SPE-187165-MS

Nanoparticle-Stabilized Foams for High-Temperature, High-Salinity Oil

Reservoirs

Robin Singh and Kishore K. Mohanty, The University of Texas at Austin

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, USA, 9-11 October 2017.

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
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Abstract
The goal of this work is to develop foams stabilized by a combination of nanoparticles and surfactants for
high-temperature, high-salinity reservoirs. Two types of silica nanoparticles (LNP1, LNP2) with different
grafted low molecular weight ligands/polymers were used. First, aqueous stability tests of these formulations
were performed at high-temperature (80 °C) and high-salinity conditions (8 wt% NaCl and 2 wt% CaCl2).
The screened nanoparticles were used in combination with a surfactant. Second, bulk foam tests were
performed to evaluate their foaming performance in bulk. Finally, oil displacement experiments were
conducted in an in-house, custom-built 2D sand pack with flow visualization. The sand pack had two layers
of silica sand — top layer with 40-70 mesh and bottom layer with 100-120 mesh, which resulted in a
permeability contrast of 6:1. Water flood with subsequent foam flood was performed. The grafting of low-
molecular-weight polymers/ligands on silica nanoparticle surfaces resulted in steric stabilization under high-
temperature and high-salinity conditions. In the oil displacement experiments in the layered sand packs,
the water flood recoveries were low (~33% OOIP) due to channeling in the top high-permeability region,
leaving the bottom low-permeability region completely unswept. Foam flooding with just the surfactant
leads to a drastic improvement in sweep efficiency. It resulted in an incremental oil recovery as high as
43.3% OOIP. Different cross-flow behaviors were observed during foam flooding. Significant cross-flow
of oil from low-permeability region to high-permeability region was observed for the case of surfactant.
Conversely, the LNP2-surfactant blend resulted in no crossflow from the low permeability layer with
complete blocking of the high-permeability region due to the formation of in-situ emulsion. Such selective
plugging of high-perm channels via nanoparticles with optimum surface coating has significant potential
in recovering oil from heterogeneous reservoirs.

Introduction
Gas enhanced oil recovery is one of the widely applied EOR methods. The displacement efficiency of
gas injection is excellent, if the reservoir pressure is above the minimum miscibility pressure where gas is
completely miscible with oil (Orr, 2007). However, due to inherent low viscosity and density of gases, gas
injection leads to viscous instability and gravity override. Reservoir heterogeneity further contributes to poor
volumetric sweep efficiency (Lake et al., 1986). Foam is a promising tool to improve sweep efficiency in
2 SPE-187165-MS

