Energy & Fuels 2007, 21, 34693476 3469

Effects of Viscous and Capillary Forces on CO2 Enhanced Oil

Recovery under Reservoir Conditions
Morteza Nobakht, Samane Moghadam, and Yongan Gu*
Petroleum Technology Research Centre (PTRC), Petroleum Systems Engineering, Faculty of Engineering,
UniVersity of Regina, Regina, Saskatchewan S4S 0A2, Canada

ReceiVed July 9, 2007. ReVised Manuscript ReceiVed September 21, 2007

Carbon dioxide flooding has been proven to be one of the most effective and viable enhanced oil recovery
(EOR) processes for light and medium oil reservoirs. In the past, an extremely large number of laboratory
experiments and numerical simulations have been conducted to study the CO2 EOR process. However, the
specific effects of viscous and capillary forces on this tertiary oil recovery process are neither thoroughly
studied nor well understood yet. In this paper, an experimental study is carried out to examine the detailed
effects of viscous and capillary forces on the CO2 EOR under the actual reservoir conditions. First, the
equilibrium interfacial tensions between a light crude oil and CO2 are measured at different equilibrium pressures.
Second, a series of CO2 coreflood tests are performed to measure the CO2 EOR at different CO2 injection pore
volumes, pressures, and rates. Each CO2 coreflood test is terminated after a total of 1.5 pore volume of CO2
is injected. The detailed experimental results show that, in general, the measured equilibrium interfacial tension
is reduced with the equilibrium pressure but the measured CO2 EOR at 1.5 pore volume of CO2 is increased
with the CO2 injection pressure and rate. Finally, the measured CO2 EOR at 1.5 pore volume versus injection
pressure data at different CO2 injection rates are related to the measured equilibrium interfacial tension versus
equilibrium pressure data in terms of the complete capillary number, which is defined as the ratio of the
viscous force to the capillary force for each CO2 coreflood test. This study shows that if the complete capillary
number is in an intermediate range, the CO2 EOR increases quickly with the complete capillary number.
Otherwise, the CO2 EOR is lower and remains almost constant for a smaller complete capillary number, or it
is higher and remains unchanged for a larger complete capillary number.

Introduction It has long been attempted to understand the effects of the

Enhanced oil recovery (EOR) becomes increasingly important
to the petroleum industry. After the primary recovery and
secondary recovery, a typical residual oil saturation in a light
or medium oil reservoir is in the range of 5060% of the original
oil in place (OOIP). For example, the total volume of unrecov-
ered oil in the existing reservoirs in Canada is about 5 billion
cubic meters.1 The extensive survey published every two years
by Oil & Gas Journal shows that, at present, the EOR processes
contribute significantly to overall oil production.2,3 Among the
EOR methods for light and medium oil reservoirs, carbon
dioxide flooding has been successful to a large extent under
some favorable reservoir conditions.1,3,4 It is worthwhile to
emphasize that the CO2 EOR method not only effectively
enhances oil recovery but also considerably reduces greenhouse
gas emissions.1 In the past five decades, there have been
extensive laboratory studies, numerical simulations, and field
applications of CO2 EOR processes. In general, it has been found
that these tertiary processes can enhance oil recovery by 816%
of the OOIP.5
* Corresponding author: Tel 1-306-585-4630; Fax 1-306-585-4855;
e-mail Peter.Gu@Uregina.Ca.
(1) Farouq Ali, S. M.; Thomas, S. J. Can. Pet. Technol. 2000, 39 (2),
711.
(2) Moritis, G. Oil Gas J. 2004, 102 (4), 4565.
(3) Moritis, G. Oil Gas J. 2006, 104 (15), 3757.
(4) Stalkup Jr., F. I. Miscible Displacement; SPE: Richardson, TX, 1983;
Monogr. Ser., Vol. 8.
(5) Rogers, J. D.; Grigg, R. B. SPE ReserVoir EVal. Eng. 2001, 4 (3),
375386.
interfacial interactions, such as the interfacial tension and
wettability, on the reservoir productivity and ultimate oil
recovery.6,7 In particular, the interfacial tension is considered
to be an important factor that may cause one-third of the OOIP
unrecoverable by solution gas drive or water flooding alone.8
In the CO2 flooding process, the oil and CO2 relative perme-
abilities and the residual oil saturation can be related to the crude
oilCO2 interfacial tension through a dimensionless number,
which compares either the capillary force with the viscous force
in the horizontal displacement processes or the capillary force
with the gravity force in the gravity drainage processes.9,10
Although there have been some studies on the effects of
interfacial tension of a crude oilCO2 system on the oil and
CO2 relative permeabilities in the CO2 flooding process,11,12
there are not enough experimental data available in the literature
for analyzing the effect of interfacial tension between a crude
oil and CO2 on the CO2 EOR in this process. It has been found
that the interfacial tension of a crude oilCO2 system is
(6) Morrow, N. R. J. Pet. Technol. 1990, 42 (12), 14761484.
(7) Rao, D. N. Pet. Sci. Technol. 2001, 19 (1), 157188.
(8) Grattoni, C. A.; Dawe, R. A. J. Pet. Sci. Eng. 2003, 39 (3), 297
308.
(9) Blom, S. M. P.; Hagoort, J. How to Include the Capillary Number
in Gas Condensate Relative Permeability Functions. Presented at SPE
Annual Technical Conference and Exhibition, New Orleans, LA, Sept 27
30, 1998; Paper SPE 49268.
(10) Grattoni, C. A.; Jing, X. D.; Dawe, R. A. J. Pet. Sci. Eng. 2001,
29 (1), 5365.
(11) Bardon, C.; Longeron, D. G. SPE J. 1980, 20 (10), 391401.
(12) Asar, J.; Handy, L. L. SPE ReserVoir Eng. 1988, 3 (1), 257264.

