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Critical review of low-salinity waterflooding

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 Journal of Petroleum Science and Engineering 120 (2014) 216224

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

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

Critical review of low-salinity waterooding

J.J. Sheng n
Texas Tech University, Lubbock, TX 79409, USA

art ic l e i nf o a b s t r a c t

Article history: It was observed that higher oil recovery could be obtained when low-salinity (LS) water ooded a core of
Received 23 January 2014 high-salinity initial water about 15 years ago. Such low-salinity waterooding benet or effect has drawn
Accepted 31 May 2014 the oil industry attention since then. In the recent years, many researchers conducted laboratory
Available online 12 June 2014
coreoods, and several companies carried eld tests. The objectives of these efforts were (1) to conform
Keywords: the benets and (2) nd the mechanisms of such benet. Although most of the results conrmed the
low-salinity waterooding positive effect, some results showed no benet. Many mechanisms have been proposed, but there is no
enhanced oil recovery consensus of the dominant mechanism(s). The oil industry is continuing the effort to discover the effect.
improved oil recovery This paper is to provide a critical review of the results and to summarize the achievements of the
waterooding
industry's effort. This paper aims to provide the status of the art. The information provided in this paper
salinity
hopefully will help to speed up our further efforts to explore this effect. The following contents are
reviewed: (1) history of low-salinity waterooding; (2) laboratory observations; (3) eld observations;
(4) working conditions of low-salinity effect; (5) mechanisms of low-salinity waterooding; and
(6) simulation of low-salinity waterooding.
In this paper, the mechanisms proposed in the literature and their validity are discussed.
& 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
2. A brief history of low-salinity waterooding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3. Laboratory observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.1. Typical behavior of low-salinity waterooding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.2. Low-salinity benets under reservoir conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.3. Effect of connate water saturation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.4. Effect of the salinity of connate water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.5. Effect of injection water salinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.6. Effect of wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4. Field observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
5. Working conditions of low-salinity effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6. Mechanisms of low-salinity waterooding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
6.1. Fine mobilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
6.2. Limited release of mixed-wet particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
6.3. Increased pH and reduced IFT similar to alkaline ooding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
6.4. Multicomponent ion exchange (MIE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
6.5. Double layer effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.6. Salt-in effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.7. Osmotic pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
6.8. Wettability alteration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222

n
Tel.: 1 806 834 8477.
E-mail address: James.sheng@ttu.edu

http://dx.doi.org/10.1016/j.petrol.2014.05.026
0920-4105/& 2014 Elsevier B.V. All rights reserved.
 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224 217

7. Further discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222

8. Simulation of low-salinity waterooding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
9. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223

