J179628 DOI: 10.
2118/179628-PA Date: 9-February-17 Stage: Page: 1
Nanoparticle-Stabilized Carbon Dioxide
Foam Used In Enhanced Oil Recovery:
Effect of Different Ions and Temperatures
Jingshan San, Solvay; Sai Wang, University of North Dakota;
Jianjia Yu, New Mexico Institute of Mining and Technology; Ning Liu, University of Louisiana at Lafayette; and
Robert Lee, New Mexico Institute of Mining and Technology
Summary
This paper reports the study of the effect of different ions (mono-
valent, bivalent, and multiple ions) on nanosilica-stabilized carbon
dioxide (CO2) foam generation. CO2 foam was generated by coin-
jecting CO2/5,000 ppm nanosilica dispersion (dispersed in differ-
ent concentrations of brine) into a sandstone core under 1,500 psi
and at different temperatures. A sapphire observation cell was
used to determine the foam texture and foam stability. Pressure
drop across the core was measured to estimate the foam mobility.
The results indicated that more CO2 foam was generated as the so-
dium chloride (NaCl) concentration increased from 1.0 to 10%. In
addition, the foam bubble became smaller and foam stability
improved with the increase in NaCl concentration. The CO2-foam
mobility decreased from 13.1 to 2.6 md/cp when the NaCl concen-
tration increased from 1 to 10%. For the bivalent ions, the gener-
ated CO2-foam mobility decreased from 19.7 to 4.8 md/cp when
CaCl2 concentration increased from 0.1 to 1.0%. Synthetic pro-
duced water with total dissolved solids (TDS) of 18,583 ppm was
prepared to investigate the effect of multiple ions on foam genera-
tion. The results showed that stable CO2 foam was generated as
the synthetic produced water and nanosilica dispersion/CO2
flowed through a porous medium. The lifetime of the foam was
observed to be more than 2 days as the foam stood at room temper-
ature. Mobility of the foam was calculated as 5.2 md/cp.
Introduction
CO2 enhanced oil recovery (EOR) is regarded as a practical tech-
nique for improving oil production, but also for mitigating carbon
emissions through their capture and storage in deep geologic for-
mations. Although the characteristics of dense CO2 are favorable
for removing oil from reservoir rock, viscous fingering, gravity
override, and reservoir heterogeneity have long been recognized
as the major problems in CO2 flooding. Use of CO2 foam as a so-
lution to gas fingering for improvement of oil recovery has been
investigated for more than 3 decades. The idea of using foam for
reducing the gaseous-phase mobility was first introduced by Bond
and Holbrook (1958). The first research on the mechanisms of the
foam-drive process was conducted by Fried (1961). Fried (1961)
reported a sharp pressure drop across the foam band and reduced
gas mobility through porous media. Since then, the mechanisms
of foam flow through porous media in CO2 flooding have been
studied extensively (Lee and Heller 1988; Wellington and Vinegar
1988; Chang and Grigg 1999).
Research results have demonstrated that surfactant-induced CO2
foam is an effective method for mobility control in CO2-foam flood-
ing. Traditionally, surfactants have been designed as the proper
hydrophilic/CO2-philic balance so the molecules can be adsorbed at
the CO2/brine interface (Johnston and da Rocha 2009). However, a
challenge to surfactant design for CO2/brine is that the low polariz-
ability/volume of CO2 results in weak solvation of the surfactant
Copyright V
C 2017 Society of Petroleum Engineers
This paper (SPE 179628) was accepted for presentation at the SPE Improved Oil Recovery
Conference, Tulsa, 11–13 April 2016, and revised for publication. Original manuscript
received for review 17 May 2016. Revised manuscript received for review 28 September
2016. Paper peer approved 23 November 2016.
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tails. Hence, the surfactant may favor water to such an extent that it
adsorbs only weakly at the CO2/water interface, resulting as insuffi-
cient for foam generation and stabilization (Worthen et al. 2013).
Because of their natural properties, such as their excellent chemical
stability and low retention on mineral surfaces, nanoparticles are
regarded as a potential alternative for producing highly stable foams
(Worthen et al. 2012, 2015; Singh and Mohanty 2014; Emrani
and Nasr-El-Din 2015). It is known that small solid particles can
adsorb at fluid/fluid interfaces to stabilize bubbles in foams without
surfactant molecules (Binks 2002). A wide variety of mineral pow-
ders can be used to stabilize such foams, such as silica, iron
oxide, hydroxides, metal sulfates, clays, and carbon. Unlike surfac-
tants, nanoparticle-stabilized CO2 foam exhibits long-term foam
stability because of its high adsorption energy. Its estimated adsorp-
tion energy is approximately 104 kBT for particles with a size
