Tetteh 2018

REE194006 DOI: 10.
2118/194006-PA Date: 10-October-18 Stage: Page: 1 Total Pages: 20
Crude-Oil/Brine Interaction as a Recovery

Mechanism for Low-Salinity Waterflooding
of Carbonate Reservoirs
Joel T. Tetteh and Reza Barati, University of Kansas
Summary
Low-salinity waterflooding in limestone formations has been less explored and hence less understood in enhanced-oil-recovery (EOR)
literature. The mechanisms leading to improved recovery have been mostly attributed to wettability alteration, with less attention given
to fluid/fluid-interaction mechanisms. In this work, we present a thorough investigation of the formation of water-in-oil microdisper-
sions generated when low-salinity brine encounters crude oil and the suppressed snap-off effect caused by the presence of sulfate con-
tent in seawater-equivalent-salinity brines as recovery mechanisms in limestone rocks. We believe this is a mechanism that leads to the
improved oil recovery experienced with low-salinity waterflooding and seawaterflooding in carbonate formations. This novel interpreta-
tion was studied by integrating petrographic and spectroscopic observations, dynamic interfacial-tension (IFT) measurements, thermo-
gravimetrical analyses, and coreflooding techniques.
Our data show that low-salinity brine caused a greater change in the crude-oil composition compared with seawater brine and
formation-water brine. Formation-water brine created nearly no changes to the crude-oil composition, indicating its limited effect on
the crude oil. These compositional changes in crude oil, caused by the low-salinity brine, were attributed to the formation of water-
in-oil microdispersions within the crude-oil phase. Fourier-transform infrared (FTIR) spectroscopy data also showed that at brine-
concentration levels greater than 8,200 ppm, this phenomenon was not experienced. Oil-production data for nonaged limestone cores
showed an improved recovery of approximately 5 and 3% for seawater and low-salinity brines, respectively. Although the wettability-
alteration effect was minimized by the use of nonaged cores, improved oil recovery was still evident. This was interpreted to represent
the formation of water-in-oil microdispersions when low-salinity water (LSW) of 8,200-ppm salinity and less was used. The formation
of the microdispersions is believed to increase the sweep efficiency of the waterflood by swelling and therefore blocking the pore
throats, causing low-salinity-brine sweeping of the unswept pore spaces. Improved recovery by seawater brine was attributed to the
changes in dynamic IFT measurement experienced using seawater brine as the continuous phase, compared with the use of LSW and
formation-water-salinity (FWS) brine. This change caused a higher surface dilatational elasticity, which leads to a suppression of the
snap-off effect in coreflooding experiments and hence causes improved oil recovery.
Our studies conclude that the formation of microdispersions leads to improved oil recovery in low-salinity waterflooding of lime-
stone rocks. Furthermore, the use of seawater as a displacing fluid succeeds in improving recovery because of its high surface elasticity
suppressing the snap-off effect in the pore throat. We also present an easy and reliable mixing procedure representative of porous
media, which could be used for screening brine and crude-oil samples for field application. Fluid/fluid interaction as well as high sur-
face elasticity should be investigated as the causes of wettability alteration and improved recovery experienced by the use of LSW and
seawater-salinity (SWS) brines interacting with limestone formations, respectively.
Introduction
High-salinity water has been used for waterflooding since the 1930s (Willhite 1986). More recently, reduced-salinity water, mostly in
the salinity range of seawater (30,000 to 50,000 ppm) and as low as 5,000 ppm, has been used in improving oil recovery both in labora-
tory experiments and field cases (McGuire et al. 2005; Seccombe et al. 2010; Yousef et al. 2012c; Nazari et al. 2017). The idea of using
a low-salinity brine as a displacing fluid in a waterflood project was investigated in sandstone formations by Bernard (1967), but it was
not until the 1990s that research interest grew in this area, mainly because of Jadhunandan and Morrow (1995), Yildiz and Morrow
(1996), and Tang and Morrow (1997, 1999). Several researchers then transferred the idea of low-salinity waterflooding into carbonate
formations. Yousef et al. (2012c) performed a field trial of smartwaterflooding with LSW (approximately 5,000 ppm) in two different
carbonate formations using a single-well chemical-tracer test to calculate the residual oil saturation after each flood. Yousef et al.
(2012c) reported a 6- to 7-unit reduction in residual oil saturation. Even with the success of this field pilot test, there has still not been a
clear consensus on the underlying cause of the improved recovery experienced, especially in carbonate formations. Improved oil recov-
ery experienced during low-salinity waterflooding has, in most cases, been attributed to wettability alteration in carbonate reservoirs
(Puntervold 2008; Yousef et al. 2010, 2012a, b; Mahani et al. 2015; Al Shalabi and Sepehnoori 2017; Tetteh et al. 2018).
The complexity of carbonate-rock mineralogy together with the inherent rock heterogeneity and rock properties makes the under-
standing of low-salinity waterflooding very complex and the scaling up of experimental studies from microscopic scale to field scale
very difficult (Afekare and Radonjic 2017). The surface charge of calcite has been reported to be positive below pH values of 9 through
11 (Hirasaki 1991; Ding and Rahman 2017). Asphaltenes and carboxylic acids are very crucial in influencing the interfacial phenom-
enon of the crude-oil/rock/brine system. Asphaltenes have a great effect on the interfacial phenomenon between the crude oil and brine
by binding to the interface and affecting the IFT (Sauerer et al. 2018). Carboxylic acid from the crude-oil components easily adsorb on
the positively charged surfaces, hence making carbonates highly oil-wet. Reverse wettability alteration is therefore very important in
improving oil recovery in carbonate formations. Low-salinity brine and smartwater brine have been proposed to alter wettability toward
more-water-wet states in carbonates (Austad 2013). Low-salinity recovery involves the reduction of brine ionic strength with or without
additional ions. Smartwater, on the other hand, involves chemically tuning the ions, mostly potentially determining ions (PDIs), and the
ionic strength of the brine to ultimately improve oil recovery (Austad 2013). The increase in PDIs, especially SO2 4 , can cause some
Copyright V
C 2018 Society of Petroleum Engineers
This paper (SPE 194006) was revised for publication from paper OTC 28023, first presented at the Offshore Technology Conference Brasil, Rio de Janeiro, 24–26 October 2017. Original
manuscript received for review 4 December 2017. Revised manuscript received for review 17 June 2018. Paper peer approved 28 June 2018.
2018 SPE Reservoir Evaluation & Engineering 1
ID: jaganm Time: 15:26 I Path: //chenas03/cenpro/ApplicationFiles/Journals/SA/SPE/REE#/Vol00000/180060/Comp/APPFile/SA-REE#180060

