Article

pubs.acs.org/EF

Oil Recovery Performance of Immiscible and Miscible CO2 Hu-and-

Pu Processes
Ali Abedini and Farshid Torabi*
Petroleum Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, S4S 0A2,
Canada

ABSTRACT: The recovery performance of immiscible and miscible CO2 hu-and-pu processes for enhanced oil recovery
(EOR) in a light crude oil sample was experimentally investigated. The minimum miscibility pressure (MMP) of the original light
crude oilCO2 system was determined by means of the vanishing interfacial tension technique and found to be MMP = 9.18
MPa. Then, the solubility of the CO2 in the light crude oil and oil swelling factor due to the CO2 dissolution in the oil phase were
determined at T = 30 C and various equilibrium pressures ranging from atmospheric pressure to Peq = 12.55 MPa. Later, series
of immiscible and miscible CO2 hu-and-pu tests were designed and carried out at various operating pressures (i.e., Pop = 5.38
10.34 MPa). The results of the experiments showed that for secondary CO2 hu-and-pu tests performed at the operating
pressures below the MMP, the ultimate oil recovery factor is quite low. It was also found that in immiscible CO2 hu-and-pu
(i.e., Pop < MMP) scenarios, the oil recovery factor substantially increased as the operating pressure approached near-miscible
conditions. The oil recovery factor almost reached its maximum value at operating pressure near MMP (i.e., miscible condition),
and further increase of operating pressure beyond MMP did not improve the recovery factor at all. The tertiary mode of miscible
CO2 hu-and-pu was also examined, and it was revealed that the oil recovery is signicantly improved after a waterooding
process. The oil recovery mechanisms during the CO2 hu-and-pu were mainly recognized to be interfacial tension reduction,
oil swelling, and extraction of lighter components by CO2, especially during miscible CO2 injections. In addition, the average
asphaltene content of produced oil and the permeability reduction of the porous medium as a result of asphaltene precipitation
were measured in each test. It was found that the amount of precipitated asphaltene in the porous medium as well as permeability
reduction are considerably higher in near-miscible and miscible CO2 hu-and-pu tests compared to those in immiscible cases.
The compositional analysis of remaining oil from CO2 hu-and-pu tests at immiscible and miscible conditions also showed that
lighter components of oil are extracted by CO2, leading the remaining oil to become heavier with greater amounts of heavy
hydrocarbons (i.e., C30+). However, it was observed that the extraction of lighter components during miscible injection processes
is more predominant than that during immiscible injections, resulting in the production of higher quality oil.

1. INTRODUCTION studies on performance of CO2 hu-and-pu in shallow light oil

CO2 hu-and-pu process, which is also known as cyclic CO2
injection, has been investigated through experimental and
simulation studies as well as eld tests as an enhanced oil
recovery (EOR) technique for the past three decades. Cyclic
CO2 injection was initially proposed as an alternative to cyclic
steam stimulation, and it was found that the cyclic CO2 injection
process has wider applications in light-oil reservoirs.1 In this
technique, after the injection of CO2 into the reservoir, the well
would be shut in for a predetermined period of time (i.e.,
soaking period) depending on the reservoir conditions (i.e.,
reservoir rock and uid properties).2,3 Then the oil production
initiates by converting the injection well to a producer. The
injected CO2 has the ability to change and modify the reservoir
rock and uid properties, ending up enhancing the oil recovery
process.4,5 Mechanisms contributing to increased oil recovery in
the hu-and-pu process include oil viscosity reduction, oil
swelling due to dissolution of gas in crude oil, solution gas drive
aided by gravity drainage in thick reservoirs, vaporization of
lighter components of oil, interfacial tension reduction, and
relative permeability eects.58
Black oil simulation of cyclic CO2 stimulation in low-pressure
gas solution drive wells shows that relative permeability
hysteresis and reservoir pressure increase are the main
mechanisms during the CO2 hu-and-pu process.4 Some
depleted reservoirs also indicate that oil swelling and viscosity
reduction eects combined with changes in gasoil relative
permeabilities resulted in improvement of oil recovery.57 It has
also been reported that the CO2 hu-and-pu process beneted
from the presence of gas cap, gravity segregation, and higher
remaining oil saturation.911 In addition, the eect of injected
CO2 volume or slug size on the oil recovery during CO2 hu-
and-pu has been investigated, and it has been observed that
higher CO2 volume injected into the reservoir is able to recover
more oil.1014
The performance of CO2 hu-and-pu in fractured systems
has also been studied to some extent, and it is found that gravity
drainage can signicantly increase oil recovery factor after a
waterooding process.15 Moreover, experimental and simulation
studies on the miscible and immiscible CO2 hu-and-pu in
matrix-fractured systems also show that higher matrix
permeability as well as presence of connate water saturation
result in substantial oil recovery, particularly in immiscible CO2
injection scenarios.16,17
Received: July 17, 2013
Revised: January 20, 2014
Published: January 22, 2014