of 30 nm at 24 C. For a comparison, the adsorption energy for a typ-
ical surfactant molecule is on the order of kBT (Aroonsri et al.
2013). (kBT is the product of the Boltzmann constant and the tem-
perature. It is used in physics as a unit of energy; for example,
kBT ¼ 4.11  1021 J at 25 C.) Hence, the presence of nanopar-
ticles at an interface may limit foam destabilization by drainage of
lamellae, bubble coalescence, Ostwald ripening, and hole formation
(Worthen et al. 2013). In addition, particle-stabilized CO2 foam dis-
played another advantage over CO2 because of its limited ability to
solvate surfactant tails (Dickson et al. 2004). However, particles at
the CO2/water interface can generate CO2/water foams without
being solubilized by the CO2 phase (Dickson et al. 2004).
Generation of foams with nanoparticles has been reported by
different researchers. Binks and Horozov (2005) reported stabili-
zation of air/water foams with fumed silica nanoparticles. Par-
ticles with 32% residual SiOH groups on the surface created the
largest air/water-foam volume. Espinoza et al. (2010) generated
stable CO2 foams in beadpacks with 5-nm silica nanoparticles.
Foam stability and normalized mixture viscosity have been
assessed for a range of values of nanoparticle concentration, water
salinity, ratio of CO2/water-flow rates, and temperature. Aroonsri
et al. (2013) studied nanosilica-stabilized CO2-foam generation in
Boise and Berea sandstone cores, investigating threshold shear
rates for foam generation in matrix and in fracture. Our laboratory
has also found that stable CO2 foam was generated with commer-
cially available silica nanoparticles both in bead packs and sand-
stone cores (Mo et al. 2012; Yu et al. 2012). Foam mobility and
stability were investigated with different factors such as CO2/
water-phase ratio, particle concentration, and injection-flow rate.
It was also observed that the foam mobility decreased with
increasing foam quality from 20 to 60% and then increased as the
foam quality increased from 60 to 80%. A small amount of CO2
foam was observed as the nanosilica concentration was 100 ppm.
However, to generate stable and large volume CO2 foam, the par-
ticle concentration in the mixture was 5,000 ppm (Mo et al. 2012).
Although the effects of different factors on nanoparticle-stabi-
lized CO2 foam and foam performance on mobility control have
been investigated, the harsh conditions of reservoir formations,
such as high salinity and high temperature, require more compre-
hensive studies on nanoparticle-stabilized CO2 foam and foam
performance under those conditions. The objective of this study
1
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Silica SiO2 93.13% procedure is described in Yu et al. (2012). Briefly, two Isco syringe
pumps (Model 260D) were used to inject nanosilica dispersion and
Alumina Al2O3 3.86% high-pressure CO2 into the core sample. Two floating-piston accu-
Ferric oxide Fe2O3 0.11% mulators were used to reserve nanosilica dispersion and supercriti-
cal CO2, respectively. Three TEMCo backpressure regulators
Ferrous oxide FeO 0.54% were used to maintain the required operation pressure. The
injected CO2 and nanosilica dispersion were mixed in the core
Table 1—Mineral composition of the core.
sample, supplying a strong shearing energy and forcing the nano-
silica to adsorb to the interface between CO2 and water. Pressure
was to understand the effect of brine salinity on nanoparticle-sta-
drop along the core was measured with a Honeywell 3000 differ-
bilized CO2-foam generation, foam stability, and foam-flow
ential-pressure transducer connected to a Daq56 data-acquisition
behavior in a porous medium. In this paper, the investigation of
system, which recorded the pressure change with time. The entire
the effects of different ions (monovalent ions, bivalent ions, and
apparatus, except for syringe pumps, was placed in an air bath to
multi ions) on nanosilica-stabilized CO2-foam generation, foam
maintain a constant temperature throughout the experiment.
mobility, and stability are described. CO2 foam was generated by
Foam generation and mobility measurement were conducted at
coinjection of CO2/nanosilica dispersion (CO2/nanosilica
25 C and 1,500 psi. The total injection rate (CO2 and nanosilica
dispersion ¼ 1:1) into a Berea-sandstone core under 1,500 psi at
dispersion) was 800 cm3/hr with the phase ratio of CO2/nanosilica
room temperature. The CO2-foam texture and foam stability were
dispersion ¼ 1:1. Each foam experiment lasted until a steady-state
observed from an in-line observation sapphire cell. Pressure drop
pressure drop was achieved. Table 3 summarizes the experimen-
across the core was measured to estimate foam mobility.
tal conditions for all the tests in this study.

