Fuel 235 (2019) 1039–1051

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Full Length Article

Effects of ions and dissolved carbon dioxide in brine on wettability T

alteration, contact angle and oil production in smart water and carbonated
smart water injection processes in carbonate oil reservoirs
⁎
Iman Nowrouzia, Abbas Khaksar Manshadb,e, Amir H. Mohammadic,d,
a
Department of Petroleum Engineering, Islamic Azad University, Omidiyeh Branch, Omidiyeh, Iran
b
Department of Petroleum Engineering, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), Abadan, Iran
c
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue, Durban 4041, South Africa
d
Institut de Recherche en Genie Chimique et Petrolier (IRGCP), Paris Cedex, France
e
Department of Petroleum Engineering, Faculty of Engineering, Soran University, Kurdistan Region, Iraq

G R A P H I C A L A B S T R A C T

90
80
70
Oil Recovery, %OOIP

60
50
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30
20
10
0
0 100 200 300 400 500 600 700 800 900
Time, h

Plug7 Plug8 Plug9 Plug10 Plug11 Plug12

A R T I C LE I N FO A B S T R A C T

Keywords: Imbibition is one of main production mechanisms in fractured carbonate reservoirs. This mechanism is very
Smart water dependent on hydrophilicity of reservoir rock and somehow is controlled by it. The contact angle tests, due to
Carbonated water the test conditions, i.e, a polished rock section-crude oil droplet system, do not easily indicate the wettability of
Dissolved ion the porous medium but generally, are accepted to expression of rock wettability. Imbibition tests with a strong
Wettability alteration
dependence on wettability can generalize contact angle tests to wettability of porous medium. Carbonated smart
Contact angle
Imbibition
water injection can active water imbibition mechanism and increase production in fractured carbonate re-
Water injection servoirs by wettability alteration to hydrophilic. In this study, the optimal concentration of saline water used
Fractured reservoirs with oil in Karanj and Gachsaran reservoirs in Iran was determined by calculating the contact angle in different
concentrations and dilutions. Then, the optimal solutions were carbonated by adding carbon dioxide at various
temperatures and pressures. The effect of carbon dioxide on wettability of pre-hydrophobized sections was
investigated by contact angle experiments.
The results show the efficiency of carbonated smart water in wettability alteration as compared with smart
water. Then, oil-saturated carbonate plugs were exposed to spontaneous imbibition by optimal solutions in the

⁎
Corresponding author at: Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George V
Avenue, Durban 4041, South Africa.
E-mail addresses: khaksar@put.ac.ir (A.K. Manshad), a.h.m@irgcp.fr (A.H. Mohammadi).

https://doi.org/10.1016/j.fuel.2018.08.067
Received 19 November 2017; Received in revised form 5 May 2018; Accepted 14 August 2018
Available online 30 August 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

presence and absence of carbon dioxide. The experiments reveal an increase in oil recovery by imbibition with
carbonated smart water. The results of these experiments indicate the water alteration efficiency of carbonated
smart water compared with the smart water. A minimum contact angle of 18.75° was obtained by adding carbon
dioxide to a smart solution at a concentration of 1000 ppm of different salts and at 10.34 MPa and 75 °C. Then,
oil-saturated carbonate plugs were exposed to imbibition process with optimal solutions in the presence and
absence of carbon dioxide. According to the results of these experiments, oil recovery increased by 78% of the
initial oil in place by imbibition in the presence of carbonated smart water.

1. Introduction
Water injection into oil reservoirs is a common practice in the
world. This method has been associated with successful field and re-
search experiences in both carbonate and sandstone reservoirs. It can be
argued that water injection has been the most successful way to en-
hance oil recovery so far [1]. Smart water and carbonated smart water
methods are among improved chemical water injection methods. Ion
management is of great importance in smart water injection. In fact,
smart water injection is a control method, meaning that the most im-
portant point is to control and manage the ions in the injection phase to
pave the way for activating the mechanisms of this procedure, espe-
cially wettability alteration of rock from hydrophobic to hydrophilic.
Thus, before implementing this method in the field, an ion in the in-
jection phase may be completely removed or the strength of another ion
should be increased by increasing concentration based on experimental
data. For example, Strand et al. introduced SO42− and Ca2+ as key ions
in wettability alteration of limestone rocks [2]. In addition, the con-
centration of some ions may be in the useful range. The injection
temperature and pressure may also change to increase the temperature
of injected smart solution. In low-temperature reservoirs, the chemical
mechanisms involved in wettability alteration may not be activated.
The injection pressure is of special importance especially when carbon
dioxide is injected with a smart solution. Although smart water may
reduce interfacial tension between oil and water, the main mechanism
to increase the efficiency of smart water injection is wettability al-
teration of reservoir rock from hydrophobic to medium and hydrophilic
wettability [3,4]. Hence, it can be said that interactions between ions in
the smart water and carbonate reservoir rocks can be strengthened by
adjusting the concentration of injected water and the type of ions as
well as temperature and pressure. Understanding the optimum values of
these parameters is a technique for more targeted implementation of
this method. In addition, knowing the optimum and controllable con-
ditions of the reservoir and the injection fluid may reduce the costs of
operations. Another point in the implementation of a water injection
operation, especially in case studies, is supply of saline water needed to
meet the volume required for injection. In reservoirs close to sea, sea-
water can be a good choice. Diversity of ions in seawater makes it a
good candidate for use as smart water. According to literature, seawater
can be used as smart water at high temperatures without changing its
concentration [5,6]. In reservoirs where access to water is difficult or
impossible, the use of water extracted from the reservoir formation can
be evaluated. Although the concentration of ions in the formation water
is usually much higher than that in seawater, cost estimation may re-
veal that the treatment and control of ion concentration will be more
affordable than transfer of water with lower salinity to the field.
According to the above discussion, the optimal conditions for injection
of seawater and formation water extracted from two reservoirs along
with dissolved carbon dioxide were investigated with regard to the
composition and properties of oil in these reservoirs. Injection of carbon
dioxide both separately or dissolved in water and/or periodically with
saline water is common. The aim of carbon dioxide injection, regardless
of the method used, is to enhance oil recovery or the storage of carbon
dioxide in reservoirs. It can be argued that carbonated water injection is
a modified carbon dioxide injection operation. Poor efficiency of CO2
injection is increased by injection of carbonated water. Carbon dioxide
dissolved in smart water is used to change the chemical composition of
saline water. When carbonated water is in the vicinity of oil, the carbon
dioxide dissolved in water is transferred to oil. As a result, the prop-
erties of oil and reservoir rock are changed during transportation of
chemicals migrating from water to oil. This reduces the viscosity and
swelling of oil as well as water-oil interfacial tension. A decrease of
more than 20% in interfacial tension has been reported [3,7].
Furthermore, carbonated water alters wettability by influencing the
reservoir rock [8]. In this study, contact angle tests were conducted on
hydrophobic sections aged in smart and carbonated smart solutions.
The optimal solutions were identified in terms of reducing the contact
angle and wettability alteration to hydrophilicity. The reservoirs stu-
died in this investigation are of fractured carbonate type. The me-
chanism of production in fractured reservoirs include: Free-fall gravity
drainage, which happens when the gravity force is the only crude oil
drainer power from the reservoir rock system, molecular diffusion,
solution gas drive or expansion of oil in under-saturated area and ca-
pillary imbibition. The capillary and gravity forces are effective on oil
recovery processes. In gravity drainage process gas phase (in the frac-
tures) replaces oil phase (in the matrixes) and the capillary pressure is
an obstacle for displacement of wet phase (oil) via non-wet phase (gas).
Thus, the matrix height should be higher than a critical value to
overcome the non-wet phase on the capillary pressure and enter the
matrix to active the gravity drainage process [9–11].
Imbibition is one of the most important processes occurring in
fractured reservoirs during oil production. Webb et al. studied sponta-
neous imbibition at reservoir conditions using the gypsum core with
seawater and saline water of the same reservoir. They found 40% im-
provement in oil production by imbibition with seawater as compared
with primary saline water [12]. Due to high permeability of fractures in
fractured reservoirs and non-wettability of carbon dioxide, it is better to
use carbonated water instead of carbon dioxide injection, since the
density of carbonated water (even in supercritical state) is higher than
that of carbon dioxide and tap water [13,14], consequently causing its
penetration down the formation. In addition, carbonated water is cap-
able of changing the wettability of reservoir rock to hydrophilic due to

Table 1
Analysis of Gachsaran crude oil.
Component C1 C2 C3 iC4 nC4 iC5 nC5 C6 C7 C8 C9 C10 C11 C12+ Total

Molar Percent 0.00 0.08 0.73 0.72 2.22 1.10 1.10 8.66 9.32 6.60 7.14 5.36 5.01 51.96 100.00

Molecular weight = 247.

Molecular weight of C12+ = 380.
Specific gravity of C12+ @ 15.55 °C = 0.9369.
Saturation pressure of reservoir fluid @ 60.6 °C = 14.04 MPa.

