Illustration of repeated contacts in the multiple-mixing-
cell method. G: injecting gas composition; O: oil composition; Y:
equilibrium gas composition; X: equilibrium liquid composition.
continuity of the key tie lines. The curve of key-tie-line lengths
vs. pressure should be monotonic without discontinuities. The
MMP is the pressure at which any one of the key tie lines first
becomes zero length. The MMP is often estimated by extrapolating
the smallest key tie line to zero length. All important information
related to “quality control” of the MMP estimate, such as the error
in the MMP (from extrapolation of key-tie-line lengths) and the
K-values and lengths of all key tie lines, is produced as output in
an Excel spreadsheet.
Multiple-Mixing-Cell Model
In this section, we describe the basic steps in our mixing-cell
method, which is remarkably simple. Our method does not cal-
culate recovery factors or transfer specific amounts of fluid based
on cell volumes. It also only relies on performing P/T flash cal-
culations using any cubic EOS, and on moving the injected and
equilibrium gas ahead of the equilibrium liquid in each cell. Our
goal in this section is to demonstrate that we achieve identical key
tie lines to those found using the MOC method.
We begin with two cells at fixed temperature and pressure,
where the injection gas is located in the upstream cell and the
reservoir fluid in the downstream cell (see Fig. 1). The reservoir
oil (xO) and injection gas (yG) are then mixed, in any mole fraction
desired, although we generally use the mass-balance equation z =
xO+α(yG–xO), with α equal to 0.5. As long as the pressure is below
the MMP, the resulting overall composition z will be either in the
two-phase region, or in the region of tie-line extensions. Thus, a
flash or negative flash (Whitson and Michelsen 1989) with a cubic
EOS can be performed at this overall composition, resulting in two
equilibrium compositions, one for liquid (x) and one for vapor
(y). The equilibrium vapor moves ahead of the equilibrium liquid
because gas is injected. This is the first contact.
The second series of contacts contains both an upstream and
downstream contact (see Fig. 1). The downstream contact mixes
the equilibrium vapor (y) with fresh oil, and the upstream contact
mixes the equilibrium liquid (x) with fresh injection gas. When
mixing vapor and liquid, we always use the same material-balance
equation, z = x+α(y–x). Two new sets of equilibrium liquid and
vapor phases result from these flash calculations, so that we now
have six cells, including the reservoir oil and injection gas. This
completes the second contact.
We then make additional contacts until all key tie lines develop
and converge to within a specified tolerance. Thus, after N contacts,
we have a total of 2N+2 cells.
The following steps summarize a possible procedure for the
estimation of MMP with our mixing-cell model. The procedure
December 2011 SPE Journal
is based on finding the key-tie-line lengths at each pressure. The
procedure can be time-consuming depending on the tolerances
specified for the convergence to each key tie line. A faster approach
given later.
1. Specify the reservoir temperature and an initial pressure
that is substantially below the MMP. We typically use an initial
pressure of 500 psia.
2. Start with two cells filled with injection gas and reservoir
oil. Mix the gas and oil, and flash the resulting overall composition
(using any cubic EOS) to obtain two new equilibrium composi-
tions, liquid x and vapor y.
vapor(s) (y), assuming gas moves ahead of the oil phase. Each
of the contacts results in new compositions for the next set of
contacts.
4. Continue with additional contacts by mixing neighboring
cells, as shown in Fig. 1, until all NC–1 key tie lines develop