REE194006 DOI: 10.2118/194006-PA Date: 10-October-18 Stage: Page: 2 Total Pages: 20
scaling issues in the wellbore, hence limiting the effectiveness of this smartwaterflooding. The use of purely LSW, on the other hand,
causes less damage to the formation and the wellbore. Zhang et al. (2007) and Puntervold (2008) outlined a potential ion-exchange mech-
anism between sulfate ions and calcite ions on the surface of chalk samples. They hypothesized the possibility of magnesium ions taking
the place of sulfate at very high temperatures. They indicated that this phenomenon causes the wettability alteration experienced in chalk
formations during low-salinity waterflooding. Ravari (2011), however, observed an insignificant increase in the Ca2þ ion concentration
and an insignificant decrease in the SO2 4 for two different limestone-outcrop cores used in their experiments after flooding the core with
seawater containing significant amounts of PDIs at a temperature of 130 C. This goes against the ionic-exchange mechanism stated by
Zhang et al. (2007) and Puntervold (2008) in chalk formations, indicating the different mechanisms existing in each carbonate-rock type.
The focus of most previously reported research has been on brine/rock interactions as the main cause of the increase in oil recovery expe-
rienced with low-salinity waterflooding in carbonate rocks, with little attention given to the role of fluid/fluid interaction.
Expansion of the electrical double layer (EDL), as explained using the extended Derjaguin-Landau-Verwey-Overbeek theory of sur-
face forces, has been implemented in explaining the observed wettability-alteration mechanism during low-salinity waterflooding in
carbonate rocks (Mahani et al. 2015; Alshakhs and Kovscek 2016; Jackson et al. 2016). Experimental evidence of the expanded EDL is
usually provided by measuring the f-potential of rock powder in aqueous brine and that of oil dispersed in aqueous brine (Mahani et al.
2015). It is proposed that for the EDL to expand, the f-potential of the rock/brine and the oil/brine interfaces must exhibit the same
polarity (Jackson et al. 2016). This would result in a thick and stable water film, causing the rock wettability to shift into intermediate- or
water-wet regions. This technique is a destructive technique and is not always representative of rock porous media, with the effect of
rock aging usually neglected.
Different aspects of brine/oil interaction have been investigated as a recovery mechanism using low-salinity brine (Zahid et al.
2010, 2011; Emadi and Sohrabi 2013; Alvarado et al. 2014, 2015; Mahzari and Sohrabi 2014; Sohrabi et al. 2017; Tetteh and Barati
2018). Sohrabi et al. (2017) used micromodels representing sandstone rocks, FTIR spectroscopy, and environmental scanning electron
microscopy (ESEM) to investigate the formation of water microdispersions when low-salinity brine encounters crude oil. Sohrabi et al.
(2017) sought to prove that these water microdispersions—formed after crude-oil/brine contact is achieved—were indeed the major
cause of improved recovery caused by low-salinity waterflooding by altering the composition of crude oil that has been contacted with
low-salinity brine. By taking out the formed water-in-oil microdispersions and hence neglecting the effect of brine/oil interactions,
Sohrabi et al. (2017) experienced a reduced recovery with the adulterated crude oil compared with the use of original crude oil for a
low-salinity-waterflood experiment. Note that the reproducibility of this claim was not demonstrated in their work. This was attributed
to the effect of brine/oil interactions causing an increase in oil recovery through the formation of water-in-oil microdispersions. Alvar-
ado et al. (2014, 2015) in two different experiments used microfluidic models representing sandstone rocks and hypothesized that the
increase in oil recovery was caused by the viscoelastic properties at the brine/oil interface during low-salinity waterflooding using brine
of 0.0067-M ionic strength (353 ppm). This interfacial viscoelasticity reduces the effect of snap-off experienced during waterflooding.
Reducing the ionic strength of the brine makes the interfacial film more elastic, suppresses the crude-oil snap-off effect, and causes the
oil to form a continuous phase with bigger oil droplets. These droplets will block the pore throat and allow water to flow toward
unswept oil-bearing pores, hence improving recovery and reducing the residual oil saturation (Alvarado et al. 2014).
Sandengen et al. (2016) proposed osmosis as a mechanism in low-salinity waterflooding, leading to improved oil recovery by using
microcomputed-tomography and 2D microfluidic models. Osmosis as a mechanism uses an oil phase serving as a semipermeable membrane,
which passes LSW and not ions. This hypothesis explains the brine/oil behavior observed by Emadi and Sohrabi (2013), leading to the forma-
tion of water-in-oil microdispersions caused by the sharp change in the osmotic gradient because of the different brine salinities in a static state.
All the aforementioned evidence indicates that in addition to the brine/rock interactions, crude-oil/brine interactions also play a role
in improved oil recovery. This shows that all three components (crude oil/brine/rock) must be included for better understanding of the
underlying mechanisms in the use of low-salinity brine to improve oil recovery in carbonate formations.
The present paper sets out to investigate the role of fluid/fluid interaction in limestone rocks during both secondary- and tertiary-
mode waterflooding using both LSW and seawater brines. Mahzari and Sohrabi (2014) used similar techniques in studying the interac-
tion between crude oil and low-salinity brine in sandstone rocks. The roles of various brine salinities (especially seawater brine) in
improving oil recovery in carbonate rocks were not explored in their work. Reproducible mixing techniques involving contacting brine
with crude oil, which is representative of an actual reservoir fluid, were not used. In this research, we seek to investigate this mechanism
for carbonate rocks and extend our investigation toward seawaterflooding in carbonate rocks. The main objective of this research is to
show the improved oil recovery experienced in carbonate formations by injecting LSW and SWS brine, providing a mechanistic study
of the novel concept of the formation of water-in-oil microdispersions and suppressed snap-off effect when LSW and seawater brine,
respectively, encounter crude oil. This understanding will be useful for oil-producing limestone formations in Kansas with potential
access to produced brine with seawater-like salinity. The findings of this work might be extended to other oolitic limestone formations
that have access to LSW or SWS water. A thorough explanation of our easy but reliable mixing procedure will be reported, capable of
being used as an easy and quick experiment for the screening of crude-oil and brine samples for field application. Techniques such as
contact-angle measurement, dynamic IFT, FTIR, thermal-gravimetric analysis (TGA), and ESEM were all used to thoroughly investi-
gate the role of fluid/fluid interactions toward improved oil recovery using low-salinity brine.
Core Material and Preparation. Six Indiana Limestone (IL) outcrop-core plugs were used for the coreflooding experiments. IL rocks
represent a uniform limestone mineralogy with no clay content, as showed by thin-section analysis and X-ray-diffraction (XRD) data
(Fig. 1). The XRD data were obtained at room temperature using monochromated CuKa radiation (k ¼ 1.54178 Å) on a Bruker
PROTEUM diffraction system. XRD data show that the IL powder had more than 99% calcium carbonate, representative of pure cal-
cite. The core was cut and dried at 90 C in an oven for 1 day. The thin-section image (Fig 1, left) illustrates the clean grainstone
texture, and no clay content (either as matrix or in stylolites). The predominant grain types are skeletal grains and ooids with
intraparticle and interparticle pores, some of which are occluded by equant calcite cement. The presence of clay and anhydrite has been
reported to be necessary to observe improved oil recovery using low-salinity brine in sandstone and limestone, respectively (Tang and
Morrow 1999; Austad et al. 2015). With the XRD data indicating pure calcite and the thin section showing no clay or anhydrite in the
rock sample, the mechanisms underlying improved oil recovery using LSW and SWS brines in these limestone rocks are limited to
limestone dissolution, EDL expansion (Mahani et al. 2015), and formation of microdispersions (AlHammadi et al. 2018).
The cores were subsequently saturated with the synthetic Lansing-Kansas City (LKC) Limestone Formation brine using a vacuum
pump. The weight of the wet core was measured, and the porosity and pore volume (PV) were calculated subsequently using brine den-
sity. The rocks were subsequently flooded with the synthetic brine using three separate flow rates, from which the permeability was cal-
culated. The rock properties are listed in Table 1.
2 2018 SPE Reservoir Evaluation & Engineering

250 1,800
Sample peaks
Intensity (counts in the thousands)

1,600
200 Pure calcite peaks
1,400
Intensity (counts)
150 1,200
1,000
100
800
50 600
400
0
0 20 40 60 80 200
100 μm –50 0
θ (degrees)
Fig. 1—Petrographic thin-section image (left) and XRD diffractogram (right) of IL powder. Thin-section pores are indicated with
blue epoxy, with rock consisting of calcitic oolitic grainstone.
3
Core Diameter (cm) Length (cm) Pore Volume (cm ) Porosity (%) Permeability (md) Oil Saturation (So)
IL-2 3.83 7.42 16.15 18.80 88.94 0.69
IL-21 3.73 7.62 14.13 16.90 23.50 0.61
IL-20 3.75 7.44 15.97 19.34 126.43 0.69
IL-12 3.83 7.41 16.09 18.88 106.92 0.57
IL-14 3.83 7.43 16.01 18.73 125.47 0.54
IL-22 3.75 7.46 16.12 19.45 117.39 0.56
Table 1—IL outcrop-core-plug properties.
Brine. Three brine salinities with original brine concentration (FWS), five-times dilution of the original brine (SWS), and 82-times
dilution of the original brine (LSW) were used for various experiments in our investigations. Different dilution factors were also used
to determine the optimal ionic strength at which the fluid/fluid interactions had the greatest effect. A second type of brine, with no sul-
fate composition, was prepared. The ionic strength of this new brine was kept the same as the corresponding brine with sulfate by
increasing the Naþ ion concentration. This approach investigated the effect of sulfate on the IFT measurement. Deionized water was
used for the dilution and preparation of the brines. The formulation of this brine was derived from the produced-water composition
from a production well. This well is producing from the LKC Limestone groups of Trembley Ranch Field, with water data collected in
April 1980. This was the first brine composition reported at the beginning of the primary production from this field. The brines were
prepared by adding different amounts of sodium chloride, potassium chloride, MgCl26H2O, CaCl22H2O, and sodium sulfate to deion-
ized water. All the salts used for the brine preparation were acquired from Fisher Scientific and were graded by the American Chemical
Society. Table 2 shows the concentration and chemical composition of the brines used for this experiment.
FWS FWS0S SWS SWS0S 20d FWS 30d FWS 50d FWS LSW LSW0S
Ions (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
2+
Ca 11,000 11,000 2,200 2,200 550 366.67 220 134 134
2+
Mg 2,800 2,800 560 560 140 93.33 56 34 34
+
Na 48,000 48,200 9,600 9,640 2,400 1,600 960 585 588
+
K 500 500 100 100 25 16.67 10 6 6
–
Cl 101,913 101,913 20,383 20,383 5,095.65 3,397.10 2,038.26 1,243 1,243
2–
SO4 260 0 52 0 13 8.67 5.2 3 0
pH 5.71 5.97 6.03 5.58 5.77 5.93 5.76 6.12 5.85
IS (mol/L) 3.27 3.27 0.65 0.65 0.16 0.11 0.07 0.04 0.04
TDS (ppm) 164,473 164,413 32,895 32,883 8,223.65 5,482 3,289.46 2,006 2,005
Table 2—LKC brine composition. “0S” in sample name signifies zero sulfate ion. IS 5 ionic strength; TDS 5 total dissolved solids; 20d, 30d,
50d 5 20 times diluted, 30 times diluted, 50 times diluted.
Crude Oil. Reservoir-oil samples from the limestone members of the LKC group were used for this experiment. Coreflooding, IFT,
and contact-angle tests were performed using unfiltered crude oil. The crude oil was not filtered to preserve the heavy-oil components
that can affect the brine/oil interactions being studied. The LKC crude oil has a viscosity and density of 5.86 cp and 0.84 g/cm3 at
40 C, respectively, and total acid and base numbers of 0.17 mg potassium hydroxide (KOH)/g and 0.11 mg KOH/g, respectively, with
asphaltenes content of 0.73 wt%.

