Fuel 178 (2016) 1–9

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Fuel
journal homepage: www.elsevier.com/locate/fuel

The influence of spreading coefficient on carbonated water alternating

gas injection in a heavy crude oil
Masoud Riazi a,⇑, Abdolah Golkari b
a
Enhanced Oil Recovery (EOR) Research Centre, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran
b
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The interfacial properties change strongly with temperature and pressure that could influence the dis-
Received 9 May 2015 placement of fluids in porous media. The main objective of this study was to measure interfacial tension
Received in revised form 4 March 2016 (IFT) of the binary systems of brine/crude oil/carbon dioxide (CO2) and carbonated brine/crude oil/CO2 at
Accepted 8 March 2016
two temperatures and different pressure conditions. Spreading coefficient (SC), which is determined from
Available online 17 March 2016
IFT data, is an important parameter in enhanced oil recovery (EOR) methods, which are based on three
phase systems. The spreading or non-spreading (the oil creates to form an immobile half sphere) oil
Keywords:
on the water–gas interface is a key factor on determining residual oil saturation during water alternating
Carbonated water alternating gas (CWAG)
Oil swelling
gas (WAG) injection process. In this work, experimental results on oil swelling and interfacial tension of
Pendant drop method crude oil, brine/carbonated brine and carbon dioxide systems at the pressure range of 2.76–13.79 MPa
Interfacial tension (IFT) and two temperatures of 40 °C and 50 °C is presented. Afterwards, by estimating spreading coefficient
Spreading coefficient (SC) of the mentioned systems an optimum condition for the enhanced oil recovery (EOR)-WAG process is
proposed.
The results indicate that, the equilibrium IFT data of the carbonated brine–crude oil system is lower
compared to that of the brine–crude oil system at the same conditions. The interfacial tension of the
carbonated brine–crude oil system decreases significantly at higher pressures. In addition to IFT
reduction due to the presence of CO2 in water, oil swelling was also observed. In this experimental work,
the dynamic oil swelling was monitored as a function of time. The IFT data of the above systems were also
used to estimate the spreading coefficient as a function of pressure at both temperature conditions. The
estimated spreading coefficient data for the brine/crude oil/CO2 and carbonated brine/crude oil/CO2
systems, indicates that the presence of CO2 in the brine phase, makes the spreading coefficient positive,
while this parameter in the brine/oil/CO2 system is negative. This means that oil would be spread on the
water phase during carbonated water alternating CO2 injection that consequently could further enhance
oil recovery.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Different stages of oil recovery are categorized into three peri-
ods of primary, secondary and tertiary. Primary production arises
from natural reservoir pressure. Recovery factor of this stage
depends to the reservoir rock properties, the oil viscosity, and
the reservoir pressure. When oil production rate during primary
stage is not economical, secondary recovery stage starts. At the
secondary recovery stage, water or gas is injected into the reservoir
to keep and build up the pressure. However, the recovery factor
after primary and secondary stages is about 30–50%. It means that
⇑ Corresponding author. Tel.: +98 71 36133714; fax: +98 71 36474602.
E-mail address: mriazi@shirazu.ac.ir (M. Riazi).
about two third of the original oil in place is trapped and remains
unrecovered due to the balance of capillary and viscous forces. To
produce the trapped oil phase enhanced oil recovery (EOR) tech-
niques are suggested and applied [1,2]. In this regard, extensive
laboratory studies and field applications of water alternating gas
injection (WAGI), cyclic injection of carbonated water (CW) and
CO2, carbon dioxide-EOR processes to investigate the potential of
carbonated water injection as an injection method for improved
oil recovery and CO2 storage have been performed [3–8]. Storing
carbon dioxide underground is being considered as a promising
sequestration technology for mitigating greenhouse gas emissions
[9–11]. In CO2-EOR and CO2 storage processes, the interfacial
tension phenomenon could strongly affect fluids (i.e. crude oil,
reservoir brine and CO2) distribution, and flow behavior within

http://dx.doi.org/10.1016/j.fuel.2016.03.021
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
2 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9
reservoir at high pressure conditions [12,13]. Two main mecha-
nisms of oil recovery that occur in the carbonated water injection
(CWI) process include swelling and coalescence of trapped oil and
the oil viscosity reduction as a result of diffusion and segregation of
CO2 from carbonated water into oil [5]. The interfacial tension
reduction can also be the other positive effect of CWI compared
to water injection (WI) process in the oil reservoir [14]. Further-
more, the interfacial properties of the crude oil, brine and CO2 sys-
tem vary significantly after CO2 injection at reservoir conditions.
Thus, it is of basic and operational importance to investigate the
interfacial tension phenomenon carefully in the crude oil–brine–
CO2 systems at high pressure and high temperature conditions.
