SPE 115941

Effect of Salinity and pH on Pickering Emulsion Stability

X. Wang, SPE, and V. Alvarado, SPE, University of Wyoming

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE Annual Technical Conference and Exhibition held in Denver, Colorado, USA, 21–24 September 2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The stability and morphology of crude-oil emulsions with and without suspended kaolinite or silica were investigated as
functions of salinity. First, synthetic reservoir brine with 1, 10 and 100 times dilution was emulsified with crude oils of
commercial interest, at several water-oil ratios, on which salinity effect on emulsion stability was studied. Also, the emulsion
was prepared by mixing this oil with 100 times dilution dispersed with particles to investigate pH effect on emulsion stability.
The clay zeta potential at different pH was measured to estimate the effect of particle charge on emulsion stability. Clay
particle-size distribution, which impacts the formation and stability of emulsions, was obtained using light diffraction. The
stability of emulsion was determined by simple bottle tests and by using an optical microscope equipped with a digital
camera. Our results show that both kaolinite and silica promote emulsion stability. Most emulsions turned out water-in-oil.
Also, kaolinite of the order of 1μm in size more easily adsorb at the oil-water interface, while silica with larger diameter,
such as 5μm, can form more stable emulsions than with 1μm and 3μm. Zeta potential measurements and bottle tests clearly
show that clay particles with zero point of charge (ZPC) at low pH become less effective at stabilizing emulsions in contrast
with reservoir conditions, while silica shows the opposite behavior, stabilizing better emulsion at ZPC. Salinity, especially
calcium concentration, affects the morphology and stability of emulsions. We can conclude that low-salinity waterflooding
provides adequate conditions for formation of relatively stable emulsions, provided kaolinite detachment occurs. This is also
apparent in reports of produced water re-injection.

Introduction
Emulsions are ubiquitous to oil production operations, often being responsible for oil productivity impairment or elevated
production cost associated with artificial lift and separation, among others. Significant effort has been dedicated to designing
protocols to break up harmful emulsions in oil production (Kokal, 2000; Kokal and Wingrove, 2005). The culprit for
undesirable emulsions has been either precipitated polar components of the crude oil such as resins and asphaltenes, or
inorganic solid particles. Among the list of particles, native clays, silicates, quartz, calcite, feldspar and pyrite have been
found to be able to stabilize emulsions (Sztukowski and Yarranton, 2004, Hunter et al., 2008). Corrosion products from
pipelines or other parts of the production infrastructure have been held responsible for stabilizing emulsions as well (Kokal,
2005).
Emulsions might be active contributors to oil recovery in chemical flooding. Bryan and Kantzas (2007) indicate that
several recovery mechanisms can be involved during the injection of alkaline agents, surfactants or their combination in
heavy-oil reservoirs. Possible mechanisms include emulsification and entraintment of droplets, emulsification and entrapment
of droplets, and wettability reversal. It is intriguing how the salinity conditions in chemical floods change the character of the
emulsions formed. Recovery in chemical flooding of heavy-oil reservoirs have been shown to depend on flow rate (shear
rate), as Bryan and Kantzas (2007) demonstrate in core flooding experiments. They propose that the recovery mechanism in
the presence of NaCl brines as the aqueous phase is emulsification and entrapment, leading to improved sweep efficiency. In
contrast, alkaline-surfactant (AS) solutions in distilled water appears to be emulsification and entrainment of droplets in the
flowing continuous phase. Lei et al. (2008) developed a mathematical model to study the effect of emulsification on recovery
during alkaline-surfactant-polymer (ASP) flooding. Evidence from pilots test in Daqing oil field, including laboratory
experiments, clearly demonstrate the generation of emulsions during ASP flooding. Entrainment and capture (entrapment) are
considered important for improving recovery by ASP flooding. A good match with experimental results was found by using
the developed model.
2 SPE 115941

