Journal of Molecular Liquids 310 (2020) 113123

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Experimental investigation of Alfalfa natural surfactant and synergistic

effects of Ca2+, Mg2+, and SO2−
4 ions for EOR applications: Interfacial
tension optimization, wettability alteration and imbibition studies
Mohammad Eslahati a, Parviz Mehrabianfar b, Ali Akbar Isari c, Hossein Bahraminejad b,
Abbas Khaksar Manshad b,⁎, Alireza Keshavarz d
a
Department of Petroleum Engineering, Amirkabir University of Technology (AUT), Tehran, Iran
b
Department of Petroleum Engineering, Abadan Institute of Technology, Petroleum University of Technology (PUT), Abadan, Iran
c
Department of Basic and Applied Sciences for Engineering, SAPIENZA University of Rome, Italy
d
School of Engineering, Edith Cowan University, Joondalup, WA 6027, Australia

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

Article history: Fractured moderate oil-wet carbonate reservoirs are the main productive formations in the Middle East. The
Received 7 December 2019 change in wettability state toward water wetness beside interfacial tension (IFT) reduction is one of the potential
Received in revised form 4 March 2020 scenarios for more oil recovery process. Smart water and natural surfactant injection into the porous media will
Accepted 9 April 2020
alter the rock wettability and reduce IFT which consequently results in more oil sweep from untouched pores. In
Available online 28 April 2020
this paper, a novel natural surfactant (Alfalfa species) is introduced for EOR applications. IFT and contact angle
Keywords:
tests were carried out between the oil phase, rock surface, Alfalfa natural surfactant, and surfactant—ion hybrid
Smart water aqueous solutions. The results of Alfalfa natural surfactant showed a 29.29 mN/m reduction of IFT (63.39% IFT op-
Natural surfactant timization) at the concentration of 4 wt% as the critical micelle concentration (CMC). Also, after addition of Alfalfa
Enhanced oil recovery the wettability of rock tends to be more water-wet from the initial oil-wet state by application of Alfalfa because
Interfacial tension of 86.84° reduction of contact angle (49.91% wettability alteration). Solutions of calcium, magnesium, and sulfate
Wettability alteration ions were prepared as modified synthetic seawater at CMC of Alfalfa natural surfactant to investigate their syn-
Carbonate reservoir ergistic influences on intensifying the optimizations of IFT and wettability alteration as hybrid solutions. IFT mea-
Alfalfa
surements of the hybrids demonstrated that among mentioned ions calcium brings the best results as it showed
good synergistic effects with mentioned non-ionic natural surfactant in advancing the optimization of IFT reduc-
tion from 63.39 (surfactant solution) to 71.0 (surfactant—ion hybrid solution) percent. Also, contact angle mea-
surements of the hybrids demonstrated that calcium ions gain the best results and advance the contact angle
optimization from 49.91 (surfactant solution) to 61.8 (surfactant—ion hybrid solution) percent. Therefore, the so-
lution of 3 times Ca concentrated seawater + CMC of surfactant selected to conduct imbibition tests as a displace-
ment experiment based on the hybrid results and the candidate solution caused a 19.2% increase in oil recovery
factor regarding seawater flooding and a total oil recovery factor of 62%.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
Increasing demand for oil shows the importance of studying and de-
veloping of carbonate reservoirs [1–4]. When the carbonate reservoir pro-
duces for a long period, the production scenario may change due to some
reasons like the tendency of carbonate rock wettability to be more oil-wet
from its initial wettability condition. The oil-wet nature of naturally frac-
tured carbonate reservoirs may enable the rock to hold more oil in pores
and decrease oil production and lower the recovery factor due to its high
capillary force [5,6]. Tertiary recovery known as enhanced oil recovery
⁎ Corresponding author.
E-mail address: khaksar@put.ac.ir (A.K. Manshad).
(EOR) is exerted on the reservoir when the primary and secondary recov-
ery is not effective enough to produce an economical amount of oil [1].
EOR methods act by altering the physical and/or chemical properties of
the rock—fluid system of a reservoir to facilitate the displacement of oil
[7–9]. There are two main EOR methods; water-based EOR and gas-
based EOR. Chemical flooding is a water-based EOR method and works
on lowering the capillary pressure. Interfacial tension reduction and wet-
tability alteration toward water wetness are the main mechanisms in
chemical EOR to evacuate trapped oil in small pores [10,11]. Smart
water injection and surfactant flooding are classified as chemical EOR
methods. Smart water is an aqueous solution with a modified concentra-
tion of ions in seawater. In fact, smart water is the ion engineering process
of the injection fluid and prepared by type and concentration adjustment

