Review

pubs.acs.org/EF

Factors and Mechanisms Governing Wettability Alteration by

Chemically Tuned Waterflooding: A Review
Prakash Purswani,# Miral S. Tawfik,# and Zuleima T. Karpyn*
John and Willie Leone Family Department of Energy and Mineral Engineering, The Pennsylvania State University, University Park,
Pennsylvania, United States

ABSTRACT: Enhanced oil recovery (EOR) techniques are aimed at improving the recovery efficiency of mature oil fields in
secondary and tertiary recovery modes. In particular, chemically tuned waterflooding (CTWF) has been a rising EOR technique
toward improving oil recovery from rocks that are difficult to produce due to their initial wetting state, e.g., oil-wet and
intermediate-wet. With an increasing oil-wetting affinity of a reservoir rock, extraction of oil becomes more challenging. As such,
wettability alteration has been identified as the primary mechanism for oil recovery from oil-wet and intermediate-wet rock types.
Recently, researchers have attempted to categorize the factors and mechanisms governing wettability alteration by CTWF.
Multiple studies have identified the importance of brine salinity and ion composition on promoting wettability alteration to a
more favorable water-wet state. Reservoir temperature, the surface charge of the rock, and the surface active components of crude
oil are also reported to influence wettability alteration and therefore oil recovery from waterflooding. In this paper, we present an
extensive literature review on the subject of wettability alteration, with an emphasis on experimental work conducted on
carbonate and sandstone rocks, as they constitute the majority of the oil reserves in the world. The purpose of this review paper is
to synthesize the current state of knowledge regarding the factors and mechanisms that govern wettability alteration by CTWF
and, through this exercise, set the platform to pose new research questions.

1. BACKGROUND ON WATERFLOODING of injected brine. Several laboratory studies have been

In 1865, the first waterflood occurred by an accidental water
leak from shallow sands in the Pithole City area in
Pennsylvania, USA.1 A significant increase in oil recovery was
observed and attributed to the flow of water through the oil
sands, which displaced the oil and increased the reservoir
pressure upon the depletion of the reservoir’s natural energy.
Since then, waterflooding has been slowly growing in
applicability until the 1950s, at which time it was recognized
as the leading secondary oil recovery mechanism.1
Reinjection of produced water has been the most common
practice in waterflooding to avoid formation damage, as well as
to dispose and make use of produced water. However, volumes
of produced water are rarely sufficient to replenish the reservoir
energy. In addition, the use of produced water requires more
complex surface facilities to separate suspended solids, oil
droplets, and dissolved hydrocarbons, as well as the corrosive
components in order to avoid scaling and/or corrosion in
injector wells.2 Surface facilities might not be readily available
on site, especially on offshore fields where space on platforms is
limited. Hence, the injection of seawater has been deemed
more economically and technically convenient than treated
produced water due to its abundance, lower cost, and
convenience for offshore use.2
It has been observed through several experimental and field
studies that the injection of seawater results in improved oil
recovery (IOR), as compared to the injection of produced
water,3,4 which has been attributed to the lower salinity of
seawater compared to the higher salinity of produced water.
Martin (1959) suggested that reducing the salinity of water
could improve oil recovery in sandstone rocks.5 Chemically
tuned waterflooding (CTWF) initially emerged in the form of
low salinity waterflooding (LSWF), which involved the dilution
conducted to explain the mechanism by which LSWF improves
oil recovery in sandstones.6−8 Zhang et al. (2006) further
suggested that brine composition rather than salinity causes
IOR in carbonate rocks.9 This triggered numerous experimental
studies that focus primarily on identifying and optimizing the
key factors that affect the success of CTWF.
Early on, the focus was only on understanding LSWF in
sandstone reservoirs due to its less complex structure, as well as
the common understanding that IOR due to LSWF is due to
interactions of the injected brine primarily with clay minerals.6
On the contrary, carbonate rocks have minimal to no clay
content,10 and hence, LSWF was not believed to be a viable
enhanced oil recovery (EOR) method for carbonate reservoirs.
However, Bagci et al. (2001) first reported IOR due to LSWF
in carbonates.11 The recovery factors of carbonate reservoirs are
lower than those of sandstone reservoirs.12 This is because of
the complex characteristics of carbonate rocks, which arise
mainly due to their initial wetting state.13,14
Anderson (1986) defined wettability as “the ability of a fluid
to spread or adhere to the rock surface in the presence of
another immiscible fluid.”15 While most sandstone reservoirs
are strongly water-wet or mixed-wet systems, most carbonate
reservoirs are either mixed-wet or completely oil-wet.13,14 The
term “mixed wettability” was first coined by Salathiel (1973),
where the author suggested that reservoirs are primarily water-
wet in nature during formative stages, but, in later stages,
organic components of oil come in contact with the rock
Received: April 17, 2017
Revised: June 13, 2017
Published: July 10, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.7b01067

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Table 1. A Summary of Coreflooding Experiments Performed on Carbonate and Sandstone Cores for a Range of Experimental
Temperatures, Recovery Modes, and Brine Compositionsa

a
Sands are highlighted in grey.

