Article

pubs.acs.org/IECR

Parametric Study of the Cyclic CO2 Injection Process in Light Oil

Systems
Ali Abedini and Farshid Torabi*
Petroleum Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, Regina, Canada

ABSTRACT: Performance of cyclic CO2 injection as an enhanced oil recovery (EOR) technique in a light crude oil system was
experimentally investigated. Series of cyclic CO2 injection tests were designed and carried out at various operating conditions.
Effects of parameters including operating pressure (Pop), injection time (tinj), soaking period (tsoaking) and connate water
saturation (Swc) were investigated on the oil recovery factor (RF) of cyclic injection tests. First, the CO2 solubility in the crude oil
sample and the oil swelling factor as a result of CO2 dissolution into the oil phase for the crude oil−CO2 system at temperatures
T = 21 and 30 °C were determined. Second, the equilibrium interfacial tension of the crude oil−CO2 system at T = 30 °C was
measured. Afterward, the minimum miscibility pressure (MMP) between crude oil and CO2 was calculated by means of the
vanishing interfacial tension (VIT) technique and found to be MMP = 9.18 MPa. Finally, a total of 12 cyclic CO2 injection tests
were performed at operating pressures Pop = 5.38, 6.55, and 8.27 MPa (i.e., immiscible to near-miscible conditions), and constant
temperature T = 30 °C and in the presence and absence of connate water saturation. CO2 injection time and soaking period were
varied at each operating pressure in order to determine how these parameters might affect the performance of cyclic CO2
injection. According to the obtained experimental results, it was found that the oil recovery factor of the cyclic CO2 injection
technique increases considerably with increased operating pressure (e.g., from RF = 32.6% at Pop = 5.38 MPa to RF = 54.4% at
Pop = 8.27 MPa). The results also demonstrated that the oil recovery factor increases by a longer soaking period particularly if the
cyclic CO2 injection performed at lower operating pressures. Moreover, it was observed that the oil recovery factor is
independent of CO2 injection time. In addition, at each operating pressure, the oil recovery factor obtained in the presence of
connate water saturation was found to be more than that when there was no connate water saturation in the system.

1. INTRODUCTION projects) revealed that the presence of a gas cap, gravity

Among all types of gas injection processes, CO2 injection has
been widely employed because of its high potential for
enhanced oil recovery. CO2 reacts with the reservoir rock
and fluids and modifies their properties, providing more
favorable conditions for oil production. Oil viscosity and
interfacial tension reduction, oil swelling, and extraction of
lighter components of oil by CO2 are the principal mechanisms
that contribute to CO2 enhanced oil recovery (EOR)
processes.1−4 Furthermore, CO2-EOR can assist CO2 storage
which is essential for reducing greenhouse effects, because of
the proven effect CO 2 on climate change and global
warming.5−8 CO2 can be injected into a reservoir under diverse
techniques such as continuous CO2 flooding, cyclic CO2
injection, carbonated water injection, water-alternating-CO2
injection, and CO 2 /hydrocarbon or flue gas mixture
injection.9−11 Along with the aforementioned techniques, the
cyclic CO2 injection process has been examined throughout
lab-scale studies as well as field-scale projects for the past three
decades.
In the cyclic CO2 injection process, first CO2 is injected into
the reservoir under different operating conditions (i.e., huff
cycle) and then the well is shut for a predetermined soaking
period. Lastly, the process is followed by the oil production
from the same well (i.e., puff cycle). Several studies have been
conducted to determine the effect of different operating
parameters on the performance of the cyclic CO2 injection
process. Additional studies on the performance of some field-
scale cyclic CO2 injection in USA (e.g., Paradis, West Cote,
Timbalier, Magnet, Picket Ridge, and Thompson, Bati field
segregation, and a higher remaining oil saturation can improve
the recovery of the cyclic injection process.12−14 Furthermore,
changes in gas−oil relative permeability curves may support the
oil production near the well-bore.15−17 Further studies on the
effect of CO2 slug size also revealed that a higher volume of
CO2 injected into the reservoir is able to recover more oil
under some specific conditions during the cyclic injection
process.18,19 It has also been reported that the cyclic CO2
injection process profited by lower crude oil viscosity since the
diffusion of CO2 into the oil is accelerated.20 Experimental
study on the cyclic injection of mixtures of CO2 with
hydrocarbon and flue gases also showed that such mixtures
increase the oil recovery if they are injected in a particular range
of volumetric ratio.21−23 A laboratory and field evaluation of the
cyclic CO2 injection process indicated that a high permeability
of the reservoir rock as well as viscous fingering phenomena
plays a positive role in the recovery efficiency.14 The laboratory
and numerical simulation results also suggest that oil recovery is
improved by a higher matrix permeability during cyclic CO2
injection in a matrix-fractured system.24,25
It is believed that more detailed studies should be conducted
to determine the influence of diverse parameters on this
technique. Therefore, this study investigates the performance of
Received: July 23, 2013
Revised: September 26, 2013
Accepted: October 1, 2013
Published: October 1, 2013

© 2013 American Chemical Society 15211 dx.doi.org/10.1021/ie402363h | Ind. Eng. Chem. Res. 2013, 52, 15211−15223
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cyclic CO2 injection in light oil systems under different

operating parameters. First, a phase behavior study was
performed on the crude oil−CO2 system in order to determine
the CO2 solubility and oil swelling factor as a result of CO2
dissolution into the crude oil, and interfacial tension between
CO2 and the crude oil sample. Then a series of cyclic CO2
injection tests were designed and carried out under various
operating conditions and constant temperature T = 30 °C.
Effects of several parameters including operating pressure (Pop),
CO2 injection time (tinj), soaking period (tsoaking) and connate
water saturation (Swc) on the oil recovery were investigated.
Stage and cumulative recovery factors, producing gas oil ratio
(GOR) as well as gas utilization factor (GUF), were
determined in each cyclic CO2 injection tests.

