Review

Cite This: Energy Fuels 2020, 34, 31−54 pubs.acs.org/EF

A Review on Wettability Alteration in Carbonate Rocks: Wettability

Modifiers
Xiao Deng,† Muhammad Shahzad Kamal,*,‡ Shirish Patil,† Syed Muhammad Shakil Hussain,‡
and Xianmin Zhou‡
†
Department of Petroleum Engineering, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia
‡
Center for Integrative Petroleum Research, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia

ABSTRACT: More than half of the global oil reserves are in carbonate reservoirs. Carbonate rocks, however, in most cases
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tend to be mixed-wet or oil-wet. Wettability alteration of carbonate reservoir rock has been proven to increase oil recovery
significantly. Several chemicals have shown their effect on wettability; however, selection of an appropriate wettability modifier
should be made on the basis of the underlying mechanisms and their behavior at reservoir conditions. This review discusses
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techniques that can help in assessing wettability alteration or reflect on the underlying mechanism and describes several
categories of wettability modifiers focusing on their structure−property relationship and factors affecting their performance at
reservoir conditions. Surfactants, nanoparticles, salts, and alkalis are four major categories of wettability modifiers that are
discussed in this review. Among surfactants, gemini surfactants have great potential and could be a major focus of future
research in this area. Nanoparticles are relatively novel materials for wettability alteration with the capability to reduce contact
angle significantly at low cost. This review also identifies the current and future challenges related to the performance of various
wettability modifiers at high-temperature and high-salinity conditions.

1. INTRODUCTION onto the rock surface, forming a monolayer lipophilic structure

More than half of the world’s proven hydrocarbon reserves are that renders carbonate rock oil-wetness.11,12
Among all organics that render carbonate rock water-
in carbonate reservoirs. Most carbonate formations are mixed-
wetness, fatty acids and carboxylate anions have proven to be
wet to oil-wet. Oil in the matrix is retained by capillary forces.
the most important.13,16−18 Carbonate rock tends to have a
Besides, carbonate formations are more likely to be fractured
positively charged surface under common formation pH
compared to sandstone formations. These fractures make it values. Negative ions from formation fluid are adsorbed onto
difficult to apply a large pressure gradient through the matrix to calcite surface, in which fatty acids and carboxylate polymers
overcome the capillary forces.1 As a result, a large portion of are believed to be the dominating components.17 Experimental
original oil in place (OOIP) may be left behind after water studies have shown that those components have a high affinity
flooding.2,3 Different enhanced oil recovery (EOR) methods toward carbonate and that their adsorption tends to be a very
have been studied and applied to increase oil production, fast process,19,20 which is irreversible.11,12,21 Thomas et al.
especially when oil prices increase rapidly (Figure 1a). A study attributed this irreversible adsorption to a combined effect of
done by Alvarado and Manrique analyzed 1507 international the increased affinity toward carbonate brought by carboxylate
EOR projects and found that much more EOR applications groups and the additional stability provided by a long, straight
have been done in sandstone rather than in carbonate, as is chain of fatty acids.12 The experiments undertaken by Wu et al.
shown in Figure 1b.4 Considering the proven reserves in have shown that within these naphthenic acids, an increase of
different lithology, the application of EOR methods has great alkyl chain length reduces their adsorption but increases the
potential in carbonate reservoirs. ultimate oil-wetness.7 They concluded that the induced oil-
Many studies have shown that modifying wettability from wetness was not directly related to the adsorption of
oil-wet or intermediate-wet to water-wet can increase recovery naphthenic acids but depends on their molecular structure
significantly in carbonate reservoirs.6−9 Wettability alteration instead. Because the acid number (AN) of oil is closely related
has been recognized as one of the mechanisms that increase to the amount of fatty acids and carboxylate anions, it can be
recovery.10 Oil-wet state of the rock surfaces has proved to be used to estimate the degree of oil-wetness of aged chalk.22
induced by organic adsorption,11−14 which depends strongly Natural petroleum base is believed to form complexes with
on the conditions such as pH, salinity, and properties of the carboxylates in the oil and prevent them from covering the
oil.15 One of the most accepted explanations was given by rock surface.23 Generally, oil wetness increases with the
Buckley et al.14 They believed that there are four possible increase in AN.14,22 There is no direct relation between the
mechanisms that induce organic adsorption in carbonate rocks, amount of asphaltenes and rock wettability, although the
which include polar interactions, surface precipitation, acid/
base interactions, and ion binding.14 Under the combined Received: October 5, 2019
contribution of different mechanisms, the surface-active Revised: November 25, 2019
material moves from the oil−water interface and adsorbs Published: December 4, 2019

© 2019 American Chemical Society 31 DOI: 10.1021/acs.energyfuels.9b03409

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Figure 1. (a) EOR projects and enhanced production trend;5 (b) EOR field projects by lithology.4

asphaltene amount is usually related to AN.19 Researchers hold 2.1. Conventional Techniques. 2.1.1. Contact Angle
different opinions about the influence of temperature on the Measurement. There are plenty of ways to measure contact
wettability of aged carbonate. Thomas et al. suggested that angle, among which the most widely used one is the sessile
increased temperature could alleviate this oil-wetness induced drop method. In the sessile drop method, a drop of fluid settles
by the organic material coating because of enhanced aqueous on the surface of the substrate. A camera is used to capture the
solubility of organic adsorbates.11 Zhang and Austad, however, angle between the solid−liquid interface and the tangent to the
argued that the effect of temperature is minimal.22 liquid−vapor interface, which is considered as the contact
As wettability alteration keeps gaining attention, several angle.29 Rock wettability is assessed according to criteria based
reviews have been reported in the literature. Negin et al. on obtained contact angle values, as given in Table 1.
studied different kinds of nanoparticles and discussed their
effect on wettability.24 Purswani et al. studied the applications Table 1. Rock Wettability and Contact Angle30
and mechanisms of chemically tuned waterflooding, which
type contact angle (deg)
basically involves carefully controlled injection fluid salinity
and salt composition.25 Olayiwola et al. studied the wettability water-wet 0−80
alteration induced by nanoparticles with low salinity water and intermediate-wet 80−100
surfactant in both sandstone and carbonate rocks.26 oil-wet 100−160
Kazemzadeh et al. reported a comprehensive review on the strongly oil-wet 160−180
use of nanoparticles in EOR processes.27 Bartels et al.
conducted a review on low-salinity waterflooding, highlighting
the influence of different scales, in which wettability alteration
was discussed. Mohammed and Babadagli did a review on the 2.1.2. Amott−Harvey Test. Amott−Harvey test is com-
posed of two spontaneous imbibitions and two forced
wettability alteration materials and methods for both sandstone
displacement processes. Imbibition oil saturation, Soi; total
and carbonate.28 Validation was taken to select the best
oil saturation, Sot; imbibition water saturation, Swi; and total
material and method for extra recovery of bitumen and heavy-
water saturation, Swt, are obtained from displaced phase
oil from fractured strongly oil-wet carbonate reservoirs.
volume and total pore volume.31 The Amott−Harvey index
To date, there is no comprehensive review available in the
IAH, the wettability assessment, is defined in eq 1:
ij S yz ij S yz
literature on chemicals that induce wettability alteration

IAH = jjj wi zzz − jjj oi zzz

j Swt z j Sot z
specifically for carbonate rocks. This review focuses on

k { k {
carbonate reservoirs and studies the potential of wettability
modifiers in wettability alteration. Four main categories of (1)
wettability modifiers, including surfactants, nanoparticles, salts, On the basis of the index, rock wettability assessment can be
and alkalis, are discussed. Various techniques that have been made according to the criteria listed in Table 2.
used to evaluate the performance of wettability modifiers and 2.1.3. USBM. USBM goes through the same process as the
underlying mechanisms are also described in this review. This Amott−Harvey test. Its wettability index, IUSBM, is defined
review identifies potential cost-effective wettability modifiers upon two parameters: the area under the oil-drive curve, Ao,
for carbonate reservoirs. and the area under the water-drive curve, Aw.31

2. WETTABILITY MEASUREMENT TECHNIQUES Table 2. Rock Wettability and Amott−Harvey Index31

This section discusses commonly used wettability measure-
type Amott−Harvey index
ment techniques. The most widely used techniques, including
contact angle measurement, Amott test, and United States water-wet 0.3−1
Bureau of Mines (USBM) method, are described. Apart from mixed-wet −0.3−0.3
that, some novel techniques are also described. oil-wet −1∼-0.3

32 DOI: 10.1021/acs.energyfuels.9b03409
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ji A zy
IUSBM = logjjj o zzz
j Aw z
shown in Figure 3, there are a one-phase flotation test and a