Among several presented techniques for measuring the interfacial
tension (IFT), the pendant/rising drop method is probably one of
the best techniques for estimating the IFT at high pressure and
temperature conditions (i.e. at reservoir conditions). For the first
time this technique was used by Jennings Jr to estimate the inter-
facial tension by taking images a pendant drop and then estimating
the drop diameters [15–17]. Moreover, when the density differ-
ence of the two phases is very small (e.g. about 0.01 g cm
3), then
the pendant/rising drop method cannot be applied to determine
the IFT [17]. Recently, this technique has been significantly devel-
oped and is widely used to estimate the IFT data. Different research
groups used this technique to determine IFT values for different
fluid systems: the IFTs of the n-paraffin-CO2 systems [18–23], the
systems of synthetic oil–CO2, the systems of live crude oil–CO2
[24,25], the systems of crude oil–CO2 [14,26,27], the systems of
n-paraffin-water/brine [28,29], the systems of crude oil–brine
[14,30,31] and the water–CO2 systems [14,32,33]. Recently, the
axisymmetric drop shape analysis (ADSA) technique for the pen-
dant drop method is known as a new advanced method for mea-
suring the interfacial tension. ADSA technique was initially
developed by several researchers [34], and was further improved
by another team [35]. With compared to the other methods, accu-
racy of the ADSA technique for the pendant/rising drop method has
been approved for the interfacial tension estimation [36,37]. In this
work, by estimating spreading coefficient of the crude oil–brine
(carbonated brine)-CO2 systems an optimum condition for the
EOR-WAG/CWAG processes is determined.
Riazi et al. using micromodel experiments investigated the
effect of carbonated water injection (CWI) instead of water injec-
tion (WI) prior to carbon dioxide injection (CO2I) on oil displace-
ment mechanisms and recovery. According to their results
carbonated water makes the Glassy micromodel more water wet.
Moreover, they observed that CO2 flooding performances after
WI and CWI are different. That was, the injection of carbon dioxide
after CWI recovered more oil compared to that after WI [5,38]. The
proposed mechanism for the higher performance of CO2I in the for-
mer process was due to the existence of a continuous oil film
between the water and the displacing CO2 phases.
The main objective of the present work is to describe how the
brine/carbonated brine (CB)-CO2 IFT, brine/carbonated brine–oil
IFT, CO2–oil IFT data can be used on optimization of CWAG pro-
cess. To study the effect of pressure on IFT of oil, gas and brine
systems, the experimental results were utilized. Finally, based on
the experimental results, the ability of the oil phase to spread on
water in the presence of CO2 gas was investigated. These results
were also applied to discover an optimum flooding pressure con-
ditions for trapped oil saturation assessment after water and gas
displacement process of an Iranian oil reservoir. Spreading coef-
ficient (SC) is defined for water–oil–gas system, as the ability of
the oil phase to spread as a thin film between the water–gas
phases. This phenomenon (i.e., spreading of crude oil phase)
occurs in water-wet rocks when spreading coefficient is positive.
Spreading coefficient (SC) is estimated by the following
equation:
SC ¼ cCO2
W
ðcO
W þ cCO2
O Þ ð1Þ
where SC is the spreading coefficient, cCO2–W, cCO2–O and cO–W are
IFT of CO2/water, CO2/oil and oil/water systems, respectively.
Spreading coefficient is usually used to describe the physically
and chemically interactions between different fluids. It can be
either positive or negative depending on the composition of fluids
in-place and the reservoir pressure and temperature conditions
[39]. Spreading coefficient would also determine the nature of dis-
tribution of the water, oil and gas within the reservoir rock pores.
Thus, it can be a key factor in gas/water/oil relative flow behaviors
and determining the additional oil recovery [40,41]. The oil recov-
ery and efficiency of an EOR process depends on the spreading
coefficient and wettability of the porous medium. In this work,
spreading coefficient is estimated for a three phase system.
Oren et al. [39,42] using the three fluids of air, refined oil and
distilled water investigated the spreading coefficient in porous
rocks with different wettability conditions. They concluded that
in a water-wet system, oil recovery for the SC > 0 was significantly
higher compared to that for the case when the SC < 0; whereas the
oil-wet system displayed an opposite trend.
In addition, Vizika and Lombard [43] using gravity drainage
experiments studied the spreading and non-spreading conditions
in three systems of water-wet, oil-wet and fractionally-wet. Their
results indicated that the highest oil recoveries were obtained for
positive value of SC and water-wet or fractionally-wet conditions.
The lowest oil recovery was obtained for negative values of SC and
the water-wet system.
In another experimental work, Sharma and Filoco [44] studied
the effect of spreading coefficient on the residual oil saturation.
They performed the drainage tests with samples the air, brine
(NaCl) and decane/dodecene on the water-wet Berea sandstone
core. A small amount of iso-butanol was added to the brine phase
aiming to change the initial spreading coefficient from positive to
negative. Their results indicated that the positive spreading coeffi-
cient (SC = 5.5) results in a very low remaining oil saturation com-
pared to the negative SC (SC =
4.1).
When the SC is positive, the oil phase will spread between the
water and gas phases. Hence, oil would easily flow within the por-
ous medium during the course of immiscible gas injection. The film
continuity of oil favors the hydraulic stability of the oil phase that
results on more oil recovery and hence reduces the trapped oil sat-
uration [45].
In the case of the negative spreading coefficient value, oil would
be trapped within the pore space as a lens of static oil on the water
phase. Since, the oil does not have the ability to spread under neg-
ative spreading coefficient conditions in a water wet rock sample.