https://doi.org/10.1016/j.molliq.2020.113123
0167-7322/© 2020 Elsevier B.V. All rights reserved.
2 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123
of ions in the seawater or formation brine. Seawater contains active ions
like calcium, magnesium cations and sulfate anions, hence modifying
the concentration of stated ions in the injection fluid can alter the wetta-
bility of rock toward water wetness and reduce the IFT concurrently [12].
Smart water flooding can performance as an individual chemical EOR
method but potentially it could be the best manner to act as a good hybrid
with other chemical materials to enhance the conditions of recovery more
efficiently [13]. Synergistic effects of used ions in smart water could inten-
sify the EOR mechanisms to gain a better condition of wettability and in-
terfacial tension. On the other hand, well-known materials applicated in
chemical EOR are amphiphilic molecules that act as oil—water intermedi-
ate materials that named surfactants [14]. Surfactant flooding is a poten-
tial method to increase the level of recovery from challenging reservoirs.
Surfactants are surface-active agents and classified into four types of an-
ionic, cationic, nonionic, and zwitterionic [15]. They can be absorbed
and concentrated on the interface of two immiscible phases to reduce sur-
face tension (gas-liquid) or interfacial tension (liquid-liquid). These com-
pounds consist of two parts of hydrophilic (the “head”) and hydrophobic
(the “tail”) affecting the absorption; the head orients toward the water
phase and the tail orients toward the oil phase and behaves as an
intermediator [16]. Zhang et al. [39] studied the effects of Ca2+, Mg2+,
and SO2−4 on mechanisms of wettability alteration. They performed core
flooding tests on chalk outcrop samples of Stevns Klint, Denmark. They
concluded that the sulfate anion alone didn't exhibit high oil recovery in-
crease but when either calcium or magnesium cations were added the re-
covery increased significantly. The recovery increased by 40% for sulfate
concentration variations from 0 to four times of the initial existing sulfate
anions in the seawater. Furthermore, the effect of calcium and magne-
sium cations on recovery was investigated. The production was reported
to be equal for calcium and magnesium cations while the concentration of
sulfate anion was similar in both experiments for two months. After two
months, due to an increase in the concentration of magnesium cation, oil
recovery was abruptly increased and became higher than calcium cation
recovery. Strand et al. [41] investigated the applicability of smart water
for the EOR applications on limestone. The imbibition oil recovery test
showed that sulfate anion was a necessary component for achieving a
more convenient recovery. The oil recovery of seawater without anions
of sulfate was 15%, and then sulfate anions were added to the seawater
in three steps but oil recovery didn't increase remarkably. They concluded
that CaSO4 was precipitated in the core. They proposed to add a cationic
surfactant in the solution to overcome the problem, and the outcome
was 60% of oil recovery. This work introduces Alfalfa species as a new non-
ionic natural surfactant to be applied in chemical EOR beside cations and
anion ions to investigate the state of synergy. IFT and contact angle mea-
surements carried out between the oil phase, rock surface, natural surfac-
tant aqueous solution, and natural surfactant—Ca/Mg/SO4 hybrids.
Experiments showed that natural surfactants could optimize IFT and wet-
tability conditions individually, but to enhance this optimization, men-
tioned ions had been applied as the synergistic form with nonionic
molecules of Alfalfa. Hybrid solutions were designed in the way that men-
tioned ions added into the optimum concentration of Alfalfa solution and
again IFT and contact angle experiments were done for these solutions to
