Review

pubs.acs.org/EF

Review on Surfactant Flooding: Phase Behavior, Retention, IFT, and

Field Applications
Muhammad Shahzad Kamal,† Ibnelwaleed A. Hussein,*,‡ and Abdullah S. Sultan§
†
Center for Integrative Petroleum Research, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia
‡
Gas Processing Center, College of Engineering, Qatar University, P. O. Box 2713, Doha, Qatar
§
Department of Petroleum Engineering, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia
Downloaded via KING FAHD UNIV PETROLEUM & MINERALS on March 28, 2020 at 19:04:33 (UTC).

ABSTRACT: Surfactant flooding is an important technique used in enhanced oil recovery to reduce the amount of oil in pore
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space of matrix rock. Surfactants are injected to mobilize residual oil by lowering the interfacial tension between oil and water
and/or by the wettability alteration from oil-wet to water-wet. A large number of cationic, anionic, non-ionic, and amphoteric
surfactants have been investigated on a laboratory scale under different conditions of temperature and salinity. Selection of the
appropriate surfactant is a challenging task, and surfactants have to be evaluated by a series of screening techniques. Different
types of surfactants along with their limitations are reviewed with particular emphasis on the phase behavior, adsorption,
interfacial tension, and structure−property relationship. Factors affecting the phase behavior, interfacial tension, and wettability
alteration are also discussed. Field applications of surfactants for chemical enhanced oil recovery in carbonate and sandstone
reservoirs are also reviewed. Finally, some recent trends and future challenges in surfactant enhanced oil recovery are outlined.
Field studies show that most of the surfactant flooding has been conducted in low-temperature and low-salinity sandstone
reservoirs. However, high-temperature and high-salinity carbonate reservoirs are still challenging for implementation of surfactant
flooding.

1. INTRODUCTION fluid (water), which improves the oil/water mobility ratio.18−21

Oil has been the most important and significant source of
energy so far, and it will contribute significantly in meeting the
future energy demand as well.1 Thus, it is necessary to enhance
the current production level in the next few decades, which can
be achieved by either discovering new fields or increasing the
production from existing oil fields. Only about one-third of the
oil present in a reservoir can be recovered using primary and
secondary recovery techniques.2−5 Oil is initially recovered
from a reservoir using the inherent pressure of the reservoir
(primary recovery). After the dissipation of the initial pressure,
oil is recovered by applying external pressure using seawater
injection into the reservoir (secondary recovery). Enhanced oil
recovery (EOR) or tertiary recovery techniques are used to
recover the remaining oil which cannot be recovered using
water flooding.6 Although chemical EOR (cEOR) is one of the
most promising methods available to recover residual and
remaining oil, it was not very commonly employed in the past
due to low oil prices and the high cost of chemicals. However,
continuous rise in oil prices and the growing demand for oil
have encouraged researchers to determine economical and low-
cost cEOR technology to recover the maximum amount of the
remaining oil.
In cEOR, a range of chemicals such as surfactants, polymers,
and/or alkalis are used to increase the microscopic efficiency
(displacement efficiency) and the macroscopic efficiency
(volumetric sweep efficiency).7−16 Macroscopic efficiency is
related to the effectiveness of the displacing fluid in sweeping
out the reservoir volume both areally and vertically as well as
moving the oil toward the production well.17 Macroscopic
efficiency can be increased using mobility control methods.
Polymers are used to increase the viscosity of the displacing
On the other hand, microscopic efficiency is related to the
displacement of oil at the pore scale. It is not possible to
displace all the oil that comes into contact with water during
water flooding, due to trapping of oil by capillary forces. The
relationship between the capillary forces and the viscous forces
results in a dimensionless capillary number (μv/γ cos θ), where
μ is the viscosity of the aqueous phase, v is the velocity, γ is the
interfacial tension between oil and water, and θ is the contact
angle.22,23 Microscopic efficiency can be improved by
decreasing the capillary forces and the oil/water interfacial
tension. Capillary number is closely related to oil recovery and
residual oil saturation (oil saturation is the volume fraction of
oil within the pore volume) and is in the range of 10−7 to 10−6
for typical brine flooding. Increasing the capillary number to
between 10−4 and 10−3 reduces the oil saturation to 90%,6 and
residual oil saturation approaches zero if the capillary number
reaches 10−2.24 In order to reach this value, the interfacial
tension (IFT) should be decreased from an initial value of 20−
30 mN/m to values in the range of 10−2 to 10−3,25 which is
achieved through the use of surfactants during flooding with
brine.26−28 Surfactants also influence the amount of residual oil
recovered via other mechanisms, including microemulsification
of trapped residual oil, changing the wettability of rock, and
improving the interfacial rheological properties.29−36 Here
wettability is defined as “the tendency of one fluid to adhere to
a solid surface in the presence of another immiscible fluid”.
Received: February 4, 2017
Revised: July 4, 2017
Published: July 6, 2017

© 2017 American Chemical Society 7701 DOI: 10.1021/acs.energyfuels.7b00353

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A large number of surfactants have been evaluated on a
laboratory scale and tested in the field.37−39 Appropriate
surfactants for a set of particular reservoir conditions are
selected after a series of evaluation steps. Evaluation is based on
the surfactant structure, reservoir temperature, reservoir
salinity, pH, permeability of rock, formation type, cost of the
surfactant, adsorption of the surfactant on the matrix rock, and,
finally, the oil recovery. The results of several experimental
investigations covering different aspects of surfactant flooding
have been published.40−43 There are several reviews that cover
various aspects of surfactant and surfactant−polymer flooding.
Seright summarized the polymer requirement in previous and
current polymer floods owing to their different viscosities and
bank sizes.44,45 Saboorian et al. established a complete data set
of laboratory experiments, pilot tests, and field applications of
polymer flood for heavy oil reservoirs.21,46 Olajire17 reviewed
alkaline-surfactant−polymer (ASP) flooding in general, discus-
sing the mechanism, prospects, and challenges of ASP flooding.
Hirasaki et al. reviewed mainly the role of alcohol, alkali, and
chain branching on phase behavior.4 Sheng reviewed the
current status of surfactant EOR technology and summarized
experimental and simulation work in carbonate and shale
reservoirs.47 Raffa et al. reviewed the polymeric surfactants that
have been utilized in EOR.48 They collected the relevant work
done in the past decade with a particular emphasis on patent
literature and biobased systems.48 This review covers different
aspects of surfactant flooding that are not covered in previous
studies. Surfactant flooding is a complex process, and there is a
lack of understanding of how a particular surfactant will behave
in typical reservoir conditions. Due to different types of
interactions of surfactant with brine and other oilfield
chemicals, conflicting results have been reported in the
literature on different aspects of surfactant flooding such as
IFT. In this review, the phase behavior, IFT, and adsorption of
surfactants are discussed in relation to surfactant structure. The
review highlights the chemical nature of various surfactants that
was ignored in previous reviews. Field implementation of
various surfactants in carbonate and sandstone reservoirs is also
part of this review. In addition, recent trends, current
challenges, and future directions of surfactant EOR are also
addressed.
The review is divided into different sections to explain
different aspects of surfactant flooding. The first section
discusses the fundamentals of surfactant EOR that can
introduce the readers to different types of surfactants, oil
reservoirs, and screening criteria of surfactants. The second
section discusses the potential surfactant systems for EOR that
include but are not limited to anionic surfactants, cationic
surfactants, zwitterionic surfactants, viscoelastic surfactants, and
fluorinated surfactants. Subsequent sections discuss the various
factors affecting phase behavior, IFT, adsorption, and
wettability alteration during surfactant flooding. Finally, field
applications and challenges of surfactant EOR are addressed.
2. FUNDAMENTALS OF SURFACTANT EOR
2.1. Surfactants. A surfactant is a long-chain molecule
which has a hydrophilic (water-soluble) head group and a
hydrophobic (oil-soluble) tail group.49 The hydrophobic group
may be a long-chain hydrocarbon, fluorocarbon, a siloxane
chain, or a short polymer chain. The hydrophilic group may be
anionic, cationic, amphoteric, or non-ionic. Surfactant classi-
fication is mainly based on the nature of the hydrophilic head
group. In anionic and cationic surfactants the hydrophilic group
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is negatively and positively charged, respectively. Non-ionic
surfactants do not ionize in aqueous solution as the hydrophilic
group is of a nondissociative nature. Water solubility of non-
ionic surfactants is due to the hydrogen bonding between the
hydrophilic group, typically an ethylene oxide chain or a similar
group, and water.50 A hydrophilic group is both negatively and
positively charged in amphoteric surfactants. Some common
hydrophilic groups are summarized in Table 1.
