SPE
International
SPE 88883
Laboratory Investigation of CO2 Flooding
Hao Yongmao, Wu Zenggui, Ju Binshan Chen Yueming, University of Petroleum( East China);
and Luo Xiangjie , Xinjiang Petro. Administrative Bureau Oil Production Technology Research Institute
Copyright 2004, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 28th Annual SPE International
Technical Conference and Exhibition in Abuja, Nigeria, August 2-4, 2004.
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Abstract
Carbon dioxide(CO2) flooding is an efficacious method
of EOR and it is a very complicated process, involving
phase behavior. To master the performance of CO2
flooding and provide accurate data for designing oil
development, a comprehensive investigation of CO2
flooding phase behavior and mechanism based on
laboratory study was conducted. In order to get
representative fluid samples of a reservoir, it was
necessary that the right operation of mixing the
separator oil and gas samples to match the bubble
point pressure be carried out. The result from PVT
experiments shows that for a certain reservoir, through
a slight manipulation of the measured PVT properties
including bubble point pressure, volume factor,
swelling factor, solubility of CO2 and viscosity, it is
possible to obtain regression curves, which can be used
to estimated the PVT behavior for any hydrocarbon
fluid-CO2 mixture of this reservoir. The result of slim
tubule tests indicates that it is more appropriate to
determine the minimum miscibility pressure of the
reservoir fluid-CO2 mixture by the position of inflexion
on the curve of oil recovery with flooding pressure than
by reaching a special oil recovery point.
Society of Petroleum Engineers
Introduction
Carbon dioxide flooding is an effective enhanced oil
recovery process. It appeared in 1930’s and had a great
development in 1970’s. Over 30 years’ production
practice, CO2 flooding has become the leading
enhanced oil recovery technique for light and medium
oils1-4. It can prolong the production lives of light or
medium oil fields nearing depletion under waterflood
by 15 to 20 years, and may recover 15% to 25% of the
original oil in place1.
CO2 flooding process involves very complicated phase
behavior, which depends on the temperature, pressure
and fluids properties of a certain reservoir. Many
factors have been found contributing to the oil recovery
in CO2 flooding. These mainly include5-11:
• low interface tensions;
• viscosity reduction;
• oil swelling;
• formation permeability improvement;
• solution gas flooding;
• density change of oil and water.
R.K Srivastava et al6 took a laboratory study of
Weyburn CO2 miscible flooding. From the PVT data
generated from the three Weyburn reservoir fluid-CO2
mixtures it was showed that viscosity reduction and oil
swelling by CO2 contributed to oil recovery. The
viscosity showed an almost linear decrease with CO2
concentration. A slight manipulation of the measured
PVT properties of the mixtures made it possible to
obtain single property curves for the three Weyburn
oils. This feature can be used to estimate the PVT
behaviour for any Weyburn oil from the reservoir.
2 Hao Yongmao, Wu Zenggui, Ju Binshan, Chen Yueming and Luo Xiangjie
When an oil field becomes a candidate for CO2
flooding, a miscible or near-miscible process is
considered to be the most desirable result. So it is very
important to measure CO2 minimum miscibility
pressure(MMP) accurately. Generally, reservoir oil
composition and temperature are accepted the key
factors which greatly influence the CO2 MMP. While
measuring CO2 MMP at laboratory, keeping the
experiments under reservoir conditions of pressure and
temperature can be easily obtained. Reconstitution of
reservoir fluid, however, is still a procedure needed to
be improved, which may be a primary problem that
introduce errors in measuring MMP. As a result, the
CO2 flooding potential of a given reservoir may be
overestimated or underestimated.
M. Dong et al.1 conducted a series of experiments to
investigate the effect of solution gas on the CO2 MMP
of reservoir fluid and partially flashed reservoir fluid at
reservoir temperature. According to their work, the CO2
MMP dropped nearly 30% from reservoir fluid to stock
tank oil. Their results showed that when the reservoir
oils had a high GOR and high methane content, the
presence of solution gas had a significant effect on CO2
