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Low-Salinity Waterflooding EOR Technique (Investigating the effect of


salinity and connate water composition changes on the reservoir wettability)

Conference Paper · September 2015

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The International Conference on New Research in Chemistry and Chemical engineering

Low-Salinity Waterflooding EOR Technique


(Investigating the effect of salinity and connate water composition changes on the reservoir wettability)

Z. Arab Abousadi1 , S. Pourhaji2, P. Foroughizadeh3, A. Heidarzadeh4


Young researchers and elit club, Marvdasht Branch, Islamic Azad University, Marvdasht, Iran

Islamic Azad University, Marvdasht Branch, Petroleum Engineering School, Marvdasht, Iran

Islamic Azad University, Gachsaran Branch, Gachsaran, Iran

Islamic Azad University, Marvdasht Branch, Petroleum Engineering School, Marvdasht, Iran

Abstract

Extensive experimental work has indicated that low-salinity waterflooding is an enhanced oil recovery
technique that improves oil recovery by lowering and optimizing the salinity of the injected water. Most of the
low-salinity waterflooding studies focused on the injection brine salinity and composition. The question
remains, how does the salinity and composition of the reservoir connate water affect the low-salinity
waterflooding performance? Therefore, in this work different connate water compositions were used to
investigate the role of reservoir connate water on the performance of low-salinity waterflooding.
Production enhancement by low-salinity waterflood in carbonate formations is a subject of intense speculation.
Several mechanisms are attributed to enhanced oil recovery by low-salinity waterflooding in carbonate
formations. Review of experimental data in the literature indicates that the main mechanism involves interaction
of and crude oil carboxylate ions (R-COO-) with the rock in the electrical double
layer (EDL) near the surface of carbonate pores, leading to wettability alteration.
This paper investigates the effect of salinity and water composition on the low-salinity waterflooding
performance by reviewing the performed experimental works in this field.

Introduction (Literature Review)


Carbonate reservoirs were flooded with high-salinity water to maintain reservoir pressure, keep the reservoir
pressure above the bubblepoint, and displace the oil by water into production wells by taking advantage of the
benefits of viscous forces. In general, injection water has two major problems that hinder its efficiency
(Schumacher 1978). First, it does not flush all the oil from the pore spaces as it moves through the reservoir rock
because of the immiscibility of the fluids or the wettability condition of the rock. The second point is that the

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water front can bypass part of the reservoir because of the well placement and rock heterogeneity (fractures and
vugs).
The waterflooding process mainly depends on the availability of water resources. The chemical analysis of the
injection water varied from high salinity (connate water), moderate salinity (seawater), and low salinity
(shallow-aquifers water) (LSW). To avoid injectivity decline, attention is given to the total suspended solids
more than to the total dissolved solids (TDS). Connate water, in general, has more divalent cations (
and ) than anions ( and ). Seawater composition varies from one place to another.
Several chemical/physical interactions occur between the displacing and displaced fluids that can lead to
efficient microscopic displacement (Green and Willhite 1998). These include the miscibility between fluids, a
decrease in the interfacial tension, oil volume expansion, and a reduction in oil viscosity, and maintenance of a
favorable mobility ratio. In general, the wettability of most of the carbonate reservoirs is classified as
intermediate-wet or oil-wet (Chilingar and Yen 1993). The stability of connate water film also affects the
rock/fluid interactions and perhaps the wettability (Kussakov and Mekenitskaya 1955; Hall et al. 1983;
Kaminsky and Radke 1997; Buckley and Liu 1998). The oil/water interface is negatively charged because of the
carboxylate groups present in the oil phase (Omotoso et al. 2002; Knecht et al. 2007). The interactions between
injection water and carbonates in the presence of crude oil are quite complicated because of the existence of
many interfaces, as seen in Fig. 1 (water/oil, oil/connate water, and connate water/rock) (Aksulu 2010).

