Journal of Petroleum Science and Engineering 205 (2021) 108840

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Journal of Petroleum Science and Engineering

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

Effect of pH on interfacial tension reduction of oil (Heavy acidic crude oil,

resinous and asphaltenic synthetic oil)/low salinity solution prepared by
chloride-based salts
Mehdi Behrang a, Seyednoorlodin Hosseini b, *, Naser Akhlaghi b
a
EOR Research Center, Department of Chemical Engineering, Omidiyeh Branch, Islamic Azad University, Omidiyeh, Iran
b
EOR Research Center, Department of Petroleum Engineering, Omidiyeh Branch, Islamic Azad University, Omidiyeh, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Chloride salts of NaCl, KCl, CaCl2, and MgCl2 are among the essential salts examined for enhanced oil recovery
Alkaline injection (EOR) purposes through chemical injection, low salinity injection, smart water injection, etc. These salts are
Acidity crucial for EOR studies since they exist in the reservoir with undeniable effects on interfacial tension (IFT),
Heavy crude oil
wettability alteration, etc. The alkaline injection that can produce in-situ soap leading to lower IFT values can be
Resin
Asphaltene
combined with low salinity injection method to form the hybrid EOR method. Among the different parameters in
pH alkaline flooding, the aqueous solution pH is essential, since there is a strong relationship between the pH of the
solution and crude oil type for ionization and generating in-situ soap. Whit this parameter, the current inves­
tigation concentrated on the effect of chloride-based salt (with a concentration of 5000 ppm to mimic the low
salinity condition) at different pH values of 3.5, 7, and 11 in contact with heavy acidic crude oil (HACO). Since
resin and asphaltene have a surfactant nature, resinous synthetic oil (8 % wt/wt) (RSO) and asphaltenic synthetic
oil (8 % wt/wt) (ASO) were prepared by dissolving isolated resin and asphaltene using IP/140 procedure and
examined. The results show that IFT can reduce to a value of 0.4 and 2.5 mN.m-1 for pH of 11 and DW solution if
RSO and HACO utilize. The results also reveal that among the examined salts, NaCl and KCl introduce the highest
impact for all types of model oils at pH values of 11, while no significant effect for pH values of 3.5 and 7 was
obtained. According to these findings, it seems that injecting alkaline chemicals such as NaOH (which enhances
aqueous solution pH) is an effective way to reduce the IFT values due to the in-situ surfactant generation and
saponification of organic acids exited in model oils. Additionally, the IFT values show that although salts can
retard the IFT reduction to some extent, no significant negative influence on the IFT reduction trends exist for the
case of NaCl and KCl.

1. Introduction regarding economic synthesizing of chemicals make this method ready

Among the enhanced oil recovery (EOR) methods, alkaline injection
is an efficient EOR method that utilizes cheap chemicals such as sodium
carbonate, sodium silicate, sodium hydroxide, and potassium hydroxide
to form in-situ surfactant by increasing the pH of an aqueous solution.
Unfortunately, this method that was proposed by F. Squires during 1917
(which is an old EOR method) faced a lack of interest and a few studies of
the lab and industrial scales conducted. Fortunately, this method is
gaining interest among researchers and oil companies since the science
of synthesizing specific-task chemicals is well matured. Besides, the low-
cost and simplicity of alkaline injection combined with progress
for EOR purposes. The alkaline chemicals react with organic acid-based
fractions of crude oils forming in-situ surfactants, which eventually
reduce the interfacial tension (IFT). Alkaline injection is desired for
reservoirs subjected to surfactant injection because alkaline can
generate in-situ surfactants that adsorb on the rock surface and act as the
sacrifice agents preventing the adsorption of surfactant molecules
(which are more expensive than alkaline). Injecting alkaline chemicals
can enhance the recovery of surfactant injection and reduce operating
costs. The alkaline injection enhances the oil recovery in the light of
other mechanisms such as emulsification/entrainment (Philip, 1942),
emulsification/entrapment (Jennings et al., 1974), wettability reversal

* Corresponding author. Department of Petroleum Engineering, Islamic Azad University, Omidiyeh Branch, Omidiyeh, Khuzestan, postcode (63731-93719), Box
post: 164, Iran.
E-mail addresses: mehdi_res_eng@yahoo.com (M. Behrang), masihanoor@gmail.com (S. Hosseini).

