Journal of Petroleum Science and Engineering 58 (2007) 173 185

www.elsevier.com/locate/petrol

CO2oil minimum miscibility pressure model

for impure and pure CO2 streams
Eissa M. El-M. Shokir
Petroleum Department, College of Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia
Received 15 April 2006; received in revised form 8 December 2006; accepted 14 December 2006

Abstract
CO2 injection processes are among the effective methods for enhanced oil recovery. A key parameter in the design of CO2
injection project is the minimum miscibility pressure (MMP), whereas local displacement efficiency from CO2 injection is highly
dependent on the MMP. From an experimental point of view, slim tube displacements, and rising bubble apparatus (RBA) tests
routinely determine the MMP. Because such experiments are very expensive and time-consuming, searching for fast and robust
mathematical determination of CO2oil MMP is usually requested. It is well recognized that CO2oil MMP depends upon the
purity of CO2, oil composition, and reservoir temperature. This paper presents a new model for predicting the impure and pure
CO2oil MMP and the effects of impurities on MMP. The alternating conditional expectation (ACE) algorithm was used to
estimate the optimal transformation that maximizes the correlation between the transformed dependent variable (CO2oil MMP)
and the sum of the transformed independent variables. These independent variables are reservoir temperature (TR), oil compositions
(mole percentage of volatile components (C1 and N2), mole percentage of intermediate components (C2C4, H2S and CO2), and
molecular weight of C5+ (MWC5+)), and non-CO2 components (mole percentage of N2, C1, C2C4, and H2S) in the injected CO2.
The validity of this new model was successfully approved by comparing the model results to the pure and impure experimental
slim-tube CO2oil MMP and the calculated results for the common pure and impure CO2oil MMP correlations. The new model
yielded the accurate prediction of the experimental slim-tube CO2oil MMP with the lowest average relative and average absolute
error among all tested impure and pure CO2oil MMP correlations. In addition, the new model could be used for predicting the
impure CO2oil MMP at higher fractions of non-CO2 components.
2007 Elsevier B.V. All rights reserved.
Keywords: Alternating conditional expectation (ACE); Minimum miscibility pressure (MMP); CO2; Miscible flooding

1. Introduction
MMP, as the name implies, is the minimum pressure
at which the injected gas (CO2 or hydrocarbon gas) can
achieve dynamic miscibility with the reservoir oil
(Stalkup, 1983; Benmekki and Mansoori, 1988; Mansoori et al., 1989; Jaubert and Wolf, 1998; Wang and
Tel.: +966 14679812; fax: +966 14674422.
E-mail address: shokir@ksu.edu.sa.
0920-4105/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2006.12.001

Orr, 2000). An inaccurate prediction of MMP may result

in significant consequences. For example, recommendation for a high operating level of MMP may result in
greatly inflated operation costs as well as occupational
health concerns. On the other hand, if the suggested
MMP is too low, the miscible displacement process
would become ineffective, leading to a high risk of
process failure. Thus, accurate estimation of MMP
would bring significant economic benefits. It is well
recognized that CO2oil MMP depends upon the purity

174

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

of CO2, oil composition, and reservoir temperature.

Various correlations reported in the literature are related
to a unique set of reservoir and fluid conditions; hence,
using of such correlations can lead to an erroneous
estimate of the MMP. From the literature review, pure
CO2oil MMP correlations have been reported in
Cronquist (1978), Lee (1979), Yellig and Metcalfe
(1980), Holm and Josendal (1982), Orr and Jensen
(1984), Alston et al. (1985), Glaso (1985), Huang et al.
(2003), and Emera and Sarma (2004). On the other
hand, impure CO2oil MMP correlations have been
reported in Kovarik (1985), Alston et al. (1985),
Sebastian et al. (1985), Eakin and Mitch (1988), Dong
(1999), and Emera and Sarma (2005). In addition, pure
or impure CO2oil MMP correlations have been
reported in Johnson and Pollin (1981), Orr and Silva
(1987), Enick et al. (1988), and Yuan et al. (2004).
Several methods can be used to measure MMP for an
oilsolvent system. Traditionally, slim tube tests were
conducted for that purpose. The rising bubble apparatus
(RBA) approach was developed in the early 1980s and
is gaining acceptance as an efficient method to measure
MMP (Christiansen and Haines, 1987). An experimental method, which measures the density of the injectiongas-rich upper phase in contact with stock tank oil as a
function of pressure was reported for measuring CO2
oil MMP at low temperatures below 50 C (Harmon and
Grigg, 1988). A similar approach was suggested using
the pressure at which the pure solvent achieves liquidlike densities (Orr and Jensen, 1984). This is obtained
by extrapolating the vapour pressure curve of the
solvent. Rao (1997), Gasem et al. (1993), and Rao and
Lee (2002) reported that direct measuring interfacial

Fig. 2. Experimental pure and impure CO2oil MMP versus the

resulted inverse of the optimal transformation of the general CO2oil
MMP dependent variable.

