Journal of Petroleum Science and Engineering 220 (2023) 111243

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

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

Manifestations of surfactant-polymer flooding for successful field

applications in carbonates under harsh conditions: A comprehensive review
Anas M. Hassan a, *, Emad W. Al-Shalabi a, Waleed Alameri a, Muhammad Shahzad Kamal b,
Shirish Patil b, Syed Muhammad Shakil Hussain b
a
Petroleum Engineering Department, Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates
b
College of Petroleum Engineering and Geosciences, King Fahad University of Petroleum and Minerals, Dhahran, Saudi Arabia

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

Keywords: Most oil fields today are mature, and the majority of the reservoirs in the Middle East are carbonate rocks
Enhanced Oil Recovery (EOR) characterized by high temperature high salinity (HTHS), heterogeneous mineral composition, and natural
Chemical Enhanced Oil Recovery (cEOR) fractures. Enhanced oil recovery (EOR) methods are used for boosting oil recovery from the aged reservoirs
Surfactant-Polymer (SP) Flooding
beyond primary and secondary recovery stages. Nevertheless, it can be a challenging task to employ EOR
High-temperature and High -Salinity (HTHS)
techniques in these aged carbonate reservoirs. This is because carbonate reservoirs have mixed-to-oil-wet
carbonate reservoirs
wettability with temperatures exceeding 85 ◦ C and salinity of over 100,000 ppm, which renders secondary
EOR-methods such as waterflooding ineffective. Therefore, even though carbonate reservoirs contain 60–65% of
world’s remaining oil, with immense intrinsic economic prospects, the oil recovery process from carbonate
reservoirs remains a considerable challenge. Chemical-EOR (cEOR) techniques, like SP based cEOR, have shown
marked promise in improved oil recovery, mainly from clastic reservoirs with medium temperature and salinity,
unlike carbonate reservoirs. During SP-floodings, the surfactants get adsorbed due to the mineral composition of
the carbonate rocks, and polymer degradation occurs due to HTHS conditions. Consequently, new surfactants
and polymers have been structurally conformed and tested to improve their robustness and related recovery
efficacy. For instance, Guerbet alkoxy-carboxylate surfactants demonstrated good stability at temperatures over
100 ◦ C and salinities up-to 275,000 ppm, yielding tertiary recovery of 94.5% and low adsorption of 0.086 mg/g
of rock. The cationic Gemini surfactants, zwitterionic or amphoteric class of surfactants are also suitable for
HTHS carbonates. Besides, effective biosurfactants sourced from plant such as, soy, corn, etc., are non-toxic and
readily biodegradable. The hydrophobically associating polyacrylamide (HAPAM) and its modified nano­
composite derivative can act as replacement surfactants, due to their wettability altering and robust charac­
teristics. Novel polymers viz., NVP-based, novel smart thermoviscosifying polymers (TVP), soft microgel, and
sulfonated polymers, are also relevant to HTHS carbonate applications. Xanthan gum, scleroglucan, and schiz­
ophyllan biopolymers have been noted to resist HTHS and low permeability conditions, requiring lower con­
centration and having low adsorption. Recent surfactant-polymer (SP) formulations also can be applicable for
HTHS carbonates with excellent ternary recoveries (93.6%) and minimal retention (0.083 μg/g of rock). Such
low retention values suggest low surfactants cost with minimal environmental impact. Moreover, several suc­
cessful field applications in carbonates were conducted in preceding years; however, the performance of some
novel surfactants under HTHS carbonates is yet to be fully understood. Hence, this comprehensive review aims to
provide renewed perspectives on surfactant and polymer optimizations for field applications in HTHS carbonates.
A list of recommendations is presented as guidelines for efficient SP-flooding designs. This critical literature
appraisal furnishes an array of potential manifestations for successful field application of SP-flooding in HTHS
carbonates, which holds both economic and environmental feasibility.

* Corresponding author.
E-mail address: anas.hassan@ku.ac.ae (A.M. Hassan).

