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Foams and Emulsions Stabilized With Nanoparticles for Potential Conformance

Control Applications

Article · January 2009

DOI: 10.2118/121744-MS

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SPE 121744

Foams and Emulsions Stabilized With Nanoparticles for Potential

Conformance Control Applications
Tiantian Zhang, Matthew R. Roberts, SPE, Steven L. Bryant, SPE, and Chun Huh, SPE,
The University of Texas at Austin

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE International Symposium on Oilfield Chemistry held in The Woodlands, Texas, USA, 20–22 April 2009.

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
While emulsions stabilized by colloidal solid particles have been widely used for industrial and consumer applications, their
use for enhanced oil recovery purposes has been very limited. This is because the colloidal solids generally cannot be
transported long distances within oil reservoirs, e.g. from injection well to production well. Nanoparticles are two orders of
magnitude smaller than colloids and thus can migrate through the pore throats in sedimentary rocks. Emulsions stabilized
with nanoparticles can withstand the high-temperature reservoir conditions for extended periods. This can substantially
expand the range of reservoirs to which EOR can be applied. Finally, nanoparticles can carry additional functionalities such
as super-paramagnetism and reaction catalysis. The former could enable transport to be controlled by application of magnetic
field. The latter could enable in situ reduction of oil viscosity.
We have employed aqueous suspensions of surface-modified silica nanoparticles (5- & 20-nm diam.) in a set of
laboratory experiments. We report the phase behavior of nanoparticle-stabilized oil/water emulsions and the transport of
these emulsions in porous media. Very stable oil/water emulsions were generated, with average droplet size between 2 and 4
microns, at ambient and at elevated temperature. The emulsion stability was not strongly dependent on nanoparticle
concentration or on salinity. The transport in glass-bead packs (ca. 20 Darcy) of the silica-stabilized oil/water emulsions
showed a sharp emulsion-bank front, with no visible loss of their integrity, and high apparent viscosity (30 cp). Permeability
to the aqueous phase post-flush was significantly reduced. It was not possible to determine whether emulsion droplets were
retained in pores during emulsion injection, or whether the post-flush fingered through the emulsion and failed to displace all
of it. An on-going modeling effort to characterize the equilibrium and stability of the emulsions suggests formation of
relatively compact interfacial layer of nanoparticles at the droplet surface.

Introduction
Oil/water emulsions are frequently used as special-purpose drilling fluids (Ali et al., 2004), as mobility control agents to
improve displacement efficiency of viscous oil (Schmidt et al., 1984; Khambharatana et al., 1998), and for other applications
in the upstream oil industry (Schramm, 1992). Emulsions in practice are generally stabilized with surfactants, but emulsions
can also be formed using colloidal solids as stabilizers. While such “Pickering emulsions” are widely used in mining, food
and cosmetics industry, they are rarely used for oil recovery purposes. This is because the colloidal solids are easily trapped
in reservoir rock by straining and deep-bed filtration, and the long-distance propagation of such emulsions in reservoir is
therefore generally not feasible.
The advantages and disadvantages of Pickering emulsions are clearly illustrated in the work of Bragg (1999) and Bragg
and Varadaraj (2003). They carried out a comprehensive laboratory study to develop solid-stabilized oil-in-water and water-
in-oil emulsions that can be effectively employed to displace viscous oil from high-permeability reservoir rocks. They also
showed that oil-in-water emulsions can enable the transport of a viscous oil through pipelines at smaller pressure drops. Two
main advantages of using such emulsions are: (i) very low-cost solids such as clays can be used as the stabilizer, and the
reservoir oil can serve as either the dispersed phase or the external phase; and (ii) by adjusting the solids concentration and/or
the water pH, a high apparent viscosity for the displacing fluid can be attained for effective mobility control. While
potentially very low cost, the process has some weaknesses. First, because of the straining/filtration tendency of the solids,
the process is applicable to only very high-permeability reservoirs. Second, the solids employed, e.g., clay, have a wide size
and shape variations, so that it is difficult to control the quality and texture of the emulsions (see below).
2 SPE 121744

