Objective The objective of this study is to develop a more reliable and less complex CO 2/oil

correlation using a combination of reservoir fluid compositional data and or reservoir fluid
properties and compare its efficiency against other commonly used correlations. The study
involves Experimental work to measure the CO 2-Oil MMP for different Oils and determining a
mathematical model for predicting CO2-Oil MMP based on the obtained CO2-Oil MMP
experimental results.

EOR
Enhanced Oil Recovery (EOR) is the oil recovery method which is applied to the depleted oil
reservoir after secondary recovery that either involves water flooding or gas injection. The EOR
methods can be classified by three main categories chemical, thermal, and Miscible. Gas
injection, as one of the non-thermal EOR, involves the injection of gases (i.e., natural gas,
enriched natural gas, a liquefied petroleum slug driven by natural gas, carbon dioxide, nitrogen,
or flue gas) into

the oil reservoir. CO 2 injection is the most non-thermal of applied EOR

processes. Both immiscible / miscible gas injection can mobilize the trapped oil by different
mechanisms. As the injected gas diffuses into the oil, the oil will swell and its viscosity will
reduce. When the injected gas exchanges components with the reservoir oil, miscibility is
reached, the capillary forces are eliminated and higher oil recovery is obtained. Miscibility
depends on pressure, temperature and properties of the oil and the injected gas.

CO2 injection in an oil reservoir is an EOR method that is widely known for its higher oil
ultimate recovery (UR) and for its use in the Carbon Capture and Storage (CCS) that leads to
desirable benefits on the environment (reducing CO2 content in the atmosphere). CO2 injection
is intended to reduce residual oil saturations (ROS) after all secondary oil displacement
processes have been exhausted. Generally, two different processes are proposed for miscibility
achievement. (1) First contact miscibility (FCM): a single phase is created when the injected gas
and the oil become fully miscible, and (2) Multiple contact miscibility (MCM): many contacts
are necessary between the injected gas and oil for them to mix with each other to reach
miscibility. Furthermore, Zick (1986) suggested three driving mechanisms MCM: vaporizing
gas drive (VGD), condensing gas drive (CGD) and combined condensing/vaporizing gas drive
(C/V). There are two common idealizations of the way in which a two-phase gas and liquid

system achieves miscibility through multiple contact. In the VGD also termed as Forward
contact, fresh (original) liquid phase is contacted with a vapor phase whose composition is
altered by repeated equilibration with the liquid. Progressively, the injection gas becomes
enriched in C2+ by multiple contacts with original oil and, at the gas front, eventually develops
miscibility with the original oil. In the CGD, the composition of the liquid phase is altered by
equilibration with fresh vapor phase.

In backward contact or CGD, the injection gas

continuously enriches the reservoir oil in C 2-C5 at the point of injection until the injection gas
and enriched reservoir oil become miscible. Zick showed that the location of miscibility (i.e.,
near-100% recovery efficiency) was not at the displacement front (VGD) or the point of injection
(CGD), but in between. He also showed that the true minimum conditions of miscibility could
be significantly lower than predicted by the VGD and CGD mechanisms. Based on Zicks
findings and his description of the mixed C/V mechanism, it is clear that the true MMP (or
MME) can be calculated only if the path of developed miscibility is modeled properly. Several
authors have suggested methods to calculate the C/V MMP.
Miscible CO2 injection would contribute towards more oil reserves and maintain production
levels for years to come. In the CO 2 flooding method, favorable conditions of reservoir pressure,
temperature, and oil composition are required to achieve the dynamic or multiple-contact
miscibility and subsequently displacement of injected CO2 and oil reservoir. The multiplecontact

miscibility can be defined as the thermodynamic equilibrium between the CO 2 gas

and the reservoir oil fluid. In other words a complete mass transfer of the CO 2 gas into the
reservoir

oil fluid, which is a condensing process, and of the components of the reservoir oil to