https://doi.org/10.1016/j.petrol.2021.108840
Received 3 January 2021; Received in revised form 10 April 2021; Accepted 16 April 2021
Available online 4 May 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
M. Behrang et al.
(oil-wet to water-wet (Mungan, 1966a; Mungan, 1966b), or water-wet
to oil-wet (Cooke et al., 1974)), and emulsification/coalescence
(Castor et al., 1981). This method can even control the mobility using a
caustic solution injection which reacts with rock and form precipitations
that can plug the high-permeability channels and modify the sweep ef­
ficiency (Sarem, 1974). In these mechanisms, investigations concen­
trated on IFT reduction because IFT directly affects the capillary number
and residual oil saturation. The investigations show if the capillary
number reaches the targeted value, microscopic displacement efficiency
increases leading to higher oil production (Melros, 1991; Morrow,
1979). On the other hand, increasing capillary numbers by reducing IFT
can substantially reduce the residual oil saturation (ROS) and the
imbibition-drainage hysteresis (Fulcher et al., 1985; Fulcher, 1983).
Previously published literature reported that according to theoretical
analysis, if the capillary number reaches a value of 10− 3, a single trap­
ped oil drop in the reservoir pores can be mobilized. If the capillary
number reaches 10− 2, complete mobilization occurs (Chatzis and
Morrow, 1984).
While observing the efficiency of IFT reduction and the possibility of
producing in-situ soap using salts in the presence of crude oil at different
pH values, it seems that investigating the possible effect of salinity at
different pH values considering the crude oil and its fractions, especially
resin and asphaltene, is vital to clarify the ambiguities found regarding
alkaline flooding. In alkaline flooding, an injected alkali reacts with the
saponifiable components (as petroleum acids (naphthenic acids)) in the
reservoir crude oil. In general, the naphthenic acid fraction is usually is
an unspecified mixture of several hydrocarbons of carboxyphenols
(Seifert, 1975), porphyrins (Dunning et al., 1953), asphaltene (Pas­
quarelli and Wasan, 1981), cyclopentyl, and cyclohexyl carboxylic acids
with a molecular weight of 120–700. It seems that the resin and
asphaltene fractions directly affect the formation of in-situ surfactants in
the solution in the presence of different salts and pH values.
A study by Hoeiland and his coworkers (Hoeiland et al., 2001) re­
ported that as the pH values increased, the IFT values reduced as the
crude oil comprised acidic compartments. They also found that the
alkaline process is an efficient method for heavy oil recovery due to the
higher indigenous acidic content presented in heavy crude oils (Liu,
2007; Liu et al., 2006; Schumacher, 1980). In addition to this, previously
published literature reports that alkaline flooding efficiency has a
meaningful functionality of the fluid properties such as pH and acidic
components of crude oil and solution (Cratin, 1993). Although pH and
acidic contents are strongly correlated, no consistent trend has existed.
For example, for low pH values, reducing IFT behavior or increasing was
obtained, which correlated to the qualitative and quantitative content of
the resin and asphaltene fractions as stabilizing components (Abdel-­
Moghny et al., 2006; Nebogina et al., 2010; Peters, 1931).
Buckley and Fan (Fan and Buckley, 2006) examined the effects of
several parameters of the acid number, asphaltene quantity, and pH on
the IFT values of crude oil and then concluded that chemical surfactants
did not follow similar IFT patterns compared to asphaltene. IFT was
found to be of great importance in alkaline flooding and other oil re­
covery processes. Although the effects of chemical surfactants are well
studied, few studies are performed regarding indigenous surfactants (i.e.
resin and asphaltene). In this respect, this experimental investigation
aimed to clarify how the indigenous surfactants in crude oil influence
the IFT of the crude oil/aqueous solution at different salinity and pH
values. To accomplish this goal, Almalik et al. (1997), isolated the resin
and asphaltene fractions from three types of crude oils, and then NaOH
solution was utilized to provide basic aqueous solutions for the oil re­
covery and IFT reduction purposes.
On the other hand, it is well accepted that oil recovery can be
improved during secondary or tertiary water-flooding if the composition