k {
two-phase separation test. In the one-phase flotation test,
(2) wettability can be assessed by dividing the volume of the
The index value is mostly in the range of −2 to 2.32 Similarly, floating grains by the total volume.7 In the two-phase
rock wettability is assessed according to the index values given separation test, wettability can be assessed by dividing the
in Table 3. volume of grains in either phase by the total volume.
The advantage of the flotation test is its extreme
Table 3. Rock Wettability and USBM Index31 convenience. This test requires no core, plug, or smooth
surface and provides an overall description of the rock wetting
type USBM index state.
water-wet >0 2.2.3. NMR. Carbonate rock is very heterogeneous even on a
mixed-wet ∼0 small scale. Correlations that describe sandstone can hardly
oil-wet <0 apply to carbonate rock. It is especially helpful to have
information about liquid distribution inside the carbonate rock
2.2. Novel Techniques. Although conventional techniques matrix. Nuclear magnetic resonance (NMR) works by agitating
are the most widely used methods, they have shortcomings the hydrogen proton that is abundant in both water and oil and
that limit their application. Contact angle measurements are detecting their response to the magnetic fields. Their response
taken on the rock surface, while wettability on the rock surface shows the existence of hydrogen protons; in the petroleum
can be different from that inside the matrix.33 Amott test and engineering case, this is the existence of water and oil. On the
USBM both give a value that describes the overall wettability other hand, water has different relaxation time (T2) than oil.
of a rock sample. However, they fail to directly show the These two phases can be differentiated by their relaxation time,
wettability state on the pore scale. Besides, the Amott test has obtaining information about residual saturations. Compared to
limited accuracy at neutral wetting conditions.32 Some other fluid in bulk, fluid in contact with the rock surface has a shorter
techniques have been reported in the literature that can be relaxation time. For partially saturated pores, the relaxation rate
used to assess the wettability alteration qualitatively or of the nonwetting phase is dominated by fluid in bulk while
quantitatively. In addition, some commonly used techniques that of the wetting phase is dominated by the fluid on the
that can reflect the mechanisms behind wettability alteration surface. In this way, the obtained relaxation time information
are also mentioned in this section. can be translated into saturation and wettability index. There
2.2.1. Chromatographic Study. The chromatographic study are several different wettability indexes based on NMR. An
is a quantitative wettability test technique.32 This test is based example of those indexes is developed by Chen et al.35 This
on a chromatographic separation between SCN− and SO42− as technique provides a way to utilize NMR data for wettability
two tracers in chalk. Both tracers are water-soluble. The description and has been shown to correlate well with the
chromatographic separation takes place only in water-wet Amott−Harvey test result. It should be noted that this
areas, because SO42− has a high affinity toward chalk while technique is based on the assumption that the rock sample is
SCN− does not. The effluent will show a difference between neutral to water-wet.
the concentrations of the two tracers (see Figure 2), which is 2.2.4. Micro-CT. Micro-CT or X-ray computed micro-
tomography (μ-CT) is a visualization tool that can provide
pore-scale images of the rock plugs, like those shown in Figure
4.36 Direct assessment on pore-size distribution and the
locations of remaining phases, such as aqueous and oil phases,
can be obtained.36 Analysis of generated tomograms provides
information about phase residual and pore-scale contact angle
on rock grains. Based on that, the wettability assessment will be
obtained. Furthermore, the obtained images can also be
analyzed to provide a more realistic pore structure in numerical
models and micromodels.
2.2.5. SEM. Scanning electron microscopy (SEM) can
provide direct visualization of intergranular fluid distribution
in rock. SEM is applied for wettability evaluation from the core
to pore-scale.18 In addition, SEM is used to provide core to
pore-scale surface images of rock samples. Surface images
Figure 2. Typical effluent concentration plot result.32 before and after EOR treatment, as shown in Figure 5, can help
to prove the efficacy of that treatment and explain the
mechanism of wettability alteration. In a word, SEM is a
closely related to the water-wet area, Awett, in rock. Taking the qualitative method that detects wettability change and helps in
area of a completely water-wet core, Aheptane, as a reference, a the understanding of the mechanisms.
new wetting index, WIchromatographic, can be derived from the 2.2.6. Infrared Spectroscopy. Infrared (IR) spectra or
results according to eq 3. Fourier transform infrared (FTIR) spectra are used to
A wet determine components in a system based on their chemical
WIchromatographic = bonding, as given in Table 4. Different bonds give different
Aheptane (3)
wavenumber in the IR. By analyzing the distribution of peaks
2.2.2. Flotation Test. The flotation test is based on the over wavenumber and their corresponding height, as shown in
concept that lesser wetted particles are easier to float.7,34 As Figure 6, the components on sample surfaces and possible
33 DOI: 10.1021/acs.energyfuels.9b03409
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Figure 3. Typical flotation test (left) and separation test (right) results, (a) oil-wet and (b) water-wet in both cases.34

Table 4. Functional Adsorbate Groups and Corresponding

Adsorption Band39
adsorption
band (cm−1) functional group
3400−3100 stretching vibration of the phenol O−H bonds (the bands
(broad band) are broadened because of hydrogen bonding)
3300−2500 broad −OH stretching vibration when a hydrogen bond is
present, −OH associated (carboxylic acids)
3100 stretching vibration of C−H bonds of aromatic compound
3000−2800 stretching vibration of the alkyl C−H bonds (CH3 and
CH2)
2805−2780 N−CH3 (aliphatic amines), CH3 asym. stretching vibration
2975−2950 asym. C−H stretching vibration in R-CH3
2955−2920 asym. CH2 stretching vibration in −OCH2−
1800−1700 stretching of the carbonyl groups C=O bonds (COOH)
Figure 4. Example of a micro-CT image.37
1600 stretching of the C=C bonds of conjugated and aromatic
compounds
1500 bending vibration of the O−H bond
1450−1370 bending of the alkyl C−H bonds
mechanisms in surface wettability change can be identified.
The changes of peaks before and after EOR treatment indicate
the mechanism and efficacy of wettability alteration.38 This mechanism of wettability alteration and assess the improve-
technique is widely used in surfactant characterization and ment brought by the EOR method.
wettability alteration mechanism studies. 2.2.8. AFM. Atomic force microscopy (AFM) measures the
2.2.7. TGA. Thermogravimetric analysis (TGA) monitors force−distance between a tip and the surface tested. By
the mass change of a sample with increasing temperature.39 repeating the measurement until the whole surface of the
Based on the relative strength of different bonds between rock sample is covered, we can obtain the image of that surface, soft
surfaces and adsorbates, mass loss at different temperatures is or hard, dry or wet.40 The difference in force−distance can be
related to the mass of the adsorbed component. For example, translated into compositional changes on the rock surface and
in Figure 7, aged wet dolomite has its weight loss occur in a thus is closely related to wettability.40 For example, in Figure 8,
staged manner, indicating physical desorption (110−230 °C), panels c and d show smaller force−distances and smoother
decomposition of chemisorbed stearic acid (∼380 °C), and surface, indicating adsorption of surfactant.39 AFM is a
degradation of dolomite mineral (>600 °C). In this way, convenient technique in showing the changes on sample
adsorption type and amount on the rock surface can be surfaces; thus, it is commonly used to study the adsorption of
obtained. This analysis is commonly used to help explain the materials such as surfactants, nanoparticles, and organic

Figure 5. SEM images of surface modification before and after treatment.38

34 DOI: 10.1021/acs.energyfuels.9b03409
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among those three. However, it requires that the rock sample is

crushed into fine powder and has no extended cases in
reservoir temperature or other types of rocks other than chalk.
Two techniques provide pore-scale wettability information,
including micro-CT and micromodel. Because of the design of
the micromodel, it is often 2D thin models that are not as
representative as micro-CT results in 3D conditions. The
advantage of the micromodel is that it provides real-time flow
and residual information. Four techniques provide qualitative
results about wettability change, including SEM, infrared
analysis, TGA, and AFM. TGA is a destructive technique that
is less repeatable than the other three techniques. Besides, it
provides mass change information that supports surface
changes and indicates adsorption types behind these changes.
Figure 6. Example of an FTIR result.39 Infrared-based techniques are more precise in reflecting
different adsorption types. SEM and AFM give direct images
of the rock surface that clearly show surface change.

3. WETTABILITY MODIFIERS
Materials that can modify the wetting state of rock surfaces are
called wettability modifiers. Different modifiers will have
different properties and thus induce a different reaction in
the formation. Modifiers for a specific formation should be
carefully selected according to the nature of the formation
rock, oil properties, formation pH, temperature, and salinity.
There are four main categories of wettability modifiers in
carbonate rock, including surfactants, salts, alkalis, and
nanoparticles.
3.1. Surfactants. Surfactants are surface-active molecules
that have hydrophilic heads and lipophilic tails (Figure 9).
Based on different charges of the head, surfactants can be
Figure 7. Example of TGA result.39 divided into cationic, anionic, nonionic, and zwitterionic
surfactants.41

materials. It is commonly used to help reflect wettability

alteration mechanisms.
Among several techniques discussed, three techniques
provide wettability indexes that are convenient for comparison,
including chromatographic study, flotation test, and NMR.
The flotation test is the fastest and most convenient technique Figure 9. Schematic diagram of conventional surfactant.

Figure 8. Example of AFM surface images.39

35 DOI: 10.1021/acs.energyfuels.9b03409
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Gemini surfactants are relatively new and have more than significantly decreased CMC value.52 A longer carbon chain of
one head and tail linked by a spacer group (Figure 10). surfactant generally means more hydrophobicity,53 thus
smaller HLB, as well as larger Krafft temperature54 and lower
CP.55
The wettability alteration using surfactants depends on
several factors like contact time, surfactant concentration,
Figure 10. Schematic diagram of gemini surfactant.
salinity, pH, temperature, rock mineral, and oil composition.
Generally, the contact angle reduces with an increase in
Surfactants have long been used to lower the interfacial tension contact time, sharply at first and slowly afterward. The effect of
between the oil and brine phases in surfactant flooding, thus temperature on wettability change induced by surfactants can
improving oil recovery. Aside from that, they can also modify be mixed. First, increased temperatures may give rise to
rock wettability.42,43 It has also been suggested for applying surfactant stability problems. Second, temperature influences
into drilling fluid to reduce carbonate formation damage and surfactant adsorption. Third, the increased temperature can
keep reservoir rock water-wet.44 reduce the contact angle directly because of enhanced aqueous
There are four fundamental properties of surfactants: critical solubility of organic materials.11 Fourth, the temperature has a
micelle concentration (CMC), Krafft temperature, hydro- significant impact on interfacial tension (IFT). Last, temper-
philic−lipophilic balance (HLB), and cloud point (CP). ature influences the diffusion efficiency of surfactants. When
Critical micelle concentration is the concentration of surfactant
these parameters change, surfactant performance will undergo
above which micelles start to form at specific conditions.30
an apparent change. One of the common issues limiting the
CMC can be measured by surface tension versus concentration
application of surfactants is their poor performance under
of the surfactants45 (Figure 11) because an increase in
harsh conditions.
surfactant concentration above CMC will not bring major
changes in surface tension. The electrical conductivity test can Researchers are currently developing novel surfactants in
also be used to measure the CMC value.46 favor of better oil recovery. Many of them find new surfactants
The Krafft temperature is the minimum temperature at with with better performance that can modify the rock surface
the micelle can form.30 HLB is a value describing the degree of wettability significantly while improving interfacial perform-
hydrophilicity or lipophilicity. HLB equal to 1 means ance.33,34,56,57 Numerical simulation has now been widely used
completely hydrophobic; HLB around 40 means completely in the wettability study using surfactants. For example,
hydrophilic.30 Surfactants for oil displacement usually have simulation results show that, when surfactants alter the rock
HLB values within a range of 6−9.47 A proper HLB value wettability to a water-wet state, an increased IFT would be
ensures favored partitioning of surfactants between oil and favored for increased recovery, though oil recovery increases
aqueous phases that achieve optimal contact angle.48 with decreased contact angle irrespective of IFT. Simulation
Cloud point is also an important value of surfactants. Cloud results also showed that the contribution of wettability
point (CP) is the temperature at which the solid phase begins alteration could increase recovery,58 especially for low-
to form in the surfactant solution, thus resulting in the solution permeability reservoirs.59,60 There are also studies on the
having two phases.49 From its definition, a surfactant should be effect of surfactant molecular structure. For example,
reconsidered when reservoir temperature is higher than the regression results on anionic and nonionic surfactants show
cloud point. Although the cloud-point phenomenon can that larger hydrophobes are needed under high temperature or
sometimes be observed in other types of surfactant high oil EACN (equivalent alkane carbon number) con-
systems,50,51 it is generally more influential in nonionic ditions.61 A developed correlation related to optimal salinity
surfactants. with the number of EO and PO groups and hydrophobe size
CMC, Krafft temperature, HLB values, and CP are closely was given by Solairaj et al. based on the regression study.61
related to the surfactant structure. Experiments on cationic In general, surfactants have a long history of application in
surfactants from the CnTAB family reported by Kumar et al. enhanced oil recovery. Besides improving oil/water interfacial
reveal that more carbon atoms in the molecule lead to a tension, they can also alter rock toward water-wet conditions.