Therefore, the water phase may flow and bypass the oil and finally,
a higher trapped oil saturation be left behind [46]. The precise IFT
estimation is also important for evaluating the oil production per-
formance of a fractured reservoir [47]. One of the most important
oil production mechanisms in fractured reservoirs, is gravity drai-
nage [43,48,49]. The distribution and displacement of reservoir flu-
ids in the pores are mainly affected by capillary forces, which
depend on interfacial properties of the rock and fluids (i.e. the rock
wettability and fluids IFT) [46,50].
Amin and Smith [46] measured the IFT of three systems of
methane against the pentane, heptane and n-decane by applying
the pendant drop method at different pressure and temperature
conditions. Using IFT measurements, they reported the spreading
coefficient (SC) values for a crude oil/brine/gas system at reservoir
conditions. They also observed a negative SC value at pressures
higher than 20.68 MPa. Thus, they suggested that operating pres-
sure for EOR process should be performed below 20.68 MPa,
because the spreading coefficient values are positive at pressures
lower than this pressure. In this experimental work, the IFT
 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9
Table 1
Specifications of the crude oil used [51].
Specification Unit
Gravity of dead oil °API
C+12 molecular weight
C+12 density at 15 °C g/cm 3
Saturates mass % 0.4268
Aromatics mass % 0.4069
Resins mass % 0.0763
Asphaltene mass % 0.0900
variation of binary systems of brine/carbonated brine (CB)-crude
oil–CO2 is investigated. Finally, the SC value is reported in order
to determine the best operational condition for the carbonated
water alternating CO2 injection process.
2. Experimental section
2.1. Materials
Stock tank crude oil from one of the Iranian oil reservoirs was
used as the oleic phase in this study. Its properties are given in
Table 1. The composition of the oil is also shown in Table 2. The
general specification reported in Tables 1 and 2, presented by
National Iranian South Oil Company. Sodium chloride supplied
by Merck Company was used to prepare brine. The brine was pro-
vided at salinity of 10,000 ppm. Toluene and acetone were utilized
for cleaning the possible contamination. The purities of carbon
dioxide and nitrogen used are 99.99% and 99.998%, respectively.
2.2. Density meter apparatus
Crude oil and brine densities were measured using densitome-
ter DMA HPM (Anton Paar, Austria) [53] with level of confi-
dence = 0.96. Fluid density is required to be measured with high
accuracy of 0.0005 g/cm3, for high accuracy IFT estimation. Fig. 1
shows the schematic view of the density measurement apparatus.
It shows that the DMA HPM is connected to the interface module
by a metal-covered cable. The measured raw data of the DMA
HPM have to be transferred to the assessment unit mPDS 2000
V3 to estimate the density. Density measurement using this appa-
ratus depends on the period of oscillation of the U-tube. Before the
measuring of the density, whole of the U-tube cell and its connec-
tions should be cleaned using toluene and acetone then, dried by
nitrogen injection. The Anton Paar densitometer has been designed
for density measurement of the fluids at high pressure and temper-
ature conditions. Prior to density measurement, the density meter
device was calibrated by pure fluids at different pressures and
required temperatures [23].
2.3. Interfacial tension (IFT) 700 device and equilibrium IFT
measurement
The equilibrium interfacial tension was measured using IFT 700
apparatus. Fig. 2 shows a schematic of the experimental setup for
IFT measurement between the liquid and CO2 samples. This device
is working at different pressure and temperature conditions (Tem-
peratures of ambient to 175 °C and pressures up to 69 MPa) [54].
Table 2
Compositional analysis of the crude oil used [52].
Component CO2 C1 C2 C3 iC4
Mole % 0.00 0.00 0.16 0.33 0.17
3
An optimized design was used for high pressure cell with 20 cm3
inner volume to conduct interfacial tension measurements at high
Value pressure and temperature conditions. The high pressure cell was
24.46 connected by four high pressure tubing with manual pressure iso-
326 therms correlated to generators (HP) equipped. The overall pres-
0.9355 sure of system is controlled by a manual pump with accuracy of
0.05 MPa. Two tanks are used to store two different fluids into
the cell that are used for bulk fluid transfer and drop fluid injection.
The view cell is formed from three port at the top and bottom (to
the bulk and drop fluids injection and draining fluid), to high-
pressure tubing connections. The temperatures of the cell and
tanks were controlled with two electrical sensors (PT100). The
overall temperature control is monitored with an accuracy of
0.1 K. A CCD camera (1.4 Mpixel) and a light source were used
for viewing the drops with high resolution. The equilibrium inter-
facial tension was estimated from images of the drops by image
analysis software, which allows a quick estimation of equilibrium
IFT. In this study, to form the pendant and rising drops in the high
pressure cell a steel needle with the outer diameter of about
1.5 mm (for the systems of oil–CO2 and water–CO2) and 0.79 mm
(for the water/carbonated water–oil system) with an uncertainty
of ±0.01 mm, was used. Eventually, the output data including the
dynamic IFT, drop volume and bond number are estimated using
the software [23].
