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Energy Sources, Part A: Recovery,

Utilization, and Environmental Effects
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A Unique Opportunity for Liquid Carbon

Dioxide as an Enhanced Oil Recovery
Method
a a a
F. Irawan , S. Irawan & M. Awang
a
Faculty of Geoscience and Petroleum Engineering , University
Teknologi PETRONAS , Tronoh , Malaysia
Published online: 24 Feb 2012.

To cite this article: F. Irawan , S. Irawan & M. Awang (2012) A Unique Opportunity for Liquid Carbon
Dioxide as an Enhanced Oil Recovery Method, Energy Sources, Part A: Recovery, Utilization, and
Environmental Effects, 34:7, 654-661, DOI: 10.1080/15567031003645551

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 Energy Sources, Part A, 34:654–661, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567031003645551

A Unique Opportunity for Liquid Carbon Dioxide

as an Enhanced Oil Recovery Method

F. IRAWAN,1 S. IRAWAN,1 and M. AWANG1

1
Faculty of Geoscience and Petroleum Engineering, University Teknologi
PETRONAS, Tronoh, Malaysia
Downloaded by [New York University] at 13:37 07 December 2014

Abstract One of the major problems agreed upon in CO2 gas injection is early
gas breakthrough attributed to unfavorable mobility in the reservoir. The objective
of this study is to study the effect of liquid CO2 injection to oil recovery. The core
was displaced with crude oil after brine saturation. The next step was water flood by
injecting 12 PV of 10,000 ppm concentration brine. Finally, the preconditioned liquid
CO2 was injected and the produced oil was recovered. The result of this study gave an
interesting oil recovery with a range of 67.7 to 72.6% depending on the temperature
of the CO2 injected.

Keywords carbon dioxide, displacement, enhanced oil recovery, mobility, viscosity

Introduction
For many years, the industry has made a practice of returning produced natural gas into
a reservoir in order to maintain reservoir pressure and to store the produced gas rather
than in the open air. In the 1970s, the industry began to show a great deal of interest in
carbon dioxide as a potential injection gas. Likewise, until present days, carbon dioxide
enhanced oil recovery (EOR) is still very interesting.
Carbon dioxide (CO2 ) shares the same sweep efficiency problem with other injection
gases (Mangalsingh et al., 1996). Water alternating gas (WAG) CO2 injection results in a
complex saturation pattern where two saturations (gas and water) will alternate increasing
and decreasing. This gives special demands for the three phases (oil, gas, and water). In
order to have an effective CO2 flood, CO2 -hydrocarbon miscible solvent bank has to be
formed and maintained to maximize the displacement. The introduction of water through
the WAG process delays this mechanism and reduces displacement efficiency. Similarly,
an adverse effect of the WAG process is the resulting oil trapped from the introduction
of water. In an experiment conducted by Raimondi and Torcasso (1963), by using long
Berea sandstone and average porosity of 20% showing that upon imbibitions of water,
oil is trapped over a range of saturation. The amount trapped oil increased rapidly as the
saturation approached the limiting value of imbibitions. The Thomas et al. (1983) study,
by using Boise sandstone with an average porosity of 24%, concluded that the dispersion
in the wetting component of a two immiscible liquid system, which was oil and water,
increased with decreasing saturation of the wetting fluid. Furthermore, Bellavance (1996)

Address correspondence to Fikri Irawan, Faculty of Geoscience and Petroleum Engineering,

University Teknologi PETRONAS, Block 16, Lt.3, Tronoh 31750, Malaysia. E-mail: irawan.fikri@
gmail.com

654
 A Unique Opportunity for Liquid CO2 as EOR Method 655

published a study about the Dollarhide Devonian Field WAG process that resulted in an
oil recovery 12 to 16% lower than under continuous CO2 injection. Christensen et al.
(1998) mentioned that in the production life of an oilfield, some operational problems
could not be avoided. The WAG injection is more demanding than a pure gas or water
injection since the injected fluid needs to be changed frequently. Although, only a small
number of operational problems have been reported, it is basically the same issues from
the fields, such as early breakthrough in production wells, reduced injectivity, corrosion,
scale formation, and even asphaltenes and hydrate formation.
Injecting gas CO2 to a low temperature oil reservoir at higher pressure would build
the liquid CO2 phase in the reservoir as the pressure exceeds its vapor pressure. In field
application, the requirement should meet a higher formation fracture gradient for success
of generating liquid CO2 in the formation (Frailey et al., 2004). Several observed fields
that fulfill this special requirement occur in the Illinois Basin (Frailey et al., 2004) and
Appalachian Basin (Bank, 2007).
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The use of CO2 to enhance oil recovery historically focused on supercritical CO2 to
achieve miscible conditions with crude oil. The only possibility of liquid CO2 injection
is in formations with temperatures less than critical temperatures of CO2 . Due to the
naturally occurring geothermal temperature gradient, most of the formations currently
considered for CO2 injection exceed the critical temperature of CO2 (Frailey et al.,
2004). Thus, relatively higher pressures are required to attain liquid CO2 , which translate
to fracture gradients as high as 1.0 psi/ft.

