Article

pubs.acs.org/EF

Enhanced Oil Recovery (EOR) Using Nanoparticle Dispersions:

Underlying Mechanism and Imbibition Experiments
Hua Zhang, Alex Nikolov, and Darsh Wasan*
Department of Chemical and Biological Engineering, Illinois Institute of Technology, Chicago, Illinois 60616, United States
*
S Supporting Information

ABSTRACT: This paper presents the results of imbibition tests using a reservoir crude oil and a reservoir brine solution with a
high salinity and a suitable nanofluid that displaces crude oil from Berea sandstone (water-wet) and single-glass capillaries. The
Illinois Institute of Technology (IIT) nanofluid is specially formulated to survive in a high-salinity environment and is found to
result in an efficiency of 50% for Berea sandstone, compared to 17% using the brine alone at a reservoir temperature of 55 °C.
We also present a direct visual evidence of the underlying mechanism based on the structural disjoining pressure for the crude oil
displacement using IIT nanofluid from the solid substrate in high-salinity brine. These results aid our understanding of the role of
the nanofluid in displacing crude oil from the rock, especially in a high-salinity environment containing Ca2+ and Mg2+ ions.
Results are also reported using Berea sandstone and a nanofluid containing silica nanoparticles.

1. INTRODUCTION More recently, a new view of oil displacement from a solid

Emerging nanotechnologies, such as nanofluids composed of
liquid suspensions of nanoparticles, may soon allow for the
accelerated recovery of hydrocarbons and stimulation fluids
from oil and gas reservoirs.1 Recently, Suleimanov et al.2
reported the results of an experimental study of nanofluids
comprising aqueous suspensions of nonferrous metal nano-
particles (70−150 nm) dispersed in an aqueous solution of an
anionic surfactant (sulfanole-alkyl aryl sodium sulfonate), which
resulted in an increase in the efficiency of the oil displacement
by 35%, compared to that obtained using a surfactant solution
alone in a homogeneous porous medium and 17% in a
heterogeneous porous medium at a temperature of 25 °C. They
used a pure hydrocarbon in their tests. These investigators
concluded that the increase in enhanced oil recovery (EOR)
was due to the decrease in the interfacial tension and change in
the flow characteristic of nanofluids moving from a Newtonian
to non-Newtonian state. They also observed that the oil
wettability practically remained unchanged with the nanofluids.
Babadagli et al.3 investigated capillary imbibition as an oil
recovery mechanism using different surfactants and polymer
solutions as they believed that the reduction in the interfacial
tension between the aqueous phase and oil was the cause of
faster and greater oil recovery. Karimi et al.4 reported that the
increase in the oil recovery using nanofluids composed of
zirconium oxide nanoparticles (24 nm) and a nonionic
surfactant (ethoxylated nonylphenol) resulted primarily from
the wettability alteration of the carbonate rocks from strongly
oil-wet to strongly water-wet. However, they showed that the
wettability alteration requires at least 2 days, while the
maximum oil recovery rate occurs shortly after contact between
the nanofluids and core plugs. In summary, two classic
mechanisms of EOR using nanofluids have been proposed,
namely, the lowering of the interfacial tension between the
aqueous phase and oil phase, and the rock wettability alteration.
In some instances, both mechanisms are believed to be
operating.5−7
substrate using nanoparticle dispersions (nanofluid) with a
wetting agent has been proposed by Wasan and Nikolov.8 The
experiment results and theoretical calculations first reported in
their paper published in the journal Nature are based on a novel
concept of nanoparticle structuring (layering) in the wedge
film. They showed that the nanoparticle (or surfactant micelles)
form two-dimensional (2-D) layered structures in the confines
of the three-phase (solid−oil−aqueous phase) contact region of
a wedge film formed between an oily soil and the solid substrate
(see Figure 1).
The nanoparticle structuring phenomenon gives rise to the
structural disjoining pressure (a force normal to the interface)
in the wedge film and the structural disjoining pressure is
higher near the tip of the wedge than that in the bulk meniscus
(Figure 2). As a result of the pressure increase, the oil/
nanofluid interface moves forward and the nanofluid spreads
over the solid surface, detaching the oily soil (Figure 1). The
magnitude of this pressure depends on the effective nano-
particle volume fraction, particle size, polydispersity, and
particle charge.
Kao et al.9 observed two distinct contact lines: an outer one
(between the oil, solid, and water film) and an inner one
(between the oil, solid, and mixed oil/water film). Wasan and
Nikolov and their co-workers10−14 further noted that the
dynamics of the contact line are dependent on the combination
of the nanoparticle formulation, contact angle, and the capillary
pressure. A suitable combination of these factors accelerates the
spreading of the nanofluid on the solid surface, thereby
detaching the oily soil from the substrate.
Funded in part by FracTech Service, LLC, an exploratory
project was carried out in Dr. Wasan’s laboratory at Illinois
Institute of Technology (IIT), in which the performance of the
Received: January 28, 2014
Revised: April 14, 2014

