SPE 89477

Effect of CO2 Impurities on Gas-Injection EOR Processes

P.Y. Zhang, SPE; S. Huang, SPE; S. Sayegh, SPE, Saskatchewan Research Council
X.L. Zhou, Protroleum Technologies Ltd.

Copyright 2004, Society of Petroleum Engineers Inc.

also from an environmental point of view. CO2 flooding can
This paper was prepared for presentation at the 2004 SPE/DOE Fourteenth Symposium on significantly increase oil recovery from depleted reservoirs
Improved Oil Recovery held in Tulsa, Oklahoma, U.S.A., 17–21 April 2004.
and be eligible for greenhouse gas credits due to CO2
This paper was selected for presentation by an SPE Program Committee following review of
information contained in a proposal submitted by the author(s). Contents of the paper, as
sequestration. A good example of this is the CO2 flood in the
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to Weyburn field in southeastern Saskatchewan, Canada. The
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at construction of a CO2 pipeline to deliver large amounts of CO2
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
from North Dakota to the Weyburn area greatly improved the
for commercial purposes without the written consent of the Society of Petroleum Engineers is feasibility and the economics of this CO2 flooding venture.
prohibited. Permission to reproduce in print is restricted to a proposal of not more than 300
words; illustrations may not be copied. The proposal must contain conspicuous It was reported that CO2 flooding is not sensitive to
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. reservoir lithology, but it is sensitive to reservoir oil
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
characteristics.[1] In general, reservoirs that have performed
well under waterflooding typically will perform well with CO2
Abstract flooding. For gas injection projects, two different
Carbon dioxide flooding is a promising enhanced oil recovery displacement mechanisms—miscible and immiscible—can
method both on technical and, if operating costs are properly occur when CO2 is injected into an oil-containing porous
controlled, economic grounds. Injecting this greenhouse gas medium. In miscible flooding, which is an ideal displacement
also has environmental merits. Flue gas from power plants is a mechanism for enhanced oil recovery (EOR), multiple-contact
ready source of CO2; however extracting CO2 for enhanced oil miscibility between the injected gas and oil can be achieved at
recovery from such a source will increase project costs. pressures above the minimum miscibility pressure and below
Furthermore, to reduce both the net CO2 utilization and the the first contact miscible pressure. If the injected fluid is
cost of purchasing gas, it is usually necessary to recycle the miscible with the reservoir oil, the interfacial tension at the
produced CO2 with as little purification as possible. Therefore, displacing front is zero, and the capillary forces that trap the
understanding the roles of impurities in fluid phase behaviour oil in the reservoir rocks disappear. Thus, the relative
and miscibility characteristics is necessary for designing a permeability becomes irrelevant resulting in an efficient
cost-effective CO2 enhanced oil recovery process. displacement. The MMP is a very important parameter that is
Laboratory studies of the effect of CO2 impurities on required in a well-designed CO2 flood project. If it is operated
phase equilibrium and minimum miscibility pressure (MMP) well below the MMP, the miscibility between the oil and the
were conducted on two Saskatchewan light oils covering a injected gas will most likely not be achieved, and the above-
range of densities from 29.5°API to 38°API. The results mentioned advantages will not be available. In this case, oil
indicate that the MMP for these light oils could increase recovery will be less than that at pressures near or above the
unfavourably as the N2 and/or CH4 concentration increased in MMP. Therefore, to properly design a CO2 EOR project, it is
the CO2 stream. The MMP changes as the type and necessary to have a good knowledge of the thermodynamic
concentration of impurities in the injected CO2 stream change. properties of the oil–gas mixtures and completely understand
However, coreflood tests showed that the near-miscible CO2 the physical and chemical mechanisms involved in oil and
displacement might employ the same mechanisms as miscible gas miscibility.
CO2 flooding to mobilize and displace oil; thus, good oil Unfortunately, CO2 sources are rarely pure; the most
recovery can be achieved in the vicinity of the MMP. While likely CO2 source is usually a stream extracted from the flue
laboratory measurements are essential in the evaluation of a gas of a power plant, which contains a certain concentration of
gas injection process, an equation of state (EOS) simulation N2 and other gases. Purifying the flue gas will increase
was demonstrated to be a useful tool in analyzing the phase operating costs significantly. In addition, to reduce the net
behaviour of various injection gases, reservoir fluids, and the CO2 utilization and the cost of purchasing CO2, field
gas-oil interactions. operations often employ staged floods and recycle the
produced gas, which usually contains CH4, without processing
Introduction it. Key questions are: How can a flooding process maintain
Carbon dioxide gas flooding, when properly designed, has miscibility if flue gas or produced gas is added to the CO2
proven to be one of the most promising tertiary oil recovery injection stream? Under what kind of operating conditions can
technologies, not only on technical and economic grounds, but the miscibility between the injected solvent and the reservoir
2 SPE 89477