10.1021/ef700388a CCC: $37.00 2007 American Chemical Society

Published on Web 11/03/2007
3470 Energy & Fuels, Vol. 21, No. 6, 2007 Nobakht et al.

significantly reduced when CO2 is injected into an oil reservoir Table 1. Compositional Analysis Result of the Weyburn Light
at a high reservoir pressure.13,14 The reduced interfacial tension Crude Oil
alters the viscous forcecapillary force balance and thus lowers carbon carbon
the residual oil saturation. Therefore, it is of fundamental and number wt % number wt %
practical importance to study the detailed effects of the viscous C1 0.00 C15 4.08
and capillary forces on various CO2 flooding processes. C2 0.00 C16 3.92
Among many existing methods for determining the interfacial C3 0.00 C17 3.75
i-C4 0.00 C18 4.33
tension, the pendant drop method is probably the most suitable n-C4 0.00 C19 3.42
for measuring the interfacial tension between a crude oil and a i-C5 0.00 C20 2.45
test solvent at high pressures and elevated temperatures.13,14 In n-C5 0.00 C21 2.55
essence, this method determines the interfacial tension from the C6 0.00 C22 1.55
C7 3.20 C23 1.87
drop shape analysis. In the past, the pendant drop method has C8 4.68 C24 1.69
been used to measure the interfacial tension by photographing C9 7.79 C25 1.57
a pendant drop and then measuring the drop dimensions from C10 6.53 C26 1.60
the negative film.15 Recently, the axisymmetric drop shape C11 4.63 C27 1.49
analysis (ADSA) technique for the pendant drop case has been C12 4.17 C28 1.48
C13 4.20 C29 1.43
developed by Neumann and co-workers16,17 and employed to C14 4.05 C30+ 23.57
measure the dynamic and equilibrium interfacial tensions of
different crude oilsolvent systems at high pressures and
compositional analysis result of this crude oil was obtained by using
temperatures.13,14,18 In comparison with the other methods, the
the simulated distillation method and is given in Table 1. It can be
ADSA technique for the pendant drop case is accurate for the seen from this table that there are no hydrocarbon components under
interfacial tension measurement ((0.05 mJ/m2), fully automatic, C7 and that heavy hydrocarbon components of C30+ are found to
and completely free of the operators subjectivity.14,16,17 be 23.57 wt %. The purity of carbon dioxide (Praxair, Canada) is
The purpose of this paper is to study the effects of the viscous 99.99%. The densities of CO2 at different pressures and T ) 27 C
and capillary forces on the CO2 flooding performance under were calculated by using the CMG Winprop module (Version
the actual reservoir conditions. More specifically, first, the 2006.11, Computer Modelling Group Limited, Canada) with the
ADSA technique for the pendant drop case is applied to measure PengRobinson equation of state.19
the dynamic and equilibrium interfacial tensions between a crude Interfacial Tension Measurement. ADSA Setup. In this study,
light oil sample and CO2 at 12 different equilibrium pressures the axisymmetric drop shape analysis (ADSA) technique for the
pendant drop case was used to measure the dynamic and equilibrium
and T ) 27 C. Second, a total of 13 CO2 coreflood tests are
interfacial tensions of the crude oilCO2 system at different
conducted at different CO2 injection pore volumes, pressures, equilibrium pressures and a constant temperature of T ) 27 C. A
and rates as well as a constant temperature of T ) 27 C to schematic diagram of the ADSA system for the pendant drop case
recover the crude oil sample from a horizontal sand pack with used in this study is shown in Figure 1. The major component of
the porosity of 36.837.2% and the permeability of 16.918.0 this experimental setup was a see-through windowed high-pressure
darcy. Both the porosity and permeability of the sand pack are cell (IFT-10, Temco). The maximum operating pressure and
measured prior to each coreflood test. The accumulative oil temperature of this pressure cell are equal to 69 MPa and 177 C,
production from the sand pack at each different injected pore respectively. A stainless steel syringe needle was installed at the
volume of CO2 is measured. Each CO2 coreflood test is top of the pressure cell and used to form a pendant oil drop, whose
terminated after 1.5 pore volume of CO2 is injected. The outer diameter and wall thickness were equal to 1.18 and 0.39 mm,
respectively. The crude oil was introduced from a crude oil sample
accumulative oil production at the end of each test is then used
cylinder (DBR, Canada) to the syringe needle by using a program-
to determine the CO2 EOR under the coreflood test conditions. mable syringe pump (100DX, ISCO Inc.). The constant temperature
Finally, the complete capillary number, which is defined as the during the interfacial tension measurement was maintained by
ratio of the viscous force to the capillary force, is calculated wrapping the pressure cell with a heating tape (HT95504x1,
for each CO2 coreflood test. The oil recovery versus complete Electrothermal), which was connected to a temperature controller
capillary number data are used to examine the detailed effects (Standard-89000-00, Cole-Parmer, Canada). The equilibrium pres-
of the viscous and capillary forces on the CO2 EOR. sure inside the pressure cell was measured by using a digital
pressure gauge (DTG-6000, 3D Instruments).
A light source and a glass diffuser were used to provide uniform
Experimental Section illumination for the pendant oil drop. A microscope camera (MZ6,
Materials. The light crude oil sample was collected from the Leica, Germany) was used to capture the sequential digital images
Weyburn oilfield in Saskatchewan, Canada. The density and of the dynamic pendant oil drop inside the pressure cell at different
viscosity of the cleaned crude oil sample were measured to be Foil times. The high-pressure cell was positioned between the light
) 901.0 kg/m3 and oil ) 16.6 mPa s at the atmospheric pressure source and the microscope camera. The entire ADSA setup and
and T ) 27 C, respectively. The asphaltene content of the crude the high-pressure cell were placed on a vibration-free table (RS4000,
oil was measured to be wasp ) 5.7 wt % (n-pentane insoluble) by Newport). The digital images of the dynamic pendant oil drop at
using the standard ASTM D2007 method and 0.2 m polytetrafluo- different times were acquired in tagged image file format (TIFF)
roethylene (PTFE) syringe filters (Target, National Scientific). The by using a digital frame grabber (Ultra II, Coreco Imaging, Canada).
A Dell desktop computer was used to store the digital oil drop
(13) Yang, D.; Tontiwachwuthikul, P.; Gu, Y. J. Chem. Eng. Data 2005, images and perform subsequent image analysis, digitization, and