the CO2 gas, which is a vaporizing process. It is also worthwhile mentioning that the miscibility
with the oil at injection pressure of MMP occurs at CO2 supercritical conditions, which is the
optimum condition to become an efficient solvent. It has very established applications both in
the field as well as in pilot tests. Significantly, CO 2 achieves miscibility in oil at low pressures,
has high density which eliminates gas overriding problems, and has the benefit of storing
greenhouse gas emissions. Depending on the compositions of the oil and injected gas and on
the reservoir pressure and temperature, CO2 extracts the light ends from the oil and dissolves in
to the oil until miscibility is achieved.

Enrichment of CO 2 EOR flooding with C2, C3, or C5

fractions was found to have a large effect on reducing the MMP (Dong etal., 2001; Bon

etal.,2005). The main challenges for a successful CO 2 process are the availability of CO2,
corrosion in the well and surface facilities, environmental constraints, and the high cost of CO 2
for use in remote fields. It is well documented that the development of miscibility in a CO 2 / oil
displacement is the result of extraction of some hydrocarbons from the oil by dense CO 2. Orr
and Jensen stated that there is considerable evidence that the extraction of hydrocarbon from
crude oil is strongly influenced by the density of CO 2. 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.

MMP
A certain pressure above which miscible displacement can be achieved is called minimum
miscibility pressure (MMP). It is an effective parameter in miscible gas injection process, at this
pressure local displacement efficiency approach 100%.

While discussing the experimental

recovery curve that exhibits two different regions; At low pressures the recovery increases more
rapidly with increasing pressure than at higher pressures. The break point on the recovery curve
has traditionally been used to determine the pressure at which a miscible displacement develops,
and it is usually considered to be at the MMP. By increasing the injection pressure above the
MMP, only a minor increase in the recovery is achieved. Thus the determination of the MMP is
of major economic importance when implementation of a gas injection project is considered.
Determining CO2-Oil Minimum Miscibility Pressure (MMP) is the key parameter for the design
and operations of successful CO2 miscible flood project. An accurate prediction of CO 2-oil
MMP is the most important key step required for the design of CO2 miscible flood. Therefore, it
is advisable to determine the CO 2-oil MMP for the correct specific candidate oil field based on
the representative reservoir pressure, temperature, and oil composition. In fact, MMP is the
pressure at which interfacial tension of two phases becomes zero and there is no difference
between oil and injected gas densities. Consequently, compressibility factor and specific volume
of two phases will be the same at miscible condition.

A vital factor that determines the

miscibility achievement is the difference between reservoir pressure and MMP. If the reservoir
pressure is higher than the MMP, a miscible drive forms with the injected gas and the recovery
from the oil reservoir can be enhanced.

Experimental Methods of Measuring MMP

Typical measurement methods of MMP are:
1. Slim-tube test and Micro Slim-tube test
2. Rising Bubble Apparatus (RBA) and Single Bubble Injection Technique
3. Pressure-Composition diagram method (P-X) and multi-contact experiments
4. Core Flooding and Sand Packed floods
5. Vanishing Interfacial Tension methods (VIFT)
6. Vapor Density of injected gas versus Pressure
7. High Pressure Visual Sapphire Cell
The primary experimental method in the literature to evaluate miscibility under reservoir
conditions is the Slim-tube test. Although RBA, P-X diagram, and IFT methods are not too
expensive and relatively fast, these methods have the major drawback of not mimicking the
actual reservoir conditions, in general and the porous medium, in particular. However, core
flooding, combined with simulation and PVT studies, is probably the best way to determine the
sensitivity of field-scale oil recovery to flooding pressure.
Non-Experimental Methods of Measuring MMP
Obviously, the experimental approach to determination of the MMP is very time consuming and
consequently expensive. This fact qualifies the massive effort spent on the development of
predictive tools.