Table 1. Some Common Hydrophilic Groups of Surfactants
type of
surfactants hydrophilic group
cationic ammonium quaternary ammonium halides (R4N+X−)
non-ionic polyoxyethylene, polyols, sucrose esters, and polyglycidyl
esters
anionic carboxyl (RCOO−M+), sulfonate (RSO3−M+),
sulfate (ROSO3−M+), phosphate (ROPO3−M+)
amphoteric betaine, sulfobetaine RN+ (CH3)2CH2CH2SO3− imidazoline
derivatives
The properties of surfactants change considerably above and
below the critical micelle concentration (cmc). At the cmc, the
surface-active ions or molecules in solution associate to form
larger aggregates known as micelles. At a given temperature and
electrolyte concentration, each surfactant has a unique cmc
value. For all surfactants, cmc depends on the chain length of
the hydrophobic tail, temperature, and salinity. The cmc
decreases by a factor of 2 for ionic surfactants and a factor of 3
for non-ionic surfactants for each addition of a methylene
group.51 Since the surfactant must be present at a concentration
higher than the cmc to obtain a lower IFT and better foam
stability, the cmc is an important criterion to be considered in
EOR applications. Also, the maximum adsorption of a
surfactant on the reservoir rock surface occurs at the cmc,
above which adsorption does not increase significantly. The
cmc is typically determined by plotting a physicochemical
property against the surfactant concentration. The cmc can be
determined by surface tension and conductivity measurement,
voltammetry, IR spectroscopy, and nuclear magnetic resonance
spectroscopy.
Another important criterion for the characterization of a
single-component surfactant or a mixture of surfactants is the
hydrophilic−lipophilic balance (HLB). It is a measure of the
degree to which a particular surfactant is hydrophilic or
lipophilic. HLB can be adjusted either by varying external
parameters, such as the electrolyte concentration and the
solution temperature, or manipulating the structure of the
surfactant, such as varying the hydrophobic chain length and
employing a more or less hydrophilic head group.52 A low HLB
value (<9) is an indication of a lipophilic surfactant, while high
HLB values (>11) indicate that the surfactant is hydrophilic.53
Another important surfactant property is the Krafft point,
which is the minimum temperature at which surfactant forms
micelles. If temperature is less than the Krafft point, there is no
value for the critical micelle concentration and micelles cannot
form.53,54 The solubility of a material undergoes a sharp
increase at the Krafft point.55
2.2. Types of Oil Reservoirs. Depending on the formation
rocks, oil reservoirs are classified either as carbonate reservoirs
or sandstone reservoirs. A sandstone reservoir rock consists of a
large amount of silica with silicate minerals, and carbonates are
only a minor fraction. Some clay minerals, such as kaolinite
andiIllite, are also present in sandstone formations.56 Sandstone
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reservoirs, which are homogeneous, are the most appropriate

for cEOR.57 Carbonate reservoirs, which are estimated to
contain 60% of the remaining oil, are composed of calcite
(CaCO3), dolomite (CaMg(CO3)2), anhydrite (CaSO4),
gypsum (CaSO4·H2O), and magnesite (MgCO3) rocks.
Carbonate reservoirs have been estimated to contain about
3000 billion barrels of the remaining oil and 3000 trillion SCF
gas.58 Some carbonate reservoirs are characterized by fractures
with a high conductivity, which are surrounded by a low-
permeability matrix. Most of these reservoirs have oil-wet to
mixed-wet conditions. Although carbonate reservoirs have a
great potential for the application of tertiary recovery
techniques, EOR research associated with carbonate reservoirs
is limited due to many technical challenges. Only a few reports
on the application of cEOR in carbonate reservoirs are
available, mainly due to the high clay content which results in
significant adsorption of surfactants.57 Also, carbonate reser-
voirs are complex and heterogeneous and cEOR is less effective
with carbonates.59,60 Precipitation of calcium carbonate and
calcium hydroxide occurs as a result of the reaction of injected
surfactants with divalent ions, particularly Ca2+ and Mg2+. Oil
recovery from fractured reservoirs is even lower due to poor
imbibition of water. In fractured carbonate reservoirs,
surfactants are normally injected to change the wettability
from oil-wet to water-wet. Wettability alteration results in the
spontaneous imbibition of water into the oil containing matrix
and in driving the oil out.58
2.3. Screening Methodology and Evaluation Criteria. Figure 1. Flowchart of the surfactant screening procedure for cEOR
applications.
A candidate surfactant for cEOR should have the following
properties: good thermal stability (at reservoir temperature),
the ability to lower the oil/water IFT to 10−3 mN/m, low the field. Phase behavior, adsorption, and IFT of different
retention on reservoir rock (<1 mg/(g of rock)), salt tolerance surfactant classes will be discussed in the following sections.
(at reservoir salinity), compatibility with the polymer used, and 3.1. Anionic Surfactants. Anionic surfactants are the most
commercial availability at an acceptable cost. The selection of a widely used type of surfactant for cEOR applications because
surfactant requires careful laboratory screening to determine most of the cEOR work has been conducted in sandstone
how it will behave in the type of reservoir, and withstand the formations. Sulfonates, sulfates, and carboxylates are three
reservoirs’ conditions, such as the reservoir temperature, important classes of anionic surfactants for cEOR applications.
formation water salinity, and the nature of the crude oil. The 3.1.1. Sulfonate Surfactants. The most commonly used
screening methodology for the selection of surfactants for surfactants for cEOR are sulfonate surfactants. Petroleum
cEOR applications is shown in Figure 1. First, the compatibility sulfonates, synthetic sulfonates, internal olefin sulfonates, α-
of the surfactant with other chemicals and the formation brine olefin sulfonates, and alkoxy sulfonates have been evaluated for
is assessed at reservoir conditions. Compatible surfactants are cEOR applications.61 The term petroleum sulfonates refers to
then subjected to phase behavior experiments, which can screen the surfactants obtained from the sulfonation of the
a large number of potential surfactants quickly. Surfactants intermediate molecular weight refinery stream. Synthetic
which form a middle-phase microemulsion are required to sulfonates are those surfactants which are obtained from the
obtain an ultralow IFT. Because the surfactant residence time in sulfonation of pure organic compounds.54 Internal olefin
a reservoir can be up to a few weeks, the candidate surfactants sulfonates (IOS), which are a mixture of surfactants produced
should possess long-term thermal stability. Next, the ability of during the sulfonation step, are branched and less viscous. IOS
the surfactant to decrease IFT and the extent of adsorption of help minimize gel production and liquid crystal structure
the surfactant on reservoir rock surfaces are determined. formation.61 High molecular weight IOS have been found to be
Finally, potential surfactant formulations are used in core more suited for crude oils with a high wax content, high
flooding experiments to determine the extent of oil recovery at asphaltene content, and a high viscosity.62 α-Olefin sulfonates
reservoir conditions. In the following sections, the phase have a linear structure and are sensitive to oxygen attack.54
behavior, IFT, and the adsorption associated with various Sulfonates are stable at high temperature, but because they are
surfactant systems that have been used in cEOR research to- sensitive to divalent cations, their performance is limited in
date will be discussed. Factors affecting IFT, phase behavior, high-salinity conditions due to precipitation. Also, the cost of
and adsorption will also be highlighted. sulfonates is higher as compared to sulfate surfactants.63 A
mixture of surfactants with a high equivalent weight and a low
equivalent weight is used to get a synergetic effect. Sulfonates
3. POTENTIAL SURFACTANT SYSTEMS FOR CEOR with a high equivalent weight are more efficient in reducing IFT
A large number of surfactants have been evaluated for cEOR but are insoluble in water and are readily adsorbed. Sulfonates
applications. This section will highlight some important classes with a low equivalent weight act as the adsorbate and solubilizer
of surfactants that have been used at the laboratory scale or in for surfactants with a high alkane number.64 Ether sulfonates
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are stable at high temperature and have a good tolerance to
hardness, but they can be expensive and only limited quantities
of a few compounds are commercially available due to
manufacturing difficulties. Ether sulfonate products have short
hydrophobes that are not that effective for crude oils with high
equivalent alkane carbon numbers (EACN).65 Alkyl glyceryl
ether sulfonates are stable at 110 °C.66 Examples of other
sulfonates include the following: alkyl methylnaphthalenesulfo-
nates; phenyltetradecanesulfonate; phenyl alkanesulfonates;
sodium dodecyl benzenesulfonate, hexadecylbenzenesulfonate,
and alkyl methylnaphthalenesulfonates; and alkyl glyceryl
sulfonates, alkyl aryl sulfonates, and alkyl benzenesulfonates.
The typical structure of a sulfonate surfactant is shown in
Figure 2. In summary, most of the sulfonate surfactants are
Figure 2. Typical example of a sulfonate surfactant (sodium dodecyl
benzenesulfonate).209
tolerant to high temperature but not tolerant to high salinity.
Therefore, sulfonate surfactants should be restricted to low-
salinity environments.