MMP, and should be carefully taken into account while
CO2 MMP was measured by experimental methods.
They also concluded that how CO2 MMP varied with
the solution gas depends on : (1) the amount of the
solution gas in the oil, and (2) the light-to-intermediate
components ratio in the solution gas. In fact, the
multiple-contact miscibility of CO2 with reservoir oil
consists of two processes: vaporizing gas drive and
condensating gas drive, which take placing
simultaneously. Under certain condition, one of the two
processes become dominating and apparently affect the
MMP. If the reservoir oils have a high GOR and high
methane content, vaporizing gas drive will become a
primary mixing mechanism. Owing to vaporization of
more and more methane into gas phase, CO2 MMP
increases , just like an impure CO2 flooding process.
In recent years, there are growing interests about CO2
injection in China. Though the CO2 resources are quite
limited, many CO2 stimulation or flooding tests have
been implemented in many oil fields12-14.
Unfortunately, most of the measured CO2 MMP are
greatly higher than the original reservoir pressure,
indicating obvious immiscible processes. In our opinion,
the measured MMP is somewhat questionable. In this
paper, we will discuss this problem on the basis of
experiments.
This paper took a comprehensive investigation of the
phase behavior and MMP of CO2 flooding based on
SPE 88883
laboratory study. Some mechanism and laws were
advanced, which have helped the field CO2 flooding
programs.
Experimental
In the PVT property experiments, the three-windows,
high pressure, high temperature RUSKA(USA)
experimental equipment for oil properties was used. It
is shown in Figure1, including a displacement pump, a
temperature controller, a viscometer, pressure meters
and oil storage vessels.
The RUSKA 2328-86 slim tube miscible equipment
was used to determine the MMP, which is shown in
Figure 2. The slim tube is a stainless steel snake tubule,
7.94mm in outside diameter, 6.16mm in inside diameter
and 18.29mm in length. The tubule is full of glass
beads, with porosity of 35% and permeability of 15D.
The maximum work pressure is 50MPa and the
maximum work temperature is 116 .
The experimental fluids are the separator oil and gas
samples collected from the Shengli Oil Field of China.
The properties of the reservoir and its fluid are reported
in Table 1 and the result of the gas chromatograph
analysis of the separator oil and gas samples is shown
in Table 2.
Result and Discussion
The preparation of fluid sample
Reconstitution of reservoir fluid is a crucial procedure.
In fact, it is very difficult to get the representative fluid
sample of a reservoir. In this experiment, the separator
oil and gas samples were combined to reconstitute the
reservoir fluid. For the separator oil and gas samples,
there are two important steps which may introduce
errors: (1) the sampling operation; (2) the reconstituting
Gas-Oil Ratio (GOR).
For the separator oil and gas samples, the most
important parameter to reconstitute the reservoir fluid is
the Gas-Oil Ratio. But the GOR measured and given by
oil field is often inaccurate. So it is unreasonable to
combine the separator oil and gas samples by GOR.
For example, when M. Dong et al.1 researched the
effect of solution gas in oil on CO2 Minimum
Miscibility Pressure, the GORs of both reservoir fluid
and separator oils were measured as 30 m3/ m3. But on
the basis of field-producted GOR data and pool
operators’ suggestions, they combined the separator oil
and gas samples to GORs of 131 m3/ m3 and 82 m3/ m3.
3 Laboratory Investigation of CO2 Flooding
In some oil fields of China, because of the limitation of
field conditions or the negligence of the operators the
separator oil and gas samples were sometimes
substituted by the dead oil and casing tube gas samples.
The dead oil and casing tube gas samples obtained by
the field men were combined in the laboratory to obtain
the reservoir fluid according to the production GOR.
This may result in unrepresentative recombination
samples of the reservoir. For example, the measured
CO2 MMPs in China were usually very high.
The bubble point pressure of oil is another important
property of oil. It is sensitive to the GOR. The
measured curve of the bubble point pressure with GOR
is shown in Figure 3. With the increase of the GOR, the
bubble point pressure is also increasing. The bubble