Emulsions have been used as well-conformance agents for water diversion to increase sweep efficiency (Romero et al.,
1996; Zeidani et al., 2007; Seright and Liang, 1995). Zeidani et al. (2007) developed oil-in-water emulsions using a mineral
oil and two heavy oils from Canada as sealants of the near wellbore region. The emulsions were stabilized with commercial
nonanionic surfactants. Results from visualization and coreflooding experiments indicate that emulsion flooding can be
“engineered” to achieve well conformance with calculated penetration length by using the appropriate surfactant
concentration and shearing to yield an adequate droplet-to-pore throat size ratio. Determining pore-scale mechanisms of non-
Newtonian fluids such as emulsions and polymer solutions will result necessary to develop predictive models at the reservoir
scale (see Xia et al., 2008).
Emulsions formed without addition of surfactants or particles might be stabilized by polar components in the crude oil
such as resins or asphaltenes (Kokal, 2005). The role of waxes is unclear, but they may also provide stabilizing conditions for
water-in-oil (W/O) emulsions. Rigidity of the water-oil interface has been attributed significant contributions to suppression
of films, hence limiting coalescence.
The primary objective of this work is to study the effect of salinity and pH on solid-stabilized emulsion stability for a
crude-oil type of commercial interest in Wyoming. The focus is on determining whether enhanced-oil recovery processes
conditions allow for emulsions to be stabilized. Proof of this has come from numerous publications on chemical flooding.
Numerous examples of commercial chemical flooding applications have taken place in Wyoming oil reservoirs (Pitts et al.,
2004; Wyatt et al., 1995). Alkaline-polymer (AP) and Alkaline-Surfactant-Polymer floodings have been particularly effective
as EOR strategies in Wyoming. Low-salinity conditions might impact the migration of fines in clastic reservoirs as well as
foster appropriate conditions for emulsion generation and stability. Pressure response in a number of low-salinity flows might
indicate the in-situ formation of dispersed phases with the ability to produce partial plugging of the porous media (Zhang and
Morrow, 2006, and references therein). Particle-stabilized emulsions offer design or self-assembly (Dinsmore et al., 2002)
opportunities for fluids with rheological properties that differ from surfactant-stabilized systems, naturally occurring or
purposely injected (Binks, 2002). This opens a window for investigation of possible routes to understand EOR mechanisms
and exploit them for the design of recovery strategies. Therefore, focus is placed on investigating emulsion stability in the
presence of fines, some of which are naturally occurring in reservoirs. Bottle tests, optical microscopy and particle-size
analysis were carried out under controlled pH and salinity conditions. A summary on Pickering (solid-stabilized) emulsions
relevant to the present work follows.

Pickering Emulsions
These emulsions were named after Pickering, who reported them for the first time at the dawn of the 20th century (Pickering,
1907). This type of emulsions is stabilized by the adsorption of fines at the water-oil interface. A number of particles of
varied affinity for the different phases can be used to stabilize Pickering emulsions, such as clays, silica, etc. The same holds
for foams, as particles can accomodate at the water-air (Hunter et al. 2008). Pickering emulsions are of interest in a number
of areas outside the realm of the oil industry (Arditty et al., 2004; Binks, 2002). This type of emulsions exhibit original
rheological properties as well as considerable kinetic stability. Arditty et al. (2004) show that silica particles whose surfaces
have been treated for wettability alteration can be used to stabilize either O/W (partially hydrophobized silica) or W/O
emulsions (hydrophobized silica). As a rule of thumb, the continuous phase of the emulsion is normally the one in which the
particles are preferentially dispersed (Binks, 2002). The rheology of high concentration emulsions reflects the rigidity of the
surface, which is not controlled by interfacial tension (Arditty et al., 2004).
A number of factors impact the stability of Pickering emulsions (Tambe and Sharma, 1993; Hunter, 2002; Sztukowski
and Yarranton, 2005):
1. Composition of the oleic phase. This includes asphaltene content and polarity of this fraction of the oil phase.
Resins and waxes can also play an important role.
2. Particle type. Hydrophobicity, size distribution and concentration appear to be the controlling characteristics in
terms of emulsion stability.
3. Phase volume fractions. The general observation is that the most abundant phase usually becomes the continuous
phase. Phase inversion occurs at a given phase concentration. In oil producing wells, as watercut reaches high
values, O/W emulsions become more frequently encountered (Janssen, van den Broek and Harris, 2001).
4. Salinity of the brine phase. Concentration of divalent cations plays an important role in the stability of Pickering
emulsions.
5. pH of the aqueous phase.
6. Temperature.
7. Stress conditions (pressure).
Regarding the composition of the crude oil, McLean and Kilpatrick (1997) studied the role of asphaltenes and their
interactions with the resins and surrounding crude medium in forming interfacial films leading to emulsion stability. They
determined that pH affected emulsion stability in a significant way. These authors attribute this result to increased charged
densinties at high pH (10-12) by polarization of the polar groups, consequently destroying mechanical properties of the
interfacial film. Lower pH results (neutral to acidic) hints on the effect of acidic components of the oils. They concluded that
emulsion stability is governed by the state of solubility of the asphaltenes. Xia, Lu and Cao (2004) as a result of their study
on stability and demulsification support McLean and Kilpatrick’s conclusion on the importance of asphaltene solubility.
SPE 115941 3