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Figure 1. Oil−solid displacement driven by film tension gradient and the role of structural forces.
Figure 2. Pressure on the walls of the wedge for a contact angle of 0.5°
at the vertex as a function of the radial distance. Particle volume
fraction, φ = 0.36; particle diameter, d = 10 nm.
IIT nanosized hydrophilic silica dioxide particles (19 nm in
diameter, 10 volume percent in concentration) and Texas crude
oil (33° API) were compared with the microemulsion additive
used in industry. The nanofluid formulation utilizing the novel
mechanism of the structural disjoining pressure by nanoparticle
structuring in the wedge film outperformed the microemulsion
additive by 20% in crude recovery when applied using the same
percentage by volume. Based on these preliminary results,
FracTech (with Holcomb, Wasan, and Nikolov) filed a patent
application on October 15, 2009.15
FracTech has subsequently explored the use of nanoparticle
dispersions in some other treatments such as paraffin,
asphaltene, slurry removal, and recovery hydrocarbon from
tar sands.16,17
The objective of the present research effort at IIT is to
develop nanoparticle formulations that will enhance oil
recovery from the petroleum reservoir. The specific aim of
the work reported here is to develop the nanoparticle
formulation to survive in a high-salinity environment containing
Ca2+ and Mg2+ ions and observe directly the underlying
mechanism based on the structural disjoining pressure concept
using the reservoir crude oil and high salinity brine. The paper
presents the results of the imbibition experiments using two
types of nanofluids: silica nanofluid and IIT nanofluid,18 and
crude oil presaturated Berea sandstone. We also present the
results of the imbibition experiments performed using single
glass capillaries to visualize the oil displacement process.
2. EXPERIMENTAL SECTION
2.1. Materials. 2.1.1. Crude Oil. Crude oil was used for all tests
without further treatment. Properties of the crude oil are given in
Table 1.
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Table 1. Crude Oil Properties
property value
asphaltene content 2.54%
acid number 2.14
density at 25 °C 0.94 (g/cm3)
viscosity of oil at 25 °C 94.88 cP
viscosity of oil at 50 °C 24.58 cP
2.1.2. Brine Solution. Brine was prepared by dissolving different
salts in deionized (DI) water based on the composition of seawater.
The density of brine was 1.02 ± 0.01 g/cm3 and pH 8.5 ± 0.5 at 25
°C. Table 2 lists the composition of the brine used in this study.
Table 2. Brine Composition
component concentration (g/L)
NaCl 18.83
KCl 0.609
MgCl2·6H2O 0.584
CaCl2 0.139
Na2SO4 0.109
NaHCO3 0.203
2.1.3. Silica Nanofluid. A colloidal dispersion of silicon(IV) oxide
in water (40 wt %, Alfa Aesar) was diluted with deionized (DI) water
to prepare the 10 vol % silica nanofluid that had a nominal (geometric)
diameter of 20 nm, with a density of 1.15 g/cm3 and pH of 9.7.
2.1.4. IIT Nanofluid. Since most reservoirs are at a high
temperature, high pressure, and high salinity, silica nanoparticles
dispersions are often unstable and agglomerate in such harsh
environments. IIT nanofluid (patent applied) is not sensitive to
electrolytes or temperature and is stable in the harsh reservoir
environment, which we can choose to formulate the nanofluid. IIT
nanofluid was dissolved in the brine solution to prepare nanoparticle
dispersion. We optimized the wetting characteristics of the solid
surface by using an appropriate amount of a wetting agentsodium
dodecyl sulfatein the IIT nanofluid in order to decrease the solid/
nanofluid/crude oil three-phase contact angle and maximize the
structural force resulting from the confinement of the nanoparticles in
the wedge film.
2.1.5. Berea Sandstone. Berea sandstone (length × width ×
thickness: 7.6 cm × 2.8 cm × 0.6 cm) was obtained from FracTech
with a porosity of 20% and permeability of 400 md.
2.2. IIT Nanofluid Characterization. In order to optimize the
nanofluid formulation and enhance the effect of the structural
disjoining pressure on the crude oil recovery process, the nanofluid
composition was selected using a multistep process.
First, the nanofluid needed have a small nanoparticle size and have a
low polydispersity. High polydispersity results in a decreased value for
the structural disjoining pressure. For example, Chu et al. indicated
that a 20% polydispersity in particle size can result in a 30% decrease
in the structural disjoining pressure.19
Second, the formulated nanofluid should have a high osmotic
pressure (e.g., higher than ∼200 Pa for a 10 vol % nanofluid).
Trokhymchuk et al.20 developed an analytical expression for the
Energy & Fuels Article