50 (4), 12421249. computation. The PC-based digital image system can grab the
(14) Yang, D.; Gu, Y. Pet. Sci. Technol. 2005, 23 (9), 10991112. sequential digital oil drop images at the speed of three digital images
(15) McCaffery, F. G. J. Can. Pet. Technol. 1972, 11 (3), 2632. per second.
(16) Rotenberg, Y.; Boruvka, L.; Neumann, A. W. J. Colloid Interface
Sci. 1983, 93 (1), 169183.
Experimental Procedure. Prior to each experiment, the high-
(17) Cheng, P.; Li, D.; Boruvka, L.; Rotenberg, Y.; Neumann, A. W. pressure cell was cleaned with kerosene and acetone, then flushed
Colloids Surf. 1990, 43 (2), 151167.
(18) Rao, D. N.; Lee, J. I. J. Colloid Interface Sci. 2003, 262 (2), 474 (19) Peng, D. Y.; Robinson, D. B. Ind. Eng. Chem. Fundam. 1976, 15
482. (1), 5864.
CO2 Enhanced Oil RecoVery
Figure 1. Schematic diagram of the experimental setup used for measuring the dynamic and equilibrium interfacial tensions between the crude oil
and CO2 by applying the axisymmetric drop shape analysis (ADSA) technique for the pendant drop case.
with nitrogen, and finally purged with CO2 for at least five times.
The pressure cell was then pressurized with CO2 to a prespecified
pressure by using a manual positive displacement pump (PMP-
500-1-10-HB, DBR, Canada). After the CO2 was injected, it usually
took 3060 min for the pressure and temperature inside the pressure
cell to reach their stable values. Then the crude oil was introduced
from the crude oil sample cylinder, whose pressure was maintained
0.10.5 MPa higher than that of CO2 phase inside the pressure cell.
The pendant oil drop was formed at the tip of the syringe needle,
which was installed at the top of the high-pressure cell. Once a
well-shaped pendant oil drop was formed, a digital image acquisi-
tion program (TciPro, Coreco Imaging, Canada) was executed to
acquire its sequential digital images as CO2 was gradually dissolved
into it. The time interval for the sequential digital drop image
acquisition was properly set so that it was smaller at the beginning
but larger when the pendant oil drop was almost saturated with
CO2. The acquired digital drop images were automatically stored
in the computer as TIFF files. For each acquired digital oil drop
image, a high-precision calibration grid was used to calibrate and
correct possible optical distortions.
After the sequential digital images of the dynamic pendant oil
drop at different times were acquired and stored in the computer,
the ADSA program for the pendant drop case was executed to
determine the dynamic and equilibrium interfacial tensions of the
pendant oil drop and the drop profile from each digital drop image.
The output data also included the radius of curvature at the apex
point, the surface area, and volume of the pendant oil drop. Only
the local gravitational acceleration and the density difference
between the crude oil and CO2 were required as input data for this
program. The interfacial tension measurement was repeated for at
least three different pendant oil drops to ensure satisfactory
repeatability at each prespecified pressure and constant temperature.
In this study, the crude oilCO2 interfacial tensions were measured
at a constant temperature of T ) 27 C and 12 different equilibrium
pressures of P ) 2.411.0 MPa.
Coreflood Test. Coreflood Apparatus. In this study, high-
pressure coreflood tests were performed to study the effects of CO2
injection pressure and rate as well as injected pore volume of CO2
on the CO2 enhanced oil recovery. A schematic diagram of the
coreflood apparatus used in the coreflood test is shown in Figure
2. The experimental setup consisted of the following major parts:
a personal computer, an automatic positive displacement pump,
three hydraulic cylinders, a sand-packed high-pressure coreholder,
a back-pressure regulator (BPR), and a gas flow meter. The
Energy & Fuels, Vol. 21, No. 6, 2007 3471
automatic positive displacement pump (PMP-1000-1-10-MB, DBR,
Canada) was used to pump the crude oil or CO2 through the sand
pack or the distilled water to apply the so-called overburden
pressure. Three hydraulic cylinders (DBR, Canada) were used to
contain and deliver the crude oil, CO2, and the distilled water. These
three hydraulic cylinders and the sand-packed coreholder were
placed inside an air bath. An electric heater (Super Electric Co.,
Canada) and a temperature controller (Standard-89000-00, Cole-
Parmer, Canada) were used to heat the air bath and keep its constant
temperature. The BPR was used to maintain the prespecified
injection pressure inside the coreholder during each CO2 coreflood
test. The gas flow meter (GFM 17, Aalborg) was used to measure
CO2 production rate during the CO2 coreflood test.
Experimental Preparations. The sand pack used in this study
was 12 in. long and 2 in. in inner diameter and was packed with
6080 mesh Ottawa sands (U.S. Silica Co.). The porosity of each
sand pack was measured by using the imbibition method and found
to be in the range of ) 36.837.2%. After the porosity
measurement, the permeability of each sand pack was measured.
A homemade manometer was used to measure the small pressure
drop along the sand pack. Two liquids were used in the manometer,
distilled water with the density of 1000 kg/m3 and 1,3-dichloroben-
zene (Fisher Scientific) with the density of 1288 kg/m3. These two
liquids were immiscible so that an interface was formed between
them. During the permeability measurement, the distilled water was
used as a working medium. The permeability of each sand pack
was in the range of k ) 16.918.0 darcy. After the permeability
measurement, the wet sands were dried by using the pressurized
air for at least 48 h. Then the dry sand pack was saturated with the
crude oil, and the initial oil saturation was found to be in the range
of Soi ) 97.299.3%. The detailed physical properties of the 13
sand packs used for the CO2 coreflood tests at T ) 27 C are
summarized in Table 2.
Experimental Procedure. The CO2 coreflood test was conducted
with each sand pack at different CO2 injection pressures and rates
and T ) 27 C. After the sand pack was initially saturated with the
crude oil, the temperature inside the air bath was set at T ) 27 C.
After at least 48 h, the crude oil was injected into the sand pack to
pressurize the sand pack. Meanwhile, the BPR was set at a slightly
higher pressure than the pressure inside the sand pack. In this way,
the pressure drop along the sand pack during the pressurization
period was small. Once the pressure inside the coreholder reached
the prespecified injection pressure, the crude oil injection was
3472 Energy & Fuels, Vol. 21, No. 6, 2007 Nobakht et al.

