Effect of Oil Composition on Miscible-Type
Displacement by Carbon Dioxide
LeRoy W. Holm, SPE. Union Oil Co. of California
Virgil A. Josendal, SPE. Union Oil Co. of California
Abstract
This paper presents additional data related to the correla-
tion between minimum miscibility pressure (MMP) for
CO 2 flooding and to the composition of the crude oil to
be displaced. Yellig and Metcalfe have stated that there
is little or no effect of oil composition on the MMP.
However, their conclusion was based on experiments
with one type of reservoir oil that was varied in C I
through C 6 content and in the amount of C 7 + present
but not varied in composition of the C 7 + fraction. We
have found that the Holm-Josendal correlation, which is
based on temperature and C 5 + molecular weight,
predicts the general trend of the MMP's required for
CO 2 flooding of various crude oils. MMP's were
predicted with this correlation and then tested for several
crude oils using oil recovery of 80% at CO 2
breakthrough and 94 % ultimate recovery as the criteria.
We now have data showing that miscible-type displace-
ment is also correlatable with the amount of C 5 through
C 30 hydrocarbons present in the crude oil and with the
solvency of the CO 2 as indicated by its density. Varia-
tions from such a correlation are shown to be related to
the C 5 through C 12 content and to the type of these
hydrocarbons.
The MMP data were obtained from slim-tube floods
with crude oils havin~ gravities between 28 and 44 ° API
(0.88 and 0.80 g/ cm ) and C 5 + molecular weights be-
tween 171 and 267. The crude oils used varied in carbon
residue between I and 4 wt % and in waxy hydrocarbon
content between 1 and 17 %. The required MMP for
these crude oils at 165°F (74°C) varied between 2,450
and 4,400 psi (16.9 and 30.3 MPa) for an oil recovery of
94 % OIP. The MMP was found to be a linear function of
the amount of C 5 through C 30 hydrocarbons present and
of the density of the CO 2 •
0197-7520/82/0002-8814$00.25
Copyrigh1 1982 Socie1y of Petroleum Engineers of AI ME
FEBRUARY 1982
Introduction
Our 1974 paper, "Mechanisms of Oil Displacement by
Carbon Dioxide," 1 discussed the various mechanisms
by which oil is displaced from reservoir rock using CO 2 .
One conclusion of this study was that multiple-contact,
miscible-type displacement of oil occurs through extrac-
tion of C 5 through C 30 hydrocarbons from the reservoir
oil by CO 2 when a certain pressure is maintained at a
given flood temperature. The mechanism of oil recovery
was described as follows. The CO 2 vaporizes or extracts
hydrocarbons from the reservoir oil until a sufficient
quantity of these hydrocarbons exists at the displacement
front to cause the oil to be miscibly displaced. At that
point, the vaporization or extraction mechanism stops
until the miscible front that has been developed breaks
down through the dispersion mechanism. When
miscibility does not exist, the vaporization or extraction
mechanism again occurs to re-establish miscibility. The
miscible bank is formed, dispersed, and reformed
throughout the displacement path; a small amount of
residual oil remains behind all along the displacement
path.
Also, an optimal flooding pressure at a given
temperature for a given oil was defined in that paper as
when oil recovery of about 94 % OIP was achieved and
above which point essentially no additional oil was
recovered. This pressure has since been termed the
"minimum miscibility pressure" by others. 2-4
We further determined in our previous study that (1)
this miscible-type displacement does not depend on the
presence of C 2 through C 4 in the reservoir oil and that
(2) the presence of methane in the reservoir oil does not
change the MMP appreciably. Those findings have been
confirmed by Yellig and Metcalfe with the qualification
that the CO 2 MMP must be greater than or equal to the
bubble-point pressure of the reservoir oil.
Finally, a graphical correlation (Fig. 1) for predicting
the pressure of miscible-type displacement with CO 2
87
 TABLE 1- OIL COMPOSITION VS. MMP FOR CO 2 FLOODING AT 165°F

Carbon Predicted MMP

(psi)
API Residue, Experimental
Gravity Cs + C s to C 30 Wax' asphaltic MMP Holm- Yellig-
Stock Tank Oil (degrees) (mol wt) (wtOfo) (wtOfo) (wtOfo) (psi) Josendal Metcalfe
Bandini, CA 38 171 80 1 2,450 2,200 2,050
North Dundas, IL 35 214 70 2 3,000 2,500 2,050
Wilmington, CA 29 254 65 7 4 3,400 3,300 2,050
Farnsworth, TX 35 267 57 17 4,400 4,250 2,050

* Paraffinic content of crude oil boiling between about 600

and 1,QOQoF determined by low-temperature dewaxing
• ·Conradson carbon residue

6000

~ 5000
I MOL. WT. C 5+ • (2.48)
~. • (lU)

... .
::;)
01267)

.....:::......
~
4000

.
(1701

~~
• 3000
...u
2000

1000
(l1l1
..
1179)
- - - YELLIG
SPE 7H7 FIG. 6
o NEw DATA
• DOE EOR PROGRESS REPORT
No. 12. 1977

O~--~----~----~----~--~L---~~--~----~--~
60 10 100 120 140 160 110 200 220 240
TEMPERATURE."F

Fig. 1-Holm-Josendal dynamic miscibility displacement correlation for CO 2 .