Grutters et al. (2007) carried out experiments to evaluate the role of aspphaltenes in the stabilization of W/O emulsions in a
20 APIo crude oil. They argue that the observed loss of stability when asphaltenes are precipitated could be related to
decreased viscosity of the continuous phase. Moreover, they point out that polar resins, such as naptheic acids, play an
important role in stabilizing the emulsions in their experiments.
Solid-stabilized emulsions represent a challenge during the production of bitumen from Canadian Athabasca oil sands
(Liu et al., 1996). Clays, mainly montmorillonite and kaolinite, have been identified as significant contributors to the
stability of bitumen emulsions. Liu et al. (2006) used zeta potential distribution measurements to study the interaction
between bitumen and clay in aqueous solutions. In the absence of calcium, a mixture of bitumen emulsion and
montmorillonite or kaolinite clay suspensions shows a bimodal zeta potential distribution. This is an indicator of the weak
interaction between the two and a poor drop coating. Calcium suppresses the zeta potential for all the three components.
When calcium is added to a mixture containing up to 1mM calcium concentration, the potential distribution became
unimodal, as opposed to results for kaolinite.
Yan and Masliyah (1996) studied the effect of pH on adsorption and desorption of clay particles at oil-water interface.
Kaolinite clay particles treated with asphaltenes were used for this purpose. Under similar emulsification conditions, higher
pH of the brine results in larger diameter of the oil droplet. At pH 7, the creamed emulsions were redispersed into the
aqueous phase at a different pH. The clays desorbed from the oil surface at pH greater than 6, but adsorbed onto the oil
droplet surface at pH<6. Asphaltene treatment conducts to wettability changes of the clay surfaces. Micropipette experiments
demonstrate the formation of a viscoplastic skin on the surface of bitumen droplets in aqueous environments with dispersed
clays (Tsamantakis et al., 2005). Increased interfacial plasticity is prominent in deionized water with montmorillonite and
calcium present. Process water for the same clay and high concentration of calcium does not lead to the same plastic
behaviour of the drop skin. A modified micropipette experiment was used to evaluate the interfacial rheology in similar
bitumen systems (Moran et al., 2006; Tsamantakis et al., 2005). The plastic behavior observed in previous experiments is
confirmed in these rheological tests.
Ngai et al. (2006) used stimulus-sensitive microgel particles as an emulsifier. The resulting emulsions were responsive to
pH, ionic strength and temperature changes which lead to changes in particles charge and hydrophobicity. Stable oil-in-water
(octanol in water) emulsions were generated at high pH, while lowering pH to below 6.0 led to continuous coarsening of the
emulsions. Tight packing of the particles at the highly charged oil-water interface suggests capillary attraction, as suggested
by a number of authors in the literature (Kruglyakov and Nushtayeva, 2005). In microgel dispersions, high salt concentration
reduces particle activity at the interface, leaving oil droplets unprotected. On the other hand, Ngai et al. argue that reduced
average emulsion drop size caused by increased concentration of microgel particles can be explained by the augmented
coverage of the surface. Phase inversion from oil-in-water to water-in-oil can be achieved by increasing the oil-water ratio.
This phenomenon is called a catatrophic phase inversion and does not occurred in emulsions stabilized by a single surfactant.
Yang et al. (2007) studied the stability of paraffin-water emulsions, stabilized with positively-charged plate-like layered
double hydroxides particles. They determined the effect of pH on the stability of this type of Pickering emulsions. They argue
that the adsorption of particles at interfaces may be controlled by adjusting the electrocstatic interaction between particles and
the interface without changing hydrophobicity, which is thought to be a main controlling factor of emulsion type and
stability. Electrostatic interactions are altered by changes in pH of the continouos phase, by addition of concentrated aqueous
solutions of either NaOH or HCl under a N2 atmosphere. Zeta potential measurements were carried out as characterization of
the surface charge of the particles. Based on arguments of reduction of interfacial energy ( E = −πR 2γ ow (1 − cos θ )2 ), the so-
called attachment energy, it is argued that a reduction in particle surface charge (or zeta potential) would lead to flocculation
and therefore would increase attachment energy. The little observed influence of this is due to the kinetic control of the
adsorption process. Increased stability with increased particle concentration is due to better surface coverage, according to
Yang et al.
Sztukowski and (2005a) studied W/O emulsion stability with clays. They used heptane, toluene, asphaltenes as model
fluids and native solids extracted from oilfield operations. They found that a combination of asphaltene and fine solids
(submicron scale) coverage produced the most stable emulsions. They argue that fine solids compete with asphaltenes to
adsorb at the interface and that a coverage of the interface by asphaltenes between 60 to 80% and the remaining area covered
by fine solids leads to the greatest stability. Coarser solids (above 1 μm) can indeed stabilize emulsions, but only if they are
in sufficiently high concentration. Apaprently, asphaltene coverage does not contribute to stability in the case of coarse
solids. Coarse solids tend to form bridges between droplets, particularly when they are present at high concentration.
Formation of particle networks has been determined by X-ray microscopy (Thieme et al., 1999). These networks could
indeed alter the rheology of the continuous phase, but this is probably insufficient to justify the stability of emulsions in these
environments. The structure and strength of particle networks are very sensitive to ionic strength and pH of the solution. A
combination of surface coverage by solid particles and hindrance of drop coalescence by these networks (and likely increase
in viscosity of the continuous phase) may lead to better stability of emulsions.