Over the last decade, LSW technology was applied in various sandstone reservoirs worldwide. In sandstone
reservoirs, the implementation of LSW injection as either secondary or tertiary recovery modes was thoroughly
investigated by several research groups for more than a decade. Morrow and Buckley (2011) noted an increase
in oil recovery when LSW was used. Necessary conditions were identified in Berea sandstone to achieve the
target recovery with low-salinity waterflooding (Tang and Morrow 1999). The conditions included significant
clay fraction, the presence of connate water, and exposure to crude oil to create mixed wet conditions. Alotaibi
et al. (2011b) studied the effect of brine salinity on contact-angle measurements with two types of sandstones as
the rock surface and three different brines. They found that the water salinity has a significant impact on the
rock wettability. Nasralla and Nasr-El-Din (2011) proposed that the surface charge of the solids is affected by
the cation type ( and ), which resulted in weak negative charges of Berea sandstone. Sodium ions
make the charges strongly negative. When the electric charges become more negative at oil/brine and rock/brine
interfaces, the repulsion forces between rock and oil increase and make the rock more water-wet as a result of
the expansion of the electric double-layer and stabilization of the water film surrounding the rock (Nasralla and
Nasr-El-Din 2014).
Several field trials were carried out to test the potential of low-salinity waterflooding to improve oil recovery at
the field scale (McGuire et al. 2005; Seccombe et al. 2008). They found that low-salinity waterflooding is an
effective technique to achieve sufficient oil recovery in sandstone reservoirs. Farida et al. (2013) tested the LSW
in the Greater Burgan field for the high-quality interval with low clay content by use of a single-well tracer test.
The Greater Burgan field is the second largest field in the world and the largest clastic field. The LSW recovered
23.7% of remaining oil left after conventional waterflooding. Also, no damage was observed in the injectivity of

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the wells when the salinity of the injected water was reduced from 140,000 to 5,000 ppm for the relatively low-
clay rock types (good-quality rock).
In the present study, more attention is given to carbonate-rock/ water/oil interactions. Ca and Mg carbonate
minerals, such as calcite, Mg calcite, and dolomite, are the most abundant forms found in carbonate formations.
In one of the Saudi Arabian seawater containing and and diluted seawater changed the aged oil-wet
calcite plates to more water-wet conditions.
The carboxylic acids in the crude oil affect the wetting parameter for carbonate rocks. The total acid number
(mg of KOH/g) represents the concentration of organic acids in the crude oil. The bond between the negatively
charged carboxylate groups and the positively charged sites on the carbonate surface is very strong. Standnes
and Austad (2000) stated that the oil recovery and imbibition rate significantly decreased as the acid number of
the oil increased.
Zahid et al. (2012) investigated the oil/seawater ion interactions at different sulfate-ion concentrations,
pressures, and temperatures. Crude-oil/brine interaction measurements were carried out in a DBR JEFRI
pressure/volume/temperature cell. Three crude oils (Latin American, Middle East-1, and Middle East-2) were
used. They investigated the effect of sulfate ions on the viscosity of crude oils. The viscosity reduction after
interactions with sulfate ions at high pressure and high temperature are possible reasons for the increment in oil
recovery. Multi-ion exchange and mineral dissolution are responsible for desorption of organic acids, which
lead to more-water-wet conditions (Chandrasekhar and Mohanty 2013).
The objectives of this study are (1) to assess the impact of the salinity of the injection water and (2) the impact
of connate water composition on oil recovery and waterflooding performance.