Methodology
The improved oil recovery by low-salinity waterflooding was first investigated using the coreflooding procedure described here with
both aged and nonaged core plugs. The use of nonaged IL core plugs for the study of the role of fluid/fluid interaction was justified by
performing contact-angle tests on both aged and nonaged limestone surfaces. The difficulty in understanding low-salinity waterflooding
in carbonate rocks is caused by confusion between the causes and the effects of low-salinity waterflooding. To make this distinction, we
designed a series of coreflooding experiments tailored toward a comprehensive understanding of the connection between causes and
effects of low-salinity waterflooding. We made use of nonaged cores in our coreflooding process to highlight the role of fluid/fluid inter-
action and suppress the ever-popular wettability-alteration mechanism supporting this assumption by measuring the rock contact angle.
In investigating the cause of the oil-production improvement in nonaged limestone cores, we performed various interfacial and bulk
measurements. IFT measurements between the various brines and the crude-oil samples were measured over a period of 1 hour.
Surface-elasticity calculations were derived from the equilibrium IFT values, giving us an indication of the possibility of suppressed
crude-oil snap-off caused by high elasticity. Three sampling techniques were used in studying the formation of water-in-oil microdis-
persions, which is recommended as one of the potential recovery mechanisms in limestone rocks. The first technique was performed
using an inline porous medium, which served as a synthetic porous medium and aided with reproducibility of the brine/crude-oil mixing
process. The second technique consisted of using effluent samples after coreflooding of core plugs with various salinities of brine. This
technique was used as a confirmation of the similarity of results between the inline mixer technique and actual in-situ fluid/fluid interac-
tion in coreflooding experiments. The third technique involved contacting brine with crude in a vial test. The purpose of using three
techniques is to show the reproducibility of results as well as to provide a simpler technique that can be used to achieve similar results
but within a shorter time. This could serve as a quick and easy but reliable method of screening crude-oil samples for low-salinity-
flooding purposes. FTIR, TGA, and ESEM analyses were performed when various brines encountered the crude oil to investigate the
possibility of the formation of water-in-oil microdispersions. FTIR was used to characterize crude-oil samples after encountering brine
by identifying compositional changes that occurred. TGA was used to support the findings of microdispersion formation. ESEM pro-
vided visual evidence of the formed water-in-oil microdispersions. Energy-dispersive X-ray (EDX) analysis reported on the composi-
tion of microdispersions in crude oil.
Coreflooding. Coreflooding experiments were conducted on three IL outcrop-core plugs with properties listed in Table 1. After satu-
rating the cores with FWS brine, the core was force flooded with LKC crude oil to attain connate-water saturation. The core was then
statically aged for 40 days in an oven at 90 C by placing the saturated core in LKC crude oil. This was performed to attain a wettability
state representative of the majority of LKC reservoirs in Kansas. Coreflooding experiments were performed on the cores by flowing
brines at 2 cm3/min with confining pressure and temperature of 1,000 psi and 40 C, respectively. The confining pressure and tempera-
ture are representative of LKC in Kansas. A high flow rate of 2 cm3/min was used for the entire experiment to overcome capillary end
effects usually experienced in tertiary coreflooding experiments. For nonaged coreflooding experiments, the oil-saturated cores were
immediately flooded with appropriate brine, significantly reducing the contact time between the crude oil and the rock. The sequence of
the coreflooding performed for this research is displayed in Table 3. Fig. 2 presents a schematic of the coreflooding setup.
Experiment Cores Aging Status Experimental Sequence Purpose

1 IL-2 Aged FWS 39.9% SWS +4.4% LSW +3.59% Aged IL core
2 IL-12 Nonaged SWS 38.13% SWS on secondary flooding
3 IL-14 Nonaged LSW 45.42% LWS on secondary flooding
2–
4 IL-20 Nonaged FWS 32.9% SWS0S +0.76% Effect of SO4 on SWS
5 IL-21 Nonaged FWS 37.8% SWS +4.8% LSW +2.5% Nonaged IL core
2–
6 IL-22 Nonaged FWS 39.9% LSW0S +3.4% Effect of SO4 on LSW
Table 3—Summary of coreflooding experiments performed. Oil recovery from each coreflood is also reported, with (1) indicating the
incremental production (%) in tertiary mode after secondary coreflooding.
Inline Mixing of Crude Oil and Brine. Fig. 3 shows the schematic of the inline mixing setup used for thorough mixing of brines of
various concentrations and LKC crude oil. Fluids are pumped simultaneously from each cylinder at a flow rate of 1 cm3/min for
5 minutes through an inline mixer, with the samples collected at the effluent for subsequent analysis. The setup was kept in a 40 C
chamber. The inline mixer is a synthetic porous medium with pore-throat size of 2 mm. The effluent samples are analyzed within 1 hour
of sampling.
Vial Tests. The vial test, sometimes called the bottle test, was performed by mixing LKC crude oil with brines of different salinity. This
test was also performed to study the stability and durability of the formed microdispersions. In preparing the samples, a 1:1 weight ratio
of LKC crude oil and appropriate brines was mixed in a vial at 40 C. The mixture was shaken vigorously for 1 minute and allowed to sit
so that it could separate. A time analysis of samples was performed, where the samples were allowed to sit from 1 to 5 hours, with further
testing performed after each hour. This was done to study the effect of time on the formation of the water-in-oil microdispersions.
Fig. 4 (left) shows the effluent samples taken for testing by inline mixing of crude oil and brine and the effluent sample from the vial
test (right) used for fluid characterization. Also highlighted in Fig. 4 is the sampling location used for TGA, FTIR, and ESEM analyses.
For all three sampling methods, samples collected for analysis were taken close to the oil/water interface and within the oil phase
(Fig. 4). Fig. 4 gives the first indication of the stability of the formed water-in-oil microdispersions, which will be discussed later.
Contact-Angle Measurement. Wettability alterations of limestone rocks were determined by the use of contact-angle measurements
on polished IL chips. Rock wettability was measured to show the wettability state of the cores used for the coreflooding experiments.
Rock chips were prepared from IL cores with surfaces polished for contact-angle measurements. All chips were vacuum saturated with
FWS brine, with synthetic-brine composition representative of the LKC Limestone formation. The aging of the rock chip was per-
formed by placing the rock chip in LKC crude oil in an oven at 80 C for a period of 40 days. For nonaged rocks, the rock chips were

placed in FWS brine after saturation and before measurement. After aging, the chips were placed in a contact-angle-measurement
chamber surrounded by the appropriate brine for approximately 1 hour to reach equilibrium before measurements were taken. Fig. 5
shows the combined IFT/contact-angle-measurement setup. The measurements were all taken at 40 C as a representation of reservoir
conditions. The contact-angle measurements were performed sequentially, from FWS to SWS and finally to LSW brines.
40°C chamber
LKC crude oil

Brine
Differential
Pressure 3
(2,000 psi)
Pump B
Pump A
Core holder
Fraction
Differential collector
Pressure 1
(100 psi)
Fig. 2—Schematic of the coreflooding setup used for the experiment. The core holder was kept in a 408C chamber to control the
temperature of the experiment.
LKC crude oil
Inline
mixer
Brine
Pump
Pump
Effluent
collector
Fig. 3—Porous-medium-flow schematic used for the mixing of LKC crude oil and different brine samples.
SWS LSW
FWS
SWS FWS
LSW
Fig. 4—Effluent samples after flowing brine samples of various salinity and LKC crude oil through an inline mixer (left image) and
mixing in a vial test (right image). The red mark indicates the point of sampling for FTIR,TGA, and ESEM analyses.

P
T
Camera
BPR
DIW Heat Heat

jacket jacket
Crude-oil
cylinder
Aqueous
cylinder Effluent
Hand pump
(a) (b)
Fig. 5—Combined high-pressure/high-temperature IFT and contact-angle-measurement device. (a) Setup configuration for the IFT
measurements. (b) Contact-angle-measurement setup. Both IFT and contact-angle measurements are taken at 40º C. PT 5 pressure/
temperature controller; BPR 5 backpressure regulator; DIW 5 deionized-water container. Modified from Nazari et al. (2018).
Dynamic IFT. To study the possibility of fluid/fluid interaction between brine and crude oil, dynamic IFT measurements were
acquired using a pendant-drop technique, with a schematic shown in Fig. 5. The pendant-drop chamber is filled with brine samples of
appropriate salinity with crude oil injected into the chamber through a needle. The measurements are conducted at 40 C. After each set
of experiments, the chamber is thoroughly washed first with toluene to dissolve all crude oil, followed by hexane and finally by acetone.
This process is repeated five times to clean the cell entirely and to avoid contamination of the chamber by previous fluids. Each experi-
ment was repeated three times to ensure the repeatability of the results.
IFT measurements were taken for each crude-oil/brine system over a period of 1 hour. With this measurement, dynamic parameters
such as interfacial dilatational elasticity were calculated with a theoretical model (Maxwell model), as used by Boury et al. (1995) and
Tewes et al. (2011). Fig. 6 is a graphical representation of the dynamic IFT model used for the calculation of the dilatational elasticity
between the crude oil and various brines.
π (mN/m)
ΔA
Ai
π0
Δπne
π∞
Δπ e
πi
Time (seconds) T Time (seconds)
(a) (b)
Fig. 6—Dynamic IFT: (a) Relative area compression and (b) surface pressure variation Dp over time T. Courtesy of Tewes et al. (2011).
Garcia-Olvera and Alvarado (2017) studied the interfacial rheology of modified brine salinity for EOR in carbonate rocks. They
reported that the elasticity of seawater when it encounters crude oil is influenced by the sulfate content. Brine with SWS range exhibited
a higher elasticity compared with a brine of similar ionic strength prepared without sulfate. This showed the influence of sulfate on the
elasticity between brine and crude oil. Garcia-Olvera and Alvarado (2017) demonstrated the relationship between elasticity and the sup-
pressed effect of snap-off in porous media, and improved oil recovery, with a coreflooding experiment.
The dilatational elasticity between different fluid systems and LKC crude oil in this work was calculated using a dynamic IFT
model, as explained here, linking these data to improved oil recovery that can be experienced using SWS brine (Boury et al. 1995;
Tewes et al. 2011).
In calculating the dilatational elasticity, we considered Fig. 6. The total surface-pressure change (i.e., the IFT between the brine and
the oil phases) is calculated as
Dp ¼ Dpe þ Dpne ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð1Þ
where Dpe represents change in the surface pressure of the equilibrium part, which can be expressed as
Ub t
Dpe ¼ Ee ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð2Þ
Ai
where Ai is the initial surface area, Ub is a constant velocity, and t is time for compression of the oil droplet.