https://doi.org/10.1016/j.petrol.2022.111243
Received 16 March 2022; Received in revised form 17 October 2022; Accepted 10 November 2022
Available online 17 November 2022
0920-4105/© 2022 Elsevier B.V. All rights reserved.
A.M. Hassan et al.
1. Introduction
Over half of the oil reserves in the world are in carbonate reservoirs
(Akbar et al., 2000). Most of these carbonates present harsh conditions i.
e., high temperature and high salinity (HTHS) along with heterogeneous
mineralogy and vuggy structure. Fig. 1 demonstrates an example of a
highly heterogeneous and vuggy carbonate reservoir core sample (Lu
et al., 2014a). A sizeable number of these carbonate reservoirs have
natural fractures while being mixed-wet to oil-wet (Chilingar and Yen,
1983; Roehl and Choquette, 2012). Previous studies have indicated that
approximately 70% of global oil reserves in carbonates are not
extractable through conventional oil recovery methods, e.g., water­
flooding (Lake et al., 2014; Hartono et al., 2017; Moreno-Arciniegas and
Babadagli, 2017). The conventional recovery methods (i.e., water­
flooding) become ineffective in incremental oil recovery, owing to the
oil-wet condition of the carbonate reservoir and the strong adsorption of
crude oil on the carbonate rocks. Consequently, enhanced oil recovery
(EOR) techniques are powerful tools to unlock a significant amount of
residual and remaining oils from the existing hydrocarbon carbonate
reservoirs through obtaining improved oil recovery beyond water cut
levels at an economical production rate.
In chemical EOR (cEOR) techniques like surfactant and polymer-
based EOR (i.e., SP-flooding), the combined effects (i.e., synergistic ef­
fect) of surfactant and polymer can (i) change the wettability of the oil-
wet carbonate rock surface toward more water-wet conditions, (ii)
reduce the interfacial tension (IFT) between crude oil and water, and
(iii) enhance the mobility control of the injected fluid (Rosen and
Kunjappu, 2012; Olajire, 2014; Ragab and Mansour, 2021). The average
incremental oil recovery achieved has been over 15% OOIP (original oil
in place) in all the known field tests so far; however, there is very little
knowledge of HTHS carbonate field applications (Liao et al., 2017).
The surfactants are typically amphiphilic organic molecules that
contain both hydrophobic (tails) and hydrophilic groups (heads).
Consequently, a surfactant molecule has both a water-soluble compo­
nent and an oil-soluble component, as shown in Fig. 2. Fig. 2a illustrates
the surfactants adsorbed between air and water or between oil and water
interfaces i.e., the oil-soluble clusters protrude out of the water into the
air or into the oil-phase, while Fig. 2b shows the water-soluble head
clusters that remain in the water-phase (El-Hoshoudy et al., 2017a).
During surfactant and polymer floodings in HTHS carbonates, the sur­
factants get adsorbed due to the mineral composition of the carbonate
rocks and gels may form in the micellar solution along with other forms
of polymer degradation (Reed and Healy, 1977; Skauge and Palmgren,
1989; Kovscek and Radke, 1993; Hirasaki et al., 2011; Lake et al., 2014).
Therefore, chemical screening of surfactants and polymers for suitability
and stability is a prerequisite for implementing surfactant and polymer
flooding projects. Accordingly, some studies have developed
custom-designed i.e., an optimized surfactant for the best possible
interactive relations with certain oils and brines at various
temperatures.
Fig. 1. A computerized tomography (CT) scan image of a highly heterogeneous and vuggy carbonate core sample (Lu et al., 2014a).
2
Journal of Petroleum Science and Engineering 220 (2023) 111243
The SP-flooding process has primarily been used in reservoirs with
mild salinity (60,000 ppm) and temperature under (80 ◦ C) (Green and
Willhite, 1998; Lake et al., 2014). However, as oilfields age, carbonate
reservoirs are becoming increasingly common and significant. The
SP-flooding is challenging in carbonate reservoirs because of the com­
plex geological structure (i.e., heterogeneity) and harsh conditions (i.e.,
HTHS), that cause instability, degradation, and chemical adsorption of
the injected SP-fluids on the rock’s surface. Moreover, the imple­
mentation of SP-based cEOR is severely impacted by high adsorption of
surfactants (e.g., anionic alkylbenzene sulfonates) on carbonates rocks
or clay surfaces due to the electrostatic interactions. This major issue of
surfactant adsorption on rocks or clay surfaces necessitates constant
surfactant re-injections, downgrading the efficiency and economic
viability (Adams and Schievelbein, 1987) of the SP-based cEOR process.
Surfactant adsorption is mainly influenced by the surface chemistry of
most of the carbonate rocks. A complex dissolution behavior is exhibited
by some minerals contained in carbonate rocks, viz., dolomite (CaMg
(CO3)2), calcite (CaCO3), and magnesite (MgCO3) (Hiorth et al., 2010).
To mitigate this surfactant adsorption problem, adding co-solvents
together with mixtures of different surfactants structures can reduce
microemulsion viscosity and lower surfactant retention (Tagavifar et al.,
2018). Another cause of retention is phase entrapment, which is mini­
mized through applying negative-salinity tong, i.e., when the polymer
drive of lower salinity (hybrid low salinity waterflooding) than the
injected surfactant slug’s salinity is applied (Hassan et al., 2022c).
Therefore, as previously mentioned, to select the most appropriate
cEOR method, proper screening of the chemicals (e.g., surfactants and
polymers) must be conducted for the reservoir conditions to increase
chemical stability as well as reduce chemical adsorption and degrada­
tion. Consequently, many studies have developed a number of potential
surfactant and polymer recipes, which may lead to successful field ap­
plications of SP-flooding in carbonates in the near future. These studies
have focused on determining the best performing surfactant structure
relationships with certain crude oils and brines at various temperatures
and salinity ranges (e.g., HTHS conditions) (Skauge and Palmgren,
1989; Levitt et al., 2006; Yang et al., 2010; Solairaj et al., 2012; Adkins
et al., 2012; Lu et al., 2014b, 2014c). During one of these studies on the
conformation of surfactants and their effects, it was observed that a
longer hydrophobic tail increases the ability to solubilize oil, i.e., higher
oil solubilization ratios are achieved along with lower optimum salin­
ities at certain temperatures (Lu et al., 2014b). However, excess length
of hydrophobe reduces the aqueous solubility. It was also found that the
branching of bulky groups like benzene rings on the hydrophobe and
other heavy clusters in the structure impart polarity to the surfactant,
enhancing the water solubility (Skauge and Palmgren, 1989).
Another highly desirable feature is creating low viscosity micro­
emulsions that equilibrate at a rapid rate while avoiding the formation
of gels or macroemulsions. To adjust the structure, propylene oxide (PO)
and ethylene oxide (EO) chains are incorporated in the hydrophobe,
which modifies the surfactant’s hydrophilic-to-lipophilic balance (HLB)
A.M. Hassan et al.
Fig. 2. A schematic of a surfactant structure where (a) shows the hydrophilic head with water affinity, and (b) the hydrophobic tail, which is oil-liking or oil-wet
(modified after El-Hoshoudy et al., 2017a).
(Skauge and Palmgren, 1989). For instance, the new Alkyl carboxylates
(AEC) have been observed to have good resistance to hardness, aqueous
solubility, and tolerance to pH alterations or changes in electrolyte
levels (Behler et al., 2001; Rosen and Kunjappu, 2012). These AEC
surfactants can be utilized in SP-based EOR, which could reduce costs as
these AEC surfactants having large-hydrophobe were synthesized that
may be used in lesser quantities to attain the required parameters.
Guerbet alkoxy sulfates (GAS), Guerbet alkoxy carboxylates (GAC),
Guerbet alkoxy betaine (GAB) and Tristyrylphenol alkoxy sulfates (TSP)
are different types of large-hydrophobe novel AEC surfactants. Several
betaine surfactants were analyzed for SP-based cEOR due to their
well-documented resistance to salt/divalent ion under HTHS reservoir
conditions. The novel surfactants with large-hydrophobe such as Guer­
bet alkoxy-sulfates (GAS), -carboxylates (GAC), and -betaine (GAB),
have exhibited stability at high temperatures (>100 ◦ C) and high sa­
linities (up to 275,000 ppm). When corefloods were conducted with
carbonate cores, the surfactant formulations yielded high tertiary oil
recovery of 94.5% (GAC formulation), and low adsorption of 0.086
mg/g rock (Lu et al., 2014a). The dynamic polymeric surfactants (sur­
face-active monomers) are another viable surfactant type, which is
structurally amphiphilic i.e., they are hydrophobic and hydrophilic at
the extremities (Gao et al., 2008). Along with this, their molecular for­
mations contain binary vinyl bonds, which can be polymerized (Reb
et al., 2000). This renders them more adaptive than conventional sur­
factants and may be used for emulsification (Guyot, 2004). In addition,
several biodegradable and non-toxic surfactants and polymers have
been designed that will offer a greener approach to chemical EOR
(Solairaj et al., 2012).
On the other hand, over the years several screening criteria for
polymers have been provided (Taber, 1983; Goodlett et al., 1986; Taber
et al., 1997; Wang and Lu, 2009; Gao, 2011; Kang et al., 2014). Novel
polymers such as ATBS, Scleroglucan, NVP-based polymers, hydropho­
bic associative polymers, novel smart Thermoviscosifying polymers
(TVP) (salt-induced viscosifiers), soft microgel polymers (SMG), and
sulfonated polymers have been synthesized and tested and exhibited
good tolerance and stability under HTHS carbonate conditions in the
core floods and field applications (Levitt et al., 2012; Hashmet et al.,
2017; Haruna et al., 2019). For instance, a high-potential polymer for
HTHS carbonates is the hydrophobically associating polyacrylamide
polymers (HAPAMs) and its nanocomposite derivative. They have
shown excellent tolerance towards temperature, pH, and ion content in
the periphery of the wells while functioning as viscosifiers or wettability
modifiers in HTHS and high-pressure reservoirs (Rodrigues et al., 2006;
Gouveia et al., 2008; C. Zhong et al., 2008). Also, in this paper, HMAs
(Hot-Melt Adhesive) polymers, sulfonated polyacrylamide (AN-125),
and certain HPAM based polymers such as Flopaam 3630 and SAV10,
have been detailed as some potential polymers for SP based cEOR in
HTHS carbonate rocks. Several successful field applications in HTHS
carbonates were conducted in the past years; however, their
3
Journal of Petroleum Science and Engineering 220 (2023) 111243
performance in carbonates is still obscure. A pilot study was conducted
using sulfonated polymer (ATBS >35 mol%) for possible use in a
gigantic carbonate field in the Middle East with 5% incremental oil re­
covery outcome (Jabbar et al., 2018). Recently, two polymer-based EOR
pilot studies have been undertaken by ADNOC in two reservoirs, which
are currently undergoing waterflooding (Masalmeh et al., 2019). Useful
correlations were derived through analyzing large data sets, which
predict the best surfactant structure by considering the impact of
changeable factors e.g., the propylene oxide (PO) and ethylene oxide
(EO) numbers, EACN of the oil, temperature, and the brine salinity (Lu
et al., 2014c). These factors had been neglected previously but have now
been deemed necessary in perfecting these correlations. Therefore, the
field applications and small-scale pilots conducted under HTHS car­
bonate conditions can be expected to have overall more accurate results
using these models.
Hence, this work is a comprehensive literature review, on the po­
tential scope of SP-flooding in carbonate reservoirs under harsh HTHS
conditions. Additionally, environmental impacts and economic viability
are discussed. The recommendations can help enhance the perspectives
of key parameters for designing successful SP based cEOR imple­
mentation in harsh carbonate conditions. To the best of our knowledge,
this contribution presents one of the few review articles existing in the
field of surfactant polymer flooding in carbonate reservoirs under harsh
HTHS conditions. An overview of the existing review articles, which
cover the topic of SP-flooding is shown in Appendix-A Table A-1. The
latter table summarizes the chemicals (i.e., surfactant and polymer
formulations) used in those studies, their HTHS tolerance, advantages,
and limitations.
2. Mechanisms of SP-flooding in HTHS carbonate reservoirs
According to previously published studies, the SP-floodings have
been found to possess vast potential in cEOR applications (Cockcroft
et al., 1988; Bera et al., 2011; Rosen and Kunjappu, 2012; Olajire, 2014;
Karović-Maričić et al., 2014; Sheng, 2010, 2015; Mandal, 2015; Liao
et al., 2017; Ragab and Mansour, 2021). The SP-flooding method was
patented by Gogarty and Tosch for Marathon oil company as Mara-flood
in the 1990s (Sheng, 2013a; Ragab and Mansour, 2021). The SP-flooding
process involves the injection of a chemical slug into the reservoir
consisting of water, polymer, surfactant, electrolyte (i.e., salt), a
co-solvent (i.e., most often alcohol), which is called the micellar solu­
tion, followed by a thick water polymer injection. At times, to improve
robustness of surfactants at certain temperatures and water salinities,
co-surfactants may be needed in the formulation fluid. The role of the
inorganic salts (i.e., the water-soluble electrolytes) in the micellar slug is
to attain greater solution viscosity regulation. The injected polymer
solution helps propagate the micellar solution slug to achieve mobility
control (Cockcroft et al., 1988). Also, decreased oil-water IFT that re­
sults from the SP-flooding helps regulate the mobility ratio by
A.M. Hassan et al.
generating a sizable oil bank and ultimately boosts the oil recovery, as
shown in Fig. 3.
In other words, simultaneous adsorption of secondary surfactant,
ionized acid, along with unionized acid on rock and solution interface
leads to the creation of a compound layer of adsorption. Consequently,
the behavior of dynamic IFT occurs (Cockcroft et al., 1988; Bera et al.,
2011; Karović-Maričić et al., 2014; Mandal, 2015). Furthermore, the
wettability changes by surfactants have been attributed to mainly pH
and potential determining ions (PDIs) i.e., Ca2+, Mg2+, and SO2− 4 . The
involved reactions are controlled by the surface charges (zeta-poten­
tials), produced precisely at the brine-oil and brine-rock interfaces (i.e.,
crude oil-brine-rock interactions or COBR system). Likewise, the types
and properties of crude oil influence the optimal salinity parameter. The
extent of recovery of oil in carbonate reservoirs is also vastly affected by
gravity, capillary, viscosity forces, and injection water composition. The
components of this micellar solution or slug, secure a phase-wise shift,
which involves water displacement to oil displacement that is devoid of
interfaces. These components of SP-flooding generally constitute the
following amounts in the solution: (i) 10–15% of surfactant, (ii) 20–60%
of water, (iii) 25–70% of oil, (iv) 3–4% of co-surfactant (Sheng, 2015).
Using alcohol as a co-solvent, increases the tendency of the micellar fluid
to incorporate both water and oil (Cockcroft et al., 1988; Bera et al.,
2011; Karović-Maričić et al., 2014; Mandal, 2015).
Thus, SP based cEOR is an effective technique that decreases oil-
water IFT, aids in mobility ratio control by creating a large oil bank,
causes wettability alterations to cumulatively improve recovery factor.
A number of experiments has demonstrated the incremental oil recov­
ery, and the fluid-rock interactions (i.e., COBR system) that constitute
the underlying mechanisms such as IFT reduction, mobility control, and
wettability alteration of the carbonate rock surface.
2.1. Interfacial tension (IFT)
One of the main considerations in surfactant-polymer (SP) flooding
cEOR processes is interfacial tension (IFT). The relationship of three
types of forces i.e., the capillary, gravitational, and viscous forces, in the
oil reservoirs, influences the amount and rate of oil recovery. Obtaining
a high capillary number, which is the ratio of viscous forces to interfacial
Fig. 3. A simple illustration of SP based cEOR process.
4
Journal of Petroleum Science and Engineering 220 (2023) 111243
forces, is a key indicator of enhanced displacement efficacy during the
cEOR processes. Thus, it is essential to either increase the displacing
fluid’s viscosity (i.e., water) or decrease the IFT between the oil and
water in order to increase the capillary number value (Sheng, 2010,
2015). Typically, the oil-wet carbonate system has negative capillary
pressure, and consequently, water is stopped from spontaneously
imbibing into the porous medium since the capillarity of the carbonate
rock surface strongly attaches the oil. SP-flooding reduces the IFT by
forming microemulsions by the oil-water interface, causing reduction of
capillary forces, which mobilizes the trapped oil.
The IFT values are primarily defined according to the factors of
surfactant concentration in aqueous solutions, molecular structure,
temperature, and salinity. In terms of ultralow IFT, high surfactant
concentrations are more desirable than a low concentration. Greater
quantities of oil are solubilized when there are high surfactant concen­
trations present, and a type III Winsor solution is anticipated to form,
which result in oil recovery enhancement (Hirasaki et al., 2011).
However, the critical micelle concentration (CMC), over which the IFT is
unaffected, must not be exceeded by the surfactant concentration. To
precisely design an effective SP-flooding, a proper understanding on the
basic mechanisms behind reduction in IFT dynamics between crude oil
and water is paramount (Sheng, 2015; Mandal, 2015). Fig. 4 illustrates
the COBR system during SP-flooding. Hence, the capillary pressures
between the aqueous and oleic phases indicate the reduced oil-water
IFT. As previously mentioned, the surfactant concentration, tempera­
ture change, and water-chemistry (i.e., salinity and composition) of the
aqueous solution have a significant impact on the extent at which this
reaction occurs at brine-oil and brine-rock interfaces (i.e., COBR
system).
Investigators conducted imbibition tests on surfactants, which
created IFT reduction, and noted that, mechanism of oil recovery during
imbibition via IFT reduction, was most probably due to buoyancy and
alteration of wettability. In case of certain anionic surfactants, extremely
low IFT values can be achieved so that the capillary pressure is
decreased to almost zero (Hirasaki and Zhang, 2003; Seethepalli et al.,
2004b; Adibhatla and Mohanty, 2006; Lu et al., 2014a). As the capillary
pressure nears zero, the various forces (i.e., gravity and viscous) can lead
to imbibition, which was seen in several experiments. In particular,
A.M. Hassan et al.
Fig. 4. A schematic diagram representing the COBR system during SP-flooding.
R-COO- denotes carboxylate ion (i.e., anionic surfactant) and Poly− denotes
polymer molecule in the aqueous solution.
simulation results by Abbasi-Asl and co-workers illustrated that the
transverse pressure gradients between the fractures and matrix can push
the surfactant deeper into the matrix in the dynamic imbibition process
(Abbasi-Asl et al., 2010).
Moreover, the quality of crude oil, water salinity, and the type of
surfactants are important factors effecting IFT reduction. The IFT for
crude oil and brine system, measures around 7 mN/m at optimum
salinity (6 wt% NaCl), and this is much lesser value than the IFT of crude
oil-water system (48 mN/m) (Anderson, 1986; Crain, 2002; Mandal,
2015). In numerous researches on surfactants, static imbibition experi­
ments were extensively used to examine different surfactants (Austad
et al., 1998; Xie et al., 2004; Seethepalli et al., 2004a; Zhang et al.,
2006a; Sagi et al., 2013; Chen and Mohanty, 2013; Bourbiaux et al.,
2014; Wang and Mohanty, 2015). It was categorically observed that, in
carbonate reservoirs the oil recovery is highly affected by gravity and
capillary forces. However, viscous forces may also play an important
role (Mohammadi et al., 2009) Several observations indicated the
Marangoni effect (Austad and Milter, 1997) and spontaneous emulsifi­
cation (Zhang et al., 2006b) to induce imbibition in some static imbi­
bition experiments. Goudarzi and co-workers (Goudarzi et al., 2012)
have suggested via static imbibition experiments, that modifying the
matrix block size affects the oil recovery. When surfactants, oil, water
and electrolytes blend, thermodynamically stable phases called micro­
emulsions are formed under certain conditions (Winsor, 1954; Bourrel
and Schechter, 2010). The dissolved micro-emulsions in oil or water, a
stable pressure gradient, and enhanced sweep efficiency via polymer
injection aid to significantly increase the oil recovery (Hill et al., 1973;
Bera et al., 2011).
Furthermore, the experimental study by Yu et al. (2010) demon­
strated that there exists an optimum IFT, which leads to highest oil re­
covery that surpasses the ultra-low IFT stated, as illustrated in Fig. 5. The
Fig. 5. Correlation between incremental recovery and IFT at varying polymer
viscosities.
5
Journal of Petroleum Science and Engineering 220 (2023) 111243
latter figure shows the correlation between incremental recovery and
IFT at varying polymer viscosities, as the IFT is progressively increased
from ultra-low values (10− 3 mN/m), the incremental recovery increases
with maximum values ranging from 10− 2 and 10− 1 mN/m and then
starts to decrease, demonstrating that the highest recovery was attained
at low IFT and not at ultra-low IFT value.
In summary, mixing surfactants, oil, water, and electrolytes forms
microemulsions due to IFT reduction, which leads to creation of oil
banks. The IFT reduction is mostly attributed to buoyancy and wetta­
bility changes along with the combination of particular temperature,
water salinity, surfactants type, crude oil characteristics, and viscous
forces. Microemulsions are reviewed in the ensuing section, as their role
is fundamental in cEOR processes.
2.1.1. Phase behavior
In SP-flooding, to identify optimum surfactants and ascertain their
stability, microemulsion phase behavior tests are conducted. These tests
help in deducing the oil and water solubilization ratios by measuring the
oil and water volumes in microemulsion phase. Microemulsions are
thermodynamically stable phases, formed under certain conditions
(Bourrel and Schechter, 2010). The thermodynamically stable micro­
emulsions are composed of homogeneous dispersions of two immiscible
fluids, which are commonly, hydrocarbons and water stabilized with
surfactant molecules, that can be either alone or blended with a
co-surfactant (Winsor, 1954). They are capable of ultra-low IFT reduc­
tion between oil and water and also cause wettability alteration of
reservoir rocks. Rather than surfactants adsorbed in the bulk phase, the
primary components of microemulsions are the surfactants adsorbed at
the interphase. The values of IFT are very low between microemulsion
and crude oil; and between microemulsion and water, usually ranging
from 10− 3 mN/m (Hirasaki et al., 2011). Examining the phase behavior
of the surfactants/co-surfactant–brine–oil system is the best approach
for defining the IFT behavior of microemulsions. It is understood that
IFT behavior is the basic factor in estimating the oil recovery perfor­
mance through the microemulsion flooding method (Winsor, 1954).
Winsor (1954), the first presented the elemental concept of the phase
behavior, studied these phase behaviors and classified them as I, II, and
III types (Winsor, 1954). The shifts from one to another microemulsion
type depends upon temperature, brine composition (i.e., salinity and
hardness), oil composition, pressure, and the concentration and chem­
ical structures of surfactants and co-solvents (Skauge and Fotland, 1990;
Bourrel and Schechter, 2010). In accordance with type of surfactant, the
microemulsion phase behavior alters from Winsor I (lower phase) to
Winsor III (middle phase) to Winsor II (upper phase) through changes in
the ensuing conditions: (1) salinity increase, (2) alcohol (co-surfactant)
concentration increase, (3) surfactant molecular weight increase, (4) oil
chain length (alkane carbon number, ACN) decrease, (5) temperature
change, (6) total surfactant concentration increase, (7) surfactant sol­
ution/oil ratio increase, (8) surfactant hydrophile-lipophile balance
(HLB) decrease, (9) brine/oil ratio increase, as shown in Fig. 6 (Salager
et al., 2005).
Furthermore, Huh (1979) observed that the solubilization ratios
correspond to the IFT between oil and water (Huh, 1979). When IFT
values are about 10− 3 dyn/cm, it is regarded as sufficiently low to
mobilize residual oil from a reservoir. According to Healy et al. (1976),
the salinity value at which oil and water solubilization ratios are equal is
called optimum salinity (Healy et al., 1976). The lowest IFT is normally
seen at the optimum salinity, which is a prerequisite for designing a
cEOR flooding. Liyanage et al. (2012) conducted a microemulsion phase
behavior test on the alkoxylated variant of the Tristyrylphenol alkoxy
sulfate-based surfactant in an active oil (Liyanage et al., 2012). They
observed excellent water solubility, good stability in hard brine, excel­
lent oil recovery, and very low surfactant retention (Adkins et al., 2012;
Lu et al., 2014c). In another phase behavior test, the new Guerbet alkoxy
carboxylate (GAC) surfactants showed several advantages over other
types of surfactants under a broad range of conditions (Iglauer et al.,
A.M. Hassan et al.
Fig. 6. Microemulsion phase-behavior of surfactant-water-crude oil as a function of several variable parameters (i.e., temperature, salinity, surfactant concentration,
brine-oil ratio, etc.).
2009, 2010; Adkins et al., 2012; Lu et al., 2014b).
Therefore, microemulsion phase behavior tests help determine the
oil and water solubilization ratios. The phase behaviors have been
classified as I, II, and III types (Winsor, 1954), and the dependency
factors for phase behaviors have also been determined. One such factor
is IFT between oil and water, and lowest IFT is observed at optimum
salinity, which is the salinity where oil and water solubilization ratios
are equivalent.
2.2. Wettability alteration
Wettability has been unanimously established as a major criterion
affecting improved and enhanced oil recovery (Zhou et al., 2000;
Morrow and Mason, 2001; Hirasaki and Zhang, 2003). Wettability is the
feature of a fluid to move around and attach onto a solid surface when
another immiscible liquid is present (Crain, 2002). Anderson, proposed
three ways to determine wettability: I) Through contact angle mea­
surement, or by using the product of the contact angle and the IFT (the
last term in Young’s equation); II) By measuring the relative quantities
of oil and water displaced in like situations; III) Observations of
displacement or surface mechanisms in relation to water or oil phases
(Anderson, 1986). This is illustrated by the following equation below
(Anderson, 1986):
σ os − σws + σ ow cos θc = 0
where σos is the interfacial energy between oil and solid, σws is the
Fig. 7. Wettability measurement of crude oil-rock-brine system.
Journal of Petroleum Science and Engineering 220 (2023) 111243
interfacial energy between water and solid, σow is the IFT between oil
and water, and θc is the contact angle, as shown in Fig. 7 (Lwisa, 2021).
In the fractured carbonate reservoirs, when wettability changes from
oil- or mixed-wet towards a more water-wetting state, it effectively
enhances the oil recovery. Thus, a fundamental factor that considerably
enhances oil recovery in surfactant flooding is the mechanism of reser­
voir wettability alteration from oil-wet to intermediate-wet or greater
water-wet state (Yang and Zhou, 2020). The wettability alteration aids
in residual oil mobilization, which creates the spontaneous imbibition
process. In general, carbonate and fractured reservoirs are considered as
oil-wet or mixed-wet; therefore, the process of water imbibition is either
deprived or unable to occur owing to the negative capillary pressure
(Andersen et al., 2014). Consequently, for increasing the oil recovery
from such reservoirs, the reservoir matrix’s wettability needs to be
altered to more beneficent ranges so that it enables imbibition of water
into the rock matrix and drive the oil out of the matrix into the fracture
(Zhang et al., 2006a). The phenomena behind carbonate reservoir
wettability change via surfactants towards a more beneficial water-wet
state are either through ion-pairing or surfactant adsorption mecha­
nisms. When using cationic surfactants, ion-pairing mechanism alters
the wettability of carbonate rock, and this occurs due to the anionic
components (primarily of the carboxylic group) adsorbed on the rock
surfaces from the crude oil reacting with the cationic surfactants’ posi­
tive heads. Consequently, ion-pairs soluble in the oleic phase shall be
created together with the surfactant monomers as a result of the elec­
(1)
trostatic forces. Accordingly, the rock surface shall be altered to more
water-wet state as the oil shall be desorbed (Salehi et al., 2008).
Moreover, during numerous pervious investigations, it was observed
that dissolved salt has considerable effect on enhanced oil recovery;
certain makeup and the concentration of various wettability-altering
components in the injection water had significant impact on
improving oil recovery (Austad et al., 2012; Qiao et al., 2016). Other
studies showed that the crude oil-brine-rock (COBR) interaction and the
related wettability changes are mainly governed by pH and potential
determining ions (i.e., PDI) (Ca2+, Mg2+, and SO2−4 ), and that the extent
of oil recovery is based on the concentration of these ions (Zhang and
Austad, 2006; Lager et al., 2008; Puntervold, 2008; RezaeiDoust et al.,
2011; Austad et al., 2012; Zhang and Sarma, 2012; Mahani et al., 2015;
Hassan et al., 2022a). However, several researchers have contended that
it is challenging, to describe ionically modified brines in the crude
oil/brine/rock system with a single mechanism, due to the complex
geochemistry involved in this process (Omekeh et al., 2012; AlQuraishi
et al., 2015; Al-Shalabi and Sepehrnoori, 2017; AlSada and Mackay,
2017). Boampong et al. (2002) devised a triple layer surface complex­
ation model (TLM) in PHREEQC geochemical simulator (Parkhurst and
Appelo, 1999), which was then coupled with UTCHEM, which is a
reservoir simulator that implements multiple phases (Luo et al., 2016).
The results showed that wettability is ultimately associated with
6
A.M. Hassan et al.
zeta-potentials at the oil-brine and rock-brine interfaces. Also, the au­
thors reported that only at extreme magnitudes of zeta-potentials at the
interfaces, the carbonate rocks could change to highly oil-wet or
water-wet (Boampong et al., 2022).
Furthermore, in a recent study, two main mechanisms, (i) the coating
process, which is associated with the use of anionic surfactants, and (ii)
the cleaning mechanism for cationic surfactants were found to influence
the wettability alteration of carbonates through surfactant injection
(Chowdhury et al., 2022). Chowdhury et al. (2022) observed that the
hydrophobic surfactant tails interact with the adsorbed oil in the
monolayer of anionic surfactant molecules that coats the carbonate rock
surface. As a result, the hydrophilic head groups of the surfactant cover a
previously oil-wet rock surface, changing the rock’s wettability toward
the condition of water-wet state. Also, the cationic surfactants are con­
nected to the second process, which is referred to as the cleaning
mechanism that also affects wettability alteration in carbonates.
Thus, wettability is recognized as a leading factor in improving oil
recovery. In carbonates, wettability shift from oil- or mixed-wet towards
more water-wet, leads to enhanced oil recovery. Dissolved salt with
certain composition and concentration of wettability-modifying ele­
ments in the injection water affect EOR. It has been proposed that the
pH, potential PDI viz., Ca2+, Mg2+, and SO24, and zeta-potentials at the
oil-brine and rock-brine interfaces affect wettability. Nonetheless, re­
searchers have concluded that it is debatable as to which particular
mechanism can fully define wettability alteration, due to many com­
plexities involved (Omekeh et al., 2012; AlQuraishi et al., 2015; AlSada
and Mackay, 2017).
2.3. Mobility control
In the SP-flooding process, the role of polymers is mobility control.
Polymers augment macroscopic displacement efficacy through mobility
ratio reduction (Hamoud, 1995). Adding polymers to injection water
fulfils the purpose of increasing viscosity and keeping mobility ratio <1.
This causes greater volumetric sweep efficiency for EOR (Mandal,
2015). Micro-emulsions are formed upon dissolving surfactants in water
or oil, causing an oil bank to form (Bera et al., 2011). As polymers are
injected, oil recovery increases considerably due to an enlarged oil bank
coupled with stabilizing of pressure and improvement in sweep effi­
ciency (Hill et al., 1973). In the SP-based cEOR slug and in the following
polymer flood injections, the amount of polymer must be sufficient so
that, desirable sweep efficiency is achieved without viscous fingering,
which is common in heterogeneous reservoir like carbonates. Thus,
appropriate mobility control is important in SP-based cEOR projects
(Dean, 2011), and is related to reduced surfactant adsorption (Nelson,
1983). Hence, the polymers are used in SP-flooding as viscosifying
agents for maintaining mobility ratio between oil and water <1, which
would lead to a sizeable oil bank formation and increased volumetric
sweep efficacy for cEOR.
3. Challenges associated with SP-flooding under harsh
conditions
A harsh condition carbonate reservoir may be defined as, any
reservoir, where two or more of the following conditions are met, and
which are the typical conditions in the Middle East oil reservoirs (Kli­
menko et al., 2020):
• Reservoir temperature of over 85 ◦ C,
• Formation water salinity above 100,000 ppm (i.e., Total Dissolved
Solids or TDS),
• The concentration of divalent cations (hardness) above 1000 ppm,
and permeability lower than 100 mD.
The cEOR methods have been successfully applied decades ago in
clastic reservoirs (i.e., sandstones). However, in carbonates, especially
7
Journal of Petroleum Science and Engineering 220 (2023) 111243
in the HTHS environment, large-scale commercial applications are yet to
be conducted. Since the majority of carbonates come with challenging
conditions such as heterogeneous composition, mixed-wet to oil-wet
rock wettability as well as HTHS conditions, SP based cEOR (i.e., SP-
flooding) becomes ineffective in recovering incremental oil due to the
instability of the surfactant and polymer solutions under these envi­
ronments (de Oliveira Silva et al., 2007; Algharaib et al., 2014;
Al-Shalabi, 2018; Diab and Al-Shalabi, 2019). In heterogeneous car­
bonates, the adsorption of the surfactant on minerals hinders the
effective implementation of SP-flooding. Furthermore, degradations
also occur at times, due to the crude oil types (i.e., polarity constituents
of crude oil) and the permeability of the porous media. In reservoirs
possessing high salinity (i.e., 270,000 ppm), high hardness brine (i.e.,
25,000 ppm), and high temperatures of 100–140 ◦ C, which are quin­
tessential in the Middle East oil reservoirs, the successful implementa­
tion of SP-based cEOR becomes highly challenging. This is owing to
solubility and incompatibility of chemicals in such hard-saline brines,
and thermal instability at such high temperatures. Divalent cations, such
as calcium and magnesium, are present in significant proportions in
carbonate reservoirs (Ca2+ and Mg2+ ions >2000 ppm), which can
reduce the efficacy of typically used (anionic) surfactants and polymers,
and aggravate adsorption (Levitt et al., 2011; Dupuis et al., 2017).
3.1. Factors affecting SP-flooding under harsh HTHS conditions
Factors including, but not limited to, temperature, salinity, adsorp­
tion, and injected fluid concentrations, may influence the effectiveness
and performance of an SP-flooding process. These factors affect the IFT,
micro-emulsion phase behavior, wettability, and mobility control,
which have an impact on the oil displacement mechanisms. In this sub-
section, the most essential factors namely, temperature, salinity, pH,
adsorption, and injected fluid concentrations are reviewed.
3.1.1. Effect of temperature
The reservoir temperature is an influential factor in the chemical
flooding process through several means. To be exact, the critical micelle
concentration (CMC) of the solution, the IFT, and the injected chemical
(e.g., surfactant) adsorption are typically impacted by the reservoir
temperature. In the case of SP-flooding, the hydrophobic tail’s solubility
in water mostly decreases as temperature increases, and the surfactant is
shifted to the oil-solution interface, lowering the IFT (Gao and Sharma,
2013). Additionally, from the perspective of surfactant flooding,
adsorption of surfactant on the rock surface poses a challenge. Never­
theless, since temperature has a substantial influence on surfactant
adsorption rate, when temperature increases, a considerable decrease in
the surfactant adsorption rate occurs. This is attributed to the kinetic
energy increase of the species (Fava and Eyring, 1956).
In a study by Azam et al. (2014), laboratory experiments were con­
ducted to evaluate the effect of temperature on the anionic surfactant
adsorption into samples of Berea sandstone. It was concluded that when
the temperature increased from 25 to 75 ◦ C the anionic surfactant
adsorption slightly reduced from 0.9604 to 0.491 mg/g. Prior to this,
Ziegler and Handy (1981) carried out laboratory experiments to deter­
mine the temperature effect on the nonionic surfactant adsorption into
samples of sandstone rock. The results obtained from the static
adsorption experiments proved that when surfactant concentrations are
low, the adsorption rate is decreased along with the increase in tem­
perature ranging from 25 to 95 ◦ C. Because of this kinetic energy in­
crease at elevated temperatures, whereupon the interaction forces
become are weakened. Whereas, at high surfactant concentrations, the
adsorption rate increased as the temperature increased.
Furthermore, the surfactant adsorption process in general is classi­
fied as exothermic process that is either one: (i) enthalpy driven, and (ii)
entropy driven; while a separate influence of temperature on surfactant
adsorption occurs based on the adsorption density (Hirasaki and Zhang,
2003; Jian et al., 2018; Belhaj et al., 2020). Consequently, when
A.M. Hassan et al.
surfactants with low adsorption density are present, and the tempera­
ture is increased, the adsorption density is increased (i.e., through
enthalpy driven adsorption). Conversely, low adsorption density is
observed for high adsorption density surfactants (i.e., through
entropy-driven adsorption) in the event of temperature increase (Kamal
et al., 2017). Moreover, through their studies, Bera et al. (2011) estab­
lished that the adsorption capacity decrease (in case of entropy-driven
adsorption) due to temperature increase, is based on two leading rea­
sons; (i) there is decrease in solution viscosity corresponding to tem­
perature increase; thus, the diffusion rate decreases of the adsorbate
amidst the external boundary layer and internal pores of reservoir rocks.
(ii) The equilibrium adsorption capacity of the sand particles is affected
by temperature based on if the adsorption process is exothermic or
endothermic.
In contrast, where non-ionic surfactant is concerned, there is
adsorption increase corresponding to temperature increase. With the
increase in temperature, the surfactants head groups are dehydrated,
rendering them loose hydrophobicity and turn more compressed, lead­
ing to increased surface activity and enhanced adsorption amounts. It
was also observed that at low concentrations, the non-ionic surfactant
adsorption onto the crushed Berea sandstone decreased as the temper­
ature increased; however, at high concentrations, the adsorption
increased as the temperature increased (Ziegler and Handy, 1981).
Furthermore, non-ionic surfactants can suffer phase separation (cloud
point) at high temperatures, causing a reduction in surfactant concen­
tration (Hirasaki et al., 2011).
A zwitterionic surfactant was synthesized with extremely low CMC
denominations at high temperature of 95 ◦ C, in order that the adsorption
rates may be decreased by reducing free monomers of the surfactant in
the solution (Bataweel and Nasr-El-Din, 2011). On the other hand, the
bulk of the surfactants will degrade or precipitate when the tempera­
tures go above 120 ◦ C (Negin et al., 2017). Likewise, it should be minded
that each surfactant has an unlike CMC value, subject to change based on
the temperature (Emrani and Nasr-El-Din, 2015; Islam et al., 2015).
When ionic surfactants are concerned, the Krafft point (Krafft temper­
ature), is the minimum temperature at which micelles may form in a
solution (Dicharry et al., 2016). Hence, if the temperatures are lowered
below the Krafft point, the solubility would decrease, rendering the
surfactant crystals to isolate from the solution. Accordingly, the ionic
surfactant solubility rises along with the temperature increase to reach
the Krafft point, at which the CMC is attained (Miyake and Oyama,
2009; Inada et al., 2017). Contrariwise, the non-ionic surfactants have
their solubility categorized based on the cloud point, which is according
to the surfactant structure, and the cloud point range is between 60 and
120 ◦ C. If this temperature range is surpassed, the surfactant degrada­
tion or precipitation begins (Negin et al., 2017; Aktar et al., 2020). At the
cloud point, the precipitation and separation of non-ionic surfactants
occurs. This decreases the surfactant concentration, which in turn up­
surges the IFT to eventually cause surfactant performance to decrease
(Hirasaki et al., 2011).
In addition, as the temperature of a non-ionic surfactant solution
meets the cloud point, the solution turns turbid, and species start to
isolate from the solution. This is attributed to the hydrating of the pol­
yoxyethylene groups in the surfactants when the cloud point tempera­
ture is surpassed (Mukhopadhyay et al., 2019). Ye et al. (2008)
conducted research to demonstrate that temperature is the principal
cause that affects the IFT of a surfactant solution; as the temperature
increases, the IFT existing amidst the crude oil and surfactant solution
decreases. Furthermore, the dynamic IFT is also affected by tempera­
ture, given that the increasing temperature causes the time requisite for
the IFT to achieve the solution equilibrium to decrease. In spite of this, at
the time surfactants are being mixed, the influence of temperature is
overlooked by reason of the synergism effect. This is ascribed to the
surfactant aggregation of molecules at the oil and solution interface;
hence, the principal mechanism of IFT reduction is the compressed
arrangement and improved capability to amend the properties of oil and
8
Journal of Petroleum Science and Engineering 220 (2023) 111243
water interfaces, and the temperature has a minor effect on decrease in
IFT.
Karnanda et al. (2013) discovered in their study that there was no
effect of either temperature or pressure on the CMC of Triton X-405,
which is a non-ionic surfactant; however, the CMC of Zonyyl FSE anionic
surfactant decreased with pressure increase and evened out as the
temperature continued to increase until 80 ◦ C, exceeding which the CMC
increased. Likewise, the study by Puerto et al. (2012) confirmed that the
cloud point of non-ionic surfactants (such as alkoxylatedglycidyl ether
sulfonate, or AGES) negatively influences the surfactant functioning in
the course of the cEOR process at high reservoir temperatures. The
adversarial consequence of separation of the aqueous saline solutions of
AGES into two liquid phases occurs at the cloud point temperatures.
Consequently, for the ionic and non-ionic surfactants, they should be
tested in advance for the Krafft and cloud points, respectively under
reservoir conditions before selection for use (Schramm, 2000; Schott,
2005).
Moreover, temperature significantly influences the process of
wettability alteration. With the increase in temperature within the car­
bonate reservoirs, the water-wetting process appears to take over. In the
investigations of Zhang et al. (2006b) and Austad et al. (2005), it was
observed that spontaneous imbibition from chalk led to an increase in oil
recovery as the temperature increased. The cause of this improvement is
due to the greater attraction of SO2−
4 ions to the carbonate surface when
temperatures are higher, which results in the negatively charged
carboxylate groups (R-COO-) of the sulfate ions becoming more attrac­
ted on the positively charged carbonate surface. This event releases the
oil from the rock surface, and alters the rock wettability to a more
water-wet condition. Moreover, non-ionic surfactants are able to
favorably affect contact angle reduction existing between the non-ionic
surfactant and carbonate surface at high-temperature situations (Gupta
and Mohanty, 2010), whereas zwitterionic surfactants display a mixed
effect on wettability alteration when temperature increases (Adejare
et al., 2012).
Furthermore, the amphoteric and nonionic surfactants exhibit min­
imal carbonate adsorption and are compatible with HTHS conditions
(Han et al., 2013; Wang et al., 2015; Jian et al., 2016; Ayirala et al.,
2019). The amphoteric surfactants can be particularly effective in
lowering the oil-water IFT, which is advantageous for mobilizing re­
sidual oil (Zhao et al., 2007a, 2007b; Guo et al., 2019; Ayirala et al.,
2021). Furthermore, the sulfates are prone to hydrolysis at high tem­
peratures and alternatives like sulfonates have to be used instead (Lu,
2014; Abalkhail et al., 2019). Also, the synergy of zwitterionic surfac­
tants, nanoparticles, and new polymers (HAPAM), have been shown to
be highly resilient and effective in inducing IFT and altering wettability
of carbonate rocks in both ambient and elevated temperatures with high
salinity (hardness) (Panthi et al., 2022; Afolabi et al., 2022; Larestani
et al., 2022; Meng et al., 2022; Joshi et al., 2022; Song and Hatzignatiou,
2022). Thus, for SP cEOR application in HTHS carbonate reservoirs, a
number of newer surfactants and polymers can be utilized for formu­
lating robust SP solutions with desirable rheological properties, as dis­
cussed in following sections.
3.1.2. Effects of salinity, hardness, and pH
Salinity strongly affects different microemulsion structures that are
influential on the wettability behavior of carbonate rock. The condition
of saline environs considerably affects SP-flooding efficiency, due to
unfavorable impact on the surfactant’s solubility by the high-salinity
conditions. This is for the reason that surfactants incline towards
remaining in the oleic phase, resulting in deterrence of achieving IFT
reduction (El-Batanoney et al., 1999). Consequently, it is crucial that
optimum salinity must be reached at which equal amounts of oil and
water is able to be solubilized so that microemulsions are formed (Hir­
asaki et al., 2011; Gao and Sharma, 2013). Chou and Shah (1981) per­