also was proposed. The correlation was based on the their observation that the measured bubble-point of the
Benham et at. S correlation for predicting miscibility oil was the MMP.
pressure for natural gas flooding with a 59% CH 4 /41 % As shown in Fig. I, the Holm-losendal correlation
CJH s mixture that appeared equivalent to a CO 2 generally predicts higher MMP's than the Yellig-
displacement process. The parameters of this correlation Metcalfe correlation. The main reason for the difference
are the reservoir temperature and the C 5 + molecular in results obtained from the two correlations has to do
weight of the oil. with the composition of the oils, and this point is
Another correlation was proposed by Yellig and Met- discussed in this paper.
calfe in which MMP is a function of reservoir The failure of the Yellig-Metcalfe correlation to
temperature only, but which incorporates bubble-point predict the MMP's of heavier crude oils (molecular
pressure when gas is present in the oil. 2 The Yellig and weight of more than about 200) makes their correlation
Metcalfe correlation was developed using various unacceptable as a general correlation. 6 (See Fig. 1 and
recombined fractions of a light west Texas oil, always Table I.) However, the more fundamental point to be
including the same C 7 + fraction. A slim-tube miscibili- addressed is whether multiple-contact miscible displace-
ty criterion and a procedure designed to measure the ment of reservoir oil by CO 2 is dependent on the amount
MMP more accurately also were described in their work, and type of hydrocarbons in the oil (C 5 + fractions). The
and, for the measured MMP data on the oil selected, the purpose of this paper is to show the effects of the crude
correlation appeared to give a more accurate prediction oil composition on the performance of CO 2 flooding and
than the Holm-losendal correlation. on any correlation to predict a miscibility pressure.
A further analysis 6 of the Yellig-Metcalfe correlation Another purpose of the paper is to show the generai
showed that this apparently improved correlation (I) ap- validity of the Holm-losendal correlation, which con-
plied only to oils that were similar (had about the same siders the molecular weight of the C 5 + fraction of the
C 7 + composition) to the oil they investigated and (2) crude oil. Finally, this paper shows the relationships be-
gave a more accurate prediction of MMP because of tween the temperature and the solvency of the CO] for