tension of an oilsolvent mixture at reservoir conditions

could provide a rapid means of determining MMP.
Because such experiments are very expensive and
time-consuming, searching or developing a high
accuracy mathematical determination of the CO2oil
MMP is usually requested. Therefore, this paper
presents a new developed model to determine the
pure and impure CO2oil MMP for miscible displacement based on the alternating conditional expectations
algorithm (ACE). The ACE reveals the underlying
statistical relationships among variables corrupted by
random error. This ACE algorithm presented by
Breiman and Freidman (1985), as other similar nonparametric statistical regression methods, is intended
to alleviate the main drawback of parametric regression, i.e., the mismatch of assumed model structure
and the actual data. In non-parametric regression a
priori knowledge of the functional relationship between the dependent variable Y and independent
variables, X1, X2, Xm, is not required. In fact, one
of the main results of non-parametric regression is
determination of the actual form of this relationship.
The objective of this paper is to develop a general
impure and pure CO2oil MMP model that relates
MMP to reservoir temperature, oil compositions, and
CO2 impurities components, compare its efficiency
against the commonly used pure and impure CO2oil
MMP correlations, and investigate the effects of nonCO2 components on the CO2oil MMP.
2. ACE algorithm

Fig. 1. Optimal transformation of the general CO2oil MMP

dependent variable versus the sum of the optimal transformations of
the independent variables.

The general form of a linear regression model for p

independent variables (predictors), say X1, X2, , Xp,

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

175

Table 1
Experimental CO2oil MMP from different literature sources
Reference

Composition of CO2 stream

Rathmell et al. (1971)

Dicharry et al. (1973)
Holm and Josendel (1974)
Shelton and Yarborough, 197
Graue and Zana (1981)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Henry and Metcalfe (1983)
Thakur et al. (1984)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Dong et al. (2001)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Dong (1999)
Dong (1999)
Dong et al. (2001)
Dong et al. (2001)

TR C

Type of CO2 stream

CO2
(%)

H2S
(%)

C1
(%)

C2C4
(%)

N2
(%)

Pure

100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
75
50
90
45
60
67.5
45
60
90
90
80
90
80
80
68
40
75
50
90
80
55
92.5
90
90.5
95
90
80
90.1
89.8

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
25
50
0
45
20
23
45
20
0
0
0
0
0
0
22
40
25
50
0
0
25
0
0
0
0
10
20
0
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
10
20
10
10
20
0
0
0
0
0
20
10
20
0
0
10
20
20
7.5
10
0
4.9
0
0
9.9
5.1

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
10
20
10
20
0
0
0
0
0
0
0
0
0
0
9.5
0
0
0
0
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.1
0
0
0
5.1

Impure

and a response variable Y is given by (Breiman and

Freidman, 1985; Wang and Murphy, 2004):
Y b0

p
X

bi Xi e

i1

where 0, 1, , p are the regression coefficients to be

estimated, and is an error term. Eq. (1) therefore

42.8
54.4
57.2
34.4
71.1
32.2
40.6
57.2
48.9
118.3
67.8
110
71.1
102.2
80
59
40.83
40.83
40.83
40.83
40.83
58.33
58.33
58.33
48.89
48.89
48.89
65.56
65.56
40.83
40.83
40.83
58.33
58.33
58.33
58.33
58.33
54.44
54.44
71.11
71.11
60
60
59
59

Oil composition
MWC5+

Interm.
(%)

Vol.
(%)

204.10
171.20
182.60
212.56
207.90
187.77
187.77
187.77
205.10
171.10
203.81
180.60
221.00
205.00
240.70
205.00
187.8
187.8
187.8
187.8
187.8
187.8
187.8
187.8
187.27
187.27
187.27
187.27
187.27
187.8
187.8
187.8
187.8
187.8
187.8
187.8
187.8
185.83
185.83
221
207.9
200
200
205
205

20.95
31.82
3.48
10.76
13.90
14.28
14.28
14.28
22.62
28.60
22.90
35.64
6.99
9.84
8.60
11.35
14.28
14.28
14.28
14.28
14.28
14.28
14.28
14.28
22.82
22.82
22.82
22.82
22.82
14.28
14.28
14.28
14.28
14.28
14.28
14.28
14.28
38.4
40.3
6.99
13.9
1.31
1.31
11.35
11.35

17.07
29.48
31.88
16.78
4.40
10.50
10.50
10.50
12.50
34.20
31.00
32.51
41.27
51.28
53.36
5.45
10.5
10.5
10.5
10.5
10.5
10.5
10.5
10.5
34.34
34.34
34.34
34.34
34.34
10.5
10.5
10.5
10.5
10.5
10.5
10.5
10.5
5.4
29.3
41.27
4.4
0
0
5.45
5.45

Exp.
MMP

10.35
11.00
13.79
10.00
15.52
6.90
8.28
11.86
10.59
23.45
16.90
20.21
23.45
28.17
26.76
12.80
7.53
6.55
11.04
8.83
14.07
12.41
10.38
17.24
10.07
9.31
9.66
13.04
10.5
14.83
10.28
12.06
10.35
8.97
15.17
18.74
16.45
10.35
13.1
18.62
16.83
11.6
11.4
16.01
20.51

assumes that the response, Y, is a combination of linear

effects of X1, X2, , Xp and a random error component
. Conventional multiple regressions require a linear
functional form to be presumed a priori for the
regression surface, thus reducing the problem to that
of estimating a set of parameters. When the relationship
between the response and predictor variables is
unknown or inexact, linear parametric regression can