and converge to a specified tolerance. We automatically identify
a converged tie line by checking the tie-line lengths between
neighboring cells. That is, we calculate for each cell the slope of
the tie-line length as a function of the cell number. A key tie line
is developed when three successive cells have a slope of zero, to
within a specified tolerance. A zero slope means that two neighbor-
ing cells have the same tie-line length to within a specified toler-
ance. This indicates the development of a key tie line and results
in a flat region when plotted as tie-line length vs. the number of
cells. In this paper, we use a very strict tolerance of 10–8 because
we want to demonstrate the accuracy of the method. Once all key
tie lines are found, we proceed to the next step.
5. Calculate the tie-line length of each key tie line found in Step
4, and store the minimum tie-line length (TL).
6. Increase the pressure and repeat Steps 2 through 5. There
are varieties of ways to determine the next pressure to use. For
the second pressure, we simply increase the pressure by a small
amount, say 200 psia. To determine the third pressure, we use a
linear extrapolation of the tie-line lengths (from the previous two
pressures) to zero tie-line length to give the first MMP estimate.
The increment in pressure ΔP is determined by dividing the differ-
ence in the estimated MMP and the current pressure by three, or by
how many additional pressure points are desired. Smaller increases
are possible, but at the expense of time and little improved accu-
racy in the final MMP estimate. For subsequent pressures, ΔP
is based on a power-law extrapolation of the minimum tie-line
lengths found at the previous three pressures. That is, we perform
a multiple-parameter regression of the minimum tie-line lengths
to determine the exponent n in TLn = aP+b, where a is the slope
and b is a constant. The three parameters are determined when
the correlation coefficient exceeds 0.999. We then determine a
first estimate of the MMP as the pressure at which the power-law
extrapolation gives zero length. Typical values for n are between
1.5 and 10, although the extrapolated MMP near the actual MMP
changes little over this range.
7. Repeat Step 6 for two or three additional pressures, fitting
the last three pressure points, until the MMP is estimated to within
the desired accuracy, say 20 psia. If the accuracy is not satisfac-
tory, then use smaller pressure increments in Step 5. This approach
not only yields the final MMP, but also gives an estimate of the
uncertainty in the MMP based on the MMP estimate from the
previous regression. We take the absolute value of the difference
between the previous MMP estimate and the final MMP estimate
as the uncertainty of the MMP. It is likely that this MMP range is
larger than the true error in the final MMP.
The proposed method has several advantages over other MMP-
estimation methods. First, compared to the analytical MOC meth-
ods, it is very robust because all flash calculations are in positive
composition space, and there are no Newton-Raphson iterations
to solve. The mixing-cell model always results in a single unique
solution compared to MOC, which requires careful checking to
ensure convergence to the correct set of key tie lines. Further,
there are no assumptions regarding whether shocks connect key
tie lines or continuous variations. Thus, the mixing-cell approach
735
 TABLE 1—COMPOSITION OF OIL AND GAS AND PROPERTIES OF THE COMPONENTS FOR
CASE 1 (ORR ET AL. 1993; WANG AND ORR 1997)
Composition Properties Binary Interaction Parameters
Oil Gas Tc (°F) Pc (psi) C1 C4 C10 CO2
C1 0.2 0.2 –116.63 667.8 0.0104 – – – –
C4 0.15 – 305.65 550.7 0.201 0.027 – – –
C10 0.65 – 652.1 305.7 0.49 0.042 0.008 – –
CO2 – 0.8 87.9 1,071 0.225 0.1 0.1257 0.0942 –