Recent explosive advances in the nanoparticle technology (see, e.g., Arney et al., 2006) offer the opportunity to
circumvent the weaknesses of colloid-stabilized emulsions. Our initial focus has been on commercially prepared spherical
nanoparticles of uniform diameter (5 nm and 20 nm), whose surface is coated with polymer to achieve a desired wettability.
Such nanoparticles have a number of advantages over conventional colloidal solids. First, the small size allows the
nanoparticles, and the micron-size emulsion droplets stabilized by them, to flow without retention in reservoir rocks of a wide
range of permeability. Second, the polymer coating on the particle surface can make the particle stay at the aqueous/non-
aqueous phase interface with a desired contact angle. This allows formation of the emulsion droplets of desired interfacial
curvature, and also helps to reduce their retention in reservoir rock. Third, with the uniform size of the spherical
nanoparticles, they can form a compact, well-structured monolayer at the aqueous/non-aqueous phase interface. This renders
the emulsion extremely stable, even under harsh reservoir conditions such as high temperature. The same structure also offers
the possibility of the controlled de-stabilization of the emulsion as described below. Fourth, the nanoparticles being solid,
they can be magnetic, magnetostrictive, or piezoelectric, raising the possibility of external control for emulsion quality,
texture and de-stabilization. Fifth, the nanoparticles can be catalytic, reactive, or associative with water-soluble polymer or
surfactant molecules.
In addition to the possibility of the controlled stabilization and de-stabilization of emulsions, the last two attributes above
offer exciting opportunities for upstream oil industry, for example, for in-situ reduction of the bitumen viscosity for its more
efficient recovery (Thompson et al., 2008), and for the external control of the rheology of the drilling fluids and mobility-
control fluids (Melle et al., 2005).
Our on-going research has the following objectives, and this paper reports our preliminary results to achieve the
objectives:
• Quantify the retention and mobility of aqueous dispersions of nanoparticles during their flow in porous media
(Brant et al., 2007).
• Investigate the formation and stability of nanoparticle-stabilized emulsions that are formed by different
hydrocarbons and brine of varying salinity at varying temperatures.
• Characterize the mobility of the nanoparticle-stabilized emulsions in porous media.
For the benefit of readers not familiar with the recent rapid developments in the use of nanoparticles to generate
emulsions for a wide variety of applications, the related literature is reviewed below in some detail.

Adsorption and Equilibrium of Nanoparticles at Oil/Water Interface. The key attribute that enables both surfactants and
particulate solids to serve as emulsion stabilizers is an affinity for the water/oil, or aqueous/non-aqueous, interface. Binks
(2002) reviewed the similarities and differences between colloidal particles and surfactants in their ability to stay at the fluids
interface and to stabilize emulsions. The hydrophile-lipophile balance (HLB) quantifies the relative preference of surfactants
to water and oil. The contact angle serves the same purpose for colloidal particles and nanoparticles. Particles with contact
angle close to 90° show surface activity useful for emulsification. As shown in Fig. 1, a contact angle less than 90° means
that the particle is hydrophilic and will make the oil/water interface curve toward oil, thus creating an oil-in-water emulsion.
If the contact angle is greater than 90°, the particle is hydrophobic and will create a water-in-oil emulsion.
A significant difference between surfactants and particles is the attachment of particles at the oil/water interface. While
surfactants adsorb and desorb relatively easily, particles require high energy for attachments to the interface and are
consequently virtually irreversibly adsorbed. The free energy of adhesion for a nanoparticle at the interface is
ΔGad = π a 2γ ow (1 − cos θ ) 2
where a is particle radius; and γow is the interfacial tension. Particles that have contact angles between 0°-20° or between
160°-180° are therefore not held as strongly by interfaces and can be more easily removed (Binks 2002; Binks and Horozov
2006).
Many researchers investigated, both with laboratory experiments and theoretically, the equilibrium states of the
nanoparticle layer adsorbed at a fluid/fluid interface. Bresme and Oettel (2007), Binks and Horozov (2006), and Fernandez-
Toledano et al. (2006) provide comprehensive reviews of these recent works. As described in the above reviews (and in
Reincke et al., 2006; Paunov et al., 2002), the free energy terms that control the equilibrium and stability of nanoparticle
layer at a fluid/fluid interface are (i) the adhesion energy as given above; (ii) the electrostatic repulsions between the
particles; and (iii) the van der Waals attraction between the particles. The electrostatic repulsions may arise from the direct
Coulomb repulsion between the portions of the particle surfaces that carry charges and are immersed in the water phase, and
also from the dipole interactions that arise due to the fact that the oil-immersed portions of the particle surfaces do not carry
the electrical double layer. From the free energy considerations, the equilibrium density of the nano-spheres at the interface
can be defined. Some qualitative comparisons of the model prediction with the measured data are discussed in the above
reviews.
Nanoparticles have freedom of lateral and perpendicular movements at the interface. Thus they will assume a position
such that the interface between the particles is flat but satisfies the contact angle condition (see Fig. 1). The capillary
interaction between the particles is expected to be small. Nikolaides et al. (2002), however, showed that the electrical field
generated by the charged particles can induce a capillary attraction between particles. Capillary interactions that may arise
SPE 121744 3

due to the particle surface roughness, line tension, and particle geometry, are discussed in detail by Fernandez-Toledano et al.
(2006) and Bresme and Oettel (2007).
One feature of the nanoparticle adsorption at a fluid/fluid interface that drew significant recent attention is their formation
of compact, structured layers (Lin et al., 2005; Murray et al., 2000). Such layers could be utilized as the basic building blocks
for many sophisticated nano structures that serve specific application purposes, such as the nano-polymer composites, smart
coatings, and nano-filters. As mentioned above, the formation of a compact nanoparticle layer at the droplet interface brings
forth the high stability of the emulsion. The capillary attraction discussed above is believed to be an important contributor for
the compact layer formation (Nikolaides et al., 2002; Bresme and Oettel 2007).