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I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

acidic properties. This facilitates improved spontaneous imbibition of Table 3

carbonated water than tap water especially that carbonate reservoirs Analysis of saline water samples.
are mostly hydrophobic [15]. In this process, the fluid adjacent to rock Component Concentration in (ppm)
blocks filling fractures surrounding the blocks enters the blocks over
time and drives oil out of the block. To study this process, imbibition Sea Water Gachsaran-fw Karanj-fw
tests should be carried out. In this study, imbibition experiments were −
Cl 11,500 39,050 48,570
carried out at atmospheric pressure and a reservoir temperature of SO42− 6860 220 160
75 °C. Imbibition was performed at optimum pressure for dissolution of HCO3− 180 210 420
carbon dioxide in terms of minimum contact angle. Mg2+ 930 1700 620
Ca2+ 1920 3500 9120
Na+ 7330 25,300 46,200
2. Materials and equipment Fe2+ Negligible 30 70
Sr2+ Negligible Negligible 90
2.1. Crude oil K+ 90 180 110
PH 7.67 7.50 7.23
TDS 33,194 74,000 105,000
Dead crude oil samples were used. The first crude oil was extracted
from Gachsaran reservoir (Iran) with an API of 31.14. The second crude
oil was extracted from Karanj reservoir (Iran) with an API of 32.02. Table 4
Tables 1 and 2 show analysis of crude oils extracted from Gachsaran Properties of the salts used in simulated saline water.
and Karanj reservoirs, respectively.
Salt Magnesium Calcium Potassium Sulfate
Sulfate Chloride
2.2. Saline water and salts
Symbol MgSO4 CaCl2 K2SO4
Molecular Wight 120.37 110.98 174.252
Four samples of saline water were used in the experiments, three of
Assay (%) > 98 > 96 > 99
which were prepared from the saline water of Gachsaran and Karanj Density (g/cm3) 2.66 2.15 2.66
reservoirs and another from Persian Gulf. Table 3 shows the composi- Dissolution in Water 255–710 600–1524 111–240
tion of these samples used in this study. The fourth sample with con- (g/lit)
centrations of 500, 1000, 1500 and 2000 ppm was prepared by dissol-
ving MgSO4, CaCl2 and K2SO4 purchased from Biomedical MP,
Netherlands. Table 4 lists the properties of the salts used in this study. PT-100 thermometer and a PID controller. The pressure and tempera-
ture display reports the pressure and temperature at any moment.
Furthermore, two pressure gauges with an accuracy of 0.5% full scale
2.3. Rock
were embedded to control the droplet pressure and one to display the
bulk pressure. During experiments, all three gauges should report the
Rock samples as cylindrical plugs with narrow sections were taken
same pressure. The setup is washed using toluene and acetone and by
from ASMARI carbonate rock outcrops in Khuzestan province (Iran).
purging high-pressure nitrogen through lines and container. The device
calibration is dependent on fittings and valves and correct washing. It is
2.4. Carbon dioxide, nitrogen and toluene
checked by testing solutions with a certain interfacial tension, such as
air-water. The camera continuously reports the container contents to
Carbon dioxide and nitrogen with 99.99% purities were purchased
the software. After placing the baseline by the user to distinct the rock-
from Aughadareh Industrial Gases Company, Iran. Toluene was pur-
droplet surface, the software draws two tangent lines in the two-di-
chased from MP-Biomedical, the Netherlands with a purity higher than
mensional image on both sides of the drop and reports the left, right,
0.99 mol fraction.
and the average angles with an accuracy of 0.2–0.5°. Fig. 1 shows the
experimental setup schematically.
2.5. Contact angle measurement device This device is capable of connecting to the gas cylinder. During the
contact angle test, carbon dioxide is injected into the cell after in-
A dual-purpose device, IFT400 (Fars EOR Company, Iran), was used troducing the aqueous solution. After applying the pressure and after
for measuring the contact angle and interfacial tension. This device spending sufficient time, carbonated water is formed in such a way that
allows the measurement of contact angle of an immiscible drop with the conditions at the time of aging and the test time are the same.
bulk fluid placed on the surface of the rock by a needle. It also allows
imaging the droplet-solid system in the range of room temperature to
180 °C up to 20 MPa. The device components include: two manual 2.6. Pressure and temperature apparatus
syringes for the storage of bulk fluid and droplets and for controlling
pressure, a steel container equipped with a glass window, one facing the The use of the IFT400 for aging of the oil-wet section during the test
light source and the other to a camera connected to a computer, a period (3 days) is a major problem, especially in the presence of carbon
thermal jacket around the container with three heating elements to dioxide. For instance, the safety of the device is not enough to test a
provide a good temperature control in the range of ± 0.3 °C using a high pressure – high temperature system during this period and that

Table 2
Analysis of Karanj crude oil.
Component C1 C2 C3 iC4 nC4 iC5 nC5 C6 C7 C8 C9 C10 C11 C12+ Total

Molar Percent 0.00 0.77 2.16 0.76 2.44 0.84 0.80 9.26 9.35 7.87 8.52 7.23 5.39 44.61 100.00

Molecular weight = 232.

Molecular weight of C12+ = 392.
Specific gravity of C12+ @ 15.55 °C = 0.9669.
Saturation pressure of reservoir fluid @ 60.6 °C = 18.58 MPa.

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I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

Fig. 1. Schematic diagram of the interfacial

and contact angle measurement device
(IFT400). 1: bulk phase pump. 2: adjustable
light source. 3: marker and temperature and
pressure controller. 4: high-pressure valve.
5: cell. 6: camera. 7: dropping needle. 8:
drain line of the cell content. 9: fluid pump
of drop. 10: Pc with installed software [16].

due to the pressure of the system and the dissolution of the gas, it is container made of stainless steel with grooves shown in Fig. 2 is able to
possible to discharge from connections and valves during this time withstand pressures up to 14 MPa and temperatures up to 180 °C and
period. For this purpose, a more secure and safe system was considered. the amounts of production have an accuracy of 0.1 cm3 based on its
The system used for applying pressure and temperature for aging grading.
sections of carbonate rocks in the carbonated saline water includes a
cylinder and piston embedded in an oven with an accuracy of 0.1 °C to 3. Methods
apply the desired temperature. A high-pressure line connected to the
bottom of accumulator exits the container which is connected to a 3.1. Preparation of cross sections and contact angle tests
manual hydraulic pump to apply desired pressure. Another high-pres-
sure line from the top of accumulator exits from the oven which is Contact angle tests were performed to identify the best ion con-
connected to a carbon dioxide cylinder after passing a valve. The sec- centration and dissolution pressure of carbon dioxide for wettability al-
tions are placed in the carbonated saline water in the cylinder and the teration of carbonate rock. For this purpose, some narrow sections of rock
door is closed, that is communication is possible only from lines to samples with a diameter of 1 in. were taken. After cutting, the sections
carbon dioxide cylinder and manual hydraulic pumps. In this case, the were cleaned from powder resulting from cutting operation by nitrogen.
piston is at the lowest possible level. Then, carbon oxide enters the The sections were washed and soaked in toluene for 24 h to remove the
cylinder at the initial pressure of cylinder and the inlet valve is closed. fatty acids from hand contact. Then the samples were washed with dis-
After reaching the desired temperature, the pressure reaches the desired tilled water and dried in an oven at 40 °C. To prepare hydrophobized
level by pump as the piston rises. A pressure gauge with an accuracy of sections, after putting them in oils, the samples were aged for 12 days at
0.5% full scale has been installed on the line from the pump to cylinder 75 °C [18]. The saline water samples used include two natural samples
to read the pressure [17]. extracted from Gachsaran and Karanj reservoirs, seawater and a simulated
saline water with different concentrations. The three natural samples were
diluted 15 times, each time by rising the volume to one third of the sample
2.7. Imbibition containers
volume. The samples used were prepared in the laboratory with
500 + 500 + 500, 1000 + 1000 + 1000, 1500 + 1500 + 1500 and
Imbibition container is the most common device that is used for
2000 + 2000 + 2000 ppm of MgSO4, CaCl2 and K2SO4. The original and
imbibition tests. Imbibition container is a glass enclosure which is
diluted saline water samples of a pre-hydrophobized section were placed
connected to a graduated cylinder from the top. The reservoir rock
within each container. In this way, 16 sections hydrophobized with
sample filled with oil is placed inside the container. Then the space
around the rock sample in the imbibition container is filled with water
or any fluid to study its effect on the imbibition process. Over time,
water enters the rock sample and oil is removed. According to the
density difference between oil and water, the extracted oil is accumu-
lated on top of water in the graduated cylinder. The volume of extracted
oil can be calculated. The main problem with this device is the very low
strength of its glass body against pressure limiting its application.
The imbibition container used in the previous experiments cannot
be used because of the low strength of glass body against pressure.
Accordingly, an imbibition container shown in Fig. 2 was made of
stainless steel 316. The narrow compartment at the top of the container
is graded. Oil production can be observed and its volume can be cal-
culated from the groove sealed with resistant glass. A similar groove is
precisely embedded in the front of the graded groove. Using a light
source, the volume of produced oil can be easily read and calculated. A
high-pressure valve is installed at the top and bottom of the container.
Carbon dioxide can be injected into the imbibition container from the
upper valve. Then the valve is closed and the smart solution is injected
from the lower valve using a cylinder-piston syringe. The container is
then placed in an oven to reach the desired temperature. Thereafter, the Fig. 2. Imbibition container made for imbibition experiments with carbonated
pressure inside the container is adjusted to the desired pressure. The smart water at 10.34 MPa and 75 °C.