3.1.2. Sulfate Surfactants. Surfactants containing the sulfate
group have a greater tolerance to divalent cations. However,
they do not have the required thermal stability and decompose
at temperatures greater than 60 °C.61,67,68 One special class of
sulfate surfactants is those based on the Guerbet alkoxy sulfate
(GAS). Guerbet reaction is used to synthesize surfactants with
a large hydrophobe through dimerization of a linear alcohol.69
Alkoxy groups such as propylene oxide and ethylene oxide can
be used as an extender of the Guerbet alcohol.69 GAS
surfactants produced by the alkoxylation of Guerbet alcohol
followed by sulfation can reduce IFT to ultralow values at high
temperature with different types of crude oil.63 GAS surfactants
are chemically stable at high temperature provided the pH is
maintained in the range of 8−11. A high hydrophobicity can be
achieved at a lower cost using GAS surfactants. Sulfate
surfactants which have been evaluated for cEOR applications
include the following: alcohol propoxy sulfates,70 tristyrylphe-
nol (TSP) alkoxy sulfate surfactants,71 alkyl ether sulfates, and
dodecyl alkyl sulfates.72 In summary, sulfate surfactants can
work well in highly saline environments, but they are not
chemically stable above 60 °C.
3.1.3. Carboxylate Surfactants. Guerbet alkoxy carboxylate
surfactants are stable at elevated temperatures and can be
synthesized with variable branching options to meet specific
reservoir conditions.69 They are stable at both alkaline and
acidic pH and generate ultralow IFT with low-viscosity
emulsions for different crude oils. These surfactants have
shown excellent performance with sandstone and carbonate
cores. Alkyl polyoxy propylene/ethylene (alkoxy) carboxylates
(AEC) have good salt tolerance, high water solubility, good
thermal stability (up to 120 °C), and high chemical stability.65
Anionic surfactant phosphate esters can also achieve low IFT at
a range of salinities, and a typical structure is shown in Figure
3.73
In summary, anionic surfactants are the most widely used
surfactant for cEOR applications. However, in general, they do
not work well both in highly saline environments and under
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Figure 3. Typical structure of a phosphate surfactant (phosphate
ester).73
high temperatures. The focus of current research is to
synthesize anionic surfactants that have good salt tolerance
and high thermal stability.
3.2. Non-ionic Surfactants. As mentioned earlier non-
ionic surfactants do not ionize in water and their solubility is
influenced by different factors including hydrogen bonding and
van der Waals interactions. An increase in temperature raises
the thermal energy and weakens the hydrogen bonding,
resulting in poor dissolution of the surfactant in water,
indicated by a turbid solution. The temperature at which a
non-ionic surfactant solution become turbid is known as the
cloud point.74 The cloud point depends on the branching of the
chain, surfactant concentration, and the number of ethylene
oxide units. Non-ionic surfactants have a good tolerance to high
salinity, but their IFT reduction ability is lower compared to
ionic surfactants.75 Non-ionic surfactants based on alkyl
polyglycosides can achieve ultralow IFT using alcohol as the
cosolvent.76 Some examples of non-ionic surfactants which
have been evaluated for cEOR applications are as follows:
polyoxyethylene stearyl ether (C18(EO)20),77 nonylphenol
oxyethylenes,78 alcohol ethoxylates,63 ethylene glycol distearate,
and propylene glycol monostearate. The typical structure of a
non-ionic surfactant is shown in Figure 4.
Figure 4. Typical example of a non-ionic surfactant (polyethoxylated
octyl phenol).209
3.3. Zwitterionic Surfactants. Amphoteric surfactants
have attracted attention due to their tolerance of high
temperature and high salinity. These properties, combined
with their very low cmc values, make them suitable to be used
under harsh reservoir conditions.79,80 Amphoteric surfactants
are expensive as compared to other surfactants. Amphoteric
surfactants that have been evaluated for cEOR applications
include the following: carboxyl betaine type surfactants,
hydroxyl sulfonate betaine type surfactants, didodecylmethyl-
carboxyl betaine, alkyl dimethylpropane sultaine, lauramido-
propyl betaine, and cocoamido-2-hydroxypropyl sulfo betaine.
The typical structure of an amphoteric surfactant is shown in
Figure 5.
3.4. Cationic Surfactants. Since most of the cEOR
projects have been conducted in sandstone reservoirs for
which cationic surfactants are not suitable due to high
Figure 5. Typical example of an amphoteric surfactant (dodecyl
betaine).209
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adsorption, cationic surfactants are the least evaluated for cEOR
applications. As most of the remaining oil is in carbonate
formations, cationic surfactants can be potential candidates for
cEOR applications, considering that they have lower adsorption
on calcite and other carbonate minerals.81 Cationic surfactants
have been used in combination with anionic surfactants to have
the desirable properties. Typically, cationic surfactants used for
cEOR applications are quaternary ammonium salts. Examples
of cationic surfactants which have been evaluated for cEOR are
as follows: quaternary ammonium salts, gemini surfactant
bis(quaternary ammonium bromide) type, cetylpyridinium
chloride, and dodecyl trimethylammonium chloride.
3.5. Other Classes of Surfactants. 3.5.1. Natural
Surfactants. Saponin is a natural surfactant, which contains
hydrophilic saccharide residues and a hydrophobic steroid
backbone and is extracted from the Ziziphus spina-christi (Z.
spina-christi) tree. Recovery of 81% of the total oil has been
reported at low-salinity conditions (15000 ppm) for a
carbonate reservoir.29 The advantage of natural surfactants
includes high biodegradability, specific activity at high temper-
ature, pH, and high salinity, low toxicity, and the synthesis from
renewable feedstock.82 The following are examples of natural
surfactants: galactomannan (non-ionic), rhamnolipid (non-
ionic),83 and the surfactant extracted from the mulberry tree51
3.5.2. Gemini Surfactants. Gemini surfactants contain two
single-chain surfactants linked by a spacer near the head groups.
The spacer may be hydrophilic or lipophilic and flexible or
rigid, and it controls the separation of the two head groups.84,85
Properties of the Gemini surfactants are dependent on the
length of the spacer group, and examples of spacers are
polymethylene and polyoxyethylene.86 Gemini surfactants have
excellent water solubility, are tolerant to high salinity,87 can
significantly lower the interfacial tension at low cmc, possess
interesting rheological properties, and have significant potential
for cEOR.88−90 Alkyl sulfate Gemini surfactants showed
excellent tolerance to high salinity of 20% NaCl, and ultralow
interfacial tension was achieved at the higher end of salinity.87
The synergy between Gemini surfactants and other commercial
surfactants can yield good results in aqueous stability and
interfacial tension reduction.87
3.5.3. Viscoelastic Surfactants. Viscoelastic surfactants
(VES) are a class of surfactants that have the desirable property
of mobility control in addition to lowering the interfacial/
surface tension. Viscoelastic surfactants can be ionic or
zwitterionic, and unlike classical surfactants which form
spherical micelles of oil in water, VES form a supramolecular
structure that causes a surprisingly high viscosity. Viscoelastic
surfactants can be used instead of the combination of a
surfactant and a polymer as it has the desirable properties of
both. Chromatographic effects in the reservoirs can be avoided
by using this single-component system. Due to their small
molecular size, VES can penetrate low-permeable zones of the
reservoir where synthetic polymers are unable to penetrate.
Only very limited literature is available on the cEOR application
of viscoelastic surfactants in sandstone reservoirs. There are no
published reports on the cEOR application of viscoelastic
surfactants in carbonate reservoirs.
One of the viscoelastic surfactants that have been studied is
triphenoxmethanes (TPM)91 (Figure 6), which has two
hydrophobic groups (R′ and R″) and a long-chain hydrophilic
group (R). The major advantage of TPM is the stability under
harsh conditions of high salinity (18.6% TDS with a large
amount of divalent cations) and high temperature (greater than
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Figure 6. Structure of TPM. R′ and R″ are hydrophobic groups, and R
is a long-chain hydrophilic group.2
70 °C). Adsorption results are also acceptable, which indicate
that even under these harsh conditions adsorption is not out of
control. However, IFT reduction is not that provided by other
dedicated cEOR surfactants. Some of the recent investigations
on VES as a cEOR fluid have been conducted by our
group.92−94
3.5.4. Polymeric Surfactants. Macromolecules having both
hydrophilic and hydrophobic parts in their molecular structure
are usually referred to as polymeric surfactants.48,95 Technically,
amphiphilic polymers, associative polymers, hydrophobically
modified polymers and micellar polymers are all polymeric
surfactants. Due to their macromolecular nature, they can have
a large variety of structures such as random, block, graft, star,
and dendrimers. They can be synthesized either by polymer-
ization of the surface-active monomer or by copolymerization
of hydrophobic and hydrophilic monomers. Polymeric
surfactants can be easily tuned to have the desired aggregation
behavior by varying external factors such as salinity, temper-
ature, and pH. Polymeric surfactants attracted attention as they
can lower the interfacial tension and improve the rheological
properties as well. Using single-component polymeric surfac-
tant in EOR can avoid segregation problems. However, the
interfacial reduction ability of polymeric surfactants is not good
compared to conventional surfactants. Another issue associated
with the polymeric surfactant is the cost associated with the raw
material used for polymeric surfactant synthesis.
