Energy Convers. Mgmt Vol. 33, No. 5-8, pp. 579-586, 1992 0196-8904/92 $5.00+0.

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Printed in Great Britain Pergamon Press Lid

APPLICATIONS OF CARBON DIOXIDE

IN ENHANCED OIL RECOVERY

P.L. Bondor

Koningklijke/Shell Exploratie en Produktie Laboratorium,

P.O. Box 60, 2280AB Rijswijk, Netherlands

ABSTRACT

Carbon dioxide has been injected into oil reservoirs for the purpose of recovery of additional oil for
the past two decades. The injection of carbon dioxide into the subsurface, combining increased
hydrocarbon recovery with the removal of carbon dioxide from the environment, might then seem to
be an obvious answer to the carbon dioxide disposal problem. In examining the use of carbon dioxide
for oil recovery, it becomes obvious that this is too simplistic a view.

In this paper, the applications of carbon dioxide in oil recovery are reviewed. The extent of the
industry effort is discussed, and the current level of effort described. The limitations, both technical
and economic, of the method, and the implications of petroleum industry research for the problem of
carbon dioxide removal from the environment are discussed.

INTRODUCTION

In "conventional" oil recovery, oil reservoirs typically undergo a development and production cycle
which begins with a "primary recovery" period, in which the natural reservoir energy is utilised to
recover the hydrocarbon fluid. This energy may come from liquid expansion, gas evolution from gas
originally dissolved in the crude oil, expansion of gas originally present in the reservoir, or from the
influx of water from an aquifer connected to the oil reservoir. This primary recovery typically is
capable of recovering from 5 to 20% of the oil originally in place in the reservoir (although in some
cases recovery may be much higher). Following primary recovery, a "secondary recovery" period
may be initiated. Injection of water or hydrocarbon gas can both augment the natural reservoir energy
and actively displace additional oil toward the production well. Although this procedure will require
additional expenditures, both capital and operating, the expenditures can frequently be justified by the
recovery of an additional 10 to 20% of the oil originally in place. At the end of conventional
recovery operations, then, 60 to 70% of the oil in the reservoir will not be recovered. This resource
constitutes the target for "tertiary" or "enhanced recovery" processes.

Much of the oil remaining in a reservoir at the end of primary or secondary recovery may be trapped
by capillary forces as discrete droplets, surrounded by water, or as a continuous phase at low
saturation with gas occupying the larger fraction of the pore space. In either case, this remaining oil
saturation (ROS) is greater than zero when the flow of oil to the well ceases, and is determined by the
flow characteristicsof the rock. This t-miteROS is a result of the fact that the displacement of oil by
either water or gas is an immiscible process. Oil and water (or gas) do not mix; interfaces are formed
which must be forced through the pore space of the rock by the available energy. The driving force
available (pressure gradient) is insufficient,and so a portion of the oil is left behind. If, however, a
material can be injected which is miscible (mixes in all proportions as a single phase) with the oil,the
capillary forces holding the oil in the pores vanish, and the oil can then be displaced toward the
production well. In fact, if the capillary forces can be reduced substantially,the ROS also is reduced.
Figure I illustratesthis. The remaining oil saturation is plotted against capillary number (the ratio of
viscous to capillary forces acting in the displacement process). As the capillary forces (intotfaelal

579
580 BONDER: APPLICATIONSOF CO2 IN ENHANCEDOIL RECOVERY

tension) decreases, additional oil is mobilised and recovered.