2014 American Chemical Society 774 dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784
Energy & Fuels
Figure 1. Compositional analysis of the original light crude oil sample at atmospheric pressure and T = 21 C (oil = 802 kg/m3; oil = 2.92 mPa s; MW
= 223 g/mol; n-C5 insoluble asphaltene content = 1.23 wt %).
In this study, the oil recovery performance of the CO2 hu-
and-pu process in a light oil system was investigated through
immiscible and miscible CO2 injections. First, a phase behavior
study was performed on the crude oilCO2 system in order to
determine the CO2oil interfacial tension (IFT), CO2 solubility
in the original crude oil, and oil swelling factor as a result of CO2
dissolution into the oil phase. Then, a series of CO2 hu-and-
pu tests as a secondary and tertiary EOR schemes was designed
and carried out at various operating pressures ranging from
immiscible conditions (i.e., Pop < minimum miscibility pressure
(MMP)) to above miscible conditions (i.e., Pop > MMP) at
constant temperature of T = 30 C. In addition, the amount of
asphaltene precipitation in the porous medium as well as
subsequent permeability reduction of the system were
determined. Stage and cumulative recovery factors, producing
gasoil ratio (GOR), and gas utilization factor (GUF) were also
calculated during each CO2 hu-and-pu test. Furthermore,
compositional analysis on the remaining crude oil in the core
after the hu-and-pu test was conducted to examine and
analyze the recovery mechanisms of CO2 hu-and-pu under
immiscible and miscible conditions.
2. EXPERIMENTAL SECTION
2.1. Materials. The crude oil under study was a mixture of various
samples from dierent locations of the Bakken oil eld in South
Saskatchewan, Canada. The density and viscosity of the original crude
oil sample at T = 21 C and atmospheric pressure were measured to be
oil = 802 kg/m3 and oil = 2.92 mPa s, respectively. The n-pentane (n-
C5) insoluble asphaltene content was determined using the standard
ASTM D2007-03 method and found to be 1.23 wt %. The
compositional analysis of the original sample crude oil is presented in
Figure 1. A DV-II+Viscometer (Can-AM Instruments Ltd.) was used to
measure crude oil viscosity at various temperatures (Table 1).
A synthetic brine with 2 wt % NaCl concentration, density of w =
1001 kg/m3 and viscosity of w = 0.98 mPa s at T = 21 C and
atmospheric pressure was also used as a representative of reservoir
brine in this study.
CO2 with a purity of 99.99%, supplied by Praxair, was used as the
injected solvent in hu-and-pu tests.
2.2. Crude OilCO2 Interfacial Tension Measurement.
Interfacial tension (IFT) between an injected phase and reservoir oil
775
Article
Table 1. Measured Viscosity Values of the Crude Oil at
Atmospheric Pressure and Various Temperatures
temperature (C) crude oil viscosity (mPa s)
21 2.92
25 2.76
30 2.64
35 2.57
40 2.51
45 2.39
in-place signicantly aects the performance of EOR techniques.
Various studies have suggested that low IFT between the injected uid
and reservoir oil can improve sweep eciency and reduce residual oil
saturation.18,19 In CO2-based EOR techniques, at specic thermody-
namic conditions (i.e., pressure, temperature, and composition), the
IFT of the crude oilCO2 system decreases to suciently low values
which leads to a more favorable displacing process.18
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 CO2.20 Figure 2 shows a schematic
diagram of the experimental setup used for measuring the equilibrium
IFT of the crude oilCO2 system at various equilibrium pressures and
constant temperature (T = 30 C). First, the see-through windowed
high-pressure IFT cell (Temco Inc.) was heated to the specic
experimental temperature of T = 30 C and then lled with the CO2 at
a prespecied 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 dierent
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 prespecied pressure and temperature of T = 30 C.
2.3. CO2 Solubility and Oil Swelling Factor Measurement.
Solubility of CO2 in the crude oil is a key parameter aecting the
performance of CO2-based EOR processes. Several studies have been
conducted and various methods have been proposed to measure and
model this parameter for various types of crude oil.2124 The amount of
CO2 solubility in the crude oil does directly have inuence on the oil
swelling factor, oil viscosity, oil density, and oilCO2 interfacial
tension. In addition, swelling of the oil as a result of dissolution of CO2
is one of the main mechanisms contributing to oil production during
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Figure 2. Schematic diagram of the experimental setup used for measuring the equilibrium IFT for crude oilCO2 system at various equilibrium
pressures and temperature of T = 30 C.

Figure 3. Schematic diagram of the experimental setup used for CO2 solubility and oil swelling factor measurements at various equilibrium pressures
and temperature of T = 30 C.

CO2-based EOR processes, particularly when applied to light oil pressure was considered as an equilibrium pressure (Peq) of the system.
reservoirs.25,26 Lastly, initial and nal CO2 volume in visual cell were determined by
Figure 3 depicts the schematic diagram of experimental apparatus for taking photos and utilizing image analysis technique. Throughout this
determining the CO2 solubility in the crude oil and the resulting oil
swelling factor at T = 30 C. The apparatus mainly consisted of a see- study, the solubility of CO2 in the oil (CO2) was dened as the ratio of
through windowed high-pressure cell (Jerguson Co.), a magnetic stirrer the total mass of dissolved CO2 in 100 gr of the original crude oil
(Fisher Scientic), and a high-pressure CO2 cylinder. A temperature sample and was calculated using the mass balance equations as given by
controller (Love Controls Co.) was also used to control the the following relationships:
experimental temperature and maintain it at a constant value. The
cell was charged with a specic volume of crude oil sample (i.e., Vo,i = mCO2,dissolved = mCO2,i mCO2,f
25 cm3). The magnetic stirrer was used to create a consistent
turbulence inside the cell. The produced turbulence signicantly PV
i CO2 ,i MWCO2 Pf VCO2,f MWCO2
accelerated the CO2 dissolution into the oil by creating convective mass =
Z iRT Zf RT
transfer. During the process, the pressure inside the see-through
windowed cell was measured and recorded using a digital pressure MWCO2 PV
i CO2 ,i Pf VCO2,f
gauge (Ashcroft Inc.). Once the visual cell was pressurized with CO2 to =
a prespecied pressure (Pi), the pressure of the cell was allowed to RT Z i Zf (1)
stabilize while CO2 was dissolving into the crude oil. The test was
terminated when the nal CO2 pressure (Pf) inside the cell reached a
stable value and no further pressure decay was observed. The nal moil = (oil Voil) (2)