structural disjoining pressure (Πst), based on a solution of the 2.2.2. Osmotic Pressure Measurement. The osmotic pressure of
Ornstein−Zernike statistical mechanics equation: the IIT nanofluid is calculated using the value of the second virial
coefficient. The second virial coefficient is calculated based on the
⎧
⎪− P 0<h<d turbidity and refractive index measurement of the nanofluid, which is
Πst(h) = ⎨
⎪ −κh −δ(h − d) represented as Debye plots. Turbidity measurements were made using
⎩ Π 0 cos(ωh + φ2)e + Π1e h>d
the Hach Model 2100A turbidimeter at a temperature of 25 ± 1 °C.
(1) The instrument was calibrated using an aqueous solution of a nonionic
surfactant, NEODOL 25−12, obtained from Shell Chemical. The
where d is the diameter of the nanoparticle, h is the wedge film calibration is shown as a Debye plot in Figure 4.
thickness, and all other parameters in eq 1 (Π0, Π1, ω, φ2, κ, δ) are
fitted as cubic polynomials in terms of the nanofluid volume fraction
(φ). P is the osmotic pressure, which is a function of the nanofluid
volume fraction shown in eq 2:
⎡ 1 + φ + φ2 − φ3 ⎤
P = ρkT ⎢ ⎥
⎣ (1 − φ)3 ⎦ (2)
where ρ is the particle number density, k the Boltzmann constant, and
T the temperature. As shown above, the structural disjoining pressure
and osmotic pressure increase as the nanoparticle volume fraction
increases. A nanofluid with a high osmotic pressure results in a high
structural disjoining pressure.
Third, a nanofluid should have a small solid/nanofluid/oil three-
phase contact angle, in order to maximize the structural force resulting
from the confinement of the nanoparticles in the wedge film.
Kondiparty et al.11 showed that a low contact angle aids in the
spreading of the nanofluid film on a solid surface by confining the
nanoparticles in the film-meniscus region and enhancing the structural
disjoining pressure. From Young’s equation, we also know that a low
oil/nanofluid interfacial tension can decrease the solid−nanofluid−oil
three-phase contact angle. Figure 4. Calibration curve for the turbidity measurements. The
Details for the measurement of the nanofluid size, osmotic pressure, quantity (c − c0) is the concentration of the surfactant present as
and solid−nanofluid−oil three-phase contact angle are shown below. micelles; (τ − τ0) is the excess turbidity of the solution over the
2.2.1. Particle Size Distribution Measurement. The size of the IIT solvent, and H is related to the refractive index of the solvent.
nanofluid was characterized by dynamic light scattering (DLS). DLS
measurements were carried out using a Zetasizer 1000Hs/3000Hs
(Malvern Instruments, Worcestershire, U.K.), which uses a helium− The refractive index measurements were made using a Fisher
neon laser light and integrated analysis software. The temperature was refractometer at a temperature of 25 ± 1 °C.
adjusted to 25 °C, and the scattering angle was set to 90° before We used the slope of the Debye plot to calculate the value of the
measurements were taken. The data were expressed as the z-average second virial coefficient and molecular weight; these were used to
and polydispersity. calculate the osmotic pressure. Figure 5 shows the Debye plot of the
Figure 3 shows that the size of the nanoparticles in the brine is ∼5 IIT nanofluid in brine.
nm and they are monodisperse in size, with a polydispersity of ∼8%. From Figures 4 and 5, we can get the value of the second virial
coefficient, B = 4.3 × 10−4 mol cm3/g2, and the molecular weight, M =
15 915 g/mol. The osmotic pressure is then calculated based on eq 3:
⎛c ⎞
P = RT ⎜ + Bc 2⎟
⎝M ⎠ (3)

