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Journal of Petroleum Science and Engineering 139 (2016) 137161
art ic l e i nf o a b s t r a c t
Article history: The low salinity/engineered water injection techniques (LSWI/EWI) have become one of the most im-
Received 3 September 2015 portant research topics in the oil industry because of their possible advantages for improving oil recovery
Received in revised form compared to conventional seawater injection. Researchers have proposed several mechanisms for the
14 November 2015
LSWI/EWI process in the literature; however, there is no consensus on a single main mechanism for the
Accepted 26 November 2015
low salinity effect on oil recovery. Because of the latter, there are few models for LSWI/EWI and especially
Available online 21 December 2015
for carbonates due to their heterogeneity and complexity. In this paper, we present a comprehensive
Keywords: state-of-the-art review on low salinity/engineered water injection for both sandstones and carbonates.
Low salinity water injection (LSWI) This review includes descriptions of underlying mechanisms, spontaneous imbibition and coreood la-
Engineered water injection (EWI)
boratory work, eld-scale pilots, numerical and modeling work, implementation, comparison between
Applications of LSWI/EWI
sandstones and carbonates, other LSWI/EWI applications, and desalination methods. List of re-
Comprehensive review on LSWI/EWI
Effects of LSWI/EWI in sandstones and car- commendations and conclusions are provided based on this vast literature review and our experiences.
bonates This paper can be used as a guide for starting or implementing laboratory- and eld-scale projects on low
Synergistic effects of LSWI/EWI salinity/engineered water injections.
& 2015 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.petrol.2015.11.027
0920-4105/& 2015 Elsevier B.V. All rights reserved.
138 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
and carbonates. In the context of this paper, we refer to the pro- the following: effect of LSWI/EWI on sandstone and carbonate
cess of diluting the injected water as low salinity water injection rocks, proposed chemical mechanisms for sandstone and carbo-
(LSWI); however, hardening or softening of the injected water is nate rocks, comparison of both rocks, modeling of LSWI/EWI, other
referred to as engineered water injection (EWI). LSWI has been applications of LSWI/EWI, and LSWI/EWI desalination methods.
applied for both sandstones and carbonates with more emphasis
on sandstones, whereas EWI has mostly been conducted for car-
bonates. The different applications of LSWI/EWI are also discussed 2. Effect of LSWI/EWI on sandstone rocks
in this paper including conformance control and the combination
of LSWI/EWI along with each of surfactants, polymers, and carbon This section includes the LSWI/EWI effect on sandstone rocks at
dioxide (CO2). This paper includes a detailed description of each of both laboratory-scale and eld-scale, and the mechanisms
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 139
2008). Fine migration is considered an auxiliary mechanism for these organic material. Organic materials are solvated in water by
low salinity water injection, but not the main. formation of a water structure using hydrogen bonds around the
hydrophobic part. Nevertheless, the presence of the inorganic
2.3.2. pH increase material (Ca2 , Mg2 , and Na ) leads to breaking this water
Increasing pH of the system due to low salinity water injection structure and decreasing the solubility of these organic molecules.
was suggested as the reason for the incremental oil recovery ob- Thus, the concentration of the divalent ions has a much stronger
tained by McGuire et al. in 2005 by forming an alkaline ood. effect on the solubility of the organic material in water. Decreasing
Lager et al. in 2006 disagreed by pointing out the need for gen- the salinity of the system below a critical ionic strength can in-
erating in-situ surfactant requires a crude oil with acid number crease the solubility of the organic material in the aqueous phase,
(AN) 40.2 mgKOH/g; however, in some cases the salinity effect which is called the salting-in effect. Doust et al. (2009) veried
was observed on oil samples with AN less than 0.05 mgKOH/g. this mechanism through a preliminary study as desorption of
Moreover, the increase in pH as noticed in many cases is not more 4-tert-butyl benzoic acid in an aqueous suspension of kaolinite
than 1 pH unit which makes the medium slightly basic and cannot increases with the decreasing salinity of brine used.
justify the obtained increments in oil recovery. In addition, the
decrease in interfacial tension (IFT) to ultralow values was not 2.3.5. Wettability alteration
pronounced in the literature. Extensive research work was performed for investigating the
Austad et al. (2010) proposed a chemical mechanism for the effect of low salinity water injection on changing the wettability of
effect of low salinity water injection. This mechanism suggests sandstone rocks. The conditions for the low salinity water injec-
that thermodynamic chemical equilibrium exists initially at re- tion effect to occur can be summarized from the work conducted
servoir conditions of pH (56). The low pH environment enhances by Tang and Morrow (1999) and Lager et al. (2007; 2008). Sand-
the adsorption of both acidic and basic components onto the clay stone as a porous medium must contain clay and type of clay
surface. The chemical equilibrium is disturbed the moment low mineral might play a role. Oil must have polar components and the
salinity water is injected; this causes interaction between brine injected water must contain divalent cations like Ca2 and Mg2 .
and rock to compensate for the loss of cations, especially Ca2 . The salinity of the injected water was usually between 1000 and
This causes H ions to get closer to compensate for the Ca2 loss 2000 ppm; effects were noticed even up to 5000 ppm. The con-
into the low saline water, which creates an increase in the pH close centration of Ca2 vs. Na plays a role and there is a little increase
to the clay surface. Local increase in pH leads to reactions between in pH of the efuent water. Fines migration might occur as pres-
the adsorbed basic and acidic material. sure increase across the core was observed. No temperature lim-
Clay minerals are unique by their cation exchange phenom- itation was reported; most of the experiments were performed at
enon. As a result of failure in the chemical structure, most of the temperatures below 100 C.
clay minerals are permanently negatively charged and so they Wettability alteration is considered the main phenomenon
need cations for balance to occur. This is usually satised by Ca2 behind increasing oil recovery using low salinity water through
cations; as a result of low salinity water injection, exchanging of various mechanisms including ne migration, pH increase leading
Ca2 ions by H ions at clay surface occurs according to Eq. (1), to interfacial tension reduction, multi-ion exchange, and double
which results in a pH increase: layer expansion. The wettability alteration in sandstone rocks was
related to the presence of clay minerals, oil composition, formation
Clay.... Ca2 + + H2 O Clay.... H+ + OH + Ca2 +. (1) water with high concentration of divalent cations (Ca2 , Mg2 ),
salinity level of water (10005000 ppm) (Tang and Morrow, 1997;
The reversibility of the pH can occur due to the injection of high
Suijkerbuijk et al., 2012).
salinity water, which leads to exchanging H ions by Ca2 ions at
Wettability alteration mechanism and oil recovery were re-
clay surface and decreasing pH according to Eq. (2):
ported to be similar to those occurring during alkaline and sur-
Clay .... H+ + Ca2 + Clay .... Ca2 + + H+ . (2) factant waterooding by McGuire et al. (2005). During low salinity
water injection (1500 ppm) experiments into sandstone core, re-
actions occurred and pH increased up to 9, causing generation of
2.3.3. Multi-ion exchange surfactant, which lowers the interfacial tension between oil and
Multi-ion exchange (MIE) mechanism, proposed by Lager et al. water and increases the water wettability leading to higher oil
(2006), states that increasing water wetness due to low salinity recovery. Zhang and Morrow (2006) suggested similar mechanism
water injection is the reason behind improving oil recovery by and they noticed an increase in the efuent brine pH, which never
exchanging ions affecting the interactions between the clay mi- exceeded 10. Clay-free sandstones provided evidence for the im-
nerals and surface-active components in the crude oil controlled portance of clays for reaction with low salinity water. Moreover,
by the presence of divalent ions such as Ca2 and Mg2 . An ad- similar reaction mechanism was suggested by Austad (2008), as
sorption model was suggested where Ca2 acts like a bridge be- with decreasing salinity below a critical value, the solubility of the
tween the negatively charged clay surface and the negatively organic materials in the aqueous phase occurs (salting-in phe-
charged carboxylic material; this organic material is removed by nomenon). As salinity of system decreases and thermodynamic
cationic ion exchange at the surface. equilibrium is disturbed, the cations desorb from the clay surface,
breaking the bridge between the clay surface and the organic
2.3.4. Salting-in material and leading to desorption of these organic material from
Doust et al. (2009) proposed salting-in mechanism, which the clay surface. The release of these cations causes increase in the
states that due to disturbing the thermodynamic equilibrium be- pH of the new equilibrium solution. This increase in the pH of the
tween the phases (water/oil/rock) by injecting low salinity water, system helps in releasing more of the organic material and ren-
the solubility of polar organic components in water changes. dering the system more water-wet (Doust et al., 2009).