Experimental
Materials. Silica nanoparticles were obtained from AkzoNobel
Pulp and Performance Chemicals as an aqueous dispersion, which
was diluted with brine to 5,000 ppm. Particle size was measured
in the range of 17–20 nm. Berea-sandstone-core samples were
purchased from Cleveland Quarries. Tables 1 and 2 show the
composition and the properties of the core, respectively.
Experiment Devices. The apparatus for generating nanoparticle-
stabilized supercritical CO2 foam is shown in Fig. 1. The detailed
Characterization. Foam Mobility. The foam mobility in this
study is defined as the total mobility of CO2/nanosilica dispersion.
The mobility can be evaluated from Eq. 1:
k ¼ ðq=AÞ=ðDp=LÞ; . . . . . . . . . . . . . . . . . . . . . . . . ð1Þ
where q is the flow rate, A the cross area of the core, Dp is the
pressure drop along the core, and L is the length of the core.
Nanosilica-Particle-Size Measurement. Nanosilica-particle-
size distribution was characterized with a dynamic-light-

Initial Brine
Diameter Permeability
3
Core Length (cm) (cm) Porosity (md) PV (cm )
Sandstone 1 11.56 5.08 19.5% 203 45.6
Sandstone 2 11.53 5.08 19.3% 200 45.1
Sandstone 3 12.4 5.08 19.1% 192 48.0

Table 2—Core properties.

Air bath

5
10
5

3 6
4 11
6
7

2 5
8
1

Fig. 1—Schematic of CO2-foam generation and mobility-test setup: (1) Isco pump; (2) three-way valve; (3) brine/nanoparticles ac-
cumulator; (4) CO2 accumulator; (5) backpressure regulator; (6) in-line filter (0.5 lm); (7) sandstone core; (8) Honeywell pressure
transducer; (9) data-acquisition system; (10) sapphire tube; (11) effluent accumulator.

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Pressure Drop
Core Length (cm) (psi) Mobility (md/cp)
NaCl concentration (%) 1 11.56 140 13.1
5 11.56 288 6.4
10 11.56 700 2.6
CaCl2 concentration (%) 0.1 11.53 93 19.7
0.3 11.53 117 15.7
0.5 11.53 185 9.9
1.0 11.53 380 4.8
Temperature (°C) 25 12.40 375 5.3
40 12.40 273 7.2
65 12.40 240 8.2

Table 3—Experimental conditions of CO2-foam generation with nanosilica as stabilizer.

