Energy Reports 6 (2020) 3150–3178

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Review article

The use of surfactants in enhanced oil recovery: A review of recent

advances
∗
Osama Massarweh, Ahmad S. Abushaikha
Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa University, Education City, Qatar Foundation, P.O. Box
34110, Doha, Qatar

article info a b s t r a c t

Article history: Currently, there is a widespread interest in the different methods of chemical enhanced oil recovery
Received 2 September 2020 (EOR) as a result of the continuous decline in the conventional oil reserves and the accelerated increase
Received in revised form 27 October 2020 in the global energy demand. Surfactant flooding is a well-established method of chemical EOR. This
Accepted 1 November 2020
method has proven successful as it increases oil recovery through a combination of mechanisms. These
Available online xxxx
include interfacial tension (IFT) reduction, wettability alteration, foam generation and emulsification.
Keywords: Despite its popularity, surfactant flooding is still challenged by issues including instability under harsh
Enhanced oil recovery (or normal) reservoir conditions and excessive adsorption. These issues affect the expected oil recovery
Surfactant flooding and thereby reduce the economic returns of EOR projects. Nevertheless, surfactants can be properly
Interfacial tension (IFT) selected according to reservoir conditions and rock type. This is usually carried out using surfactant
Wettability alteration
screening methods, which impose limits related to the IFT, surfactant adsorption and other factors
under given temperature and salinity conditions. This paper reviews surfactant characterization and
phase behavior, the role of surfactants in oil recovery, surfactant adsorption onto reservoir rock,
and the application of surfactants in EOR on both laboratory and field scales. Finally, the review
presents current research trends and future prospects based on recently published studies in the area
of surfactant flooding.
© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

Contents

1. Introduction..................................................................................................................................................................................................................... 3151
2. Background on surfactants ............................................................................................................................................................................................ 3152
2.1. Definition of surfactants ................................................................................................................................................................................... 3152
2.2. Characterization of surfactants ........................................................................................................................................................................ 3152
2.2.1. Critical micelle concentration ........................................................................................................................................................... 3153
2.2.2. Krafft temperature and Krafft point ................................................................................................................................................ 3153
2.2.3. Cloud point ......................................................................................................................................................................................... 3153
2.2.4. Hydrophile–lipophile balance ........................................................................................................................................................... 3154
2.2.5. Solubilization parameters.................................................................................................................................................................. 3154
2.2.6. Microemulsion systems ..................................................................................................................................................................... 3155
2.2.7. Winsor’s R-ratio.................................................................................................................................................................................. 3155
2.2.8. Hydrophilic–lipophilic deviation (HLD) ........................................................................................................................................... 3155
2.2.9. Molecular packing parameter ........................................................................................................................................................... 3156
3. The role of surfactants in oil recovery ........................................................................................................................................................................ 3156
3.1. Interfacial tension reduction ............................................................................................................................................................................ 3156
3.2. Wettability alteration ........................................................................................................................................................................................ 3157
3.3. Foam generation ................................................................................................................................................................................................ 3158
3.4. Emulsification ..................................................................................................................................................................................................... 3158
4. Surfactant adsorption onto reservoir rock .................................................................................................................................................................. 3159
4.1. Influence of surfactant adsorption on EOR..................................................................................................................................................... 3159
4.2. Surfactant adsorption isotherms ...................................................................................................................................................................... 3159

∗ Corresponding author.
E-mail address: aabushaikha@hbku.edu.qa (A.S. Abushaikha).

https://doi.org/10.1016/j.egyr.2020.11.009
2352-4847/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

4.3. Factors affecting surfactant adsorption ........................................................................................................................................................... 3160

5. Application of surfactants in chemical EOR ................................................................................................................................................................ 3160
5.1. Anionic surfactants ............................................................................................................................................................................................ 3160
5.1.1. Sodium dodecyl sulfate ..................................................................................................................................................................... 3160
5.1.2. Internal olefin sulfonates .................................................................................................................................................................. 3161
5.1.3. Alpha olefin sulfonates ...................................................................................................................................................................... 3162
5.1.4. Alkyl aryl sulfonates .......................................................................................................................................................................... 3163
5.2. Cationic surfactants ........................................................................................................................................................................................... 3163
5.2.1. Cetyltrimethylammonium bromide (CTAB)..................................................................................................................................... 3164
5.2.2. Dodecyltrimethylammonium bromide (DTAB) ............................................................................................................................... 3164
5.2.3. Alkyltrimethylammonium chlorides ................................................................................................................................................ 3164
5.3. Nonionic surfactants.......................................................................................................................................................................................... 3164
5.4. Zwitterionic surfactants .................................................................................................................................................................................... 3165
5.5. Surfactant screening criteria............................................................................................................................................................................. 3166
5.6. Field-scale application of surfactant-assisted chemical EOR ........................................................................................................................ 3166
5.7. Application of nanoparticles in surfactant flooding ...................................................................................................................................... 3168
6. Summary and future prospects .................................................................................................................................................................................... 3170
Declaration of competing interest................................................................................................................................................................................ 3170
Acknowledgments .......................................................................................................................................................................................................... 3170
References ....................................................................................................................................................................................................................... 3170

Once primary oil recovery is no more feasible, secondary oil

1. Introduction
Worldwide energy demand is estimated to increase by 30%
in 2040 compared to 2010 (Karatayev et al., 2019). It is also
estimated that by 2040, oil consumption will reach 111.1 mil-
lion barrels per day (Zhang et al., 2020). With depleting oil
reserves and growing energy demand, due to population growth
and rapid industrial development, it has become more important
to improve oil recovery from the declining oil reservoirs (Joshi
et al., 2015). The process of oil recovery is divided into three
main phases including primary, secondary and tertiary phases.
In the petroleum industry, the primary and secondary phases
are referred to as the conventional methods of oil extraction. On
the other hand, the tertiary phase is referred to as enhanced oil
recovery (EOR) (Pogaku et al., 2018).
The primary recovery produces less than 30% of original-oil-
in-place (OOIP) through natural flow and artificial lift (Pogaku
et al., 2018; Saravanan and Keerthana, 2017). Initially, crude oil
naturally flows out of a reservoir due to its own pressure (Grassia
et al., 2016; Miller and Sorrell, 2014). Several mechanisms are
involved in this process including solution-gas drive (important
in heavy-oil reservoirs) (He et al., 2019), gas-cap drive (Rezaei
et al., 2020b), water drive (Tayari et al., 2018), rock and liquid
expansion (Agi et al., 2018; Gyan et al., 2019) and gravity drainage
(Aljuboori et al., 2019). In many cases, the primary recovery is
supported by a combination of these driving mechanisms (Gyan
et al., 2019).
Continuous oil extraction causes the pressure gradient to drop
in the reservoir and hence oil production rates decrease, in accor-
dance with Darcy’s law (Höök et al., 2014). To achieve higher rates
of oil production, the drawdown pressure is usually increased by
lowering the bottom-hole pressure (BHP) in the production well.
This is accomplished by applying artificial lift, which compensates
for the reduction in energy supplied by natural drive mechanisms
after years of oil production (Davarpanah and Mirshekari, 2018).
There are several artificial lift systems that have been used world-
wide. Examples of these systems include hydraulic jet pumping,
gas lift, plunger lift, beam pumping, hydraulic piston pumping
and others. The selection of an artificial lift system depends on
determining factors including downhole pressure/temperature,
fluid properties, completion type and hole characteristics. The
factors also include well location, operating and service per-
sonnel, surface climate, available power sources, economics and
others (Brown, 1982).
3151
recovery is implemented to drive additional crude oil out of the
reservoir using pressure maintenance techniques such as water-
flooding and gas injection (Haq et al., 2020b,a). In waterflooding,
water is injected into a reservoir using a number of injection
wells to maintain the pressure. The displaced oil is collected
and produced using a number of production wells. However,
water injection does not extract all the oil from the reservoir
for two main reasons. Firstly, due to reservoir heterogeneities,
water may flow in highly permeable pathways that exist between
injection wells and production wells. This leaves several regions
of the reservoir unswept by the waterflood. Secondly, oil ganglia
surrounded by water are trapped within the small interstices of
the rock matrix due to oil–water surface tension preventing oil
from flowing (Blunt et al., 1993).
As indicated in Table 1, significant quantities of crude oil
remain unrecovered following the primary and secondary phases
of oil recovery. For this reason, a tertiary recovery phase, also
known as EOR, has been introduced to boost the recovery from oil
reservoirs. EOR involves a variety of operations such as chemical
flooding (Brantson et al., 2020; Jin et al., 2020), gas injection (Song
et al., 2020; Yu et al., 2020), microbial recovery (Nikolova and
Gutierrez, 2020; Niu et al., 2020) and thermal recovery (Dorane-
hgard and Siavashi, 2018; Mokheimer et al., 2018). Fig. 1 presents
the main methods of EOR.
The different EOR operations ultimately aim to improve the
overall oil displacement efficiency, which depends on the mi-
croscopic and macroscopic displacement efficiencies (Kumar and
Mandal, 2017b; Riahinezhad et al., 2017). Such improvement is
achieved by influencing one or more of the following: oil viscosity
(Zhu et al., 2018), rock wettability (El-hoshoudy et al., 2017),
interfacial tension (IFT) (AfzaliTabar et al., 2020) and capillary
forces (You et al., 2018) in addition to altering the mobility ratio
between the displacing and displaced fluids to more favorable
values (Haruna et al., 2020).
A wide variety of chemical agents are employed in chemical
EOR including surfactants (Sheng, 2015), ionically modified water
(Rezaeian et al., 2020), alkalis (Fakher et al., 2019), polymers
(Agi et al., 2018) and nanoparticles (Olayiwola and Dejam, 2019).
Surfactants are widely used in the petroleum industry because
they have the ability to affect the water/oil interface and the
properties of the rock surface (Zulkifli et al., 2020).
Surfactant formulations should be optimized under reservoir
conditions before being employed in oil recovery applications.
Usually, this is carried out using surfactant screening, which is
O. Massarweh and A.S. Abushaikha
Fig. 1. Main methods of EOR (Brantson et al., 2020; Gbadamosi et al., 2019b, 2018; Mokheimer et al., 2018; Shafiai and Gohari, 2020).
Table 1
Recovery factors following the primary and secondary phases of oil recovery.
Reference Oil recovery factor
Maurya et al. (2017) 20%–30%
Sengupta et al. (2012) 30%–40%
Riazi and Golkari (2016) 30%–50%
Kok (2012) 30%–50%
Desnelli et al. (2015) 40%–50%
Kumar and Mandal (2017b) ∼30%
Ali et al. (2020) ∼50%
Ahmadi et al. (2016) <50%
still a challenging process that requires time and material re-
sources (Jin et al., 2017; Wang et al., 2019). There are two main
reasons that make surfactant screening a difficult task. First, most
types of surfactants are highly affected by the conditions present
in the oil reservoir in addition to the type of the reservoir rock
(Ivanova et al., 2020; Riswati et al., 2019). Second, there is a wide
range of surfactants that have the potential to be used for EOR
(Miller et al., 2020; Trickett et al., 2010); therefore, starting with
a certain group of surfactants to be screened is also challenging.
Because of the significance of this issue, we present in this review
the parameters and the methods that are usually considered
during surfactant screening. We also present a classification of
the most commonly applied surfactants in chemical EOR.
Surfactant adsorption is an important parameter that affects
the efficiency of surfactant flooding and hence the economic
viability of EOR projects (Amirmoshiri et al., 2020; ShamsiJazeyi
et al., 2014). Research studies showed that surfactant adsorption
is affected by the temperature, salinity, pH and other reservoir
parameters (Puntervold et al., 2018; Zhang et al., 2019a). Re-
cently, significant research effort has focused on improving the
methods used to control surfactant adsorption, thereby reducing
its negative impacts on oil recovery. Common examples of these
methods include tuning the salinity and ionic composition of
the injection water (Ahmadi and Shadizadeh, 2018; Hossein-
zade Khanamiri et al., 2016a), alkali addition (Hazarika and Gogoi,
2020; Phukan et al., 2020) and nanoparticle (NP) addition (Cher-
aghian, 2017; Cheraghian and Nezhad, 2016; Kumar and Mandal,
2020). Beside reducing surfactant adsorption, some types of NPs
tend to improve the rheological properties of surfactant solutions
(Almahfood and Bai, 2018; Cheraghian, 2016a; Cheraghian et al.,
2017) and foams (Guo et al., 2017; Suleymani et al., 2020); there-
fore, oil recovery is improved. It is noteworthy that NPs provide
other benefits to chemical EOR processes (Cheraghian et al., 2020;
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Energy Reports 6 (2020) 3150–3178
Foroozesh and Kumar, 2020), which are discussed in other parts
of this review.
In this paper, we review the literature on the use of surfac-
tants in chemical EOR. The review covers the following topics:
background on surfactants (Section 2), the role of surfactants
in oil recovery (Section 3), surfactant adsorption onto reservoir
rock (Section 4) and application of surfactants in chemical EOR
(Section 5). Finally, in Section 6, we summarize the review and
present future prospects based on recently published studies.
2. Background on surfactants
Prior to discussing surfactants in relation to EOR, a brief back-
ground on surfactants is provided in this section. This background
includes the definition of surfactants and the main parameters
examined during surfactant characterization.
2.1. Definition of surfactants
Surfactants (surface active agents) are usually organic com-
pounds consist of two distinctive parts: a hydrophilic head and
a hydrophobic tail. There are four classifications of surfactants
according to the charge existing on the hydrophilic head. These
classifications include non-ionic (without any charge), anionic
(carrying negative charge), cationic (carrying positive charge),
and zwitterionic (carrying both negative and positive charges)
(Kume et al., 2008), as shown in Fig. 2. Generally, surfactants
have a chain structure (Azam et al., 2013; Burnham et al., 2013),
which is mainly attributed to the structure of the hydrophobic
tail. According to Gbadamosi et al. (2019b), the tail group of
a surfactant is often formed of a short polymer chain, a long
hydrocarbon chain, a siloxane chain or a fluorocarbon chain. The
head group, on the other hand, is formed of moieties such as
sulfates, sulfonates, polyoxyethylene chains, carboxylates, alco-
hols or quaternary ammonium salts. The presence of these groups
dictates the amphiphilic nature of the surfactant.
2.2. Characterization of surfactants
It is necessary characterize surfactants for technical and eco-
nomic reasons. Before using a surfactant in any application, it is
important to assure its effectiveness and stability over its period
of use. In this part of the review, the main parameters studied to
characterize surfactants are presented.
O. Massarweh and A.S. Abushaikha
Fig. 2. Types of surfactants according to the headgroup charge: (a) non-ionic,
(b) cationic, (c) anionic, and (d) zwitterionic (amphoteric) surfactants.
Source: Modified from Soleimani Zohr Shiri et al. (2019).
2.2.1. Critical micelle concentration
Micelle is a term refers to an aggregate form of surfactant
molecules dispersed in a liquid colloid (Bhosle et al., 2020; Naseri
et al., 2018), as shown in Fig. 3. The critical micelle concentration
(CMC) is the surfactant concentration above which micelles can
be formed. At the CMC, several physicochemical properties of the
solution (e.g., thermal and electrical conductivities, viscosity and
surface tension) vary abruptly (Sabahi et al., 2017). The CMC of a
particular surfactant depends on factors such surfactant molec-
ular structure (e.g., hydrophobic chain length) (Glennie et al.,
2006), pressure conditions (Thiruvengadam et al., 2020), solution
salinity (Bratovcic and Nazdrajic, 2020), ionic composition, pH,
temperature and others (Harutyunyan and Harutyunyan, 2019).
More than 30 methods have been developed for measuring the
CMC. These include the surface tension method, the dye adsorp-
tion method, the solubilization method and others (Suzuki, 1970).
According to Nesměrák and Němcová (2006), the methods that
are used for measuring the CMC are classified into direct and indi-
rect methods. In the direct methods, the change of some property
of the surfactant solution is observed in response to the change
in the surfactant concentration. Therefore, the CMC is determined
based on discontinuity or slope change of the observed solution
property such as viscosity, electrical conductivity, refractive index
and osmotic pressure. On the other hand, the indirect methods
are used to find the CMC by observing the change of a certain
property of a probe (a substance added to the surfactant solution)
in response to the change in the concentration of the surfactant.
Examples of such methods include the spectrometric method
Fig. 3. Micelle formation upon reaching the CMC.
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Energy Reports 6 (2020) 3150–3178
and the voltammetric method (Nesměrák and Němcová, 2006).
In terms of surfactant EOR applications, IFT measurement is a
commonly used method to determine the CMC (Haq et al., 2020b;
Liu et al., 2020a).
2.2.2. Krafft temperature and Krafft point
An important parameter related to the CMC is the Krafft tem-
perature (TK ), which is also known as the critical micelle temper-
ature (Nazrul Islam et al., 2015; Roy et al., 2014). Generally, the
Krafft temperature is regarded as the melting temperature of a
hydrated solid surfactant (Roy et al., 2014). Below the Krafft tem-
perature, surfactant micelles cannot be formed (Dicharry et al.,
2016; Dölle et al., 2012) and the surfactant tends to be insoluble
(Makavipour et al., 2019; Moon et al., 2001). At the Krafft temper-
ature, however, the solubility of the surfactant increases sharply,
and further increase in temperature allows for micelle formation
upon reaching the CMC (Malik and Ali, 2016). One of the methods
used to determine the Krafft temperature involves measuring
the electrical conductivity of a surfactant solution of a certain
concentration at different values of temperature. In this case,
the Krafft temperature is identified by the temperature point at
which a break is shown by the conductivity-vs-temperature plot
(Bales et al., 2002; Song et al., 2009), as depicted in Fig. 4. Another
related concept is the Kraft point that refers to the temperature
at which the surfactant solubility equals the CMC (Peris-Vicente
et al., 2016; Zapf et al., 2003). The Krafft point can be determined
experimentally using solubility measurements. The value for the
Krafft point corresponds to the intersection between the CMC
curve and the solubility curve (Inada et al., 2017; Miyake and
Oyama, 2009; Shinoda and Hutchinson, 1962), as shown in Fig. 5.
2.2.3. Cloud point
The cloud point is defined as the temperature at which aque-
ous solutions of nonionic surfactants exhibit sudden cloudiness
or turbidity (Aktar et al., 2020; Khattab et al., 2020). The solu-
bility of a broad range of nonionic surfactants, such as those of
the polyethoxylated type, depends on forming hydrogen bonds
between the headgroups of the surfactant and water molecules
(Álvarez et al., 2019; Illous et al., 2020). The increase in so-
lution temperature, however, weakens these bonds and results
in the dehydration of polyoxyethylene chains existing in the
headgroups of the surfactant (Mukhopadhyay et al., 2019; Turan
et al., 2020). Therefore, above the cloud point, surfactant solutions
tend to undergo phase separation (i.e., they separate into two
distinguished phases). The first phase is a surfactant-rich phase
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