Figure 2. Schematic diagram of the coreflood apparatus used for measuring the CO2 EOR.

Table 2. Physical Properties of Sand Packs and the Experimental Conditions, Complete Capillary Numbers and EOR Data for 13 CO2
Coreflood Tests at T ) 27 Ca
test no. (%) k (m2) Soi (%) P (MPa) qCO2 (cm3/min) CO2 (Pa s) eq (mJ/m2) NCA R (%)
1 37.2 18.0 97.8 2.77 0.5 16.3 16.61 6.72 10-4 13.2
2 37.1 17.4 99.0 5.51 0.5 18.7 7.89 1.65 10-3 14.4
3 37.1 18.0 98.1 5.93 0.5 19.6 6.34 2.12 10-3 15.7
4 37.0 17.6 99.3 6.48 0.5 21.7 4.22 3.57 10-3 33.7
5 36.9 17.7 98.6 7.17 0.5 62.6 2.11 2.06 10-2 53.7
6 36.9 17.1 98.8 9.58 0.5 87.8 1.47 4.21 10-2 57.7
7 36.9 17.1 97.5 11.03 0.5 101.2 1.13 6.32 10-2 57.8
8 37.2 18.0 98.7 2.43 1.0 16.2 17.53 1.27 10-3 13.7
9 37.1 18.0 99.1 4.51 1.0 17.4 11.68 2.04 10-3 14.5
10 37.2 17.1 99.0 5.17 1.0 18.2 9.28 2.76 10-3 21.8
11 37.2 17.3 97.9 6.45 1.0 21.6 4.33 6.97 10-3 47.1
12 37.0 17.4 97.2 9.31 1.0 85.3 1.53 7.79 10-2 58.0
13 36.8 16.9 98.9 10.69 1.0 98.0 1.21 1.15 10-1 58.2
a Notes: ) porosity, k ) permeability, S ) initial oil saturation, P ) CO injection pressure, q
oi 2 CO2 ) CO2 volume injection rate, CO2 ) viscosity
of the injected CO2, eq ) equilibrium interfacial tension between the crude oil and the injected CO2, NCA ) complete capillary number, and R ) CO2
EOR at 1.5 injected pore volume of CO2.
terminated and the CO2 injection was commenced with a constant injection was stopped, a blow-down process was commenced. This
volume injection rate to recover the crude oil from the sand pack. process was continued until the pressure inside the coreholder
After the produced oil from the sand pack passed through the BPR reached the atmospheric pressure and no more oil and CO2 were
and flowed to an oil sample collector, it was weighed at a certain time produced.
interval to determine the accumulative oil production. The CO2
dissolved into the produced oil was flashed from the oil sample Results and Discussion
collector and passed through the gas flow meter, where the CO2
production rate was measured every second and automatically stored Dynamic Interfacial Tension. As described in the interfacial
in a personal computer. The CO2 production rate versus time data were tension measurement, the high-pressure cell was first filled with
then integrated to determine the accumulative CO2 production. CO2 at a prespecified pressure and a constant temperature of T
In this study, each CO2 coreflood test was terminated when a ) 27 C. Then a crude oil sample was introduced into the
total of 1.5 pore volume of CO2 was injected. After the CO2 pressure cell. Once the pendant oil drop was formed, CO2 was
CO2 Enhanced Oil RecoVery
Figure 3. Measured dynamic interfacial tensions between the Weyburn
crude oil and CO2 at 12 different equilibrium pressures and T ) 27
C.
gradually dissolved into the oil drop. The dissolution of CO2
into the pendant oil drop was continued until the latter was
completely saturated with the former.20 In order to examine the
effect of dissolution of CO2 into the pendant oil drop on the
crude oilCO2 interfacial tension, the dynamic interfacial tension
was measured during the CO2 dissolution process. In the past,
the dynamic interfacial tension phenomenon was studied for
different EOR processes.13,14,2123 The measured dynamic
interfacial tension of the crude oilCO2 system versus time data
under 12 different equilibrium pressures at T ) 27 C are shown
in Figure 3. All the dynamic interfacial tension measurements
lasted about 140 min, except at P ) 6.6 MPa. It was found that
the pendant oil drop could only stay at the tip of the syringe
needle for about 30 min at P ) 6.6 MPa. This is probably due
to wettability alteration of the oil phase on the stainless steel
syringe needle surface,14 which is caused by phase change of
the injected CO2. It should be mentioned that the density of the
oil with dissolved CO2 is assumed to be constant for the dynamic
interfacial tension measurement, as variations of the oil density
with the CO2 dissolution at these pressures are negligible.13,14,24
Figure 3 shows that the measured dynamic interfacial tensions
reach their equilibrium values after at most 30 min under
different equilibrium pressures. This fact indicates that the
pendant oil drop surface is quickly saturated with CO2, whereas
the CO2 dissolution into the entire pendant oil drop proceeds