40 ~ R F . A S~qDSTO~/E
-~ SAMPLE 1

BI~REA SANDSTONE
S/~4PLE 2

( x ~ J o s ~ I

, .,,,.,l : ....... I ........ I , ,,,J.Jl , ,,.,,,,I . ,jx,,,,I , ,,,,,,

o-' lo " ~o" 1o -~ ;o-" l o -3 l o -2 Io-'
CAPILLARY NUMOER

Fig. 1. Dependence of Remaining Oil Saturation on Capillary Number (after Stalkup)

In an effort to recover additional oil, the injection of miscible agents into oil reservoirs has been
investigated since the 1950's. First, light hydrocarbon components such as propane were tested (see,
e.g, Stalkup, 1983). These substances act as solvents, and thus are miscible whenever they contact
crude oil. However, they are (relatively speaking) extremely costly, and thus could be used only in
very small injection volumes. In such applications, the displacement process in the reservoir (see
below) resulted in very inefficient recovery. The use of these hydrocarbons could not be developed to
the point of economic application. Miscible flooding investigations then began examining other
alternatives. Other light hydrocarbons, such as field-produced natural gas, can be miscible with crude
oils under some conditions. In general, these conditions are very resu-ictive, although successful
hydrocarbon miscible projects have been and continue to be carried out. Another alternative,
investigated since the 1960's, is the use of non-hydrocarbon substances which, although not first-
contact miscible, develop miscibility in the reservoir by a gradual process of extraction of lighter
components of the crude oil. If these materials are less costly than the hydrocarbon solvents, then a
larger injection volume could be affordable and result in a more effective displacement process. One
such substance is carbon dioxide.

The Carbon Dioxide FIoodin~ Process

When carbon dioxide contacts crude oil, several physico-chemical processes occur: the carbon dioxide
dissolves in the crude oil, swelling the oil and lowering its viscosity, and light components of the
crude ,~;.Itransfer to the carbon dioxide, developing a more hydrocarbon-rich mixture in place of the
origi~ cai'~;o~dioxide alone. If the pressure of the system in which this contact takes place is
sufficie~tly hig~ (at or above the "minimum miscibility pressure", or MMP), then the exchange
process will proceed until the enriched carbon dioxide mixture is completely miscible with the crude
oil. The MMP varies with type of crude oil and system temperature, but in general is above 100-150
bars (see Matthews, 1989). This developed miscibilityprocess (see e.g., Gardner, et.al.,1981) results
in a miscible fluid that is capable of displacing all of the oil which itcontacts in the reservoir,and thus
has the potential to recover a large fraction of the ROS after conventional recovery is complete. A
favourable feature of carbon dioxide as a miscible agent is that the pressure and temperature
conditions for developed miscibility are less restrictive than for hydrocarbon gases, and thus the
potential target for application can be greater.

This favourable picture is tempered, however, by the fact that the carbon dioxide will not contact all
the oil remaining in place in the reservoir. The physical process of displacement of one fluid by
 BONDOR: APPLICATIONSOF CO2 IN ENHANCEDOIL RECOVERY 581

another in a porous medium is governed by both rock characteristics and fluid properties; of these, the
relative permeability (a rock characteristic) and the viscosity (a fluid property) of each fluid determine
the case by which fluids can be displaced through the reservoir to the production well. The efficiency
of this displacement is controlled by the mobility (ratio of relative permeability to viscosity) of each
fluid; if the displacing fluid (i.e., carbon dioxide) is more mobile than that being displaced (i.e., crude
oil), then the displacement will be relatively inefficient. Some of the ROS in the reservoir will never
come into contact with carbon dioxide; the carbon dioxide will pass rapidly through a portion of the
reservoir and appear at the production wells. However, by careful design of the process and project,
and by reinjecting produced carbon dioxide to the extent necessary, it is possible to recover a
significant fraction of the ROS.

Technical ADnlicabilitv of the Process

The carbon dioxide miscible process is applicable when the pressure at which the project will be
operated is above the MM1~, as reservoir pressure is related to depth, a result of this restriction is that
candidate reservoirs will be deeper than roughly 1000 metres. Reservoir temperatures at this depth
will normally be above the critical temperature of carbon dioxide (31 oc), so that carbon dioxide will
be a single fluid phase. Its density will often be similar to that of crude oil, but its viscosity is very
low, usually in the range of 0.1 cp. This viscosity is low enough so that displacement of crude oil by
carbon dioxide will usually be an unfavourable displacement process. Both laboratory and field tests
have indicated that even under very favourable conditions, injection of 5-20 thousand cubic feet (0.15-
0.6 thousand cu. m.) of carbon dioxide is required for recovery of an additional barrel (0.16 cu. m.) of
oil.