Materials and Procedures

To determine the effect of particle size and to draw a comparison, three different solid particles are employed in the
experiments, as described below. Aqueous phase ressembling brine from a Wyoming reservoir was prepared with analytic-
4 SPE 115941

grade reagents. Oil from a Wyoming reservoir was used in all the experiments. A brief description of the materials and
methods for preparation and characterization of materials follow.
Solid Particles
In the present study, a number of micro-particles are employed. Two different kaolinite particles were obtained. The first
one was purchased from Ward’s Natural Science. The presentation of the purchased clay is as a block of material that is
subject to grinding to produce a micro-particulate. Average grain size corresponds to 6 μm. Due to the size distribution
obtained in preliminary dispersion experiments in brine, yielding relatively large average particle size (5-8 μm), Kaofine (a
commercial name of this Kaolinite) was purchased from Thiele Kaolin Company. The product was delivered as a powder
with 98% in diameter smaller than 2µm. Kaofine represents fine clay particles in the experiments. Silica (Polysicences, Inc.)
was purchased in 3 average sizes, namely 1, 3 and 5µm in diameter of the spherical beads. The silica particles come
suspended in distilled water to keep them dispersed. Upon arrival, the silica is dried according to a standard procedure
specified by the vendor:
• Centrifuge for 5 min to form a tight pellet
• Draw off supernatant and resuspend in 25% solvent/75% water
• Repeat with 50, 70 and 100% solvent solutions
• Heat in an oven at 70oC for 24hr, after which crush the pellet and dry again
Solid Dispersions Preparation and Characterization
Solids are suspended in one of the fluids (typically in the brine phase) followed by dispersion using an ultrasonic probe at
50% of the maximum power delivery capacity of the probe (500watt) for 2min. The dispersion of solids in brine is
subsequently mixed with the second phase (generally crude oil) to form emulsions.
X-ray diffraction (XRD) is used to determine the chemical composition of particles. The clays are observed using an
electron microscope in SEM mode and micrographs are used to infer the shape of the clay particles. Particle size distribution
for the solids in aqueous media is measured using a size distribution analyzer (Microtrac S3500) based on light diffraction.
Zeta potential is measured using a Malvern Zetasizer using electrophoresis to estimate changes in surface charge.
Aqueous Phase
Synthetic brine (MLB), ressembling brine from a Minnelusa reservoir, is prepared from reagent grade chemicals and
distilled water. The composition of the brine in these studies can be found in Table 1. The mole concentration ratio of
monovalent to divalent cations is about 23:1 and the total dissolved solid (TDS) concentration is 38,651 ppm.

Table 1. Synthetic brine composition.

It should be noticed that bicarbonates are not present in the synthetic brine, but have been reported in production water
(personal communication with Dr. G. Thyne from the Enhanced-Oil Recovery Institute, Wyoming). The role of some ions in
solution was not investigated in this work.
Oil phase
Filtered Minnelusa crude oil (MLO) was used as the oil phase in all tests. Its viscosity and density are 73.5cp @ 25oC and
0.9211 g/ml @ 22oC, respectively. Besides its commercial value, this oil was selected because of its high asphaltene content,
~9-10%. Asphaltenes play a role in the stability of crude oil emulsions.
Emulsion Preparation
Emulsions are prepared by adding a given amount of oil to a known volume of brine with or without particles. Then a
homogenizer (Ultra Turrax T 25 basic, IKA WERKE) at 6,500rpm for 3min or 5min is used to create the emulsion by
shearing. The lowest homogenizing speed, 6,500 rpm, is selected to avoid cavitation and generation of air bubbles observed
under more energetic mixing conditions. The initial tests were carried out using an 18mm dispersion tool, which was later
replaced with a 10mm in diameter tool to further limit bubble generation and to allow for lower liquid volumes. The smaller
dispersion tool reduces fluid losses on the surface of the tool and in the channel between stator and rotor down to almost 2/3.
The comparison of different oil-water ratio on emulsion stability is performed by changing the volume fraction of oil and
water. The brine salinity was changed by diluting the original brine to 10 times and 100 times. For each salinity value, five
SPE 115941 5