The non-experimental methods available to estimate the MMP include

correlations, numerical, and analytical methods. The numerous suggestions for such predictive
tools, documented in the literature, can be organized in six main groups:

Empirical correlation
Ternary representation/ Limiting tie line approach
Slimtube simulation
Single cell simulation
Multicell simulation
Semi-analytical methods by the intersecting tie line approach

Empirical Correlations:
Various authors have developed empirical correlations for the purpose of predicting the MMP.
Most of these are based on the theorem of corresponding states or methods derived from this
theorem. Experimental MMPs are correlated with properties like pseudocritical temperature and
pressure, gas densities and molecular weight of the C7+ fraction. Most of the methods are based
on studies of pure injection gases (e.g. CO2) or slightly contaminated injection gases. As in any
other application of the corresponding states principle, the predictions become unreliable upon
extrapolation. Hence, good results can only be obtained for systems very similar to the reference
system. The correlations are easy to use and give a fast result, but as soon as the correlations are
used for other systems than the reference, the predicted MMPs are of very little use.
Consequently, more general methods for prediction of the MMP are needed. Many correlations
relating the MMP to the physical properties of the oil and the displacing gas have been proposed
to facilitate screening procedures and to gain insight into the miscible displacement process.
Enich et al pointed out that, ideally, any correlation should account for each parameter known to
affect the MMP, should be based on thermodynamic or physical principles that affect the
miscibility of fluids, and should be directly related to the multiple contact miscibility process.
For an initial and quick estimate, operators use correlation currently available in the literature.
For screening purposes, they give a fair first guess depending on the data used. Moreover, they
are inexpensive and can be detained by simple hand calculation. However, the success of the
correlations is usually limited to the composition range in which these correlations were
developed. The MMP correlations fall into two categories: the pure and impure CO 2; while the
other category treats MMPs of other gases. Extension of correlation to account for impure CO 2
streams is sometimes made using a correction factor. In other words, a two-step procedure is
followed to obtain the MMP for CO2 mixed with contaminants. First, the original correlation is
used to predict MMP for CO2. Next, a correction factor is applied to obtain MMP for impure gas
mixture. The correction factor may be dependent either on the composition of injected gas or the
compositions of both injected gas and reservoir oil.

Numerous empirically derived and

thermodynamic models for predicting CO 2 MMP have been reported in the literature. In 1964 R.
Simon and D. J. Graue developed correlations for predicting the solubility, swelling and viscosity
behavior of CO2-Oil systems. The correlations were based on experimental data obtained by the

authors for nine different oils. Some of the empirical correlations disregarded the C 1 through C4
fraction and were based only on the reservoir temperature and the molar weight of C 5+ fraction in
the oil (Holm and Josendal, 1974). Holm and Josendals correlation is based upon Benhams
method. Yellig and Metcalfe (1980) used temperature alone as the independent variable and
included a bubble point pressure correction, i.e., if the oils bubble point pressure exceeds the
estimated MMP, the miscibility pressure is set equal to the bubble point pressure of the oil. They
concluded that

the CO 2 MMP increases at approximately 15 psi/F. Alston et al. (1985)

correlated the pure CO2 miscibility pressure with temperature, C5+ molecular weight, volatile oil
fraction, and intermediate oil fraction. The Johnson and Pollin equation (1981) requires the oil
gravity, molecular weight, and reservoir temperature. Alston et al. and Johnson and Pollin
correlations were also used for impure CO2 gas streams by the inclusion of an injection gas
critical property function. The Johnson and Pollin correlation, however, is limited to the binary
mixtures of CO2 with N2 or CH4. Zuo et al. (1993) modified the correlation derived by Johnson
and Pollin (1981) by introducing two compositional parameters: the mole fractions of the light
and the intermediate components in reservoir fluids. Although these two correlations account for
the effect on MMP of solution gas, it was found (Dong et al., 2000) that they could not provide
satisfactory prediction of MMP for reservoir

oils that had high solution gas-to-oil ratios and

high volatile-component fractions. Dong et al. realized that, to improve the MMP prediction
accuracy, the effects of solution gas in CO 2 (and thus the amounts of volatile and intermediate
fractions in oil) should be considered. Among the empirical models, only those of Alston et al.
(1985) and Sebastian et al. (1985) took into account the effects on CO2 MMP of contaminants in
the CO2 stream. Results of the two models were tested, with the outcomes indicating that the
effects of impurities on CO 2 MMP were not effectively reflected.