1. Introduction
3.1. Typical behavior of low-salinity waterooding

Injection of low-salinity (LS) water has widely been practiced

Typical behavior of low-salinity waterooding may be sum-
because the water sources are available and relatively cheaper
marized as follows. (1) As the injection brine salinity was reduced
among other practical advantages. But the EOR potential was not
lower (often much lower) than the initial brine salinity in the core,
recognized until Morrow and his co-workers (Jadhunandan, 1990;
more oil was produced. (2) During the stage the injection brine
Jadhunandan and Morrow, 1991, 1995; Yildiz and Morrow, 1996;
salinity was reduced, a higher-pressure drop was observed. This
Tang, 1998; Tang and Morrow, 1997, 1999) observed from their
phenomenon was interpreted by Tang and Morrow (1999) as
experimental work that oil recovery depended on water composi-
permeability reduction caused by ne migration. This phenom-
tion. Since then, many coreood tests have been published to
enon was also observed by Zhang et al. (2007). (3) When the water
address the low-salinity effect on waterooding oil recovery. Most
of reduced salinity was injected, maximum pH values were about 9
of the results (but not all) showed that higher oil recovery could be
or lower.
obtained when the salinity of injection water is much lower than
that of the formation water. Meanwhile, different mechanisms
3.2. Low-salinity benets under reservoir conditions
have been proposed to explain this low-salinity effect. There is no
consensus about dominant mechanisms. Apparently, people
BP used a coreood facility in which live oil could be used and
believe that low salinity waterooding could provide higher oil
the reservoir conditions could be simulated (Webb et al., 2005a).
recovery. Some doubt it because some experiments did not show
In a presented case of secondary waterooding, the formation
the benet.
water salinity was 28,000 ppm and the injection water salinity
This paper is to summarize and analyze the published labora-
was 1400 ppm. The recovery factor increased from 69.5% to 83.5%
tory and eld observations. The mechanisms proposed in the
the original oil in place (OOIP). In another secondary ood, a
literature and their validity are discussed.
higher incremental oil recovery was obtained.
For two tertiary oods, 1500 ppm water injection followed
15,000 ppm secondary waterooding. The oil recoveries increased
2. A brief history of low-salinity waterooding from 63% to 71% and from 75% to 84% for these two tertiary oods.
They concluded that to get a low-salinity benet the salinity
When Morrow and his coworkers studied the wettability effect should be as low as 4000 ppm.
on waterooding recovery, they found that changes in injection
brine composition affected oil recovery (Jadhunandan, 1990; 3.3. Effect of connate water saturation
Jadhunandan and Morrow, 1991, 1995). Subsequently, Yildiz and
Morrow (1996) conrmed that brine composition could indeed Tang and Morrow (1999) observed that when the initial water
affect the waterooding oil recovery, but they stated that whether saturation was zero, the oil recovery from a high-salinity (HS)
more oil could be obtained depended on specic conditions of water injection was almost the same as that from a LS (1% of the
crude oil/brine/rock systems. HS) water injection. Zhang and Morrow (2006) observed that the
Tang and Morrow (1997, 1999) advanced the research on the oil recovery generally increased with initial water saturation for
impact of brine salinity on oil recovery. It was followed by the secondary recovery by injection of LS brine. In other words, to
active research by the oil company British Petroleum (BP) (Webb have the LS effect, the existence of connate water was needed.
et al., 2004, 2005a, 2005b; McGuire et al., 2005). BP's work
includes numerous core oods at ambient and reservoir conditions 3.4. Effect of the salinity of connate water
with live oils in both secondary and tertiary modes, single-well
tracer tests, and loginjectlog tests. The company's work led to Sharma and Filoco (1998) found that the salinity of connate
the registration of the LoSalEOR process trademark. Meanwhile, water was the primary factor controlling the oil recovery. When
the researchers from several oil companies (e.g., TOTAL, Shell, the salinities of connate water were 0.3%, 3% and 20% NaCl while
Statoil) and universities worked on this topic as well. In recent the injection water salinity was 3% NaCl, the oil recovery was
years, many companies and universities have been actively doing greater for lower connate brine salinities. They attributed this
the research. The number of published papers increased from 5 in dependence to alteration of the wettability to mixed-wet condi-
2007 to 25 in 2010 (Morrow and Buckley, 2011). tions from water-wet conditions during the drainage process.
Mixed-wet cores showed lower residual oil saturations than
strongly water-wet or oil-wet cores (Jadhunandan and Morrow,
3. Laboratory observations 1995). Such result that higher oil recovery was obtained with the
lower salinity of connate water is also supported by McGuire et al.
Since Morrow's group presented additional oil recovery from (2005) data and Zhang and Morrow's (2006) data.
low-salinity waterooding, many experimental coreood tests
have been conducted. Apparently, most of coreood tests show 3.5. Effect of injection water salinity
positive results. In some core oods, no incremental oil recovery
was observed. In this section, we only present typical observations. When we talk about the low-salinity benet, we mean that
More experimental data will be presented when the mechanisms higher oil recovery will be obtained when the salinity of injection
are discussed later. water is lower than that of existing or initial (connate) formation
218 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224
water. However, this result is not supported by all the published
experimental data. Sharma and Filoco (1998) observed that the
salinity of connate water was the primary factor controlling the oil
recovery, and the salinity of injection brine did not affect oil
recovery. As the salinity is increased, electrostatic repulsion
decreases owing to screening of the surface charges (Adamson
and Gast, 1997). Higher salinity should, therefore, result in less
stable brine lms. However, this was not observed in their
experiments. Zhang and Morrow (2006) even presented data
showing lower-injection water salinity resulted in a lower recov-
ery than that from higher-salinity water, although more cases
showed that lower-salinity injection water resulted in higher
recovery.
In Yildiz and Morrow's (1996) experiments, two brine and two
oils were used. Brine 1 4% NaCl0.5% CaCl2. Brine 2 2% CaCl2.
The two oils were Moutray crude oil and Alaskan oil. When the
Moutray oil was used and when the formation water and injection
water had the same brines, the oil recovery factor for Brine 2 was
5.5% higher than that for Brine 1. However, when the Alaskan oil