(5) different oil-water ratios corresponding 1:3, 1:2, 1:1, 2:1, 3:1 were used to prepare the emulsions. An 18-mm dispersion
tool was used for 3min to prepare the emulsions in the homogenizer.
To determine the contribution of suspended particles to emulsion stability, a set of emulsions is prepared without the
addition of particles to the aqueous phase. These emulsions form without addition of either surfactants or particles and they
probably owe their stability to polar components such as resin or asphaltene in the crude oil (Hunter, 2002).
Assessment of Emulsion Stability
Emulsion stability is determined by resolving the volume of the dispersed phase (typically water) separated from the
emulsion, which is called bottle test (Kokal, 2005). In contrast, in some of the results, the percentage of water in W/O
emulsions is reported. Data is recorded at 20min, 1hour, 3hours and 1 day after the emulsion is prepared. For cases where
there is no water resolved by gravitational segregation, centrifugation is carried out at a fixed speed for up to 3 hours and the
volume of water resolution is again determined. To distinguish between a bicontinuous phase and W/O emulsions, a
conductivity probe is used.
Results and Discussion
To establish a base line for comparison, emulsions without participation of suspended solids were prepared under the
same conditions as those prepared in the presence of particles, i.e. brine salinity values and mixing time. All the systems
obtained by stirring oil and brine turned out water-in-oil (W/O) emulsions. Each sample of 10ml volume in total was found to
have 3 phases after centrifugation (see Figure 1). The bottom phase in Figure 1 (bottle on the left side of the figure) consists
of a very small amount of brine, only 0.2~1ml, the middle portion of the sample is a tight emulsion (brown phase), as
corroborated by viscosity measurements, and at the top, oil is always found. The brown phase when observed under
microscope appears to be a tight W/O emulsion, with a viscosity value between 200 and 700cp. The right portion in Figure 1
is a micrograph under transmitted optical microscopy at a magnification of 20X. The bright spots in the image are water
droplets or clusters of them. Notice that the resulting emulsion is tightly packed. In comparison, the viscosity of the oil is less
than 100cp. Conductivity measures of the viscous (brown) phase was not detectable (zero in the instrument), corroborating
the fact that this is W/O emulsion.
Figure 2 shows the amount of water calculated to reside in the brown phase during the bottle test at three different values
of salinity (1MLB: full brine; 0.1MLB:10 times dilution and 0.01MLB:100 times dilution) and pH~7 (since no inert
atmosphere was used during preparation of the brine, slight changes in pH were observed as likely result of CO2 dissolution
in the brine; upon mixing, the upper oily phase reduces exposure to atmospheric CO2). As may be observed in Figure 1(a), at
full brine salinity, the emulsion has small amounts of water dispersed in oil, with the exception of 1-to-2 oil/water ratio,
which leads to a significant amount of water dispersed in the oil phase. Under more scrutinity, it can be noticed that the
results for 1-to-3 ratio (oil/water) produce no stable emulsions after 1hr, as all the water is resolved in the experiments. As the
relative amount of oil is increased, more stable emulsions are found. For pure MLB, the highest percentage of water in the
experiment can be dispersed in the oil phase at the 1-to-2 ratio, but the W/O is not long-lived. However, for more diluted
brine at the same ratio (Figure 1(b) and (c)) a significant amount of water remains dispersed in the oil phase, indicating
higher stability at lower salinity (higher dilution). Overall, as the oil-to-water ratio is increased, higher amounts of water are
found stabilized in the form of W/O emulsions, being higher at lower salinity. The effect is not pronounced at 1-to-3 oil-to-
water ratio. The results so far suggest that lower salinity favors emulsion formation. A possibility is that low salinity brine
favors the the onset of asphaltene, but this will require further investigation. Whatever it is, components in the crude oil
appears to provide enough stabilization of W/O emulsions, but the amount of water in the emulsion is generally lower than
35% v/v. A different presentation of the bottle test results can be seen in Figure 3. The volume of water dispersed in the W/O
emulsion was normalized by the total volume of water used to prepared the emulsions. A value of “1” would indicate that the
totality of the water volume is dispersed in the emulsion, providing the maximum stability possible for the system (if it
remains dispersed for long periods of time). It can be notices that for 1-to-1 and 1-to-2 oil-to-water ratios, the lower the
salinity, the higher the stability of the emulsion. At higher oil-to-water ratio (1-to-3) all the emulsions contain the maximum
amount of water in the form of an emulsion.

Figure 1. Emulsion after centrifuging during a bottle test (left). Optical micrograph of the brown phase on the left.
6 SPE 115941

Water% in W/O emulsion

Oil-water ratio
Figure 2. Water percentage in the W/O emulsion in bottle tests. (a) 100%MLB, (b) 10 times (90% dionized water/10%
MLB) dilution of MLB and (c) 100 times dilution.

          

   

Figure 3. Normalized water fraction in W/O emulsion corresponding to results in Figure 2. (a) 100%MLB, (b) 10
times (90% dionized water/10% MLB) dilution of MLB and (c) 100 times dilution.

Most experiments with solid particles suspended are carried out at 1-to-1 oil-to-water ratio.

Solids Characterization
Before providing results for Pickering emulsions, the characterization of the solid particles is presented. SEM images of
all particles are shown in Figure 4. On the left portion of the figure, 3μm-in-average silica particles can be seen (the
SPE 115941 7

micrograph was provided by the vendor). The particles are quite round and monodisperse. This is verified by particle-size
analysis. Kaolinite (central micrograph in Figure 4) exhibits the plate-like shape typical of naturally occurring kaolinite, but
the sheets of the aluminosilicate are flocculated, probably due to the ionic strength of the aqueous phase used to prepared the
material for SEM. Kaofine (fine kaolinite) material is shown on right portion of Figure 4. Although not as evident as
kaolinite, kaofine appears to consist of fine plate-like grains. Intense flocculation probably occurs during dispersion of
kaofine and subsequent coating with distilled water.