The development of

correlations for CO2 MMP prediction has been a subject that involved extensive research efforts,
resulting in many publications (Cronquist, 1978; Mungan, 1981; Sebastian et al., 1985; Alston et
al., 1985; Kovarik, 1985). However, the main concern with correlation techniques is that each
correlation relates to a unique set of reservoir and fluid conditions, which implies difficulties in
satisfying many rigid assumptions that are essential for justifying their applications. These
correlations, nevertheless, serve a useful purpose as being a powerful and convenient tool to
guesstimate the more likely range of the MMP for a given CO 2/oil system, leading to a better
experimental design.

A genetic algorithm (GA) based correlation has been developed to estimate the CO 2/oil MMP.
Although the concept of GA has been used in various applications elsewhere, it has not been
previously applied to predict CO2/oil MMP. The correlation uses the key input parameters:
reservoir temperature, molecular weight of C5+, and the ratio of volatiles to intermediates. The
GA software is particularly suited to problems with nonlinearity and variable continuity.
Noteworthy advantage offered by GA-based correlation is that this correlation can be used when
there is a lack of experimental data and also to design an optimal laboratory program to estimate
MMP. Moreover, the correlation errors could be minimized further through a series of iterative
optimization runs.

MMP Numerical Methods:

The other way to determine MMP is to calculate it numerically; from an appropriate equation
of state (EOS) based representation of phase behavior characterization for mixtures of the oil
displaced with the injected gas.

A good EOS is an essential component in the overall

determination of the miscible injecting efficiency. A comprehensive laboratory program is

strongly recommended to develop and verify the EOS and its reliability depends on the quality of
the data used and the oil composition. In addition, the presence of asphaltene makes MMP
estimation by EOS rather difficult. Both experimental Slim-tube measurements and properly
interpreted Slim-tube simulations provide reliable determination of minimum miscibility
conditions for a system without assuming anything about the displacement mechanism or path of
developed miscibility.
One-dimensional (1D) Slim-tube compositional simulation
Wang and Peck have reported that among the numerical MMP calculation approaches, 1D
compositional simulation is shown to be able to predict MMPs that are consistent with

Slim-

tube test data, provided that appropriate fluid phase behavior characterization is available and
care is taken to account for the effect of numerical dispersion. Zick have also showed that the
MMP could be estimated by 1D compositional simulation, provided sufficient care was taken to
account for the effects of numerical dispersion. Without taking into account grid effects, Slimtube simulation results can overestimate MMPs severely and with a large degree of subjectivity.
Numerical dispersion can be a serious problem for gas-condensate systems exhibiting the C/V

mechanism. Stalkup (1982) suggested a procedure for Slim-tube simulations, using an EOS
based compositional reservoir simulator, to estimate dispersion-free MMP. Oil recovery at a
fixed pore volume injection was tabulated for a number of simulations with varying numbers of
grid cells.