gas floods (Rossen, 1996). It can reduce the mobility of gas by several orders of magnitude by increasing the
apparent viscosity of gas (Hirasaki and Lawson, 1985) while the liquid phase mobility remains unchanged
(Eftekhari and Farajzadeh, 2017). Moreover, gas trapping further reduce the gas mobility during foam flow
in porous media (Tang and Kovscek, 2006). The concept of foam was first introduced by Boud and Holbrook
in 1958. Since then, several successful foam field trials has been reported (Hoefner et al., 1995; Rossen et
al., 2017; Skauge et al., 2002).
Foam stability under high-temperature and/or high-salinity (HTHS) conditions is quite challenging
because of two main reasons. First, foam strength typically decreases with increase in temperature. This
is because of reduction of liquid phase viscosity at higher temperatures, which expedites the liquid
drainage process in foam lamellae. Second, the aqueous stability of surfactants limits their use under HTHS
conditions. Several researchers have investigated novel surfactant-stabilized foams for HTHS conditions.
Chen et al. (2015) reported CO2-in-water (C/W) foam using a non-ionic surfactant with a high degree of
ethoxylation. Similarly, Cui et al. (2016) studied Ethomeen C12 surfactant-stabilized C/W foam for HTHS
applications in carbonates. This surfactant was only stable at lower pH (close to 4) as it required complete
protonation of C12 to be soluble. Xue et al. (2015) reported viscous C/W foams at a high salinity of 14.6%
TDS brine at 120 °C using CO2-soluble ionic surfactants. Recently, Alzobaidi et al. (2017) reported highly
stable C/W foams of viscosity more than 100 cp using zwitterionic surfactants at 120 °C. The high apparent
viscosity of the foam was attributed to the viscoelastic nature of the surfactant. Such surfactant-stabilized
foams could potentially be made more robust using nanoparticles with specific surface coatings.
In the last decade, there is a recent surge in the research of nanomaterials for oilfield applications. It
includes use of nanoparticle in Foam EOR (Emrani et al., 2017; Kim et al., 2016; Singh et al., 2015),
nanofluid EOR (Hendraningrat et al., 2013; Zhang et al., 2014), hydraulic fracturing fluids (Barati et
al., 2012), wettability alteration (Karimi et al., 2012) and drilling fluids (Zakaria et al., 2012). One of
the advantages of nanoparticles is that they could be grafted with different functional groups to impart
desirable characteristics for subsurface applications. These include viscosity increment (Ponnapati et al.,
2011), improved aqueous stability (Griffith and Daigle, 2017), and desired surface-wettability (Panthi et
al., 2017). It makes the nanoparticles quite lucrative for oilfield applications. However, colloidal stability
of nanoparticles under high temperature and high salinity conditions is a challenge. According to the
Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, the sum of attractive van der Waals (vdW) forces
and repulsive electrostatic forces dictates the stability of the nanoparticles (Israelachvili, 2015). The
presence of high amount of monovalent and divalent ions screens the inherent charges on nanoparticles,
which reduces the electrostatic repulsion between particles. The Debye length, which is a measure of the
distance over which the electrostatic repulsion is felt in the solution, decreases with an increase in salinity
(Eslahian et al., 2014). For example, for a salinity of 150 mM, the Debye length is only 0.8 nm (Jiang
et al., 2009). In such cases, nanoparticles aggregate due to the van der Waals forces (Elimelech et al.,
2013). Moreover, if the nanoparticles are negatively charged such as bare silica nanoparticles at pH 7, the
presence of oppositely charged ions such as Ca+2 could result in interparticle bridging which expedites the
nanoparticle aggregation (Wuelfing et al., 2001).
Several approaches can be adopted to stabilize nanoparticles under harsh conditions. One such approach
is steric stabilization which involves grafting macromolecules or ligands on the nanoparticle surface
(Worthen et al., 2016; Yang and Liu, 2010). The presence of these ligands results in steric hindrance, which
reduces the probability of two nanoparticles to collide or interact. Additionally, the ligands should have the
ability to solvate under the given harsh conditions in aqueous media and form hydration shell around the
nanoparticles. Such ligands can provide steric stabilization to the core nanoparticles (Napper, 1983).
In our previous study (Singh and Mohanty, 2015), we reported the synergistic effects of the mixture of
hydrophilic silica nanoparticles and anionic surfactant on foam stabilization in both bulk and homogeneous
porous media. We demonstrated that as the concentration of nanoparticles increases, the mobility reduction
SPE-187165-MS 3

factor of surfactant-NP foam in homogeneous Berea core increases up to a factor of two. Recently, we
showed that such synergy is even more pronounced in a heterogeneous layered sand pack system by
performing visualization experiments (Singh and Mohanty, 2017). These experiments allowed us to identify
different cross-flow behavior governing the foam flow in such heterogeneous media such as flow diversion
from high-perm to low-perm regions (Ayesh et al., 2017). In this work, the first objective was to investigate
the stability of two types of silica nanoparticles (grafted with different ligands) under high-temperature
and high-salinity conditions. The screened nanoparticle system was then evaluated as a foam stabilizer in
bulk and porous media. Finally, we evaluated and visualized the foaming performance of ligand-grafted
nanoparticles along with anionic surfactant in layered, heterogeneous sand packs.

Methodology
Materials
Two different types of surface-modified silica nanoparticles were used in the study. These
nanoparticles were coated with two different low-molecular-weight ligands - polyethylene glycol and (3-
Glycidyloxypropyl)trimethoxysilane, (GLYMO). These nanoparticles are referred in this paper as LNP1
and LNP2. The sizes of LNP1 and LNP2 in DI water at pH 7 were 20 and 12 nm, respectively. An
anionic surfactant with a sulfonate head group (68% active) was used in these experiments. Sand (US
Silica) of two different mesh sizes, 100-120# and 40-70#, were used to prepare heterogeneous sand packs.
Crude oil was obtained from a reservoir, and it had a viscosity of 32 cp at 25 °C and density of 0.825
g/cm3. The viscosity was measured using an AR-G2 rheometer from TA instruments. Sodium chloride
(Fisher Chemical), calcium chloride (Sigma-Aldrich) and nitrogen (research grade, Matheson) were used
as received. Ultrapure water with a resistivity greater than 18.2 MΩ-cm was used to prepare brine solutions.
The zeta-potential of nanoparticles solutions were characterized with a Delsa Nano analyzer.