88 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 INITIAL OIL VOLUME
1.' 0.3 • CELL VOLUME
w' 1.'
lIE
3 1.4
o
>
-'
o in
~ 0.'
!c...I 0.'
w 0.2
a: 0.4
I'IIAIlIIVElIIOI
0.2
o 500 1000 1500 2000 2500
PRESSURE, PSIG
Fig. 2-Change in volume of Cabin Creek stock-tank oil as
CO 2 was added at increasing pressure.
hydrocarbons in the crude oil, and the amount and
distribution of those hydrocarbons in the crude oil; it
leads to an improved correlation that involves CO 2 den-
sity and the amount and distribution of extractable
hydrocarbons (C 5 through C 30) in the crude oil.
Experimental Procedures
The slim-tube displacement tests for determining oil
recovery with CO 2 were conducted in a 52-ft (l6-m)
stainless steel tube packed with No. 60 crystal sand, a
washed beach sand produced by the Crystal Silica Co.
After packing with sand, the straight tube was bent into a
coil 7 in. (18 cm) high. Porosity of the 0.5-in. (13-mm)
ODxO.232-in. (6-mm) ID tube was 39%, and
permeability was 20 darcies. Three-way valves at each
end facilitated flushing the tube with solvent after each
displacement and resaturating with oil for the next run.
The inlet end was connected to a 5-micron (5-jlm)
Teflon® filter and to cylinders containing CO 2 and mer-
cury, and mercury and water. The outlet end was con-
nected to a Ruska viewing cell and then to a Grove
6,000-psi dome-loaded backpressure regulator. All this
equipment was contained in a constant-temperature air
bath. External to the bath was an Altex Model 1O0™ con-
stant rate water pump at the inlet end. and an at-
mospheric pressure oil-gas separator and a wet test meter
at the outlet end. During a run, CO 2 displaced the oil
downward at an initial rate of 80 ftlD (24 mid). The rate
was increased gradually to as high as 200 ftiD (61 mid)
so that a flood could be completed in 10 hours. CO 2 in-
jection volumes, oil recovery, and gas volumes and com-
positions were measured. Flooding was stopped at a
GaR of 40,000 scf/bbl (7100 std m 3 /m 3 ).
The CO 2 swelling tests were conducted in a Jerguson
sight glass gauge placed in a temperature-controlled air
bath. As illustrated in Fig. 2, our standard test consisted
of charging the cell 30% full of stock-tank oil and then
pressuring with CO 2 , At the start. the space above the
oil was filled with CO 2 at atmospheric pressure.
Relative oil phase volume was 1.0. Next. CO 2 was add-
ed in increments and the cell was rocked to equilibrium.
Pressure was measured by a Heise gauge in the mercury
FEBRUARY 1982
=
..,
~
Cit 0.8
~
~. 0.4
Q
0
3000 80 100 140 180
TEMPERATURE, OF
Fig. 3-Density of CO 2 as a function of pressure and
temperature, Vukalovich and Altunin data. 7
system, and mercury and liquid phase levels were
measured with a cathetometer. For the Cabin Creek oil
shown in Fig. 2, at 95°F (35°C) the oil phase first
swelled to a relative volume of 1.7 as the pressure was
increased to 1,000 psi (6.9 MPa) and then shrank steadi-
ly to a relative volume of 0.44 at 3,000 psi (2.7 MPa).
Definition of Terms
There has been some confusion as to the mechanism of
oil recovery since the introduction of the concept I that
oil recovery by CO 2 flooding resulted from the extrac-
tion of a fraction of the crude oil and the development of
a solvent slug that can displace crude oil frontally. The
terms dynamic miscibility, generated miscibility,
multiple-contact miscibility, minimum miscibility
pressure, and miscible-type displacement have been used
to describe the oil recovery mechanism. In this paper, as
in our previous papers, the first three terms refer to
miscibility between displaced oil and displacing fluids
developed within the porous media containing the oil to
be displaced.
Miscible-type oil displacement is defined here as oil
recovery from long slim-tube displacement experiments
that occurs as a result of hydrocarbon extraction from a
reservoir oil by injected CO 2 . The so-called "minimum
miscibility pressure" is defined as the pressure at which
80% of the alP is recovered at C02 breakthrou~h and
94% at a GaR of 40,000 scflbbl (7100 std m 1m 3 ).
This represents the practical maximum oil recovery ob-
tainable by CO 2 flooding and, as is shown in this paper,
does not represent truly minimum miscibility conditions.
Other experimentalists have defined MMP in slightly
different ways, using different breakthrough or ultimate
recovery values or using the point on the recovery plot at
which maximum or nearly maximum recovery is ob-
tained, along with observations of the effluent fluid.
These different definitions have resulted in small but not
fundamental differences in MMP determined by the dif-
ferent experimentalists.
CO2 Properties
Further clarification of the displacement mechanism us-
89
 TABLE 2- PRESSURE AND CO 2 DENSITY FROM SWELLING-EXTRACTION TESTS
Start of Substantial Hydrocarbon Extraction *
Temperature
Crude Oil (OF)
Tar Zone* * 123
Upper Terminal * * 148
Ford zone* * 207
Ford zone 165
North Dundas 91
North Dundas 165
Cabin Creek 95
Mead-Strawn 135
Mead-Strawn 190
Bandini 130
Bandini 165
Farnsworth 165
. Peak of swelling-extraction curve .
. 'Wilmington field.
ing CO 2 is necessary because of the extreme com-
pressibility at practical reservoir temperatures and
pressures. As shown in Fig. 3, the density of CO 2 above
its critical temperature [87.9°F (31.0°C)] varies from
0.1 to 0.8 g/cm 3 at pressures between 1,000 and 4,000
psi (6.9 and 27.6 MPa). Even as a liquid, CO 2 density
varies from about 0.5 to 1 g/cm 3. This variation in den-
sity has a marked effect on the solvent action of CO 2 ,
The increase in the solvent action of CO 2 with
pressure and therefore density can be illustrated by data
from Simon et al. 8 For a mixture of 75 mol % CO 2 in
their Reservoir Oil A at 130°F (54°C), the liquid phase
decreased from more than 20 vol % liquid at 1,500 psi
(10.3 MPa) to zero as pressure was increased to 5,000
psia (34.5 MPa). At 5,000 psia (34.5 MPa), the dew-
point pressure, the CO 2 dissolved all the oil except for a
solid phase that precipitated. CO 2 density is 0.365
g/cm 3 at 1,500 psia and 130°F (10.3 MPa and 54°C)
and 0.88 g/cm 3 at 5,000 psia and 130°F (34.5 MPa and
54°C). It is reasonable that the increased solvent power
of CO 2 with pressure is associated with increased CO 2
density.
Hydrocarbon Extraction
CO 2 (liquid or dense gas) selectively extracts com-
ponents from a solution of hydrocarbons (reservoir oil)
because these components are more readily soluble than
others in CO 2 . It is evident that liquid CO 2 (or dense gas
C02) is a better solvent for reservoir oil than gaseous
CO 2 . Gaseous CO 2 effects separation of hydrocarbons
by vaporization of the components. This limits the
removal of components from reservoir oil by gaseous
CO 2 to C 6 and lighter hydrocarbons. Liquid CO 2 or
dense gas CO 2 can extract and solubilize hydrocarbons
as heavy as C 30 and probably heavier. Fig. 2 shows how
CO 2 first swells the oil as CO 2 gas at 70°F (21°C) con-
denses into it, and then shrinks the oil as CO 2 liquid ex-
tracts hydrocarbon components. Extraction becomes
pronounced as the pressure approaches 840 psia (5.8
MPa)-the saturated liquid CO 2 pressure at 70°F
(21°C). Fig. 2 also shows similar extraction perfor-
mance for CO 2 as a dense gas at 95 ° F (35 ° C) (above the
critical temperature) at pressures starting near 1,000 psi
(6.9 MPa) and continuing with increased pressure to a
point where the oil-rich phase volume is about half the
90
Pressure CO 2 Density CS-C'2
(psi g) (g/cm3) in Crude (%)
1,450 0.36 5
1,600 0.34 13
2,100 0.33 25.5
1,720 0.32 25.5
1,060 0.29 22.5
1,660 0.30 22.5
1,020 0.22 31
1,450 0.29 34
1,700 0.27 34
1,350 0.29 33
1,680 0.31 33
1,850 0.38 15
original volume. These swelling curves merely
demonstrate the extractive capabilities of CO 2 at certain
pressures (densities). Phase diagrams such as those of
Orr et at. 9 describe the phase behavior more accurately.
The data in Table 2 indicate that the start of substantial
hydrocarbon extraction by CO 2 from a number of crude
oils at various temperatures occurs at pressures where the
density of CO 2 is 0.25 to 0.35 g/cm 3 . The temperature
is a variable only in that it determines the pressure re-
quired to achieve these CO 2 densities (Fig. 3). The
pressures and corresponding densities at which enough
hydrocarbon extraction takes place to cause an ap-
preciable shrinkage of the oil phase are above these in-
itial extraction conditions (Fig. 4) and they depend on
the nature of the oil as well as the temperature. We have
found that the minimum density at which sufficient
hydrocarbon extraction takes place to give approximate-
ly 94% recovery is about 0.42 g/cm 3 . This is close to
the critical density of CO 2 (0.468 g/cm 3). At this densi-
ty, CO 2 has enough solvency to dissolve pure hydrocar-
bons completely up to about C 12. 7 . 12 And, if there are
sufficient C 5 through C 12 hydrocarbons in a reservoir
oil (as in the case of the oils used by Yellig and Metcalfe,
which had a higher fraction of C 5 through C 12 in the C 5
through C 30 cut than any oil in Table 3), miscible-type
displacement and maximum recovery of this oil can be
achieved with the low-density CO 2 • If the reservoir oil
contains a lower amount of C 5 through C 12 hydrocar-
bons (only 34 wt% as shown for the Mead-Strawn crude
in Table 3, for example) the density of the solvent must
be greater than 0.5 g/cm 3 to achieve maximum oil
recovery.
At a density of about 0.5 g/cm 3, CO 2 achieves
multiple-contact displacement and very high oil recovery
with a C 5 through C 30 hydrocarbon mixture as indicated
in Fig. 5. We have found that maximum displacement
efficiency of reservoir oils tends to be a linear function of
the amount of C 5 through C 30 in the oil (or alternately,
the amount ofC 31 + in the oil). As shown in Fig. 5, the
density of CO 2 required for maximum displacement of.
oil at any temperature between 90 and 190°F (32 and
88°C) varies from slightly above 0.5 g/cm 3 for reservoir
oils containing about 80 wt % C 5 through C 30 to about
0.65 g/cm 3 for oils containing 70% C 5 through C 30 to
more than 0.75 g/cm 3 for oils containing less than 60%
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 0.8r------------------,

'1~ 0.7
........ -
~
ell

.
Vol

z ~
;::: 1.6 :=Ii
<..>
c :=Ii 0.6
'"'
.....
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I N
CD
Z o(J 6 FARIISWORTH
o
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....I FARNSWORTH
165DF
.... IL. 0.5
WILMIIIGTOI FORD ZOIE
• WEST POISOII SPIDER
115'

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0 800 1800 2400 3200 4000 4800
....I
C; CS-C30 CONTENT OF OIL, CS-C30 , WTOfo
'"' PRESSURE. PSIG CT
Fig. 4-Standard swelling-extraction tests and CO 2 floods on Fig. 5-C0 2 density required for miscible-type displacement
Mead-Strawn and Farnsworth stock-tank oils. vs. C s through C 30 content.