1042
I. Nowrouzi et al.
Gachsaran crude oil were placed in Gachsaran formation water and its
diluted samples. Similarly, 16 sections hydrophobized with Karanj crude
oil were placed in Karanj formation water and its diluted samples. In the
case of seawater and saline water prepared in the laboratory, the experi-
ments were performed with sections hydrophobized with Gachsaran and
Karanj crude oil samples. All sections were kept for 3 days at atmospheric
pressure and 75 °C. Then the contact angle of a droplet of oil on the section
was measured in the presence of aging solutions.
To apply conditions of carbonated water contact angle tests on the
section hydrophobized with Gachsaran crude oil, the carbonated water
of the same formation with 9 dilutions was used. Similarly, the section
hydrophobized with Karanj crude oil was aged in Karanj formation
water containing carbon dioxide with 10 times dilution. Two optimized
samples of seawater with 6 times dilution for sections hydrophobized
with Gachsaran crude oil and 7 times dilution for sections hydro-
phobized with Karanj crude oil were used. The simulated carbonated
saline water at a concentration of 1000 ppm of each salt was used for
aging the sections hydrophobized with both Gachsaran and Karanj
crude oils. The sections were kept in the solutions for 3 days.
Temperature, pressure, and the dissolved solid content are among the
factors affecting solubility of carbon dioxide in water. In the case of
optimal solutions, the concentration of dissolved solids is constant in
the series of experiments. The experiments were performed at 35, 55
and 75 °C and constant pressures of 0.101, 3.45, 6.89 and 10.34 MPa.
3.2. Imbibition tests
Oil production from naturally fractured reservoirs normally occurs
by spontaneous imbibition. Spontaneous imbibition is the most im-
portant mechanism for production of oil from these reservoirs [18].
From a geo-mechanical perspective, a fracture is a gap between two
surfaces of matrices. Fractures are highly permeable compared with
matrix. This results in the movement of injected fluid (e.g. water) in
fractures and the lack of entrance to the matrix blocks. Whereas, a
significant portion of oil exists in the matrix due to the high storage
volume. Once the oil in the fractures was swept by water and when
matrix block is fully or partially in contact with water, oil will be
produced by spontaneous imbibition [19]. Flooding tests are not nor-
mally recommended for naturally fractured reservoirs. The rock plug is
placed in a plug holder where a rubber tube embedded in the holding
chamber usually surrounds the plug with hydraulic pressure of an oil
and only the plug ends remain open and the fluid cannot enter into the
plug from surroundings. Using this device, the effect of viscous forces
on the movement of fluids in porous media can be studied. That is why
this system is not a good simulator for matrix and fracture conditions.
3.3. Compatibility with formation water and selection of salts to simulate
saline water
Deposit formation is one of the main problems in water injection
operation. Mixing two heterogeneous waters with incompatible com-
positions, temperature changes and pressure changes in the solution,
changes in the partial pressure of H2S/CO2, evaporation (which affects
concentration), turbulence, time and pH are among the factors affecting
sedimentation in oil reservoirs [20]. The major deposits of oil fields
include carbonates, sulfates, and halite or iron deposits formed due to
the aforementioned reasons [21,22]. Sometimes, injected gas is in-
compatible and forms asphaltene deposits and oil solids [23]. Deposits
can alter the wettability and permeability of reservoir rock. As a result,
they affect the flow performance in the reservoir. In addition, deposits
may cause devastating effects around wells and wellhead equipment
[24]. Incompatibility of injected fluid with formation water in re-
servoirs causes deposits and reduces the permeability with damaging
effects on the quality of reservoir rock. In this particular case, in ad-
dition to ions, carbon dioxide in the injected fluid can be deposited with
changes in temperature and pressure in addition to chemical reactions.
1043
Fuel 235 (2019) 1039–1051
Fig. 3. The compatibility of formation water by observing the samples A: sea-
water- Gachsaran formation water, B: seawater-Karanj formation water, C: si-
mulated saline water-Gachsaran formation water, D: simulated saline water-
Karanj formation water. E: incompatibility and deposit formation in the pre-
sence of FeCl3.
For this reason, compatibility of formation water should be tested prior
to the injection process. It can be argued that tests for evaluating
compatibility of injected fluid with formation water are among key tests
for screening and selecting injected fluid for a successful enhanced oil
recovery (EOR) operation by chemical injection methods.
The tests were performed for examining the compatibility of sea-
water and simulated saline water with two formation water samples. To
perform this test, seawater at its initial concentration and simulated
saline water at the highest concentration of 2000 ppm of each salt (a
total of 6000 ppm) were mixed with same ratios with two samples of
formation water in separate containers and then placed in an oven at
75 °C for two weeks [17]. Then, the samples were observed (Fig. 3). In
the next stage, the prepared solutions were separately placed in a cy-
linder-piston system and exposed to carbon dioxide. After reaching a
temperature of 75 °C and bringing the chamber pressure to 10.34 MPa
(the highest pressure for dissolution of carbon dioxide in this study) by
a manual hydraulic pump, it was left for 3 days. Then the pressure was
discharged and the solution was investigated in terms of deposits. Be-
fore proceeding, incompatible salts were completely discarded. For
example, solutions containing FeCl3 and FeSO4 (iron compounds) were
deposited when exposed to both water samples. However, the seawater
and the final simulated saline water were compatible with both for-
mation water samples and no precipitation was observed. The other
factor in selecting salts used in saline water made in the laboratory is
the mechanisms involved in wettability alteration and performance of
salts. Accordingly, CaCl2, MgSO4, and K2SO4 were selected to make
saline water with concentrations of 500, 1000, 1500 and 2000 ppm.
Compatibility of formation water was also tested after selecting the
optimal concentration and pressure. Therefore, the compatibility of the
selected solution in optimum concentrations was ensured from the
standpoint of minimum contact angle in the presence and absence of
carbon dioxide.
4. Results and discussion
4.1. Contact angle tests
Contact angle tests were performed to identify the best ion con-
centration. Table 5 shows the results of these tests. Figs. 4 and 5 show
the data reported in Table 5.
Based on the data in Table 5 and Figs. 4 and 5 on the change of
contact angle with a simulated smart solution in the laboratory, it can
be said that although the values obtained from the aging of the sample
at different concentrations in facing with hydrophobic rocks in both
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

Gachsaran and Koranj oils, they would be situated in the range of hy-

1000 + 1000 + 1000

1500 + 1500 + 1500
2000 + 2000 + 2000
Concentration (ppm)
drophilic, but this function is more powerful in Gachsaran oil due to

500 + 500 + 500

lower contact angle values, so that at a minimum contact angle, con-
centration of 3000 ppm, this value for Koranj and gachsaran oil is equal
to 33.69 and 28.86°, respectively. The difference is due to the fact that
the compositions of saline water and carbonate rock are constant which
can be found in heavier compositions of Koranj oil.
We considered the constant concentration for each salt in each step
Brine Simulated and Karanj

in the simulation of smart water by CaCl2, MgSO4 and K2SO4 salts. This
was done solely by the input information order in research and keeping
away from the margins of extra laboratory tests, but the power of so-
luble ions in smart water resulting from the dissolution of these salts is
not the same in changing the carbonaceous wettability, for example, in
a study by Khaksar et al. This ability was evaluated in part by each salt
47.72
33.69
43.25
43.54
Oil

at concentrations in facing with the rock of current research and the

Gachsaran crude oil. According to their reports, the ions released by
Brine Simulated and Gachsaran

K2SO4 salt have the potential to better reduce the contact angle, al-
though the difference is not more than 4° considering the contact angle
values [17]. Of course, the solution containing different ions has a
Contact angle of two droplets of oil on sections aged in 4 different samples of saline water with different concentrations and dilutions and aqueous bulk.

different performance than the single-species solution resulting from

the dissolution of one salt. For this case, various concentrations of sea
water and formation water can be considered as a set of different
conventions.
45.14
28.86
37.92
40.27

Among data in Tables 5 and 6, a representative was selected as the

Oil

optimal concentration and dilution according to minimum contact

angle and optimal efficiency of wettability alteration. It is important to
Sea Water and Karanj

note that in selecting the best concentration of saline water made in the
laboratory, a concentration of 1000 ppm of each salt for pre-hydro-
phobized sections in Gachsaran and Karanj crude oils gives the best
performance in wettability alteration and contact angle reduction.
81.50
75.34
64.12
51.77
48.11
42.05
36.80
33.61
33.57
33.50