of the injected water is controlled, especially by reducing the total
salinity to values less than 5000 ppm (for comparison, seawater salinity
is 35,000 ppm and many formation brines have salinities greater than
200,000 ppm (Mahzari et al., 2019; Tang and Morrow, 1996). The
2
Journal of Petroleum Science and Engineering 205 (2021) 108840
extensive laboratory studies and field tests performed during the past
decades revealed that for both clastic and carbonate rock systems, in­
jection of low salinity water can enhance the oil recovery (Aladasani
et al., 2014; Bernard, 1967; Jackson et al., 2016; Martin, 1959; Tang and
Morrow, 1996, 1999, 2002; Zhang and Morrow, 2006). Researchers and
oil companies such as BP published results from their field trial which
demonstrated that injection of low salinity brine (<3000 ppm) in a
clastic reservoir reduced the residual oil saturation relative to the in­
jection of seawater or high salinity formation brine (Webb, 2004).
Several experiments demonstrated that it is possible to enhance the
oil recovery up to 35% compared to re-injection of formation brine have
been observed in laboratory core flooding experiments (Aladasani et al.,
2014; Austad et al., 2010; Ligthelm et al., 2009; McGuire et al., 2005;
Yousef et al., 2010). Field examinations revealed a reduction in the re­
sidual oil saturation of 50% compared to conventional water injection
(Seccombe et al., 2010; Webb, 2004). In a recent review by Sheng
(2014) and Jackson (Jackson et al., 2016) more than 17 separate
mechanisms have been proposed to demonstrate how low salinity
flooding can enhance oil recovery.
According to the previous findings and the lack of reporting on the
effects of these salts and since there is no report regarding the effect of
these salts on heavy acidic crude oil and resinous and asphaltenic syn­
thetic oil, the current investigation concentrated on examining the
possible influence of chloride salts (CaCl2, MgCl2, NaCl, and KCl in the
low salinity range concentrations of 5000 ppm) as one of the most
effective salts on the interfacial properties and their correlation to the
pH values of 3.5 (acidic condition), 7 (neutral condition) and 11 (basic
condition). The effects of resin and asphaltene fractions were examined
as a function of pH values during low salinity conditions isolating these
fractions from the crude oil using IP143/90 method.
2. Material and method
2.1. Material and solutions
Heavy acidic crude oil with density of 0.908 g cm− 3 @ 15 ◦ C was
kindly provided by Offshore Oil Company, Iran. The crude oil was
analyzed based on IP/143 procedure and gas chromatography (GC) to
evaluate the resin and asphaltene content and the other fractions of the
crude oil. The analysis shows that the heavy acidic crude oil comprises
11.1% 13.3% asphaltene and resin and the fractions of other compart­
ments were N. Paraffins (10.25%), I. Paraffins (10.884%), Olefinic
(0.05%), Naphthenes (9.888%), Aromatics (6.383%),Saturates (C15 <
C20) (6.489%),Aromatics (C15 < C < C20) (3.486%), Unknowns (C < 20)
(14.537%), C+ 20 (37.653%).
Calcium sulfate (CaSO4), sodium sulfate (Na2SO4), magnesium
sulfate (MgSO4), toluene, acetone, dichloromethane, and n-heptane,
were prepared from Merck, USA, with a minimum purity of 99.5%. The
required aqueous solutions were prepared with a concentration of 5000
ppm (except for CaSO4) to mimic low salinity conditions (which is one of
the desired enhanced oil recovery (EOR) methods). A CaSO4 concen­
tration of 1500 ppm was selected to prepare CaSO4 solutions, to ensure
no salt precipitation occurs, as it is known that CaSO4 will precipitate at
a concentration above 2100 ppm.
2.2. Extraction of Asphaltene and Resin
Crude oil is a complex mixture with thousands of different com­
partments categorized into resin, asphaltene, saturates, and aromatics,
making it impossible to characterize the crude oil by the individual
molecular types. It is difficult to analyze it by each individual element,
as a limited amount of information is given about the constitution of
petroleum. (Demirbas and Taylan, 2015). Instead of an elemental
analysis, hydrocarbon group type analysis is commonly employed with
the knowledge of the distribution of major structural classes of hydro­
carbons (Demirbas, 2016; Muhammad et al., 2013). Among these
M. Behrang et al.
fractions, resin and asphaltene are the most active fraction and can even
act as natural surfactant and react with the other chemicals present in
the solution. It can guarantee the stability and structure of crude oil. In