Stability of Nanoparticle-Stabilized Oil/Water Emulsions. The principles applied to define the equilibrium and stability
of colloid-stabilized emulsions can also be applied to define those properties for nanoparticle-stabilized emulsions, with few
exceptions. Thus it is useful to understand those principles, established during extensive previous studies of colloid-stabilized
emulsions. Tambe and Sharma (1994) discussed the different properties that could be manipulated to stabilize an emulsion
with colloidal particles.
Comprehensive reviews on more recent studies on the equilibrium and stability of emulsions, stabilized with colloidal
particles and nanoparticles, are given by Binks and Horozov (2006), Fuller et al. (2006), Lopetinsky et al. (2006), and Hunter
et al. (2008). One important parameter that controls emulsion stability is the particle concentration: an increase in particle
concentration increases the emulsion’s stability and volume. The average size of the emulsion droplets also decreased with
increased concentration, allowing additional particles to be accommodated at the interface. Emulsion stability increases with
a decrease in particle size. As the concentration of electrolyte ions increases, emulsion stability decreases. This may be due
to the decreased electrostatic repulsion at high electrolyte concentrations, which increases the tendency of particles to
coagulate. Our phase behavior experiments show that the type of oil also influences the emulsion stability.
Several of the above observations, such as the dependence on the oil type, can be explained in terms of the particle
surface wettability. For a contact angle other than 90°, a curved droplet interface has a lower free-energy state than a flat
interface. This allows a dispersion of one fluid phase in another fluid phase to occur (Binks and Lumsdon 2000; Kruglyakov
and Nushtayeva 2004). Different polymer or surfactant coatings impart different wettability to particle surfaces, as described
in detail by Bourgeat-Lami and Duguet (2006), Binks and Lumsdon (2000), Saleh et al. (2005) and others. It is therefore
possible to tailor particles to individual applications, e.g. to a specific crude or reservoir.
To help quantify the conditions for equilibrium and stability of emulsions, theoretical models have been developed
(Levine and Bowen, 1992, 1993; Kralchevsky et al., 2005; Reincke et al., 2006). The first requirement for such modeling is
the definition of the equilibrium state of the nanoparticle layer adsorbed at the oil/water interface, as briefly described above.
In addition, the preferred interfacial bending moment needs to be defined to obtain the emulsion droplet size as a function of
the interfacial density of the adsorbed particles (Kralchevsky et al., 2005). The consideration of emulsion stability requires
accounting for the interactions between the emulsion droplets. The well-established DLVO theory, together with the viscous
resistance to the thinning of the liquid film between the droplets, explains the emulsion stability reasonably well. Stability
mechanisms other than the above conventional approach have also been proposed (Friberg, 2005; Lopetinsky et al., 2006).

Potential Oil-Industry Applications

In addition to our focus on the improved recovery of viscous oil, the supercritical CO2-in-water “emulsion” studied by
Dickson et al. (2004) and the water-in-supercritical CO2 “emulsion” developed by Adkins et al. (2007) are of particular note
for other improved oil recovery processes. To create a CO2/water emulsion, they mixed water containing 1 to 50 wt % silica
nanoparticles with CO2 at 25 °C at pressures varying between 34 bars and 700 bars. They studied the effects of particle
hydrophilicity, particle concentration, dispersed phase volume fraction, and CO2 density on the emulsion stability. Their
results showed that for a given set of temperature, pressure, CO2 density, and concentration, a decrease in hydrophilicity
improved emulsion stability. They also found that emulsion stability increased as particle concentration increased. Adkins et
al. (2007) recently showed that water-in-CO2 emulsions could be stabilized by hydrophobic silica particles that were less than
10 nm in diameter. The water-in-CO2 emulsions made with nanoparticles were very stable, forming a compact layer of
nanoparticles at the droplet’s water/CO2 interface. The nanoparticle-stabilized emulsions thus showed potential to overcame
many limitations encountered with emulsions stabilized by surfactants, such as the difficulty to maintain stability at high-
temperature and high-salinity conditions.
Another potential oil-industry application is the use of paramagnetic nanoparticles to generate emulsions. The stability of
such emulsions could be controlled by applying a magnetic field (Melle et al., 2005). In employing the emulsions for the
conformance control purpose or as the drilling fluid, it is conceivable to control their rheology at specific locations at or near
the wellbore. Emulsion droplets that have a compact interfacial layer of nanoparticles (“armored droplets”) can be extremely
stable, and the dispersion of such droplets can be made to be the internal phase for another emulsion, known as double
emulsion or even multiple emulsion (Lee and Weitz, 2008; Dinsmore et al., 2002; Utada et al., 2005). Such double emulsions
can be employed as a carrier of special-purpose chemicals deep into the reservoir formations, avoiding the contact of such
chemicals to the wellbore zone.
In the next Section, the nanoparticles and fluids used to form emulsions, and the bead-pack flood set-up, are described. In
Section III, the phase behavior of (i) silica-stabilized toluene-in-deionized water emulsions; and (ii) silica-stabilized crude
4 SPE 121744

oil-in-brine emulsions were studied. Section IV describes columnfloods (bead-packs initially saturated with water) into which
toluene-in water emulsions were injected, then displaced by water. In Section V, a brief description of the emulsion
generation with the iron-oxide nanoparticles is given, followed by the conclusions.