select the optimum solution to obtain the best state of capillary pressure
which needs the lowest value of IFT and the finest water-wet state of the
rock surface. Imbibition tests as displacement experiments were con-
ducted once with seawater as the base state and once with the optimum
hybrid solution. The recovery factors of these were compared and showed
a good potential of a synergistic effect of applicated nonionic surfactant
with smart water that causes a high recovery factor.
2. Materials and methods
Flowchart of the experimental procedure and the steps of the pro-
cesses from material preparations, characterization steps, and experi-
mental conductions is shown in Fig. S1 (Supplementary data to this
article can be found online at https://doi.org/10.1016/j.molliq.2020.
113123.).
2.1. Fluids
2.1.1. Smart water and brine samples
Formation water (FW) is prepared from one of the Iranian oil fields
located in the Southwest of Iran. Concentrations of dissolved compo-
nents in FW are shown in Table 1.
The based Sea Water (SW) used in the experiments is collected from
the Persian Gulf and the composition of different ions in the SW is given
in Table 2. The ion engineering section of the hybrid investigation is con-
ducted in the way that concentration of Ca, Mg, and sulfate ions are in-
creased in seawater while the concentration of other components in the
seawater remained constant. The hybrid of smart water and natural sur-
factant solutions are prepared in three types of (nCaSW, nMgSW, and
nSO4SW) + (CMC of natural surfactant aqueous solutions). General ter-
minology of modified SW is nXSW; where X is a specific ion existing in
the water, i.e. SO2− 2+
or Ca2+ and n is the ratio of the amount of X
4 , Mg
in the modified synthetic seawater to its amount in based seawater.
Salts were prepared in standard conditions and purity.
2.1.2. Oil
Two types of oil are applied in this study. Kerosene is used for the IFT
and contact angle measurement experiments as the oil phase instead of
crude oil because of cleanness. The studied oil sample for the imbibition
test is taken from an Iranian carbonate oil reservoir. The oil sample is
prepared and analyzed by the SARA test (Saturates, Aromatics, Resins,
and Asphaltenes Test) and the result is given in Fig. 1, then it is filtered
to remove any particles and contaminants. Furthermore, compositional
analysis is performed on the crude oil and the result is presented in
Table 3. Used oil was the residual crude oil and does not contain H2S,
N2, CO2, and C1, while C12+ content is relatively high (approximately
63%). Density and viscosity of the crude oil were placed in the range of
0.7998–0.8801 g/cm3 and 2.5–7.2 cp respectively for the pressure
range of 14.7 to 6043 psia.
2.2. Rock sample
Two rock samples used in this study are drilled from outcrops of
Asmari-Jahrom formation with the main lithology of limestone, dolo-
mite, and dolomitic limestone [17]. The samples were cleaned by
flooding 5 pore volumes of ethanol followed by 5 pore volumes of Dis-
tilled Water (DW) at 50 °C to remove any possible contaminations
and pre-existed or precipitated ions on surfaces of pores, for instance,
SO4 ions. Sample dried in an oven at 90 °C for 2 days to ensure the sol-
vents are completely removed. Basic petrophysical properties such as
porosity and permeability were measured and the average porosity
and permeability are 20% and 30md respectively. Cores saturated with
synthetic formation brine by the flooding method and then FW satura-
tion was established to Swirr by crude oil flooding. The oil-saturated core
was aged at 80 °C for three weeks to restore the reservoir wettability
conditions. The basic properties of the prepared core samples are
given in Table 4.
Table 1
Composition of dissolved components in the formation water.
Component Concentration (mmol/L)
HCO−3 20.27
Cl− 4015.5
2−
SO4 1.815
Ca2+ 89.03
Mg2+ 32.98
K+ 20.04
Na+ 3060.8
 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123 3