other words, asphaltene and resin fractions can act as a natural surfac­
tant in which they can manipulate the IFT values and stability of crude
oil and water emulsions. Resin fractions of crude oil consists of polar
molecules containing heteroatoms such as nitrogen, oxygen, or sulfur
(Demirbas et al., 2015). The resin fraction is soluble in light alkanes such
as pentane and heptane, but insoluble in liquid propane. In the litera­
ture, few works have reported the properties of the resins (Aske et al.,
2001). The H/C ratio of resins is between 1.2 and 1.7 higher than that of
asphaltenes and the H/C ratio of asphaltenes is between 0.9 and 1.2.
Resins are structurally similar to asphaltenes, but smaller in molecular
weight. Naphthenic acids are commonly considered a part of the resin
fraction (Ficken et al., 2002). The asphaltene and resin fractions were
isolated (IP 143/90) from crude oil and then solubilized in toluene to
prepare resinous and asphaltene types of synthetic crude oils for
investigation on the individual effect of these fractions at the different
pH values.
Although these fractions are active with an essential role through
aqueous interactions, their effects are not well understood (Lashkarbo­
looki et al., 2014), especially regarding resin fraction. The results ob­
tained from spectroscopic investigations revealed that both resins and
asphaltene consisted of hydroxyl groups, ester, acid, carbonyl functions,
and long paraffinic chains with naphthenic rings and polar functions
present in the structure, which give them an enhanced surfactant nature
(Lashkarbolooki et al., 2016; Wu et al., 1998), although they are
different in size, aromaticity, polarity, and physical appearance. The
resin and asphaltene fractions were isolated from crude oil using IP
143/90 procedure, known as the standard method for asphaltene and
resin extraction (using n-heptane as solvent) (Petroleum, 1985).
In brief, using n-heptane with a ratio of 40:1, asphaltene fraction was
isolated and further purified using soxhlet extraction. The resin fraction
was isolated from the same de-asphalted oil with the column chroma­
tography method described elsewhere (Amin et al., 2011; Soorghali
et al., 2014). The maltene (de-asphalted oil + n-heptane) adsorbed to a
silica gel column (Merck, 35–70 mesh ASTM); followed by rinsing of
saturates and aromatics by a solution of 70:30 n-heptane and toluene.
Finally, an acetone/dichloromethane/toluene mixture with a ratio of
40:30:30) was used to extract the resins from the column (Miller, 1982;
Yarranton et al., 2000) (see Table 1). For elemental analysis purposes,
CHNSO analyzer (Thermo Flash EA 1112 series) was used to determine
the mass ratios of C, H, N, S, and O atoms present in the resin and
asphaltene samples. A close look into Table 1 shows that the extracted
asphaltene has higher aromaticity than resin since the H/C ratio of
asphaltene is about 1.12 more than the H/C ratio of the resin (1.44).
Considering the H/C ratio, the resin is a branched molecule compared
with asphaltene molecules, which gives it the potential to trap the ions
or other molecules with lower repulsive forces.
In addition, the existence of heteroatoms of sulfur and oxygen with
negative charges makes the resin molecules similar to surfactant mole­
cules composed of heads and tails. It is possible to consider tail and head
combination for resin structure that makes resin similar to surfactant
molecules. Surfactants are molecules with hydrophobic and hydrophilic
nature that can reduce the interfacial tension of aqueous solutions. So,
the resin molecules extracted in the current investigation can act as a
natural surfactant.
Table 1
Elemental analysis of heteroatoms of resin and asphaltene fractions.
H/C ratio wt % of heteroatoms of resin and Fractions Crude oil type
asphaltene fractions
S, O and N S O N
1.12 11.01 3.71 7.30 0.00 Asphaltene Heavy Acidic
1.44 10.35 6.59 3.76 0.00 Resin
3
Journal of Petroleum Science and Engineering 205 (2021) 108840
2.3. IFT measurement
The IFT values for different solutions were measured using a pendant
drop method (Fanavari Atiyeh Pouyandegan Exir Co., Arak. Iran) (see
Fig. 1).
The reasoning behind using the pendant drop method is due to its
proper accuracy and simplicity for IFT measurements (Yang et al.,
2014). Generally, the equipment is comprised of three sections including
the measuring chamber where the bulk and drop phases come in contact
with each other for IFT measurement. The other section is the injection