176

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

a linear relationship between the transformed response variable and the sum of transformed predictor
variables. For a given data set consisting of a response
variable Y and predictor variables X1, X2, , Xp, the
ACE algorithm starts out by defining arbitrary measurable zero-mean transformations functions (Y), 1
(X1), , p(Xp). However, the error variance (2) of a
linear regression of the transformed dependent variable
on the sum of transformed independent variables
(under the constraint, E2(Y) = 1) has the following
equation:
("
e h; /i ; N ; /p E

hY

Fig. 3. Resulted CO2oil MMP from the new ACE-based model versus
the experimental impure and pure CO2oil MMP measurements.

yield erroneous and even misleading results. This is the

primary motivation for the use of non-parametric
regression techniques, which make few assumptions
about the regression surface (Freidman and Stuetzle,
1981). These non-parametric regression methods broadly classified into those, which do not transform the
response variable such as generalized additive models,
and those, which do such as the ACE, which is the focus
of this paper. The general form of the non-parametric
ACE algorithm is as following (Breiman and Freidman,
1985; Wang and Murphy, 2004):
hY a

p
X

/i Xi e

# )2
/i Xi

=Eh2 Y

i1

3
ACE algorithm minimizes 2 by holding E2(Y) = 1,
E(Y) = E1(X1) = = Ep(Xp) = 0 through a series of
single-function minimizations, involving bivariate conditional expectations. Thus, for a given set functions 1
(X1), , p(Xp) minimization of 2 with respect to (Y)
yields the following equation:
"
hY E

p
X

/i Xi jY = E

i1

"

p
X

#
/i Xi jY

i1

On the other hand, for a given (Y) minimization of

2 with respect to a single function k(Xk) yields the
following equation:

i1

"

where is a function of the response variable, Y, and i

are functions of the predictors X1, X2, , Xp. Thus, the
ACE model replaces the problem of estimating a linear
function of a p-dimensional variable X = (X1, X2, , Xp)
by estimating p separate one-dimensional functions i,
and using an iterative method. These transformations
are achieved by minimizing the unexplained variance of

p
X

/j;1 Xj E hY

p
X

#
/i Xi jXk

ipj

The real-valued measurable zero-mean functions i

(Xi), i = 1, , p, and (Y) after iterative process of
minimizing 2 are called optimal transformations i (Xi),
i = 1, , p, and (Y) (Breiman and Freidman,

Table 2
Resulting coefficients for all the input parameters
n
1
2
3
4
5
6
7
8

Oil components

Non-CO2 components

A3

A2

A1

A0

TR
Vol., %
Interm., %
MWC5+
C1, %
C2C4, %
N2 , %
H2S, %

2.3660E 06
1.3721E 05
3.5551E 05
3.1604E 06
1.0753E 04
6.9446E 06
0
3.9068E 06

5.5996E 04
1.3644E 03
2.7853E 03
1.9860E 03
2.4733E 03
7.9188E 05
3.7206E 03
2.7719E 04

7.5340E 02
7.9169E 03
4.2165E 02
3.9750E 01
7.0948E 02
4.4917E 02
1.9785E 01
8.9009E 03

2.9182E + 00
3.1227E 01
4.9485E 02
2.5430E + 01
2.9651E 01
7.8383E 02
2.5014E 02
1.2344E 01

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

1985; Wang and Murphy, 2004). In the transformed

space, the response and predictor variables are related as
following:

177

where e is the error not captured by the use of the ACE

transformations and is assumed to have a normal distribution with zero mean. The minimum regression error,
e, and maximum multiple correlation coefficient, are
related by e2 = 1 .

to CO2 and recycled CO2. The separation of such

components from the injected gas is difficult and
costly. The current trend is to use the flue gas stream as
it is, if such impurities are below certain optimum level
in the injected gas stream. Therefore, the developed
model using the ACE algorithm was designed to reach
the optimal regression between the pure or impure
CO2oil MMP and the reservoir temperature, mole
percentage of oil components (volatiles (C1 and N2),
and intermediate components (C2C4, H2S and CO2)),
MW C5+ , and mole percentage of the non-CO 2
components (C1, N2, H2S, and C2C4) in the injected
CO2.