2. FLUIDS
Figure 1. Measured values of crude oil density and viscosity as a
The crude oil under study was a mixture of various samples change of temperature at atmospheric pressure.
from different locations of the Bakken oil field in South
Saskatchewan, Canada. The density and viscosity of the sample
crude oil at the temperature T = 21 °C and atmospheric
pressure was measured to be ρoil = 802 kg/m3 and μoil = 2.92 3. CO2 SOLUBILITY AND OIL SWELLING FACTOR
mPa·s, respectively. The n-C5 insoluble asphaltene content was The solubility of CO2 in the crude oil and the oil swelling
determined using the standard ASTM D2007-03 method to be process as a result of this phenomenon are the main
1.23 wt %. The compositional analysis of the original crude oil mechanisms associated in the CO2-EOR techniques. In
sample is presented in Table 1. Figure 1 also shows the addition to oil swelling, other recovery mechanisms such as
oil viscosity reduction and oil interfacial tension reduction
Table 1. Compositional Analysis of the Crude Oil under remarkably depend on the solubility of CO2 in crude oil.
Study at T = 21° C and Atmospheric Pressure Although vapor−liquid equilibrium (VLE) equations of state as
well as some developed correlations are able to predict the CO2
carbon carbon carbon solubility and oil swelling factor at a specified pressure and
number mole % number mole % number(s) mole %
temperature,26−28 the experimental methods can determine
C1 0 C12’s 4.48 C28’s 0.44 these parameters more accurately. In this study, a high-pressure,
C2 1.58 C13’s 4.02 C29’s 0.33 high-temperature visual cell was used to determine the CO2
C3 0.92 C14’s 3.32 C30+’s 2.85 solubility and oil swelling factor for crude oil−CO2 system at
i-C4 0 C15’s 3.06 various equilibrium pressures and constant temperature T = 30
n-C4 3.88 C16’s 2.37 C1−C6’s 22.48 °C. The schematic diagram of experimental setup for
i-C5 2.20 C17’s 2.06 C7+’s 77.52 determining the CO2 solubility in the crude oil is depicted in
n-C5 4.03 C18’s 1.91 Figure 2. The apparatus mainly consisted of a see-through-
C5’s 0.49 C19’s 1.51 C1−C14’s 78.82 windowed high-pressure cell (Jerguson Co.), a magnetic stirrer
i-C6 3.07 C20’s 1.29 C15+’s 21.18 (Fisher Scientific), and a high pressure CO2 cylinder. The
n-C6 2.95 C21’s 1.29 entire setup was placed in an airbath in order to be maintained
C6’s C22’s C1 − C29’s
3.37 0.76 97.15
at a constant temperature T = 30 °C which was controlled by a
C7’s 13.87 C23’s 0.87 C30+’s 2.85
temperature controller (Love Controls Co.). The visual cell was
C8’s 10.46 C24’s 0.71
charged with a specific volume of crude oil sample (i.e., Vo,i= 25
C9’s 8.19 C25’s 0.66
cm3) and placed on top of the magnetic stirrer. A magnetic bar
C10’s 6.38 C26’s 0.57
was also submerged in the crude oil to create a consistent
C11’s 5.61 C27’s 0.49
turbulence inside the cell. The produced turbulence as a result
property value unit
of the rotation of the magnetic bar greatly accelerated the CO2
molecular weight 223 g/mol dissolution into the oil by creating convective mass transfer.29,30
density @ (21 °C and Patm) 802 kg/m3 Along the process, the pressure inside the visual cell was
viscosity @ (21 °C and Patm) 2.92 mPa·s measured by using a digital pressure gauge (Ashcroft Inc.).
n-C5 insoluble asphaltene 1.23 wt % Once the visual cell was pressurized with CO2 to a
prespecified pressure (Pi), the pressure of the cell was allowed
variation of the crude oil density and viscosity as a change of to stabilize while CO2 was dissolving into the crude oil. The test
temperature. The viscosity values were measured using a was terminated when the final CO2 pressure (Pf) inside the cell
rotational DV-II+Viscometer (Can-AM Instruments Ltd.). reached a stable value (i.e., the difference of final pressure
A synthetic brine with 2 wt % NaCl concentration, density of readings was less than 1 kPa for 1 h). As it is mentioned earlier,
ρb = 1011 kg/m3 and viscosity of μb = 0.98 mPa·s at the the CO2 dissolution process was expedited using the magnetic
temperature T = 21 °C and atmospheric pressure was also used bar inside the cell. Lastly, initial and final CO2 volume in visual
as a representative of reservoir brine in this study. cell, VCO2,i and VCO2,f, respectively, were determined by taking
Carbon dioxide (CO2) with a purity of 99.99%, supplied by photos and utilizing image analysis technique. Throughout this
Praxair, was used as the injected solvent in the cyclic injection procedure and by application of the mass balance analysis
tests. shown in eq 1, the amount of dissolved CO2 in the crude oil
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Figure 2. Schematic diagram of the experimental setup used for CO2 solubility and oil swelling factor measurements.