These data were plotted versus the inverse of grid-cell numbers, with the

extrapolation providing an estimate for dispersion-free recovery. Dispersion-free recoveries

were plotted versus pressure and the data were used to define the break point where dispersionfree recovery stabilized at 100%. This point defines the MMP. A subsequent paper by Stalkup
confirmed Zicks results and outlined a procedure for

extrapolation of the number of grid

blocks to eliminate effects of numerical dispersion. The papers by Zick and Stalkup demonstrate
clearly that the MMP can always be found by compositional simulation, though fine grids and
repeated simulations at multiple pressures will mean that significant computation times will be
required. Conclusions from Wang and Peck, Zick, Stalkup and others indicate that numerical
simulation and 1D Slim-tube simulation give excellent matching to the experimental data,
particularly slim-tube data.
2D or 3D compositional simulation models
Alternatively, 2D or 3D compositional simulation models can also be used to calculate MMPs
accurately, assuming that enough number of cells is used to mitigate the effect of numerical
dispersion. Considering, the fact that a large number of grid blocks required to limit the effect of
numerical dispersion, the simulation type approaches are generally time consuming. In addition,
when the number of pressure points at which simulations are performed is not large enough to
obtain a reasonably well defined recovery curve, the numerically calculated MMPs are subject to
the visual interpretation of the recovery curve.

MMP Analytical Methods:

The analytical MMP calculation methodology offers a viable alternative. It is based on the
analytical theory of multicomponent gas injection processes. Because of their improved speed,
analytical methods offer significant promise for developing improved fluid correlations and for
use in compositional streamline simulations.

Ternary Diagram
The earliest attempts to calculate MMPs were based on ternary theory for multicontact
miscible displacement. Benham constructed approximate ternary diagrams and used extensions
of critical tie lines to estimate minimum enrichments for condensing gas drive systems. Ternary
diagrams are constructed by lumping all components into three pseudo components, e.g. light (C1
and N2), intermediate (C2-C6 and CO2), and heavy (C7+) hydrocarbons. The MCM pressure is
obtained as the pressure, at which the extension of the critical tie line is passing through the
composition of either the reservoir oil (vaporizing drive) or the injection gas (condensing drive).
Jensen and Michelsen investigated the ideas of critical tie lines from ternary systems. They
showed that for systems with more than three components, the pressures required to force critical
tie lines to extend through the injection gas composition or the initial oil composition do not
necessarily indicate the correct MMP. They advocated use of a mixing cell approach instead.
Monroe et al., showed that three key tie lines control displacement behavior in four-component
systems:

The tie line that extends through injection gas composition,

The tie line that extends through the oil composition,

A third tie line called the crossover tie line.

Single Mixing Cell Algorithm

Either process (VGD and CGD) can be modeled with a single-cell calculation algorithm

where

the critical tie-line is located by appropriate multiple contacts of injection gas and reservoir oil.
Kuo used a single-cell version of the mixing cell approach for CGDs. In his method, gas was
mixed with oil and flashed. The resulting vapor was removed and fresh injection gas added to
the liquid in the cell (reverse contacts), and the flash calculation was repeated, the mixing
process was then repeated until the liquid phase composition converged. If it converged to a
critical mixture (vapor and liquid identical), the system was taken to be miscible. If not the
pressure was incremented and the process repeated to find the MMP. Luks et al. used a similar
technique as Kuo for both VGDs and CGDs. For VGDs, vapor from each flash was mixed with
fresh oil (forward contacts). Both forward and reverse contacts were performed, and the MMP
was taken to be the lower of the pressures required to produce a critical mixture by repeated

contacts. Generally, using a single-cell calculation algorithm, the calculated VGD MMP is
almost always lower than or equal to the CGD MMP, unless the gas is highly enriched. Wang
and Orr showed that the single-cell technique can also lead to inaccurate MMPs for that system.
The reason

for the inaccuracies encountered in the critical tie line and single-cell

methods became apparent when analytical solutions were obtained for one-dimensional,
dispersion-free flow of four-component mixtures.
Multicell Algorithm

Metcalfe et al. described a method for CGDs based on multiple equilibrium mixing cells. In this
method, a sort of simplified finite difference compositional simulation, gas was mixed with oil in
the first cell and flashed.

Liquid and vapor in excess of the cell volume

were moved

downstream to the next cell, and process was repeated. The MMP was determined as the
pressure required to produce near-critical mixtures in downstream cells.