4. SURFACTANT ADSORPTION
Surfactant retention is one of the most critical parameters
which can affect the economics of flooding using surfactants, or
surfactant−polymer (SP) or ASP combinations.96,97 Surfactant
retention may be due to precipitation, adsorption, or phase
trapping. It is possible to stop surfactant loss due to
precipitation and phase trapping by selecting temperature and
salt tolerant surfactants and adjusting relevant parameters.
Although surfactant loss due to adsorption on reservoir rock
cannot be avoided, it can be minimized. Surfactant retention
can decrease the efficiency of the chemical slug and increase the
oil−water IFT.98 From an economic point-of-view, surfactant
retention should be less than 1 mg/(g of rock)99 to be
acceptable. Various aspects of adsorption, which is the main
contributor of surfactant retention in different reservoir rock
surfaces, are discussed in the following sections.
4.1. Mechanism of Surfactant Adsorption on Mineral
Surfaces. The solid−liquid interface develops a surface charge
which depends mainly on the pH and ionic strength.100
Positively charged surfaces attract anionic surfactants while
cationic surfactants are attracted toward negatively charged
surfaces.101,102 Typically silica and calcite are used as
representative surfaces for sandstone and carbonate formations
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for cEOR adsorption experiments. However, they sometimes
behave differently from natural rock due to the presence of
impurities on natural rock.81 The isoelectric point (IEP), which
is the pH where a particular molecule or surface carries no net
electrical charge, for silica and calcite is roughly at pH 2 and 9,
respectively.103,104 At pH below the IEP the surface carries a
positive charge, and at pH above the IEP the surface carries a
negative charge. Therefore, at neutral pH carbonate rock is
positively charged whereas sandstone is negatively charged.105
Silica contains siloxane units which are bonded together in a
tetrahedral lattice.84 For silica, the density of negative charges
remains low below pH 6 and increases sharply above pH 6.106
Electrostatic interaction and van der Waals interactions
between the surfactant hydrophobic group and the solid surface
are believed to be the main mechanism of surfactant adsorption
on the rock surface.107 Surfactant loss can also be due to ion
exchange, mineral transformation due to hydrophobic bonding,
ion paring, π electron polarization, and the precipitation of
surfactant with dissolved minerals.49,101,107 However, surfactant
adsorption is a complex phenomenon, and the driving force of
surfactant adsorption at the solid−liquid interface may be a
combination of electrostatic interactions, chemical interactions,
hydrogen bonding, nonpolar interactions, covalent bonding,
and desolvation of the adsorbate moieties.108
Adsorption isotherms are obtained by determining the
surfactant concentration either in the supernatant liquid in
static adsorption experiments or in the effluent liquid from
dynamic core flood experiments. Adsorption obtained from the
static adsorption test performed on crushed rock samples is
always higher than the dynamic adsorption due to the increased
surface area of the rock.68 Surfactant concentration can be
determined using the following techniques: conductivity
measurements, two-phase titration, UV spectroscopy, gel
permeation chromatography, potentiometric titration, nuclear
magnetic resonance (NMR) spectroscopy, gas chromatography,
high-performance liquid chromatography (HPLC), and total
organic carbon analysis (TOC).
Surfactant structure is most critical in determining the
adsorption of the surfactant. For example, in general adsorption
of anionic surfactants is higher on carbonate rocks, while the
adsorption of cationic surfactants is lower because carbonate
rocks are typically positively charged. On the hand, sandstone
rocks are negatively charged, resulting in a lower adsorption of
anionic surfactants. Adsorption of amphoteric surfactants on
sandstone rock is higher compared to anionic surfactants due to
the electrostatic interactions of the positive charge on the head
group of betaine amphoteric surfactant and the negative
kaolinite surface.79 Surfactants with longer chains have a higher
tendency to aggregate resulting in a low cmc value.84
4.2. Factors Affecting Surfactant Adsorption. In this
section, the main factors affecting the adsorption of a surfactant
on the reservoir rock surface are discussed.
A typical adsorption isotherm has four distinct regions as
shown in Figure 7. In region 1, at low surfactant concentration,
the main factor which determines the extent of adsorption is
the charge in the electrical double layer.79 In this region, there
are electrostatic interactions between the surfactant head group
and the net charge present on the solid surface, and adsorption
increases linearly and obeys Henry’s law. In region 2, at higher
concentrations, lateral interactions between the adsorbed
surfactant molecules lead to an increase in the adsorption
density due to the formation of surface aggregates.79 The
combination of lateral interactions and electrostatic attractions
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Figure 7. Typical surfactant adsorption isotherm on Berea sandstone.
Reprinted with permission from ref 49. Copyright 2013 Springer.
in this region causes a sharp increase in the surfactant
adsorption. In region 3, adsorption increases with a lower
gradient because only lateral interactions are present. Electro-
static interactions are diminished due to neutralization of the
solid surface by adsorbed surfactant ions.79 In region 4, further
addition of surfactant has no significant effect and a plateau
develops. In this region, the surfactant concentration reaches
the cmc and additional surfactant contributes only in
micellization and adsorption remains constant.
For various ALFOTERRA surfactants (anionic surfactants)
adsorption increases with increasing surfactant concentra-
tion.109 Tiberg et al.110 observed that non-ionic surfactant
adsorption on silica is a function of the surfactant
concentration. At low surfactant concentrations, adsorption is
low. But at some specific concentrations ((0.6−0.9) cmc),
surface aggregation takes place and a large increase in the
adsorption is observed. But at concentrations above the cmc,
adsorption achieved a plateau and further increase in the
concentration has no effect on the adsorption.
Increase in the surfactant hydrophobicity can increase the
adsorption of the surfactant. The longer the hydrophobic chain,
the lower the charge is on the surfactant, and when
hydrophobicity increases, the surfactant moves from the
aqueous phase to the solid−liquid interface.98 Propoxy (PO)
group can also affect the adsorption of the surfactant. It was
found for various ALFOTERRA surfactants that the increase in
the number of propoxy groups can decrease the surfactant
adsorption on kaolinite.109 Propoxy groups increase the
hydrophobicity of the surfactant. However, Wu et al. have
proposed that the decrease in the surfactant adsorption is due
to the increase of the interactions among hydrophobic chains
rather than the interaction of the head group of the surfactant
and the kaolinite surface.109
Ethoxylated alkyl aryl sulfonate surfactant demonstrated
lower adsorption on calcite as compared to its non-ethoxylated
counterpart. Equilibrium adsorption for the alkyl aryl sulfonate
surfactant is 3.5 mg/m2, while for the ethoxylated alkyl aryl
sulfonate surfactant it is 0.8 mg/m2.111 Similar observations
were made for the non-ionic ethoxylated surfactants. A
significant decrease in the adsorption of poly(ethylene glycol)
monoalkyl ethers on silica was observed with the increase of the
ethylene oxide to hydrocarbon ratio.110
An alkali such as sodium carbonate can reduce the
adsorption of anionic surfactants on carbonate rock.112 The
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addition of alkali increases the pH, and at pH higher than the
IEP the charge on the carbonate rock reverses. The IEP of
calcite is 8.5−9,113 and increasing the pH will reverse the
charge and decrease the adsorption of anionic surfactants. It
was found that the adsorption decreased from 0.22 to 0.08 mg/
g when pH was increased from 6 to 11.68 For anionic alkyl aryl
sulfonate surfactants, equilibrium adsorption decreased from
3.5 to 0.15 mg/m2 when 0.3 M Na2CO3 solution was added.111
Propoxylated sulfates, sodium lauryl ether sulfate, and sodium
nonyl phenol ethoxylated sulfate showed very low adsorption
on calcite in the presence of Na2CO3. Adsorption of sodium
lauryl ether sulfate decreased by about 90% when Na2CO3 is
added,112 and similar results have been reported by others.114
Silica, for which IEP is 2, behaves in a similar manner. At
normal formation pH, silica carries a negative charge and the
adsorption of anionic surfactants will be low while the
adsorption of cationic surfactants will be high. Adsorption of
ALFOTERRA 63 (an anionic surfactant) on silica was found to
increase with decreasing pH.109 Alkalis have the additional
advantage of consuming divalent cations present in the
formation and flooding water. However, if anhydrites are
present in the reservoir, the use of sodium carbonate should be
avoided due to the risk of calcium carbonate precipitation.70
Besides the commonly used alkali Na2CO3, some novel alkalis
such as sodium tetraborate and sodium metaborate have also
been used. These alkalis form complexes with multivalent
cations instead of precipitation which can cause plugging in
carbonate rocks.79 Sodium metaborate can tolerate a salinity
equivalent to 6000 ppm Ca2+ and Mg2+,79 and it has been found
to be more efficient than sodium carbonate.79 Alkali is
consumed by reacting with the acid present in the oil, by ion
exchange with the clay, and by mixing in the formation water.