Aqueous Stability of Nanoparticles and Surfactants

The aqueous stability of nanoparticles or surfactant solutions were evaluated under varying salinity
conditions at three different temperatures 25, 60 and 80 °C. To prevent evaporation of the samples, custom-
made borosilicate glass vials were used. These vials were sealed from the top using Teflon-threaded caps
and chemical-resistant O-rings. 10 ml of 0.5 wt% nanoparticles solution with varying salinity (of 1 to 8 wt
% NaCl and API brine) were taken in the vials and placed in different ovens operating at 25, 60 and 80 °C.
The aqueous stability of the samples was monitored visually for two months.

Bulk Foam Stability

The morphology of foam flowing in bulk is different from foam in porous media. The bubble sizes of foam,
which is a key foam characterization parameter, in bulk is the order of magnitude smaller than the size of
the medium holding it, whereas the bubble sizes are similar to pore sizes for the cases of foam flow in
porous media. Albeit these differences, bulk foam stability tests are often conducted as a basic screening
tool to compare and evaluate foaming tendency of different formulations (Singh and Mohanty, 2016a). One
of such common tests is the static foam test in which decay of foam volume with time is monitored (Singh
and Mohanty, 2016b). In this work, bulk foam stability of nanoparticle-surfactant mixtures is evaluated at
25 °C and 80 °C. The salinity of the system was kept constant; API brine (8wt% NaCl + 2wt% CaCl2) was
used. A 10-ml sample was taken in a glass vial and was sealed using a PTFE-lined cap. The sample was
kept in an oven for more than 3 hours to attain thermal equilibrium before making foam. The vial was hand
shaken vigorously for 15 seconds to generate foam. The foam height (above the drained liquid phase) was
recorded as a function of time.
4 SPE-187165-MS

Preparation of 2D Heterogeneous Sandpack

Foams can divert flow from high permeability regions to low permeability regions in heterogeneous porous
media. The foam flow phenomenon in a heterogeneous medium is much complex as compared to foam
flow in 1D, homogenous system such as cores which are typically studied in the literature. To understand
and visualize the foam flow dynamics in a heterogeneous medium, a simplified layered sand pack model
was fabricated. An in-house sand pack holder made of stainless steel was designed with one face made of a
transparent plate (thickness: 0.75 inches) for visualization. The dimension of the interior of the holder was
5.4 inch × 2.9 inch × 1 inch. There were three injection ports on the left side and three production ports on
the right side, as shown in Figure 1. Stainless steel screens (400 mesh) were welded on these ports to prevent
sand flow. The holder was packed with two layers of silica sand: the top layer using 40-70 mesh and the
bottom layer using 100-120 mesh. The permeability of the top layer was 22.6 Darcy while that of the bottom
layer was 3.8 Darcy. Thus, the permeability contrast was about 6:1. The layer permeability was measured
by flowing water through a 1D tube (1 ft long; 1 inch in diameter) packed with each sand. The permeability
and the porosity of the two-layer system were measured to be 15.7 Darcy and 31%, respectively.

Figure 1—Schematic of the apparatus for oil displacement experiments

Oil Displacement Experiments

Foam flow experiments were conducted to investigate the dynamics of foam flow in a heterogeneous
porous medium in the presence of reservoir crude oil. Foams were stabilized by either a surfactant or a
surfactant-nanoparticle blend. Petrophysical properties such as porosity and permeability of the sand pack
were determined before performing the vacuum saturation with crude oil. The conventional technique of
oil saturation is to displace the brine-saturated porous media with crude oil at a constant high pressure.
However, due to the high permeability contrast (6:1) in the present system, it was not possible to achieve
high initial oil saturation using this technique. Therefore, the initial oil saturation was obtained by vacuum
saturation which resulted in 100% initial oil saturation for every case.
Figure 1 shows the experimental schematic. Two series-D syringe pumps from Teledyne ISCO (Lincoln,
NE) were used in the setup which is capable of low injection rates (as low as 0.001 cc/min). The apparatus
was built to co-inject nitrogen gas and aqueous (brine/surfactant/surfactant-nanoparticle blend) solution
SPE-187165-MS 5