formed a laboratory study to show that highest oil recovery was attained
at the point where connate water salinity and polymer solution were at
A.M. Hassan et al.
the optimum surfactant formulation salinity.
The anionic surfactants are vulnerable to high-salinity aqueous so­
lutions, as the surfactants precipitation starts owing to the salt ions and
surfactant molecules interacting (Al-Hashim et al., 1988). Furthermore,
when there is an increase in salinity, the adsorption of anionic surfac­
tants increases correspondingly on Berea sandstone because of the sur­
face acidity increase and the electrical double layer (EDL) composition
that diminishes the electrostatic repulsion existing between the surfac­
tant monomers and the clay mineral surface (Kwok et al., 1993). In
addition, for the conventional anionic surfactants utilized in chemical
cEOR processes, they adsorb more on limestone and sandstone as the
divalent cations increase. This is because of the cations present and their
adsorptions on the rock surface, resulting in diminished repulsion forces
existing between the anionic surfactant molecules and the rock surface’s
negative charges; which consecutively, lets the surfactant molecules to
be adsorbed on the surface of rock (Azam et al., 2013). Also, when high
Ca2+ concentration is present in limestone rocks, it causes increase in the
surfactant precipitation (Al-Hashim et al., 1988). Conversely, when
divalent cations are present, they may lessen the cationic surfactants
adsorption onto carbonate rocks due to the strong positively charged
cations (Ma et al., 2013). Moreover, anionic surfactants can alter car­
bonate rock wettability towards greater water-wet states only if the
brine salinity is low, predominantly in the presence of divalent ions such
as Mg2+ and Ca2+. The interaction of multivalent cations with anionic
surfactants leads to precipitation and the wettability altering effect in
carbonate rocks is diminished (Deng et al., 2021). It was experimentally
shown by Gupta and Mohanty (2011) that along with salinity increase,
there was decrease in the optimum surfactant concentration, that lead to
the optimal contact angle increase.
Experimental investigations by Baviere et al. (1988) showed pro­
spective efficiency of alpha-olefin sulfonate (AOS), which is an anionic
surfactant, for cEOR applications under HTHS and high-hardness situ­
ations. Their outcomes demonstrated the high salt tolerance of AOS
surfactant even though there were calcium ions present. Addition of an
alcohol or increasing the temperature, can achieve solubility for the AOS
surfactant in high-salinity brines. Consequently, AOS surfactants have
high solubility and IFT reduction at elevated temperatures throughout a
vast salinities range. There was slight increase in surfactant adsorption
on kaolinite with salinity increase even though the surfactant concen­
trations were high. Salinity affects the solubility, the surface activity and
the non-ionic surfactants’ adsorption. Triton X-100 (a non-ionic sur­
factant) was found by Nevskaia et al. (1998) to display three distinctive
categories of adsorption behavior when NaCl was present with the use of
different quartz rocks types (QA, QB and QC). They observed that the
adsorption of Triton X-100 was reduced after NaCl was mixed to the
solution on the QA sample and the adsorption increased after testing on
the QB rock; in addition, there were no changes noticeable from the QC
rock tests. This distinct behavior is related to the salt cations and
different surface hydroxyl group’s interactions, on top of the surface
impurities being present instead of the interactions between salt and
TX-100.
Moreover, another critical factor influencing the efficiency of SP-
flooding is pH, as the surfactant adsorption rate is impacted by surface
charges of the rock that are subject to variations by way of pH alter­
ations. The pH value at which the net charge on the surface (surface
charge density) is zero is called the point of zero charge (PZC). It is a
crucial attribute of the rock for the reason that at pH levels greater than
their PZC, the surfaces turn into negatively charged (Grigg et al., 2004).
By way of example, the anionic surfactants, when used in cEOR pro­
cesses provide a window of opportunity; because they do not undergo
significant losses through adsorption on account of the negative surface
charge on sandstone when pH levels are high (Azam et al., 2013). In a
pH environment lower than PZC, the rock’s hydroxyl minerals tend to
attain a positive charge, leads to an anionic surfactant adsorption in­
crease by reason of the negative charges of the surfactant’s group having
affinity to the rock surface. Although, when pH is greater than PZC, the
9
Journal of Petroleum Science and Engineering 220 (2023) 111243
number of hydroxyl groups on the surface of the rock is decreased due to
the rock minerals reacting with the hydroxyl groups in the solution.
Hence, cationic surfactant is adsorbed by the negatively charged hy­
drated mineral oxides existing on the solid rock surface (Liu et al., 2010;
Hanamertani et al., 2018; Azam et al., 2013; Belhaj et al., 2020). These
are described through the ensuing reactions regarding the mechanism of
Berea sandstone attaining positive and negative charges due to low pH
and high pH, respectively. The same mechanism can be applied in the
case of carbonate rock having positive and negative surface charges
based on the variation in pH values (Hassan et al., 2020).
As a result, for adsorption on Berea sandstone to be decreased when
anionic surfactant is present, alkalis like sodium hydroxide or sodium
carbonate are utilized, which enhance the pH and the positive charge
density on the rock surfaces is decreased (Azam et al., 2013; Hirasaki
et al., 2011). This was substantiated in the study by Azam et al. (2013),
in which they conducted laboratory investigations on the pH effect
causing static adsorption onto Berea sandstone by means of synthesized
anionic surfactant. The outcomes showed that a positive charge was
attained by the silica fraction in Berea sandstone at low pH, while at high
pH, a negative charge was attained. Thus, the anionic surfactants
adsorption on the rock surface will be decreased at high pH (above 9.0),
caused by the repulsive forces existing amid the surfactant head group
and the negative rock surface charges. In another study, Mushtaq et al.
(2014) provided a description of the effect that pH changes in the near
the PZC (pH of 7.98) value has on the anionic surfactant adsorption onto
the Malaysian sandstone surface. When there was no alkali, the surfac­
tant’s static adsorption was greater (3.66 and 4.49 mg/g) at pH values
lesser than 7.98, whereas, when there was alkali present at pH values
higher than 7.98, substantial decrease in surfactant adsorption (0.43 and
0.86 mg/g) was observed. Likewise, studies were conducted by Bera
et al. (2011) using the cationic surfactant (cetyltrimethylammonium
bromide) to determine its adsorption behavior on the clean sand parti­
cles for samples. Their study concluded that cationic surfactant
adsorption increases correspondingly to pH increases of the solution, for
the reason that at high pH values, the cationic surfactant, which has
positively charged head groups, is highly attracted to
negatively-charged sand rock surfaces.
On the other hand, it is apparent from the results of Tagavifar et al.
(2018) that the adsorption of anionic surfactant on Indiana limestone
(ILS) declines virtually directly with pH values above 9. In high pH
conditions (i.e., pH values above 9), the dominant mode of adsorption
on calcite is through significant hydrogen bonding. However, at low pH
values, the foremost adsorption type on calcite and clay surfaces is
charge-regulated monodentate (i.e., carboxylate or sulfate), irrespective
of surface loading (Tagavifar et al., 2018). Figs. 8 and 9 illustrate the
progression of the surfactant’s adsorption on ILS core-samples in rela­
tion to surfactant concentration, pH, ionic strength, and temperature.
Initially, the adsorption isotherms is estimated for both systems A
(78 ◦ C) and B (24 ◦ C) when salinity, temperature, and pH were constant,
which is depicted in Fig. 8. Further, the pH was estimated to be 7.6 and
Fig. 8. Langmuir isotherm for systems A (78 ◦ C) and B (24 ◦ C) for surfactant
adsorption on Indiana limestone (ILS). Dotes and Lines represent experiment
and model calculations respectively (Tagavifar et al., 2018).
A.M. Hassan et al.
8.6 for A and B systems, respectively, which was not attuned; while the
rock–water interactions (primarily the calcite dissolution) controlled it.
Symbols were employed to denote the experimental data, and the range
of experimental error was between 1 and 5% of the absolute measure­
ment value. Solid lines were used to signify the results of surface
complexation modeling using the Phreeqc software. Both the systems
were similar to Langmuir monomer adsorption in their adsorption re­
sults with comparable adsorption capabilities (i.e. approximately 3
mg/g of rock). The earlier results acquired for anionic surfactant
adsorption on calcites (Ahmadali et al. 1993; Ma et al. 2013; Shamsi­
Jazeyi et al., 2014a) coincide with the adsorption plateau of 3 mg/g of
rock at low pH values that agrees to 5.3 and 4 μmol/m2 for systems A
and B, respectively, as shown in Fig. 9. In Fig. 9, the surfactant
adsorption plateau on ILS rock in relation to pH at the constant ionic
strength and temperature is shown for both A and B systems. One can
observe that both A and B systems demonstrate very comparable
adsorption profiles and are primarily determined by pH for the surfac­
tant adsorption on ILS rock. At pH values below 9, the same adsorption
plateau of 3 mg/g of rock is obtained for both systems, that analogous to
the adsorption isotherm plateau, as shown in Fig. 8. In case the pH
values exceed 9, the adsorption amount diminishes almost aligned with
the pH values. The adsorption reduction alongside pH is partially
attributable to the positive charge decrease and the subsequent charge
reversal alongside the pH values. Because of this, the like charged
anionic surfactant and calcite repel one another. Nevertheless, adsorp­
tion is observed as remaining high at around 1 mg/g of rock at a pH of
11.9.
3.1.3. Effect of adsorption
When evaluating SP-flooding in cEOR processes, surfactant adsorp­
tion on rock surfaces in porous media is a crucial factor believed to be
the leading mechanism behind surfactant retention on rock. The sur­
factant adsorption process into the reservoir rocks eventually creates a
decrease in surfactant concentration that consecutively depreciates the
beneficial properties for the process of displacement and decreases the
SP-flooding efficiency (Liu et al., 2020). Thus, surfactant adsorption is a
primary factor contributing to the economics of the SP-flooding project.
Several parameters are in control of the adsorption process such as the
surfactant type, rock morphology and mineralogy characteristics,
charges on the rock surface, the electrolytes types present in the solu­
tion, and the co-surfactant and alcohols present (Liu et al., 2004). As
surfactant retention is controlled, it will enable to secure low costs and
environmental preservation. For this purpose, additives (e.g., Alkali) are
incorporated with surfactants to cause pH increase and surfactant
adsorption to be reduced (Nelson et al., 1984; Delshad et al., 2011;
Solairaj et al., 2012; Sharma et al., 2015; Southwick et al., 2016, 2018;
Wang et al., 2018, 2019).
Moreover, it is essential to precisely measure the static and dynamic
Fig. 9. Static surfactant adsorption plateau on Indiana limestone (ILS) versus
pH for systems A (78 ◦ C) and B (24 ◦ C). Dotes and Lines represent experiment
and model calculations, respectively (Tagavifar et al., 2018).
10
Journal of Petroleum Science and Engineering 220 (2023) 111243
behaviors of adsorption in order to minimize surfactant adsorption.
Researchers have examined the effects of solid surface interactions,
surfactant properties, water chemistry, and functional groups on sur­
factant adsorption (Chandar et al., 1987; Zhu and Gu, 1991; Hu and
Bard, 1997; Somasundaran and Krishnakumar, 1997; Yu et al., 2003; Ma
et al., 2013; Zhong and Claverie, 2013; Levitt and Bourrel, 2016). For
some of the well-known adsorbents, studies have defined the adsorption
sequence, the adsorbed layer structure (Bohmer and Koopal, 1992),
adsorption mechanisms (Zhang and Somasundaran, 2006), and
adsorption kinetics (Tabor et al., 2009; Ahmadi and Shadizadeh, 2015).
Although, for carbonate rock formations (Levitt and Bourrel, 2016) and
carbonate soil (Ishiguro and Koopal, 2016), which as we know have
heterogeneous mineral composition and in rock surface interactivities,
the underlying mechanisms and their degree of impact on adsorption are
hard to predict. In fact, there is yet to be conclusive numerical or
experimental evidence about the workings and the extent of the effect of
minerals on adsorption based on the variations in ionic strength and pH
in the environment. This is firstly due to the reason that pure mineral
samples are used in adsorption tests, while the difference in mineral
composition of carbonates (e.g., limestone and calcite) causes very
different adsorption behaviors in the actual reservoirs. Ma et al. (2013)
studied this aspect and observed negligible cationic surfactant adsorp­
tion on artificial calcite, yet significant adsorption was observed on
samples of natural limestone which can be clearly linked to aluminum
and silicon present in the rock (Ma et al., 2013). This also shows the
existence of trace amounts of minerals viz., magnesite, Fe-dolomite,
anhydrite, clay, and oxides of metal in carbonate rocks (Folk, 1959;
Ma et al., 2013; Levitt et al., 2015). The second reason is that mineral
components have varying surface charges and dissolution behaviors.
Generally, metal oxides have a point of zero charges greater (PZC) than
carbonate minerals components, which eventually causes the oxides and
carbonates to become polar opposites in sign at certain pH levels (Kos­
mulski, 2002; Stumm and Morgan, 2012). This means that there will be
contiguous heterogeneous surface potential and this generates the
following (Na et al., 2007):
• In carbonate dust, the zeta potential is unreliable in fully explaining
adsorption associated with charges (Moulin and Roques, 2003; Chen
et al., 2014; Kasha et al., 2015; Mahani et al., 2017).
• Adsorption in non-uniform forms such as the charge-controlled
forms against the hydrogen-bonded forms, and the form dynamics
effectively cause patch-wise adsorption sometimes (Nwidee et al.,
2017).
• Also, when the surfactant solution contacts the rock, the ionic
constitution will be different from one at the start owing to the
dissolution of mineral components (Cui et al., 2015).
• Furthermore, with a decrease in pH, usually the adsorption of
anionic surfactants decreases too (Somasundaran and Fuerstenau,
1966; Seethepalli et al., 2004b; Pham et al., 2015; Sharma et al.,
2015; Southwick et al., 2016) and there is a slight increase noticed
when ionic strength increases, and with the increase in the concen­
tration of divalent cations (ShamsiJazeyi et al., 2014b; Budhathoki
et al., 2016).
The third reason is that adsorption on clay platelets extremities at
locations that are like oxides, which has polymorphic tendency i.e., the
water chemistry might affect both the size and dynamics in a non-
uniform manner, as demonstrated in Fig. 10. In the latter figure, the
charge-regulated adsorption is the leading mechanism on both calcite
and platelets. There is presence of hydrogen bonding mechanism on
both minerals. However, calcite sites show higher adsorption capacity
than oxide-like sites on clay platelets edges. This was proven by Levitt
and Bourrel (2016), who observed that in cases of montmorillonite clay,
and in an outcrop rock that had undergone oxidization, that was
composed of sizeable amounts of clay and iron, using a simple sodium
chloride rinse, the extent of the adsorption could be decreased. They
A.M. Hassan et al.
Fig. 10. Adsorption degree and manner on a low surface-area calcite and high
surface-area clay platelets at a pH of approximately 8 (Tagavifar et al., 2018).
associated the reduced adsorption to the exchange of divalent cations
from clays due to rinsing, as it decreased the surface charges (Levitt and
Bourrel, 2016). Furthermore, the carbonate surface geochemistry and
the surface charge of carbonate rock can influence the retention values
of the surfactants. For example, in a coreflood by Klimenko et al. (2020),
it was observed that even a small density of calcium sites on the surface
is sufficient to retain the carboxylate surfactant used (Klimenko et al.,
2020).
Also, injection of microemulsions (i.e., composed of surfactants
mixed with co-solvents, alkali, oil, and brine constituents) that are
highly viscous and have non-Newtonian behavior results in elevated
surfactant adsorption in the field, higher gradients of pressure that are
unsustainable, lower sweep efficiency, and immobile microemulsions
owing to the high viscosity at low shear rates. To alleviate micro­
emulsion viscosity, generally, surfactant formulation is optimized via a
suitable co-solvent and/or via incorporating increased branching into
the hydrophobe of surfactant structure. The co-solvents of proper
amounts are added to create microemulsions of low viscosity. Never­
theless, co-solvents can raise the price and intricacy of the process while
causing increased IFT. In addition, studies on the microemulsions
formed by novel surfactants mixed with polymers (and co-solvents and
alkali), have shown that the SP (co-solvent or alkali) formulations which
are weakened by shear will cause an increase in surfactant adsorption
(Walker et al., 2012; Suniga et al., 2016).
Furthermore, it is recommended to use anionic surfactants in sand­
stone reservoirs for the reason that they adsorb relatively less in com­
parison to other types of surfactants. Sandstone rocks comprise of
substantial portion of silica minerals and tiny portions of carbonates and
silicates. The negatively charged silica causes the electrostatic repulsion
forces existing amid the sandstone formation and the anionic surfactant
to be high, which averts surfactant adsorption into the sandstone surface
(Ma et al., 2013). Nevertheless, there could be adsorption on account of
the clay minerals (mainly kaolinite and illite) present in sandstone,
because the clay’s surface charges have originated from isomorphous
substitution, lattice defects, and broken bonds. Thus, the anionic sur­
factant adsorption on the clay minerals is regulated by the forces of
electrostatic and van der Waals (Kwok et al., 1993; Iglauer et al., 2010).
In carbonate reservoirs, zwitterionic surfactants adsorption on car­
bonate rock surface grows with surfactant concentration increase by
means of electrostatic and hydrophobic interactions, along with micellar
systems. On the other hand, as temperature or salinity increased the
adsorption is deemed as low (Nieto-Alvarez et al., 2014). In contrast,
cationic surfactants exhibit significantly low adsorption onto carbonate
rocks, on account of positive surface charge of calcite and dolomite
minerals. For that reason, cationic surfactants are considered appro­
priate chemicals for carbonate reservoir applications (Lippmann, 2012).
On the other hand, it is shown in certain studies that hydrogen ions act
as potential determining ions (PDIs) for carbonates, which connotes that
the equilibrium pH of the solution regulates the surface charge on the
11
Journal of Petroleum Science and Engineering 220 (2023) 111243
mineral. Due to the complication of carbonate surface charges, it is
difficult to conclude if it is the cationic or the anionic surfactants that
should be utilized in order to diminish the electrostatic attraction forces
between the surfactant molecules and the formation surfaces (Ahmadali
et al., 1993; Ma et al., 2013). Ahmadali et al. (1993) conducted exper­
imental valuations regarding the cationic surfactant’s adsorption on
carbonate minerals. They used two cationic surfactants (i.e., cetylpyr­
idinium chloride, or CPC, and dodecylpyridinium chloride, or DPC) with
synthetic calcite and natural dolomite as samples. They concluded that
the cationic surfactants proved to have considerably lesser adsorptions
in contrast to the anionic surfactant that had comparable hydrophobic
chain lengths. When salts were added with multivalent cations, cationic
surfactant adsorption decreased; however, the anionic surfactant
adsorption increased. This is as a result of the cations addition and the
lattice ions contained in carbonate rocks considerably influenced the
surface charge of the minerals causing anionic surfactant adsorption to
increase. Additionally, their investigations concluded the likelihood of
lessening the surfactant loss caused by adsorption into carbonate
reservoir rocks by way of using cationic surfactants mixed with the
additive multivalent electrolyte in appropriate concentrations.
In summary, surfactant retention can occur due to heterogeneity in
mineral composition and surface interactivities of rock. The surface
geochemistry and the surface charge of carbonate rock can influence the
extent of surfactants retention. For instance, natural limestone has
aluminum and silicon present that causes retention, and even tiny cal­
cium sites on rock surface led to carboxylate surfactant adsorption.
Adding alkali to reduce pH, and pre flush with low salinity water
flooding before SP-based EOR can reduce surfactant adsorption.
4. Novel surfactant formulations for SP-flooding
The most commonly used surfactants types are the Anionic, Cationic,
Zwitterionic and Non-ionic surfactants. Anionic surfactants possess an
anionic effective cluster at their head, like the carboxylates, sulfate,
phosphate, and sulfonate. Cationic head groups surfactants are pH-
dependent primary, secondary, or tertiary amines; i.e., the primary
and secondary amines are positively charged when pH < 10. One of the
cationic surfactants is octenidine hydrochloride. Zwitterionic surfac­
tants have cationic and anionic heads together on the same molecule.
The cationic head is composed of primary, secondary, or tertiary amines
or quaternary ammonium cations, while the anionic head could be more
flexible and have sulfonates included in it (Lwisa, 2021). Non-ionic
surfactants are constituted by covalent bonds of oxygen-containing hy­
drophilic groups, which are attached to hydrophobic parent structures.
The hydrogen bonding imparts the oxygen groups’ water-solubility,
which is inversely proportional to temperature increase; i.e.,
increasing temperature causes the water solubility of non-ionic surfac­
tants to decrease. Non-ionic surfactants are affected to a lesser degree by
water hardness than anionic surfactants, and their foamability is also
less strong. A pictorial chart which details the various classes of sur­
factant and their common types are given below in Fig. 11.
There are only minor differences among each type of non-ionic
surfactants, and their selection is mainly dependent on the costs based
on distinct/required properties (e.g., effectiveness and efficiency,
toxicity, dermatological compatibility, biodegradability) or based on
their approved usage as food ingredient. In the design stage, when it
comes to selecting the surfactants, many times anionic surfactants are
the preferred choice as they tend to have less adsorption at pH ranging
from neutral to high on sandstones and carbonates alike (Sheng, 2010,
2015). They may be modified to suit a wide array of environments and
are easily available at low cost in certain cases. The sulfates are suitable
for implementation in low temperature while the sulfonates are useable
in harsh temperatures. A cationic scan may be applied as co-surfactants
since the performance of non-ionic surfactants for SP-based EOR is
poorer, in comparison to anionic surfactants. Furthermore, the sulfo­
nated hydrocarbons viz., alcohol propoxylate sulfate and alcohol
A.M. Hassan et al.
Fig. 11. Flow diagram of surfactant categories based on head group nature.
propoxylate sulfonate is frequently applied for usage in Surfactant
flooding.
Requirements of an effective surfactant for SP-flooding can be sum­
med up as follows (El-Hoshoudy et al., 2017b): The role of a surfactant is
to reduce IFT between the trapped oil and injected water interfaces to
ultralow values (0.001 mN/m), which would increase the capillary
number (Nc) by a factor of at least three orders of magnitude. This
further reduces the capillary force, leading to decreased oil contact angle
thereby changing the wettability (Wu et al., 2010) which solubilizes
trapped oil and increases mobilization. A surfactant is also selected or
designed to alter the matrix rock wettability toward more water-wet
conditions, as this increases brine-imbibition rates. Another use of sur­
factants is the ability to modify the properties of polymeric systems that
enables a range of applications (Holmberg, 2003). Further useful fea­
tures of surfactants in the process of enhanced oil recovery include,
particle dispersion, emulsion stabilization, foam generation, reservoir
wetting or wettability alteration, and many more (Schramm, 2000; Maia
et al., 2009). Ultimately, a desirable surfactant has the characteristic of
minimal adsorption on reservoir rocks and, long-term temperature sta­
bility, brine salinity, and hardness under reservoir conditions along with
easy compatibility with reservoir fluids, and most importantly have
tolerance to divalent cations such as Ca2+ and Mg2+ ions.
Therefore, the most common surfactant types include the Anionic,
Cationic, Zwitterionic and Non-ionic surfactants, which differ in their
structure and properties. The surfactant is chosen according to its
robustness and long-term thermal and brine salinity, and its capacity to
shift wettability and cause IFT reduction.
4.1. Potential surfactants for SP-flooding under HTHS conditions
As cEOR is extended to extreme reservoir environments (i.e., HTHS),
it becomes evidence that traditional surfactants and polymers,
commonly used in previous decades, are intolerant under harsh HTHS
conditions. The HTHS conditions necessitate the need for formulating
12
Journal of Petroleum Science and Engineering 220 (2023) 111243
surfactants and polymers that are high-yielding in harsh conditioned
carbonates. Therefore, many novel surfactant and polymer families have
been developed recently, which have been assessed carefully for appli­
cability. Since existing surfactants lack the required properties for
extremely reduced IFT, water stability (i.e., wettability alteration to­
wards more water-wet), robustness at elevated temperatures, minimal
adsorption, resistance to extreme salinity and hardness. Formulating
new surfactants with these desirable properties is incumbent. Literature
in this area have introduced three categories of recent large-hydrophobe
surfactants such as Guerbet alkoxy sulfates, Guerbet alkoxy carboxyl­
ates, and Tristyrylphenol alkoxy sulfate surfactants. Other novel sur­
factants are Guerbet Alkoxy Sulfate surfactants (GAS), Guerbet Alkoxy
Carboxylate Surfactants (GAC), Guerbet alkoxy betaine surfactant
(GAB), and polymeric surfactant or surfmers. Their suitability for large
harsh conditioned carbonate reservoirs is described below. Additionally,
latest surfactant structure correlation is detailed further in the paper,
that may be used as benchmark for determining surfactant formulations
that are high-performing.
4.1.1. Guerbet Alkoxy Sulfate surfactants (GAS)
The Alkyl alkoxy sulfates having hydrophobes between 12 and 18,
and have been used widely for cEOR, (Levitt et al., 2006; Flaaten et al.,
2008). However, they are susceptible to higher equivalent alkane carbon
number (EACN) of crude oil and high temperatures. Also, a majority of
these alkyl alkoxy sulfates possess restricted branching. But when a
significantly high carbon number is used for branching Guerbet alcohols
(GA), it turns them into viable surfactant hydrophobes, which can be
very costly when in very-pure form. Even then, Guerbet alcohols may be
produced in cost effective manner if lower than quantitative conversion
is done during the procedure of alcohol dimerization. In addition, this
version of surfactants can exhibit below par hydrolytic stability when
temperatures exceed 60 ◦ C. The half-life of ether sulfate surfactants, i.e.,
the time for decay is approximately 4–6 years, at temperature of 85 ◦ C
(Adkins et al., 2010). Thus, they are recommended to be mixed with one
A.M. Hassan et al.
or more of other classes of surfactants (i.e., as co-surfactants) that have
varying structures, to improve the efficacy of SP-flooding in HTHS car­
bonates. Co-surfactants may also potentially improve aqueous stability
or limit microemulsion viscosity (Adkins et al., 2010). Likewise, by
introducing propylene oxide (PO) and ethylene oxide (EO) to the GAC
surfactant molecules, alkyl alkoxy carboxylates surfactants are formed,
which are better suited for SP-flooding under harsh HTHS carbonates
conditions.
4.1.1.1. Laboratory experiments of novel GAS. A formulation containing
0.25 wt% C32–7PO-14EO-sulfate, 0.25 wt% C20–24-IOS, and 0.5 wt%
TEGBE cosolvent was examined in a phase behavior test at 100 ◦ C (Levitt
et al., 2006). A light oil (API of 29, μo of 4.0 cP) with a limited acid
number signifying an inactive oil, was employed for this formulation.
Upon observing the microemulsion phase behavior, the solubilization
ratio at optimal salinity was seen to be around 17, which was correlated
to an exceedingly reduced IFT of 1.0 × 10− 3 dyn/cm. In the water-based
solution, 500 ppm Flopaam 3630 polymer was added, which was clear
and stable at temperature of 100 ◦ C in the presence of 35,000 ppm of
sodium carbonate (Levitt et al., 2006). The authors also conducted a
coreflood to deduce the efficacy of the surfactant formulation. The
core-samples possessed a permeability of 2500 mD and a porosity of
0.217. A 0.5 pore volume (PV) of surfactant mixture having a 0.5 wt%
formulation density, was injected and afterwards a polymer drive was
introduced. There was 94.7% oil retrieval of the total residual oil satu­
ration following the waterflood process and the eventual oil saturation
was approximately 0.02. On the rock, the retained surfactant was noted
as 0.11 mg/g of rock, which is a favorable reduction for limiting the
expenses of the projects. Through the chemical flood, pressure declined
to 0.4 psi/ft at a 1 ft/day frontal velocity. This minor pressure decline is
greatly advantageous as the pressure gradient inside reservoirs, gener­
ally tend to hover around 1 psi/ft (Levitt et al., 2006). Thus, the in­
vestigations show that GAS surfactants with co-surfactants and
cosolvent are resilient and effective under high temperature, which
could be potentially applicable for SP flooding in harsh HTHS carbonate
reservoirs.
4.1.2. Guerbet Alkoxy Carboxylate Surfactants (GAC)
Since the Guerbet alkoxy sulfates cannot tolerate temperatures over
60 ◦ C, except when the pH is between 10 and 11 (Adkins et al., 2010).
This elevated pH is maintained by means of traditional alkali additives.
However, this is not possible in cases where there is exposure to gypsum
or anhydrite in the reservoir rock or when softening of water injection is
not available.
Ether sulfonates can be an alternative as they can tolerate extreme
temperature and extreme hardness (Puerto et al., 2012). However, they
are difficult to produce; rendering them expensive and their commercial
procurement is limited. In this regard, Alkyl alkoxy carboxylates are a
potential substitute as they are of an anionic surfactant family that can
be applied in SP-flooding (Shaw, 1984; Li et al., 2000, 2005). Adding
propylene oxide (PO) and ethylene oxide (EO) to the molecule, can
create alkyl polyoxy propylene/ethylene (alkoxy) carboxylates (AEC)
which are multifunctional. When compared with alkyl carboxylates
(soap), these AECs have been shown to have excellent resistance to
hardness, together with a favorable aqueous solubility and tolerance to
pH alterations or changes in electrolyte levels (Behler et al., 2001; Rosen
and Kunjappu, 2012). Therefore, the AEC are great substitutes for alkoxy
sulfates in certain types of reservoir environments. Other attractive
features of the AEC are that, they can be paired with versions from all the
varieties of surfactant categories and are also quite convenient to use
(Behler et al., 2001). Above all, the AEC can maintain stable state at very
high thermal conditions, can remain chemically constant and can be
used in acidic and alkaline pH alike (Mayer et al., 1983; Thomas, 2008;
Ramsey, 2019; Abalkhail et al., 2020), with no decay in carboxylate
functional group, which makes them especially suitable for cEOR
13
Journal of Petroleum Science and Engineering 220 (2023) 111243
(Behler et al., 2001; Rosen and Kunjappu, 2012). Therefore, to employ
AEC surfactants for SP-based EOR with minimal expenses incurred,
large-hydrophobe AEC surfactants have been designed. The structure of
Guerbet alkoxy carboxylate (GAC) surfactant can be modified according
to the particular cEOR requirements. This design modifications are done
by changing the carbon numbers in the Guerbet alcohol and though
change of the propylene oxide (PO) and ethylene oxide (EO) groups’
numbers (Adkins et al., 2012). Fig. 12 shows an example of the poly­
meric non-ionic surfactants structures namely, the Propylene oxide (PO)
and Ethylene oxide (EO). These design modifications are conducted by
changing the carbon numbers in the Guerbet alcohol and the PO and EO
groups’ numbers, which ere formulated by Nakagawa et al. (1998).
Additionally, these novel surfactants when used in combination with
cosurfactants and cosolvents have proven to form effective formulations
with desirable properties shown via microemulsion phase behavior and
coreflooding experiments (Lu et al., 2014c). These experiments were
conducted successfully on different types of oils with varying composi­
tions and were performed under harsh HTHS reservoir conditions (Lu
et al., 2014a, 2014c).
4.1.2.1. Laboratory experiments of novel GAC. A new formulation con­
taining 0.5 wt% C28–45PO-60EO-carboxylate and 0.5 wt% C15–18-IOS
was tested, which displayed excellent phase behavior at 120 ◦ C without
a co-solvent when a medium gravity oil (API = 22, μo = 1.1 cP) was
employed. At an optimal salinity, the solubilization ratio was 13 (Lu
et al., 2014c).
The formulation of 1.0 wt% C32–7PO-32EO-carboxylate and 1.0 wt
% C19–23-IOS was tested for microemulsion phase behavior at 100 ◦ C
after 545 days for a light oil (API = 34, μo = 0.5 cP) with a low TAN. The
optimal salinity was 36,000 ppm and the optimal solubilization ratio of
11 showed corresponding IFT reduction to be satisfactory at about
0.003 dyn/cm, which is feasible for majority of cEOR schemes. To
develop a substitute and to create cheaper co-surfactants, a C11-linear
alkyl benzene sulfonate (ABS) was formulated and examined in order
to replace the IOS with the same oil (API = 34, μo = 0.5 cP). Another
formulation with 0.7 wt% C28–25PO-55EO-carboxylate and 0.3 wt%
C11-ABS was observed to have excellent microemulsion phase behavior
in hard brine and its maximum solubilization ratio was 11 at optimal
salinity of 30,000 ppm. It is well known that ABS cannot be used in hard
brine but, this experiment showed a harmonious combination of the
GAC and the ABS that enhanced the efficacy and the stability in water
for both these surfactants (Lu et al., 2014c).
Founded on the results of a preceding microemulsion phase behavior
experiment, a core flood was performed (Lu et al., 2014c). A Silurian
dolomite core was taken, having highly vuggy form and high hetero­
geneity (through visual inspections and CT scans), the brine perme­
ability was of 478 md and the porosity was 0.168. As GAC was being
investigated for the first time in a dolomite core, a larger surfactant slug
was injected into the core of (PV × C of 50) %, after which a polymer
drive was injected. The pore volumes of the surfactant slug multiplied
with the surfactant concentration (PV × C) provides the total mass of
injected surfactant and is an important indicator when comparing cor­
eflood efficiencies. Here PV stands for pore volume and C denotes sur­
factant concentration. Having a low surfactant retention allows for
Fig. 12. Structure of Propylene oxide (PO) and Ethylene oxide (EO) polymeric
non-ionic surfactants (modified after Nakagawa et al., 1998).
A.M. Hassan et al.
successful corefloods when (PV × C) % is low. The results showed the oil
recovery at 90.5% of residual oil after the waterflood having a Sorc of
0.044 (HPLC i.e., High-Performance Liquid Chromatography was used
to gauge the surfactant concentration and retention on the effluent
specimens). The overall surfactant retention on the rock was observed to
be 0.33 mg/gm rock, the pressure decline throughout the chemical flood
was noted as 1.5 psi/ft at a 2 ft/day frontal velocity and this low
pressure-drop is beneficial as is near to the gradient of field pressure.
In order to further evaluate the efficacy of the formulation, a lesser
concentration of surfactant was used in the slug, for the very same oil, a
different coreflood was performed in relatively homogenous Estaillade
limestone core having permeability of 187 md and a porosity of 0.276,
and containing 0.15 wt% C28–25PO-45EO-carboxylate, 0.15 wt%
C15–18-IOS. This core was injected with a 1.0 PV surfactant/polymer
(SP) slug with (PV × C of 30) % and afterwards a polymer drive was
injected. It was observed that the oil output was 94.5% with Sorc at 0.008
and the overall retention of surfactant on rock surface was 0.34 mg/g
rock. In case of C15–18-IOS, there was overall surfactant retention of
0.16 mg/g rock and for C28–25PO-45EO-carboxylate the final value of
retention of surfactant on rock was 0.18 mg/g rock. Furthermore,
chromatographic separation was not observed, neither was any prefer­
ential retention of these chemicals noticed. Moreover, because there are
high divalent cations (hardness) concentration and high salinity in many
reservoirs, robust surfactant formulations are necessary for these
extreme conditions (Lu et al., 2014c).
Furthermore, another SP formulation for high optimum salinity and
extreme hardness for a light oil (API of 36.5, μo of 1.8 cP) is 1.0 wt%
C28–25PO-55EO-carboxylate, 0.5 wt% C15–18-IOS, 0.5 wt% C19–23-
IOS, and 1.0 wt% TEGBE, which was investigated at 83 ◦ C. In this
formulation, TEGBE stands for triethylene glycol monobutyl ether used
as co-solvent. Both the co-surfactant (IOS i.e., internal olefin sulfonate
was used here) and the co-solvent (TEGBE) aid in averting the surfactant
molecules from packing tightly in the micelles which can lead to weak
mobility or high retention on formation rock surfaces. This formulation
examined was on an Estaillade limestone core specimen having
permeability of 144 md and porosity of 0.24. At the beginning, the
salinity of (formation) brine was 230,800 ppm and there was a 21,700-
ppm divalent cation concentration. For the preparation of the slug, brine
with a salinity of 67,000 ppm TDS was used and with a divalent cation
concentration of 3700 ppm present. It was discovered that this GAC
surfactant was very efficient in enhanced oil recovery and upon intro­
duction of 0.2 PV SP slug, the oil recovery was observed at 92% whereas,
the ultimate saturation was noted at 0.016, and surfactant adsorption
value was 0.3 mg/g rock (Lu et al., 2014c).
In another experiment, a potential surfactant formulation based on
novel large-hydrophobe Guerbet alkoxy carboxylate surfactant was used
and an IOS co-surfactant was designed for HTHS carbonate reservoir (Lu
et al., 2014a). Initial temperature was 100 ◦ C and salinity was 116,969
ppm. They performed both static and dynamic core experiments, and in
the dynamic coreflood experiment, the oil saturation decreased to 0.14
when surfactant was used in a small amount without polymer and the
core was extremely vuggy and fractured. The surfactant retention was
only 0.086 mg/g rock. The resultant oil recovery was excellent with the
dynamic coreflood delivering a higher yield than the static imbibition
experiment at similar conditions, even though, there were fractures in
the core and it was especially vuggy. Moreover, it is to be noted that
mobility control was discarded, and a very small amount of the surfac­
tant slug had been inoculated. Therefore, the results of dynamic core­
flood showed much greater oil retrieval as opposed to the results from
similar static imbibition experiments.
These investigations indicate that GAC formulations are effective in
SP-based EOR techniques in harsh carbonate conditions, making them
apposite for field applications.
4.1.3. Guerbet alkoxy betaine surfactant (GAB)
The recent years have seen significant development in various
14
Journal of Petroleum Science and Engineering 220 (2023) 111243
betaine surfactants that have been well assessed for SP flooding that
have high interfacial activity at oil-water interface, have superior ther­
mal stability and resistance to salt (divalent ion) under HTHS reservoir
conditions. In order to be able to resist HTHS conditions and handle
severe technical challenges, surfactant structure was needed to be
enhanced (Han et al., 2013). Thus, to improve thermal tolerance, salt
resistance and emulsification enhancement, Guerbet alkoxy betaine
surfactant (GAB) was formulated and evaluated for a HTHS low
permeability reservoir. The branched hydrophobic group and EO in the
novel GAB surfactant formulation significantly heightened the emulsi­
fying ability. On the other hand, sulfonate hydrophilic group in the GAB
structure imparted exceptional thermal stability. It was tested effec­
tively at TDS of high formation brine (274,823 mg/L) with divalent ion
content of approximately 27,000 mg/L and at reservoir temperature of
95 ◦ C and formation permeability within 10–30 mD (Cai et al., 2019).
Hence, the GAB surfactants are high potential candidates for HTHS
carbonate application using SP-flooding technique. This is also evinced
from the experimental studies in ensuing sections.
4.1.3.1. Laboratory experiments of novel GAB. A novel Guerbet alkoxy
betaine surfactant (GAB) was designed for SP flooding and its charac­
teristics were investigated (Cai et al., 2019). The betaine surfactant
molecule was incorporated with ethylene oxide (EO) functional group to
enhance the emulsification ability and Guerbet alcohol was chosen as
the hydrophobic group. In the first step, glycidyl ether was derived by a
reaction of alkoxylated Guerbet alcohol and epoxy chloropropane, fol­
lowed by deriving tertiary amine through glycidyl ether and dimethyl
amine. Finally, through quaternization reaction of tertiary amine with
3-chloro-2-hydroxyl propane-sulfonic acid sodium salt, the GAB sur­
factant was developed. Lab investigative methods such as IFT, long term
stability, contact angle, and phase behavior were conducted for this GAB
surfactant to assess its overall performance. An excellent tolerance and
desirable conformity to high temperature, high salinity (HTHS) reser­
voir conditions were observed. This new GAB surfactant could be
applied in salinity up to 275,000 mg/L and temperatures ranging to
120 ◦ C. The diluted GAB solutions when used for crude oil exhibited
ultralow IFT having the concentration of weight from 0.03% to 0.20%.
Other formulation containing 0.5% GAB and 0.5% amid-betaine,
showed Winsor III middle phase microemulsion formation with dehy­
drated light oil in HTHS carbonate reservoir. At reservoir temperature of
95 ◦ C and optimal salinity of 50,000 mg/L, the solubilization ratio
reached a value of 16.
Thus, the improved betaine surfactant GAB showed better thermal
stability, higher interfacial activity, and intensified emulsification fea­
tures under HTHS carbonate conditions, in comparison to Guerbet
alkoxy sulfate surfactant and conventional sulfobetaine with similar
structure.
4.1.4. Tristyrylphenol alkoxy sulfate surfactants (TSP)
The TSP-based EOR surfactants were designed and tested for the
purpose of creating large quantities and variations of feed-stocks of
effective and reliable cEOR surfactants for use in prospective schemes. It
is possible to reproduce this petrochemical based hydrophobe in huge
amounts so that it can be useful for large scale field schemes. TSP is a
large hydrophobe that is widely marketed, with the ethoxylated variant
of TSP being well established as agricultural dispersants and in surfac­
tant formulations for pesticides (Derian et al., 1993; Gubelmann-Bon­
neau et al., 1995). When in the state of a phenol, it readily becomes
alkoxylated with propylene oxide (PO) and ethylene oxide (EO) forming
nonionic surfactant with massive molecular weight. Also, the degree of
the propylene oxide (PO) and ethylene oxide (EO) levels can be grafted
to suit the HLB according to the oil/brine mixture’s requirements and
when it is sulfated with sulfamic acid, it forms anionic surfactant of
substantial molecular weight which is a very inexpensive procedure,
thus, TSP alkoxy sulfates can be easily bulk produced and marketed
A.M. Hassan et al.
(Liyanage et al., 2012). A pictorial diagram of synthesis sequence of a
TSP surfactant for large-scale production is shown in Fig. 13.
Hence, in the investigations by Lu and co-workers, the micro­
emulsion phase behavior experiments of the new TSP surfactants
showed extremely reduced IFT and a transparent water-based solution,
beyond optimum salinity, for a highly viscous oil (difficult oil), when
every other formulation for this case had failed to perform effectively
(Yang et al., 2010). Furthermore, these surfactants’ efficacies and
employability, were tested via corefloods using a surrogate oil and a live
oil at high-pressure, and the observations signified exceptional perfor­
mance with increased oil output (92.8% of the residual oil post water­
flood with a final oil saturation of 0.013) and negligible retention of
surfactant on rock surface (0.10 mg/g of rock) (Lu et al., 2014c).
Thus, a series of experimental laboratory studies using many TSP
surfactants have demonstrated the capability of these surfactants in
effective SP-based cEOR trails. The TSP surfactants are stable in HTHS
environment and effective in recovering highly-viscous oils.
4.1.4.1. Laboratory experiments of novel TSP. In a micro-emulsion phase
behavior test, Liyanage and co-workers demonstrated the capability of
the alkoxylated variant of these TSP-based surfactants in an active oil of
medium type (API = 28, μo = 14 cP) that had a complete acid number of
1.0 mg KOH/g oil at 62 ◦ C. To suit this surfactant and this experiment,
finding an ASP formulation having existing surfactants for this partic­
ular oil proved to be a challenging task. Nevertheless, superb solubility
in water was observed for TSP alkoxy sulfates even as it retained the
activity at the surface of this oil, resulting in phase behavior and core­
flood experiments with successful conclusions. These synthesized for­
mulations were then examined in outcrops as well as reservoir
corefloods by taking a surrogate oil and also an artificial live-oil, in
which excellent oil output was yielded and there was minimal surfactant
adsorption thus meeting the experimental objectives (Liyanage et al.,
2012).
An expansive set of TSP alkoxy sulfates, that had molecular weights
ranging from 1250 to 3600 g/mol were developed and tested. In the
selected oil, the surfactant with the highest potential had the formula­
tion containing 0.18 wt% TSP-35PO-20EO-sulfate and 0.12 wt%
C20–24-IOS. There were no cosolvents added in this formulation, even
then, at the temperature of 62 ◦ C in the reservoir, it performed well for