Salting-out and salting-in terminologies are well known in the Nasralla and Nasr-El-Din (2011) investigated the effect of cation
chemical literature, as adding salt to the system (salting-out) leads type and concentration in the injected water on oil recovery from
to decrease the solubility of the organic material in water; how- Berea Sandstone cores. Wettability alteration was reported to be
ever, salting-in, which is decreasing the salinity of the system by the reason for oil recovery by changing the electrical charge for
salt removal from the water leads to increase in the solubility of both oil/brine and rock/brine interfaces to highly negative,
142 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
promoting repulsive electrical forces in the double layer and re- mapping of adhesion forces. In the experimental work, the authors
sulting in a more stable water lm and water wetting state. Also, used surfaces from real core samples, carboxylic acid end groups,
they reported the dominance of cation type effect on oil recovery and articial seawater solutions with salinity of 36,000 and
compared to the water salinity. Nasralla et al. (2011a) supported 1500 ppm. They observed a pronounced decrease in adhesion
their previous ndings of wettability alteration by cation exchange forces between the quartz grain surfaces and carboxylic acid when
and reported the advantage of applying low salinity water injec- decreasing the salinity of brine solution from 36,000 ppm to
tion in the secondary mode compared to the tertiary mode. 1500 ppm, which might be responsible for incremental oil re-
Moreover, in another work Nasralla et al. (2011b) showed that covery by LSWI. In a later work, Hassenkam et al. (2014) further
contact angle increases with increasing temperature and pressure, highlighted the use of force mapping combined with core plug
and decreases with decreasing water salinity. In a later work, testing for gathering information about incremental oil recovery
Nasralla and Nasr-El-Din (2012) investigated the expansion of the by LSWI. They observed a salinity threshold of 5000 to 8000 ppm
electric double layer as a primary mechanism by low salinity water for adhesion forces to decrease, which is similar to that of ex-
injection through different coreoods on Berea sandstone cores. perimental core plugs and reservoir tests. Hence, nanometer scale
Results of this study showed that the double layer expansion observations complement and explain those of micrometer and
mechanism is dominant in improving oil recovery by LSWI in the even kilometer scales.
secondary mode. Nevertheless, no additional oil recovery was re- After discussing the low salinity water ooding effect on
ported in the tertiary mode as they proposed that the dis- sandstones, its effect on carbonates is discussed in the section
continuity of oil phase mitigates expansion of the double layer. below.
Moreover, reduction of pH of low salinity injected water reduces
repulsion forces between oil and rock and results in a more un-
favorable oil-wet system. 3. Effect of LSWI/EWI on carbonate rocks
Rivet et al. (2010) reported wettability alteration to be the
reason for the incremental oil recovery due to low salinity water This section includes the LSWI/EWI effect on carbonate rocks at
injection from their coreoods on both Berea and reservoir cores. both laboratory-scale and eld-scale, and the mechanisms un-
This mechanism was supported by observations of decreasing end- derlying this effect.
point water relative permeability and increasing end-point oil
relative permeability. They reported a more stable water front case 3.1. Laboratory Applications of LSWI/EWI on carbonate rocks
when the system is water-wet, which helps in delaying break-
through and improving oil recovery. Moreover, although the re- The effect of low salinity/engineered water injections on car-
sidual oil saturation is lowest when rock is mixed-wet, water-wet bonates is not well covered compared to sandstones due to pre-
case results in the most favorable mobility ratio. Mahani et al. vious thoughts of relating wettability alteration by low salinity
(2014) investigated the mechanism by which wettability alteration water to the presence of clay, which is not the case in carbonate
occurs through their glass micromodel experiments on clay sub- rocks. Nevertheless, the effect of low salinity/engineered water
strate. They observed the decrease in contact angle after injecting injections on oil recovery from carbonate rocks was investigated at
high salinity water followed by low salinity water. They stressed laboratory-scale using both spontaneous imbibition and core-
on the importance of the kinetics of oil detachment when exposed ooding studies, and to a limited extent at eld-scale.
to low-salinity brine. Also, they reported that diffusion alone is not
responsible for the long-time observed for wettability alteration. 3.1.1. Spontaneous imbibition tests
An electro-kinetic ion-transport can explain the delay in formation For spontaneous imbibition experiments, Hognesen et al.
of cation-bridging, direct chemical bonds or acid/base effects. It is (2005) concluded from their experiments on reservoir limestone
worth mentioning that the viscous force was absent in this study cores, outcrop chalk cores, seawater and formation water that in-
and the main present forces were buoyant and adhesion forces. creasing sulfate ion concentration at high temperature leads to
Shehata and Nasr-El-Din (2015) conducted several zeta potential increasing oil recovery because of the role of sulfate ion as a
experiments to evaluate the effects of electrical surface charge and wettability-modifying agent for carbonate rocks from mixed-wet
double layer expansion for common sandstone minerals. Results to water-wet. Webb et al. (2005b) investigated the effect of sulfate
showed that the monovalent cations are more efcient in in- on oil recovery from North Sea carbonate core samples through
creasing the absolute values of zeta potential than divalent cations spontaneous imbibition experiments. They found that seawater
at 25 C. Moreover, with decreasing the salinity of the injected has the ability to alter wettability of the carbonate system to a
brine, the zeta potential becomes more negative. more water-wet state compared to sulfate free water. Moreover,
Sohrabi et al. (2015) focused on uiduid interactions as the Webb et al. (2005b) proved the effect of seawater on Valhall chalk
cause of wettability alteration by LSWI. They reported that the cores from the change in the capillary pressure curves with sea-
injection of low salinity water rearranges the natural active surface water injection compared to formation water. It was noticed that
component of crude oil, which coalesces in the form of micro- 40% of OOIP was recovered from chalk cores spontaneously using
dispersions in the oil phase. These micro-dispersions desorb the seawater compared to formation water and the recovery even
previously adsorbed natural active surface component from the increased from 40 to 60% with forced seawater injection.
rock interface rendering the rock surface more water-wet. The Zhang et al. (2007b) studied wettability alteration of North Sea
authors supported their ndings through direct ow visualization chalk reservoirs in Ekosk eld. The study was performed using an
(micromodel), crude oil characterization through infrared spec- oil with AN of 2.07 mgKOH/g and NaCl brine with different con-
troscopy, coreood, and spontaneous imbibition experiments. centrations of sulfate. Later, the effect of adding calcium or mag-
They claimed that the proposed mechanism works for both nesium ions was investigated at various temperatures. As seen in
sandstones and carbonates, and insensitive to the presence of clay. Fig. 2, they concluded that wettability alteration occurs if the im-
Some of the researchers believe that the effect of low salinity bibing water contains either Ca2 and SO42 or Mg2 and SO42 .
water on incremental oil recovery should be interpreted at the Both spontaneous and forced displacement tests on chalk using
nanoscale rather than the microscale. Hassenkam et al. (2012) a crude oil of AN 1.9 mgKOH/g were conducted by Strand et al.
utilized atomic force microscopy (AFM) to justify the incremental (2008a). This work has veried the improvement in water wetness
oil recovery obtained by LSWI from sandstones by measuring and of carbonate rocks using seawater at high temperature, which
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 143
the higher concentration of sulfate ion leads to higher oil recovery cation surfactants affect wettability alteration, turning carbonate
up to a certain limit. They suggested that smart water with four rocks more water-wet at different degrees regarding carbonate
times sulfate concentrations might be the optimum sulfate rock type (Calcite, Dolomite and Magnesite).