was used, an opposite result was obtained where the oil recovery
factor for Brine 1 was 16% higher than that for Brine 2.
When the Moutray oil was used, the formation water was Brine 2,
and the core was ooded by Brine 2 rst followed by Brine 1, only
0.5% more oil was obtained. When the formation water was Brine 1,
and the core was ooded by Brine 1 rst followed by Brine 2, 2.9%
more oil was obtained. Such results are not consistent with the
expectation from the LS effect, because Brine 1 had less ionic strength
than Brine 2. Yildiz and Morrow attributed the above results to the
wettability difference caused by crude oil and aging conditions.
Nevertheless, in most of the published cases, a higher oil
recovery was obtained when the salinity of injection water is lower
than that of connate water. And the injection water salinity was low
enough. Tang and Morrow (1999) used 10% connate water salinity.
McGuire et al. (2005) did not see the effect when the salinity was
higher than 7000 ppm in their single-well chemical tracer test
(SWCTT) tests. Webb et al. (2005a) used 10004000 ppm which
was less than 5% of formation total dissolved solids (TDS)
(80,000 ppm). Zhang et al. (2007) observed that the low salinity
of 1500 ppm which was about 5% formation water salinity resulted
in sharp increase in the tertiary recovery and in the differential
pressure. 8000 ppm was not sufcient even removing divalents. 4%
additional recovery was obtained when additional divalent ions
were added to the injection brine of 1500 ppm salinity. Jerauld et al.
(2008) proposed 1025% of connate water salinity or 1000
2000 ppm based on practices in the laboratory and eld. Probably,
10% of connate water salinity is a good start.
3.6. Effect of wettability
Jadhunandan and Morrow (1995) found that the wettability
related to initial water saturation in the cores. With higher initial
water saturation, the cores showed more water-wet. And the oil
recovery increased from strongly water-wet to a maximum close
to neutral wet, which was agreed by Sharma and Filoco (1998).
Their objective of that paper was not to correlate oil recovery with
the water salinity. But their data showed that cores with lower
calcium concentration (or ionic strength) were more water-wet.
The LS effect may be related to wettability. For the cores with high
initial salinity, LS water injection will make the cores more water-
wet and result in a higher oil recovery.
4. Field observations
BP has run four sets of SWCTT in Alaska North Slope and
conrmed that the favorable laboratory results could be replicated
in the eld after injection of LS water of 510% of formation water
salinities. The reductions in residual oil saturations were 4%, 4%,
8%, and 9% in these four tests (McGuire et al., 2005). Another eld
test in a BP mature offshore oil eld, Endicott eld, located on the
North Slope of Alaska demonstrated that reduced-salinity water-
ooding worked at inter-well distances (1040 ft in this case). The
reduced-salinity waterooding reduced water cut from 95% to 92%
(Seccombe et al., 2010).
In a loginjectlog test, typically 0.10.15 pore volumes of high-
salinity brine were injected rst to obtain the baseline residual oil
saturation. This was followed by sequences of more dilute brine
followed by high-salinity brine. Multiple log passes were con-
ducted during each brine injection. At least three further passes
were run to ensure that a stable saturation value had been
established after injection of each type of brine. The results
showed 0.250.5 reduction in residual oil saturation when water-
ooding with low-salinity brine (Webb et al., 2004).
In a Middle Eastern sandstone reservoir, the formation wett-
ability is mixed-wet to oil-wet. The formation water salinity was
100,000 ppm. The salinity of injection water was changed to
1000 ppm in March 2000. An oil bank arrived at the production
end in 2003 with a temporary drop in water cut (Ligthelm et al.,
2009).
Robertson (2007) compared three waterooding eld perfor-
mances in Wyoming. These analog elds had been under LS
waterooding with the salinity ratios of injection water to forma-
tion water of 0.0621, 0.0787, and 0.1667. The oil recoveries at
0.3 Pore Volume (PV) of produced uid are almost linearly
correlated with the salinity ratios. With a lower salinity ratio, a
higher oil recovery was obtained.
Preush using LS water before surfactantpolymer ooding
was carried to condition the reservoir in the early days. Such
preush water should bring incremental oil if low-salinity water-
ooding worked. However, apparently, no oil rate increase was
observed during the fresh water preush in the North Burbank
Unit surfactantpolymer pilot in Osage County, Oklahoma
(Trantham et al., 1978) and Loudon surfactant pilot (Pursley et
al., 1973). No injectivity issue was reported. Thyne and Gamage,
2010 evaluated the LS waterooding effects in the elds in the
Powder River Basin of Wyoming. They found no increase in
recovery for the 26 elds where low salinity water was injected,
when they compared with the 25 elds where mixed water or
formation water was injected. Among these 51 elds, the salinity
of injected water was signicantly reduced in 38 elds, whereas
there was little reduction in salinity in the rest of 13 elds. There
was no correlation observed between the salinity reduction and oil
recovery factor.
Skrettingland et al. (2011) evaluated LS waterooding for the
Snorre eld. The core ooding results showed that Statfjord cores
had an incremental oil recovery of 2% of OOIP by injection of
diluted seawater, while the Lunde cores did not show response. A
SWCTT did not show reduction in residual oil saturation. Their
explanation was that the reservoirs were already in optimum
wetting conditions so that a signicant improvement in oil
recovery could not be obtained by LS waterooding.
5. Working conditions of low-salinity effects
Based on the coreoods and research work published so far, the
working conditions of the LS waterooding effect may be sum-
marized as follows. (1) Presence of clays. It is believed that clays
are important in the LS effect. It may be necessary to have
kaolinite. Kaolinites and illites are non-swelling clays that tend
to detach from the rock surface and migrate when the colloidal
conditions are conducive for release (Mohan et al., 1993).
 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224
However, the types and amount of clays are not clearly dened in
the literature. Different authors reported the importance of differ-
ent types of clays (Skrettingland et al., 2011). (2) Presence of polar
oil (Tang and Morrow, 1999; Suijkerbuijk et al., 2012). (3) Presence
of initial or connate water (Sharma and Filoco, 1998; Tang and
Morrow, 1999; Zhang and Morrow, 2006). (4) Presence of divalents
in the initial water (Lager et al., 2006). (5) Salinity shock the
salinity of injected water must be signicantly lower than the
preceding water salinity (Mohan et al., 1993; Webb et al., 2005a;
Zhang et al., 2007; Buckley and Morrow, 2010). This effect will be
reduced in eld scale because of salinity buffering.