Wettability Alteration
Low salinity waterflooding is gaining some attention in the recent literature as a means of improving oil
recoveries. However, a clear understanding of the key mechanism(s) of low-salinity waterflooding does not
seem to have emerged although wettability alteration is repeatedly cited as the cause for the observed effects,
albeit without much experimental evidence. Moreover, much of the reported low-salinity work appears to be
related to sandstone reservoirs.
In this part of study, it is attempted to investigate the role wettability alteration plays in low-salinity
waterflooding by investigating performed studies conducting dual-drop-dual-crystal contact angle measurements
to characterize wettability changes and coreflood experiments for oil recovery and oil/water relative
permeability measurements using a dolomite reservoir rock-fluids system and conducted experiments to
examine the roles of brine chemistry and the temperature in altering wettability in low-salinity waterfloods.
In carbonate formations, the carbonate rock surface attains a positive charge in presence of formation brine. The
positive charge results from carbonate dissolution in brine, which also increases the solution pH (Navratil 2012).
In presence of oil, the brine-soluble acidic components of the oil (carboxylate ions, R-COO_) are attracted to the
positively charged carbonate rock surface. Some of these acidic oil molecules attach to the positively charged
carbonate surface, which makes the surface oil-wet. This is why restoring core wettability is critical factor in
any IOR/EOR experiments.
In presence of brine, the positively charged carbonate surface is amenable to anion exchange, which might be
the reason for wettability alteration by the seawater in seawater flooding. In the latter, the sulfate, calcium and
magnesium ions (SO4 2_, Ca2_, Mg2_) compete with the carboxylate (R-COO_) ions (Austad et al., 2012) to
partially alter the rock wettability from oil wet to water wet.
Wettability alteration is a complex issue which, in addition to the brine ionic composition, also depends on
reservoir temperature. Austad et al. (2005) conducted experiments using cores from Ekofisk, Valhall, and Yates
fields to improve spontaneous imbibition of water into oil-saturated samples. They observed that the presence of
SO4 2_ improved the spontaneous imbibition regardless of the wetting conditions. Furthermore, studies on low-
salinity waterflooding in carbonate reservoirs, with reduced Na_, indicate that Ca2_, Mg2_, and SO4 2_ play a
major role in the wettability alteration (Fathi et al., 2012, Austad et al., 2012, Awolayo et al., 2014).

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Gupta et al., 2011 reported an increase in oil recovery through experiments involving carbonate cores using
Advanced Ion Management (AIMSM), where it adds/removes different ions from the injected water. Al Harrasi
et al., 2012 conducted low-salinity waterflood experiments on different carbonate cores. In their study,
carbonate cores were used for both coreflooding and spontaneous imbibition experiments at 70 °C. Synthetic
brine was mixed with distilled water in four ways (diluted twice, 5 times, 10 times, and 100 times). From these
experiments, it was reported an increase of 16–21% in oil recovery.
Study by Zekri et al., 2012 reported contact angle change with time with low-salinity brine, both on limestone
and sandstone cores from Libyan oil reservoirs. Several brine injection concentrations were used in the
experiment to examine the effect of salinity in oil recovery by varying sulfate concentrations. The study
concluded that wettability alteration is the main mechanism to increase recovery in carbonate formations by
low-salinity water flooding. Zahid et al., 2012 experimental results show improved oil recovery during low-
salinity waterflood in carbonate reservoirs. Their experiments were conducted with live oil both at ambient and
high temperatures (90 °C). It was also observed no effect of low salinity waterflooding on oil recovery at
ambient temperature. However, an increase in oil recovery was observed with runs at high temperatures (90 °C).
Moreover, due to the increase in pressure drop, migration of fines or dissolution effects may have occurred and
may contribute to the increase in oil recovery.

The contact angle results clearly indicate the wettability alteration from an oil-wet state to an intermediate state
caused by diluting the reservoir brine to one-fiftieth of its original strength (A. Kafili 2014). A similar result was
obtained when the sulfate concentration in the reservoir brine was doubled and when the temperature was
increased to 250oF from the reservoir temperature of 80 F (A. Kafili 2014). These wettability alterations as
measured by contact angles were confirmed by coreflood experiments that yielded significantly higher
recoveries (usually from about 46% to about 76%) due to low-salinity flooding, alteration of brine composition
and temperature (A. Kafili 2014). The performed experimental studies confirm the major influence of
wettability in low-salinity waterflooding of a dolomite reservoir (Standnes and Austad (2000), Chandrasekhar
and Mohanty 2013, Kafili 2014).