Experimental Set-Up and Materials

Materials. Two different size silica nano spheres (5-nm and 20-nm diameters) were received from 3M Co., St. Paul, MN.
The sphere surfaces were coated with polyethylene glycol (with about 7 EG units), covalently attached to the silica surface
through silicon-oxygen-silicon bonds. These surface-modified silica spheres were dispersed in de-ionized water, and were
provided to us as a 22.11 wt% dispersion (for 5 nm) and a 42.77 wt% dispersion (for 20 nm). The 5-nm dispersion was a
visually clear liquid with a viscosity of about 2 cp; the 20-nm dispersion was a slightly opaque liquid with a viscosity of
about 9 cp (both at room temperature). The viscosity showed no shear-rate dependence. The iron-oxide spheres have a
diameter of approximately 3 nm, and their surface was modified with adsorption of citric acid. (Some excess citric acid was
believed to be in the dispersing, de-ionized water, which was not quantified.) A 1.5 wt% dispersion, which has a dark brown
color, was used as received.
The crude oil used has a API gravity of 45° without any dissolved gas. It has virtually no C1-C9 fraction, and the mole %
for the C10-C19, C20-C29, C30-C39, and C40+ fractions are 40.92, 33.23, 17.84, and 7.63, respectively. The water used to
make emulsions was de-ionized water. The brine used to make emulsions with the crude oil has total dissolved solids of
22,310 ppm with NaCl = 1.78 wt%. Experiments were conducted at room temperature, which is only slightly cooler than
reservoir temperature.
Other materials (toluene, decane, NaCl) were reagent grade.

Procedure to Make Emulsions. Brines containing different loadings of nanoparticles and different salinities were prepared
by mixing the received dispersions with de-ionized water and reagent grade NaCl. We conducted two series of tests:
preliminary scoping, and phase behavior scan. To make emulsions during preliminary scoping, equal volumes of toluene (or
other hydrocarbons or crude oil tested) and brine (or de-ionized water) that contains nanoparticles were placed in a container.
The sample container was then sealed, and vigorously agitated with a magnetic stir bar in it. The mixture was usually stirred
for 24 hours, after which the emulsion was allowed to settle for a minimum of 24 hours. The emulsions were developed at
ambient temperatures and pressures. As the emulsion slowly settles, the volumes of the emulsion phase and any excess
phases were recorded with respect to time. To facilitate the emulsification process, sometimes a sonification gun was
employed.
To make emulsions during phase behavior scan, only the sonification gun was used. Equal masses (typically 10 g) of
aqueous and nonaqueous phases were added to a container, and energy was supplied via sonification for three minutes. This
provided very reproducible results. Some of the input energy was dissipated as heat, warming the emulsions to as much as
60 °C. The emulsions were allowed to cool by natural convection to ambient temperature.

Emulsion Droplet Size Measurements. The emulsion droplet size measurement equipment consists of one Nikon Digital
Sight DS-Fi1 camera attached to one Nikon Labophot-Pol microscope. The microscope apparatus is connected to a PC
running Nikon NIS-Elements D3.00 Build 449 imaging software.

Emulsion Viscosity Measurements. The steady-state viscosity of the emulsion was measured across a range of shear rates
of using the TA Instruments’ Advanced Rheometric Expansion System (ARES) LS-1 rheometer.

Bead-Pack Flood Set-Up. The bead pack floods were conducted using a 7-inch long, 1-inch diameter cylinder filled with
0.180 mm washed glass beads. The pore volume of the bead pack was 25mL. The schematic of the coreflood set-up is shown
in Fig. 2. Emulsions were prepared as described above, separated from any excess phase by pipette and transferred to a closed
vessel. To obtain two to three pore volumes of emulsion several small batches were prepared consecutively. The emulsion
was injected into the bead pack within an hour of preparation.

Nanoparticle-Stabilized Oil/Water Emulsions

The goal of this component of research was to create a set of emulsions of different composition and particle concentrations,
thereby mapping their phase behavior. The work was conducted in two stages, a preliminary scoping followed by a phase
behavior scan. During the preliminary scoping, emulsion behavior was characterized in terms of stability, droplet size and
rheology. An emulsion that persisted for at least one week was deemed stable. During the phase behavior scan, the emulsion
volume and composition (volume ratio of nonaqueous to aqueous phase) and the volume(s) of excess phase(s) were measured
at 24 °C and 55 °C.