Crude oils most favourable for the process application will be light, low viscosity crudes. The low
viscosity somewhat aids the efficiency of the displacement procesS, and such crudes contain a large
fraction of light hydrocarbons, which aids in the development of miscibility. Considerable quantities
of such crude oils arc currendy being produced, and the fields contain a significant resource for
tertiaryrecovery by miscible carbon dioxide. A recent report (Combe, et.al.,1989) indicates a tertiary
oil potential for carbon dioxide flooding in Western European reservoirs ranging from 80 to 160
million cu.m. This report also statesthat the potential application is restrictedby the lack of a carbon
dioxide source.

FIELD APPLICATIONS OF CARBON DIOXIDE FLOODING

The first field applications took place in west Texas, U.S.A., in the early 197ffs. Subsequent to the oil
price shocks of the 1970's, carbon dioxide was applied both in pilot tests and in full field applications,
primarily in the U.S. Tbe most recent data available (Moritis, 1990), indicate the growth and extent in
the I.).S. of both the number of projects and the amount of oil produced (ca. 100,000 barrels (16,500
cu.m.) per d~-¢in 1990) attributable to carbon dioxide miscible flooding. These data arc shown in Fig.
2. It is aotable that the number of projects has not shown significant growth in the past 8 years. The
oil pric~ drop in the mid-1980's and subsequent reduced expectations for oil price increases has
resulted in new projects being deferred or cancelled, although a limited scope exists where previous
capital expenditures have resulted in the existance of pipelines with surplus capacity. Although carbon
dioxide applications in Canada have been investigated and tested, hydrocarbon miscible flooding is
more prevalent there, both because carbon dioxide is less readily available than natural gas and
because many Canadian reservoirs are amenable to hydrocarbon miscible flooding. Elsewhere in the
world, carbon dioxide has been used only in a few tests in Eastern Europe, mainly in Hungary. The
availability of low-cost carbon dioxide has been a serious constraint to applications outside North
America.
582 BONDOR: APPLICATIONS OF CO 2 IN ENHANCED OIL RECOVERY

1 0 0 Number of active pro|ect| Peoductlon ratl, M B b l s l d a y 1 0 0

8° [- ~ ' ° " " ° ' ~ 0 " "°"' ~ / 8o

60 6O

40 40

2O 2O

0 0
1980 1982 1984 1986 1988 1990
Year

Fig. 2. Active Carbon Dioxide Miscible Projects (after Moritis)

Problems in Carbon Dioxide Field Projects

As experience is gained in the field, some common problems have become apparent. These can be
separated into process (or reservoir) problems and operational problems.

~ocess Problems. Most of the process problems experienced are related to either the unfavourable
nature of the displacement process, or to the complexity of the geology of the reservoir. As has been
stated above, the high mobility of carbon dioxide results in an unfavourable mobility ratio, so that the
carbon dioxide will bypass the oil/water system in place in the reservoir. Viscous fingers will develop,
and the injectam will break through to the production well without contacting all the oil present. This
situation is illustrated in Fig.3a. In addition, if the reservoir is relatively flat, has high permeability
and good vertical continuity, the density difference between carbon dioxide and the crude oil can lead
to a gravity-induced overlay of the more dense by the less-dense fluid. This is illus~ated in Fig. 3b.

i i : ..........

SOLVENT

! r i J ---
OIL-

Fig. 3a. Viscous Instability (after Matthews) Fig.3b. Gravity instability (after Stalkup)

In addition to the unstable-displacement-induced early appearance of carbon dioxide at the production

well, inhomogeneities in reservoir geology can cause problems. Thin, high permeability layers termed
"thief zones" will take a disproportionately large share of the injection fluid, resulting in premature
breakthrough of injection fluids.