concentration. Moreover, Hognesen et al. (2005) conducted imbibition ex-
After discussing the experimental work of LSWI/EWI on car- periments on chalk and limestone cores for investigating the effect
bonates, the limited application on eld-scale is discussed in the of cationic surfactants as well as sulfates as wettability modiers
subsection below. using seawater. They found that with increasing the temperature
(90130 C), sulfate acts as a catalyst causing an increase in oil
3.2. Field applications of LSWI/EWI on carbonate rocks recovery by imbibition in the presence of surfactants. The sulfate
concentration used was 2.31 g/L, even higher than the sulfate
The rst ever LSWI application in carbonate reservoirs was concentration used by Strand et al. (2003), which resulted in a
reported by Yousef et al. (2012a). Two single well chemical tracer higher oil recovery due to the increase of sulfate adsorption on
tests (SWCTTs) were applied in an Upper Jurassic carbonate re- surface. The increase in sulfate afnity to carbonate surface with
servoir using a diluted version of Qurayyah seawater. The tests increasing temperature was veried to be the reason for such
resulted in about 7 saturation units reduction in the residual oil sulfate catalytic behavior at higher temperatures. The increase in
beyond conventional seawater injection. Two wells (A and B) were the afnity of sulfate changes the rock charge locally from positive
selected for the tests based on certain screening criteria. The ob- to negative and causes repulsion with carboxylic group, rendering
jective of the test on well A was to conrm the effect of LSWI in the the system water-wet. The use of cationic surfactants and sulfates
tertiary mode where three slugs were injected: two seawater slugs is in lowering IFT besides wettability alteration. Therefore, in-
to assure achieving residual oil saturation conditions, followed by creasing the temperature of the system not only decomposes the
the smart water slug (10 times diluted). After each slug, three carboxylic group, but also increases the adsorption of sulfates on
tracers were injected to determine the reduction in residual oil
the rock surface, which promotes retention of water wetness. They
saturation. The SWCTT on well B was conducted to determine the
stated that the benet in using sulfate as a wettability modier has
effect of various dilutions of smart water on residual oil saturation,
limitations depending on initial brine salinity and temperature, as
where three slugs were injected: a seawater slug, followed by a
the concentration of Ca2 in the connate brine should be known
twice-diluted smart water slug, and nally a 10 times diluted
with certainty to avoid CaSO4 precipitation.
smart water slug. Results obtained matched with their previous
Wettability alteration in carbonate rocks using LSWI/EWI can be
experimental work (Yousef et al., 2011), which is encouraging to
achieved by injecting water containing SO42 and either Ca2 or
plan a multi-well demonstration pilot.
Mg2 or both of them in the presence of high temperature (490 C).
As seen from this section, most of the conducted laboratory
Both proposed mechanisms for wettability alteration in carbonate
experiments were mainly spontaneous imbibition experiments
rocks are shown in Fig. 4. It was proposed that with increasing
with few coreooding experiments. The reason behind this is the
temperature, the afnity of sulfate to chalk rock surface increases and
attempt to understand the mechanism that controls the increase
sulfate adsorption occurs. At the same time, Ca2 adsorption in-
in oil recovery from carbonate rocks with low salinity/engineered
creases as well as the initial positive charge of the rock decreases.
water injections.
Hence, more excess Ca2 ions are present close to the surface, which
3.3. Proposed mechanisms for LSWI/EWI effect on carbonate rocks reacts with the carboxylic material and releases some of them.
Moreover, with increasing temperature, Mg2 becomes more active,
3.3.1. Wettability alteration Ca 2 substitution by Mg2 occurs, and sulfate becomes less active as
The thermodynamic equilibrium has long been established it reacts with Mg2 . Otherwise, CaSO4 precipitation occurs and
between the rock/oil/formation brine systems initially in the re- causes injection problem. This is shown in Fig. 4 for case (B), while
servoir. Nevertheless, this equilibrium is not favorable in certain case (A) in Fig. 4 shows the effect of low temperature (less than
cases concerning wettability phenomenon, especially in carbonate 100 C), where Mg2 becomes less active and both Ca2 and SO42-
rocks. Extensive research was performed by Austad and other becomes more active and CaSO4 might occur (Zhang et al., 2006).
coworkers (Standnes and Austad, 2000; Hognesen et al., 2005; Both wettability alteration mechanisms by Ca2 and SO42- and by
Zhang et al., 2006; Puntervold et al., 2007), which opened the Mg2 and SO42- at the chalk surface can be seen clearly in Fig. 2,
possibility of wettability alteration and enhancement of oil re- which shows experimental results of the work performed by Zhang
covery from carbonate rocks by modifying the ionic composition et al. (2007b) conrming their proposed mechanism.
in the injected water. Wettability alteration is the main and most
acceptable mechanism for the incremental oil recovery achieved in
carbonate rocks with the use of low salinity/engineered water
injections. The wettability alteration phenomenon can occur due
to change in the surface charge of the rock or dissolution.
For the case of changing the surface charge of the rock, several
researchers related wettability alteration by low salinity water to
sulfate adsorption on rock surface. Strand et al. (2003) investigated
the sulfate concentration on wettability alteration with and
without cationic surfactant solution using chalk, dolomite cores,
and different crystals of carbonate rocks for spontaneous imbibi-
tion. They found that the effect of sulfate as a catalyst for im-
bibition rate in the presence of surfactants is more pronounced at
high temperature and below a certain concentration of 1.0 g/L. The
role of sulfate as a catalyst for improving imbibition rate comes
from adherence on the rock surface. This makes this location
partially negatively charged due to the presence of other positively Fig. 4. Proposed mechanisms for wettability alteration in carbonate rocks (Zhang
charged metal ions. They also concluded that both sulfates and et al., 2006).
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 145
Previous studies indicated that wettability alteration process is (2004) reported that the detachment of oil-wet nes from pore
related to the presence of Ca2 , Mg2 , and SO42 active ions with walls exposes the underlying clean water-wet pore surface.
increasing temperature. Moreover, it was reported that a chemical Schembre et al. (2006) proposed ne migration as a mechanism
mechanism occurs involving interactions between Ca2 and for wettability alteration from their water imbibition tests. One of
SO42 and between Mg2 and SO42 at the chalk surface, which the main proposed mechanisms for wettability alteration is related
cause displacement of negatively charged carboxylic materials in to the presence of key ions (SO42-, Ca2 , Mg2 ) in the injected
crude from the positively charged chalk surface. For Ca2 and water, which enters to the rock matrix by molecular diffusion.
SO42 interactions, the adsorption of SO42 to chalk surface in- Then, a non-thermodynamic equilibrium state is created which
creases with increasing temperature. This leads to decrease in the results in chemical interactions in the aqueous phases as well as
positive surface charge, more attachment of Ca2 to chalk surface interactions between water and rock in terms of precipitation/
as the electrostatic repulsion force is decreased and reactions with dissolution of rock minerals and/or changing the rock surface
carboxylic material occur (Zhang et al., 2007b). This is according to charge (Evje and Hiorth, 2009).