However, in dilution of formation water and seawater, the performance

Oil

–
–
–
–
–
–

of each step should be evaluated in addition to dilution and contact

angle measurements. Table 5 and Fig. 4 show the results for saline
Sea Water and Gachsaran

water samples extracted from Gachsaran and Karanj formations and

seawater. Fig. 5 shows the results obtained for the saline water made in
the laboratory. As can be seen, wettability alteration is not uniform for
dilution of Gachsaran and Karanj formation water and seawater. With
further dilution in early stages, the performance of ions in wettability
79.42
63.15
54.02
47.24
43.37
39.01
28.75
28.22
28.00
27.87

alteration is improved and the contact angle significantly changes. This

Oil

good performance was obtained with 9 times dilution of Gachsaran

–
–
–
–
–
–

formation water, 10 times dilution of Karanj formation water, 6 times

dilution of seawater in the presence of sections hydrophobized with
Karanj Oil and Formation

Gachsaran crude oil and 7 times dilution in the presence of sections

hydrophobized with Karanj crude oil. After these steps, although
wettability is altered to further hydrophilicity with no turning point,
this change takes place slowly. It seems that further dilution in the la-
boratory or treatment in the field is not affordable. In other words, no
105.41
Water

94.72
88.25
80.13
72.24
63.41
55.02
51.79
47.96
40.62
37.44
37.12
36.89
32.61
32.50
32.45

more effort and cost is required for poor performance of ions at con-
centrations lower than this limit. After these stages, the best perfor-
mance was determined in terms of wettability alteration of carbonate
Gachsaran Oil and Formation

rocks and minimum contact angle. Finally, it can be said that the ability
of seawater and water to form diluted formation water is less than the
ability of engineered smart water in the laboratory. Nevertheless, the
obtained numbers in this case, especially in the final stages of dilution,
Contact Angle (°)

are reasonable values to describe the hydrophilicity of the reservoir

rock, thus, for formation water of the Gachsaran, Kranj and sea water in
facing with the oleophilic sections with both Gachsaran and Kranj oil
Water

84.37
77.63
75.42
63.28
61.14
52.59
48.12
44.15
39.71
31.49
31.12
30.96
30.90
30.55

were obtained at 31.49, 37.44, 28.75 and 33.61°, respectively, in op-

–
–

timal dilution.
Fourteen Times Diluted
Thirteen Times Diluted

Wettability alteration from hydrophobic to hydrophilic one can be

Twelve Times Diluted

Fifteen Times Diluted

Eleven Times Diluted
Seven Times Diluted
Three Times Diluted

Eight Times Diluted

Nine Times Diluted
Four Times Diluted
Five Times Diluted

Ten Times Diluted

interpreted in different ways. In the mechanism described by Zhang

Six Times Diluted
Double Diluted

et al., they provided a model for the behavior of ions on the surface of
Once Diluted
Main Brine

calcite based on chromatography results. They examined temperature

Dilution

and flow rate of injected fluid and concentration of Mg2+ and Ca2+.
Table 5

According to their results, wettability alteration was due to the removal

of fatty acids adsorbed on the surface of reservoir rock [25]. They found

1044
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

120
Gachsaran Oil & fw
100

Contact Angle, Degree

80 Karanj Oil & fw

60
Gachsaran Oil & Sea
water
40

20 Karanj Oil & Sea

water

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Delution, Time
Fig. 4. The changes in contact angles of two droplets of oil on sections aged in different samples of saline water with different dilutions and aqueous bulk (based on
the data in Table 5).

60 Table 6
Contact Angle, Degree

The contact angles of droplets of oil on the section aged in 4 samples of car-
50 bonated saline water at different pressures and temperatures with optimal
concentrations and dilutions of aqueous bulk.
40 Pressure Temperature (°C) Contact Angle (Degree)
(MPa)
30 A B C D E F

0.101 35 45.13 48.84 48.22 37.39 45.87 45.01

20
55 34.73 42.51 47.43 36.50 39.12 44.71
75 31.49 37.44 28.75 33.61 28.86 33.69
10
3.45 35 38.89 40.76 44.07 32.76 37.80 43.06
55 33.64 37.17 40.46 32.26 28.52 40.19
0 75 27.32 34.51 25.15 28.01 21.19 24.72
1500 3000 4500 6000
6.89 35 33.70 37.22 41.27 30.44 35.41 41.31
Total Concentration, ppm
55 29.50 36.84 30.60 27.56 25.93 33.64
Brine Simulated & Gachsaran Oil Brine Simulated & Karanj Oil 75 22.81 28.16 23.74 21.90 19.45 20.56

Fig. 5. The changes in contact angles of two droplets of oil on sections aged in 10.34 35 30.72 33.25 40.70 26.54 21.34 32.03
55 25.45 31.70 28.17 20.25 19.50 27.49
saline water prepared in the laboratory with different concentrations and
75 19.64 25.78 19.08 18.83 18.75 19.07
aqueous bulk (based on the data in Table 5).
A: Gachsaran formation water with 9 times dilution and Gachsaran crude oil, B:
that SO42− ions in seawater decrease positive surface charge and the Karanj formation water with 10 times dilution and Karanj crude oil, C: seawater
anion increases the ability of cations to approach the carboxylic acid with 6 times dilution and Gachsaran crude oil, D: seawater with 7 times dilution
adsorbed on gypsum rock. By increasing concentration of cations in and Karanj crude oil, E: saline water simulated at a concentration of 1000 ppm
of each salt and Gachsaran crude and F: saline water simulated at a con-
smart water, the ability of cations for the removal of divalent carboxylic
centration of 1000 ppm of each salt and Karanj crude oil
acid adsorbed with a negative head on the rock surface increases. This
increases hydrophilicity of the rock. SO42− ion in carbonate rocks also
high temperatures. In fact, wettability alteration by Ca2+ and Mg2+ is
decreases positive surface charge as found in gypsum rock. As a result,
improved at elevated temperatures. According to Lager et al., multi-ion
divalent cations can more easily approach the surface of rock and ad-
exchange is a mechanism of wettability alteration in smart water
sorbed acids [25]. Rezaie and Hamoda found that calcite surface in
method. In this mechanism, divalent cations adsorbed on the solid
contact with sulfate solution shows a higher tendency to adsorb water
surface are exchanged with monovalent cations, and polar oil molecules
than pure calcite. They showed that the wettability of calcite surface is
bind to divalent cations and are released, leading to hydrophilicity of
dependent on the structure of fatty acids, pH, and the composition of
the rock [28,29]. Double layer effects were discussed by Ligthelm et al.
formation water [26]. Rezaiedoust et al. found that sulfate is hydrated
and Lee et al. that are mainly observed in clay formations. Reduction of
by hydrogen bonds and the reactivity of SO42− on the surface of
salinity of saline water and concentration of multivalent ions decreases
limestone increases at high temperatures due to hydrogen bond
dual electronic propagation between clay particles. By increasing
cracking. As a result, SO42− is more strongly adsorbed on the surface of
electrostatic repulsion, it may exceed the force threshold between clay
rock at high temperatures, causing a decrease in the repulsive force
and oil and thus oil is released from the surface of rock. This alters
between the positive surface charges and cations. This in turn increases
wettability to hydrophilic [30,31].
the ability of cations for adsorbing carboxylic groups. According to
These mechanisms are generally useful in high salinity. A me-
Rezaiedoust et al. [27], there is a chemical mechanism for wettability
chanism that is useful in low salinity was introduced by Lashkarbolooki
alteration, so that Ca2+ may react with carboxylic groups adsorbed on
et al. They considered the alteration in the carbonate rock's wettability
the surface of rock to release them at both low and high temperatures.
by low-salt water due to reactions that would dissolve the rock at its
On the other hand, Mg2+ may remove Ca2+-carboxylate complex at