Figure 11. CMC measured by surface tension52 and electrical conductivity.46

36 DOI: 10.1021/acs.energyfuels.9b03409
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Table 5. Wettability Alteration of Cationic Surfactantsa

conc. water temp contact angle change before-after treatment oil
entry surfactant (wt %) rock type (°C) (deg) recovery % ref
1 C8TAB 4.0 chalk brine 40 NG 3 Standnes and Austad,
200020
2 C10TAB 2.5 chalk brine 40 NG 60 Standnes and Austad,
200020
3 C12TAB 0.13 chalk brine 40 NG 5 Standnes and Austad,
200020
4 C12TAB 0.2 chalk brine 40 NG 7 Standnes and Austad,
200020
5 C12TAB 0.4 chalk brine 40 NG 24 Standnes and Austad,
200020
6 C12TAB 1.0 chalk brine 40 NG 60 Standnes and Austad,
200020
7 C12TAB 1.0 chalk brine 70 NG 70 Standnes and Austad,
200020
8 C12TAB 5.0 chalk brine 40 NG 56 Standnes and Austad,
200020
9 C12TAB 5.0 chalk brine 70 NG 70 Standnes and Austad,
200020
10 C16TAB 1.0 chalk brine 40 NG 16 Standnes and Austad,
200020
11 Hyamine 0.2 chalk brine 40 NG 8 Standnes and Austad,
200020
12 ADMBACl 0.5 chalk brine 40 NG 8 Standnes and Austad,
200020
13 C12TAB 1.0 limestone FW, SW 50 NG 45 Ravari et al., 20112
14 Dodigen 0.5 limestone FW, SW 50 NG 55 Ravari et al., 20112
5462
15 DTAB 1 calcite FW 92 NG 72 Sharma and Mohanty,
201367
16 Arquad C-50 0.2 calcite FW 100 no change NG Sharma and Mohanty,
201367
17 Arquad T-50 0.2 calcite FW 100 no change NG Sharma and Mohanty,
201367
18 DTAB 1.0 carbonate brine 25 intermediate-wet-66 NG Seethepalli et al., 200768
19 C10TAB 0.4 limestone brine 25 NG 12 Wu et al., 20087
20 C12TAB 0.4 limestone brine 25 NG 48 Wu et al., 20087
21 C10TPPB 0.4 limestone brine 25 NG 62 Wu et al., 20087
22 C12TPPB 0.4 limestone brine 25 NG 52 Wu et al., 20087
a
Oil recovery data come from spontaneous imbibition experiments, which reflect wettability change in the rock matrix. Concentration values
without units are of the default unit (wt %). DW, deionized water; FW, formation water; SW, seawater; NG, not given.

To obtain optimal wettability change, the underground

environment and surfactant system itself should be carefully
examined.
In the following subsections, different types of surfactants
that have been used for wettability alteration are discussed.
3.1.1. Cationic Surfactant. Cationic surfactants are
surfactants with positively charged heads. The most commonly
used cationic surfactants in EOR are quaternary ammonium
salts.62 Table 5 shows typical cationic surfactants and their
corresponding effect on carbonate rock wettability. Cationic Figure 12. Wettability alteration mechanism of cationic surfactants.
surfactants have been proved to be more effective than anionic, Circles are surfactants, and squares are surface-active organic materials
nonionic, and zwitterionic surfactants in wettability modifica- in the oil.20
tion of carbonate surface2,39 by adsorbing onto rock sur-
face.39,52 They have the ability to modify oil-aged calcite
irreversible wettability modification on the carbonate sur-
toward a more water-wet state even in hard brines and high face.20,52,64,65
temperatures.3 As shown in Figure 12, they are believed to Generally, higher cationic surfactant concentrations lead to
form ion pairs with adsorbed carboxylate group (−COO−) on more water-wetness on treated rock samples. An increased
the rock surface.20 This ion pair is suggested to be stabilized by surfactant concentration significantly induced higher imbibi-
the electrostatic force and hydrophobic interactions.20 The tion recovery, which indicated more water-wetness (entries 4−
product will not dissolve in the aqueous phase. It will either be 6 in Table 5). However, entries 6 and 8 seem to give a curious
trapped in surfactant micelles or dissolved in the oil phase.63 comparison, where faster but reduced recovery is observed
This irreversible desorption of organic materials leads to with increased surfactant concentration. This recovery drop is
37 DOI: 10.1021/acs.energyfuels.9b03409
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Energy & Fuels Review

explained by noting that although the rock surface is changed There are results showing increased oil recovery in
to more water-wet by higher surfactant concentration, part of surfactant solution imbibition brought by increased temper-
the desorbed oil is trapped in an increased number of micelles ature, such as entries 6 and 7, and 8 and 9 in Table 5.
inside the aqueous phase, thus reducing oil phase recovery.20 However, these increases could be explained by reduced oil
Higher hydrophobicity makes cationic surfactants easier to viscosity or reduced IFT, not necessarily by improved
form ion pairs with adsorbed organic materials. However, wettability change brought by surfactants.
higher hydrophobicity reduces the CMC value of the The adsorption of cationic surfactants is very low because of
surfactant, resulting in the presence of a smaller amount of the abundance of Ca2+ ions in the aqueous phase that leads to
surfactant monomers, which will impair the desorption a positively charged surface.20 This adsorption can be further
efficiency.20 As a result, a cationic surfactant as a wettability reduced by increasing multivalent cations’ concentration.66 It is
modifier must have a molecular structure that gives proper found to be well described by the Langmuir and the Freundlich
HLB value. One way to increase its hydrophobicity is by isotherms.52
increasing the length of the carbon chain in the tail. The In summary, cationic surfactants are good wettability
experiments conducted by Standnes and Austad showed that modifiers for oil-wet carbonate rock because they can form
imbibition recovery increased and then decreased with an ion-pair connection between organic materials and desorb
increasing carbon chain length, indicating the existence of an them from the rock surface irreversibly. They can turn
optimal hydrophobicity level. Besides, functional groups inside carbonate rock into strongly water-wet and achieve high
a molecule will affect each other. In their experiments, recovery, especially under high temperatures. However,
surfactants with a methyl group bonded to a nitrogen atom attention should be paid to their stability under high-
had a larger influence on wettability than surfactants with a temperature and high-salinity conditions. Adsorption of
benzyl group bonded20 (Figure 13). cationic surfactants is relatively low in carbonate reservoirs
because of the presence of Ca2+ ions that can help to reduce
adsorption and alter rock surface charge.
3.1.2. Anionic Surfactant. Anionic surfactants have
negatively charged heads (Figure 14). Widely used anionic

Figure 14. Examples of anionic surfactants.

surfactants include alkylbenzenesulfonates, alpha-olefin sulfo-

nates, sulfates, ether sulfates, carboxylates, isethionates, and
phosphate surfactants.69 Table 6 shows typical anionic
surfactants and their corresponding effect on carbonate rock
wettability.
Generally speaking, anionic surfactants are less effective in
rendering carbonate rock water-wetness compared to other
types of surfactants.39 As shown in Figure 15, they are believed
to form a layer over the adsorbed organic layer by hydrophobic
interaction, forming a double-layer structure on the rock
surface.20 Because hydrophobic interaction is a relatively weak
connection, the desorption of carboxylates, and thus the
wettability alteration, induced by anionic surfactants is
probably completely reversible.20
There are results obtained by Alvarez et al. showing that
increased concentration leads to reduced contact angle
Figure 13. Illustration of methyl and benzyl groups in cationic between the anionic surfactant system and carbonate rock
surfactants. surface.70 There are also results obtained by Gupta and
Mohanty showing the existence of an optimal concentration at
Experiments show that an optimal salinity exists for cationic a given formation environment of anionic surfactant Alf-38 and
surfactants to have the smallest contact angle.52 Oppositely B27. 48 This difference may be induced by different
functioning mechanisms are proposed.52 Increased salinity concentration ranges (0.2−2 gpt and 0−0.6 wt %), different
leads to increased repulsive electrostatic forces that prevent the salinity values, or different kinds of anionic surfactants. Similar
aqueous phase from spreading. On the other hand, increased optimal concentration has not yet been observed in other types
salinity reduces the solubility of surface-active material in the of surfactants, and the mechanisms behind need further
aqueous phase. Because of oppositely directed mechanisms, investigation.
there exists an optimum salinity that strikes a balance and gives From the Alf surfactants series (entries 12, 14, 15, and 21−
the optimum wettability alteration effect. 23) listed in Table 6, it is clear that molecular structures also
38 DOI: 10.1021/acs.energyfuels.9b03409
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Table 6. Wettability Alteration of Anionic Surfactantsa

conc. water temp contact angle change before-after treatment oil
entry surfactant (wt %) rock type (°C) (deg) recovery % ref
1 S-150 0.5 chalk brine 40 NG 20 Standnes and Austad,
200020
2 B 1317 0.5 chalk brine 40 NG 10 Standnes and Austad,
200020
3 S-74 0.5 chalk brine 40 NG 6 Standnes and Austad,
200020
4 APES 1.0 chalk brine 40 NG 5 Standnes and Austad,
200020
5 Cropol 0.5 chalk brine 40 NG 1 Standnes and Austad,
200020
6 Akypo 0.5 chalk brine 40 NG 0.5 Standnes and Austad,
200020
7 Gafac 0.5 chalk brine 40 NG 0 Standnes and Austad,
200020
8 SDS 0.1 chalk brine 40 NG 0 Standnes and Austad,
200020
9 SDS 0.23 limestone brine NG NG Ahmadi et al., 201534
10 AV-70 0.1 calcite FW 100 oil-wet to intermediate-wet NG Sharma and Mohanty,
201367
11 AV-150 0.1 calcite FW 100 oil-wet to intermediate-wet NG Sharma and Mohanty,
201367
12 Alf 68 0.05 limestone brine 25 oil-wet-70 40 Gupta et al., 20099
13 DF 0.05 limestone brine 25 oil-wet-155 NG Gupta et al., 20099
14 Alf 38 0.05 limestone brine 25 oil-wet-32 60 Gupta et al., 20099
15 Alf 35 0.05 limestone brine 25 oil-wet-62 62 Gupta et al., 20099
16 B 27 0.05 limestone brine 25 oil-wet-133 NG Gupta et al., 20099
17 TX 0.3 limestone brine 25 oil-wet-127 NG Gupta et al., 20099
18 4-22 0.05 carbonate brine 25 intermediate-wet-140 NG Seethepalli et al., 200768
19 5-166 0.05 carbonate brine 25 intermediate-wet-87 NG Seethepalli et al., 200768
20 SS-6656 0.05 carbonate brine 25 intermediate-wet-68 NG Seethepalli et al., 200768
21 Alf 65 0.05 carbonate brine 25 intermediate-wet-67 NG Seethepalli et al., 200768
22 Alf 63 0.05 carbonate brine 25 intermediate-wet-84 NG Seethepalli et al., 200768
23 Alf 33 0.05 carbonate brine 25 intermediate-wet-95 NG Seethepalli et al., 200768
a
Oil recovery data come from spontaneous imbibition experiments, which reflect wettability change in the rock matrix. Concentration values
without units are of default unit (wt %). DW, deionized water; FW, formation water; SW, seawater; NG, not given.