through a sand pack (0.6-inch diameter and 6-inch long) to ensure proper mixing and foam generation. The
pre-generated foam was then injected through the three ports on the left side of the heterogeneous sand
pack. The downstream pressure of the experiment was maintained by a back-pressure regulator (Equilibar,
NC and Swagelok, OH) at 110 psi which was installed downstream of the sandpack. The experiment was
performed at the room temperature. After the crude oil saturation, the whole setup was pressurized with a
back pressure of 110 psi and more than 0.5 PV of oil was injected. The brine flood was then conducted at
10 ft/D for 4 PV until no oil was produced. Nitrogen gas and surfactant or surfactant-NP blend were then
co-injected through the foam generator to make a foam of 80% quality (volume fraction of gas). This foam
was injected into the two-layer sand pack at an average interstitial velocity of 4 ft/D. This pre-generated
foam was injected through the ports on the left side of the heterogeneous sandpack for more than 20 PV.
Oil recovery and pressure drops were monitored at each step. The displacement of crude oil by injection
fluid was captured using a microscope. The pressure drop across the 2D sandpack was measured using
Rosemount differential pressure transducers. An automated data acquisition system (LabView, National
Instruments) was used to record the pressure.

Results
Aqueous Stability of Nanoparticles and Surfactants
First, the aqueous stability of two different nanoparticles was evaluated under varying salinity conditions
at three different temperatures 25, 60 and 80 °C. Figure 2 shows the stability of both the nanoparticles.
Both nanoparticles were stable for the wide range of salinity at room temperature (25 °C). The stability and
salt tolerance of both nanoparticles decreased with an increase in the temperature. LNP1 was found stable
only below 2 wt% NaCl and 1 wt% NaCl salinity at 60 °C and 80 °C, respectively. At higher salinities,
precipitation of the nanoparticles was observed indicating severe aggregation. However, LNP2 was found
to be more stable than LNP1 with a salt tolerance of 8 wt% at 60 °C and 2 wt% at 80 °C. This shows that the
GLYMO surface coating was more efficient than PEG surface coating in providing steric stabilization of
the silica nanoparticles under high salinity. Based on these results, LNP2 nanoparticles were chosen in the
subsequent experiments. Note that the pH of the LNP2 solutions was 8.5 and was not modified in this test.

Figure 2—Aqueous stability of (a) LNP1 and (b) LNP2 at different temperatures and varying
salinity: hollow markers and filled markers represent clear solution and precipitation, respectively.
6 SPE-187165-MS

The LNP2 nanoparticles are highly negatively charged under natural pH of 8.5 as confirmed via zeta
potential measurements. A decrease in surface charge (less negative) of the nanoparticle (to a limit) is
desirable as it would reduce the interaction with the divalent ions and thus increasing stability and salt
tolerance of the system. A decrease in pH of the solutions is expected to reduce the surface charge of the
system and hence can increase the stability of the nanoparticles. Therefore, the pH of LNP2 solutions was
varied from 8.5 to 2. The salinity of the solutions was kept constant and equal to API brine (8 wt% NaCl
and 2 wt% CaCl2) which represents a high salinity brine with high hardness. Figure 3 shows the results
of the aqueous stability of the nanoparticles after two months. The solutions were found to be completely
clear for the cases of pH 2 and 3.5 at the three temperatures. For pH 5 and 6.5, cloudy solutions were
observed indicating some aggregations of nanoparticles at 60 and 80 °C. For higher pH such as 7 and 8.5,
precipitations of nanoparticles were observed indicating poor aqueous stability at 60 and 80 °C.

Figure 3—Aqueous stability of LNP2 at varying pH and constant API brine salinity (8 wt% NaCl + 2wt% CaCl2). The hollow
markers, semi-filled markers, and filled markers represent a clear solution, cloudy solution, and precipitation, respectively.