1045
I. Nowrouzi et al.
surface, releasing some OH-ions. According to Eqs. (1) and (2) [32,33]:
CaCO3 (s) ⇔ Ca2 + (aq) + CO32 − (aq) (1)
CO32 − (aq) + H2 O (l) ⇔ HCO−3 (aq) + OH− (aq) (2)
They argued that by reducing the salinity, wettability will go to-
wards the hydrophilic resulting in a further reduction in the contact
angle. In addition, the salting-in effect can be considered in low sali-
nities. The effect of salting-out is a phenomenon in which organic
components with increasing the salinity tend more likely to move in the
oil phase, while the salting-in is the revers effect of this, i.e. at salting-
in, organic particles tend to dissolve in water. More clearly, what is
happening is that non-organic ions break down the structure of water
created around organic molecules, and thus reduce the solubility of
organic molecules in the aqueous phase. It can be said that the effect of
salting-in increases the distribution of active components of the surface
of the solvent at a low salt concentration, in other words, in low sali-
nity, the solubility of different types of soluble hydrocarbon of crude oil
in the aquifer increases [34–36].
Experiments were performed by adding carbon dioxide to the op-
timal solutions and aging hydrophobized sections in two crude oil
samples as applied in the previous step. Table 6 shows the results of
experiments. Figs. 6–11 clearly show the results presented in Table 6.
As can be seen, by increasing carbon dioxide pressure, the efficiency of
wettability alteration to hydrophilic increases and contact angle de-
creases. This is probably due to more carbon dioxide dissolved at higher
pressures. As already mentioned, more carbon dioxide is dissolved in a
smart solution by increasing pressure. As a result, acid strength of the
solution increases and thus the ability of carbonated smart water for
dissolution of carbonate rock minerals increases as one of the me-
chanisms for alteration of carbonate rock wettability to hydrophilic.
Chemical reactions resulted in the production of carbonic acid and
dissolution of carbonate rocks (Eqs. (3)–(6)) are widely reported in
literature [37–40]:
H2 O+ CO2 ⇔ H2 CO3 (3)
H2 CO3 ⇔ H+ + HCO−3 (4)
H2 O+ CO2 + CaCO3 ⇔ Ca(HCO3)2 (5)
H2 O+ CO2 + MgCO3 ⇔ Mg (HCO3)2 (6)
H2 O+ CO2 + CaMg(CO3)2 ⇔ 2HCO−3 + Mg2 + + Ca2 + (7)
These reactions control the dissolution of minerals in carbonate
rocks. Eqs. (3) and (4) are related to the formation of carbonic acid, and
they themselves are related to the solubility of carbon dioxide in in-
jected water. During the reaction of carbonic acid obtained from the
previous step with the rock, Eqs. (5)–(7) respectively, are related to the
reaction of calcite, magnesite and dolomite with carbonic acid. The
importance of Eqs. (3) and (4) is the same in all carbonate water in-
jection processes, but the importance of Eqs. (5)–(7) is related to the
reservoir rock. For example, Eq. (5), in facing the dominant calcite
reservoir, due to the frequency of the primary reaction, is more im-
portant. Temperature, pressure, salinity and saline water density are
the most important factors affecting the solubility of carbon dioxide in
water but at special conditions of the reservoir and the variation of ions
in the injected water, other factors such as the type of ions in the in-
jected water and the ions that are supposedly added from the formation
through dissolution and leaching can also be considered.
As temperature increases, the contact angle decreases and the
wettability alters to hydrophilic. In this case, although dissolution of
carbon dioxide in smart solution decreases by increasing temperature,
some mechanisms in smart water are strengthened. For example, as
mentioned earlier, Mg2+ and SO42− show a higher activity in im-
proving wettability at higher temperatures. Stumm and Morgan found
that the rate of dissolution is a function of saline water pH. This is in
1046
Fuel 235 (2019) 1039–1051
turn dependent on carbon dioxide solubility in water, temperature,
pressure and the amount of dissolved solids. They found that dissolu-
tion may be responsible for the removal of organic acid groups from the
rock surface [41]. Thus, the wettability changes from hydrophobic to
hydrophilic. On the other hand, the major part of the carbonate rock
consists of calcite, the calcite level has a positive charge at pH below 9.5
[42,43], so it tends to absorb negative oil, but as mentioned earlier,
during the presence of Mg2+, SO42− and Ca2+ levels of calcite tend to
be hydrophilic. In fact, the concentrations of these ions will determine
the amount of calcite's hydrophilicity. When carbon dioxide is added to
the system, according to reactions (5)–(7), which are the products of the
dissolution, the amounts of these ions would increase and the surface of
the rock is further advanced to the hydrophilicity [44].
4.2. Imbibition tests
Imbibition tests were performed at atmospheric pressure and 75 °C
on optimal solutions in the absence of carbon dioxide. To this end, 6
carbonate plugs with characteristics shown in Table 7 (samples 1–6)
were used. Table 8 lists the results of imbibition production from plugs
1 to 6 by optimal solutions. Fig. 12 shows the recovery percentage
versus time using the data in Table 8. The plugs were saturated with oil
and aged for 12 days after evacuation at 75 °C and 17.24 MPa. The
experiments continued as long as the end of oil production by imbibi-
tion mechanism was ensured through recording numbers very close
together and obtaining a horizontal curve for production versus time.
Imbibition experiments of optimal solutions with soluble carbon
dioxide were performed at optimal pressure and temperature.
According to the results of experiments conducted at dissolution tem-
peratures and pressures of carbon dioxide, the optimum temperature
was 75 °C in all experiments with a pressure equal to the maximum test
pressure of 10.34 MPa. The plugs used in this series of experiments are
specified with numbers 7–12 in Table 7.
Table 8 shows the results of imbibition tests with carbonated smart
water at given temperature and pressure. Fig. 13 shows the data in this
table as recovery percentage versus time. The experiments continued
until oil production by imbibition was stopped or was very negligible.
The duration of each imbibition experiment can be determined with
a point on the charts. After this time, oil production is almost zero or
sufficiently small so that the experiment can be stopped. This point is
shown in both Figs. 12 and 13. According to the results of imbibition
tests and the position of this point in Figs. 12 and 13, the duration of
imbibition by carbonated smart water at 10.34 MPa (between 16 and
22 days) is less than imbibition with a smart solution lacking carbon
dioxide at atmospheric pressure (between 26 and 38 days). In addition,
oil recovery in this case (from 52 to 76% of the original oil) is higher
than that from imbibition at atmospheric pressure without carbon di-
oxide (from 33 to 61% of the original oil). There are several reasons for
45.13
38.89
34.73
33.64
Contact Angle, Degree
33.7
31.49
30.72
29.5
27.32
25.45
22.81
19.64
0.101353 3.447378 6.894757 10.342135
Pressure, MPa
35°C 55°C 75°C
Fig. 6. The contact angle of a droplet of Karanj crude oil on the section aged in
Gachsaran carbonated formation water with 9 times dilution at different
pressures and temperatures.
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

48.84

45.87
39.12
42.51

Contact Angle, Degree

40.76

37.8

35.41
Contact Angle, Degree

37.44

37.22
37.17

36.84
34.51

33.25

28.86

28.52
31.7
28.16

25.93
25.78

21.34
21.19

19.45

18.75
19.5
0.101353 3.447378 6.894757 10.342135 0.101353 3.447378 6.894757 10.342135
Pressure, MPa Pressure, MPa

35°C 55°C 75°C 35°C 55°C 75°C

Fig. 7. The contact angle of a droplet of Karanj crude oil on the section aged in Fig. 10. The contact angle of a droplet of Gachsaran crude oil on the section
Karanj carbonated formation water with 10 times dilution at different pressures aged in carbonated simulated saline water at a concentration of 1000 ppm of
and temperatures. each salt at different pressures and temperatures.
48.22

45.01
44.71
47.43

43.06
44.07

41.31
40.19
41.27
40.46

40.7
Contact Angle, Degree

33.69

33.64

32.03
28.75

30.6

28.17

Contact Angle, Degree

25.15

23.74

27.49
19.08

24.72

20.56

19.07
0.101353 3.447378 6.894757 10.342135
Pressure, MPa

35°C 55°C 75°C

0.1013535 3.447378 6.894757 10.342135
Pressure, MPa
Fig. 8. The contact angle of a droplet of Gachsaran crude oil on the section aged
35°C 55°C 75°C
in carbonated seawater with 6 times dilution at different pressures and tem-
peratures. Fig. 11. The contact angle of a droplet of Karanj crude oil on the section aged in
carbonated simulated saline water at a concentration of 1000 ppm of each salt
at different pressures and temperatures.
37.39
36.5
33.61