alteration effect in carbonate.66 As a result, the presence of a

sequestration agent can improve the wettability modification
effect of anionic surfactants significantly with the presence of
multivalent cations.3 Experiments reported by Gupta and
Mohanty showed that there existed an optimal salinity for each
surfactant concentration because salinity influences surfactant
partitioning between oil and aqueous phases.48 They also
found that as salinity increased, the optimal surfactant
concentration decreased and the optimal contact angle
increased.8 Besides, the optimal salinity for the anionic
Figure 15. Wettability alteration mechanism of anionic surfactants. surfactant to have the best wettability alteration performance
Ellipses are surfactants, squares are organic materials.20
decreased or remained unchanged when temperature in-
creased.71 Optimal salinity has also been well-correlated with
have a significant influence on anionic surfactants’ perform- the natural soap/surfactant model ratio.72 The temperature
ance. It is found that increasing the number of EO groups can increase is observed to reduce the contact angle between the
increase the temperature tolerance of anionic surfactant9 and anionic surfactant system and carbonate rock surface.71
the extent of wettability alteration induced.20,48 Sulfate has
Compared to cationic surfactants, anionic surfactants have
better multivalent ion tolerance than sulfonates and is more
significantly higher adsorptions on carbonate rock.66 Adibhatla
widely used under low temperature.1 Under high temperature,
sulfonates become a better choice because they have better and Mohanty found the adsorption process of anionic
temperature tolerance than sulfate.9 surfactants to be dependent on pH, salinity, and temperature.
Anionic surfactants have the potential to modify carbonate As pH increases, adsorption decreases; as salinity decreases,
wettability to strongly water-wet only under low brine salinity, adsorption decreases. The addition of alkalis can reduce the
especially low divalent-ion concentration such as Mg2+ and adsorption of the studied anionic surfactant. The relationship
Ca2+.3 Multivalent cations can interact with anionic surfactant between adsorption and temperature change differs between
and cause possible precipitation, reducing its wettability enthalpy-driven and entropy-driven adsorption.73
39 DOI: 10.1021/acs.energyfuels.9b03409
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In summary, the application of anionic surfactants in For zwitterionic surfactants, it is observed that increased
carbonate reservoirs could be expensive. Besides, anionic concentration leads to reduced contact angles on carbonate
surfactants generally change the carbonate wetting state from rock surface.80 The molecular structure has an influence on the
strongly oil-wet to intermediate-wet conditions (refer to Table properties of zwitterionic surfactants. For example, saturated
6), because their wettability modification comes from a alkyl and unsaturated alkyl chain in the tail give different
reversible hydrophobic interaction with organic materials. properties to zwitterionic surfactants with the same head
However, with carefully designed molecular structures and groups.76 Generally, as the separation between different
some additives like alkalis, the wettability modification effect of charges in the head part increases, the CMC value of this
anionic surfactants can be as good as commonly used cationic surfactant increases as well.38,81
surfactant systems. For example, a surfactant system of guerbet Contact angle measurements after surfactant postflush and
alkoxy carboxylates with internal olefin sulfonates (IOS) as zwitterionic surfactant solution treatment show an increased
cosolvent showed good results in IFT reduction and wettability and then decreased contact angle value with increasing
alteration and obtained excellent oil recovery from an temperature, indicating a mixed influence of temperature on
extremely fractured HTHS carbonate reservoir.74 In the wettability alteration induced by zwitterionic surfactants.82 The
presence of Na2CO3, some anionic surfactants are also found adsorption of zwitterionic surfactants on carbonate rock
to be as good as the cationic surfactants in modifying surface is suggested by Alvarez et al. to be driven by
wettability.68 electrostatic and hydrophobic interactions as well as amicellar
3.1.3. Zwitterionic Surfactant. Zwitterionic surfactants are systems.83 It was observed to increase with increased surfactant
also called amphoteric surfactants. They have both positive and concentration.84 The adsorption of zwitterionic surfactants in
negative charges on their heads and remain electrically neutral seawater on limestone is found to follow a monolayer
(Figure 16). Ammonium and pyridinium ions are examples of Langmuir tendency.83 In the connate water system, however,
a doubled adsorption is observed.83 The difference is explained
by different concentrations of divalent ions (Ca2+ and Mg2+) in
different aqueous systems,83 indicating that brine composition
and salinity have an influence on zwitterionic surfactant
adsorption on carbonate rocks. In the connate water system,
adsorption decreases after the maximum value with increases
in surfactant concentration. Alvarez et al. attributed this
phenomenon to the transition of surfactants from micelles to
vesicles which had lower adsorption.83 Because most of the
zwitterionic surfactant adsorption is an exothermic process,
temperature increase leads to adsorption decrease.82,83
Figure 16. Examples of zwitterionic surfactants.76 In summary, zwitterionic surfactants are found to have
excellent tolerance toward high salinity and temper-
ature.41,45,76,85 They have relatively low adsorption on
positive parts, and the negative parts can be phosphate, carbonate rock, and the adsorption further reduces with
carbonate, sulfonate or sulfate.45 Because of their special increased temperature or salinity.83 Because of their special
structural properties, they are compatible with other structure, they are good cosurfactants with other surfactants
surfactants.75 Table 7 shows typical zwitterionic surfactants and contribute salinity and temperature tolerance to the
and their corresponding effect on carbonate rock wettability. system. Zwitterionic surfactants are also able to alter oil-wet
Because of their high cost, zwitterionic surfactants were less carbonate rock to water-wet. However, their application is
investigated in the past.41,77 Therefore, the mechanism of limited because of high cost.
wettability alteration is not well addressed as well. Some 3.1.4. Nonionic Surfactant. Nonionic surfactants do not
suggested that the wettability alteration process in carbonate have a charged hydrophilic head and do not ionize in the
rock induced by zwitterionic surfactants is rapid because of aqueous phase. The temperature has a significant influence on
amphoteric charges on the heads.78 A few experiments have nonionic surfactant solution stability. As was mentioned
shown that this type of surfactant can modify originally oil-wet before, the cloud point phenomenon is most observed in this
carbonate rock toward becoming strongly water-wet.77,79 type of surfactant. Figure 17 shows two examples of nonionic

Table 7. Wettability Alteration of Zwitterionic Surfactantsa

conc. water temp contact angle change before-after treatment oil
entry surfactant (wt %) rock type (°C) (deg) recovery % ref
1 HABSA 3000 ppm carbonate brine 25 150−76 NG Souraki et al., 201980
2 NX-2760 1000 mg/L carbonate FW 80 137−46 NG Ahsaei et al., 201979
3 NX-1510 1000 mg/L carbonate FW 80 137−37 NG Ahsaei et al., 201979
4 TR-880 1000 mg/L carbonate FW 80 137−57 NG Ahsaei et al., 201979
5 OCT-2 0.2 carbonate brine 75 155−67 NG Ahsaei et al., 201986
6 OCT-2 0.2 carbonate SW 75 NG 70 Ahsaei et al., 201986
7 OCT-3 0.2 carbonate brine 75 132−58 30 Ahsaei et al., 201986
8 OCT-3 0.2 carbonate SW 75 NG 26 Ahsaei et al., 201986

a
Oil recovery data come from spontaneous imbibition experiments, which reflect wettability change in the rock matrix. Concentration values
without units are of default unit (wt %). DW, deionized water; FW, formation water; SW, seawater; NG, not given.

40 DOI: 10.1021/acs.energyfuels.9b03409
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surfactants. Table 8 shows typical nonionic surfactants and

their corresponding effect on carbonate rock wettability.

Figure 17. Examples of nonionic surfactants. Figure 18. Procedure proposed for nonionic surfactant treatment.39

The mechanism of nonionic surfactant-induced wettability for nonionic surfactant properties. Wettability modification
change can be the formation of a bilayer structure between the induced by nonionic surfactants has been proven to depend
oil-wet rock and aqueous phase as was believed by Standnes et heavily on surfactant molecular structure. Higher hydro-
al. based on its reversible nature.65 Another mechanism phobicity of surfactant is found to lead to more water-wetness
hypothesis is the proposed “coating and sweeping” process after surfactant processing.87 Gupta et al. proposed a relation
of Das et al. In the beginning, there is an oil coat covering the between the number of EO groups (P) and the cloud point
rock surface. When the surfactant solution is introduced, the (CP) of nonionic surfactants:9
surfactant−water combination moves into micro defects of that P − Po
“coat” and sweeps it.87 According to the enhanced wettability = a + b(P − P o)
CP (4)
modification induced by nonionic surfactants with more EO
groups, Souayeh et al. suggested the formation of hydrogen where a, b, and Po are constants.
bonds between the EO group in the surfactant and carboxyl or Temperature is observed to have a positive effect on
hydroxyl group in oil components to be another mechanism reducing contact angle between nonionic surfactant solution
aside from the bilayer model mentioned previously.88 and carbonate rock surface.44,71,87 From Table 8, nonionic
However, experimental results from Sharma and Mohanty surfactants generally can only alter oil-wet carbonate to
show that increased EO groups lead to decreased water- intermediate-wet, except in the case when the temperature is
wetness of treated calcite samples.67 Those two opposite high (90 °C). Entries 2 and 3, 4 and 5, and 13 and 14 in Table
conclusions may be induced by different molecular structure 8 show the positive effect of temperature. The optimal salinity
and thus different HLB values of surfactants. Jarrahian et al. for the nonionic surfactants to have the best wettability
observed that the adsorption of surfactant reduced the zeta alteration performance is found to decrease or remain
potential of rock surface.39 They proposed a mechanism that unchanged when the temperature increases.71
adsorption of surfactant released stearic acid on the rock Adsorption of a nonionic surfactant can be described by
surface and changed the wettability, as shown in Figure 18. equilibrium adsorption models such as linear, Langmuir,89
An increased concentration of nonionic surfactants can lead Temkin, and Freundlich90 models. It can be significantly
to the reduction of contact angle to some extent. After that, no reduced by either preflushing or coinjecting polymer.91 It is
major wettability alteration is induced by surfactant addi- found to be influenced by the clay content in the carbonate as
tion.33,39 The molecular structure is also an important factor well. Generally, the greater the clay content, the more hydroxyl