oil be maintained without risking the entire miscible flooding combination with CO2 mixed with Steelman reservoir fluid
project? In general, contamination of the CO2 injection stream were studied to compare the effect on MMP of using the
by N2 or CH4 could substantially increase the CO2 MMP, hydrocarbon gas in the CO2 stream.
while the presence of H2S, C2H6, or intermediate hydrocarbons
(such as C3 or C4) can reduce the CO2 MMP.[2] Coreflood Procedures. Three coreflood tests were conducted
Studies aimed at addressing the effect of impure CO2 using Weyburn reservoir fluid to investigate the oil recovery
streams on the MMP were carried out at Saskatchewan behaviour resulting from CO2 injection. The ultimate oil
Research Council (SRC) with light oils mixed with pure or recoveries of the tests at operating pressures above, near, and
impure CO2. The primary effort was focused on measuring the below the measured MMP at 59°C were compared. These data
minimum miscibility pressure and saturation pressures were later used for numerical simulation to predict the field
(pressure-composition phase diagrams) for these mixtures. It recovery at Weyburn. All coreflood tests were conducted in a
is beneficial to measure the effects of impure CO2 streams on linear core displacement mode. The coreflood system consists
the miscibility because CO2 sources diluted by impurities are of a core holder, an injection system, a production system and
common in practice and can substantially improve the a data acquisition system. More details of the coreflood
economic prospects of an EOR project. apparatus can be found in previous SRC papers and reports.[8-
12]
In addition, gravity-stable CO2 displacement tests with After preserved Marly composite cores were saturated with
composite reservoir cores were conducted to evaluate the the dead oil and aged to re-establish wettability, the
flood efficiency at pressures above, near and below the MMP reconstituted Weyburn reservoir fluid was injected to displace
for tertiary oil recovery of the Weyburn light oil. the dead oil. The live oil injection was continued until the
produced gas−oil ratio (GOR) was constant and equaled that
Experimental Details of the originally injected reservoir fluid. Following the live oil
Phase Behaviour, MMP and Saturation Pressure Studies. injection, the initial waterfloods were carried out in a
The pressure–volume–temperature (PVT) properties, the horizontal model, whereas the tertiary CO2 injections were
MMP, and the bubblepoint pressure of an oil–CO2 mixture conducted in a gravity-stabilized (vertical downward
depend on the oil characteristics and the reservoir temperature. direction) mode. After the coreflood tests, the plugs were
Therefore, laboratory procedures are very important for cleaned by Dean-Stark Analysis to determine the residual oil
evaluating various oil–CO2 mixtures under simulated and water saturations. The final oil recovery and connate
reservoir conditions. water saturation of the composite cores were determined by
Two light oils were collected from Weyburn and material balance.
Steelman fields in southeast Saskatchewan and used to
investigate the effects of CO2 impurity on solubility, PVT Results and Discussion
properties, and MMP behaviour. The samples were Effect of Gas Solvent on Saturation Pressure of Mixture.
characterized physically and chemically. Basic sediment and Measurement of the solubility of injection gases in oils is the
water in the oil was removed by high-speed centrifugation. basis of the so-called “swelling tests”. These tests also provide
The data, along with the molecular weight and chemical the opportunity of measuring some of the physical properties
composition, are listed in Table 1. The stock tank oils from of these mixtures, such as their densities, swelling factors, and
Weyburn and Steelman fields had API oil gravity of 29.5° and viscosities. These data are essential for characterizing fluids in
38°API, and asphaltene contents of 6.7% and 1.0% by equation of state simulations, and help understand the various
weight, respectively. oil recovery mechanisms, such as swelling and
The PVT properties and MMP of the oils mixed with pure viscosity reduction.
CO2 and contaminated CO2 as injection gases were The saturation pressures of several mixtures of the
investigated. The MMP experiments were conducted in the Weyburn reservoir fluid as a function of gas solvent (pure and
rising bubble apparatus (RBA) at the reservoir temperature of impure CO2) concentration at 59°C were measured and are
59°C for Weyburn reservoir fluid, and 61°C for Steelman field plotted in Figure 1. The figure depicts an almost linear
stock tank oil. Details of the RBA and experimental increase in saturation pressure of the fluid mixture with
procedures can be found in previous SRC papers and addition of CO2 to the reservoir fluid. The saturation pressure
reports.[3-7] Table 2 shows the measured minimum miscibility increased from 5.5 MPa at 23.9 mol% CO2 loading, to 8.49
pressures for the two light oils using nine different gases, of MPa at 44.1 mol% CO2.
which the compositions are also listed in the table. The most likely source of CO2 for field flooding projects
CO2 streams containing C2 or C3 were also used in the gas is that extracted from stack gas, followed by oilfield-produced
flooding process to study the MMP reduction from the pure gas. These gas streams have nitrogen and methane as the
CO2 and the oil. Such a reduction of MMP is beneficial when predominant components. To reduce operating costs, it is
an adjustment is required to maintain miscibility in the field expected that the produced CO2 from the field can be recycled
injection process. The experiments found that the CO2 MMP and reinjected without further purification. The curves in
of Steelman reservoir fluid was 16.5 MPa at 67°C. This Figure 1 indicate that the saturation pressures increased
pressure was considered too high for gas injection in the field. greatly when CO2 was contaminated by N2 and CH4. For
It was decided to bring down the CO2 MMP to a desirable example, whereas the saturation pressure of Weyburn
operating pressure through enrichment of the injection gas. reservoir fluid containing about 58 mol% CO2 was 10.8 MPa,
Two types of hydrocarbon solvents (C2H6 and C3H8) in it rose to 13 MPa when the CO2 was contaminated by 9.9
SPE 89477 3