scattering particle-size analyzer from Microtrac Zetatrac (Model
NPA 152-31A). To test the ion-concentration effect on nanosil-
ica-size distribution, nanosilica dispersion was first diluted with
different concentrations of NaCl or CaCl2 solution. The mixture
was stirred for approximately 5 minutes, and then the silica-parti-
cle size was measured. After the measurement, the mixture was
left standing at room temperature for 24 hours and the particle
size was measured again. The measurement was completed if no
particle size change was observed in 24 hours.
Results and Discussion
Effect of Monovalent Ions on Nanosilica-Stabilized CO2
Foam. Fig. 2 shows CO2-foam texture and stability from the
online observation cell as 1.0% NaCl was added in the nanosilica
dispersion. Large volume of CO2 foams with small bubble size
were formed as the CO2 and nanosilica dispersion flowed through
the core. The calculated share rate in the core was 350.7 1/sec-
onds, which is similar to the reported share rate by Aroonsri et al.
(2013) to generate stable CO2 foam. The generated CO2 foam, af-
ter standing at room temperature and 1,500 psi, displayed very-
good stability. A slight collapse was observed after 24 hours. Half
of the foams collapsed after standing at room temperature for 5
days. All the foams disappeared after standing at room tempera-
ture for 7 days. The long-term stability of nanoparticle-stabilized
CO2 foam, as discussed previously, contributes to the high
adsorption energy of nanosilica particles at the CO2/brine inter-
face. Similarly, Cervantes Martinez et al. (2008) also observed a
9-month lifetime for nanosilica-stabilized N2 foam. Worthen et al.
(2013) and Binks and Horozov (2005) reported long-term stable
CO2/air foams generated by nanoparticles. By comparing the CO2
foam generated with nanosilica and surfactants, Adkins et al.
(2007) observed that no coalescence of water drops occurred over
many hours, even days, when silica nanoparticles were used.
However, coalescence of water drops has been observed for sur-
factant-stabilized CO2 foam within 3 to 4 hours at 15 MPa stabi-
lized by 1 wt% of poly(dimethylsiloxane)-b-poly(acrylic acid)
with 50% CO2 by weight.
Fig. 3 shows the pressure drop along the core when CO2 and
5,000 ppm nanosilica dispersion (dispersed in 1.0% of NaCl) were
injected into the core. For each of the coreflooding tests, the core
was first flushed with brine to determine the permeability. Next,
CO2/nanosilica-dispersion injection began into the core. The pres-
sure drop started to increase as CO2/nanosilica dispersion was
injected into the core, indicating CO2 foam generated in the core.
After approximately 10 pore volumes (PV) of CO2/nanosilica dis-
persion were injected into the core, the pressure drop along the
core leveled off at 139.6 psi, indicating that steady state was
obtained. CO2-foam mobility at this condition was estimated as
13.1 md/cp.
The effect of NaCl concentration on nanosilica-stabilized
CO2-foam generation and foam stability is displayed in Fig. 4.
With the increased NaCl concentration in nanosilica dispersion
from 1.0 to 10%, more CO2 foam was generated and the foam-
bubble size became smaller. The foam color also changed from
grayish tan to milky white. More-uniform smaller bubbles were

(a) 0 hours (b) 0.5 (c) 24 (d) 48 (e) 72 (f) 96 (g) 120 (h) 144 (i) 168
hours hours hours hours hours hours hours hours

Fig. 2—Images of CO2 foam and foam stability in 1.0% of NaCl.

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160

Pressure Drop (psi) 140

120

100

80

60

40

20

0 0 0.5 24 48 72 96 120 144 168

0 5 10 15 20 seconds hours hours hours hours hours hours hours hours
Injection Volume (PV)
(a) 1.0% NaCl
Fig. 3—Pressure drop along the core during the coreflooding
test of CO2/nanosilica dispersed in 1.0% of NaCl.