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Energy & Fuels
Figure 4. Schematic diagram of the experimental setup used for CO2 hu-and-pu tests conducted at various operating pressures and temperature of T
= 30 C.
mCO2,dissolved
CO = 100
2 moil
MWCO2 PV i CO2 ,i Pf VCO2,f
= (mD)
oil VoilRT Z i Zf (3)
The swelling factor (SF) of the oil due to the dissolution of CO2 at
any specic operating condition was also determined by the ratio of the
nal volume of the oil to its initial value at the beginning of the
experiment:
Vo,f
SF =
Vo,i (4)
2.4. CO2 Hu-and-Pu Tests. Figure 4 shows the experimental
setup used for CO2 hu-and-pu tests in this study. It consisted of a
high-pressure stainless steel core holder (Hassler, Inc.) with inner and
outer diameters of 6.1 and 7.9 cm, respectively. A consolidated Berea
core sample with the height of h = 30.21 cm and diameter of d = 5.05
cm was used as a physical porous medium. The core sample had a
porosity, absolute permeability, and pore volume of = 18.5%, kabs =
70.8 mD, and PV = 111.82 cm3, respectively. The core sample was also
initially water-wet. Table 2 presents the properties of the core sample
and core holder. A strong rubber sleeve (Viton) supported by an
overburden pressure of POB = 14 MPa was used to insulate the core in
the core holder, allowing uids to pass through the cross-section of the
core and along the horizontal direction, and to prevent ows of uid
around the core. A Teledyne ISCO syringe pump (ISCO Inc., 500D
series) was used to inject uids (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 pipes (Swagelok Company). To maintain desired back
pressure in the system, a back pressure regulator (Temco, Inc.) was
Article
Table 2. Properties of the Core Sample and Core Holder
Used for CO2 Hu-and-Pu Tests
permeability porosity height diameter pore volume
(%) (cm) (cm) (cm3)
core 70.8 18.5 30.21 5.05 111.82
sample
core 35.59 6.12 1046.94
holder
connected to the end of the core holder. Prior to each experiment, the
core was cleaned, vacuumed, and completely saturated with the brine.
During the brine saturating process, the brine injection ow rate was
varied in the range of qwinj = 0.252 cm3/min to determine the
absolute permeability of the core sample in each test. The measured
absolute permeability for each test was in the range of kabs = 70.671.0
mD. Thereafter, the oil sample was injected into the system with
constant ow rate of qoinj = 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 = 45.145.8%, and the
initial oil saturation was in the range of Soi = 54.254.9% for all hu-
and-pu tests. These saturations can be obtained when no more water
is produced. Negligible dierence in porosity, absolute permeability,
connate water, and initial oil saturations showed almost no changes in
the characteristics of the core sample during all tests. The initial oil
eective permeability (koi) can also be determined using dierential
pressure between the inlet and outlet of the core holder. After the core
was saturated with oil, the core was allowed to remain for 24 h to reach
a proper equilibrium condition at constant temperature of T = 30 C.
Because cyclic CO2 injection tests were performed at various operating
pressures, the above procedure was repeated for all experiments.
For the CO2 hu-and-pu tests, the pressure of the CO2 in the
transfer cell was increased to a desired operating pressure for each test
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Table 3. Experimental Conditions, Total and Stage Oil Recovery Factors, Total Producing GOR, Final GUF, Precipitated
Asphaltene Content, and Permeability Reduction of All Five CO2 Hu-and-Pu Tests at Dierent Operating Pressures
test 1 2 3 4 5
operating pressure (MPa) 5.35 6.55 8.27 9.31 10.34
miscibility condition immiscible immiscible near-miscible miscible Miscible
porosity (%) 18.4 18.7 18.6 18.6 18.5
absolute permeability (mD) 70.6 70.8 71.0 70.9 71.0
connate water saturation (%) 45.4 45.9 44.7 44.9 44.3
ultimate recovery factor (%) 33.2 47.5 55.8 60.9 61.5
rst stage recovery factor (%) 7.6 12.9 16.8 23.9 23.9
second stage recovery factor (%) 5.8 9.8 11.2 15.1 16.13
total producing GOR (cm3 gas/cm3 oil) 1610.3 1560.0 2083.1 932.2 979.6
nal GUF (cm3 oil/cm3 inj. gas) 342.8 379.4 320.8 574.3 537.5
CO2-produced oil asphaltene content (wt %) 0.59 0.53 0.48 0.46 0.45
precipitated asphaltene in the core (wt %) 0.64 0.70 0.75 0.77 0.78
permeability reduction factor to the oil (%) 9.81 10.72 13.34 13.95 13.79