mol% CH4. When the impurity in the CO2 stream consisted of The MMPs at these three locations in the Weyburn reservoir
5.1 mol% N2 + 5.1 mol% CH4, the saturation pressure was as are also presented in Figure 4. Under the same temperature
high as 16.3 MPa. All three mixtures had essentially the same (59°C) condition, the CO2 MMPs at the north well (12-25-6-
reservoir fluid/gas molar ratio: ~42/58 (reservoir fluid to gas). 14 W2M) and at the east well (14-17-6-13 W2M) were 11.5
The experimental results indicate that CH4 in the CO2 stream MPa and 12 MPa, respectively. However, the CO2 MMP was
is less effective than N2 in raising the saturation pressure of as high as 15.4 MPa at the south well (8-12-6-14 W2M). The
Weyburn reservoir fluid. different oil properties resulted in noticeably different CO2
Figure 2 shows a comparison of saturation pressure MMPs within the Weyburn reservoir, wherein the lighter oils
changes with pure CO2 and with a CO2–C2H6 mixture as (high API gravity) have lower MMPs than the heavier oils
solvents in Steelman reservoir fluid. Because the reservoir (lower API gravity).
fluids were reconstituted from two separate oil samples For a CO2 EOR project, determining the CO2 MMP and
collected from two wells, which resulted in having two the level of contaminants the CO2 stream can tolerate are key
baseline live oil saturation pressures, the saturation-pressure factors in the technical success of the EOR project and its
increase ratio versus the solvent concentration is reported here. economics feasibility. Table 2, and Figure 5 summarize the
The saturation-pressure increase ratio is defined as: MMP behaviour of Weyburn reservoir fluid with pure CO2
P mixture − P liveoil and three impure CO2 solvent compositions (referred to as
Ratio = sat sat × 100 Gas-2 to Gas-4).[7] The MMP for the Weyburn reservoir fluid
P liveoil with these impure CO2 solvents at 59°C varied from 14.5 MPa
sat to 20.5 MPa. These results indicate that pure CO2 and impure
The two curves in Figure 2 show clearly that the CO2 containing up to 9.9 mol% CH4 or 3.1 mol% N2 + 2.8
saturation pressure increased much faster using CO2 as mol% CH4 are promising EOR solvents owing to their
injection gas than using a mixture of 60 mol% CO2 + 40 mol% relatively low miscibility pressure compared to the reservoir
C2H6. For example, at a solvent concentration of 50 mol%, the pressure. However, when N2 contamination in the CO2 stream
saturation-pressure increasing ratio for solvent CO2 was was increased to 5.1 mol% in combination with 5.1 mol%
116%, which is almost twice the value for the CO2 + C2H6 CH4, the MMP rose above the reservoir fracture pressure.
mixture. The results suggest that CO2 in combination with The MMP measurements for the Steelman stock tank oil[3]
intermediate hydrocarbons, such as ethane, is a favourable with six gases (CO2, Gas-5 to Gas-9) are also listed in Table 2.
solvent for controlling the rise of the saturation pressure of the The results in Figure 6 show that the presence of SO2 and H2S
fluid systems. in the CO2 gas stream can reduce the CO2 MMP, whereas N2
and O2 tend to have the opposite effect. It indicates that an