Zick (1993) has

developed an efficient (C/V) multi-cell algorithm that mimics the development of miscibility as
it appears in a slim-tube simulation. The approach uses a series of PVT cells similar to what has
been proposed by both Cook et al. and Metcalfe et al.
complex methods have

Zick and Stalkup illustrated that more

to be used in order to capture the true nature of the general 1-D gas

injection process. These methods fall into two categories: A mathematical approach and a
physical approach.

The mathematical approach is the slimtube simulations where the

conservation equations governing

1D two phase dispersion-free flow are solved by a finite

difference (FD) approach. A variety of different FD methods can be found in the literature, of
which the simplest and most widely used is the fully explicit one-point upstream weighting
scheme. The slim tube simulations are used to generate recovery curves and the MMP can be
determined by the breakpoint on these curves. In the physical approach, the slim tube is
described by a sequence of interconnected tanks. The tanks are initially filled with reservoir
fluid and gas is added in batches. Each batch is added to the first cell. The resultant overall
composition in the cell is flashed and the excess volume is moved to the neighboring cell. This
procedure is repeated for each cell until the production cell (cell n) is reached and a new batch is
added to the first cell. The excess volumes are moved according to some specified fractional
flow function. As for the FD approach, recovery curves are generated and the MMP can be

estimated.

It is common to both approaches that the simulation results, and hence the

determination of the MMP, are strongly affected by numerical dispersion. Numerical dispersion
originates from the discretization of the flow problem. The coarser grid blocks (lower number of
cells) used in the simulation the larger the effect of numerical dispersion. The presence of
numerical dispersion has the effect of smearing out the recovery curves and make the
determination of a break point more difficult/inaccurate. Hence, the task of determining the
MMP by FD/multicell approaches becomes a balance between acceptable accuracy and
acceptable CPU time consumption. Zick, however, tracks the path of developed miscibility with
a physical parameter (sometimes called miscibility indicator) describing the distance from
criticality in each cell. By interpreting the historical minimum of this parameter for each cell
(which decreases with increasing cell number), results are extrapolated to infinite grid cells and a
dispersion free value for the distance parameter.

An automated algorithm determines the

pressure (or enrichment) where the miscibility distance parameter approaches zero. Typical
miscibility indicator may be relative density difference, gas-oil interfacial tension (IFT) or tieline length indicators involving the equilibrium K values. To determine the MMP, the process is
simulated for a range of pressures until the MMP is detected. Hier and Whitson has tested the
multi-cell model for a multitude of fluid systems and verified the robustness and accuracy of the
model. Various attempts to eliminate the numerical dispersion have been suggested, starting with
the paper of Stalkup. The general

idea is to extrapolate the recovery factors from coarse

grid/cell simulations to an infinite number of grid blocks/cells. A comparison of different

extrapolation procedures is found in Hier. Even if extrapolation procedures are combined with
FD/MC simulations the CPU time consumption for determination of the MMP is still quite
extensive. Thus, development of new and faster methods for calculation of the MMP is required.
The Tie-Line Algorithm
Nouar and Flock used the properties of ternary systems in a different way. They calculated
critical compositions and tie line slopes directly (for ternary systems only) and used them to
estimate MMP for VGD systems. The MMP was taken to be the pressure at which the oil
composition was intersected by the extension of the critical tie line. Systems with more than
three components were handled by correlating calculated ternary MMPs with variable molecular
weight for the intermediate and heavy hydrocarbon components. The MMP can be determined
by finding the pressure at which the oil composition (for a VGD), or the injected gas

composition (for a CGD), is located on the extension of a critical tie line. That tie line can be
found directly by one of the mixing cell methods or by performing negative flash calculations.