Table 2
Relation between HLB values and the expected properties/applications of
surfactants (Sheng, 2010).
HLB value Property/application
0–3 Antifoaming agent
4–6 W/O (water in oil) emulsifier
7–9 Wetting agent
8–18 O/W emulsifier
13–15 Detergent
10–18 Hydrotrope or solubilizer

for low-salinity formations. Analogously, a high-HLB surfactant

should be selected for high-salinity formations (Sheng, 2010).
Researchers developed some equations to calculate the HLB
values of surfactants. Research reported by Griffin (1954, 1949)
and Davies (1957) was among the earliest research to provide
such equations. Royer et al. (2018) stated Griffin’s equation to
Fig. 4. Determination of the Krafft temperature (Tk ) for surfactants from the
calculate the HLB for nonionic ethoxylated surfactants as follows:
conductivity-vs-temperature plot (Bales et al., 2002; Song et al., 2009).
( )
1 MH
HLBGriffin = ∗ 100 (1)
5 MT
where MH denotes the molecular mass of the hydrophilic part
of the surfactant molecule and MT denotes the total molecular
mass of the surfactant molecule (Royer et al., 2018). Davies (1957)
found that HLB values for surfactants can be calculated from their
chemical formulae based on group numbers, as shown in the
following equation:
∑
HLBDavies = 7 + (hydrophilic group numbers)
∑ (2)
− (lipophilic group numbers)
According to Davies (1957), given a surfactant containing a num-
ber n of –CH2 – groups, the HLB value is calculated as follows:

Fig. 5. Determination of the Krafft point from the phase diagram of surfactant
solutions (Inada et al., 2017; Miyake and Oyama, 2009).
that contains a high surfactant concentration. The second phase is
a bulk aqueous phase that contains a low surfactant concentration
compared with the first phase (Kachangoon et al., 2020; Pan
et al., 2019). According to Puerto et al. (2012), the cloud-point
phenomenon of nonionic surfactants, such as AGES (alkoxylatedg-
lycidyl ether sulfonate), adversely affects their EOR-performance
in reservoirs of high temperature. Solutions of AGES surfactant
separate into two phases upon reaching the cloud temperature,
which has lower values in the presence of salt (NaCl). Never-
theless, this problem can be alleviated by combining AGES with
a surfactant such as IOS (internal olefin sulfonate), which is an
anionic surfactant. This is because IOS exhibits higher solubility
in aqueous solutions of NaCl as temperature increases.
2.2.4. Hydrophile–lipophile balance
An important criterion for surfactant characterization is the
hydrophile–lipophile balance (HLB). This criterion measures the
extent to which a surfactant is lipophilic or hydrophilic (Kondo
et al., 2007; Reham et al., 2015). The HLB is a number on a
scale from 0 to 20 that indicates relatively the tendency of a
surfactant to dissolve in oil or water. On that scale, a value of 0
correlates with a completely hydrophobic (lipophilic) molecule,
while a value of 20 correlates with a molecule composed entirely
of hydrophilic components. Table 2 shows surfactant properties
predicted using the HLB values. To form proper microemulsions
during oil recovery, a low-HLB surfactant needs to be selected
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∑
HLBDavies = 7 + (hydrophilic group numbers)
(3)
− n(group number per CH2 group)
where the value of CH2 -group number is substituted as 0.475
and the hydrophilic group numbers are obtained from tables
provided by Davies (1957). Later, other researchers developed
experimental methods to determine the HLB values. Some of
these methods are based on the emulsion inversion point (EIP)
(Marszall, 1978, 1976), the phase-inversion temperature (PIT)
(Kunieda and Ishikawa, 1985; Kunieda and Shinoda, 1985; Shin-
oda and Sagitani, 1978) and others.
2.2.5. Solubilization parameters
Oil (or water) solubilization ratio is defined as the volume of
oil (or water) solubilized per surfactant volume in a microemul-
sion phase (Das et al., 2020; Sarmah et al., 2020). According
to Abalkhail et al. (2020), the solubilization ratio (SR) can be
expressed as follows:
Volumeoil
SRoil = (4)
Volumesurfactant
Volumewater
SRwater = (5)
Volumesurfactant
Bera et al. (2011) and Hamidi et al. (2015) reported that the
optimum solubilization, which produces the ideal microemulsion
formulation needed for oil recovery, occurs when SRwater and
SRoil are equal. This is obtained by drawing oil-SR curve and
water-SR curve, where the intersection point between the two
curves represents the optimum solubilization occurring at the
optimum salinity, as shown in Fig. 6. Liyanage et al. (2015) and
O. Massarweh and A.S. Abushaikha
Fig. 6. Determination of the optimal salinity for an oil–water–surfactant system
using the solubilization-ratio curves (Das et al., 2020; Hamidi et al., 2015).
Khaledialidusti et al. (2017) stated that studying the solubilization
parameters is important to optimize the oil recovery process. This
is because the lowest oil–water IFT is normally observed at the
optimum salinity.
2.2.6. Microemulsion systems
At equilibrium, microemulsion systems are classified, accord-
ing to Winsor (1948), into four main types. These systems are
shown in Fig. 7. Winsor’s Type I systems consist of an O/W (oil-
in-water) microemulsion that coexists with an excess oil phase.
Conversely, in Type II systems, a W/O microemulsion coexists
with an excess water phase. In Type III systems, three separate
phases coexist including microemulsion, water and oil. Finally,
Type IV systems can be described as homogeneous, single-phase
systems formed entirely of one microemulsion phase (Nordiyana
et al., 2016; Salleh et al., 2019). Type IV microemulsions are
extension of Type III systems. However, they are formed by
increasing the concentration of the surfactant until the whole
liquid transforms into a single phase (Salleh et al., 2019). For
EOR applications, microemulsions of Type III are usually preferred
as they provide the lowest IFT compared to the other systems
(Nordiyana et al., 2016).
Fig. 7. Winsor’s classification of microemulsions.
Source: Modified from Winsor (1948).
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Energy Reports 6 (2020) 3150–3178
2.2.7. Winsor’s R-ratio
Winsor’s R-ratio is a useful tool to understand the phase
behavior of surfactant–oil–water systems, and it is defined as
follows:
ACO
R= (6)
ACW
where ACO and ACW denote the interactions of the surfactant
adsorbed at the interface with the oil molecules and the water
molecules, respectively (Nguyen et al., 2010; Salager et al., 2005;
Winsor, 1954). The value of R is interpreted as shown in Table 3,
where S, O and W indicate surfactant, oil and water phases,
respectively.
The interactions given in Table 3 change upon changing any
of the tuning parameters (e.g., temperature and salinity). For
instance, increasing the salinity will decrease the S–W interaction
(i.e., ACW decreases). As a result, the R-ratio will increase and
a transition from Type I to Type III microemulsion system may
happen. That is, increasing the salinity of water will increase the
hydrophobicity of the surfactant system and intensify the S–O
interaction, which in turn raises the R-ratio. This implies that
surfactants with higher hydrophilicity require higher salinity to
form proper microemulsions (Nguyen et al., 2010; Salager et al.,
2005).
2.2.8. Hydrophilic–lipophilic deviation (HLD)
The HLB concept and Winsor R ratio, presented earlier, have
limitations when applied to calculate the optimum surfactant
formulation for EOR and other surfactant-based processes. For
instance, the HLB concept does not consider the effects of vari-
ables such as salinity, temperature, the nature of the oil and the
presence of co-surfactants or alcohols in the system (Bouton et al.,
2009; Nguyen et al., 2019; Witthayapanyanon et al., 2008). On the
other hand, the parameters related to Winsor R ratio are difficult
to estimate (Budhathoki et al., 2016b; Wang et al., 2019). Because
of these limitations, researchers including Salager et al. (1979),
Bourrel et al. (1980) and Antón et al. (1997) proposed correlations
that lead to more accurate prediction of microemulsion phase be-
havior for different types of surfactants. Unlike the HLB concept,
these correlations take into account several variables that have a
O. Massarweh and A.S. Abushaikha
Table 3
Interpretation of R ratio in relation to microemulsion systems (Nguyen et al., 2010; Salager et al., 2005).
R-ratio Interpretation
R < 1 W–S interaction is stronger than O–S interaction
R > 1 O–S interaction is stronger than W–S interaction
R = 1 W–S and O–S interactions are balanced (optimum formulation)
significant impact on the performance of surfactants used for oil
recovery.
Later, these proposed correlations led to the emergence of
the HLD concept (Salager et al., 2005, 2000, 2003). For ionic and
nonionic surfactants, HLD is numerically expressed according to
Eqs. (7) and (8), respectively:
HLD = ln (S) − kACN + f (A) + σ − aT (T − T0 )
HLD = α − EON + bS − kACN + f (A) + cT (T − T0 )
where S is the salinity (as wt.% NaCl in the aqueous phase), ACN
denotes the alkane carbon number for an alkane oil, b, k, aT and cT
are empirical constants that depend upon the type of the system,
f(A) is a function of alcohol type and concentration, σ and α
are characteristic parameters of the surfactant structure, T is the
temperature (◦ C) and T0 has a value of 25 ◦ C (Antón et al., 1997;
Bourrel et al., 1980; Salager et al., 2005, 2003, 1979).
Based on Eqs. (7) and (8), the HLD basically measures the
departure from a reference state at which a surfactant–water–
oil formulation represents a Winsor Type III emulsion. At this
reference state (i.e., HLD = 0), the oil–water IFT becomes ex-
tremely low. However, when HLD is negative or positive, the
formulation represents an oil-in-water (O/W) emulsion or a W/O
emulsion, respectively (Salager et al., 2003). Recently, several
research studies have investigated the use of the HLD concept to
screen surfactants for EOR processes. These studies indicated that
the HLD concept is an effective tool that can be employed in the
design and optimization of surfactant–water–oil formulations for
specific temperature and salinity conditions (Budhathoki et al.,
2016b; Cholpraves et al., 2017; Jin et al., 2015; Nguyen et al.,
2019; Wang et al., 2019).
2.2.9. Molecular packing parameter
The molecular packing parameter (PC ) is a concept that de-
scribes the relation between the geometry of a surfactant
molecule and its aggregate structure in aqueous solutions. Exam-
ples of aggregate structures include spherical micelles, rod-like
micelles, bilayer vesicles, etc. To calculate the Pc, the following
equation is used (Nagarajan, 2002):
vo
PC = (9)
lo a
where vo is the volume of the surfactant tail, lo is the length of
the surfactant tail, and a is the surface area of the hydrophilic
headgroup at the surface of the aggregate (Nagarajan, 2002). Fig. 8
depicts the terms used in the equation of the packing parameter.
According to the value of the packing parameter, the
molecules of the surfactant self-assemble into different micelle
geometries, as shown in Fig. 9. These geometries affect the bulk
properties of the solution such as its viscoelastic properties (van
Zanten, 2011) and its solubilization capacity (Nagarajan, 2002).
3. The role of surfactants in oil recovery
Generally, surfactants affect the processes of oil recovery
through four main mechanisms: interfacial tension reduction,
wettability alteration, foam generation and emulsification. In this
part of the review, a brief discussion of these mechanisms is
presented.
Energy Reports 6 (2020) 3150–3178
Microemulsion system
Type I
Type II
Type III
(7)
(8)
Fig. 8. Definition of the terms used in equation of the packing parameter
(Lombardo et al., 2015; Sheng, 2010).
3.1. Interfacial tension reduction
The interfacial tension is generally defined as the attraction
force between the molecules existing at the interface of two
fluids (Cong et al., 2020; Kalantari Meybodi et al., 2015). The
interfacial tension between hydrocarbons and water molecules
causes an increase in the capillary force that plays an essential
role in hydrocarbon trapping within porous media. Therefore,
surfactant injection is used as an option to reduce the interfacial
tension (Hosseininoosheri et al., 2016). Studies showed that many
types of surfactants can be used at low concentrations (∼0.05–
0.2%) to achieve low interfacial tension on the order of 10−2
dynes/cm or less (Ge and Wang, 2015; Hosseinzade Khanamiri
et al., 2016b; Kumar and Mandal, 2017a; Rosen et al., 2005). In the
absence of oil, the presence of a surfactant in water reduces the
surface tension because the molecules of the surfactant replace
part of the water molecules at the water surface. The attraction
forces between the water and surfactant molecules are less than
the attraction forces between the water molecules themselves.
Subsequently, the contraction force responsible for the surface
tension is reduced (Hu et al., 2016; Mohapatra et al., 2014).
In water–oil–surfactant systems, on the other hand, surfactant
molecules replace some of the oil and water molecules at the
original oil–water interface in a process called surfactant adsorp-
tion. This new arrangement of molecules involves an interaction
between the hydrophobic components of the surfactant and oil
on one side of the interface, and between the hydrophilic com-
ponents of the surfactant and water on the other side. In fact,
the new interaction across the oil–water interface is significantly
stronger than the original interaction between water and oil
prior to surfactant addition. Therefore, the interfacial tension is
reduced (Azodi and Nazar, 2013; Xu et al., 2013).
The ability of surfactants to reduce the interfacial tension
between crude oil and brine is highly sensitive to the type and
concentration of ions existing in the brine. As stated earlier, there
is an optimal salinity at which the interfacial tension between
crude oil and brine is reduced to ultra-low values. Usually, this
optimal salinity is expressed in terms of NaCl content that is
dissolved in the solution (Tichelkamp et al., 2014). However,
research studies showed that introducing divalent/multivalent
cations to a surfactant solution containing a given NaCl con-
centration reduces the value of the optimal salinity. This means
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O. Massarweh and A.S. Abushaikha
Fig. 9. Effect of the critical packing parameter (PC ) on the aggregate structure of surfactants (Cornwell, 2018; Lombardo et al., 2015; van Zanten, 2011).
that the surfactant becomes less tolerant to NaCl salinity in the
presence of these divalent/multivalent cations, which adversely
affects the interfacial tension between oil and brine. In a study
conducted by Bansal and Shah (1978), the effect of divalent
cations on the interfacial tension properties of a surfactant for-
mulation was investigated. The formulation contained petroleum
sulfonate and ethoxylated sulfonate. It was demonstrated that
increasing the concentration of divalent cations (Ca2+ and Mg2+ )
in surfactant–oil–brine systems drastically reduces the optimal
salinity. In a similar study, Kumar et al. (1984) showed that
increasing the concentration of Ca2+ and Mg2+ in surfactant
solutions containing petroleum sulfonate and lignosulfonate was
detrimental to their ability to reduce the oil–brine interfacial ten-
sion. Therefore, this effect should be considered during surfactant
screening because natural connotate water normally contains
these divalent cations (Kumar et al., 1984). In fact, this phe-
nomenon is mainly observed with anionic surfactants that tend
to precipitate out of the bulk solution upon reacting with the
divalent/trivalent cations, and thus, oil recovery is expected to be
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Energy Reports 6 (2020) 3150–3178
reduced (Jha et al., 2018; Maneedaeng and Flood, 2017; McGuire
et al., 2005; Salager et al., 2013).
3.2. Wettability alteration
Wettability is the ability (or tendency) of a fluid to adhere to,
or spread on, a solid surface in the presence of other immiscible
fluids (Jing et al., 2019; Yang and Zhou, 2020). Basically, this
type of adhesion occurs due to various forces including van der
Waals forces, structural forces and electrostatic forces, which
result in stable distribution of fluids in porous media (Wang
et al., 2018). In the presence of two liquids, the one that has the
strongest adhesion to the surface is referred to as the wetting
phase (Khaleel et al., 2019). Sandstones and carbonates have
different wettability characteristics. Generally, sandstones exhibit
water-wet to intermediate-wet properties. On the other hand,
carbonates frequently exhibit intermediate-wet to oil-wet prop-
erties (Schön, 2015). Several methods have been used to alter the
rock wettability toward more water-wet states. These methods
O. Massarweh and A.S. Abushaikha
include surfactant injection (Nowrouzi et al., 2020), nanofluid
injection (Zargar et al., 2020), low salinity waterflooding (Liu and
Wang, 2020), and thermal recovery processes (Doranehgard and
Siavashi, 2018).
Rock wettability has a significant impact on oil recovery from
naturally fractured carbonate reservoirs. Commonly, waterflood-
ing is conducted to recover additional oil after the primary re-
covery period. The effectiveness of waterflooding in fractured
reservoirs depends on the spontaneous imbibition of water to
displace the oil contained in the matrix to the system of fractures
(Abushaikha and Gosselin, 2008). The process of spontaneous
imbibition is mostly effective in water-wet reservoirs in which
the capillary driving forces are strong. However, in fractured
reservoirs of mixed- or oil-wet properties, the capillary driving
forces for the spontaneous imbibition are weak, and hence the oil
recovery from waterflooding is low (Andersen et al., 2014; Salehi
et al., 2008).
In many cases, capillarity can retain oil, and it may not be pos-
sible to apply an adequate pressure gradient across the fractured
oil-wet carbonate formations. Consequently, high oil saturation
remains in those formations. Therefore, oil recovery from car-
bonates (e.g., chalk and dolomite) relies largely on wettability
alteration, which can be achieved by injecting proper surfactants
(Leslie Zhang et al., 2006).
Wettability alteration in carbonates by surfactant injection is
explained according to two main mechanisms. The first mecha-
nism is called the coating mechanism, and it is related to anionic
surfactants. In this mechanism, the molecules of anionic surfac-
tants create a monolayer on the carbonate rock surface where
the hydrophobic surfactant tails interact with the adsorbed oil.
This arrangement implies that the originally oil-wet rock surface
is covered with hydrophilic head groups of the surfactant. These
groups modify the rock wettability to more water-wet conditions.
The second mechanism is called the cleaning mechanism, and it
is related to cationic surfactants. This mechanism is based on
forming ion pairs between the surfactant cationic heads and the
acidic portions of crude oil adsorbed onto the carbonate rock
surface. The formed ion pairs can strip the adsorbed oil layer off
the rock surface, which exposes the originally water-wet surface.
Generally, the cationic surfactants exhibit a better performance
of wettability alteration in carbonates compared with the anionic
surfactants. This is because the ion-pair interactions are stronger
than the hydrophobic interactions (Hammond and Unsal, 2011;
Salehi et al., 2008). In sandstones with oil-wet properties, wetta-
bility alteration toward water-wet conditions also occurs due to
ion-pair interactions or hydrophobic interactions depending on
the type of the injected surfactant (Hou et al., 2016).
As stated earlier, carbonates tend to exhibit more oil-wet
characteristics compared to sandstones. Because of that, a large
amount of research has been devoted to study the interactions
between surfactants, brine, oil and carbonate surfaces in relation
to rock wettability. According to Standnes and Austad (2003),
the brine in carbonate reservoirs usually has basic nature, with
a pH approximately equal to 8. At this pH, the carboxylic groups
existing in the crude oil become negatively charged in contact
with the formation brine, and they strongly adsorb onto the
positively charged carbonate surface. Normally, carboxylic ma-
terials are found in the heavy-end fractions of crude oil, such
as asphaltene and resin. These carboxylic materials perform as
‘‘anchors’’ for the polar molecules to adsorb onto the carbonate
surface, which occurs mainly due hydrophobic and dipole–dipole
interactions. As a result, an organic layer will cover the entire
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Energy Reports 6 (2020) 3150–3178
surface of the carbonate rock, turning it into an oil-wet surface
(Standnes and Austad, 2003). Several studies also reported that
carboxylates present in crude oil are strongly adsorbed on car-
bonate rocks causing them to be oil-wet (Awolayo et al., 2018; Bai
et al., 2020; Karimi et al., 2015). Therefore, in order to effectively
change the wettability of carbonates using surfactant flooding,
carboxylates usually need to be targeted in the process. In a
study carried out by Standnes and Austad (2000), fourteen types
of anionic and cationic surfactants were examined in terms of
their ability to alter the wettability of chalk, which is a carbonate
rock. The results showed that cationic surfactants have signifi-
cantly larger potential to change the wettability of the rock. This
change is attributed to the mechanism of ion-pair formation. In
this mechanism, cationic surfactants have the ability to desorb
the negatively charged surface-active materials (i.e., carboxylates)
from the carbonate surface (Standnes and Austad, 2000). As a
result, the surface returns to its original water-wet state, making
spontaneous imbibition possible.
3.3. Foam generation
Foam is a dispersion consists of two fluids: a gas and an
aqueous surfactant solution. The gas is trapped in the dispersion
in the form of bubbles separated by thin films of liquid known
as lamellae (Farajzadeh et al., 2020; Samimi et al., 2020). Several
gases can be used in the process of foam generation including air,
nitrogen, carbon dioxide, natural gas and others (Zhao and Torabi,
2020). Typically, gas injection in subsurface porous media is chal-
lenged by issues such as formation heterogeneities and the low
gas density/viscosity compared to in-situ fluids. Therefore, foam
has been introduced to EOR applications as it provides several
advantages. First, foam can alleviate the viscosity issue and re-
duce the gas mobility. Second, foam has the ability to block some
layers of the reservoir, especially those with high permeability,
in favor of injecting fluids into less permeable layers. Third,
foam can increase the lateral pressure gradient which relatively
reduces the gravity effect and hence reduces the phenomenon
of gravity segregation. As a result, these advantages increase the
volume fraction of the reservoir that is swept by the injected
fluids (Farajzadeh et al., 2020). According to Pal et al. (2018), foam
injection is used as a method of mobility control in circumstances
where polymer flooding, gas injection or water–alternating-gas
(WAG) injection are not feasible. This mostly occurs in formations
with unfavorable characteristics such as high heterogeneity or
high salinity and temperature affecting the polymer stability.
3.4. Emulsification
Emulsification is one of the mechanisms that can increase
oil recovery in the tertiary phase. Emulsions mostly form dur-
ing alkaline and/or surfactant flooding under the conditions of
low/ultra-low IFT and under shear resulting from fluid flow in
rock pores (Bryan and Kantzas, 2009; Li et al., 2020d). Emulsi-
fication usually improves oil recovery through two main mecha-
nisms: (1) emulsification and entrainment; and (2) emulsification
and entrapment (Mehranfar and Ghazanfari, 2014; Shi et al.,
2015; Türksoy and Bağci, 2000). In the case of emulsification
and entrainment, the IFT is significantly reduced allowing the
droplets of crude oil to be emulsified into the water phase.
Then, the droplets are transported along with the water phase.
This means that oil bulks are gradually produced in the form
of fine particles. Usually, the emulsification-entrainment mech-
anism occurs when the formed emulsion droplets have sizes that
are equal to or smaller than the pore sizes. On the other hand,
emulsification-entrapment mechanism involves the formation of
emulsion droplets that plug pore throats and water channels. As
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