generated with NaCl-concentration increase. Meanwhile, the sta-

bility of the foam also improved as NaCl concentration increased.
For example, all the generated CO2 foams collapsed after 7 days
when NaCl concentration in nanosilica dispersion was 1.0%; how-
ever, as NaCl concentration increased to 10.0%, less than one-
third the volume of CO2 foam collapsed after 7 days. Kostakis
et al. (2006) also observed that a threshold of NaCl concentration
existed as a low concentration of nanosilica was deployed to gen-
erate foams. The presence of a background electrolyte alters the
free energy of double-layer formation at the particle surface, as 0 0.5 24 48 72 96 120 144 168
well as at the air/water interface. These changes in turn are seconds hours hours hours hours hours hours hours hours
reflected in the value of the contact angle and the tendency of the
particles to adsorb at the air/water interface (Kostakis et al. 2006). (b) 5.0% NaCl
Binks et al. (2007) reported that the contact angles increased with
increasing salt concentration in a nanosilica dispersion. They sug-
gested that the increase in the contact angle was caused by both
the influence of existing ions screening the repulsion between
neighboring charged silanol groups and the decrease in the thick-
ness of the repulsive hydration layer on silica being the structural
component (Churaev and Derjaguin 1985). The increase in the
particles’ hydrophobicity causes a higher adsorption energy at the
CO2/brine interface, leading to more-stable foam generation.
The effect of NaCl concentration on CO2-foam mobility is dis-
played in Fig. 5. As the NaCl concentration increased, more-sta-
ble CO2 foams were generated in the sandstone core, resulting in
0 0.5 24 48 72 96 120 144 168
a decrease in CO2/brine mobility. The CO2-foam mobility seconds hours hours hours hours hours hours hours hours
decreased from 13.1 to 2.4 md/cp as NaCl concentration increased
from 1.0 to 10.0%. Similarly, Aroonsri et al. (2013) also observed (c) 10% NaCl
that the apparent viscosity of foam increased with the salinity of
the nanosilica dispersion. Further increase in NaCl concentration Fig. 4—CO2 foam and foam stability in different concentrations
caused aggregation of silica particles. For example, as the NaCl of NaCl.
concentration increased to 15%, the pressure drop along the core
was observed to continuously increase. The outlet fluids were col- core. After the test, the core was flushed with 2.0% brine and the
lected and particle concentrations were measured by inductively permeability of the core was observed to decrease to approxi-
coupled plasma atomic emission spectroscopy. The results indi- mately 70 md. These results implied that particle aggregration
cated that less than 80% of the nanosilica particles flowed out the and core plugging occurred as NaCl concentration increased to
15%. Fig. 6 shows the particle-size change with NaCl
14
30
12
25
Particle Size (nm)

10
Mobility (md/cp)

20
8
15
6
4 10

2 5

0 0
0 2 4 6 8 10 12 0 5 10 15 20 25
NaCl Concentration (%) NaCl Concentration (%)

Fig. 5—CO2-foam-mobility change with NaCl. Fig. 6—Silica-particle-size change with NaCl concentration.

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0 2 12 24 36 45 0 2 12 24 36 48 60 70
hours hours hours hours hours hours hours hours hours hours hours hours hours hours

(a) (b)

0 2 24 48 72 96 116 0 2 24 48 72 96 120 144 168

hours hours hours hours hours hours hours hours hours hours hours hours hours hours hours hours

(c) (d)

Fig. 7—CO2 foam and foam stability in different concentrations of CaCl2: (a) 1,000 ppm; (b) 3,000 ppm; (c) 5,000 ppm; and (d)
10,000 ppm.

concentration. The coreflooding results indicated that the core
was plugged when NaCl concentration was more than 10%.
Effect of Bivalent Ions on Nanosilica-Stabilized CO2 Foam.
CaCl2 was used to study the effect of bivalent ions on CO2-foam
generation and stability. Fig. 7 indicates the generated CO2 foam
and foam stability in different concentrations of CaCl2. The
results are similar to those in monovalent ions. As Ca2þ concen-
tration increased from 1,000 to 10,000 ppm, the volume of the
generated CO2 foam increased. At the same time, the foam stabil-
ity also improved as Ca2þ concentration increased, which is simi-
lar to those in NaCl solutions. As discussed previously, the
presence of electrolyte ions in nanosilica dispersion may change
25
20
Mobility (md/cp)
the double-layer formation at the particle surface and in turn
increase particle hydrophobicity. However, the presence of biva-
lent ions displayed more-significant effects on CO2-foam genera-
tion compared with that of monovalent ions. CO2 foam was
generated as 1,000 ppm CaCl2 was added in nanosilica dispersion.
When 1.0% CaCl2 was used, the generated CO2 foam displayed
similar foam texture and foam stability as with 10% NaCl. On the
other hand, the generated CO2 foam in 5,000 ppm CaCl2 dis-
played less stability compared with 1.0% NaCl (Figs. 4a and 7c),
although both systems have similar ionic strength (0.14 mol/L for
CaCl2 and 0.17 mol/L for NaCl). These results demonstrated that
increased stabilization of CO2 foam by use of NaCl is not simply
the result of increased screening of electrostatic repulsion between
the silica particles as a function of the ionic strength, but probably
a more-specific interaction between NaCl and the silica-particle
surface (Binks et al. 2007).
Fig. 8 shows the change in CO2-foam mobility with increase
in CaCl2 concentration. Foam mobility decreased from 19.7 to 4.8
md/cp as CaCl2 concentration increased from 1,000 to