C 5 through C 30. However, the required density (solven-
cy) of the CO 2 for miscible-type displacement is af-
fected further by the distribution of the individual C 5
through C 30 hydrocarbons in the reservoir oil, as in-
dicated previously for the amount of C 5 through C 12
fraction in the oil. The required density is much less af-
fected by the type of hydrocarbons in the C 5 through
C 30 portion of the crude. This was demonstrated by ex-
periments in which the paraffinic hydrocarbons in the
Farnsworth crude oil were replaced by the more aromatic
hydrocarbons of the Ford zone crude oil (Fig. 6). This
topic is discussed in more detail in a later section.
Correlating MMP for CO2 Flooding
with API Gravity, Molecular Weight,
or Extractable Hydrocarbon Content
API Gravity
Oil gravity could be expected to be the simplest cor-
relating parameter for showing the effect of oil composi-
tion on MMP required for CO 2 flooding. This correla-
tion was attempted by the Natl. Petroleum Council. 3
MMP vs. API gravity is given in Fig. 7 for our
measurements on stock-tank oils and distillation cuts at
165°F (74°C). There is an approximate relationship,
with MMP increasing with decreasing oil gravity. The
correlation is poor and the Farnsworth oil point is well
off the trend.
Molecular Weight
Molecular weight of the C 5 + fraction of the reservoir
oil was used in our previous correlation. 1 This correla-
tion is shown in Fig. I with data points from Table 3 and
other data. MMP is plotted against temperature with
separate curves for C 5 + molecular weights from 180 to
240. It can be seen that, in general, higher pressures are
required to achieve miscibility with higher molecular
weight oils. MMP vs. C 5 + molecular weight is plotted
in Fig. 8 for a temperature of 165°F (74°C). Molecular
weight gives a much better straight-line correlation than
API gravity, but again the Farnsworth point is off the
trend.
C 5 Through C 30 Content
The amount of light hydrocarbons extracted by C02 in
generating a miscible bank should be related reasonably
to MMP. The greater the concentration of extractable
hydrocarbons in the reservoir oil, the lower the MMP
should be. In fact, MMP is in'versely proportional to ex-
tractable hydrocarbons concentration. Fig. 9 shows
MMP vs. weight percent C 5 through C 30 for five of our
seven stock-tank oils at 165°F (74°C). The reason for
the high Farnsworth MMP becomes apparent: Farns-
worth contains much less C 5 through C 30 material than
the other oils. Farnsworth contains only 57 wt % C 5
through C 30 compared to about 80 % for the Mead-
Strawn and Bandini oils. Fig. 5 shows how MMP is
related to extractable hydrocarbon content at all
temperatures. Rather than plotting MMP, we have plot-
ted CO 2 density at MMP. CO 2 density at MMP is little
different at high and low temperatures. Therefore, MMP
data at different temperatures can be compared. The use
of CO 2 density as a correlating parameter is discussed in
a later section. The order of ranking of the different oils
is the same in Fig. 5 as in Fig. 9. MMP's are much
higher for Farnsworth and Wilmington field Ford zone,
which are low in C 5 through C 30 content, than for
Mead-Strawn and Bandini, which are moderately high in
the C 5 through C 30 fraction.
The C 5 through C 30 content is given as weight percent
C 5 through C 30 in the C 5 and heavier fraction of the
reservoir oil. Selection of the C 5 through C 30 range of
hydrocarbons was based on our previous experimental
finding that hydrocarbons as heavy as C 30 were ex-

FEBRUARY 1982 91
 4500
100r---------------------~------~
ULTIMATE
•
FARNSWORTH
FARNSWORTH/FORD
HYBRID OIL (40.000 GOR)
(MORE AROMATIC) 92.8%
4000
~--

n- 90
O \
ULTIMATE
(40.000 GOR)
89.6%
ci
w 80
a:
w
o>
w
o
a: 70
...J
o
60 HYBRID OIL PREPARED BY REPLACING
THE 400-850o F CUT OF FARNSWORTH STO
WITH THE 400-850o F CUT FROM WILMINGTON
FIELD FORD ZONE STO.

0.6 0.7 0.8 0.9 1.0 1.1

C02INJECTED,POREVOLUMES MOLECULAR WEIGHT C 5+

Fig. 6-C0 2 floods of paraffinic oil and aromatic oil at 4,400 Fig. 8-MMP at 165°F (74°C) vs. molecular weight Cs +.
psi (30.3 MPa) and 165°F (74°C).