3. Factors affecting CO2oil MMP

4. Developing impure and pure CO2oil MMP model

The main factors affecting CO2oil MMP are

reservoir temperature, oil composition, and purity of
injected gas (Johnson and Pollin, 1981; Alston et al.,
1985; Sebastian et al., 1985; Zuo et al., 1993; Nasrifar
and Moshfeghian, 2004; Yuan et al., 2004; Emera and
Sarma, 2005). The reservoir temperature has a big
impact on CO2oil MMP; as the temperature increases
the MMP increases and vice versa. Rathmell et al. (1971)
reported that the presence of volatile components, like
methane in the crude oil, leads to an increase in CO2oil
MMP while the presence of intermediates C2 to C6 can
reduce the CO2oil MMP. Metcalfe and Yarborough
(1974) argued that any CO2oil MMP correlation should
take into consideration the presence of light ends and
intermediates in the crude oil. Alston et al. (1985) in their
experimental slim tube tests proved that the oil recovery
at gas breakthrough is decreased, and CO2oil MMP is
increased by increasing the ratio between the amounts
of volatiles to intermediates in the crude oil composition.
In addition, Alston et al. (1985) stated that molecular
weight of C5+ is better for the correlation purpose than
oil API gravity. In addition, Cronquist (1978) used the
temperature and molecular weight of C5+ as correlation
parameters in addition to the volatile mole percentage of
C1 and N2 in the crude oil.
Furthermore, the presence of non-CO2 (e.g., C1,
H2S, N2, or intermediate hydrocarbons components
(such as C2, C3, and C4)) in the injected gas leads to a
big impact on the CO2oil MMP, either raising or
lowering it depending on the component type. In
general, the presence of H2S, or intermediate hydrocarbon components in the injected gas decreases the
CO2oil MMP, while the presence of C1 or N2 in the
injected gas substantially increases the CO2oil MMP
(Lake, 1989). Nitrogen from flue gas and C1 from
reinjected CO2 are the large possible contaminants

As mentioned before, the ACE algorithm was

applied to correlate the pure or impure CO2oil MMP
to the independent variables of reservoir temperature,
mole percentage of oil components, molecular weights
of the heavy fractions (C5+), and mole percentage of
CO2 impurities components. The experimental data that
were used to develop and validate the new model are
presented in Table 1. These experimental data were used
as reported in the literature without any modification or
manipulation and they have different miscibility criteria
and experimental conditions. This is contrary to the
approach of Alston et al. (1985), who interpreted the
data to satisfy their experimental miscibility criteria
(90% recovery at solvent breakthrough).
A graphical user interface program, GRACE (Xue
et al., 1997), was used to derive a general pure or impure
CO2oil MMP model. Fig. 1 shows the resulted optimal
transformation of the general CO2oil MMP dependent

h Y

p
X

/
i Xi e

i1

Fig. 4. The resulted pure CO2oil MMP from the new ACE-based
model versus the calculated pure CO2oil MMP from Cronquist
(1978), Lee (1979), Yellig and Metcalfe (1980), Alston et al. (1985),
Glaso (1985), and Emera and Sarma (2004) correlations.

178

Reference

Rathmell et al. (1971)

Dicharry et al. (1973)
Holm and Josendel (1974)
Shelton and Yarborough (1977)
Graue and Zana (1981)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Henry and Metcalfe (1983)
Thakur et al. (1984)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Dong et al. (2001)

Exp. pure CO2oil MMP,

MPa

10.35
11.00
13.79
10.00
15.52
6.90
8.28
11.86
10.59
23.45
16.90
20.21
23.45
28.17
26.76
12.80
ARE
AARE
Standard deviation of error
Correlation coefficient

ACE based

Emera and
Sarma (2004)

Alston et al.
(1985)

Glaso (1985)

Cronquist
(1978)

Lee (1974)

Yellig and
Metcalfe (1980)

Model

Model

Model

Model

Model

Model

Model

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

10.27
10.66
14.23
10.13
15.16
7.29
8.74
11.51
10.73
23.30
16.66
20.65
22.19
27.65
27.06
13.07

0.75
3.13
3.22
1.31
2.29
5.62
5.53
2.95
1.36
0.66
1.41
2.19
5.39
1.84
1.11
2.13
0.25
2.55
3.11
0.998

10.35
10.28
14.92
9.83
14.97
7.36
8.82
11.80
11.18
22.09
16.32
21.37
22.15
28.15
27.75
12.96

0.04
6.51
8.22
1.72
3.56
6.64
6.49
0.52
5.52
5.80
3.45
5.72
5.55
0.07
3.71
1.27
0.65
4.05
4.25
0.993

10.09
8.99
14.31
10.17
13.60
7.05
8.26
10.67
10.65
17.93
15.38
17.82
22.57
26.50
29.20
12.07

2.52
18.29
3.79
1.73
12.36
2.16
0.28
10.01
0.57
23.54
8.99
11.84
3.75
5.92
9.11
5.73
5.37
7.54
7.26
0.967

10.01
11.39
17.32
8.69
14.76
8.19
9.44
11.92
11.10
20.44
13.60
19.11
23.61
25.18
24.24
12.52

3.31
3.51
25.63
13.09
4.92
18.72
14.05
0.46
4.84
12.85
19.56
5.47
0.67
10.61
9.44
2.16
0.85
9.33
7.18
0.970

8.33
9.77
11.07
6.96
12.83
5.60
7.01
9.77
9.27
21.70
14.57
21.07
18.09
26.17
25.01
10.61

19.49
11.16
19.75
30.45
17.31
18.83
15.34
17.66
12.48
7.45
13.79
4.23
22.85
7.10
6.54
17.13
15.54
16.10
9.50
0.983

8.52
10.41
10.90
7.31
13.59
7.02
8.19
10.90
9.48
25.77
12.92
23.27
13.59
21.06
15.52
11.23

17.65
5.36
20.93
26.89
12.45
1.67
1.05
8.06
10.44
9.90
23.57
15.15
42.06
25.23
42.02
12.27
14.75
18.31
21.40
0.816