3. Experimental process
To estimate the IFT between binary systems of crude oil/CO2,
brine/CO2 and brine/crude oil, it needs that the oil, brine and gas
densities to be previously measured accurately at the required
temperatures and pressures. DMA HPM (Anton-Paar, Austria)
apparatus for density measurement, was utilized. The U-tube cell
is linked to a high temperature circulating bath, which is able of
keeping the cell at the desired temperature. It is connected to a
high-pressure piston-cylinder and a high pressure pump, which
transports the fluids inside the cell at the desired pressure. The cal-
ibration of the densitometer device was performed using three
pure fluids (deionized water, dodecane, and nitrogen) at tempera-
ture ranges of 40–80 °C for deionized water and 40–120 °C for both
dodecane and nitrogen [23]. The densities of brine and crude oil
were then measured at various pressures (2.76–13.79 MPa) and
at two different temperatures (i.e. 40 and 50 °C). Prior to running
each experiment, the whole system was examined with distilled
water for leakage and then cleaned with toluene (for cleaning
crude oil) and acetone, it was finally drained with nitrogen [37].
The heater was adjusted at the required temperature. When the
equilibrium conditions were reached (at the selected temperatures
and pressures), pure CO2 was gradually injected into the storage
tank and the high pressure cell. Then the cell was allowed to reach
equilibrium conditions. It should be mentioned that pressure was
slowly increased by bulk fluid injection (0.7 MPa per 60 s) [54].
It is worth mentioning that, for systems of crude oil–CO2 and
brine–CO2, before running the interfacial tension tests the crude
oil and brine phases with CO2 were not pre-equilibrated. In fact
the objective of this experimental procedure was to estimate the
dynamic and equilibrium IFTs. To provide the equilibrium condi-
tions for a two phase system of crude oil and CO2, 10–15 oil drops
are placed in the bottom of the cell before transferring CO2 gas into
the high pressure cell. This is utilized to simulate the process of
nC4 iC5 nC5 C6 C7 C8 C9 C10 C11 C+12
0.41 0.30 0.33 4.83 7.40 7.90 7.22 6.76 4.13 60.06
4 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9

Fig. 1. A schematic of the densitometer Anton Paar apparatus. 1, mPDS 2000 V3; 2, interface module; 3, DMA HPM; 4, pressure generator; 5, heating and cooling bath [23].

Fig. 2. Experimental apparatus of IFT measurement for case of the water/carbonated water–oil systems. 1, pressure generator; 2, bulk and drop tanks; 3, light source; 4, high
pressure view cell; 5, pressure and temperature display unit; 6, CCD camera; 7, personal computer.

CO2-EOR and CO2 storage into the reservoir, during which CO2 con-
tacts with the reservoir fresh fluids (i.e. crude oil and brine) [37].
For the carbonated brine–crude oil–CO2 system, the brine and
CO2 brought in contact together to reach equilibrium conditions
before formation of the rising oil drop. This is to simulate the pro-
cess at conditions, which CO2 dissolved into the crude oil phase
after it passes through a brine barrier in an oil reservoir during a
CO2-EOR process. The experimental procedure for the dynamic
and equilibrium IFTs measurements is designated as follows. For
the equilibrium systems of the crude oil or brine against the CO2,
after the cleaning whole the apparatus, a stainless steel needle
was installed at the top of the high pressure cell that a pendant
drop of brine or crude oil could be introduced inside the CO2 bulk.
After the crude oil or brine drop was introduced inside the CO2
bulk, their images were saved automatically in a personal com-
puter memory. Using each drop image, the ADSA technique for
the pendant drop method was implemented to estimate the
dynamic and equilibrium interfacial tensions of the brine and
crude oil drops [37]. The output results of this program are the
dynamic IFT, the bond number, the surface area and the volume
of the pendant/rising drop. In other words, the densities of two
phases involved, and calibration of the syringe needle outer diam-
eter are required as input data for this software to estimate the IFT.
For the systems of crude oil–brine and crude oil–carbonated brine,
the syringe needle was installed at the bottom of the high pressure
cell to form a rising crude oil drop. For the brine–crude oil system,
 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9 5

Table 3
Experimental data of interfacial tension and density as a function of pressure and temperature for oil–brine–CO2 system.

Pressure (MPa) Temperature (°C) Salinity CO2 density Brine density Oil density c CO2-b c O-b c O–CO2
(mg/l) (g/cm3) (g/cm3) (g/cm3) (mN/m) (mN/m) (mN/m)
2.76 40 10 0.0534 1.00021 0.8994 48.18 28.51 16.32
3.45 40 10 0.0696 1.0005 0.8999 45.36 28.55 14.66
4.83 40 10 0.1079 1.0011 0.9009 39.65 28.71 11.26
6.89 40 10 0.1920 1.0020 0.9024 29.93 28.96 6.21
9.65 40 10 0.5977 1.0032 0.9044 24.84 29.17 2.27
13.79 40 10 0.7593 1.0050 0.9074 25.68 29.59 1.29
2.76 50 10 0.0509 0.9948 0.8957 48.68 27.77 16.18
3.45 50 10 0.06591 0.9963 0.8962 46.59 27.83 14.89
4.83 50 10 0.1001 0.9969 0.8972 40.69 28.03 12.24
6.89 50 10 0.1677 0.9978 0.8988 32.85 28.24 8.12
9.65 50 10 0.3453 0.9990 0.9008 25.85 28.62 4.11
13.79 50 10 0.6654 1.0007 0.9039 25.94 29.12 1.72

Table 4
Experimental results of interfacial tension and density data as a function of pressure and temperature for carbonated brine–crude oil–CO2 system.