the equation: In case of injecting water containing Mg2 and SO42-, Mg2 has
the ability to substitute Ca2 ions from the surface lattice of the
RCOO Ca CaCO3 (s) + Ca2 + + SO24 = RCOO Ca+ + Ca CaCO3 (s) + SO24 . (3)
chalk. The presence of SO42- plays a catalyst role for the sub-
2 stitution process (Zhang et al., 2007b). The substitution equation is
In this reaction, SO4 acts like a catalyst for promoting the
increase of Ca2 concentration ions close to the surface. Strand as follows:
et al. (2006) observed this mechanism, as with increasing tem- RCOO Ca CaCO3 (s) + Mg 2 + + SO 24 = Mg CaCO3 (s) + RCOO Ca+ + SO 24 . (4)
perature, the retention of SO42 increases and the concentration
of Ca2 decreases. Lager et al. (2007) reported multi-ion exchange The substitution was observed by Strand et al. (2008b); by
(MIE) mechanism in carbonate reservoir when anion exchange ooding sea water through a limestone core at 130 C, they no-
adsorbed on carboxylate. The authors agreed with the Strand et al. ticed that concentration of Ca2 increased, that concentration of
(2006) mechanism of wettability alteration in carbonate rocks Mg2 decreased, and that concentration of SO42 was not much
using seawater. Nevertheless, they stated that MIE does not re- affected as the precipitation of CaSO4(s) was small. Water weak-
quire low salinity to decrease oil saturation, as there is no ex- ening effect of carbonate rocks was reported in the literature by
pandable electric double layer. Therefore, they did not expect low adding SO42 and Mg2 to the imbibing uid causing a decrease
salinity water to work in carbonate reservoir. in the yield point of the chalk rock and dramatic compaction at
The key behind increasing oil recovery from chalk reservoir high temperatures. This means that the chemical interaction be-
using sea water is related to sea water ions (SO42 , Ca2 , Mg2 ) tween components of seawater and the chalk rock affects the
that have the capability of changing rock surface charge, releasing mechanical strength of the chalk. The weakening effect of imbib-
adsorbed carboxylic material to rock surface, altering rock wett- ing water is related to both CaCO3 solubility and substitution of
ability, and eventually improving oil recovery. More pronounced Ca2 by Mg2 . The presence of Mg2 along with SO42 enhances
effect of improving oil recovery using high concentration of sea- the substitution of Ca2 by Mg2 . The different sizes between
water ions, high temperature formations (490 C), and sulfate Ca2 and Mg2 causes stress changes and reduction in the me-
free formation water was addressed (Yousef et al., 2011). chanical strength in the chalk rock. This is added to the formed
Moreover, diluting the injected water was reported as a cause MgCO3 that is more soluble in water compared to CaCO3 (Austad
for wettability alteration. Yousef et al. (2011) conrmed that the et al., 2008).
incremental oil recovery due to low salinity water injection is due Nuclear Magnetic Resonance (NMR), contact angle measure-
to wettability alteration, not reduction of interfacial tension (IFT). ment, and zeta potential studies were utilized to demonstrate that
This was possible by measuring both IFT and contact angle at re- wettability alteration is the reason behind LSWI (Yousef et al.,
servoir conditions. Results indicated that IFT has no signicant 2012b). The results showed that wettability alteration occurs
effect on incremental oil recovery due to low salinity water in- through changing the surface charge from the zeta potential
jection and wettability alteration is the main mechanism behind measurements and dissolution of CaSO4 from NMR tests. More-
this additional oil increase. They concluded that incremental oil over, the study addressed the importance of multivalent ions in
recovery due to low salinity water injection is caused by wett- enhancing wettability alteration. They studied the rock surface
ability alteration (uidrock interactions) rather than IFT reduc- chemistry by measuring zeta potential, which describes the
tion (uiduid interactions). They also proposed that wettability magnitude of charge present on a charge particle. Charge particles
alteration due to change in surface charge and dissolution pro- with high zeta potential are self-stabilizing. The change in surface
cesses as a result of Nuclear Magnetic Resonance (NMR) technique. charge of carbonate rocks is supported by NMR tests showing fast
Left shifting in amplitudes obtained for the post test case as well surface relaxation and zeta potential measurements showing
as overlapping between low and high amplitudes, which means shifting towards more negative state with successive injection of
higher rate of relaxation due to change in the carbonate rock seawater dilutions. Later, Yousef et al. (2012c) investigated the
surface charge and improvement in pore by dissolution, respec- applicability of LSWI in both secondary and tertiary modes. The
tively. This study of smart waterooding is different from seawater results conrmed the effect of LSWI in the tertiary mode as about
chalk carbonate rock studies in terms of water salinity as diluted 14% of OOIP was obtained by injection of seawater, twice diluted,
water was used and it was not rich with key ions (SO42 , Ca2 , 10 times diluted, and 100 times diluted in succession. Moreover,
Mg2 ) as seawater chalk carbonate rock case. the study showed the potential of LSWI in the secondary mode as
In the case of rock dissolution, collapsing some of the pore 10% additional oil recovery was obtained using 10 times diluted
spaces occurs and hence oil is expelled. Pressure, temperature, seawater compared to the seawater. Also, the temperature effect
chemistry of pore water, and oil play a role in wettability alteration on wettability alteration was highlighted by comparing the results
and oil recovery by rock dissolution (Hiorth et al., 2010). Tang and of this study with their previous work of Yousef et al. (2011).
Kovscek (2004) reported the decrease in residual oil saturation Romanuka et al. (2012) reported two ways for modifying the
from eld and outcrop diatomite as a result of temperature in- wettability of carbonate rocks using LSWI/EWI, increasing the
crease. They also reported that wettability alteration correlated concentration of surface interacting ions (SO42 , BO33 or PO43 )
with nes production at high temperature. Schembre and Kovscek in the injected brine, and lowering ionic strength of the injected
146 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
Fig. 5. Wettability alteration by dissolution (Al-Shalabi et al., 2015a). Few modeling works for LSWI/EWI exist in the literature
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 147
because the researchers focused their works on checking the ap- This was conrmed using the viscous ngering theory and 2D
plicability of this technique and understanding the mechanism numerical simulation model. They concluded that low salinity
underlying the related incremental oil recovery. In this section, we water injection is expected to be mildly unstable at the rear front.
highlight the main modeling works for both sandstones and For conventional and fractured medium, Wu and Bai (2009)
carbonates. proposed mathematical model for wettability alteration modeling
Jerauld et al. (2008) introduced one of the simplest models for due to low salinity waterooding. In this model, salt is treated as
predictions of low salinity water injection oil recovery at eld- an additional component in the aqueous phase, which is trans-
scale based on coreoods and single well tests. The proposed ported, by advection and diffusion, including the adsorption effect
model considers salt as an additional single lumped component in on the surface of the rock. Improving oil recovery was in-
the aqueous phase and the density and viscosity of the aqueous corporated by treating relative permeability, capillary pressure,
phase, relative permeability and capillary pressure curves all de- and residual oil saturations as salinity dependent.
pend on salinity. Moreover, both clay content effect and dispersion The importance of dynamic wettability alteration models was
were considered as dispersion was assigned a value of 5% of the highlighted in the literature. Spontaneous imbibition experiments
system's length. Equations included in the model for representing of Stevns Klint Chalk core plugs using low salinity water injection
capillary curves and relative permeability curves with upper and were simulated using a 1D model proposed by Yu et al. (2009). The
lower salinity limits are model accounts for molecular diffusion, salt adsorption, gravita-
HS * LS *
tional and capillary forces for simulating the dynamic wettability
k rw = k rw (S ) + (1 ) k rw (S ), alteration process. The dynamic changes in both capillary pressure
HS * LS *
k ro = k ro (S ) + (1 ) k ro (S ), and relative permeability curves from oil-wet to water-wet were
HS
Pcow = Pcow LS
(S*) + (1 ) Pcow (S*), made dependent on wettability alteration agent or salt con-
centration. In addition, the salt concentration in the model was
( LS
= Sorw Sorw )(
HS
/ Sorw LS
Sorw , ) considered as ca wa 1 (mole fraction) where ca is the mass
S* = ( So Sorw )/( 1 S wr Sorw ). fraction of slat component in aqueous phase, and wa is the mass
(5)
fraction of water component in aqueous phase. Moreover, the
For investigating the stability of the low salinity waterfront, adsorption isotherm of salt onto rock (cr) was introduced and
Tripathi and Mohanty (2008) modeled instability of low salinity made as a function of salt concentration, cr f (ca). The adsorption
water injection oods in the tertiary mode without including coefcient (cr)a1ca/(1 a2ca) with constants a1, a2 4 0 (Langmuir
wettability alteration effect on capillary pressure. The analytical type isotherm relation for adsorption). The effect of wettability
1D solution shows two shocks with probability of instability in the alteration on capillary pressure and relative permeability was
rear shock (low salinity shock) due to the adverse mobility ratio. considered by interpolation between the oil-wet and water-wet
148 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
the cores. This study contradicts with the observations from NMR components (e.g., CO2, CH4, and acidic/basic components of the
T2 distribution curves by Yousef et al. (2011) which shows that crude oil) on buffering the aqueous pH and more generally, on the
changing surface charge is more important than dissolution; crude oil, brine, and rock reactions.