Wettability Alteration investigation

Effect of Brine Composition and Salinity on Wettability at Ambient Conditions


The effect of brine with sulfate on wettability was evaluated to be significant as the water-advancing contact
angle decreased for brine with 4.4 g/l sulfate- indicating a shift in wettability from strongly oil-wet to
intermediate-wet. This is because the amount of sulfate in the brine, (4.4 g/l), has been more than the total
amount of magnesium and calcium (3.425 g/l). Therefore, sulfate ions can be attracted by the positively charged
surface and thus more negative charges will be created on the rock surface to cause the oil to leave the surface
and to change the wettability to intermediate state (Kafili et. al. 2014). On the other hand, the decrease in water-
advancing contact angle is attributed to the ion exchange between the key ions ( ) present in
brine which release some adsorbed carboxylic oil components from the rock surface, and consequently altering
rock wettability towards a more water-wet condition (Strand, et al., 2008; Zhang and Austad, 2006; Zhang, et
al., 2007, Ligthelm et al, 2009).
The water-advancing contact angle changed from 158° for the Yates synthetic brine to 150° and 144° for the
twice and ten times diluted Yates brines, respectively (Kfili 2014). This means, diluting the brine to half and one
tenth the original concentration did not alter the system from being oil–wet. This is because the amount of salt in
the brines was large enough that caused the thin wetting film of water removed from the dolomite surface and as

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a result oil adhered on the dolomite surface strongly. A significant change was observed in the water advancing
angle with 50-times-diluted brine. The contact angle changed the wettability of the system from oil-wet to
intermediate- times-diluted brine indicating the rock wettability showed weakly oil wet for 100 times diluted
brine (Kafili 2014). The significant change of water-advancing contact angle for 50 and 100 times diluted brines
can be explained because the amount of total dissolved solids in the system was quite low and thus there were
insufficient ions in the brine to weaken the thin water film between oil and rock (Kafili 2014).. Also, migration
of fines, dissolution of rock particles could be other possible mechanisms of shifting the system to more water-
wet.
The water-advancing angle decreased more for 50-times diluted brine than for 100 times diluted Yates brine and
thus it was more effective (Kafili 2014). This may be because for the 100 times diluted brine the concentration
of key ions (SO4 -2, Ca2+ and Mg2+) reduced more than a certain level where they could act as active ions. On
the other hand, the amount of salinity in 100 times diluted brine was not able to change the surface charge of the
carbonate rock toward more negative, leading to more interactions with water molecules, and eventually altering
rock wettability less than that in 50 times diluted brine. This conclusion appears in agreement with Jabbar et al,
2013 that “there may be an optimal composition of the dissolved solids in the injection water that would yield
the lowest water advancing angle and highest oil recovery”. Also it was confirmed by Alotaibi (2009) that for
the best oil recovery there is an optimum salinity level that should not be exceeded to recover more oil.
Wettability alteration has been experimentally confirmed to be the main mechanism for the effectiveness and
low-salinity waterflooding. It was concluded that the presence of a relatively stable wetting water film on the
rock surface which results in weak adhesion between oil and rock surface would occur by diluting the Yates
reservoir brine.

Comparison of Water-Advancing Contact Angles at Ambient and Reservoir Conditions

The following diagram shows the comparison of contact angle at ambient and reservoir conditions which presents the
significant effectiveness of salinity on both conditions.

(Kafili Kamaei2014)

Effect of Temperature on Wettability Using the High-Pressure High-Temperature DDDC Apparatus at 250°F

From the literature, it was known that temperature has a significant effect on wettability unlike the pressure. It
tends to decrease water-advancing contact angle and make the carbonates more water-wet at higher
temperatures. Surface reactivity of key ions increase with increase in temperature, adsorption of SO4 2- with co-
adsorption of Ca+2 on carbonate surface occurs, which creates more negative charges (Zhang and Austad 2006;
Zhang et al 2007).