Effect of Gas Solvent on MMP. Minimum miscibility impurity may decrease the CO2 MMP if it enhances the
pressure has been used as an essential criterion for screening solubility of the driving gas.
and selecting reservoirs for the miscible displacement process. If the CO2 minimum miscibility pressure is too high, i.e.
For CO2 injection projects, it has been recognized that the CO2 close to the reservoir fracture pressure, it will be impossible to
MMP is not sensitive to reservoir lithology, but depends upon apply a miscible EOR process. In this case, some intermediate
the purity of CO2, reservoir oil characteristics, and hydrocarbon gas solvents can be added to the CO2 stream to
reservoir temperature. bring the CO2 MMP down to a reasonable level. Figure 7
The MMP of pure CO2 with the Weyburn reservoir fluid illustrates the MMP measurements for two hydrocarbon gas
was determined by using a rising bubble apparatus. A distinct solvents mixed with Steelman reservoir fluid.[10] The MMP of
pattern was depicted by the CO2 bubbles (see Figure 3). The 16.5 MPa for pure CO2 decreased by nearly 25% for the
left photo in Figure 3 shows the shape of a rising bubble at a addition of about 16 mol% propane (C3H8) in CO2, and by
pressure below the MMP. The tail formation on the bubble approximately 45% for the addition of 37 mol% propane in
shown in the right photograph indicates a dramatic reduction CO2. In comparison, even when 40 mol% ethane (C2H6) was
in the interfacial tension and the diminishing interface added to the CO2 stream, the MMP was determined to be 13.6
between the CO2 phase and the oil phase as the pressure rises MPa, a reduction of only 18% from the MMP with pure CO2.
above the MMP. The larger reduction in CO2 MMP for propane than for ethane
Because of the depositional environment of Weyburn at the same hydrocarbon concentration in CO2 indicates that
reservoir, the oil-bearing strata dip from north (shallow depth) propane is a more effective enriching agent for CO2
to south (substantially deeper). The depth of the reservoir on than ethane.
the west side is deeper than on the east side. The oil
characteristics can be significantly different within the EOS Simulation. An EOS simulation package[13] with the
reservoir area. The measurements from previous SRC tests[7, required functionalities and an extensive standard component
12]
on samples collected from three different locations are library was utilized for tuning and matching the experimental
mapped in Figure 4. The stock tank oil density was as high as results and predicting the MMP with respect to various
885.3 kg/m3 (28.3°API) at the south well (8-12-6-14 W2M) injection gases with impurities. The Peng-Robinson (PR)
and as low as 861.9 kg/m3 (32.7°API) at the north well (12-25- equation of state model was used in this work. The MMP
6-14 W2M). At the east well (14-17-6-13 W2M) the density algorithm is based on the tie-line intersection approach[14,15]
was measured to be 884.0 kg/m3 (29.5°API). that calculates the minimum miscibility pressure analytically
when an equation of state model is defined.
4 SPE 89477