point pressure can be easily and accurately determined.
So the better method to get eligible reservoir fluid is
mixing the separator oil and gas samples to match the
bubble point pressure.
In this experiment, the GOR given by oil field is 87 m3/
m3. Based on this GOR, the measured bubble point
pressure is 20.5 MPa for the reconstituted reservoir
fluid, which is apparently contradictory to 11.4 MPa
given by the field. In order to get the representative
reservoir fluid, the separator oil and gas samples were
combined to GOR of 44 m3/ m3. The corresponding
measured bubble point pressure is 11.7 MPa, which is
very close to the 11.4 MPa.
PVT Properties of Reservoir Fluid-CO2
Mixtures
The reconstituted reservoir fluid was recombined with
CO2 at a concentration range from 25.20 mol% to 62.83
mol%. PVT properties of each reservoir fluid-CO2
mixture were measured. Through the swelling
behaviour and reduction in viscosity of the mixture, the
mechanism of CO2 flooding was investigated.
Figure 4 shows the P-V curves with CO2 concentrations.
When the CO2 concentration is lower, there is a clear
inflexion on each curve. This means that the gas phase
appears at the inflexion and the pressure at the inflexion
is the bubble point pressure. With the increase of the
CO2 concentration, the clear inflexion on the curve
disappears. While the CO2 concentration reaches 62.83
mol%, the bubble point pressure can not be directly
determined from the P-V curve. That is to say the
reservoir fluid and CO2 reaches the one-contact
miscible state at the CO2 concentration of 62.83 mol%.
Many papers reported the similar critical CO2
concentration: Weyburn reservoir (60 mol%)6•Jilin Oil
Field (65 mol%)12, Jiangsu Oil Field (62 mol%)14 and
SPE 88883
Shengli Oil Field (59 mol%)13. A conclusion can be
drawn that the reservoir fluid and CO2 can normally
reach the one-contact miscible state above the CO2
concentration of 60 mol%.
From the measured P-V data, the bubble point pressure
(BPP), the formation volume factor, the swelling factor
and the solubility of CO2 with CO2 concentrations were
calculated and shown in Figure 5 to Figure 8. The
formation volume factor (FVF) is the ratio of the
volume of the mixture at the saturation pressure and the
reservoir temperature and the volume of the oil at 1 atm
and 15•. The swelling factor (SF) is the ratio of the
volume of the mixture at the saturation pressure and the
reservoir temperature and the volume of the oil at the
reservoir pressure and the reservoir temperature. For
this test, the swelling factor is as high as 1.4. This
means that CO2 can greatly swell oil and contribute to
the oil recovery.
There are curves of several other oil fields in Figure 5
to Figure 8. R.K Srivastava et al.6 noted that for the
three Weyburn reservoir fluids, if using the relative
bubble point pressure(BPP of mixture – BPP of
reservoir fluid) and the normalized FVF(normalized by
FVF of the reservoir fluid), the data points of the
relative BPP, the normalized FVF, the SF or the
solubility of CO2 with CO2 concentration nearly
collapse to a single curve. These curves can be used for
estimating the BPP, the FVF, the SF or the solubility of
CO2 of any unknown Weyburn reservoir oil-CO2
mixture.
Comparing these curves in Figure 5 to Figure 8, it is
noted that their shapes are very similar. So the
conclusion of R.K Srivastava et al. can be extended: for
different oil samples of a certain reservoir, the curves
of the relative BPP, the normalized FVF, the SF or the
solubility of CO2 with CO2 concentration are similar. A
single curve can be regressed and can be used to
estimate the BPP, the FVF, the SF or the solubility of
CO2 of any unknown oil-CO2 mixture in the reservoir.
The pressure dependence of the viscosity of the
reservoir fluid-CO2 mixtures at six CO2 concentrations
is shown in Figure 9. The injection of CO2 can lower
the viscosity from 0.89 mPa·s to 0.60 mPa·s. The
statistic data indicate that the injection of CO2 can
lower the viscosity by 10%-70%. The reduction in
viscosity is an important factor on improving the oil
recovery.
Relative viscosity is defined as the viscosity normalized
to the initial reservoir fluid viscosity. Figure 10 shows
the relative viscosity with CO2 concentration. Similarly,
the conclusion of R.K Srivastava et al.6 can be extended:
for different oil samples of a certain reservoir, the