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The effect of temperature on wettability for all the experiments was significant and water-advancing contact
angle decreased for all the cases with increasing temperature. The effect of temperature can be explained
according to the chemical model of Hiorth et al. 2010 to predict the surface potential of calcite and the
adsorption of sulfate ions from the pore water. At higher temperatures, calcium in the brine reacts with sulfate
and anhydrite is precipitated. When anhydrite is formed the aqueous phase loses calcium, and calcium has to be
supplied from the rock for the solution to remain in equilibrium with calcite. The source of Ca2+ ions must be
calcite dissolution. If the calcite dissolution takes places where the oil is adsorbed, then the oil can be liberated
from the rock. The present of magnesium can also help the dissolution of calcite.
The conclusion reached in this study is in agreement with the findings of Yousef et al. 2011, 2012, 2011 a, 2011
b, 2011
c). They reported that reservoir temperature has a significant impact on carbonate surface charge, rock
wettability, and ultimately has potential to enhance oil recovery in carbonate reservoirs.

The Effect of Brine Salinity and Composition on Oil Recovery and Relative Permeability at Reservoir
Conditions

Comparison between water-advancing angles obtained for ambient, reservoir and high temperature conditions

(Kafili et al. 2014)

Effect of low salinity and amount of sulfate in brine on oil recovery

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(Kafili et al. 2014)

Effect of low salinity and amount of sulfate in brine on fractional water flow

(Kafili et al. 2014)

The Effect of Connate Water Composition


Extensive experimental work has indicated that low-salinity waterflooding is an enhanced oil recovery
technique that improves oil recovery by lowering and optimizing the salinity of the injected water. Most of the
low-salinity waterflooding studies focused on the injection brine salinity and composition (Ahmed M. et al
2014). The question remains, how does the salinity and composition of the reservoir connate water affect the
low-salinity waterflooding performance?
Recent laboratory and field observations have indicated the possibility of reducing the residual oil saturation
when the injection of conventional water is replaced with the injection of low-salinity brines. Low-Salinity

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Waterflooding (LSW) has been capturing an ever-increasing share of hydrocarbon production since the 1990s.
Experimental work indicated that LSW is a technique that improves oil recovery by reducing and optimizing the
salinity of the injected water. The LSW has been reported for brine compositions of up to 5,000 ppm (Yildiz and
Morrow 1996; Tang and Morrow 1997; Sorop et al. 2013; Rotondi et al. 2014). Many laboratory tests have been
carried out to investigate the different major LSW mechanisms. The various mechanisms are summarized here:
fines migration (Tang and Morrow 1997), multi-component ion exchange (Lager et al. 2006), double layer
expansion (Lee et al. 2010; Nasralla et al. 2014), wettability alteration toward water-wet (Alotaibi et al. 2011),
and pH increase (Tang and Morrow 1999; Austad et al. 2010). There is no consensus about dominant
mechanisms.
There are several studies that were carried out at the field scale to test the potential of LSW to improve oil
recovery compared to conventional waterflooding (McGuire et al. 2005; Seccombe et al. 2010). Also,
Log/inject/log measurements indicated a reduction of 60% of residual oil within approximately 4 in. of a
wellbore (Webb et al. 2004). The Burgan field in Kuwait is the second largest field and the largest clastic field
in the world. Farida et al. (2013) tested the LSW in the greater Burgan field for high-quality intervals with low
clay contents using a SWCT. Two pairs of SWCT tests were conducted on two different wells. The Sor before
and after LSW injection was measured. The LSW recovered 23.7% of remaining oil left after conventional
waterflood. Also, they observed no damage in the injectivity of the wells when reducing salinity from 140,000
to 5,000 ppm for relatively low clay rock types (good quality rock).
Jia et al. (1991) explored the control of wetting using crude oils at various aging conditions using the
Amott wettability test. Berea sandstone core plugs with 1.5 in. diameter and 1.75 to 2 in. length were
used. The cores were saturated with 2.5% CaCl2 because previous studies showed that it tended to
promote wettability alteration in cores exposed to Moutray crude oil. Aging temperature and initial
water saturation have a predominant influence on the wettability induced by a given crude oil. Zhou et
al. (1995) studied the effect of crude oil aging time and temperature on the rate of water imbibition for
crude oil/brine/rock systems (Alaskan crude oil, 2% CaCl2 brine, and Berea sandstone). Also, they
investigated the short-term rates of imbibition of water and long-term recovery by SI. The cores were
1.5 in. diameter and 2.7 to 2.9 in. length. They found that increasing the aging time and temperature
decreased the early time rate of imbibition in water. Moderately water-wet plugs gave the highest
recovery by long-term imbibition.
Suijkerbuijk et al. (2012) performed a series of SI experiments on sandstone Berea outcrop core plugs
and some reservoir rock core plugs with 1.5 in. diameter and 2 in. length. They examined the impact of
formation water composition and crude oil composition on wettability and on wettability modification
by LSW flooding. SI experiments with formation brine and low-salinity brine executed on Berea
outcrop material aged with crude oil showed excellent reproducibility. They suggested that improved
oil recovery occurs after exposure of the aged plugs to NaCl brines when the imbibing phase was
either higher or lower in salinity than the formation brine. An increasing concentration of divalent
cations in the formation brine makes a crude oil/brine/rock system more oil-wet. Also, the extent of
wettability modification towards more oil-wet depends on the types of cations present in the formation
brine.
Polar crude oil components can either adsorb directly onto charged surfaces or multivalent cations can
bind polar crude oil components to the mineral surfaces by cationic bridging (Fjelde et al. 2014). The
retention of polar oil components onto the reservoir rock mineral surface has been found to depend on
both the composition of brine and/or crude oil. Fjelde et al. (2013a) reported that the retention of polar
crude oil components onto clay minerals and reservoir rock increases with increasing total
concentration of divalent cations onto clay surfaces. Fjelde et al. (2013b) reported that the water
wetness was found to increase with decreasing retention of polar oil components.
Reservoir connate water salinity and composition vary from one reservoir to another. Na_, Ca2_, and
Mg2_ are the main cations. The salinity of the brine is represented by the Total Dissolved Solids (TDS).