9.24
11.24
11.69
7.57
13.83
7.08
8.83
11.69
10.33
20.98
13.33
19.67
13.83
18.47
15.15
11.98

10.71
2.21
15.21
24.32
10.90
2.61
6.62
1.41
2.48
10.55
21.11
2.66
41.03
34.42
43.37
6.42
14.21
15.73
17.56
0.853

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

Table 3
Comparison of the pure CO2oil MMP resulted from the new ACE-based model to the calculated pure CO2oil MMP from different literature correlations

Table 4
Comparison of the impure CO2oil MMP resulted from the new ACE-based model to the calculated impure CO2oil MMP from different literature correlations
Reference

7.53
6.55
11.04
8.83
14.07
12.41
10.38
17.24
10.07
9.31
9.66
13.04
10.50
14.83
10.28
12.06
10.35
8.97
15.17
18.74
16.45
10.35
13.10
18.62
16.83
11.60
11.40
16.01
20.51
ARE
AARE
Standard deviation of error
Correlation coefficient

ACE based

Emera and
Sarma
(2005)

Sebastian et al.
(1985)

Alston et al.
(1985)

Dong (1999)

Kovarik (1985)

Eakin and
Mitch
(1988)

Model

Model

Model

Model

Model

Model

Model

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

MPa

Error
(%)

7.46
6.34
11.24
8.60
13.53
13.03
11.49
16.92
10.44
10.44
8.61
13.18
11.14
14.78
9.99
11.99
10.16
8.81
14.45
18.24
16.51
9.93
13.26
19.80
16.81
11.72
11.07
15.89
20.60

0.90
3.25
1.84
2.60
3.84
4.98
10.70
1.87
3.70
12.17
10.86
1.10
6.10
0.34
2.83
0.56
1.80
1.80
4.74
2.68
0.39
4.04
1.25
6.32
0.10
1.01
2.94
0.72
0.43
0.14
3.30
4.67
0.998

7.49
7.36
10.10
8.07
12.34
12.63
11.43
17.49
10.29
8.84
9.88
12.54
9.65
13.86
8.94
10.80
10.62
10.43
14.31
19.63
17.04
10.79
13.59
18.91
16.69
11.25
10.97
15.74
21.93

0.53
12.37
8.51
8.61
12.30
1.77
10.12
1.45
2.18
5.05
2.28
3.83
8.10
6.54
13.04
10.45
2.61
16.28
5.67
4.75
3.59
4.25
3.74
1.56
0.83
3.02
3.77
1.69
6.92
0.62
5.72
7.15
0.970

7.42
6.68
10.55
8.65
12.29
13.54
12.26
17.41
11.01
9.61
10.99
13.42
10.26
13.38
9.58
11.27
10.52
9.46
14.95
18.95
17.04
11.38
14.19
20.56
17.55
11.49
11.00
16.28
17.58

1.46
1.98
4.44
2.04
12.65
9.11
18.11
0.99
9.33
3.22
13.77
2.91
2.29
9.78
6.81
6.55
1.64
5.46
1.45
1.12
3.59
9.95
8.32
10.42
4.28
0.95
3.51
1.69
14.29
1.37
5.93
7.55
0.950

7.13
6.27
10.11
7.22
11.12
12.00
10.22
15.75
10.43
8.89
9.88
12.71
9.34
13.84
8.50
9.16
10.10
8.88
14.32
19.61
15.06
10.91
13.60
19.05
17.00
11.26
10.63
15.73
19.75

5.31
4.27
8.42
18.23
20.97
3.30
1.54
8.64
3.57
4.51
2.28
2.53
11.05
6.68
17.32
24.05
2.42
1.00
5.60
4.64
8.45
5.41
3.82
2.31
1.01
2.93
6.75
1.75
3.71
5.05
6.64
7.51
0.960

7.16
6.17
10.32
8.04
11.47
12.93
11.39
16.25
11.05
12.02
11.06
13.47
15.92
12.71
9.15
10.32
10.15
8.74
14.62
18.01
15.83
11.20
13.88
25.43
17.46
11.34
10.70
15.93
21.37

4.91
5.80
6.52
8.95
18.48
4.19
9.73
5.74
9.73
29.11
14.49
3.30
51.62
14.30
10.99
14.43
1.93
2.56
3.63
3.90
3.77
8.21
5.95
36.57
3.74
2.24
6.14
0.50
4.19
2.28
10.19
15.17
0.910

0.30
0.90
14.20
1.50
12.90
9.80
1.90
16.40
11.10
7.80
11.10
13.50
6.90
19.90
6.50
6.00
3.10
5.60
17.60
23.40
14.60
13.90
17.00
20.40
18.60
8.60
5.20
18.60
20.50

103.98
113.74
28.62
116.99
8.32
21.03
81.70
4.87
10.23
16.22
14.91
3.53
34.29
34.19
36.77
50.25
70.05
162.43
16.02
24.87
11.25
34.30
29.77
9.56
10.52
25.86
54.39
16.18
0.05
23.43
39.48
51.69
0.830

17.50
20.90
20.40
20.00
21.80
21.10
21.70
23.10
17.60
17.80
18.20
18.30
18.30
18.40
18.40
20.30
19.00
20.50
21.10
24.10
21.20