the selected oil. Also, upon conducting a survey of salinities using the
surrogate oil, elevated optimum solubilization ratios were observed
along with a large extremely low IFT sites for WORs (water-to-oil ratios)
ranging from 1 to 9. Also, in the representative activity diagram it was
observed that, there was a small negative descent across the tested
WORs, which was highly desirable. Furthermore, in the coreflood for
Bentheimer sandstone having permeability of k ≈ 2 Darcy, and porosity
of φ ≈ 0.24, this very same surfactant formulation performed very well
by retrieving 92.1% of the post waterflood residual oil leaving the
Fig. 13. A schematic of TSP synthesis sequence with x (PO)-y (EO) sulfate surfactants (modified after Liyanage et al., 2015).
15
Journal of Petroleum Science and Engineering 220 (2023) 111243
saturation of oil at 0.024 towards the end. When HPLC (High-Perfor­
mance Liquid Chromatography) quantifications were conducted, the
surfactant adsorption value was 0.10 mg/g of rock, and the two sur­
factant constituents, showed no visible chromatographic separation in
the core (Liyanage et al., 2012).
For the corefloods by Lu and co-workers, a surfactant formulation
with content of 0.20 wt% of the TSP-7PO12EO-sulfate and 0.05 wt% of
sodium dihexyl sulfosuccinate was investigated in an unconsolidated
reservoir-sand (k ≈ 4.6 Darcy, φ ≈ 29%) with the aim of retrieving live
oil that had been reconstituted. This live oil had 31 mol% of methane
and 9 mol % of carbon dioxide content in it, with the pressure at satu­
ration being 1490 psi. Additionally, this coreflood experiment was
conducted in a pressure of 1700 psi that was a marginally higher.
Eventually, this surfactant formulation was able to recover 92.8% of the
total post waterflood residual oil after leaving the saturation value
0.013 at the end, and on the rock the surfactant adsorption was at a
value of 0.10 mg/g (Lu et al., 2014c).
In summary, the TSP surfactants have proven to be highly stable
during the laboratory experiments and delivered the desired outcomes.
They have yet to be extensively studied for stability and efficacy in very
high temperature and salinity.
4.1.5. Gemini surfactants
To assuage the problems of hydrolysis and precipitation in HTHS
carbonate reservoirs, cationic gemini surfactants have been synthesized
and characterized recently. The cationic gemini surfactants with aro­
matic rings in varying numbers within the spacer group, along with
diverse counter ions, were synthesized (Hussain et al., 2019). The out­
comes of the thermogravimetric characterizations reveal that these
novel gemini surfactants decompose at approximately 300 ◦ C. This ex­
ceeds the prevailing temperature of ≥100 ◦ C of current oilfields.
Moreover, with the addition of ethoxy units amid the lipophilic tail and
lipophobic head groups, a considerably improved solubility is obtained
in both highly saline brine and in ordinary water with no precipitate or
any murkiness. It was also observed that when there were two aromatic
phenyl rings in the spacer groups, the gemini surfactants present a
reduced CMC than one phenyl ring gemini surfactants (Hussain and
Kamal, 2017; Hussain et al., 2019; Mahboob et al., 2022). Also, previous
studies observed that with short spacer length, the gemini surfactants
produced single-phase microemulsions, and with more extended spacer
groups, gemini surfactants exhibited typical (conventional) surfactant
behavior (Mahboob et al., 2022).
Besides, gemini surfactants were applied for field trials in Algyo field,
Hungary and exhibited high tolerance to hardness which is much higher
than the prevailing temperatures of ≥100 ◦ C in current oilfields (Puskas
et al., 2017). In one of the field applications, at Cottonwood Creek,
Bighom Basin, Wyoming, USA, the nonionic-surfactant polyoxyethylene
alcohol was used with satisfactory field application results.
To sum it up, gemini surfactants have exceptionally high heat and
A.M. Hassan et al.
salinity tolerance with excellent solubility. With supplementary studies,
they can be developed to perform exceedingly well for SP-based EOR in
carbonates under harsh conditions.
4.1.5.1. Laboratory experiments of gemini surfactant. Through enduring
laboratory research of over 10 years, Puskas and co-authors (Puskas
et al., 2017, 2018) developed optimal compositions of surfactant mix­
tures, which consist of highly effective gemini surfactants, and supple­
mentary surfactants (co-surfactants), which were produced from waste
materials or inexpensive raw materials. The gemini surfactants are a
type of novel surfactants with multiple hydrophilic head groups and
hydrophobic tail groups connected by a spacer at or near the head
groups. The exceptional properties of gemini surfactants, is the low
critical micelle concentration (CMC), desirable aqueous solubility, and
uncommon micelle structures and aggregation behavior. Also, because
they are highly efficient in oil/water IFT reduction and have certain
rheological properties, they have caught the interest of the researchers
dedicated to EOR applications in field projects (Páhi et al., 2008, 2009;
Bergström et al., 2015; Kamal, 2016). The synthesized gemini surfac­
tants molecules with improved properties in comparison to conventional
surfactants based on laboratory studies of parameters such as critical
micelle concentration, surface tension, IFT, and wettability. The new
surfactant compositions contained both gemini surfactants and
co-surfactants, to function as adsorption reducing agents for gemini
surfactants on the reservoir rock surface and to provide greater tolerance
to both salinity and hardness. The past decade has seen the development
of over 300 non-ionic surfactants (and co-surfactants), which were
examined and evaluated based on several parameters such as acid
number that demonstrates the total content of acidic additives that are
water soluble and insoluble. Apart from this, the saponification number
was analyzed as a parameter which is expressed in milligrams of po­
tassium hydroxide, as it is essential for the saponification of all free and
bonded acid in 1 g sample. Another important parameter was water
solubility of surfactants measured, which was measured by determining
the water number, which characterizes the relative solubility of sur­
factants in both water and oil (Bergström et al., 2015). Next, the HLB
was evaluated due to its involvement in the hydrophilic/lipophilic na­
ture of the surfactants, and may allude to the surfactant’s efficacy, and
indicate if the main groups in the surfactant mixtures are the water
soluble or the oil soluble functional groups (Puskas et al., 2018).
In addition, over 1000 surfactant mixtures were developed from
Geminis and co-surfactants, and were tested in the laboratory selection
phase via complex laboratory screening methods, to determine the
surface-active properties and their potential efficacy for SP based cEOR.
The screening methods of surfactant mixtures that were most essential
are, the solubilization efficiency and determining the oil displacement
effect by thin layer chromatography. In solubilization efficiency tests,
special laboratory equipment was used to shake together the mixture of
surfactant solution and crude oil at room temperature (ambient). After a
duration of rest, separation of the phases had occurred and the formed
phase’s volumes were measured. Also, after storage for 24 h at reservoir
temperature (98 ◦ C), the phase volumes were repeatedly evaluated. The
aqueous phase, emulsion and oil amounts were measured in comparison
to the total liquid volume. The solubilization efficiency was studied with
regards to the diverse effects of the surfactant mixture on the emulsions
types that would typically form in the natural reservoir due to the
original phases. Then, using thin layer chromatography, the displace­
ment effect was determined after the thin layer was prepared on a glass
plate, from original core sand. Crude oil was introduced to the thin layer
and allowed to dry. Following which, the glass plate was submerged into
the glass cylinder of surfactant aqueous solution mixture. Several hours
later, the distance between the drop and the edge of the oil spill was
measured, which specifies the displacement efficiency of the surfactant
mixture. From the results of the single laboratory tests, it could be said
that the displacement efficiency of surfactant packages would be
16
Journal of Petroleum Science and Engineering 220 (2023) 111243
attained by only a well-balanced combination of surfactant properties
(Puskas et al., 2018). These formulations have been employed at Algyo
field; Hungary for SP based cEOR. The field is a sandstone reservoir with
depth of 1800–1900 m TVD, 191.3 bars original formation pressure,
98 ◦ C reservoir temperature, 70 mD oil permeability, and 23.7% average
porosity. The formation oil is of low viscosity (0.64 cP at 98 ◦ C and 190
bars) (Puskas et al., 2017).
Thus, even though a finely balanced combination is required for
achieving the target properties, gemini surfactants have exceptionally
high heat and salinity tolerance with excellent solubility. With supple­
mentary studies, they can be developed to perform exceedingly well for
SP-based EOR in carbonates under harsh conditions.
4.1.6. Zwitterionic or amphoteric surfactant
Surfactants are typically categorized into four main types: anionic,
cationic, non-ionic and zwitterionic (or amphoteric) surfactants (Gupta
et al., 2020; Lu and Pope, 2017; Mejia et al., 2019; Pei et al., 2018;
Saxena et al., 2019). The zwitterionic (amphoteric) surfactants exhibit
either of the positive or negative charge depending on the solution pH
(Lv et al., 2011). The presence of cationic moieties such as, amines or
quaternary ammonium groups create the positive charge whereas the
negative charge is created due to the anionic moieties such as sulfonic
acid, carboxylic acid (Zhang et al., 2019). The amphoteric surfactants
can shift the wettability state of both sandstone and carbonate rocks
effectively into more water-wet surfaces. The amphoteric surfactants
alter the sandstone surface wettability by way of ion-pairing between
the amphoteric hydrophilic head and the adsorbed basic crude oil con­
stituents on sandstone rock. As the surfactant concentration increases
the crude oil components are increasingly desorbed causing more
water-wet rock surfaces. For carbonate rock surfaces, the wettability is
altered due to the ammonium ions and the adsorbed acidic crude oil
constituents forming ion pairs on carbonate surfaces changing it to
water-wet (Kumar and Mandal, 2019). Moreover, increasing zwitter­
ionic surfactant concentration results in contact angle reduction in
carbonate rocks (Souraki et al., 2019; Amirpour et al., 2015). For the
reason that of the zwitterionic surfactants heads have amphoteric
charges on them, the wettability alteration process in carbonate rocks
swift (Kumar and Mandal, 2017). The zwitterionic surfactants that
demonstrated favorable characteristics for cEOR process are carboxyl
betaine type, hydroxyl sulfonate betaine type, didodecylmethylcarboxyl
betaine, and alkyl dimethylpropane surfactants (Kamal et al., 2017;
Massarweh and Abushaikha, 2020). Furthermore, the amphoteric sur­
factants, which have low Critical Micelle Concentration (CMC) are
applicable for HTHS conditions. However, when compared to other
surfactants, these zwitterionic surfactants are significantly costlier (Lv
et al., 2011).
4.1.6.1. Laboratory experiments of zwitterionic surfactant. In an experi­
ment, OCT-1 amphoteric surfactant was studied for IFT reduction and
phase behavior with different surfactants in Saudi Arabian seawater of
salinity 57,000 ppm. The results showed desirable IFT reduction,
without significant microemulsion phase behavior. However, these
surfactants are expensive and used only in certain conditions (Butt et al.,
2003; Fuseni et al., 2013; El-Hoshoudy et al., 2015a). Similarly, Chen
et al. (2019) showed that adding zwitterionic co-surfactants to
oil-swollen micelles can significantly improve the high salinity colloidal
stability of alkylbenzene sulfonates. Through investigational and
atomistic molecular dynamics simulations it was found that the less stiff
oil/water interfaces with mixed surfactants, which created fewer but
larger homogeneous micelles, significantly reduced the poly-dispersity
of surfactant mixed with oil-swollen micelles. In addition, it was
observed that sulfonates underwent significant dehydration as a result of
shielding from more bulged zwitterionic co-surfactants at the oil/water
interfaces. The co-surfactants successfully reduced the total exposures of
sulfonates to the aqueous phase, which could lead to divalent ion
A.M. Hassan et al.
bridging and formation of large aggregates. Thus, it was discovered that
the highest levels of sulfonate dehydration are found at flat oil/water
interfaces of extremely big oil-swollen micelles, which show that small
quantity of mineral oils could further increase the high salinity colloidal
stability (Chen et al., 2019). Thus, even with a higher price point, the
zwitterionic surfactants can provide robust performance in HTHS car­
bonates. By using hybrid SP-based cEOR and improving SP formulations
the surfactant retention and project cost may be reduced to optimize the
implementation.
4.1.7. Other surfactants formulations
Other SP formulations were developed by Panthi et al. (2022) at a
high temperature (100 ◦ C), high salinity (57,000 ppm), and particularly
high hardness (2760 ppm) carbonate reservoir, resulting in extremely
low interfacial tension. Acrylamido-tertiary-butyl sulfonate copolymer
SAV10xv was discovered to be stable in these HTHS environments. A
formulation of three surfactants viz., carboxylate, an IOS, and a betaine
in combination with a pre-flush, according to coreflooding results,
generated cumulative oil recovery in the range of 77–82% OOIP and a
residual oil saturation of 8–11%. The surfactant retention was 0.133
mg/g of rock without the use of NaPA; however, after pre-flushing with
NaPA, the retention was reduced to 0.017–0.038 mg/g of rock.
SP-flooding projects in HTHS carbonate reservoirs can be improved by
using these surfactant formulations with a preflush of sodium poly­
acrylate and very low surfactant retention.
In Appendix-A, Table A-2 summarizes the several novel surfactants
formulations, which can be suitable for HTHS conditions in carbonate
reservoirs during SP-based cEOR.
5. Novel polymer formulations for SP-flooding
Polymers are used for mobility control and for imparting viscoelastic
characteristics to the injection fluid in SP-based cEOR systems. Most
commercial polymers such as HPAM cannot be employed in HTHS
carbonate reservoirs owing to thermal instability, adsorption on rock,
loss of viscosity, mechanical degradation, etc. Lately, researchers have
developed novel polymers that are capable of withstanding HTHS and
low permeability of carbonates with good viscous power and shear
tolerance. These novel polymer formulations with their respective ex­
periments have been listed in the following sections.
5.1. Potential polymers for SP-flooding under HTHS conditions
The novel polymers investigated for SP-flooding in HTHS carbonates
include the hydrophobically associating polyacrylamide polymers
(HAPAMs) and its derivatives, surfmers, HMAs, NVP based polymers,
and certain biopolymers. These were evaluated for their physio-
chemical properties, for instance, viscosity, rheology, salt tolerance,
and emulsification. Also, micro-models and coreflooding tests were
conducted to determine the mechanism and the effectiveness of the
polymers during the SP based cEOR process. Furthermore, field appli­
cations were carried out using some novel polymers. Moreover, to study
the chemical structure of these polymers (latexes), many methods were
used such as, FTIR (Fourier-transform infrared spectroscopy), 13C-NMR
(13C Nuсleаr Mаgnetiс Resоnаnсe), 1 H-NMR (Hydrogen 1 Nuсleаr
Mаgnetiс Resоnаnсe), SEM (scanning electron microscope), X -ray
diffraction, and TEM (transmission electron microscope). The results
and potential implication for field applications in HTHS carbonates have
been described in the ensuing sections.
5.1.1. Polymeric surfactant
Polymeric surfactants are a type of functional surfactants, having an
amphiphilic structure i.e., a hydrophobic tail and hydrophilic head
group (Gao et al., 2008) but with an additional feature of polymerizable
vinyl double bonds (Reb et al., 2000) in their molecular conformation,
which imparts physicochemical properties that are more dynamic
17
Journal of Petroleum Science and Engineering 220 (2023) 111243
compared to conventional surfactants (Guyot, 2004). Polymeric sur­
factants are also a feasible substitute for traditional chemical processes
as they have excellent tolerance to harsh conditions and have better
mobility with lower molecular weight than most polymers. They provide
multifunctional mechanisms including interfacial tension (IFT) reduc­
tion and increased viscosity. They are considered to be more adaptable
in improving recovery as a result of mobility control and fluid redistri­
bution caused by induced wettability alteration (Raffa et al., 2015,
2016a; Raffa, 2021; Afolabi et al., 2022). It must be noted that there is
rarely any explicit performance calculation of polymeric surfactants to
be found in literature regarding EOR (Raffa et al., 2016b). Nonetheless,
polymeric surfactants can be suitable alternatives for use in cEOR via
SP-based techniques.
5.1.1.1. Laboratory experiments of polymeric surfactants. The synthesis,
rheology, surface/interfacial tension, wettability, adsorption phenom­
ena, and recovery performance of polymeric surfactants have been
covered extensively in the literature. The majority of research on poly­
meric surfactants has focused on synthetic, high molecular weight (over
1 million Daltons or g/mol) polymeric surfactants, particularly those
that are hydrophobically modified or associate with polyacrylamides. It
was observed that unlike traditional polymers like HPAM, they possess
more remarkable rheological and emulsifying capabilities. The
hydrophobically-associating features of polymeric surfactants are the
basis of their greater tolerances to salinity, temperature, and shear.
However, because of their restricted surface activities, they are unable to
lower IFT to the extremely low levels required to create microemulsions
and successfully mobilize the oil trapped in micropores. Even so, an
ultra-low IFT is not always necessary for an effective SP-flood, as newer
studies suggest (Raffa, 2021; Afolabi et al., 2022). Also, the technical
problems present in chemical flooding techniques can be eliminated
with polymeric surfactants, which include unwanted fluid-fluid in­
teractions and chromatographic separation caused by selective adsorp­
tion and mechanical entrapment (Raffa et al., 2016a). The
multi-component injection slugs like the SP slugs, are vulnerable to
failure in complicated and highly heterogeneous reservoirs due to the
gravity segregation of fluid components. For tertiary recovery applica­
tions in these formations, amphiphilic polymers are expected to be
successful. In addition, polymeric surfactants can eliminate surface fa­
cility operational complications such as, scale buildup and corrosion
caused by alkali chemicals in ASP (Olajire, 2014).
Concerning rheological characteristics, polymeric surfactants exhibit
comparatively mild surface-active properties (Raffa et al., 2016b; Guo
et al., 2016; Negin et al., 2017), which is potentially due to molecular
size of the high-weighted polymeric surfactants. It has been generally
observed that low-weighted amphiphilic polymers are some of the few
that can achieve extremely low IFT (Barakat et al., 1989; Cao and Li,
2002; Wu et al., 2017). At their best, polymeric surfactants have been
observed to achieve IFTs of 0.5–1 mN/m (Cao and Li, 2002) and surface
tensions of 25–30 mN/m (Mehrabianfar et al., 2021). The emulsification
capacity of polymeric surfactants depends on the length of the hydro­
phobic branch chains (Maltesh and Somasundaran, 1992; Li et al.,
2018). The surfactant concentration increases the properties of emulsi­
fication and surface tension/IFT reduction until the CMC is reached.
Beyond CMC, the additional surfactant molecules mainly migrate from
surfaces into solutions, to form aggregates with various morphologies,
and based on either oil or brine being the dwelling medium, the mor­
phologies are cylindrical, spherical, or even club-shaped (Cao and Li,
1999; Hong et al., 2007). When these assemblies can capture oil globs,
emulsification follows. The non-ionic amphiphilic polymers are tolerant
to divalent cations up to reasonably high levels (Sarsenbekuly et al.,
2017). By adding functional groups to the scheme, such as through
fluorination and sulfonation (Akbari et al., 2017; Li et al., 2018), the
functionality of the hydrophobically modified polyacrylamide is
improved. Till date, the cEOR capacity of the low molecular weight
A.M. Hassan et al.
(102–106 Da) polymeric surfactants have been investigated in a number
of studies, although the findings are not conclusive, and requires further
research. In addition, the EOR potentials have not been sufficiently
substantiated by the coreflood or sand-pack tests, despite the fact that
the bulk rheology as well as surface and interfacial tension tests pro­
duced positive findings. The lack of investigations on in-situ fluid-rock
interactions and displacement experiments, also made it difficult to
establish key tendencies in rheological and interfacial behaviors so far
(Afolabi et al., 2022).
Furthermore, Li et al. (2018) designed two new polymeric surfac­
tants, SP-1 and SP-2. These were synthesized by incorporating varying
hydrophobic groups on to polymer chains, and then the physio-chemical
properties such as viscosity, rheology, salt tolerance and emulsification,
were gauged. Micro-models and coreflooding tests were conducted to
identify the mechanism and the effectiveness of the surfmers during EOR
application. Later, a field application was carried out in order to
investigate the field applicability of polymeric surfactants for EOR. Re­
sults showed that the viscosity of both the surfmers was considerable in
comparison to a polymer with moderate molecular weight. The surfmer
SP-1 (with alkyl sulfonate functional groups) showed greater viscosity
and salt tolerance in comparison to the SP-2 (with benzene sulfonic acid
functional groups), whereas SP-2 exhibited superior emulsification.
Based on the results of micro-models and coreflooding experiments,
both SP-1 and SP-2 were able to achieve over 10% extra oil recovery
factor following the tertiary polymer flooding, with SP-1 having a better
performance due to its higher viscosity than SP-2. Moreover, in the pilot
test it was observed that, if a proper injection strategy was employed,
there could be considerable improvement in oil recovery using poly­
meric surfactant flooding (Li et al., 2018).
Hence, the polymeric surfactants are potential candidate for SP-
based cEOR techniques on account of their tolerance under HTHS, and
shear, which can be further researched for low-cost, biodegradable al­
ternatives to conventional polymers and surfactants that are much more
expensive and non-biodegradable.
5.1.2. Surfmer and hydrophobically associating polyacrylamide polymers
(HAPAMs)
Contrary to conventional surfactants, the surface activity of surfmers
is akin to vinyl monomers in its capability of being initiated and poly­
merized. Surfmers are of high importance in cEOR (Wang and Wu, 2015)
owing to their amphipathic property and polymerizable characteristics.
Moreover, surfmers can be employed for several processes, such as,
in synthesizing inorganic/organic nanocomposite, surfmers can be used
as polymerizable emulsifiers, as surface modification of solid substances,
and more importantly in generating novel water-soluble hydrophobi­
cally associating polymers (HAPAM) that have exceptional viscous
power (Summers and Eastoe, 2003). Fig. 14 shows the structure of a
Fig. 14. A structural illustration of the synthesis of a Surfmer by combining
0.106 mol of 1-vinylimidazole drops with 0.106 mol of 4-dodecyl benzene
sulfonic acid in presence of ethyl acetate (i.e., 150 ml), under N2 bath (modified
after El-Hoshoudy et al., 2017a).
18
Journal of Petroleum Science and Engineering 220 (2023) 111243
surfmer created by adding 0.106 mol of 1-vinylimidazole drops into
0.106 mol of 4-dodecyl benzene sulfonic acid in presence of ethyl ace­
tate (150 ml), which was kept in an ice immersion under N2 ambiance
(El-Hoshoudy et al., 2017a). The first synthesis of vinyl monomers
(Suresh KI and Bartsch E. 2013) was reported by Freedman et al. (1958),
which were used as emulsifying agents (Summers and Eastoe, 2003;
Tsvetkov et al., 2014). Common polymerizable groups such as vinyl,
allyl, acrylate, methacrylate, styryl, and acrylamide have by employed
for various uses. The position of the polymerizable group “H-type” on
the hydrophilic head group or the position of “T-type” polymerizable
group in the hydrophobic tail have a major influence on the
self-assembly and properties and property of the surfactant (Samakande
et al., 2006, 2007).
Therefore, surfmers are highly dynamic structural components that
are useful as polymerizable emulsifiers, as solid surface modifiers, and
for synthesizing highly viscous water-soluble HAPAM polymers.
In addition, when surfmers are employed as hydrophobic monomers
and copolymerized with acrylamide (AM) it forms hydrophobically
associating polyacrylamide (i.e., HAPAM), an extensively used chemical
in enhanced oil recovery techniques, due to improved viscosifying
power and the ability of salt tolerance (Xue et al., 2004). These polymers
are developed by either micellar copolymerization of hydrophilic and
hydrophobic monomers (Camail et al., 2000) or via grafting
cross-linking segments of hydrophobic chain onto the main chain of
HPAM. A large quantity of surfactants with small molecules are required
so that the hydrophobic monomer is solubilized into micelles, even
though, these small molecule surfactants additives impart many un­
wanted effects (Guyot, 2004). In the process of HAPAM polymerization,
the hydrophilic surfmers dissolve in an aqueous phase leading to a ho­
mogeneous phase copolymerization of hydrophilic surfmers and acryl­
amide (Gao et al., 2007), which does not require any surfactant additive.
Moreover, when CMC of surfmer is surpassed, a micro block copoly­
merization mechanism is performed involving surfmer that is inserted
onto backbone of acrylamide main chain structure. This imparts greater
hydrophobic properties, viscosifying property of HAPAM, and enhanced
tolerance of HAPAM towards salinity (Gao et al., 2004; Yasin et al.,
2015). The surfmer cannot separate from the polymer chain due to the
surfmer being copolymerized with monomer and attached in its main
chain (Xu and Chen, 2004). These enhanced stability properties of these
polymers (Texter, 2001) imply greater mechanical stability (Borzenkov
et al., 2015), electrolyte stability of the latex (Atta et al., 2014), reduced
surfactant migration (Xu and Chen, 2004), and surface charge density
control (Borzenkov and Hevus, 2014).
HAPAMs have become the subject of many research and industrial
laboratories for SP-based cEOR (Bastiat et al., 2004; Feng et al., 2005).
They have potentially advantageous characteristics such as the capa­
bility of the hydrophobic groups to form intermolecular hydrophobic
associations in nanodomains in water-based solutions, when a critical
association concentration (C*) is surpassed (Niu et al., 2001). This
causes the formation of a 3D-transient network structure (Candau and
Selb, 1999; Niu et al., 2001) of heightened ionic strength medium,
lending exceptional viscosifying ability (Shashkina et al., 2003; Gao
et al., 2005), better rheological characteristics, and enhanced tolerance
towards salts compared to the unmodified HPAM (Maia et al., 2009). It
can cause IFT reduction at the rock/fluid confluences because of hy­
drophobic moieties that form aggregates or micelles. These polymers
have exhibited a singular kind of adsorption isotherm (Hu et al., 2015)
which is seen as a wettability altering capacity.
These polymers resist mechanical degradation due to high shear
stress which commonly occur in pumps and the surrounding of the well
bore area, the reason being that the physical links between chains are
disrupted prior to any irreversible degradation and these polymers re­
form and can maintain their viscosity when shear decreases (Evani and
Rose, 1987). They have shown very good tolerance towards tempera­
ture, pH, and ion content in the periphery of the wells.
Thus, HAPAM polymers are potential candidates for SP based EOR,
A.M. Hassan et al.
by functioning as viscosifiers or wettability modifiers in HTHS and high-
pressure reservoirs (Rodrigues et al., 2006; Gouveia et al., 2008; Zhong
et al., 2008). They may also be used for reservoir simulation models and
for tertiary oil recovery processes (Ranjbar and Schaffie, 2000).
5.1.2.1. Laboratory experiments of surfmer and HAPAMs. El-Hoshoudy
and co-workers (El-Hoshoudy et al., 2017b) authored works on hydro­
phobically associating polyacrylamide (HAPAM) and its modified
nanocomposite derivative, developed through free radical emulsion
polymerization. The chemical structure of these latexes was determined
using various methods viz., FTIR (Fourier-transform infrared spectros­
copy), 13C-NMR (13C Nuclear Magnetic Resonance), 1 H-NMR
(Hydrogen 1 Nuclear Magnetic Resonance), SEM (scanning electron
microscope), X-ray diffraction and TEM (transmission electron micro­
scope). The DLS or dynamic light scattering was used to establish the
particle sizes and distribution of particle sizes, whereas to determine the
thermal characteristics, TGA (thermal gravimetric analysis), and
through the aid of DSC (differential scanning calorimetry) methods
(El-Hoshoudy et al., 2015a, 2016).
Fig. 15 illustrates the structure and the synthesis of a HAPAM-SiO2
nanocomposite, with “n” number of the copolymer chain unit
(El-Hoshoudy et al., 2017a). The synthesis of this polymer was done via
polymerization method, in which 3-aminopropyl triethoxy silane and
KPS-initiator were independently incorporated at the identical time at
60 ◦ C reaction temperature (El-Hoshoudy et al., 2017b). Then rheo­
logical and solution properties studies were conducted under virtual
reservoir conditions, based on concentration of the polymer, salinity and
temperature of reservoir, and the shear rate. Results showed decent
robustness towards temperature and salinity, good IFT reduction and
better viscosity features (El-Hoshoudy et al., 2017a).
The evaluation of the rheological properties included tolerance to­
wards salinity, temperature, polymer concentration, and shear robust­
ness. Corefloods were conducted using linear pressurized packed model
(El-Hoshoudy et al., 2015b, 2016, and 2017a). The team concluded the
following from the investigations: That the HAPAM-SiO2 nanocomposite
was developed by incorporating silica nanoparticles through a single
shot synthesis using the Aza-Michael addition reaction, to alleviate the
shortages that occur due to agglomeration and coagulation of modified
silica particles as the emulsion polymerization reactions are undergoing.
This HAPAM copolymer and HAPAM-SiO2 nanocomposite had the
exact desired characteristics such as retaining the original viscosity and
Fig. 15. Illustration of HAPAM-SiO2 nanocomposite copolymer structure, synthesized by polymerization of 3-aminopropyl integrated with triethoxy silane and KPS-
initiator at the same period when reaction temperature was at 60 ◦ C (modified after El-Hoshoudy et al., 2017a).
19
Journal of Petroleum Science and Engineering 220 (2023) 111243
exceptional non-Newtonian behaviors (i.e., shear thinning behavior).
These correspond well to in situ reservoir stimuli such as temperature,
ionic strength, pH, and shear stress and also, have thermal, rheological,
and salt resistant capability in reservoir conditions, apart from
enhancing the sweeping efficiency as well. Their behavior is very similar
to IFT agents such as surfactants, as these also reduced the IFT to ul­
tralow values, which mobilizes residual crude oil. Upon evaluating the
wettability using static sessile drop method, it was observed that
HAPAM copolymer and HAPAM-SiO2 nanocomposite were capable of
altering rock wettability from oil-wet to water-wet, which significantly
increases recovery factor based on the unanimous agreement of petro­
leum engineers that more oil is recovered from water-wet reservoirs
than oil-wet reservoirs. According to the team, this was the first ever
observation of polymers that altered sandstone rock wettability and the
recovered oil amount reached 26% from OOIP.
Thus, this novel copolymer and its nanocomposite may be used as
wettability-modifying agents in SP based cEOR in HTHS oil fields unlike
the commercial polyacrylamides, which renders them very high-
potential candidates for industrial scale energy supply via EOR appli­
cations. For applicability in HTHS carbonates, more conclusive research
may be needed.
5.1.3. Hot-Melt Adhesive (HMA) polymers
Hot-melt Adhesive (HMA) polymers are categorized according to the
hydrophobic moieties into four groups, i.e., i) the associative polymers
with a single associating block, ii) telechelic, iii) multisticker, and iv)
combined HMA polymers. When HMA polymers contact surfactants,
viscosity of the HMA polymers is either enhanced or reduced, based on
the concentration of the added surfactant and the competition between
intermolecular and intramolecular relations. The adsorption of HMA
polymers initially decreases with increasing salt concentration, but
above a certain concentration the adsorption increases with increasing
salinity. Thus, due to desirable rheological properties and low adsorp­
tion of HMA polymers with random monomer distribution rather than
HMA polymers with blocky microstructure which form hydrophobic
associations (Tanaka et al., 1992; Huang and Santore, 2002), researchers
are attempting to extend applications of HMA polymers to HTHS car­
bonate reservoirs.
5.1.3.1. Laboratory experiments of HMA polymer. HMA polymer type
was created by Zhong et al. (2009) by modifying the AM hydrophilic
A.M. Hassan et al.
backbone of a terpolymer with AMPS and hydrophobic monomer
2-vinylnaphtahlene was synthesized. This was intended for medium and
low permeability oil reservoirs with HTHS. Compared to PAM, this
terpolymer displayed better firmness and its viscosity increased with the
increase in both salts concentration and temperature during laboratory
testing. In another study, an HMA was designed by Gouveia et al.
(2009), where an associating PAM using poly (propylene glycol) Mon­
omethacrylate was synthesized as the hydrophobic oligomer through a
micellar copolymerization using an SDS as a surfactant. A
thermo-thickening behavior was exhibited by the HMA polymer in the
presence of SDS. It was suggested by the authors that low IFT could be
expected owing to the presence of the surfactant although experimental
evidence was not provided. The above-mentioned characteristics render
HMA polymers a potential candidate for possible SP-based EOR appli­
cation in HTHS carbonates, although more dedicated studies and
required.
5.1.4. Other polymers formulations
In an investigation by Klimenko et al. (2020), Superpusher™ SAV10
(SNF Floerger), a terpolymer with functional groups of acrylamides
(AM), Acrylamido-Tert-Butyl-Sulfonate (ATBS), and N-Vinyl-­
Pyrrolidone (NVP) was used for SP based EOR injections and all of them
exhibited good thermal stability in the presence of divalent cations
(Masalmeh et al., 2019). These were all of medium molecular weight.
The polymer solutions were pre-sheared with a mixer, in order to mimic
degradation at surface facilities. The pre-shear before injecting also
helps to achieve better polymer injectivity by approximately 30%
decrease in viscosity (at 10 sec− 1) (Jouenne et al., 2019). The concen­
tration of polymer used was 2350 ppm in SP slug and 5300–5400 ppm in
Polymer slug. The number of viscosity measurements is difficult to
reduce at such high temperatures, the extended model of Jouenne et al.
(2019) aided in predicting the polymer concentration essential to attain
the target viscosity. Whereby, upon measuring the differential pressure
value on the capillary installed at the core inlet, there was noticed
excellent concurrence with the calculated value. Viscosity measure­
ments helped in evaluating the stability. The recorded pressure profiles
taken during the cEOR flooding, showed no evidence of polymer accu­
mulation and plugging, even if the injection time could have been too
short for this phenomenon to ensue. Fairly low polymer adsorption is
expected, based on the observation that aqueous phase of the effluent
turned viscous instantaneously after the polymer bank arrived. The
temperature for experiments was between 105 and 120◦ and the for­
mation water salinity was 297,000 TDS ppm (Klimenko et al., 2020).
Thus, most re HPAM, AM, ATBS, and NVP based polymers, proved to be
tolerant towards HTHS conditions during laboratory trails.
In Appendix-A, Table A-3 summarizes several novel polymers for­
mulations, which can be suitable for HTHS conditions in carbonate
reservoirs during SP-based cEOR.
6. Field applications for SP-based cEOR and lessons learned
Large field trials of SP-based cEORs have been implemented world­
wide since 1980 (Ragab and Mansour, 2021). Approximately 32
SP-based cEOR field applications had been conducted worldwide;
however, that number has risen since, with more recent reported works
of SP-based cEOR field pilots. These field applications show that on
average, SP-flooding can achieve over 15–25% OOIP (Liao et al., 2017).
Nevertheless, most of the target oilfields have been sandstone forma­
tions, while the field trails for carbonate oilfields are far less in number,
especially of carbonates under harsh conditions (HTHS). Among these
few SP field applications in carbonate reservoirs are Abu Al Bukhoosh
(ABK), Abu Dhabi, UAE (Al-Amrie et al., 2015) and Raudhatain Lower
Burgan Reservoir, Kuwait (Al-Murayri et al., 2018, 2019a, and 2017).
Thus, meticulous efforts have been put into improving SP-formulations
by synthesizing novel surfactants and polymers especially designed to
have higher temperature and salinity tolerance in HTHS carbonate
20
Journal of Petroleum Science and Engineering 220 (2023) 111243
reservoirs.
Therefore, this section details and reviews the latest surfactant-based
field projects successfully conducted in carbonates. Moreover, we
discuss the essential lessons learned from these recent SP-based cEOR
field trails, which would ultimately improve the operative know-how for
successful SP-flooding designs and field projects in HTHS carbonate
reservoirs.
6.1. Field applications for SP-based cEOR
The following are examples of successful SP-based cEOR field ap­
plications in carbonate reservoirs, along with some relevant stand-alone
surfactant and polymer flooding field trails that have been effective in
achieving their inception goals.
6.1.1. Abu Al bukhoosh (ABK), Abu Dhabi, UAE (Al-Amrie et al., 2015)
A one-spot surfactant-polymer (SP) pilot in Middle East (i.e., Abu
Dhabi, UAE) was successfully conducted. The offshore target field,
known as Abu Al Bukhoosh (ABK), was a high-temperature, high-
salinity, low-permeability carbonate reservoir. The oil-bearing carbon­
ate reservoir is of a Lower Cretaceous age, located 180 km offshore of
Abu Dhabi, and since 1974, it is operated by Total (Al-Amrie et al.,
2015). The SP-formulation was synthesized by Total Research and
Development (R&D) labs, according to a new, hydrophilicity-enhanced
molecule that is tolerant to reservoirs with high-temperature, high-­
salinity. Moreover, a new technique was fostered for optimization of
polymer molecular weight distribution, with the aim of in-situ viscosity
decoupling from near-wellbore injectivity. The final synthesized
formulation contained 0.4 pore volume (PV) SP slug with 1.35% of
active surfactant, plus 1% clarifier, and SAV-225 polymer (SNF
Floerger) in an 80 g/L brine equivalent to a hypothetical softened
mixture of seawater and water from local aquifer. Subsequently, a
polymer drive of softened seawater consisting of AN-125 polymer (SNF
Floerger) was injected, for enforcing a negative salinity gradient amidst
the 230 g/L formation brine, 80 g/L SP slug, and 42 g/L seawater. There
was no requirement of a pre-flush owing to the SP-formulation design
and its application. In the analog limestone cores, the measured value
for the residual oil saturation to chemicals (Sorc) was 5% ± 2%, which
was consistent with a recovery factor (RF) of 90% ± 4%.
6.1.1.1. Key implications. Despite, the one-spot pilot test recovery
agreed strongly with the recovery in analog cores with Sorc of 4%, and
recovery factor = 90% (Al-Amrie et al., 2015). However, it was noted
that, due to the substantial heterogeneity on the core-scale of the
reservoir limestone, the oil bank formation was probably thwarted,
which resulted in smaller recoveries of Sorc: 13% ± 2%, RF: 84% ± 4%.
The cause for the lesser recovery in reservoir cores could be mainly due
to the short length of the core relating to the mixing zone (Levitt et al.,
2012). Nonetheless, the injectivity of water injection preceding the
Single Well Tracer Tests (SWTT) was considerably lower than the ex­
pected rate derived from the design process due to the low formation
permeability. Also, the surfactant-slug had to be diluted in order to
mitigate this injectivity issue. In addition, controlled shear degradation
would optimize the distribution of polymer molecular weight for
maximized injectivity in tight reservoirs (Jouenne et al. 2019). The
ultra-high molecular weight polymer fraction can be eradicated by
employing a minimum of 20–25% (by viscosity) of shear-degradation,
which is executed on a moderate molecular weight polymer, instead
of a low-molecular weight (MW) polymer. Notwithstanding, in this pilot
case, surfactant alone was adequate to desaturate oil in the
near-wellbore area; granting that mobility control could still be required
for attaining satisfactory sweep efficiency when reservoir scale appli­
cations were conducted. The two thermally stable polymers selected
showed poor injectivity in the in low-permeability carbonates, thereby
could not by completely assessed owing to the tested well having low
A.M. Hassan et al.
injectivity. Even when MW distribution modification was done for
SAV-225, it did not suffice for the 5-mD formation, still, further observed
justifications of injectivity loss could be possible. On the other hand, the
optimized AN-125 polymer, was injected effectively in a 2 mD core,
indicating its utility in low-permeability carbonate reservoirs. These
polymer injectivity trails were conducted concurrent to the surfactant
slug injection operations in the1-spot pilot area. Thus, regardless of
having no mobility control due to lack of polymer, the developed sur­
factant slug efficaciously mobilized the oil in the near-wellbore area.
However, surfactant retention was undesirably high with 0.5–0.7 mg/g
of rock. A cost-effective project may be designed by achieving surfactant
reduction via decreasing the phase trapping via cosolvents or additives
(Tagavifar et al. 2016). Surfactant retention can also be restricted
through diminishing the electrostatic interactions with calcite minerals
via swapping the cationic surfactants and polymers with other appro­
priate surfactants and polymers (Levitt et al., 2016). It is also worth
mentioning that specifically designed topsides were dedicated and
installed for this SP cEOR pilot plan. Moreover, an analysis of the results
obtained with the analog core, reservoir core, and one-spot pilot, shows
that whenever the heterogeneity of the core-scale thwarts oil bank for­
mation, the functioning of homogeneous analog cores could be better
predictors of the pilot performance in the field. Thus, this pilot project
proved the efficacy of SP-based cEOR in HTHS carbonate reservoirs,
through appropriate SP-formulations.
6.1.2. Raudhatain Lower Burgan Reservoir, Kuwait (Al-Murayri et al.
2019a)
SP-based cEOR was implemented in Raudhatain Lower Burgan
(RALB) reservoir in Kuwait that has 82 ◦ C temperature and in-situ
salinity of over >200,000 ppm with light-oil. A Single Well Chemical
Tracer Test (SWCTT) was performed with the objective of determining
the efficacy of lab-optimized surfactant-polymer formulation (Al-Mur­
ayri et al. 2017 and Al-Murayri et al., 2018) for the target reservoir. The
SWCTT design work would validate the optimal injection/production
sequence identified during the core scale floods regarding minimal
volumes, rates, and duration. There were several sensitivity scenarios
tested in order to establish the ambiguities. Subsequently, the field
application of SWCTT took place and the results were evaluated and
matched with the formerly attained results of laboratory as well as
simulation tests. The SWCTT was conducted with the purpose of vali­
dating the polymer and surfactant solutions efficiencies in relation to the
reduction in residual oil saturation and injectivity of water. For this, the
before and after the chemical flooding values of residual oil saturation
were appraised during which the injection rates and corresponding
wellhead pressures were continuously monitored. The injection
sequence of the SWCTT included the preliminary water-flooding, then
tracer injection followed, with subsequent phases of soaking and pro­
duction to measure the oil saturation after water flooding. The pre-flush
was subsequently trailed by a main-slug containing surfactant concen­
tration of 5000 ppm and polymer concentration of 500 ppm, which was
followed by a post-flush with the polymer only. Next, with in order to
quantify the oil saturation after chemical flooding, sea-water push, fol­
lowed by tracer injection, soaking and production were conducted
(Al-Murayri et al., 2019a).
6.1.2.1. Key implications. The result of simulation work before the
SWCTT test had been conducted, had resulted in positive oil desatura­
tion levels following chemical flooding within 10 ft from the well. Then
again, the pilot results showed that a difference existed between the real
SWCTT results and the lab and simulation results attained beforehand.
The probable causes for the noticeable difference amid the real field data
and lab/simulation results are under investigation to optimize the SP-
based cEOR for improved oil recovery from the aged reservoirs (Al
Murayri et al., 2019a).
21
Journal of Petroleum Science and Engineering 220 (2023) 111243
6.1.3. Offshore, south China sea (Harris et al., 2020)
Shell directed a single well chemical tracer (SWCT) test using a low
complexity SP-formulation for offshore environments in the South China
Sea (Harris et al., 2020), which is mainly composed of organic reef li­
thology. The SP formulation was seawater-based to prevent the water
treatment complexities from occurring when under commercial appli­
cation circumstances (Southwick et al. 2019). Following the
SP-injection, the residual oil saturation decreased from 20-27% to 7–9%
range. The SP-formulation was composed of an alkyl propoxy sulfate
(APS) and an alkyl ethoxy sulfate (AES) mixture devoid of any cosol­
vents. In the case of application with seawater only (no salinity gradient)
the APS and AES combined formulation yielded exceptionally greater oil
recovery in comparison to the APS and internal olefin sulfonate (IOS)
mixture in the selected outcrop. The SP-formulation utilized seawater
without any supplementary water treatment other than those that are
typically employed for water flooding such as, filtration,