d DA Ub
Because ¼ , Eq. 2 can be reduced to
dt Ai Ai
DA
Dpe ¼ Ee ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð3Þ
Ai
where DA is the difference between the initial surface area of the oil droplet after compression and the final surface area of the oil drop-
let after relaxation. From Eq. 3, Ee , which is the equilibrium surface dilatational elasticity, can be calculated because Dpe and the sur-
face areas of the droplet vs. time are known from IFT measurements.
FTIR and TGA Methods. In studying the possibility of the formation of water-in-oil microdispersions, we made use of the
attenuated-total-reflection (ATR)-FTIR spectroscopy. Roonasi and Holmgren (2009) explained that the ATR-FTIR technique helps
with the measurement of strong absorbance of water that can be experienced compared with using the normal infrared spectroscopy.
This technique will therefore be appropriate for our research because we will be investigating compositional changes caused by the for-
mation of microemulsions. FTIR spectroscopy was used by several researchers to study the compositional changes caused by the forma-
tion of microemulsions and to characterize crude-oil composition (MacDonald et al. 1986; Mahzari and Sohrabi 2014). Aske et al.
(2001) used near-infrared spectroscopy in determining the saturate/aromatic/resin/asphaltene (SARA) components of 18 crude-oil types
from the North Sea and some parts of West Africa. Wilt et al. (1998) also used FTIR in determining the asphaltene composition of
several crude-oil samples across the world. This technique will detect the O-H and H-O-H bonds that will be formed because of the
presence of water molecules within the crude-oil phase. Other bonds such as the aromatic C¼C stretching, carboxylic group C¼O
stretching, and other chemical bonds of the crude-oil component can be identified using FTIR spectroscopy.
TGA is a technique also used to study the changes in a composition of a sample that could occur because of chemical or physical
adsorption measured as a function of increasing temperature. Rudolph et al. (2012) used TGA as a supporting technique in identifying
compositional changes observed using FTIR. Kök et al. (2016) combined FTIR with TGA to characterize different crude-oil samples
by determining the various bonds within the crude oil. FTIR and TGA might not provide the chemical components of the oil forming
the microdispersions but will provide qualitative analyses of a possible change in oil composition and bond interactions that could help
explain the mechanism involved with low-salinity waterflooding in carbonate rocks.
In this study, FTIR analysis was performed on samples collected at the effluent of an inline mixer and mixed in a vial test, and the
effluent of the coreflooding tests. This was further characterized using a PerkinElmer Spectrum 400 FT-IR spectrometer provided by
the Bioengineering Research Center (BERC) at the University of Kansas (KU). The samples were taken close to the oil/water interface
and within the oil phase, as shown in Fig. 4. The equipment made use of 10 mL of the water-in-oil microemulsion samples, which
was placed on a diamond crystal with infrared signals emitted toward the sample to measure the relative attenuation of the compound.
PerkinElmer PYRIS 1 TGA also provided by BERC was used for the TGA for both the inline mixer and vial tests with the same sam-
pling techniques used for the FTIR analysis. The samples were placed in a microbalance and weighed. The sample was then heated at a
scanning rate of 20 C/min until the temperature of the sample reached 600 C, after which the percentage weight of the sample remain-
ing in relation to the original weight at each temperature was calculated for analysis. The results from the TGA were used as a support-
ing analysis for compositional-change identification experienced using FTIR spectroscopy.
ESEM. ESEM provides a good visualization image of the microdispersions formed in the crude oil after contacting with different brine
samples. LKC crude oil, which was not contacted with any of the brines, was imaged as a controlled sample with which all other images
were compared. The FEI Versa 3D Dual Beam, which is used for field-emission-electron microscopy at the Microscopy and Analytical
Imaging Laboratory of KU, was used in taking the images required for this experiment. A 5-mL sample of the emulsion was placed on
an aluminum stub, after which images were taken. The ESEM variable-pressure mode of the Versa 3D Dual Beam was enabled with a
chamber pressure of 0.0015 psi (0.08 Torr), and a low vacuum secondary electron detector with a working distance of 10.3 mm was
used in acquiring the ESEM images.
After acquiring images using ESEM, EDX analysis was performed on several selected spots to highlight the chemical composition
of the images for a better understanding of the mechanisms involved with low-salinity waterflooding.
Results and Discussion

Coreflooding Experiments. Various researchers have demonstrated improved oil recovery by applying low-salinity waterflooding
(Yousef et al. 2010, 2012a, b; Romanuka et al. 2012). In most cases, an average of approximately 5 to 9% incremental recovery is expe-
rienced when brine is switched to a salinity range of approximately 5,000 ppm. Fig. 7 shows the oil-recovery plot of a coreflooding
experiment performed on the aged IL-2 core plug using different brine salinities. A summary of all the coreflooding data is presented in
Table 3. In the coreflooding experiment, IL-35 was flooded first with FWS brine for approximately 5 PV, after which the brine was
switched to SWS and finally to LSW, each for approximately 5 PV. Coreflooding of the IL-2 core plug with FWS brine generated oil
recovery of approximately 39.75% of the oil initially in place (OIIP). The recovery was improved to 44.15%, representing an increase
of approximately 4.4% of the original oil in place (OOIP), when the brine was switched to SWS. After sequentially flooding IL-2 with
LSW, the recovery was further improved to 47.74%, representing a further increase on the OOIP of 3.59%. This provides evidence of
the effect of reducing the brine ionic strength on improving the overall oil recovery in limestone rocks.
Wettability alteration has been commonly attributed to the improved recovery experienced by the low-salinity brine both in sand-
stone and carbonate rocks. The improved recovery experienced in IL-2 coreflooding could be partly because of the changes in rock
wettability, which will be explained with contact-angle data. To investigate if wettability alteration is the sole contributor to the
improved oil recovery in limestone rocks, we performed a waterflood experiment using a nonaged core. This test was performed using
a nonaged core to minimize the effect of wettability alteration and to investigate if other recovery mechanisms could have caused the
improved oil recovery experienced by the use of brine systems of lower ionic strength. Fig. 8 shows the shift in the wettability of non-
aged rocks from a strongly oil-wet to an intermediate-wet rock surface after reducing brine salinity. The high contact-angle values for
the aged limestone chip were mainly caused by a long aging time compared with the values measured by Abdallah and Gmira (2014),
who used a shorter aging period of 5 days. The oil-wet condition observed with this contact-angle measurement is representative of res-
ervoir conditions for the LKC Limestone formations. The use of nonaged rocks resulted in minimum wettability alteration, with the
rock-surface wettability staying within the water-wet region. To confirm the wettability state of the cores used for the waterflooding,
endpoint relative permeability was calculated after establishing residual oil saturation for aged IL-2 and nonaged IL-21. Nonaged IL-21
had an endpoint relative water permeability of 0.094 at Sor of 0.39, while aged IL-2 had endpoint relative water permeability of 0.27 at

Sor of 0.42. This supports the findings of the contact-angle measurements indicating a water-wet state for nonaged cores and an oil-wet
state for the aged cores. The vast difference between the initial wettability state of both the aged and nonaged rocks does signify the
effectiveness of the aging process used for the experiments and does support the assumption made by using nonaged IL cores for inves-
tigating fluid/fluid interactions.
60 60
FWS SWS LSW
50 50
Pressure Drop (psi)

Oil Recovery (%)
40 40
30 30 Oil recovery
Pressure drop
20 20
10 10
0 0
0 5 10 15 20
PV Injected
Fig. 7—Oil-recovery plot of coreflooding of aged IL-2 core. IL-2 was first flooded with FWS brine followed by SWS brine after 5 PV
of injection, and was finally flooded with LSW. The experiment was performed at 2 cm3/min, temperature of 408C, and a confining
pressure of 1,000 psi.
180
160
Contact Angle (degrees)
140
120
Aged
100
Nonaged
80
60
40
20
0.01 0.1 1 10
Brine Ionic Strength
Fig. 8—Contact-angle measurements for aged and nonaged IL rock chips.
Fig. 9 shows the plots of oil recovery vs. PVs of brine injected using FWS, SWS, and LSW. Each brine was pumped for approxi-
mately 5 PV or until no further oil recovery was experienced. Using FWS, 37.8% of the OIP was recovered. The shift to SWS improved
the oil recovery to approximately 42.6% of the OIIP, showing an improved recovery of approximately 4.8%. LSW caused an improved
oil recovery of approximately 2.5%, resulting in an overall oil recovery of 45.12% of the OIIP.
50 300
45
250
40
Pressure Drop (psi)
Oil Recovery (%)
35
200
30
Oil production
25 150 Pressure
20
100
15
10
50
5
FWS SWS LSW
0 0
0 5 10 15
PV Injected
Fig. 9—Oil-recovery plot for coreflooding of nonaged IL-21 core. IL-21 was first flooded with FWS brine followed by SWS brine after
5 PV of injection, and then flooded with LSW. The experiment was performed at 2 cm3/min, temperature of 408C, and a confining
pressure of 1,000 psi.