section which is composed of a motorized injection syringe that can be
used to inject the accurate volume of drop into the bulk phase for IFT or
other analysis and measurements. The last section is the image capturing
and analyzing section which takes a picture from the formed drop at the
tip of the nozzle and then calculates the IFT values using drop shape
analysis approach (See Eq. (1)) (Adamson and Gast, 1967; Andreas et al.,
2002; Stauffer, 1965).
Δρ g D2
γ= (1)
H
Respectively, Δρ, g, and H are the density difference (bulk and drop
phases), acceleration of gravity, and the shape-dependent parameter.
The value of H depends on the shape factor value, i.e. S = d/D (Drelich
et al., 2002), where D is the equatorial diameter and d is the diameter at
the distance D from the top of the drop. A point worth mentioning is that
through the IFT measurements, cleanliness is an essential issue that must
be carefully performed for each independent measuring as it can affect
the accuracy of the measurements.
Since the IFT of several samples were lower than the threshold
pendant drop equipment can measure, the spinning drop method was
used for IFT measurement (Fanavri Atiyeh Pouyandegan Exir, APEX
Technologies Co., Iran). For solutions with an IFT value lover than 1 mN
m− 1, the spinning drop method spinning drop methods was used for
more reliable measurements. In the first step, the transparent solution
was injected into the main chamber as a bulk phase and then the oil drop
(crude or synthetic) was injected with volume of about 3–4 μL as inner-
phase. Then, the rotational speed was increased to no more than 2000
ppm to reach a threshold which is L/D > 4. At this point, it is possible to
calculate the IFT value using the following equation (1) below (Aoudia
et al., 2010; Hezave et al., 2013; Kopczynska and Ehrenstein, 2007;
Rosen et al., 2005; Saha et al., 2018; Zeinolabedini Hezave et al., 2014):
Δρω2 D3
γ= (1a)
32
Where, ω, D and Δρ are the angular velocity, diameter of oil drop and
density difference between outer-phase and inner-phase (mg.L− 1).
The last point worth mentioning is that the maximum uncertainty of
the measured IFT values which is the average of at least three inde­
pendent measurement for each data point was about ±0.1 mN m− 1
which was impossible to indicate these uncertainties for the measured
IFT values in the plotted IFT values due to a broad range of IFT values
measured in the current investigation.
2.4. Total acid number (TAN)
The other measured parameter for crude oil, asphaltenic, and
resinous solutions is the total acid number (TAN). This parameter is a
good indication of the surface activity of chemicals in crude oil. Crude
oil is acidic if the measured TAN number is higher than 0.5 mg KOH/g
(Xinheng and Songbai, 2011). In this way, the crude oil TAN is measured
using a potentiometric titration based on the ASTM D 664 method to
find if the used crude oil is acidic or basic. The TAN of crude oil is the
quantity of base, expressed as milligrams of KOH required to neutralize
the acidic components in 1 g of crude oil. According to this definition,
the TAN of crude oil and resinous and asphaltenic synthetic oils
M. Behrang et al.
Fig. 1. Schematic diagram of the used apparatus for IFT and contact angle measurements; (a) pendant drop case for IFT measurements.
prepared by dissolving 8 % wt resin and asphaltene in toluene were
measured (Table 2). The results demonstrated that the used crude oil is
acidic and the prepared synthetic resinous crude oil is more acidic than
the crude oil sample while the asphaltenic solution is neutral.
3. Result and discussion
3.1. Evaluation of performance of pH variation on the IFT of oleic phase
The influence of pH on the IFT reduction has been investigated using
different model oils and DW. The measured IFT values show that
increasing pH from 3.5 to 11 can reduce the IFT of HACO, RSO, and ASO
reduces from 27.3 to 2.5, 23.5 to 0.4, and 20.7 to 0.4 mN m− 1, respec­
tively. Increasing pH from 3.5 (acidic condition) to 7 (neutral condition)
had a slight effect on the IFT reduction (Table 3 and Fig. 2 (see Sup­
plementary Data # 1)). This observed trend is related to ionization and
saponification of organic acid compounds as OH− can produce in-situ
soap, and surfactants can reduce the IFT of binary solutions. A saponi­
fication reaction can occur between an organic acid, and caustic alkali
can form soap according to the below reaction:
HA + OH− ↔ A− + H2O
In this reaction, the required organic acid is provided by an acidic
