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 nanouid that displaces crude oil from Berea sandstone (water-wet) and single-glass capillaries. The
Illinois Institute of Technology (IIT) nanouid is specially formulated to survive in a high-salinity environment and is found to
result in an eciency 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 nanouid from the solid substrate in high-salinity brine. These results aid our understanding of the role of
the nanouid 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 nanouid containing silica nanoparticles.

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

Emerging nanotechnologies, such as nanouids composed of
liquid suspensions of nanoparticles, may soon allow for the
accelerated recovery of hydrocarbons and stimulation uids
from oil and gas reservoirs.1 Recently, Suleimanov et al.2
reported the results of an experimental study of nanouids
comprising aqueous suspensions of nonferrous metal nano-
particles (70150 nm) dispersed in an aqueous solution of an
anionic surfactant (sulfanole-alkyl aryl sodium sulfonate), which
resulted in an increase in the eciency 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 ow characteristic of nanouids moving from a Newtonian
to non-Newtonian state. They also observed that the oil
wettability practically remained unchanged with the nanouids.
Babadagli et al.3 investigated capillary imbibition as an oil
recovery mechanism using dierent 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 nanouids 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 nanouids and core plugs. In summary, two classic
mechanisms of EOR using nanouids 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.57
substrate using nanoparticle dispersions (nanouid) with a
wetting agent has been proposed by Wasan and Nikolov.8 The
experiment results and theoretical calculations rst reported in
their paper published in the journal Nature are based on a novel
concept of nanoparticle structuring (layering) in the wedge
lm. They showed that the nanoparticle (or surfactant micelles)
form two-dimensional (2-D) layered structures in the connes
of the three-phase (solidoilaqueous phase) contact region of
a wedge lm 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 lm 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/
nanouid interface moves forward and the nanouid spreads
over the solid surface, detaching the oily soil (Figure 1). The
magnitude of this pressure depends on the eective 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 lm) and an inner one
(between the oil, solid, and mixed oil/water lm). Wasan and
Nikolov and their co-workers1014 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 nanouid 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. Wasans 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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Energy & Fuels
Figure 1. Oilsolid displacement driven by lm 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, = 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 nanouid formulation utilizing the novel
mechanism of the structural disjoining pressure by nanoparticle
structuring in the wedge lm 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) led a patent
application on October 15, 2009.15
FracTech has subsequently explored the use of nanoparticle
dispersions in some other treatments such as paran,
asphaltene, slurry removal, and recovery hydrocarbon from
tar sands.16,17
The objective of the present research eort at IIT is to
develop nanoparticle formulations that will enhance oil
recovery from the petroleum reservoir. The specic 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 nanouids: silica nanouid and IIT nanouid,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 dierent
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
MgCl26H2O 0.584
CaCl2 0.139
Na2SO4 0.109
NaHCO3 0.203
2.1.3. Silica Nanouid. 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 nanouid 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 Nanouid. 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 nanouid (patent applied) is not sensitive to
electrolytes or temperature and is stable in the harsh reservoir
environment, which we can choose to formulate the nanouid. IIT
nanouid 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 agentsodium
dodecyl sulfatein the IIT nanouid in order to decrease the solid/
nanouid/crude oil three-phase contact angle and maximize the
structural force resulting from the connement of the nanoparticles in
the wedge lm.
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 Nanouid Characterization. In order to optimize the
nanouid formulation and enhance the eect of the structural
disjoining pressure on the crude oil recovery process, the nanouid
composition was selected using a multistep process.
First, the nanouid 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 nanouid should have a high osmotic
pressure (e.g., higher than 200 Pa for a 10 vol % nanouid).
Trokhymchuk et al.20 developed an analytical expression for the
Energy & Fuels Article

structural disjoining pressure (st), based on a solution of the 2.2.2. Osmotic Pressure Measurement. The osmotic pressure of
OrnsteinZernike statistical mechanics equation: the IIT nanouid is calculated using the value of the second virial
coecient. The second virial coecient is calculated based on the