92 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 TABLE 3-EXPERIMENTAL DATA
,
Extractable Solvent Content
cd
Characterization of C'3 through C 30
Gasoline Conradson
CO 2 Density Range. K,Watson Carbon
Run at Temperature Molecular Cs throug~l flO (C s Through Cdl Para!- Naph- Arc- Character- Pour Residue ell +
Temperature MMP and MMP Gravity .Welght Amount (C s Through C 30 ) f,n thenes matles Izallon Pomt Wax (089) Gravity
Stock Tank Oils (OF) (pslg) (g/cm3) (OAPI) C,+ (wt%) (WI traction) (wt%) (wt%) (wt%) Factor (OF) (wl%) (wt%) (OAPI)
------- ----- -- ._-----
Farnsworth. TX 165 4,400 0778 359 267 57 027 492 36.0 14.8 122 + 75 17 071 276

Wilmington Ford
zone. CA 130 2,450 0701 289 254 65 041 322 404 27.4 116 +25 48 99
165 3.400 0698

North Dundas, IL 165 3.DOO 0651 345 214 70 033 377 427 196 11.85 21 184
(McCloskey
sand)

West POlson
Spider, WY 171 2,600 0.561 443 172 70 056 + 10 nd 261
(Mesa Verde
group)

Dominguez. CA 150 2,300 0582 335 219 73 050 321 454 225 117 -15 3.5 112
185 3,050 0592

Sandlnl, CA 137 1.850 0.515 36.8 171 80 042 329 47.3 198 11.75 - 60 17 154
165 2,450 0552

Mead-Strawn. TX 71 1250 0.823 401 183 815 042 376 441 183 118 -5 12 19.2
135 1.900 0.553
190 2,750 0521

Other Oils
,
Yellig and Met- 100 1.198 0.387 063
calfe carre- 160 2,000 0442
!ahon 165 2.054 0437
(west Texas) 196 2,400 0427

C s through C 30 165 2,300 0513 415 100 0.42 376 441 183 118
cut Mead-
Strawn

C s through C'2 165 2,000 0420 585 113 100 100

cut. Mead-
Strawn

a Extractable solvent taken to be the 70 to 850°F distill alton cuts, approximately C s through C JO hydrocarbons
GaSOline-range hydrocarbons are taken to be the 70 to 400°F cut, C s through C'2 hydrocarbons
b Weight percent C s through C 30 In C s + fraction of the OIL The stock-tank Oils contained 0 6 wt% or less butanes and
lighter
C ParaffinS. naphthenes, and aromatics In the 400 through 850°F cut were determined by universal high mass
compound-type analYSIS. normalized on a sulfur. oxygen and nitrogen-free baSIS
d oetermmed from ASTM 01160 dlsl1l1a\lOn and specific gravity at 60°F
e Weight percent calculated from mole percent using Katz and Firoozabadl molecular weights 10

tracted by CO 2 in generating the miscible bank. We will precipitate in an insoluble phase.

have disregarded the C I through C 4 fraction because To study how MMP is affected by variations in the
these light gases tend to finger through the reservoir properties of the seven stock tank oils we considered the
ahead of the miscible bank and do not affect MMP to any following parameters.
appreciable extent. 1,2 Of course, methane will affect the
MMP if enough methane is present to raise the bubble- Boiling-Point Range of C 5 Through C 30
point pressure above what would otherwise be the The molecular weight indicated by the boiling-point
mInimum miscibility pressure. The bubble-point range of C 5 through C 30 hydrocarbons also influences
pressure would then be the MMP, as Yellig and Metcalfe MMP. The lower boiling point (lower molecular weight)
found. 2 hydrocarbons in the gasoline range are more soluble in
CO 2 than is kerosene or light gas-oil. An MMP of 2,300
Properties of C s Through C 30 and psi (15.9 MPa) was measured at 165°F (74°C) for the
C 31 + Affecting MMP C 5 through C 30 material [70 to 850°F (21 to 454°C)]
The normally liquid components in a reservoir oil affect distilled from Mead-Strawn crude oil, while a pressure
MMP. First, some of the components are extracted by of only 2,000 psi (13.8 MPa) was needed for the C 5
CO 2 so as to generate a miscible bank. As we have seen, through C 12 gasoline range material [70 to 400°F (21 to
the amount of the extractable hydrocarbon solvent pres- 204°C)] (Fig. 9).
ent in the oil is of major importance. But also whether Another experiment confirmed the greater effec-
this extractable solvent is relatively light or heavy and tiveness of the lighter gasoline-range components in pro-
whether it is aromatic or paraffinic can affect MMP. Sec- ducing a miscible-type displacement. In this experiment
ond, the heavier components that are not extracted have we compared oil recovery in slim-tube displacements
greater or less solvency in the generated bank. The least before and after adding a small amount of C 5 through
soluble, high molecular weight material (i.e. asphalt) C 9 hydrocarbon blend to the oil. The oil was a different
FEBRUARY 1982 93
 TABLE 4-EFFECT ON MMP OF ADDITION
OF LIGHT HYDROCARBON!? TO A FARNSWORTH STOCK-TANK OIL

Oil Recovered at 165°F

and 4,400 psi (%OIP)
Volume Gravity Cs Through C 30 MMP
Oil at 60°F (mL) °API (wt%) Breakthrough Ultimate (psi)
Farnsworth Stock-tank oil 1,000 34.0 about 56 76.4 89.6 estimated 4,700

Stock-tank oil plus added 1,000 stock-tank oil 35.9 2.1 % greater, 81.0 97.6 estimated 4,100
Cs through C 9 * plus 62.9 mL Cs about 58.1
through C9

• Sufhdent C s through C 9 blend was added to bring the API gravity to 35.9°, the gravity of our prevIous
sample CompOSItion of the blend was

Liquid
Volume (%)