Note that the above conditions cannot guarantee the LS effect,
as some cases did not show the effect, even though the conditions
were apparently met. And all of these conditions may not be
necessary, as some cases had the low-salinity effect, but all the
conditions were not met, as discussed later in this paper.
6. Mechanisms of low-salinity waterooding
Seventeen mechanisms of low-salinity waterooding have
been proposed in the literature, as follows: (1) ne migration
(Tang and Morrow, 1999); (2) mineral dissolution (Buckley and
Morrow, 2010); (3) limited release of mixed-wet particles (Buckley
and Morrow, 2010); (4) increased pH effect and reduced interfacial
tension (IFT) (McGuire et al., 2005); (5) emulsication/snap-off
(McGuire et al., 2005); (6) saponication (McGuire et al., 2005);
(7) surfactant-like behavior (McGuire et al., 2005); (8) multicom-
ponent ion exchange (MIE) (Lager et al., 2006); (9) double layer
effect (Ligthelm et al., 2009); (10) particle-stabilized interfaces/
lamella (Buckley and Morrow, 2010; Morrow and Buckley, 2011);
(11) salt-in effects (RezaeiDoust et al., 2009); (12) osmotic pressure
(Buckley and Morrow, 2010); (13) salinity shock (Buckley and
Morrow, 2010); (14) wettability alteration (more water-wet)
(Buckley and Morrow, 2010); (15) wettability alteration (less
water-wet) (Buckley and Morrow, 2010); (16) viscosity ratio
(Buckley and Morrow, 2010); and (17) end effects (Buckley and
Morrow, 2010).
Most of these mechanisms are related to each other. For
example, to have ne mobilization, nes must be available in the
injection uid. The available nes could be mineral dissolution or
released particles. Thus the limited release of mixed-wet particles
and mineral dissolution are related to ne migration. As a result of
mineral dissolution, the viscosity of LS solution has a higher
viscosity. Saponication, surfactant-like behavior, and emulsica-
tion/snap off are related to increased pH effect and reduced IFT.
Osmotic pressure and salinity shock are directly related to salinity
contrasts between the initial water and displacing water. The end
effect occurs in laboratory scale. In this section, we will discuss
major mechanisms and their working conditions.
6.1. Fine mobilization
In principle, clay tends to hydrate and swell when contacting
with fresh water. In other words, insufcient salts in water cannot
prevent clay hydration and swelling. Fine migration occurs if the
ionic strength of injected brine is less than a critical occulation
concentration. The critical occulation concentration is strongly
dependent on the relative concentration of divalent cations.
Divalent cations lower the repulsive force by lowering the Zeta
potential. Therefore, they have been known to stabilize clay. A
less-saline solution destabilizes clay and silt in the formation. The
clay and silt, upon dispersion, ow with water. Water preferen-
tially ows along high permeability channels or zones. The clay
and silt dispersing in water become lodged in the smaller pores or
pore throats. Then the formation permeability is reduced, and the
219
water is forced to take other ow paths. As a result, the sweep
efciency is improved. Poorly cemented clay particles, such as
kaolinite and illite, can become detached during aqueous ow,
especially when owing brines become fresher (Boston et al.,
1969).
Martin (1959) and Bernard (1967) observed that clay swelling
and/or dispersion accompanied by increased differential pressure,
and incremental oil recovery resulted. Kia et al. (1987) reported
that when sandstones were previously exposed to sodium salt
solutions, ooding these sandstones by fresh water resulted in the
release of clay particles and a drastic reduction in permeability.
The permeability reduction was lessened, however, when calcium
ions were also present in the salt solution. Formation damage was
virtually eliminated when the solution composition was adjusted
to give calcium surface coverage greater than a critical value of
75%, or when a solution Ca2 fraction is greater than 2030%.
Tang and Morrow (1999) concluded that ne mobilization
(mainly kaolinite) increased recovery based on their observations:
(1) a red/acidized Berea core did not show the sensitivity of
salinity on oil recovery, whereas an unred Berea core did; (2) for
clean sandstones, the increase in oil recovery with the decrease in
salinity was less than that for the clay sands. Khilar and Fogler
(1984) results showed a 30% reduction in permeability when the
pretreatment was carried out with cesium-salt solutions, a reduc-
tion of more than 95% with a sodium-salt pretreatment, and
virtually no reduction when the cation in the solution was
divalent.
However, Lager et al. (2006) reported that no ne migration or
signicant permeability reductions was observed during numer-
ous BP LS coreoods under reduced conditions and full reservoir
conditions, although these coreoods had all shown increased oil
recovery. Zhang and Morrow (2006) reported that limited produc-
tion of clay particles was observed, but permeability damage, if
any, was minimal. Zhang et al. (2007) reported that no clays were
produced at the efuent stream. Valdya and Fogler (1992) reported
that a gradual reduction in salinity kept the concentration of nes
in the owing suspension low, with formation damage minimized
or totally avoided. Boussour et al. (2009) reported no LS effect but
with sand production in their experiments.
Many coreood experiments showed an increase in the differ-
ential pressure in the beginning but decrease later during LS water
injection (Tang and Morrow, 1999; Zhang and Morrow, 2006;
Zhang et al., 2007). The increases in the differential pressure in the
beginning of LS waterooding are shown in Table 1. In many cases,
the differential pressures were doubled. Brine/rock interaction
may result in the increase in differential pressure. However, the
small or no response in ooding mineral oils implies that clay
swelling and clay migration is of second order. Polar oil must
participate in this blockage of pores. Complex crude oil/brine/rock
interaction must come into play. In other words, the LS effect is not
caused by simple mechanical ne migration. Then what is it? If we
believe that low-salinity can result in more water-wet, then the
differential should decrease rather increase.
In addition to ne migration, osmotic effect, decrease in ion
binding (Lager et al. 2006), oil viscosity, interfacial viscosity,
transient emulsion formation, interfacial tension gradient result-
ing from gradients in brine composition, might also play a role in
oil mobilization (Zhang et al., 2007). The formation of interfaces,
especially in the form of clay-stabilized lamella, will enhance the
possibilities to develop capillary structures that cause the large
resistance to brine ow.
6.2. Limited release of mixed-wet particles
Tang and Morrow (1999) explained this mechanism. Crude oil
initially coats nes which attach to pore walls. When the salinity is
220 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224