given here will locate all key tie lines, whether composition paths
have shocks or continuous variations that connect key tie lines. In
theory, these key tie lines could include ones that are transitional
in nature, although we did not locate them in this research (Seto
et al. 2006; Seto and Orr 2008). As discussed later, the proposed
mixing model should also be able to handle displacements where
three or more phases are present, something that is currently very
difficult with MOC methods (LaForce and Johns 2005). Because
the mixing-cell method does not incorporate volumetric informa-
tion, the mixing-cell method only finds the key tie lines of the
displacement, not the 1D composition path.
The mixing-cell approach examined here requires neither the
entry of petrophysical parameters nor the solution of the flow
equations. Our approach also corrects for dispersion by continuing
cell-to-cell contacts until all key tie lines are converged, without the
need for determining recoveries or making plots of recovery as a
function of the number of cells. In addition, the approach is auto-
matic, and it gives an estimate of the MMP and its uncertainty.
Example MMP Calculations
In this section, we give examples of MMP calculations for gas-
floods published in the literature. We also show the effect of the
assumed relative mobility of the phases on the MMP calculation.
We use the Peng-Robinson EOS (1978) for all calculations in this
research.
Case 1: Four-Component CV Displacement. Consider first a
simple example of a CV displacement of three-component oil
(CH4, C4, and C10) by a two-component injection gas (CH4, CO2)
at a temperature of 160°F. The MMP and the key tie lines for this
displacement using the MOC are reported by Orr et al. (1993) and
Wang and Orr (1997). The composition of oil and gas considered
and the EOS properties are shown in Table 1.
For such a displacement, there are three key tie lines: the oil tie
line, the gas tie line, and the crossover tie line. Fig. 2 presents four
profiles of the key-tie-line lengths for the displacement at 2,000
psia (approximately 300 psia below MMP) as a function of the cell
number and the number of contacts made. As is shown, the three
key tie lines develop as the number of contacts proceeds. The key
tie lines are nearly fully developed after 25 contacts, although after
125 contacts, all three key tie lines converge to within the slope
tolerance of 10–8 described in the preceding section. As shown, the
crossover tie line for this displacement controls miscibility because
its tie-line length is shorter than either the gas or oil tie line. Fig. 3
illustrates the CV behavior further in that the K-values for the
crossover tie line are nearest to 1.0. The condensing portion of the
displacement occurs at the leading edge (downstream), while the
vaporizing portion occurs at the trailing edge (upstream). Miscibil-
ity is developed in the middle of the displacement for CV drives.
Fig. 1 illustrates that for CV drives, miscibility occurs in a cell
somewhere between the oil and gas tie lines, whereas for vapor-
izing drives, miscibility occurs at the oil tie line (most-downstream
tie line), and for condensing drives, it occurs at the gas tie line
(most-upstream tie line).
Fig. 4 shows the key-tie-line lengths for this displacement as
a function of pressure. The dashed lines are the key tie lines from
Wang and Orr, while the symbols are the converged key tie lines
from our mixing-cell model. Agreement between the two is identi-
cal within the tolerances specified. The MMP is estimated by the
power-law extrapolation using n = 1.8 for the last three pressure
points (see Fig. 5). For this system, the calculated MMP from our
mixing-cell method is 2,303±4 psia. This compares well to the
MMP reported in Wang and Orr (1997) of 2,297 psia.
The K-values for each component in each cell at a pressure
(2,305 psia) just slightly greater than our estimated MMP are given
in Fig. 6. The profile of the K-values clearly shows the develop-
ment of miscibility in the middle of the displacement, characteristic
of a CV drive. At this pressure, however, the crossover tie line
does not exist for MOC methods, but for our mixing-cell model, a
slight amount of dispersion causes some two-phase flow so that the
crossover tie-line is retained. Continued contacts would decrease
its length further, although zero length cannot be reached. This is
not a problem for our mixing-cell method because the MMP can
be estimated accurately based on tie-line lengths determined for
pressures below the estimated MMP. We show later that we can
extrapolate the minimum tie-line lengths as a function of the num-
ber of contacts to obtain a negative minimum tie-line length at an
infinite number of contacts at pressures above the MMP.