Figure 3. IIT nanofluid size distribution by dynamic light scattering

(DLS). Figure 5. Debye plot of IIT nanofluid in brine.

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where P is the osmotic pressure, R the gas constant (R = 8.314 J/(mol
K)), T the temperature, and c the concentration of the nanofluid in the
brine solution (g/cm3).
Figure 6 shows the IIT nanofluid’s osmotic pressure (π) versus the
concentration. We can see that the osmotic pressure is very high; for
Figure 6. Osmotic pressure of IIT nanofluid in brine versus
concentration.
example, a nanofluid at a very low concentration of 2.8 × 10−3 g/cm3
can result in an osmotic pressure as high as 441 Pa.
2.2.3. Measurement of Interfacial Tension and Contact Angle.
The classical method of drop-shape analysis was used to calculate the
oil/brine and oil/nanofluid interfacial tension and the solid−
nanofluid−oil three-phase contact angle. We monitored the shape of
the crude oil drop of 1.2 ± 0.2 μL under a glass surface after
introducing the nanofluid or brine. After the drop-shape profile
stopped changing, indicating a constant interfacial tension, we used a
CCD camera to take pictures. This side-view profile was used to
evaluate the interfacial tension by fitting the Laplace equation to it.
Twenty-one (21) data points from the profile were used for the drop-
shape analysis. The error in the interfacial tension measurement using
our experimental setup was found to be ∼10%. Figure 7 shows the
Figure 7. (a) Side-view illustration and (b) image of crude oil under
the glass slide in the IIT nanofluid at 25 °C. (c) The corresponding
digitalized drop profile, fitted using the Laplace equation.
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side-view image of the crude oil under the glass slide in the IIT
nanofluid and the corresponding experimental drop profile fitted by
the drop profile equation. The contact angle was obtained from the
drop-shape analysis when the contact angle was small, and we
measured the contact angle by the goniometric method using Image
Pro when the contact angle was large.
Table 3 lists the interfacial tension of the oil/nanofluid and oil/brine
interfaces and solid−nanofluid−oil three-phase contact angle on a
glass substrate at 25 ± 1 °C.
Table 3. Interfacial Tension of Oil/Nanofluid and Oil/Brine
and Solid−Nanofluid−Oil Three-Phase Contact Angle on a
Glass Substrate at 25 ± 1 °C
interfacial tension (mN/m) contact angle (deg)
IIT nanofluid 1.4 ± 0.3 1.2 ± 0.2
brine 16 ± 2 74 ± 5
2.3. Reflected Light Interference Microscopy To Directly
Observe Crude Oil Displacement from a Solid Substrate. We
used a recently developed advanced microscope technique11 to directly
observe the spontaneous spreading of the nanofluid on a solid surface.
The spreading dynamics of the nanofluid were monitored using the
digital optical apparatus shown in Figure 8.
Figure 8. Apparatus and experimental setup for monitoring nanofluid
spreading dynamics and micrographs depicting the top and side views
of the crude oil drop.
A crude oil drop of 1.2 ± 0.2 μL was deposited from a syringe under
the lower surface of a hydrophilic, optically smooth, thoroughly
precleaned microscopic glass surface. The glass slide with the crude oil
drop then was immersed in the nanofluid in a transparent experimental
cell (length = 8.5 cm, width = 8.5 cm, height = 3 cm) in a controlled
environment to form a sessile drop. Two square supports were used to
lift the glass slide in order to provide for good visual observation. A
sessile oil drop was formed when the air was displaced by the
nanofluid around the oil drop on the glass surface. The buoyancy in
this configuration presses the drop toward the supporting glass surface.
The dynamics of the crude oil displacement from the glass substrate in
the nanofluid were monitored and recorded at 30 frames per second
by two sets of CCD cameras and video cameras from the top and side
views. This optical setup is unique because it enables the simultaneous
monitoring of the crude oil drop from both the top and side views.
The top view gives the formation and spreading of the nanofluid film.
The position of the spreading edge of the nanofluid film was observed
with time. The side view gives the drop-shape profile.
2.4. Preparation of Crude-Oil-Presaturated Berea Sand-
stone. The Berea sandstones were saturated and aged with crude
oil for 1 week at 55 °C. The oil-saturated sandstones were then taken
out from crude oil and kept vertical in glass jars for another week to
Energy & Fuels Article