Table 1 LS water injection in the literature. In most of the cases, pH was

Differential pressure (p) and pH in low-salinity coreoods. lower than 7. In some cases, pH was unchanged. To explain why
such a low pH works, Austad et al. (2010) proposed a hypothesis
Test # pH Before pH After p Before p After Sources
psi psi that cation exchange resulted in local pH increase close to clay
surfaces. Zhang et al. (2007) reported that after LS brine injection,
A1 6.2 6.2 4 9 Zhang et al. (2007) a slight rise and drop in pH were observed. But no clear relation-
A2 8 8 2.8 4.9 Zhang et al. (2007) ship between efuent pH and recovery was observed.
A3 5.6 6.3 1 4.8 Zhang et al. (2007)
A4 6 6.2 1.9 2.5 Zhang et al. (2007)
Under high pH conditions, organic acids (saponiable compo-
A5 6 6.3 1.8 4.2 Zhang et al. (2007) nents) in crude oil react to produce in situ surfactant (soap) that
B1 8 7 2.6 4.5 Zhang et al. (2007) can lower oil/water interfacial tension. The generated soap helps
B2 7 5.8 2 3.8 Zhang et al. (2007) forming oil/water or water/oil emulsions due to lower IFT. This
B3 5.6 6.1 0.56 4.8 Zhang et al. (2007)
emulsication may improve water sweep efciency. However, in a
B4 6 7.6 2.7 9.7 Zhang et al. (2007)
T1F1 8 9 1.8 2.4 Tang and Morrow (1999) typical alkaline solution, pH is usually 1113. To be able to
T1F2 8 9 2 2.6 Tang and Morrow (1999) generate soap, pH needs to be greater than 9 (Sheng, 2011).
T1F3 8 9 2.5 3.7 Tang and Morrow (1999) Another fact is that the oil/water interfacial tension in LS
1 5 6 Lager et al. (2006) waterooding is not too low. Zhang and Morrow (2006) reported
2 6.5 9.5 Lager et al. (2006)
1 2 2 Zhang and Morrow (2006)
IFT of 16 dyn/cm. Buckley and Fan (2007) measured IFT values
2 2 5.8 Zhang and Morrow (2006) were above 10 mN/m with pH o9. Such IFT is not low enough to
3 2 15 Zhang and Morrow (2006) reduce residual oil saturation in tertiary LS waterooding.
4 5.2 6 0.5 4.5 Zhang and Morrow (2006) It has been observed from many eld projects that the level of
1 8 9 McGuire et al. (2005)
improved oil recovery from alkaline ooding is low. Based on
2 8 10 McGuire et al. (2005)
analysis of the data reported by Mayer et al. (1983), the incre-
mental oil recovery factor over waterooding was 12% in most of
the projects, and 56% in a few projects. If the low-salinity
reduced, the electrical double layer in the aqueous phase between mechanism is related to increased pH and reduced IFT similar to
particles is expanded and the tendency to strip nes is increased. alkaline ooding, the improved oil recovery factor should be even
The stripped nes migrate and aggregate so that the oil coalesces. lower than that from alkaline ooding.
Thus limited removal of mixed-wet nes from pore walls results in Because the pH from actual tests was lower than what is
locally heterogeneous wetting conditions so that oil recovery is required to achieve saponication or emulsication and ne
improved. This mechanism combines the DLVO theory and ne migration, the pH mechanism similar to alkaline ooding may
migration. The DLVO theory is named after Derjaguin, Landau, not work in LS waterooding. The pH value at the efuent end
Verwey, and Overbeek. could increase or decrease depending on other chemical reactions,
as explained by Austad (2013). Therefore, the pH value cannot be
6.3. Increased pH and reduced IFT similar to alkaline ooding used to conrm the low-salinity waterooding.