32.76
32.26

30.44
Contact Angle, Degree

28.01

27.56

could be another reason for more oil production compared with smart
26.54

water imbibition in the absence of carbon dioxide. As previously

21.9

20.25
18.83

0.101353 3.447378 6.894757
Pressure, MPa
35°C 55°C
Fig. 9. The contact angle of a droplet of Karanj crude oil on the section aged in
carbonated seawater with 7 times dilution at different pressures and tempera-
tures.
this difference. First, the pressure in imbibition with carbonated smart
water is high, causing penetration of mobile phase in the plugs and thus
improving the removal of oil in the plugs. Another reason is dissolution
of rock by carbonic acid produced from dissolution of carbon dioxide in
smart solution [17]. After draining the imbibition container at carbon
dioxide pressure, the aqueous solution was analyzed by titration. An
increase in the concentration of Mg2+ and Ca2+ confirms the above
conclusion. According to literature, the dissolution of carbonate rocks
by carbonic acid formed from carbonated water can increase both
porosity and permeability [17,37,45,46]. This in turn increases oil
production. On the other hand, with the dissolution of surface minerals
by carbonated water, alteration of wettability toward hydrophilicity is
enhanced. This improves imbibition process. The contact angle also
decreases in all cases by adding carbon dioxide. Oil swelling in the plug
due to the transfer of carbon dioxide from the aqueous phase to oil [47]
mentioned, oil swelling causes the flow of oil from the plug.
The mass transfer of carbon dioxide from water to oil is very im-
portant in the carbonated water injection process. It is due to solution,
diffusion and dispersion mechanisms [48]. The solubility of a material
in another material is proportional to the distance between solvent
molecules, so this is compatible with the van der Waals forces between
10.342135
the intended molecules. This is while diffusion is defined as the pro-
pagation of a substance in another matter by random molecular motion.
75°C
Temperature effect on gases solution and diffusion in liquids has dif-
ferent properties. It means, the solubility of gas in liquid decreases,
while its diffusion increases with increasing temperature. When the
fluids move in the porous medium, there is more to be mixed or dis-
persed, which is more than diffusion alone. At medium velocities both
of diffusion and convective dispersion are important and total disper-
sion factor is the totality of these two factors. However, at reservoir
velocities, the width of the CO2 distribution area is also largely influ-
enced by molecular diffusion [48]. Phase behavior in carbonated water-
oil is a unilateral system unlike carbon dioxide-oil. It means, in car-
bonated water injection, carbon dioxide is gradually transferred from
the water phase to the oil phase, and changes the crude oil properties.
In fact, as a result of the mass transfer, the concentration of carbon
dioxide in water decreases and increases in oil, and causes oil swelling
and decreases oil viscosity, which, due to the gradual and stable
transfer, is expected to be continuous [49,50]. In reservoir, when car-
bonated water is placed adjacent to crude oil, carbon dioxide is dis-
solved in oil, but oil components cannot be dissolved in carbonated
water. Therefore, the transfer of carbon dioxide to live oil in the re-
servoir results in a competition between hydrocarbon gas and carbon

1047
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

dioxide transferred from carbonated water to oil, which will create a

Carbonated-Simulated brine (1000 ppm of salt)

Carbonated-Simulated brine (1000 ppm of salt)

new gas phase. The growth of this new phase can enhance oil recovery

Carbonated Gachsaran-fw (9 times diluted)

by a mechanism similar to oil swelling [51]. The solubility of carbon

Carbonated-Sea water (6 times diluted)

Carbonated-Sea water (7 times diluted)

Carbonated Karanj-fw (10 time diluted)
dioxide in oil and the change in the phase behavior of oil in the re-

Simulated Brine (1000 ppm of salt)

Simulated brine (1000 ppm of salt) servoir, such as reservoir temperature, oil components including light,
Gachsaran-fw (9 times diluted)

Karanj-fw (10 times diluted)

middle, and C5+ components and the percentage of carbon dioxide gas
Sea water (6 times diluted)

Sea water (7 times diluted)

purity play a major role and at the same time, the reservoir temperature
is more effective than the other parameters and affects the miscibility
pressure and dissolution of carbon dioxide [52].
Imbibition Fluid

Another point in a carbonated water injection program in fractured

reservoirs is to challenge the production of water and getting fast to the
breakthrough point for water. Although there is some dissolved carbon
dioxide in carbonated water, it is a water injection program. In frac-
tured reservoirs, a high density of vertical fractures creates the worst
OOIP (cm3)

case during oil production [53], particularly by supplying water

through the injection of water to the injected front, it can progress in
12.75
14.32
18.44
10.56
13.80
16.04
19.55
17.13
14.76
14.09
17.87
16.61

the fractures and reach the well.

With comparing the production values from the imbibition tests and
66.58●●
81.08●●
80.44●●

85.03●●
82.58●●
87.05●●
75.55●
79.30●
91.78●

91.78●
86.17●
83.06●
Soi (%)

the values obtained from the contact angle tests, a meaningful re-
lationship is obtained. Accordingly, the amount of production under
imbibition is correlated conversely with the values of contact angle
Mass of Oil-Saturated Plug ± 0.0001 (g)

reduction. This topic can be researched in the imbibition mechanism

definition. In this process, which occurs in the porous medium, the
wetting phase around the matrix is pulled into it and at the same time,
non-wetting phase flows out of the rock from the opposite direction. If
the matrix is hydrophilic and the source of water around it, it will work
properly in carbonated smart water injection system, this mechanism
will be strengthened by the wettability alteration of the matrix to the
hydrophilicity.
Another noteworthy is that in carbonated water injection in re-
201.2380
200.1946
205.4611
200.2030
202.8866
205.0561
211.3231
210.7051
201.2669
204.4698
211.4451
205.2652

servoirs, we would have a water-gas-oil-rock system and the possible

reactions in this regard, from the point of view of changes of the
properties of rock and reservoir fluids and their confrontation, will be
Mass of Dry Sample ± 0.0001 (g)

determinative. The reactions that lead to the production of carbonic

acid and its confrontation with the reservoir rock and injecting brine
were explained earlier. In the presence of carbonated water with oil in
the reservoir, it can be added that Eqs. (3) and (4) cause the acid-
ification of carbonated water to be followed a decrease in pH and pH of
the solution is proportional to Eq. (8) [54]:
190.1457
187.7361
189.4182
191.0652
190.9451
191.1763
194.3145
195.8019
188.4256
192.2774
195.9817
190.8921

pH = A [−log10 (X )] + B (8)

In Eq. (8), X is the mole fraction of CO2 in carbonated water. A and B

Total VP (cm3)

are calculated empirically.

This acidification of injecting water in the vicinity of oil produces
in-situ surfactants in the common oil/water interface and it is due to
16.88
18.06
20.09
15.86
17.02
19.94
21.30
19.88
17.77
16.57
21.64
19.08

reactions of carbonic acid produced from carbon dioxide dissolution in

water and nitrogenous alkalis of crude oil. This factor is strongly in-
L ± 0.02 (cm)

fluenced by the composition of oil and the surfactants formed at the

common water/oil interface can change some properties, such as in-
The characteristics of plugs used in imbibition tests.

terfacial tension [48,55].

7.00
6.98
7.00
7.00
7.03
7.11
7.21
7.30
6.98
7.14
7.35
7.12

These cases lead to a limitation to comparison of the two methods

studied in this work. In other words, if we compare the performances of
Por. ± 0.2 (%)

Initial water saturation is zero in all cases.

the smart water and carbonated smart water methods in this study, all
the conditions, especially the pressure and temperature, should be the
21.16
22.71
25.19
19.89
21.25
24.61
25.93
23.90
22.34
20.37
25.84
23.52

All samples are 1.5 in. in diameter.

same for the tests of both techniques, while herein, although the test
Saturated with Gachsaran oil.
Saturated with Karanj oil.

temperatures are the same, the tests for smart water were undertaken at
atmospheric pressure and experiments involving carbonated smart
Perm. ± 0.5 (md)

water were performed at various and higher pressures. It is worth

mentioning that our aim was not to compare the two techniques, and
the main objective, in addition to examining the combination of these
14.63
14.05
15.76
11.80
13.92
14.33
17.63
15.00
14.63
15.12
14.30
14.72

two methods, was to increase the intake of smart water by dissolving

carbon dioxide in an engineered system of ions in injected water with
Plug No.

increasing pressure followed by more carbon dioxide solubility.

Table 7

●●
10
11
12

●
1
2
3
4
5
6
7
8
9

1048
I. Nowrouzi et al. Fuel 235 (2019) 1039–1051

Table 8
Oil production by imbibition using optimal smart solutions at 75 °C and atmospheric pressure in the absence of carbon dioxide (plugs 1–6) and at a pressure of
10.34 MPa in the presence of carbon dioxide (plugs 7–12) with production recording every 48 h.
Time (h) Production in Periods of Time (cm3)