10,000 ppm.
15

Effect of Multiple Ions on Nanosilica-Stabilized CO2-Foam

10
Generation. A synthetic produced water, similar in composition
to that from the Permian Basin, was prepared to represent a mix-
5 ture of different ion sources. The composition of the produced
water is listed in Table 4 with TDS of 18,583 ppm. Fig. 9 shows
0 the CO2 foam in the synthetic produced water. As a comparison,
0 0.2 0.4 0.6 0.8 1 1.2
Naþ concentration in the synthetic produced water was
CaCl2 Concentration (%) 6,622 ppm, which is between 1.0 and 5.0% NaCl, as shown in Fig.
4. However, the amount of CO2 foam generated in the synthetic
Fig. 8—CO2-foam-mobility change with CaCl2 concentration. produced water is obviously more than in both the 1.0 and 5.0%

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 J179628 DOI: 10.2118/179628-PA Date: 9-February-17
+ 2+
mg/L Na
Permian Basin 6622
Table 4—The compositions of Permian Basin produced waters (Bond and Holbrook 1958).
(a) 0 hours (b) 0.5 (c) 24 (d) 38
hours hours hours
Fig. 9—CO2 foam and foam stability in synthetic produced
water.
NaCl concentrations. This could be the synergistic effect of multi-
ple ions on CO2 foam generation. In the presence of multiple
ions, the double layer at the nanosilica surface was further
squeezed and the particles became more hydrophobic. On the
other hand, because valences are different for different ions,
which results in their different capabilities for changing the dou-
ble-layer and particle hydrophobicity, the generated CO2 foam in
synthetic produced water displayed less stability compared with
both the 1.0% and the 5.0% NaCl concentrations. Fig. 10 shows
the pressure drop along the core during the coreflooding test. The
results are similar to the previous results. The core was first
flushed with 3.0 PV of brine and then flooded with CO2/brine and
nanosilica dispersion (50:50). The pressure drop remained stable
at 375.3 psi as 16.3 PV of CO2/brine and nanosilica dispersion
were injected. The foam mobility in the synthetic produced water
is calculated as 5.2 md/cp.
Effect of Temperature on Nanosilica-Stabilized CO2 Foam.
Temperature is a critical reservoir parameter that effects the foam
performance in CO2 EOR. The effect of temperature on nanosil-
ica-stabilized CO2-foam generation, foam stability, and foam-
flow behavior was investigated. The tests were started with coin-
jection of CO2 and 5,000 ppm nanosilica dispersion at different
600
500
Pressure Drop (psi)
400
300
200
100
0
0 50
Fig. 10—Pressure drop along the core during the coreflooding test with CO2/synthetic produced water and nanosilica dispersion.
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2+ + – 2– –
Ca Mg K Cl SO 4 HCO3 TDS
179 33 53 8800 1225 1671 18 583
temperatures of 25, 40, and 65 C. Fig. 11 shows the foam stability
under different temperatures. The results indicate that the foam
stability decreases as the temperature increases from 25 to 65 C.
For example, it takes more than 65 hours as all the foam collapses
under the temperature of 25 C, but 12 hours and 7 hours for the
temperatures of 40 and 65 C, respectively. It was known that the
foam stability was influenced by the coupling of coarsening and
drainage (Saint-Jalmes 2006). The foam becomes drier faster
when drainage rate increases, in which the foam stability
decreases. Kapetas et al. (2016) studied CO2 foam generated by a
surfactant under different temperatures and concluded that the
drainage rate increased with temperature. In addition, coarsening
increases the foam-bubble size and leads to foam collapse. Coars-
ening is accelerated at higher temperature because the foam films’
permeability to gas increases with increasing temperature (Faraj-
(e) 55 (f) 65 (g) 70 zadeh et al. 2009). Fig. 12 shows the results of foam mobility
hours hours hours under different temperatures. The mobility increases from 5.2 to
8.2 md/cp as temperature increases from 25 to 65 C. The magni-
tude of the increase between the tests performed at 25 and 65 C is
57.7%. In addition, the results of Fig. 12 indicate that as the tem-
perature increases from 25 to 40 C, the foam mobility increases
more quickly than that of the temperature from 40 to 65 C. By
comparing with Fig. 11, the foam stability also presents a similar
trend, in which the foam-stability change is more pronounced in
the range of 25 to 40 C than 40 to 65 C. Similar results were also
reported by Sharma et al. (1985). They found that the foam half-
life changed strikingly in the temperature range of 20 to 40 C and
exhibited small changes between 40 and 80 C.
The test results of nanosilica-stabilized CO2 foam under differ-
ent ions and temperatures indicated that nanosilica was a promis-
ing alternative to stabilize CO2 foam in CO2 EOR. However, the
results also demonstrated that particle aggregation could occur
under high-salinity brine, such as the 15% NaCl solution in this
study. The foam stability decreased as the temperature increased.
All these results imply that more experimental tests may need to
be performed before the field application of this technology. To
evaluate the field performance of the nanosilica as the stabilizing
agent, the stability of the particles under reservoir conditions
needs to be determined. Coreflooding tests to evaluate the per-
formance of nanosilica-stabilized CO2 foam under the same reser-
voir conditions, such as brine composition, temperature, and
operation pressure, should be performed. Nanosilica-stabilized
CO2-foam stability in the presence of crude oil and the perform-
ance of the foam for residual oil recovery need to be determined
before the field application.
100 150 200 250
Injection Volume (PV)
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(a) 25°C (b) 40°C (c) 65°C