B DOI: 10.1021/acs.energyfuels.7b01067
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surface, rendering some portions of the reservoir oil-wet.16 The
degree of wettability of a rock is governed by the nature of the
crude oil−brine−rock system. The oil-wet nature of carbonate
rocks can be attributed to the tendency of organic components
from the oil to adsorb onto the surface of the rock more
strongly, making carbonate reservoirs harder to produce. One
of the earliest works on wettability modification was carried out
by Wagner et al. (1959), where they performed a series of
waterflooding experiments on synthetic calcite and quartz cores
with brines of different salinities and pH to observe the positive
effects of wettability modifications for improving oil recovery.17
Furthermore, the importance of ion composition present in
seawater was recognized as a critical factor affecting the process
of wettability alteration. This led to the use of tailored brine
solutions made from seawater in the secondary and tertiary
recovery stages for improving oil recovery. Work has also been
done on seawater flooding to prove that wettability alteration
indeed plays an important role in improving oil recovery.9,18−23
Many laboratory studies were conducted on carbonate and
sandstone reservoirs to verify whether the injection of brines of
different salinities and ion compositions could disturb the
chemical equilibrium between the rock and crude oil to
facilitate oil recovery. Mg2+, Ca2+, and SO42− ions present in
seawater were experimentally proven to be the potential
determining ions responsible for incremental oil recov-
ery.9,19,20,24,25 Further, the contribution of the nonparticipating
ions was analyzed, where it was seen that Na+ and Cl− ions did
not contribute toward oil recovery, and therefore, seawater
salinity and composition could be tuned by optimizing the
potential ions at the expense of the nonparticipating ions.23,26
Despite the numerous experimental, numerical, and field
studies on CTWF, there is still little consensus on the
mechanism(s) by which it improves oil recovery.27−30 The
mechanistic explanation for IOR by CTWF in carbonates is
even less explored compared to sandstone reservoirs.30 This
lack of understanding of the underlying mechanism(s) of
CTWF leads to inconsistency in the reported results, where
some experimental studies report an IOR by CTWF,31−33 while
others report no additional recovery.34−36 The primary focus of
this work is to document and analyze experimental work done
thus far about CTWF as a potential EOR technique, provide a
comprehensive report of the key factors affecting the success of
CTWF, and propose mechanisms by which CTWF improves
oil recovery in carbonate and sandstone reservoirs. Some of the
most relevant experiments discussed in this literature review are
presented in Table 1, as a comparative presentation of tested
conditions and reported gains in oil recovery. The effects of
surface properties of the rock, crude oil, and brine composition,
the salinity of the imbibing fluid, and reservoir temperature,
together with characterizing techniques like zeta potential
measurement and acid number measurement, have been
studied to understand the interactions that take place at the
oil/rock/brine interface. This paper presents a comprehensive
literature review in the area of wettability alteration for
enhancing oil recovery, and it is intended to assist further
development of the existing and emerging mathematical models
for predicting oil recovery through CTWF. In addition, we
explore a series of research questions and expose knowledge
gaps that could guide further studies to improve our
understanding of wettability alteration via CTWF.
C DOI: 10.1021/acs.energyfuels.7b01067
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2. BRINE SALINITY AND ION COMPOSITION
LSWF is considered a subset of CTWF as it involves the overall
dilution of the injected brine while maintaining a constant ion
composition. Early experimental studies focused on LSWF in
sandstone and slowly progressed toward carbonates.6,10,11
Several of these experiments concluded that decreasing the
salinity of injected water leads to an increase in oil recovery, as
well as a corresponding increase in the water-wetness of the
rock in both carbonate and sandstone reservoirs.17,44−48 To
illustrate the phenomenon of LSWF in carbonate reservoirs,
zeta potential measurements were conducted by Yousef et al.
(2012). Zeta potential, also known as “electrokinetic potential,”
is useful toward understanding the interactions among particles
in a suspension and has been widely used for finding the surface
charge of a rock in a particular brine environment. The
measurements showed that as the salinity of brine decreases,
zeta potential of the carbonate surface decreases, thereby
suggesting that Ca2+ ions from the rock surface migrate toward
the low salinity brine to re-establish chemical equilibrium
between the rock and the brine.49 This effect is commonly
known as mineral dissolution and is considered one of the
possible mechanisms contributing to an improvement in oil
recovery by CTWF in carbonate rocks. Also, the decrease in the
positive charge on the carbonate surface, when exposed to low
salinity water, leads to the expansion of the electric double layer
(EDL), which results in a thicker, more stable water film. EDL
expansion is also considered one of many mechanisms used for
explaining wettability alteration by LSWF that highly depends
on the electrostatic interaction between the brine/oil and
brine/rock interfaces.50,51 A similar trend in the results was
obtained by Alotaibi et al. (2011), where zeta potential values
of sandstone rocks with differing clay contents were measured
in brines of different salinities. It was observed that as the brine
salinity was decreased, there was an decrease in zeta potential
for all sandstone rock types, suggesting a thicker EDL with a
lower salinity brine.52
With the advancement in technology, techniques like X-ray
microcomputed tomography (micro-CT) have been used to
study the effect of LSWF. This pore scale methodology helps to
track fluid flow behavior during waterflooding techniques in
porous media. In the study conducted by Khishvand et al.
(2016), micro-CT image analysis was used to investigate in situ
changes that occurred in fluid saturations via wettability
alteration upon waterflooding with brines of different salinities
in sandstone rocks.53 They reported higher oil recovery for the
brine of lower salinity, suggesting that wettability alteration,
caused by mineral migration and/or multi-ion exchange (MIE)
at the rock surface, potentially enabled the deeper invasion of
the brine into larger oil-filled pores to improve oil recovery.
This was analyzed by measuring oil−water contact angles using
high resolution images captured during the experiments.53
Although the majority of the experimental studies report a gain
with LSWF, it is valuable to note that the injection of low
salinity brine, incompatible with the formation water, could
lead to formation damage and consequently a decrease in
production. Therefore, maintaining an optimum salinity level,
in which the improvement in oil recovery outweighs formation
damage, is crucial.5,6
In 1999, the effect of injected brine composition rather than
overall salinity was first experimentally investigated by
coreflooding and spontaneous imbibition experiments using
Berea sandstone cores.45 Further studies investigated the effect
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of individual ions in seawater, including Ca2+, Mg2+, SO42−,
Na+, and Cl−. Almost all experimental results concluded that
Ca2+, Mg2+, and SO42− are potential determining ions, owing to
the tendency of these ions to influence the rock surface charge
by altering the wettability to a more water-wet system.25,54,55 It
is worth noting, however, that the overall salinity (ionic
strength) of the injected brine influences the activity of the
potential determining ions, which is in accordance with the
extended Debye−Hückel model that states that the activity
coefficient of individual ions in a solution can be determined
using the following equation:
Azi2 I
−log γi =
1 + aiB I
where γi is the activity coefficient of ionic species i, zi is the
charge of ionic species i, I is the ionic strength of the solution, A
and B are constants depending on temperature and dielectric
constant, and ai is the effective diameter of the ion. Hence, both
ion composition and salinity are key parameters for engineering
an optimum injection brine for maximum incremental oil
recovery.56
Zeta potential measurements of rock particles suspended in
brine solutions have also been valuable in identifying these
potential determining ions responsible for improving oil
recovery. It was found that both Ca2+ ions and SO42− ions
are able to change the surface charge of chalk particles when
added to the chalk suspension.57 This was further verified in the
work by Zhang and co-workers (2006, 2007), where the zeta
potential of chalk suspension was measured at a fixed pH of 8.4
by increasing the concentration of the potential determining
ion in consideration. They observed that increasing Mg2+ and
Ca2+ ion concentrations increased the zeta potential of the rock
sample, owing to the affinity of these ions toward the rock
surface. For SO42− ions, a decrease in zeta potential was
observed with an increasing SO42− ion concentration, owing to
the possible adsorption of the negative ion onto the rock
surface.9,54
Tang and Morrow (1999) studied the effect of cation valency
on the performance of low-salinity waterflooding (LSWF) in
sandstones.45 Monovalent (Na+), divalent (Ca2+), and trivalent
(Al3+) cations were used in different injection brines. The study
suggested that, at relatively higher salinities, lower valence
cations lead to a higher recovery by spontaneous imbibition.