20.40
17.90
18.00
18.20
21.20

132.40
219.08
84.78
126.50
54.94
70.02
109.06
33.99
74.78
91.19
88.41
40.34
74.29
24.07
78.99
68.33
83.57
128.54
39.09
28.60
28.88

21.21
54.31
57.89
13.68
3.36
63.11
70.40
46.83
0.50

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Metcalfe (1982)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Alston et al. (1985)
Dong (1999)
Dong (1999)
Dong et al. (2001)
Dong et al. (2001)

Exp. impure CO2Oil

MMP, MPa

179

180

References

Eakin and Mitch

(1988)
Eakin and Mitch
(1988)
Alston et al.
(1985)
Harmon and Grigg
(1988)
Harmon and
Grigg (1988)
Harmon and
Grigg (1988)
Harmon and
Grigg (1988)
ARE
AARE
Standard deviation
of error

Type
of CO2
stream

Pure

C2
C4

CO2

H2S C1

(%)

(%) (%) (%)

N2

TR

MWC7+ Interm. MWC5+ C2

C6

(%) (C)

(%)

(%)

Vol.

Exp. ACE based model Yuan et al. (2004) Emera and

MMP
Sarma (2004)

(%)

MPa

MMP
MPa

Alston et al.
(1985)

Yellig and
Metcalfe (1980)

Cronquist (1974)

Lee (1974)

Correlation

Correlation

Correlation

Correlation

Correlation

Correlation

Error
(%)

MMP
MPa

Error
(%)

MMP
MPa

MMP
MPa

MMP
MPa

MMP
MPa

Error
(%)

MMP Error
MPa (%)

Error
(%)

Error
%

Error
(%)

100

82.2

281

20.59

261.64

26.09

6.74 21.35 19.22

0.10

18.61

0.13

23.10

0.08

23.24

0.09 15.48

0.27 20.26

0.05

16.02 0.25

100

115.6

281

20.59

261.64

26.09

6.74 25.31 25.50

0.01

16.51

0.35

31.20

0.23

31.34

0.24 20.54

0.19 28.90

0.14

24.93 0.02

100

112.2

220

28.10

213.50

28

32.70 24.15 25.06

0.04

21.35

0.12

27.59

0.14

28.11

0.16 20.02

0.17 30.40

0.26

28.32

100

104.4

173

24.10

153.96

27.05 42.71 22.00 23.06

0.05

19.51

0.11

17.76

0.19

14.02

0.36 18.82

0.14 18.61

0.15

21.68 0.01

100

76.7

224

5.17

217.67

39.63 20.69 22.39

0.08

23.97

0.16

23.97

0.16

24.24

0.17 14.66

0.29 19.00

0.08

14.77 0.29

100

54.4

190

29.43

168.39

37.12 29.73 11.78 10.97

0.07

9.73

0.17

10.20

0.13

8.83

0.25 11.25

0.04

9.66

0.18

10.42 0.12

100

81.1

220

16.78

198.40

26.78

0.00

18.60

0.16

17.00

0.06

15.19

0.05 15.32

0.04 14.44

0.10

15.77 0.01

2.31
13.76
0.16

7.49
12.30
0.16

7.4

9.82 15.97 15.89

0.04
4.98
0.06

7.95
17.18
0.18

5.05
14.39
0.16

0.01
18.90
0.23

16.50
16.51
0.10

0.17

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

Table 5
Comparison of CO2oil MMP estimated from the new ACE-based model to the experimental slim tube CO2oil MMP, and to the calculated CO2oil MMP from different literature correlations