Table 4
List of the surfactants that appear in the review.
Surfactant name Abbreviation Type
Dodecyltrimethylammonium chloride DTAC Cationic
Tetradecyltrimethylammonium chloride TTAC Cationic
Octadecyltrimethylammonium chloride OTAC Cationic
Hexadecyl-N,N-dimethyl-2-ammonio-1-ethanecarbonate C16DmCB Zwitterionic
Triton X-100 TX-100 Nonionic
Cetyltrimethylammonium bromide CTAB Cationic
Sodium dodecyl sulfates SDS Anionic
Alkyl polyglycoside APG Nonionic
Internal olefin sulfonates IOS Anionic
Tridecyl alcohol propoxy sulfate TDA Anionic
Guerbet alkoxylate carboxylate GAC Anionic
Cocamidopropyl betaine CAPB Zwitterionic
Sodium laurilsulfate or sodium lauryl sulfate SLS Anionic
1-dodecyl-3-methylimidazolium chloride (surface-active ionic liquid) M12 Cationic
Alpha olefin sulfonates AOS Anionic
Alkyl aryl sulfonates AAS Anionic
Alkyl aryl disulfonate ADS Anionic
Naphthenic aryl sulfonate NAS Anionic
Alkyl aryl monosulfonate AMS Anionic
Dodecyltrimethylammonium bromide DTAB Cationic
Tergitol 15-s-7 Tg7 Nonionic
Tergitol 15-s-9 Tg9 Nonionic
Tergitol 15-S-12 Tg12 Nonionic
N, N-Dimethyl-N-[2-hydroxy-3-sulfopropyl]-N′ -phenyloctadecanoyl-1,3-diaminopropane SPODP Zwitterionic
Oleyl polyoxyethylene amidopropyl carboxybetaine OPAC Zwitterionic
Oleyl polyoxyethylene amidopropyl hydroxy sulfobetaine OPAH Zwitterionic
Oleyl polyoxyethylene amidopropyl sulfobetaine OPAS Zwitterionic
N-phenyloctade-canoicamidopropyl-N, N-dimethylcarboxylbetaine POAPMB Zwitterionic
Alcohol propoxy sulfate APS Anionic
Alkyl benzene sulfonate ABS Anionic
Cocamidopropyl hydroxysultaine CAHS Zwitterionic
Alkyl ether sulfate AES Anionic
Alkyldimethylamine oxides ADAO Zwitterionic
Lauryl alcohol polyoxyethylene ether LAPE Nonionic
Alkyl dimethyl ammonium chloride ADAC Cationic
Alkyl trimethyl ammonium chloride ATAC Cationic

a result, the water-to-oil mobility ratio is reduced and surfactant
solution is diverted to upswept areas, which improves the areal
and vertical sweep efficiencies. This effect is important, particu-
larly in the production of viscous oils where the sweep efficiency
of waterflooding is poor. It is noteworthy that the entrapment
in this mechanism occurs because the IFT is not low enough to
reduce the average size of the emulsion droplets below that of
the pores in the reservoir rock (Bryan and Kantzas, 2009; Castor
et al., 1981; Johnson, 1976).
4. Surfactant adsorption onto reservoir rock
In Section 3, we discussed the role of surfactants in the process
of oil recovery. In this section, we will discuss the adsorption
of surfactants during EOR processes. In addition, we will present
the factors that affects the adsorption process based on recently
published research that considered different types of surfactants.
Table 4 provides a list of abbreviations of surfactants as they
appear in the following parts of the review.
process (Belhaj et al., 2020). This in turn may result in significant
economic drawbacks (Liu et al., 2020c; Ojo et al., 2020; Venancio
et al., 2020).
In reservoirs with intermediate to oil-wet nature, on the other
hand, surfactant adsorption can play a beneficial role in wet-
tability alteration. This occurs when surfactant molecules are
adsorbed at the sites where crude oil was desorbed by the flood-
ing process. Subsequently, further interactions between crude oil
and the surface of the rock are prevented. Therefore, the rock
wettability is altered to water wet. However, excessive adsorption
of surfactants reduces their concentration in the aqueous phase
and adversely impacts the efficiency of surfactant-EOR processes
(Saxena et al., 2019). For instance, the use of cationic surfactants
in carbonates has a positive effect on the wettability state. How-
ever, cationic surfactants exhibit strong adsorption in sandstones
and hence they cannot be used in sandstone reservoirs (Sheng,
2010).
4.2. Surfactant adsorption isotherms

4.1. Influence of surfactant adsorption on EOR
During the flooding process, surfactant retention in porous
media occurs according to three main mechanisms: precipita-
tion, adsorption and phase trapping. Surfactant precipitation and
phase trapping can be prevented by selecting a surfactant that
tolerates temperature and salinity. However, the adsorption of
a surfactant onto reservoir rock can be only minimized. The
adsorption process decreases the concentration of the surfactant
in the injected solution, which affects its ability to reduce the
oil–water IFT. Consequently, the effectiveness of surfactant-based
EOR to mobilize the trapped oil is influenced by this adsorption
3159
Adsorption of ionic surfactants on oppositely charged reservoir
rock can be described using surfactant adsorption isotherms, as
shown in Fig. 10. Typically, an adsorption isotherm is divided
into four regions. In region I, adsorption occurs over low concen-
trations of the surfactant as a result of electrostatic interactions
between the surfactant monomers and the solid surface (Bud-
hathoki et al., 2016a; Zhang and Somasundaran, 2006). The ad-
sorption in this region increases linearly with the increase in the
concentration of the surfactant, following Henry’s law (Grządka
and Matusiak, 2020). In region II, surface aggregates of the sur-
factant start to form by reason of lateral interactions between
the hydrocarbon chains. Examples of surface aggregates include
O. Massarweh and A.S. Abushaikha
Fig. 10. Surfactant adsorption isotherm (Budhathoki et al., 2016a; Zhang and Somasundaran, 2006).
surface colloids (solloids), hemimicelles (monolayer), admicelles
(bilayers), etc. In addition to the lateral interactions, the adsorp-
tion process is still influenced by active electrostatic interactions.
Hence, a sharp increase in the slope of the isotherm occurs. In
region III, the solid surface becomes electrically neutralized by
the adsorbed ions of the surfactant. Therefore, the electrostatic in-
teractions become no longer active, which decreases the slope of
the isotherm. At this stage, surfactant adsorption occurs only due
to the lateral interactions. Finally, the surfactant concentration
reaches the CMC as indicated by region IV. This means that any
increase in the concentration contributes only to the formation of
micelles in the solution without increasing the adsorption density
(Budhathoki et al., 2016a; Zhang and Somasundaran, 2006).
4.3. Factors affecting surfactant adsorption
There are several factors that affect surfactant adsorption onto
reservoir rock. Examples of these factors include surfactant type,
rock surface charge, salinity, pH and temperature. Therefore, ex-
tensive study is needed prior to selecting a surfactant for a
particular oil reservoir. Table 5 summarizes several research stud-
ies highlighting the effect of salinity, temperature and pH on
surfactant adsorption. The summarized studies considered the
type of the surfactant, such as cationic and anionic surfactants, in
addition to the type of the mineral surface including carbonate,
sandstone, shale, clay, Kaolinite, etc.
5. Application of surfactants in chemical EOR
There is a broad range of surfactants that have been em-
ployed in EOR applications. The use of such a wide range of
surfactants is attributed to technical, economic and environmen-
tal considerations. This section of the review presents surfactants
frequently used in EOR. The surfactants are presented according
to their type: anionic, cationic, nonionic and zwitterionic sur-
factants. In addition, this section presents field-scale application
of surfactant-based EOR. Finally, it discusses the role of NPs in
surfactant flooding, which is an emerging research topic.
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Energy Reports 6 (2020) 3150–3178
5.1. Anionic surfactants
5.1.1. Sodium dodecyl sulfate
Sodium dodecyl sulfate (SDS) belongs to a group of sur-
factants called alkyl sulfates, and it has the chemical formula
CH3 (CH2 )11 SO4 Na (Li et al., 2020a). SDS is also known as sodium
laurilsulfate or sodium lauryl sulfate (SLS) (Bondi et al., 2015;
Wołowicz and Staszak, 2020). This surfactant has a linear molec-
ular structure that consists of a 12-carbon hydrophobic chain
attached to a negatively charged sulfate group (Hou et al., 2020;
Khan et al., 2019).
Recent research investigated the use of SDS incorporated with
nanoparticles (NPs) in EOR applications. For instance, Wu et al.
(2017) studied SDS adsorption and its EOR performance in the
presence hydrophilic silica NPs. Static adsorption tests of SDS on
quartz sand showed that the use of 0.2 to 0.3 wt% silica NPs
is optimal to effectively reduce surfactant adsorption. Core-flood
experiments showed that 0.2 wt% SDS could achieve incremental
oil recovery of 4.43% following waterflooding. This percentage
was raised to 9.11% using 0.2 wt% SDS and 0.2 wt% silica NPs.
Rezk and Allam (2019) reported that the flooding of 0.2 wt%
SDS achieved about 16% increase in oil recovery in the tertiary
phase. However, the use of 0.2 wt% SDS with 0.05 wt% ZnO NPs
raised the value to 35%. This improvement was attributed to the
wettability alteration and significant reduction in the IFT between
water and oil (n-dodecane) caused by ZnO NPs.
Researchers also studied the effect of SDS combined with
other surface-active compounds on solution properties and EOR.
For example, Jia et al. (2019) investigated the synergistic effects
of SDS and 1-dodecyl-3-methylimidazolium chloride (M12) on
properties such as IFT, rock wettability and oil-recovery perfor-
mance. It was demonstrated that mixed-surfactant systems have
higher capability to reduce the IFT compared to SDS or M12
systems at conditions of high salinity and temperature. It was
also demonstrated that all surfactant systems had the ability to
alter rock wettability. However, mixed systems exhibited higher
tendency to alter the wettability due to the pseudo two-tailed
co-surfactant formed upon mixing anionic (SDS) and cationic
(M12) surfactants. Lastly, Jia et al. (2019) demonstrated the ability
of SDS–M12 systems to improve oil recovery, at high temper-
ature and salinity, by more than 10%. However, the effect of
single-surfactant systems on oil recovery was not studied.
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