For Weyburn oil, the available experimental data are the As discussed in the previous section, the CO2 MMP for the
saturation pressure of the reservoir fluid and the swelling test Weyburn reservoir fluid was determined to be 11.5 MPa.
results with the injection gas, which provide the measured Therefore, the CO2 injection pressures selected for the
saturation pressure points at selected solvent concentrations in coreflood tests were 10 MPa (below the MMP, Run 5), 12
the mixture. Since all data involved are related to the fluid MPa (near and at the MMP, Run 4), and 16 MPa (above the
phase behaviour, only saturation pressure points were selected MMP, Run 2).
for the tuning processes. The plus fraction C6+ of the original Figure 9 presents the cumulative oil recovery as a
reservoir fluid was first characterized into five pseudo- function of pore volumes of fluid injected for the three tests. It
components using its molecular weight and specific gravity. should be noted that all these total (or ultimate) oil recovery
Typically, in the compositional analysis, the heavy end values include the initial waterflood, CO2 and extended
compositions are corrected by using the stabilized stock tank waterflood (EWF) stages. Figure 10 is a comparison of
oil molecular weight measured using the freezing point enhanced oil recovery (CO2 plus EWF stages only) expressed
depression method. The molecular weight measurement as residual oil in place for the tests. Overall, the 12 MPa flood
usually has an error in the range of 10%, which implies that it (Run 4) exhibited the highest tertiary (57.0% ROIP or 29.9%
is adequate to adjust the plus fraction molecular weight by IOIP) and total oil recovery (77.3% IOIP). The coreflood
10%. In this simulation, 4.2% of the plus fraction molecular conducted at 10 MPa (Run 5) displayed the lowest tertiary
weight was added to improve the tuning results of the EOS (39.1% ROIP or 21.5% IOIP) and total oil recovery (66.5%
model. Using the automatic regression function, the model IOIP). Run 2 carried out at 16 MPa showed tertiary (46.4%
was tuned to match the pressure-composition (P-x) data ROIP or 25.9% IOIP) and total oil recovery (70.1% IOIP)
resulting from the swelling test given in Figure 8. The comparable to but slightly lower than that obtained for the 12
selected regression parameters include the critical pressure, MPa run, possibly because of the considerably smaller CO2
critical temperature and accentric factor of the heaviest slug size. These test results indicate that the tertiary CO2 flood
pseudo-component, and all binary interaction coefficients. All conducted at pressures near or above the MMP would result in
P-x data matched the experimental results very well as shown a higher oil recovery than those conducted below the MMP.
in Figure 8. The tuned model was then used for calculating the
MMPs of the oil−gas system. The calculated MMP results are Conclusions
compared in Table 2. All MMP predictions were consistent The following conclusions can be drawn on the basis of
with the experimental measurements, except the system with experimental and theoretical studies presented above.
5.1% N2 for which the MMP is slightly off. All calculations 1. The minimum miscibility pressure for Weyburn reservoir
show the miscibility mechanism as combined vaporizing fluid with CO2 containing about 10% impurity can
and condensing. increase by 70% from 11.8MPa to 20.5MPa. The MMP is
For Steelman stock tank oil, there were no phase a strong function of the impurity in the CO2 stream and
behaviour data available for tuning the EOS model. reservoir oil characteristics.
Nevertheless, the EOS model can predict the MMP for the oil 2. Pure CO2 and impure CO2 containing up to 9.9 mol% CH4
system with the various gas mixtures listed in Table 2 using or 3.1 mol% N2 + 2.8 mol% CH4 are promising solvents
default parameter values. The C6+ fraction of the dead oil, for enhanced oil recovery in the Weyburn field because of
which amounts to over 96% of the oil composition, was again their relatively low MMP. However, any further
characterized into five pseudo-components using its molecular contamination would make it necessary to further purify
weight and specific gravity. Applying similar reasoning as the CO2 or enrich it with intermediate hydrocarbon gases.
above, 2.3% of the plus fraction molecular weight was added 3. For Steelman oil, the addition of hydrocarbon gas in the
to improve the prediction results of the model. It was found CO2 stream was shown to reduce the MMP. Carbon
that setting all binary interaction coefficients relating to CO2 dioxide containing 37 mol% propane reduced the pure
to zero can improve the MMP prediction with pure CO2. The CO2 MMP by 45%. Propane was a more effective
same EOS model was used to predict the MMPs with different enriching agent in the CO2 stream than ethane for
solvent mixtures. The results are compared in Table 2. The MMP reduction.
Steelman oil MMPs with pure CO2, CO2 + H2S, and CO2 + 4. EOS simulation was demonstrated to be an effective tool
SO2 are adequate, while the MMPs with the remaining three in analyzing the miscibility of oil−gas systems. A tuned
gas streams show significant discrepancies, which appear to EOS model adequately predicted the MMP with various
have some correlation with the existence of N2 in the gas injection gases when they were within the tuning scope.
stream. The gas streams containing H2S and SO2 appear to be The by-product of the MMP calculation was the ability to
able to reduce the MMP value, which is consistently determine the miscibility mechanism of the fluid system.
demonstrated in the EOS results. All calculations show the 5. The gravity-stabilized tertiary CO2 floods using the
miscibility mechanism as combined vaporizing stacked composite Weyburn core showed that floods
and condensing. conducted at near or above the MMP are likely to result in
a higher oil recovery than that conducted below the MMP.
Effect of Miscibility on Oil Recovery. Three gravity- Near-miscible CO2 displacement can result in good
stabilized tertiary CO2 coreflood experiments (Runs 2, 4, and oil recovery.
5) using the stacked composite Weyburn cores (preserved/
restored) were conducted to determine the effect of injection
pressure, (above, near and below the MMP) on oil recovery.
SPE 89477 5