Plug1 Plug2 Plug3 Plug4 Plug5 Plug6 Plug7 Plug8 Plug9 Plug10 Plug11 Plug12

48 0.0 0.1 0.3 0.0 0.0 0.0 1.4 0.7 1.7 0.9 1.8 0.6
96 0.0 0.8 0.8 0.0 0.1 0.0 2.6 1.9 3.4 1.6 3.6 1.4
144 0.2 1.2 1.4 0.1 0.9 0.0 3.1 2.8 5.0 2.7 5.1 2.5
192 0.6 1.9 2.3 0.5 1.8 0.3 4.0 4.2 6.4 3.9 6.6 3.3
240 0.9 2.5 2.9 0.8 2.3 0.7 5.2 5.7 8.1 4.6 8.2 5.1
288 1.4 3.3 3.7 1.4 2.7 1.2 5.8 7.0 9.3 5.5 9.9 6.4
336 2.0 4.1 4.5 1.9 3.4 1.9 6.9 8.3 10.5 6.1 11.0 8.8
384 2.8 5.6 5.1 2.0 3.9 2.4 8.2 9.5 11.5 7.0 12.3 10.4
432 3.4 7.2 6.7 2.3 4.5 3.0 9.3 10.8 11.5 7.2 12.5 11.1
480 4.5 8.0 7.8 2.4 5.1 3.7 10.5 10.8 11.5 7.3 12.5 11.1
528 4.9 8.7 8.5 2.6 5.3 4.4 10.7 10.8 11.5 7.3 12.5 11.1
576 5.6 9.1 9.8 2.6 5.4 4.4 10.7 10.8 11.5 7.3 12.5 11.1
624 6.1 9.3 10.4 2.7 5.4 5.0 10.7 10.8 11.5 7.3 12.5 11.1
672 6.4 9.3 10.8 2.8 5.6 5.6 10.7 10.8 – 7.3 12.5 11.1
720 6.5 9.3 11.2 3.0 5.8 5.7 10.7 – – 7.3 – –
768 6.5 9.3 11.2 3.1 5.9 5.7 10.7 – – – – –
816 6.5 9.3 11.2 3.1 6.0 5.8 – – – – – –
864 6.5 9.4 11.2 3.1 6.0 5.9 – – – – – –
912 6.5 9.4 11.2 3.2 6.0 5.9 – – – – – –
960 6.5 9.4 11.2 3.2 6.0 5.9 – – – – – –
1008 6.5 9.4 11.2 3.2 6.0 5.9 – – – – – –
1056 – 9.4 – 3.2 6.0 5.9 – – – – – –
1104 – 9.4 – 3.2 6.0 5.9 – – – – – –
1152 – 9.4 – 3.2 – 5.9 – – – – – –
1200 – – – 3.2 – – – – – – – –

70 5. Conclusion
Oil Recovery, %OOIP

60
Based on the results of spontaneous imbibition and contact angle
50
tests obtained in this study for investigation of the capability of smart
40 water and carbonated smart water technologies, the combination of
30 these two methods can be considered as an effective method for en-
hancing oil recovery from carbonate reservoirs. The results of this
20
study, in addition, indicate that:
10

0 • Wettability alteration as the main mechanism of smart water is in-

0 200 400 600 800 1000 1200 1400 fluenced by many mechanisms. Depending on the temperature,
Time, h pressure and the composition of rock and oil, these mechanisms can
Plug1 Plug2 Plug3 Plug4 Plug5 Plug6 exhibit different strengths and each may be more effective in any
circumstance.
Fig. 12. Oil production by imbibition using optimal smart solutions at atmo-
spheric pressure and 75 °C and 0.101 MPa in the absence of carbon dioxide • The ability to reduce the contact angle and subsequently wettability
alteration of carbonate rock by smart water is confirmed. We have
based on the data in Table 8 for the plugs 1–6.
observed a wettability alteration from oil-wet to water-wet in aged
sections by smart water at different concentrations of different ions.
This capability was enhanced by increasing the pressure of carbon
dioxide resulting in severe wettability alteration from oil-wet to
90 water-wet under these conditions.
80 • The saline water samples used in this study were consistently
Oil Recovery, %OOIP

70 compatible with formation water in both carbonated smart water

60 under pressure and smart water at atmospheric pressure at a re-
50 servoir temperature of 75 °C. No deposition was observed.
40 • In addition to wettability alteration, carbon dioxide dissolved in
30 injected water is associated with beneficial effects such as oil
20 swelling, dissolution of rocks and changes in the viscosity and
10
density of both oil and water phases. Thus, although not always
effective, carbon dioxide injection is recommended to overcome
0
0 100 200 300 400 500 600 700 800 900 shortcomings of smart water method. The chemistry of injected
Time, h water is changed by dissolution of rock by changing the con-
Plug7 Plug8 Plug9 Plug10 Plug11 Plug12
centration of ions dissolved from the rock. This change in con-
centration can be monitored. The modified saline water may cause
Fig. 13. Oil production by imbibition using carbonated smart water based on incompatibilities. Besides, coarse particles separated from the rock
the data in Table 8 for the plugs 7–12 at 10.34 MPa and 75 °C. by dissolution may stuck in narrow throats and reduce permeability.
It is recommended that the effects of these changes are investigated