n Cs 13
n C& 19
n C7 41
isooctane 18
n C9 9
100

Density at 60°F = 06812 g/cm3

sample of Farnsworth stock-tank oil from that shown in for west Poison Spider and Dominguez, rich in C s
our tables and figures. Its gravity was only 34.0° API through C 12 components, lie below the line.
(0.854 g/cm 3), compared with 35.9° (0.845 g/cm 3) for
the earlier sample. Gas chromatograph analysis showed Characterization of the C 5 Through C 30 Fraction
that the oil was deficient in C s through C 9 components Whether the C s through C 30 extractable fraction is
compared with our previous sample. Accordingly, suffi- paraffinic or aromatic should have some effect on the
cient C s through C 9 hydrocarbon blend was added to the minimum miscibility pressure. 12 The character of the
crude oil to boost the gravity from 34.0 to 35.9° API fraction will affect (1) how much hydrocarbon is incor-
(0.85 to 0.84 g/cm 3). Thus, the C s through C 30 content porated into the CO 2 -rich miscible bank and (2) the
was raised by 2. 1 wt %. The effect on oil recovery and solvency between the formed bank and the reservoir oil
MMP of this enrichment is shown in Table 4. Ultimate that must be displaced. Lower boiling hydrocarbons (C 5
recovery at 4,400 psi (30.3 MPa) and 165°F (74°C) in- through C 12) will be extracted into the bank whether
creased from 89.6 to 97.6% OIP. We estimate the cor- they are paraffinic or aromatic. But the more aromatic
responding MMP's (for 94% recovery) as roughly 4,700 hydrocarbons should provide better solvency for most
and 4,100 psi (28 and 28.2 MPa), a decrease of some reservoir oils, and thus tend to cause lower MMP's. The
600 psi (4.1 MPa) for the lighter oil. character of the higher boiling hydrocarbons (C 13
Using Fig. 9, an increase in the total C s through C 30 through C 30) should affect both the amount extracted at
content from 56 to 58.1 % should lower MMP by only a given CO 2 density and the attainment of miscibility
about 250 psi (1.7 MPa), not 600 psi (4.1 MPa). We between the generated bank and the reservoir oil.
conclude that the C s through C 9 hydrocarbons added We devised an experiment to show the effect of the
were about twice as effective in reducing MMP as the character of the extractable hydrocarbons in crude oils.
addition of more C s through C 30 material would have We selected our most paraffinic oil, Farnsworth [the
been. 34.0° API (0.85-g/cm 3 ) sample], and the most aromatic
The amount of gasoline-range material in each of the oil, Wilmington field Ford zone. Slim-tube oil recovery
oils investigated is shown in Table 3, and it is expressed and MMP of Farnsworth oil was compared to the
as weight fraction (C s through C I2)/(C s through C 30 ). recovery and MMP of a hybrid oil that was mostly
The average (C s through C 12 )/(C s through C 30) for the Farnsworth but had its higher boiling extractable fraction
seven stock-tank oils is 0.42. Wilmington Ford zone, replaced by Ford zone hydrocarbons. Table 5 shows
Bandini, and Mead-Strawn are all average (gasoline- compositions and our results. Farnsworth oil contains
range contents of 0.41, 0.42, and 0.42, respectively). 40.7 wt% 400 to 850°F (204 to 454°C) material. In the
Farnsworth and North Dundas contain less gasoline- hybrid oil, we replaced this fraction with an equal weight
range material (0.27 and 0.33). West Poison Spider and of more aromatic Ford zone 400 to 850°F (204 to
Dominguez contain more (0.56 and 0.50). 454°C) material. Both 400 to 850°F (204 to 454 0c)
Our plot in Fig. 5 of CO 2 density at MMp vs. C s fractions had similar boiling point ranges. Thus, the only
through C 30 content shows that low fractional gasoline difference in the two oils was that Farnsworth had highly
contents cause high MMP's and high gasoline contents paraffinic midrange hydrocarbons, while the hybrid oil
cause low MMP's. A straight line has been drawn was more aromatic. CO 2 floods were made on each 'Oil.
through the scattered points in this figure. The points for Oil recovery was greater for the more aromatic oil (Fig.
Farnsworth and North Dundas, relatively lean in lighter 6). At 4400 psi (30.3 MPa) and 165°F (74°C), 92.8% of
gasoline-range hydrocarbons, lie above the line, in- the hybrid oil was recovered, compared to only 89.6% of
dicating higher MMP's than the trend line. The points unaltered Farnsworth oil. MMP was probably about