The presence of higher valence cations promotes the
adsorption of polar organic compounds onto the negatively
charged sandstone rock surface by “cationic bridging,” thus
decreasing its water-wetness, and consequently, trapping more
oil and leading to lower recovery. However, at lower salinity,
the effect of cation valency on the wetting condition and oil
recovery was less significant.45 As opposed to the conclusion
arrived at by Tang and Morrow (1999) for sandstones,
coreflooding and spontaneous imbibition of oil from carbonate
cores (particularly limestone) show that an increase in divalent
cation concentrations (Ca2+ and/or Mg2+) in injected brine,
and a decrease in monovalent cations (Na+), lead to an increase
in oil recovery in the presence of SO42− ions.20,25,54,55 This can
be explained by the adsorption of SO42− ions onto the
positively charged carbonate surface at the brine-rock interface,
which, in turn, leads to the attraction of Ca2+ and Mg2+ closer
toward the carbonate surface. In addition, at the brine−oil
interface, divalent cations form bonds with the carboxylate
D DOI: 10.1021/acs.energyfuels.7b01067
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groups (R-COO−) in crude oil, thus decreasing the chances of
readsorption of oil onto the carbonate surface.58
In the study by Gupta et al. (2011), coreflooding
experiments were performed to investigate the effect of
replacing sulfate ions with other anions, including phosphate
(PO42−) and borate (B(OH)4−).41 The coreflood experiments
were performed on several limestone and dolomite cores in
tertiary mode, where the cores were first flooded with
formation water, then with chemically tuned water. It was
observed that adding four times the amount of SO42− ions in
seawater resulted in an additional recovery of 6% of the original
oil in place (OOIP). Replacing SO42− ions with B(OH)4− ions
caused an incremental recovery of 15.6% of OOIP, whereas
replacing SO42− ions with PO42− ions led to an even higher
incremental recovery of 21.3% of OOIP.41
Connate water is also identified as a primary factor for a
successful LSWF in sandstone reservoirs, without which there is
no additional oil recovery.45,59 This is because the connate
water saturation history and ion composition dictate the
stability of the water film formation over the rock surface, and
therefore, has a direct effect on the initial wetting condition of
the rock. Most experimental studies pertaining to CTWF focus
on the effect of the salinity and composition of injected brine
on oil recovery, whereas very few studies attempt to investigate
the effect of connate water properties on oil recovery. A study
conducted by Shehata et al. (2016) investigated the effect of
connate water salinity and concentrations of different cations
on the performance of LSWF in two types of cores: Bandera,
and Buff Berea sandstone cores.46 The study did not focus on
the effect of the concentration of anions because connate water
normally has a low concentration of sulfate ions. This is
partially due to the precipitation of anhydrite (CaSO4),
especially at higher temperatures.39,60 The study concluded
that a higher salinity connate water results in a higher
incremental recovery (7% of OOIP) by LSWF. Also, connate
water with a high concentration of cations, particularly, divalent
cations resulted in higher incremental oil recovery when a low
salinity brine is injected. These conclusions are consistent with
the explanation provided earlier, where, in sandstones, higher
salinity and higher valence cations lead to thin unstable water
films on grain surfaces, and therefore, promotes the cationic
bridging of crude oil onto the clay surface, which in turn results
in an increased initial oil-wetness and more trapped oil that can
then be recovered by means of CTWF.
2.1. Open Questions. Experimental studies conducted thus
far focus on the effect of potential determining ions on
recovery. The effect of other ions in seawater has not been
explicitly investigated, including HCO3− and K+. Also, the effect
of SO42− ions has been widely studied due to its presence in
seawater. However, a high SO42− ion concentration increases
the risk of reservoir souring and scaling.25 Hence, the effect on
oil recovery of replacing SO42− ions with other anions such as
borate and phosphate, and their behavior, needs to be further
examined.41 Exploring the possibility of using anions other than
SO42− to find the optimal injection brine composition is key.
Other anions such as nitrate (NO3−) can have lower associated
risks and operational problems compared to SO42− ions, and
therefore, its ability to improve oil recovery needs to be
investigated. In addition, only a few studies tackled the effect of
connate water on the performance of CTWF. The effects of
salinity and cation valence have been addressed in the study by
Shehata et al. (2016). However, the effect of different anions in
the connate water on the performance of LSWF has not been
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studied because formation water has more cations than
anions.61 More importantly, the effects of salinity and the
composition of connate water on incremental oil recovery via
CTWF need to be quantified as connate water properties
significantly affect the optimum injection water design due to
the inevitable injected and in situ brine mixing in the reservoir.
3. MINERAL COMPOSITION OF THE ROCK
One important factor that is often neglected when comparing
results from various studies is the fact that reservoirs are often
heterogeneous systems. Because of the reactive nature of
CTWF, and its dependence on oil/rock/brine interactions,
understanding the effect of rock properties on the success of
CTWF is necessary for valid comparisons. Different rock types
greatly differ in mineral composition, which directly impacts the
nature of the surface charge of the rock, and is therefore
important in deliberating the initial wetting state of the
reservoir.
Carbonate reservoirs are normally composed of a variety of
minerals, primarily calcite (CaCO3), dolomite (CaMg(CO3)2),
anhydrite (CaSO4), and quartz (SiO4). The degree of
improvement in oil recovery has been observed to vary based
on the mineral composition of carbonate rocks.58 According to
Austad et al.,62 injecting diluted seawater into chalk cores
resulted in a drastic decrease in oil recovery compared to
injecting seawater. This showed that low salinity waterflooding
is not the reason for IOR in chalk. In the same study, coreflood
experiments were performed on limestone core sample-
s―one that did not contain an anhydrite mineral as part
of its composition, and on another limestone sample that did.
The study concluded that LSWF effect could only be seen in
the presence of anhydrite, indicating that the presence of
anhydrite plays an important role toward wettability alter-
ation.62 Injection of low-salinity water into carbonate cores in
the presence of anhydrite promotes the dissolution of anhydrite
due to the low concentration of Ca2+ in the injected brine
compared to that of formation water (common ion effect).