Pressure (MPa) Temperature (°C) Salinity CO2 density CB density Oil density c CO2-Cb c O-Cb c O–CO2
(mg/l) (g/cm3) (g/cm3) (g/cm3) (mN/m) (mN/m) (mN/m)
2.76 40 10 0.0534 1.0039 0.8994 48.18 22.62 16.32
3.45 40 10 0.0696 1.0056 0.8999 45.36 22.40 14.66
4.83 40 10 0.1079 1.0079 0.9009 39.65 22.25 11.26
6.89 40 10 0.1920 1.0108 0.9024 29.93 21.94 6.21
8.27 40 10 0.3138 1.0120 0.9034 25.17 21.97 4.19
9.65 40 10 0.5977 1.0130 0.9044 24.84 21.72 2.27
11.03 40 10 0.6848 1.0140 0.9054 25.86 21.70 1.90
13.79 40 10 0.7593 1.0158 0.9064 25.68 21.67 1.28
2.76 50 10 0.0509 0.9982 0.8957 48.68 22.56 16.18
3.45 50 10 0.0659 0.9999 0.8962 46.59 22.23 14.89
4.83 50 10 0.1001 1.0021 0.8972 40.69 21.90 12.24
6.89 50 10 0.1677 1.0049 0.8988 32.85 21.78 8.12
8.27 50 10 0.2348 1.0062 0.8998 28.92 21.73 5.70
9.65 50 10 0.3453 1.0073 0.9008 25.85 21.48 4.10
11.03 50 10 0.5059 1.0082 0.9018 25.32 21.48 2.61
13.79 50 10 0.6654 1.0099 0.9039 25.95 21.46 1.72

the bulk of the cell was completely filled with brine at desired
pressures. Then, oil drop was injected through the stainless steel
needle within the brine phase. The details of the rest of the
experiments for the system of crude oil–brine were similar to that
of the systems of brine–CO2 and crude oil–CO2. For the crude oil–
carbonated brine system, a total of 15 cm3 of brine was injected
inside the high pressure cell, and CO2 was slowly transferred
through the brine phase to pressurize the system to a desired pres-
sure. There is of about 5 cm3 from cell volume for the excess CO2 as
gas cap to make sure of formation of carbonated water. Then, about
6–8 h (as long as the cell pressure was stabilized) was rested to the
water and carbon dioxide system to attain the equilibrium condi-
tions. Then an upward oil drop was introduced from the bottom
port and formed in the CO2-saturated brine phase by following
the procedure described above for the brine drop formation. It
should be noted that the volume of oil injected in the carbonated
brine phase is related to the needle outer diameter and oil charac-
teristics. In this experimental study, the needle diameter of
0.79 mm was used to fully observe the drops image of crude oil
in the monitor screen. The IFT tests were repeated three times
and their average was reported in this study. The error in the
oil–CO2 IFT, the oil–brine/CW IFT and the water–CO2 IFT systems
at each temperature and pressure was less than 0.18 mN/m,
0.45 mN/m and 0.6 mN/m, respectively. The error analysis also
showed that the maximum standard deviation of gas–oil, brine–
oil and brine–CO2 IFT measurements in the above systems was
±0.18 mN/m, ±0.45 mN/m and ±0.6 mN/m, respectively. In this
study, about of eight pressures in the range of (2.76–13.79) MPa
and two temperatures of 40 °C and 50 °C were designed for the
IFT tests.
4. Experimental results and discussion
4.1. Fluids density
In order to measure exactly the IFT, dependable density data are
required. Therefore, sodium chloride (NaCl) solution was prepared
at the concentration of 10,000 ppm. The density results for NaCl
brine at different pressures and two temperatures of 40 and
50 °C are reported in Table 3. In addition, heavy crude oil density
data are presented in Table 3. Due to the difference of the oil den-
sity regardless the solubility of carbon dioxide than that with the
CO2 dissolved at high pressure is small [55], in this work, the oil
density is assumed to be constant. As it can be seen from Table 4,
the carbonated brine density changes nonlinearly with pressure.
This trend is related to the behavior of CO2 solubility in the brine
phase that varies nonlinearly with pressure. It was determined
from the empirical equation presented by other researchers
[56,57]. The CO2 density was extracted from National Institute of
Standards and Technology source data [58].