and kept for 24 h to equilibrate at the experimental temperature. Then determined using the dierential pressure across the core in the core
the CO2 was injected into the oil saturated core under constant holder. Finally, the permeability reduction factor to the oil phase was
operating pressure for a denite injection time of tinj = 120 min. After calculated through the eq 5. There was also no water produced during
completion of CO2 injection (hu cycle), CO2 was allowed to soak for a the reinjection of the crude oil into the system.
soaking period of tsoak = 24 h. The pu cycle was then started by the oil kof
production at the end of the core holder while the back pressure DFo = 1
regulator was set at the pressure of PBPR = 3.45 MPa using a nitrogen koi (5)
cylinder. It is noted that during production in each pu cycle of cyclic
CO2 injection, no connate water was produced. Because the hu-and-
pu process is a single-well injectionproduction technique, both CO2
3. EXPERIMENTAL RESULTS AND DISCUSSION
injection and oil production in this study were conducted in the same 3.1. IFT and MMP of Crude OilCO2 system. Figure 5
side (i.e., outlet) of the core holder. When the rst hu-and-pu cycle depicts the measured IFT values of the crude oilCO2 system at
was completed, the second cycle was started with a procedure that was
the same as that of the rst cycle. These cycles were continued until no
considerable oil production was obtained. The volume of the produced
oil and gas in each pu cycle was measured to calculate the oil recovery
factor (RF), producing gasoil ratio (GOR), and gas utilization factor
(GUF). It is worth noting that GUF is dened as the ratio of the
produced oil volume to the injected gas volume.
Five secondary CO2 hu-and-pu tests were performed at dierent
operating conditions followed by the aforementioned procedure. The
experimental conditions (i.e., saturation data and operating pressure)
for each test are presented in Table 3. The cyclic CO2 injection tests
were carried out at ve operating pressures of Pop = 5.38, 6.55, 8.27,
9.31, and 10.34 MPa and constant temperature of T = 30 C. In
addition, a secondary waterooding test with water injection rate of
qwinj = 0.75 cm3/min at Pop = 3.45 MPa followed by a miscible CO2
hu-and-pu test at Pop = 9.31 MPa were conducted to investigate the
recovery performance of the CO2 hu-and-pu technique as a tertiary
oil recovery process.
2.5. Asphaltene Precipitation and Permeability Reduction
Measurement. Precipitation and deposition of asphaltene particles in
the pore spaces of reservoir rocks result in wettability alteration and Figure 5. Measured CO2oil IFTs at dierent equilibrium pressures
permeability reduction in hydrocarbon reservoir which considerably and multicontact MMP of crude oilCO2 system obtained from
reduce the oil recovery.2730 Asphaltenes are high-molecular-weight vanishing interfacial tension (VIT) technique at T = 30 C.
solids which are soluble in aromatic solvents such as benzene and
toluene but insoluble in paranic solvents (i.e., n-pentane and n-
heptane).31 In CO2 immiscible and miscible displacement processes, various equilibrium pressures in the range of Peq = 0.6614.64
the injected CO2 can induce occulation and deposition of asphaltenes MPa and T = 30 C. Accordingly, it was found that the
and other heavy organic particles which consequently cause numerous equilibrium IFT of the crude oilCO2 system decreases linearly
production problems.3234 Thus, it is of great importance to determine in two distinct ranges. In range I, with the pressure range of Peq =
how much asphaltene precipitates in the porous system during CO2 0.666.41 MPa, the IFT reduces linearly because of CO2
injection processes. In this study, the cumulative average asphaltene dissolution into the oil phase. In range II, with the pressure
content of the CO2-produced oil in the rst and second cycles of each
hu-and-pu test was measured using the standard ASTM D2007-03
range of Peq = 7.3514.64 MPa, the governing mechanism
method and the n-pentane was used as precipitant. Furthermore, to which leads to linear IFT reduction of the crude oilCO2
determine the permeability reduction of the system after each CO2 system is extraction of lighter hydrocarbon components by CO2.
hu-and-pu test, the original light crude oil was reinjected into the The measured equilibrium IFT decreased from IFTeq = 19.41
core holder with a constant ow rate of qoinj = 0.25 cm3/min after the mJ/m2 at the equilibrium pressure of Pop = 0.66 MPa to its
last cycle of production. The nal eective oil permeability (kof) was minimum value of IFTeq = 2.4 mJ/m2 at Peq = 14.64 MPa.
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Table 4. Pressure Range, Correlated Equations and Their Accuracy, and Calculated Multicontact and First-Contact MMPs
Obtained from VIT Technique at T = 30 C
IFT phase pressure range (MPa) correlated equation
range I 0.666.41 IFTeq = 2.3127Peq + 21.1750
range II 7.3514.64 IFTeq = 0.3864Peq + 8.0042
The vanishing interfacial tension (VIT) technique was applied
on the measured equilibrium IFTs to determine the minimum
miscibility pressure (MMP) of the crude oilCO2 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.23 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 (Peq
= 0.666.41 MPa and Peq = 7.3514.64 MPa) were regressed
linearly to correlate with equilibrium pressures as presented in
Table 4 and shown in Figure 5. The intersection of the linear
equation representing the equilibrium IFTs in range I with the
abscissa (i.e., IFTeq = 0) gives the multicontact or minimum
CO2 miscibility pressure, which was found to be MMP = 9.18
MPa. The second linear regression intersects with IFTeq = 0 at
20.44 MPa. Because at this pressure almost all intermediate and
heavy components become miscible with CO2, this pressure
may be interpreted as the rst contact CO2 miscibility pressure
with the oil. The intersection of the two linear correlations at the
extraction pressure of Pext = 6.84 MPa is the point at which the
interaction mechanism between the crude oil and CO2 changed
from the CO2 solubility to extraction of lighter components by
CO2.
3.2. CO2 Solubility and Oil Swelling Factor in the
Crude OilCO2 System. The experimental results of CO2
solubility in the crude oil sample and oil swelling factor at T = 30
C are depicted in Figure 6. This gure illustrates that the
Figure 6. Measured CO2 solubility in the crude oil and oil swelling
factor of crude oilCO2 system at various equilibrium pressures and T
= 30 C.
solubility of the CO2 increases as the equilibrium pressure of the
system increases. The concentration of dissolved CO2 is
proportional to the partial pressure of the CO2. The CO2
partial pressure controls the number of CO2 molecule collisions
in contact with the surface of the crude oil sample. Because
higher partial pressure (i.e., equilibrium pressure of the system)
results in an increase in the number of collisions that occur in
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Article
accuracy (R2) calculated MMP (MPa)
0.9983 9.18 (multicontact)
0.9673 20.44 (rst-contact)
contact with the surface, more CO2 is dissolved in the crude oil
with increased equilibrium pressure. In addition, the volume of
the crude oil increases by increasing the equilibrium pressure,
which is mainly due to the higher solubility factor of CO2 in the
crude oil at higher pressures; as a result of this phenomenon, the
crude oil swells in the visual cell. At higher equilibrium
pressures, the CO2 phase changes from gas to liquid. Because
liquid-phase CO2 has the greater ability to extract hydrocarbon
components of crude oil,26 especially the lighter components,
compared to the gaseous CO2 phase, the volume of the crude oil
in the visual cell is reduced. At the start of the experiment, the
solubility of CO2 and swelling factor of crude oil are 0 and 1
respectively. As shown in Figure 6, the solubility of CO2 and
swelling factor in the crude oil increase with equilibrium
pressure and reach their maximum values at Peq = 6.79 MPa.
The maximum CO2 solubility and swelling factor of the crude
oil at this pressure are CO2 = 31.46 wt % and SF = 1.32,
respectively. After this point, the extraction phase dominates the
swelling phase and leads to a decrease in the volume of the crude
oil in the visual cell and a decline in swelling factor because
lighter hydrocarbon components are extracted by CO2 and
vaporized into the gaseous phase. Results of the swelling tests
indicate that extraction phase of crude oilCO2 system starts at
a pressure near Pext = 6.79 MPa, which is in good agreement with
the Pext = 6.84 MPa obtained from IFT tests.
3.3. Oil Recovery Factor, Producing GOR, and GUF. In
this study, a total of ve secondary CO2 hu-and-pu tests were
carried out at dierent operating pressures ranging from Pop =
5.38 to 10.34 MPa and at a temperature of T = 30 C under
immiscible, near-miscible, and miscible conditions. In each
cycle, the CO2 was injected into the system for tinj = 120 min,
then the system was shut in for the soaking period of tsoak = 24 h;
nally, it was allowed to produce. The cycle numbers were
continued until no considerable oil production was obtained. It
is worth noting that there was no water production during
secondary CO2 hu-and-pu tests and the connate water
saturation remained constant during the whole process.
Figure 7 shows the measured oil recovery factor versus cycle
numbers and pore volume of injected CO2 for ve hu-and-pu
tests at dierent operating pressures. The oil recovery factor
increased with the cycle numbers and pore volume of injected
CO2. The results showed that for tests performed at immiscible
conditions, specically test 1 (i.e., Pop = 5.35 MPa) and test 2
(i.e., Pop = 6.55 MPa), the oil recovery factor increases
remarkably from RF = 32.2% to 47.5% as the operating pressure
increases and reaches RF = 55.83% at the near-miscible
condition (i.e., test 3) with Pop = 8.27 MPa. The measured oil
recovery factor reached its almost maximum value of RF =
60.9% at operating pressure near MMP, Pop = 9.31 MPa (i.e.,
test 4). Further increase of operating pressure to Pop = 10.34
MPa (i.e., test 5) did not result in noticeable oil recovery, and a
recovery factor of only RF = 61.5% was obtained. However, it
was found that in hu-and-pu tests performed at the miscible
condition, the ultimate recovery factor was achieved by fewer
cycles or pore volume of injected CO2 (i.e., 7 cycles) compared
to that in immiscible conditions (i.e., 1011 cycles). This was
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Energy & Fuels Article