otherwise higher amplitudes can be obtained in NMR T2 dis- A systematic way for history matching LSWI coreoods was
tribution curves indicating slower rate of relaxation. also presented in the literature. Al-Shalabi et al. (2014a and 2014b)
Aladasani et al. (2012b) reported that intermediate wetting presented a systematic way of history matching published LSWI
condition is the ideal wettability alteration condition as capillary coreoods including Yousef et al. (2011, 2012c) and Chandrasekhar
pressure is low and the increase in oil relative permeability is the and Mohanty (2013). The study highlighted the sensitivity of re-
main controller of recovery mechanism. Moreover, the validity of sidual oil saturation, capillary pressure curve, and relative per-
the simulator and recovery mechanism presented was conrmed meability parameters (endpoints and Corey's exponents) on LSWI
by matching Yousef et al. (2011) experimental work. This was through history matching both oil recovery and pressure drop data
achieved by considering a linear relationship between salt con- for the coreoods investigated. It is worth mentioning that the
centration and each of residual oil saturation, contact angle and previously discussed LSWI/EWI models have treated the water and
IFT. Nevertheless, some of the disadvantages of this history match oil phases similarly with respect to capillary pressure (Pc) and
are: the original laboratory data were not shown in matching the relative permeability (kr) in the sense that both phases are shifted
data, the overall recovery values were not exactly in match, the using a similar scaling factor. Al-Shalabi et al. (2015b, 2015c)
initial jumps in oil recovery were not properly matched, pressure showed that oil relative permeability is more sensitive to LSWI
drop data were not matched, and the dependence of residual oil compared to water relative permeability and hence water and oil
saturation on trapping number was not considered due to ex- phases should be treated separately. Based on the latter nding,
ceeding the critical trapping number value. we proposed several models for the effect of LSWI on oil recovery
In addition, Omekeh et al. (2012) developed a model that de- from carbonates that are discussed briey. It should be noted that
scribes dissolution/precipitation processes in carbonate rock along the simulation and modeling work at this stage was performed
with multi component ions exchange to simulate the additional oil using the UTCHEM simulator. Moreover, the capillary pressure
recovery by LSWI/EWI. In this mode, the release of divalent cations contributions were neglected in the proposed models as different
from the rock surface changes the relative permeability such that capillary pressure curves were assumed in the simulation runs
additional oil is achieved. A scaling function (F), which depends on with minimal effect added to the facts of using relatively long
desorption of the divalent ions, was dened for interpolating be- cores and applying high pressure gradient in the laboratory for the
tween predetermined high salinity and low salinity sets of relative coreoods investigated.
permeability as follows: An Empirical LSWI Model was proposed by Al-Shalabi et al.
k (S, Ca , Mg ) = F (Ca , Mg ) k HS (S ) + 1 F (Ca , Mg ) k LS (S ) , (10)
(2014c), which was implemented in UTCHEM and captures the
change in residual oil saturation, oil endpoint relative perme-
as Ca and Mg are the absorbed calcium and magnesium ca- ability, and oil exponent while maintaining constant water relative
tions, respectively. The suggested model was validated by history permeability curve. The assumption of using constant water re-
matching a two-phase coreooding experiment. They concluded lative permeability parameters is based on the negligible change in
that calcite dissolution and ion exchange are responsible for the water relative permeability parameters for the coreoods in-
LSWI/EWI effect on oil recovery. vestigated (Yousef et al., 2011, 2012c; Chandrasekhar and Mo-
Some of the presented LSWI models capture the effect of dif- hanty, 2013). In case experimental data are available, an average
ferent geochemical reactions on oil recovery. Dang et al. (2013b) constant water relative permeability values can be considered for
proposed a low salinity water model by coupling a comprehensive the seawater dilution cycles; otherwise, the water relative per-
ion exchange model with geochemical processes to a multi-phase meability values can be assumed constant and equal to the sea-
multi-component ow equation-of-state compositional simulator. water injection cycle. In this model, residual oil saturation, oil
The interpolating factor they used to interpolate between relative endpoint, and oil exponent are functions of contact angle mea-
permeability curves is dened as follows: surements upon which a third degree polynomial function is used
Ca X2 CEC to express contact angle as function of total injected water salinity.
= , Initial and injected water salinities are specied as input para-
CECmax (11)
meters. The injected brine is mixed with the initial reservoir brine
where Ca-X2 is the equivalent fraction of Ca2 on the clay ex- and during the mixing process, the salinity wave moves and
changer, CEC is the cation exchange capacity of clays, and CECmax is changes the contact angle in each gridblock using the proposed
the maximum cation exchange capacity of clay. The proposed polynomial function. Once the contact angle changes, then re-
mode was validated using low salinity coreoods reported by sidual oil saturation, oil exponent, and oil relative permeability
Fjelde et al. (2012) for a North Sea reservoir and heterogeneous endpoint are calculated using the proposed correlations. The
coreoods by Rivet (2009) for a Texas reservoir. equations implemented in the UTCHEM simulator are as follows:
Also, Korrani et al. (2013) coupled IPHREEQC, the state-of-art LS HS
geochemical engine (Parkhurst and Appelo, 2013), with UTCHEM, Sor (Altered) = S Sor + (1 S ) Sor , (12)
a 3D non-isothermal chemical compositional ow simulator de-
veloped at The University of Texas at Austin (UTCHEM 9.0 Tech- ( HS )
S = ,
nical Documentation, 2000), to develop a robust, accurate, and ( LS HS ) (13)
exible tool named as UTCHEM-IPHREEQC simulator. The latter
simulator was used for modeling low salinity water injection and *LS k ro
k ro *HS
other geochemically related IOR/EOR processes. In a later work, * =
k ro *HS ,
+ k ro
e
Korrani et al. (2014) couple IPHREEQC with UTCOMP, a three-di-
1+ ()a (14)
mensional, equation-of-state (EOS) compositional reservoir simu-
lator, developed at The University of Texas at Austin (UTCOMP no max noLS
no = + noLS .
3.8 Technical Documentation, 2011). The motive behind the latter e
coupling is to show the effect of water-soluble hydrocarbon
1+ ()
a (15)
150 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
r 0 kB T
1 = ,
2NA e2I (17)
1.0
0.9
Sor decreases as Tl
0.8 increases at a constant
0.7 NT due to wettability
0.6 alteration
0.5
0.4
0.3
0.2
0.1
0.0
1.0E-10 1.0E-09 1.0E-08 1.0E-07 1.0E-06 1.0E-05 1.0E-04 1.0E-03 1.0E-02 1.0E-01
Trapping Number (NT)
Experimental Data Twice Diluted Seawater
10 Times Diluted Seawater 20 and 100 Times Diluted Seawater
Fig. 9. Relative permeability curves with the Empirical LSWI Model (Al-Shalabi
et al., 2014c). Fig. 10. CDC Model used in the Fundamental LSWI Model (Al-Shalabi et al., 2014d).
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 151
0.6
imum and minimum salinity. The retention and adsorption of the
0.4
amount of salt as a result of varying the salinity of injected water
were modeled using the Langmuir adsorption isotherm.