Anhydrite dissolution leads to the in situ generation of free
SO42− ions, which adsorb onto the positively charged carbonate
surface and catalyzes desorption of carboxylic groups, altering
the wettability to a more water-wet state and thereby improving
oil recovery. On the other hand, the injection of the same low-
salinity water into limestone cores in the absence of anhydrite
shows no improvement in oil recovery. This shows that the
presence of anhydrite is necessary for IOR in carbonate rocks,
where the injected brine contains minimal SO42− ions. It has
been experimentally observed that the dissolution of anhydrite
is dependent on temperature, connate water salinity, and
concentration of Ca2+ ions in the injected brine.39
In the study conducted by Shariatpanahi et al. (2016), a
comparison between the low salinity effect in Silurian outcrop
dolomite cores, and in chalk and limestone from previous
studies, was presented.43 The study concluded that similar to
limestone rocks, the presence of sulfate ions (whether in the
injected brine or as a result of dissolution of anhydrite) is
critical to observing wettability alteration, as well as an
improvement in oil recovery. However, the extent of adsorption
of sulfate ions onto the dolomite surface is observed to be
weaker compared to chalk and limestone cores. This was also
confirmed in the study performed by Mahani et al. (2015),
where CTWF in dolomites showed a smaller or no contact
angle change compared to limestones (which are mainly
composed of calcite), implying fewer wettability modifications,
E DOI: 10.1021/acs.energyfuels.7b01067
Review
as well as stronger adhesion forces between dolomite and oil.63
Also, contrary to outcrop limestones, outcrop dolomite
responds to chemically tuned water in the same way as
reservoir dolomite cores.43
Sandstone reservoirs, on the other hand, are composed of
different minerals, most commonly quartz and feldspar. These
minerals make up the matrix and are bound by secondary
minerals, known as “cement” that form after the deposition of
the sandstone matrix. There is a wide variety of minerals that
make up cement, including anhydrite, dolomite, and clay
minerals such as kaolinites, chlorites, and Illites, which are
nonswelling clays, as well as montmorillonites, which are
swelling clays.64 In sandstones, clays are believed to play a
significant role in the success of CTWF due to their abundance
and large specific surface area compared to matrix-forming
minerals.34 However, clays that swell and clays that have
positive zeta potential are considered detrimental to oil
recovery. Studies by Tang and Morrow (1999) and
Wickramathilaka et al. (2011) suggest that sandstone core
samples with higher clay content exhibit higher incremental
recovery. However, none of these studies reported which
type(s) of clay minerals have a greater impact on the low-
salinity effect.8,65 According to Rezaei Gomari et al. (2015),
both, the amount and the type of clay play a significant role in
LSWF.66 Some clays act as cation exchangers, whereby clays
tend to swap or exchange cations with cations from the fluids in
the pore space due to the deficiency in their positive charge,
which must be countered by cations from the surrounding
formation water if the clay particles are to remain electrically
neutral.67 Cation exchange capacity (CEC) is a measure of the
excess negative charge on the clay particles. CEC varies by clay
type in the following descending order: montmorillonites,
Illites, and kaolinites.68 According to Austad et al. (2010), clays
with higher CEC, coupled with the presence of divalent cations
in formation water, and coadsorption of these cations and the
polar oil components on the clay surface, are more favorable for
observing low-salinity effects.38 Additionally, it was noted in
this study that for clayey sandstones, the main parameter that
needs to be optimized in the injected brine is the concentration
of divalent cations, which should be low. An experimental study
conducted by Cissokho et al. (2010) confirmed these findings,
where an incremental oil recovery of 10% was observed when a
sandstone core sample with 9.2% clay content was flooded with
low-salinity brine.69 The clays included chlorite, muscovite, and
Illite, which indicates that the low-salinity effect can be
witnessed in the absence of kaolinite. On the other hand,
other studies suggest that kaolinite is considered a requirement
for effective LSWF, due to its oil-wet nature and high surface
charge density, which makes its surface electric effect much
greater when compared to other clay minerals.70 The study
concluded that a variation in kaolinite content from 5 to 30%
results in a change in the overall cation exchange capacity
(CEC) of 47−270 eq/m3, which translates to ∼2.65%
incremental recovery at 30% kaolinite content. The importance
of kaolinite mineral was also investigated in the pore scale study
conducted by Lebedeva et al. (2011). The authors used X-ray
micro-CT imaging to quantify the effect of LSWF via
wettability alteration on sand packs coated with or without
kaolinite mineral.71 Micro-CT image analysis helped track oil-
blob occupancy changes that occurred during waterflooding
experiments. They found that, for the sand packs coated with
kaolinite mineral, low salinity brine injection improved oil
recovery as opposed to the high salinity brine, suggesting that
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the oil-wetness caused by the presence of kaolinite mineral was
altered to a favorable water wetting state, facilitating oil
recovery. Because of the lower resolution of the micro-CT
images (sufficient for distinguishing oil, brine, and rock entities
to suitably quantify fluid saturations), wettability analysis was
performed using receding and advancing oil-drop contact angle
measurements conducted on quartz slices that mimicked the
rock used for waterflooding experiments. These confirmed the
process of wettability alteration during LSWF.71
Carbonate rock surfaces are mostly positively charged,
whereas sandstone rock surfaces are negatively charged. The
positive charge on the carbonate surface can be attributed to
the hydration of the calcite surface to form >CaOH2+,58
whereas the negative surface charge in the case of sandstones is
attributed to the presence of negatively charged clay particles as
described previously.15,58 The surface charge of the rock is
sensitive to changes in the surrounding environment, including
the ionic concentration and pH of the brine around the rock,
which in turn affects the wetting state of the rock.15 Therefore,
efforts have been made to carefully measure the rock surface
charge in different brine environments to more accurately study
the interactions of oil and brine with the rock surface. One
approach of estimating the surface charge of the rock is through
zeta potential measurements as described earlier. In the work
by Vdovic and Biscan (1998), zeta potential values of synthetic
and natural calcite in simple NaCl brine environment were
investigated. They found that the zeta potential value of
synthetic calcite was positive at lower pH due to the prevalence
of positive surface species like Ca2+, CaHCO3+, whereas natural
calcite showed negative zeta potential, which was attributed to
the adsorption of organic material onto the calcite surface.72 As
CTWF gained momentum in the oil industry, zeta potential
measurements were performed in more complex brine
environments. Experiments conducted by Mahani et al.
(2015) focused on the importance of ion composition and
pH of the brine system on the oil/rock interface.30 Zeta
potentials of carbonate rock samples and oil droplets were
measured as a function of pH, in different brine environments,
namely, formation water, seawater, and diluted seawater. An
increase in the zeta potential values was seen for both dolomite
and limestone rock particles with an increasing pH for all brine
systems, suggesting that the surface of the rock acted more
positively charged at higher pH ranges, whereas, at lower pH
ranges, the rock particles showed a negative zeta potential
owing to the increased adsorption of SO42− ions in seawater.30
In a different set of experiments performed by Karimi et al.