Figure 8. Ultimate, rst, and second stage oil recovery factors of ve

CO2 hu-and-pu tests performed at immiscible, near-miscible, and
miscible conditions.

subsequent cycles, resulting in a higher oil recovery factor in the

rst and second cycles and lower one during preceding cycles of
CO2 hu-and-pu process.
The producing gasoil ratio (GOR) and gas utilization factor
(GUF) of ve cyclic CO2 injection tests performed at dierent
operating pressures are shown in Figure 9. In addition, Figure 10

Figure 7. Cumulative oil recovery factor versus (a) cycle numbers and
(b) pore volume of injected CO2 for ve CO2 hu-and-pu tests at
dierent operating pressures.

mainly attributed to the faster and stronger CO2 extraction

mechanism at miscible conditions, which leads to a signicant
ultimate oil recovery factor by less pore volume of injected CO2.
The ultimate oil recovery factor and rst and second stage
recovery factors of ve secondary CO2 hu-and-pu tests versus
operating pressure in three discrete regions of immiscible, near-
miscible, and miscible conditions are plotted in Figure 8 and
presented in Table 3. As can be seen from this gure, in the
range of immiscible to near-miscible CO2 hu-and-pu
processes, the ultimate recovery factor highly depends on
operating pressure and increases considerably with pressure.
Similarly, the same results were obtained for the rst and second
stage recovery factors in the aforementioned regions. Moreover,
it was found that 4060% of the recovered oil in hu-and-pu
tests was produced in the rst and second cycles. During the
initial oil saturation of the core sample, because the rock sample
was water-wet, the oil phase occupies the porous media starting
with larger pore spaces because of lower wateroil capillary
pressure. Therefore, the oil saturation is generally higher in
larger pores.35 On the other hand, because the capillary pressure
of the oilgas phase is also lower in larger pore spaces of the
core, the CO2 molecules begin to occupy and diuse into the
larger pores during initial cycles (i.e., rst and second cycles). As Figure 9. (a) Producing gasoil ratio and (b) gas utilization factor
a result, the CO2 interacts with a higher volume of the oil in- versus pore volume of injected CO2 for ve CO2 hu-and-pu tests at
place during initial cycles and a lower volume during the dierent operating pressures.

780 dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784

Energy & Fuels
Figure 10. Total producing GOR and nal GUF of ve CO2 hu-and-
pu tests at dierent operating pressures.
portrays the total producing GOR and nal GUF of the tests. It
was found that the total producing GOR of miscible CO2 hu-
and-pu tests is relatively less than that of immiscible and near-
miscible CO2 hu-and-pu tests. This is due to a smaller volume
of CO2 (i.e., fewer injection cycles) is required to be injected
into the core holder in miscible injection, and more oil was
recovered as well. For this same reason, the nal GUF of
miscible CO2 hu-and-pu tests is higher than that of
immiscible tests because a greater volume of the original oil
in-place is recovered by injecting a smaller volume of CO2 into
the system.
Figure 11 depicts the cumulative oil recovery factor,
producing GOR, and producing WOR of secondary the
waterooding test followed by a miscible CO2 hu-and-pu
(i.e., P op = 9.31 MPa). The results showed that the
waterooding process is able to produce 53.9% of original oil
in-place (i.e., ultimate RF = 53.9%). It was also observed that the
oil recovery factor at the water breakthrough is RF = 43.2%,
showing that most of the produced oil during waterooding was
recovered before the water breakthrough. The producing
wateroil ratio (WOR) increased drastically after the water
breakthrough and reached WOR = 1.68 at the end of the
secondary waterooding process. The results also indicated that
Figure 11. Cumulative oil recovery factor, producing GOR, and producing WOR during secondary waterooding and tertiary miscible CO2 hu-and-
pu tests.
781
Article
the conducted tertiary miscible CO 2 hu-and-pu test
signicantly increases the oil production by an extra recovery
factor of RF = 16.3%. The ultimate oil recovery factor of RF =
70.2% was achieved by conducting both secondary water-
ooding and tertiary CO2 hu-and-pu tests. The producing
wateroil ratio started to decline gradually during the tertiary
CO2 hu-and-pu test, while the producing gasoil ratio was
signicantly increased.
3.4. Asphaltene Precipitation and Permeability Re-
duction. The cumulative average asphaltene content of CO2-
produced oil of the rst and second cycles of CO2 hu-and-pu
tests as well as precipitated asphaltene in the core are plotted in
Figure 12 and presented in Table 3. The initial n-pentane
insoluble asphaltene content of original light crude oil was 1.23
wt %, whereas the measured values asphaltene content of CO2-
produced oil in ve CO2 hu-and-pu tests were lower than this
value. This is an indication of asphaltene precipitation and
deposition phenomena in the pore spaces of the core sample as a
result of CO2 injection. As shown in Figure 12, for the CO2 hu-
and-pu tests carried out at a pressure lower than MMP (i.e.,
immiscible conditions), specically test 1 (i.e., Pop = 5.35 MPa)
and test 2 (i.e., Pop = 6.55 MPa), the values of cumulative
asphaltene content of the CO2-produced oil obtained from the
rst and second cycles are considerably higher than those of the
tests performed at pressures near and above MMP (i.e., near-
miscible and miscible conditions). Conversely, it can be
concluded that in the near-miscible and miscible CO2 hu-
and-pu tests, the amount of precipitated asphaltene in the
porous media is drastically higher. It is again due to the stronger
light component extraction process by CO2 at pressures near
and above MMP that leads to asphaltene particles becoming
unstable and a reduction in their association with other
hydrocarbon groups, particularly resins.
The permeability reduction of the core sample after
termination of cyclic CO2 tests at each operating pressure was
determined and is illustrated in Figure 12 and tabulated in Table
3. The permeability reduction was calculated using eq 5. The
permeability reduction of the core sample is mainly attributed to
the rock wettability alteration from water-wet to mixed or oil-
wet because of the precipitation and deposition of asphaltene
dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784
Energy & Fuels Article