Table 5
Effect of salinity (S), temperature (T) and pH on surfactant adsorption.
Reference Surfactant name and
type
Effect of salinity
Chen et al. (2014) DTAC (cationic)
TTAC (cationic)
OTAC (cationic)
Kumar and Mandal (2019) (C16DmCB)
(zwitterionic)
Saxena et al. (2019) Soap-nut surfactant
(anionic)
Yekeen et al. (2019) TX-100 (nonionic)
CTAB (cationic)
Zhong et al. (2019) BW (zwitterionic)
CA (zwitterionic)
CS-50 (zwitterionic)
Abbas et al. (2020) Aerosol-OT (anionic)
Effect of temperature
Azam et al. (2014) Synthesized
surfactant consists
mainly of C18 carbon
chain and a sulfonate
headgroup (anionic)
Type of adsorbent Experimental Main findings
or solid surface conditions
Carbonate S = 13987.7, - Surfactant adsorption on limestone
27975.4, 55950.7, surfaces increased as the salinity
111901.4 and increased.
223802.8 ppm
Carbonate S = 0, 15000, - At the CMC, higher adsorption
Sandstone 30000 and 45000 occurred due to salt addition which
ppm (NaCl) reduces the surfactant solubility and
T = 30 ◦ C reduces the repulsion between the
adsorbed surfactant molecules.
- Surfactant adsorption was higher in
carbonate rock compared to sandstone
rock.
Sandstone S = 0, 10000, - UV spectroscopy can be used to study
Carbonate 20000 and 30000 surfactant adsorption in the presence of
Bentonite ppm (NaCl) salts.
- Surfactant adsorption increased as the
salinity increased.
- Surfactant adsorption was highest in
bentonite clay and lowest in sandstone.
- Rock mineralogy and morphology
affected the adsorption process.
Shale S = 0, 10000 and - The adsorption of CTAB was 2.57, 2.76
30000 ppm (NaCl) and 2.90 mg/g at 0, 10000 and 30000
ppm, respectively.
- The adsorption of TX-100 was 1.51,
1.82 and 1.99 mg/g at 0, 10000 and
30000 ppm, respectively.
- The high adsorption of the cationic
surfactant CTAB was related to the high
quartz content in the shale.
Bakken rocks and S = 500 and - CS-50 exhibited a slight increase in the
Berea sandstone in 289820 ppm adsorption with the increase in salinity.
addition to other T = 20 ◦ C BW and CA exhibited a reduction in the
minerals (calcite adsorption with the increase in salinity.
and clay) - Unlike CS-50, –COO− functional groups
in BW and CA have the potential to be
protonated in acidic solutions. Hence,
the cationic surfactant parts partially
overweigh the anionic parts, which
increases adsorption onto negatively
charged mineral surfaces.
Quartz sand S = 0, 20000, - In the presence of minerals, the value
Illite 35000 and 60000 of CMC increased as the salinity
Kaolinite ppm increased.
Montmorillonite T = 25 ◦ C - The minimum and maximum rates of
adsorption were observed in quartz sand
and kaolinite, respectively.
Berea sandstone T = 25 and 70 ◦ C - The titration method was used to
determine the surfactant adsorption
based on the surfactant concentration.
- Surfactant adsorption at 25 ◦ C was
0.9604 mg/g, and it decreased to 0.7491
mg/g at 70 ◦ C.
- Onset of higher translational kinetic
energy led to the reduction in surfactant
adsorption.

(continued on next page)