P 0<h<d turbidity and refractive index measurement of the nanouid, which is
st(h) =
h (h d) represented as Debye plots. Turbidity measurements were made using
0 cos(h + 2)e + 1e 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 2512, obtained from Shell Chemical. The
where d is the diameter of the nanoparticle, h is the wedge lm calibration is shown as a Debye plot in Figure 4.
thickness, and all other parameters in eq 1 (0, 1, , 2, , ) are
tted as cubic polynomials in terms of the nanouid volume fraction
(). P is the osmotic pressure, which is a function of the nanouid
volume fraction shown in eq 2:
1 + + 2 3
P = kT
(1 )3 (2)
where 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 nanouid with a high osmotic pressure results in a high
structural disjoining pressure.
Third, a nanouid should have a small solid/nanouid/oil three-
phase contact angle, in order to maximize the structural force resulting
from the connement of the nanoparticles in the wedge lm.
Kondiparty et al.11 showed that a low contact angle aids in the
spreading of the nanouid lm on a solid surface by conning the
nanoparticles in the lm-meniscus region and enhancing the structural
disjoining pressure. From Youngs equation, we also know that a low
oil/nanouid interfacial tension can decrease the solidnanouidoil
three-phase contact angle. Figure 4. Calibration curve for the turbidity measurements. The
Details for the measurement of the nanouid size, osmotic pressure, quantity (c c0) is the concentration of the surfactant present as
and solidnanouidoil three-phase contact angle are shown below. micelles; ( 0) 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.
nanouid 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 coecient 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 nanouid 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
coecient, B = 4.3 104 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 nanouid size distribution by dynamic light scattering

(DLS). Figure 5. Debye plot of IIT nanouid 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 nanouid in the
brine solution (g/cm3).
Figure 6 shows the IIT nanouids osmotic pressure () versus the
concentration. We can see that the osmotic pressure is very high; for
Figure 6. Osmotic pressure of IIT nanouid in brine versus
concentration.
example, a nanouid at a very low concentration of 2.8 103 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/nanouid interfacial tension and the solid
nanouidoil three-phase contact angle. We monitored the shape of
the crude oil drop of 1.2 0.2 L under a glass surface after
introducing the nanouid or brine. After the drop-shape prole
stopped changing, indicating a constant interfacial tension, we used a
CCD camera to take pictures. This side-view prole was used to
evaluate the interfacial tension by tting the Laplace equation to it.
Twenty-one (21) data points from the prole 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 nanouid at 25 C. (c) The corresponding
digitalized drop prole, tted using the Laplace equation.
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side-view image of the crude oil under the glass slide in the IIT
nanouid and the corresponding experimental drop prole tted by
the drop prole 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/nanouid and oil/brine
interfaces and solidnanouidoil three-phase contact angle on a
glass substrate at 25 1 C.
Table 3. Interfacial Tension of Oil/Nanouid and Oil/Brine
and SolidNanouidOil Three-Phase Contact Angle on a
Glass Substrate at 25 1 C
interfacial tension (mN/m) contact angle (deg)
IIT nanouid 1.4 0.3 1.2 0.2
brine 16 2 74 5
2.3. Reected 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 nanouid on a solid surface.
The spreading dynamics of the nanouid were monitored using the
digital optical apparatus shown in Figure 8.
Figure 8. Apparatus and experimental setup for monitoring nanouid
spreading dynamics and micrographs depicting the top and side views
of the crude oil drop.
A crude oil drop of 1.2 0.2 L 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 nanouid 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
nanouid around the oil drop on the glass surface. The buoyancy in
this conguration presses the drop toward the supporting glass surface.
The dynamics of the crude oil displacement from the glass substrate in
the nanouid 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 nanouid lm.
The position of the spreading edge of the nanouid lm was observed
with time. The side view gives the drop-shape prole.
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 Nanouid into Crude-Oil-
Presaturated Berea Sandstone. Crude-oil-presaturated Berea
sandstones were used in the imbibition experiment to test the
performance of the silica nanouid 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 nanouid or pH 9.7 DI water).
As the test solution imbibes into the Berea sandstone, oil is expelled
and oats 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 Nanouid into Crude-Oil-
Presaturated Berea Sandstone. Crude-oil-presaturated Berea
sandstones were used in displacement experiments to test the
performance of the IIT nanouid and brine. The experiment setup
was exactly the same as described above. Figure 10. Imbibition of silica nanouid 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 m) were water may not be considered as recovered oil, because it is just
purchased from ColeParmer, USA. In order to ll 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 eect 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 signicant dierences in the amount of oil recovered.
capillaries were placed in a vertical position and immersed in a test However, the silica nanouid 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 uid is subjected to changes in pH or encounters
increased salinity and/or temperature. Agglomeration renders
the uid ineective and causes severe damage to the formation.
Thus, the development of stable nanouid dispersions at a high
salinity and high temperature is important. In this study, the
performance of the formulated IIT nanouid and the crude oil
displacement from oil-presaturated Berea sandstone is shown
below.
3.2. Imbibition of IIT Nanouid 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 nanouid and brine solution. Approximately 50% of the
crude oil was displaced from the Berea sandstone by the
nanouid compared with 17% by the brine solution.