Table 8. Wettability Alteration of Nonionic Surfactantsa

conc. temp contact angle change before−after oil
entry surfactant (wt %) rock type water type (°C) treatment (deg) recovery % ref
1 TDA 30EO <0.2 calcite FW 80 oil-wet to intermediate-wet NG Sharma and Mohanty,
201367
2 15S 0.1 limestone brine 25 oil-wet-145 NG Gupta et al., 20099
3 15S 0.1 limestone brine 90 oil-wet-20 50 Gupta et al., 20099
4 NP 0.1 limestone brine 25 oil-wet-118 NG Gupta et al., 20099
5 NP 0.1 limestone brine 90 oil-wet-75 NG Gupta et al., 20099
6 Tergitol 0.4 limestone brine 25 NG 12 Wu et al., 20087
15-S-3
7 Tergitol 0.4 limestone brine 25 NG 23 Wu et al., 20087
15-S-7
8 Tergitol1 0.4 limestone brine 25 NG 6 Wu et al., 20087
5-S-40
9 Igepal CO-530 0.4 limestone brine 25 NG 52 Wu et al., 20087
10 Neodol 25-7 0.4 limestone brine 25 NG 7 Wu et al., 20087
11 Triton X-100 1 carbonate brine 25 150−60 NG Amirpour et al., 201533
12 Cedar 2 carbonate brine 25 150−80 NG Amirpour et al., 201533
13 PEG 7% vol carbonate drilling 25 1−18 (oil) NG Amirpour et al., 201533
fluid
14 PEG 7% vol carbonate drilling 80 1−40 (oil) NG Kiani et al., 201844
fluid
15 EA 3500 ppm carbonate brine 25 133−107 NG Standnes et al., 200265

a
Oil recovery data come from spontaneous imbibition experiments, which reflect wettability change in the rock matrix. Concentration values
without units are of default unit (wt %). DW, deionized water; FW, formation water; SW, seawater; NG, not given.

41 DOI: 10.1021/acs.energyfuels.9b03409
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Figure 19. Gemini surfactants with a spacer located between the head (a) and between tail (b).

Figure 20. Examples of different spacers in gemini surfactants.

groups on the rock surface, and the greater the adsorption.92 tend to undergo more complex processes than micelle ⇋
The higher the surfactant concentration, the greater the monomers equilibria in conventional surfactants.95 Salt
adsorption of the nonionic surfactant.90 tolerance is found to increase as the carbon atom number in
In summary, commonly used nonionic surfactants are not the spacer increases.96 There exists an optimal spacer length
good wettability modifiers for oil-wet carbonate rocks because for lowest IFT.97 Depending on the charges on its heads,
of their poor stability and limited effect of wettability alteration gemini surfactants can also be classified as anionic, cationic,
under reservoir conditions. and zwitterionic gemini. The degree of asymmetry, which
3.1.5. Gemini Surfactant. Gemini surfactants have more describes how different the two parts on the sides of the spacer
than one headgroup and more than one tail linked by a are, also has a significant influence on the properties of gemini
spacer.69 The spacer can be located between heads or between surfactants.69
tails (Figure 19). There are different types of spacers (Figure Gemini surfactants have been proven to be effective in
20). For the same number of carbon atoms per hydrophilic changing an oil-wet surface to water-wet.98,99 In sandstone
head, gemini surfactants have much lower CMC93,94 and better formation, contact angle reduction of 140 to 40100 and 110 to
oil solubility93 than conventional surfactants. The most widely 1096 as well as higher imbibition recovery than conventional
studied gemini surfactants are usually referred to as m−s−m surfactants100,101 are observed. The extent of how much gemini
type, where m is the number of carbon atoms of the alkyl chain surfactants change carbonate rock wettability and the related
and s is the number of carbon atoms of the spacer.30 Most mechanisms are discussed in only a few papers. Qi et al.
studies on gemini surfactants focus on their IFT reduction observed contact angle results showing carbonate changing
potential and rheology. They are about 3 orders of magnitude from intermediate-wet to strongly water-wet after treatment by
more efficient in reducing IFT and more than 2 orders of gemini surfactants.102 Ghosh and Mohanty observed the
magnitude in forming micelles.95 wetting state of mineral calcite plates changed from oil-wet
To obtain the anticipated properties of gemini surfactants, to intermediate-wet by gemini cationic surfactants.103,104
the molecular structure has to be optimized by adjusting Because of these encouraging results and their outstanding
polarity and hydrophobicity. Polarity can be added by ester, properties compared to conventional surfactants, gemini
ether, amide, sulfide, and cyclodextrin groups. Hydrophobicity surfactants can be good wettability modifiers for oil-wet
can be added by some fluorine groups or introduced by a carbonate rocks. Adsorption of gemini surfactants is found to
dehydroabietylamine derivative.69 Their oil solubility (and be captured by the Langmuir model and is dependent on the
hence hydrophobicity) increases as hydrocarbon chain length condition and structure. Higher salinity, as well as longer alkyl
increases.93 However, according to the hypothesis proposed by chains and spacer groups, leads to higher adsorption.105
Menger and Littau, higher hydrophobicity does not ensure Further investigation of gemini surfactants on the wettability
lower CMC for gemini surfactants because of self-coiling.95 of carbonate rocks is needed. However, considering the
They also proposed that Gemini surfactants with long tails outstanding interfacial properties and micellization behavior,
42 DOI: 10.1021/acs.energyfuels.9b03409
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Table 9. Surfactant-Based Chemical EOR Field Applications in Carbonate Reservoirs114

entry field year chemicals used oil recovery ref
1 Wichita County Regular 1975 Surfactants: petroleum solfonates + alkyl ether sulfate; 22.0% OOIP Leonard, 1984126
Gunsight reservoir, Texas, Polymers: polyacrylamide
USA
2 Wesgum field, Arkansas, USA 1980 Surfactants: petroleum solfonates + alkyl ether sulfate; 26.7% OOIP Leonard, 1986127
Polymers: polyacrylamide
3 Bob Slaughter Block Lease, 1980 Surfactants: alkyl ether sulfates and Witco petroleum 12.0% OOIP Adams and Schievelbein,
Texas, USA sulfonate, alkyl aryl ether sulfates, synthetic sulfonate 1986128
4 Cambridge Minnelusa, 1993 Surfactant: Petrostep B-100; Alkali: Na2CO3; Polymer: 36.0% OOIP Vargo et al., 2000129
Wyoming, USA Alcoflood 1175A
5 Yates Field, Texas, USA 1998 Surfactants: nonionic ethoxy alcohol (Shell 91−8) and 15.0% OOIP Yang and Wadleigh,
anionic ethoxy sulfate (Stepan CS-460) 2000,130 Chen et al.,
2000115
6 Mauddud reservoir, Bahrain 1999 Surfactants: Not given; Alkali: Na2CO3 10−15% OOIP Zubari and Sivakumar,
2003131
7 Cottonwood Creek field, 1999 Surfactant: nonionic polyoxyethylene alcohol (POA) 10.4% OOIP Weiss et al., 2006116
Wyoming, USA
8 Semoga field, Indonesia 2009 Surfactants: nonionic surfactants 5800 bbl accumulated Rilian et al., 2008132
production over 3
months

as well as their performance in other types of surfaces, gemini other advantages including ease of preparation, environmental
surfactants can be very efficient wettability modifiers for friendliness, and low cost.111 Pal et al. proposed a nonionic
carbonate rocks. gemini surfactant derived from sunflower oil. They found that
3.1.6. Natural Surfactants. In the previous sections, the proposed surfactant had favorable salt and hardness
surfactants are categorized either by the charge(s) on the tolerance and good foaming performance, showing potential
headgroup(s) or by molecular structure. It is also common to for EOR purposes.112
categorize surfactants by their origins, namely, natural There are also studies on the wettability effect of natural
surfactants and synthesized surfactants. Strictly speaking, surfactants on carbonate rocks. In the study of a natural
natural surfactants are surfactants that can be obtained directly surfactant derived from roots of Glycyrrhiza glabra, Ahmad et
from natural origins including plants and animals by separation al. found the surfactant had intermediate wettability effect
processes such as extraction, precipitation, and distillation. which contributes to increased oil recovery.34 The study
Throughout the production, no organic synthesis should be reported by Standnes and Austad showed that a natural tertiary
involved. However, only a few surfactants, such as lecithin, ammonium surfactant derived from coconut palm was very
meet this strict requirement. A much more general definition is efficient in wettability alteration from completely oil-wet to
commonly used that a surfactant is considered as a natural more water-wet.57 A natural surfactant (cedar) showed strong
surfactant if one of its main building blocks, headgroup or tail, wettability alteration efficiency in the study done by Sofla et
is obtained from a natural source. In this review, the general al.113
definition is used.106 In summary, natural surfactants have advantages like lower
Compared to synthesized surfactants, natural surfactants can cost and higher environmental friendliness and have been
have advantages such as lower cost, less environmental impact, proposed as alternatives for synthesized surfactants in the EOR
and better local availability. Because of those advantages, process. They have been intensely studied in recent years.
natural surfactants have been an important topic recently. In Besides their potential in lowering IFT and forming foam and
2001, Holmberg presented a review on three types of natural emulsions, their influence on wettability also contributes to
surfactants, i.e., surfactants produced from bacteria and yeast, increased oil recovery.
surfactants based on either sugar or an amino acid as a polar Among all kinds of surfactants, cationic surfactants are
headgroup, and surfactants based on either fatty acid or sterol relatively effective in wettability alteration of carbonate rock
as the hydrophobic tail. In his review, the origins, molecular while weak in reducing IFT. Anionic surfactants, however,
structures, and properties of these most popular types of show strong potential in reducing IFT, are weak in wettability
natural surfactants were discussed. He concluded that the latter alteration, and endure high surfactant retention in the
two types of natural surfactants showed great promise.106 carbonate reservoir. Zwitterionic surfactants have good
Torres et al. compared the solution surface tension between a performance, but their application is limited by their high
group of synthesized surfactants and three nonionic natural cost. Nonionic surfactants tend to have moderate wettability
surfactants: guar gum, locust bean gum, and rhamnolipid.107 alteration. Some encouraging experimental results have shown
They concluded that the tested natural surfactants gave the potential of natural surfactants in wettability modification.
promising results for the EOR process, especially rhamnolipid. The type of surfactant with the most potential as a wettability
Ahmad and Shadizadeh studied the adsorption of a natural modifier is the gemini surfactant. Gemini surfactants can reach
surfactant derived from the leaves of a plant called Zyziphus ultralow IFT and have very low adsorption in carbonate
spina-christi on carbonate108 and shale-sandstone109 and the reservoirs. Although further study on their wettability effect on
influence of nano silica.110 Ahmad et al. proposed a new carbonate rock is needed, their performance in sandstone and
natural surfactant prepared by simply milling the leaves of other types of surfaces implies their successful application in
mulberry trees down to microsize and mixing those micro- carbonate rock.
particles with distilled water. They found this new surfactant to 3.1.7. Field Applications and Economic Evaluation.
be efficient in lowering IFT between oil and water aside from Research interest over surfactant-based chemical EOR has
43 DOI: 10.1021/acs.energyfuels.9b03409
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Energy & Fuels Review