The result of early breakthrough and production of carbon dioxide at production wells is a reduction in
the economic attractiveness of the project. A less efficient displacement results in lower oil recovery
 BONDOR: APPLICATIONSOF CO2 IN ENHANCEDOIL RECOVERY 583

per unit volume of carbon dioxide injected. To (partially) remedy the unfavourable mobility ratio
displacement and effect of thief zones, the injection of alternate slugs of carbon dioxide and water has
been used (e.g., see Rowe, et. al., 1981; Pritchard and Nieman, 1992). Other techniques, including the
use of foams, have been proposed to modify the gravity layover problem (see, e.g., Bernard, et.al.,
1980; Heller, et.al., 1985a,b; Kuhlman, et.al., 1990; and Martin, et.al., 1992).

Ooerational Problems. Among the operational problems found in carbon dioxide flooding projects are
corrosion and scale formation. Carbon dioxide, in combination with water, is a very corrosive fluid.
This problem can be controlled in the injection system by proper dehydration of the injectant. Where
alternate slugs of carbon dioxide and water are used, stainless steels and/or plastic-coated tubing have
been used to prevent corrosion damage. In production wells, carbon dioxide is always present in
contact with water, plastic linings, epoxy or other resistant coatings, and chemical corrosion inhibitors
have been used. Where scale formation has been a problem, scale inhibition treatments are necessary.

An additional operational problem arises when carbon dioxide breaks through to the production well.
At this point, substantial quantities of injectant are produced which must be handled. At first, the
carbon dioxide is present at a low concentration in the produced natural gas. but the concentration of
carbon dioxide increases very rapidly to high levels. As a result of the process constraints, this
problem is foreseen, and plans include the ability to handle this production, Usually, this gas is either
compressed and reinjected, or the carbon dioxide is separated out and the pure stream is compressed
and reinjected. Usually, it is anticipated that one-quarter to one-half of the total carbon dioxide
requirement will be purchased, and will be recycled (reinjected) one to three times.

Carbon Dioxide Supply for Field Projects

In the projects carded out to date in the U.S., carbon dioxide has been obtained from 1) natural carbon
dioxide underground sources; 2) natural gas processing plants; and 3) fertilizer plants. The largest
source is the underground reservoir: locations and approximate reserves in place are shown on Fig. 4.

""2722.J21"/ Jackson Dome (3-5 tcf)

Fig. 4. Natural CO 2 Deposits in the USA (after Matthews)

The McElmo Dome, Bravo Dome, and Sheep Mountain accumulations supply in excess of one billion
cubic feet (330 million cu.m.) per day to carbon dioxide flooding projects in west Texas. A secondary
underground source is made up of natural gas deposits which contain a large fraction of carbon
dioxide that is separated from the natural gas prior to sale. The advantages of the underground
reservoir include high purity, large volume, and high pressure. Fertilizer plants are also able to supply
high purity carbon dioxide in reasonable volumes (say 25-50 million cubic feet (0.7-1.4 million
cu.m.)) per day, but this stream is at or near atmospheric pressure, and thus requires substantial
584 BONDOR: A P P L I C A T I O N S OF CO 2 IN E N H A N C E D O I L R E C O V E R Y

compression for use in an oil recovery project. We note here that although flue gas (i.e., the effluent
from a combustion process) has been examined as a carbon dioxide source, in general the cost of
extraction the ca. 20% carbon dioxide from the effluent stream, and subsequent compression to the
required injection pressure has precluded it from serious consideration.

IMPACT OF CARBON DIOXIDE SUPPLY ON PROJECT ECONOMICS

The intent of this section is not to provide an exposition of the economics of carbon dioxide miscible
recovery projects, but rather to indicate the impact of the carbon dioxide source on the project. The
economics of a specific project depends on many factors, including the target oil in place, the need for
new wells and facilities, and the additional operating costs attributable to the project. All these
factors, however, are independent of and in addition to the carbon dioxide source, if we assume a cost
per unit volume of carbon dioxide delivered at injection conditions to the reservoir. We can then
calculate the technical cost of an additional barrel of oil recovered as a function of carbon dioxide
cost, under various discount rates and injection/produodon assumptions.