Zeta potential of the LNP2 system was then measured as a function of pH to better understand this
stability trend. The zeta potential of these nanoparticles at their natural pH of 8.5 was −30 mV. As the pH of
the solution was reduced, the magnitude of zeta potential was reduced (becomes less negative) from −30 to
−7 mV corresponding to pH 8.5 and 2, respectively, as shown in Figure 4. Such reduction in particle charge
reduces the interaction with divalent ions such as Ca+2 and increases nanoparticle stability. For very high
salinity and high temperature conditions, these nanoparticles are stable at low pH < 3.5. The equilibrium
in-situ pH of the reservoir fluids during carbon dioxide flooding are reported to be less than 4. Thus, these
nanoparticles could be used to stabilize carbon dioxide-in-water foams under reservoir conditions.
SPE-187165-MS 7

Figure 4—Zeta potential of LNP2 as a function of pH

Bulk Foam Stability

Based on the aqueous stability results, the LNP2 nanoparticles were chosen for further foam studies in bulk
and porous media. Static foam test is the most common bulk foam stability tests. Recently, Jones et al. (2016)
reported a good correlation between bulk foam stability and apparent foam viscosity in the absence of oil.
The LNP2 nanoparticles, when mixed in a vial in the presence of air, does not have any affinity to form foam
irrespective of the salt concentration. It is due to the hydrophilic nature of the nanoparticles (even though
the coating has small hydrophobic chains). Therefore, to stabilize foam, an anionic surfactant was used in
addition. The objective of the static foam tests in the present study was to investigate an optimum surfactant
concentration, if any, to be used in the blend of LNP2 and surfactant blend. In this test, the total nanoparticle
concentration was kept constant at 0.5 wt%, and salinity was API brine. The surfactant concentration was
varied from 0 wt% to 1 wt%. A small amount of blend was taken in a glass vial and was shaken vigorously
for 15 seconds to make static foam. The decay in foam height was recorded at 25 ° C and 80 °C.
Figure 5 shows the static foam in the vials with varying concentration of surfactant at time t = 0 minutes.
Figure 5a shows the vial with only 0.5 wt% LNP2 nanoparticles solutions. It can be seen that nanoparticles
alone show negligible foaming tendency. The initial foam height, which is often referred in the literature
as foamability, increases with the increase in surfactant concentration. Note that the CMC of this surfactant
is close to 0.125 wt% as measured in a previous study (Panthi et al., 2017). Figure 6 shows the decay
of foam heights at 25 °C (Figure 6a) and 80 °C (Figure 6b). The foam heights were normalized with
respect to maximum possible height (which is the maximum foam height for the case of 1 wt% surfactant
at t=0 minutes) to obtain relative foam height. Several observations can be made from the plots. Foam
strength increases monotonically with the increase in surfactant concentration and no optimum surfactant
concentration was observed for foam stability as evident from foamability as well as foam decay behavior.
Note that the decay of foam was increased significantly at the higher temperature of 80 °C as compared
to 25 °C. Based on this test, a surfactant concentration of 0.5 wt% was chosen for foam flooding in the
subsequent oil displacement experiments.
8 SPE-187165-MS

Figure 5—Static foam at time t = 0 min at 25 °C formed using 0.5 wt% LNP2 nanoparticles and increasing concentrations
of surfactant. The concentration of surfactant was (a) 0 wt%, (b) 0.0625 wt%, (c) 0.125 wt%, (d) 0.25 wt%, (e) 0.5 wt
%, and (f) 1 wt%. The salinity was constant in each sample and equal to API brine (8 wt% NaCl and 2 wt% CaCl2)

Figure 6—Static foam test with formulations containing 0.5 wt% LNP2 nanoparticles and varying concentration of surfactant
at (a) 25 °C and (b) 80 °C. The salinity was constant in each sample and equal to API brine (8 wt% NaCl and 2 wt% CaCl2)

Oil Displacement Experiments

The oil displacement experiments were performed to evaluate and visualize foaming performance of the
surfactant and the surfactant-nanoparticle mixture under high salinity conditions. Since the visualization
required the use of transparent acrylic sheet whose pressure/temperature rating was not very high, the
experiments were performed under low pressure (~110 psi) and room temperature. As high-pressure CO2,
which would have yielded an equilibrium pH<4, could not be used, the pH of the aqueous phase was adjusted
using a weak acid. Before conducting the oil displacement experiments, another independent experiment
was performed in which API brine of pH 3.5 was injected in a brine-saturated (pH 7) sandpack. When HCL
was used to lower the pH of the injection brine, the effluent pH was found to be close to 5.5 even after
several pore volumes of injection. This was possibly because of strong reactivity of HCL acid with the
SPE-187165-MS 9