0.001
0.07
0.00
0.07
0.04

17.58
16.06
19.28
20.59
18.50

1.22
0.25
0.30
0.06
0.10

7.90
12.66
14.85
7.90
17.64

0.004
0.02
0.00
0.28
0.05

7.61
13.53
21.30
17.44
17.10

6.74 16.66 16.80

0.01

22.96

0.38

17.30

0.04

17.28

26.09

6.74 19.07 17.24

0.10

22.45

0.18

17.43

0.09

261.64

26.09

6.74 21.31 23.07

0.08

19.62

0.08

20.51

20.59

261.64

26.09

6.74 18.86 19.71

0.05

24.30

0.29

115.56 281

20.59

261.64

26.09

6.74 22.76 23.52

0.03

19.26

20.35 0

115.56 281

20.59

261.64

26.09

6.74 21.69 20.67

0.05

0.00 0

115.56 281

20.59

261.64

26.09

6.74 24.04 24.90

0.00 0

115.56 281

20.59

261.64

26.09

6.74 23.38 23.69

45.7 20.00 4.3

82.22 216

42.44

187.88

45.7 20.00 4.3

82.22 281

20.59

261.64

80
80
80
81
75

0
0
0
0
0

0
0
20
19
0

90

91.183

90

20.00
20.00
0.00
0.00
25.00

0
0
0
0
0

48.89
65.56
40.83
41.25
115.56

4.38
13.40
19.81
19.06
18.70

0.45
0.04
0.34
0.02
0.11

0.04 18.78

0.13 18.61

0.12

22.98

0.38

17.31

0.09 19.31

0.01 19.20

0.01

22.63

0.19

0.04

20.49

0.04 22.26

0.04 22.57

0.06

27.25

0.28

17.47

0.07

16.94

0.10 17.89

0.05 18.46

0.02

30.22

0.60

0.15

20.67

0.09

20.53

0.10 22.90

0.01 23.17

0.02

26.84

0.18

23.38

0.08

17.80

0.18

16.98

0.22 19.48

0.10 19.96

0.08

29.11

0.34

0.04

19.62

0.18

23.94

0.00

24.39

0.01 24.08

0.00 21.81

0.09

23.99

0.00

0.01

24.30

0.04

23.23

0.01

23.77

0.02 22.43

0.04 16.57

0.29

21.99 0.06

40.76 32.99 34.38 34.95

0.02

15.19

0.56

153.00

3.45

20310.07 589.73 49.77

0.45 52.14

0.52

73.24

1.13

26.09

0.11

38.04

0.38

148.45

4.39

19705.23 715.06 48.29

0.75 51.48

0.87

71.05

1.58

200
200
206
240
216

22.82
22.82
14.28
17.01
42.44

187.27
187.27
187.80
223.00
187.88

26.39
26.39
24.44
23.62
40.76

10.00 0

82.22 281

20.59

261.64

26.09

8.14 0

82.22 281

20.59

261.64

10.00 0

115.56 281

20.59

75

25.00 0

115.56 281

91.183

8.14 0

77.95

90

10

75

25

30

30

34.34
34.34
10.50
16.48
32.99

7.93
12.88
14.83
19.42
16.79

7.94
12.01
14.82
18.02
16.15

6.74 27.52 30.65

0.19
4.47
0.06

19.00
25.42
0.35

5.30
6.69
0.09

0.04
0.05
0.44
0.10
0.02

0.90
9.72
0.15

7.88
13.38
12.25
11.80
18.06

0.01
0.04
0.17
0.39
0.08

3.54
8.26
0.13

2.00
12.64
0.19

13.06 0.65
13.58 0.05
12.75 0.14
12.23 0.37
30.50 0.82

22.41
31.20
0.34

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

Metcalfe (1982)
Impure
Metcalfe (1982)
Metcalfe (1982)
Sebastian et al. (1985)
Eakin and
Mitch (1988)
Eakin and
Mitch (1988)
Eakin and
Mitch (1988)
Eakin and
Mitch (1988)
Eakin and
Mitch (1988)
Eakin and
Mitch (1988)
Eakin and Mitch
(1988)
Eakin and Mitch
(1988)
Eakin and Mitch
(1988)
Eakin and Mitch
(1988)
Eakin and Mitch
(1988)
ARE
AARE
Standard deviation
of error

181

182

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

variable versus the sum of the optimal transformations

of the independent variables. The linear regression
between these dependent and independent variables is
shown in Eq. (7).
X
h CO2  oil MMP
/
1 TR
oil components

z}|{

/
2 Vol: /3 Interm: /4 MWC5
NonCO2 components

z}|{

f/
5 C1 /6 C2  C4 /7 N2 /8 H2 Sg
7
Fig. 2 shows the experimental measurements of the
pure and impure CO2oil MMP versus the resulted
inverse of the optimal transformation of the general
CO2oil MMP dependent variable, whereas the inverse
optimal transformation yielded a final impure or pure
model in the following form:
General CO2  oil MMP
0:068616  z3 0:31733  z2 4:9804
 z 13:432

where
z

8
X

zn ; and

n1

zn A3n x3n A2n x2n A1n xn A0n

10

where, the values of the coefficients A3, A2, A1, and A0

are listed in Table 2.
Fig. 3 shows a perfect match between the predicted
MMP from the new model versus the experimental
impure and pure CO2oil MMP.
5. Validation of the new model
Firstly, to test the ability of the developed CO2oil
MMP model to reproduce the experimental observation,
it was tested against the literature pure CO2oil MMP
correlations. Although nearly all of the data sets used in
building this new model were also used in building the
other early correlations, especially Emera and Sarma
(2004) correlation, the new model yields the accurate
CO2oil MMP estimation. As shown in Fig. 4, Emera
and Sarma (2004), and Alston et al. (1985) correlations
provide a closer match to the new model.
Table 3 shows that the average relative error (ARE),
average absolute relative error (AARE), and the standard