5.1.2. Internal olefin sulfonates
Internal olefin sulfonates (IOS) are a group of anionic surfac-
tants that are widely used in EOR due to their remarkable ability
to withstand harsh reservoir conditions of temperature and salin-
ity (i.e., monovalent ions). However, IOS surfactants (i.e., C15−18
IOS, C19−13 IOS, and C24−26 IOS) tend to precipitate when used
alone in the presence of divalent ions such as Ca2+ (Rattanaudom
et al., 2019). As reported by (Nourafkan et al., 2018), IOS surfac-
tants have several advantageous properties when used in EOR.
3161
These surfactants are twin-tailed, high resistant to temperature,
of high solubilization activity and of low cost.
Rudyk et al. (2019) studied the effect of salinity on the foama-
bility of 0.5% IOS (C14 –C17 ). At a temperature of 22 ◦ C, the volume
of foam generated in test tubes increased as the salinity increased
from 1% to 11% NaCl, with surfactant precipitation starting at
6% NaCl. At 60 ◦ C, however, foam generation was observed at a
salinity of up to 7% NaCl and the onset of surfactant precipitation
occurred at 8% NaCl salinity. To improve the effectiveness of
O. Massarweh and A.S. Abushaikha
Table 5 (continued).
Reference
Effect of salinity
Li et al. (2016)
Yekeen et al. (2017a)
Ahmadi et al. (2018)
Wei et al. (2020)
Abbas et al. (2020)
Effect of pH
Li and Ishiguro (2016)
Southwick et al. (2016)
Tagavifar et al. (2018)
Saxena et al. (2019)
EOR in liquid-rich shales, Teklu et al. (2018) investigated the
effect of IOS and salinity on oil recovery using the process of
spontaneous imbibition in Bakken cores. It was found that low-
salinity brine imbibition (20,000 ppm KCl) expels larger amount
of oil compared to high-salinity brine imbibition (240,000 ppm
KCl). Moreover, the addition of 1000 ppm IOS to the low-salinity
brine resulted in further increase in the amount of expelled oil.
Energy Reports 6 (2020) 3150–3178
Surfactant name and Type of adsorbent Experimental Main findings
type or solid surface conditions
Nonylphenyl Sandstone S = 5002 ppm - At 76.5 ◦ C, the adsorption of Sa and
ethoxylate T = 76.5 ◦ C Sc was ∼0 and 0.55 mg/g.
carboxylate surfactant - A mixture of both surfactants (Sa/c )
(Sa ) (anionic) exhibits adsorption values between
Quaternary those of Sa and Sc .
ammonium salt (Sc ) - Sa is an anionic surfactant. Therefore,
(cationic) it exhibits low adsorption on the
Surfactant mixture negatively charged sandstone rock even
(Sa/c ) at high temperature.
SDS (anionic) Kaolinite S = 0 ppm, 1000 - Surfactant adsorption was determined
ppm (CaCl2 ) and by measuring the surface tension.
10000 ppm (NaCl) - In the presence and absence of
T = 25.85, 49.85 electrolytes, surfactant adsorption
and 79.85 ◦ C decreased as the temperature increased.
Saponin (nonionic) Shale–sandstone T = 28, 40, 60 - The conductivity method was used to
surface and 75 ◦ C determine the surfactant adsorption
based on the surfactant concentration.
- At various surfactant concentrations,
surfactant adsorption decreased as the
temperature increased.
APG (nonionic) Sandstone T = 20, 50, 80 - The adsorption of 0.6 wt% APG at
and 115 ◦ C 20 ◦ C was 24.2 mg/g, and it decreased
to 21.6 mg/g at 115 ◦ C.
- The change in adsorption was slight
due to the stable hydrophilicity of the
surfactant despite temperature change.
Aerosol-OT (anionic) Quartz sand S = 35000 ppm − Surfactant adsorption decreased as
Illite T = 25, 45 and the temperature increased. This was
Kaolinite 85 ◦ C attributed to the exothermic nature of
Montmorillonite the adsorption process.
SDS (anionic) Porous SiO2 pH = 3 to 7 - SDS adsorption on SiO2 surface
powder gel decreased as the pH increased because
of the increased electrostatic repulsion.
- Further increase in electrostatic
repulsion prevented the detection of
SDS adsorption.
IOS 2024 (anionic) Sandstone pH = 8.24 to 9.57 − At a concentration of 3000 ppm of
IOS 2024, increasing the pH from 8.24
to 9.57 decreased surfactant adsorption
from 0.760 to 0.161 meq/100 gram of
rock.
IOS (anionic) Indiana limestone T = 24 and 78 ◦ C - The adsorption of two surfactant
TDA (anionic) pH = ∼7.6 to ∼12 mixtures was examined with the pH
GAC (anionic) adjusted using Na2 CO3 . The adsorption
decreased almost linearly as the pH
exceeded a value of 9.
- Experimental data did not clearly
exhibit the effect of temperature on
adsorption affinity unlike surface
complexation modeling.
Soap-nut surfactant Sandstone Alkali addition = - Surfactant adsorption decreased as the
(anionic) Carbonate 0, 1, 2 and 3% Na2 CO3 concentration increased.
Bentonite (Na2 CO3 ) - Na2 CO3 dissociates in water to form
H2 CO3 and OH− ions. This increases the
pH and the negativity of the surface
leading to more electrostatic repulsion
of anionic surfactants.
(continued on next page)
5.1.3. Alpha olefin sulfonates
Alpha olefin sulfonates (AOS) are a group of anionic surfactants
that exhibit high biodegradability and low toxicity. These sur-
factants are also distinguished by excellent wetting, dispersing,
foaming, emulsifying, and stabilizing abilities (Harutyunyan and
Harutyunyan, 2019). A general chemical formula of an AOS
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O. Massarweh and A.S. Abushaikha
Table 5 (continued).
Reference Surfactant name and Type of adsorbent
type or solid surface
Effect of salinity
Liu et al. (2019) Alcohol alkoxy sulfate Clay surface
(anionic)
Rezaei et al. (2020b) CAPB (zwitterionic) Dolomite
surfactant can be expressed as R–CH==CH–(CH2 )n –SO3 Na, where
R is C10 –C20 (Negin et al., 2017). AOS surfactants are typically pre-
pared by reacting sulfur trioxide (SO3 ) with linear alpha-olefins.
When the length of the hydrophobic chain of AOS surfactants
ranges between C12 –C18 , they show some excellent character-
istics. These include stability over a broad range of pH, high
resistance to water hardness and other metal ions, solubility in
cold water and excellent foaming (Abed et al., 2004).
In many cases, AOS surfactants were studied for EOR applica-
tions in combination with other materials such gases (e.g., CO2
and N2 ) and nanoparticles. For instance, Farajzadeh et al. (2010)
investigated the performance of an AOS surfactant (with C12
hydrophobic chain) by conducting core-flood experiments in
quartz-rich Bentheimer sandstone. In their experiments, CO2 was
injected in the presence and absence of AOS under miscibility
conditions. They found that AOS injection prior to CO2 injection
could improve the oil recovery by 40% of OOIP compared to 28%
achieved by the injection of CO2 only. On a reservoir scale, they
indicated that surfactant flooding forms foam in regions of low
oil saturation rather than in those of high oil saturation. This, in
turn, reduces CO2 mobility in regions of low oil saturation and
divert CO2 to regions of high oil saturation.
Chen et al. (2019a) studied the effect of clay NPs on foaming
properties of AOS (C14 –C16 ). They found that clay NPs increased
the bulk foam stability according to the concentration and hy-
drophobicity of the NPs. It was also found that the addition of
clay NPs to AOS foam enhanced its viscoelasticity modulus at
bulk and liquid film scales. Therefore, incorporating clay NPs with
AOS foam can be useful in chemical EOR applications. Rezaei
et al. (2020a) investigated the performance of AOS with and
without hydrophilic silica NPs. It was shown that AOS causes a
significant reduction in oil–water IFT. Further reduction in the
IFT was achieved with the addition of silica NPs. The optimum
concentration of the NPs was determined to be 0.1 wt%. It was
also shown that an aqueous solution of AOS and silica NPs had
the ability to alter the wettability and increase the oil recovery
by 2.5–8.6% of OOIP in carbonate rocks. Despite that, Rezaei et al.
(2020a) did not conduct wettability and EOR experiment using an
AOS solution in the absence of silica NPs.
5.1.4. Alkyl aryl sulfonates
Alkyl aryl sulfonates (AAS) are anionic surfactants, which are
the most common type of the sulfonate surfactants (Cn H(2n+1)
SO− +
3 X ). In sulfonate surfactants, the sulfur atom is connected
directly to the carbon atom in the alkyl group. Therefore, the
molecules of sulfonate surfactants tend to have high stability
against the hydrolysis reaction (Tadros, 2014). In 1930s, AAS
surfactants were introduced to the market as detergents. By 1945,
these surfactants became the main type of synthetic detergents
used for laundry applications. The early preparation of AAS was
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Experimental Main findings
conditions
T = 23 ± 0.1 ◦ C - The concentration of Na+ and Ca2+ in
pH = 6 to 11 the surfactant solution was raised by
the addition of NaCl and CaCl2 .
- In the presence of Na+ ions,
adsorption of alcohol alkoxy sulfate
decreased as pH increased. However, the
opposite was observed in the presence
of Ca2+ ions.
pH = 7.3 to 11.2 − The addition of 0.1 wt% Na2 CO3
increased the solution pH from 7.3 to
11.2. It also reduced CAPB adsorption
from 0.795 to 0.320 mg/g-rock.
based on reacting propylene tetramer with benzene to form a
group of alkyl aryl. Then, sulfonation of alkyl aryl was used
to produce AAS (Showell, 1997). Recently, AAS surfactants have
been frequently used in EOR processes (Machale et al., 2019a;
Tackie-Otoo et al., 2020). Generally, these anionic surfactants
are preferred to be used in sandstones and clays due to their
low adsorption onto their surfaces. They are also stable at high
temperatures and can be customized according to reservoir con-
ditions (Machale et al., 2019b). Furthermore, these surfactants are
suitable to be used with polymers, such as polyacrylamide, during
surfactant–polymer (SP) flooding (Han et al., 2019; Yan and Ding,
2019).
Luan et al. (2019) investigated the behavior of AAS surfac-
tants in terms of surface tension, micellization and adsorption
properties to screen them for EOR. The selected surfactants in-
cluded alkyl aryl disulfonate (ADS), raw naphthenic aryl sulfonate
(NAS) and alkyl aryl monosulfonate (AMS). It was shown that
the surface tension was significantly reduced by each of the
surfactants in their aqueous solution. The lowest surface tension
was attained by AMS at a value of 29.2 mN/m. The CMC varied
slightly between the surfactants and it was highest for AMS as
it had the shortest hydrophobic chain. The highest adsorption
capacity of the surfactants at air–water interface was for AMS at
all surfactant concentrations. Luan et al. (2019) also determined
the micelle aggregation number (N), which indicates the num-
ber of the molecules aggregated in a formed micelle at a given
concentration. They found that N increased as the surfactant
concentration increased, and it was highest for AMS. Core-flood
experiments demonstrated that the micelle size of AMS increased
from 100 nm to 1000 nm as crude oil exists in the produced
solution.
Suleimanov et al. (2011) studied the performance of sulfanole
(alkyl aryl sodium sulfonate) in the presence and absence of
nonferrous metal nanoparticles (NPs) of sizes ranging from 70 nm
to 150 nm. The NPs were used at a concentration of 0.001 wt%
in surfactant solution. It was found that the IFT was reduced
as the surfactant concentration increased. The presence of the
NPs in surfactant solution caused further reduction in the IFT.
EOR experiments showed that the surfactant solution was capable
of increasing oil recovery by 1.7–2.1% of OOIP, which was then
increased by 6.9–8.5% of OOIP using the NPs.
5.2. Cationic surfactants
The chemical structure of surfactants has a significant effect
on their ability to alter the wettability of carbonates such as
limestone rock (Hosseini et al., 2020; Pan et al., 2020). In general,
cationic surfactants have significantly larger potential to change
the wettability of carbonates compared with anionic surfactants.
The positively charged carbonate surfaces repulse the polar parts
O. Massarweh and A.S. Abushaikha
of the cationic surfactants. Accordingly, the nonpolar parts will
be oriented toward the rock surface. This in turn leaves the polar
parts in contact with water at the rock–fluid interface, which
results in a more water-wet conditions (Castro Dantas et al.,
2014). In the following parts, we present several types of cationic
surfactants that are mostly used in carbonates.
5.2.1. Cetyltrimethylammonium bromide (CTAB)
CTAB is a cationic surfactant that is also known as cetrimo-
nium bromide (Shahbazi et al., 2020) or hexadecyltrimethylam-
monium bromide (Anas et al., 2020). It has the molecular formula
of C19 H42 BrN (Qian et al., 2020). CTAB can be used effectively
to improve oil recovery in carbonate reservoirs (Daghlian Sofla
et al., 2016; Souraki et al., 2019). Mechanisms responsible for this
improvement of oil recovery include the ability of CTAB to (1)
reduce the oil–water IFT (Kumari et al., 2019); (2) generate foam
in porous media (Telmadarreie and Trivedi, 2016); and (3) modify
rock wettability toward more water-wet conditions (Derikvand
et al., 2020).
Nandwani et al. (2017) studied the performance of CTAB under
high salinity conditions. Their experiments showed that the sur-
face tension of aqueous solutions decreased due to the addition
of CTAB. However, the effect of CTAB was higher in brine (3 wt%
NaCl) compared to distilled water. In addition, the IFT between
brine (3 wt% NaCl) and oil decreased as the CTAB concentra-
tion increased. Core-flood experiments demonstrated that the
addition of CTAB resulted in an EOR of 32.1–54.8% of OOIP.
Kumari et al. (2019) investigated the effect of CTAB and SDS
on the IFT and oil recovery. A brine solution that had a salinity
of 3 wt% was used in the experiments. They reported that the
oil–water IFT was substantially reduced with the addition of the
surfactants. The impact of CTAB on the IFT was larger compared
to SDS. However, a mixture of CTAB and SDS caused the largest
reduction in the IFT. Kumari et al. (2019) also showed that oil
recovery could be increased using CTAB, SDS and their mixtures
by 18.3%, 14.6% and 24.0–39.2% of OOIP, respectively.
5.2.2. Dodecyltrimethylammonium bromide (DTAB)
DTAB, also denoted as C12 TAB, is a cationic surfactant that has
the molecular formula of C15 H34 BrN (Hosseini et al., 2020). In a
study conducted by Sharma and Mohanty (2013), spontaneous
imbibition tests were used to investigate the ability of DTAB
to improve oil recovery from limestone at a high temperature
(92 ◦ C). Using a formation brine of high salinity, oil recovery
reached up to 14.6% of OOIP. After brine imbibition, a solution
of 1 wt% DTAB could achieve oil recovery of 72% of OOIP. Such
increase in oil recovery indicated that DTAB possesses the capa-
bility to improve the wettability of carbonates, as demonstrated
by spontaneous imbibition tests.
Mohsenatabar Firozjaii et al. (2018) performed a study to
identify the effect of DTAB on wettability and oil recovery in
carbonates. First, they found the CMC to be 3 wt%, 4.4 wt%
and 4.8 wt% using the IFT, conductivity and pH techniques, re-
spectively. Next, the change in rock wettability was determined
using the static sessile drop technique at DTAB concentrations
of 1 wt% to 10 wt%. The measurements indicated that DTAB had
the ability to alter rock wettability to more water-wet conditions.
Furthermore, EOR experiments showed that surfactant flooding
(4 wt% DTAB) achieved additional 19% oil recovery above that of
waterflooding.
In a study conducted by Karimi et al. (2016), the effect of DTAB
on oil recovery from limestone was investigated by conducting
spontaneous imbibition tests. Using a formation brine with a
salinity of 196,014 ppm, oil recovery was 8% of OOIP. After that,
a formation brine containing 0.5 wt% DTAB raised oil recovery
to about 55.9% of OOIP. Moreover, the use of 100 times diluted
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Energy Reports 6 (2020) 3150–3178
formation brine in the presence of 0.5 wt% DTAB achieved higher
levels of oil recovery. According to Karimi et al. (2016), three
factors could influence limestone wettability to different extents.
These include brine dilution, the use of the cationic surfactant
DTAB and the presence of sulfate and magnesium ions.
5.2.3. Alkyltrimethylammonium chlorides
This group of surfactants can be expressed as Cn H(2n+1) N+
(CH3 )3 Cl− . In a study conducted by Chen et al. (2014), the ad-
sorption performance of three cationic surfactant onto limestone
powder was investigated. The studied surfactants include dode-
cyltrimethylammonium chloride (DTAC), tetradecyltrimethylam-
monium chloride (TTAC) and octadecyltrimethylammonium chlo-
ride (OTAC). A broad range of salinities reaching up to 223802.8
ppm was used during the adsorption measurement. Results
showed that surfactant adsorption increased due to the increase
in salinity. Adsorption of DTAC was the lowest and it was rela-
tively close to that of TTAC. However, adsorption of OTAC was
substantially higher than that of the two surfactants. Chen et al.
(2014) attributed the high adsorption of OTAC to its stronger
hydrophobic force resulted from its long hydrophobic chain.
Therefore, it is easier for OTAC to leave the water phase and
adsorb onto limestone.
5.3. Nonionic surfactants
Nonionic surfactants show hydrophilic behavior due to the
presence of polymerized glycol ether or glucose units in their
structure (Nollet, 2005). These surfactants typically contain a
polar head, such as glucose in alkyl polyglucosides, and a linear or
branched alkyl tail. To synthesize nonionic surfactants, ethylene
oxide or propylene oxide are usually added to compounds such
as fatty acids, alkylphenols, fatty acid amides, fatty amines or
fatty alcohols (Castro et al., 2014). Nonionic surfactants are em-
ployed in a wide range of applications such pesticides, medicine,
food industry (Xia et al., 2020), detergents (Cheng et al., 2020)
and EOR processes (Bustamante-Rendón et al., 2020; Moham-
madshahi et al., 2020). There are different types of nonionic
surfactants; however, they are commonly classified as shown in
Fig. 11.
Triton X-100 (TX-100) is a nonionic surfactant that belongs
to the alkylphenol ethoxylates (APEOs) (Farsang et al., 2019). On
the other hand, Tergitol 1-s-7 (Tg7) and Tergitol 15-s-9 (Tg9)
belong to a class of nonionic surfactants called secondary alco-
hol ethoxylates (Yıldız and Demir, 2019). These surfactants have
been widely used in EOR applications. In a study conducted by
Sarmah et al. (2020), the performance of Tg7, Tg9 and TX-100
was investigated in terms of surface tension, IFT and oil recovery.
The three surfactants were able to reduce the surface tension
of the solution. However, Tg7 and Tg9 induced higher impact
on the surface tensions compared to TX-100. At their CMC, the
surface tension was 27.8, 29.0 and 41.0 mN/m in the presence of
Tg7, Tg9 and TX-100, respectively. When different blends of the
surfactants were used (at the CMC), the resulted surface tension
was in the range of 27.5 to 29.2 mN/m. Regarding the crude
oil–water IFT, a blend of Tg7 and TX-100 achieved the lowest
IFT. Sarmah et al. (2020) also performed core flood experiments
using Tg7, TX-100 and their blend. They found that additional oil
recovery of 21.0% to 25.7% of OOIP was achieved.
Bera et al. (2017) investigated the EOR performance of three
Tergitol surfactants including Tg7, Tg9 and Tergitol 1-S-12 (Tg12),
which are ethoxylated nonionic surfactants. First, they found
that Tg12 provides the highest foamability and foam stability
in solutions of different salinities (distilled water, 2 wt% and
4 wt% NaCl and synthetic seawater). Moreover, Tg12 exhibited
the largest micelle sizes, which was attributed to its longest
O. Massarweh and A.S. Abushaikha
Fig. 11. Basic classification of nonionic surfactants (Nollet, 2005).
chains of ethylene oxide (EO). Bera et al. (2017) also reported
that additional oil recovery from sand packs was 22.1%, 24.6%
and 26.9% of OOIP, which was achieved by Tg7, Tg9 and Tg12,
respectively.
Hosseini (2019) investigated the effect of TX-100 on rock
wettability in the presence of asphaltene deposition. Sandstone
wettability was determined by measuring the contact angle (θ )
of an oil drop using the sessile drop technique. First, the rock
exhibited water-wet properties (θ = 21◦ ). However, asphaltene
precipitation changed rock wettability into oil-wet state (θ =
112◦ ). TX-100 was used to prevent this unfavorable change in
wettability. As a result, the contact angle (θ ) of the oil drop was
reduced from 112◦ to 34◦ , indicating that the water-wet state
was restored. Hou et al. (2018) compared the effects of TX-100,
CTAB (cationic surfactant) and their mixture on surface tension
and quartz wettability. The results showed that TX-100 and the
surfactant mixture achieved higher reduction in surface tension
compared to CTAB. It was also shown that both surfactants could
change quartz wettability toward water-wet conditions to differ-
ent extents. However, the surfactant mixture presented a higher
impact on wettability.
Alkyl polyglucosides (APGs), shown previously in Fig. 11, are
nonionic biosurfactants (do Vale et al., 2020; Li et al., 2020b)
that can be produced from natural sources such as vegetable
oil, sugar and starch. APGs readily biodegrade in aerobic envi-
ronments. Therefore, they tend to impose a low environmental
burden compared to other surfactants (Ríos et al., 2016). Wei et al.
(2020) studied the potential for APG surfactant to be used for EOR
applications in sandstone at high salinity and temperature. The
used APG was basically synthesized from glucose (C6 H12 O6 ) and
lauryl alcohol (C12 H26 O). The results showed that APG could sig-
nificantly reduce the surface tension at 90 ◦ C. It was also shown
that static APG adsorption decreased slightly as the temperature
increased from 20 to 50, 80 and 115 ◦ C. In terms of the salinity
effect, static APG adsorption increased due to the addition of salts
at different concentrations. However, the impact of salinity was
lower when investigated using dynamic adsorption tests in sand
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Energy Reports 6 (2020) 3150–3178
packs. Wei et al. (2020) also reported that APG substantially influ-
enced the contact angle and oil–water IFT even at concentrations
close to 0.01 wt%. Therefore, APG surfactant can be possibly used
in EOR projects.
APG (lauryl glucoside) was also considered by do Vale et al.
(2020) for chemical EOR. They reported that the surface tension
of the surfactant solution decreased as the APG concentration
increased. They also reported that APG flooding at a concentration
of 2% could effectively increase oil recovery by 52.1% of OOIP
after waterflooding. Experiments conducted by Li et al. (2019)
demonstrated that APG has outstanding emulsification and in-
terfacial activity properties. Moreover, core-flood experiments
showed that APG could increase heavy oil recovery by 10.1% of
OOIP at a salinity of 30 g/L under 90 ◦ C.
5.4. Zwitterionic surfactants
Zwitterionic surfactants are surface active compounds that
comprise both positive and negative charge centers located at
the headgroup and separated by a short methylene segment
(Gerola et al., 2017b,a). The structure of a zwitterionic surfactant
molecule is shown in Fig. 12. Zwitterionic surfactants contain long
hydrophobic chains that are usually connected to the positive
charge center. The adsorption and micellization characteristics of
zwitterionic surfactants rely on specifics of their structure. These
include, for instance, the nature of the headgroup, the length of
the inter-charge spacer (n) and the length of the hydrophobic
alkyl tail (m). For example, as the value of m increases, micel-
lization becomes more favored. However, it reaches a maximum
at n equals 3 or 4 denoting the number of methylene groups in
the inter-charge spacer (Gerola et al., 2017a).
The positive charge in zwitterionic surfactants results from
cationic moieties such as amines or quaternary ammonium
groups. On the other hand, the negative charge occurs due to the
presence of anionic moieties such as sulfonic acid, carboxylic acid
and esters of phosphoric and sulfuric acids (Kwaśniewska et al.,
2020; Zhang et al., 2019b; Zhao et al., 2015). Recently, research
O. Massarweh and A.S. Abushaikha
Fig. 12. Structure of a zwitterionic surfactant molecule.
Source: Modified from Gerola et al. (2017b).
has shown that zwitterionic surfactants can be incorporated in
chemical EOR. These surfactants have high water solubility, no-
table interfacial effects, high foam stability and good resistance to
elevated temperature and salinity (Kamal et al., 2019; Zhao et al.,
2015).
There are several types of zwitterionic surfactants that were
shown to be promising for chemical EOR applications. For ex-
ample, Da et al. (2018) reported that a surfactant called cetyl
betaine could significantly reduce the IFT between CO2 and brine
of high salinity. In addition, they reported that cetyl betaine could
stabilize CO2 -in-water (C/W) foam in carbonates. The C/W foam
was found to be stable at temperatures reaching up to 150 ◦ C
and under high salinity conditions. Their results indicated that
cetyl betaine can be a suitable zwitterionic surfactant to be used
for CO2 mobility control under elevated temperature and salinity.
Chen et al. (2019b) synthesized a zwitterionic surfactant called
SPODP through modification of oleic acids. By investigating its
effect on the crude oil–water IFT, SPODP was found to have
remarkable interfacial properties at high temperature and salinity
conditions without alkali addition.
Kamal et al. (2019) investigated thermal and foaming char-
acteristics of betaine-based polyoxyethylene surfactants. The in-
vestigated surfactants were denoted as OPAC, OPAH and OPAS
and they contained carboxybetaine-, hydroxysulfobetaine- and
sulfobetaine-headgroups, respectively. It was found that the three
zwitterionic surfactants were thermally stable over 3 months of
exposure to a temperature of 90 ◦ C. Regarding the foamability,
the three surfactants exhibited a comparable foaming behavior in
synthetic seawater (SW) and in deionized water (DW), regardless
of the headgroup type. However, foam height was lower using
DW compared with SW. Lastly, Kamal et al. (2019) recommended
that the effect of these surfactants be investigated using core-
flood experiments. Hussain et al. (2019) reported that OPAC,
OPAH and OPAS have high solubility in DW, SW and formation
water (FW). They also reported that the surfactants could tolerate
high temperature (90 ◦ C) in DW, SW and FW without observing
phase separation or precipitation.
C16DmCB is a zwitterionic surfactant that is based on car-
boxybetaine. Kumar et al. (2019) studied the performance of
C16DmCB using wettability measurement and core flooding tests.
Different brines were prepared in the presence of C16DmCB (0
to 0.020 wt%) and alkali (0 to 2 wt%). The results demonstrated
that C16DmCB could alter the wettability of a quartz surface
from oil wet to water wet. Furthermore, the addition of alkali
to the surfactant solution induced larger effect on the wetta-
bility. Regarding core-flood tests, surfactant flooding increased
the pressure difference across sandstone cores, and it also in-
creased oil recovery by 20.0% of OOIP. However, incorporating
alkali with surfactant flooding increased oil recovery by 26.8% of
OOIP. This occurred due to the increased viscosity of the injected
solution. Kumar and Mandal (2019) investigated the adsorption
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behavior of C16DmCB and its effects on rock wettability and
spontaneous imbibition. The results showed that C16DmCB ad-
sorption was higher in carbonates compared with sandstones.
In addition, C16DmCB adsorption increased due to the increase
in salinity and alkalinity in both types of rocks. In terms of
rock wettability, it was altered by C16DmCB toward more water
wet. However, wettability alteration occurred faster in sandstones
than in carbonates. Finally, spontaneous imbibition experiments
demonstrated that the addition of C16DmCB increased oil recov-
ery by 3.1% and 18.9% of OOIP in carbonates and sandstones,
respectively.
5.5. Surfactant screening criteria
Surfactant screening studies aim to identify efficient surfac-
tant formulations that are stable under normal and harsh reser-
voir conditions. Furthermore, these studies may predict technical
problems and provide solutions to these problems before they are
encountered during field application. In order to be a good candi-
date for chemical EOR, a surfactant should exhibit the following
properties: (1) tolerance to reservoir salinity/hardness; (2) ther-
mal stability at reservoir temperature; (3) capability of reducing
the IFT to ∼0.01–0.001 dynes/cm under reservoir conditions; (4)
effectiveness at low concentrations (0.1–0.3%); (5) low adsorp-
tion onto reservoir rock (< 1 mg/g rock); (6) compatibility with
other additives (alkalis, polymers, NPs, etc.) to be incorporated in
EOR; and (7) commercial availability at reasonable cost (Al-Amodi
et al., 2016; Foo et al., 2016; Han et al., 2013; Khalilinezhad et al.,
2018).
Based on the previous criteria, surfactant screening can be
performed. First, the compatibility of the candidate surfactants
with polymers and other additives, if any, should be examined
at reservoir conditions. Next, phase behavior tests are conducted
under reservoir temperature and salinity to evaluate the long-
term stability of the compatible surfactants. Common examples
of these tests include aqueous stability and salinity scans. At this
stage, surfactant formulations exhibiting the characteristics of a
Winsor Type III microemulsion are selected. Following that, the
effect of the selected surfactants on the IFT between crude oil
and brine is evaluated. Next, surfactant adsorption onto reservoir
rock is measured. Finally, core-flood experiments are conducted
under reservoir conditions using the surfactant formulations that
showed acceptable thermal stability, salt tolerance, ultra-low IFT
and low adsorption. Based on oil recovery and other laboratory
results and by considering the cost of the surfactants, a decision
can be made regarding pilot tests and field application.
5.6. Field-scale application of surfactant-assisted chemical EOR
The number of studies reporting on the EOR performance of
surfactants in the field is very limited compared to the labora-
tory studies. As shown in Table 6, there are different types of
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