94 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 TABLE 5-EFFECT ON MMP OF MAKING FARNSWORTH STOCK-TANK OIL
MORE AROMATIC BY SUBSTITUTION OF WILMINGTON FIELD FORD ZONE MIDRANGE HYDROCARBONS
70 to 400 to
400°F 850°F
Oil (wt%) (wt%)
Farnsworth Stock- Farnsworth Farnsworth'"
tank oil 15.3 40.7
Farnsworth/Ford Farnsworth Ford'
Hybrid stock-tank 15.3 40.7
oil
·See Table 3 for the paraffins, naphthenes, and aromatics compositions of the
two 400 to 850°F dIstillation cuts. The more aromatic Ford zone cut was
substituted for the highly paraffinic Farnsworth cut.
4,500 psi (31.0 MPa) (extrapolating to 94% recovery)
for the hybrid oil, compared to perhaps 4,700 psi (32.4
MPa) for the Farnsworth oil. We conclude that increas-
ing aromatlclty correlated with lower miscibility
pressure, but we cannot be certain of the reason.
Our finding that an aromatic oil has a lower miscibility
pressure than a paraffinic oil may seem surprising. The
opposite result might be expected because aromatics and
naphthenes are known to be less miscible in CO 2 than
paraffin compounds. II • 12 -However, the miscibility
studies showing this poorer aromatics/C0 2 miscibility
were for simple systems with no high molecular weight
heavy ends. Leder and Irani, 12 for example, measured
the critical locus for decalin/C0 2 and tetralin/C0 2 mix-
tures, and compared their data with Schneider's curves
for normal paraffins. 13 At 80°C, Leder and Irani found
the tetralin/C0 2 critical locus to be 3,050 psia (21.0
MPa). But the normal paraffin, which has about the
same boiling point as tetralin, is n-dodecane; at 176°F
(80°C) its critical locus curve lies at 2,250 psia (15.5
MPa), 800 psi (5.5 MPa) below that for tetralin. This
means that for CO 2 to displace tetralin miscibly (first
contact miscible), a pressure of 3,050 psia (21.0 MPa)
would be required, but to displace n-dodecane miscibly
only 2,250 psia (15.5 MPa) would suffice. Although
aromatics and naphthenes are less compatible with CO 2
than paraffin hydrocarbons, aromatics and naphthenes
are better solvents for petroleum heavy ends. Our Farns-
worth and Farnsworth/Ford CO 2 floods apparently
reflected the net effect of these offsetting solubilities.
Heavy Fraction Properties
The properties of the heavy fraction present in a crude oil
also must influence MMP. Dense, asphaltic, high boil-
ing point material should result in higher MMP's than if
the heavy fraction materiaris less dense, less asphaltic,
and lower boiling. Conradson carbon number, given in
Table 3, is a measure of the amount of asphaltenes pres-
ent. Gravity of the C 31 + material [850°F (454°C) +
boiling point], in the last column, shows a wide range of
values.
Wilmington field Ford zone and Dominguez oils are
the most asphaltic and have the most dense heavy frac-
tions. Carbon residues are 4.8 and 3.5 wt %, and C 31 +
API gravities are 9.9 and 11.2° (1 and 0.9 g/cm 3),
respectively. Farnsworth and West Poison Spider are the
least asphaltic with the least dense heavy ends. Carbon
FEBRUARY 1982
400 to 850°F
Fraction,
Volumetric
Average Oil Recovered at 165°F
850°F + GravIty C, Through C,o Boiling and 4,400 psi (%OIP)
MMP
(wt%) (OAPI) (wt%) Point (OF) Breakthrough Ultimate (psi)
Farnsworth 34.0 -56 631 76.4 89.6 estimated
44.0 4700
Farnsworth 32.2 -56 626 78.7 92.8 estimated
44.0 4,500
residues are 0.71 and nil, and C 31 + API gravities are
27.6 and 26.1 ° (0.88 and 0.89 g/cm 3), respectively for
the latter two oils. These four oils exhibit a wide contrast
in the properties of their heavy ends. Presumably, the
heavy material in Wilmington and Dominguez oils
should cause high MMP's and the lighter high boiling
material in Farnsworth and West Poison Spider should
cause low MMP's. Our data indicate that the influence
of the properties of these heavy fractions is much less
than their amount (or the amount of C 5 through C 30 ),
however.
Example Comparison
Both North Dundas and West Poison Spider oils contain
70 wt% C 5 through C 30 . Table 6 shows measured
MMP's and properties that may affect the MMP's. West
Poison Spider MMP [2,500 psi (17 MPa)] is lower than
that for North Dundas [3,000 psi (20 MPa)] even though
both oils contain the same concentration of C 5 through
C 30 extractable hydrocarbon. The lower MMP for West
Poison Spider results primarily from the high C 5 through
C 12 content. The fact that West Poison Spider oil con-
tains a lighter and less asphaltic C 31 + fraction is of
secondary importance.
Mechanism of Oil Displacement
The study described in this paper confirms the
mechanism of the miscible-type displacement of oil by
CO 2 as described in our previous paper. I CO 2 extracts
hydrocarbons from the reservoir oil until a sufficient
quantity of these hydrocarbons exists at the displacement
front to cause the oil to be miscibly displaced (frontal
displacement). At that point, the extraction stops until
the miscible front that has been developed breaks down
through the dispersion mechanism. When miscibility
does not exist, the extractioh mechanism again occurs to
re-establish miscibility. A small amount of residual oil
remains all along the displacement path; the amount of
residual oil is dependent on the density of the CO 2 at
reservoir conditions. A minimum density CO 2 condition
is required to achieve the extraction and the miscible-
type displacement. Maximum oil recovery and the
pressure required to achieve it (MMP) is additionally a
function of the molecular weight of the oil, and more
specifically of the composition of the oil.
For a given oil, a certain density CO 2 fluid is required
for maximum oil recovery as shown in Fig. 10. The
95
 TABLE 6-COMPARISON OF MMP's AND OIL PROPERTIES
OF NORTH DUNDAS AND WEST POISON SPIDER STOCK-TANK OILS
North
Dundas
MMP, psig 3,000 at
165°F
C5 through C30 , wt% 69.7
(C 5 through C 12 )/(C5 through
C30 ), weight fraction 0.33
Carbon residue, wt% 2.1
Stock-tank oil gravity, °API 34.5
C31 + gravity, °API 18.4
C5 +, mol wt 214
'An MMP of 2,600 psig at 171°F is equivalent to about 2,500 psig at 165°F. (Determined using Fig. 10.)
pressure required for that density CO 2 is dependent on
the temperature, as shown in Fig, 3. The different slopes
of oil recovery vs. flood pressure curves for the same oil
at different temperature (Ref. 2, Fig. 5) is a reflection of
the greater pressure increase necessary to achieve
solvency (density) of CO 2 at higher temperatures. The
di fferent shapes of the oil recovered vs. flood pressure of
different oils at the same temperature (Fig. 11) is a
reflection of the amount of heavier hydrocarbons
(C 31 +) in the different oils and the increased solvency
of CO 2 required to recover a given percentage of that
oil.
As shown on Fig. 4, highest oil recoveries by CO 2
flooding are obtained at pressures where the hydrocarbon
extraction occurs. The pressure at which this displace-
ment mechanism begins is truly the MMP. The pressure
at which little, if any, oil recovery occurs with further
pressure increase (previously termed MMP) is the op-
timal miscible pressure.
The residual phase deposited in the reservoir rock dur-
ing a CO 2 flood reduces permeability to the COz-rich
drive fluid. Mobility ratio may be more favorable
because of this residual phase, and, if it is, flood sweep
efficiency would be improved. How much residuum is
deposited will depend on oil composition as well as flood
pressure. Thus, oil composition affects not only MMP
but also mobility ratio, which in tum affects sweep
efficiency.
Conclusions
1. This study shows that displacement of oil by CO 2
can develop miscibility by extraction of hydrocarbon
components into a COz-rich phase. This liquid-type ex-
traction occurs at temperatures above the critical
temperature [88 OF (31°C)] of CO 2 because of the high
compressibility of CO 2 . At a given temperature and
crude oil composition, sufficient pressure must be ap-
plied to compress CO 2 to a density where it has adequate
solvency to dissolve (or extract) enough hydrocarbons to
promote miscibility with the crude oil (Fig. 5).
2. The minimum density of CO 2 required to achieve
maximum oil recovery (-94% OIP) is about 0.42
96
West
Poison
Spider Comparison
2,500 at
165°F*
69.7 expect same MMP
0.56 expect lower MMP for
West Poison Spider
nil expect lower MMP for
West Poison Spider
44.3 expect lower MMP for
West Poison Spider
26.1 expect lower MMP for
West Poison Spider
172 expect lower MMP for
West Poison Spider
g/ cm 3 , close to the critical density of CO 2, 0.468
g/cm 3 . The reservoir temperature is a variable only in
that it determines the pressure needed to achieve the re-
quired CO 2 densities.
3. The flooding pressure required (MMP) for max-
imum displacement efficiency with CO 2 is related in-
versely to the amount of extractable C 5 through C 30
hydrocarbons present in the reservoir oil, and tends to be
a linear function of that amount (Fig. 5).
4. The MMP is affected further by the molecular
. weight distribution of hydrocarbons in the reservoir oil.
Low molecular weight gasoline-range hydrocarbons are
particularly effective in promoting miscibility. The
general correlation with molecular weight of C 5 +
presented by Holm and 10sendal l is valid.
5. The MMP also is affected but to a lesser degree by
the type of hydrocarbons present in the crude oil. We
found that aromatic midrange hydrocarbons resulted in a
lower MMP compared to paraffins of the same boiling
range. Further studies are necessary to determine quan-
titatively the solvent interactions between C02,
aromatic vs. paraffinic light and midrange hydrocarbons,
and aromatic vs. more paraffinic heavy ends.
Acknowledgment
We acknowledge L.F. Weidner for his performance of
the experimental work.
References
1. Holm, L.W. and Josendal, V.A.: "Mechanism of Oil
Displacement by Carbon Dioxide," 1. Pet. Tech. (Dec.
1974) 1427-1436; Trans., AIME. 257.
2. Yellig, W.F. and Metcalfe, R.S.: "Determination and
Prediction of the CO 2 Minimum Miscibility
Pressures," 1. Pet. Tech. (Jan. 1980) 160-168.
3. Enhanced Oil Recoverv-An Analysis of the Potential
for Enhanced Oil Recovery from Known Fields in the
United States-1976 to 2000, Natl. Petroleum Council,
Washington, DC (Dec. 1976). •
4. Sigmund, P.M. et at.: "Laboratory CO 2 Floods and
Their Computer Simulation," Proc., 28th World Pet.
Cong., Bucharest, Sept. 1979, P D 10 (5).
5. Benham, A.L., Dowden, W.E., and Kunzman, W.J.:
"Miscible Fluid Displacement-Prediction of Miseibili-
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 fj. FARNSWORTH
~ 0.78 g/em 3
o WILMINGTON FORD ZONE
go: 5000 o NORTH DUNDAS
-
~
~
•
•
WEST POISON SPIDER
DOMINGUEZ
, /
/
C02 DENSITY
AT MMP AND T
en
.778
>- • BANDINI
a:
~ 4000
o MEAD - STRAWN
• YELLIG & METCALFE CORRELATION
(.)
UJ
a:
o C5-C30 CUT (MEAD - STRAWN)
....I
• C5-C12 CUT (MEAD-STRAWN)
c X CABIN CREEK
UJ
~ 3000
~
i=
....I
~