grown very rapidly because many existing reservoirs have gone different types of surfactants, anionic surfactants are generally
into a mature phase while hydrocarbon demand keeps less expensive than cationic surfactants.122 Zwitterionic
increasing rapidly. A keyword search of “surfactant EOR” in surfactants are expensive compared with other types of
the Web of Science database shows a spike of publications surfactants.62 Economic evaluation is widely used to assess
from 15 articles in 2009 to 150 articles in 2019. The same the risk of the project and optimize the surfactant EOR
keyword search in Google Scholar shows a spike from 647 in technique for specific field conditions. The most important
2009 to 2380 in 2019. Surfactant-based EOR techniques have factors include the cost of surfactants, the cost of water
been considered as robust EOR techniques for field flooding, environmental impacts, formulations, oil price, and
application. Microemulsion generation as well as foam estimated incremental oil recovery. An evaluation was done in
generation and stabilization used to be the primary reason 1993 for dilute surfactant flooding which had been proven in
for surfactant application in EOR. Recently, the potential of the laboratory to recover 80−90% of the residual oil after
surfactants to modify rock wettability has also been recognized waterflooding at a low concentration (1%). A negative
as a contributor to incremental oil recovery.114 Conventional conclusion was obtained because of limitation of facilities,
techniques, including surfactant flooding, alkali−surfactant chemical volume requirements, and associated technical cost
flooding, and alkali−surfactant−polymer (ASP) flooding, per barrel. In that case, the chemical cost alone was about $20/
have been widely used in sandstone reservoirs and have also bbl.123 Alkaline flooding is characterized by low operational
attracted attention recently for their potential in carbonate costs. ASP is a cost-effective process.122 Reported ASP projects
reservoirs.114 A few field applications in the carbonate reservoir in the United States in 1988 and 1994 were all profitable.124 By
can be found in the literature, as shown in Table 9. numerical simulation, the cost per barrel incremental oil for
Among those field cases, wettability modification due to ASP application in Sabriyah Lower Burgan was obtained to be
surfactant contributed to part of the increased recovery in the $28.63, $10.42, and $10.95 for pilot sizes of 2.2, 5.4, and 60
Yates field case.115 The incremental oil recovery in the case of MMbbl, respectively. The corresponding rate of return was up
the Cottonwood Creek field is believed to be primarily induced to 14%.125
by wettability change because the surfactant they used could 3.2. Nanoparticles. Nanoparticles refer to particles smaller
not reduce IFT significantly.116 Both cases show the than 100 nm and composed of a core and a thin shell, as shown
importance of a good understanding of how surfactants in Figure 21. The chemical nature of the shell will determine
would modify carbonate rock wettability.
To achieve a wide adoption of surfactant EOR techniques in
fields, several technical problems need to be solved. For
example, Ca2+ and Mg2+ ions usually have high concentrations
in carbonate formation brine. These divalent ions could form
sulfonates with typical commercial surfactants that either
precipitate or partition into oil phase.117 Besides, brine salinity
and hardness also have an impact on the performance of
surfactants, as mentioned in the above sections. Furthermore,
some surfactants are toxic and dangerous for workers and the
environment, which by a large extent limits the field Figure 21. Typical nanoparticle structure.133,134
application of surfactants.
Apart from technical problems, surfactant flooding suffers
from high cost because synthetic surfactants are usually costly. the solubility of the nanoparticle into one of two types: (1)
On the other hand, surfactant retention in the reservoir also lipophobic and hydrophilic nanoparticles (LHP) that are easier
adds to the quantity of consumed surfactants and thus the cost. to dissolve in a polar solvent or (2) hydrophobic and lipophilic
As mentioned in the anionic surfactant section, the addition of nanoparticles (HLP) that dissolve in nonpolar solvents. The
alkalis can reduce the adsorption of anionic surfactants because shell generally is composed of three separate regions: tail
it changes the pH value of formation brine. However, the group, hydrocarbon chain, and active headgroup.133,134
addition of alkalis could induce other problems like scaling, Because of the importance of the shell, surface modification
negative effect of viscosity, and production of very stable is usually performed on nanoparticles to obtain favored
foams.73 Many researchers currently work on natural properties, such as hydrophobicity.135 The small sizes of
surfactants that are less expensive and eco-friendly. Some nanoparticles enable them to diffuse into reservoir pores.136
work to find less expensive synthetic surfactants.118 Some look They can be reinjected without a major change in perform-
for ways to reduce the price of surfactant by local production ance.137 However, nanoparticles have to be applied with
and large quantity production. For example, Guo et al. caution if a high concentration is needed in low-permeability
reported that the surfactant price has been reduced to about 20 reservoir in case they block the pore network and impair
USD/bbl in Daqing oilfield, China. They also did an recovery.134 Table 12 shows typical nanofluids and their
estimation on the ASP cost (30−45 USD/bbl) and weak corresponding effect on carbonate rock wettability.
alkali ASP cost (27 USD/bbl).119 Some researchers and The isoelectric point is an important indicator of surface
engineers look for methods that help optimize EOR processes charge of nanoparticles. It is, by definition, the pH value at
based on economic evaluation. For example, Odi et al. applied which the object has no electric charge. At a pH above this
the ensemble-based method to EOR optimization.120 Rom- point, the object will have a positive surface charge and vice
merskirchen et al. concluded that EOR optimization should versa. Experiments show that pH is an important factor in
consider both chemical prices and their performance.121 wettability change.138 When preparing nanofluids, it is also
Because of the high cost of surfactants, surfactant-based common to add chemicals for pH value control.139 Dolomite
EOR techniques could be risky to apply in fields. Among rock has an isoelectric point 2−3 units lower than that of
44 DOI: 10.1021/acs.energyfuels.9b03409
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limestone rock, indicating that dolomite has a more positive Silica (SiO2) nanoparticles can modify the wettability of oil-
surface charge and thus is more attractive toward negatively wet calcite to strongly water-wet by adsorbing on the rock
charged materials. As a result, negatively charged nanoparticles, surface, with a minimum effective concentration of 1−2 wt
uncoated SiO2 for example, reach better wettability alteration %. 137 Different observations have been proposed by
performance on dolomite than limestone.140 researchers about whether this adsorption is reversible or
Changing pH results in changed surface charges (Table 10). not. Arain et al. found that this adsorption is mostly reversible
As a generally accepted case, the surface charge of rock and easy wash off by a solvent such as deionized water,135
while Al-Anssari et al. found that this adsorption is mainly
Table 10. Carbonate Rock Surface Charge and pH Value141 irreversible.137 These conflicting results may be induced by
insufficient exposure time to solvent applied in the experiment
pH value carbonate rock surface charge
taken by Al-Anssari et al., where silica nanofluid had a higher
>9 negative concentration (2 wt %). Uncoated silica nanoparticles are
=9 isoelectric point negatively charged and thus are naturally attracted by positively
<9 positive charged carbonate rock.140 With their adsorption onto the rock
surface, part of the positive charge on the rock surface is
dominates wettability. SiO2 particles can reduce the pH of the neutralized and previously adsorbed organic materials are
solution. Al2O3 nanoparticles can slightly increase pH. SiO2 desorbed. Their interaction with the carbonate surface leads to
nanofluid is much more effective in wettability alteration than partial desorption of organic materials by competitive
Al2O3 nanofluid.138 adsorption.138,142 However, uncoated silica nanoparticles
Because of the high surface area-to-particle size ratio, aggregate rapidly over time, and the average particle size was
nanoparticles have relatively high surface energy, making observed to grow up to 1000 nm in the first 40 min. Hybrid
them easy to aggregate in solution.135 The stability of (coated by silane agent) silica nanofluid showed a small
nanofluids is one of the most critical screening criteria for average particle size increase and an improved stability.135
their application. Zeta-potential analysis can be used to Another proposed mechanism that enhances wettability
measure the stability based on Table 11. modification is silica nanoparticles gradually forming a wedge
film in the three-phase contact area, leading to the generation
Table 11. Zeta Potential Value and Nanofluid Stability141 of structural disjoining pressure due to the coexistence of
electrostatic repulsion and Brownian motion between nano-
zeta-potential (mV) stability level
particles. When this structural disjoining pressure increases
>60 high stability
above oil droplet adhesion, oil droplets on rock surface start
30−60 good stability
peeling off, resulting in a more water-wet surface and higher oil
10−30 relative stability
recovery.142
<10 weak stability
Most metallic oxide nanoparticles, such as zirconium oxide
0 instability
nanoparticles, are hydrophilic in nature. Their adsorption onto
a carbonate surface will confer strong water-wetness to
originally oil-wet rock. Researchers proposed a wettability
3.2.1. Nanofluid Preparation. Experimentally used nano- alteration mechanism that metallic oxide nanoparticles move
fluids are usually prepared by adding nanoparticles into the and gather by the formation of a wedge film, and then the oil
water, magnetic stirring, and a sonication process.142 To keep drop is peeled. Free imbibition tests revealed the strong
the nanoparticle solution stable, materials called “dispersion capability for oil recovery from oil-wet carbonate of metallic
agents” are usually added. Commonly used dispersing agents oxide nanoparticles.145
include surfactants, small molecules, inorganic electrolytes, and Bare Fe3O4 nanoparticles show clearly good hydrophilicity.
polymers. 142 Properties of nanofluids are significantly Shalbafan et al. performed experiments to study the perform-
influenced by chemicals added, such as surfactants and acids. ance of differently coated Fe3O4 NPs.141 EDTA- or SLS-coated
With different additives, nanofluids can have very different Fe3O4 nanoparticles are more stable and hydrophilic than bare
performance in wettability alteration or even fail in changing Fe3O4 NPs. Increased concentration (0−0.9 wt %) of coated
wettability.139 A mixture of nanoparticles and surfactants can Fe3O4 nanofluid results in reduced and then increased contact
result in a significant change in surfactant surface activity due angles, suggesting an optimal concentration of 0.2 and 0.3 wt
to strong interaction between nanoparticles and surfactant % for EDTA- or SLS-coated nanoparticles, respectively.
molecules.136 Recently, a new type of nanofluid has been EDTA-coated Fe3O4 nanoparticles can alter wettability at
proven to improve carbonate recovery remarkably without low concentration, while SLS-coated Fe3O4 nanoparticles
surfactant and stabilizer.143 achieve better stability and oil recovery enhancement. The
3.2.2. Types of Nanoparticles. There are different nano- contact angle did not stabilize until after 48 h of exposure time.
particles, including zirconium dioxide (ZrO2), calcium Reducing the salinity (0−30 000 pm) leads to a decrease in
carbonate (CaCO3), titanium dioxide (TiO2), magnesium contact angle. Pressure (1−35 bar) has a negligible effect on
oxide (MgO), aluminum oxide (Al2O3), cerium oxide (CeO2), the wettability effect of nanoparticles. Temperature increase
silicon dioxide (SiO2), and carbon nanotubes (CNTs). Among leads to contact angle reduction. Changes in pH affect rock
them, SiO2, TiO2, ZrO2, CNTs, and CaCO3 are shown to have surface charge, and their attraction on nanoparticles leads to
potential in wettability alteration on carbonate rocks. CaCO3 different wetting states.141
and SiO2 have been proven to have the best salinity tolerance. Experiments on ZrO2 nanofluid (0.05−0.10 g/mL) and
Between them, SiO2 out-performs CaCO3 in recovery calcite surface reported by Karimi et al. indicate the existence
improvement from carbonate but requires a long time to of optimal concentrations that provide the smallest contact
take effect.144 angle. The mixture of ZrO2 nanofluid and nonionic surfactant
45 DOI: 10.1021/acs.energyfuels.9b03409
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Table 12. Wettability Alteration of Nanoparticlesa