Table 6
Field cases of surfactant-assisted chemical EOR.
Field name Location Formation Formation properties Oil properties Surfactants Other chemicals Performance References
type
Daqing China Sandstone k = 670 mD ρo = 0.864 g/cm 3
ABS (0.1–0.3%) HPAM polymer An incremental oil Sun et al. (2020)
Oilfield P = 858.6 psi µo = 8.2 − 9.3 cp (1300–2000 mg/L) recovery of 30% was
(B-1-D T = 42.4 ◦ C NaOH (0.8–1.2%) achieved using
Block) S = 5611 ppm alkaline-surfactant–
polymer
(ASP).
East Texas-USA Carbonate k = 3 mD Oil gravity = 31 ◦ API Linear ethoxylated CO2 Surfactant solution Alcorn et al. (2020)
Seminole P = 3400 psig alcohol (C12−14 EO22 ) reduced CO2
Field (San T = 40 ◦ C (0.5 wt%) injectivity by 70%
Andres S = 70,000 ppm indicating an
Formation) increased control of
CO2 mobility.
– Colombia Sandstone P = 1350.3 psi Oil gravity = 19 ◦ API Anionic surfactants SiO2 NPs (100 mg/L) An incremental oil Franco et al. (2020)
T = 50 ◦ C (350–1000 mg/L) Salts (27,137 ppm) recovery of 30,035
bbls was achieved
from two pilot wells
after around 5
months.
West West Sandstone k = 10–250 md ρo = 0.87 g/cm3 IOS 24–28 (0.5 wt%) FLOPAAM 3230 An incremental oil Volokitin et al. (2018)
Salym Siberia– T = 83 ◦ C µo = 2 cp IOS 15–18 (0.2 wt%) polymer (0.25 wt%) recovery of 16% was
Field Russia S = 14,000–16,000 Na2 CO3 (0.8–2.0 wt%) achieved from ASP
ppm C4 H10 O (2.0 wt%) pilot.
Dagang China Sandstone Average µo = 67 cp Petroleum sulfonate Associative polymer Field-pilot results Guo et al. (2018)
Oilfield kg = 161×10−3 pm2 surfactant PS-985 AP-P7 (2000 mg/L) showed that oil
(Guan-109 T = 78 ◦ C (0.3 wt%) production increased
Reservoir) S = 26,983 ppm from 27.7 to 51.7
m3 /d using
surfactant–polymer
(SP) flooding.
Tanjung Indonesia Sandstone k = 10–100 md Oil gravity = 40 ◦ API Anionic surfactant – Surfactant flooding Aslam et al. (2017)
Field (Zone T = 60–63 ◦ C µo = 1.14 cp A127 (2.05%) caused a noticeable
A) S = 3800 ppm increase in oil
recovery.
Reservoir Oklahoma- Sandstone k = 0.8–300 md Oil gravity = 40 ◦ API SATa (0.084%) as a CPXG biopolymer SP flooding achieved Hsu et al. (2012)
SF USA Average k = 74 md µo = 4 cp primary surfactant (1800 ppm) an incremental oil
T = 42 ◦ C SST (0.105%) and SC01 recovery of 19%, as
S = 165,000 ppm (0.042%) as shown by Single-well
co-surfactants field test.
Semoga Indonesia Carbonate k = 3.79–14.9 md µo = 0.98 − 1.28 cp Nonionic surfactants – Water cut decreased Rilian et al. (2010)
Field P = 845–895 psi by 8% and the and Syaifudin (2002)
(Baturaja 3-month oil recovery
Formation) increased by 5800
bbls.
Daqing China Sandstone k = 18.5×10−3 µm2 – Nonionic alkanol acid Auxiliary agent The oil recovery Yin and Pu (2008)
Oilfield amide increased by 30% for
(Chao 522 Surfactant (1.0%) single well.
Block)
Cotton- Wyoming- Carbonate kg = 0.2 − 130 md Oil gravity = 30 ◦ API Polyoxyethylene – Surfactant-soak Weiss et al. (2006)
wood USA (based on cores) µo = 24.3 cp alcohol (1500 ppm) treatments of 23 and Xie et al. (2005)
Creek Field T = 60 ◦ C wells failed in 70% of
S = 30,755 ppm the treated wells.
Northern China Sandstone k = 577 md ρo = 0.86 g/cm3 ABS (0.1–0.15%) as a HPAM polymer The total ASP pilot Daoshan et al. (2004)
part of T = 45 ◦ C µo = 9–10 cp primary surfactant (800–1800 mg/L) recovery was 16.6% of
Daqing S = 4456 ppm RH biosurfactant NaOH (1.2%) OOIP, with a
Oilfield (0.2%) as a sacrificial significantly reduced
agent cost.
Cambridge Wyoming- Eolian k = 845 md Oil gravity = 20 ◦ API Petrostep B-100 Na2 CO3 (1.25 wt%) The incremental oil Vargo et al. (1999)
Minnelusa USA sandstone P = 1792 psi µo = 31 cp surfactant (0.1 wt%) Alcoflood 1275A recovery achieved
Reservoir with T = 55.6 ◦ C polymer (1450 mg/L) using ASP flooding
dolomite was estimated by
and 26.8% of OOIP.
anhydrite
cement

a
SAT, SST and SC01 are sodium sulfosuccinate, sodium alkyl ethoxylate sulfate and branched sodium diphenyl oxide disulfonate, respectively. RH is a rhamnolipid-fermentation-liquor biosurfactant.