component of the crude oil. After soap generation, it can act as an in-situ
surfactant that lowers the IFT value between crude oil and aqueous
solution and emulsifies the crude oil. The importance of in-situ surfac­
tant generation is evident when surfactant injection follows alkaline
injection. The in-situ surfactant can act as a sacrifice agent and adsorb on
the rock surface to reduce the adsorption of chemical surfactants in­
creases the surfactant flooding efficiency (which is more expensive than
alkaline agents). The IFT values reported for different oil samples and
DW show that resin can act as a surfactant since the IFT can reduce from
27.3 to 20.7 for pH value of 3.5 and 22.5 to 19.5 for pH value of 7, while
this effect is lower for ASO. This trend probably is related to resin
structure consisting of more branches. In detail, both asphaltene and
resin (Table 1) have similar contents of heteroatoms with negative
charges while the H/C ratio shows the higher aromaticity of asphaltene
compared to resin means lower surfactant structure-nature of
Table 2
Measured TAN for different sample oils.
Sample oil TAN
Crude oil 1.41
Resinous synthetic oil (8 wt/wt % extracted resin) 1.81
Asphaltenic synthetic oil (8 wt/wt % extracted asphaltene) 0.45
4
Journal of Petroleum Science and Engineering 205 (2021) 108840
asphaltene. So, it seems that a heteroatom can form a head with a
negative charge and the branches form a tail of surfactant-like molecules
which means more surface activity of the resin molecule than the
asphaltene. This effect is more evident for the pH value of 11 which the
IFT of RSO is about 0.4 and the IFT of ASO is about 4.4 which is 10 times
larger than the RSO IFT value. The other reason is the higher acidity of
the resin fraction compared with the asphaltene fraction (see Table 2).
When observing the results, the results, tabulated in Table 2 and IFT
values measured for pH value of 11 using different sample oils at the
presence of DW, showing that the higher acidity leads to higher IFT
reduction since it is possible to generate more in-situ surfactants in the
presence of OH- (IFT value of ASO (TAN = 0.45 mg KOH/g) > IFT value
of HACO (TAN = 1.41 mg KOH/g) > IFT value of RSO (TAN = 1.81 mg
KOH/g).
More research shows that at pH values of 3.5 and 7, divalent cations
(Mg2+ and Ca2+) can reduce the IFT values for HACO/aqueous solutions
systems compared to monovalent cations (K+ and Na+), while for pH
value of 11 the situation is more complicated. For the two other model
oils (RSO and ASO), there is no specific correlation between the divalent
and monovalent cations, although the overall results show the higher
efficiency of RSO for IFT reduction for pH value of 11 without consid­
ering the salts dissolved in the solution.
A closer examination also shows that among the examined salts,
calcium salt introduces the worst effect on IFT reduction which is likely
due to a larger molecular radius which can adsorb more in-situ surfac­
tant molecules and form stable complex molecules in the bulk phase and
reduce the influence of generated in-situ surfactants for IFT reduction.
Asphaltenic model oil/brines, and c) resinous model oil/brines at the
presence of different sulfate salts.
Moreover, the reason behind better efficiency of monovalent cations
(Na+ and K+) on the IFT reduction than divalent cations (Ca2+ and
Mg2+) correlates to the smaller molecular size of monovalent cations.
The smaller molecular size allows them to easily pack between the
branches of big resin molecules (with an empirical formulation of
C60H87O4S according to the elemental analysis aforementioned in the
section under the heading of “2.4. Extraction of Asphaltene and Resin”)
and reduce the surface charge of this molecule leading to more stability
which can easily pack in the interface with lower repulsive forces.
For better comparison, the calculated IFT values are normalized
based on the neutral condition (pH = 7) (see Fig. 3). In other words,
ΔIFT1 (acidic) defined as difference between the (IFT value at pH= 7 – IFT
value at pH=3.5) and ΔIFT1 (basic) defined as difference between the (IFT
value at pH= 7 – IFT value at pH=13). For all of the examined salts, as the pH
values increases to 11, higher IFT reduction is achieved for crude oil and
resinous synthetic oil. According to this figure, increasing pH value from
3.5 to 7 has a lower effect on IFT reduction compared with the situation
M. Behrang et al. Journal of Petroleum Science and Engineering 205 (2021) 108840