Figure 4. SEM image of a silica (left), Kaolinite (center) and kaofine (right).

X-Ray Diffraction (XRD) was carried out on the kaolinite and kaofine samples under electron microscopy to confirm that
the chemical composition of the two minerals were similar as follow the expected formula as Al2Si2O5(OH)4. Figure 5 shows
the XRD spectra, including the reference (in blue), which confirms that the two minerals are similar in chemical composition.

Figure 5. XRD spectra for kaolinite (top) and kaofine (bottom). Reference is in blue.
8 SPE 115941

Zeta potential measurement

Due to excessive polarization of the electrodes at high salinity, results for zeta potential are presented for 0.01MLB and
0.01MLB brines only. Each zeta potential measurement was repeated 3 times to determine reproducibility for most samples.
The error bar is not shown, because it was typically smaller than the symbols in the plots.
Experimental results show that clay concentration did not have a significant effect on zeta potential and size distributions
(not shown). Either 0.02g kaolinite or 0.04g silica were suspended in 50ml 0.01MLB, forming dispersion with 0.04 wt% or
0.08wt% particle concentration, respectively. Zeta potential for clay particles was measured as a function of pH, as shown in
Figure 6. It may be easily seen that particles in the brine with the lowest salinity have larger negative zeta potentials, which is
a result of lower ionic strength available to suppress the electrical double layer of the dispersed solids.

Figure 6. Zeta potential of kaofine and kaolinite particles as a function of pH.

Similar pH sweeps were carried out for silica with diameter of 1µm, 3µm, 5 µm in average as depicted in Figure 7. It may
be noticed that the larger the silica particles, the more negative the zeta potential is, hence the larger the negative the surface
charge This is because larger surface area of smaller silica particles, i.e. larger specific surface.

Figure 7. Zeta potential of silica particles in aqueous solution for different particle radii.

Particle-size Distribution
Due to the impact of particle size and structure in suspension, analysis of the particle size at several pH values is
presented. Zeta potential results were used to guide the choice of pH values to capture the behavior of the suspensions at the
zero-point of charge (ZPC) or isoelectric point (IEP), and also at the largest surface charge value.
Figure 8 shows the size distribution for kaolinite dispersed in brine at pH~7 for 100% MLB and 100 times dilution. It was
indicated before that brines were prepared without inert atmospheres. Therefore, slight changes in pH were observed as a
function time, but these changes were mitigated by preparing fresh synthetic brine frequently and by sealing the containers
with brine. The insets in the figure are optical micrographs of particle suspension samples taken immediately (initially) and
after preparation of the suspension and then 1 day later.
SPE 115941 9

4
Initial 1 day after
(a)
3

Fraction (%)
2

0
0 10 20 30 40 50 60 70 80 90 100

Size (μm)
Initially 1 day later 2 days later

4
Initial 1 day after
(b)
3
Fraction (%)

0
0 10 20 30 40 50 60 70 80 90 100

Size (μm)
Initially 1 day later 2 days later

Figure 8. Particle size distribution of kaolinite at pH~7. (a) 1MLB, (b) 0.01MLB.

Figure 9 depicts particle size distributions for kaofine at pH~7. The distributions are significantly narrower than those for
kaolinite. What is a bit surprising is that particle aggregates observed at the initial conditions in Figure 9(a), corresponding to
100% MLB can be clearly observed, despite the relatively small size reflected in light diffraction measurements. Perhaps this
result is a matter of sampling. The particle size distribution in the case of kaofine widens somewhat at 100% MLB, but the
majority of the particles appear to be under 5μm in size. For the most diluted brine, the size distribution appears to be almost
invariable.
6

Initial 1 day after

(a)
5

4
Fraction (%)

0
0 5 10 15 20 25 30

Size (μm)
Initially 1 day later 2 days later
10 SPE 115941

Initial 1 day after

(b)
4

Fraction (%)
3

0
0 5 10 15 20 25 30

Size (μm)
Initially 1 day later 2 days later

Figure 9. Particle size distribution of kaofine at pH~7. (a) 1MLB, (b) 0.01MLB.

Figure 10 shows the results of particle size distribution for 3μm silica at pH~7 for two values of brine salinity. In this
case, the silica aggregates can be identified in the insets, particularly after 1day after the initial preparation of the suspension.
Under these conditions, silica has a mild tendency to aggregate. Results from zeta potential measurements would indicate a
negative value of this potential at this pH, at least from values of salinity of 1MLB and 0.1MLB.
Table 2 contains the results for average particle size for 3 values of pH~2.5, 7 and 11. As before, measurements were
taken immediately after preparing the suspensions and then 1 and 2 days later. Notice that silica remains at about 3μm in
average size, except for pH~11, value at which increasing salinity leads to very large silica aggregates. Similar results are
found for kaofine and kaolinite at the same pH value. At this pH, zeta potential measurements seem to indicate either a flip in
surface charge or very small surface charge at higher salinity values, which could explain the tendency to aggregate.