0.2 Al-Shalabi et al. (2015e) investigated modeling and simulation
of SWCTT of low salinity water injection in a Middle Eastern car-
0 bonate reservoir using UTCHEM. Both Radial and Cartesian grid
0 0.2 0.4 0.6 0.8 1
models were setup for a eld-scale pilot. Two approaches were
Water Saturation (Sw) (Fraction)
used to estimate remaining oil saturation to LSWI including ana-
First Cycle Second Cycle Third Cycle Fourth Cycle
lytical and numerical methods. The results showed that both ap-
proaches give consistent values for remaining oil saturation for
Fig. 13. Fractional ow curves (Empirical LSWI Model-Quarter 5-spot Field Model) homogeneous Radial grid model. The Cartesian grid model was
(Al-Shalabi et al., 2014e). used to investigate the effect of heterogeneity on SWCTT where a
new numerical approach was proposed for estimating remaining
is as the following: oil saturation. The authors consider the area in which oil satura-
tion is below the original residual oil saturation is affected by the
(r1) S1= S wf LSWI. Hence, the equation used to calculated the average residual
M= ,
(r1 + r2 ) S1= SOB (26) oil saturation is
In this case, the mobility ratio is dened as the ratio of the i So, i Vi HS
Sor = i: So, i < 0.99 Sor ,
relative water mobility at the shock front to the total relative i Vi (27)
mobility at the oil bank front. This denition physically makes
more sense because it maintains the denition of mobility ratio as where Sor is the average residual oil saturation and Vi is the
the mobility of the displacing uid to the displaced uid and the pore volume of gridblock i. The results validate the approach used
chosen saturations physically exist. Fractional ow curves were and the implementation of both tracer reactions and LSWI model
analyzed to nd the shock front and oil bank front saturations at in UTCHEM.
each injection cycle, which is needed for calculating the corre- Minimizing risk and uncertainty is a major part of any pro-
sponding relative mobility values. posed IOR technique by highlighting the most signicant design
Tracers were used to model low salinity water injection. Tracers parameters and optimizing the entire process. Al-Shalabi et al.
are usually used for tracking the details of uid movement in- (2014f) optimized the LSWI process at eld-scale for carbonate
cluding the advancing uid front, the breakthrough, the sweep reservoirs by considering seven uncertain and decision para-
efciency, detection of ow barriers and others. Modeling of tracer meters. 5-spot LSWI pilot models were simulated using UTCHEM
ow helps in interpreting complex eld tracer tests upon which simulator with the Empirical LSWI Model. The Design of Experi-
advectiondiffusion equations are used and the diffusion term is ment (DoE) method was used for sensitivity analysis and screening
usually neglected for most practical cases. Both active and passive out the insignicant parameters (Fig. 14). The Response Surface
traces as well as partitioning and non-partitioning trances are Methodology (RSM) was implemented to optimize the LSWI cu-
included in the model. Passive tracers are the ones that do not mulative oil recovery where a response surface was built (Fig. 15).
change the physical properties of the phase in which they exist In this study, the numerical optimization option in Design Expert
and they used mainly for tracking injected uid. Nevertheless, software was utilized for the optimization process (Design-Expert
active tracers are used for modeling physical and chemical effects Software, 2011). The performed sensitivity analysis showed that
that are not possible to model using black oil or compositional the three most important design parameters are LSWI slug size,
simulators such as variation of water viscosity due to polymer, reservoir heterogeneity characterized through DykstraParson
salinity effect on wettability, residual oil, relative permeability and Coefcient (VDP), and injected water salinity. Moreover, an opti-
capillary pressure, water PVT properties, mixing oils of different mized design was suggested and the results were validated against
viscosity, and oil vaporization effect. Non-partitioning tracer is the UTCHEM.
one exists in a single phase; however, partitioning tracers partition Moreover, Attar and Muggeridge (2015) evaluated the effect of
between phases like single well chemical tracer test in which the
tracer partitions between oil and water phases (Verma et al., Seawater Slug Size and LSWI Slug Size
2009). kv/kh
Verma et al. (2009) described modeling of improved oil re- Sorw and Injected Water Salinity
covery processes using tracers in an unstructured grid simulator. Seawater Slug Size
Design Parameters
Also, modeling single well chemical tracer tests is possible using LSWI Slug Size and Injected Water
this approach, which is used for determining the residual oil sa- Sorw
turation before and after applying improved oil recovery methods.
Soi
Negligible tracer can be used for modeling polymers and salinity
Injected Water Salinity
effect on improving oil recovery. Decoupling of tracer equations
Reservoir Heterogeneity
from other component equations is the main advantage of using
LSWI Slug Size
tracer for improved oil recovery modeling. Verma et al. (2009)
modeled improving oil recovery by low salinity water injection 0 5 10 15 20 25 30 35 40
using tracers that affect the rock and uid properties. This was % Contribution
possible by modifying the relative permeability and capillary Fig. 14. Effect of design parameters on cumulative oil recovery (Al-Shalabi et al.,
pressure curves, residual saturations along with water viscosity, 2014f).
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 153
ooding by investigating the effects of low-salinity-water slug gas slug size, timing of injection, and WAG ratio (Jiang et al., 2010).
size, water salinity, and polymer viscosity. The results showed that The main experimental and numerical works conducted for in-
both LSWI slug size and polymer viscosity have a pronounced vestigating the combined effect of low salinity water and CO2
effect on low-salinity polymer ooding. Nevertheless, a negligible ooding is discussed.
effect was noticed for water salinity on the process. Kulkarni and Rao (2005) conducted miscible and immiscible
WAG with varying brine composition on Berea sandstone cores.
5.4. LSWI/EWI and surfactant ooding application They reported a decrease in oil recovery with decreasing the
salinity of the injected water due to the increase in the solubility of
Spildo et al. (2012) investigated the effect of combining low CO2 in brine. Jiang et al. (2010) investigated the effect of injection
salinity water injection and reduced capillarity by surfactants in brine salinity on CO2-WAG performance in the tertiary mode on
terms of EOR additional oil recovery and cost efciency. If capillary Berea sandstone cores by changing the salinity of the injected
pressure is high, then re-trapping of the LSWI mobilized oil might brine systematically up to 32,000 ppm. The coreooding experi-
occur. Hence, surfactants are recommended to lower the capillary ments were run at 60 C and at a pressure 20% above the mini-
forces and avoiding re-trapping of the mobilized oil. In the latter mum miscibility pressure (MMP) to ensure miscible CO2 ooding.
study, coreooding experiments were conducted on Berea sand- The results revealed that the WAG recovery increases with in-
stone core plugs. The results concluded that surfactant injection of creasing the salinity of the injection brine; this was explained due
Winsor I phase behavior (lower phase microemulsion) at low to the salting out effect, as the solubility of CO2 in water decreases
salinity yields good recovery and low surfactant retention. Also, with increasing the salinity. This allows more CO2 available for oil
intermediate-water conditions seem to be more favorable com- displacement resulting in higher oil recovery.
pared to water-wet conditions. Moreover, surfactant injection with Other than CO2 solubility, wettability alteration is another im-
low salinity water gives higher oil recovery than the expected portant factor for incremental oil recovery by combined low sali-
performance using only surfactant ooding. nity and CO2 injections. Fjelde and Asen (2010) investigated
Moreover, Alagic and Skauge (2010) investigated the combined wettability alteration during water ooding and CO2 ooding on
effect of injecting low salinity water with surfactant ooding on oil reservoir chalk rocks from the North Sea at different temperatures
recovery from Berea sandstones. The authors conducted several (50 and 130 C). The experimental work started with formation
coreoods and highlighted the positive response obtained using water as a rst phase, followed by seawater as a second phase and
the combined injection. In a later work, Alagic et al. (2011) con- nally a cycle of seawater alternating Carbon Dioxide ooding
rmed their previous ndings on longer cores to minimize capil- (CO2-WAG) as a third phase. The results showed that wettability
lary-end effects and investigated the effect of aging on recovery. alteration towards more water-wet was observed after the WAG
They reported higher oil recovery using the combined injection slug resulting in residual oil saturation between 3 and 5%.