contact angle change
conc. temp before-after
entry nanoparticle surfaces modification (wt %) rock water type (°C) treatment (deg) oil recovery % ref
1 30% NiO/SiO2 PEG 6000 8 v/v% carbonate DW 80 170−40 NG Dahkaee et al.,
2019136
2 30% NiO/SiO2 polydimethylsiloxane 8 v/v% carbonate DW 80 170−60 NG Dahkaee et al.,
2019136
3 30% NiO/SiO2 PEG 6000 8 v/v% carbonate SW 80 170−105 NG Dahkaee et al.,
2019136
4 30% NiO/SiO2 polydimethylsiloxane 8 v/v% carbonate SW 80 170−80 NG Dahkaee et al.,
2019136
5 SiO2 uncoated 500 mg/L dolomite brine 25 166−60 NG Aghajanzadeh et
al., 2019140
6 SiO2 uncoated 500 mg/L limestone brine 25 166−66 15 (nanofluid) 18 Aghajanzadeh et
(nanofluid +50000 al., 2019140
mg/L NaCl)
7 SiO2 0.05 calcite brine 25 140−76 20 (nanofluid +0.10 Hou et al.,
wt % NaCl) 2019142
8 SiO2 0.05 calcite brine 25 NG 17 (nanofluid +0.05 Hou et al.,
wt % NaCl) 2019142
9 SiO2 0.10 calcite brine 25 140−57 NG NaCl) Hou et al.,
2019142
10 MgO 50 g/L carbonate solution with 70 180−70 NG Khiabani et al.,
surfactants 2019139
and acid
11 Fe3O4 SLS 0.3 limestone solution 25 140−20 NG Shalbafan et al.,
2019141
12 Fe3O4 SLS limestone solution 25 NG 20 Shalbafan et al.,
2019141
13 Fe3O4 EDTA 0.2 limestone solution 25 140−23 NG Shalbafan et al.,
2019141
14 SiO2 0.1 calcite solution 25 69.7−58.1 NG Rezaei et al.,
2019138
15 SiO2 2 calcite solution 25 69.7−28.8 NG Rezaei et al.,
2019138
16 SiO2 3 calcite brine 25 69.7−16 NG Rezaei et al.,
2019138
17 ZnO/SiO2 xanthan 2000 ppm carbonate low-salinity 25 132.62−34.08 19.28 Ali et al.,
nanocomposite solution 2019150
18 SiO2 0.4 limestone brine 22 167−146 NG Haeri et al.,
2019148
19 SiO2 0.4 limestone brine with 22 167−98 NG Haeri et al.,
surfactant 2019148
2000 ppm
a
Oil recovery data come from spontaneous imbibition experiments, which reflect wettability change in the rock matrix. Concentration values
without units are of default unit (wt %). DW, deionized water; FW, formation water; SW, seawater; NG, not given.