Table 2 Table 3
Composition of different ions in the sea water. Compositional analyzing results on crude oil.

Ion Concentration (mmol/L) Components Residual oil Associated gas Reservoir oil

K+ 2.37 (Mole %) (Mole %) (Mole %)

Ca2+ 96
H2S 0.00 0.00 0.00
Na+ 319
N2 0.00 0.79 0.30
Mg+2 78
CO2 0.00 2.49 0.93
SO−2
4 143.6
C1 0.00 50.60 18.91
Cl− 324
C2 0.49 18.44 7.20
HCO−3 3
C3 0.73 12.72 5.21
iC4 0.47 2.17 1.11
nC4 0.94 6.26 2.93
5 g of the rock sample is cut and washed by toluene and ethanol to iC5 0.55 1.90 1.05
remove any contaminations and precipitated ions. The washed chip is nC5 0.55 2.14 1.14
dried in the oven at 100 °C for a day. The clean sample is crushed to pro- C6 7.64 1.77 5.44
C7 6.18 0.64 4.11
vide very fine-grained powders followed by placing again in the hot
C8 5.44 0.07 3.43
oven at 100 °C to assure that the sample is dried and all moisture is C9 4.90 0.00 3.07
completely removed. XRD (X-Ray Diffraction) analysis has been con- C10 4.71 0.00 2.95
ducted to identify the mineralogy of the rock samples and the analysis C11 4.14 0.00 2.59
is presented in Fig. 2. The XRD results indicate that the sample consists C+12 63.26 0.00 39.62
Total 100 100 100
of 84% dolomite, 12% limestone and 4% other minerals as seen in Table 5.

2.3. Natural surfactant 2.4. Interfacial tension measurements

Alfalfa (Medicago sativa) is a perennial flowering plant that has trifo-
liate dentate leaves with an underground stem that is often woody. Al-
falfa grows to approximately 0.9 m. During these years saponins
extracted from the roots and aerial parts of Alfalfa have been character-
ized thoroughly and used in medicine and food industries [18]. Saponin
molecules of Alfalfa plant contain a hydrophobic part, composed of a
triterpenoid or steroid backbone, and a hydrophilic part consisting of
several saccharide residues, attached to the hydrophobic scaffold via
steroid backbone, and a hydrophilic part consisting of several saccharide
residues, attached to the hydrophobic scaffold via glycoside bonds
(Fig. 3) [19,20]. The percentage of total saponin in aerial parts of Alfalfa
is 0.95 [21].
Aerial parts of Alfalfa (leaves and stems) were collected, air-dried,
spray-dried, and finely powdered before extraction [22]. Table 6 repre-
sents the properties of the obtained powder and Fig. 4 presents the
image of the Alfalfa plant.
The pendant drop method has been used to measure the interfacial
tension and drop shape analyzer Korus DSA 100 applicated. As practical
steps, a known volume of an aqueous solution of probe fluid is poured
into a transparent glass container, then a pendant drop of the oil
phase is injected into the container. The injection is performed by a sy-
ringe and a needle where the drop of crude oil is kept upward and the
drop of kerosene kept downward at the needle tip (Fig. 5). After the
oil drop becomes stable, a camera is used to capture pictures of the
drop shapes, then a special software is used to calculate the interfacial
tension by curve fitting method. Fig. 5 shows schematically the IFT mea-
surement experimental setup. The pendant drop method is based on
curve fitting and the following relationships are used to determine the
IFT.
2
Δρgb
Ɣ¼ ð1Þ
β

d
S¼ ð2Þ
D

β ¼ 0:12836−0:7577S þ 1:7713S2 −0:5426S3 ð3Þ

D
b¼ ð4Þ
2ð0:9987 þ 0:1971β−0:0734β2 þ 0:34708β3

where Δρ is the difference between densities of the material of the drop

and the material by which the drop is surrounded. β is a dimensionless
number, and b is the radius of curvature at the drop apex [23]. Both are
calculated from Eqs. (3) and (4) respectively. Ɣ is the surface or interfa-
cial tension, g is gravitational acceleration, D is the equatorial diameter
of the drop, d is the distance of D from the apex [24,25]. A density-
meter apparatus (DMA) is used to measure the densities of solutions
with different material concentrations.

Table 4
Properties of used core samples.