and subsequently the CO2 solubility in the crude oil sample

(χCO2) was determined.
mCO2,dissolved = mCO2,i − mCO2,f

i CO2 ,iMWCO2 ⎞
⎛ PV
=⎜ ⎟
⎝ Z iRT ⎠
⎛ Pf VCO2,f MWCO2 ⎞
−⎜ ⎟
⎝ Zf RT ⎠
MWCO2 ⎡⎛ PV i CO2 ,i ⎞
= ⎢⎜ ⎟
RT ⎢⎣⎝ Z i ⎠
⎛ Pf VCO2,f ⎞⎤
−⎜ ⎟⎥
⎝ Zf ⎠⎥⎦ (1)

Furthermore, the oil swelling factor (SF) due to the dissolution

Figure 3. Solubility of CO2 in the light crude oil sample at
of CO2 at the specific operating condition was also calculated temperatures T = 21 and 30 °C.
by the ratio of the final volume of the oil to its initial value at
the beginning of the experiment as presented in eq 2:
SF = Vo,i /Vo,f (2)

The experimental results of CO2 solubility in the crude oil

sample at the two temperatures T = 21 and 30 °C are depicted
in Figure 3. This figure illustrates that the solubility of the CO2
increases with the equilibrium pressure of the system. This is
mainly attributed to the reason that the concentration of
dissolved CO2 is proportional to the pressure of the CO2. The
CO2 pressure controls the number of CO2 molecule collisions
in contact with the surface of the crude oil sample. Since higher
pressure (i.e., equilibrium pressure of the system) results in an
increase of the number of collisions which occurs in contact
with the surface, more CO2 is dissolved in the crude oil with
increased equilibrium pressure. It was also observed that the
solubility of CO2 at the lower temperature (i.e., T = 21 °C) is
relatively higher than that at the higher temperature (i.e., T =
30 °C). Figure 4 shows the obtained experimental values of the Figure 4. Oil swelling factor of crude oil−CO2 system at temperatures
oil swelling factor for the crude oil−CO2 system at temper- T = 21 and 30 °C.
atures T = 21 and 30 °C. The volume of the crude oil increases
by increasing the equilibrium pressure mainly due to the higher
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solubility of CO2 in the crude oil at higher pressures, and as a
result of this phenomenon the crude oil swells in the visual cell.
As the pressure increases further, the density of CO2 increases
and the CO2 phase changes from gas to liquid. Since liquid-
phase CO2 has a higher ability to extract lighter hydrocarbon
components,3,31 CO2 starts to vaporize or extract hydrocarbons
from the crude oil. As a result, the volume of the crude oil in
the visual cell is therefore reduced. It was also observed that the
oil swelling factor of the crude oil−CO2 system is relatively
higher at lower temperature (i.e., T = 21 °C) compared to that
at higher temperature (i.e., T = 30 °C) in the range of
equilibrium pressures lower than the pressure at which the
extraction of light components occurs. However at pressures
beyond this range, the oil swelling factor was relatively higher at
a higher temperature T = 30 °C. This is mainly because a larger
amount of CO2 is dissolved in the oil at lower temperatures. In
addition, it was found that the extraction process of the
hydrocarbon components starts earlier at lower temperature.
Figure 5 presents the CO2 solubility together with the oil
swelling factor curves for the crude oil−CO2 system as well as
Figure 5. Solubility of CO2 in the crude oil, oil swelling factor, and
extraction point of the crude oil−CO2 system at temperatures T = 21
and 30 °C.
Figure 6. Schematic diagram of the experimental setup used for measuring the equilibrium IFT for the crude oil−CO2 system at various equilibrium
pressures.
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the extraction pressure at two experimental temperatures T =
21 and 30 °C. At the start of the experiment, the solubility of
CO2 and swelling factor of crude oil are zero and one
respectively for both temperatures. The solubility of CO2 and
swelling factor in the crude oil start to increase as the pressure
increases and reach their maximum values at the pressures Peq =
5.95 MPa for T = 21 °C and Peq = 6.79 MPa for T = 30 °C. The
maximum CO2 solubility and swelling factor of the crude oil at
the temperature T = 21 °C are χCO2 = 65.04 mol% and SF =
1.37, respectively. When the temperature was increased to T =
30 °C, the CO2 solubility and oil swelling factor were reduced
to χCO2 = 61.45 mol% and SF = 1.32, respectively. After this
point, the extraction mechanism dominates the oil swelling one
and leads to reduction of the volume of the crude oil in the
visual cell and decline in swelling factor. This because the
lighter hydrocarbon components were extracted by CO2 and
vaporized into the gaseous phase. Also at this point, the
solubility cannot be measured using the method which was
used in this study. The reason is that the assumption
incorporated in the solubility measurement (i.e., there is no
extraction and vaporization of hydrocarbon components in
liquid phase) is not valid anymore. During the extraction
mechanism, the compositional analysis of both liquid and gas
phase at each pressure should be employed in order to
determine the solubility of CO2 in the crude oil.
4. INTERFACIAL TENSION (IFT) AND MINIMUM
MISCIBILITY PRESSURE (MMP) OF THE CRUDE
OIL−CO2 SYSTEM
Interfacial tension (IFT) between the crude oil and CO2
considerably affect the performance of CO2-EOR techniques.
Low IFTs between oil and CO2 can improve sweep efficiencies
and reduce residual oil saturation considerably.32
In this study, the axisymmetric drop-shape analysis (ADSA)
technique for the pendant drop case was applied to determine
the IFT between the crude oil and CO2.33 Figure 6 depicts a
schematic diagram of the experimental setup used for
measuring the equilibrium IFT of the crude oil−CO2 system
at various equilibrium pressures and constant temperature T =
30 °C. First, the see-through windowed high-pressure IFT cell
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(Temco Inc.) was heated to the specific experimental
temperature T = 30 °C and then filled with the CO2 at a
prespecified equilibrium pressure. Afterward, the crude oil was
introduced to the IFT cell through a stainless steel syringe
needle which was installed at the top of the IFT cell. Once a
well-shaped pendant drop was formed at the tip of the syringe