deviation of error for the new model are 0.25%, 2.55%, and
3.11% respectively. In the second order Emera and Sarma
(2004) correlation gives an ARE equal to 0.65%, AARE
equal to 4.05%, and standard deviation of error equal to
4.9%. Finally, Alston et al. (1985) give an ARE equal to
5.37%, AARE equal to 7.54, and standard equal to
8.55%. In the decreasing order of accuracy, Glaso (1985),
Cronquist (1978), Yellig and Metcalfe (1980), and Lee
(1979) correlations came in sequence order.
Secondly, the resulted impure CO2oil MMP values
from the new model were compared to the commonly
used impure CO2oil MMP correlations (Emera and
Sarma, 2005; Dong, 1999; Alston et al., 1985; Sebastian
et al., 1985; Kovarik, 1985), as shown in Table 4. From
this table, the new model yields the lowest ARE equal to
0.142%, lowest AARE equal to 3.3%, and lowest
standard deviation of error equal to 4.67%. Fig. 5 shows
that the new model presents the optimum match with the
experimental data. Also, Emera and Sarma (2005)
correlation is a closer match to the new model; however,
Sebastian et al. (1985) and Alston et al. (1985) come in
the third and fourth order, respectively.
Finally, to test and validate the accuracy of the new
model, MMPs were calculated for 22 systems not used in
building the model for pure and impure CO2 displacements
of crude oils. The new model successfully predicted the
experimental slim-tube CO2oil MMP, with high accuracy,
for presence of different non-CO2 components up to 70mol
%, and up to 45.7mol% of C1 in the injected CO2 stream (as
shown in Table 5). On the other hand, all the tested impure
CO2oil MMP correlations failed in predicting the MMP's
values for the last two systems in Table 5, due to the higher
content of methane in the injected CO2. However, Yuan et
al. (2004) correlation is strictly limited for methane content
in the injected CO2 up to 40mol.%, and the other
correlations are limited for methane content up to 23mol
%. From Table 5, although the last two systems were not
considered in the error calculation for all the compared
correlations, the new model yields the accurate prediction
of the experimental slim-tube CO2oil MMP for all the
tested systems with the lowest average relative and average
absolute error among all tested impure and pure CO2oil
MMP correlations.
6. Sensitivity analysis
@Risk (2005) software was used to demonstrate the
sensitivity analysis of the new model and the dependence of the dependent variable (CO2oil MMP) on
each of the independent variables. The results of the
sensitivity analysis (shown in Fig. 6) are based on the
rank correlation coefficient that calculated between the

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

output variable (CO2oil MMP) and the samples for

each of the input distributions. The higher the
correlation between any input variable and output
variable means higher significant influence of that
input in determining the output's value. From Fig. 6, it is
obvious that the reservoir temperature has the major
impact on the CO2oil MMP, and as the temperature
increases the CO2oil MMP increases which confirms
with all published correlations. Also, the effects of oil
compositions on the predicted MMP confirms with all
published correlations whereas increasing MWC5+ or
volatiles mole percent leads to an increase in CO2oil
MMP. On the other hand, any increase in the mole
percent of the intermediate components (C2C4, H2S,
and CO2) causes a decrease in the CO2oil MMP. In
addition, the existence of non-CO2 components such as
H2S and hydrocarbon components (C2 to C4) in the CO2
stream has a positive impact on the MMP, whereas they
contribute to the decrease in MMP. In contrast, the
existence of non-CO2 components such as C1 and N2 in
the CO2 stream has a higher negative impact on the
MMP, because they cause a higher increase in the CO2
oil MMP.

Fig. 6. Sensitivity analysis of the new CO2oil MMP model and the
dependence of CO2oil MMP on each of the independent variables.

2.

7. Conclusions
3.
A new model has been developed to predict the
impure and pure CO2oil MMP. A comparison between
its predicted values against experimental data, and the
widely used impure and pure CO2oil MMP correlations has been carried out. Based on the results of this
new model, the following conclusions are drawn:
1. The new CO2oil MMP model yields the accurate
prediction with the lowest average relative and

Fig. 5. The resulted impure CO2oil MMP from the new ACE-based
model versus the calculated impure CO2oil MMP from Alston et al.
(1985), Sebastian et al. (1985), Kovarik (1985), Dong (1999), and
Emera and Sarma (2005) models.

183

4.

5.

average absolute error among all tested impure and

pure CO2oil MMP correlations.
The effects of CO2 impurities components on the
CO2oil MMP are in the following order in terms
of their impact: N2, C1, hydrocarbon components
(C2C4), and H2S. Whereas C1 and N2 have a
higher negative impact on the MMP, H2S and
hydrocarbon components (C2C4) have a positive
impact on the MMP.
The new CO2oil MMP model can be used to predict
the impure CO2oil MMP with high accuracy for
methane content in the injected CO2 stream up to
45.7 mol%, and different non-CO2 components (e.g.,
C1, N2, H2S, and C2C4) up to 70%.
The new model is strictly valid only for C1, N2,
H2S, and C2C4 contents in the injected CO2
stream.
The new model can be used as an effective tool to
estimate the MMP for initial design of economical
CO2-miscible flooding project.

Nomenclature
Interm. Intermediates components, C2C4, H2S, and
CO2, %
MMP Minimum miscibility pressure, MPa
MWC5+ Molecular weight of C5+ fraction
TR
Reservoir temperature, C
Vol.
Mole percentage of the volatiles (C1 and N2), %
X, X1, , Xp Independent or predictor variables
Y
Dependent or response variable
e
ACE regression error

Gaussian random noise

E()
Mathematical expectation
()
Transformation for dependent variable
() Optimal transformation for dependent variable

184

E.M.E.-M. Shokir / Journal of Petroleum Science and Engineering 58 (2007) 173185

i()
i ()

Transformation for independent variable

Optimal transformation for independent variable

Average relative error, ARE, %:

ARE

N
100 X
ycalculated ymeasured
N 1
ymeasured

Average absolute relative error, AARE, %:

AARE

N
100 X
ycalculated ymeasured
N 1
ymeasured

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