Figure 12. Asphaltene content of CO2-produced oil, precipitated asphaltene in the core, and permeability reduction of the core sample in all CO2 hu-
and-pu tests conducted at dierent operating conditions and under immiscible, near-miscible, and miscible conditions.

Figure 13. Compositional analysis of original crude oil and remaining crude oil of CO2 hu-and-pu tests performed at Pop = 6.55 and 9.31 MPa.

particles on the rock surfaces. The results showed that the

permeability reduction of the core sample in near-miscible and
miscible CO2 hu-and-pu tests is considerably higher than that
in immiscible cases because the remaining and deposited
asphaltene particles and heavy components in the porous
medium are larger in CO2 hu-and-pu tests carried out at
pressures near and above MMP.
3.5. Compositional Analysis of Remaining Oil. Figures
13 and 14 depict the compositional analysis and grouped carbon
number distributions of remaining crude oil for CO2 hu-and-
pu tests performed at Pop = 6.55 MPa (i.e., immiscible
condition) and 9.31 MPa (i.e., miscible condition), respectively.
The remaining crude oil was collected at the beginning of the
production time during the reinjection of the fresh oil into the
core holder. As mentioned earlier, the mechanism of light Figure 14. Grouped carbon number distributions of original crude oil
component extraction by CO2 removed all lighter components and remaining crude oil of CO2 hu-and-pu tests performed at Pop =
ranging C1C4s and C1C5s from the oil phase at Pop = 6.55 6.55 and 9.31 MPa.
and 9.31 MPa, respectively. Accordingly, the mole percent of
782 dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784
Energy & Fuels Article

intermediate to heavy hydrocarbons including C10C19s, C20 CO2 extraction is much stronger at pressures near and
C29s, C30+, and molecular weight of the remaining oil were above MMP.

relatively higher than those in the original crude oil. On the
other hand, comparing the composition of remaining oil at Pop =
6.55 and 9.31 MPa shows that the mechanism of light
component extraction is much stronger at Pop = 9.31 MPa,
which is a miscible CO2 hu-and-pu test. As a result, the
remaining oil in the core after miscible CO2 hu-and-pu tests
contained a greater amount of heavy hydrocarbons (C10C19s,
C20C29s, and C30+) and greater molecular weight. This
comparison also conrms that the precipitated asphaltene in
the core during miscible CO2 hu-and-pu processes was
substantially greater than that during immiscible cases.
AUTHOR INFORMATION
Corresponding Author
*Petroleum Systems Engineering, Faculty of Engineering and
Applied Science, University of Regina, Regina, SK, S4S 0A2,
Canada. E-mail: Farshid.Torabi@uregina.ca. Tel: 1(306)585-
5667. Fax: 1(306)585-4673.
Notes
The authors declare no competing nancial interest.