(2015), the zeta potential of carbonate rock samples was
measured both before and after aging,73 which is the
accelerated process of exposing the core sample to reservoir
conditions in order to assist in the development of an initially
oil-wet sample.74 This helped in finding the change in the
nature of the surface charge, which is necessary for under-
standing the surface wetness. They found that the zeta potential
of the rock sample changed from +29.6 mV to −33.4 mV for
preaged and postaged calcite samples, respectively, at a pH of 8.
The positive nature of the surface charge before aging was
attributed to the prevalence of positive divalent Ca2+ and Mg2+
ions present in the calcite sample below pH of 10. The authors
suggested that at a higher pH, the calcite surface acts more
negatively charged due to the possible adsorption of CO32−
ions. The negative nature of the surface charge postaging was
attributed to the adsorption of polar oil components onto the
rock surface, making the rock surface more negatively
F DOI: 10.1021/acs.energyfuels.7b01067
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charged.73 The variety of experimental work on zeta potential
measurements clearly showcases the variation in the surface
charge response of the rock samples with different injected
brine properties, indicating that rock properties have a
significant effect on the performance of CTWF.
3.1. Open Questions. The inconsistencies observed in
experimental results using sandstone cores show difficulty in
generating repeatable and reproducible data due to the
heterogeneity of the sandstone rock mineralogy, as well as
the wide variety of clays involved. The contradictions in the
experimental studies on sandstones can also be attributed to the
interplay of several pore-scale mechanisms, contributing to the
overall low-salinity effect. Controlled experiments have been
conducted on carbonates to assess the effect of particular
minerals such as calcite, dolomite, and anhydrite on the
performance of CTWF. However, more controlled experiments
are yet to be conducted to map the effect of different minerals
and clay types in sandstones.
In addition, some studies suggest that zeta potential varies
with particle size;75 however, there has been little work focusing
on the sensitivity of zeta potential to particle size. Further, most
conventional methods of measuring zeta potential at a
laboratory scale, like the electrophoretic mobility measurements
or the electroacoustic measurements, assume that zeta potential
does not depend on particle size.76 However, Nakatuka et al.
(2015) studied the importance of particle size distribution on
zeta potential by the application of the liquid sedimentation
method. They discovered that the negative zeta potential values
for the silica particles do indeed depend on the particle size,
such that the zeta potential values increased with the decrease
in particle size. The authors attributed the increase in the zeta
potential values to particles with smaller size, due to the
increased random movements of smaller particles rather than
larger particles.76 Therefore, the reliability of zeta potential
measurements at the laboratory scale, and their true
interpretation at the field scale, remain an area of investigation.
4. CRUDE OIL COMPOSITION
Heavier components of crude oil, like asphaltenes or resins, are
believed to carry compounds bearing oxygen, nitrogen, and
sulfur atoms.77 These compounds are responsible for the
acidity and/or basicity of crude oils. Tests done by Seifert and
Howell (1969) confirmed the presence of carboxylic groups in
California crude, which, the authors suggested, were active at a
particular pH of the system.78 Fathi et al. (2011) further
reinforced that the wetting properties of crude oil were affected
by the chemical properties of the carboxylic material present in
the crude oil.79 The presence of carboxylic acids in the crude oil
was further confirmed by the electrokinetic study conducted by
Mahani et al. (2015). They measured the zeta potential of oil
droplets, as suspended particles, in different brine environments
and observed that the oil particles showed a negative zeta
potential over the range of pH measurements in different brine
salinities, owing to the presence of negative carboxyl groups in
the crude oil.63
It is therefore understood that the acidic and basic
components present in the crude oil are crucial in under-
standing the extent of the adsorption of hydrocarbon
components on the rock surface, as well as the initial wetting
characteristics of rocks.15,80 According to Zhang et al. (2007),
in order to obtain a satisfactory oil recovery from carbonate
reservoirs with low water wetness, initial wetting conditions
must be altered.17 For carbonate rocks, where the surface is
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primarily positively charged, the adsorption of the negatively
charged acidic components from the crude oil plays a key role
in determining the potential for oil recovery from these
reservoirs. Therefore, the quantification of the acidic content of
crude oil has gained importance in the recent past.
One way of quantifying the amount of acidic or basic
components in crude oil is through acid and base number
measurements. The widely accepted method for estimating
these measurements is by potentiometric titration. Standardized
workflows were developed by the American Society for Testing
and Materials (ASTM) and have seen several revisions over
time. The most updated revisions are ASTM D664 (2011) for
acid number measurements81 and ASTM D2896 (2015) for
base number measurements.82 In recent years, there have been
improvements in the application of these methods. One widely
accepted improvement in the measurement of acid number was
proposed by Fan and Buckley (2007). They suggested that the
application of a small quantity of spiking solution, prepared by
the addition of a small concentration of stearic acid, could assist
in achieving clear inflection points. This method also led to a
much lower consumption of valuable crude oil.80
With the importance of the acid number of crude oil toward
improving oil recovery, together with the ease of acid number
measurements, more research has been performed to explore
this domain. In the work by Stadness and Austad (2000), it is
seen that the oil recovery was about 70% when the acid number
was 0 mg KOH/g, implying that the oil had no acidic polar
components to adsorb onto the rock surface, indicating a water-
wet system. On the other hand, when the acid number
increased up to 1.73 mg KOH/g, oil recovery decreased
dramatically.18 Similar observations were found in the work
conducted by Fathi and co-workers (2010, 2010, 2011).21−23
Several spontaneous imbibition experiments were performed
on cores aged with oils of different acid number, where the acid
number of each crude oil was tailored by extracting the acidic
components from the oil. It was observed that the oil with the
maximum quantity of acidic components showed the least
recovery, as well as the lowest water-wet fraction at the end of
the recovery process.22,79 This was also validated in the surface
complexation model developed by Qiao et al. (2015), which
predicted a lower recovery potential by increasing the acid
number of the crude oil.58 These studies suggest that the acid
number of the crude oil plays a critical role in determining the
incremental oil recovery and whether a reservoir could be
considered a good candidate for CTWF.
4.1. Open Question. The investigation of acid number
emphasizes the importance of organic acids present in crude oil
toward enhancing oil recovery. However, there is little
understanding about the origin of the acidic groups in the
crude oil, which could be attributed to the oxidation process
that occurs during the developmental stages of hydrocarbon
formation. It is understood that underground water plays a key
role in transporting the crude oil to its producing zone in the
reservoir. It can be inferred that in the process of this migration
and interaction with water molecules the hydrocarbons are
oxidized and begin to possess the acidic groups. However, little
experimental work supports this argument. In addition, acid
number measurement is not an accurate way of identifying the
amount of acidic components in oil that are reactive with, and
have an affinity to, the rock surface (i.e., acidic components
with surface active species). It is rather a measure of the total
acidic components in oil, both reactive and nonreactive.