30

25

20
Fraction (%)

15

10

0
0 1 2 3 4 5 6 7 8 9 10

Size (μm)
Initially 1 day later 2 days later
SPE 115941 11

30
Initial 1 day after
(b)
25

20

Fraction (%)
15

10

0
0 1 2 3 4 5 6 7 8 9 10

Size (μm)
Silica Initially Silica 1 day later Silica 2 days later

Figure 10. Particle size distribution of 3μm silica at pH~7. (a) 1MLB, (b) 0.01MLB.

Table 2. Average particle size determined through light diffraction.

pH~2.5 pH~7 pH~11

Conditions
Initial 1 day 2 days Initial 1 day 2 days Initial 1 day 2 days
(μm) (μm) (μm) (μm) (μm) (μm) (μm) (μm) (μm)
Kaofine 0.01MLB 1.75 2.15 2.29 1.17 1.55 1.34 1.06 1.21 1.62

Kaofine 0.1MLB 1.85 2.11 2.24 - - - 1.62 4.44 3.43

Kaofine 1MLB 2.55 1.70 1.84 0.81 1.25 1.29 5.15 7.93 7.72

Kaolinite 0.01MLB 5.86 11.37 7.85 6.38 7.77 8.36 7.32 8.91 9.48

Kaolinite 0.1MLB 5.27 10.59 8.63 - - - 7.4 8.46 10.16

Kaolinite 1MLB 4.96 8.42 9.51 5.14 7.99 7.7 8.35 10.05 12.58

3μm Silica 0.01MLB 2.98 3.11 3.12 2.86 3.52 3.62 3.11 3.72 3.74

3μm Silica 0.1MLB 3.16 3.35 3.5 - - - 3.69 7.98 6.77

3μm Silica 1MLB 3.03 3.3 3.36 2.86 3.23 3.41 4.65 13.64 17.84

Solid- stabilized Emulsions

Clay stabilized emulsion
Results of kaolinite and kaofine stabilized emulsions at pH~2 an pH~7, the effect of brine pH on emulsion are presented
in this section. The oil-to-water ratio was 1-to-1, which for systems without particles, the maximum water content was 25%
at most for stable emulsions. From the bottle test, at pH~2, the emulsion resolved 9ml of water out of 10ml total used to
prepare the emulsion, as shown in Figure 11 for the case of kaofine. The viscosity of the W/O emulsion was 93.1cp, being
just slightly higher than the viscosity of oil 73.5cp. On the other hand, at pH~7, only 5.5ml of water were resolved. The
viscosity varied according to the location of the aliquot taken. The upper part of oil phase exhibited a viscosity value of
75.4cp, which indicates that the top portion of the fluid was pure oil, while the lower part, close to the oil and water interface,
exhibited a very high viscosity value of about 293cp (Figure 11). And the microscopic image at 400X magnification shows
the emulsion at pH~7 is tighter than the one at pH~2.
At pH7, the zeta potential of kaofine (-44mV) is much higher than that at pH2, which is close to the ZPC. At ZPC, the
particles easily flocculate due to the lack of electrical repulsion force between them and make them not as efficient at
stabilizing emulsions. A side-by-side comparison with kaolinite stabilized emulsions can be seen in Figure 12. A turbid
suspension can be observed for pH2 in the case of kaolinite, which might represent the initial stages of phase inversion.
Kaofine, with a significantly smaller particle size, appears to exhibit a better capacity for emulsifying water into the oil phase.
Figure 13 shows visual comparisons between the W/O emulsions stabilized with the two forms of kaolinite.
12 SPE 115941

Figure 11. Kaofine stabilized emulsions. On the left, optical micrograph of the W/O emulsion at pH~2. On the right, micrograph of the
W/O emulsion at pH~7. Magnification was 400X.

Figure 12. Bottle test of clay stabilized emulsions with pH2 and pH7. (a). Kaolinite stabilized; (b). Kaofine stabilized
SPE 115941 13

Figure 13. Microscope image of clay stabilized emulsions. (a)Kaolinite stabilized emulsion, at pH=2 (b)Kaolinite stabilized emulsion, at pH=7;
(c)Kaofine stabilized emulsion, at pH=2; (d) Kaofine stabilized emulsion, at pH=7.

Preliminary experiments with the larger dispersion tool indicated that kaolinite-stabilized emulsions were in general more
stable than emulsions without kaolinite. Figure 14 depicts these results at pH7. As can be easily observed, emulsions with
kaolinite are more stable than those without kaolinite, except for 10 times dilution of the initial brine. Significant changes in
interfacial tension could be attributed some of the stabilizing conditions. To determine this, values of interfacial tension
wwere determined. Table 3 contains the values of brine density and IFT for systems with and without kaolinite. Although the
trend appears to signal a correlation with the stability results, the changes in IFT are not considered significant enough to be
responsible for the stability results.