from aged cores compared to unaged cores. They reported that the On the other hand, the combined effect of injection on carbo-
combined low salinity and surfactant oodings prevents re-trap- nates was studied by Aleidan and Mamora (2010). They studied
ping of the mobilized oil by LSWI. Tavassoli et al. (2015) used the the effect of different CO2 injection modes on oil recovery by
UTCHEM-IPHREEQC simulator to investigate the combined effect conducting coreooding experiments including continuous gas
of LSWI and surfactant ooding. The authors history-matched the injection (CGI), water-alternating gas (WAG), and simultaneous
experimental work of Alagic and Skauge (2010) including oil re- water alternating gas injection (SWAG). The experiments were
covery, efuent ionic composition, and pressure gradient data. conducted at 120 F and 1900 psi, which is 100 psi more than the
Moreover, they performed several simulations from which they MMP using outcrop limestone carbonate cores. The salinity of the
concluded that the high salinity surfactant ood performs better injected water was varied between 0, 6, and 20 wt%. The results
than the low salinity surfactant ood. They stressed on the im- showed that waterooding recovery alone was not affected by
portance of surfactant selection and design rather than the ben- salinity; this indicates that wettability alteration is not affecting oil
ets of low salinity on a surfactant ood. recovery and the only controlling parameter is CO2 solubility in
Also, Khanamiri et al. (2015) studied the performance of sur- water. SWAG and WAG resulted in higher oil recovery than CGI
factant injection when low salinity surfactant is combined with due to mobility control of the displacement front. SWAG resulted
LSWI as well as the combination of near optimal salinity surfactant in the highest oil recovery and lowest CO2 requirements. For both
with LSWI. The authors conducted several coreoods on Berea SWAG and WAG, decreasing salinity level leads to increasing CO2
sandstone cores. They concluded that tertiary injection of low solubility in water and increasing oil recovery.
salinity surfactant after a secondary LSWI outperforms after-ter- Moreover, Teklu et al. (2014) conducted several coreoods on
tiary low salinity surfactant when high salinity and low salinity carbonate and sandstone cores to investigate the combined effects
waters are injected in secondary and tertiary modes, respectively. of injecting low salinity water and CO2 on oil recovery. Consecutive
Also, they found that near-optimal salinity surfactant performs injections of seawater, low-salinity water, and continuous CO2
better after a secondary injection of a high salinity water com- resulted in further reduction in the residual oil saturation. Contact
pared to a low salinity water; however, the latter performs better if angle and IFT were measured for the different rock samples and
it is followed with a high salinity chase-water injection. uids to justify the underlying mechanism. Results showed a fur-
ther decrease in both contact angle and IFT using the combined
5.5. LSWI/EWI and CO2 ooding application CO2 and low salinity water. The authors believe that wettability
alteration is furtherly enhanced using the combined LSWI and CO2
Simultaneous water alternating gas (SWAG) and water alter- as reducing the salinity of injected water increases the solubility of
nating gas (WAG) are two proposed injection forms for gas mo- CO2, which deceases the brine-CO2 IFT and the latter even further
bility control. The idea of having a mixture of CO2 and water decreases the CO2-saturated-brine and oil IFT and alters wett-
whether in WAG or SWAG mode, is to contact the bypassed oil ability towards a more water-wet state.
after the CO2 slug. Hence, the properties of the injected water play From a simulation point of view, Dang et al. (2014) presented a
a vital role in affecting the level of incremental oil recovery detailed evaluation of CO2 LSWAG from a one-dimensional het-
(Aleidan and Mamora, 2010). Several factors may affect CO2-WAG erogeneous model into full eld simulation. They highlighted
including reservoir heterogeneity, uid properties, miscibility through simulations the combined benets of gas and low salinity
condition, rock wettability, and WAG parameters such as water water oods by including geochemical reactions associated with
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 155
monovalent ions (Yousef and Ayirala, 2014). reaction model which illustrates the MIE mechanism in sandstone
Several patents were proposed for membrane-based desalina- with decreasing salinity; there exists a net desorption of adsorbed
tion method in which RO alone or a series conguration of NF/RO ions from the clay surface into the aqueous phase. Doust et al.
is used. Nevertheless, Yousef and Ayirala (2014) highlighted that (2009) reported that salting-in effect does not work in carbonate
the proposed conguration just work for smart waterooding in rock due to strong bonding of organic mater, whereas it is effective
Sandstone. Moreover, they proposed a novel water ionic compo- in sandstone rocks due to the weak bonding of the organic ma-
sition optimization technique upon which nano-ltration and re- terial to the clay surface.
verse osmosis membrane processes are used in parallel cong- At low pH, crude oils are positively charged; as the pH value
uration. The latter conguration generates multiple product water starts increasing, crude oil charge decreases to zero at the iso-
streams to cover the entire range of ionic content and variation, electric point (point of zero charge (PZC)) and then becomes
which are suitable for both sandstone and carbonate rocks. Yousef strongly negatively charged at high pH (Takamura and Chow,
and Ayirala stressed on the importance of the rejected NF and 1985). Sandstone rocks are negatively charged above pH of 2
rejected RO streams, which are important in case of low salinity/ (Menezes et al., 1989). The point of zero charge for limestone is
engineered water injections in carbonate rocks. around 9.2 while the PZC for dolomite is about 7.4 (Gupta and
Mohanty, 2010). The point of zero charge for calcite and dolomite
depends on pH and solution composition, where calcite PZC ran-
7. Discussion: comparison between carbonate and sandstone ges from 7 to 12 while dolomite PZC ranges from 6 to 8.8 (Pok-
rocks rovsky et al., 2002). Lichaa et al. (1993) reported PZC values of
4.6 and 3.4 for two carbonate rocks located in Saudi Arabia. The
This section highlights the main differences in the applicability cores were tested in deionized water and they compose of 40%
of low salinity/engineered water ooding techniques on carbonate calcite and 60% dolomite. The PZC of dolomite is lower than that of
compared to sandstone rocks. Almost all producing sandstone limestone (Alotaibi et al., 2011).
rocks contain clays as a coating on individual sand grains and/or Stability of water lm depends on the electrical double layer
discrete particles mixed with the sand. Carbonates may contain repulsion, which results from the surface charge at both solid/
clays as well, but these clays are usually encapsulated in the rock water, and water/oil interfaces. In case both interfaces have similar
matrix and not signicantly affected by the invading uids. Sands charges, a repulsive electrostatic force occurs maintaining high
that contain clay from 1 to 5% are called clean sands, but dirty sand disjoining pressure and a thick water lm forms, which results in a
is used usually for describing sands with 5 to more than 20% clay. water-wet rock surface (Dubey and Doe, 1993). Lee et al. (2010)
Clay types present in sandstone rocks are usually smectite, illite, measured the water lm thickness using sophisticated physical
mixed-layer clays (primarily illite-smectite), kaolinite, and chlorite chemistry techniques such as the small angle scattering technique.
(Alotaibi and Nasr-El-Din, 2009). They reported that the decrease in water salinity (ionic strength)
Low salinity/engineered water injection disturbs the initially causes increase in water layer thickness, which gives a more wa-
established thermodynamic equilibrium between rock/oil/forma- ter-wet state for both sand and clay type particles. Moreover, a
tion brine, which leads to a new equilibrium between the different lower divalent cation concentration in the injected brine com-
phases resulting in favorable wettability alteration and increase of pared to the connate brine results in a larger low-salinity im-
oil recovery during production period. In this process of wett- proved oil recovery (IOR) response.
ability alteration, the activation energy is important as it controls Ayirala and Yousef (2014) highlighted the importance of water
the rate of chemical reactions between the mineral surface and chemistry for different improved/enhanced oil recovery (IOR/EOR)
injected water. If the reaction rate is too slow, there will be no processes including offshore waterooding. Moreover, they de-
improvement in wettability and oil recovery during the water in- ned SmartWater as a special type of water cocktail consisting of
jection period. Reservoir temperature plays a catalytic role in in- varying composition of different water ions. They stressed on the
creasing the rate of chemical reactions, as there is strong relation need for reducing the non-active salts concentrations (Na and
between activation energy and temperature as was reported by Cl-) as they prevent the accessibility of active potential de-
Puntervold et al. (2007). termining ions to the rock surface. Also, they suggested for oil
The activation energy needed for wettability modication de- recovery improvement from sandstone rocks to use water salinity
pends on both the strength of bonding between the polar oil of less than 5000 ppm with a lower ionic strength and a small
components and the mineral surface, and the reactivity of the ions amounts for divalent cations (o500 ppm) to avoid clay swelling.