needle, the appropriate sequential digital images of the dynamic
pendant oil drop at different times were acquired. Finally, the
ADSA program for the pendant drop case was executed to
determine the equilibrium IFT between the oil and CO2 at each
prespecified pressure and at a temperature T = 30 °C
Figure 7 depicts the measured IFT values of the crude oil−
CO2 system at various equilibrium pressures and at T = 30 °C.
Figure 7. Measured CO2−oil IFTs at different equilibrium pressures
and multiphase contact MMP of the crude oil−CO2 system obtained
from the VIT technique at T = 30 °C.
Accordingly, it was found that the equilibrium IFTs of the
crude oil−CO2 system decrease linearly in two distinct ranges.
In range (I) with the pressure range of Peq = 0.66−6.41 MPa,
the IFT reduces linearly because of CO2 dissolution into the oil
phase. In range (II) with the pressure range of Peq = 7.35−
14.64 MPa, the governing mechanism which leads to linear IFT
reduction of the crude oil−CO2 system is the extraction of
lighter hydrocarbon components by CO2.
The vanishing interfacial tension (VIT) technique was
applied on the measured equilibrium IFTs to determine the
MMP of the crude oil−CO2 system. This technique is based on
the concept that the interfacial tension (IFT) between a crude
oil and CO2 approaches zero when they become miscible.34
Therefore, the MMP can be determined by linearly
extrapolating the measured equilibrium IFT values versus
equilibrium pressure to the point of zero equilibrium IFT. The
measured equilibrium IFTs in the two pressure ranges were
regressed linearly to correlate with equilibrium pressures as
shown in Figure 7. The intersection of the linear equation
representing the equilibrium IFTs in Range (I) with abscissa
(i.e., IFTeq = 0) gives the multicontact MMP which was found
to be MMP = 9.18 MPa. The second linear regression
intersects with IFTeq = 0 at Peq = 20.44 MPa. Since at this
pressure, almost all intermediate and heavy components
become miscible with CO2, this pressure may be interpreted
as first contact MMP between the crude oil and CO2. The
intersection of the two linear correlations at pressure Peq = 6.84
MPa is the point at which the interaction mechanism between
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the crude oil and CO2 changed from the CO2 solubility or oil
swelling factor to the extraction of lighter components by CO2.
Results of the IFT test at T = 30 °C indicate that the extraction
of the light component begins at pressure Pext = 6.84 MPa,
which is in good agreement with the Pext = 6.79 MPa obtained
from the oil swelling test at the same temperature.
5. CYCLIC CO2 INJECTION TESTS
5.1. Experimental Apparatus. Figure 8 shows the
schematic diagram of the experimental setup used for cyclic
CO2 injection tests in this study. It consists of a high pressure
stainless steel core holder (Husler, Inc.) with inner and outer
diameters of 6.12 cm, and 7.91 cm, respectively. The other
specifications of the core holder as well as the core sample are
presented in Table 2. A strong rubber sleeve (Viton, Co.) was
used to insulate the core in the core holder so that fluids flow
through the cross section of the core in the horizontal direction
and prevent the flow of fluids around the core. A Teledyne
ISCO syringe pump (ISCO Inc., 500D series) was used to
inject fluids (i.e., brine, crude oil, and CO2) into the core
through high pressure transfer cells and 1/8 in. i.d. high pressure
stainless steel tubes (Swagelok Company). To maintain the
desired back pressure in the system, a back pressure regulator
(Temco, Inc.) was connected to the end of the core holder.
5.2. Core Saturating. Prior to each experiment, the core
was cleaned, vacuumed, and saturated with the brine
completely. During the brine saturating process, the injection
flow rate was varied in the range of qb‑inj = 0.25−2 cm3/min in
order to determine the absolute permeability of the core sample
in each test. Thereafter, the oil sample was injected to the
system with constant flow rate of qo‑inj = 0.25 cm3/min to reach
the connate water saturation (Swc) and establish the initial oil
saturation (Soi). The connate water saturation was found to be
Swc = 43.3−45.9%, and the initial oil saturation was in the range
of Soi = 54.1−56.7% in all cyclic injection tests. After being
saturated with oil, the core was allowed to stand for 24 h to
reach a proper equilibrium condition at the temperature T = 30
°C. Since cyclic CO2 injection tests were performed at various
operating conditions, the above procedure was repeated for all
experiments.
5.3. Cyclic Injection. For the cyclic CO2 injection the
pressure of CO2 in the transfer cell was increased to the desired
operating pressure for each test and kept for 24 h to equilibrate
at the experimental temperature. Then CO2 was injected into
the oil saturated core under constant operating pressure for a
definite injection time (i.e., tinj = 30 and 120 min). To inject
CO2 into the saturated core under constant operating pressure,
the “constant pressure injection mode” of the pump was used.
After completion of CO2 injection (i.e., huff cycle), the core
was shut for a specific soaking period (i.e., tsoaking = 24 and 48
h). The puff cycle was then implemented by the oil production
at the end of the core holder (i.e., injection point) while the
back pressure regulator was set at pressure PPBR = 3.45 MPa
using a nitrogen cylinder (i.e., puff cycle). When the first huff-
and-puff cycle was completed, the second cycle was started with
the same procedure of the first cycle. These cycles were
continued until there was no considerable oil production
obtained. The volume of the produced oil and gas in each puff
cycle was measured to determine the oil recovery factor (RF),
producing gas−oil ratio (GOR), and gas utilization factor
(GUF). The gas utilization factor is defined as the ratio of the
produced oil volume to the injected gas volume. Since CO2 was
injected into the core holder under constant pressure injection
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Figure 8. Schematic diagram of the experimental setup used for cyclic CO2 injection tests.