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

glass capillary (ID = 300 m) in the presence of the IIT nanouid at
55 C.

(crude oil/nanouid) 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 Nanouid at 25 C.
Figure 10 shows the crude oil recovery versus time from the
displacement experiments with the silica nanouid and pH 9.7
DI water. As expected, the crude oil displacement performance
in the silica nanouid 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 nanouid, compared to only 2% recovered with the Figure 11. Imbibition of the IIT nanouid 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
reected-light interference microscopy technique.
3.3. Reected-Light Interference Microscopy To
Monitor Crude Oil Displacement from a Glass Substrate
by IIT Nanouid. We rst 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; (bd)
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 12bd). 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 lm between the oil
drop and the solid surface.
We then studied nanouid 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 nanouid 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 rst 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;
(bd) photographs taken at increasing times after the addition of the
nanouid ((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 nanouid.
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shrinking line represents the macroscopic dynamic contact
angle of the oil/glass/nanouid 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 nanouid lm between the oil drop and the solid
surface. The dynamics of the inner line were driven by the
nanouid structural disjoining pressure. The inner line advances
until the crude oil from the glass plate was displaced by the
nanouid lm (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 nanouid
replaced the air surrounding the oil drop, the drop prole
changed rapidly from a spherical cap to an almost-spherical
shape. The drop-shape prole 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 nanouid, 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 nanouid introduction.
Porous rock is constructed from dierent 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 m) in the nanouid and brine
solution at 55 C. It was observed that 60% of the crude oil was
displaced in the nanouid, 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 dened 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 dierences lie in the
Energy & Fuels
Figure 15. Crude oil displacement from a glass capillary (ID = 300
m) in the nanouid 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 dierent. 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
veried using a newly formulated IIT nanouid. We studied the
crude oil displacement from a glass surface using the new
nanouid. The movement of the three-phase contact lines for
the nanouid was monitored using reected-light interference
microscopy. The three-phase contact line initially shrinks
rapidly, because of unbalanced capillary forces in the presence
of the nanouid. However, after a while, when the wedge lm
formed, the structural disjoining pressure starts to play a role
and the nanouid wedge lm spreads under a small contact
angle. These results conrm the structural disjoining pressure
mechanism due to the wedge lm surface connement, as rst
reported by Wasan and Nikolov.8 It is the rst 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 nanouid formulations were used to
displace crude oil from the rock samples: silica nanoparticle
suspension and IIT nanouid. We rst conducted crude oil
displacement from oil-presaturated Berea sandstone using silica
nanouid. Fifty ve percent (55%) crude oil was recovered by
silica nanouid, 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 nanouid formulation was then
developed. The IIT nanouid was formulated with small,
monodispersed nanoparticles with a high osmotic pressure and
small solid/nanouid/oil three-phase contact angle in order to
enhance the eect of the structural disjoining pressure. We also
tested the newly formulated IIT nanouids 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 nanouid,
compared to 17% by the brine solution alone. The oil recovery
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experiments showed clearly that the IIT nanouid had a good
performance in the harsh saline environment in which silica
nanoparticle suspensions cannot survive.
We nally 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 nancial interest.
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