4. CONCLUSIONS
ACKNOWLEDGMENTS
The authors thank the Petroleum Technology Research Centre
In this study, the oil recovery performance of secondary CO2 (PTRC) and Faculty of Graduate Studies and Research (FGSR)
hu-and-pu process in a light crude oil system under at the University of Regina for their funding support. The
immiscible, near-miscible, and miscible conditions was exper- authors also extend their gratitude to Mr. Nader Mosavat for
imentally investigated. The CO2 solubility, oil swelling factor, technical assistance during some of the experimental portions,
and equilibrium interfacial tension of the crude oilCO2 system and Dr. Y. Gu and Mr. Y. Gong for their help with the IFT
was determined at a wide range of equilibrium pressures and a measurement test.
constant temperature of T = 30 C. In addition, the MMP of
CO2 with the oil sample was determined by means of the VIT
technique. A total of six CO2 hu-and-pu tests at various
NOMENCLATURE
Symbols
operating pressures and temperature of T = 30 C with the DFo = permeability reduction factor to the oil phase
injection time of tinj = 120 min and soaking period of tsoak = 24 h IFTeq = equilibrium IFT (mJ/m2)
were carried out. According to the obtained experimental kabs = absolute permeability (mD)
results, the following conclusions have been drawn: koi = initial oil eective permeability (mD)
The multicontact MMP of the CO2 with the original light kof = nal oil eective permeability (mD)
crude oil was determined by applying the VIT technique MW = molecular weight (g/mol)
on the measured equilibrium IFTs of the crude oilCO2 m = mass (gr)
system and found to be MMP = 9.18 MPa at T = 30 C. n-C5 = normal pentane
This pressure was used as a reference to determine the Pop = operational pressure (MPa)
miscibility condition of CO2 hu-and-pu tests. Peq = equilibrium pressure (MPa)
The CO2 solubility in the crude oil as well as the oil Pext = extraction pressure (MPa)
swelling factor were experimentally determined. On the PBPR = pressure of back pressure regulator (MPa)
basis of the results of IFT and swelling tests, it was found POB = over burden pressure (MPa)
that the hydrocarbon extraction mechanism initiates at qwinj = water injection ow rate (cm3/min)
extraction pressure of Pext = 6.8 MPa. qoinj = oil injection ow rate (cm3/min)
The ultimate oil recovery factor increased considerably R = universal gas constant (J/(mol K))
when operating pressure increased and reached the Swc = connate water saturation
maximum value at miscible condition (i.e., operating Soi = initial oil saturation
pressures near the MMP). Further increase of operating T = temperature (C)
pressure beyond the MMP did not noticeably enhance oil Texp = experimental temperature (C)
recovery. The results also indicated that the tertiary tinj = CO2 injection time (min)
miscible CO2 hu-and-pu has a great potential to tsoak = soaking period (hr)
increase the oil recovery from waterooded reservoirs. V = volume (cm3)
The precipitated asphaltene in the core as a result of CO2 Z = gas compressibility factor
injection into the system in near-miscible and miscible Greek Letters
CO2 hu-and-pu tests was substantially higher than that oil = oil density (kg/m3)
in immiscible tests. Furthermore, because of higher w = water density (kg/m3)
asphaltene precipitation at both near-miscible and oil = oil viscosity (mPa s)
miscible conditions, the permeability reduction of the w = water viscosity (mPa s)
core was drastically higher for both of those scenarios. = porosity
Compositional analysis showed that the remaining oil in CO2 = CO2 solubility in crude oil (wt %)
the core after CO2 hu-and-pu tests contained a greater Abbreviations
amount of heavy components and its molecular weight ADSA = axisymmetric drop shape analysis
was much higher than that for the initial oil sample EOR = enhanced oil recovery
because of light component extraction mechanism by GOR = gasoil ratio
CO2. Moreover, it was found that in miscible CO2 hu- GUF = gas utilization factor
and-pu tests, the remaining oil is relatively heavier than IFT = interfacial tension
that in immiscible CO2 hu-and-pu tests because the MMP = minimum miscibility pressure
783 dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784
Energy & Fuels
VIT = vanishing interfacial tension
REFERENCES
(1) Thomas, G. A.; Monger, T. G. The Feasibility of Cyclic CO2
Injection for Light Oil Recovery. Presented at the SPE/DOE Seventh
Symposium on Enhanced Oil Recovery, Tulsa, OK, April 2225, 1990;
Paper SPE/DOE 20208.
(2) Mohammed-Singh, L.; Singhal, A. K.; Sim, S. Screening Criteria
for Carbon Dioxide Hu n Pu Operations. Presented at SPE/DOE
Symposium on Improved Oil Recovery, Tulsa, OK, April 2226, 2006;
Paper SPE 100044.
(3) Shi, R.; Schnitzler, J.; Kantzas, A. Preliminary Results of Enhanced
Heavy Oil Recovery by CO2 Cyclic Injection. Presented at World
Heavy Oil Congress, Edmonton, Canada, March 1012, 2008; Paper
2008321.
(4) Towler, B. F.; Wagle, Y. A. Modeling the CO2 Huff n Puff
Process in Solution-Gas Drive Reservoirs Using a Black-Oil Simulator.
J. Pet. Sci. Eng. 1992, 8, 167179.
(5) Miller, B. J. Design and Results of Shallow, Light Oileld-Wide
Application of CO2 Hu n Pu Process. Presented at the SPE/DOE
Seventh Symposium on Enhanced Oil Recovery, Tulsa, OK, April 22
25, 1990; Paper SPE/DOE 20268.
(6) Miller, B. J.; Bardon, C. P.; Corlay, P. CO2 Hu nPu Field Case:
Five-Year Program Update. Presented at the SPE Permian Basin Oil
and Gas Recovery Conference held in Midland, TX, March 1618,
1994; Paper SPE 27677.
(7) Bardon, C.; Corlay, P.; Longeron, D.; Miller, B. CO2 Huff n Puff
Revives Shallow Light-Oil-Depleted Reservoirs. SPE Reservoir Eng.
1994, 9 (2), 92100.