Table 2. Properties of the Core Sample and Core Holder A total of 12 cyclic CO2 injection tests were conducted at
Used for Cyclic CO2 Injection Tests different operating conditions using the aforementioned
procedure. The experimental conditions (i.e., saturation data,
permeability porosity height diameter pore volume
(mD) (%) (cm) (cm) (cm3) injection pressure, CO2 injection time, and soaking period) for
core 70.82 18.51 30.21 5.05 111.82
each test are presented in Table 3. The cyclic injection tests
sample were carried out at three operating pressures Pop = 5.38, 6.55,
core 35.59 6.12 1046.94 and 8.27 MPa under immiscible to near-miscible condition,
holder while the temperature was set to be constant at T = 30 °C. At
each operating pressure, parameters including CO2 injection
mode by the pump, the volume of injected CO2 was time, soaking period, and connate water saturation were varied
determined volumetrically through readings of the pump. to determine how these parameters affect the performance of
Additionally, during production in each puff cycle of cyclic CO2 the cyclic CO2 injection process. Two different values of tinj =
injection, no connate water was produced. 30 and 120 min were used to study the effect of CO2 injection

Table 3. Experimental Conditions, Ultimate and Stage Oil Recovery Factors, Total Number of Cycles, Total Producing GOR
and Total GUF for all 12 Cyclic CO2 Injection Tests

test ϕ k Swc Soi Pop tinj tsoaking ultimate 1st stage 2nd stage no. of total prod. GOR total GUF (×106)
no. (%) (mD) (%) (%) (MPa) (min) (h) RF (%) RF (%) RF (%) cycles (cm3gasprod/cm3oil) (cm3oil/cm3gasinj)
1 18.5 70.8 44.7 55.3 5.38 30 24 32.6 7.1 5.5 11 1479.4 405.7
2 18.4 70.6 45.4 54.6 5.38 120 24 33.2 7.6 5.8 11 1610.3 342.8
3 18.3 71.3 43.3 56.7 5.38 30 48 36.9 8.1 6.2 11 1368.9 422.2
4 18.5 70.9 45.8 54.2 5.38 120 48 37.5 8.2 5.9 11 1516.9 337.7
5 18.3 71.4 0 100 5.38 120 24 29.4 7.3 6.0 11 860.0 480.4
6 18.7 70.8 45.9 54.1 6.55 120 24 47.5 12.9 9.8 11 1560.0 379.4
7 18.5 71.3 45.5 54.5 6.55 120 48 51.3 13.9 9.4 11 1670.1 317.3
8 18.4 70.5 0 100 6.55 120 24 34.9 10.1 7.3 11 877.9 466.0
9 18.6 71.0 44.7 55.3 8.27 120 24 55.8 16.8 11.2 10 2083.3 320.8
10 18.4 70.6 45.4 54.6 8.27 120 48 58.7 17.9 11.4 10 2231.4 299.5
11 18.4 70.8 43.3 56.7 8.27 30 24 54.4 15.4 10.7 10 2200.4 323.0
12 18.7 71.2 0 100 8.27 120 24 53.2 15.2 11.3 10 1377.7 317.4