minerals present in sand grains. However, when citric acid was used, the pH was able to propagate along
the sand pack, and the effluent pH was found to be 3.5. Therefore, in these experiments, citric acid was
used to adjust the pH.
Flood 1 was conducted with the surfactant as the foaming agent. The sandpack was vacuum-saturated
with crude oil which resulted in the initial oil saturation of 100%. Figure 7 shows the injection schedule,
cumulative oil recovery (secondary y-axis) and overall pressure drop (primary y-axis) across the sandpack.
First, brine flood was conducted at 10 ft/D to mimic a waterflood in a reservoir. It was continued for more
than 4 PV until no oil was produced. The pH of injected brine was adjusted to 3.5 using citric acid. The
waterflood oil recovery was 33.6 %OOIP (original oil in place), and oil saturation was reduced to 66.4%.
The pressure drop during water flood was very low (0.04 psi). The oil recovery during this stage was low
due to channeling of injected brine from the top high permeability layer. Note that the permeability contrast
between the top and bottom layer was 6:1. Figure 8a shows the oil displacement profile after 4 pore volume
of brine injection. Although the mobility ratio of brine (1 cp) displacing oil (32 cp) is unfavorable, the
sweep in the top layer was good (visually), as seen from the Figure 8a, because of the high permeability of
the layer. The pH of the effluent was tested at the end of water flood, and it was close to 3.5. Then, foam
flooding was performed at 4ft/D using the anionic surfactant as the foaming agent. The formulation has 0.5
wt% surfactant in API brine. The pH was lowered to 3.5 using the citric acid. The foam quality (volume
fraction of gas) was kept constant at 80%.

Figure 7—Pressure drop profile (black, left axis) and cumulative oil recovery (blue, right axis) for Flood 1
10 SPE-187165-MS

Figure 8—Oil distributions during Flood 1 (A to H) and Flood 2 (I to P) at different pore volumes of foam injection
SPE-187165-MS 11

Figure 8 B-H shows the oil displacement profiles during foam injection; injected foam PV is indicated
(does not include water flood). In the first 2 PV of foam injection, the foam only swept the top layer only
(Figure 8b) and recovered about 11.5 % OOIP oil. It is to be noted that the even though the top layer looked
clean after brine flood visually, it has a significant amount of residual oil left which was recovered by foam
in the first 3 PV (7 PV including water flood). The pressure drop during this stage increased (as compared
to brine injection) indicating an increase in apparent foam viscosity. Figure 8C shows how foams start
diverting injection fluid from the high permeability layer to the low permeability layer. The displacement
in the lower layer is almost piston-like at 6 PV foam injection (Figure 8D). The oil from the lower layer
moves into the upper layer without much oil production from the cell during 4-8 PV foam injection. This
cross-flow behavior has been typically observed during foam flow in heterogeneous systems and has been
reported in a previous study (Singh and Mohanty, 2017). The oil pushed into the upper layer is eventually
produced between 8 and 14 PV of foam injection. The foam flood was continued for more than 18 PV.
The pressure drop across the sand pack increased to 1.4 psi by the end of the experiment. The ultimate
cumulative oil recovery was 76.9 %OOIP, the incremental oil recovery by foam was 43.3 %OOIP, and the
final oil saturation was 23.1%. The foam tends to generate easily in the high permeability layer and blocks
it due to the formation of viscous foams. This shows the self-regulating capabilities of foam which make it
lucrative as a conformance control tool in a heterogeneous system such as the present one.
In Flood 2, we wanted to explore the potential synergism of using the LNP2 nanoparticles with the
anionic surfactant. The sand pack was again packed with clean, dry sand in a similar way as before and
was vacuum-saturated with crude oil with an initial saturation of 100%. After an initial water flood, a foam
flood was conducted using a mixture of the surfactant (0.5 wt%) and LNP2 nanoparticles (0.5% LNP2)
as the foaming agent. The formulation was prepared in API brine (8 wt% NaCl and 2 wt% CaCl2) with a
pH of 3.5. Figure 9 shows the injection procedure, cumulative oil recovery (secondary y-axis) and overall
pressure drop (primary y-axis) across the sandpack.