0 24 50 65 70 0 4 8 11 12 0 2 4 6 7
hours hours hours hours hours hours hours hours hours hours hours hours hours hours hours

Fig. 11—CO2 foam and foam stability under different temperatures.

10 aid of Liz Bustamante for her assistance in editing this

manuscript.
8
Mobility (md/cp)

References
6
Adkins, S., Gohil, D., Dickson, J. L. et al. 2007. Water-in-Carbon Dioxide
Emulsions Stabilized with Hydrophobic Silica Particles. PCCP Phys.
4 Chem. Ch. Ph. 9 (48): 6333–6343. http://dx.doi.org/10.1039/
B711195A.
2 Aroonsri, A., Worthen, A. J., Hariz, T. et al. 2013. Conditions for Generat-
ing Nanoparticle-Stabilized CO2 Foams in Fracture and Matrix Flow.
0 Presented at the SPE Annual Technical Conference and Exhibition,
20 30 40 50 60 70 New Orleans, 30 September–2 October. SPE-166319-MS. http://
Temperature (°C) dx.doi.org/10.2118/166319-MS.
Binks, B. P. 2002. Particles as Surfactants–Similarities and Differences.
Fig. 12—CO2-foam mobility at different temperatures. Curr. Opin. Colloid In. 7 (1–2): 21–41. http://dx.doi.org/10.1016/
S1359-0294(02)00008-0.
Binks, B. P. and Horozov, T. S. 2005. Aqueous Foams Stabilized Solely
Conclusions by Silica Nanoparticles. Angew. Chem. Int. Ed. 44 (24): 3722–3725.
http://dx.doi.org/10.1002/anie.200462470.
The following conclusions can be made by use of the laboratory
Binks, B. P., Duncumb, B., and Murakami, R. 2007. Effect of pH and Salt
results.
Concentration on the Phase Inversion of Particle-Stabilized Foams.
1. CO2 foam was generated when CO2 and NaCl solution with
Langmuir 23 (18): 9143–9146. http://dx.doi.org/10.1021/la701393w.
5,000 ppm nanosilica were flowed through a sandstone core
Bond, D. and Holbrook, O. C. 1958. Gas Drive Oil Recovery Process. US
under pressure of 1,500 psi. The amount of CO2 foam and
Patent No. 2,866,507.
foam stability increased with the increase of NaCl concentra-
Cervantes Martinez, A., Rio, R., Delon, G. et al. 2008. On the Origin of
tion from 1.0 to 10%. However, further increase in NaCl con-
the Remarkable Stability of Aqueous Foams Stabilised by Nanopar-
centration to 15% resulted in nanosilica-particle aggregation
ticles: Link with Microscopic Surface Properties. Soft Matter 4 (7):
and core plugging.
1531–1535. http://dx.doi.org/10.1039/B804177F.
2. The CO2-foam mobility decreased from 13.1 to 2.6 md/cp as
Chang, S.-H. and Grigg, R. B. 1999. Effects of Foam Quality and Flow
NaCl concentration increased from 1.0 to 10.0%.
Rate on CO2-Foam Behavior at Reservoir Temperature and Pressure.
3. Bivalent ions such as Ca2þ displayed more-significant effects
SPE Res Eval & Eng 2 (3): 248–254. SPE-56856-PA. http://
on CO2-foam generation and stability. CO2 foam was gener-
dx.doi.org/10.2118/56856-PA.
ated as 1,000 ppm CaCl2 was used. More CO2 foams were gen-
Churaev, N.V. and Derjaguin, B. V. 1985. Inclusion of Structural Forces
erated and the foam became more stable as CaCl2
in the Theory of Stability of Colloids and Films. J. Colloid Interf.
concentration increased from 1,000 to 10,000 ppm.
Sci. 103 (2): 542–553. http://dx.doi.org/10.1016/0021-9797(85)90129-
4. Stable CO2 foam was generated in synthetic produced water
8.
(TDS ¼ 18,583 ppm). The different ions present displayed syn-
Dickson, J. L., Binks, B. P., and Johnston, K. P. 2004. Stabilization of Car-
ergistic effects on CO2-foam generation. However, the stability
bon Dioxide-in-Water Emulsions with Silica Nanoparticles. Langmuir
of the generated CO2 foam decreased in the synthetic produced
20 (19): 7976–7983. http://dx.doi.org/10.1021/la0488102.
water because of the unbalanced effect of ions on particle dou-
Emrani, A. S. and Nasr-El-Din, H. A. 2015. Stabilizing CO2-Foam using
ble-layer and surface properties.
Nanoparticles. Presented at the SPE European Formation Damage
5. The stability of the CO2 foam decreased as temperature
Conference and Exhibition, Budapest, Hungary, 3–5 June. SPE-
increased from 25 to 65 C. The foam mobility increased with
174254-MS. http://dx.doi.org/10.2118/174254-MS.
temperature increase from 25 to 65 C.
Espinoza, D. A., Caldelas, F. M., Johnston, K. P. et al. 2010. Nanopar-
ticle-Stabilized Supercritical CO2 Foams for Potential Mobility Con-
Acknowledgements trol Applications. Presented at the SPE Improved Oil Recovery
AkzoNobel Pulp and Performance Chemicals generously pro- Symposium, Tulsa, 24–28 April. SPE-129925-MS. http://dx.doi.org/
vided samples of silica nanoparticles. The authors appreciate the 10.2118/129925-MS.