1049
I. Nowrouzi et al.
in future studies.
• According to the results obtained from seawater and formation
water at different concentrations in wettability alteration tests, to
implement the plans in the field, feasibility studies on the transfer of
seawater or modification and the use of formation water should be
conducted.
•
Imbibition experiments were carried out with carbon dioxide at high
pressure in a container designed for this study made from tem-
perature and pressure-resistant stainless steel. It seems that the ex-
periments can be performed at higher pressures by modifying and
developing the design.
• The results of contact angle measurements show that the diluted
samples of saline water can be more efficient in wettability altera-
tion. Such tests to find optimum conditions may reduce unnecessary
costs for treatment of saline water.
•
The results of the imbibition experiments show that the application
of both smart water and carbonated smart water techniques is sui-
table in carbonate oil reservoirs. However, carbonated water at high
pressure and with the help of carbon dioxide-related mechanisms
can promote the smart water technique.
• The use of simulated saline water with seawater and formation
water can help to understand the mechanism of ions and pave the
way for targeted treatment and ion engineering.
• It is suggested to conduct feasibility studies for the use of flue gas
instead of carbon dioxide for reservoirs close to plants producing a
large volume of flue gas.
• In addition to the extraction of water from oil reservoirs, saline
water found in layers near oil layer can be used. The possibility of
injection can be further investigated by analyzing saline water,
wettability alteration tests and compatibility with formation water
and imbibition process.
References
[1] Al-Shalabi EW, Sepehrnoori K, Pope GA. Mysteries behind the low salinity water
injection technique. J Petrol Eng 2014;vol. 2014. 11 Pages, Article ID 304312.
[2] Strand S, Henningsen SC, Puntervold T, Austad T. Favorable temperature gradient
for maximum low-salinity enhanced oil recovery effects in carbonates. Energy Fuels
2017;31(5):4687–93.
[3] Khaksar MA, Olad M, Aldin-Taghipour S, Nowrouzi I, Mohammadi AH. Effects of
water soluble ions on interfacial tension (IFT) between oil and brine in smart and
carbonated smart water injection process in oil reservoirs. J Mol Liq
2016;223:987–93.
[4] Nowrouzi I, Manshad AK, Mohammadi AH. Effects of dissolved binary ionic com-
pounds and different densities of brine on interfacial tension (IFT), wettability al-
teration, and contact angle in smart water and carbonated smart water injection
processes in oil reservoirs. J Mol Liq 2018;254:83–92.
[5] Strand S, Austad T, Puntervold T, Høgnesen EJ, Olsen M, Barstad SMF. “Smart
water” for oil recovery from fractured limestone: a preliminary study. Energy Fuels
2008;22(5):3126–33.
[6] Kamath KI, Yan SJ. Enhanced oil recovery by flooding with dilute aqueous chemical
solutions. J Energy Res Technol 1981;103(4):285–90.
[7] Miller JS, Jones RA. A laboratory study to determine physical characteristics of
heavy oil after CO2 saturation. In: SPE/DOE enhanced oil recovery symposium,
Tulsa, Oklahoma; 1981 [SPE-9789-MS].
[8] Dong Y et al. An experimental investigation of carbonated water flooding. In: SPE
annual technical conference and exhibition. Denver (Colorado, USA): Society of
Petroleum Engineers; 2011 [SPE-145380-MS].
[9] Zendehboudi S, Chatzis I. Experimental study of controlled gravity drainage in
fractured porous media. J Can Pet Technol 2011;50(2).
[10] Zendehboudi S, Rezaei N, Chatzis I. Effects of fracture properties on the behavior of
free-fall and controlled gravity drainage processes. J Porous Media 2012;15(4).
[11] Zendehboudi S, Rezaei N, Chatzis I. Effect of wettability in free-fall and controlled
gravity drainage in fractionally wet porous media with fractures. Energy Fuels
2011;25(10):4452–68.
[12] Webb KJ, Black CJJ, Tjetland G. A laboratory study investigating methods for im-
proving oil recovery in carbonates. In: IPTC10506, paper presented at the inter-
national petroleum technology conference, Doha, Qatar; November 21–23, 2005
[IPTC-10506-MS].
[13] Garcia JE. Density of Aqueous solution of CO2. LBNL-49023; 2001. http://
repositories.cdlib.org/lbnl/LBNL-49023.
[14] Srivastava RK, Huang SS, Dong M. Laboratory investigation of Weyburn CO2 mis-
cible flooding. J Can Pet Technol 2000;39(2):41–51.
[15] Chilingar GV, Yen TF. Some notes on wettability and relative permeability of car-
bonate rocks. II. Energy Sources 1983;7:67–75.
1050
Fuel 235 (2019) 1039–1051
[16] Manshad AK, Rezaei M, Moradi S, Nowrouzi I, Mohammadi AH. Wettability al-
teration and interfacial tension (IFT) reduction in enhanced oil recovery (EOR)
process by ionic liquid flooding. J Mol Liq 2017;248:153–62.
[17] Khaksar MA, Nowrouzi I, Mohammadi AH. Effects of water soluble ions on wett-
ability alteration and contact angle in smart and carbonated smart water injection
process in oil reservoirs. J Mol Liq 2017;244C:440–52.
[18] Qasem FH, Nashawi IS, Gharbi R, Mir MI. Recovery performance of partially frac-
tured reservoirs by capillary imbibition. J Petrol Sci Eng 2008;60(1):39–50.
[19] Morrow NR, Mason G. Recovery of oil by spontaneous imbibition. Curr Opin Colloid
Interface Sci 2001;6(4):321–37.
[20] Mackay JE. Modeling in-situ scale deposition: the impact of reservoir and well
geometries and kinetic reaction rates. SPE Prod aqd Facilit 2003:45–56. SPE-
81830-PA.
[21] Moghadasi J, Jamialahmadi M, Muller-Steinhagen H, Sharif A, Ghalambor A,
Izadpanah RM, Motaie E. Scale formation in Iranian oil reservoir and production
equipment during water injection [SPE-80406-MS]. 5th international oilfield scale
symposium and exhibition, January 29–302003. p. 1–14.
[22] Collins RI, Jordan MM. Occurrence prediction and prevention of zinc sulfide scale
within gulf coast and north sea high temperature/high salinity production wells.
The SPE third international symposium on oilfield scale, January 30–31. 2011. p.
1–17.
[23] Mousavi Dehghani SA, Vafaie Sefti M, Mirzayi B, Fasih M. Experimental in-
vestigation on asphaltene deposition in porous media during miscible gas injection.
Iran J Chem Chem Eng (IJCCE) 2007;26(4):39–48.
[24] Zick AA. A combined condensing/vaporizing mechanism in the displacement of oil
by enriched gases [ SPE annual technical conference and exhibition. Society of
Petroleum Engineers; 1986. SPE-15493-MS].
[25] Zhang P, Tweheyo MT, Austad T. Wettability alteration and improved oil recovery
by spontaneous imbibition of seawater into chalk: impact of the potential de-
termining ions Ca2+, Mg2+, and SO42−. Colloids Surf, A 2007;301(1):199–208.
[26] Gomari KR, Hamouda AA. Effect of fatty acids, water composition and pH on the
wettability alteration of calcite surface. J Petrol Sci Eng 2006;50(2):140–50.
[27] RezaeiDoust A, Puntervold T, Strand S, Austad T. Smart water as wettability
modifier in carbonate and sandstone: a discussion of similarities/differences in the
chemical mechanisms. Energy Fuels 2009;23(9):4479–85.
[28] Lager A, Webb KJ, Black CJJ, Singleton M, Sorbie KS. Low salinity oil recovery – an
experimental investigation. Paper SCA2006-36 presented at the international
symposium of the society of core analysts, Trondheim, Norway, September 12–16.
2006. [SPWLA-2008-v49n1a2].
[29] Lager A, Webb KJ, Black CJJ. Impact of brine chemistry on oil recovery. Paper A24
presented at the 14th European symposium on improved oil recovery, Cairo, Egypt.
2007.
[30] Ligthelm DJ, Gronsveld J, Hofman J, Brussee N, Marcelis F, van der Linde H. Novel
waterflooding strategy by manipulation of injection brine composition. EUROPEC/
EAGE conference and exhibition. Society of Petroleum Engineers; 2009. [SPE-
119835-MS].
[31] Lee SY, Webb KJ, Collins IR, Lager A, Clarke SM, O’Sullivan M, Routh AF. Low
salinity oil recovery–increasing understanding of the underlying mechanisms of
double layer expansion. IOR 2011-16th European symposium on improved oil re-
covery. 2011. [SPE-129722-MS].
[32] Lashkarbolooki M, Riazi M, Hajibagheri F, Ayatollahi S. Low salinity injection into
asphaltenic-carbonate oil reservoir, mechanistical study. J Mol Liq
2016;216:377–86.
[33] Lashkarbolooki M, Ayatollahi S, Riazi M. Mechanistical study of effect of ions in
smart water injection into carbonate oil reservoir. Process Saf Environ Prot
2017;105:361–72.
[34] Yi C, Xie Sh, Qiu X. Salting-out effect of dipotassium hydrogen phosphate on the
recovery of acetone, butanol, and ethanol from a prefractionator. J Chem Eng Data
2014;59:1507–14.
[35] Piero M, Hans A, Karlsson T. Salting-out parameters for organic acids. J Chem Eng
Data 1982;27:155–6.
[36] Standal SH, Blokhus AM, Haavik J, Skauge A, Barth T. Partition coefficient and
interfacial activity for polar components in oil/water model systems. J Colloid
Interface Sci 1999;212:33–41.
[37] Luquot L, Gouze P. Experimental determination of porosity and permeability
changes induced by injection of CO2 into carbonate rocks. Chem Geol
2009;265(1):148–59.
[38] Ross GD, Todd AC, Tweedie JA, Will AG. The dissolution effects of CO2-brine sys-
tems on the permeability of UK and North Sea calcareous sandstones. SPE enhanced
oil recovery symposium. Society of Petroleum Engineers; 1982. [SPE-10685-MS].
[39] Bathurst RG. Carbonate sediments and their diagenesis. Elsevier; 1972.
[40] Sayegh SG, Krause FF, Girard M, DeBree C. Rock/fluid interactions of carbonated
brines in a sandstone reservoir: Pembina Cardium, Alberta, Canada. SPE Format
Evaluat 1990;5(04):399–405.
[41] Stumm W, Morgan JJ. Aquatic chemistry: chemical equilibria and rates in natural
waters. John Wiley & Sons; 2012.
[42] Morrow NR, Cram PJ, McCaffery FG. Displacement studies in dolomite with wett-
ability control by octanoic acid. Society of Petroleum Engineers; 1973.
[43] Thomas MM, Clouse JA, Longo JM. Adsorption of organic compounds on Carbonate
minerals: 1. Model compounds and their influence on mineral wettability. Chem
Geol 1993;109(1–4):201–13.
[44] Seyyedi M, Sohrabi M, Farzaneh A. Investigation of rock wettability alteration by
carbonated water-contact angle measurement. IOR 2015-18th European symposium
on improved oil recovery. 2015.
[45] Grigg RB, McPherson BJ, Svec RK. Laboratory and model tests at reservoir condi-
tions for CO2-brine-carbonate rock systems interactions. Second annual conference
I. Nowrouzi et al.
on carbon sequestration, May 2003. 2003. [SPE-80228-MS].
[46] Bacci G, Korre A, Durucan S. An experimental and numerical investigation into the
impact of dissolution/precipitation mechanisms on CO2 injectivity in the wellbore
and far field regions. Int J Greenhouse Gas Control 2011;5(3):579–88.
[47] Riazi M, Golkari A. The influence of spreading coefficient on carbonated water
alternating gas injection in a heavy crude oil. Fuel 2016;178:1–9.
[48] Rojas GA, Ali SM. Dynamics of subcritical CO2/brine floods for heavy-oil recovery.
SPE Reservoir Eng 1988;3(01):35–44. SPE-13598-PA.
[49] Seyyedi M, Mahzari P, Sohrabi M. An integrated study of the dominant mechanism
leading to improved oil recovery by carbonated water injection. J Indus Eng Chem
2017;45:22–32.
[50] Shu G, Dong M, Chen S, Hassanzadeh H. Mass transfer of CO2 in a carbonated
water–oil system at high pressures. Indus Eng Chem Res 2016;56(1):404–16.
[51] Bakhshi P, Kharrat R, Hashemi A, Zallaghi M. Experimental evaluation of
1051
Fuel 235 (2019) 1039–1051
carbonated waterflooding: a practical process for enhanced oil recovery and geo-
logical CO2 storage. Greenhouse Gas Sci Technol 2017;8(2):238–56.
[52] Chen G, Wang X, Liang Z, Gao R, Sema T, Luo P, et al. Simulation of CO2-Oil
Minimum Miscibility Pressure (MMP) for CO2 Enhanced Oil Recovery (EOR) using
Neural Networks. Energy Procedia 2013;37:6877–84.
[53] Zendehboudi S, Elkamel A, Chatzis I, Ahmadi MA, Bahadori A, Lohi A. Estimation of
breakthrough time for water coning in fractured systems: experimental study and
connectionist modeling. AIChE J 2014;60(5):1905–19.
[54] Peng C, Crawshaw JP, Maitland GC, Trusler JM, Vega-Maza D. The pH of CO2-
saturated water at temperatures between 308K and 423K at pressures up to 15MPa.
J Supercrit Fluids 2013;82:129–37.
[55] Lashkarbolooki M, Riazi M, Ayatollahi S. Effect of CO2 and natural surfactant of
crude oil on the dynamic interfacial tensions during carbonated water flooding:
Experimental and modeling investigation. J Petrol Sci Eng 2017;159:58–67.