imbibed rapidly into carbonate core and reached 40% oil choice. Longer than 3 days, some disorder on the nano-
recovery in half a day. ZrO2 nanoparticles can change structured surface could happen, which increased the contact
carbonate from strongly oil-wet to strongly water-wet. It angle. They suggested that different treatment times resulted in
changes wettability by adsorbing and forming nanostructured different nucleation rates, which in turn leads to different
ribbons. This process requires at least 2 days.145 crystal structures on rock surfaces.139
MgO nanoparticles seem to perform differently from other A mixture of different kinds of nanoparticles can also bring
types of nanoparticles under changing environmental param- interesting properties. For example, a mixture of 30% NiO/
eters. For MgO nanofluid, Nahid et al. suggested it to have SiO2 showed the self-cleaning property (heavy oil been
proper contact time, temperature, and nanoparticle concen- conveniently removed) which was not observed separately in
tration to ensure the desired nucleation rate. MgO nano- the NiO or SiO2 cases. The suggested mechanism attributes
particles form different nanostructures on carbonate rock this property to the high energy level of the nanoparticle
because of different nucleation rate, thus resulting in different mixture that enables them to penetrate the layers of oil,
rock surface roughness. Below that desired value, an increase in lightening and dispersing heavy oil into the solvent by forming
each of these three parameters has a positive effect on hydrogen bonds with asphaltene.136
wettability alteration. Above that value, it has adverse effects. 3.2.3. Influencing Factors. There are several important
Temperature increases may either strengthen or impair the parameters that influence the wettability effect of nanoparticles,
wettability effect of MgO nanoparticles, depending on the including particle size, contact time, nanoparticle concen-
composition of the nanofluid. However, by using the tration, temperature, and salinity.
composition of the best wettability alteration performance, Nanoparticle size can have an influence on wettability
increased temperature resulted in further contact angle alteration and oil recovery from the carbonate reservoir.
reduction. A treatment time of 3 days is the most satisfying Nanoparticles of smaller size (11−14 nm) were observed to
46 DOI: 10.1021/acs.energyfuels.9b03409
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lead to smaller contact angle and higher recovery compared to low nanoparticle concentration.150 In entries 1 and 3; 2 and 4;
larger ones (30−40 nm). Researchers believed that this 6; and 7 and 8 in Table 12, nanoparticles have poor wettability
improvement brought by size difference was because smaller alteration performance under high salinity conditions,
particles can be transported better through porous media. especially at low concentration.138 However, impaired stability
Besides, by dissolving into solution, nanoparticles also does not necessarily lead to impaired wettability modification.
aggregate. Thus, the average size of nanoparticles in water is For example, it is observed that the addition of NaCl can
usually much bigger than the average size of nanopowder.146 decrease silica nanoparticles’ stability but improve the
This average size difference was also proven by the study of wettability modification because sodium ions compress the
Arain et al.135 electric double layer.140,142 Al2O3 nanoparticles are observed to
Increased contact time inside the nanofluid leads to more have a better wettability effect in deionized water rather than
water-wet rock surfaces.140,142 It is observed that wettability brine. They tend to precipitate very fast in high-salinity
modifications induced by different types of nanoparticles were water.138 A study on Fe3O4 shows that reduced brine salinity
slow changes that take at least 2 days to stabilize.141,142,145 induces reduced contact angle due to better stability and
However, there are also results showing that the adsorption of wettability modification effect of nanoparticles.141 It is
silica nanoparticles is a fast process. Al-Anssari et al. found that suggested that the presence of electrolyte neutralizes part of
3 h is enough for the silica nanofluid. They observed that most the zeta potential and decreases the electrostatic repulsion
of the wettability modification happened during the first 1 h.137 forces among nanoparticles as well as between nanoparticles
Roustaei and Bagherzadeh also observed that the wettability and rock surface, resulting in more and faster adsorption of
modification happened in about 1 h.147 This difference might nanoparticles onto the carbonate surface.140 Enhanced
be caused by different nanoparticle types and concentrations. adsorption can lead to enhanced wettability modification, as
The nanoparticles studied by Shalbafan et al.141 and Karimi et was observed by Nazari et al. in SiO2; in TiO2 nanofluid cases,
al.145 were Fe3O4 and ZrO2, respectively. The concentration of salinity increased from 30 000 to 120 000 ppm.144 On the
silica nanoparticles studied by Al-Anssari et al. and Roustaei other hand, partial agglomeration would happen among
and Bagherzadeh were 2 and 0.4 wt %, much higher than the nanoparticles, leading to an irregularly coated rock surface
0.1 wt % value which was used in the study of Hou et al.142 due to adsorption which indicates reduced wettability
Increased nanoparticle concentration has a positive influence modification.137 There seems to be a threshold electrolyte
on wettability alteration toward water-wet conditions.136,140,142 concentration value. Below this value, little aggregation
For example, an increased concentration of silica nanoparticles happens among nanoparticles with surface charge. Above this
(from 0 to 0.8 wt %) improved the wettability modification value, however, average particle size increases sharply, and they
effect. 148 However, Al-Anssari et al. found that after adsorb onto the rock surface.140 Depending on the different
concentration reached a threshold value, this positive influence coating, increased salinity may have the opposite effect. For
became insignificant. They suggested controlling the nanofluid example, for the NiO/SiO2 nanocomposite, increased salinity
concentration at the corresponding threshold value from an seems to have a positive effect on PEG 6000-coated
economic perspective.137 There are also observations that nanocomposite, while a negative effect is seen on poly-
increased concentration (3 wt %) led to an increased contact dimethylsiloxane-coated nanocomposite with respect to
angle, which was explained by the enhanced precipitation of interfacial behavior.136
acids on the rock surface.138 The oil recovery results obtained In summary, nanoparticles can change the wettability of
by Maghzi et al. showed decreased recovery after silica carbonate rocks from strongly oil-wet to water-wet at relatively
nanoparticle concentration went beyond 3 wt %.149 Those low concentrations. It is important to ensure the stability of the
results suggest the existence of concentration limit beyond nanofluid under reservoir conditions, especially high salinity.
which increased concentration leads to an impaired wettability Temperature’s influence on the performance of nanoparticles
modification effect. differs according to different temperature ranges and different
Temperature leads to different wettability results in kinds of nanoparticles. Pressure has a negligible effect on
carbonate rock treated with nanoparticles. Shalbafan et al. nanoparticle behavior.135,141
found that increased temperature rendered more water- 3.3. Salt. Electrolytes have been proven to be efficient
wetness to carbonate rock treated with Fe3O4 nanoparticle wettability modifiers. Among all electrolytes, potential-
solution. They suggested this effect of temperature to be due to determining ions (PDIs) play an important role in the
the reduction in IFT and oil viscosity.141 The experiments wettability alteration process.151 PDI are ions that determine
performed Arain et al. showed that temperature lower than 50 the surface potential. Generally, they are ions that can dissolve
°C had little effect on silica nanoparticle adsorption. As the from or precipitate onto the rock surface. For carbonate rocks,
temperature increased from 50 to 70 °C, bare silica the most influencing PDI are SO42−, Mg2+, and Ca2+. Water
nanoparticle adsorption was reduced while hybrid silica carefully treated with potential-determining ions is known as
nanoparticle adsorption was enhanced. They suggested that smart water and is applied for improved recovery.64 Seawater is
this difference was due to surface charge difference of also considered as a “smart EOR fluid” that reduces the contact
nanoparticles and the surface charge of carbonate rock angle of carbonate in formations that have low initial
changing from positive to negative along with increased salinity.152−154
temperature.135 Generally, increased temperature leads to 3.3.1. Different Electrolytes and Corresponding Mecha-
more aggregation of nanoparticles because of enhanced nisms. As one of the PDIs for carbonate rock, sulfate (SO42−)
Brownian motion while changing the surface charge of plays a dominant role in changing rock surface wetting state
carbonate rock, thus resulting in different adsorption behavior under high temperature.48 Adsorption of sulfate onto chalk can
under different conditions. change the surface charge and desorb attracted carboxylic
Salinity has a relatively negative effect on nanofluid. An materials.151 Under higher temperatures, sulfate has a stronger
increase in salinity reduces nanofluid stability, especially under affinity toward the carbonate surface.23,151,152,154,155 This is
47 DOI: 10.1021/acs.energyfuels.9b03409
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because sulfate is solvated by hydrogen bonds in water. A part wettability modifier. Minor mineral contents also have an
of these bonds is broken under high temperature, giving rise to influence on that. There is a so-called “low-salinity effect” that
a higher affinity toward the carbonate surface of sulfate.153 An reduction of brine salinity leads to increases recovery in
increase in sulfate concentration leads to an increase in carbonate formations because of surface charge and possibly
recovery.155 However, experiments taken separately by two dissolution.159 In the experiment performed by Austad et al., it
groups (Gupta and Mohanty; Abdallah and Gmira) showed turned out that low-salinity brine contributed to tertiary oil
that sulfate was not able to obtain significant wettability change recovery only when there was anhydrite inside the rock
unless magnesium ions were introduced.8,156 The presence of material, whose amount had a great impact on the recovery.
Ca2+ can also promote the effect of sulfate as a wettability They believed that sulfate came out of anhydrate and modified
modifier.151 At high salinity hard brine conditions, sulfate is the wetting state of the rock.160 Oil composition also has an
not suitable as a wettability modifier because of possible effect. Experiments have shown that the recovery efficiency of
CaSO4 precipitation.152 Besides the implementation in brine injection with carefully prepared salt composition
wettability alteration, sulfate seems to have other effects on depends partly on oil composition.155 It is observed that
carbonate that contribute to additional recovery.155 these three mentioned kinds of ions have better performance at
Mg2+ seems not able to change wettability alone.8 Karimi et high temperature.8 pH is also an important factor. It is
al. proposed the possible mechanisms behind wettability observed that instead of rendering water-wetness, sulfate
modification induced by Mg2+ as follows: the addition of changes carbonate surface to slightly more oil-wet at pH
Mg2+ can increase rock surface zeta potential to more positive, greater than 7.17 No such phenomenon is observed in the cases
substitute Ca2+ on rock surface, desorb attached carboxylate of Mg2+ and Ca2+.
group, and form complexes between carboxylate group and In general, salts or electrolytes can affect carbonate rock
Mg2+, resulting in irreversible desorption of lipophilic groups wettability either directly by influencing the surface charge or
on the rock surface.64 The synergic effect has been observed indirectly by influencing the performance of other wettability
between Mg2+ and surfactants on contact angle changes.64 At modifiers. Among all electrolytes, three PDIs, including sulfate,
low temperature, Mg2+ is highly hydrated in water. Increased magnesium, and calcium ions, are the main functioning ions.
temperature causes dehydration, reduced solubility of Mg2+, Among these three, sulfate turns out to be the dominating one
fewer ion pairs between Mg2+ and SO42−, and thus higher in wettability modification. It has a strong affinity toward
activity of Mg2+. Under high temperature, Mg2+ is so active carbonate surface, especially under high temperature and with
that it was observed to replace Ca2+ on the rock surface.153 By the presence of the other two kinds of ions. Mg2+ and Ca2+ are
replacing Ca2+ or in other words adsorbing onto the carbonate less effective. For a given reservoir and surfactant injection
surface, the presence of Mg2+ was observed to modify program, there exists an optimal salinity that helps achieve the
carbonate wettability to a more water-wet state.64,156 lowest contact angle.
There are results showing that the addition of Ca2+ can also 3.4. Alkalis. The application of alkalis in the EOR process
lead to an increase in oil recovery.8,154,156,157 Ca2+ ions can has been investigated since 1917.161 It creates an in situ
react with adsorbed organic materials and desorb them from surfactant that lowers the IFT and changes the wettability of
the carbonate rock surface.156 Although Ca2+ ions can alter rock, resulting in a much lower cost than the surfactant
carbonate rock wettability alone, higher concentration and flooding process.161 It is usually used in a synergic effect with
temperature are favored for a major change in wettability.48 surfactant and polymers to form an ASP flooding process in
The ratio between ions also influences wettability, as EOR cases.162,163 Alkalis can be used to modify the brine pH
observed in the experiment performed by Zhang and and improve the wettability performance of surfactants72 by
Austad.154 As the Mg2+/Ca2+ ionic ratio increases, surface shifting the surface charge of carbonate.1,9 A combined system
dissolution increases and thus wettability alteration is of alkali and surfactant showed better wettability modification
improved. The ratio between SO42− and Ca2+ is related to performance than alkali alone in recovery.164 The addition of
the zeta potential of the rock surface. As the SO42−/ Ca2+ ionic an alkali into surfactant solutions tends to significantly reduce
ratio increases, significant surface change happens mainly surfactant consumption21,72,165 and extend surfactant applica-
because of the desorption of carboxylic materials with the tion into harsh-condition reservoirs.163,164
change of zeta potential. Commonly used alkalis include Na2CO3, NaOH, and
Salinity increase will reduce the optimal surfactant NaHCO3.166 Considering ion composition in brine, strong
concentration while suppressing the extent of wettability alkalis, such as Na2CO3, NaOH, and KOH, are not suitable for
modification under optimal conditions,8 and it can reach a high salinity with hard brines because of precipitation issues.
salinity level that no wettability modification is induced by NaHCO3 can be considered under such conditions.9
specific surfactants.9 For specific oil and surfactant systems,
under a given surfactant concentration, there is an optimal 4. CHALLENGES AND PROSPECTS
salinity for wettability alteration and vice versa.8 The Most of the commercial surfactants for oilfield applications are
experiment reported by Nazari et al. showed that an optimal expensive. Surfactant retention, especially of anionic surfac-
salinity existed in the wettability effect of CaCO3 nanoparticles tants, significantly reduces the profit of increased incremental
but not in that of SiO2 and TiO2 nanoparticles.144 Apart from oil recovery induced by surfactants. Many researchers now turn
their influence on surfactant performance, salinity also has a their interest to natural surfactants in pursuit of lower costs.
significant effect on nanofluid stability. Some researchers have investigated additives or conditions that
3.3.2. Influencing Factors. Rock mineral composition has a reduce surfactant retention. Surfactant stability issues under
considerable influence on the wettability alteration effect of high-temperature, high-salinity conditions limit their applica-
electrolytes. The effect of sulfate on wettability is much larger tion in such reservoirs. New solution systems are proposed to
in chalk than in dolomite,158 indicating that major mineral improve their performance under harsh conditions. Gemini
difference results in different sulfate performance as a surfactants have shown promising results about wettability
48 DOI: 10.1021/acs.energyfuels.9b03409
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Energy & Fuels Review

alteration on sandstone rocks and other types of rock surfaces. ORCID

Further investigation of their application on carbonate rock is Muhammad Shahzad Kamal: 0000-0003-2359-836X
required. Natural surfactants have shown their advantages with Xianmin Zhou: 0000-0002-1347-0760
lower cost and better eco-friendliness.
Notes
Nanoparticles are relatively novel materials for wettability
alteration. They can substitute surfactants in solution in the The authors declare no competing financial interest.
aspect of wettability change of rock. They can also be used
alone for wettability modification. Low cost is one of the major
advantages of nanoparticles. To date, a high concentration of
■ ACKNOWLEDGMENTS
This work was supported by the College of Petroleum
nanoparticles in injection fluid is not recommended for low- Engineering & Geoscience (CPG) at KFUPM through a
permeability formations because it may block the pores. The collaborative project with the University of Texas at Austin.

■
stability problem is also a limiting issue for nanoparticles,
especially in high-salinity formations. Researchers are studying
the effect of different coatings, different solution compositions,
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