for a relatively long time.20 It can also be seen from this figure
that the dynamic interfacial tension is lower at a higher
equilibrium pressure. This is because the solubility of CO2 in
the crude oil is higher when the equilibrium pressure is
higher.13,14 In addition, the dynamic interfacial tension reaches
its equilibrium value more quickly at a higher equilibrium
pressure.
In the dynamic interfacial tension measurement, one important
physical phenomenon was observed. At the equilibrium pres-
sures equal to or higher than 6.6 MPa, the light hydrocarbon
components were observably extracted from the pendant oil drop
into CO2 phase at the beginning, which is referred to as the
(20) Yang, C.; Gu, Y. Ind. Eng. Chem. Res. 2005, 44 (12), 44744483.
(21) Borwankar, R. P.; Wasan, D. T. AIChE J. 1986a, 32 (3), 455
466
(22) Borwankar, R. P.; Wasan, D. T. AIChE J. 1986b, 32 (3), 467
476
(23) Taylor, K. C.; Hawkins, B. F.; Islam, M. R. J. Can. Pet. Technol.
1990, 29 (1), 5055.
(24) Sayegh, S. G.; Rao, D. N.; Kokal, S.; Najman, J. J. Can. Pet.
Technol. 1990, 29 (6), 3139.
Energy & Fuels, Vol. 21, No. 6, 2007 3473
Figure 4. Measured equilibrium interfacial tension of the Weyburn
crude oilCO2 system versus equilibrium pressure data at T ) 27 C.
initial strong light-components extraction process.14 During this
strong extraction process, the crude oil was continuously
introduced from the crude oil sample cylinder such that a well-
shaped pendant oil drop could be formed eventually for the
interfacial tension measurement. Hence, some light components
of the original crude oil were quickly extracted, and the final
pendant oil drop formed at the tip of the syringe needle was
mainly composed of the heavy components of the original crude
oil. These remaining heavy components made the measured
dynamic interfacial tension between the crude oil and CO2
slightly reduced with the equilibrium pressure at P g 7.2 MPa.
Equilibrium Interfacial Tension. In the dynamic interfacial
tension measurement, it was found that at any equilibrium
pressure the dynamic interfacial tension for the crude oilCO2
system ultimately reaches a constant value, which is referred
to as the equilibrium interfacial tension. The average value of
the equilibrium interfacial tensions of three repeated dynamic
interfacial tension measurements at the same equilibrium
pressure and temperature is reported in this paper. The measured
equilibrium interfacial tensions between the crude oil and CO2
at different equilibrium pressures and T ) 27 C are plotted in
Figure 4. It is found from this figure that the measured
equilibrium interfacial tension is reduced almost linearly with
the equilibrium pressure as long as the equilibrium pressure is
equal to or lower than 7.2 MPa. The interfacial tension reduction
with the equilibrium pressure is attributed to the increased
solubility of CO2 in the crude oil at an increased equilibrium
pressure.13,14 Figure 4 also shows that once the equilibrium
pressure is higher than a threshold pressure (i.e., 7.2 MPa), an
equilibrium interfacial tension of as low as 12 mJ/m2 is
achieved. In this case, the equilibrium interfacial tension
reduction is small if the equilibrium pressure is further increased.
Similar results were also reported for other crude oilCO2
systems in the literature.13,14 On the basis of these experimental
results, it becomes obvious that there is no need to overem-
phasize the pressure effect on the equilibrium interfacial tension
for the crude oilCO2 system as long as the reservoir pressure
exceeds the threshold pressure, e.g., P ) 7.2 MPa at T ) 27
C in the present case.
Effects of CO2 Injection Pressure and Rate on Oil Re-
covery. In this study, a total of 13 CO2 coreflood tests were
carried out along the horizontal sand packs at a constant
temperature of T ) 27 C to examine the effects of CO2 injection
pressure and rate on the enhanced oil recovery by CO2 flooding.
Parts a and b of Figure 5 show the measured oil recovery versus
3474 Energy & Fuels, Vol. 21, No. 6, 2007
Figure 5. (a) Measured CO2 EOR versus the injected pore volume of
CO2 at a constant volume injection rate of qCO2 ) 0.5 cm3/min and T
) 27 C. (b) Measured CO2 EOR versus the injected pore volume of
CO2 at a constant volume injection rate of qCO2 ) 1.0 cm3/min and T
) 27 C.