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TDS is the total mass content of dissolved ions and molecules or suspended micro granules in a liquid
medium (Sheng 2011). The ions were divided into two groups: monovalent (represented by the sodium
ion, Na_) and divalent (represented by calcium Ca2_ and magnesium Mg2_ ions). Tang and Morrow
(1999), Sharma and Filoco (2000), and Zhang and Morrow (2006) observed that there was no benefit
from the LSW if no connate water saturation was present and the connate water should contain
divalent cations.
Nasralla and Nasr-El-Din (2011) investigated the effect of injected brine on LSW performance for
sandstone rocks. NaCl, CaCl2, and MgCl2 brine solutions were tested. NaCl brine gave the highest oil
recovery. Increasing the concentration of NaCl brine improved the oil recovery. Lager et al. (2006)
concluded that cation exchange between the mineral surface and the invading brine was the primary
mechanism underlying the improved waterflood recovery seen by low-salinity brine injection.
The peak production rate for Core O-3 appeared earlier after 28 days of imbibition compared to Cores
O-2 and O-1 which reached maximum production after 37 and 38 days, respectively. This recovery
range agrees with similar determined previously (Yildiz and Morrow 1996). They stated that
waterflood recoveries of Moutray crude oil, which could be ascribed to differences in initial and
injected brine composition and neutral brine saturation ranged from 59-72% of original oil-in-place.
Lee et al. (2010) concluded that exchange of divalent ions for monovalent ions at low concentration
can significantly enhance the thickness of water layer of mineral surface. They reported that the
sodium chloride water layer increased from 10.8 to 11.8 Å for a reduction in salinity from 0.1 Molar to
0.001 Molar (6000 ppm to 60 ppm). For MgCl2 the water layer thickness increased from 8.14 to 14.8
Å. Nasralla et al. (2011) demonstrated the occurrence of cation exchange between LSW, connate-
water, and the rock surface. They showed that LSW leaches cations from the rock surface, which
results in a change of the surface charges of the rock. Skrettingland et al. (2010) suggested that the
initial wetting condition is crucial to the performance of a low-salinity drive. They demonstrated that
when multivalent cations were present in the connate brine, flooding with LSW led to higher oil
recovery. Polar crude oil components can either adsorb directly onto charged surfaces or multivalent
cations can bind polar crude oil components to the mineral surfaces by cationic bridging (Fjelde et al.
2014). The retention of polarn components onto rock surfaces has been found to depend on both the
composition of brine and crude oil (Fjelde et al. 2014).
In addition, (Shehata et al. 2014) reported two SI experiments were performed at a temperature of
150°F using Buff Berea sandstone Cores O-4 and O-5. The objectives of these two experiments were
to study the influence of temperature on the recovery performance using SI tests. Cores O-4 and O-5
were saturated with high salinity conventional connate water (174,156 ppm) similar to core O-2. One
of the cores was immersed in low-salinity imbibition brine (5,000 ppm NaCl), while the other core was
immersed in brine with the same composition of the connate water (H-1) to simulate conventional
waterflooding. Then, the two cells were placed in an oven set at 150°F. The pH of the imbibition fluid
for Cores O-4 and O-5 at the beginning of the experiments were 6.86 and 6.34, respectively (Shehata et
al. 2014).
The oil recovery by using (5,000 ppm NaCl) as imbibition fluid could reach 63.8% of OOIP in 40 days
(Shehata et al. 2014). It is even higher than the oil recovery of 52.2% of OOIP using high salinity
imbibition fluid. Lee et al. (2010) suggested that during high salinity water flooding the polar and
charged components of the oil are retained on the surface of the clay resulting in a higher post water
flood residual oil saturation. Reducing the water salinity developed a thicker water film compared to
high salinity water, which demonstrated the expansion of the double layer by LSW which provided a
greater opportunity for the oil to be swept (Shehata et al. 2014). The comparison between core O-2 and
O-4, confirms that the imbibition rate is influenced by the temperature condition. An additional oil
recovery up to 15.8% of OOIP was clearly observed when the temperature increased from 77 to 150°F.
The imbibition time decreased with an increased temperature. The initial fast production during the
first days was due to thermal fluid expansion . An increase in temperature reduces the oil to the water