Core number L D Vb Φ K PV Swir

(cm) (mm) (cc) (%) (md) (cc) (%)

#1 9.1 37 97.79 18 30 17.60 9.5

#2 9.1 38 103.15 19.5 33 20.11 10
Fig. 1. SARA test results of the studied oil sample.
4 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123

Fig. 2. XRD pattern of used carbonate rock.

2.5. Contact angle measurements 3. Result and discussion

Contact angle tests are also carried out by using a drop shape ana-
lyzer Korus DSA 100 employing a sessile drop method. Fig. 5 shows
the contact angle measuring apparatus schematically. A polished car-
bonate plate is placed in the probe solution. The contact angle method
is similar to the IFT method, and a sessile oil drop is injected throughout
the needle into a solution containing EOR solution and then the oil drop
rests on the bottom surface of the plate [26]. Once the oil drop is
inserted and adhered to the rock surface, time should pass for a while
until the angles of the drop are stabilized. Then the camera captures
the shape of the sessile drop and finally, the contact angle is measured
by the software [26,27]. When a solid surface and two or more fluids
meet together in one system, especially like what happens in the reser-
voir, one fluid shows more tendency to stick and adhere to the surface of
the solid than the other fluid. The contact angle created between fluid
and rock surface as shown in Fig. 5 indicates the wettability of the sur-
face [27–30].
2.6. Spontaneous imbibition
After the establishment of irreducible water saturation (Swir) of
formation water in plug by crude oil flooding method, the original
oil in place (OOIP) is calculated, and spontaneous imbibition experi-
ments are carried out by standard Amott cells. First, the aged-cores
are placed vertically in the 500 cc volume cells (Fig. 6), which are ful-
filled by the imbibed solution. Then, the Amott cells are kept in the
oven at 70 °C for 90 days. The researching solution surrounding the
core sample imbibes into pore spaces and pushes oil out of pores.
The produced oil moves upward and measured in the upper scaled
section of Fig. 6 and reported as a function of time. The production
raw data is then processed and the recovery factor is achieved versus
time.
3.1. Interfacial tension measurements
Interfacial tension measurements have been conducted and effects
of Alfalfa natural surfactant, calcium and magnesium cations, and sulfate
anions on IFT changes are investigated. Alfalfa natural surfactant differ-
ent concentrated solutions are prepared in the base of DW and influence
of the concentration on the interfacial tension of surfactant aqueous so-
lution and the oil phase system is reported in Fig. 7. As the surfactant
concentration increases from zero to 4 wt% — which is the critical mi-
celle concentration (CMC) of the used surfactant—the value of IFT re-
duces from 46.2 to 16.91 mN/m (63.39% optimization) and remains
almost stable at concentrations above 4 wt%. The concentration of the
lowest value of IFT (4 wt%) is defined as the critical concentration of Al-
falfa natural surfactant that micelle structures form and addition of
extra amphiphilic molecules of this surfactant go to micelles. At the in-
terface of water and oil phase, nonionic Alfalfa surfactant molecules ori-
ent in such a way that hydrophobic part resides in the oil phase and
hydrophilic part points to water molecules of the bulk solution. Before
CMC, surfactant molecules reside between the oil phase and water
phase and organize strong interactions with both phases, therefore
they act as a two-phase friendly boundary, and consequently the

Table 5
Mineralogical analysis results of XRD analysis of used carbonate rock.

Compound name Percentage Chemical formula

Dolomite 84% CaMgCO3

Limestone 12% CaCO3
Fig. 3. Molecular structure of saponins of the Alfalfa plant. Structure governed by
Other compounds 4% –
Stanimirova et al. [19].
 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123 5

Table 6
Properties of the watery surfactant solution.