remove the crude oil on the surface. The system was kept in a nitrogen
atmosphere to avoid crude oil oxidation during the aging and draining
process.
2.5. Imbibition Test of the Silica Nanofluid into Crude-Oil-
Presaturated Berea Sandstone. Crude-oil-presaturated Berea
sandstones were used in the imbibition experiment to test the
performance of the silica nanofluid and pH 9.7 DI water. The crude oil
recovery experiment was conducted using rectangular glass jars.
Crude-oil-saturated Berea sandstone was placed into a glass jar
containing the test solution (the silica nanofluid or pH 9.7 DI water).
As the test solution imbibes into the Berea sandstone, oil is expelled
and floats on the top of the glass jar. A glass pipet was used to collect
the crude oil and centrifuged at 3000 rpm for 30 min to get rid of the
test solution. The jars were maintained at 25 °C, and oil recovery
(expressed as a percentage of the original oil in place) versus time was
recorded.
2.6. Imbibition Test of IIT Nanofluid into Crude-Oil-
Presaturated Berea Sandstone. Crude-oil-presaturated Berea
sandstones were used in displacement experiments to test the
performance of the IIT nanofluid and brine. The experiment setup
was exactly the same as described above. Figure 10. Imbibition of silica nanofluid and pH 9.7 DI water into
2.7. Crude Oil Displacement from a Glass Capillary. We crude-oil-presaturated Berea sandstone at 25 °C.
conducted crude oil displacement experiments from a glass capillary to
directly visualize the crude oil displacement process from the solid
surface. Glass capillaries (inner diameter (ID) = 300 μm) were water may not be considered as recovered oil, because it is just
purchased from Cole−Parmer, USA. In order to fill the capillaries with oil removed from the Berea sandstone surface. After 15 days,
crude oil, the capillaries were placed vertically in crude oil. Under the we increased the temperature to 55 °C to study the effect of the
capillary pressure, the crude oil was sucked into the capillaries, which temperature on oil recovery. The experimental results showed
were then kept for 2 days in a nitrogen atmosphere. After 2 days, the no significant differences in the amount of oil recovered.
capillaries were placed in a vertical position and immersed in a test However, the silica nanofluid is often unstable in the harsh
solution. The upper part of each capillary was covered with crude oil brine environment, so the dispersion can quickly agglomerate
(Figure 9) to avoid the formation of a second meniscus in the capillary
when the fluid is subjected to changes in pH or encounters
increased salinity and/or temperature. Agglomeration renders
the fluid ineffective and causes severe damage to the formation.
Thus, the development of stable nanofluid dispersions at a high
salinity and high temperature is important. In this study, the
performance of the formulated IIT nanofluid and the crude oil
displacement from oil-presaturated Berea sandstone is shown
below.
3.2. Imbibition of IIT Nanofluid into Oil-Presaturated
Berea Sandstone at 55 °C. Figure 11 shows the results of the
crude oil recovery in oil-presaturated Berea sandstone using the
IIT nanofluid and brine solution. Approximately 50% of the
crude oil was displaced from the Berea sandstone by the
nanofluid compared with 17% by the brine solution.

Figure 9. Experimental setup of crude oil displacement from a single

glass capillary (ID = 300 μm) in the presence of the IIT nanofluid at
55 °C.

(crude oil/nanofluid) and also mimic what actually happens in a crude

oil reservoir during the crude oil displacement process. The
experiment was conducted at 55 °C.