CO2 Fluid Properties

Pure CO2 has a critical temperature and pressure of 87.8ı F and 1,071 psia, respectively.
The triple point of CO2 is at a temperature much less than possible for oil reservoir
applications ( 56.6ı C), as shown in Figure 1. Thus, identified as neither gas nor liquid,
CO2 as a critical fluid is also possible in EOR (Jarrel et al., 2002).
At a constant temperature, CO2 changes phase from gas to liquid as pressure in-
creases, which causes dramatic changes in fluid properties like fluid density and viscosity.
For example, by doubling the pressure from 500 to 1,000 psia, CO2 density increases
drastically from 5 to 50 lbm/ft3 and its viscosity increases from 0.017 to 0.074 cp.
Consequently, a liquid CO2 has a liquid-like density, but gas-like viscosity.
For common reservoir pressure, temperature, and crude oil composition, supercritical
CO2 often became miscible with crude oil forming a single phase liquid. As a result of
this interaction, the volume of oil swells, its viscosity was reduced, and surface tension
effect was reduced, improving the recovery of the oil from the reservoir (Al-Quraini
et al., 2007).

Experiment

Core Properties
The CO2 flooding process was evaluated by means of short core displacement tests
at 1,500 psi and three different liquid CO2 temperatures of 68, 53, and 41ı F. All the
displacement took place at a room temperature of 80ıF. The core utilized in this study
was fresh consolidated Berea sandstone with a diameter of 1.5 inches and a length of 3
inches, with an average permeability of 200 md and average porosity of 19%.
 656 F. Irawan et al.
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Figure 1. Phase behavior of CO2 .

Churcher et al. (1991) described that the formation is made up of well-sorted and
well-rounded sand grains, ranging in size from 70 to 400 m. The grains consist of
predominantly quartz (85 to 90%) and feldspar (3 to 6%). The mercury capillary pressure
curve indicates that most of the Berea sandstones have similar pore geometry.

Fluid Properties
The reservoir fluid that is used in this study is crude oil from Angsi field, one of Malaysia
Basin’s light oil. The major oil-bearing reservoirs are sandstones and are normally water-
flooded to improve oil recovery (Othman, 2003). The measured crude oil viscosity is
2.31 cp at 70ıF while the density is 0.81gr/cm3 at 60ıF. The API gravity is 43ı , which
is classified as light oil type.
Water composition analysis by Jakobsson et al. (2007) indicated that there was a trend
of increasing salinity with increasing depth. Total water salinity increases from around
12,000 to 15,000 ppm. Brine concentration of 10,000 ppm was used in this experiment
and consisted of NaCl, CaCl2 , MgCl2, and KCl.

Experimental Apparatus
The porosity was measured by using PoroPerm Equipment (Vinci Technologies, Nanterre,
France) as shown by Figure 2. The equipment is occupying nitrogen gas for confining
pressure and valves operating, and helium gas as the displacement fluid.
 A Unique Opportunity for Liquid CO2 as EOR Method 657
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Figure 2. Equipment to measure porosity. (color figure available online)

The core flood experiment was conducted by means of the Relative Permeability
Test System RPS-830 (Temco Inc., Amsterdam, The Netherlands). This equipment was
completed with three separated accumulators to gather each of the injection fluids that
sustain pressure until 10,000 psi and a temperature of 200ıC.
Since the tests on this experiment require low temperature conditioning, a water bath
was attached to level down the temperature of the CO2 accumulator as shown in Figure 3.
The schematic of experiment apparatus is shown by Figure 4.

Figure 3. RPS-800 modification by installing a water bath for CO2 temperature conditioning.
(color figure available online)
 658 F. Irawan et al.
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Figure 4. Schematic of experiment apparatus. (color figure available online)

Tests Procedure
Initially, the core sample was saturated with brine for 8 to 10 h by using a manual
saturator at 1,200 psi. Afterwards, the core sample was installed into the core holder to
initiate the core flood experiment. The injection was started by injecting brine into the
core sample. The purpose of this step was to measure the initial permeability of the core
sample. Afterward, the crude oil injection was initiated with a lower injection rate to
prevent significant upturn of the inlet pressure.
When the flow was stabilized and no more brine produced on the collector, the
second brine injection was initiated for water flood with a flow rate of 12 ft/day. All of
the fluid produced during this injection was collected by means of a measuring tube.
The last injection was liquid CO2 . The CO2 was set to its liquid phase by compressing
gas CO2 in the accumulator along with the temperature maintenance by way of a cooling
water bath. The volume of the CO2 accumulator was 1 liter precisely. At 1,500 psi,
this volume of gas CO2 could generate around 200 cc of CO2 liquid on an applied
temperature range on this experiment (68, 53, and 41ıF). And then, the liquid CO2
injection was initiated with a 4 ft/day flow rate injection.