0.8 2.5
Gas Tie Line C1
0.7
2
0.6
Tie-Line Length

Oil Tie Line

0.5
K-Value

1.5 CO 2
0.4 25 Contacts
1
0.3 50 Contacts

0.2 100 Contacts

0.5 C4
125 Contacts
0.1 Crossover Tie Line C10
0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Cell Number Cell Number

Fig. 2—Development of key tie lines using our mixing-cell Fig. 3—K-values for the four-component displacement (Case
model for the four-component displacement (Case 1) at 2,000 1) at 2,000 psia and 160°F after all key tie lines are developed
psia and 160°F. after 125 contacts.

736 December 2011 SPE Journal

 1.2 0.06
Crossover Tie Line Gas Tie Line
1 0.05

Tie-Line Length 0.8

Oil
0.04

TL 1.8
0.6 0.03
Gas
0.4 0.02

0.2 0.01
Crossover
0 0
500 1000 1500 2000 2500 2000 2100 2200 2300
Pressure, psi Pressure, psi
Fig. 4—Key tie-line lengths as a function of pressure for the
Fig. 5—Extrapolation of the tie-line lengths for Case 1 (see
four-component displacement of Case 1. The MMP occurs
Fig. 4).
where the crossover tie line has zero length at approximately
2,303 psia.
Johns and Orr predicted an MMP of 1,350 psia for the system
C1 based on an extrapolation of Crossover Tie-Line 1 becoming zero
length. Wang and Orr calculated tie-line lengths, however, well
2
above 1,300 psia and obtained an MMP estimate of 1,466 psia
for the same system. The difference between the two models was
1.6 attributed to the fact that Johns and Orr did not have a robust
CO2 cubic EOS for tie lines above 1,300 psia. However, our MMP
K-Value

1.2 prediction using an in-house MOC code, PennPVT, gives nearly

0.8
0.4
0 converge. Fig. 8 shows a close-up view of Fig. 7, which shows
0 400 800 1200
Cell Number
Fig. 6—K-values for the four-component displacement (Case
1) at 2,305 psia and 160°F. The crossover tie line is approach-
ing zero length as the pressure is slightly above the estimated
MMP.
Case 2: CO2 Displacement of 10-Component Oil. Our second
example is the displacement of 10-component oil at 120°F by pure
CO2, a case that was previously examined by both Johns and Orr
(1996) and Wang and Orr (1997) using MOC. As in Case 1, the
displacement is CV because a crossover tie line controls miscibility.
Table 2 gives the composition of the oil and EOS properties of
the components.
exact agreement with that of Johns and Orr, up to 1,300 psia. In
addition, the key-tie-line lengths calculated from PennPVT and
our new mixing-cell method agree to within four-digit accuracy
(see Fig. 7). As is shown, Crossover Tie Line 2 becomes the mini-
C4
mum-length tie line at approximately 1,283 psia, nearly the same
C10 pressure at which the cubic EOS for Johns and Orr could no longer
1600 2000 that crossover tie line 2 (using our MOC code) drops suddenly to
the MMP (estimated to be 1,298 +/– 2 psia). This is confirmed by
our mixing-cell method, which also finds that Crossover Tie Line
2 becomes the smallest tie line at 1,283 psia. Our new mixing-cell
method also agrees well with the MMP predicted from our MOC
code, in that it indicates an MMP of approximately 1,298 +/– 5 psia
using power-law extrapolation (see Fig. 9).
The agreement between our new mixing-cell method, our MOC
code (PennPVT), and the results by Johns and Orr (1996) reinforces
the idea that we have the correct MMP and key tie lines for this dis-
placement. Further, the small differences in the key-tie-line lengths
observed with our mixing-cell model and that of MOC show a trend
in the errors. That is, the magnitudes of the errors from the gas to
oil tie lines are 0.0 (gas tie line), 10–4 (Crossover Tie Line 1), 10–5,
10–5, 10–6, 10–7, 10–7, 10–8, 10–9 (Crossover Tie Line 8), and 0.0 (oil tie
line). The trend is explained by the fact that, unlike our mixing-cell

TABLE 2—COMPOSITION OF OIL AND KEY EOS PARAMETERS FOR CASE 2 (METCALFE AND YARBOROUGH 1979;
JOHNS AND ORR 1996)
Composition Properties Binary Interaction Parameters
Oil Gas Tc (°F) Pc (psi) CO2 C1 C2 C3 C4
CO2 – 1 87.6 1,071 0.225 – – – – –
C1 0.35 – –116.6 667.8 0.01 0.1 – – – –
C2 0.03 – 89.7 708.4 0.099 0.13 0 – – –
C3 0.04 – 205.8 617.4 0.152 0.135 0 0 – –
C4 0.06 – 294.6 543.3 0.187 0.13 0 0 0 –
C5 0.04 – 366.5 475.3 0.252 0.125 0 0 0 0
C6 0.03 – 453.9 431 0.296 0.12 0.02 0.03 0.03 0.03
C7 0.05 – 512.9 397 0.351 0.12 0.03 0.03 0.03 0.03
C8 0.05 – 564.4 364 0.394 0.12 0.035 0.03 0.03 0.03
C10 0.3 – 647.6 320 0.491 0.12 0.04 0.03 0.03 0.03
C14 0.05 – 790 230 0.755 0.12 0.06 0.03 0.03 0.03