3. RESULTS AND DISCUSSION

3.1. Imbibition Tests Using a Silica Nanofluid at 25 °C.
Figure 10 shows the crude oil recovery versus time from the
displacement experiments with the silica nanofluid and pH 9.7
DI water. As expected, the crude oil displacement performance
in the silica nanofluid is much better than that in the pH 9.7 DI
water. After 15 days, ∼55% of the crude oil was recovered using
the silica nanofluid, compared to only 2% recovered with the Figure 11. Imbibition of the IIT nanofluid and brine solution into
pH 9.7 DI water. The very small amount of oil in the pH 9.7 DI crude-oil-presaturated Berea sandstone at 55 °C.

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In the next section, we investigate the underlying mechanism
of crude oil displacement from a solid surface by using the
reflected-light interference microscopy technique.
3.3. Reflected-Light Interference Microscopy To
Monitor Crude Oil Displacement from a Glass Substrate
by IIT Nanofluid. We first monitored the movement of the
crude oil three-phase contact line by introducing the brine
solution as a control experiment. We noticed that, after
introducing the brine, the outer contact region shrinks rapidly
because of the change in the interfacial tension between the
crude oil and brine. However, after the wedge region is formed
(∼30 s, Figure 12b), the position of the outer contact region
Figure 12. Dynamics of three-phase contact region: (a) photograph
showing the crude oil drop placed on a glass surface in air; (b−d)
photographs taken at increasing times after the addition of the brine
solution ((b) 30 s, (c) 5 min, and (d) 7 min).
does not change with time (see Figures 12b−d). Video Clip 1
(see the Supporting Information) depicts the dynamics of the
macroscopic three-phase contact line during shrinking after
adding the brine solution. The oil drop is not detached,
indicating no spreading of the aqueous film between the oil
drop and the solid surface.
We then studied nanofluid spreading dynamics simulta-
neously from the top view and side view by the optical setup
described above. From the top view, it was observed that after
the IIT nanofluid was added, the original equilibrium three-
phase contact line at the crude oil/glass/air interface began
shrinking rapidly, moving forward to the center of the oil-
wetted area; it was driven by the imbalance of the surface
tension forces at the three-phase contact line. While shrinking,
the three-phase contact line first advanced at a constant rate
(the outer contact line) and then stopped moving after ∼55 s
until a new balance in the surface forces at the three-phase
contact line was established (as shown in Figure 13b). The
Figure 13. Dynamics of the three-phase contact region: (a)
photograph showing crude oil drop placed on a glass surface in air;
(b−d) photographs taken at increasing times after the addition of the
nanofluid ((b) 55 s, (c) 3 min, and (d) 5 min).
Figure 14. Sketch illustrating the nature of the forces operating at the three-phase contact line after introducing the nanofluid.
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shrinking line represents the macroscopic dynamic contact
angle of the oil/glass/nanofluid formulation. Meanwhile, a
second wetting line (inner contact line) in front of the
macroscopic contact line began to slowly advance to oil-wet
region at a constant rate. The line was visually observed as a
distinct second wetting line at the front of the stationary
macroscopic line (Figure 13c). The inner contact line was
formed by the nanofluid film between the oil drop and the solid
surface. The dynamics of the inner line were driven by the
nanofluid structural disjoining pressure. The inner line advances
until the crude oil from the glass plate was displaced by the
nanofluid film (Figure 13d). Video Clip 2 (see Supporting
Information) depicts the dynamics of the macroscopic three-
phase contact line during shrinking and the formation of the
second wetting line. From the side view, when the nanofluid
replaced the air surrounding the oil drop, the drop profile
changed rapidly from a spherical cap to an almost-spherical
shape. The drop-shape profile stopped changing after the outer
contact line ceased to move.
Thus, it can be concluded that the presence of nanoparticles
forming ordered structures in the three-phase contact region
enhances the spreading of the nanofluid, resulting in the
formation of the inner contact line.
The sketch presented in Figure 14 illustrates the nature of
the forces operating at the three-phase contact line during
shrinking after nanofluid introduction.
Porous rock is constructed from different sizes of capillaries
in varying orientations (e.g., a complex network structure).