Property Explanation

Used part Leaves and stems

Preparation Air drying, spray drying, extraction
Sample state Fine powder
Color Brown
Density 0.99 (g/ml)
pH (10% aqueous solution) 5.9
Clarity Clear liquid
Solubility in water Soluble
Solubility in hydroglycol Soluble
Solubility in hydroalcohol Soluble

interfacial tension decreases. In this state an increase in surfactant mol-

ecules concentration cause a reduction in the tension of the interface
and this reduction maximizes at CMC, therefore the lowest value of
IFT gained at this concentration. At concentrations higher than CMC,
the interface will not be able to be adopted with any extra molecules
of surfactant because of the tendency of surfactant molecules to form
a structure by themselves named micelles. In this situation none of the
surfactant molecules is added to the interface, hence the value of IFT re-
mains constant or even increases by separation of previously interface
added molecules and their transmission into micelles [31]. The IFT re-
duction from 46.2 to 16.91 mN/m (63.39% optimization) indicates that
the Alfalfa natural surfactant can be considered as an effective additive
to improve the performance of the smart water in recovery enhance-
ment. The transmission rate of surfactant molecules from bulk to the

Fig. 4. Image of Alfalfa plant.

Fig. 6. Schematic view of the used Amott cell imbibition instrument: contains a
transparent body for holding the solution, a graduated section for measuring the
evacuated oil and a sealing rubber for holding the plug of rock.

vicinity of the interface is high at low concentrations and gradually de-

Fig. 5. The schematic of pendant and sessile drop experimental setup.
creases by an increase in their concentration [32]. This feature of surfac-
tants leads to reduce the IFT and at CMC it makes the system of oil-water
stable and balanced in its lowest IFT value. Here, as shown in Fig. 7 an
approximate IFT value firmness is observed at higher concentrations
of CMC.
The impacts of calcium and magnesium cations and sulfate anions
have been studied by the addition of mentioned ions in the aqueous so-
lution of the nonionic natural surfactant at CMC. In this manner of study,
the effects of ions are investigated as the synergistic forms of hybrid
6 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123

Fig. 7. IFT values of different concentrations of Alfalfa natural surfactant in DW at ambient temperature and pressure.

solutions. Therefore, the following types of solutions were provided to
specify their effects on the IFT modification:
I) (Constant ion concentration synthetic SW, with the different in-
creased concentrations of Ca2+) + (CMC of Alfalfa).
II) (Constant ion concentration synthetic SW, with the different in-
creased concentrations of Mg2+) + (CMC of Alfalfa).
III) (Constant ion concentration synthetic SW, with the different in-
creased concentrations of SO2−
4 ) + (CMC of Alfalfa).
The study of ions in this type results in a comparison between the
best IFT of natural surfactant and best IFT of hybrid solutions of natural
surfactant and ions. Fig. 8 presents the concentrations of cations of cal-
cium and magnesium and anions of sulfate at CMC of surfactant versus
IFT values. The IFT reduction depends on the concentration of the ions.
As illustrated in this figure, when the concentrations of calcium, magne-
sium, and sulfate in the modified synthetic SW were increased, the IFT
of the oil-water system reduced until an optimum concentration after
which the IFT fairly stabled as the concentration of the ions increased.
The IFT reduced from 46.2 mN/m to 13.36 mN/m (71% optimization)
by calcium ions, from 46.2 mN/m to 16.77 mN/m (63.7% optimization)
by magnesium ions and from 46.2 mN/m to 15.45 mN/m (66.55% opti-
mization) by sulfate ions for optimum concentrations of 5, 4.5, and 4