December 2011 SPE Journal 737

 0.9 0.25
0.8
0.23

Tie-Line Length
0.7 Crossover 1 Tie Line
Tie-Line Length

0.6 0.21

0.5
0.19
0.4
0.3 0.17 Crossover 2 Tie Line
0.2
0.15
0.1 1260 1270 1280 1290 1300
800 900 1000 1100 1200 1300
Pressure, psi
Pressure, psi
Fig. 8—Close-up view of Fig. 7 showing key tie lines for Case 2
Fig. 7—Comparison of key tie lines for Case 2 found from mix- from MOC (PennPVT 2010), and those from the new mixing-cell
ing-cell method (solid dots) and MOC using PennPVT package method (solid dots). Only the minimum tie-line length is tracked
(lines). by the mixing-cell method.

5.E-06 the wrong set of key tie lines above 1,300 psia. This displacement is
a very difficult one for MOC methods to calculate primarily because
of the steep drop in Crossover Tie Line 2 over just a few psia. Our
4.E-06
in-house MOC code, PennPVT, has been developed to ensure that
the correct set of key tie lines are found, as is evidenced here by
3.E-06 good agreement with our mixing-cell model.
TL 8

2.E-06 2
R =0.9998
1.E-06
0.E+00
1270 1275 1280 1285 1290 1295
Pressure, psi
Fig. 9—Extrapolation of the minimum tie-line lengths from the
mixing-cell method for Case 2. The MMP is estimated to be
1,298 psia based on the last four data points.
method, MOC assumes that all key tie lines are connected by shocks
along their nontie-line paths, and there is no nontie-line rarefaction
wave present. Johns and Orr (1996), however, showed that the actual
composition path takes a rarefaction wave (continuous variation)
between the oil tie line and Crossover Tie Line 1, which is exactly
where the differences between the two methods are greatest.
Our results explain why Johns and Orr (1996) could not converge
to key tie lines above 1,300 psia. We do not know why Wang and
Orr (1997) failed to locate these key tie lines. It is likely they used
different EOS parameters than they reported, or they converged to
Case 3: Rich-Gas Displacement of Eight-Component Oil. Con-
sider next a displacement of eight-component oil by a five-compo-
nent gas, as is described by Hearn and Whitson (1995) and Wang
(1998). Table 3 lists the composition of the oil and rich gas and
the EOS properties. The temperature for this system is 212°F.
The minimum tie-line length from the mixing-cell method as
1300 1305 a function of pressure is shown in Fig. 10. The MMP from the
mixing-cell method is 3,179 +/– 10 psia (see Fig. 11). This agrees
favorably with Hearn and Whitson, who reported an MMP of 3,190
psia from compositional simulation. They also reported a slim-tube
MMP of 3315+/– 100 psia for this system. Wang also reported a
similar MMP of 3,259 psia from MOC. (Wang actually reported
3,279 psia in his text, but his figure clearly shows an MMP of
3,259 psia). This displacement combines condensing and vapor-
izing because a crossover tie line controls miscibility.
Case 4: Fast MMP Approximation With Mixing-Cell Method
for Gas Displacement of 12-Component Oil. A novel algorithm
is developed in this subsection to estimate the MMP using a mini-
mum number of contacts. Instead of continuing contacts until a tie
line is converged to a small tolerance, we find the smallest tie-line
length with each additional contact at a fixed pressure. The mini-
mum tie-line length is plotted as a function of the inverse of the
number of contacts raised to some constant (1/Nm). We extrapolate