It should be noted that, with the minimization of the effect of wettability alteration as shown by the contact-angle data, improved oil
recovery was still experienced because of the injection of SWS and LSW brines. The overall recoveries experienced in aged and non-
aged limestone cores were very similar. It should also be noted that SWS waterflooding caused an improvement in oil recovery for a
nonaged core. This shows that there is a possibility of some other form of recovery mechanism involved in improvement of oil recovery
in a waterflooding situation together with wettability alteration.
The low-salinity-waterflooding effect in carbonate reservoirs has still not been fully understood. In chalk formations, selective ionic
composition with salinity as high as that of seawater brine has been reported as the appropriate brine for tertiary recovery (Zhang et al.
2007; Puntervold 2008). In limestone rocks, however, Romanuka et al. (2012) reported 3% improved oil recovery by merely reducing the
brine ionic strength (from 3.75 to 0.25 mol/L) and 4% improvement by use of low ionic strength with no sulfate concentration (0.2 mol/L).
They suggested that reducing the brine ionic strength, rather than selective brine ionic composition, could be effective in improving oil
recovery. Nasralla et al. (2016), on the other hand, showed a reduction in residual oil saturation from 0.62 after secondary flooding of for-
mation water (3.65 mol/L) to 0.585 for seawater (0.86 mol/L) and 0.55 for 25-times-diluted seawater (0.035 mol/L) after sequential terti-
ary flooding. The concentration of sulfate in their seawater was increased by approximately 14 times that of the formation water. On the
basis of the reported mechanism (Zhang et al. 2007; Puntervold 2008) of the effect of sulfate in improving recovery, we attempted to
investigate the effect of sulfate concentration on fluid/fluid interactions and hence on overall oil recovery in limestone rocks. IL-20 and
IL-22 were first flooded with FWS brine and then sequentially flooded with SWS0S and LSW0S, respectively, in the tertiary mode.
Fig. 10 shows oil recovery from nonaged IL-20 and IL-22 cores with SWS0S and LSW0S brines injected, respectively, as a tertiary
mode. IL-20 experienced an improved recovery of 0.76% compared with 3.1% for IL-22. This gave an indication of the effect of sulfate
on fluid/fluid interactions leading to improved oil recovery. It must be noted that the brine compositions used in all experiments do not
have excess sulfate ions (Table 2). In IL-20, taking out the sulfate ions only results in a minimal recovery improvement. IL-22, on the
other hand, experienced a significant improvement, hence highlighting the minimal effect of sulfate ions within the LSW brine. The
improved recovery experienced in this coreflooding experiment is also consistent with the limestone low-salinity flooding reported by
Romanuka et al. (2012). The concentration of sulfate in our LSW brine is very insignificant compared with our SWS brine (Table 2).
For this reason, it should be expected that the effect of sulfate would be more pronounced on the SWS tertiary coreflooding than on the
LSW tertiary coreflooding, hence explaining the observation in our improved-recovery data. Further testing was performed to gain a
better understanding of the difference in mechanisms responsible for improved recovery using both SWS and LSW brine by conducting
FTIR, TGA, dynamic IFT, and ESEM measurements.
50 50
40 40
Recovery (%)
Recovery (%)
30 30
20 20
Flooded Flooded
10 with FWS 10 Flooded Flooded
with SWS0S
with FWS with LSW0S
0 0
0 1 2 3 4 5 6 7 8 9 10 11 0 2 4 6 8 10 12
PV Injected PV Injected
Fig. 10—Oil-recovery plot of coreflooding of nonaged IL-20 (left) and nonaged IL-22 core (right). IL-20 was first flooded with FWS
brine, followed by SWS0S. IL-22 was first flooded with FWS brine, followed by LSW0S. The experiment was performed at 2 cm3/min,
temperature of 408C, and a confining pressure of 1,000 psi.
Secondary coreflooding using SWS and LSW brines was performed to investigate the influence of brine salinity on secondary flood-
ing. This would help provide better insight into the mechanisms responsible for the low-salinity-waterflooding effects observed with the
previous coreflooding. Cores with similar permeability, porosity, and oil saturation to those of IL-20 and IL-22 were selected for the
secondary-mode coreflooding for comparative analysis. The flow rate, confining pressure, and temperature were kept constant, similar
to conditions for the flooding of both IL-20 and IL-22 cores. It would be expected that the performance of both the SWS and the LSW
brines on the secondary mode would be higher than that of the FWS brine used in the secondary mode. Suppression of the crude-oil
snap-off during coreflooding has been proposed to be responsible for improved recovery experienced with seawaterflooding (Alvarado
et al. 2014, 2015). This was explained to be caused by the increased elasticity between the crude oil and the seawater brine, mainly
because of the presence of sulfate ions. Fig. 11 shows coreflooding experiments performed in secondary mode using the SWS and LSW
brines. Coreflooding performed using the SWS brine resulted in an oil recovery of 38.13% compared with 32.95% using the FWS brine
in the secondary mode with IL-20. This significant improvement highlights the possibility of crude-oil snap-off suppression, as will be
explained in detail in the subsequent sections. For low-salinity brines, an oil recovery in secondary mode of 45.42% was observed, sig-
nificantly higher than that of SWS and FWS brine flooding in secondary modes. We propose that this improvement was mainly because
of the formation of microdispersions, which are formed when our crude-oil sample encounters brine salinity lower than 8,000 ppm. In
the next subsections, we explain thoroughly the causes of the observed improvements in oil recovery resulting from reduced brine salin-
ity. Controlled sets of experiments were performed and analyzed with techniques such as FTIR, TGA, ESEM, and dynamic IFT to pro-
vide a comprehensive understanding of the role of the fluid/fluid interaction toward EOR during waterflooding.
Dynamic IFT Measurements. Dynamic IFT measurements were conducted between LKC crude oil and brines of various salinities
(FWS, SWS, and LSW). Fig. 12 shows the trends experienced with the IFT measurements. The reproducibility of the IFT measure-
ments is shown in Figs. 13. An interesting aspect of this set of measurements was the behavior of SWS compared with both LSW and
FWS brines. FWS brine vs. LKC crude oil showed an initial IFT value of 22.4 mN/m, with LSW vs. LKC crude oil showing an initial
IFT of 22.6 mN/m. SWS brine vs. LKC crude oil, on the other hand, showed a significantly lower initial IFT value of 15.6 mN/m.

This shows that there is an optimal salinity/composition range at which IFT would be at a minimum value. This result is consistent
with Lashkarbolooki et al. (2014a, b), Xu (2005) and Mahani et al. (2015, 2017), where IFT was lower at SWS levels (15,000 to
40,000 ppm) compared with low-salinity brine (2,000 to 5,000 ppm).
50 60
40 50
Pressure Drop (psi)

Recovery (%)
40
30
30
20
20
10 LSW LSW
10
SWS SWS
0 0
0 2 4 6 0 2 4 6 8
PV Injected PV Injected
(a) (b)
Fig. 11—(a) Oil-recovery and (b) pressure-drop plots of secondary flooding of nonaged IL-12 and IL-14. IL-12 was flooded with
SWS brine, and IL-14 was flooded with LSW brine, all in secondary mode. Coreflooding was performed at a flow rate of 2 cm3/min,
with confining pressure and temperature of 1,000 psi and 408C, respectively.
24
22
20
FWS
IFT (mN/m)
18 SWS
LSW
16 SWS without sulfate
FWS without sulfate
14
12
10
0 500 1,000 1,500 2,000 2,500 3,000 3,500 4,000
Time (seconds)
Fig. 12—Dynamic IFT measurement between brines of various salinity with LKC crude oil. Measurements were taken over 1-hour
intervals at 408C.
25
Initial Final
20
IFT (mN/m)
15
10
0
FWS SWS LSW FWS0S SWS0S LSW0S
Fig. 13—IFT measurement showing reproducibility for all brines used. Initial value was taken immediately after bubble generation,
while the final value represents the equilibrium IFT measurement after 1 hour of bubble generation.

The IFT measurements were taken over a period of 1 hour to establish equilibrium. The FWS-brine vs. LKC crude-oil system
recorded an equilibrium IFT measurement of 19.54 mN/m, similar to the LSW vs. LKC crude-oil system that recorded an equilibrium
IFT measurement of 19.82 mN/m. The SWS brine vs. LKC crude-oil system, however, recorded a significantly lower equilibrium IFT
measurement of 10.94 mN/m.
In an attempt to explain the low IFT for the SWS system, we prepared a new brine without sulfate ions while keeping the ionic
strength the same. By taking away the sulfate concentration of the SWS system, the initial IFT increased to 20.5 from 15.6 mN/m and
equilibrated at an IFT value of 17.2 mN/m. This observation shows that sulfate concentration has a significant effect on dynamic IFT
measurements between SWS brine and LKC crude oil. Sulfate improves the interfacial rheology, mainly the surface elasticity, hence
leading to a firm interface between crude oil and SWS brine. FWS and LSW brines without sulfate systems showed trends very similar
to those when sulfate was present in the brine. This indicates that sulfate concentration has a huge effect on the interfacial rheology of
our SWS brine and significantly less effect on FWS and LSW brines. Garcia-Olvera and Alvarado (2017) studied the effect of sulfate
on interfacial phenomena such as dynamic IFT and elasticity. They used brine-salinity levels in the range of SWS brine (17,000 to
60,000 ppm). Garcia-Olvera and Alvarado (2017) showed that sulfate affects the interfacial rheology by reducing the IFT and increas-
ing the surface elasticity, which leads to suppression of the snap-off effect and hence to improved oil recovery.
Using Eq. 3, equilibrium dilatational elasticity can be calculated from the dynamic IFT measurements generated using the pendant-
drop technique. Surface area of the generated oil bubble is also captured by the IFT equipment with time, which is used for the
dilatational-elasticity calculations. DA is calculated from the difference between the initial oil-bubble area and the final equilibrium oil-
bubble surface area. Dp was also calculated from the difference between the final IFT at equilibrium and the initial IFT of the generated
oil bubble. In Fig. 14, equilibrium elasticity was plotted against the ionic strength of the brines used in our experiments. The equilib-
rium surface dilatational elasticity was 1140.3 mN/m for the FWS system but increased substantially to 11 229.9 mN/m for the SWS
system because of the low IFT measurements. This value later dropped to 3428.2 mN/m for the LSW system. This trend is very similar
and consistent with our IFT measurements.
12 000
10 000
Elasticity (mN/m)
8000
Elasticity with sulfate