Alkali consumption is normally high in sandstone, while in
carbonate formations there is no significant consumption of
alkali.112
Salinity is another important factor affecting the retention of
surfactants. Anionic surfactants can precipitate in high-salinity
water due to the interaction between different ions and the
surfactant.114 Precipitation is severe in limestone reservoirs due
to the high concentration of Ca2+.114 In other cases, partial
solubility of the surfactant due to high salinity will increase the
adsorption of the surfactant. The increase in salinity can
increase the adsorption of surfactants on mineral surfaces due
to the decrease in the Debye screening length and the decrease
in the repulsion between adsorbed molecules.112 Adsorption of
ALFOTERRA 63 increases with increasing NaCl concen-
tration.109 Adsorption of anionic, betaine, and sulfobetaine
surfactants increases on limestone and sandstone with the
increase of divalent cations. Increasing the salinity increases the
charged sites on mineral surfaces, and the adsorption of anionic
surfactants will increase on negatively charged surfaces.49 The
presence of divalent cations can reduce the adsorption of
cationic surfactants on carbonates as divalent cations make a
carbonate surface more positive.81,115
The acid number of oil is another important parameter that
determines the retention of surfactants. Oil with a higher acid
number can decrease the retention of surfactants. The in situ
generation of surfactant will be higher in oil with a higher acid
number. The decrease in the adsorption from 0.25 to 0.05 mg/
(mg of rock) was observed when the acid number of the oil was
increased from 0 to 3 mg/KOH.68
Adsorption of surfactants may increase or decrease with
temperature depending on the adsorption density.112 Surfactant
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adsorption can be either enthalpy-driven or entropy-driven.
Both the enthalpy and entropy of the system decrease with
increasing temperature. In the case of enthalpy-driven
adsorption (surfactants with low adsorption density) increasing
the temperature will increase the adsorption density. However,
in the case of entropy-driven adsorption (surfactants with high
adsorption density) increasing the temperature will decrease
the adsorption density.112 Adsorption of ALFOTERRA 63
increases with increasing temperature.109
Sacrificial agents are also used to decrease the adsorption of
surfactants. Sacrificial agents are low-cost surfactants that have a
higher competitive adsorption. Daoshan et al. used the
biosurfactant rhamnolipid-fermentation liquor (RH) to de-
crease the adsorption of alkyl benzenesulfonate (ORS) on
sandstone.116 The cost of RH is only 15% of that of ORS, and
using RH decreases ORS adsorption by 50%, resulting in an
overall reduction in the cost of the ASP system to 30%.116 It
has been shown that the presence of polyacrylate reduces the
adsorption of anionic surfactants on dolomite above a critical
molecular weight,117 indicating competitive adsorption between
the polymer and the surfactant. The flushing sequence is also
important in controlling the extent of adsorption of the
surfactant. When the sacrificial agent and the surfactant are
mixed together, adsorption of the surfactant is higher than
when the sacrificial agent is used as a preflush.116
5. MICROEMULSION AND PHASE BEHAVIOR
Phase behavior experiments are helpful in understanding the
performance of different chemicals and the interactive behavior
of brine, surfactants, and crude oil.118,119 Phase behavior
experiments can be a very useful tool for screening many
surfactant systems. In phase behavior experiments, phase
volume ratios of an oil/water mixture in the presence of
surfactants are determined. Surfactants form micelles in either
the oleic phase or in the aqueous phase depending upon the
hydrophobicity of the surfactant and the salt concentration.
These micelles solubilize some of the excesses of the oleic or
the aqueous phase to generate a microemulsion, which is an
isotropic, transparent or translucent, and thermodynamically
stable dispersion of water or brine, surfactant, and oil.10
Microemulsions can recover residual oil efficiently from
sandstone and carbonate reservoirs due to their low interfacial
tension.120−122 Many authors have reported the principle of
microemulsion phase behavior and its relationship with
IFT.123−126 Winsor123 classified microemulsions as Type I
(oil in water), Type II (water in oil), and Type III (middle
phase). In Type I microemulsions, the surfactants form micelles
in the aqueous phase and solubilize some of the excess oil in the
cores. In Type II microemulsions, the surfactant forms micelles
in the oleic phase and solubilizes some of the aqueous phase in
the cores. In Type III microemulsions, the oleic and aqueous
phases make a bicontinuous network.127 The microemulsion
phase can be changed from Type I to Type II by tuning the
salinity at constant temperature and pressure.128,129 An
emulsion with a low viscosity and without any gel is required
to get low IFT values.130 It has been shown that IFT is the
lowest when the surfactant has a similar affinity for oleic and
aqueous phases.131,132
In phase behavior experiments the volume of the aqueous
phase, oil phase, and the microemulsion, determined using a
graduated pipet, is used to calculate water and oil solubilization
ratios, which can then be related to IFT.133 Optimum salinity,
oil solubilization ratio, water solubilization ratio, and the
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optimum solubilization ratio are important terms used in the
phase behavior experiments. Optimum salinity is defined as the
salinity where an equal volume of water and oil is solubilized in
a Type III microemulsion. Oil solubilization ratio is defined as
the ratio of the volume of oil solubilized (Vo) to the volume of
the surfactant (Vs). Similarly, water solubilization ratio is
defined as the ratio of the volume of water solubilized (Vw) to
the volume of the surfactant. Optimum solubilization ratio (σ)
is the value of the solubilization ratio at the intersection of the
curves of oil and water solubilization ratios plotted against
salinity. Salinity corresponding to the intersection point gives
the optimum salinity.62 IFT is inversely related to σ by eq 1;
C However, WOR is significant only if the acid number of oil is
γ=
σ2 (1)
where C is constant for a typical crude oil system and its value
is approximately 0.3 dyn/cm.62 The optimum solubilization
ratio should be higher than 10 to achieve a low IFT. Phase
behavior experiments are also useful to determine the
equilibration time and the quality of a microemulsion. Longer
equilibration times are due to high microemulsion viscosity, the
formation of a gel, and liquid crystal structure.71 These viscous
structures can reduce the oil recovery due to high surfactant
retention.
5.1. Factors Affecting Phase Behavior. Several factors
affect the phase behavior of the oil−water system in the
presence of surfactant. Important factors included but not
limited to are the molecular structure of surfactant, the PO/EO
group, the ionic nature of the surfactant, cosolvent,
cosurfactant, salinity, temperature, the nature of the oil,
water−oil ratio, and the nature of the alkali. This section will
highlight the details of these factors on phase behavior.
Surfactant structure is one of the most important properties
which determine phase behavior. For example, two samples of
an internal olefin sulfonate, which were sulfonated at different
temperatures and with different SO3/alkene ratios, were
compared. The surfactant which was sulfonated at a high
temperature and possessing a high SO3/alkene ratio has a
higher optimum salinity as compared to the surfactant which
was sulfonated at low temperature and possessing a lower SO3/
alkene ratio.61 IOS with greater branching have a higher
optimum salinity compared to IOS with lesser branching, most
likely due to higher branching increasing the solubility and,
thus, increasing the optimum salinity. Branching and bulky
groups in the hydrophobic part reduce the equilibration time
due to the generation of microemulsions of low viscosity and
the prevention of developing viscous and liquid crystal
structures.71 Increasing the carbon chain number of IOS
makes it difficult to solubilize the surfactant in saline water.61
When the carbon chain number of IOS was increased from
C15−C18 to C20−C24, the optimum salinity decreased from 13%
to 4% due to the increase of the hydrophobicity of the
surfactant. Meanwhile, the solubilization parameter increased
from 7 to around 19.61 The numbers of the PO groups of alkyl
alcohol propoxylated sulfate surfactants also affect their
solubilization. For solutions prepared in deionized water,
increasing the number of PO groups causes more water to be
solubilized.109 The addition of more PO groups will increase
the oil solubilization ratio while the optimum salinity will
decrease.71 The alkyl chain of the surfactant is another
parameter which can affect the surfactant phase behavior.