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viscosity ratio, so as to yield a less resistant force to water imbibition, and also enhances the water
wetness of solid surfaces (Shehata et al. 2014).
Hoffman and Kovscek (2004) stated that the wettability of the reservoir rock was a key factor in
thermal displacement efficiency. Tang and Morrow (1997) demonstrated that an increase in
temperature always results in increased water wetness and increased oil recovery.
Alotaibi et al. (2010) reported higher magnesium concentrations in the effluent sample than in
injection water suggesting that cation exchange occurred between clays in the sandstone rock and
injection brines. Nasrallah and Nasr-El-Din (2011) stated that the absence of CaCl2 in the injected brine
allowed leaching Ca2_ from the rock surface; that resulted in change the rock surface charge, hence
higher oil recovery.
Sheng (2014) reported that 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. Meyers and Salter (1984) observed that the steady-state effluent
concentrations of calcium and magnesium were observed to be slightly greater than the injected
concentrations. These excess on concentration increased as the injection concentrations decreased.
These results indicated that the rock quality has a significant effect in the performance of LSWSharma
and Filoco (2000) found that the salinity of reservoir connate water was the primary factor controlling
the oil recovery. They used different salinities of connate water 0.3, 3, and 20% NaCl. The oil recovery
was greater for lower connate brine salinities. They attributed this dependence to alteration of the
wettability to mixed-wet conditions from water-wet conditions during the drainage process.
Jadhunandan and Morrow (1995) performed more than 50 slow-rate laboratory waterfloods to
investigate the relationship between wettability and oil recovery by waterflooding using Berea
sandstone. The cores were 3.79 cm in diameter and 8 cm long. They observed that wettability
depended on the initial water saturation, aging temperature, crude oil, and brine composition.
(Shehata et al. 2014) Nine spontaneous imbibitions experiments were performed. Two sandstone types
(Bandera and Buff Berea) with different clay contents were used. The mineralogy of the rock samples
was assessed by X-ray powder diffraction, scanning electron microscopy, and X-ray fluorescence.
They described the experimental studies of the spontaneous imbibition of oil by low-salinity and high-
salinity brines using 20 in. length outcrop samples. The main objectives of the spontaneous imbibition
study was to investigate the role of the composition of the reservoir connate water (Na_, Ca2_, and
Mg2_), the effect of rock permeability, and test the effect of temperature (77 and 150°F) on the
performance of the low-salinity waterflooding recovery. The volume of the produced oil was
monitored and recorded against time on a daily basis. Imbibition brine samples were analyzed at the
end of each experiment (Shehata et al. 2014).
(Shehata et al. 2014) Results demonstrate that the spontaneous imbibition oil recovery ranged from 38
to 69% OOIP for high permeability Buff Berea cores (164-207.7 md), while oil recovery of the low
permeability Bandera cores (31.1-39.2 md) ranged from 20 to 51.5% OOIP at 77°F and 14.7 psia. The
oil recovery decreased when the average pore-throat radius decreased. The reservoir connate water
composition has a dominant influence on the oil recovery rate. The changes in the ion composition of
reservoir connate water (Ca2_, Mg2_, and Na_) showed a measurable change in the oil production trend.
Reservoir cores saturated with connate water containing divalent cations of Ca_2 and Mg_2 showed
higher oil recovery than for cores saturated with monovalent cations Na_. In all cases, a measurable ion
exchange was observed, while there was no significant change in the pH of the imbibition brine during
the experiment. The ions exchange effect was more pronounced than the pH effect in the low-salinity
waterflooding performance for Buff Berea and Bandera sandstone. As the temperature increased from
77 to 150°F, an additional oil recovery up to 15.4% of OOIP was observed by spontaneous imbibition
for Buff Berea cores (Shehata et al. 2014).