According to Hoeiland et al. (2001), identifying the acid type
G DOI: 10.1021/acs.energyfuels.7b01067
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and molecular structure is more important than measuring the
amount of acids in regard to interfacial and wettability
properties.83 Hence, additional experimental studies are needed
for a more accurate quantification of the effects of different
types and structures of polar components that contribute to the
initial oil-wetting extent of the reservoir rocks.
5. EFFECT OF TEMPERATURE ON SURFACE
REACTIONS
Because of the reactive nature of CTWF, temperature is a
crucial factor that affects the wettability alteration process. The
role of temperature is 2-fold, as it affects the activity of the ionic
species present in the brine, as well as the interaction of the
polar organic compounds in crude oil with the rock surface.
Together, these can affect the type of chemical reactions that
take place at the oil−water and fluid−rock interfaces.
In the experiments conducted by Zhang et al. (2006) and
Austad et al. (2005), an increase in oil recovery was observed
along with an increase in temperature through spontaneous
imbibition from chalk.3,54 This improvement was attributed to
the higher affinity of SO42− ions to the carbonate surface at
higher temperatures, which results in the displacement of the
negatively charged carboxylate groups (R-COO−) of the sulfate
ions onto the positively charged carbonate surface, freeing the
oil from the rock surface, and altering the wettability of the rock
to a more water-wet state.3,25 This relation between the
improvement in oil recovery and the increased adsorption of
sulfate ions onto the carbonate surface at elevated temperatures
has been further verified using the chromatographic wettability
test developed by Strand et al. (2004), where an increase in the
degree of water-wetness was simultaneously observed along
with a decrease in the concentration of sulfate ions in the
effluent at higher temperatures.84
In the absence of sulfate ions in the injected fluid, as
discussed in section 3, an improvement in oil recovery due to
LSWF can still be observed in carbonates, but only in the
presence of anhydrite minerals. However, the dissolution of
anhydrite is adversely affected by an increase in temperature,
where higher temperature results in a lower dissolution
rate.39,60 Additionally, the efficiency of wettability alteration
increases as temperature increases.62 Hence, a reduced
dissolution rate can be compensated by a higher wettability
alteration efficiency, and vice versa. It is therefore critical to
understand what type of chemical reactions are taking place in
the system based on the ionic composition of the brine and the
rock mineralogy. Further, it is also important to see which of
these reactions are more active, and at which particular
temperature.
In the electrokinetic study conducted by Alotaibi et al.
(2011), they measured the zeta potential of the limestone and
dolomite particles in different brine environments, and at
different temperature values. They observed that in a seawater
environment at a pH of 7 at 25 °C, the zeta potential of
limestone was about +6.8 mV, suggesting a positive charge of
the limestone surface. Further, when the temperature was
increased to 50 °C, they observed a decrease in zeta potential,
owing to the increased dissolution of Ca2+ ions from the
limestone surface due to the higher activity of these ions at the
elevated temperature. Similar results were obtained for
dolomite particles at higher temperatures.52
The activity of cations in injected brine is highly affected by
temperature. In the study conducted by Zhang et al. (2007),
adding Mg2+ ions resulted in a higher incremental oil recovery
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Energy & Fuels
than by adding Ca2+ ions at 100 °C.9 This was attributed to the
higher activity of Mg2+ ions as compared to Ca2+ ions at higher
temperatures. This effect was more pronounced as the
temperature was further increased. The increase in the activity
of Mg2+ observed at 130 °C overshadowed the effect of adding
twice the amount of SO42− ions to an injected brine that had
Ca2+ ions instead of Mg2+ ions, where a larger incremental oil
recovery (∼20% of OOIP) was observed,9 as shown in Figure
1.
Figure 1. Spontaneous imbibition of different brines into chalk at 70,
100, and 130 °C to study the effect of temperature on the activity of
ions affecting the process of oil recovery.9
Another factor where temperature plays a role in CTWF is
the dependence of the oil-wet characteristic of carbonate rocks
on temperature. This property is mostly attributed to the
adsorption of carboxylic materials onto the rock surface, due to
their high affinity to carbonate surfaces compared to other polar
components that naturally exist in crude oil.85 Hence,
decarboxylation of carboxylic materials can lead to the
wettability alteration of carbonate surfaces to a more water-
wet state. Thermal decarboxylation at higher temperatures is
possible, especially on a carbonate surface, where CaCO3(s)
acts as a catalyst for the decarboxylation reaction.86
5.1. Open Questions. In the simulation work by Khorsandi
et al. (2016), the authors modeled the effects of low salinity
waterflooding together with polymer flooding based on the
concepts of reactive transport, wettability alteration, reaction
network, and multiphase fluid flow.87 They modeled the effects
of preflushing with low salinity water because of its ability to
prevent the degradation of polymer viscosity. The model
successfully accounted for the degradation in viscosity caused
by a high salinity brine and was validated against the
experimental work performed by Shiran and Skauge (2013),88
showing a good match.87 These mathematical models are
successful in predicting oil recoveries; however, they do not
consider all of the factors that may affect the process of
wettability alteration, and in particular, the importance of
temperature in changing the activity of the ionic species that
affect recovery rates.
Further, there is limited understanding in the literature as to
why Ca2+ ions show higher activity at lower temperature ranges
as compared to Mg2+ ions. Also, to the best of our knowledge,
no studies have been performed to identify the temperature
threshold at which a shift in the activity of Ca2+ and Mg2+ ions
takes place, and whether this threshold changes with rock type.
H DOI: 10.1021/acs.energyfuels.7b01067
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6. PROPOSED MECHANISMS FOR WETTABILITY
ALTERATION IN SANDSTONE RESERVOIRS
It has been well accepted that wettability alteration in oil-wet
and mixed-wet systems is the primary means for IOR by
CTWF. Several authors have proposed different physicochem-
ical mechanisms to validate wettability alteration as the primary
cause for IOR by CTWF. These include MIE,9,18,24 salting-
in,10,89 fines migration,8 EDL expansion,50,90 mineral dissolu-
tion,7,31 pH modification,8,62 and in situ emulsification. Some of
these mechanisms were proposed for sandstone rocks and
others for carbonate rocks. Authors have also tried to establish
various similarities and differences among these mechanisms.89
There still exists a lack of consensus as to which mechanism is
more prevalent, and under what conditions. In this section, we
elaborate on the proposed mechanisms that are relevant toward
wettability alteration in sandstone reservoirs, while section 7
discusses mechanisms relevant toward wettability alteration in
carbonate reservoirs.