~
o
CQ
2000
~
CQ
eN
C
:!.
~ 1000
~

80 100 120 140 160 180 200

TEMPERATURE, OF
Fig. 10-Density of CO 2 required for miscible displacement of various oils at 90° to 190°F (32° to 88°C).

100r-----------------------------------~

0-
Q. 90
~
0

-----
~

c 80 .",...--
W
a: p'
, "W'
w /
,."
",
> I ~
0

, ,/
0 70 I :I' /
w '/ /
a: I /
I
0-
....I

60

2000
~
I
I

2500
, /

3000
/
/
UlTIMATE RECOVERY
- - - C02 BREAKTHROUGH

3500 4000 4500

FLOOD PRESSURE, PSIG

Fig. 11-0il recovery by CO 2 flooding at 165°F (74°C).

FEBRUARY 1982 97
 ty," Trans., AIME (1960) 219, 229-237. Systems," -J. Chern. Eng. Data (March 1975) 20,
6. Holm, L.W. and Josendal, V.A.: "Discussion of Deter- 323-327.
mination and Prediction of CO 2 Minimum Miscibility 13. Schneider, G.: "Phase Equilibria in Binary Fluid
Pressures," J. Pet. Tech. (May 1980), 870·-871. Systems of Hydrocarbons with Carbon Dioxide, Water,
7. Vukalovich, M.P. and Altunin, V.V.: Therrnophysical and Methane," CEP Symposium Series, No. 88, 64
Properties of Carbon Dioxide, Collet's Ltd., London (1968) 9-15.
(1968) 243-263, 351.
8. Simon, R., Rosman, A., and Zana, E., "Phase-
Behavior Properties of CO 2-Reservoir Oil Systems," SI Metric Conversion Factors
Soc. Pet. Eng. J. (Feb. 1978) 20-26.
9. Orr, F.M., Yu, A.D., and Lien, C.L.: "Phase Behavior °API 141.5/(131.5+ ° API)
of CO 2 and Crude Oil in Low Temperature Reservoirs," OF (OF-32)/1.8
Soc. Pet. Eng. J. (Aug. 1981) 480-492.
10. Katz, D.L. and Firoozabadi, A.: "Predicting Phase mL x 1.0*
Behavior of Condensate/Crude-Oil Systems Using psi x 6.894757 E-03
Methane Interaction Coefficients," J. Pet. Tech. (Nov. *Convcr~i{)n factor exact
1978) 1649-1655.
I:'
SPEJ
II. Francis, A.W.: "Ternary Systems of Liquid Carbon
Original manuscript received in Society of Petroleum Engineers office Feb. 13, 1980.
Dioxide," J. Phys. Chern. (1954) 58, 1099. Paper accepted for publication Nov. 30, 1981, Revised manuscript received Nov. 23,
12. Leder, F., and Irani, C.A.: "Upper Critical Solution 1981. Paper (SPE 8814) first presented at the SPE/DOE Enhanced Oil·Recovery
Temperatures in Carbon Dioxide-Hydrocarbon Symposium held in Tulsa. April 20-23, 1980.

98 SOCIETY OF PETROLEUM ENGINEERS JOURNAL