the injected pore volume of CO2 at different injection pressures
and two different constant volume injection rates of 0.5 and
1.0 cm3/min, respectively. The ordinate of these two figures
represents the CO2 EOR and is defined as the ratio of the mass
of the produced oil to that of the initial oil in the sand pack. It
is seen from Figure 5a,b that, expectedly, the CO2 EOR is
increased with the injected pore volume of CO2. However, the
oil recovery at each injection pressure and rate reaches its
maximum after 1.5 pore volume of CO2 is injected. Therefore,
each CO2 coreflood test was terminated when the injected pore
volume of CO2 reached 1.5.
The measured oil recovery at 1.5 pore volume of CO2 versus
injection pressure data at two different volume injection rates
and a constant temperature of T ) 27 C are further summarized
in Figure 6. It is noted from this figure that, roughly speaking,
there are three different regions in the injection pressure range
tested. First, at the injection pressures equal to or lower than
4.51 MPa, the CO2 EOR is low and almost independant of CO2
injection pressure and rate. In this injection pressure range, the
injected CO2 is in gas phase with an extremely low viscosity,
which causes the early CO2 breakthrough in the coreflood tests.
Low oil recovery in this region is attributed to the early CO2
breakthrough and relatively high equilibrium interfacial tensions
of the crude oilCO2 system. Second, as the injection pressure
increases, the CO2 EOR increases significantly. In this region,
the oil recovery also increases with the volume injection rate.
Nobakht et al.
Figure 6. Measured CO2 EOR at 1.5 pore volume of CO2 versus the
injection pressure at two different constant CO2 volume injection rates
and T ) 27 C.
The increased oil recovery with CO2 injection pressure is due
to the increased viscosity of injected CO2 and the reduced
equilibrium interfacial tension of the crude oilCO2 system. The
latter is caused by the increased CO2 solubility in the crude oil
at an increased injection pressure. Third, when the CO2 injection
pressure exceeds 7.17 MPa, the CO2 EOR remains high but
becomes insensitive to the injection pressure and rate. In this
case, the maximum oil recovery at 1.5 pore volume of CO2 is
achieved, and the residual oil saturation in the sand pack is
reached. It is worthwhile to note that the equilibrium interfacial
tensions between the crude oil and CO2 remain low and almost
constant at the equilibrium pressures higher than 7.2 MPa, which
makes the CO2 EOR almost unchanged with the CO2 injection
pressure and rate in the third region.
Complete Capillary Number. In general, viscous, capillary,
hydrodynamic, and gravity forces control fluid flow through a
porous medium. A ratio between any two of these four forces
can be expressed as a dimensionless number.10 Thus, a total of
three independant dimensionless numbers can be defined and
used to quantify the effects of these four controlling forces on
the CO2 EOR process. One important dimensionless number is
the capillary number, which is defined as the ratio of the viscous
force to the capillary force and is traditionally calculated by
using the following equation:4,25,26
vCO2CO2
Nca ) (1)
where vCO2 is the linear velocity of the injected CO2 through
the porous medium, which is equal to the CO2 volume injection
rate divided by the cross-sectional area of the porous medium;
CO2 is the viscosity of the injected CO2 at a given injection
pressure; is the porosity of the porous medium; and is the
interfacial tension between the crude oil and CO2. In general,
the capillary number can be used to study the effects of the
viscous and capillary forces on the oil recovery during an
immiscible displacement, whether it is an imbibition or drainage
process. In this study, the equilibrium interfacial tensions, eq,
between the crude oil and CO2 under different coreflood
experimental conditions are used to calculate the capillary
number. This is because the dynamic interfacial tension of the
crude oilCO2 system reaches the equilibrium interfacial tension
within a relatively short period (at most 30 min) in the
(25) Chatzis, I.; Morrow, N. R. SPE J. 1984, 24 (5), 555562.
(26) Islam, M. R.; Bentsen, R. G. AOSTRA J. Res. 1987, 3 (2), 6990.
CO2 Enhanced Oil RecoVery Energy & Fuels, Vol. 21, No. 6, 2007 3475