Acknowledgment
The authors wish to express their thanks to Saskatchewan
Research Council for permitting publication of this paper.
Acknowledgment is gratefully extended to B. Tacik for her
assistance in the preparation of the manuscript.

References
1. “CO2 Flooding Increase Recovery,” www.pttc.org/solution/
12.htm, July 9, 2003.
2. Alston, R.B., Kokolis, G.P. and James, C.F.: “CO2 Minimum
Miscibility Pressure: A Correlation for Impure CO2 Streams and
Live Oil Systems,” Society of Petroleum Engineers Journal,
(April 1985).
3. Huang, S. and Dong, M.: “Potential of Greenhouse Gas Storage
and Utilization through Enhanced Oil Recovery,” Saskatchewan
Research Council Publication No. P-110-468-C-99,
(September 1999).
4. Huang, S. and Dyer, S.B.: “Miscible Displacement in the
Weyburn Reservoir − A Laboratory Study,” Journal of
Canadian Petroleum Technology, (September 1993), 42−52.
5. Srivastava, R.K. and Huang, S.: “New Interpretation for
Determining Minimum Miscible Pressure by Rising Bubble
Apparatus for Enriched-Gas Drives,” SPE 39566 presented at
the 1998 SPE India Oil and Gas Conference and Exhibition held
in New Delhi, India, April 7-9, 1998.
6. Dong, M., Huang, S., Schnell, B. and Meyer, G.: “Analysis of
Miscibility Development by Rising Bubble Technique for CO2
Miscible Injection,” paper CIM 200-37 presented at the
Petroleum Society’s Canadian International Petroleum
Conference 2000, Calgary, June 4-8, 2000.
7. Dong, M., Huang, S., Dyer, S.B., and Mourits, F.M.: “A
Comparison of CO2 Minimum Miscibility Pressure
Determinations for Weyburn Crude Oil,” Journal of Petroleum
Science and Engineering (2001) 31, 13-22.
8. Srivastava, R.K. and Huang, S.: “Technical Feasibility of CO2
Flooding in Weyburn Reservoir − A Laboratory Investigation,”
Journal of Canadian Petroleum Technology,
(November 1997), 48−55.
9. Srivastava, R.K., Huang, S.S. and Dong, M.: “Laboratory
Investigation of Weyburn CO2 Miscible Flooding,” Journal of
Canadian Petroleum Technology, (February 2000), 41−51.
10. Dong, M., Huang, S. and Srivastava, R.: “A Laboratory Study
on Near-Miscible CO2 Injection in Steelman Reservoir,” Journal
of Canadian Petroleum Technology, (February 2001), 53−61.
11. Dong, M., Huang, S. and Srivastava, R.: “Coreflood Studies of
Tertiary CO2 Flood in Naturally Fractured Midale Formation in
Southeast Saskatchewan,” Journal of Canadian Petroleum
Technology, (February 2002), 41−46.
12. Zhang, P.Y., Freitag, N., and Huang, S.: “Baseline Study of Oil
Recovery Parameters at Pre-CO2-Injection Conditions−Weyburn
CO2 Monitoring and Storage Study,” Saskatchewan Research
Council Publication No. P-110-557-C02, (February 2002).
13. PVTprop – An EOS Simulation Package, Version 4.0;
Protroleum Technologies Ltd., http://www.pvtprop.com
14. Wang, Y. and Orr Jr., F.M.: “Calculation of Minimum
Miscibility Pressure,” SPE 39683 presented at the 1998
SPE/DOE Improved Oil Recovery Symposium held in Tulsa,
Oklahoma, April 19-22, 1998.
15. Jessen, K., Michelsen, M.L. and Stenby, E.H.; “Effective
Algorithm for Calculation of Minimum Miscibility Pressure”,
SPE 50632 presented at the 1998 SPE European Petroleum
Conference held in The Hague, The Netherlands,
October 20-22, 1998.
6 SPE 89477