When all other conditions are the same, ALFOTERRA 2n
(C12) did not solubilize all the water and more oil solubilization
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was observed, while ALFOTERRA 3n (C14) solubilized all the
water.109
As the alkane number increases, the optimum salinity
increases while the solubilization parameters decrease for
IOS.61 This was also observed for docusate sodium and the
single-tail anionic surfactant sodium dodecyl benzenesulfonate
and a mixture of these surfactants.134 The addition of ethoxy
(EO) groups will increase the optimum salinity.71
Water/oil ratio (WOR) is another important parameter
which can affect the phase behavior. Changing the WOR will
form soap in situ in the presence of alkali. Increasing the WOR
will decrease soap formation and decrease the optimum salinity.
very high.134
Salts affect the phase behavior of various surfactant
formulations. When solutions were prepared in deionized
water, ALFOTERRA alkyl alcohol propoxylated sulfate
surfactants solubilized all the oil. On the other hand all the
water was solubilized when surfactant solutions were prepared
in 2 wt % NaCl.109 Middle-phase microemulsions are normally
not observed without salts.129
Varying results have been reported in the literature on the
effect of temperature on the phase behavior, optimum salinity,
and the solubilization ratio. For example, for docusate sodium
and single-tail anionic surfactant sodium dodecyl benzenesul-
fonate, it has been reported that the increase in temperature
increases the optimum salinity from 1.5 to 5.5% when the
temperature was increased from 20 to 90 °C.134 On the other
hand, increasing the temperature from 84 to 96 °C for IOS has
no effect on the optimum salinity, but a decrease in the
solubilization parameter was observed. However, an increase in
temperature to 150 °C causes a decrease in the optimum
salinity, which is one of the few cases where results obtained at
high temperatures have been reported, most likely due to the
effect on the optimum salinity. In most other cases results
reported have been obtained at temperatures not much higher
than the ambient.61
Alkali type can also affect the phase behavior and increasing
the alkali concentration increases the optimum salinity to a
critical concentration. Above the critical concentration,
optimum salinity decreases with increasing alkali concentration.
Under the same conditions, sodium metasilicate has the highest
optimum salinity at room temperature, followed by sodium
metaborate and sodium carbonate. The effect of temperature
on the optimum salinity is higher in the presence of Na2CO3 as
compared to sodium metasilicate.134
Cosolvents are added to prevent the formation of a viscous
gel and liquid crystal structures. The nature of the cosolvent
can affect the optimum salinity differently; a hydrophilic
cosolvent, when used with an anionic surfactant, increases the
optimum salinity, while a lipophilic cosolvent reduces the
optimum salinity.135 Similarly, a short-chain cosolvent, such as
propanol, increases the optimum salinity, while a long-chain
cosolvent decreases the optimum salinity.136 Cosolvents can
decrease the equilibration time and the solubilization ratio,
which has been verified for most of the surfactants systems.62
The decrease in the solubilization ratio at the optimum
concentration indicates an increase in IFT. Because the
addition of cosolvent increases the cost of ASP or SP flooding,
only the minimum amount required to obtain a clear solution
should be used.62 Several strategies have been proposed as an
alternative to the use of a cosolvent including the following: use
of a surfactant with branching in the hydrophobic chain, adding
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an ethoxylated/propoxylated group, and using a mixture of
surfactants with different chain lengths to match the
components of the crude oil.137,138
Chelating agents can be used to prevent the precipitation of
surfactants in hard brine due to the action of divalent cations.
As the chelating agents form complexes with divalent cations
they remain in solution without precipitating the surfactants.
5.2. Characterization Methods. Although the phase
behavior experiments are typically conducted by measuring
the volume of different phases with graduated tubes, the use of
advanced techniques has been reported. Morvan et al.
introduced the Matlab image processing tool box to measure
the volume of microemulsions in the aqueous and oleic phases.
A four-step method was used to process the digital images of
vials containing the oil/water mixture. Then a separation
algorithm was applied to the processed images to determine the
relative amount of each phase.73 The particle size distribution
of microemulsions can be determined using a laser diffraction
method.10 While most of the reported phase behavior test
methods are for low reservoir temperatures, Shell laboratories
have fabricated the tubes required for phase behavior studies at
high temperature and high pressure (up to 11 bar). Phase
behavior tests at 150 °C have been conducted using specially
designed glass pressure tubes.61
6. INTERFACIAL TENSION
Surfactants can reduce the IFT in several ways, including
adsorbing at the oil/water interface or forming mixed
micelles.139 The general rule of thumb is that IFT should be
reduced to 0.001 mN/m in order to overcome the capillary
forces holding the oil in a reservoir.109 Reduction of IFT to
such a low value means an increase in the capillary number by
about 3 orders of magnitude. Although SP or ASP formulations
with ultralow IFT are expected to give the maximum oil
recovery, ultralow values do not necessarily guarantee the
highest oil recovery.48,140 Other factors can affect the recovery,
and there are reports of cases where the maximum oil recovery
is not from the composition with the lowest IFT,141,142
particularly in heterogeneous reservoirs. Even though ultralow
IFT can improve the displacement efficiency, it has a lower
effect on the sweep efficiency. On the other hand, a low IFT
value can improve the sweep efficiency due to the larger grain
size of the emulsion.142 Also, if the surfactant changes the
wettability to water-wet conditions, high IFT will give higher
recoveries. Under water-wet conditions, if IFT is low, the
recovery process will be gravity-driven, while if it is high (>1
mN/m), the process will be capillary-driven143
6.1. Factors Affecting Interfacial Tension. Most of the
surfactants showed dynamic IFT behavior between crude oil
and water. IFT decreases with time to a transient minimum
value and increases after achieving a transient minimum
value.40,144,145 Dynamic IFT can be used as a test to determine
whether the crude oil is free from surface-active species or not.
A change of IFT between crude oil and brine with time
indicates that there are surface-active species in the oil, which
diffuse slowly and result in a decrease in IFT with time. These
surface-active species may include emulsion breakers, scale
inhibitors, or rust inhibitors.112
6.1.1. Addition of Polymer. Varying results have been
reported on the effect of polymers on the minimum IFT value.
Hongyan et al.146 obtained similar IFT values with and without
a polymer and concluded that the addition of a polymer has no
effect on the ability of the surfactant to reduce IFT. Similar
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observations have been made by other groups for HPAM and
xanthan gum.147,148 However, Li et al.139 found that a polymer
can decrease the minimum IFT value and attributed it to the
decrease in the dissociation rate of surface-active species owing
to the high viscosity of the aqueous phase. Taylor and Nasr-El-
Din149 reported that the addition of a polymer reduces IFT
down to a specific concentration of the surfactant. If the
surfactant concentration is above this minimum concentration,
the IFT of the SP solution will be lower than that of the
surfactant solution alone. However, a polymer may increase the
time required to attain the minimum IFT value due to the
decrease in the diffusion rate of the surfactant to the oil−water
interface.146 Enhanced viscosity due to the addition of a
polymer increases the mass transfer resistance and decreases
the mass transfer rate at the interface.
6.1.2. Surfactant Concentration. IFT displays three types of
behavior in different concentration ranges. At low concen-
trations of the surfactant, IFT normally decreases with the
increasing surfactant concentration up to an optimum value. At
intermediate concentrations, a further increase in the surfactant
concentration above the optimum value increases the
IFT,116,150,151 and at high concentrations, IFT decreases
again. The dependence of IFT on the surfactant concentration
is due to the adsorption/desorption of the surfactant at the oil−
water interface and the formation of a stable emulsion. The
surfactant concentration at which the rate of adsorption and
desorption is equal will result in the minimum IFT. IFT
decreases with increasing surfactant concentration up to this
optimum surfactant concentration. Further increase in the
surfactant concentration above the optimum value increases the
IFT due to the high desorption rate of the surfactant from the
interface. Continued increase in the surfactant concentration
results in the formation of a stable emulsion, and IFT starts
decreasing again.152 The increase in the IFT at intermediate
concentrations of the surfactant is also due to the formation of
micelles. At low concentrations, the surfactant is in the
monomer form and a further increase of the concentration
reduces the IFT due to a large number of monomer units. The
maximum number of monomer units in solution will be at the
critical micelle concentration. As the concentration of the
monomer decreases due to the formation of micelles, IFT
increases above the cmc.152,153 Further increase in the
surfactant concentration results in the formation of a stable
emulsion, which decreases IFT again.152 This type of behavior
is not characteristic of all surfactants.
6.1.3. Molecular Structure of Surfactant. Since the
interfacial energy is higher for the CH2 group compared to
the CH3 group, the presence of more CH3 groups in the
outermost layer will result in a low interfacial tension.154,155
Surfactants with larger hydrophobes are more efficient in
lowering IFT as compared to the surfactants with shorter
hydrophobes.156 Although the number of PO groups has no
effect on the IFT for the ALFOTERRA 3n series at various
salinities,109,111 IFT decreases with increasing number of PO
groups for the ALFOTERRA 2n series109 and ALFOTERRA 6n
series.111 Even though more hydrophilic surfactants have higher
aqueous stability even under high-salinity conditions, the high
hydrophilicity reduces their ability to lower the IFT. Increasing
the hydrocarbon chain length makes surfactants more lip-
ophilic87 and favors their movement from the bulk aqueous
phase to the oil−water interface. Thus, increasing the
hydrophobic tail length lowers the IFT.
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6.1.4. Presence of Alkali. Alkalis react with the acidic
components of crude oil at the oil−water interface and generate
an in situ surfactant according to following reaction:139
HA + OH− ⇌ A− + H 2O
where HA is an organic acid and A− is the ionized acid. The
ratio of ionized to un-ionized acid is the main factor that
determines the IFT, and the concentration of the ionized
species depends on their adsorption and desorption rate at the
interface. If the rate of adsorption is high, the ionized species
accumulate at the interface resulting in the decrease in IFT.