Preliminary Scoping: Silica-Stabilized Hydrocarbon-in-Water Emulsions. Several different hydrocarbons (toluene,

decane, hexane, mineral oil) were mixed individually with an aqueous phase (de-ionized water containing 5 wt% or 10 wt %
of 5-nm-diameter nanoparticles). Toluene developed very stable emulsions, usually coexisting in the preparation tube with a
SPE 121744 5

(small) excess toluene phase and/or a (large) excess aqueous phase. These emulsions were stored at ambient conditions and
remained stable for months. In contrast, the emulsion of hexane broke almost immediately after preparation. Emulsions of
mineral oil and of a decane/toluene mixture also broke, although over the course of hours or days. Evidently the contact
angle with water on the particle surface varies significantly between these organic liquids.
Changing the particle loading by a factor of two (5% vs. 10%) did not affect the volume of emulsion produced. Salinity
did not have an obvious effect in these experiments, but it did in the phase behavior scan (described below), possibly because
of the difference in preparation protocol. Several of the emulsions prepared at ambient conditions were transferred to ovens
held at 55 °C and at 85 °C. All remained stable for weeks.
The toluene emulsions were very shear-thinning, Fig. 3, exhibiting viscosities from ~10 cp to ~10,000 cp.

Preliminary Scoping: Silica-Stabilized Crude Oil-in-Brine Emulsions. Aqueous dispersions of 5-nm silica nanoparticles
were prepared with particle concentrations of 10%, 5%, 1%, and 0.1% in weight. These were agitated with crude oil with
varying ratios of crude oil and brine volumes at ambient conditions. (This is representative test, because the oil comes from a
shallow reservoir.) The oil readily emulsified with water containing 10% or 5% nanoparticle loading, as illustrated in Fig. 4.
The upper dark brown phase is excess crude oil, and the light brown lower phase is the oil-in-water emulsion. The emulsions
remained stable up to 2 months, except when prepared with a large ratio of oil volume to water volume. Most emulsions
made with 1 wt% and 0.1 wt% nanoparticles broke down within 5 days; this is likely attributable to the preparation method
(see Phase Behavior Scan below). However, emulsions stable for up to two weeks were prepared with large excess of water
(oil-to-water ratio of 1:16 or smaller) containing 1 wt% nanoparticles.
In most emulsions the droplets could be clearly observed with the microscope. The droplet size was about 3 μm, Figs. 5
(10 wt% nanoparticles in aqueous phase) and 6 (5 wt% nanoparticles in aqueous phase). The size did not depend on the
volume ratio of oil and water used to prepare the emulsion nor on the concentration of nanoparticles, at least for these
loadings. Some coarsening of the droplets occurred in the emulsions prepared with 5 wt% nanoparticles; the droplet size
increased about 1 micron during a week at ambient conditions. The emulsions are warm after preparation, but cooling to
room temperature did not appear to be the cause of coarsening.
The crude oil emulsions are shear-thinning but less viscous than the toluene emulsions, Fig. 7. The viscosity of an
emulsion made with field brine (one part oil to two parts brine) exhibited viscosities in the range of ~5 cp to ~100 cp. Theory
suggests that in addition to the shear rate, emulsion viscosity should depend on the volume fraction of the dispersed phase
and the droplet size; different empirical correlations have been proposed (Pal et al., 1992). We are currently investigating
whether such relationships hold for this emulsion.

Phase Behavior Scan: Silica-Stabilized Emulsions. Toluene and the crude oil were selected for the phase behavior scan, in
which the nanoparticle loading and the salinity were varied independently. All emulsions were prepared with equal masses of
aqueous and nonaqueous phase. All emulsions were prepared twice; no variation in behavior between replicates was
observed.

Toluene-in-Water Emulsions. All samples appeared to be a single emulsion phase without excess toluene or water just
after sonification. Within hours, however, most of the excess water separated from the emulsion. Excess water continued to
separate slowly over the course of 3 to 4 days before reaching the final steady state. Examples are shown in Figs. 8(a) and
8(b). The viscosity of the emulsion appeared to increase as the initially entrained water escaped. Table 1 and Figs. 8(c) and 9
summarize the influence of nanoparticle concentration in the aqueous phase, of salinity and of temperature on the emulsion
volume, excess phase volumes, and the toluene/water volume ratio Vo/Vw within the emulsion.
Except for the smallest nanoparticle loading of 0.1 wt%, all the samples yielded about the same emulsion volume fraction.
At higher temperature, the volume fraction of emulsion phase is slightly smaller than at ambient conditions, except for the
high-salinity (10% NaCl), high-particle-loading (10 wt%) sample.
The emulsion volume fraction was similar in nearly all samples because at loadings above 0.2 wt% nanoparticles, the
entire initial volume of toluene can be emulsified in a fraction of the initial volume of water. This is simply because the
presence of more nanoparticles per unit volume water enables a greater number of toluene droplets to be stabilized within that
water. The value of Vo/Vw is a direct measure of this effect: in fresh water, Vo/Vw increases as nanoparticle loading increases,
Fig. 10. The increase is rapid at small loadings, and becomes smaller and linear at larger loadings. The rate of increase is
much greater at 55 °C than at 24 °C. Evidently the particles are more efficient at stabilizing droplets at higher temperature, or
else a greater number density of particles can be accommodated at a droplet surface, increasing the emulsion stability. For
large particle loading (10 wt%), the value of Vo/Vw decreases as salinity increases, Fig. 11. The decrease is modest at ambient
temperature but significant at 55 °C, especially from 0 wt% NaCl (deionized water) to 0.1 wt% NaCl. Evidently the reduction
of electrostatic repulsion at large salinity is more effective at high temperature, counteracting the ability of the large particle
concentration to suspend a large number density of droplets.