TABLE 3—COMPOSITION OF OIL AND GAS AND THE EOS PROPERTIES FOR CASE 3
(HEARN AND WHITSON 1995)
Composition Properties EOS Constant Correction Factors Binary IPs
Oil Gas Tc (°F) Pc (psi) Ωa Ωb C1+N2 C2+CO2
C1+N2 0.341 0.646 –120.87 661.5 0.0127 1.00351 1.0855 – –
C2+CO2 0.056 0.124 89.73 760.9 0.1113 1.0175 1.03587 0.01511 –
C3 0.055 0.103 206.03 616.3 0.1454 1 1 0.00326 0.01828
C4’s 0.059 0.089 294.93 543.1 0.1868 1.00229 0.99748 0.00344 0.01708
C5’s–C6 0.092 0.038 417.53 462.2 0.2693 0.99558 0.9928 0.00391 0.01682
C7+(1–2) 0.195 – 632.43 376.8 0.3663 0.98309 0.99562 0.02678 0.01682
C7+(3–4) 0.155 – 932.63 237.8 0.6797 0.96443 0.99911 0.0434 0.01682
C7+(5) 0.047 – 1,186.03 158.2 1.0468 1.00216 1.00958 0.05834 0.01682

738 December 2011 SPE Journal

 0.45 0.08
0.4
0.35
0.06
Tie-Line Length
0.3 Wang and Orr (1997)

TL 1.7
0.25
0.04
0.2
0.15 2
R =0.999
0.1 0.02
Mixing Cell
0.05
0 0
1500 1800 2100 2400 2700 3000 3300 3600
2500 2600 2700 2800 2900 3000 3100 3200
Pressure, psi
Pressure, psi
Fig. 10—Minimum tie-line length for Case 3 from the mixing-cell
method, as compared with that of Wang and Orr (1997). The Fig. 11—Power-law extrapolation to the MMP for Case 3, using
MMP is controlled by Crossover Tie Line 4, and is approxi- our mixing-cell model. The MMP is 3,179 +/– 10 psia.
mately 3,179 +/– 10 psia from our mixing-cell method.

0.2 estimation finds that pressure at which the extrapolated tie-line

0.15 length for an infinite number of contacts (TL∞) is exactly zero.
Minimum Tie-Line Length

From our experience, only four or five trial pressures are needed
0.1 to accurately estimate the MMP.
We demonstrate the procedure that is implemented in PennPVT
0.05 m=1 m=0.5 m=0.2 with an example as reported by Zick (1986) and Jessen et al.
0 (1998). First, the MMP is found assuming a purely condensing and
0 0.2 0.4 0.6 0.8 purely vaporizing drive. This calculation is very fast because we
–0.05 find the pressure at which the tie-line extension through the oil (for
the vaporizing case) or the gas (for the condensing case) becomes
–0.1 zero length. The minimum of these two MMP values is the upper
–0.15 estimate for the MMP of a combined CV drive.
The first trial pressure is equal to the upper bound of the MMP
–0.2 divided by four. The advantage of this approach is that the first trial
(1/N) m pressure is likely below the MMP, although this is not necessary
for the method to converge successfully. We then make N con-
Fig. 12—Extrapolation of the minimum tie-line length for Case tacts, depending on the accuracy required and determine TL∞. For
4 at a pressure of 3,774 psia to determine TL∞. A value of m = example, Fig. 12 gives the minimum tie-line lengths as a function
0.2 gives the best straight line. This value of TL∞ = –0.16 cor- of the number of contacts (1/Nm) for a 12-component oil displaced
responds to Point 2 in in Fig. 13. by five-component gas, as described in Table 4. Here, different
values of m are used so that the data fall on a straight line. We find
that trend to find the minimum tie-line length at an infinite number that m = 0.2 generally produces a relatively straight line, although
of contacts. When the pressure is below the MMP, the minimum this can be adjusted if necessary. In this example, we fit a straight
tie-line length for an infinite number of contacts will be positive. line through the last 10 contacts to determine TL∞.
When the pressure is above the MMP, the minimum tie-line length The second trial pressure is set to one-half of the upper bound
for an infinite number of contacts will be negative. That is, repeated of the MMP. Contacts are repeated again at this pressure to deter-
contacts will yield a composition outside of the region of tie-line mine TL∞. Based on these two pressures, we linearly interpolate (or
extensions for a finite number of contacts. The procedure for MMP extrapolate) to where TL∞ = 0 (see Fig. 13 and Table 5). This gives