However, if the rate of desorption of the active species is high
due to the large concentration gradient, then IFT increases.
Alkalis affect both the minimum IFT and the time required to
achieve the minimum IFT. Because it will take some time for
the acid at the interface to diffuse and react with the alkali, the
minimum IFT is normally achieved after a time lapse and it is a
dynamic process. The concentration of ionized acid at the
interface increases with time causing the reduction of the IFT.
The minimum IFT will be at the time when the ratio of ionized
acid to un-ionized acid is equal to 1.139,157 Because increasing
the concentration of the alkali increases the rate of diffusion
and reaction, the time required to reach the minimum IFT
decreases with increasing alkali concentration.139 However, an
opposite trend has been reported by Nasr-El-Din et al.158
Although increasing concentration of the alkali can reduce the
IFT, after a critical concentration IFT may in-
crease.98,111,139,158−160 This behavior has been observed for
alkyl aryl sulfonate, sodium lauryl ether sulfate, and
propoxylated sulfate surfactant, which is related to the
concentration of the ionized acid and pH at the interface.
The initial decrease in the IFT is due to the increase in the pH
and the concentration of ionized species at the interface. After a
critical value, the concentration of the ionized acid decreases
due to shifting of the equilibrium or due to the salting-out
effect.139 Tong et al. proposed another mechanism for the
increase of the IFT at higher alkaline concentration.161 They
proposed that the decrease in the ionic species at high alkali
concentration is due to the formation of micelles and the
compression of the electric double layer at high ionic strength.
6.1.5. Cosurfactant. In certain cases, the addition of a
cosurfactant helps achieve low IFT values, which depends on
the synergism between the two surfactants. An extensive
amount of literature on the impact of adding a cosurfactant on
the IFT is available.116,151,162,163 For example, the combination
of alkyl alcohol amide (cosurfactant) and naturally mixed
carboxylate (surfactant) gives a much lower IFT compared to
naturally mixed carboxylate alone.139 A similar synergism has
been reported for a biosurfactant and alkyl benzenesulfonate116
and other systems.151 The synergic effect depends on the
interactions between the surfactants and their interactions with
the aqueous and oleic phases. If the surfactant is lipophilic, then
the hydrophilic surfactant may be required to balance the
hydrophilic−lipophilic interactions.151 The ratio of the
surfactant to cosurfactant is also important. When the
interactions between the surfactants are not strong, equimolar
concentrations will give the minimum IFT.164 In another study,
it was reported that the combination of a non-ionic surfactant
(Tx-100) and an anionic surfactant (sodium dodecyl
benzenesulfonate) has lower IFT as compared to the IFT of
the anionic surfactant.146 This reduction in the IFT is attributed
to the aromatic groups present in the surfactant interacting with
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the aromatic hydrocarbons of crude oil to lower the interfacial
tension.
An optimum amount of alcohol can be used to obtain an
ultralow IFT. At low alcohol concentrations, the IFT decreases
with increasing alcohol concentration, but IFT increases after
reaching a minimum with further increase.165 This behavior is
attributed to the competitive adsorption of the alcohol and the
surfactant at the oil−water interface.
6.1.6. Salinity. Under high-salinity conditions, extremely
hydrophilic surfactants are required for aqueous stability.63
Surfactants with long carbon chains phase separate under high-
salinity conditions.63 Therefore, short-chain surfactants are
preferred in high-salinity conditions, but they have poor oil
solubilization.63 Salts can significantly change the interfacial
properties and can result in a change in IFT for various types of
surfactants. At low salt concentration, most of the surfactants
dissolve in the aqueous phase, while at high salt concentration
surfactants stay in the oleic phase. However, at the optimum
salinity, the surfactant dissolves equally in the oil and aqueous
phases resulting in the minimum IFT.164 For the Shengli crude
oil/naturally mixed carboxylate system, IFT decreases as the
divalent ion concentration is increased to 300 mg/dm3, but
further increase of the divalent ion concentration increases the
IFT.139 Similarly, for various ALFOTERRA surfactants, IFT
decreases dramatically to a minimum value when the NaCl
concentration is increased and a further increase in NaCl
concentration increases the IFT.109 Similar behavior has been
reported for other surfactant systems.166 Liu observed that IFT
increases in the presence of divalent cations, but the tests were
conducted only at a fixed divalent concentration.167 The
decrease in the IFT with the addition of salt can be attributed
to the decreased hydrophilicity of the surfactant and its
movement to the oil−water interface.87 However, adding more
salt will result in moving the surfactant from the oil−water
interface to the oleic phase resulting in an increase in IFT.
6.1.7. Temperature. Temperature affects the solubility of
surfactants in water and brine solution and changes the
interaction energy of the head and tail groups. The increase of
the temperature can increase the solubility of the hydrophobic
tail in the water and move the surfactant to the oil−water
interface resulting in a decrease in the IFT.87 IFT typically
increases with temperature for most of the reported surfactant
systems.144 For ALFOTERRA 35 series, a decrease of IFT
between n-decane and distilled water (DW) with temperature
has been reported.109 For various ether sulfonate surfactants, a
decrease in the IFT with temperature was observed up to a
certain temperature, and a further increase in the temperature
resulted in an increase of the IFT.40 The decrease of the IFT
with increasing temperature is due to the decrease in the
viscosity of the oil, which enhances the surfactant migration to
the interface.40 The effect of temperature on the IFT also
depends on the type of crude oil. Varying IFT−temperature
behavior was reported for standard, paraffinic, aromatic, and
naphthenic oils. For aromatic oil, IFT was constant up to 50 °C
and increased after 50 °C, while for naphthenic oil a decrease in
IFT with temperature was observed. Paraffinic oil showed
exactly the opposite IFT−temperature behavior to that of
aromatic oil.40
6.2. Measuring Techniques. IFT is measured using the
spinning drop technique, which is useful when the surfactant is
available in small quantities. This method is a non-equilibrium
measurement method, and results obtained may be influenced
by the time taken for the temperature to stabilize and the
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Figure 8. Mechanism of wettability alteration for cationic surfactants. Circles represent the cationic surfactant molecules, and squares represent the
anionic surface-active material present in the oil. Reprinted with permission from ref 210. Copyright 2000 Elsevier.

Figure 9. Mechanism of the formation of the bilayer with ethoxylated sulfonate. Ellipses represent the anionic surfactant, and squares represent the
carboxylate material present in the oil. Reprinted with permission from ref 210. Copyright 2000 Elsevier.

variability of the oil drop in different experiments.130 Other
methods include the pendant drop method51 and the duNouy
ring method.168
7. WETTABILITY ALTERATION
Oil reservoirs can be water-wet, mixed-wet, or oil-wet. Most of
the carbonate reservoirs are fractured, oil-wet, and mixed-wet in
nature.169−171 Wettability concept can be understood by
measuring the contact angle (θ) between the rock surface
and an oil droplet placed on it (contact angle is the angle of
macroscopic meniscus when extrapolated to zero thickness172).
If θ > 90°, the rock is more oil-wet, and if θ < 90°, the rock is
more water-wet. In the case of oil-wet rock, oil is retained by
the matrix rock due to capillarity and the oil flow is reduced due
to trapping of water globules as the nonwetting phase.170 In the
case of water-wet and mixed-wet carbonate reservoirs, injected
water imbibes into a matrix block and displaces the crude oil
(imbibition is defined as the process in which water is
displacing oil173). Fractures act as the transport zone for both
water and displaced oil. However, in the case of oil-wet
reservoirs, spontaneous imbibition of water cannot take place
and the injected water will move toward the production well
through the fractures168 (spontaneous imbibition is defined as
the imbibition that takes place by the action of capillary
pressure and/or buoyancy when the matrix block is surrounded
by formation brine173). Therefore, wettability is altered from
oil-wet to water-wet to recover additional oil.
Use of surfactants to change wettability is one of the
techniques adopted by many researchers to recover oil from oil-
wet fractured carbonate and sandstone reservoirs.174 Cationic,
7711
non-ionic, and ionic surfactants have been reported to alter the
wettability of initially oil-wet rock.
7.1. Wettability Alteration by Cationic Surfactants.
Organic components of crude oil containing negatively charged
groups are normally adsorbed on the positively charged mineral
surfaces of carbonates.175 Interactions occur between the
cationic surfactant monomer and the anionic material (mostly
carboxylate) adsorbed on the rock surfaces from crude oil. Due
to ion pair formation between the cationic monomer and
anionic groups, adsorbed material at the oil, water, and rock
interface will be desorbed from the rock. The ion pair is not
soluble in the aqueous phase but soluble in the oleic phase.