Emulsication/snap-off, saponication, and surfactant-like 6.4. Multicomponent ion exchange (MIE)

behavior are all related to increased pH and reduced IFT mechan-
isms. They are discussed in this section collectively.
McGuire et al. (2005) proposed that low-salinity mechanisms
could be due to increased pH and reduced IFT similar to alkaline
ooding. This increase in pH is due to exchange of hydrogen ions
in water with adsorbed sodium ions (Mohan et al., 1993). Another
related mechanism is that a small change in bulk pH can impose a
great change in the zeta potential of the rock. When pH is
increased, organic materials will be desorbed from the clay
surfaces (Austad, 2013).
In Kia et al.'s (1987) experiments, the sandstone was saturated
with sodium chloride and/or calcium chloride solutions and
ooded by fresh water. The pH of the solutions entering the
sandstone was about 6.5 for all experiments. The pH of the
efuent, however, was found to be about 7.5 during the CaCl2 salt
ow, 8.6 during NaCl salt, and 8.3 with fresh water ow. The
increase in pH is a result of the solubilization of trace amounts of
dissolvable minerals, such as calcite.
Valdya and Fogler (1992) studies showed that dispersion of
clays was minimized at low pH.
Ion exchange between the adsorbed Na and H in solution
in LS water injection resulted in an increased OH  concentration
in bulk solution (i.e. pH increase). The pH increase amplied the
release of nes and led to a drastic reduction in permeability. They
reported little change in permeability when uids with increasing
pH were injected until an injection pH of 9 was reached. At a
pH 411, a rapid and drastic decrease in the permeability was
observed.
However, in a typical low-salinity ooding, pH was lower than
9, as shown in Table 1. Table 1 lists the pH values before and after
Owing to the different afnities of ions on rock surfaces, the
result of multicomponent ion exchange (MIE) is to have multi-
valents or divalents such as Ca2 and Mg2 strongly adsorbed on
rock surfaces until the rock is fully saturated. Multivalent cations
at clay surfaces are bonded to polar compounds present in the oil
phase (resin and asphaltene) forming organo-metallic complexes
and promoting oil-wetness on rock surfaces. Meanwhile, some
organic polar compounds are adsorbed directly to the mineral
surface, displacing the most labile cations present at the clay
surface and enhancing the oil-wetness of the clay surface. During
the injection of LS brine, MIE will take place, removing organic
polar compounds and organo-metallic complexes from the surface
and replacing them with uncomplexed cations.
Lager et al. (2006) reported that their experimental results
matched the prediction from this hypothesis. First, the North Slope
core sample was prepared to the representative initial water
saturation and aged in the dead crude oil. The initial screening
experiments were conducted at 25 1C. A conventional high-salinity
(HS) waterood gave a recovery of 42% OOIP, and a tertiary LS
ood resulted in a total recovery of 48% OOIP (i.e., an additional 6%
OOIP). A second suite of experiments was conducted at the
reservoir temperature (102 1C). A conventional HS waterood
resulted in a recovery of 35% OOIP. The core was ushed with
the brine containing only HS NaCl until Ca2 and Mg2 was
effectively eluted from the pore surface. The initial water satura-
tion was re-established, and the sample was aged in the crude oil.
A HS waterood consisting of NaCl (no Ca2 and Mg2 ) resulted
in a recovery of 48% OOIP. A tertiary LS ood was then conducted
(again no Ca2 and Mg2 ), and no additional recovery observed.
 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224
Fig. 1. Diagram showing the relationship among pH, salinity and wettability
(Drummond and Israelachvili, 2002).
This sequence indicated that HS connate brine containing Ca2
and Mg2 resulted in the low recovery factors (42% and 35%).
Removing Ca2 and Mg2 from the rock surface before water-
ooding led to a higher recovery factor (48%) irrespective of
salinity. They noted that no improvement in oil recovery was
observed, when LS water was injected into a clastic reservoir
where the mineral structure was preserved.
Apparently, their proposed MIE explains why LS waterooding
did not work when a core was acidized and red. The reason is
that the cation exchange capacity of the clay minerals was
destroyed. This explains why LS water injection has little effect
on mineral oil, as reported by Tang and Morrow (1999) and Zhang
et al. (2007), because no polar compounds are present to strongly
interact with the clay minerals. Another supporting result is that
adding divalent (Ca2 ) in LS brine did not result in additional oil in
Tang and Morrow's coreoods. The proposed mechanism of multi-
component exchange (MIE) is also supported by the pore-scale
model proposed by Sorbie and Collins (2010).
However, Zhang et al. (2007) reported that additional recovery
was obtained when switched from 8000 ppm brine to 1500 ppm
brine even with divalent ions added. Yildiz and Morrow's (1996)
data showed the highest oil recovery when the initial formation
brine contained 2% CaCl2 ooded by the brine with 4% NaCl 0.5%
CaCl2 and then by 2% CaCl2. The MIE mechanism cannot explain
the Sharma and Filoco (1998) experiments either where more oil
was recovered in lower initial salinity cases while the injected
water composition was the same.
Here is a further discussion about cation (ion) exchange. During
the isotherm and cation exchange capacity (CEC) measurements,
Meyers and Salter (1984) observed that the steady-state efuent
concentrations of calcium and magnesium were observed to be
slightly greater than the injected concentrations. These excess con-
centrations increased as the injection concentrations decreased.
When NaCl brine was injected into the cores, residual calcium
and magnesium concentrations were still observed in the efuent.