Table 1−Chemical and Physical Properties of Cleaned Dead Oils

Samples Weyburn (14-17-6-13 W2M) Steelman (8-16-4-6 W2M)
Temperature (°C) 15 20 59 15 20 67
3 878.2 834.4
Density (kg/m ) @ 1 atm 874.0 846.1 832.0 804.3
(29.5°API) (38°API)
Viscosity (mPa·s) @ 1 atm - 11.3 4.2 4.02 3.44 1.64
BS&W (vol%) Trace Trace
Oil MW (g/g-mol) 232 191
Saturates (wt%) 39.5 57.1
Aromatics (wt%) 45.4 32.2
Resins (wt%) 8.4 9.7
Asphaltenes (wt%) 6.7 1.0

Table 2−Comparison of Experimental and EOS Calculated Minimum Miscibility Pressures

1 2
Oil Sample Weyburn Live Oil at 59°C Steelman STO at 61°C
Exp. Calc. Exp. Calc.
Error Error
Type of Gas in CO2 Stream MMP MMP MMP MMP
(%) (%)
(MPa) (MPa) (MPa) (MPa)
Pure CO2 11.7 12.0 2.6 11.8 12.0 1.7
Gas-2 (94.1% CO2 + 3.1% N2 + 2.8% CH4) 14.5 14.0 3.4 - -
Gas-3 (90.1% CO2 + 9.9% CH4) 16.0 16.3 1.9 - -
Gas-4 (89.8% CO2 + 5.1% N2 + 5.1% CH4) 20.5 18.3 10.7 - -
Gas-5 (70% CO2 + 30% H2S) - - 10.4 10.8 3.8
Gas-6 (70% CO2 + 30% SO2) - - 8.7 7.7 11.5
Gas-7 (85% CO2 + 15% N2) - - 33.0 22.5 31.8
Gas-8 (65% CO2 + 15% N2 + 20% SO2) - - 34.0 17.3 49.1
Gas-9 (80% CO2 + 5% N2 + 5% O2 + 10% SO2) - - 22.5 16.8 25.3
1− Weyburn Live Oil was reconstituted by the separator oil and separator gas collected from Well 14-17-6-13 W2M.
2− Steelman Stock Tank Oil (STO) was collected from Well 3B-15-4-6 W2M.