Since rock pores are nontransparent, it is impossible to monitor
the crude oil displacement process in the pores. In the
following section, we conduct model studies of crude oil
displacement using single glass capillaries to directly visualize
the crude oil displacement process from inside the pore.
3.4. Crude Oil Displacement from a Glass Capillary.
Figure 15 shows the crude oil displacement versus time from a
glass capillary (ID = 300 μm) in the nanofluid and brine
solution at 55 °C. It was observed that 60% of the crude oil was
displaced in the nanofluid, compared to 3% in the brine. The
crude oil displacement from a single capillary versus time was
driven by the buoyancy, capillary, and friction forces. The crude
oil displacement process may be defined as a two-stage process.
During the initial stage, the buoyancy force is dominant and the
rate of crude oil displacement is fast. As time goes on, the rate
of the crude oil displacement decreases and reaches the
equilibrium stage at which the buoyancy force equals the
capillary force plus friction force, causing the oil displacement
process to stop.
As seen from Figures 10, 11, and 15, the shapes of the oil
displacement curves from a glass capillary are similar to those
from the naturally saturated disk rock and crude-oil-
presaturated Berea sandstone. The main differences lie in the
Energy & Fuels
Figure 15. Crude oil displacement from a glass capillary (ID = 300
μm) in the nanofluid and brine solution versus time at 55 °C. The
inset illustrates the forces during crude oil displacement from a glass
capillary.
amount of crude oil recovered and time scale, since the pore
sizes are different. Smaller pore sizes need much more time and
the amount of crude oil recovered is small when compared to a
recovery done with a large pore size.
4. CONCLUSIONS
In this work, the structural disjoining pressure mechanism of
crude oil displacement from a glass substrate and rock was
verified using a newly formulated IIT nanofluid. We studied the
crude oil displacement from a glass surface using the new
nanofluid. The movement of the three-phase contact lines for
the nanofluid was monitored using reflected-light interference
microscopy. The three-phase contact line initially shrinks
rapidly, because of unbalanced capillary forces in the presence
of the nanofluid. However, after a while, when the wedge film
formed, the structural disjoining pressure starts to play a role
and the nanofluid wedge film spreads under a small contact
angle. These results confirm the structural disjoining pressure
mechanism due to the wedge film surface confinement, as first
reported by Wasan and Nikolov.8 It is the first time that this
mechanism of crude oil displacement from a solid substrate is
demonstrated experimentally.
We then employed the structural disjoining pressure
mechanism to the crude oil displacement from the rock
samples. Two types of nanofluid formulations were used to
displace crude oil from the rock samples: silica nanoparticle
suspension and IIT nanofluid. We first conducted crude oil
displacement from oil-presaturated Berea sandstone using silica
nanofluid. Fifty five percent (55%) crude oil was recovered by
silica nanofluid, compared to only 2% recovered using pH 9.7
deionized (DI) water at room temperature. Since the silica
nanoparticle suspension is unstable in harsh reservoir environ-
ments, a more universal IIT nanofluid formulation was then
developed. The IIT nanofluid was formulated with small,
monodispersed nanoparticles with a high osmotic pressure and
small solid/nanofluid/oil three-phase contact angle in order to
enhance the effect of the structural disjoining pressure. We also
tested the newly formulated IIT nanofluid’s performance by
conducting crude oil displacement from oil-presaturated Berea
sandstone. The results showed that 50% crude oil can be
recovered from Berea sandstone by using the IIT nanofluid,
compared to 17% by the brine solution alone. The oil recovery
G dx.doi.org/10.1021/ef500272r | Energy Fuels XXXX, XXX, XXX−XXX
Article
experiments showed clearly that the IIT nanofluid had a good
performance in the harsh saline environment in which silica
nanoparticle suspensions cannot survive.
We finally conducted crude oil displacement from single glass
capillaries to visualize the crude oil displacement process from
the solid surface.
■
*
ASSOCIATED CONTENT
S Supporting Information
Video clip descriptions. This material is available free of charge
via the Internet at http://pubs.acs.org/.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: wasan@iit.edu.
Notes
The authors declare no competing financial interest.
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H dx.doi.org/10.1021/ef500272r | Energy Fuels XXXX, XXX, XXX−XXX