Crude-oil-in-Water Emulsions
Identification of phases was more difficult in these experiments. Any excess aqueous phase was opaque and light tan in color
after sonification, and thus difficult to distinguish from the emulsion, Figs. 12(a) and 12(b) and Table 2. As a result the phase
6 SPE 121744

volume are identified only as “upper” and “lower” in Table 2, and the estimate of the oil/water volume ratio within the
emulsion is not reliable. Nevertheless several samples exhibit only one phase which is clearly an emulsion.
Unlike the toluene emulsions, the crude oil emulsions tend to have more water than oil. This is a practical advantage, as
less oil would be required to make a desired volume of emulsion. The ratio Vo/Vw increases as nanoparticle concentration
increases and decreases as salinity increases. This is qualitatively the same trend as observed in the toluene emulsions. A
notable difference is that 10wt % NaCl is sufficient to destabilize an emulsion with 10 wt% nanoparticles; see rightmost
sample in Fig. 12(b). This suggest a simple means of breaking these nanoparticle-stabilized crude oil emulsions: contacting
with high salinity brine. To test this idea, a small volume of a very stable emulsion (crude oil, deionized water, 10 wt%
nanoparticles) was added to a similar small volume of 10 wt% NaCl brine. Within twelve hours most of the emulsified oil
had spontaneously separated, Fig. 13.

Transport of Hydrocarbon/Water Emulsions in Porous Media

We conducted a series of columnflood experiments to study the transport of these emulsions within a porous medium. In each
experiment a toluene-in-water emulsion, generated with a 1:1 toluene/water ratio and an aqueous phase loaded with 10 wt%
5-nm silica nanoparticles, was injected into a glass-bead pack previously saturated with deionized water. The emulsion was
immediately displaced with deionized water. Different volumes of emulsion were injected in each experiment. The behavior
of all experiments was qualitatively the same, so only one is discussed here. The emulsion was injected at a rate of 2
cm3/min or 4.8 PV/hr, corresponding to a Darcy velocity u of 1.86 ft/day. At these conditions the shear rate within pores in
the bead pack is estimated from the formula (Lake, 1989) to be about 50 s-1.
As shown in Fig. 14, the emulsion slug displaced the initially present water as a piston-like front with minimal dispersion.
Fig. 15 shows the fit of a “resistance in series” model of the piston-like displacement to the overall viscosity during the
displacement. The latter is related to the observed pressure drop by if all multiphase flow effects are
negligible. The emulsion viscosity is related to the slope a of the trend by . Emulsion viscosities in the
range of 30 cp to 40 cp were inferred for all the columnflood experiments. Figure 16 shows that this value is reasonably
consistent with the shear rate estimate given above.
Figure 15 shows that the overall viscosity continues to increase during the 2nd pore volume of emulsion injection.
However, the piston-like displacement model predicts that overall viscosity is constant after one pore volume has been
injected. It is likely that the assumption of negligible multiphase flow effects is not applicable, and emulsion droplets are
being trapped in pores, thereby reducing the permeability of the column. This means that the estimated emulsion viscosity in
the core is likely to be too large. Thus it may be that the rheology of the emulsion during flow in a porous medium differs
from its bulk phase rheology.
At the trailing edge of the slug, the chase water was observed to finger rapidly into the viscous emulsion bank (not shown
here). This is expected for an unstable miscible displacement. The overall viscosity computed from the pressure drop
approaches a value much larger than that of water. This would be consistent with a large residual saturation of emulsion
droplets trapped in pores during emulsion injection (Kokal et al., 1992). It would also be consistent with a large volume of
emulsion remaining in the bead pack, bypassed by the less viscous chase water. It is important to note that the emulsion did
not break as it flowed through the bead pack.