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Figure 9. Oil recovery factors, cumulative producing GOR, and cumulative GUF of the cyclic CO2 injection tests performed at the operating
pressure Pop = 5.38 MPa and temperature T = 30 °C.
time. Also, to investigate the effect of the soaking period, two
sets of cyclic injection tests at each operating pressure were
conducted while soaking periods of tsoaking = 24 and 48 h were
applied.
5.4. Recovery Performance, Producing GOR and GUF.
A total of 12 cyclic CO2 injection tests were performed at
various operating conditions and at a temperature T = 30 °C.
Figure 9 panels a−e show the experimental results obtained
from five cyclic injection tests (i.e., Test # 1−5) carried out at
the operating pressure Pop = 5.38 MPa. Figure 9 panels a and b
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depict the stage and cumulative recovery factor versus cycle
number and pore volume of injected CO2, respectively. The
production cycles (i.e., 11 cycles) were continued until no
considerable amount of oil was produced. The maximum and
minimum ultimate recovery factor obtained from the five tests
performed at Pop = 5.38 MPa was RF = 37.5% (i.e., Test # 4: tinj
= 120 min, tsoaking = 48 h and Swc = 45.8%) and RF = 29.5%
(i.e., Test # 5: tinj = 120 min, tsoaking = 24 h and Swc = 0),
respectively. As it is shown, almost for all tests, the first and
second cycles recovered about 40% of total amount of
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Figure 10. Oil recovery factors, cumulative producing GOR, and cumulative GUF of the cyclic CO2 injection tests performed at the operating
pressure Pop = 6.55 MPa and temperature T = 30 °C.
recoverable oil, and the recovery factor of other cycles are
relatively lower. The stage recovery factor is defined as the ratio
of the produced oil volume in each cycle to the initial oil
volume in the porous medium.
The cumulative producing GOR and cumulative GUF versus
cycle number and pore volume of injected CO2 are depicted in
Figure 9 panels c and d. It was found that the cumulative GOR
is extremely lower in the initial cycles of the production;
however, it increases noticeably in subsequent cycles. On the
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other hand, the cumulative GUF is considerably higher in initial
cycles since the volume of the recovered oil is relatively high
compared to the volume of the CO2 injected into the core,
while it declined drastically when the cycles are continued until
the test was terminated. Figure 9 panels c and d demonstrate
that the trend of the cumulative GOR and cumulative GUF
curves are in the opposite direction along the production time
for each experiment. It is noteworthy to mention that there was
no brine production during cyclic production. Figure 9e shows
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Figure 11. Oil recovery factors, cumulative producing GOR, and cumulative GUF of the cyclic CO2 injection tests performed at the operating
pressure Pop = 8.27 MPa and at temperature T = 30 °C.
a comparison between the ultimate, first, and second stage
recovery factors. This graph clearly indicates that first and
second cycles significantly contribute to the total oil volume
recovered by cyclic CO2 injection.
A total of 7 cyclic CO2 injection tests (i.e., Test # 6−8 at Pop
= 6.55 MPa and Test # 9−12 at Pop = 8.27 MPa) were also
carried out to investigate the performance of this technique at
higher operating pressures. Figures 10a−e and 11a−e graphi-
cally present the measured stage recovery factors, cumulative
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recovery factors, cumulative GOR, and cumulative GUF versus
cycle numbers and pore volume of injected CO2 for cyclic CO2
injection performed at Pop = 6.55 and 8.27 MPa, respectively. It
can be observed that the cyclic CO2 injection process has
potential to recover considerable volume of oil if carried out at
higher operating pressures. Higher CO2 injection pressures
increase the ultimate recovery factor of cyclic CO2 injection
processes because of higher CO2 solubility in the oil, oil
swelling factor, and a stronger solution−gas drive mechanism.
dx.doi.org/10.1021/ie402363h | Ind. Eng. Chem. Res. 2013, 52, 15211−15223
Industrial & Engineering Chemistry Research
It is noteworthy to mention that the oil swelling factor declines
from Peq = 6.55 MPa to Peq = 8.27 MPa (shown in Figure 5)
which may consequently have negative impact on the ultimate
oil recovery factor. However, at an operating pressure Pop =
8.27 MPa which is greater than the extraction pressure (i.e., Pext
= 6.79 MPa at T = 30 °C) as well as near miscible condition,
the mechanism of light component extraction by CO2 is
noticeably stronger and dominates the oil swelling mechanism.
Consequently, it results in increase of the ultimate oil recovery