(8) Rudyk, S.; Spirov, P.; Sogaard, E. Application of GCMS
Chromatography for the Analysis of the Oil Fractions Extracted by
Supercritical CO2 at High Pressure. Fuel 2013, 106, 139146.
(9) Wolcott, J.; Schenewerk, P.; Berzins, T.; Karim, F. A Parametric
Investigation of the Cyclic CO2 Injection Process. J. Pet. Sci. Eng. 1995,
14, 3544.
(10) Thomas, G. A.; Monger-McClure, T. G. Feasibility of Cyclic CO2
Injection for Light-Oil Recovery. SPE Reservoir Eng. 1991, 6 (2), 179
184.
(11) Monger, T. G.; Coma, J. M. A Laboratory and Field Evaluation of
the CO2 Huff n Puff Process for Light Oil Recovery. SPE Reservoir Eng.
1988, 3 (4), 11681176.
(12) Palmer, F. S.; Landry, R. W.; Bou-Mikael, S. Design and
Implementation of Immiscible CO2 Displacement Projects (CO2 Hu
n Pu) in South Louisiana. Presented at the SPE Annual Technical
Conference and Exhibition, New Orleans, LA, October 58, 1986;
Paper SPE 15497.
(13) Brock, W. R.; Bryan, L. A. Summary Results of CO2 EOR Field
Tests. Presented at the Low Permeability Reservoirs Symposium,
Denver, CO, March 68, 1989; Paper SPE 18977.
(14) Haskin, H. K.; Alston, R. B. An Evaluation of CO2 Huff n Puff
Tests in Texas. J. Pet. Technol. 1989, 41 (2), 177184.
(15) Li, H.; Putra, E.; Schechter, D. S.; Grigg, R. B. Experimental
Investigation of CO2 Gravity Drainage in a Fractured System.
Presented at the SPE Asia Pacic Oil and Gas Conference and
Exhibition, Brisbane, Australia, October 1618, 2000; Paper SPE
64510.
(16) Torabi, F.; Asghari, K. Effect of Operating Pressure, Matrix
Permeability and Connate Water Saturation on Performance of CO2
Huff-and-Puff Process in Matrix-Fracture Experimental Model. Fuel
2010, 89, 29852990.
(17) Torabi, F.; Qazvini Firouz, A.; Kavousi, A.; Asghari, K.
Comparative Evaluation of Immiscible, Near Miscible and Miscible
CO2 Huff-n-Puff to Enhance Oil Recovery from a Single Matrix
Fracture System (Experimental and Simulation Studies). Fuel 2012, 93,
443453.
(18) Gasem, K. A. M.; Dickson, K. B.; Shaver, R. D.; Robinson, R. L.,
Jr. Experimental Phase Densities and Interfacial Tensions for a CO2/
Synthetic-Oil and a CO2/Reservoir-Oil System. SPE Reservoir Eng.
1993, 8 (3), 170174.
784
Article
(19) Gu, Y.; Yang, D. Interfacial Tensions and Visual Interactions of
Crude OilBrineCO2 Systems Under Reservoir Conditions.
Presented at the Canadian International Petroleum Conference,
Calgary, Alberta, Canada, June 810, 2004.
(20) Cheng, P.; Li, D.; Boruvka, L.; Rotenberg, Y.; Neumann, A. W.
Automation of Axisymmetric Drop Shape Analysis for Measurements
of Interfacial Tensions and Contact Angles. Colloids Surf. 1990, 43 (2),
151167.
(21) Simon, R.; Graue, D. J. Generalized Correlations for Predicting
Solubility, Swelling and Viscosity Behavior of CO2-Crude Oil Systems.
J. Pet. Technol. 1965, 17, 102106.
(22) Jamaluddin, A. K. M.; Kalogerakis, N. E.; Chakma, A. Predictions
of CO2 Solubility and CO2 Saturated Liquid Density of Heavy Oils and
Bitumens Using a Cubic Equation of State. Fluid Phase Equilib. 1991,
64, 3348.
(23) Nobakht, M.; Moghadam, S.; Gu, Y. Determination of CO2
Minimum Miscibility Pressure from Measured and Predicted
Equilibrium Interfacial Tensions. Ind. Eng. Chem. Res. 2008, 47 (22),
89188925.
(24) Costa, G. M. N.; Rocha, P. S. M. V.; Riberio, A. L. C.; Menezes,
P. R. F.; Lima, R. C. A.; Costa, P. U. O.; Rodrigues, E. A. An Improved
Method for Calculating CO2 Minimum Miscibility Pressure Based on
Solubility Parameter. J. Pet. Sci. Eng. 2012, 98, 144155.
(25) Yang, C.; Gu, Y. Diffusion Coefficients and Oil Swelling Factors
of Carbon Dioxide, Methane, Ethane, Propane and Their Mixtures in
Heavy Oil. Fluid Phase Equilib. 2006, 243, 6473.
(26) Tsau, J. S.; Bui, L. H.; Willhite, G. P. Swelling/Extraction Test of
a Small Sample Size for Phase Behavior Study. Presented at the SPE
Improved Oil Recovery Symposium, Tulsa, OK, April 2428, 2010;
Paper SPE 129728.
(27) Ashoori, S.; Abedini, A.; Abedini, R.; Qorbani Nasheghi, Kh.
Comparison of Scaling Equation with Neural Network Model for
Prediction of Asphaltene Precipitation. J. Pet. Sci. Eng. 2010, 72, 186
194.
(28) Abedini, A.; Ashoori, S.; Torabi, F. Reversibility of asphaltene
precipitation in porous and non-porous media. Fluid Phase Equilib.
2011, 308, 129134.
(29) Abedini, A.; Ashoori, S.; Torabi, F.; Saki, Y.; Dinarvand, N.
Mechanism of the reversibility of asphaltene precipitation in crude oil. J.
Pet. Sci. Eng. 2011, 78, 316320.
(30) Khaksar Manshad, A.; Edalat, M. Application of Continuous
Polydisperse Molecular Thermodynamics for Modeling Asphaltene
Precipitation in Crude Oil Systems. Energy Fuels 2008, 22 (4), 2678
2686.
(31) Mansoori, G. A. Modeling of asphaltene and other heavy organic
depositions. J. Pet. Sci. Eng. 1997, 17, 101111.
(32) Srivastava, R. K.; Huang, S. S. Asphaltene Deposition During
CO2 Flooding: A Laboratory Assessment. Presented at the SPE
Production Operations Symposium, Oklahoma City, OK, March 911,
1997; Paper SPE 37468.
(33) Wang, X.; Gu, Y. Oil Recovery and Permeability Reduction of a
Tight Sandstone Reservoir in Immiscible and Miscible CO2 Flooding
Processes. Ind. Eng. Chem. Res. 2011, 50 (4), 23882399.
(34) Jafari Behbahani, T.; Ghotbi, C.; Taghikhani, V.; Shahrabadi, A.
Investigation on Asphaltene Deposition Mechanisms during CO2
Flooding Processes in Porous Media: A Novel Experimental Study
and a Modified Model Based on Multilayer Theory for Asphaltene
Adsorption. Energy Fuels 2012, 26 (8), 50805091.
(35) Abedini, A.; Torabi, F.; Tontiwachwuthikul, P. Reservoir Rock
Type Analysis Using Statistical Pore Size Distribution. Special Topics &
Reviews in Porous Media An International Journal 2012, 3 (2), 97
103.
dx.doi.org/10.1021/ef401363b | Energy Fuels 2014, 28, 774784