TABLE 4—COMPOSITION OF OIL AND GAS AND THE EOS PROPERTIES FOR CASE 4 AT 185°F
(ZICK 1986)
Composition Properties Binary IPs
Oil Gas Tc (°F) Pc (psi) CO2
CO2 0.0656 0.1775 87.79 1,069.443 0.228 –
CH4 0.3711 0.3878 –116.59 666.018 0.008 0.12
C2 0.0538 0.188 90.05 707.094 0.098 0.15
C3 0.0373 0.2196 205.97 614.673 0.152 0.15
C4 0.0261 0.0271 305.69 550.125 0.193 0.15
C5 0.0187 0 385.61 488.511 0.251 0.15
C6 0.0218 0 453.65 429.831 0.296 0.15
C7+(1) 0.1791 0 649.49 418.095 0.454 0.15
C7+(2) 0.091 0 798.35 280.197 0.787 0.15
C7+(3) 0.0605 0 927.05 240.588 1.048 0.15
C7+(4) 0.0447 0 1,075.91 221.517 1.276 0.15
C7+(5) 0.0302 0 1,342.49 212.715 1.299 0.15

December 2011 SPE Journal 739

 0.3
1 We have developed a true mixing-cell model to estimate MMP (or
0.2
0.1
5
TL ∞
3 for a displacement, regardless of the number of components in
4 the injection gas and reservoir fluid. Unlike other mixing-cell
0 methods, our method automatically corrects for dispersion by
1500 2000 2500 3000 3500 4000
–0.1
2 2. The results of the mixing-cell method agree well with the
–0.2
Pressure, psi
Fig. 13—Trial pressures and interpolation to obtain the pres-
sure (MMP) at which TL∞ = 0. The first trial pressure is labeled
“1” and so forth.
the third trial pressure at which TL∞ is estimated. This procedure
is repeated until convergence within a specified tolerance (say, 10
psi). The MMP can also be estimated for different values of m to
see the sensitivity of the MMP to this value. PennPVT reports a
range of MMPs for m = 0.15, 0.2, and 0.25. The estimation of
MMP with this approach is very fast, typically less than a minute
when 30 contacts are used.
The value of MMP from our mixing cell is 3,104 psia when 30
contacts are used and m = 0.2. Zick reported an MMP of 3,125 psia
from slim-tube experiments, and Jessen et al. reported a value of
3,095 psia using MOC. Using the simple approach previously pre-
sented for Cases 1 through 3, the MMP is estimated to be 3,188 +/– 50
with 700 contacts. More contacts can be used for greater accuracy.
We also used the fast MMP approach to estimate the MMP for
Case 1 to be 2,215 +/– 90 psia, 1,307 +/– 15 psia for Case 2,
and 2,970 +/– 100 psia for Case 3. These are close to the MMPs
estimated from slim-tube experiments and MOC, as described
previously. Using more than 30 contacts would result in more-
accurate MMP estimates.
Discussion
Many have claimed (including the authors of this paper) that the
MMP is independent of fractional flow (relative permeability and
viscosities), and thus mobility of the phases (Zhao et al. 2006a, b;
Pires and Bedrikovetsky 2005). This hypothesis is reinforced using
our mixing-cell model in that we obtained the same key tie lines for
any value of α, where α determines how much of the equilibrium oil
(xO) and gas (yG) are mixed from cell to cell using z = xO+α(yG –xO).
Thus, no matter the amount of fluid that moves ahead, the key tie
lines remain unchanged.
The literature is also replete with statements that equilibrium
gas moves out ahead of the equilibrium liquid during mixing-cell
contacts because the gas phase is more mobile than the oil. While
gas is more mobile than liquid, the reason that equilibrium gas
moves ahead of liquid is the result of the simple fact that gas must
move ahead because it is the injected phase. Simple 1D simulations
can show that even if the gas-phase mobility is decreased below
that of oil (a favorable mobility ratio), the same key tie lines are
obtained as those for an adverse mobility ratio.
TABLE 5—TRIAL PRESSURES FOR MMP CALCULATION OF CASE 4
Trial Pressure (psi) TL for m = 0.2
1,887 0.23251
3,774 –0.16285
2,996 0.03399
3,131 –0.00816
3,105 –0.00017
Note: The pressures converge to the MMP shown in bold.
740