Figure 9—Pressure drop profile (black, left axis) and cumulative oil recovery (blue, right axis) for Flood 2
12 SPE-187165-MS

Similar to Flood 1, first a brine flood was conducted at 10 ft/D. It was continued for more than 5 PV. The
brine flood oil recovery was 31.7 %OOIP, and oil saturation was reduced to 68.3 % which is similar to the
Flood 1. Then, nanoparticle-surfactant solutions and nitrogen gas were coinjected with a quality of 80% at 4
ft/D. Figure 8 shows the comparison of oil distribution due to foam flooding at different pore volumes (PV)
of foam injection for the surfactant case (left) and the blend case (right). The initial oil displacement process
by the blend foam (<6 PV) was similar to the surfactant case in Figure 8 (A-D vs. I-L). The foam first
swept the high permeability layer resulting in 10 %OOIP additional oil recovery where as the corresponding
recovery in Flood 1 was 20 %OOIP. The pressure drop during this stage increased to 0.2 psi compared to
0.04 psi during waterflood. (Note that brine flood was performed at 2.5 times faster rate). The cross-flow
of foams from high permeability to low permeability was clearly evident from Figure 8 K-M. However,
during this flood, no cross-flow of oil from low-permeability layer to high-permeability was observed as
opposed to the surfactant foam case, as shown in Figure 10. The flow in the high permeability layer was
completely blocked. This could be due to formation nanoparticle-assisted oil-water emulsions. The foam
flood, in this case, was continued for more than 21 PV. The ultimate cumulative oil recovery was 60.8
%OOIP, the incremental oil recovery by foam was 29.0 %OOIP, and the final oil saturation was 39.2 %.
The pressure drop never built up above 0.25 psi in Flood 2, much lower than about 1.2 psi in Flood 1.

Figure 10—Cross-flow mechanisms observed during oil displacement experiments

Although the final recovery in the LNP2-surfactant blend case was low, it resulted in selective plugging of
the high permeability layer which is desirable in the field applications. Such flow behavior was not observed
when hydrophilic silica nanoparticles were used in our previous study (Singh and Mohanty, 2017). It shows
that nanoparticle surface-coating can alter foam flow dynamics in heterogeneous porous media. A detailed
understanding of the mechanism of emulsion generation via nanoparticles in the particular region would
SPE-187165-MS 13

allow one to design and optimize the surface coating of silica nanoparticles. Such tailored surface-modified
nanoparticles show immense potential to act a foam EOR agent under harsh reservoir conditions such as
high temperature and high salinity conditions.

Conclusions
The following conclusions can be drawn from this work:
1. The grafting of low-molecular-weight ligands such as polyethylene glycol (PEG) and (3-
Glycidyloxypropyl)trimethoxysilane, (GLYMO) on silica nanoparticles resulted in steric stabilization
and improved the aqueous stability in both high and low temperatures as compared to bare silica
nanoparticles.
2. Silica nanoparticles were sterically stabilized using GLYMO coating under high salinity (API brine)
at 80 °C for pH < 3.5. These nanoparticles show no signs of aggregation even after 2 months. The
enhanced stability is attributed to the high degree of solvation of GLYMO ligands that remain soluble
in the concentrated brine at the high temperature.
3. Foam flood in heterogeneous sand packs with a reservoir crude oil showed that incremental oil
recovery of 29.0 % to 43.3% OOIP (over waterflood) using immiscible foams.
4. Despite the presence of a permeability contrast (6:1), which induces channeling of gas through the
high-permeability region, the foam was effective in diverting fluid to the low-permeability region even
in the presence of crude oil. This crossflow behavior was observed in both cases: foams stabilized by
surfactant alone and surfactant-LNP2 mixture.
5. Significant cross-flow of oil from low-permeability region to high-permeability region (L→H) was
observed for the case of surfactant foam flood. However, the LNP2 foam flood resulted in no (L→H)
crossflow with complete blocking of the high-permeability region possibly due to the formation of in-
situ emulsion. Such selective plugging of high-permeability channels via nanoparticles with optimum
surface coating could have significant potential in recovering oil from heterogeneous reservoirs.

Acknowledgement
We are thankful to the sponsors of Gas EOR Industrial Affiliates Project at The University of Texas at
Austin for partial funding of this work.

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dioxide-in-water foam stabilized with viscoelastic zwitterionic surfactants. J. Colloid Interface Sci. 488, 79–91.
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