de-oxygenation, and such (Harris et al., 2020).
6.1.3.1. Key implications. From the field test, it was realized that the
seawater-based formulations can be efficiently combined on a barge and
injected to a production well installed on platforms. It was observed that
the highest oil recovery was obtained through using surfactant mixtures
that produce formulations, which are below optimum (i.e., Winsor Type-
1 phase behavior) with reservoir crude oil. Correspondingly, these
below optimum formulations evade high injection pressures that are
observed for optimum formulations in low permeability outcrop rocks.
The recovery from these SP-formulations is an identical amount of oil in
the swept zone of the reservoir rock. The total recovery in the reservoir
rock is lower than that in the selected outcrop because of more hetero­
geneity that leads to crude oil getting bypassed (Harris et al., 2020;
Southwick et al. 2019).
6.1.4. Block X in tahe oilfield, China (Yin et al., 2021)
In the channel reservoir of in Tahe oilfield, China, which has high-
temperature of 100–110 ◦ C, high-salinity of over >2.1 × 105 mg/L,
and is part of thick carbonate strata. In order to conform, regulate and
enhance the oil recovery, the combined flooding was conducted by
employing dispersed particle gel (DPG) and surfactant. The pilot test
comprised of an introduction to the geological backgrounds and devel­
oping history of the block X. In combined flooding, the DPG is useful as
an in-depth conformance control agent in order to enhance the sweep
efficiency, and a subsequent surfactant solution slug is utilized for
displacement efficiency improvement. The long-term stability of DPG
lasts 15 days, which warrants the efficacy of in-depth conformance
control. Wherein it increases from its original 0.543 μm–35.5 μm
following the 7 days of aging in the 2.17 × 105 mg/L reservoir water at
110 ◦ C reservoir temperature. The optimization process revealed that
0.35% NAC-1+ 0.25% NAC-2 surfactant solution having IFT of 3.2 ×
10− 2 mN/m can easily create a moderately stable emulsion with the
dehydrated crude oil. During the double core flooding, the conformance
control performance is validated through the fluid diversion following
the combined flooding leading to incremental EOR of 21.3% conse­
quently. Following the 14 years of the utilization of Block X, the for­
mation energy declined rapidly owing to deficiency of large bottom
water. While, the water fingering also resulted in a reduced production
rate and water cut increase. Next, following the combined flooding in Y
well group comprised of 1 injector and 3 producers, there was marked
increased in the average dynamic liquid level, daily production, and the
breakthrough time of the tracing agent. While there was noted a
decrease in the water cut and injectivity index. Also, the injected fluid’s
distribution rate and real-time monitoring verified the performance of
conformance control and the oil recovery from this group of wells was
augmented by an excess of 3000 tons of oil (Yin et al., 2021).
6.1.4.1. Key implications. The examination of this combined flooding
A.M. Hassan et al.
from laboratory experiments to field case analysis, showed that the
heterogeneity was adjusted via DPG used in conjunction with EOR
surfactant to increase displacement efficiency, and occurs synergisti­
cally in this HTHS carbonates. The selection and performance standards
of the combined flooding also provided some hands-on experiences and
principles for combined flooding (Yin et al., 2021).
6.1.5. Baturaja formation, semoga field, Indonesia (Rilian and Sumestry,
2010; Sheng, 2013b)
The Semoga field reservoir rock located in Indonesia is highly oil-wet
with initial water contact angle measured as 78◦ . The Baturaja Forma­
tion, a carbonate reservoir in the Semoga field had a confirmed volume
of approximately 317,856 acre-ft (77 ft net pay thickness), and was in
low production due to depletion. The formation has 127 wells, including
17 shut-in wells, 28 water injection wells, and 82 producing wells. In
this project surfactant works and wettability changes acquired in the
laboratory were mirrored in the field pilot, and increased oil mobility
and water-wet wettability state to a certain degree were observed. A
non-ionic surfactant was used for the field application for the reason that
the homogeneity of reservoir could not accommodate a cationic sur­
factant. The wettability changes in the laboratory tests coincided with
those observed in the field application, i.e., the wettability changed by a
small degree from oil-wet towards water-wet, thereby improving
mobility of oil. Further studies are ongoing to analyze the efficacy of the
surfactant work in the field project, to secure the water cut reduction
using the surfactant, and to prevent reverse conning and other unde­
sirable effects. Surfactant stimulation resulted in a reduction of water
cut of around 8% and an increase in total oil production for this project
of roughly 5800 bbls over the course of three months. Further investi­
gation is underway to determine the effectiveness of the surfactant work
in this project and to confirm if the reduction in water cut was caused by
the surfactant and no other effects, such as reverse conning etc. To
reduce “subjectivity” in pressure build-up (PBU) analysis, the results
have to be verified using the techniques such as, coring analysis, time-
lapse saturation logs, and single well tracers, which are used to eval­
uate the influence of surfactant stimulation on changes in reservoir
characteristics. In conclusion, the increased oil output was around 5800
bbls over the course of three months. The net present value (NPV) at
three months was $24,013; at one year, it was 58,189; and in 11 days the
pay-out time (POT) of the project was $15,180. Hence, the outcomes
were optimistic, and the oil recovery was expected to be more sub­
stantial if the technique i.e., surfactant huff and puff method was to be
applied in high production wells instead of high water cut wells (Rilian
and Sumestry, 2010).
6.1.5.1. Key implications. The surfactant stimulation resulted in inten­
sification in skin damage in the X-2 well, which was observed through
the pressure build-up (PBU) test analysis (Rilian and Sumestry, 2010).
Nevertheless, the decrease in water cut in both the wells was attributed
to the surfactant stimulation rather than any other cause (such as reverse
conning). In conclusion, the surfactant works and the wettability alter­
ations in the laboratory corroborated with the field project, in which the
oil mobility had increased and the wettability conditions had been
transformed from oil-wet towards slightly water-wet state (Rilian and
Sumestry, 2010).
6.1.6. Block 5, Al-shaheen field, Qatar (Rohilla et al. 2021)
A chemical based EOR application in Block 5, Al-Shaheen Field,
Qatar, which is a giant offshore carbonate reservoir was performed using
a surfactant formulation with wettability altering capability. The car­
bonate reservoir has low permeability (i.e., 5 mD), and is extended with
elongated horizontal wells with injection well and production wells in
an alternate sequence. Surfactant injection method for cEOR was sys­
tematically conducted in stages to reduce the risks involved in field-wide
cEOR applications (Rohilla et al., 2020; 2021). The project was initiated
22
Journal of Petroleum Science and Engineering 220 (2023) 111243
in April 2019, with continuous mode surfactant injection though 2
corresponding long-horizontal production wells at 4000 ppm of active
concentration in sea water. The injection continued for 7 months with
the entire injection volume of 1000 MT. The surfactant injection ended
in November 2019, and subsequently seawater injection was carried out.
The objective of the project was mainly to estimate the field scale effi­
cacy of the developed solution (Rohilla et al. 2021).
6.1.6.1. Key implications. The outcomes of the surfactant flooding pilot
demonstrated that there was no injectivity loss or viscous emulsions
formation in the reservoir from the surfactant injection, indicating the
developed surfactant formulations efficacy and stability under the car­
bonate reservoir conditions. One of the injectors (Injector-01), in which
surfactant had been injected, achieved 8% yearly water injectivity on
account of the surfactant injection. Furthermore, both the producer
wells for the pattern exhibited incremental oil response. So far, no sur­
factant breakthrough from produced water analysis have been observed.
Further details of the project, the chemicals used and acquired experi­
ences from the field project may be found elsewhere (Rohilla et al.
2021).
6.1.7. Bashkirian reservoirs, bobryk, Ukraine (Varfolomeev et al., 2020)
The Bashkirian dolostone reservoirs of Bobryk oil and gas condensate
field in Ukraine is a fractured carbonate reservoir with heavy oil. The
reservoir has low temperature of 23 ◦ C and an ultra-high salinity of
217.5 g/L, and low injectivity restricts the reservoir’s effective devel­
opment. Thus, the efficiency of surfactant injection (developed in prior
laboratory experiments) was investigated through a pilot test. A
nonionic surfactant was selected for the pilot test based on its demon­
strated capability to cause IFT reduction and wettability alteration, as
well as its oil displacement efficacy, ability to reduce injectivity, pro­
duction performance, cost-effectiveness, and availability (Varfolomeev
et al., 2020). During the pilot test the nonionic surfactant exhibited
excellent influence on water injectivity improvement. Following the
surfactant injection, the decrease in the wellhead pressure and down­
hole pressure ranged from 40 at and 171.5 at to 24 at and 153.4 at,
respectively. The incremental oil production due to the surfactant in­
jection was approximately 1094 tones.
6.1.7.1. Key implications. The successful effect of the selected nonionic
surfactant projects its superb potential as a candidate for SP applications
in high salinity carbonates. Each surfactant was measured at three
different concentrations while screening so that the optimum surfactant
formulation was acquired. Whereas, it is expected that using the sur­
factant will result in well-injectivity enhancement along with increased
oil displacement efficacy for composite heavy oil carbonate deposits
(Varfolomeev et al., 2020). Therefore, this benchmark study strengthens
the technological basis for furthering the field application plans of
surfactant-based flooding towards harsh conditioned carbonate
reservoirs.
6.1.7.2. Lower Shaunavon oilfield, Canada (Stephenson et al., 2019). In a
separate field application case, microemulsion additives were employed
in Lower Shaunavon oilfield located in SW Saskatchewan, Canada. The
Shaunavon oilfield is classified as unconventional oilfield based on
permeability, temperature, calcite mineralogy, and oil with higher
content of asphaltene, along with high-salinity formation water. The
ability of microemulsion additive to function as delivery platform for
solvent (terpene) and surfactant mixtures across a given rock volume
was used as a basis for the analysis There are numerous formulations
available, each of which is customized for a specific set of reservoir and
fluid properties (Stephenson et al., 2019). Microemulsion additives
lessen the impairment and transform the energetics of surfaces, and can
improve oil mobilization. The optimized microemulsion additives were
created according to the fluid-fluid and fluid-rock interactions for the
A.M. Hassan et al.
target reservoir through laboratory experiments. The increases in oil
production from the field trail were attributed to changes in injectivity
of water, which was the key markers of success for both core floods and
pilot tests (Stephenson et al., 2019).
6.1.7.3. Key implications. The core flood response in unconventional
reservoirs was insignificant with <5% incremental oil recovery
observed, partly attributed to the asphaltenes coating formed on the
surface of the core during wettability restoration. Nevertheless, the pilot
response was optimistic with high recovery. Through evaluating this
inconsistency, it was inferred that using dependable screening tools for
unconventional reservoirs was necessary prior to core flood tests.
Moreover, it was clear that the microemulsions had positive influence in
conventional as well as unconventional reservoirs, which could be
further improved with optimization according to fluid-fluid and fluid-
rock interactions within the crude oil-rock-brine system. More details
of the chemicals used, adopted mythology and field operation data may
be found in the given publications (Stephenson et al., 2019).
6.1.8. Abu Dhabi, UAE (Baloch et al. 2021)
The Abu Dhabi National Oil Company (ADNOC) planned for a
Polymer-based cEOR, with the intention of enhanced displacement and
sweep efficiencies in carbonate reservoirs. These polymer-based EOR
methods included polymer injections (polymer injection test/PIT),
simultaneous injection of miscible gas and polymer (SIMGAP), simul­
taneous injection of water and polymer (SIWAP), low salinity polymer,
and others. The target reservoirs in Abu Dhabi are carbonate reservoir
formation with high temperature (~100–130 ◦ C), high salinity forma­
tion brine (~200,000 ppm), along with high concentrations of divalent
ions brine in the formation brine (~18,000 ppm of Ca++ and Mg++).
Since, ADNOC planned on widening the polymer flooding scope towards
harsher oilfield conditions, which had higher content of H2S. Conse­
quently, a PIT was designed to prepare for a multi-well pilot test, in
which polymer flooding is applied to dissolve H2S concentrations of
20–40 ppm and to substantiate the injectivity at typical field conditions,
and in-situ polymer functioning. As stable polymers in these harsh en­
vironments, experimental studies identified a polyacrylamide-based
polymer with high 2-acrylamido-tertiary-butyl sulfonic acid (ATBS)
content called SAV 10. The SAV 10 polymer was stable in the presence of
H2S (500 ppm) and/or O2 (up to 150 ppb) as well. Also, this ATBS
polymer had favorable injectivity behavior that could be easily modified
for injection according to the target reservoirs settings (Masalmeh, S.
et al. 2019). In 2019, a primary polymer injectivity test (PIT) was per­
formed at 121.1 ◦ C and salinity of over 200,000 ppm, as well as at low
H2S content (Rachapudi et al., 2020; Leon et al., 2021). The PIT was
completed over a duration of five months, i.e., February 2021 to July
2021, and then was followed by chase water flood till December 2021.
During the PIT, the overall polymer solution injection volume was 108,
392 barrels (Baloch et al. 2021).
6.1.8.1. Key implications. Initial outcomes from the PIT indicated the
key performance indicators had been attained, including an expected
viscosity yield and beneficial injectivity at target rates that matched
with the laboratory data. The near-wellbore polymer behavior was
ascertained using a down-hole shut-in tool (DHSIT) to measure the
pressure fall-off (PFO) data, in order to help in the PIT program opti­
mization. It is anticipated to enable the polymer cEOR assessments of
many other massive heterogeneous carbonate reservoirs in the middle
east, which possess harsh conditions. Hence, based on the properties of
novel polymer established over the course of the PIT, the optimization of
the models for field and sector can be done in the future (Baloch et al.
2021).
Finally, a list of published field studies on SP-based cEOR for car­
bonate reservoirs has been summarized in Table A-4 in Appendix-A.
Likewise, some of the chemical-based cEOR projects worldwide are
23
Journal of Petroleum Science and Engineering 220 (2023) 111243
summarized in Table A-5 in Appendix-A.
6.2. Essential lessons learned (i.e., key points summary)
• Evaluation of Chemical SP-Formulation Synthesis. It was Low
complexity chemical combinations for SP-formulations are prefer­
able, such as the surfactant formulations that used seawater without
any other water treatment. Besides, the usually performed water
treatment viz., filtration, and de-oxygenation methods are preferable
too. Novel hydrophilicity-enhanced molecule are stable under HTHS
carbonate reservoirs. Moreover, no pre-flush is required for SP-
formulation designs that use appropriate designs such as, softened
seawater mixtures. Novel polymers proven to be stable under harsh
carbonate environments include hydrophilicity-enhanced surfac­
tants; SAV-225 (AM-AMPS-NVP terpolymer), AN-125 SH (AM-AMPS
copolymer) and a polyacrylamide-based polymer with high 2-acryl­
amido-tertiary-butyl sulfonic acid (ATBS) content called SAV 10.
Also, a new technique cultivated for optimization of polymer mo­
lecular weight distribution can achieve in-situ viscosity decoupling
from near-wellbore injectivity.
• Injectivity of SP-Based cEOR. It was observed that nonionic sur­
factant shows excellent effect on improving water injectivity, which
can achieve enhanced well-injectivity accompanied by increased oil
displacement efficiency for HTHS carbonate reservoirs. For low
permeability formations, the injectivity of water injection preceding
the Single Well Tracer Tests (SWTT). In certain scenarios of low
permeability outcrop rocks, below optimum formulations. Can avoid
the high injection pressures that are observed for optimum formu­
lations and are more preferred in such conditions was considerably
lower, where in diluting the surfactant slug may mitigate this
injectivity problem. Additionally, for oil-wet carbonates reservoirs
with low permeability, water injectivity can be improved via sur­
factant injection by wettability alteration towards water-wetness.
Furthermore, the use of controlled shear degradation optimizes the
polymer molecular weight distribution, which leads to maximized
injectivity in tight reservoirs such as, carbonate reservoirs with low-
permeability formations.
• SP-Based cEOR Injection Equipment. The optimal chemical in­
jection facilities for SP offshore oilfields that use the seawater-based
formulations are the portable injection skid-mounted units on the
platform applicable in the case of shallow water fields. In the case of
deepwater fields, the floating production storage and offloading
(FPSO) system is preferable.
• involve combining it on a barge and then injecting it to a production
well installed on platforms. In other words, these are the portable
injection skid-mounted unit on the platform applicable in the case of
shallow water fields (Han et al. 2006). Another facility is the polymer
preparation in maturation tank on FPSO and the polymer injection
pump installed the platform and injection facilities on the FPSO for
deepwater fields.
• Timing to Start a SP-Based cEOR Project. The appropriate sched­
uling for the commencement of a SP-based cEOR field trial requires
further research. In general, at the earliest stage of expansion of the
SP field operations the anticipated favorable results are observed,
nonetheless the base case reference in water flooding is absent.
7. Overcoming challenges in SP-based cEOR: future perspectives
As stated previously, carbonate reservoir is characterized by high
temperature of over 85 ◦ C, high formation water salinity above 100,000
ppm (TDS), divalent cations (hardness) above 1000 ppm, and perme­
ability lower than 100 mD, and make up nearly 60% the world’s oil
assets (Akbar et al., 2000). Critical problems are produced due to these
harsh conditions when applying oil recovery techniques including ter­
tiary recovery methods of cEOR. In the last decade, the SP-based cEOR
technologies have been further developed to overcome many of the
A.M. Hassan et al.
challenges of harsh carbonates reservoirs, which are evidenced through
a number of successful experimental and field investigations. However,
on account of the complex carbonate reservoir characteristics, which
also include fractures, heterogeneity and oil-wet wettability, the SP in­
jection cEOR applications, may not always be successful.
Therefore, in this review, we enumerate the primary challenges of
SP-based cEOR application in carbonate reservoirs, and discuss the new
and upcoming technologies and materials (i.e., chemicals) that mitigate
these issues, to pave the way for more efficient SP-flooding imple­
mentations in HTHS carbonate rocks. These advanced approaches can
tackle chemical instability, adsorption on carbonate surface, as well as
environmental and economic concerns. Also, the novel SP formulations
are able to withstand HTHS conditions of carbonates and create very low
retention on carbonates, while inducing IFT reduction and wettability
alteration of carbonate rock from oil-wet to water-wet state. Moreover,
the synergic effect created through combining low salinity water, smart-
water, and foam flooding with SP-flooding, by way of hybrid SP-based
techniques, can further augment the residual oil displacement effect,
resulting in high oil recoveries. Thus, the review enlightens concisely on
the imminent perspectives of SP-based cEOR in HTHS carbonate reser­
voirs via the most recent and effective approaches for successful field
applications.
7.1. Hybrid low salinity water (LSW) injection with SP-flooding (i.e.,
LSW-SP)
The polymers and surfactants are prone to destabilization under high
salinity and high temperature during SP-based cEOR process. The
typical problems encountered when polymers are used for cEOR include
low injectivity as viscosity is lost or complete plugging of injection wells,
degradation of polymers, incomplete polymer dissolution, and pump
failures. The low injectivity creates reduced sweep efficiency and
diminished residual oil displacement. Furthermore, polymer retention
on rock surface can permanently impair the formation and prevent
further successful cEOR applications. Hence, a very promising new
approach to polymer plugging and polymer degradation is the hybrid
low salinity water polymer (LSW-P) flooding, which combines low
salinity water (LSW) injection (Gbadamosi et al., 2022) and polymer
flooding (Al-Murayri et al., 2019b; Hassan et al., 2022d) techniques.
The LSP process is initiated by treating the source brine so that its
salinity is much lower than the formation brine salinity, after which the
polymer is mixed with the lower salinity brine. This creates synergies in
the LSWP method, which is capable of improving both displacement
efficiency and sweep efficiency (Al-Shalabi et al., 2022). The polymers
play the role of mobility controller of the injected fluid that leads to
improved sweep efficiency (Sorbie, 1991, 2013), whereas the hybrid
synergy of polymers employed together with low salinity aqueous so­
lutions, modifies the wettability state of the formation and results in
reduced water-cut and water/oil ratio (Karimov et al., 2020). Also, due
to reduced salinity of the injection water, the polymer concentration
required for the LSWP process is low (Vermolen et al., 2014; Shiran and
Skauge, 2014), which is likely to reduce project costs, and as smaller
injection facilities are enough, back-produced polymer in high concen­
trations is mitigated. Thus, combined LSW injection with polymer (and
SP) floodings is a comparatively new hybrid EOR technology, which
provides a synergic effect to enhance the displacement and sweep effi­
cacies (Al-Shalabi et al., 2022). Hence, with the breakthrough in LSWP
and LSWSP techniques, greater oil recovery is expected in a
cost-effective process from HTHS carbonate reservoirs.
7.2. Hybrid smart water assisted foam (SWAF) injection with SP-flooding
(i.e., SWAF-SP)
The SP-flooding cEOR for an oil-wet HTHS carbonate reservoir may
not be successful at all times due to these harsh conditions. In fractured
carbonate formations, high-permeability fractures can act like ‘‘thief
24
Journal of Petroleum Science and Engineering 220 (2023) 111243
zone’’ that cause early water/gas breakthrough and loss of oil produc­
tion. To surmount this issue, mobility control agents, such as foam, may
be taken as a practicable measure (Talebian et al., 2014, 2015). Foam is
suggested for countering the channeling, viscous fingering, and gravity
override problems during Gas (e.g., CO2 and N2) flooding, which occurs
due to carbonate matrix heterogeneity (Taber et al., 1997; Masalmeh
et al., 2011; Lake et al., 2014; Yuncong et al., 2014). The Foam Assisted
Water Alternating Gas (FAWAG) injections are proposed as measures to
improve volumetric sweep efficiency and lower the gas-oil ratio, leading
to effective oil recovery (Aarra et al., 2002; Blaker et al., 2002; Masal­
meh et al., 2011, 2012; Tunio et al., 2012). If the foam films can
maintain stability during propagation, a successful FAWAG injection can
be performed. However, foam stability in the presence of oil is still a
challenge during foam injection (i.e., FAWAG), which requires consid­
erable attention. Based on this concept, a novel hybrid EOR technology,
which merges smart water (i.e., ionically modified composition brine)
for stabilization of the foam and water films and foam flooding for IFT
reduction and wettability alteration called smart water assisted foam
(SWAF) flooding was introduced by Hassan et al. (2020, 2022b),
particularly for harsh carbonate reservoirs. Fig. 16 illustrates the injec­
ted scheme scenarios of the SWAF technology, which start with smart
water injection followed by surfactant aqueous solution (SAS) and gas
(Hassan et al., 2022a).
The numerical and laboratory investigations demonstrated the effi­
ciency of the hybrid SWAF method, with highly encouraging results
pertaining to foamability and foam stability; while the dual-
improvement effects (i.e., water and foam films stability) of the
method, produced exceptional cumulative oil recovery of 92%, as shown
in Fig. 17 (Hassan et al., 2020, 2021; 2022a, and 2022b). The latter
figure shows smart water-assisted foam (SWAF) injection process for the
best-case scenario (i.e., MgCl2). The method works as an improve­
d/enhanced (IOR/EOR) recovery method for the ionically-modified
brine, which goes up to 39% RF for the primary stage (i.e., formation
water), 11% RF (i.e., 50% cumulative oil original in core, OIIC) for the
secondary stage (i.e., smart water injection), and 92% cumulative OIIC
for the tertiary stage (SAG injection i.e., SAS, gas, SAS, and gas).
7.3. Biosurfactants, biopolymers, nanoparticles (NPs), and ionic liquids
(ILs)
Recently, applying modern techniques like biotechnology, nano­
technology (NPs), and ionic liquids (ILs) technology in cEOR is
becoming more prevalent, due to the perceived environmentally, eco­
nomic, and productivity enhancement potentials.
7.3.1. Biosurfactants and biopolymers formulations
The scope of biosurfactants and biopolymers in cEOR and their ca­
pacity for IFT reduction, wettability alteration, and mobility control,
which are advantageous in SP-based cEOR, have been the subject of
numerous studies (Al-Wahaibi et al., 2014; Gao, 2018; Geetha et al.,
2018; Seo et al., 2018; Hassan et al., 2019; Musa et al., 2021; Tack­
ie-Otoo et al., 2022).
The bio-cEOR floodings can be a potentially effective approach to
improving sweep efficiency in fractured carbonate reservoirs, according
to Gomari (2022), who researched the impact of polymer, biopolymer,
and biosurfactant elements of chemical EOR and bio-cEOR on oil re­
covery performance in fractured carbonate reservoirs. The findings
showed that the suggested method can enhance oil recovery, with bio­
surfactant/polymer/water flooding showing the greatest rates up to
16%. It was discovered that the inclusion of the biosurfactant into the
system changed the rock matrix’s wettability from oil-wet to
neutral-wet, facilitating the oil movement toward fractures (Gomari
et al. 2021; Gomari, 2022). Furthermore, several more recent laboratory
investigations have successfully demonstrated the efficacy of bio­
surfactants with polymers (or biopolymers) and/or alkali, which can
affect IFT reduction and wettability alteration of carbonates, and can
A.M. Hassan et al.
Fig. 16. Schematic diagram of SWAF process. (a) Injection of SWAF solution in presence of crude oil, (b) SWAF solution interacts with crude oil, and (c) oil detaches
from rock and moves toward production well (Hassan et al., 2022b).
Fig. 17. Smart water-assisted foam (SWAF) injection process for the best-case scenario (i.e., MgCl2). (Hassan et al., 2022b).
prove to be a cheaper low-risk alternative to conventional surfactants
(Al-Ghailani et al., 2018; Bassir and Shadizadeh, 2020; Nasiri and Biria,
2020; Bera et al., 2021; Udoh and Vinogradov, 2021; Janaghi et al.,
2022; Gomari, 2022; Wu et al., 2022).
Moreover, Biosurfactants’ hydrophilic head and hydrophobic tail
interact with the molecules of water and crude oil, respectively. In
recent studies, Pseudomonas aeruginosa HAK01, was discovered by
Khademolhosseini et al. (2019a), who produced a rhamnolipid bio­
surfactant that demonstrated remarkable capacity in IFT reduction and
wettability alteration from oil-wet to the water-wet state of the sample
glass surface. Moreover, good performance in EOR can be achieved as,
biosurfactants showed high stability in harsh temperature, pH, and
salinity conditions.
Furthermore, Scleroglucan biopolymer has a rigid structure, imparts
high viscosity and shear resistance in aqueous solution with its triple
helix nature that enhances its thermal stability (Kulawardana et al.,
2012). However, the reported thermal stability data studies vary. Ac­
cording to Davison (Davison and Mentzer, 1982), scleroglucan remains
intact in original state for 500 days at 90 ◦ C whereas, Rivenq et al.
(1992) reported that the thermal stability limit to be 100 ◦ C for 60 days.
25
Journal of Petroleum Science and Engineering 220 (2023) 111243
Moreover, Kalpakci et al. (1990) stated that scleroglucan was stable
thermally for 720 days at 100 ◦ C. The main issue with application of
scleroglucan for cEOR is its very low filterability (Kulawardana et al.,
2012). Xanthan gum is another biopolymer which can be mixed with a
range fluid additives and surfactants for application in tertiary oil re­
covery formulations at temperatures up to 90 ◦ C (Olajire, 2014). Also,
according to some studies, Schizophyllan, which is also a biopolymer,
can be a potential polymer for SP based EOR under HTHS reservoirs with
low permeability (Huang and Sorbie, 1993; Leonhardt et al., 2014).
Newly developed modifications of polyacrylamides (e.g., NVP-AM) have
been designed to be functional and stable at higher temperature appli­
cations (Kulawardana et al., 2012). Hence, some biopolymers and bio­
surfactants can withstand HTHS carbonate reservoir conditions, and can
be modified and improved to function aptly for SP flooding in harsh
environments.
7.3.2. Nanoparticles (NPs) formulations
Many studies showed that nanoparticles (NPs) may change the
wettability to more water-wet conditions and successfully recover oil
(Moghaddam et al., 2015; Al-Anssari et al., 2016; Ali et al., 2018;
A.M. Hassan et al.
Moghadam and Salehi, 2019; Patel et al., 2022) while reducing IFT
(El-Diasty and Aly, 2015; Zhang et al., 2016; Youssif et al., 2018; Kuang
et al., 2018). In addition, various studies suggested that the use of NPs
and surfactants can enhance oil recovery through synergistic effects
(Khademolhosseini et al., 2015; Mohajeri et al., 2015; Eshraghi et al.,
2017; Emadi et al., 2017). For instance, Zargartalebi et al. (2015)
demonstrated that the use of hydrophilic silica NPs and sodium dodecyl
sulfate (SDS) decreased IFT and improved oil recovery from sandstone
rocks. The outcomes were in agreement with Ahmadi and Shadizadeh’s
reports (Ahmadi and Shadizadeh, 2013). Furthermore, a combination of
NPs and surfactants changed the system’s wettability to the water-wet
condition, as demonstrated by Nwidee et al. (2017). Zhao et al. (2018)
examined the synergistic effects of silica NPs and TX-100 (a non-ionic
surfactant) on oil recovery, and the outcomes demonstrated that silica
nanoparticles combined with this surfactant were more capable to affect
wettability than a pure surfactant solution.
Joshi et al. (2022) conducted evaluations via visual settling, dynamic
light scattering (DLS) technique, high Zeta potential, and turbiscan
analysis. They found that the SiO2 nanoparticles (NPs) nano-fluids were
very stable for use in SP based EOR. When nanoparticles were spread in
the polymer solution or the zwitterionic surfactant CPAB (Cetylpir­
idinium bromide), SiO2 nanofluid stability was significantly improved.
For flooding investigations, a SiO2 NPs concentration of 800 ppm was
determined to be adequate. However, in low permeability carbonates
the SP flooding was slightly more effective in oil recovery, which was
attributed to nanoparticles clogging pores. Also, high permeability
surfactants were considered the most suitable for these NPs nanofluid
approach. Using 10–60 nm oil swollen micelles dispersed by cocami­
dopropyl hydroxysultaine zwitterionic cosurfactant at high salinity (56,
000 mg/L) and temperature (100 ◦ C), a highly stable “Nano-Surfactant
(NS)" fluid was created via encapsulating Petroleum sulfonate (PS) salt
surfactants, which are insoluble in high-salinity water. The
nano-surfactant fluid can be created swiftly in the field through a
straightforward process at room temperature requiring minimal energy.
The NS fluid preparation and evaluations show their enduring chemical
and colloidal stability at 100 ◦ C, along with a IFT reduction of 3 orders of
magnitude i.e., from 10 to 0.008 mN/m, between crude oil and
high-salinity water, and enriched mobilization of the trapped crude oil
from the carbonate rock, as described by Gizzatov et al. (2019). Their
work illustrated the use of NS formulations to improve oil mobilization
for a range of reservoir conditions during Surfactant-based cEOR. The PS
salt surfactants, which are among the most widely available and inex­
pensive industrial surfactants, can be delivered with precision using the
nano-surfactant (NS) fluid, which is lucrative, effective, and ecologically
benign.
Finally, according to the investigation of Khademolhosseini et al.
(2019b), high uniformity of spherical NPs led to better distribution and
more efficient interactions with crude oil components, which increased
recovery. Furthermore, in the coreflooding test, they noticed that the
biosurfactant-spherical NP solution produced 26.1% more oil recovery
after brine flooding than the biosurfactant-sponge-like NP solution
(25.1%). Finally, biosurfactant-NP solutions outperformed biosurfactant
solutions in terms of improving the wettability alteration of the oil-wet
carbonate rock.
7.3.3. Ionic liquid (ILs) formulations
Recently, a number of research works have suggested surface-active
ionic liquids (SAILs), which are functional ionic liquids with amalgam­
ated properties of surfactant and ionic liquid as an alternative to con­
ventional surfactant, polymer, and alkaline-based cEOR technologies.
These novel functional ionic liquids represent an exciting alternative,
particularly for EOR processes in harsh reservoir conditions of
carbonates.
A study on the physicochemical properties of synthesized SAILs using
FT-IR, 1H NMR, and TGA validated the chemical structure and thermal
stability of the synthesized C12mimBr and C16mimBr, for increased oil
26
Journal of Petroleum Science and Engineering 220 (2023) 111243
recovery application. To ascertain their surface and interfacial behavior
under reservoir conditions, SAILs were examined in aqueous solution.
The synthesized SAILs had good surface-active characteristics, high ef­
ficiency on the interface adsorption, and a decreased critical micellar
concentration of 200 ppm (C16mimBr). The IFT was decreased to
extremely low values (between 10− 4 and 10− 3) across a variety of
salinity, concentration, and temperature ranges, providing important
support for the use of surfactants in EOR. The development of the
Winsor-III micro-emulsion was also proven by the phase behavior ex­
periments, rendering it a robust performance formulation (Pillai and
Mandal, 2022).
Moreover, combinatory flooding approaches were explored through
gauging the potential of an alkali-surfactant (AS) formulation for
improved oil recovery that combines monoethanolamine (ETA) and 1-
hexadecyl-3-methyl imidazolium bromide (C16mimBr). The study
compared the usual formulation of sodium metaborate and cetyl­
trimethylammonium bromide (CTAB) (NaBO2). The research proved
that CTAB and C16mimBr exhibited comparable surface activity and
aggregation patterns. The ETA-C16mimBr system was shown to work
well with brine that has large divalent cations content. With an ultra-low
IFT of 7.6 × 10− 3 mN/m, studies on interfacial characteristics revealed
that the ETA-C16mimBr system outperformed the NaBO2-CTAB system
in terms of IFT reduction capabilities. In the presence of salt, the ETA-
C16mimBr system’s IFT reduction performance improved, resulting in
an ultra-low IFT of 2.3 × 10− 3 mN/m. Even under highly salinized cir­
cumstances with a 15 % wt. NaCl solution, the system maintained an
ultra-low IFT. Although the wetting power of CTAB was not increased by
the addition of NaBO2, synergism was visible for the ETA-C16mimBr
system in modifying the carbonate rock surface. Even at high tempera­
tures, the ETA-C16mimBr and NaBO2-CTAB systems both demonstrated
the ability to create stable emulsions (Tackie-Otoo et al., 2022).
Finally, several other studies have shown the potential of ionic fluids
as an alternative cEOR approach by being an alternative to conventional
chemicals, with the capacity to reduce IFT and alter wettability partic­
ularly in carbonates at HTHS conditions, affording a low-cost high
performing alternative (Sakthivel, 2021; Atilhan and Santiago, 2021;
Esfandiarian et al., 2021; Sanati et al., 2021; Barari et al., 2021; Somoza
et al., 2021, 2022).
7.4. Environmental impact
In the process of SP-based cEOR, majority of the chemicals used i.e.,
surfactants, polymers, alkali, co-solvents, etc., are toxic and non-
biodegradable, which leads to environmental concerns such as,
contamination of ground water and formation damage. The environ­
mental concerns become significant if these chemicals are retained in
the reservoir at high levels. Moreover, because carbonate reservoirs are
naturally fractured and possess heterogeneity, the oil recovery is greatly
decreased due to high adsorption of surfactants. In addition, reservoir
damage caused by surfactant adsorption hinders any further EOR-
process implementations, which makes the extraction of oil recovery
more energy intensive and thus, leading to high CO2 footprint. There­
fore, to maintain reasonable expenditure for SP-based EOR and for
preservation of pristine reservoir condition, surfactant retention must be
abated. One of the suggested approaches of reducing surfactant reten­
tion is using greener alternatives to existing surfactants (i.e., such as new
plant sourced surfactants or biosurfactants) since they exhibited
remarkable stability in HTHS carbonates environments. Laboratory
studies have successfully tested the effectiveness of biosurfactants in
reducing IFT and altering carbonate rock wettability towards more
water-wet, which increases recovery (Al-Ghailani et al., 2018; Bassir and
Shadizadeh, 2020; Nasiri and Biria, 2020; Bera et al., 2021; Udoh and
Vinogradov, 2021; Janaghi et al., 2022; Gomari, 2022; Wu et al., 2022).
Similarly, widely used polymers such as HPAM, could have potential
groundwater impacts and formation damage due to HPAM having very
low biodegradation (Millemann et al., 1982). Additionally, polymer
A.M. Hassan et al.
adsorption may lead to successive cEOR processes becoming ineffective.
Therefore, biopolymers such as Xanthan gum sourced from bio-waste
can be employed, which is easily biodegradable and compatible with
various fluid additives and surfactants (and biosurfactants) for appli­
cation in SP-based flooding at temperatures up to 90 ◦ C. Additionally,
Scleroglucan is stable for long durations at temperatures up to 100 ◦ C
(Davison and Mentzer, 1982; Kalpakci et al., 1990; Rivenq et al., 1992;
Kulawardana et al., 2012) and Schizophyllan is also applicable in HTHS
conditions, which are both biodegradable biopolymers (Huang and
Sorbie, 1993; Leonhardt et al., 2014).
In summary, eco-friendly chemicals such as biosurfactants and bio­
polymers could be good alternative candidates for SP-flooding under
HTHS carbonates conditions in case of high-levels of surfactant and
polymer adsorptions.
8. Summary, conclusions, and recommendations
Significant amounts of remaining and residual oil saturations exist in
the fractured low-permeability HTHS carbonate reservoirs. In order to
achieve maximum total oil production, SP-based cEOR technologies are
adapted. At the moment, a growing number of SP-based cEOR pilot
projects are in progress worldwide. The highly challenging temperature
and salinity (i.e., HTHS) environments render it difficult to procure the
appropriate surfactants and polymers required. The harsh HTHS
conditioned carbonate reservoirs hold over two thirds of the world’s oil
reserves, and are characterized by fractured formations, heterogeneous
mineral composition, and vuggy structure. In carbonate reservoirs, oil
recovery by SP-flooding is severely impacted as surfactants and poly­
mers degrade significantly in extreme temperature, and salinity (HTHS).
Moreover, surfactant retention can occur due to heterogeneity in min­
eral composition and surface interactivities of rock. The surface
geochemistry and the surface charge of carbonate rock can influence the
extent of surfactants retention. For instance, natural limestone has
aluminum and silicon present that causes retention, and even tiny cal­
cium sites on rock surface led to carboxylate surfactant adsorption.
Adding alkali to reduce pH, and pre-flush with low salinity water
flooding before SP-based cEOR can reduce surfactant adsorption.
Therefore, in order to meet the prerequisites for HTHS, heterogeneity
in mineral composition, and surface interactivities of carbonate reser­
voirs, there is still a lack of availability of suitable surfactants and
polymers for SP-based cEOR implementations, except the surfactants
that exhibited potential in the laboratory scale experiments such as
those described in this paper. Fortunately, the laboratory and field trials
of these surfactants demonstrate high potential.
Furthermore, in SP systems (i.e., COBR-system), polymers are the
major mobility control employed, hence, both surfactants and polymers
that are appropriate for carbonate reservoirs must be regarded for
advanced cEOR applications. For this reason, recently, many novel
surfactant and polymer formulations have been designed in a way that
can withstand the harsh environment of HTHS carbonate rocks. In
addition, the laboratory and field trials demonstrate high potential of
hybrid SP-based cEOR methods that are combined with low salinity
water (LSW) injection, and foam flooding via low salinity water polymer
(LSWP) flooding and smart-water assisted foam (SWAF) flooding pro­
cesses, respectively. These superior imminent technologies will be able
to decrease quite a few operational and logistic problems (i.e., increase
productivity, and reduce cost and environmental impact) of SP-based
EOR for carbonate rocks. These technologies are anticipated to be
adopted in the life-cycle methodology of SP-based EOR, which involves
reservoir stimulations that are carefully prepared, starting from the field
planning and development phase. Thus, for prospective projects, the
framework and operative know-hows learned from experimental out­
comes can be utilized for the considerable growth of efficient oil pro­
duction globally. Therefore, advancing EOR to new heights requires
imperative development of cEOR methods that have been improved on
cost-effectiveness, HTHS tolerance, and eco-conscious parameters. The
27
Journal of Petroleum Science and Engineering 220 (2023) 111243
most recent extrapolations described in this analysis will progress our
understanding to a great extent for enhanced designs of systemized
cEOR projects meant for harsh HTHS carbonate reservoirs.
Hence, this paper presents a comprehensive literature review on the
potential of SP-based cEOR applications in carbonates under harsh
conditions of HTHS from the perspective of successful laboratory, core-
flood, and field applications. The main conclusions of this work can be
summarized as follows:
• Studies showed the predominant factors influencing oil recovery in
carbonates to be the capillary forces, concentration of potential
determining ions, gravity and viscous forces, and pH.
• The new Guerbet alkoxy sulfates (GAS), Guerbet alkoxy carboxylates
(GAC), and Guerbet alkoxy betaine surfactant (GAB), demonstrated
good stability at temperatures over 100 ◦ C and salinities up to
275,000 ppm with very low adsorption on carbonates and high ter­
tiary oil recovery.
• This study also includes novel cationic Gemini surfactant formula­
tions with their temperature tolerance being approximately 300 ◦ C
and salinity tolerance of over 220,000 ppm.
• The hydrophobically associating polymers (HAPAM), that are highly
viscosifying chemicals, and its modified nanocomposite derivative
have good wettability altering capabilities as well as tolerance to
high temperature and high heterogeneity.
• Hot-melt Adhesive (HMA) has desirable rheological properties and
low adsorption in HTHS carbonates. E.g., SAV10, an HPAM based
polymer, and Sulfonated Polyacrylamide (AN-125) showing excel­
lent thermal and salinity tolerance in SP based EOR under HTHS
carbonates.
• Furthermore, Polymeric surfactants, biopolymers like Xanthan gum,
Scleroglucan and Schizophyllan, can be applied in tertiary oil re­
covery formulations for SP-based cEOR, in HTHS and low perme­
ability reservoir conditions effectively.
• Surface-active ionic liquids (SAILs) reduce IFT to ultra-low values
and induce wettability alteration towards a more water-wetting state
in harsh conditioned carbonates.
• Nano-technology innovations include the nanoparticles (NPs) as
potential surfactant careers for SP-based EOR in HTHS carbonates,
causing wettability alteration and high oil recovery, especially, the
biosurfactant-NP solutions that are highly effective in carbonate
rocks.
• Novel polymers such as, ATBS, NVP-based, hydrophobic associative,
smart thermoviscosifying polymers (TVP), soft microgel polymers,
and sulfonated polymers have shown to be tolerant to harsh
carbonates.
• SWAF-SP flooding techniques can mitigate retention and improve oil
recovery by combining smart-water assisted foam flooding with SP-
flooding (i.e., up to 92% cumulative OIIC for the tertiary stage).
• LSW-SP flooding can create as negative salinity gradient and it can
reduce retention while also augmenting the efficiency of surfactant
flood, and is used for preconditioning the reservoir.
• The progressive engineering of novel surfactants and polymers that
can withstand HTHS carbonate conditions is aimed at exploitation of
previously inaccessible oil reservoirs. Thus, this paper reiterates the
fact that surfactants, SP formulations, and other technologies have
evolved to be highly stable in harsh carbonate environments. Newer
works have focused on explaining the fluid-rock interactions during
SP flooding process with respect to these chemical agents.
Finally, the analysis of the latest progress suggests that surfactant-
polymer formulations can be optimized for improved chemical stabil­
ity, as well as lower surfactant/polymer adsorption and degradation
(polymers) in HTHS carbonate reservoirs. This would create environ­
mentally acceptable, cost-effective SP-based flooding designs. However,
there are more conclusive works to anticipate since there are very few
field applications so far.
A.M. Hassan et al. Journal of Petroleum Science and Engineering 220 (2023) 111243