Conclusions
Toluene-in-water and crude oil-in-water emulsions that maintained their stability for weeks at ambient conditions and at
elevated temperatures were generated with 5-nm and 20-nm silica spheres. This is possible because the surface of the spheres
is coated with a short-chain polyethylene oxide polymer with a silane end group. Other hydrocarbon phases (decane, mineral
oil, hexane) did not form stable emulsions with these particles. As nanoparticle concentration increases, the volume ratio of
nonaqueous phase to aqueous phase within the emulsion increases. Increasing salinity has the opposite effect. At large
salinity (10 wt% NaCl), in fact, the crude oil emulsion was no longer stable. A stable emulsion was broken by contact with
highly saline brine. The emulsions exhibit large viscosities, as expected, and are shear-thinning. Droplets in the crude oil-in-
brine emulsions had a fairly uniform diameter of 2 to 3 microns.
The toluene-in-water emulsion banks injected into a high-permeability glass-beads pack moved with a sharp bank front
with little dispersion. The emulsion did not break and exhibited a large apparent viscosity consistent with its bulk phase
rheology. This is an important consideration for oil recovery applications.

Acknowledgments
Jimmie Baran of 3M kindly provided the concentrated aqueous dispersions of nanoparticles. Elliott Hu developed the
preliminary scoping protocol and with Kenny Yu conducted many of the phase behavior experiments. Walter Bauer carried
out the emulsion drop size analysis. Prof. Keith Johnston of UT Chemical Engineering kindly provided expert advice on use
of nanoparticles. This work was supported in part by the Advanced Energy Consortium, and by the Miscible Gas Flooding
Joint Industry Project at The University of Texas at Austin.
SPE 121744 7

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Table 1—Phase Behavior Scan for Toluene-in-Water Emulsions

Sample Mixture Nanoparticle Salinity Final Emulsion Vo/Vw in
(mass ratio) Weight Percent (%) Volume Fraction Emulsion Phase
(%) T=24°C T=55°C T=24°C T=55°C
1 Toluene/Water=1 0 0 0 0 0 0
2 Toluene/Water=1 0.1 0 0.10 0.06 1.25 1.33
*
4 Toluene/Water=1 0.2 0 0.66 0.67 2.62 3.97
*
3 Toluene/Water=1 0.5 0 0.69 0.67 3.54 3.96
5 Toluene/Water=1 1 0 0.61 0.57 5.06 10.94
6 Toluene/Water=1 5 0 0.62 0.55 6.72 29.09
7 Toluene/Water=1 10 0 0.60 0.55 8.65 54.57
8 Toluene/Water=1 10 0.1 0.62 0.56 6.21 25.12
9 Toluene/Water=1 10 1 0.63 0.58 5.89 12.97
10 Toluene/Water=1 10 10 0.64 0.87 5.20 1.62
*
Measurements made 32 hours after sample preparation; all other measurements made 5 days after sample
preparation.

Table 2—Phase Behavior Scan for Crude-Oil-in-Water Emulsions

Sample Nanoparticle Salinity Final Final Estimated Vo/Vw
Weight Percent Phase 1 Phase 2 in Emulsion
**
(%) volume/ml color
**** ***
components volume/ml color components Phase
emulsion, emulsion,
1 0.1 0 2.6 yellow 5.4 dark 0.41
water excessive oil
emulsion, emulsion,
2 0.2 0 2.9 yellow 5.5 dark 0.66
water excessive oil
emulsion, dark emulsion,
3 0.5 0 2.8 yellow 5.6 0.91
water brown excessive oil
emulsion, emulsion,
4 1 0 2 yellow 6 brown 1.11
water excessive oil
dark *
5 5 0 8.3 emulsion NA 1.16
yellow
*
6 10 0 7.3 tan emulsion NA 1.16
*
7 10 0.1 7.8 tan emulsion NA 1.16
emulsion, emulsion,
8 10 0.6 4.2 yellow 3.9 dark 0.66
water excessive oil
emulsion, emulsion,
9 10 1 4.6 yellow 4.3 dark 0.41
water excessive oil
emulsion, emulsion,
10 10 10 4.4 yellow 4.6 dark 0.00
water excessive oil
*
There is only single phase observed in the tube.
**
The values are estimated from the color of each phase.
***
Phases identified by pipetting a small volume and dropping it into water, and repeating with brine instead of water. The behavior
(dispersion or phase separation) indicates the nature of the phase.
****
Better view of the color of the phases in Fig. 12.
SPE 121744 9

Fig. 1—Contact angle on particle surface and its relation with emulsion structure.

Fig. 2—Schematic of glass-beads pack flood set-up; (a) syringe pump, (b) accumulator, (c) bead pack, (d) transducer, and (e) sample
collector.
10 SPE 121744

100000

10000
Viscosity (cP)

1000

100

10

1
0.01 0.1 1 10 100 1000
-1
Shear Rate (sec )

Fig. 3—Steady shear viscosity of toluene-in-water emulsion. The aqueous phase contains 10 wt% of 5-nm silica particles and
de-ionized water.