However, Valocchi et al. (1981) injected fresh water in a
brackish water aquifer and noticed that the concentration of
Ca2 and Mg2 in different control wells were lower than the
invading water and the connate brine. Lager et al. (2006) reported
similar results. In their coreood, the injected brine had Mg2
concentration (55 ppm) similar to the connate water, but the
chlorite concentration was lower. The efuent concentration
showed a sharp decrease in Mg2 in the beginning. This indicated
that Mg2 was strongly adsorbed by the rock matrix. Heriot Watt
University performed two different oods on the same system.
221
Both Ca2 and Mg2 were strongly adsorbed until the rock matrix
was fully saturated.
When the salinity of injection water is different from that of
initial water, a new equilibrium must be reached. The equilibrium
must be governed by the law of mass action. Whether cations
adsorbed or desorbed is not only determined by the injected brine
composition, but also by the adsorbed concentrations.
6.5. Double layer effect
The double layer theory or the DLVO theory describes the force
between charged surfaces interacting through a liquid medium. It
combines the effects of the van der Waals attraction and the
electrostatic repulsion due to the so-called double layer of counter
ions. Low salinity brine reduces clayclay attraction by expansion
of the electric double-layer. Limited release of clay particles may
depend on subtle oil/brine/rock interactions that involve the
charge distributions of individual kaolinite platelets. Cryo scanning
electron microscopy (Cryo-SEM), environmental scanning electron
microscope (ESEM) and X-ray photoelectron spectroscopy (XPS)
studies showed attachment of crude oil to kaolinite (Zhang and
Morrow, 2006). LS water makes water lm more stable owing to
this expanded double layer effect, resulting in more water-wet on
clay surfaces and more oil is detached.
On the opposite site, the adsorption of divalents at the oil/water
and water/sand interfaces changes the water-wet to oil-wet (Liu et al.,
2007). Kia et al. (1987) have reported that in the presence of Na , the
surface of kaolinite carries a negative charge, and the electrical charge
present on the edge surface is a strong function of the solution pH.
Most of the reported values show that edges of kaolinite particles are
negatively charged when pH is higher than 68. For some brine
compositions, both oil/brine and brine/solid interfaces have the same
charge (Buckley et al., 1998). Thus, there is electrostatic repulsion
between these interfaces. When LS brine is injected, the repulsion is
increased. When HS brine is injected, due to screening of the surface
charges (Adamson and Gast, 1997), the repulsion is decreased. For the
exactly same mechanism that the electrostatic repulsion is increased
when LS brine is injected, the water lm between the oil/brine and
brine/particle will be more stable. The rock surfaces change from oil-
wet to more water-wet or mixed-wet. Mixed-wet cores show lower
residual oil saturations than strongly water-wet or oil-wet cores. The
oil recovery is higher. This mechanism is supported by the experi-
ments reported by Ligthelm et al. (2009).
However, Sharma and Filoco (1998) observed that water lm
was more stable at high salinities in their experiments, incon-
sistent with the DLVO theory or the above observations.
6.6. Salt-in effect
The solubility of organic material in water can be drastically
decreased by adding salt to the solution, that is the salting-out
effect, and the solubility can be increased by removing salt from
the water, that is the salting-in effect (RezaeiDoust et al., 2009).
Therefore, a decrease in salinity below a critical ionic strength can
increase the solubility of organic material in the aqueous phase, so
that oil recovery is improved. This mechanism is similar to the
wettability alteration from oil-wet to more water-wet. The
increase of organic solubility in the water phase is equivalent to
desorption of oil drops from the clay surfaces. However, this
mechanism cannot explain the dependence of mineral composi-
tion, pH, salinity shock, etc.
6.7. Osmotic pressure
Sandengen and Arntzen (2013) demonstrated using experi-
ments that oil droplets acted as semi-permeable membranes; oil
222 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224
droplets could move under an osmotic pressure gradient. They
proposed that such osmotic gradient relocates oil by expanding an
otherwise inaccessible aqueous phase in a porous rock medium.
They hypothesized that LS water could relocate oil and open new
water pathways (a microscopic diversion mechanism) in a eld
case. This is due to water being transported away from the main
ow paths and into a less conductive network by diffusion through
oil. They believed that a system on the oil-wet side, with high oil
saturation, high temperature and a wide pore size distribution
should represent the ideal case for osmosis to have an effect. This
mechanism cannot explain the need of existence of crude (polar)
oil and clays.
6.8. Wettability alteration
As mentioned earlier, brine lms are more stable at a lower
salinity. This suggests that LS water will cause cores to become
mixed-wet (less water-wet). Mixed-wet cores show lower residual
oil saturations or higher oil recoveries than strongly water-wet or
oil-wet cores (Morrow, 1990; Morrow et al., 1998). Buckley et al.
(1998) explained wettability alteration as a result of the interac-
tion between crude oil and reservoir rock. Berg et al. (2010)
experimentally showed that wettability alteration could be
achieved by LS water. Nasralla et al. (2011) showed that LS water
could decrease contact angles. Yousef et al. (2011) and Zekri et al.
(2011) reported that LS water injection could change wettability to
more water-wet in carbonates. Vledder et al. (2010) even provided