           

     
Figure 14. Comparison between emulsions with and without kaolinite at pH7. Normalized water content is calculated dividing the
amount of water in the emulsion by the total amount of water available. (a) 100%MLB, (b) 10 times (90% dionized water/10% MLB)
dilution of MLB and (c) 100 times dilution.
14 SPE 115941

Table 3. Density and interfacial tension (IFT) measurements for systems with and without kaofine.

0.01 Minnelusa brine pH=2.7 pH=7 pH=11

ρ at 22°C g/cm3 0.9983 0.9983 0.9983

IFT with Minnelusa oil 
mN/m 20.99 17.67 15.55
(use 0.9211g/cm3)
0.01 Minnelusa brine 
pH=2.7 pH=7 pH=11
with Kaofine
ρ at 22°C g/cm3 0.9990 0.9990 0.9990
IFT with Minnelusa oil 
mN/m 17.45 20.58 15.70
(use 0.9202g/cm3)

Silica stabilized emulsion

Bottle test and microscope observation were also made for silica stabilized emulsions at pH~11 and pH~3. Figure 15
shows the amount of water resolved at the two values of brine pH. It is apparent that silica with the largest size (5µm) can
stabilize emulsions better than smaller ones (1µm and 3µm). For water in oil emulsion, strong hydrophilic silica will mostly
mmersed into the water droplets, with only an edge left in the oil phase. Silica, indeed, would tend to disrupt the stability of
W/O emulsions, if access to the water-oil interface is gained. In this sense, silica particles with 1µm and 3µm in diameter will
inot be large enough to form steric barriers between the droplets to prevent coalescence, which would be the only stabilizing
mechanism. Perhaps at a higher concentration of silica particles, it may be possible to produce enough coverage of the
interface.
From results of zeta potential measurements, silica with 3µm in diameter in 0.01 MLB at pH11 has a higher zeta
potential in absolute value (-26.23mV) than at pH3 (-1.88mV), which is close to ZPC. However, the emulsion appears more
stable at ZPC as opposite to the results of kaolinite stabilized emulsion. At pH11, the volume of water resolved was 9.5ml,
and particles settled at the bottom of the bottle, while at pH3, the water volume resolved was 8.5ml and many oil stains
existed in water phase. The viscosity values of the W/O emulsions were close to each other, namely 87.2cp for pH11 and
81.1cp for pH3, respectively. From the microscopic image, it was also seen that silica in very acidic brine can stabilize
emulsions better. The reason for this can be attributed to the fact that aggregation of silica favors the interfacial strength of
water droplets, as Stig E. Friberg (2005) points out in studying emulsion stabilization by solid spherical particles: “Such
aggregated particles would be more efficient as emulsion stabilizers than individual and independent particles.” Also, at
pH=2, the acid favors the asphaltene adsorption to the particles resulting in changing its hydrophobicity towards more oil-
wet, and asphaltenes can also adhere to the droplets interface together with silica to stabilize the emulsions at this condition.
SPE 115941 15

Figure 15

Figure 16. Microscope image of silica stabilized emulsion at pH11 (left) and at pH2.6 (right).

Conclusions
1. All stable systems, with or without particles, turned out to be water-in-oil emulsions.
2. Stability studies were successfully carried out through analysis of bottle tests and optical microscopy for the three
particle systems used in this work.
3. Zeta potential results in a good predictor of solid particles flocculation as a function of brine salinity and pH.
4. Overall, low-salinity conditions favor the formation of stable water-in-oil emulsions, even in the absence of
microparticles. For kaolinite, neutral conditions are more favorable to formation of stable emulsion than acid
conditions. However, the presence of kaolinite increases the stability of emulsions in general. Stability results at oil-
to-water ratios indicate that a fully emulsified water fraction can be formed at 3-to-1 oil-to-water ratio. This is
perhaps due to the abundance of polar components to stabilize water-oil interfaces and hinder coalescence.
5. Results for silica-stabilized emulsions indicate that larger silica particles (and flocculates) are better stabilizing
agents than smaller silica particles. This result is likely due to the stabilizing mechanism via steric repulsion. This
might explain why silica stabilizes emulsions better at acid pH than at neutral pH conditions, as opposed to systems
stabilized with kaolinite particles. As the particle clusters exceed 6μm or so in average size, typically at high pH,
stabilization is lost, as previously reported in ther literature.
16 SPE 115941

Acknowledgements
The authors would like to thank Prof. N. Morrow for providing oil samples and access to instruments including an optical
microscope. Financial support was provided by the University of Wyoming through startup funding. Acknowledgements are
due to Dr. G. Thyne for discussions and for providing information on properties of the oil.
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