6.1. Wettability Alteration by “Salting-In”. Austad et al.
(2010) propose a low salinity mechanism in sandstone
reservoirs, where they suggest that clay particles act as cation
exchangers on the sandstone surface.38 Initially, in the natural
state of the reservoir, both basic and acidic materials are
adsorbed onto the clay surface, owing to the negative surface
charge of clay particles and their large specific surface area
compared to quartz. As shown in Figure 2, at initial conditions,
Figure 2. Schematic representation of the “salting-in” mechanism of
wettability alteration in sandstones, showing the liberation of acidic
and basic components attached to the sandstone surface upon low
salinity water injection (used with permission, Austad et al. 2010).38
clay particles are exposed to an environment of formation brine,
which has high salinity levels. The divalent ions in the rock
samples establish a chemical equilibrium with the surrounding
high salinity formation brine. After the low salinity water is
injected, the chemical equilibrium is disturbed and the divalent
ions from the rock surface tend to free themselves to re-
establish the chemical equilibrium. Water molecules in the
neighborhood help facilitate this process by dissociating into
H+ and OH− ions. H+ ions from the water molecules adsorb
onto the clay surface, due to having the highest affinity to the
clay surface,67 and OH− ions remain in solution, resulting in a
local increase in pH near the clay surface.38 These OH− ions
react with the acidic/basic material adsorbed onto the rock
surface, releasing them from the surface. This is described as
the “salting-in” mechanism by Rezaeidoust et al. (2009).89
The following reactions describe the salting-in mechanism in
sandstones:
Clay − Ca 2 + + H 2O = Clay − H+ + Ca 2 + + OH−
For the basic component binding to the rock surface
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Energy & Fuels
Clay − NHR+3 + OH− = Clay + R3N + H 2O
For the acidic component binding to the rock surface
Clay − RCOOH + OH− = Clay + RCOO− + H 2O
6.2. Electric Double Layer (EDL) Expansion. An EDL,
first proposed by Von Helmholtz, is a structure that appears on
portions of rock minerals that are exposed to fluids in the pores,
as well as at rock−fluid and fluid−fluid interfaces. It refers to
two parallel layers of charge. The first layer is referred to as the
surface charge, which comprises oppositely charged ions
adsorbed onto the surface, whereas the second layer, known
as the dif f use layer, is composed of ions that are loosely
attracted to the surface charge.34 EDL expansion is dependent
on the electrical surface charge and is a function of the pH and
salinity of the brine, as well as the cation type surrounding the
clay or sandstone particle. Zeta potential, as shown in Figure 3,
Figure 3. Schematic representation of the electric double layer (EDL)
around a charged particle in a brine suspension.50
is the potential measured at the shear plane of the EDL and is
useful toward the estimation of the double layer thickness. High
pH, low salinity brines result in a thicker EDL.50 A more
Figure 4. Schematic representation of “fines migration” mechanism of wettability alteration in sandstones showing the liberation of fines attached to
the rock surface during low salinity waterflooding (recreated from Tang and Morrow (1999), with permission).8
I DOI: 10.1021/acs.energyfuels.7b01067
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negative zeta potential value means a thicker EDL, which is
indicative of a higher likelihood of water-wetting conditions.
Lee et al. (2010) reported that the water layer thickness of
the sandstone rock surface increased from 10.8 to 11.8 Å as
salinity was decreased from 0.1 to 0.001 M (6000 ppm to 60
ppm) by changing the amount of NaCl dissolved in brine.
However, when decreasing the salinity of brine by altering the
concentration of MgCl2, the water layer thickness increased
from 8.1 to 14.8 Å, therefore suggesting the importance of both
salinity and ion type toward the change in the thickness of the
double layer.90
As lower salinity water is injected, reducing multivalent
cations, the EDL expands both at the oil/brine interface and at
the rock/brine interface. This expansion causes an overlap
between both EDLs, which in turn leads to an increase in the
repulsive forces between them. Once the repulsive forces
exceed the binding forces involved in cationic bridging of acidic
groups in oil to the clay surface, the water layer between the oil
and clay surface expands, and oil particles desorb from the clay
surface, increasing water-wetness and improving oil recov-
ery.51,64 Also, decreasing the salinity of injected brine leads to
more negative zeta potentials at both the oil−brine and clay-
brine interfaces, which results in a stronger water-wet state and
IOR.51 However, the trend of increased production as salinity
decreases is not indefinite. If salinity is further lowered,
repulsive forces within clay minerals can exceed the binding
forces that keep clay particles intact. This results in
deflocculation of clay minerals and formation damage.91
Hence, an optimum injection brine salinity has to be identified
to avoid hindering oil flow and jeopardizing oil recovery.
6.3. Fines Migration. Early experiments conducted by
Bernard (1967) suggest that improved sweep efficiency can be
attributed to fines migration and clay swelling as a result of
freshwater injection.6 This was considered the main mechanism
for improving oil recovery and was further confirmed by the
study conducted by Tang and Morrow (1999).8 These authors
proposed an interplay between the mechanical capillary forces
that bind the oil particles to the fines and the viscous forces of
the low salinity waterflood. Further, the authors commented on
the stability of the fines particle in the suspension, suggesting
that low-salinity water helps expand the electrical double
layer,50,90 which assists in the stripping of fines and increased
oil recovery, as shown in Figure 4.8 This was also seen in the
coreflood experiments by Pu et al. (2010), where an increase in
pressure drop was found to assist in oil recovery. The authors
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Energy & Fuels
Figure 5. A schematic representation of the “MIE” mechanism of wettability alteration in carbonate reservoirs showing the sequential process of
liberation of the crude oil particles from the carbonate surface by a cumulative participation of the PDIs. (a) Low temperature ranges below 70 °C.