Fig. 4—Crude-oil-in-water emulsions prepared with oil-to-brine ratios of 1:1, 1:2, … to 1:10 (left to right). The brine is synthetic field
brine and 5 wt% 5-nm particles.
SPE 121744 11

Fig. 5—Droplet Radius for crude-oil-in-water emulsions made with different initial oil/brine ratio (10 wt % nanoparticles in aqueous
phase).

Fig. 6—Emulsion droplet radius for emulsions made with different initial oil/brine ratio (5 wt % nanoparticles).
12 SPE 121744

1000

100
Viscosity (cp)

10

1
0.01 0.1 1 10 100 1000
-1
Shear Rate (sec )

Fig. 7—Steady shear viscosity of crude oil-in-synthetic field brine emulsion prepared with 1 part oil to 2 parts brine; the brine
contained 10 wt% 5-nm silica particles.
SPE 121744 13

(a) (b)
T=24°C T=55°C
Water Emulsion Toluene Emulsion Toluene
100% 100%

80% 80%
Volume Fraction

Volume Fraction

60% 60%

40% 40%

20% 20%

0% 0%
0 0.1 0.2 0.5 1 5 10 0 0.1 0.2 0.5 1 5 10
Nanoparticle Weight Percent (%) Nanoparticle Weight Percent (%)

(c)
Fig. 8—Phase behavior scan for toluene-in-water emulsions at various nanoparticle concentration at different temperatures. Mass
ratio: Toluene/Water =1, no salt; see Table 1 and notes therein. (a) Sample containers (left to right) with 0.1%, 0.2%, 0.5%, 1%, 5%
and 10% nanoparticle loadings, respectively. (b) Replicates of (a) held at 55 °C. (c) Phase volume fractions. The first bar in each plot
is a control (toluene, water, no salt, no nanoparticles) that also serves to show the initial volume fractions of the two phases in each
sample.

T=24°C T=55°C
Water Emulsion Toluene Water Emulsion Toluene
100% 100%

80% 80%
Volume Fraction
Volume Fraction

60% 60%

40% 40%

20% 20%

0% 0%
0 0.1 1 10 0 0.1 1 10
Salinity (%) Salinity (%)

Fig. 9—Phase behavior scan for toluene-in-water emulsions at various salinities and two temperatures. Mass ratio: toluene/water=1,
nanoparticle wt%=10%; see Table 1 and notes therein.
14 SPE 121744

60

50
Vo / Vw in Emulsion Phase

40

T=24°C
30 T=55°C

20

10

0
0 1 2 3 4 5 6 7 8 9 10
Nanoparticle Weight Percent (%)

Fig. 10—Ratio of toluene volume to water volume within emulsion for various nanoparticle concentrations, for emulsions shown in
Fig. 8.

60

50
Vo / Vw in Emulsion Phase

T=24°C
40
T=55°C

30

20

10

0
0 1 2 3 4 5 6 7 8 9 10
Salinity (%)

Fig. 11—Ratio of toluene volume to water volume within emulsion for various salinities for emulsions shown in Fig. 9.
SPE 121744 15

(a) (b)
Lower Phase Upper Phase Lower Phase Upper Phase
100% 100%
Phase Volume Fraction

Phase Volume Fraction

80% 80%

60% 60%

40% 40%

20% 20%

0% 0%
0.1 0.2 0.5 1 5 10 0 0.1 0.6 1 10
Nanoparticle Weight Percent (%) Salinity (%)

(c) (d)
Fig. 12—(a) Samples of crude-oil-in-water emulsions stabilized with different nanoparticle concentration (0.1%, 1%, 5%, and 10% by
weight from left to right) and no salt in the aqueous phase 1.5 days after preparation. (b) Samples of crude oil in water emulsions
stabilized with 10 wt% nanoparticles for different salinities (0, 0.1 wt% NaCl, 1 wt% and 10 wt %, left to right). (c) Phase volume
fractions corresponding to (a). (d) Phase volume fractions corresponding to (b).
16 SPE 121744

Fig. 13—Contacting a very stable emulsion (prepared from crude oil, deioinzed water containing 10 wt% nanoparticles) with a saline
brine (10 wt % NaCl) caused the emulsion to break within hours. (Photo is taken 12 hours after initial contact.)

Fig. 14—Emulsion bank displacing water in glass-beads pack forms a sharp front (arrow).
 SPE 121744 17

60

50
Apparent Viscosity (cP)

40

30

20

10 y = 31.089x + 2.6691
2
R = 0.9729

0
0 1 2 3 4 5 6 7
tD (pv)

Fig. 15—Injection of 2 PV of toluene-in-water emulsion causes the apparent viscosity of the fluids in the core to increase
monotonically. The slope of the apparent viscosity is related to the emulsion viscosity.

1000
Viscosity (cP)

100

Test 1
Test 2
Test 3
Test 4

10
1 10 100 1000
-1
Shear Rate (sec )

Fig. 16—Viscosities of emulsions flowing through beadpacks (inferred from piston-like displacement model assuming no
multiphase flow effects) are consistent with the bulk phase rheology of these emulsion.

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