For simplicity, we will make the following assumptions:

1) One barrel of incremental oil can be recovered by the use of 5 mcf of purchased carbon dioxide.
(This carbon dioxide may be reinjected several times, but the additional incremental cost of
reinjection is an operating expense independent of purchase price.)
2) There will be a substantial lag between injection and the oil recovery. We will examine the
impact on technical cost of a five-year and a ten-year delay between initial injection of carbon
dioxide and production of the resulting barn'el of oil.
3) Delivered cost of US$1 and $2 per thousand cu. ft. of carbon dioxide.
4) Discount factors of 0, 5, I0, and 15%.

Te~nl~l Cost. US$/Bbl

50

40

30 ...................................... ~
Production aelay (yr.) • l O j US$2/Mc!

20 ..........................

~ U851,01©!
101 ~

0 i i
0 5 10 15
Discount Rate. %

Fig. 5. Impact of Purchased CO 2 Cost on Technical Cost of an Inerernental Barrel of Oil

Figure 5 illustrates the impact on technical cost per incremental barrel of oil of the factors listed
above. The interaction between production lag time and discount rate results in the cost of carbon
dioxide alone (delivered at US$1 per thousand cu. ft.) in the recovery of one additional barrel of oil
increasing from US$5/barrel (at 0% discount rate) to US$10/barrel for a 5-year and US$20/barrel for a
10-year lag in production, when a 15% discount rate is considered. These values are doubled if the
delivered cost of carbon dioxide is US$2 per thousand cu. ft. Earlier work (Hendriks, et. al., 1989,
and van der Harst and van Nieuwland, 1989) have indicated that the cost of carbon dioxide delivered
to a reservoir from a 600MW coal-fired power plant through a 100 kin. pipeline is of the order of 71
Dfl per tonne of carbon dioxide (64 Dfl for carbon dioxide removal from plant effluent gas,
dehydration and compression, and 7,50 Dfl for a 100 km pipeline and field facilities). 71Dfl per tonne
 BONDOR: APPLICATIONSOF CO2 IN ENHANCEDOIL RECOVERY 585

is approximately US$2 per thousand cu.ft. (with 2 Dfl = US$1). Hendfiks, et. al. indicate that an
Integrated Gasification Combined Cycle power plant could supply carbon dioxide at 26 Dfl per tonne,
for a total cost of 33,50 Dfl, a cost of about US$ 0.95 per thousand cu. ft.

Thus the data in Fig. 5 provide realistic discounted technical costs of carbon dioxide supply from
power plants for oil field use. When it is realised that substantial capital investments and increased
operating costs are normally required for the implementation of an EOR project, it appears that it is
unlikely that carbon dioxide flooding projects using surface sources for the supply of miscible fluid
can be economically justified at present.

CONCLUSIONS

The application of carbon dioxide as a miscible flooding agent in oil recovery operations is a reality.
Field projects have bc~n operating with success sin~ the early 1970's, and the knowiedge exists to
allow the design and implementation of additional projects. However, further development has been
stalled by the economics of the process. To date, implementation has occurred only where there is
access to an underground source of carbon dioxide, since such sources are able to provide injectants at
low cost. Alternative (surface) sources have significantly higher capital and operating cost
requirements, and thus have not been able to provide compressed carbon dioxide to the field at a cost
low enough to develop a profitable project.

The availability of carbon dioxide at a delivered cost of US$ 0.50 to 1.50 per thousand cu. ft. has been
a price sufficiently low to allow projects to go forward in the U.S., during an era of higher oil price
expectations. Under current conditions, we have shown that delivered costs of carbon dioxide from
surface facilities cannot compete with underground sources.

ACKNOWLEDGEMENTS

Permission to publish this paper from Shell International Research Maatschappij, b.v., and Shell
Internationale Petroleum Maatschappij, b.v., is gratefully acknowledged.