4.2. Effect of pressure on the brine–crude oil–CO2 IFT
The equilibrium IFT data for the defined systems (brine–crude
oil–CO2) and (carbonated brine–crude oil–CO2) as a function of
temperature at different pressures were estimated. These equilib-
rium data were obtained by averaging the dynamic IFT at the last
moments. The results of equilibrium IFTs of the brine–crude oil–
CO2 system as a function of pressure at two temperatures of 40
and 50 °C and low brine salinity of 0.171 M are presented in
6 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9
Table 3. As it can be seen from this Table, the equilibrium IFT of
brine–CO2 decreases with pressure, while it increases with increas-
ing temperature. It decreases linearly at low pressures, then
reaches to plateau and constant value at high pressures. However,
the similar trend has been also presented by different researchers
for the water–CO2 systems [32,59–62]. The IFT variation observed
versus pressure under specified temperature for the NaCl solution-
CO2 system is similar to that presented already by other authors
[63,64]. These variations are due to CO2 solubility in the brine
phase. CO2 dissolution increases when the pressure increases, but
decreases when the temperature increases. Experimental results
show that the impact of pressure on the IFT is higher than the
effect of temperature for the brine–CO2 system. The experimental
results of equilibrium IFT for the crude oil–CO2 system is shown
in Table 3. As reported in this Table, at pressures higher than
9.65 MPa and at 40 °C, a constant interfacial tension as low as
1–2 mN m
1 is obtained. Also, the equilibrium interfacial tension
approaches to 2.87 mN m
1 at pressures greater than 11.03 MPa
and temperature of 50 °C. The interfacial tension reduction is
insignificant at high pressures. According to the experimental
results, it was observed that the effect of the pressure increase
on the equilibrium interfacial tension reduction is negligible at
the pressures higher than 9.65 MPa at 40 °C and 11.03 MPa at
50 °C. As it can also be seen from Table 3, the equilibrium interfa-
cial tension of crude oil–CO2 decreases linearly with pressure,
whereas it increases with temperature. These observed behaviors
are due to the mechanism of dissolution of CO2 in the crude oil that
increases when the pressure increases, however, decreases when
temperature increases.
These effects were also presented for the systems of pure
hydrocarbon-CO2 and live crude oil–CO2 at different temperatures
at miscibility conditions [23–25,65] and the crude oil–CO2 system
at high pressure conditions [36,37,66]. According to the experi-
mental results, at low pressures (i.e. lower than CO2 miscibility
conditions), the pressure effect on the equilibrium interfacial ten-
sion between the crude oil and CO2 is dominant with compared
to the temperature effect.
Table 3 also lists the equilibrium IFTs of the crude oil–brine sys-
tem without any dissolved CO2 in the systems under various pres-
sures at two temperatures of 40 °C and 50 °C. It can be seen that
the equilibrium IFT data increases slightly with a very gentle slope
as the pressure increases, however, it decreases with temperature.
This means that the effect of pressure on the interfacial tension
variations of the crude oil–brine system is low, but the tempera-
ture has a more effect on the interfacial tension reduction
[15,28,31,37,67]. However, the opposite trends in IFT have been
also presented by researchers. For instance, the IFT of oil–water
system showed a decreasing trend with pressure [68] and for sys-
tem of normal decane–water an increasing trends with tempera-
ture was reported [69].
The likely reason of IFT reduction with temperature could be due
to increasing the kinetic energy and mobility of the molecules at the
crude oil–water interfaces that will obviously increase the total
entropy of the two phase surface and consequently, reduce its free
energy (DG) and then resulting a lower IFT value [31,70–72].
Increasing IFT values with pressure is related to the strengthened
intermolecular forces or decreased distance between molecules at
the crude oil and brine interface at high pressures [31] (see Table 3).
In addition, behavior of the pressure effect on equilibrium IFT is
significantly dependent on the system type [31,73]. For instance,
the equilibrium interfacial tension versus pressure changes with
a sharper slope for the n-paraffin-water systems than that for the
crude oil (asphaltene and resin contents)-water system [29,31]
(see Table 3). These results are similar to those reported for the
crude oil–brine/water systems [46,74] and for the pure hydrocar-
bon–water systems [15,28,75–77].
4.3. Effect of pressure on the carbonated brine–crude oil–CO2 IFT
The equilibrium interfacial tension of the carbonated brine–
crude oil–CO2 system is presented in Table 4. As it can be seen from
the data of this Table, carbonated brine (CB)-crude oil IFT decreases
with both pressure and temperature. This is likely due to dissolved
CO2 in both phase of crude oil and brine that increases with pres-
sure. Oil swelling is one of the most important mechanisms that
have also been observed at carbonated water injection prior to
the CO2 injection in the micromodel tests using the light and heavy
oils [5]. Under the same pressure, increase in IFT is expected due to
the lower solubility of carbon dioxide in the brine and oil phases at
higher temperature. However, entropy is another mechanism that
increases with temperature and reduces the IFT. Nevertheless, the
experimental results show that the mechanism of entropy is dom-
inant with compared to the impact of solubility of carbon dioxide.
The results in Table 4 show that at 40 °C the equilibrium interfacial
tension between the crude oil and CO2-saturated brine almost
unchanged at pressures higher than 6.9 MPa. This is due to CO2 sol-
ubility in the brine phase that reaches to its maximum at pressures
more than 6.9 MPa. Also, at a higher temperature of 50 °C, the
equilibrium interfacial tension decreases with pressure at pres-
sures lower than 8.2 MPa and almost unchanged at pressure of
8.2 MPa. This is also attributed to CO2 solubility in the brine phase
that approaches to its maximum at pressures about of 8.2 MPa.