6000
Elasticity without sulfate
4000
2000
0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
Ionic Strength
Fig. 14—Variation of surface dilatational elasticity vs. ionic strength.
Fluid/Fluid Interactions During Seawaterflooding. The results from the dynamic IFT and dilatation surface elasticity discussed
previously could provide a better understanding of the role of fluid/fluid interactions during waterflooding using seawater brine. These
observations were affected by the significant sulfate content in the SWS system compared with the LSW system, as proved by Garcia-
Olvera and Alvarado (2017). McGuire et al. (2005) recommended that the improved oil recovery experienced because of low-salinity
waterflooding could be attributed to the reduction of IFT, as can be seen in alkaline flooding. The results from our experiments, which
are supported by the literature, prove otherwise. Reduction in IFT for SWS brine would improve the capillary number, but this improve-
ment is insufficient to affect the overall recovery, as proposed by McGuire et al. (2005). The IFT will have to be reduced to a magnitude
of 103 for the capillary number to affect recovery (Green and Willhite 1998). Surface elasticity provides a better picture of the effect of
IFT on improved recovery. Removing the sulfate content in the LKC brines resulted in an insignificant decrease in the elasticity for
FWS and LSW brines, but a significant change in the elasticity of the SWS brine was observed (Fig. 14). The significantly high sulfate
content in the SWS system has made that system more elastic compared with the LSW system (Fig. 14). Results from IFT and surface
dilatational-elasticity measurements show that tertiary waterflooding using SWS brine and LSW have different interfacial properties.
Figs. 12 and 14 give an indication that these changes in the interfacial properties were because of the sulfate content, which is consistent
with Garcia-Olvera and Alvarado (2017). Garcia-Olvera and Alvarado (2017) studied the effect of sulfate on seawater and LSW for ter-
tiary recovery. In their work, seawater enriched with sulfate only responded to improved recovery when residual oil was continuous.
This shows that sulfate-enriched seawater does enhance recovery by suppressing the effect of snap-off caused by the high elasticity.
Chávez-Miyauchi et al. (2016) also observed a nonmonotonic elasticity when using salts with monovalent and divalent ions. They also
correlated the high surface elasticity to the suppression of the snap-off effect, leading to improved recovery of approximately 5 to 10%
in tertiary mode using a microfluidic model. The presence of sulfate in SWS brine enriched the interfacial film, hence improving the
surface elasticity. Because the affinity of divalent ions for polar species in the crude oil—the natural surface-active agents—is higher
compared with monovalent ions, taking out the sulfate content in the seawater deprived the solution of more divalent ions. The divalent
ions will attract some of the natural surface-active agents of the crude oil to assemble at the oil/brine interface (Wei et al. 2017). This
would result in the IFT for SWS0S (with less divalent ions) to be higher than that of SWS. At lower salinities, the aqueous phase is
deprived of ions to attract the surface-active agents to the brine/oil interface, and the ionic concentration of the sulfate is almost negligi-
ble. This led to negligible changes in IFT and low surface dilatational elasticity at low-salinity brines. In our coreflooding, the effect of
sulfate in the seawaterflooding is pronounced. Taking out the sulfate concentration from our seawater for tertiary waterflooding resulted
in lowering the improved recovery experienced from 4.8 to 0.76% of the OOIP, supporting the IFT and surface-elasticity-data analysis.
In the secondary-mode coreflooding (Fig. 11), seawater brine resulted in a higher oil recovery than FWS brine in secondary mode

(IL-20). We propose that the sulfate presence in seawater brine caused a rigid interfacial film, leading to a higher surface dilatational
elasticity. This reduces the snap-off effect during coreflooding, and hence residual oil remains continuous for improved recovery. It
should also be noted that fluid snap-off is dependent on other factors such as pore-throat size, rock heterogeneity, and rock surface wet-
tability. Investigating of these other factors is not within the scope of this current study. However, the understanding gathered from cal-
culating the surface elasticity is a step in the right direction to provide a clearer understanding of the role of fluid/fluid interaction in
seawaterflooding. This, however, does not explain the improved recovery experienced by using LSW brine. To investigate this, FTIR,
TGA, and ESEM were combined with dynamic IFT measurements in proving two different fluid/fluid-interaction mechanisms for the
SWS and LSW applications, respectively.
Investigation of Fluid/Fluid Interactions Using FTIR. To investigate the fluid/fluid interaction as a recovery mechanism, it is
important to know the possibility of compositional changes that could occur when brine meets crude oil. This was investigated using
FTIR spectroscopy, ESEM, and TGA. Sohrabi et al. (2017) proposed the formation of water-in-oil microdispersions that could be
formed when a lower-salinity brine is brought into contact with crude oil, linking this phenomenon to sandstone oil recovery that is
experienced in coreflooding experiments. We sought to investigate this phenomenon to help understand the complexity of fluid/fluid
interaction in limestone rocks, first using FTIR spectroscopy and then different mixing techniques. The identification of bond changes
and how they relate to the formation of water-in-oil microdispersions is studied and explained using FTIR.
The purpose of the inline mixing method was to mimic the vigorous and reproducible mixing that occurs within the pore spaces in a
rock, thereby giving an exact representation of fluid/fluid interactions in carbonate rocks. Fig. 15 shows the compositional changes
experienced on the LKC crude-oil image after contacting with brines of various salinities using the inline mixing method. “Control”
indicates pure LKC crude-oil samples that have not contacted any brine. It is evident from Fig. 15 that there is a change in the spectrum
range of 3100 to 3600 cm1, which corresponds to O-H bonds for LSW brine. This O-H bond can be associated with the introduction
of water molecules in the form of water-in-oil microdispersions, which will be discussed later. SWS and FWS showed almost no
changes in the spectrum range associated with O-H bonds. Other spectra changes that can be observed include 1550 to 1700 cm1 and
650 to 750 cm1 ranges, also listed in Table 4.
0.3
0.25
0.2
Absorbance
Control
0.15 FWS
SWS
0.1
LSW
0.05
0
3600 3100 2600 2100 1600 1100 600
–0.05
Wave Number (cm–1)
Fig. 15—FTIR spectrum for LKC crude oil in contact with brines of various salinity. Samples were analyzed 3 hours after prepara-
tion. An inline mixer was used for preparation of microdispersions.
Wave Number (cm–1) Functional Group Identified

3100–3600 O-H bond stretching
2800–3000 C-H stretching
1550–1700 C=O carboxylic group stretching
1400–1500 C-O stretching from carboxylic acid
650–750 C=H group rocking
1330–1370 S=O sulfonate group
Table 4—Absorbance changes of functional groups identified using

FTIR spectroscopy.
Fig. 16 shows the FTIR spectrum when the actual limestone rocks were flooded with brines of various salinity and the effluent sam-
ples were analyzed. Similar characteristics as in Fig. 15 were identified. Again, LSW showed a significant absorbance change (range of
approximately 3100–3600 cm1) compared with the SWS and FWS brines. This again gives a clear indication of the effect of fluid/fluid
interactions when the LSW brine is used for a waterflooding project. These observations made the absorbance change at 3100 to
3600 cm1 be potentially associated with the formation of water-in-oil microdispersions. The limiting effect of the SWS brine on the
compositional changes is very evident from Figs. 15 and 16. This shows that there might be two different fluid/fluid-interaction mecha-
nisms responsible for the improved recovery of carbonate rocks when the SWS brine is used compared with when the LSW brine is
used. This is backed by the IFT data in addition to FTIR analysis.
For a good performance of any fluid used for EOR processes, mobility and stability of the displacing front is very important
(Alvarado et al. 2011). For this reason, formation of the microdispersions was studied with time in a vial test, as explained previously,
to investigate the stability of the formed water-in-oil microdispersions within the porous media. Fig. 17 shows the stability of the micro-
dispersions formed with the LSW brine, even after 5 hours.

0.35
0.008
0.3 0.006
0.004 Control
0.25
0.002 FWS
Absorbance
0.2 0 SWS
3700 3500 3300 3100
0.15 –0.002 LS
0.1
0.05
0
3600 3100 2600 2100 1600 1100 600
–0.05
Fig. 16—FTIR spectrum for LKC crude-oil effluent sample from coreflooding of IL. Analysis was performed after the samples had
settled for more than 24 hours.
0.3
0.25
0.2 Control
Absorbance
1 hour
0.15 2 hours
3 hours
4 hours
0.1
5 hours
0.05
0
3600 3100 2600 2100 1600 1100 600
–0.05
(a) FTIR analysis for LKC FWS in contact with crude oil
0.3
0.25
0.2
Absorbance
1 hour
2 hours
0.15 3 hours
4 hours
0.1 5 hours
Control
0.05
0
3600 3100 2600 2100 1600 1100 600
–0.05
(b) FTIR analysis for LSW in contact with crude oil
Fig. 17—FTIR spectra of LKC crude oil contacted by brines of different salinity for different times. Experiments were performed
over 5 hours, with data gathered after every hour. (a) FTIR analysis for LKC FWS brine in contact with crude oil. (b) FTIR analysis
for LSW in contact with crude oil.
Fig. 17a shows the effect of high-salinity brine on the fluid/fluid-interaction mechanism. It is evident that there were minimum
changes in the composition when the FWS brine encountered the LKC crude oil, with Fig. 17a showing none of the expected peaks
across the entire spectrum but behavior just like crude oil. Fig. 17b, however, showed great changes in the FTIR spectrum for the three
peaks of interest after 5 hours of sampling with low-salinity waterflooding. This gives us an indication of a greater influence of low-
salinity brine on crude-oil composition. This also gives an indication of the stability of the formed water-in-oil microdispersions that
could lead to a better mobility control and hence a better sweep efficiency.
In the peak range of 3100 to 3600 cm1 from Fig. 17, LSW brine had an absorbance of approximately 0.05 after 1 hour of mixing.
This value dropped to approximately 0.02 after 4 hours. This shows that the microdispersions formed in LSW brine are more durable
and stable than those possibly formed in FWS brine. Wang and Alvarado (2012) studied the effect of ionic strength on water-in-oil
emulsions and reported that lowering the ionic strength of the brine phase by use of the bottle test improved the stability of the formed
water-in-oil emulsions suitable for improved oil recovery. A visualization of the stability of LSW brine in crude oil can be seen in
Fig. 3. The water height remained low after a few hours compared with SWS and FWS brines (Fig. 3), demonstrating the durability and
stability of emulsions formed in the LSW system and hence supporting our vial-test results. Stability and durability of the emulsion
front is a very important factor for a good recovery method (Alvarado et al. 2011). For this reason and with the FTIR results as support-
ing evidence, the improved oil recovery experienced with LSW can be partially attributed to the formation of durable and stable water-
in-oil microdispersions.