equilibrium pressure range tested. However, the retention time

in each CO2 coreflood test, which is equal to the pore volume
of the sand pack divided by the CO2 volume injection rate, was
approximately 8 and 4 h at qCO2 ) 0.5 and qCO2 ) 1.0 cm3/min,
respectively.
It should be noted that the above-defined capillary number,
Nca, does not take account of the length and pore size of a porous
medium,27 which affect the viscous force through the porous
medium. In the literature, the complete capillary number, NCA,
for a circular capillary, is defined as27
4vCO2CO2l
NCA ) (2)
eqr
where l and r are the length and radius of the circular capillary,
respectively. In comparison of eq 1 and eq 2, it becomes clear
that Nca defined in eq 1 represents the ratio of the viscous force
to the capillary force when r ) 4l. Figure 7. Calculated complete capillary number versus injection
pressure data for the CO2 coreflood tests at two different constant CO2
In consideration of the actual pore size and shape distributions
volume injection rates and T ) 27 C.
in a real oil reservoir, it is useful to relate the above-defined
complete capillary number, NCA, to some measurable reservoir
characteristics, such as permeability and porosity of the oil
reservoir. For conduit flow through a bundle of identical circular
capillaries, Dullien27 derived the following relation:

r2
k) (3)
8
Here, k is the permeability, is the porosity, and r is the radius
of the identical circular capillaries. Alternatively, the complete
capillary number can be defined in terms of the permeability
and porosity of the porous medium:

2vCO CO l
NCA )
2 2
(4)
eqk
It is worthwhile to mention that a capillary number, which is
similar to the above-defined complete capillary number, NCA,
has been recently used for fluid flow through different porous
media.28,29
Based on eq 4, with known permeability, porosity, length,
and cross-sectional area of the porous medium and CO2 volume
injection rate, the complete capillary number, NCA, can be
calculated from the CO2 viscosity and the equilibrium interfacial
tension of the crude oilCO2 system. In this study, the CO2
viscosity is calculated by applying the JossiStielThodos
correlation.30 The equilibrium interfacial tension between the
crude oil and CO2 at a prespecified injection pressure is obtained
by applying the linear interpolation of the measured equilibrium
interfacial tension versus equilibrium pressure data at T ) 27
C given in Figure 4. The length and cross-sectional area of
the sand packs used in the CO2 coreflood tests are equal to 30.48
and 20.27 cm2, respectively. The complete capillary numbers,
NCA, for the 13 CO2 coreflood tests are calculated and listed in
Table 2. Furthermore, the variations of the calculated complete
capillary number, NCA, with the CO2 injection pressure for these
CO2 coreflood tests at two different constant CO2 volume
injection rates and T ) 27 C are shown in Figure 7. It is seen
from this figure that at a constant CO2 volume injection rate
(27) Dullien, F. A. L. Porous Media: Fluid Transport and Pore
Structure, 2nd ed.; Academic Press: San Diego, CA, 1992.
(28) Melean, Y.; Bureau, N.; Broseta, D. SPE ReserVoir EVal. Eng. 2003,
6 (4), 244254.
(29) Cinar, Y.; Orr Jr., F. M. SPE ReserVoir EVal. Eng. 2005, 8 (1),
3343.
(30) Jossi, J. A.; Stiel, L. I.; Thodos, G. AIChE J. 1962, 8 (1), 5963.
Figure 8. Measured CO2 EOR versus the calculated complete capillary
number for the CO2 coreflood tests at two different constant CO2 volume
injection rates and T ) 27 C.
the complete capillary number, NCA, increases with the CO2
injection pressure. This is because the viscosity of the injected
CO2, CO2, is increased (i.e., larger viscous force), but the
equilibrium interfacial tension, eq, of the crude oilCO2 system
is reduced (i.e., smaller capillary force) at an increased injection
pressure. Figure 7 also shows that at a given injection pressure
the complete capillary number slightly increases with the
injection rate due to a larger viscous force at an increased CO2
volume injection rate (i.e., an increased CO2).
Combining Figures 6 and 7 together, Figure 8 shows the
relation between the measured CO2 EOR and the calculated
complete capillary number. This figure shows that, in general,
the CO2 EOR increases with the complete capillary number.
The remaining oil in the porous medium can be displaced by
an increased viscous force, which pushes the oil out, and/or by
a reduced capillary force, which holds the oil in the porous
medium.31 This can explain a higher CO2 EOR at a larger
complete capillary number. There are also three regions in the
complete capillary number range tested. First, at small complete
capillary numbers (NCA e 2.12 10-3), the CO2 EOR increases
marginally with the complete capillary number. This is the
region where the large capillary force dominates the CO2
(31) Lake, L. W. Enhanced Oil RecoVery; Prentice Hall: Englewood
Cliffs, NJ, 1989.
3476 Energy & Fuels, Vol. 21, No. 6, 2007
displacement process, which leads to low CO2 EOR. In this
case, because of small viscous force relative to large capillary
force, CO2 displaces the oil from the largest pores, which have
the lowest capillary entry pressures.5 Second, as the complete
capillary number becomes larger, the CO2 EOR increases more
drastically with the complete capillary number. For example,
the CO2 EOR at NCA ) 2.06 102 is 53.7%, which is about
3.4 times the 15.7% CO2 EOR at NCA ) 2.12 103. In this
region, the CO2 displacement changes from the capillary force
dominated displacement to a rather different process, in which
there is an obvious competition between the viscous force and
the capillary force. This change occurs in the range of NCA )
2.12 1034.21 102. Finally, if the complete capillary tests also show that there are three different regions in the CO2
number is equal to or larger than 4.21 102, the CO2 EOR
reaches its maximum and becomes the least sensitive to the
complete capillary number. The maximum oil recovery at 1.5
pore volume of CO2 is achieved, and the unrecovered crude oil
(i.e., the residual oil saturation) remains in the smallest pores,
which have the highest capillary entry pressures. Because of
extremely high capillary entry pressures in the small pores, the
viscous force is still not strong enough to completely overcome
the capillary force and mobilize the remaining oil in the smallest
pores. Also, the oil-phase network loses its continuity due to
low residual oil saturation in this case.5 As a result, the
displacement efficiency of the residual oil by CO2 flooding is
maximized, and an almost constant high oil recovery is reached
at a large complete capillary number.
Conclusions
In this paper, the dynamic and equilibrium interfacial tensions
between a crude oil and CO2 are measured at 12 different
equilibrium pressures and T ) 27 C by using the ADSA
technique for the pendant drop case. It is found that the dynamic
interfacial tension is reduced to a constant value in a short time.
It is also found that the measured equilibrium interfacial tension
is reduced almost linearly with the equilibrium pressure as long
Nobakht et al.
as the equilibrium pressure is lower than a threshold pressure.
Once the equilibrium pressure is higher than the threshold
pressure, the measured equilibrium interfacial tension is slightly
reduced. In addition, a total of 13 CO2 coreflood tests are
conducted to study the effects of injection volume of CO2,
injection pressure, and rate on the CO2 enhanced oil recovery
(EOR). The CO2 EOR data versus the injected pore volume of
CO2 at different injection pressures and rates show that, in
general, the CO2 EOR is increased with the injected volume of
CO2. However, the CO2 EOR at a given injection pressure and
rate achieves its maximum after 1.5 pore volume of CO2 is
injected. The detailed experimental data of the CO2 coreflood
EOR versus injection pressure plot at two different injection
rates. The measured CO2 EOR is increased almost linearly with
the injection pressure when the injection pressure is in an
intermediate range. In this case, the measured oil recovery is
found to increase with the CO2 injection rate under the same
injection pressure. Otherwise, the measured oil recovery at a
lower or higher injection pressure remains almost unchanged,
regardless of the injection rate. Finally, the complete capillary
number is calculated and related to the CO2 EOR for each CO2
coreflood test. This experimental study shows that the CO2 EOR
versus complete capillary number plot can be roughly divided
into three regions. In an intermediate range of the complete
capillary number, the oil recovery is increased quickly with the
complete capillary number. Otherwise, the CO2 EOR has an
almost constant lower or higher value if the complete capillary
number is smaller or larger.
Acknowledgment. The authors acknowledge the discovery grant
from the Natural Sciences and Engineering Research Council
(NSERC) of Canada and the innovation fund from the Petroleum
Technology Research Centre (PTRC) at the University of Regina
to Y. Gu.
EF700388A