Table 3
Measured IFT values at different pH values using different salts and model oils.
pH = 3.5 pH = 7 pH = 11

HACO RSO ASO HACO RSO ASO HACO RSO ASO

DW 27.3 23.5 20.7 22.5 27.3 19.5 2.5 0.4 4.4

KCl 26.5 22.5 21.7 21.5 26.0 19.1 10.8 0.4 6.4
NaCl 25.6 20.5 21.1 20.2 24.5 17.9 4.9 0.4 4.4
MgCl2 24.8 18.8 21.1 9.5 4.2 9.8 5.1 3.9 7.7
CaCl2 22.5 23.5 22.5 14.8 16.8 15.3 13.6 10.6 10.9

Fig. 3. Evaluation of pH variation on the IFT of different aqueous solution/

oleic phase.

Fig. 4. Evaluation of salt type on the IFT of oleic phase at pH = 7.

Fig. 2. IFT values of a) crude oil/brines at different pH conditions, b).

in which pH value increases from 7 to 11. As it is evident, the effect of

monovalent cations is higher than the effect of divalent cations although
the effect of divalent cations was higher than monovalent cations for the
cases pH value was increased from 3.5 to 7.
Finally, the IFT variation (ΔIFT2 = IFT value for distilled water – IFT value
for salts) was investigated to find the effect of salinities at each pH value of
3.5, 7, and 11 (see Figs. 4–6).
The results demonstrated in Fig. 4 revealed that at a pH value of 7, Fig. 5. Evaluation of salt type on the IFT of oleic phase at pH = 11.
while excluding solutions composed of CaCl2, increasing salinity can