In studying the effect of brine ionic strength and to investigate the salinity level at which fluid/fluid interaction becomes significant,
FTIR analysis was conducted for different salinity levels. All measurements in Fig. 18 were performed twice, and the average value
was used for the plot. Fig. 18 shows the changes in absorbance for the three peaks of interest, as stated in Table 4. For the O-H bonding
group associated with the water-in-oil microdispersions, we can conclude that at salinity values of 6,000 ppm and greater, the effect of
fluid/fluid interaction becomes very negligible. There exists a sharp change in gradient from ionic strength of 0.164 (8,224 ppm) to
0.109 (5,482 ppm) for all peaks of interest (O-H, C¼O, and C-H functional groups), indicating the effect of low-salinity brine on micro-
dispersion formation. Tang and Morrow (1999) and Sheng (2014) stated the low-salinity range for improved oil recovery to be less than
5,000 to 7,000 ppm. With this analysis, fluid/fluid interaction leading to the formation of microdispersions can be a dominant mecha-
nism for the experienced improved oil recovery for low-salinity waterflooding in carbonate formations.
0.08
0.07
0.06
Absorbance
0.05 O-H bond

C=O stretching
0.04
C-H rocking
0.03
0.02
0.01
0
0 0.5 1 1.5 2 2.5 3 3.5
Ionic Strength (mol/L)
Fig. 18—Effect of ionic strength of brine solutions on FTIR absorbance using the inline mixing method. All analysis was performed
within 1 to 2 hours after sampling at 408C.
Effect of Brine Salinity on LKC Crude Oil Using TGA. TGA was used as supporting evidence to the possibility of the formation
of water-in-oil microdispersions, which develops when LSW encounters crude oil. The TGA analysis was performed on the same sam-
ples used for FTIR analysis. TGA helps with the quantification of the amount of water molecules that would be adsorbed within the
water/oil interface because of the formation of microdispersions. The analysis is performed by calculating the weight percentage of the
samples remaining after heating the sample to a specific temperature, which in this case is 600 C.
In Fig. 19, TGA analysis was performed for 5 hours after the vial test. Two slopes of interest were identified. The first slope was
identified at a temperature range of 80 to 150 C, which can be associated with the evaporation of any water molecules present in the
solution. The second slope of interest was identified in a temperature range higher than 150 C and is associated with the disintegration
of light-to-heavy oil components. It can be deduced from Fig. 19 that the LKC crude oil contacted with LSW brine adsorbed more water
molecules at the oil/water interface, hence leading to a sharper change in slope in the temperature range of 80 to 150 C, caused by the
low boiling point of water molecules. This is because of the formation of microdispersions when LSW brine is exposed to crude oil, as
explained with FTIR spectra.
100
90
Weight Remaining (%)
80
70
Control
60
LSW
50 SWS
40 FWS
30
20
10
0
50 100 150 200 250 300 350 400 450 500 550 600
Sample Temperature (°C)
Fig. 19—TGA analysis of LKC crude oil mixed with brines of different salinity. The vial-test method was used before the analysis,
which was of the weight percentage of the sample remaining with increasing temperature. TGA analysis was performed after
5 hours.
Fig. 20 shows the TGA analysis using the inline mixer method. There are two distinctive slopes of interest demonstrated in Fig. 20.
The characteristic feature of this plot is the sharp gradient of crude oil contacted with the LSW brine at temperature range of 80 to
150 C, caused by the large presence of water molecules within the sample. The LKC crude oil contacted with SWS brine showed a
steep slope within the same temperature range as LSW brine, but not as significant as that caused by using LSW. In Figs. 19 and 20,
FWS caused almost no change to the TGA curve, hence showing again the very negligible effect of FWS brine on the formation of
microdispersions. The finding in this TGA analysis does support those from the FTIR spectrum, which paints a clear picture of the for-
mation of microdispersion within the water/oil interface using LSW brine when it encounters crude oil. Furthermore, TGA findings con-
firmed the effectiveness of our fluid-mixing method using an inline porous medium.

100
90
Control
Weight Remaining (%)

80
FWS
70
SWS
60 LSW
50
40
30
20
10
0
50 100 150 200 250 300 350 400 450 500 550 600
Sample Temperature (°C)
Fig. 20—TGA analysis of LKC crude oil. The inline mixer method was used as the sampling technique. The analysis was of the
weight percentage of the sample remaining with increasing temperature. TGA analysis was performed within 2 hours of sampling.
Microdispersion Characterization Using ESEM. The ESEM analysis of the crude-oil samples was performed as described previ-
ously. ESEM was used because the sample can be kept in the original state as microscopy is being performed. A crude-oil sample with
no exposure to brine was used as a baseline and analyzed using ESEM. Using this controlled system, all other samples can be studied
for a comparative and qualitative analysis. EDX analysis is performed afterward to determine the composition of the sample after con-
tacting various brines. The mixing technique used for crude-oil-to-brine contact was to use an inline mixer as the porous media. This
technique was selected because it provides a better analogy to porous-media mixing in carbonate rocks. Fig. 21 shows the ESEM
images of the control sample compared with the LKC crude oil mixed with the LSW-brine system. The ESEM images show the forma-
tion of some particles highlighted in red, with the size of approximately 50 mm.
(a) (b)
Fig. 21—ESEM of LKC crude oil. (a) LKC crude oil as a controlled sample. (b) LKC crude oil contacted with LSW brine. Microdisper-
sions are marked in red circles. The blue square is the area of interest for EDX analysis.
EDX analysis was performed on the blue square, as indicated in Fig. 21. EDX analysis provides an elemental analysis of the compo-
sition of the crude-oil sample. In this study, carbon analysis was neglected to enhance elements associated with brine composition.
Fig. 22 shows this elemental analysis. Weight composition shows that the analyzed surface contains chloride, sodium, calcium, sulfur,
and magnesium, which is very consistent with our brine composition. To obtain a better understanding of the distribution of these com-
pounds, Fig. 23 shows the elemental map from the EDX analysis. The concentrations of sodium, chlorine, magnesium, and calcium
around the same location support our analysis of the formation of water-in-oil microdispersions. Our ESEM data also support the pro-
posed fluid/fluid-interaction accession made with FTIR and TGA techniques and provide a better visualization of this phenomenon.
With this size range of microdispersions, pore throats might be blocked, causing brine to move into unswept pores and hence improving
microscopic sweep efficiency, which will eventually lead to improved oil recovery, as experienced with our nonaged cores. The forma-
tion of these microdispersions is instantaneous and hence can occur within the period of waterflooding experiments. The findings from
these experiments are very consistent with the findings of Mahzari and Sohrabi (2014), indicating that this phenomenon occurs irrespec-
tive of brine and crude-oil type.
Fig. 24 shows ESEM images when the LKC crude oil was contacted with both FWS and SWS brines. These images are nothing like
those for LKC crude oil being contacted with LSW, as can be seen in Fig. 21. EDX analysis performed on Figs. 24a and 24b confirmed
the existence of crude oil and the absence of any ion present in the brines. This proves that for FWS and SWS brines, the formation of
water-in-oil microdispersions is very much nonexistent compared with those formed in LKC crude oil contacted with LSW brine. This
also indicates that the fluid/fluid-interaction mechanisms involved in the improved oil recovery experienced in waterflooding processes
are different when SWS brine is used compared with LSW brine.

Map sum spectrum

wt% σ
Cl 37.6 1.3
8 O 29.6 1.5
Na 16.5 0.9
S 7.3 0.8
Ca 5.5 1.2
Mg 3.0 0.6
6 K 0.6 0.9
cps/eV
Ca Na
O Mg S Cl K Ca Ca
0
0 1 2 3 4 5 6 7 8 9 keV
Fig. 22—EDX analysis of microdispersions formed in an LKC crude-oil/LSW-brine system.
CI Kα1 Na Kα1_2
100 μm 100 μm
O Kα1 Ca Kα1
100 μm 100 μm
Fig. 23—Elemental map from EDX analysis of an LKC crude-oil/LSW-brine system.
(a) (b)
Fig. 24—ESEM of LKC crude-oil samples contacted with different brines. (a) LKC crude oil contacted with FWS brine. (b) LKC
crude oil contacted with SWS brine. Inline mixing was the technique used for mixing at 408C.