Ternary Representation/Limiting Tie Line Approach

With the discovery of the vaporizing and the condensing mechanism in the late 1950s, pseudo
ternary representations of the phase behavior of gas-oil systems were used to predict the
development of multi contact miscibility in gas injection processes. Two tie lines (the injection
and the initial tie line) are extended through the injected gas composition and the initial oil
composition respectively. A miscible displacement, in the pseudo ternary sense, develops at a
pressure where one of these tie lines becomes a critical tie line (tangent to the two-phase
boundary). If the initial tie line becomes a critical tie line at a lower pressure than that of the
injection tie line. This corresponds to VGD in the sense that the initial oil becomes multi contact
miscible with a richer gas phase. If the injection tie line becomes critical, the mechanism
controlling the development of miscibility is a CGD as the injected gas becomes miscible with a
lighter oil phase. Hence, in the pseudo ternary sense, the VGD MMP would be considered as the
MMP. The pressure at which the initial and the injection tie lines become critical can be
calculated by using a negative flash algorithm (Whitson and Michelsen) or by using the mixing
cell approach. Use of the pseudo ternary representation for prediction of the MMP give rise to
the problem that the result can only be rigorously correct for true ternary systems because of the
partitioning of intermediate components (C2-C6) during the displacement. In other words, the
properties of the pseudo component C2-6 change along the displacement process and the shape of
the two-phase region changes accordingly. Another more fundamental problem of using the
ternary representation is that the development of miscibility can only take place at the injection
site (CGD) or at the displacement front (VGD).

Or stated in another way, the ternary

representation cannot predict the existence of a combined VGD / CGD mechanism. Orr et al.
showed that multi contact miscibility develops if any of the three key tie lines is a critical tie line
(shrinks to a point). In many displacements, it is the crossover tie line that approaches the
critical locus at the lowest pressure, and in such cases that tie line determines the MMP. Johns et

al. showed that the condensing/vaporizing mechanism described by Zick arises when a crossover
tie line controls development of miscibility. Hence, methods that identify only the critical tie
lines associated with the injection gas or the initial oil tire doomed to failure for
condensing/vaporizing systems. They also provided a simple geometric construction to locate
the crossover tie line; the crossover tie-line extension must intersect the oil and gas tie lines.
Single Cell Simulators
To account for the deficiencies of the pseudo ternary approach to determination of the MMP,
several methods based on a single mixing cell have been suggested (Jensen and Michelsen). In
the mixing cell approach, the thermodynamic behavior of the reservoir fluid and the injected gas
is described as a multicomponent system by an equation of state (EOS). The mixing cell
approach consists of two different numerical experiments. In the first case (forward contact
scheme) a cell of constant volume, temperature and pressure is filled with the injected gas. A
batch of the reservoir fluid is added and the resultant mixture is flashed. The excess volume of
the cell is then removed. Any liquid formed by the contact is removed before gas is removed.
After removing the excess volume a new batch of fresh oil is added, and the procedure is
repeated until the composition in the cell no longer changes. If the mixing cell forms a single
phase during any of the contacts, the pressure is above the MMP and a new experiment is
performed at a lower pressure. On the other hand, if the simulation converges as a two-phase
system, the pressure is below the MMP and a new run is performed at a higher pressure. The
pressure can be updated by a simple bisection approach. The MMP one-cell is defined as the
pressure at which the simulation converges at a critical composition. The simulation will
converge at a composition different

from the initial tie line. This is why different values of the

MMP in some cases are obtained from one-cell simulations and limiting tie line approaches
based on negative flash calculations. Such difference has been reported for reservoir fluids by
Jensen and Michelsen and described in detail by Wang and Orr. In the second case (backward
contact scheme) the cell is initially filled with oil and fresh injection gas is added in batches.
Excess gas is removed before excess liquid and the rest of the scheme is similar to that of
forward contacts. The physical locations corresponding to the one-cell simulations are the
displacement front (forward contacts) and the injection site (backward contacts). If the features
of the combined vaporizing and condensing mechanism are recalled, miscibility developed by a