Thus, water will penetrate and oil will be expelled from the core
material. When the adsorbed material is desorbed from the
surface, it becomes more water-wet and oil can be expelled.168
The mechanism of wettability alteration by cationic surfactants
is shown in Figure 8. Standnes and Austad showed that cationic
surfactants can recover additional oil by spontaneous counter-
current imbibition from a chalk core.168,176
7.2. Wettability Alteration by Anionic Surfactants.
Anionic surfactants are not able to desorb negatively charged
groups of carboxylate from the rock surface. Anionic surfactants
generate weak capillary forces through hydrophobic interaction
between the tail of the surfactant and the negatively charged
adsorbed groups.168 Minor oil displacement by ethoxylated
sulfonates from carbonate cores is associated with the
formation of a water-wet bilayer between the carbonate surface
and oil. The mechanism of the formation of the bilayer is
shown in Figure 9. Alkyl propoxylated sulfates and alkyl aryl
sulfonate change the wettability of calcite from water-wet to oil-
wet.177,178
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Table 2. Reported Fields Where Surfactants Have Been Used in EOR Either As a Surfactant Flood or SP Flood
formation
country field type surfactant ref
USA Louden sulfonate 211, 212
213
Borregos sulfonate
Benton Sulfonate 214
Bradford field sulfonate 215
Cretaceous upper Edwards carbonate petrostep-B100 216
the cottonwood creek carbonate polyoxyethylene alcohol 217, 218
Bob slaughter block mixture of petroleum sulfonate and alkylaryl ether sulfate 219
Yates fields carbonate non-ionic ethoxy alcohol 217
Tanner sandstone ORS-41 220
Sho-vel-tum 221
Cambridge minnelusa sandstone 222
China Daging sandstone petroleum sulfonate, lignosulfonate, alkyl benzenesulfonate, petroleum carboxylate, 223−227
biosurfactant
Gudong sandstone 228
Karamay sandstone petroleum sulfonate 229, 230
Xing long tai sandstone 231
India Viraj sandstone petroleum sulfonate 232
West kiehl sandstone petrostep B-100 233
Indonesia Minas sandstone petroleum sulfonate 234
Baturaja carbonates 235
Argentina Chihuido de la sierra negra SS-6066 236
Germany Bramberge sandstone olefin sulfonate 237

Wettability can be measured by calculating the Amott−
Harvey index of a core before and after spontaneous
imbibition,168,179 and the contact angle measurement of a
water droplet placed on the planar surface before and after
exposure to the surfactant solution. Wettability alteration
depends on the aging time, surfactant type, concentration,
temperature, crude oil composition, brine composition, nature
of the rock, and water saturation.173,180 The increase of the
temperature changes the solubility of adsorbed components,
leading to desorption from the matrix rock, making it more
water-wet.181−183 A decrease in the contact angle with
temperature was observed, which confirms the formation of a
more water-wet state.183
8. FIELD APPLICATIONS AND FUTURE CHALLENGES
OF SURFACTANT EOR
8.1. Comparison of Field and Laboratory Data. Some
important surfactants that have been reported for EOR
applications in different oil fields are listed in Table 2. Data
indicate that surfactant flooding has been utilized in a number
of oil fields around the world. Most of these oil reservoirs are
sandstone reservoirs, and sulfonate surfactants are the most
widely used surfactant. Field applications on chemical EOR
show incremental oil recovery of ∼12−30% of the original oil
in place.184 However, most of the laboratory reports are
showing 20−30% incremental oil recovery.20
8.2. Economic Overview of Surfactant−Polymer
Flooding. No recent updates on the cost of chemical EOR
are available in the literature especially at current oil prices that
are in the range of $50/bbl. However, the costs of polymers and
surfactants are dropping, and their consumption is low. An
incremental barrel of oil is produced by ∼1−2 lbs of polymer,
which costs about $1.5/lb. With current oil prices in the range
of $50/bbl chemical EOR is still economical.184
8.3. Challenges and Future Alternate. Challenges for
surfactant flooding are in the high-temperature, high-salinity,
fractured carbonate reservoirs. From the foregoing discussion, it
7712
is evident that for mild conditions (low temperature, low
salinity) most of the surfactant formulations perform very well.
In the case of high-temperature and low-salinity conditions,
sulfonate surfactants can do the job. However, in high-
temperature and high-salinity sandstone and carbonate
reservoirs, many problems arise including the surfactant
precipitation, high adsorption of surfactants, and chemical
degradation. Many attempts have been made to develop
surfactants that can tolerate a high-temperature, high-salinity
environment. A recent trend in surfactant EOR is the use of a
chelating agent or a sequestration agent together with the
surfactant in high-salinity environments to sequester divalent
cations.185 Some commonly used chelating agents are ethyl-
enediaminetetraacetic acid (EDTA), tetrasodium EDTA, and
sodium acetate.186,187 Recently acrylic acid has been used in a
high-salinity environment to avoid precipitation.57 The acrylic
acid reacts with sodium ions and forms the precipitation
inhibitor sodium acrylate, which reacts with mineral divalent
ions and prevents the formation of precipitates.188 Alkalis are
used to lower the adsorption on mineral surfaces in soft brines.
In the case of hard brines, conventional alkalis precipitate and
there is a risk of maintaining the reservoir integrity. Novel
alkalis such as sodium metaborate are recommended for hard
brines.189,190 However, a complementary evaluation has shown
that high pH generated by the addition of alkali will eventually
lead to the reaction of calcium ions with dissolved carbonate
ions and result in precipitation.191 The alternative solution to
prevent precipitation is the use of a chelating agent that makes
the economics of the process questionable.192 Proprietary
adsorption inhibitors have also been proposed as an alternative
to alkalis.191
The combination of other chemicals such as polymers and
alkalis is not a new idea. It has been used in the field and
laboratories for decades to achieve better mobility and oil
recovery. Now the synergetic effect of the surfactant and
chemicals other than alkalis and polymers has received
attention. In addition, the focus is on the combined injection
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Energy & Fuels
of the surfactant and gas to generate foam as a mobility control
agent.
Recently, encouraging results were obtained in using
nanoparticles in EOR applications. Nanoparticles such as
polysilicon, iron oxide, and silica nanoparticles have been
reported to alter the wettability, to stabilize oil-in-water and
water-in-oil emulsions, to stabilize CO2 foam, to reduce the IFT
between oil and water, and finally, to increase oil
recovery.193−201 Based on these results, attempts were made
to investigate combined effects of the surfactant and nano-
particles.202−204 A surfactant solution with nanoparticles has a
lower IFT compared to the surfactant solution without
nanoparticles. Adsorption of the surfactant also decreases in
the presence of nanoparticles. Moreover, oil recovery is better
as compared to the surfactant alone. Similarly using nonferrous
metal particles with an anionic surfactant resulted in higher oil
recovery and lower surface tension.205 Other nanoparticles
which are investigated in nanoparticles−surfactant systems are
alumina, zirconia, and silica.203,206,207 Oil recovery efficiency is
higher for slightly hydrophobic nanoparticles as compared to
hydrophilic nanoparticles. Zirconia particles also increase the
viscosity of the surfactant solution and change the flow
characteristics from Newtonian to non-Newtonian.203 Surfac-
tant alternating gas (SAG) injection is now being used in
heterogeneous formations to prevent early breakthrough due to
overriding and fingering.208 The generated foam increases the
viscosity of the gas, and better mobility control is obtained
using SAG injection.
9. CONCLUDING REMARKS
A range of surfactant systems is reviewed for EOR applications.
Mainly these surfactants are sulfonates, sulfates, carboxylates,
cationic surfactants, non-ionic surfactants, and amphoteric
surfactants. Some special classes of surfactants including
Gemini surfactants, surfactants based on Guerbet alcohol,
fluorinated surfactants, and viscoelastic surfactants are also
discussed. Phase behavior, interfacial tension, adsorption,
wettability alteration, and field applications are discussed as
well. Reservoir conditions such as the temperature, salinity,
type of rock, charges on rock, pH, and heterogeneity are main
parameters that should be considered before the selection of a
surfactant. Surfactants for EOR applications are screened using
a series of evaluation criteria based on the compatibility, phase
behavior, thermal stability, interfacial tension measurement,
adsorption, and core flooding. Field studies show that most of
the surfactant flooding has been conducted in low-temperature
and low-salinity sandstone reservoirs, and sulfonate surfactants
are the most widely used surfactants in these applications.
However, sulfonate surfactants do not tolerate high salinity and
hard brines, and most of the remaining oil is in high-
temperature and high-salinity carbonate reservoirs. To extend
surfactant flooding to high-temperature and high-salinity
reservoirs, work on different strategies is underway. For
carbonate reservoirs, amphoteric surfactants can be a better
option due to good thermal stability and aqueous stability.
Polymeric surfactants are a possible alternative to surfactant−
polymer and alkali-surfactant−polymer flooding.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: ihussein@qu.edu.qa.
7713
Review
ORCID
Muhammad Shahzad Kamal: 0000-0003-2359-836X
Ibnelwaleed A. Hussein: 0000-0002-6672-8649
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research is supported by Saudi Aramco through Project
No. CPM 2297. We thank the Center for Integrative Petroleum
Research, King Fahd University of Petroleum & Minerals
(KFUPM) for supporting this research.
■
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