Fluid/Fluid Interactions During Waterflooding Using Low-Salinity Brine. The influence of fluid/fluid interactions on seawater-
flooding has been explored with dynamic IFT measurements and surface-elasticity calculations. Further investigations were performed
using FTIR, TGA, and ESEM analyses to understand the fluid/fluid-interaction effects observed when low-salinity brine encounters crude
oil. FTIR analysis showed compositional changes when LSW brine is contacted with the LKC crude oil in all peaks of interest, as outlined
in Table 4, regardless of the sampling technique. These findings are consistent with those of Mahzari and Sohrabi (2014) for sandstone
rocks. FTIR analysis was later performed using a wider range of brine-salinity values to test the salinity range at which these changes in
the absorbance can be observed. From these analyses, it was concluded that compositional changes in the FTIR spectrum would be experi-
enced at ionic strength of 0.164 mol/L (approximately 8,200 ppm) and lower. This provides an insight that the formation of these micro-
dispersions becomes more significant at lower ionic strength. The compositional changes that occur in the wave number range of 3100 to
3600 cm1 give a clear indication of the formation of water-in-oil microdispersions. TGA analysis also did support this finding, with steep
slopes experienced at temperature ranges corresponding to the evaporation of water molecules of the water-in-oil microdispersions.
Crude oils are usually made up of surface-active agents with hydrophobic and hydrophilic (polar) components such as carboxylates
and sulfonates, which are all present in this crude oil (Table 4). These surface-active agents accumulate and interact at the water/oil
interface, with the hydrophilic end pointing toward the water phase and the hydrophobic end pointing toward the oil phase, forming a
weak intermolecular force. In a situation where the ionic strength of the brine is lowered (LSW brine), the weak intermolecular forces
formed at the interface will be broken because of insufficient ions at the interface (Wei et al. 2017), causing the polar components of
the surface-active agents to move from the oil/water interface into the bulk-oil phase (Emadi and Sohrabi 2013). This will result in the
formation of reverse micelles and has been observed in FTIR, TGA, and ESEM as water-in-oil microdispersions. At SWS levels
(30,000 to 40,000 ppm), these surface-active agents still do line up at the oil/brine interface, leading to a stable interfacial film that
causes reduction in IFT and an increase in surface elasticity, as has already been explained. When these microdispersions are formed,
the oil phase becomes more continuous and small pores can be blocked to aid the movement of new brine into other unswept pores
and improve recovery. The stability of microdispersions was because of the acidity of the aqueous brines used. As explained by
Subramanian et al. (2017), with an acidic aqueous phase, the basic components of the asphaltenes (caused by heteroatoms) will
usually interact with the acidic components of the brine used (i.e., the Hþ group), leading to a stable emulsion. With the pH value of
the brines used being less than 7 and hence acidic, and with the total acid number and total base number of our crude being almost
equal—indicating a more neutral crude—we expect the basic functionalities of the crude oil (usually the surface-active agents) to inter-
act with the acidic brine, leading to microdispersion stability. At higher salinities (in this case, greater than 8,200 ppm), the water mole-
cule will hydrate the ions in the brine rather than interact with the basic moieties from crude oil. This leads to less interaction and hence
less-stable microdispersion. FTIR provides proof of changes in the absorbance of O-H bonds, which we explained as water-in-oil micro-
dispersions. FTIR also provides details that the crude oil used contains carboxylates and sulfonates, both of which are polar components
of the crude oil. This supports our hypothesis of the formation of these microdispersions. More evidence of these water-in-oil microdis-
persions was provided using TGA and was visualized with ESEM. Elemental analysis using EDX proved that the compositions of these
particles are representative of the ions from our brine solution. These formed water-in-oil microdispersions did not exist in both crude-
oil/FWS-brine and crude-oil/SWS-brine systems, hence supporting our proposed mechanism. Coreflooding experiments performed
with nonaged core in secondary mode using LSW brine resulted in more oil production than both SWS and FWS brines. This was
because of water-in-oil microdispersions formed when crude-oil samples encounter the LSW brine, as explained previously, showing
that these microdispersions are the cause of the improved recovery, at water salinity of 8,200 ppm and lower, rather than just an effect.
Improved oil recovery observed in Fig. 10 shows that a different recovery mechanism than suppressed snap-off effect was responsible
for the observed increase in oil recovery. The observation of these formed microdispersions proves that the observed improvement in
tertiary coreflooding using LSW brine was caused by these water-in-oil microdispersions. In Sohrabi et al. (2017) and AlHammadi
et al. (2018), microdispersion formation was attributed to the wettability alteration observed during low-salinity waterflooding. A com-
prehensive wettability study on the role of these microdispersions was not fully provided. Spontaneous imbibition of brine in cores satu-
rated with crude oil with and without the indigenous surface-active agents was used as proof of wettability alteration. This only
provides part of the picture of wettability alteration using the standardized Amott-Harvey index. A complete set of controlled experi-
ments on contact-angle measurements, the Amott test, and unsteady-state relative permeability measurements are needed to make a
definitive statement on the role of these microdispersions in wettability alteration. Contact-angle data in addition to endpoint water rela-
tive permeability data reported in this work can be used as a preliminary set of results in understanding the effect of these mechanisms
on rock wettability because of exposure to different brine systems.
Conclusions
Understanding the underlying mechanism of low-salinity waterflooding in carbonate formations has recently become a topic of interest.
The consensus in the literature points to wettability alteration (rock/fluid interaction) as the main factor responsible for the observed
improvement with lowering brine salinity. The cause of this wettability alteration has been very controversial. Little effort has been
made in recent years to understand the contributing factors of the fluid/fluid interaction toward EOR because of reduced brine salinity.
In this work, we presented a thorough investigation of fluid/fluid-interaction mechanisms using both seawater and LSW encountering
crude oil as a complement to the wettability alteration. We proposed suppression of the snap-off effect because of the presence of sul-
fate content, resulting in high surface elasticity, as a mechanism responsible for the enhancement observed with seawater brine. A fur-
ther proof of this hypothesis using pore-scale visualization techniques, such as a micromodel, is currently under way in our laboratory.
This will consider other factors of fluid snap-off, such as pore-throat size. At an optimal salinity range of less than 8,200 ppm, we also
proposed that water-in-oil microdispersions will be formed when low-salinity brines encounter crude oil. This was proved to be respon-
sible for the observed production enhancement using low-salinity brine by performing a control set of coreflooding experiments using
nonaged cores. The use of the inline porous media, combined with analytical and imaging techniques in investigating the fluid/fluid
interactions, provides the oil industry with an easy but reliable technique to quickly screen crude-oil and brine samples for field applica-
tion. From this comprehensive study, we outline the following conclusions:
1. From the measurement of the contact angle, the wettability of IL is shown to be altered toward a mixed-wet or water-wet state,
respectively, with SWS and LSW brines.
2. Improved oil recovery using SWS and LSW brines for waterflooding is experienced in both aged and nonaged cores. This shows
that wettability alteration might not be the only recovery mechanism involved because the contact-angle measurement on the non-
aged limestone chip indicated a water-wet wettability state.
3. Dynamic IFT measurements showed reduced IFT values for SWS brine compared with both FWS and LSW brines. This was
explained to be caused by the sulfate content in the seawater compared with the low-salinity brine. This led to a higher surface

dilatational elasticity, reduced the effect of snap-off in coreflooding experiments, and hence improved oil recovery using SWS brine
for tertiary waterflood from nonaged cores.
4. FTIR and TGA data pinpointed compositional changes that occurred specifically when the LSW brine was exposed to the LKC crude
oil. These changes occurred within the O-H bond range in FTIR and the water-boiling-point range in TGA, giving an indication of
the formation of water-in-oil microdispersions. These observations were confirmed by the use of ESEM, which provided a visual
qualitative analysis of these microdispersions.
5. Formation of water-in-oil microdispersions was observed to occur at salinity range less than 8,200 ppm. This was observed when
brines of various salinities encountered the crude-oil sample.
6. Formation of the water-in-oil microdispersions causes the improved oil recovery experienced in both aged and nonaged cores when
LSW brine was injected.
7. Low-salinity brine would be the most appropriate brine for EOR purposes depending on the coreflooding data, but significant
enhancement in production was also observed with seawater brine. This makes brine with seawater-like salinity an economically via-
ble alternative for EOR where such water is available and affordable for the producers. This is a very significant finding because
most carbonate formations in Kansas have access to produced water within this range of salinity.
Nomenclature
Ai ¼ initial area at bubble generation, m2
Ee ¼ equilibrium surface dilatational elasticity, mN/m
Ub ¼ velocity, m/s
p ¼ surface pressure, mN/m
pe ¼ equilibrium surface pressure, mN/m
pne ¼ nonequilibrium surface pressure, mN/m
Acknowledgments
The authors would like to thank Dr. Charles Ye of BERC of KU for his help with FTIR and TGA data acquisition. We would also like
to thank Dr. Prem Thapa for his help using SEM at the KU Microscopy Analytical Imaging Laboratory. Our appreciation is extended to
Dr. Eugene Rankey and Dr. Hassan Eltom from KU’s Geology Department for conducting thin-section analysis on our samples and
helping us with interpretation of the results. In addition, the authors would like to thank Zach Kessler for helping with setting up and
fixing equipment in the Unconventional Resources Laboratory at KU. Our appreciation is also extended to the Kansas Interdisciplinary
Carbonates Consortium for providing funding to this project.
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Joel T. Tetteh is a graduate research assistant and PhD-degree candidate in the Chemical and Petroleum Engineering Depart-
ment at KU. His research interests include low-salinity waterflooding, fluid flow through porous media, geomechanics, and oilfield
chemistry. Tetteh holds a master’s degree in petroleum engineering from the University of Utah, where he conducted research
on geomechanical modeling for sand-production prediction. He also holds a bachelor’s degree in petroleum engineering from
the Kwame Nkrumah University of Science and Technology, Ghana. Tetteh is a member of SPE. He has authored two SPE papers
and has presented his work at industry gatherings such as the American Chemical Society Annual Meeting and the 13th Interna-
tional Wettability Symposium.
Reza Barati is an associate professor of petroleum engineering at KU, which he joined as a faculty member in 2012. Previously, he
worked for the Enhanced Oil Recovery Institute in Wyoming. In addition to his academic career, Barati has extensively worked on
several industry and state-funded projects as a consultant. He has also worked as a visiting researcher with Schlumberger, Halli-
burton, and Kinder Morgan for nearly 2 years. Barati’s research areas of interest include enhanced waterflooding through modifi-
cation of injection brine, carbon dioxide EOR mobility control, waterless/foam fracturing, EOR for shale oil, characterization of
tight oil/gas reservoirs, and improvement of hydraulic-fracturing fluids and proppants. He has authored or coauthored more than
40 technical papers. Barati holds a PhD degree in chemical and petroleum engineering from KU. He has received several SPE
awards, including the 2012 SPE Petroleum Engineering Junior Faculty Research Initiation Award, the 2015 SPE Faculty Innovative
Teaching Award, and the 2017 SPE Reservoir Evaluation & Engineering Technical Editor Award for outstanding service.

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REE194006 DOI: 10.

2118/194006-PA Date: 10-October-18 Stage: Page: 1 Total Pages: 20

Crude-Oil/Brine Interaction as a Recovery

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Intensity (counts in the thousands)

Table 1—IL outcrop-core-plug properties.

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Experiment Cores Aging Status Experimental Sequence Purpose

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LKC crude oil

LKC crude oil

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DIW Heat Heat

Dp ¼ Dpe þ Dpne ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð1Þ

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Results and Discussion

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Pressure Drop (psi)

Fig. 8—Contact-angle measurements for aged and nonaged IL rock chips.

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Pressure Drop (psi)

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Elasticity with sulfate

Fig. 14—Variation of surface dilatational elasticity vs. ionic strength.

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Wave Number (cm–1) Functional Group Identified

Table 4—Absorbance changes of functional groups identified using

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0.05 O-H bond

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Weight Remaining (%)

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Map sum spectrum

Fig. 22—EDX analysis of microdispersions formed in an LKC crude-oil/LSW-brine system.

Fig. 23—Elemental map from EDX analysis of an LKC crude-oil/LSW-brine system.

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