combined mechanism cannot take place at the injection site or at the displacement front. Hence,
the one cell simulators can only predict the rigorously true MMP for a pure condensing or pure
vaporizing displacement. Pure vaporizing displacements exist for e.g. injection of N 2 or natural
gases mainly consisting of CH4 into oil. For more complex injection gases the displacements are
always combined by nature and the use of one-cell simulations will lead to an overestimation of
the MMP. Pure condensing displacements have not, so far, been reported for multicomponent
fluid descriptions.
Semi-analytical Calculation of the MMP
The semi-analytical approach to calculation of the MMP is based on the analytical theory for 1D
dispersion-free two-phase flow. The backbone of the semi analytical approach is that the
composition path specifying the solution to the 1D flow problem has to travel through a
sequence of key tie lines. For some systems where the solution to the 1D problem consists of
shocks only, the extensions of key tie lines (the initial tie line, the injection tie line and crossover
tie lines)

have been proven to intersect rigorously. In the general case and for the purpose of

calculating

the MMP, the assumption about intersecting key tie lines has proven to be a very

good approximation. Dindoruk used the intersection approach to study the MMP behavior of
four-component N2 systems and Johns and Orr extended the approach to fluid descriptions with
up to 11 components, considering only pure component injection gases. Wang and Orr extended
the previous works to multicomponent mixtures with an arbitrary number of components in the
injection gas. They used an iterative scheme based on successive substitution to solve their
formulation of the intersection equations, but reported numerical problems due to singularities
for some systems. Their work formed the basis for a new approach developed in the course of
this study. The new approach is also presented in Jessen et al.
Global Approach for Calculation of the MMP
A new algorithm has been developed for calculation of MMP for the displacement of oil by
multicomponent gas injection. The algorithm is based on the key tie line identification approach
initially addressed by Wang and Orr. A number of deficiencies of the sequential approach have
been eliminated, resulting in a robust and highly efficient algorithm. The time consumption for
calculation of the MMP in multicomponent displacement processes has been reduced

significantly and calculation of the MMP can now be performed within a few seconds on a PC
for a 15-component gas mixture.

Therefore the algorithm is particularly suitable for gas

enrichment studies or other case studies where a large number of MMP calculations are required.
Predicted results from the key tie line identification approach are shown to be in excellent
agreement with slim tube data and with other MC/FD simulators presented in the literature.

Miscellaneous (EOS based)

Applying Wang and Orr method of MMP calculation needs reliable EOS to describe phase
behavior of crude oil and injected gas. Nasrifar and Moshfeghian applied an improved EOS to
describe phase behavior of oil and gas in MMP calculations; in addition, Esmaeilzadeh and
Roshanfekr presented a new cubic EOS and consequently, computed MMP by this new cubic
EOS. Fazlali et al. presented an algorithm for rapid calculation of MMP using a cubic EOS.
Chapman et al. extended Wertheims theory to develop an EOS, based on the statistical
associating fluid theory (SAFT) for associating fluid. Huang and Radosz assumed the segment
segment interaction to be described by the square-well potential to improve the SAFT-EOS for
real compounds.
components.

This EOS has been applied to both pure no-associating and associating

Huang and Radosz, then, extended the SAFT-EOS to mixtures containing

associating compounds. In the SAFT-EOS of Huang and Radosz, the residual Helmholtz energy
for a pure component has four contributions: the hard sphere, dispersion, chain, and association
terms. The hard sphere, chain, and association terms were derived from statistical
thermodynamics. For the dispersion term, Huang and Radosz used a double power series in
temperature and density which had been fit to argon physical property data. Fu and Sandler
simplified the SAFT-EOS by using the single attraction terms of Lee et al. for the square-well
fluid to replace the multi-term double series dispersion term, while keeping the original hard
sphere, Chain, and association terms.