REFERENCES

Bernard, G.G., Holm, L.W. and Harvey, C.P. (1980). Use of surfactant to reduce CO 2 mobility in oil
displacement. Soc. Pet. Eng. J. 20 (8), 281-292.
Combe, J., Coday, P., Valentin, E., Champion, D., Bosio, J., de Haan, H.J., Hawes, R.I., Pusch, G.,
Schlocchi, G. and Stockenhuber, F. (1989). EOR in Western Europe: Status and Outlook. 5th
European Symposium on Improved Oil Recovery, Budapest, April 25-27.
Gardner, J.W., Orr, F.M., Jr. and Patel, P.D. (1981). The effect of phase behaviour on CO 2 flood
displacement efficiency. J. Pet. Technol. 33 (11), 2067-2081.
Harst, A.C. van der and Nieuwland, A.J.F.M. van (1989). Disposal of Carbon Dioxide in Depleted
Natural Gas Reservoirs. In: Climate and Energy: The Feasibility of Controlling CO2 Emissions
(P.A. Okken, R.J. Swart, and S. Zwerver, eds.). 178-188.
Heller, J.P., Lien, C.L. and Kuntamukkula, M.S. (1985a). Foam-like Dispersions for Mobility Cona'ol
in CO2 Floods. Soc. Pet. Eng. J. 25 (8), 603-613.
Heller, J.P., Boone, D.A. and Watts, R.J. (1985b). Field Test of CO 2 Mobility Control at Rock
Cre~k. 1985 SPE Annual Technical Conference and Exhibition, Las Vegas, Nee., September 22-25,
SPE 14395.
586 BONDOR: APPLICATIONSOF CO2 IN ENHANCEDOIL RECOVERY

Hcndriks, C.A., Blok, K. and Turkcnburg, W.C. (1989). The Recovery of Carbon Dioxide from
Power Plants. In: Climate and Energy: The Feasibility of Controlling CO2 Emissions (P.A.
Okkcn, R.J. Swart, and S. Zwcrvcr, eds.). 125-142.
Kuhlman, M.I., Falls, A.H., Hara, S.K., Borchardt, J.K. and Monger, T.G. 0990). Carbon Dioxide
Foam with Suffactants Used Below Their Critical Miccllc Concentration. Soc. Pet. Eng. EOR
Syrup., Tulsa, Okla., April 22-25, SPE 20192.
Martin, F.D., Heller, J.P., Weiss, W.W., Tsau, J-S., Zomcs, D.R., Sugg, L.A., Stevens, J.E. and Kim,
J.E. (1992). CO2 Foam Field Verification Pilot Test at EVGSAU Injection Project - Phase I:
Project Planning and Initial Results. To be presented at:Soc. Pet. Eng. EOR Syrup., Tulsa, Okla.,
April 22-24, SPE 24176.
Matthews, C.S. (1989). Carbon Dioxide Flooding. Chapter 6 in: Enhanced Oil Recovery, II -
Processes and Operations (E.C. Donaldson, G.V. Chilingarian, and T.F. Yen, exis.). Elsevier,
Amsterdam.
Mofitis, G. (1990). CO2 and HC injection lead EOR production increase. Oil & Gas J. April 23,
1990, 49-81.
Pritchard, D.W.L. and Nieman, R.E. (1992). Improving Oil Recovery Through WAG Cycle
Optimization in a Gravity-Override-Dominated Miscible Hood. To be presented at:Soc. Pet. Eng.
EOR Syrup., Tulsa, Okla., April 22-24, SPE 24181.
Rowe, H.G., York, S.D., and Adcr, J.C. (1981). Slaughter Estate Unit tertiary pilot performance.
Soc. Pet. Eng. EOR Syrup., Tulsa, Okla., April 5-8, SPE 9796.
Stalkup, F.I., Jr. 0983). Miscible Displacement. Society of Petroleum Engineers of AIME, Dallas,
Texas, U.S.A.