Fig. 8. IFT data at different concentrations of calcium, magnesium and sulfate ions in the solution of nXSW + CMC of natural surfactant; where X is the probe ion existing in the seawater,
i.e. SO2−
4 , Mg
2+
or Ca2+ and n is the ratio of the amount of x in the modified synthetic seawater to its initial amount in the seawater.
 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123
times of concentration of probe ion in seawater, respectively. As repre-
sented by Fig. 8 cations of Ca gained the best state of synergy with nat-
ural surfactant among cations of Ca, Mg, and anion of SO4, therefore for
modification of IFT Ca should be selected. Sulfate anions are added to the
aqueous solution thorough addition of Na2SO4 and can cause an extra
induced adsorption capability to asphaltenes and resins from the oil
phase bulk to the aqueous phase bulk. This phenomenon controls the
IFT reduction with the Sulfate anion. When the aqueous solution con-
tains cations like calcium and magnesium, the cations cover the interac-
tions of acid and base existing in oil-brine and brine-solid interface
which result in the optimizations of IFT and wettability respectively
[33–35]. Furthermore, the cations affect the polar organic components
existing in the oil (i.e. asphaltene and resins) and pull them to the inter-
face and make the interface to be in a better intermediate state [33]. The
presence of asphaltene and resin in the interface of oil-water can sup-
port the formation of a two-phase friendlier interface that causes IFT re-
duction. The justification of observed stabilized (or even a slight
increasing) trend of IFT at the concentrations above the optimum con-
centrations of these salts is that as the concentration increases, the pop-
ulation of ions rises and cause scaling or the overlapping of hydrophobic
chains of surfactant molecules which violates the adsorption of these
amphiphilic moleculaes at the oil-water interface [31,32,36].
3.2. Contact angle measurements
Contact angles in the system of oil phase—aqueous solution—rock
were measured. The dependency of wettability alteration on various pa-
rameters such as rock morphology, hydrophobic forces, and attraction
between polar molecules and components of crude oil have been inves-
tigated and studied. The following mechanisms are proposed to explain
the wettability alteration by non-ionic surfactant of Alfalfa:
I. The surfactants have two parts; hydrophobic and hydrophilic parts.
The hydrophobic part of the non-ionic surfactant attracts the resin/
asphaltene molecules that exist in the oil phase. This attraction
would promote the molecules toward the oil-brine interface. A sub-
stitution between the desorbed organic compounds in the oil phase
and non-ionic surfactants in brine would take place and eventually
the rock surface undergoes a wettability alteration as the result of
this process [37,38].
II. The positive charge of natural surfactants would attract and pull up
the negatively charged adsorbed species like asphaltene and then
they desorb from the surface of the rock [37,38].
The results of contact angle tests of the natural surfactant are shown
in Fig. 9 for the different concentrations of the used Alfalfa in DW. The
Fig. 9. Effect of different concentrations of Alfalfa natural surfactant in DW on modification of contact angle.
7
contact angle was 174° when using pure DW and strong oil-wet pellet
of rock. It reduced to 87.16° at CMC of surfactant in the solution.
Several contact angles have been measured to investigate the impact
of different ions like calcium and magnesium cations as well as sulfate
anions with different concentrations in the synthetic seawater + CMC
of the surfactant solution on wettability alteration of the rock surface.
The results are shown in Fig. 10. When the total concentration of each
ion increased the contact angle decreased and the reduction of contact
angle for each ion is not uniform due to their different synergy. For
Mg2+, the contact angle has been decreased from 150° to 66°, while
for the Ca2+ and SO2− 4 ions, the contact angle has lowered from 144°
to 55° and from 147° to 76° respectively for optimum concentrations
of 2, 3, 2.5 nXSW in turn. As reported reductions, optimizations of con-
tact angle are 56.0, 61.8, and 48.3% for Mg, Ca, and SO4. Therefore, re-
garding outcomes of IFT and contact angle measurements, Ca2+
should be selected as the effective synergistic ion as a hybrid material
for the CMC solution of natural surfactant. Calcium cation at the concen-
tration of 3CaSW and Alfalfa natural surfactant at the concentration of
CMC has been selected to be used to prepare the EOR candidate hybrid
solution, hence for the following section, the candidate solution pre-
pared. It should be noted that increasing concentration of Mg ion in-
creases the risk of precipitation and deposition in porous media which
can lead to change in pH, temperature, pressure, and presence of
other ions may also contribute to scale formation. This phenomenon
has a negative impact on the contact angle of oil drops.
Integrated investigations of Zhang et al. [39,40] and Strand et al. [41]
proposed a theory for altering the wettability of carbonate surfaces
when the sulfate anion concentration increases. According to their pro-
posals, as the concentration and the population of the anions increases,
the number of anions approaches to the vicinity of the rock surface in-
creases. Consequently, due to this process, some positive charges of
rock's surface will be neutralized. Anions attarcted to the positive
chared surface and creates a thin film. Carboxylic groups will removed
from surface and the wettability of the anion modified surface changes
to a water-wet state. Calcium and magnesium cations are also capable
to approach the vicinity of the rock's surface because of negative charges
of carboxylic groups. Then, the cations approaching to the vicinity of
surface will react with the rock's carboxylic groups, so oil-wetting
agents got desorbed from surface and change [39–41].
3.3. Imbibition tests
Spontaneous imbibition tests were conducted on the core samples
to examine the potential effects of Ca synergized with Alfalfa natural
surfactant in enhancing the oil recovery. The optimized solution was
8 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123