a proof of wettability alteration in a eld scale.
Drummond and Israelachvili (2002) showed that the wettabil-
ity was altered from oil-wet to water-wet at pH 49 and from
water-wet to intermediate-wet at pH o 9, as shown in Fig. 1. In
other words, wettability alteration is possible in all the pH ranges
(either higher or lower than 9). In LS waterooding, pH is most
likely below 9 (see Table 1). The possibility is that the wettability is
changed from water-wet to intermediate-wet or mixed-wet. This
can also explain why connate water is needed for the LS effect
because the existence of connate water makes water-wettability
possible. The wettability alteration is the most frequently sug-
gested mechanism (Morrow and Buckley, 2011). Many other
mechanisms can be related to this mechanism. Wettability altera-
tion could be the end result of other mechanisms. This is likely an
explanation of the LS effect on oil recovery.
7. Further discussion
From the above discussions, we can see that there is no
consensus about the primary mechanisms. For each mechanism,
counter examples of data can always be found. This is the
challenge to dene LS waterooding mechanisms. Another puzzle
is that the incremental oil recovery is relatively high compared
with other chemical ooding processes, such as surfactant ood-
ing. Is the low-salinity waterooding so powerful? In Daqing
chemical EOR oods, fresh water (o 1000 ppm) was injected into
reservoirs of about 7000 ppm. The average incremental oil recov-
ery from Chinese polymer ooding project is about 9% according
to our survey (not published). Then how much incremental
recovery is due to the freshwater ooding? If the real mechanisms
of LS waterooding can be identied, the result should denitely
help to design chemical ooding. Another interesting observation
is that some of the listed mechanisms do not actually require the
salinity change from high to low.
This review focuses on the LS waterooding in sandstone
reservoirs. Strictly speaking, it is not the LS effect in carbonate
reservoirs; it is the effect of sea water ooding. The research work
in seawater ooding has been almost exclusively done by Austad
and his co-workers, which is summarized in Austad, 2013.
8. Simulation of low-salinity waterooding
Several authors tried to simulate LS waterooding. Their
general approach is to modify relative permeability and capillary
pressure curves as a function of salinity. For example, Jerauld et al.
(2008) modeled low-salinity waterooding using an empirical
approach. The residual oil saturation is interpolated by salinity
between a low salinity and a high salinity. Relative permeability
curves and capillary pressure curves for LS and HS are input. The
actual relative permeability and capillary pressure values at a
specic saturation are the weighted averages of their HS and LS
values. The weighing factor, w, is based on
Sorw  SLS
w orw
1
SHS LS
orw  Sorw
where Sorw are input values as a function of salinity, the super-
script HS and LS donate high salinity and low salinity.
In Mahani et al's. (2011) model, wettability changes suddenly
from oil-wet to water-wet in a specic simulation block when the
volume fraction of the LS water is above a dened volume fraction
threshold value, f, which is called the mixing factor dened as
TDSHS  TDSThreshold
f 2
TDSHS  TDSLS
where TDS is the salinity, the subscript Threshold is the salinity at
which the LS effect starts to work. Wu and Bai (2009) included the
salt as a separate composition and modeled the relative perme-
ability changes with salt concentration.
Omekeh et al. (2012) considered the effect of dissolution/
precipitation of various carbonate minerals and multiple ion
exchange (MIE). The total release of divalent cations from the rock
surface gives rise to a change of the relative permeability such that
more oil is mobilized. The combined effect of MIE and dissolution/
precipitation is modeled to determine how pH and the total
release of divalent cations are affected. They used a black-oil
modeling approach but included Na , Ca2 , Mg2 , SO24  and
Cl  ions in water phase. Dang et al. (2013) used a compositional
simulator to include geochemical processes like intra-aqueous and
mineral reactions.
9. Concluding remarks
From the above discussion, we can see that there is no
consensus regarding which mechanism works in the low-salinity
waterooding. Most likely, several mechanisms work under a
specic condition. And different mechanisms work in different
conditions. Among the proposed mechanisms, probably most
plausible mechanism is wettability alteration. This mechanism
can be used to explain more cases, because wettability can be
changed from oil-wet to water-wet, or from water-wet to inter-
mediate or mixed wet. In either way, oil recovery factor could be
improved. Many mechanisms could result in wettability alteration.
In other words, wettability alteration may not be a cause, rather it
is an effect.
From the reported results both in laboratory and in eld, low-
salinity has a positive effect or benet to oil recovery. However, the
magnitude of incremental oil recovery should not be expected as
high as observed in laboratory, because many pore volumes of LS
water were injected in laboratory, which is not realistic in actual
eld waterooding projects. Another fact is that generally LS
water is used in chemical ooding. Consider the magnitude of
 J.J. Sheng / Journal of Petroleum Science and Engineering 120 (2014) 216224
incremental oil recovery from chemical ooding projects, the
incremental oil recovery from low-salinity effect only should not
be too high.
Because the low-salinity effect deems to be positive, and more
importantly, low-salinity waterooding is environmentally friendly
and does not require much more investment in facility, efforts to
improve understanding the low-salinity effect will continue.
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