5
M. Behrang et al.
Fig. 6. Evaluation of salt type on the IFT of oleic phase at pH = 3.5.
reduce the IFT values means the positive effect of salts on the IFT
reduction behavior which for CaCl2 the influence is reversed. In other
words, the presence of CaCl2 negatively affects the IFT of an aqueous
solution, and different model oils increase the equilibrium IFT value.
This trend correlates to the aforementioned phenomenon regarding the
larger radius adsorbing in-situ surfactant and keeping them solubilized
in the bulk phase to form a stable complex. On the other hand, in basic
conditions (Fig. 5) (pH = 11), salts, especially CaCl2 and KCl, have a
detrimental effect on IFT reduction. In other words, the salinity in­
troduces a considerable negative influence on IFT reduction for HACO,
especially if CaCl2 and KCl dissolve in the solution. Due to their mo­
lecular radius, they can adsorb more in-situ surfactants or organic acid
compounds and form a stable complex to prevent diffusion of molecules
into the interface for IFT reduction purposes.
Finally, the effect of salinity on the IFT reduction for a solution
prepared at a pH value of 3.5 was investigated. The results show that
dissolving salinity positively affects the IFT reduction of HACO and RSO
while for ASO, monovalent or divalent cation negatively affects the IFT
reduction trend (see Fig. 6).
In total, it seems that all the chloride salts (monovalent cation or
divalent cation) can prevent diffusion of in-situ soaps toward interface
for the basic condition (pH = 11) while for the neutral condition (pH =
7) salinity can introduce positive effects on IFT reduction and
compensate the repulsive forces that may exist in the interface. In
regards to the acidic condition, the situation is slightly complex
regarding ASO model oil, showing a negative correlation between
salinity and IFT reduction. The results reported by Shepherd et al.
(2005) revealed that an oil phase containing no naphthenic acid if
contacted with distilled water experiences no significant change in IFT
which indicates that the toluene used contains no dissolved
surface-active impurities, which is similar to the result obtained in the
current investigation. They reported that for 1% wt acid solutions and
lower pH conditions, IFT values are less than the IFT values reported for
pure water/toluene. This is likely due to the surface activity of the un­
dissociated acid form at the interface. For stearic acid, pKa = 5 and the
IFT decrease would be more evident as pH values increase, especially for
more alkaline (pH > 8) conditions described in detail by Cratin (1994).
Further investigations carried out by Shepherd et al. (2005) revealed
that presence of dissociated acid introduces a great surface activity into
the solution, reducing the IFT value. This correlated with the observed
trend demonstrating the absorption of dissociated acid species at the
oil/water interface as described by the Gibbs isotherm (Adamsom and
Gast, 1997). The other noteworthy point by Shepherd et al. (2005)
regarded the effect of Na+ and Ca2+ dissolved in the solution concom­
itant with the naphthenic acid compartment. The results demonstrated
that the dissolving sodium ions can substantially reduce the IFT values
especially for the pH value of 10 while calcium ions introduced no sig­
nificant IFT change over the examined pH range. They described the
6
Journal of Petroleum Science and Engineering 205 (2021) 108840
observed trend regarding the effect of Na+ on the IFT values based on
the Gouy-Chapman Theory (Adamsom and Gast, 1997) which is that a
large amount of available cations in the aqueous phase would decrease
the amount of H+ ions (counter-ions) at the interface, thus increasing the
tendency of the acidic groups to ionize, while the higher IFT values
observed for calcium solutions was correlated to precipitation or binding
with the naphthenic acid molecules at higher pH values, which renders
them more surface inactive which theoretically and experimentally
verified by others (Cooke et al., 1974; Goldszal et al., 2002; Healy and
White, 1978; Mohammed and Sorbie, 2010; Spildo and Høiland, 1999).
However, in the current investigation, a rather different effect regarding
calcium cation was observed which can be correlated to the following
phenomenon. Calcium ions can react with two acid groups neutralizing
the molecule and reduces its solubility, which can significantly reduce
the surface activity of the molecule. On the other hand, magnesium
introduces less activity and influence than calcium likely due to a higher
degree of hydration in the solution reducing its influence on the IFT
especially for the solutions with higher pH values.
4. Conclusions
The current investigation focused on the effects of chloride salts of
CaCl2, MgCl2, KCl, and NaCl on the IFT reduction of heavy acidic crude
oil for different pH values of 3.5, 7, and 11 as a situation that may occur
during the alkaline injection. The influence of these salts as a pH func­
tion examined in the presence of resinous synthetic oil (RSO) and
asphaltenic synthetic oil (ASO) prepared by dissolving asphaltene and
resin (8 wt/wt %) extracted from the heavy acidic crude oil in toluene to
find the sole effect of asphaltene and resin fractions (which can act as the
natural surfactant for IFT reduction). the TAN numbers measured for the
crude oil, asphaltenic, and resinous synthetic oils ensured the nature of
the used oil samples. The measurements revealed that the resinous and
crude oil were acidic (1.81 and 1.41, respectively) while asphaltenic
synthetic oil was neutral (TAN = 0.45). The IFT values measured in pH
values of 3.5, 7, and 11 revealed that increasing pH values from 3.5 to 11
substantially reduced the IFT due to the saponification of organic acid
compounds, and the generation of in-situ soap can act as a surfactant
during the alkaline injection. The measurements also show that for pH
value of 11, the salts weaken the IFT reduction behavior while for the
acidic and neutral conditions (pH values of 3.5 and 7), they have posi­
tive effects on the IFT reduction, although the effects for CaCl2 differed
from this observation. In detail, although chloride salts (except CaCl2)
have a clear influence on IFT, the CaCl2 impact is complex since its
molecular radius is large enough to form a stable complex to keep the in-
situ surfactant molecules solubilized in the bulk phase. In conclusion, it
appears that regardless of the presence of chloride-based salts in the
aqueous solution, the alkaline injection is a feasible and applicable
method for higher oil recovery from the reservoir with the heavy acidic
crude oil. It appears that investigating the wettability alteration and core
flooding experiments are the next and complementary phases of the
current investigation.
Credit author statement
Mehdi Behrang, Conceptualization; Data curation; Formal analysis;
Investigation; Methodology; Writting. Seyednoorlodin Hosseini: Project
administration; Resources; Software; Supervision; Validation; Writing –
review & editing. Naser Akhlaghi: Visualization; Writing – original draft;
Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
M. Behrang et al. Journal of Petroleum Science and Engineering 205 (2021) 108840

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