factor as well as stage recovery factors. Table 3 presents the
recovery data, total cumulative GOR and GUF, and the total
number of cycles to achieve the ultimate oil recovery factor for
all 12 cyclic CO2 injection tests.
5.5. Parametric Analysis of Cyclic CO2 Injection Tests.
In addition to the effect of the operating pressure on the
performance of the cyclic CO2 injection process in the light oil
system, the effects of other key parameters such as CO2
injection time, soaking period, and connate water saturation
on this process were investigated. CO2 injection time was
changed from tinj = 30 min to tinj = 120 min, and the soaking
period was changed from tsoaking = 24 h to tsoaking = 48 h to
determine how these two parameters affect the oil recovery. To
investigate the effect of connate water saturation on the
performance of the cyclic CO2 injection technique, at each
injection pressure, one complete cyclic injection test was
performed in the core when it was 100% saturated with the oil
sample (i.e., Swc = 0), and the results were compared with those
obtained by the cyclic injection tests carried out in the presence
of connate water saturation.
Effect of the CO2 Injection Time. Figure 12 shows the effect
of the CO2 injection time on the performance of cyclic CO2
Figure 12. Ultimate oil recovery factor of cyclic CO2 injection tests
performed at operating pressures Pop = 5.38 and 8.27 MPa, with CO2
injection times of tinj = 30 and 120 min, and identical soaking period of
tsoaking = 24 h.
injection tests performed at operating pressures Pop = 5.38 and
8.27 MPa. As it is shown, a comparison of the recovery factors
of cyclic CO2 injection tests performed with tinj = 30 min with
those tests carried out with tinj = 120 min reveals that an
increase of the CO2 injection time did not improve the
recovery efficiency of this technique noticeably. The ultimate
oil recovery factor of tests carried out at Pop = 5.38 and 8.27
MPa with tinj = 30 min were RF = 32.6% and 54.4%,
respectively, while these values for the tests implemented with
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tinj = 120 min were RF = 33.2% and 55.8%. The reason is
mainly attributed to the physical size of the porous media in
this study. Since the physical size of the model in this study was
very limited compared to the real reservoir case, the core
sample was going to be saturated by CO2 rapidly in each huff
cycle. As a result, higher CO2 injection time did not result in
the injection of more significant volume of CO2 into the system
and higher oil recovery factor. However, this parameter may
play an effective role in the field-scale cyclic CO2 injection
processes. To investigate the influence of injection time on the
cyclic CO2 injection test, it is recommended that such tests be
performed on a larger experimental model which has a greater
pore volume which can be occupied by more CO2.
Effect of the Soaking Period. Figure 13 depicts the impact
of the soaking period on the ultimate oil recovery factor of
Figure 13. Ultimate oil recovery factor of cyclic CO2 injection tests
performed at operating pressures Pop = 5.38, 6.55 and 8.27 MPa, with
soaking periods of tsoaking = 24 and 48 h, and identical CO2 injection
time of tinj = 120 min.
cyclic CO2 injection tests performed at operating pressures Pop
= 5.38, 6.55, and 8.27 MPa and temperature T = 30 °C. It was
observed that the ultimate recovery factors of cyclic CO2
injection tests performed with longer soaking period (i.e.,
tsoaking = 48 h) are higher than those carried out with tsoaking = 24
h. By increasing the soaking period from tsoaking = 24 h to tsoaking
= 48 h, the ultimate recovery factor of cyclic injection process
increased from RF = 33.2% to RF = 37.5% at Pop = 5.38 MPa,
from RF = 47.5% to RF = 51.3% at Pop = 6.55 MPa, and from
RF = 55.8% to RF = 58.7% at Pop = 8.27 MPa. Mass transfer
phenomena particularly for the gas−liquid systems in the
porous media are time-consuming processes and highly
dependent on the molecular diffusion mechanism (specifically
apparent molecular diffusion) in the absence of convective-
diffusion term.29,30 A longer soaking period intensifies the
interaction between oil and CO2 phases in the porous media
and aids the diffusion process of CO2 in crude oil. As a result,
more CO2 diffuses into the oil phase and the CO2 recovery
mechanisms (i.e., CO2 solubility, oil swelling factor, interfacial
tension reduction, and extraction of lighter components)
become more effective.
Effect of the Connate Water Saturation. Two different sets
of cyclic CO2 injection tests were performed at operating
pressures Pop = 5.38, 6.55 and 8.27 MPa, in the presence and
absence of connate water saturation to determine the effect of
dx.doi.org/10.1021/ie402363h | Ind. Eng. Chem. Res. 2013, 52, 15211−15223
Industrial & Engineering Chemistry Research Article