4 Hao Yongmao, Wu Zenggui, Ju Binshan, Chen Yueming and Luo Xiangjie
curves of the relative viscosity with CO2 concentration
can be regressed to get a single curve, which can be
used to estimate the viscosity of any unknown oil-CO2
mixture in the reservoir.
Slim tubule tests
Slim tubule tests were performed to determine the CO2
minimum miscibility pressure(MMP) for the Shengli
Oil Field reservoir fluid. The MMP is the pressure at
which the reservoir fluid is expected to develop multi-
contact miscibility with CO2. It is the most important
factor in flooding process and determine the reservoir
operating pressure6.
The geometrical shape and flooding parameters of the
slim tubule have important effect on the oil recovery5.
A perfect slim tubule should provide the process of
one-dimensional and indiffusible flooding. So the
outside diameter of the filled material should be smaller
than the 1/10 of the inside diameter of the slim tubule.
Carbon dioxide - CO2- should be injected at the top and
the injection speed should be kept between 1.5 m/h and
2.5m/h.
The breakthrough point of CO2 must be monitored at
any moment during the flooding process. The
monitoring methods may include:
• observing the color changement of the
production fluid through the inspecting
window;
• paying attention to the reading of the gas
flowmeter: it means CO2 has broken through if
the reading rises up abruptly;
• taking a view of the reading of the pressure
meter on the pump: it means CO2 has broken
through if the reading descends abruptly;
The MMP is customarily defined as the pressure at
which the oil recovery reaches 80% when CO2
breakthroughs or the final oil recovery reaches 90-95%5.
But the oil recovery relates to the slim tubule shape and
the operation condition. The oil recovery may be only
80% when the miscibility has reached. The oil recovery
increases with the flooding pressure; but the increase
in range is very small at the MMP. So it is more
appropriate to determine the minimum miscibility
pressure of the reservoir fluid-CO2 mixture by the
position of inflexion on the curve of oil recovery with
flooding pressure than by reaching a special oil
recovery point. That is to say the pressure at the
inflexion point of the curve is the MMP.
Figure 11 shows the measured oil recovery curve with
the flooding pressure. Using the above rule, the MMP
is determined as 26 MPa, which is lower than the
SPE 88883
reservoir pressure. So the miscible CO2 flooding can be
actualized in this reservoir.
Conclusions
The following conclusions can be drawn from the
results of the above laboratory investigation of CO2
flooding:
1. The better method to get eligible reservoir fluid is
mixing the separator oil and gas samples to match
the bubble point pressure.
2. The reservoir fluid and CO2 can normally reach
the one-contact miscible state above the CO2
concentration of 60 mol%. The oil swelling and
the reduction in viscosity are the main factors to
enhance the oil recovery in CO2 flooding.
3. For different oil samples of a certain reservoir, the
curves of the relative BPP, the normalized FVF,
the SF, the solubility of CO2 or the relative
viscosity with CO2 concentration can be regressed
to get a single curve. These curves can be used to
estimate the PVT properties of any unknown oil-
CO2 mixture in the reservoir.
4. It is more appropriate to determine the minimum
miscibility pressure of the reservoir fluid-CO2
mixture by the position of inflexion on the curve
of oil recovery with flooding pressure than by
reaching a special oil recovery point.
References
1. M. Dong, S. Huang and R. Srivastava, “Effect of
Solution Gas in Oil on CO2 Minimum Miscibility
Pressure”, JCPT(November 2000)53.
2. HSU, C.F., Koinis, R.F. and Fox, C.E, “Technology,
Experience Speed CO2 Flood Design”, Oil and Gas
Juurnal(October 1995)51.
3. Grigg, R.B. and Schechter, D.S., “State of the
Industry in CO2 Floods”, paper SPE 38849 presented
at the SPE Annual Technical conference and
Exhibition held in San Antonia, TX. 5-8 October,
1997.
4. M. Dong, S.S. Huang and R. Srivastava, “A
Laboratory Study on Near-Miscible CO2 Injection in
Steelman Reservoir”, JCPT(February 2001)53.
5. Ali Danesh, PVT and Phase Behaviour of Petroleum
Reservoir Fluids, Elsevier, 1998.
6. R.K Srivastava, S.S. Huang and M. Dong,
“Laboratory Study of Weyburn CO2 Miscibile
Flooding”, JCPT(February 2000)41.
 5 Laboratory Investigation of CO2 Flooding SPE 88883