surfactants that have been employed in chemical EOR projects.
Most of these surfactants were applied in sandstone formations
with a limited application in carbonates. Unlike laboratory-scale
studies, field-scale studies show that surfactants are mainly used
in the presence of other additives. The majority of these additives
are alkalis (e.g., NaOH and Na2 CO3 ) and polymers (e.g., HPAM
and AP-P7). Alkalis are usually incorporated to increase the pH,
hence reducing surfactant adsorption on reservoir rock. They also
contribute to additional IFT reduction by in situ generation of
surfactants. On the other hand, polymers are added to provide
further mobility control.
Fig. 13 compares the incremental oil recovery obtained using
surfactants at field and laboratory scales, it also provides details
of incremental oil recovery provided by each type of surfactant at
laboratory scale. According to Fig. 13, surfactants could achieve
an incremental oil recovery of ∼16%–30% of OOIP in the field,
which incorporated additives such as alkalis and polymers. On the
other hand, incremental oil recovery obtained at laboratory scale
extended over a wide range of ∼1.7% to 54.0% of OOIP, with most
values ranging between 7.2% and 26.0%. However, incremental oil
3167
recovery at laboratory scale was obtained using surfactants only,
unlike that obtained in the field. Therefore, it can be concluded
that the laboratory studies (i.e., core-flood experiments) do not
accurately predict the performance of surfactants in the field.
This may occur because the conditions for core-flood experi-
ments are more controlled compared to the conditions of the
field tests. Furthermore, these experiments are usually conducted
using carefully selected core samples, which are frequently ob-
tained from outcrops that vary from reservoir rock. Therefore,
the 1-D displacement inside these cores is different from the
displacement in oil reservoirs. In many cases, these reservoirs are
highly heterogeneous, and contain complex systems of fractures,
vugs, faults, etc., which may adversely affect the sweep efficiency.
Despite its ability to increase oil recovery, surfactant flooding
has some limitations and challenges that require further research.
First, surfactant screening is a high resource-consuming process.
It is usually necessary to examine several types of surfactants
to identify the optimal formulations for specific reservoir con-
ditions. Second, surfactant adsorption onto reservoir rock can
be only minimized, which imposes additional material costs to
O. Massarweh and A.S. Abushaikha
Fig. 13. Incremental oil recovery obtained by employing surfactants at field and laboratory scales.
Fig. 14. Possible stabilization mechanisms of a liquid film by: (a) monolayer of bridging particles, (b) bilayer of closed-packed particles, and (c) network of particle
aggregates inside the film.
Source: Reproduced from Horozov (2008).
EOR projects. Third, the produced oil can be part of an emulsion,
thereby increasing the difficulty of oil–water separation. Fourth,
field experience with surfactant flooding shows that they need to
be incorporated with alkalis and/or polymers in order to obtain
significant oil recovery. This means that more costly chemicals
are required to be transported to remote locations (e.g., off-
shore production facilities) where the storage capacity is usually
limited. In addition, the presence of such chemicals in the pro-
duced fluids requires more processing and disposal operations.
Finally, several types of surfactants do not tolerate high salinity;
therefore, seawater cannot be used with these surfactants.
5.7. Application of nanoparticles in surfactant flooding
Nanoparticles (NPs) are usually defined as particulate sub-
stances with sizes or dimensions ranging between 1 nm and
100 nm (Auffan et al., 2009; Boverhof et al., 2015). Recently, NPs
have gained prominence in petroleum research. Several studies
have reported the use of clay, silica/fumed silica, aluminum ox-
ide, zinc oxide and titanium oxide NPs to change the interfacial
properties of fluids and rocks aiming for improved oil recov-
ery (Cheraghian, 2017, 2016b; Cheraghian and Tardasti, 2012;
3168
Energy Reports 6 (2020) 3150–3178
Gbadamosi et al., 2019a; Rezk and Allam, 2019; Sharma et al.,
2016; Zargar et al., 2020). Research showed that NPs improve the
performance of EOR through multiple mechanisms, which mainly
include: (1) wettability alteration; (2) application of disjoining
pressure between oil droplets and rock surfaces; (3) pore channel
plugging; (4) IFT reduction between crude oil and the injected
fluids; and (5) inhibition of asphaltene precipitation (Cheraghian
and Hendraningrat, 2016; Hemmat Esfe and Esfandeh, 2020; Rez-
vani et al., 2018; Rosestolato et al., 2019; Yousefvand and Jafari,
2018; Zhang et al., 2014). In addition, NPs can be utilized to
reduce the viscosity of heavy and semi-heavy crude oil depending
on the type, size and concentration of the NPs (Cheraghian et al.,
2020) as well as the temperature of the bulk fluid containing
crude oil, brine, NPs, etc. (Patel et al., 2018).
Beside the previous effects, NPs provide some additional ad-
vantages when incorporated in surfactant-assisted EOR. In gen-
eral, experiments demonstrated that nanoparticle–surfactant
flooding improves oil recovery by ∼4%–11% of OOIP above that
obtained by surfactant flooding (Betancur et al., 2020; Li et al.,
2020c; Liu et al., 2020b; Wu et al., 2017; Zhong et al., 2020). In
a study conducted by Cheraghian (2016a), it was found that the
addition of TiO2 NPs (2.4 wt%) to a surfactant solution (SDS, 1800
O. Massarweh and A.S. Abushaikha Energy Reports 6 (2020) 3150–3178

Table 7
Current research trends on the use of surfactants in chemical EOR.
Reference
Ge et al. (2021)
Han et al. (2020)
Kurnia et al. (2020)
Franco et al. (2020)
Xu et al. (2020)
Omidi et al. (2020)
Chaturvedi and Sharma (2021)
Alsmaeil et al. (2020)
Ojo et al. (2020)
Romero-Zerón et al. (2020)
Chen and Schechter (2020)
Dashtaki et al. (2020)
do Vale et al. (2020)
Khayati et al. (2020)
Eslahati et al. (2020)
Surfactants used Focus of study Remarks
POAPMB (zwitterionic) Development of a proper An SP system was developed to
surfactant–polymer (SP) system for increase oil recovery by ∼15% of
EOR applications without alkali to OOIP under high-salinity conditions
alleviate scale formation
AOS (anionic) Development of a proper SP system Different SP systems increased oil
APS (anionic) for EOR applications without alkali to recovery by 24.5–34.8% of OOIP
ABS (anionic) alleviate scale formation
CAHS (zwitterionic)
APS (anionic) Identification of proper mixtures of Anionic–zwitterionic surfactant
ABS (anionic) anionic and zwitterionic surfactants solutions reduced the IFT below
AAS (anionic) for EOR applications without alkali to 0.001 dynes/cm unlike singular
AES (anionic) alleviate scale formation surfactant solutions
ADAO (zwitterionic)
CAHS (zwitterionic)
Commercial anionic Incorporating nanoparticles in Silica NPs (100 mg/L) improved the
surfactants surfactant flooding for improved EOR EOR performance of surfactant
performance flooding by 5% OOIP
SDS (anionic) Incorporating nanoparticles in Silica NPs (1 wt%) improved the EOR
Aerosol-OT (anionic) surfactant flooding for improved EOR performance of methane-surfactant
LAPE (nonionic) performance foam by 30% OOIP
Betaine-based surfactant
(zwitterionic)
CTAB (cationic) Incorporating nanoparticles in CTAB solution (1000 ppm) and
TR-880 (zwitterionic) surfactant flooding for improved EOR nanofluid prepared from
performance Fe3 O4 /eggshell (500 ppm) increased
oil recovery by 8.16% OOIP
SDS (anionic) Stabilization of nanofluids using Certain SDS concentrations can
surfactant for EOR applications prevent salt-induced NP
agglomeration depending on solution
salinity
CTAB (cationic) Development of nano-capsules for Only 46% of CTAB was released after
controlled surfactant release during 12 days of exposure to a saline brine
EOR (56,000 mg/L salts)
Alkyl betaine surfactant Encapsulation of surfactant with Surfactant encapsulation increased oil
(zwitterionic) halloysite nanotubes for controlled recovery of surfactant flooding by
surfactant release during EOR 17%–26% of OOIP
SDS (anionic) Molecular encapsulation of surfactant Surfactant encapsulation reduced
with β -cyclodextrin (β -CD) for dynamic surfactant adsorption onto
controlled surfactant release during sand–kaolin surfaces by 43.3%
EOR
ADAC (cationic) Investigation of the effect of Compared to ionic surfactants,
ATAC (cationic) surfactant molecular structure on nonionic surfactants provide higher
APS (anionic) rock wettability wettability alternation depending on
IOS (anionic) the tail length and EO number
AES (nonionic)
CAPB (zwitterionic)
Vitagnus plant extract Development of natural surfactant for Vitagnus surfactant solution (3000
EOR applications ppm) achieved a tertiary recovery of
10.6% OOIP
APG (nonionic) Utilization of biosurfactant in EOR APG solution (2%) achieved a tertiary
applications recovery of 52.1% OOIP
Saponin (nonionic) Utilization of natural surfactant in Saponin solution (5 g/L) achieved a
EOR applications tertiary recovery of 6.2–8.4% OOIP
Saponin (nonionic) Utilization of natural surfactant in Saponin solution (4 wt%) increased
EOR applications the total recovery using spontaneous
imbibition by 19.2%

ppm) improves oil recovery by 4.85% above that obtained using
solutions containing SDS alone. Flooding experiments in a glass
micromodel showed that TiO2 NPs provides more uniform flow
patterns as well as a more stable front when compared to flooding
in the absence of the NPs. Such results indicate that TiO2 NPs have
the ability to improve the rheological properties of the injected
fluids during EOR processes.
NPs can be used to stabilize foams such as those containing
CO2 and N2 , which are generated using surfactants for EOR pur-
poses. Horozov (2008) reported a mechanism through which NPs
stabilize emulsion droplets and foam bubbles in the presence of
3169
surfactants. This mechanism involves the arrangement of parti-
cles during foam film drainage. As depicted in Fig. 14, stabilization
of a liquid film occurs according to three cases: (1) formation of
a monolayer of bridging particles; (2) formation of a bilayer of
close-packed particles; and (3) formation of a network of particle
aggregates inside the film, which all hinder foam drainage and
coalescence (Horozov, 2008). In addition to foam stabilization,
some types of NPs have the ability to reduce surfactant adsorp-
tion onto reservoir rock, thus increasing the availability of the
surfactant for the process of oil recovery. Several types of NPs
were identified to induce such a positive effect. These include,
for example, clay, silica and aluminum oxide NPs (Cheraghian and
O. Massarweh and A.S. Abushaikha
Nezhad, 2016; Wu et al., 2017; Yekeen et al., 2017b). Regarding
the mechanism of adsorption reduction, a frequently reported
mechanism is the competitive adsorption. In this mechanism, the
surfactant molecules and the NPs compete on the adsorption sites
existing on the rock surface, thereby decreasing the adsorption
area available for the surfactant molecules (Venancio et al., 2020;
Wu et al., 2017; Zargartalebi et al., 2014).
6. Summary and future prospects
In this paper, we provided a review on the use of surfactants
in chemical EOR. First, we presented a background on surfactants,
which mainly discussed surfactant characterization and phase
behavior. Second, we presented the role of surfactants in the pro-
cess of oil recovery. Third, we discussed the process of surfactant
adsorption onto reservoir rock during surfactant flooding. Fourth,
we reviewed the different types of surfactants that have been
used in chemical EOR in addition to the experimental and field
application of surfactant flooding.
In most oil reservoirs, more than 50% of OOIP remains trapped
in the reservoir rock after the primary and secondary phases
of oil recovery. Researchers have investigated surfactant flood-
ing as a method that has the potential to recover additional
quantities of oil in the tertiary phase. They showed that there
are several mechanisms through which surfactants improve oil
recovery. These mechanisms mainly include IFT reduction, wetta-
bility alteration, foam generation and emulsification. Based on the
reviewed experimental studies, incremental oil recovery obtained
using surfactants usually ranges between 7% and 26% of OOIP,
with several cases exceeding 50% of OOIP. On the other hand, field
application of surfactants showed that surfactants can achieve
incremental oil recovery of ∼16%–30% of OOIP. However, this
increase in oil recovery could be obtained only with the assistance
of substances such as alkalis and polymers.
Surfactant flooding is usually challenged by problems that are
aggravated by harsh reservoir conditions. These problems mainly
include surfactant adsorption and instability under high (or nor-
mal) values of temperature and salinity. As a result, researchers
proposed criteria to be applied during surfactant screening for
certain reservoir conditions and rock type. Based on that, it is
recommended that surfactant adsorption not to exceed 1 mg/g
rock. Furthermore, the surfactant under evaluation should pos-
sess the capability to reduce the oil–water IFT to ∼0.01–0.001
dynes/cm. In addition, the surfactant should be effective at low
concentration ranging between 0.1% and 0.3%. Otherwise, exceed-
ing the concentration limit may affect the economic viability of
surfactant flooding.
Table 7 provides current research trends according to recently
published studies in the field of surfactant-based EOR. According
to Table 7, future research regarding the application of surfactants
for chemical EOR can be grouped around five research areas: (1)
development of surfactant or surfactant–polymer mixtures that
can be employed in chemical EOR without using alkalis; there-
fore, alleviating the problem of scale build-up; (2) incorporating
nanoparticles that can improve the performance of surfactant
flooding; (3) development of surfactant encapsulation techniques
to control surfactant release during the process of EOR; (4) in-
vestigation of the effect of surfactant molecular structure on
rock wettability and oil recovery; and (5) development of nat-
ural surfactants/biosurfactants to reduce the environmental costs
associated with EOR processes. Generally, experimental research
on the use of surfactants to improve the efficiency of EOR in
forthcoming years is expected to revolve around the previously
mentioned fields of study.
3170
Energy Reports 6 (2020) 3150–3178
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
We acknowledge Qatar National Library (QNL) for funding
the open access publication of this article. We also acknowledge
the support for this publication provided by the National Prior-
ities Research Program grant NPRP11S-1210-170079 from Qatar
National Research Fund.
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