Declaration of competing interest Acknowledgments

The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
This work was supported by the KFUPM-KU Joint Research Program.
Author(s) at Khalifa University acknowledge the support received under
award # KFUPM-KU-2020-14. Author(s) at KFUPM would like to
acknowledge the support received under grant # KU-201-001.

No data was used for the research described in the article.

Appendix-A
Table A1
An overview of the existing review articles, which cover the topic of SP-based cEOR including the materials used in these studies, temperature and salinity ranges,
advantages, and limitations

Reference Chemicals Used Experimental Conditions Remarks

Temp Salinity (ppm) Advantages (OIIP%) Limitations

(◦ C)

Gao et al. Petroleum sulfonate, HPAM, Comb shaped 71–80 3904–12,404 The work discusses the projects that Ranges of temperature and salinity do not
(2014) polymer successfully used SP-flooding. The meet HTHS carbonates conditions. The
recovery reached 5.5% OIIP. study is concentrated on oil fields in
China.
Raffa et al. A tapered copolymer of vinyl acetate, acrylic – – According to the study, using polymeric The application of polymeric surfactants
(2016a) acid, Alternate co-polymers of styrene and surfactants may improve EOR is the only focus of the research. HTHS
secondary amines, HPAM modified with performance. It provides an OIIP carbonates conditions are not highlighted
hydrophobic monomer recovery between 17 and 41%. in the study. The temperature and salinity
ranges are excluded.
Pal et al. Anionic, nonionic, and cationic surfactants, 25–100 Up to 11,000 Application of surfactant-based cEOR in Instead of SP-flooding, the study
(2018) Co-surfactant alkanols, biosurfactant, sugar- carbonate formations with a 12–36% concentrated more on surfactant-assisted
based surfactant OIIP oil recovery range. flooding. Salinity range does not meet the
criteria for high salinity.
Jain et al. Anionic surfactant, co-surfactant, polymer, 93.3 – The significance of surfactant and The study provides an overview of
(2022) alkali polymer floodings is emphasized in the surfactant and polymer flooding (i.e., not
paper. Depending on the reservoir emphasizing SP-flooding). The
characteristics, it can recover between formulations of surfactant and polymers
7% and 26% OIIP. used are not specified. No salinity range is
given.
Bashir Anionic: Alkyl-aryl sulfonic acid. Anionic: 25–120 2800–117,000 The review study classifies the The study focuses on surfactant flooding
et al. Internal olefin sulfonate. Cationic: surfactants-based flooding’s oil recovery without taking the co-surfactant (i.e.,
(2022) Hexadecyltrimethylam. Non-ionic: synthetic techniques. It can recover between 13% polymer) effect into account. The study is
biosurfactant and 90% OIIP. focused on sandstone and carbonate
reservoirs.
Han et al. Polyacrylamide-type polymers, Surfactant 50–80 3000–150,000 The study reviews field applications and The study’s primary focus is on surfactant
(2013) type learnings from offshore chemical flooding potential, assessment of the co-
flooding. It provides a recovery of 5%– surfactant (i.e., polymer) effect. The two
15% OIIP. main areas of research are sandstone and
carbonate reservoirs.

Table A2
Description of different novel surfactants viable for SP-based cEOR in HTHS carbonate reservoirs

Surfactant Formulation Temperature Salinity (ppm) Function

(◦ C)

Guerbet Alkoxy Sulfate 0.25 wt% C32–7PO-14EO-sulfate, 0.25 wt% C20–24- 100 35,000 ppm of Solubilization ratio at optimal salinity was around 17,
Surfactants (GAS) IOS, and 0.5 wt% TEGBE cosolvent sodium with exceptionally low IFT, surfactant retention of
carbonate 0.11 mg/g of rock with 94.7% oil retrieval
Guerbet Alkoxy 0.5 wt% C28–45PO-60EO-carboxylate and 0.5 wt% 120 30,000 Excellent phase behavior at 120 ◦ C, oil recovery at
Carboxylate C15–18-IOS 90.5% of residual oil and surfactant retention of 0.33
Surfactants (GAC) mg/g of rock
Guerbet Alkoxy 1.0 wt% C28–25PO-55EO-carboxylate, 0.5 wt% 83 230,800 Oil recovery was observed at 92% and Surfactant
Carboxylate C15–18-IOS, 0.5 wt% C19–23-IOS, and 1.0 wt% TEGBE adsorption value was 0.3 mg/g of rock
Surfactants (GAC)
Guerbet Alkoxy 0.5 wt% C28–25PO-25EO-carboxylate and 0.5 wt% 100 116,969 Excellent oil recovery of 65.9% with surfactant
Carboxylate C15–18-IOS retention was 0.086 mg/g of rock
Surfactants (GAC)
Tristyrylphenol Alkoxy 0.18 wt% TSP-35PO-20EO-sulfate and 0.12 wt% 62 55,000 92.1% oil retrieval with 0.10 mg/g of rock adsorption
Sulfate Surfactants C20–24-IOS (No cosolvents added) and no chromatographic separation visible in the core
(TSP)
0.50% GAB + 0.50% ADB + 1.0% n-butanol (for phase 120 275,000
behavior test)
(continued on next page)

28
A.M. Hassan et al. Journal of Petroleum Science and Engineering 220 (2023) 111243

Table A2 (continued )
Surfactant Formulation Temperature Salinity (ppm) Function
(◦ C)

Novel Guerbet Alkoxy Excellent tolerance to (HTHS) reservoir conditions

Betaine Surfactant and exhibited ultralow IFT for crude oil and
(GAB) intensified emulsification features
Gemini Surfactants – 98 – Field application at 190 bars reservoir pressure in
Hungary
Alkaline-Surfactant- 0.50 wt% C28–35PO-65EO-COONa, 0.25 wt%, C15-18 100 60,000 Exceptional tertiary oil output and minimal surfactant
Polymer Formulation IOS, 0.25 wt% C19–28IOS, 1.0 wt% ethoxylated adsorption
diisopropylamine (DIPA-10EO) and 0.75 wt% NH3

Table A3
Description of different novel polymers viable for SP-based cEOR in HTHS carbonate reservoirs

Polymer Monomer Group Use Main Function

Polymeric Surfactant Polymerizable groups viz., vinyl, allyl, Surface modification of solid substances, generating Altering properties of the surfactant for EOR
(surfmer) acrylate, methacrylate, styryl, and novel water-soluble hydrophobically associating
acrylamide polymers with high viscous power
Hydrophobically Micellar copolymerization of hydrophilic Resistant towards temperature, pH, and ion content Function as viscosifiers or wettability
Associating and hydrophobic monomers in the periphery of the wells modifiers in HTHS and high-pressure
Polyacrylamide Polymers reservoirs
(HAPAMs)
Flopaam 3630 HPAM based polymer Good tolerance of high temperature (100 ◦ C) at Mobility control with less shear sensitive
35,000 ppm salinity behavior under HTHS conditions
HAPAM Copolymer and HAPAM Retention of original viscosity and excellent non- Substitute for current surfactants, through
HAPAM-SiO2 Newtonian behaviors (i.e., correspond well to in- wettability altering nature and outstanding
Nanocomposite situ shear thinning behavior) tolerance to high temperature and high
heterogeneity oil fields
Hot-melt Adhesive (HMA) AM hydrophilic backbone of a terpolymer Surfactants could either enhance or reduce the Low adsorption in HTHS carbonates, better
Polymers modified with AMPS and hydrophobic viscosity of the HMA polymers depending on the rigidity, increased viscosity with salts and
monomer 2-vinylnaphtahlene (and other concentration added and the intermolecular and temperature, possible IFT reduction
variations) intramolecular associations
SAV10 ATBS-based polymer Tested at 297 g/L TDS and 105–120 ◦ C Thermally stable polymer for SP based EOR
in HTHS carbonates
Sulfonated Polyacrylamide Copolymer of AM and ATBS (25% Tested at formation brine with TDS of 229,870 ppm Low retention on carbonate rocks with
(AN-125) sulfonation) at 100 ◦ C HTHS

Table A4
Summary of reported literature on SP-based cEOR field applications in carbonate reservoirs

Reference Oilfield Temp Chemicals Used & Salinity (ppm) Remarks

(◦ C)
Recovery (%) Flooding Scheme

Al-Amrie et al. ABK oilfield, 83 Novel stable classes of hydrophilicity- Oil recovery of OOIP 90% SP slug and the polymer drive, although
(2015); Levitt Offshore, Abu Dhabi, enhanced surfactants; SAV-225 (AM- OOIP; Effective Sor reduction during actual operation the polymer
et al., (2016) SP UAE. AMPS-NVP terpolymer) from SNF from 40% to 4% in a tight drive was not required in this case.
Floerger; AN-125 SH (AM-AMPS carbonate with HTHS and low
copolymer) from SNF Floerger; Salinity permeability
is 230,000 (ppm)
Al-Murayri et al. Raudhatain Lower 82 Surfactant concentration of 5000 ppm; Positive oil desaturation Pre-flush was injected before the main-
(2019a, 2018, and Burgan (RALB) Polymer concentration of 500 ppm; In- levels following chemical slug injection, then followed by a post-
2017) SP Reservoir, Kuwait situ salinity of over >200,000 ppm flooding within 10 ft from the flush with the polymer only.
well Afterwards, sea-water push conducted,
then tracer injection, soaking and
production was conducted
Harris et al. (2020) Offshore the South – Alkyl propoxy sulfate (APS) and an alkyl The residual oil saturation Single Well Chemical Tracer Test
SP China Sea Field, ethoxy sulfate (AES) mixture with no co- decreased from 20-27% to (SWCTT)
China solvents; The salinity formulation was 7–9% range.
seawater-based
Yin et al., (2021) SP Block X, Tahe 100–110 Dispersed particle gel (DPG) and Incremental cEOR of 21.3% Combined flooding of DPG for in-depth
oilfield, Xinjiang, surfactant of the formulation 0.35% OIIP; The oil recovery from conformance control to enhance the
China NAC-1+ 0.25% NAC-2. In-situ salinity given well group was sweep efficiency, followed by surfactant
around 220,500 (ppm) increased by 3000 tons solution slug for improving
displacement efficiency
Rilian and Sumestry Semoga field, 83 Nonionic surfactants; Oil with 38 API◦ Oil recovery volume of Surfactant well stimulation via Huff-n-
(2010); Sheng Baturaja Formation, and 0.84 cP viscosity 58,000 bbl during the course Puff processes; Operation implemented
(2013b) Indonesia of 3 months in 3 steps: (i) pre-flush, (ii) main flush
and (iii) over-flush
Rohilla et al. (2021) Offshore Al-Shaheen 60 Surfactant concentration of 200,000 Incremental cEOR of 30–35% Long-term surfactant injection through
Surfactant Field, Block 5, Qatar (ppm); Salinity is 79,700 (ppm) OIIP due to wettability continuous mode at 4000 ppm of active
(continued on next page)

29
A.M. Hassan et al. Journal of Petroleum Science and Engineering 220 (2023) 111243

Table A4 (continued )
Reference Oilfield Temp Chemicals Used & Salinity (ppm) Remarks
(◦ C)
Recovery (%) Flooding Scheme

alteration; No surfactant concentration in sea water, after which

breakthrough sea water was injected
Varfolomeet al., Bashkirian 23 Nonionic surfactant; In-situ salinity Incremental cEOR of 1094 After surfactant injection, the nonionic
(2020) Surfactant Reservoirs, Ukraine around 217,500 (ppm) tones, via IFT reduction and surfactant showed good influence on
wettability alteration water injectivity enhancement and in
reducing wellhead and downhole
pressure
Stephenso et al., Lower Shaunavon 82 Emulsions additives; In-situ salinity of Pilot test showed optimistic Microemulsions additives act as a
(2019) Additives Saskatchewa, Canada over >200,000 ppm results with high cEOR delivery platform for surfactants,
solvents, and co-solvents into the
reservoir for enhanced waterflooding
Baloch et al. (2021) Abu Dhabi, UAE, The 121.1 SAV 10, which is a polyacrylamide- Good injectivity recover Polymer injection test/(PIT).; The
Polymer Abu Dhabi National based polymer with high 2-acrylamido- through achieving favorable overall polymer solution injection
Oil Company tertiary-butyl sulfonic acid (ATBS) indicators (PIT) volume was 108,392 barrels
(ADNOC) content; In-situ salinity of over
>200,000 ppm

Table A5
Surfactant-polymer based cEOR field projects worldwide (information was taken from Llano et al., 2013)

Project Name Location Operator Type of SP-flooding

ANGSI CEOR Asia PETRONAS SP, and ASP

St. Joseph Asia Petronas ASP
Daqing Asia Daqing Oilfield Polymer, ASP trials
Shengli Oilfield Asia Shengli Oilfield Polymer, SP, ASP
Dagang Oilfield Asia Petrochina cEOR
Mangala Field Asia Cair Energy India Pty Ltd ASP-flooding
Unnamed Middle East TOTAL SP-flooding
Oman Middle East Shell Polymer, SP, and ASP
Al Shaheen Middle East Maersk Oil Polymer and ASP
Battrum North America Hyak Energy ASP-flooding
Trembley Oilfield North America – ASP-flooding
ASP flooding pilot North America OXY ASP-flooding
Lawrence North America Rex Energy ASP-flooding
Saskatchewan North America Talisman ASP-flooding
ASP Colombia South America Williams Energy ASP-flooding
HTHS EOR Project – Total SP-flooding

References Ahmadi, M.A., Shadizadeh, S.R., 2013. Induced effect of adding nano silica on adsorption
of a natural surfactant onto sandstone rock: experimental and theoretical study.
J. Petrol. Sci. Eng. 112, 239–247.
Aarra, M.G., Skauge, A., Martinsen, H.A., 2002. FAWAG: a breakthrough for EOR in the
Ahmadi, M.A., Shadizadeh, S.R., 2015. Experimental investigation of a natural surfactant
north sea. In: SPE Annual Technical Conference and Exhibition.
adsorption on shale-sandstone reservoir rocks: static and dynamic conditions. Fuel
Abalkhail, N., Liyanage, P.J., Upamali, K.A.N., Pope, G.A., Mohanty, K.K., 2020.
159, 15–26.
Alkaline-surfactant-polymer formulation development for a HTHS carbonate
Akbar, M., Vissapragada, B., Alghamdi, A.H., Allen, D., Herron, M., Carnegie, A.,
reservoir. J. Petrol. Sci. Eng. 191, 107236.
Dutta, D., Olesen, J.-R., Chourasiya, R.D., Logan, D., 2000. A snapshot of carbonate
Abbasi-Asl, Y., Pope, G.A., Delshad, M., 2010. Mechanistic modeling of chemical
reservoir evaluation. Oilfield Rev. 12 (4), 20–21.
transport in naturally fractured oil reservoirs. In: SPE Improved Oil Recovery
Akbari, S., Mahmood, S.M., Tan, I.M., Ghaedi, H., Ling, O.L., 2017. Assessment of
Symposium.
polyacrylamide-based co-polymers enhanced by functional group modifications with
Adams, W.T., Schievelbein, V.H., 1987. Surfactant flooding carbonate reservoirs. SPE
regards to salinity and hardness. Polymers 9 (12), 647.
Reservoir Eng. 2 (4), 619–626.
Aktar, S., Saha, M., Mahbub, S., Halim, M.A., Rub, M.A., Hoque, M.A., Islam, D.S.,
Adejare, O.O., Nasralla, R.A., Nasr-El-Din, H.A., 2012. The effect of viscoelastic
Kumar, D., Alghamdi, Y.G., Asiri, A.M., 2020. Influence of polyethylene glycol on the
surfactants and a mutual solvent on the wettability of a carbonate rock. In: SPE
aggregation/clouding phenomena of cationic and non-ionic surfactants in
International Production and Operations Conference & Exhibition. OnePetro.
attendance of electrolytes (NaCl & Na2SO4): an experimental and theoretical
Adibhatla, B., Mohanty, K.K., 2006. Oil Recovery from Fractured Carbonates by
analysis. J. Mol. Liq. 306, 112880.
Surfactant-Aided Gravity Drainage: Laboratory Experiments and Mechanistic
Al-Amrie, O., Peltier, S., Pearce, A., Al-Yafei, A., Morel, D., Bourrel, M., Bursaux, R.,
Simulations. SPE/DOE Symposium on Improved Oil Recovery.
Cordelier, P., Jouenne, S., Juilla, H., Klimenko, A., 2015. The first successful
Adkins, S., Arachchilage, G.P., Solairaj, S., Lu, J., Weerasooriya, U., Pope, G., 2012.
chemical EOR pilot in the UAE: one spot pilot in high temperature, high salinity
Development of thermally and chemically stable large-hydrophobe alkoxy
carbonate reservoir. In: Abu Dhabi International Petroleum Exhibition and
carboxylate surfactants. In: SPE Improved Oil Recovery Symposium.
Conference. OnePetro.
Adkins, S., Liyanage, P.J., Pinnawala Arachchilage, G.W., Mudiyanselage, T.,
Al-Anssari, S., Barifcani, A., Wang, S., Maxim, L., Iglauer, S., 2016. Wettability alteration
Weerasooriya, U., Pope, G.A., 2010. A new process for manufacturing and stabilizing
of oil-wet carbonate by silica nanofluid. J. Colloid Interface Sci. 461, 435–442.
high-performance EOR surfactants at low cost for high-temperature, high-salinity oil
Al-Ghailani, T., Al-Wahaibi, Y.M., Joshi, S.J., Al-Bahry, S.N., Elshafie, A.E., Al-Bemani, A.
reservoirs. In: SPE Improved Oil Recovery Symposium.
S., 2018. Alkaline-biosurfactant-biopolymer process and its potential for enhancing
Afolabi, F., Mahmood, S.M., Yekeen, N., Akbari, S., Sharifigaliuk, H., 2022. Polymeric
oil recovery in Omani oil field. In: SPE EOR Conference at Oil and Gas West Asia.
surfactants for enhanced oil recovery: a review of recent progress. J. Petrol. Sci. Eng.
Al-Murayri, M.T., Kamal, D.S., Suniga, P., Fortenberry, R., Britton, C., Pope, G.A.,
208, 109358.
Liyanage, P.J., Jang, S.H., Upamali, K.A., 2017. October. Improving ASP
Ahmadali, T., Gonzalez, M.V., Harwell, J.H., Scamehorn, J.F., 1993. Reducing surfactant
performance in carbonate reservoir rocks using hybrid-alkali. In: SPE Annual
adsorption in carbonate reservoirs. SPE Reservoir Eng. 8 (2), 117–122.
Technical Conference and Exhibition. OnePetro.
Algharaib, M., Alajmi, A., Gharbi, R., 2014. Improving polymer flood performance in
high salinity reservoirs. J. Petrol. Sci. Eng. 115, 17–23.