20
Pure CO2 (Gas-1)
18
90.1% CO2 + 9.9% CH4 (Gas-3)

16 89.8% CO2 + 5.1% N2 + 5.1% CH4 (Gas-4)

Saturation Pressure (MPa)

14

12

10

2
0 10 20 30 40 50 60 70
Gas Solvent Concentration in Reservoir Fluid (mol%)

Figure 1− Saturation Pressure as a Function of Gas Solvent Concentration in

Weyburn Reservoir Fluid at 59°C
SPE 89477 7

120

CO2 (Oil Sample from Well 3-21-4-5 W2M)

60% CO2 + 40% C2H6 (Oil Sample from Well 8-16-4-6 W2M)
Saturation Pressure Increase Ratio (%)

100

80

60

40

20

0
0 5 10 15 20 25 30 35 40 45 50 55
Gas Concentration in Reservoir Fluid (mol%)

Figure 2−Saturation Pressure Increasing Ratio as a Function of Gas Concentration in

Steelman Reservoir Fluid at 67°C

MMP = 12 MPa

At 7.3 MPa and 59°C At 12.9 MPa and 59°C

(Below MMP) (Above MMP)

Figure 3−CO2 MMP from Rising Bubble for Weyburn Oil Sample at 59°C (Well 14-17-6-13 W2M)
8 SPE 89477

R 14W2 R 13W2

25 30 29
12-25-6-14W2 (32.7°API)
MMP = 11.5 MPa

24 19 20
14-17-6-13W2 (29.5°API)
MMP = 12 MPa
T6 T6

13 18 17

8-12-6-14W2 (28.3°API)
MMP = 15.4 MPa

12 7 8

Figure 4−CO2 MMP Distribution within Weyburn Reservoir

22
89.8% CO 2 + 5.1% N 2 + 5.1% CH 4

20

18
Minimum Miscibility Pressure (MPa)

90.1% CO2 + 9.9% CH4

16
94.1% CO2 + 3.1% N2 + 2.8% CH4
MMP of Pure CO2
14

Pure CO2
12

10

0
Gas-1 Gas-2 Gas-3 Gas-4
Type of Gas Solvent in System

Figure 5−Effect of Contaminated CO2 on MMP for Weyburn Reservoir Fluid at 59°C
SPE 89477 9

35

Minimum Miscibility Pressure (MPa) 30

25

20

MMP of Pure CO2

15

10

0
Pure CO2 Gas-5 Gas-6 Gas-7 Gas-8 Gas-9
Type of Gas Solvent in System

Figure 6−Effect of Contaminated CO2 on MMP for Steelman Stock Tank Oil at 61°C

17

Propane in CO2
16
Ethane in CO2
Minimum Miscibility Pressure (MPa)

15

14

13

12

11

10

8
0 10 20 30 40 50 60 70 80 90 100
Gas Solvent Concentration in CO2 Stream (mol%)

Figure 7−Measured MMP for Steelman Reservoir Fluid with CO2/C2 and CO2/C3
Gas Mixtures at 67°C
10 SPE 89477

20
Calculated for Pure CO2 (Gas-1)
Exp. Data for Pure CO2 (Gas-1)
18
Calculated for Gas-4
Exp. Data for Gas-4
16 Calculated for Gas-3
Exp. Data for Gas-3
Saturation Pressure (MPa)

14

12

10

2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Solvent Concentration (mole fraction)

Figure 8−Measured and Matched Saturation Pressure for Mixtures of Weyburn Reservoir Fluid
with Pure and Impure CO2 at 59°C

80

70
Cumulative Oil Recovery (% IOIP)

60

50

Started EWF
40

30
Started CO 2 Injection
20
12 MPa (Run 4)

10 16 MPa (Run 2)

10 MPa (Run 5)
0
0 1 2 3 4 5 6 7 8 9 10 11 12
Fluid Injected (PV)

Figure 9−Effect of CO2 Pressure on Cumulative Oil Recovery for Weyburn Reservoir Fluid at 59°C
SPE 89477 11

60

50
Total Enhanced Oil Recovery (%ROIP)

40

30

20

10

0
10 12 16
CO2 Injection Pressure (MPa)

Figure 10−Effect of CO2 Injection Pressure on Total Enhanced Oil Recovery for Weyburn
Reservoir Fluid at 59°C