Similar trends in the literature, have been also reported [37]. Up
to now, several experimental studies have been performed on IFT
of the systems of pure hydrocarbon and light crude oil in the pres-
ence of brine. However, in this study the experiments were carried
out on heavy crude oil and carbonated water. Literature suffers
from the lack of information in this field. In this experimental
study, it was found that at pressures higher than 6.9 MPa and
40 °C and at pressures higher than 8.2 MPa and 50 °C the effect
of temperature on the equilibrium IFT is stronger than the effect
of pressure.
4.4. Dynamic oil swelling
Oil swelling is one of the main oil recovery mechanisms that
occurs during carbonated water injection. It is as a result of CO2
diffusion and partitioning from carbonated water into the oil
phase. Fig. 3 shows the dynamic oil swelling and IFT data measured
for the systems of crude oil-CW versus time at temperature of
40 °C and pressure of 4.83 MPa. Fig. 3 shows the oil volume
increases while IFT decreases with time. These are because of the
CO2 dissolution into the crude oil drop that increases with time.
According to the presented results in Fig. 3, the oil swelling is about
11.4% for this crude oil type at pressure of 4.83 MPa. This oil swel-
ling is as a result of CO2 dissolved in the carbonated water phase
and its partitioning at the interface of CW/oil and its diffusion
and dissolution in the oil phase.
4.5. Oil spreading on the aqueous solution
The results estimated for the brine–oil–CO2 IFT and the carbon-
ated brine–oil–CO2 IFT (see Tables 3 and 4) were applied to deter-
mine the spreading coefficient value by Eq. (1). Fig. 4 demonstrates
the spreading coefficient (SC) values of two systems of brine–crude
oil–CO2 and carbonated brine–crude oil–CO2 at two temperatures
versus pressure. The variations of equilibrium spreading coefficient
with pressure shows that it severely decreases at low pressures.
This sharp reduction is due to the solubility of carbon dioxide,
which substantially increases in the water and the crude oil phases
with pressure that consequently reduces the IFT of oil–CO2 and
water–CO2 systems. Then, SC reaches to a minimum value that
shows the worst conditions for gas EOR operations. Finally, the
 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9
t=0 s, t=500 s,
IFT= 27.4 mN/m , IFT=24.8 mN/m,
V=42.66 mm3 V= 45.92 mm3
Fig. 3. A comparison of volume changes for the system of crude oil-CW, as function of time at 40 °C and 4.83 MPa.
CB-O at 40 °C CB-O at 50 °C B-O at 50 °C B-O at 40 °C
12
10
8
6 become negative. This can be due to that with increasing temper-
EQ. SC (mN/m)
4 ature, solubility of carbon dioxide in water and oil, substantially
2 Based on the results obtained from this study and from practical
0 point of view for oil reservoir with low pressures SC of both sys-
0 2 4 6 8 10 12 14
-2
-4
-6
-8
Pressure (MPa)
Fig. 4. Comparison of the spreading coefficient of two systems brine–crude oil–CO2
and carbonated brine–crude oil–CO2 at two temperature and different pressure
conditions.
trend of spreading coefficient versus pressure slightly increases.
The last trend is due to the fact that the IFT reduction of the oil–
CO2 system is greater than the variation of the IFT of the other
two systems. As it can be seen from Fig. 4, the SC of carbonated
brine–crude oil–CO2 system is greater and positive compared to
that of brine–crude oil–CO2 system. This can be one of the benefits
of the carbonated water, in which in the CW–oil–gas system, oil
would easily spread on water in presence of gas and keep
continuity via thin films. In addition, Fig. 4 shows that the spread-
ing coefficient values increases slightly as temperature increases,
especially at lower pressure conditions. This can be due to decreas-
ing the solubility of CO2 in the brine phase with temperature that
will increase the brine–CO2 IFT. Besides, total entropy increases
with temperature that leads a subsequent reduction of the
brine/carbonated brine–oil IFT. The both mechanisms mentioned
have positive effect on SC. The results also indicate that for both
systems, SC decreases to a minimum value, and then it increases
by pressure. In Fig. 4 for the carbonated brine–crude oil–carbon
dioxide system, a negative SC was also observed at 40 °C at the
pressure range of 7.58–8.96 MPa and at 50 °C at almost 9.65 MPa.
The results indicate that for the maximum recovery, the suitable
operating pressure of the oil recovery process for this particular
reservoir is at pressures above 11.03 MPa and below 7.58 MPa,
because at the intermediate pressures, value of spreading coeffi-
cient is almost negative.
Also, according to Fig. 4, for the brine–crude oil–carbon dioxide
system, negative SC was observed at 40 °C, at pressures higher than
7
t=1000 s, t=2485 s,
IFT=24.1 mN/m, IFT=22.8 mN/m,
V= 46.8 mm3 V=47.52 mm3
4.83 MPa and at 50 °C, at pressures higher than 5.17 MPa. The
results presented show that for maximum recovery, operating
pressure for any gas enhanced oil recovery process, for this partic-
ular reservoir, should be below 5.17 MPa. These results show that
SC with increasing temperature at the higher pressure conditions
decreases.