30
A.M. Hassan et al.
Al-Hashim, H.S., Celik, M.S., Oskay, M.M., Al-Yousef, H.Y., 1988. Adsorption and
precipitation behaviour of petroleum sulfonates from Saudi Arabian limestone.
J. Petrol. Sci. Eng. 1 (4), 335–344.
Ali, J.A., Kolo, K., Manshad, A.K., Mohammadi, A.H., 2018. Recent advances in
application of nanotechnology in chemical enhanced oil recovery: effects of
nanoparticles on wettability alteration, interfacial tension reduction, and flooding.
Egyptian journal of petroleum 27 (4), 1371–1383.
Al-Murayri, M.T., Hassan, A.A., Abdullah, M.B., Abdulrahim, A.M., Marlière, C.,
Hocine, S., Tabary, R., Suzanne, G.P., 2019a. Surfactant/polymer flooding: chemical-
formulation design and evaluation for Raudhatain lower burgan reservoir, Kuwait.
SPE Reservoir Eval. Eng. 22 (3), 923–940.
Al-Murayri, M.T., Kamal, D.S., Al-Sabah, H.M., AbdulSalam, T., Al-Shamali, A.,
Quttainah, R., Glushko, D., Britton, C., Delshad, M., Liyanage, J., 2019b. Low-
salinity polymer flooding in a high-temperature low-permeability carbonate
reservoir in west Kuwait. In: SPE Kuwait Oil and Gas Show and Conference.
Al-Murayri, M.T., Al-Qenae, A., AlRukaibi, D., Chatterjee, M., Hewitt, P., 2017. Design of
a partitioning inter-well tracer test for a chemical EOR pilot targeting the Sabriyah
Mauddud carbonate reservoir in Kuwait. In: SPE Kuwait Oil & Gas Show and
Conference. OnePetro.
AlQuraishi, A.A., AlHussinan, S.N., AlYami, H.Q., 2015. Efficiency and recovery
mechanisms of low salinity water flooding in sandstone and carbonate reservoirs.
Offshore Mediterranean Conference and Exhibition.
AlSada, A., Mackay, E., 2017. Low salinity water flooding possible mechanisms and the
impact of injected sulphate variation on oil recovery in carbonate reservoirs:
compositional modeling approach. In: SPE Kingdom of Saudi Arabia Annual
Technical Symposium and Exhibition.
Al-Shalabi, E.W., 2018. Numerical modeling of biopolymer flooding in high-temperature
high-salinity carbonate cores. In: Offshore Technology Conference Asia.
Al-Shalabi, E.W., Alameri, W., Hassan, A.M., 2022. Mechanistic modeling of hybrid low
salinity polymer flooding: role of geochemistry. J. Petrol. Sci. Eng. 210, 110013.
Al-Shalabi, E.W., Sepehrnoori, K., 2017. Low Salinity and Engineered Water Injection for
Sandstone and Carbonate Reservoirs. Gulf Professional Publishing.
Al-Wahaibi, Y., Joshi, S., Al-Bahry, S., Elshafie, A., Al-Bemani, A., Shibulal, B., 2014.
Biosurfactant production by Bacillus subtilis B30 and its application in enhancing oil
recovery. Colloids Surf. B Biointerfaces 114, 324–333.
Amirpour, M., Shadizadeh, S.R., Esfandyari, H., Ahmadi, S., 2015. Experimental
investigation of wettability alteration on residual oil saturation using nonionic
surfactants: capillary pressure measurement. Petroleum 1 (4), 289–299.
Andersen, P., Evje, S., Kleppe, H., 2014. A model for spontaneous imbibition as a
mechanism for oil recovery in fractured reservoirs. Transport Porous Media 101 (2),
299–331.
Anderson, W., 1986. Wettability literature survey-part 2: wettability measurement.
J. Petrol. Technol. 38 (11), 1246–1262.
Atilhan, M., Santiago, A., 2021. Review on chemical enhanced oil recovery: utilization of
ionic liquids and deep eutectic solvents. J. Petrol. Sci. Eng. 205, 108746.
Atta, A.M., Dyab, A.K.F., Al-Lohedan, H.A., AlJenady, K.A., 2014. Novel reactive
polymerizable nonyl phenol ethoxylate surfactants as emulsifier in non-aqueous
emulsion polymerization. Polym. Sci. B 56 (6), 770–787.
Austad, T., Matre, B., Milter, J., Saevareid, A., Øyno, L., 1998. Chemical flooding of oil
reservoirs 8. Spontaneous oil expulsion from oil-and water-wet low permeable chalk
material by imbibition of aqueous surfactant solutions. Colloids Surf. A
Physicochem. Eng. Asp. 137 (1–3), 117–129.
Austad, T., Milter, J., 1997. Spontaneous imbibition of water into low permeable chalk at
different wettabilities using surfactants. International Symposium on Oilfield
Chemistry.
Austad, T., Shariatpanahi, S.F., Strand, S., Black, C.J.J., Webb, K.J., 2012. Conditions for
a low-salinity enhanced oil recovery (EOR) effect in carbonate oil reservoirs. Energy
Fuel. 26 (1), 569–575.
Austad, T., Strand, S., Høgnesen, E.J., Zhang, P., 2005. Seawater as IOR fluid in fractured
chalk. In: SPE International Symposium on Oilfield Chemistry.
Ayirala, S.C., Boqmi, A., Alghamdi, A., AlSofi, A., 2019. Dilute surfactants for wettability
alteration and enhanced oil recovery in carbonates. IOR 2019–20th European
Symposium on Improved Oil Recovery 2019 (1).
Ayirala, S., Sofi, A., Li, Z., Xu, Z., 2021. Surfactant and surfactant-polymer effects on
wettability and crude oil liberation in carbonates. J. Petrol. Sci. Eng. 207, 109117.
Azam, M.R., Tan, I.M., Ismail, L., Mushtaq, M., Nadeem, M., Sagir, M., 2013. Static
adsorption of anionic surfactant onto crushed Berea sandstone. J. Pet. Explor. Prod.
Technol. 3 (3), 195–201.
Azam, S., Darlington, A., Gibbs-Davis, J.M., 2014. The influence of concentration on
specific ion effects at the silica/water interface. J. Phys. Condens. Matter 26 (24),
244107.
Baloch, S.A., Leon, J.M., Masalmeh, S.K., Chappell, D., Brodie, J., Romero, C., Al
Mazrouei, S.H., Al Tenaiji, A., Al Balooshi, M., Igogo, A., Azam, M.U.F., 2021.
Expanding polymer injectivity tests on a second giant carbonate UAE oil reservoir at
high salinity & high temperature conditions. In: Abu Dhabi International Petroleum
Exhibition & Conference. OnePetro.
Barakat, Y., Gendy, T.S., Mohamad, A.I., Youssef, A.F.M., 1989. Polymeric surfactants for
enhanced oil recovery. Part I—critical micelle concentration of some ethoxylated
alkylphenol—formaldehyde nonionics. Br. Polym. J. 21 (5), 383–389.
Barari, M., Lashkarbolooki, M., Abedini, R., 2021. Interfacial properties of crude oil/
imidazolium based ionic liquids in the presence of NaCl and Na2SO4 during EOR
process. J. Mol. Liq. 327, 114845.
Bashir, A., Haddad, A.S., Rafati, R., 2022. A review of fluid displacement mechanisms in
surfactant-based chemical enhanced oil recovery processes: analyses of key
influencing factors. Petrol. Sci.
31
Journal of Petroleum Science and Engineering 220 (2023) 111243
Bassir, S.M., Shadizadeh, S.R., 2020. Static adsorption of a new cationic biosurfactant on
carbonate minerals: application to EOR. Petrol. Sci. Technol. 38 (5), 462–471.
Bastiat, G., Grassl, B., Khoukh, A., François, J., 2004. Study of sodium dodecyl sulfate−
poly (propylene oxide) methacrylate mixed micelles. Langmuir 20 (14), 5759–5769.
Bataweel, M.A., Nasr-El-Din, H.A., 2011. Alternatives to minimize scale precipitation in
carbonate cores caused by alkalis in asp flooding in high salinity/high temperature
applications. In: SPE European Formation Damage Conference.
Baviere, M., Bazin, B., Noik, C., 1988. Surfactants for EOR: olefin sulfonate behavior at
high temperature and hardness. SPE Reservoir Eng. 3 (2), 597–603.
Behler, A., Biermann, M., Hill, K., Raths, H.-C., Victor, M.E.S., Uphues, G., Texter, J.,
2001. Industrial surfactant syntheses. Surfactant Sci. Ser. 1–44.
Belhaj, A.F., Elraies, K.A., Mahmood, S.M., Zulkifli, N.N., Akbari, S., Hussien, O.S., 2020.
The effect of surfactant concentration, salinity, temperature, and pH on surfactant
adsorption for chemical enhanced oil recovery: a review. J. Pet. Explor. Prod.
Technol. 10, 125–137.
Bera, A., Kumar, S., Foroozesh, J., 2021. Biosurfactant role in microbial enhanced oil
recovery. Green Sustainable Process for Chemical and Environmental Engineering
and Science 1–33.
Bera, A., Ojha, K., Mandal, A., Kumar, T., 2011. Interfacial tension and phase behavior of
surfactant-brine–oil system. Colloids Surf., A 383 (1–3), 114–119.
Bergström, L.M., Tehrani-Bagha, A., Nagy, G., 2015. Growth behavior, geometrical
shape, and second CMC of micelles formed by cationic gemini esterquat surfactants.
Langmuir 31 (16), 4644–4653.
Blaker, T., Aarra, M.G., Skauge, A., Rasmussen, L., Celius, H.K., Martinsen, H.A.,
Vassenden, F., 2002. Foam for gas mobility control in the Snorre field: the FAWAG
project. SPE Reservoir Eval. Eng. 5 (4), 317–323.
Boampong, L.O., Rafati, R., Haddad, A.S., 2022. A calibrated surface complexation model
for carbonate-oil-brine interactions coupled with reservoir simulation-Application to
controlled salinity water flooding. J. Petrol. Sci. Eng. 208, 109314.
Bohmer, M.R., Koopal, L.K., 1992. Adsorption of ionic surfactants on variable-charge
surfaces. 1. Charge effects and structure of the adsorbed layer. Langmuir 8 (11),
2649–2659.
Borzenkov, M., Hevus, O., 2014. Surface Active Monomers: Synthesis, Properties, and
Application. Springer.
Borzenkov, M., Mitina, N., Lobaz, V., Hevus, O., 2015. Synthesis and properties of novel
surface-active monomers based on derivatives of 4-hydroxybutyric acid and 6-
hydroxyhexanoic acid. J. Surfactants Deterg. 18 (1), 133–144.
Bourbiaux, B., Fourno, A., Nguyen, Q.-L., Norrant, F., Robin, M., Rosenberg, E.,
Argillier, J.-F., 2014. Experimental and numerical assessment of chemical EOR in oil-
wet naturally-fractured reservoirs. In: SPE Improved Oil Recovery Symposium.
Bourrel, M., Schechter, R.S., 2010. Microemulsions and Related Systems: Formulation,
Solvency, and Physical Properties. Editions Technip.
Budhathoki, M., Barnee, S.H.R., Shiau, B.-J., Harwell, J.H., 2016. Improved oil recovery
by reducing surfactant adsorption with polyelectrolyte in high saline brine. Colloids
Surf. A Physicochem. Eng. Asp. 498, 66–73.
Butt, H., Graf, K., Kappl, M., 2003. Physics and Chemistry of Interfaces. Wiley-VCH
Verlag GmbH and Co. KGaA, Weinheim, FRG, FRG.
Cai, H., Wang, Q., Luo, W., Wang, H., Zhou, X., Li, J., Zheng, Y., 2019. Guerbet alkoxy
betaine surfactant for surfactant-polymer flooding in high temperature, high salinity
reservoirs. SPE International Conference on Oilfield Chemistry.
Camail, M., Margaillan, A., Martin, I., Papailhou, A.L., Vernet, J.L., 2000. Synthesis of N-
alkyl-and N-arylalkylacrylamides and micellar copolymerization with acrylamide.
Eur. Polym. J. 36 (9), 1853–1863.
Candau, F., Selb, J., 1999. Hydrophobically-modified polyacrylamides prepared by
micellar polymerization. Adv. Colloid Interface Sci. 79 (2–3), 149–172.
Cao, Y., Li, H., 1999. Synthesis of a novel family of polymeric surfactants with low
interfacial tension by ultrasonic method. Polym. J. 31 (11), 920–923.
Cao, Y., Li, H., 2002. Interfacial activity of a novel family of polymeric surfactants. Eur.
Polym. J. 38 (7), 1457–1463.
Chandar, P., Somasundaran, P., Turro, N.J., 1987. Fluorescence probe studies on the
structure of the adsorbed layer of dodecyl sulfate at the alumina—water interface.
J. Colloid Interface Sci. 117 (1), 31–46.
Chen, H., Gizzatov, A., Abdel-Fattah, A.I., 2019. Molecular assembly of surfactant
mixtures in oil-swollen micelles: implications for high salinity colloidal stability.
J. Phys. Chem. B 124 (3), 568–576.
Chen, L., Zhang, G., Wang, L., Wu, W., Ge, J., 2014. Zeta potential of limestone in a large
range of salinity. Colloids Surf. A Physicochem. Eng. Asp. 450, 1–8.
Chen, P., Mohanty, K.K., 2013. Surfactant-mediated spontaneous imbibition in carbonate
rocks at harsh reservoir conditions. SPE J. 18 (1), 124–133.
Chilingar, G. v, Yen, T.F., 1983. Some notes on wettability and relative permeability of
carbonate rocks. II. Energy Sources 7 (1), 67–75.
Chou, S.I., Shah, D.O., 1981. The effect of H2O and D2O on colloidal properties of
surfactant solutions and microemulsions. J. Colloid Interface Sci. 80 (1), 49–57.
Chowdhury, S., Shrivastava, S., Kakati, A., Sangwai, J.S., 2022. Comprehensive review
on the role of surfactants in the chemical enhanced oil recovery process. Ind. Eng.
Chem. Res. 61 (1), 21–64.
Cockcroft, P., Anli, J., Duignan, J., 1988. EOR Potential of Indonesian Reservoirs.
Crain, E.R., 2002. Crain’s Petrophysical Handbook. Spectrum 2000 Mindware Limited.
Cui, L., Ma, K., Abdala, A.A., Lu, L.J., Tanakov, I., Biswal, S.L., Hirasaki, G.J., 2015.
Adsorption of a switchable cationic surfactant on natural carbonate minerals. SPE J.
20 (1), 70–78.
Davison, P., Mentzer, E., 1982. Polymer flooding in north sea reservoirs. Soc. Petrol. Eng.
J. 22 (3), 353–362.
De Oliveira Silva, H.G., Pires, A.J.V., da Cunha Neto, P.A., de Carvalho, G.G.P., Veloso, C.
M., Ferreira daSilva, F., 2007. Digestibilidade de dietas contendo silagem de capim-
A.M. Hassan et al.
elefante amonizado e farelo de cacau ou torta de dendê em ovinos. Rev. Bras. Zootec.
36 (2).
Dean, R.M., 2011. Selection and Evaluation of Surfactants for Field Pilots. The University
of Texas at Austin. M.Sc. thesis.
Delshad, M., Han, C., Veedu, F.K., Pope, G.A., 2011. A simplified model for simulations
of alkaline-surfactant-polymer floods. In: SPE Reservoir Simulation Symposium.
Deng, X., Kamal, M.S., Patil, S., Hussain, S.M.S., Zhou, X., Mahmoud, M., 2021.
Wettability alteration of locally synthesized cationic gemini surfactants on carbonate
rock. J. Mol. Liq. 344, 117817.
Derian, P.-J., Guerin, G., Fiard, J.-F., 1993. Microemulsions of pyrethroids: phase
diagrams and effectiveness of tristyrylphenol based surfactants. In: Pesticide
Formulations and Application Systems: Twelfth Volume. ASTM International.
Diab, W.N., Al-Shalabi, E.W., 2019. Recent developments in polymer flooding for
carbonate reservoirs under harsh conditions. Offshore Technology Conference Brasil.
Dicharry, C., Diaz, J., Torré, J.P., Ricaurte, M., 2016. Influence of the carbon chain
length of a sulfate-based surfactant on the formation of CO2, CH4 and CO2–CH4 gas
hydrates. Chem. Eng. Sci. 152, 736–745.
Dupuis, G., Antignard, S., Giovannetti, B., Gaillard, N., Jouenne, S., Bourdarot, G.,
Zaitoun, A., 2017. A new thermally stable synthetic polymer for harsh conditions of
Middle East reservoirs. In: Part I. Thermal Stability and Injection in Carbonate Cores.
Abu Dhabi International Petroleum Exhibition and Conference.
El-Batanoney, M., Abdel-Moghny, T., Ramzi, M., 1999. The effect of mixed surfactants on
enhancing oil recovery. J. Surfactants Deterg. 2 (2), 201–205.
El-Diasty, A.I., Aly, A.M., 2015. Understanding the mechanism of nanoparticles
applications in enhanced oil recovery. In: SPE North Africa Technical Conference
and Exhibition.
El-Hoshoudy, A.N., Desouky, S.E.M., Al-Sabagh, A.M., Betiha, M.A., My, E.,
Mahmoud, S., 2017b. Evaluation of solution and rheological properties for
hydrophobically associated polyacrylamide copolymer as a promised enhanced oil
recovery candidate. Egyptian Journal of Petroleum 26 (3), 779–785.
El Hoshoudy, A., Desouky, S., Al-sabagh, A., El-kady, M., Betiha, M., Mahmoud, S.,
2015a. Synthesis and characterization of polyacrylamide crosslinked copolymer for
enhanced oil recovery and rock wettability alteration. Int. J. Oil Gas Coal Eng. 3 (4),
43–55.
El-Hoshoudy, A.N., Desouky, S.E.M., Betiha, M.A., Alsabagh, A.M., 2016. Use of 1-vinyl
imidazole based surfmers for preparation of polyacrylamide–SiO2 nanocomposite
through aza-Michael addition copolymerization reaction for rock wettability
alteration. Fuel 170, 161–175.
El-Hoshoudy, A.N., Desouky, S.M., Betiha, M.H., Alsabagh, A.M., 2017a. Hydrophobic
polymers flooding. Application and Characterization of Surfactants. InTechopen
75–95.
El-Hoshoudy, A.N., Desouky, S.E.M., Elkady, M.Y., Alsabagh, A.M., Betiha, M.A.,
Mahmoud, S., 2015b. Investigation of optimum polymerization conditions for
synthesis of cross-linked polyacrylamide-amphoteric surfmer nanocomposites for
polymer flooding in sandstone reservoirs. International Journal of Polymer Science,
2015.
Emadi, S., Shadizadeh, S.R., Manshad, A.K., Rahimi, A.M., Mohammadi, A.H., 2017.
Effect of nano silica particles on Interfacial Tension (IFT) and mobility control of
natural surfactant (Cedr Extraction) solution in enhanced oil recovery process by
nano-surfactant flooding. J. Mol. Liq. 248, 163–167.
Emrani, A.S., Nasr-El-Din, H.A., 2015. Stabilizing CO2-foam using nanoparticles. In: SPE
European Formation Damage Conference And Exhibition. OnePetro.
Esfandiarian, A., Maghsoudian, A., Shirazi, M., Mohammadi, M., Kord, S., Tamsilian, Y.,
2021. Experimental investigation of using ionic-liquids as alternatives of surfactants
in enhanced-oil-recovery processes for harsh carbonate reservoirs. 82nd EAGE
Annual Conference and Exhibition 2021. No. 1.
Eshraghi, S., Kazemzadeh, Y., Qahramanpour, M., Kazemi, A., 2017. Investigating effect
of SiO2 nanoparticle and sodium-dodecyl-sulfate surfactant on surface properties:
wettability alteration and IFT reduction. J. Petrol Environ. Biotechnol. 8, 349–353.
Evani, S., Rose, G.D., 1987. Water soluble hydrophobe association polymers. Polym.
Mater. Sci. Eng. 57, 477–481.
Fava, A., Eyring, H., 1956. Equilibrium and kinetics of detergent adsorption–a
generalized equilibration theory. J. Phys. Chem. 60 (7), 890–898.
Feng, Y., Billon, L., Grassl, B., Bastiat, G., Borisov, O., François, J., 2005.
Hydrophobically associating polyacrylamides and their partially hydrolyzed
derivatives prepared by post-modification. 2. Properties of non-hydrolyzed polymers
in pure water and brine. Polymer 46 (22), 9283–9295.
Flaaten, A., Nguyen, Q.P., Zhang, J., Mohammadi, H., Pope, G.A., 2008. ASP chemical
flooding without the need for soft water. In: SPE Annual Technical Conference and
Exhibition.
Folk, R.L., 1959. Practical petrographic classification of limestones. AAPG (Am. Assoc.
Pet. Geol.) Bull. 43 (1), 1–38.
Freedman, H.H., Manson, J.P., Medalia, A.I., 1958. Polysoaps. II. The preparation of
vinyl soaps1. J. Org. Chem. 23 (1), 76–82.
Fuseni, A., Han, M., Al-Mobith, A., 2013. Phase Behavior and Interfacial Tension
Properties of an Amphoteric Surfactant for EOR Application, pp. 1–14.
Gao, B., Sharma, M.M., 2013. A new family of anionic surfactants for enhanced-oil-
recovery applications. SPE J. 18 (5), 829–840.
Gao, B., Guo, H., Wang, J., Zhang, Y., 2008. Preparation of hydrophobic association
polyacrylamide in a new micellar copolymerization system and its hydrophobically
associative property. Macromolecules 41 (8), 2890–2897.
Gao, B., Wu, N., Li, Y., 2004. Study on tercopolymer of acrylamide containing strong
anions and hydrophobic association blocks. Acta Polym. Sin. 5, 736–742.
Gao, B., Wu, N., Li, Y., 2005. Interaction between the strong anionic character of strong
anions and the hydrophobic association property of hydrophobic blocks in
32
Journal of Petroleum Science and Engineering 220 (2023) 111243
macromolecular chains of a water-soluble copolymer. J. Appl. Polym. Sci. 96 (3),
714–722.
Gao, B., Yu, Y., Jiang, L., 2007. Studies on micellar behavior of anionic and surface-
active monomers with acrylamide type in aqueous solutions. Colloids Surf. A
Physicochem. Eng. Asp. 293 (1–3), 210–216.
Gao, C.H., 2011. Scientific research and field applications of polymer flooding in heavy
oil recovery. J. Pet. Explor. Prod. Technol. 1 (2–4), 65–70.
Gao, C., 2018. Experiences of microbial enhanced oil recovery in Chinese oil fields.
J. Petrol. Sci. Eng. 166, 55–62.
Gao, C., Shi, J., Zhao, F., 2014. Successful polymer flooding and surfactant-polymer
flooding projects at Shengli Oilfield from 1992 to 2012. J. Pet. Explor. Prod.
Technol. 4 (1), 1–8.
Gbadamosi, A., Patil, S., Al Shehri, D., Kamal, M.S., Hussain, S.S., Al-Shalabi, E.W.,
Hassan, A.M., 2022. Recent advances on the application of low salinity
waterflooding and chemical enhanced oil recovery. Energy Rep. 8, 9969–9996.
Geetha, S.J., Banat, I.M., Joshi, S.J., 2018. Biosurfactants: production and potential
applications in microbial enhanced oil recovery (MEOR). Biocatal. Agric. Biotechnol.
14, 23–32.
Gizzatov, A., Mashat, A., Kosynkin, D., Alhazza, N., Kmetz, A., Eichmann, S.L., Abdel-
Fattah, A.I., 2019. Nanofluid of petroleum sulfonate nanocapsules for enhanced oil
recovery in high-temperature and high-salinity reservoirs. Energy Fuel. 33 (11),
11567–11573.
Gomari, K.E., 2022. Hybrid Polymer/biopolymer/biosurfactant Flooding Influence on
the Displacement Efficiency in Fractured Carbonate Reservoirs. PhD Dissertation.
Teesside University.
Gomari, K.E., Hughes, D., Islam, M., Gomari, S.R., 2021. Application of water-soluble
polymer/biopolymer combined with a biosurfactant in oil-wet fractured carbonate
reservoirs. ACS Omega 6 (24), 15674–15685.
Goodlett, G.O., Honarpour, M.M., Chung, F.T., Sarathi, P.S., 1986. The role of screening
and laboratory flow studies in EOR process evaluation. In: SPE Rocky Mountain
Regional Meeting.
Goudarzi, A., Delshad, M., Mohanty, K.K., Sepehrnoori, K., 2012. Impact of matrix block
size on oil recovery response using surfactants in fractured carbonates. In: SPE
Annual Technical Conference and Exhibition.
Gouveia, L.M., Grassl, B., Müller, A.J., 2009. Synthesis and rheological properties of
hydrophobically modified polyacrylamides with lateral chains of poly (propylene
oxide) oligomers. J. Colloid Interface Sci. 333 (1), 152–163.
Gouveia, L.M., Paillet, S., Khoukh, A., Grassl, B., Müller, A.J., 2008. The effect of the
ionic strength on the rheological behavior of hydrophobically modified
polyacrylamide aqueous solutions mixed with sodium dodecyl sulfate (SDS) or
cetyltrimethylammonium p-toluenesulfonate (CTAT). Colloids Surf. A Physicochem.
Eng. Asp. 322 (1–3), 211–218.
Green, D.W., Willhite, G.P., 1998. Enhanced Oil Recovery, vol. 6. Henry L. Doherty
Memorial Fund of AIME, Society of Petroleum Engineers.
Grigg, R.B., Baojun, B., Yi, L., 2004. Competitive adsorption of a hybrid surfactant system
onto five minerals, berea sandstone, and limestone. In: SPE Annual Technical
Conference and Exhibition. OnePetro.
Gubelmann-Bonneau, I.V., Mailhe, P.A., Perrin, M.A., 1995. Tristyrylphenol surfactants
in agricultural formulations: properties and challenges in applications. In: Pesticide
Formulations and Application Systems: Fourteenth Volume.
Guo, H., Li, Y., Kong, D., Ma, R., Li, B., Wang, F., 2019. Lessons learned from alkali/
surfactant/polymer-flooding field tests in China. SPE Reservoir Eval. Eng. 22 (1),
78–99.
Guo, L., Han, M., Fuseni, A., AlSofi, A., 2016. Laboratory investigation of polymeric
surfactants for EOR in high salinity and high temperature reservoir. In: SPE EOR
Conference at Oil and Gas West Asia.
Gupta, R., Mohanty, K.K., 2010. Temperature effects on surfactant-aided imbibition into
fractured carbonates. SPE J. 15 (3), 588–597.
Gupta, R.A., Mohanty, K.K., 2011. Wettability alteration mechanism for oil recovery
from fractured carbonate rocks. Transport Porous Media 87 (2), 635–652.
Gupta, S.K., Sharma, A., Tapadia, K., 2020. A convenient nanodrop spectrophotometric
approach to determine cationic surfactant Tetraoctylammonium bromide (TOAB) in
environmental and biological samples. Chem. Pap. 74 (6), 1791–1798.
Guyot, A., 2004. Advances in reactive surfactants. Adv. Colloid Interface Sci. 108, 3–22.
Hamoud, A.S., 1995. Enhanced Oil Recovery in Carbonate Reservoirs. Al Baath
University, Hims.
Hanamertani, A.S., Pilus, R.M., Idris, A.K., Irawan, S., Tan, I.M., 2018. Ionic liquids as a
potential additive for reducing surfactant adsorption onto crushed Berea sandstone.
J. Petrol. Sci. Eng. 162, 480–490.
Han, M., AlSofi, A., Fuseni, A., Zhou, X., Hassan, S., 2013. Development of chemical EOR
formulations for a high temperature and high salinity carbonate reservoir. In: IPTC
2013: International Petroleum Technology Conference, Cp-350.
Harris, R.R., Paramanathan, S., Dickson, S.J., Bouwmeester, R.C., Southwick, J.G.,
Keijzer, E., van Rijn, C.H., Batenburg, D.W., 2020 August. Evaluation of seawater
based surfactant polymer formulation in a single well test offshore. In: SPE Improved
Oil Recovery Conference. OnePetro.
Hartono, A.D., Hakiki, F., Syihab, Z., Ambia, F., Yasutra, A., Sutopo, S., Efendi, M.,
Sitompul, V., Primasari, I., Apriandi, R., 2017. Revisiting EOR projects in Indonesia
through integrated study: EOR screening, predictive model, and optimization. In:
SPE/IATMI Asia Pacific Oil and Gas Conference and Exhibition.
Haruna, M.A., Nourafkan, E., Hu, Z., Wen, D., 2019. Improved polymer flooding in harsh
environments by free-radical polymerization and the use of nanomaterials. Energy
Fuel. 33 (2), 1637–1648.
Hashmet, M.R., AlSumaiti, A.M., Qaiser, Y., AlAmeri, W., 2017. Laboratory investigation
and simulation modeling of polymer flooding in high-temperature, high-salinity
carbonate reservoirs. Energy Fuel. 31 (12), 13454–13465.
A.M. Hassan et al.
Hassan, A.M., Ayoub, M., Eissa, M., Al-Shalabi, E.W., Almansour, A., Alquraishi, A.,
2022a. Foamability and foam stability screening for smart water assisted foam
flooding: a new hybrid EOR method. In: International Petroleum Technology
Conference.
Hassan, A.M., Ayoub, M., Eissa, M., Al-Shalabi, E.W., Al-Mansour, A., Al-Quraishi, A.,
2022b. Increasing reservoir recovery efficiency through laboratory-proven hybrid
smart water-assisted foam (SWAF) flooding in carbonate reservoirs. Energies 15 (9),
3058.
Hassan, A.M., Al-Shalabi, E.W., AlAmeri, W., Kamal, M.S., Patil, S., Shakil Hussain, S.M.,
2022c. New insights into hybrid low salinity polymer (LSP) flooding through a
coupled geochemical-based modeling approach. In: SPE Annual Technical
Conference and Exhibition. OnePetro.
Hassan, A.M., Al-Shalabi, E.W., Ayoub, M.A., 2022d. Updated perceptions on polymer-
based enhanced oil recovery toward high-temperature high-salinity tolerance for
successful field applications in carbonate reservoirs. Polymers 14 (10), 2001.
Hassan, A., Ayoub, M., Eissa, M., Bruining, H., Al-Mansour, A., Al-Quraishi, A., 2021.
A new hybrid improved and enhanced oil recovery IOR/EOR process using smart
water assisted foam SWAF flooding in carbonate rocks; A laboratory study approach.
In: International Petroleum Technology Conference.
Hassan, A.M., Ayoub, M., Eissa, M., Bruining, H., Zitha, P., 2020. Study of surface
complexation modeling on a novel hybrid enhanced oil recovery (EOR) method;
smart-water assisted foam-flooding. J. Petrol. Sci. Eng. 195, 107563.
Hassan, A.M., Ayoub, M., Eissa, M., Musa, T., Bruining, H., Farajzadeh, R., 2019. Exergy
return on exergy investment analysis of natural-polymer (Guar-Arabic gum)
enhanced oil recovery process. Energy 181, 162–172.
Healy, R.N., Reed, R.L., Stenmark, D.G., 1976. Multiphase microemulsion systems. Soc.
Petrol. Eng. J. 16 (3), 147–160.
Hill, H.J., Reisberg, J., Stegemeier, G.L., 1973. Aqueous surfactant systems for oil
recovery. J. Petrol. Technol. 25 (2), 186–194.
Hiorth, A., Cathles, L.M., Madland, M.V., 2010. The impact of pore water chemistry on
carbonate surface charge and oil wettability. Transport Porous Media 85 (1), 1–21.
Hirasaki, G.J., Miller, C.A., Puerto, M., 2011. Recent advances in surfactant EOR. SPE J.
16 (4), 889–907.
Hirasaki, G., Zhang, D.L., 2003. Surface chemistry of oil recovery from fractured, oil-wet,
carbonate formation. In: International Symposium on Oilfield Chemistry.
Holmberg, K., 2003. Novel Surfactants: Preparation Applications and Biodegradability,
Revised and Expanded, vol. 114. Crc Press.
Hong, P., Fa, C., Wei, Y., Sen, Z., 2007. Surface properties and synthesis of the cellulose-
based amphoteric polymeric surfactant. Carbohydr. Polym. 69 (4), 625–630.
Hu, K., Bard, A.J., 1997. Characterization of adsorption of sodium dodecyl sulfate on
charge-regulated substrates by atomic force microscopy force measurements.
Langmuir 13 (20), 5418–5425.
Hu, S.-S., Zhang, L., Cao, X.-L., Guo, L.-L., Zhu, Y.-W., Zhang, L., Zhao, S., 2015. Influence
of crude oil components on interfacial dilational properties of hydrophobically
modified polyacrylamide. Energy Fuel. 29 (3), 1564–1573.
Huang, Y., Santore, M.M., 2002. Dynamics in adsorbed layers of associative polymers in
the limit of strong backbone− surface attractions. Langmuir 18 (6), 2158–2165.
Huang, Y., Sorbie, K.S., 1993. Scleroglucan behavior in flow through porous media:
comparison of adsorption and in-situ rheology with xanthan. SPE International
Symposium on Oilfield Chemistry.
Huh, C., 1979. Interfacial tensions and solubilizing ability of a microemulsion phase that
coexists with oil and brine. J. Colloid Interface Sci. 71 (2), 408–426.
Hussain, S.M.S., Kamal, M.S., 2017. Effect of large spacer on surface activity, thermal,
and rheological properties of novel amido-amine cationic gemini surfactants. J. Mol.
Liq. 242, 1131–1137.
Hussain, S.M.S., Kamal, M.S., Murtaza, M., 2019. Effect of aromatic spacer groups and
counterions on aqueous micellar and thermal properties of the synthesized
quaternary ammonium gemini surfactants. J. Mol. Liq. 296, 111837.
Iglauer, S., Wu, Y., Shuler, P., Tang, Y., Goddard III, W.A., 2009. Alkyl polyglycoside
surfactant–alcohol cosolvent formulations for improved oil recovery. Colloids Surf. A
Physicochem. Eng. Asp. 339 (1–3), 48–59.
Iglauer, S., Wu, Y., Shuler, P., Tang, Y., Goddard III, W.A., 2010. New surfactant classes
for enhanced oil recovery and their tertiary oil recovery potential. J. Petrol. Sci. Eng.
71 (1–2), 23–29.
Inada, T., Koyama, T., Tomita, H., Fuse, T., Kuwabara, C., Arakawa, K., Fujikawa, S.,
2017. Anti-ice nucleating activity of surfactants against silver iodide in water-in-oil
emulsions. J. Phys. Chem. B 121 (27), 6580–6587.
Ishiguro, M., Koopal, L.K., 2016. Surfactant adsorption to soil components and soils. Adv.
Colloid Interface Sci. 231, 59–102.
Islam, N., Sharker, K.K., Sarker, K.C., 2015. Salt-induced modulation of the Krafft
temperature and critical micelle concentration of
benzyldimethylhexadecylammonium chloride. J. Surfactants Deterg. 18 (4),
651–659.
Jabbar, M., Xiao, R., Teletzke, G.F., Willingham, T., Al Obeidli, A., Al Sowaidi, A.,
Britton, C., Delshad, M., Li, Z., 2018. Polymer EOR assessment through integrated
laboratory and simulation evaluation for an offshore Middle East carbonate
reservoir. In: Abu Dhabi International Petroleum Exhibition and Conference.
Jain, S., Pachisia, H., Sharma, A., Patel, S., Patel, S., Ragunathan, B., 2022. A systematic
review–Chemical EOR using surfactants and polymers. Mater. Today Proc.
Janaghi, P., Amani, H., Naseri, A., Kariminezhad, H., 2022. Accurate prediction of
enhanced oil recovery from carbonate reservoir through smart injection of
nanoparticle and biosurfactant. J. Petrol. Sci. Eng. 216, 110772.
Jian, G., Puerto, M., Wehowsky, A., Dong, P., Johnston, K.P., Hirasaki, G.J., Biswal, S.L.,
2016. Static adsorption of an ethoxylated nonionic surfactant on carbonate minerals.
Langmuir 32 (40), 10244–10252.
33
Journal of Petroleum Science and Engineering 220 (2023) 111243
Jian, G., Puerto, M., Wehowsky, A., Miller, C., Hirasaki, G.J., Biswal, S.L., 2018.
Characterizing adsorption of associating surfactants on carbonates surfaces.
J. Colloid Interface Sci. 513, 684–692.
Joshi, D., Maurya, N.K., Kumar, N., Mandal, A., 2022. Experimental investigation of
silica nanoparticle assisted Surfactant and polymer systems for enhanced oil
recovery. J. Petrol. Sci. Eng., 110791
Jouenne, S., Levache, B., Joly, M., Hourcq, C., Questel, M., Heurteux, G., 2019. Universal
viscosifying behavior of acrylamide-based polymers used in EOR-application for QA/
QC, viscosity predictions and field characterization. IOR 2019–20th European
Symposium on Improved Oil Recovery 1, 1–23.
Kalpakci, B., Jeans, Y.T., Magri, N.F., Padolewski, J.P., 1990. Thermal stability of
scleroglucan at realistic reservoir conditions. In: SPE/DOE Enhanced Oil Recovery
Symposium.
Kamal, M.S., 2016. A review of gemini surfactants: potential application in enhanced oil
recovery. J. Surfactants Deterg. 19 (2), 223–236.
Kamal, M.S., Hussein, I.A., Sultan, A.S., 2017. Review on surfactant flooding: phase
behavior, retention, IFT, and field applications. Energy Fuel. 31 (8), 7701–7720.
Karnanda, W., Benzagouta, M.S., AlQuraishi, A., Amro, M.M., 2013. Effect of
temperature, pressure, salinity, and surfactant concentration on IFT for surfactant
flooding optimization. Arabian J. Geosci. 6 (9), 3535–3544.
Kang, P.-S., Lim, J.-S., Huh, C., 2014. Screening criteria for application of EOR processes
in offshore fields. In: The Twenty-Fourth International Ocean and Polar Engineering
Conference.
Karimov, D., Hashmet, M.R., Pourafshary, P., 2020. A laboratory study to optimize ion
composition for the hybrid low salinity water/polymer flooding. In: Offshore
Technology Conference Asia.
Karović-Maričić, V., Leković, B., Danilović, D., 2014. Factors influencing successful
implementation of enhanced oil recovery projects. Podzemni Radovi 22 (25), 41–50.
Kasha, A., Al-Hashim, H., Abdallah, W., Taherian, R., Sauerer, B., 2015. Effect of Ca2+,
Mg2+ and SO42− ions on the zeta potential of calcite and dolomite particles aged with
stearic acid. Colloids Surf. A Physicochem. Eng. Asp. 482, 290–299.
Khademolhosseini, R., Jafari, A., Mousavi, S.M., Hajfarajollah, H., Noghabi, K.A.,
Manteghian, M., 2019a. Physicochemical characterization and optimization of
glycolipid biosurfactant production by a native strain of Pseudomonas aeruginosa
HAK01 and its performance evaluation for the MEOR process. RSC Adv. 9 (14),
7932–7947.
Khademolhosseini, R., Jafari, A., Mousavi, S.M., Manteghian, M., 2019b. Investigation of
synergistic effects between silica nanoparticles, biosurfactant and salinity in
simultaneous flooding for enhanced oil recovery. RSC Adv. 9 (35), 20281–20294.
Khademolhosseini, R., Jafari, A., Shabani, M.H., 2015. Micro scale investigation of
enhanced oil recovery using nano/bio materials. Procedia Materials Science 11,
171–175.
Klimenko, A., Molinier, V., Dubos, F., Joly, M., Saint-Loubert, M., Jouenne, S., Passade-
Boupat, N., Bourrel, M., 2020. Surfactant–polymer flooding at high temperature and
high salinity: promising lab scale experiments in challenging conditions. In: Abu
Dhabi International Petroleum Exhibition and Conference.
Kosmulski, M., 2002. The pH-dependent surface charging and the points of zero charge.
J. Colloid Interface Sci. 253 (1), 77–87.
Kovscek, A.R., Radke, C.J., 1993. Fundamentals of Foam Transport in Porous Media.
Kuang, W., Saraji, S., Piri, M., 2018. A systematic experimental investigation on the
synergistic effects of aqueous nanofluids on interfacial properties and their
implications for enhanced oil recovery. Fuel 220, 849–870.
Kulawardana, E.U., Koh, H., Kim, D.H., Liyanage, P.J., Upamali, K.A., Huh, C.,
Weerasooriya, U., Pope, G.A., 2012. Rheology and transport of improved EOR
polymers under harsh reservoir conditions. In: SPE Improved Oil Recovery
Symposium.
Kumar, A., Mandal, A., 2017. Synthesis and physiochemical characterization of
zwitterionic surfactant for application in enhanced oil recovery. J. Mol. Liq. 243,
61–71.
Kumar, A., Mandal, A., 2019. Critical investigation of zwitterionic surfactant for
enhanced oil recovery from both sandstone and carbonate reservoirs: adsorption,
wettability alteration and imbibition studies. Chem. Eng. Sci. 209, 115222.
Kwok, W., Nasr-El-Din, H.A., Hayes, R.E., Sethi, D., 1993. Static and dynamic adsorption
of a non-ionic surfactant on Berea sandstone. Colloids Surf. A Physicochem. Eng.
Asp. 78, 193–209.
Lager, A., Webb, K.J., Black, C.J.J., Singleton, M., Sorbie, K.S., 2008. Low salinity oil
recovery-an experimental investigation1. Petrophysics-The SPWLA Journal of
Formation Evaluation and Reservoir Description 49 (1).
Lake, L.W., Johns, R., Rossen, B., Pope, G.A., 2014. Fundamentals of Enhanced Oil
Recovery, vol. 1. Society of Petroleum Engineers Richardson, TX.
Larestani, A., Mousavi, S.P., Hadavimoghaddam, F., Ostadhassan, M., Sarapardeh, A.H.,
2022. Predicting the surfactant-polymer flooding performance in chemical enhanced
oil recovery: cascade neural network and gradient boosting decision tree. Alex. Eng.
J. 61 (10), 7715–7731.
Leon, J.M., Masalmeh, S.K., Xu, S., AlSumaiti, A.M., BinAmro, A.A., Baslaib, M.A., 2021.
December. Analysis of the World’s First Polymer Injectivity Test in a Carbonate
Reservoir Under Extreme Harsh Conditions in ADNOC’s Reservoirs. In: Abu Dhabi
International Petroleum Exhibition & Conference. OnePetro.
Leonhardt, B., Ernst, B., Reimann, S., Steigerwald, A., Lehr, F., 2014. Field testing the
polysaccharide Schizophyllan: results of the first year. In: SPE Improved Oil
Recovery Symposium.
Levitt, D., Bourrel, M., 2016. Adsorption of EOR chemicals under laboratory and
reservoir conditions, part III: chemical treatment methods. In: SPE Improved Oil
Recovery Conference.
A.M. Hassan et al.
Levitt, D., Dufour, S., Pope, G.A., Morel, D.C., Gauer, P.R., 2011. Design of an ASP flood
in a high-temperature, high-salinity, low-permeability carbonate. Int. Petrol.
Technol. Conf.
Levitt, D., Jackson, A., Heinson, C., Britton, L.N., Malik, T., Dwarakanath, V., Pope, G.A.,
2006. Identification and evaluation of high-performance EOR surfactants. In: SPE/
DOE Symposium on Improved Oil Recovery.
Levitt, D., Klimenko, A., Jouenne, S., Chamerois, M., Bourrel, M., 2012. Design
challenges of chemical EOR in high-temperature, high salinity carbonates. In: Abu
Dhabi International Petroleum Conference and Exhibition.
Levitt, D., Klimenko, A., Jouenne, S., Passade-Boupat, N., Cordelier, P., Morel, D.,
Bourrel, M., 2016. April. Designing and injecting a chemical formulation for a