Results and Discussions

A summary of the experimental results obtained on light crude oil with a Berea sandstone
system is shown in Table 1 and Figure 5. The core porosity of each core plug is 18.1,
18.5, and 19.4%, which is a common value for Berea sandstone.
 A Unique Opportunity for Liquid CO2 as EOR Method 659

Table 1
Core flood procedure and result of enhanced oil recovery by means of
water flood and CO2 injection
Water flood Water flood CO2 CO2 Liquid CO2
Exp. K brine, OOIP, Swc, injected, oil recovery, Sorw, temperature, injected, oil recovery,
ı
no. md ˆ, % %PV %PV PV % OOIP %PV F PV %ROIP

1 199.8 18.1 95.2 4.8 12.7 38.0 62.0 68 10 67.7

2 198.8 18.5 95.1 4.9 12.4 36.6 63.4 53 10 69.1
3 199.6 19.4 90.0 10.0 11.8 37.5 62.5 41 10 72.6

The original oil in place was ranging from 90 to 95% of pore volume, which leaves
the value of initial water saturation of 5 to 10%. This condition was generated by injecting
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the crude oil with an average flow rate of 0.8 ml/min. A higher injection flow rate would
cause significant pressure difference in the porous medium because of the viscosity effect
of crude oil.
Results of liquid CO2 displacement to the remaining oil saturation in the core is
also displayed in Table 1. Oil recovery on Experiment 1 was 67.7% of the remaining
oil in place by injecting the total of 10 PV liquid CO2 . High recovery of crude oil was
produced as the consequences of early CO2 injection until 3 PV injections.
In Experiment 2, which was set on a lower CO2 injected temperature of 53ıF, the
same circumstance happened where high oil produced occurs during the early production
until around 3 PV of CO2 injected. A total of 62% of crude oil was recorded at the end
of 3 PV injected. The cumulative oil of 69.1% was produced by injecting 10 PV liquid
CO2 .
In Experiment 3, where CO2 injected temperature was the lowest of all the core
flooding, like in Experiments 1 and 2, high oil recovery resulted during the early CO2
injection until around 3 PV injected. Cumulative oil produced until 10 PV of liquid CO2
injected was 72.6% of residual oil in place.
As discussed above and displayed in Table 1, the decreasing temperature of CO2
injected would result in the increase of oil recovery. This occurrence happens as a result

Figure 5. Cumulative oil produced as an effect of CO2 injected. (color figure available online)
 660 F. Irawan et al.

Table 2
Viscosity of CO2 at different temperatures

CO2 viscosity
at temperature, cp

Pressure (psi) 68ıF 53ı F 41ı F

1,500 0.0890 0.1014 0.1119

of the viscosity difference of the liquid CO2 displacing crude oil as displayed in Table 2.
Higher viscosity of a displacing agent would reduce bypassing phenomena that commonly
happens in conventional gas CO2 flooding, and finally more CO2 would be soluble in
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the CO2 -crude oil bank.

All of the above tests showed that high oil recovery occurred since early production
until 3 PV of liquid CO2 injected. Injecting more CO2 above this value caused a small
effect to escalate oil recovery. Residual oil saturation after tertiary recovery was reached
by injecting nearly an unlimited volume of CO2 .
Subcritical solubility of CO2 -crude oil and liquid condensation mechanisms were
expected to reduce CO2 gas bypassing. High recovery was reached due to high viscosity
of CO2 compared to its gas state. Table 2 shows the value of liquid CO2 viscosity range
in this experiment. The average value on Table 2 shows that liquid CO2 viscosity is
approximately seven times higher compared to its gas state. This circumstance reduces
the mobility of the CO2 , and thereby reduces bypassing. Therefore, a huge solvent bank
will be created and a longer sweep time will be expected due to CO2 low mobility.

Conclusion
The results of these experiments have indicated the following:
1. The injection of liquid CO2 to light oil reservoir gives a satisfying and interesting
recovery over the residual oil in place.
2. High oil recovery occurs during the early displacement of liquid CO2 until 3 PV
of injection. Beyond this condition, a small volume of oil is still recovered at the
outlet.
3. Different temperature of CO2 injected gives a different oil recovery because of
the viscosity differences.

References
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injection. SPE EUROPEC/EAGE Annual Conference and Exhibition, London, June 11–14.
Bank, G. G. 2007. CO2 -enhanced oil recovery potential of the Appalachian Basin. SPE Eastern
Regional Meeting, Lexington, KY, October 17–19.
Bellavance, J. F. R., and Unocal Corp. 1996. Dollarhide Devonian CO2 flood: Project performance
review 10 years later. SPE Permian Basin Oil & Gas Recovery Conference, Midland, TX,
March 27–29.
Christensen, J. R., Stenbey, E. H., and Skauger, A. 1998. Review of WAG experience. SPE
International Petroleum Conference and Exhibition, Villahermosa, Mexico, March 3–5.
 A Unique Opportunity for Liquid CO2 as EOR Method 661

Churcher, P. L., French, P. R., and Shaw, J. C. 1991. Properties of Berea sandstone, Baker dolomite,
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Raimondi, P., and Torcasso, M. A. 1963. Distribution of oil phase obtained upon imbibition of water.
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