7. Mark A.Klins, Carbon Dioxide Flooding Basic

Mechanisms and Project Design, International Table 1: The properties of the reservoir and its fluid
Human Resources Development Corpration, 1984. Reservoir Depth 3143-3152 m
8. Huang. S.S., De Wit.P., Srivastava R.K and Jha. Reservoir Pressure 31.56 MPa
K.N., “A Laboratory Miscible Displacement Study Reservoir Temperature 116
for the Recovery of Saskatchewan’s Crude Oil”, Saturation Pressure 11.4 MPa
JCPT(April 1994)43. Gas-Oil Ratio 87.2 m3/ m3
9. Huang. S.S. and Dyer. S.B., “Miscible Displacement Density 714.6kg/ m3
in the Weyburn Reservoir -- A Laboratory Study”, Viscosity 0.89 mPa·s
JCPT(September 1993)42.
10. Metcalfe R.S. and Yarborough L., “The Effect of Table 2: The result of the gas chromatograph
Phase Equilibrium on the Displacement Mechanism”, analysis
SPEJ(August 1979)242. Gas Oil Fluid
11. Shyeh-Yung, J.-G. J., “Mechanisms of Miscible Oil Componet
(mol%) (mol%) (mol%)
Recovery: Effect of Pressure on Miscible and Near- N2 1.71 0.00 0.556
Miscible Displacements of Oil by Carbon Dioxide”,
CO2 2.60 0.00 0.847
SPE 22651 presented at the SPE Annual Technical
CH4 72.45 0.00 23.586
Conference and Exhibition held in Dallsa, TX,
C2H6 10.45 0.00 3.401
October 6-9, 1991.
12. Laboratory Investigation Report of Jilin Oil Field C3H8 8.08 0.00 2.629
CO2 Flooding, 2001, University of Petroleum ,China. i-C4H10 0.71 0.00 0.231
13. Laboratory Investigation Report of Shengli Oil Field n-C4H10 2.40 0.00 0.782
CO2 Flooding, 1997, University of Petroleum ,China. i-C5H12 0.43 0.00 0.139
14. Li Yanhui, High Pressure Properties of Injecting Gas n-C5H12 0.59 0.24 0.350
Reservoirs and Enhanced Oil Recovery, doctorial C6H14 0.59 4.39 3.156
thesis of University of Petroleum ,China, 1998.2 C7H16 0.00 5.29 3.569
C8H18 0.00 7.30 4.924
C9H20 0.00 5.64 3.807
C10H22 0.00 6.52 4.398
C11+ 0.00 70.61 47.626
6
Total 100.0 100.0 100.0
8 9 10 11
Bubble Point Pressure,

22
5 3
2 19
1
MPa

12 16
7 13
13
4
Figure1: RUSKA experimental equipment for oil
10
properties
40 50 60 70 80 90
GOR,m3/m3

Figure 3: Bubble point pressure with gas-oil ratio

Figure2: RUSKA experimental equipment for slim

tubule test
 6 Hao Yongmao, Wu Zenggui, Ju Binshan, Chen Yueming and Luo Xiangjie SPE 88883

1.5 320

3
solubility of CO2 , m /m
0.00% Shengli
280

3
1.4 25.20%
Jilin
Relative Volume
30.03% 240
1.3 Weyburn1
39.61% 200
47.86%
Weyburn2
1.2 160
55.07% Weyburn3
1.1 62.83%
120
80
1.0
40
0.9 0
5 10 15 20 25 30 35 0 10 20 30 40 50 60 70
Pressure, M Pa
CO2 concentration, mol%
Figure 4: P-V curves with CO2 concentration
Figure 8: Solubility of CO2 with CO2 concentration
35 Shengli
Jilin
1.2 0.00%
30 Jiangsu 25.20%
1.1 30.03%

Viscosity• mPa.s
25 Wey burn1
BPP, MPa

Wey burn2 47.86%

1.0
20 Wey burn3 55.07%

0.9 62.83%
15
10 0.8
5 0.7
0
0.6
0 10 20 30 40 50 60 70 80
0 5 10 15 20 25 30 35
CO2 concentration• mol%
Pressure, MPa
Figure 5: BPP with CO2 concentration
Figure 9: Viscosity as a function of pressure
1.8 Shengli Shengli
1.7 Jilin 1.0 Jilin
1.6 Wey burn1 Jiangsu
Relative viscosity

0.8
1.5 Wey burn2 Wey b1
FVF

Wey burn3
1.4 0.6
Wey b2
Wey b3
1.3
1.2 0.4
1.1
0.2
1.0
0 10 20 30 40 50 60 70 0.0
CO2 concentration• mol% 0 10 20 30 40 50 60 70 80
CO2 concentration,mol%
Figure 6: FVF with CO2 concentration
Figure 10: Relative viscosity with CO2 concentration
1.7
Shengli 100
1.6
Jilin
1.5 Jiangsu
oil recovery, %

Weyburn1 90
1.4
SF

Weyburn2
1.3 Weyburn3
80
1.2
1.1
70
1.0
0 10 20 30 40 50 60 70
60
CO 2 concentration• mol%
23 24 25 26 27
Figure 7: Swelling factor with CO2 concentration flooding pressure, MPa
Figure 11: Oil recovery with flooding pressure