Fig. 10. Effect of different ions on modification of contact angle in the solutions of nXSW + CMC of natural surfactant; where X is the probe ion existing in the seawater, i.e. SO2−
4 , Mg
2+
, or
Ca2+ and n is the ratio of the amount of X in the modified synthetic seawater to its initial amount in the seawater.

selected to owe the best state of its water—wetting tendency and the
lowest IFT, therefore an optimized aqueous solution with 3Ca 2
+
SW + 4 wt% natural surfactant was prepared. 3Ca2+SW solution
of the aforementioned ions was selected because of its contact
angle reduction potential and the critical micelle concentration of
surfactant solution is selected either to bring a low value of IFT. IFT
reduction of Ca ion synergized with contact angle reduction of sur-
factant as lateral potentials of this optimum solution to increase
the oil recovery. An imbibition test has been done for the EOR hybrid
solution on one rock sample and another imbibition test has been
done on SW with the purpose of comparison of the gained recovery
factor of EOR fluid with SW, noted that SW plays an important com-
parison fundamental. Fig. 11 illustrates produced oil recovery per-
centage of optimized 3Ca2+SW + CMC of natural surfactant in
comparison with produced oil recovery of seawater imbibition. The
results indicate that SW has a total recovery of 42.8% while the
total recovery with the optimized 3Ca2+SW + 4 wt% of Alfalfa natu-
ral surfactant is 62%. Comparison of imbibition experiments showed
that only the modification of Ca ion concentration among potential
determining ions of Ca, Mg, and SO4 with the use of low concentra-
tion of 4 wt% of natural surfactant of the Alfalfa plant advances the re-
covery factor of crude oil by 19.2%.
4. Conclusion
In this paper, a natural surfactant (Alfalfa species) has been studied,
the interfacial tension and contact angle changes are measured during
introducing the surfactant into DW and optimum concentration of
4 wt% determined as CMC. 63.39 (reduction from 46.2 to 16.91 mN/m)
and 49.91 (reduction from 174° to 87.16°) percent reduction optimiza-
tion of IFT and contact angle were the outcomes of the use of this
novel surfactant respectively. Impacts of different concentrations of
SO24, Mg2+and Ca2+ ions on the properties of interface and wettability
were investigated in their synergistic manner with a natural surfactant
as hybrid solutions. The resulted IFT and contact angle measurements
indicate that compared to Ca, for the concentration of 3Ca2+SW, SO2− 4
and Mg2+ ions showed weaker impacts. A synergistic state investigation
of hybrid solutions showed that previous 63.39% IFT optimization of nat-
ural surfactant advanced to 71% and 49.91% contact angle optimization
of using natural surfactant solely, improved to 61.8% at the state of hy-
brid. Candidate solution determined as 3Ca2+SW + 4 wt% Alfalfa nat-
ural surfactant and undergoes an imbibition test to be compared with
the imbibition of seawater. Results of imbibition experiments showed
that the final recovery factor of candidate hybrid solution was 62%
while seawater imbibition gained only 42.8%.

Fig. 11. SW and the optimized ion-natural surfactant solution oil recovery derived from imbibition tests at 70 °C and ambient pressure versus production time.
 M. Eslahati et al. / Journal of Molecular Liquids 310 (2020) 113123 9

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