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Conclusions
1- The results showed that improvement in oil recovery with sulfate ions and low salinity can be explained by the
rock wettability alteration.
2- The DDDC contact angles demonstrated significant wettability alteration by 50-times diluted brine at both
ambient and reservoir conditions.
3- The effect of temperature on wettability was significant and water-advancing contact angle decreased with
increasing temperature. For both the brine with 4.4 g/l sulfate content and 50-times diluted brine, water advancing
contact angle decreased from 157° to 86° by increasing the temperature.
4- The gradual rightward shift in relative permeability ratio curves indicating wettability alteration to intermediate-
wet was induced by brine containing 4.4g/l sulfate and 50-times diluted brine. The water-advancing contact angles
measured using the DDDC technique in this system also confirmed the wettability shift from oil-wet to
intermediate-wet due to lowered salinity and increased sulfate ion concentrations.
5- The oil recovery increased by increasing the sulfate content in the brine.
6- The oil recovery increased by decreasing the salinity of the brine.
7- Results indicate that low salinity brine could provide significant oil recovery enhancements in carbonate
reservoirs. This could avoid extensive investments associated with conventional EOR methods.
8- The spontaneous imbibition oil recovery increased OOIP for high permeability Buff Berea cores (164-207.7 md),
while oil recovery of the low permeability Bandera cores (31.1-39.2 md) ranged from 20 to 51.5% OOIP at 77°F
and 14.7 psia. The oil recovery decreased when the average pore-throat radius decreased. (Shehata et al. 2014)
9- The reservoir connate water composition had a dominant influence on the oil recovery rate. The changes in the ion
composition of reservoir connate water (Ca2_, Mg2_, and Na_) showed a measurable change in the oil production
trend. Reservoir cores saturated with connate water containing divalent cations of Ca_2 and Mg_2 showed higher
oil recovery than for cores saturated with monovalent cations Na.
10- In all cases, a measurable ion exchange was observed, while there was no significant change in the pH of the
imbibition brine during the experiment. The ions exchange effect was more pronounced than the pH effect in the
low-salinity waterflooding performance for Buff Berea and Bandera sandstone.
11- As the temperature increased from 77 to 150°F, an additional oil recovery up to 15.4% of OOIP was observed by
spontaneous imbibition for Buff Berea cores.

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