Conclusions
MME) and the key tie lines in the composition path. The method is
simple, robust, and faster than conventional 1D slim-tube simula-
tion. The main conclusions from this research are as follows:
1. The mixing-cell method can accurately find all key tie lines
performing additional contacts until a small tolerance in the
tie-line slopes is met.
MMP and key tie lines from our analytical MOC software and
from slim-tube experiments. The tie lines determined from our
mixing-cell method may be slightly more accurate than those
obtained by an MOC calculation that is based on the assumption
that all the tie lines are connected by shocks when the actual
displacement includes rarefactions between tie lines.
3. Our mixing-cell method is accurate for all displacement types,
including combined CV drives.
4. The relative value of the phase mobilities (fractional flow) does
not affect the MMP. In all cases examined here, we converge
to the same key tie lines independently of the fraction at which
equilibrium gas and oil are mixed.
5. The speed of the mixing-cell method in estimating MMP can
be substantially increased by a novel extrapolation technique
as described in Case 4 that allows for positive and negative
tie-line lengths.
Nomenclature
N = number of contacts
Nc = number of components
P = pressure, m/Lt2, psia
T = temperature, T, °F
TL = tie-line length
TL∞ = extrapolated tie-line length for an infinite number of contacts
x = liquid composition
y = vapor composition
z = overall composition
α = dilution factor
ΔP = increment in pressure, m/Lt2, psi
Acknowledgments
The authors gratefully thank Exxon, Maersk, Marathon, OMV,
Occidental, and Shell for their financial support of this research
through the Gas Flooding JIP at the Pennsylvania State University
at University Park, Pennsylvania (formerly at the University of
Texas at Austin). We also thank Franklin M. Orr for his useful
comments on this paper.
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Kaveh Ahmadi is a reservoir engineer with BP America, Gulf of
Mexico Deepwater Production. His research interests include
phase-behavior modeling, theory of gas-injection processes,
and gas injection for enhanced oil recovery. He holds a BS
degree in reservoir engineering from the Petroleum University
of Technology, Iran, an MS degree in petroleum engineering
from the University of Kansas, and a PhD degree in petroleum
engineering from the University of Texas at Austin. Russell T.
Johns is a professor of petroleum and natural gas engineer-
ing in the Department of Energy and Mineral Engineering at
741
Pennsylvania State University, where he holds the Victor and
Anna Mae Beghini Faculty Fellowship. His research interests
include enhanced oil recovery, unconventional gas engineer-
ing, theory of gas-injection processes, multiphase flow in porous
media, and well testing. In these areas, he has published over
160 technical papers, reports, and books. Prior to his current
position, he served on the faculty at the University of Texas
at Austin from 1995 to 2010. He also has 9 years of industrial
experience as a petrophysical engineer with Shell Oil and as
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a consulting engineer for Colenco Power Consulting in Baden,
Switzerland. He holds a BS degree in electrical engineering
from Northwestern University and MS and PhD degrees in
petroleum engineering from Stanford University. Johns received
the SPE Ferguson medal in 1993 for his research on the com-
bined condensing/vaporizing gas-drive process. He served
as Co-Executive Editor for the SPE Reservoir Evaluation and
Engineering journal from 2002–2004. In 2009, he was awarded
the SPE Distinguished Member Award.
December 2011 SPE Journal