successful off-shore chemical EOR pilot in a high-temperature, high-salinity, low-
permeability carbonate field. In: SPE Improved Oil Recovery Conference. OnePetro.
Levitt, D.B., Weatherl, R.K., Harris, H.W., McNeil, R.I., Didier, M., Loriau, M., Gaucher, E.
C., Bourrel, M., 2015. Adsorption of EOR chemicals under laboratory and reservoir
conditions, Part 1-iron abundance and oxidation state. In: IOR 2015-18th European
Symposium on Improved Oil Recovery cp-445.
Li, B., Liu, Z., Fei, C., Lv, J., Chen, X., Li, Y., 2018. Polymeric surfactant for enhanced oil
recovery-microvisual, core-flood experiments and field application. In: SPE EOR
Conference at Oil and Gas West Asia.
Li, G., Xu, J., Mu, J., Zhai, L., Shui, L., Chen, W., Jiang, J., Chen, F., Guo, D., Lin, W.,
2005. Design and application of an alkaline-surfactant-polymer flooding system in
field pilot test. J. Dispersion Sci. Technol. 26 (6), 709–717.
Li, G.-Z., Mu, J.-H., Li, Y., Xiao, H.-D., Gu, Q., 2000. What is the criterion for selecting
alkaline/surfactant/polymer flooding formulation: phase behavior or interfacial
tension. J. Dispersion Sci. Technol. 21 (3), 305–314.
Liao, G., Wang, Q., Wang, H., Liu, W., Wang, Z., 2017. Chemical flooding development
status and prospect. Acta Pet. Sin. 38 (2), 196–207.
Lippmann, F., 2012. Sedimentary Carbonate Minerals, vol. 6. Springer Science &
Business Media.
Liu, S., Li, R.F., Miller, C.A., Hirasaki, G.J., 2010. Alkaline/surfactant/polymer processes:
wide range of conditions for good recovery. SPE J. 15 (2), 282–293.
Liu, Y., Lee, J.Y., Hong, L., 2004. In situ preparation of poly (ethylene oxide)–SiO2
composite polymer electrolytes. J. Power Sources 129 (2), 303–311.
Liu, Z., Zhou, G., Li, S., Wang, C., Liu, R., Jiang, W., 2020. Molecular dynamics
simulation and experimental characterization of anionic surfactant: influence on
wettability of low-rank coal. Fuel 279, 118323.
Liyanage, P.J., Lu, J., Arachchilage, G.W.P., Weerasooriya, U.P., Pope, G.A., 2015.
A novel class of large-hydrophobe tristyrylphenol (TSP) alkoxy sulfate surfactants for
chemical enhanced oil recovery. J. Petrol. Sci. Eng. 128, 73–85.
Liyanage, P.J., Solairaj, S., Arachchilage, G.W., Linnemeyer, H.C., Kim, D.H.,
Weerasooriya, U., Pope, G.A., 2012. Alkaline surfactant polymer flooding using a
novel class of large hydrophobe surfactants. In: SPE Improved Oil Recovery
Symposium.
Llano, V., Henthorne, L., Walsh, J., 2013. Water management for EOR applications-
sourcing, treating, reuse and recycle. In: Offshore Technology Conference.
Lu, J., 2014. Development of Novel Surfactants and Surfactant Methods for Chemical
Enhanced Oil Recovery. The University of Texas at Austin. PhD Dissertation.
Lu, J., Britton, C., Solairaj, S., Liyanage, P.J., Kim, D.H., Adkins, S., Arachchilage, G.W.,
Weerasooriya, U., Pope, G.A., 2014b. Novel large-hydrophobe alkoxy carboxylate
surfactants for enhanced oil recovery. SPE J. 19 (6), 1024–1034.
Lu, J., Goudarzi, A., Chen, P., Kim, D.H., Delshad, M., Mohanty, K.K., Sepehrnoori, K.,
Weerasooriya, U.P., Pope, G.A., 2014a. Enhanced oil recovery from high-
temperature, high-salinity naturally fractured carbonate reservoirs by surfactant
flood. J. Petrol. Sci. Eng. 124, 122–131.
Lu, J., Liyanage, P.J., Solairaj, S., Adkins, S., Arachchilage, G.P., Kim, D.H., Britton, C.,
Weerasooriya, U., Pope, G.A., 2014c. New surfactant developments for chemical
enhanced oil recovery. J. Petrol. Sci. Eng. 120, 94–101.
Lu, J., Pope, G.A., 2017. Optimization of gravity-stable surfactant flooding. SPE J. 22 (2),
480–493.
Luo, H., Al-Shalabi, E.W., Delshad, M., Panthi, K., Sepehrnoori, K., 2016. A robust
geochemical simulator to model improved-oil-recovery methods. SPE J. 21 (1),
55–73.
Lv, W., Bazin, B., Ma, D., Liu, Q., Han, D., Wu, K., 2011. Static and dynamic adsorption of
anionic and amphoteric surfactants with and without the presence of alkali. J. Petrol.
Sci. Eng. 77 (2), 209–218.
Lwisa, E., 2021. Chemical Enhanced Oil Recovery.
Ma, K., Cui, L., Dong, Y., Wang, T., Da, C., Hirasaki, G.J., Biswal, S.L., 2013. Adsorption
of cationic and anionic surfactants on natural and synthetic carbonate materials.
J. Colloid Interface Sci. 408, 164–172.
Mahani, H., Keya, A.L., Berg, S., Bartels, W.-B., Nasralla, R., Rossen, W.R., 2015. Insights
into the mechanism of wettability alteration by low-salinity flooding (LSF) in
carbonates. Energy Fuel. 29 (3), 1352–1367.
Mahani, H., Menezes, R., Berg, S., Fadili, A., Nasralla, R., Voskov, D., Joekar-Niasar, V.,
2017. Insights into the impact of temperature on the wettability alteration by low
salinity in carbonate rocks. Energy Fuel. 31 (8), 7839–7853.
Mahboob, A., Kalam, S., Kamal, M.S., Hussain, S.M.S., Solling, T., 2022. EOR Perspective
of microemulsions: a review. J. Petrol. Sci. Eng. 208, 109312.
Maia, A.M.S., Borsali, R., Balaban, R.C., 2009. Comparison between a polyacrylamide
and a hydrophobically modified polyacrylamide flood in a sandstone core. Mater.
Sci. Eng. C 29 (2), 505–509.
Maltesh, C., Somasundaran, P., 1992. Binding of sodium dodecyl sulfate to polyethylene
oxide at the silica—water interface. J. Colloid Interface Sci. 153 (1), 298–301.
Mandal, A., 2015. Chemical flood enhanced oil recovery: a review. Int. J. Oil Gas Coal
Technol. 9 (3), 241–264.
34
Journal of Petroleum Science and Engineering 220 (2023) 111243
Masalmeh, S., AlSumaiti, A., Gaillard, N., Daguerre, F., Skauge, T., Skuage, A., 2019.
Extending polymer flooding towards high-temperature and high-salinity carbonate
reservoirs. In: Abu Dhabi International Petroleum Exhibition and Conference.
Masalmeh, S.K., Wei, L., Blom, C.P., 2011. Mobility control for gas injection in
heterogeneous carbonate reservoirs: comparison of foams versus polymers. In: SPE
Middle East Oil and Gas Show and Conference.
Masalmeh, S.K., Wei, L., Hillgartner, H., Al-Mjeni, R., Blom, C., 2012. Developing high
resolution static and dynamic models for waterflood history matching and EOR
evaluation of a Middle Eastern carbonate reservoir. In: Abu Dhabi International
Petroleum Conference and Exhibition.
Massarweh, O., Abushaikha, A.S., 2020. The use of surfactants in enhanced oil recovery:
a review of recent advances. Energy Rep. 6, 3150–3178.
Mayer, E.H., Berg, R.L., Carmichael, J.D., Weinbrandt, R.M., 1983. Alkaline injection for
enhanced oil recovery-A status report. J. Petrol. Technol. 35 (1), 209–221.
Mehrabianfar, P., Bahraminejad, H., Manshad, A.K., 2021. An introductory investigation
of a polymeric surfactant from a new natural source in chemical enhanced oil
recovery (CEOR). J. Petrol. Sci. Eng. 198, 108172.
Mejia, L., Tagavifar, M., Xu, K., Mejia, M., Du, Y., Balhoff, M., 2019. Surfactant flooding
in oil-wet micromodels with high permeability fractures. Fuel 241, 1117–1128.
Meng, R., Wang, C., Jin, J., Wang, R., Deng, L., 2022. Self-assembly of hydrophobically
associating amphiphilic polymer with surfactant and its effect on nanoemulsion.
Colloids Surf. A Physicochem. Eng. Asp. 642, 128599.
Millemann, R.E., Haynes, R.J., Boggs, T.A., Hildebrand, S.G., 1982. Enhanced oil
recovery: environmental issues and state regulatory programs. Environ. Int. 7 (3),
165–177.
Miyake, M., Oyama, N., 2009. Effect of amido alkyl group as spacer on aggregation
properties of guanidine-type surfactants. J. Colloid Interface Sci. 330 (1), 180–185.
Moghadam, A.M., Salehi, M.B., 2019. Enhancing hydrocarbon productivity via
wettability alteration: a review on the application of nanoparticles. Rev. Chem. Eng.
35 (4), 531–563.
Moghaddam, R.N., Bahramian, A., Fakhroueian, Z., Karimi, A., Arya, S., 2015.
Comparative study of using nanoparticles for enhanced oil recovery: wettability
alteration of carbonate rocks. Energy Fuel. 29 (4), 2111–2119.
Mohajeri, M., Hemmati, M., Shekarabi, A.S., 2015. An experimental study on using a
nanosurfactant in an EOR process of heavy oil in a fractured micromodel. J. Petrol.
Sci. Eng. 126, 162–173.
Mohammadi, H., Delshad, M., Pope, G.A., 2009. Mechanistic modeling of alkaline/
surfactant/polymer floods. SPE Reservoir Eval. Eng. 12 (4), 518–527.
Moreno-Arciniegas, L., Babadagli, T., 2017. Experimental analysis of optimal
thermodynamic conditions for heavy-oil/bitumen recovery considering effective
solvent retrieval. SPE Reservoir Eval. Eng. 20 (1), 149–160.
Morrow, N.R., Mason, G., 2001. Recovery of oil by spontaneous imbibition. Curr. Opin.
Colloid Interface Sci. 6 (4), 321–337.
Moulin, P., Roques, H., 2003. Zeta potential measurement of calcium carbonate.
J. Colloid Interface Sci. 261 (1), 115–126.
Musa, T.A., Ibrahim, A.F., Nasr-El-Din, H.A., Hassan, A., 2021. New insights into guar
gum as environmentally friendly polymer for enhanced oil recovery in high-salinity
and high-temperature sandstone reservoirs. Journal of Petroleum Exploration and
Production 11 (4), 1905–1913.
Mukhopadhyay, C., Suba, M., Sivakumar, D., Dhamodharan, K., Rao, R.V., 2019. Cloud
points extractive spectrophotometric method for determination of uranium in
raffinate streams during spent nuclear fuel reprocessing. J. Radioanal. Nucl. Chem.
322 (2), 743–750.
Mushtaq, M., Tan, I.M., Ismail, L., Lee, S.Y., Nadeem, M., Sagir, M., 2014. Oleate ester-
derived nonionic surfactants: synthesis and cloud point behavior studies.
J. Dispersion Sci. Technol. 35 (3), 322–328.
Na, C., Kendall, T.A., Martin, S.T., 2007. Surface-potential heterogeneity of reacted
calcite and rhodochrosite. Environ. Sci. Technol. 41 (18), 6491–6497.
Nakagawa, H., Watanabe, S., Fujita, T., Sakamoto, M., 1998. Characteristic properties of
cutting fluid additives made from the derivatives of some polymeric nonionic
surface-active agents. J. Surfactants Deterg. 1 (2), 207–211.
Nasiri, M.A., Biria, D., 2020. Extraction of the indigenous crude oil dissolved
biosurfactants and their potential in enhanced oil recovery. Colloids Surf. A
Physicochem. Eng. Asp. 603, 125216.
Negin, C., Ali, S., Xie, Q., 2017. Most common surfactants employed in chemical
enhanced oil recovery. Petroleum 3 (2), 197–211.
Nelson, R.C., 1983. The effect of live crude on phase behavior and oil-recovery efficiency
of surfactant flooding systems. SPE J. 23 (3), 501–510.
Nelson, R.C., Lawson, J.B., Thigpen, D.R., Stegemeier, G.L., 1984. Cosurfactant-enhanced
alkaline flooding. In: SPE Enhanced Oil Recovery Symposium.
Nevskaia, D.M., Guerrero-Ruız, A., López-González, J.D.D., 1998. Adsorption of
polyoxyethylenic nonionic and anionic surfactants from aqueous solution: effects
induced by the addition of NaCl and CaCl2. J. Colloid Interface Sci. 205 (1), 97–105.
Nieto-Alvarez, D.A., Zamudio-Rivera, L.S., Luna-Rojero, E.E., Rodríguez-Otamendi, D.I.,
Marín-León, A., Hernández-Altamirano, R., Mena-Cervantes, V.Y., Chávez-
Miyauchi, T.E., 2014. Adsorption of zwitterionic surfactant on limestone measured
with high-performance liquid chromatography: micelle–vesicle influence. Langmuir
30 (41), 12243–12249.
Niu, Y., Jian, O., Zhu, Z., Wang, G., Sun, G., 2001. Research on hydrophobically
associating water-soluble polymer used for EOR. In: SPE International Symposium
on Oilfield Chemistry.
Nwidee, L.N., Lebedev, M., Barifcani, A., Sarmadivaleh, M., Iglauer, S., 2017. Wettability
alteration of oil-wet limestone using surfactant-nanoparticle formulation. J. Colloid
Interface Sci. 504, 334–345.
A.M. Hassan et al.
Olajire, A.A., 2014. Review of ASP EOR (alkaline surfactant polymer enhanced oil
recovery) technology in the petroleum industry: prospects and challenges. Energy
77, 963–982.
Omekeh, A., Friis, H.A., Fjelde, I., Evje, S., 2012. Modeling of ion-exchange and solubility
in low salinity water flooding. In: SPE Improved Oil Recovery Symposium.
Páhi, A.B., Király, Z., Mastalir, Á., Dudás, J., Puskás, S., Vágó, Á., 2008. Thermodynamics
of micelle formation of the counterion coupled gemini surfactant bis (4-(2-dodecyl)
benzenesulfonate)-Jeffamine salt and its dynamic adsorption on sandstone. J. Phys.
Chem. B 112 (48), 15320–15326.
Páhi, A.B., Király, Z., Puskás, S., 2009. Mass spectrometric characterization of the non-
ionic gemini surfactant Surfynol 465 and a microcalorimetric study of its micelle
formation in water. Colloids Surf. A Physicochem. Eng. Asp. 345 (1–3), 13–17.
Pal, S., Mushtaq, M., Banat, F., Al Sumaiti, A.M., 2018. Review of surfactant-assisted
chemical enhanced oil recovery for carbonate reservoirs: challenges and future
perspectives. Petrol. Sci. 15 (1), 77–102.
Panthi, K., Sotomayor, M., Balhoff, M.T., Mohanty, K.K., 2022. Low retention surfactant-
polymer process for a HTHS carbonate reservoir. J. Petrol. Sci. Eng. 214, 110516.
Parkhurst, D.L., Appelo, C.A.J., 1999. User’s guide to PHREEQC (Version 2): a computer
program for speciation, batch-reaction, one-dimensional transport, and inverse
geochemical calculations. Water-Resources Investigations Report 99 (4259), 312.
Patel, M.C., Ayoub, M.A., Hassan, A.M., Idress, M.B., 2022. A novel ZnO nanoparticles
enhanced surfactant based viscoelastic fluid systems for fracturing under high
temperature and high shear rate conditions: synthesis, rheometric analysis, and fluid
model derivation. Polymers 14 (19), 4023.
Pei, H., Shu, Z., Zhang, G., Ge, J., Jiang, P., Qin, Y., Cao, X., 2018. Experimental study of
nanoparticle and surfactant stabilized emulsion flooding to enhance heavy oil
recovery. J. Petrol. Sci. Eng. 163, 476–483.
Pham, T.D., Kobayashi, M., Adachi, Y., 2015. Adsorption of anionic surfactant sodium
dodecyl sulfate onto alpha alumina with small surface area. Colloid Polym. Sci. 293
(1), 217–227.
Pillai, P., Mandal, A., 2022. Synthesis and characterization of surface-active ionic liquids
for their potential application in enhanced oil recovery. J. Mol. Liq. 345, 117900.
Puerto, M., Hirasaki, G.J., Miller, C.A., Barnes, J.R., 2012. Surfactant systems for EOR in
high-temperature, high-salinity environments. SPE J. 17 (1), 11–19.
Puntervold, T., 2008. Waterflooding of Carbonate Reservoirs: EOR by Wettability
Alteration.
Puskas, S., Vago, A., Toro, M., Ordog, T., Kalman, G., Hanzelik, P., Bihari, Z., Blaho, J.,
Tabajdi, R., Dekany, I., 2018. Surfactant-polymer EOR from laboratory to the pilot.
In: SPE EOR Conference at Oil and Gas West Asia.
Puskas, S., Vago, A., Törő, M., Ördög, T., Kálmán, G.Y., Tabajd, R., Dekany, I., Dudas, J.,
Nagy, R., Bartha, L., 2017. First surfactant-polymer EOR injectivity test in the Algyő
field, Hungary. IOR 2017-19th European Symposium on Improved Oil Recovery 1,
1–18.
Qiao, C., Johns, R., Li, L., 2016. Understanding the chemical mechanisms for low salinity
waterflooding. 78th EAGE Conference and Exhibition 1, 1–13.
Rachapudi, R.V., Alshehhi, S.S., BinAmro, A.A., Masalmeh, S.K., Dey, A., Al Nuimi, S.M.,
Kenawy, M.M., Fabbri, C., Romero, C., Xu, S., Mabrook, M., 2020. November. World
First Polymer Injectivity Test in High Salinity and High Temperature Carbonate
Reservoir, Case Study from a Giant Reservoir in UAE. In: Abu Dhabi International
Petroleum Exhibition & Conference. OnePetro.
Raffa, P., 2021. Design and synthesis of low molecular weight and polymeric surfactants
for enhanced oil recovery. In: Surfactants in Upstream E and P. Springer, Cham,
pp. 3–37.
Raffa, P., Broekhuis, A.A., Picchioni, F., 2016a. Polymeric surfactants for enhanced oil
recovery: a review. J. Petrol. Sci. Eng. 145, 723–733.
Raffa, P., Broekhuis, A.A., Picchioni, F., 2016b. Amphiphilic copolymers based on PEG-
acrylate as surface active water viscosifiers: towards new potential systems for
enhanced oil recovery. J. Appl. Polym. Sci. 133 (42).
Raffa, P., Wever, D.A.Z., Picchioni, F., Broekhuis, A.A., 2015. Polymeric surfactants:
synthesis, properties, and links to applications. Chem. Rev. 115 (16), 8504–8563.
Ragab, A., Mansour, E.M., 2021. Enhanced oil recovery: chemical flooding. Geophysics
and Ocean Waves Studies 51.
Ramsey, M., 2019. Schlumberger Oilfield Glossary. Schlumberger.
Ranjbar, M., Schaffie, M., 2000. Improved treatment of acrylamide co-and terpolymers
for water control in gas-producing and storage wells. J. Petrol. Sci. Eng. 26 (1–4),
133–141.
Reb, P., Margarit-Puri, K., Klapper, M., Müllen, K., 2000. Polymerizable and
nonpolymerizable isophthalic acid derivatives as surfactants in emulsion
polymerization. Macromolecules 33 (21), 7718–7723.
Reed, R.L., Healy, R.N., 1977. Some physicochemical aspects of microemulsion flooding:
a review. Improved Oil Recovery by Surfactant and Polymer Flooding 383–437.
RezaeiDoust, A., Puntervold, T., Austad, T., 2011. Chemical verification of the EOR
mechanism by using low saline/smart water in sandstone. Energy Fuel. 25 (5),
2151–2162.
Rilian, N.A., Sumestry, M., 2010. Surfactant stimulation to increase reserves in carbonate
reservoir: a case study in Semoga Field. In: SPE EUROPEC/EAGE Annual Conference
and Exhibition.
Rivenq, R.C., Donche, A., Nolk, C., 1992. Improved scleroglucan for polymer flooding
under harsh reservoir conditions. SPE Reservoir Eng. 7 (1), 15–20.
Rodrigues, J. de A., Lachter, E.R., de Sá, C.H., de Mello, M., Nascimento, R.S.V., 2006.
New multifunctional polymeric additives for water-based muds. In: SPE Annual
Technical Conference and Exhibition.
Roehl, P.O., Choquette, P.W., 2012. Carbonate Petroleum Reservoirs. Springer Science
and Business Media.
Rohilla, N., Katiyar, A., Rozowski, P.M., Gentilucci, A., Patil, P.D., Pal, M., Saxena, P.,
2020, August. Field Trial for Wettability Alteration Using Surfactants: Formulation
35
Journal of Petroleum Science and Engineering 220 (2023) 111243
Development In Laboratory to the Implementation and Production Monitoring in an
Offshore Reservoir. In SPE Improved Oil Recovery Conference. OnePetro.
Rohilla, N., Katiyar, A., Saxena, P., Pal, M., Rozowski, P., Gentilucci, A., 2021. Successful
wettability alteration pilot in an offshore reservoir: laboratory analysis to support
planning, implementation and interpretation. In: IOR 2021, vol. 2021. European
Association of Geoscientists & Engineers, pp. 1–14. No. 1.
Rosen, M.J., Kunjappu, J.T., 2012. Surfactants and Interfacial Phenomena. John Wiley
and Sons.
Sagi, A.R., Puerto, M., Bian, Y., Miller, C.A., Hirasaki, G.J., Salehi, M., Thomas, C.P.,
Kwan, J.T., 2013. Laboratory studies for surfactant flood in low-temperature, low-
salinity fractured carbonate reservoir. In: SPE International Symposium on Oilfield
Chemistry.
Sakthivel, S., 2021. Wettability alteration of carbonate reservoirs using imidazolium-
based ionic liquids. ACS Omega 6 (45), 30315–30326.
Salager, J.L., Antón, R.E., Sabatini, D.A., Harwell, J.H., Acosta, E.J., Tolosa, L.I., 2005.
Enhancing solubilization in microemulsions—state of the art and current trends.
J. Surfactants Deterg. 8 (1), 3–21.
Salehi, M., Johnson, S.J., Liang, J.T., 2008. Mechanistic study of wettability alteration
using surfactants with applications in naturally fractured reservoirs. Langmuir 24
(24), 14099–14107.
Samakande, A., Hartmann, P.C., Cloete, V., Sanderson, R.D., 2007. Use of acrylic based
surfmers for the preparation of exfoliated polystyrene–clay nanocomposites.
Polymer 48 (6), 1490–1499.
Samakande, A., Hartmann, P.C., Sanderson, R.D., 2006. Synthesis and characterization of
new cationic quaternary ammonium polymerizable surfactants. J. Colloid Interface
Sci. 296 (1), 316–323.
Sanati, A., Rahmani, S., Nikoo, A.H., Malayeri, M.R., Busse, O., Weigand, J.J., 2021.
Comparative study of an acidic deep eutectic solvent and an ionic liquid as chemical
agents for enhanced oil recovery. J. Mol. Liq. 329, 115527.
Sarsenbekuly, B., Kang, W., Fan, H., Yang, H., Dai, C., Zhao, B., Aidarova, S.B., 2017.
Study of salt tolerance and temperature resistance of a hydrophobically modified
polyacrylamide based novel functional polymer for EOR. Colloids Surf. A
Physicochem. Eng. Asp. 514, 91–97.
Saxena, N., Kumar, A., Mandal, A., 2019. Adsorption analysis of natural anionic
surfactant for enhanced oil recovery: the role of mineralogy, salinity, alkalinity and
nanoparticles. J. Petrol. Sci. Eng. 173, 1264–1283.
Schott, H., 2005. Krafft points and cloud points of polyoxyethylated nonionic surfactants.
Part 1 Krafft points in binary surfactant-water systems. Tenside Surfactants Deterg.
42 (6), 356–367.
Schramm, L.L., 2000. Surfactants: Fundamentals and Applications in the Petroleum
Industry. Cambridge university press.
Seethepalli, A., Adibhatla, B., Mohanty, K.K., 2004a. Physicochemical interactions
during surfactant flooding of fractured carbonate reservoirs. SPE J. 9 (4), 411–418.
Seethepalli, A., Adibhatla, B., Mohanty, K.K., 2004b. Wettability alteration during
surfactant flooding of carbonate reservoirs. In: SPE/DOE Symposium on Improved
Oil Recovery.
Seo, S., Mastiani, M., Mosavati, B., Peters, D.M., Mandin, P., Kim, M., 2018. Performance
evaluation of environmentally benign nonionic biosurfactant for enhanced oil
recovery. Fuel 234, 48–55.
ShamsiJazeyi, H., Verduzco, R., Hirasaki, G.J., 2014b. Reducing adsorption of anionic
surfactant for enhanced oil recovery: Part I. Competitive adsorption mechanism.
Colloids Surf. A Physicochem. Eng. Asp. 453, 162–167.
ShamsiJazeyi, H., Verduzco, R., Hirasaki, G.J., 2014a. Reducing adsorption of anionic
surfactant for enhanced oil recovery: Part II. Applied aspects. Colloids Surf. A
Physicochem. Eng. Asp. 453, 168–175.
Sharma, H., Dufour, S., Arachchilage, G.W.P.P., Weerasooriya, U., Pope, G.A.,
Mohanty, K., 2015. Alternative alkalis for ASP flooding in anhydrite containing oil
reservoirs. Fuel 140, 407–420.
Shashkina, Y.A., Zaroslov, Y.D., Smirnov, V.A., Philippova, O.E., Khokhlov, A.R.,
Pryakhina, T.A., Churochkina, N.A., 2003. Hydrophobic aggregation in aqueous
solutions of hydrophobically modified polyacrylamide in the vicinity of overlap
concentration. Polymer 44 (8), 2289–2293.
Shaw, J.E., 1984. Carboxylate surfactant systems exhibiting phase behavior suitable for
enhanced oil recovery. JAOCS (J. Am. Oil Chem. Soc.) 61 (8), 1395–1399.
Sheng, J.J., 2010. Modern Chemical Enhanced Oil Recovery: Theory and Practice. Gulf
Professional Publishing.
Sheng, J.J., 2013a. A comprehensive review of alkaline-surfactant-polymer (ASP)
flooding. In: SPE Western Regional and AAPG Pacific Section Meeting 2013 Joint
Technical Conference.
Sheng, J.J., 2013b. Enhanced Oil Recovery Field Case Studies. Gulf Professional
Publishing.
Sheng, J.J., 2015. Status of surfactant EOR technology. Petroleum 1 (2), 97–105.
Shiran, B.S., Skauge, A., 2014. Similarities and differences of low salinity polymer and
low salinity LPS (linked polymer solutions) for enhanced oil recovery. J. Dispersion
Sci. Technol. 35 (12), 1656–1664.
Skauge, A., Fotland, P., 1990. Effect of pressure and temperature on the phase behavior
of microemulsions. SPE Reservoir Eng. 5 (4), 601–608.
Skauge, A., Palmgren, O., 1989. Phase behavior and solution properties of ethoxylated
anionic surfactants. SPE International Symposium on Oilfield Chemistry.
Solairaj, S., Britton, C., Lu, J., Kim, D.H., Weerasooriya, U., Pope, G.A., 2012. New
correlation to predict the optimum surfactant structure for EOR. In: SPE Improved
Oil Recovery Symposium.
Somasundaran, P., Fuerstenau, D.W., 1966. Mechanisms of alkyl sulfonate adsorption at
the alumina-water interface1. J. Phys. Chem. 70 (1), 90–96.
Somasundaran, P., Krishnakumar, S., 1997. Adsorption of surfactants and polymers at
the solid-liquid interface. Colloids Surf. A Physicochem. Eng. Asp. 123, 491–513.
A.M. Hassan et al.
Somoza, A., Arce, A., Soto, A., 2021. Oil recovery tests with ionic liquids: a review and
evaluation of 1-decyl-3-methylimidazolium triflate. Petrol. Sci.
Somoza, A., Tafur, N., Arce, A., Soto, A., 2022. Design and performance analysis of a
formulation based on SDBS and ionic liquid for EOR in carbonate reservoirs.
J. Petrol. Sci. Eng. 209, 109856.
Song, W., Hatzignatiou, D.G., 2022. On the reduction of the residual oil saturation
through the injection of polymer and nanoparticle solutions. J. Petrol. Sci. Eng. 208,
109430.
Sorbie, K.S., 1991. Introduction to polymer flooding. In: Polymer-Improved Oil
Recovery. Springer, Dordrecht, pp. 1–5.
Sorbie, K.S., 2013. Polymer-improved Oil Recovery. Springer Science and Business
Media.
Souraki, Y., Hosseini, E., Yaghodous, A., 2019. Wettability alteration of carbonate
reservoir rock using amphoteric and cationic surfactants: experimental investigation.
Energy Sources, Part A Recovery, Util. Environ. Eff. 41 (3), 349–359.
Southwick, J., van den Pol, E., van Rijn, C.H.T., van Batenburg, D.W., a Manap, A.A.,
Mastan, A.K., Zulkifli, N.N., 2019. Surfactant flooding in offshore environments. In:
IOR 2019–20th European Symposium on Improved Oil Recovery, vol. 2019.
European Association of Geoscientists & Engineers, pp. 1–21. No. 1.
Southwick, J.G., Brewer, M.L., Pieterse, S.G., van Batenburg, D.W., 2018. Ammonia as
alkali for high acid number oils. In: SPE EOR Conference at Oil and Gas West Asia.
Southwick, J.G., van den Pol, E., van Rijn, C.H., van Batenburg, D.W., Boersma, D.,
Svec, Y., Mastan, A.A., Shahin, G., Raney, K., 2016. Ammonia as alkali for alkaline/
surfactant/polymer floods. SPE J. 21 (1), 10–21.
Stephenson, T., Oswald, D., Dwyer, P., Brown, D., Ndefo, E., Smith, J., Gaffney, B.,
Kiran, S., 2019. Core floods vs. Field pilot–effectiveness of microemulsions in
conventional and unconventional waterfloods. In: SPE Annual Technical Conference
and Exhibition. OnePetro.
Stumm, W., Morgan, J.J., 2012. Aquatic Chemistry: Chemical Equilibria and Rates in
Natural Waters, vol. 126. John Wiley and Sons.
Summers, M., Eastoe, J., 2003. Applications of polymerizable surfactants. Adv. Colloid
Interface Sci. 100, 137–152.
Suniga, P.T., Fortenberry, R., Delshad, M., 2016. Observations of microemulsion
viscosity for surfactant EOR processes. In: SPE Improved Oil Recovery Conference.
Taber, J.J., 1983. Technical screening guides for the enhanced recovery of oil. In: SPE
Annual Technical Conference and Exhibition.
Taber, J.J., Martin, F.D., Seright, R.S., 1997. EOR screening criteria revisited-Part 1:
introduction to screening criteria and enhanced recovery field projects. SPE
Reservoir Eng. 12 (3), 189–198.
Tabor, R.F., Eastoe, J., Dowding, P., 2009. Adsorption and desorption of nonionic
surfactants on silica from toluene studied by ATR-FTIR. Langmuir 25 (17),
9785–9791.
Tackie-Otoo, B.N., Mohammed, M.A.A., Zalghani, H.A.B.M., Hassan, A.M., Murungi, P.I.,
Tabaaza, G.A., 2022. Interfacial properties, wettability alteration and emulsification
properties of an organic alkali–surface active ionic liquid system: implications for
enhanced oil recovery. Molecules 27 (7), 2265.
Tagavifar, M., Jang, S.H., Sharma, H., Wang, D., Chang, L.Y., Mohanty, K., Pope, G.A.,
2018. Effect of pH on adsorption of anionic surfactants on limestone: experimental
study and surface complexation modeling. Colloids Surf. A Physicochem. Eng. Asp.
538, 549–558.
Tagavifar, M., Herath, S., Weerasooriya, U.P., Sepehrnoori, K., Pope, G., 2016.
Measurement of microemulsion viscosity and its implications for chemical EOR. In:
SPE Improved Oil Recovery Conference. OnePetro.
Talebian, S.H., Masoudi, R., Tan, I.M., Zitha, P.L.J., 2014. Foam assisted CO2-EOR: a
review of concept, challenges, and future prospects. J. Petrol. Sci. Eng. 120,
202–215.
Talebian, S.H., Tan, I.M., Sagir, M., Muhammad, M., 2015. Static and dynamic foam/oil
interactions: potential of CO2-philic surfactants as mobility control agents. J. Petrol.
Sci. Eng. 135, 118–126.
Tanaka, R., Williams, P.A., Meadows, J., Phillips, G.O., 1992. The adsorption of
hydroxyethyl cellulose and hydrophobically modified hydroxyethyl cellulose onto
polystyrene latex. Colloid. Surface. 66 (1), 63–72.
Texter, J., 2001. Reactions and synthesis in surfactant systems. Surfactant Science Series,
ACS.
Thomas, S., 2008. Enhanced oil recovery-an overview. Oil and Gas Science and
Technology-Revue de l’IFP 63 (1), 9–19.
Tsvetkov, N.V., Lebedeva, E.V., Lezov, A.A., Podseval’nikova, A.N., Akhmadeeva, L.I.,
Zorin, I.M., Bilibin, A.Y., 2014. Macromolecules of poly-(12-
acryloylaminododecanoic acid) in organic solvent: synthesis and molecular
characteristics. Polymer 55 (7), 1716–1723.
Tunio, S.Q., Chandio, T.A., Memon, M.K., 2012. Comparative study of FAWAG and
SWAG as an effective EOR technique for a Malaysian field. Res. J. Appl. Sci. Eng.
Technol. 4 (6), 645–648.
Udoh, T., Vinogradov, J., 2021. Controlled salinity-biosurfactant enhanced oil recovery
at ambient and reservoir temperatures-an experimental study. Energies 14 (4), 1077.
Varfolomeev, M.A., Ziniukov, R.A., Yuan, C., Khairtdinov, R.K., Sitnov, S.A., Sudakov, V.
A., Zhdanov, M.V., Mustafin, A.Z., Usmanov, S.A., Sattarov, A.I., Glukhov, M.S.,
2020 October. Optimization of carbonate heavy oil reservoir development using
surfactant flooding: from laboratory screening to pilot test. In: SPE Russian
Petroleum Technology Conference. OnePetro.
Vermolen, E., Almada, P.M., Wassing, B.M., Ligthelm, D.J., Masalmeh, S.K., 2014. Low-
salinity polymer flooding: improving polymer flooding technical feasibility and
economics by using low-salinity make-up brine. In: International Petroleum
Technology Conference.
36
Journal of Petroleum Science and Engineering 220 (2023) 111243
Walker, D.L., Britton, C., Kim, D.H., Dufour, S., Weerasooriya, U., Pope, G.A., 2012. The
impact of microemulsion viscosity on oil recovery. In: SPE Improved Oil Recovery
Symposium.
Wang, D., Maubert, M., Pope, G.A., Liyanage, P.J., Jang, S.H., Upamali, K.A., Chang, L.,
Tagavifar, M., Sharma, H., Ren, G., 2019. Reduction of surfactant retention in
limestones using sodium hydroxide. SPE J. 24 (1), 92–115.
Wang, J., Han, M., Fuseni, A.B., Cao, D., 2015. Surfactant adsorption in surfactant
polymer flooding in carbonate reservoirs. SPE 172700-MS. In: SPE Middle East Oil
and Gas Show Conference.
Wang, J., Xiao, L., Liao, G., Zhang, Y., Guo, L., Arns, C.H., Sun, Z., 2018. Theoretical
investigation of heterogeneous wettability in porous media using NMR. Sci. Rep. 8
(1), 1–14.
Wang, L., Mohanty, K., 2015. Enhanced oil recovery in gas flooded carbonate reservoirs
by wettability-altering surfactants. SPE J. 20 (1), 60–69.
Wang, W., Lu, X., 2009. Property evaluation of EOR technology by means of expansive
granular crosslinked polymer. In: SPE Production and Operations Symposium.
Wang, Y., Wu, F., 2015. Amphiphilic acrylamide-based copolymer with porphyrin
pendants for the highly selective detection of Hg2+ in aqueous solutions. Polymer 56,
223–228.
Winsor, P.A., 1954. Solvent Properties of Amphiphilic Compounds. Butterworths
Scientific Publications.
Wu, B., Xiu, J., Yu, L., Huang, L., Yi, L., Ma, Y., 2022. Biosurfactant production by
Bacillus subtilis SL and its potential for enhanced oil recovery in low permeability
reservoirs. Sci. Rep. 12 (1), 1–10.
Wu, G., Yuan, C., Ji, X., Wang, H., Sun, S., Hu, S., 2017. Effects of head type on the
stability of gemini surfactant foam by molecular dynamics simulation. Chem. Phys.
Lett. 682, 122–127.
Wu, Y., Iglauer, S., Shuler, P., Tang, Y., Goddard III, W.A., 2010. Branched alkyl alcohol
propoxylated sulfate surfactants for improved oil recovery. Tenside Surfactants
Deterg. 47 (3), 152–161.
Xie, X., Weiss, W.W., Tong, Z., Morrow, N.R., 2004. Improved oil recovery from
carbonate reservoirs by chemical stimulation. In: SPE/DOE Symposium on Improved
Oil Recovery.
Xu, X., Chen, F., 2004. Modified emulsifier-free emulsion polymerization of butyl
methacrylate with ionic or/and nonionic comonomers. J. Appl. Polym. Sci. 92 (5),
3080–3087.
Xue, W., Hamley, I.W., Castelletto, V., Olmsted, P.D., 2004. Synthesis and
characterization of hydrophobically modified polyacrylamides and some
observations on rheological properties. Eur. Polym. J. 40 (1), 47–56.
Yang, H., Britton, C., Liyanage, P.J., Solairaj, S., Kim, D.H., Nguyen, Q.,
Weerasooriya, U., Pope, G.A., 2010. Low-cost, high-performance chemicals for
enhanced oil recovery. In: SPE Improved Oil Recovery Symposium.
Yang, J., Zhou, Y., 2020. An automatic in situ contact angle determination based on level
set method. Water Resour. Res. 56 (7).
Yasin, A., Zhou, W., Yang, H., Li, H., Chen, Y., Zhang, X., 2015. Shape memory hydrogel
based on a Hydrophobically-Modified polyacrylamide (HMPAM)/α-CD mixture via a
host-guest approach. Macromol. Rapid Commun. 36 (9), 845–851.
Ye, F., Guo, H., Zhang, H., 2008. Biomimetic synthesis of oriented hydroxyapatite
mediated by nonionic surfactants. Nanotechnology 19 (24), 245605.
Yin, X., Zhao, T., Yi, J., 2021, November. The Combined Flooding of Dispersed Particle
Gel and Surfactant for Conformance Control and EOR: From Experiment to Pilot
Test. In: SPE International Conference on Oilfield Chemistry. OnePetro.
Youssif, M.I., El-Maghraby, R.M., Saleh, S.M., Elgibaly, A., 2018. Silica nanofluid
flooding for enhanced oil recovery in sandstone rocks. Egyptian Journal of
Petroleum 27 (1), 105–110.
Yu, K.M.K., Steele, A.M., Zhu, J., Fu, Q., Tsang, S.C., 2003. Synthesis of well-dispersed
nanoparticles within porous solid structures using surface-tethered surfactants in
supercritical CO2. J. Mater. Chem. 13 (1), 130–134.
Yu, Q., Jiang, H., Zhao, C., 2010. Study of interfacial tension between oil and surfactant
polymer flooding. Petrol. Sci. Technol. 28 (18), 1846–1854.
Yuncong, G.A.O., Mifu, Z.H.A.O., Jianbo, W.A.N.G., Chang, Z.O.N.G., 2014. Performance
and gas breakthrough during CO2 immiscible flooding in ultra-low permeability
reservoirs. Petrol. Explor. Dev. 41 (1), 88–95.
Zargartalebi, M., Kharrat, R., Barati, N., 2015. Enhancement of surfactant flooding
performance by the use of silica nanoparticles. Fuel 143, 21–27.
Zhang, D.L., Liu, S., Puerto, M., Miller, C.A., Hirasaki, G.J., 2006a. Wettability alteration
and spontaneous imbibition in oil-wet carbonate formations. J. Pet. Sci. Eng. 52
(1− 4), 213–226.
Zhang, D., Liu, S., Yan, W., Puerto, M., Hirasaki, G.J., Miller, C.A., 2006b. Favorable
attributes of alkali-surfactant-polymer flooding. In: SPE/DOE Symposium on
Improved Oil Recovery.
Zhang, H., Ramakrishnan, T.S., Nikolov, A., Wasan, D., 2016. Enhanced oil recovery
driven by nanofilm structural disjoining pressure: flooding experiments and
microvisualization. Energy Fuel. 30 (4), 2771–2779.
Zhang, P., Austad, T., 2006. Wettability and oil recovery from carbonates: effects of
temperature and potential determining ions. Colloids Surf. A Physicochem. Eng. Asp.
279 (1–3), 179–187.
Zhang, R., Somasundaran, P., 2006. Advances in adsorption of surfactants and their
mixtures at solid/solution interfaces. Adv. Colloid Interface Sci. 123, 213–229.
Zhang, W., Mao, J., Yang, X., Zhang, H., Zhao, J., Tian, J., Lin, C., Mao, J., 2019.
Development of a sulfonic gemini zwitterionic viscoelastic surfactant with high salt
tolerance for seawater-based clean fracturing fluid. Chem. Eng. Sci. 207, 688–701.
Zhang, Y., Sarma, H., 2012. Improving waterflood recovery efficiency in carbonate
reservoirs through salinity variations and ionic exchanges: a promising low-cost
Smart-Waterflood approach. In: Abu Dhabi International Petroleum Conference and
Exhibition.
A.M. Hassan et al.
Zhao, M., Lv, W., Li, Y., Dai, C., Wang, X., Zhou, H., Zou, C., Gao, M., Zhang, Y., Wu, Y.,
2018. Study on the synergy between silica nanoparticles and surfactants for
enhanced oil recovery during spontaneous imbibition. J. Mol. Liq. 261, 373–378.
Zhao, Z., Bi, C., Qiao, W., Li, Z., Cheng, L., 2007b. Dynamic interfacial tension behavior
of the novel surfactant solutions and Daqing crude oil. Colloid. Surface.
Physicochem. Eng. Aspect. 294 (1–3), 191–202.
Zhao, Z., Li, Z., Qiao, W., Wang, G., 2007a. Surface and interfacial tension behavior of
novel alkyl methylnaphthalene sulfonate surfactant solutions. Chapter 1. In: Fong, P.
A. (Ed.), Colloid and Surface Research Trends. Nova Science Publishers Inc.,
pp. 1–76
Zhong, C., Huang, R., Xu, J., 2008. Characterization, solution behavior, and
microstructure of a hydrophobically associating nonionic copolymer. J. Solut. Chem.
37 (9), 1227–1243.
Zhong, C., Luo, P., Ye, Z., Chen, H., 2009. Characterization and solution properties of a
novel water-soluble terpolymer for enhanced oil recovery. Polym. Bull. 62 (1),
79–89.
37
Journal of Petroleum Science and Engineering 220 (2023) 111243
Zhong, W., Claverie, J.P., 2013. Probing the carbon nanotube-surfactant interaction for
the preparation of composites. Carbon 51, 72–84.
Zhou, X., Morrow, N.R., Ma, S., 2000. Interrelationship of wettability, initial water
saturation, aging time, and oil recovery by spontaneous imbibition and
waterflooding. SPE J. 5 (2), 199–207.
Zhu, B.-Y., Gu, T., 1991. Surfactant adsorption at solid-liquid interfaces. Adv. Colloid
Interface Sci. 37 (1–2), 1–32.
Ziegler, V.M., Handy, L.L., 1981. Effect of temperature on surfactant adsorption in
porous media. Soc. Petrol. Eng. J. 21 (2), 218–228.
Al-Murayri, M.T., Al-Kharji, A.A., Kamal, D.S., Al-Ajmi, M.F., Al-Ajmi, R.N., Al-
Shammari, M.J., Al-Asfoor, T.H., Badham, S.J., Bouma, C., Brown, J. and Suniga, H.
P., 2018, March. Successful Implementation of a One-Spot Alkaline-Surfactant-
Polymer ASP Pilot in a Giant Carbonate Reservoir. In SPE EOR Conference at Oil and
Gas West Asia. OnePetro.