16 tems are positive. Thus there might not be such need to replace
brine injection with carbonated brine injection before CO2 injec-
tion, although SC value of carbonated brine system is higher than
that of brine system. That is, at 3.45 MPa and 50 °C spreading coef-
ficient of brine–oil–CO2 system and carbonated brine–oil–CO2 sys-
tem are 4.73 and 9.93, respectively. However, at high pressure
conditions, which are expected for the most cases, SC of carbonated
brine–oil–CO2 system is positive (for instance, at pressure of 13.79
Mpa and 50 °C it is equal to 2.7), while, SC of brine–oil–CO2 system
is negative (at the same conditions as the former it is equal to

4.7). Thus, these results would suggest considering injection of
a slug of carbonated water prior to CO2 injection, especially at high
pressure conditions.
5. Conclusions
In this experimental study, using the axisymmetric drop shape
analysis (ADSA) technique, the interfacial tensions of the brine–
CO2 system, the crude oil–CO2 system, the crude oil–brine system,
and the crude oil–carbonated brine system were estimated under
specified temperature and pressure conditions.
The following conclusions can be drawn according to the results
obtained in this study:
1. The experimental results indicate that for the systems of brine/
CO2 and crude oil/CO2 the equilibrium interfacial tension
decreases with pressure, whereas it increases with tempera-
ture. This is more likely attributed to higher CO2 solubility at
higher pressure but lower CO2 solubility at higher temperature
conditions.
2. The variations of the equilibrium interfacial tension of the
brine–crude oil system versus pressure slightly increases,
whereas it decreases for the carbonated brine–oil system at
lower pressures until the IFT reaches a constant value at higher
pressures. This is because CO2 transports from carbonated brine
bulk and dissolves in the crude oil drop at low pressures. The
CO2 dissolution reaches to its maximum value at high pres-
sures. That is why that variation of IFT is lower at high pressure
8 M. Riazi, A. Golkari / Fuel 178 (2016) 1–9
conditions. IFT values, however, slightly decrease as tempera-
ture increases. Furthermore, with compared to the interfacial
tension data of the crude oil–brine system at the same pressure
and temperature conditions, the equilibrium interfacial tension
reduces if CO2 is introduced into the system. That is, the equilib-
rium interfacial tension of the crude oil–carbonated brine sys-
tem is lower than that of crude oil–brine system at the same
pressure and temperature conditions.
3. The volume of crude oil drop increases with time in the CW–
crude oil system. The oil volume expansion is mainly due to
the CO2 diffusion from the carbonated water phase toward
the crude oil phase that is known as one of the advantage of
CW injection process.
4. The variation of equilibrium spreading coefficient with pressure
shows that it severely decreases at low pressures. This sharp
reduction is due to the solubility of carbon dioxide, which sub-
stantially increases in the water and crude oil phases with pres-
sure that consequently results of reduction of IFT of oil–CO2,
water–CO2 systems and carbonated water–oil. At a specific
pressure conditions, SC reaches to a minimum value that shows
the worst conditions for EOR operations. Above that specific
pressure conditions the trend of spreading coefficient versus
pressure slightly increases. The latter trend is due to the fact
that the IFT reduction of the oil–CO2 system is greater than
the variation of the IFT of the other two systems. According to
the results obtained the spreading coefficient values increase
slightly as temperature increases, especially, at lower pressure
conditions. This could be due to the following two factors. First
factor is that the solubility of CO2 in the brine phase reduces by
temperature that would increase the brine–CO2 IFT. Second fac-
tor is the increase of total entropy by temperature that would
mainly reduce the brine/carbonated brine–oil IFT. Both above
mentioned mechanisms have positive effects on increasing
the spreading coefficient.
5. With compared to the results of the two systems of carbonated
brine–crude oil–CO2 and brine–crude oil–CO2 for this particular
reservoir oil type, equilibrium spreading coefficients for carbon-
ate brine–oil–CO2 observed to be positive and greater. This
means that carbonated water alternating carbon dioxide injec-
tion (CWAG) could have higher recovery performance than
water alternating carbon dioxide (WAG) injection.
6. The results demonstrate that the spreading coefficient values of
the carbonated brine–crude oil–CO2 system are positive in the
whole of suitable pressure range, except in a region (i.e. close
the critical point of CO2) that the spreading coefficient value
of carbonated brine–oil–CO2 system is almost negative at lower
temperatures (40 °C). Moreover, for the brine–crude oil–CO2
system illustrated that the spreading coefficient values
became positive at the lower pressures and two temperature
conditions.
List of symbols
ADSA axisymmetric drop shape analysis
API oil API gravity (American Petroleum Institute)
CW/B carbonated water/brine
EOR enhanced oil recovery
IFT, c interfacial tension, mN/m
O oil
P pressure, MPa
ppm parts per million
SC spreading coefficient, mN/m
T temperature, °C
Acknowledgments
Authors would like to thank Dr. M. Escrochi and Dr. A. Zolghadr
for their valuable advices. We would also like to thank Mr. Y.
Kazemzadeh and Dr. M. Lashkarblooki for their helps over the
course of this study. Special thanks also to the core analysis labo-
ratory director, Mrs. Meratian, for providing a suitable situation
and work space.
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