this parameter on the performance of cyclic CO2 injection

process. Figure 14 portrays how this parameter affected the

Figure 15. Ultimate oil recovery factor of all cyclic CO2 injection tests
performed at operating pressures Pop = 5.38, 6.55, and 8.27 MPa and
under different operating conditions.
Figure 14. Ultimate oil recovery factor of cyclic CO2 injection tests
performed at operating pressures Pop = 5.38, 6.55, and 8.27 MPa in the
presence and absence of connate water saturation.

ultimate oil recovery factor of cyclic CO2 injection tests. It can

be seen that the presence of connate water in the porous
medium is a beneficial parameter in cyclic CO2 injection tests
resulting in a larger amount of oil production and higher
ultimate oil recovery factor. The presence of connate water in
the porous media improves the oil recovery by increasing the
interaction of crude oil and CO2 through enlarging the contact
area between these two phases. The CO2 can diffuse and
dissolve in the water and move into the oil phase through the
contact area between the oil and the connate water. Another
reason that may occur in longer injection schemes is the
generation of carbonated water as a result of the co-presence of
CO2 and water. Carbonated water provides an acidic
environment and can dissolve reservoir rock which results in
improvement of rock permeability.
Variation of Ultimate Recovery Factor, Total Producing
GOR, and GUF. The ultimate oil recovery factor of all cyclic
CO2 injection tests performed at operating pressure Pop = 5.38,
6.55, and 8.27 MPa, and various operating conditions are
plotted in Figure 15. The results reveal that at any specific
operating conditions (i.e., the same values for CO2 injection
time and soaking period), the recovery performance of cyclic
CO2 injection process benefits from the higher operating
pressure. In other words, the oil recovery of this technique
increases with the increased operating pressure. In addition,
Figure 16 panels a and b show the variation of total producing
GOR and GUF for all CO2 cyclic injection tests. As shown in
Figure 16a, the total producing GOR was somehow
independent of CO2 injection time and soaking period for
cyclic injection tests carried out at all operating pressures;
however, it was significantly lower for the tests (i.e., Test # 5, 8 Figure 16. Effect of injection time, soaking period, and connate water
and 12) which were performed in the absence of connate water saturation on the (a) measured total producing GOR and (b) total
saturation (i.e., Swc = 0). It was also observed that the total GUF, in cyclic CO2 injection tests at three operating pressures Pop =
producing GOR increases as the cyclic injection tests are 5.38, 6.55 and 8.27 MPa.
operated at higher pressures. Figure 16b depicts the total GUF
versus injection pressure for all cyclic CO2 injection tests. As
against total producing GOR, the total GUF varied
considerably if the injection time and soaking period changed total producing GOR, the total GUF decreases as the operating
in an experiment. Moreover, it was seen that in contrast with pressure increases. The results also indicated that at each
15221 dx.doi.org/10.1021/ie402363h | Ind. Eng. Chem. Res. 2013, 52, 15211−15223
Industrial & Engineering Chemistry Research Article

operating pressure, the total GUF reached its highest value for k = absolute permeability (mD)
those experiments performed at Swc = 0. MW = molecular weight (g/mol)
m = mass (g)
6. CONCLUSIONS n-C5 = normal pentane
In this work, the performance of cyclic CO2 injection process in qb‑inj = brine injection flow rate (cm3/min)
a light crude oil system for the purpose of enhanced oil qo‑inj = oil injection flow rate (cm3/min)
recovery was experimentally investigated. A total of 12 cyclic Pop = operational pressure (MPa)
CO2 injection tests at various operating conditions under Patm = atmospheric pressure
immiscible to near-miscible injection modes were carried out to Peq = equilibrium pressure (MPa)
determine the effect of several key parameters including Pext = extraction pressure (MPa)
operating pressure, injection time, soaking period, and connate PPBR = pressure of back pressure regulator (MPa)
water saturation on the oil recovery obtained by this technique. Swc = connate water saturation
According to the results, the followings are concluded: Soi = initial oil saturation
T = temperature (°C)
• CO2 solubility, oil swelling, interfacial tension reduction,
tinj = CO2 injection time (min)
solution gas drive, and vaporization and extraction of
tsoaking = soaking period (h)
lighter components are the main oil recovery mecha-
Vo,i = initial oil volume in the cell (cm3)
nisms contributing to cyclic CO2 injection process in Vo,f = final oil volume in the cell (cm3)
light oil systems. VCO2,i = initial CO2 volume in the cell (cm3)
• The ultimate oil recovery factor of the cyclic CO2 VCO2,f = final CO2 volume in the cell (cm3)
injection test increases with the operating pressure Z = CO2 compressibility factor
from immiscible condition to near-miscible. At higher
pressures, the CO2 solubility in crude oil, oil swelling, Greeks
and light-component-extraction mechanisms become ρb = brine density (kg/m3)
more effective leading to achieve higher oil recovery. In ρoil = oil density (kg/m3)
addition, first and second stage recovery factors are μb = brine viscosity (mPa.s)
relatively higher than the other subsequent stage μoil = oil viscosity (mPa.s)
recovery factors in the cyclic CO2 injection. ϕ = porosity
• The soaking period can assist the cyclic oil production χCO2 = CO2 solubility in crude oil (mole percent)
and increase the ultimate oil recovery factor by Abbreviations
enhancing the CO2 recovery mechanisms through ADSA = axisymmetric drop shape analysis
providing more time for the phase interaction and ASTM = American Standard Test Method
mass transfer phenomena in the crude oil−CO2 system EOR = enhanced oil recovery
inside the porous media. GOR = gas oil ratio
• In contrast with the effect of the soaking period, it was GUF = gas utilization factor
found that the oil recovery factor is independent of the IFT = interfacial tension
CO2 injection time. The effect of this parameter seems to RF = oil recovery factor
be more dominant in a larger lab-scale physical model. SF = oil swelling factor
• The presence of connate water saturation in the porous VIT = vanishing interfacial tension
media can be considered as a beneficial condition in the VLE = vapor−liquid equilibrium
cyclic CO2 injection process, mostly by enlarging the Unit Conversion
contact area between the crude oil and CO2 phases. mD = 0.000987 μm2

■ AUTHOR INFORMATION
Corresponding Author
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■ ACKNOWLEDGMENTS
The authors wish to thank Petroleum Technology Research
Centre (PTRC) and Faculty of Graduate Studies and Research
at the University of Regina for their funding support. The
authors also extend their gratitude to Mr. Nader Mosavat for
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