(b) high temperature ranges of above 100 °C (adapted from Zhang et al. 2007).9
attributed this to the cumulative effect of anhydrite dissolution
and fines migration in the Tensleep reservoir in Wyoming.31
However, some other authors reported little to no generation
of fines or decrease in permeability changes during low salinity
brine injection and proposed for a mechanism based on the
specific interactions between the rock mineral and the organic
components in the crude oil. This was termed as the MIE
mechanism and is described in the following section.10
7. PROPOSED MECHANISMS FOR WETTABILITY
ALTERATION IN CARBONATE RESERVOIRS
7.1. Wettability Alteration by “Salting-In”. In the
experiments conducted by Yousef et al. (2012)49 with
carbonate rocks and low salinity water injection, the authors
concluded that wettability alteration takes place due to rock
dissolution. They proposed that a chemical equilibrium is set
up in the predisturbed state when the rock is exposed to high
saline formation water. Once the system is exposed to a low
salinity environment, the divalent ions (Ca2+, Mg2+) present in
the rocks tend to displace toward the brine to re-establish
equilibrium. During this process, the polar ends of the crude oil
attached to the carbonate surface are liberated, in a way,
increasing the solubility of crude oil in the surrounding brine,
thereby improving oil recovery.49,89 This is similar to the
“salting-in” mechanism described in the previous section for
sandstone reservoirs. Some authors describe this as “rock
dissolution” mechanism, which is a consequence of the process
of wettability alteration as the divalent ions migrate from the
rock surface toward the brine.
7.2. Multi Ion Exchange (MIE). Lager et al. (2008)
proposed this mechanism based on the different interactions,
including, cation exchange, anion exchange, ligand exchange,
protonation, cation bridging, hydrogen bonding, van der Waals
interaction, or water bridging, that may happen between the
rock mineral and the various organic functional groups present
in the crude oil. Upon the injection of brine, rich in multivalent
ions, stronger ligand bonding between the carboxylic material
and the metal cation in the brine overcomes the weaker cation
bridging associations between the carboxylic material and the
J DOI: 10.1021/acs.energyfuels.7b01067
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rock surface. This releases the organometallic complexes
(RCOO-M, where M is the multivalent cation) from the
rock.10 A similar mechanism for carbonate rocks was proposed
by Zhang et al. (2007).9 The cumulative interplay of the
divalent ions from the brine, together with the rock and crude
oil, impacts the process of wettability alteration. The
mechanism is a sequential process that can be understood as
follows: Owing to the positive surface charge of the carbonate
surface, SO42− ions are attracted toward the surface, lowering
the surface potential and subsequently attracting the divalent
positive ions closer to the surface. As discussed earlier,
temperature plays an important role toward the activity of
these ionic species. Hence, the mechanism is divided into two
cases with respect to temperature. At lower temperature ranges
of about 70 °C, the activity of Ca2+ ions is higher, and
consequently, more Ca2+ ions are seen close to the surface than
Mg2+ ions. This is reversed at temperatures above 100 °C,
where Mg2+ ions show higher activity. During the interaction of
the positive ions with the SO42− ions, the positive ions interact
with the negative carboxylic end of the crude oil attached to the
carbonate surface. More positive ions in the solution form a
stronger interaction with the carboxylic end, as opposed to the
attraction between crude oil and carbonate surface releasing the
oil particles off the surface, resulting in IOR.9 The mechanism is
summarized in the schematic shown in Figure 5.
The following chemical reactions help explain the mecha-
nism:89,92
RCOO− − Ca − CaCO3(s) + Ca 2 + + SO24 −
= RCOO − Ca 2 + + Ca − CaCO3(s) + SO24 −
RCOO− − Ca − CaCO3(s) + Mg 2 + + SO24 −
= RCOO − Ca 2 + + Mg − CaCO3(s) + SO24 −
At high temperatures, Mg2+ ions, due to their higher activity,
interact with the surface Ca2+ ions and replace them with a
process called dolomitization.9 These interactions release the
Ca2+ ions from the surface which react with the crude oil at the
surface releasing the carboxylic material.
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Energy & Fuels
The simulation model developed by Qiao et al. (2015) is
based on this mechanism for altering wettability and for
predicting incremental oil recovery from mixed wet carbonate
reservoirs.93 The model accounted for the effect of the surface
active components in the crude oil, the surface charge of
carbonate rock and temperature. It was successfully validated
against the coreflood experiments performed by Fathi et al.
(2010).22
8. CONCLUDING REMARKS
CTWF is an expanding technique in EOR, with the particular
attribute of enabling wettability alteration of oil- and
intermediate-wet rock systems in order to assist in oil
production. The success of a chemically tuned waterflood is
highly determined by the interplay of many factors, such as
crude oil properties, brine salinity, brine composition, rock
mineral composition, and reservoir temperature. Proper
integration of surface analytical techniques like zeta potential,
acid number, X-ray diffraction, etc. can be useful for the
characterization of rock and crude oil compositions for
quantification of mineral content in the rock and acid/base
content in the crude oil. These analyses can be key in assessing
the optimum chemical tuning of injected brine for the most
effective waterflood scheme. Reservoir temperature is also
recognized to be a critical factor impacting the activity of ionic
species as is evident from the “MIE” mechanism for wettability
alteration in carbonate rocks. Several other mechanisms
including “rock/mineral dissolution”, “fines migration”, “elec-
trical double layer expansion”, etc., have been proposed for
understanding wettability alteration in carbonate and sandstone
reservoirs. These mechanisms display both similarities and
disparities in the two rock types. For instance, low salinity water
injection helps to disturb the chemical balance between the
rock and the brine, leading to the release of oil particles in both
carbonates and sandstones, with the exception of those
carbonate rocks devoid of anhydrite mineral. Although some
studies indicate the importance of low salinity brine injection in
carbonate reservoirs, most point toward the role of potential
determining ions for improving oil recovery. A holistic
understanding of these factors affecting wettability alteration,
and their interplay, can help improve the current understanding
of the simultaneous chemical reactions that occur at the rock
surface. These can include salt precipitation, mineral dissoci-
ation, crude oil desorption/solubilization, etc. Their appropriate
identification according to the crude oil/rock/brine system can
lead to the development of more robust mathematical models
that are better equipped to optimize waterflooding practices
and oil recovery estimations.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: (814) 863-2273. Fax: (814) 865-3248. E-mail:
ZKarpyn@psu.edu.
ORCID
Zuleima T. Karpyn: 0000-0002-2418-7653
Author Contributions
# (26) Puntervold, T.; Strand, S.; Ellouz, R.; Austad, T. J. Pet. Sci. Eng.
P.P. and M.S.T. contributed equally.
Notes
The authors declare no competing financial interest.
■
ABBREVIATIONS
ASTM = American Society for Testing and Materials
K DOI: 10.1021/acs.energyfuels.7b01067
Review
CEC = cation exchange capacity
CTWF = chemically tuned waterflooding
EDL = electric double layer
EOR = enhanced oil recovery
IOR = improved oil recovery
LSWF = low-salinity waterflooding
MIE = multi-ion exchange
micro-CT = microcomputed tomography
OOIP = original oil in place
PDI = potential determining ion
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