present in the injected water. In general, the bonding energy be- On the other hand, low to moderate salinity diluted seawater (2
tween the negative polar crude oil components and carbonates are 10 times dilution/28,0006000 ppm) or modied seawater de-
stronger than the one existing in clays and silicate (sandstone pleted in monovalent ions and enriched in potentially determining
rocks) as reported by Thomas et al. (1993). Doust et al. (2009) divalent ions were recommended for better oil recovery by low
stated that there is difference between the chemical bonding of salinity from carbonates.
crude oil negative polar components (carboxylic material) with In general, the mechanism behind wettability alteration of
positively charged carbonate rocks and negatively charged sand- sandstone rocks using low salinity/engineered water injections is
stone rocks which promotes the difference in wettability alteration considered more complicated compared to carbonates due to the
mechanism. Thus, removal of the organic material in carbonate involved mechanisms with their various contributions including
rock is achieved by increasing the surface reactivity of the po- ne migration, pH increase, multi-ion exchange (MIE), and salting
tential determining ions Ca2 , Mg2 , and SO42 at high tem- in effects (Tang and Morrow, 1999; McGuire et al., 2005; Lager
peratures. Adsorption of organic material is essential for low et al., 2006; Doust et al., 2009).
salinity/engineered water effect in sandstone rocks; however, A comparison between carbonates and sandstones in terms of
desorption of these material at high temperature helps in having incremental oil recovery obtained by LSWI/EWI is presented in
more pronounced effect for LSWI/EWI on carbonate rocks. Table 1. The table shows a summary of the main LSWI/EWI core-
In carbonates, seawater can cause wettability alteration effect; oods conducted in both carbonate and sandstone rocks. Several
however, low salinity water injection (less than 5000 ppm) is re- parameters are listed in the table, which we believe they affect
quired in case of sandstone rocks. As stated by Lager et al. (2006), incremental oil recovery. These parameters are rock type, tem-
contrary to chalk rocks, it is difcult to have a reliable chemical perature, pressure, salinity of injected and formation waters, oil
E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161 157
Table 1
Summary of main LSWI/EWI coreoods in carbonates and sandstones.
Coreood study Rock type Temperature (C) Pressure Injected water salinity Formation Oil visc- Oil Injection Additional
(psi) (ppm) water sali- osity (cP) TAN model oil recovery
nity (ppm) (mg (% OOIP)
KOH/g
oil)
LSWI in sandstones
Reiter (1961) Sandstone 15.56 14.70 3100 12,100 37.0 @ Secondary 21.3
25.56 C
Bernard (1967) Synthetic and Be- 15.56 14.70 10,0001000 NaCl 150,000 Tertiary 2.636.98
rea Sandstone NaCl
Al-Mumen (1990) Berea Sandstone 90 1500 5500200,000 NaCl 200,000 2.48 @ SC Secondary 810
NaCl
Zhang et al. Sandstone 75 250 1480 SW 29,690 20.1 @ RC 1.46 Secondary 29.2
(2007a) 1500 NaCl FW Tertiary 714
Patil et al. (2008) Sandstone 93 300 550050 SW 22,000 SW Secondary 1428
Webb et al. Sandstone 1500 SW 250,000 FW Secondary 14
(2005a) Tertiary 89
Agbalaka et al. Berea Sandstone 80 1500 10,000 NaCl 40,000 NaCl 8.24 @ SC Secondary 56
(2009) Tertiary 2535
Rivet et al. (2010) Berea and Field 55 14.70 8701140 SW 30,510 SW 7.93 @ RC Secondary 15
Sandstone Tertiary 0
Gamage and Berea and Field 1% FW FW 8.0 0.074 Secondary 1022
Thyne (2011) Sandstone 11.50@ SC Tertiary 26
Fjelde et al. Sandstone 80 72.19 1054.96105.49 SW 105,496 FW 1.5 @ RC Secondary 9
(2012) Tertiary 3
Suijkerbuijk et al. Sandstone 87 14.70 FW 2.95 @ RC 4 Secondary 6
(2014) 0.01 Tertiary 5
LSWI in carbonates
Bagci et al. (2001) Unconsolidated 50 145 10,00040,000 NaCl 46.5 @ RC Secondary 14
Limestone 20,000 KCl 18.4
Yousef et al. Carbonate 100 3000 28,8355,76.7 SW 213,000 FW 1.26 @ RC 0.25 Tertiary 18
(2011)
2
Gupta et al. (2011) Dolomite and 121.11 4000 33,484 SW 4 SO4 181,273 FW 1.13 @ RC 0.11 Tertiary 59
Limestone 33,375 SW 79
29,970 SW BO33 15
29,970 SW PO43 20
Zahid et al. (2012) Carbonate Chalk 90 72.52 28,8352883 SW 213,734 FW 3.21 @ RC 0.96 Tertiary 1520
Outcrop 0
Chandrasekhar Limestone 120 50 2181872 SW 179,700 FW 1 @ RC 2.45 Secondary 40
and Mohanty Tertiary 32
(2013)
Al-Attar et al. Carbonate 25 100 10005000 SW 197,584 3.08 @ SC Secondary 21.5
(2013) 224,987 FW
Awolayo et al. Carbonate 110 3000 43,000 SW 0.58 SO42 261,210 FW 1.927 @ Tertiary 10
(2014) 70 C
Alameri et al. Carbonate 90.56 1800 25,6791027 SW 100,000 FW 3.0 @ RC Tertiary 57
(2015)
viscosity, oil total acid number, and injection mode. Rock type obtained in the secondary injection mode compared to the tertiary
matters as previously discussed even at the mineralogical level. injection mode. This might be related to wettability alteration by
Also, it is worth mentioning that the effect of low salinity water is expansion of the double electric layer, where the double layer
more pronounced on eld core plugs as compared to outcrop functions better in the presence of a continuous oil lm as op-
plugs. For temperature and pressure conditions, usually higher posed to the presence of discontinuous oil blobs, which is present
incremental oil recovery by low salinity is obtained at reservoir in the tertiary injection mode. Table 1 shows there are always
conditions for both rock types compared to ambient conditions. exceptions for the trends discussed above. Therefore, the bottom
Hence, it is advisable to conduct experimental coreoods at re- line is that the improvement of oil recovery by LSWI/EWI in both
servoir conditions for more representative results. Sandstones and sandstone and carbonate rocks is case dependent because all the
carbonates result in more incremental oil recovery when the dif- parameters discussed above matters and should be optimized to
ference in salinity between injection and formation brines is more enhance the oil recovery.
pronounced. It should be highlighted that dilution of seawater is
the common practice in sandstones (LSWI); however, tuning of
injected water salinity is common in carbonates (EWI). For oil 8. Concluding remarks
properties, usually lower oil viscosity and higher oil total acid
number result in higher incremental oil recovery for both sand- This paper is a comprehensive state-of-the-art review on low
stones and carbonates. In terms of injection mode, both rock types salinity/engineered water injection for both sandstones and car-
are consistent as mostly higher incremental oil recovery is bonates. The different aspects of low salinity/engineered water
158 E.W. Al-Shalabi, K. Sepehrnoori / Journal of Petroleum Science and Engineering 139 (2016) 137161
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Acknowledgments Al-Shalabi, E.W., Sepehrnoori, K., and Pope, G., 2014g. Modeling the Combined Ef-
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The authors wish to acknowledge Abu Dhabi National Oil Conference, Kuala Lumpur, Malaysia.
Company (ADNOC) for funding this research. Al-Shalabi, E.W., Sepehrnoori, K., and Pope, G., 2015a. Geochemical Interpretation
of Low Salinity Water Injection in Carbonate Oil Reservoirs. SPEJ, Paper SPE
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