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 J179628 DOI: 10.2118/179628-PA Date: 9-February-17
Farajzadeh, R., Krastev, R., and Zitha, P. L. J. 2009. Gas Permeability of
Foam Films Stabilized by an a-Olefin Sulfonate Surfactant. Langmuir
25 (5): 2881–2886. http://dx.doi.org/10.1021/la803599z.
Fried, A. N. 1961. Foam Drive Process for Increasing the Recovery of
Oil. Report RI-5866, US Department of the Interior, Bureau of Mines,
Washington, DC.
Johnston, K. P. and da Rocha, S. R. P. 2009. Colloids in Supercritical Flu-
ids Over the Last 20 Years and Future Directions. J. Supercrit. Fluid.
47 (3): 523–530. http://dx.doi.org/10.1016/j.supflu.2008.10.024.
Kapetas, L., Vincent Bonnieu, S., Danelis, S. et al. 2016. Effect of Tem-
perature on Foam Flow in Porous Media. J. Ind. Eng. Chem. 36 (25
April): 229–237. http://dx.doi.org/10.1016/j.jiec.2016.02.001.
Kostakis, T., Ettelaie, R., and Murray, B. S. 2006. Effect of High Salt Con-
centrations on the Stabilization of Bubbles by Silica Particles. Lang-
muir 22 (3): 1273–1280. http://dx.doi.org/10.1021/la052193f.
Lee, H. and Heller, J. 1988. Carbon Dioxide—Foam Mobility Measure-
ments at High Pressure. In Surfactant-Based Mobility Control, ed. D.
H. Smith, Vol. 373, Chap. 19, 375–386. Washington, DC: American
Chemical Society.
Mo, D., Yu, J., Liu, N. et al. 2012. Study of the Effect of Different Factors
on Nanoparticle-Stablized CO2 Foam for Mobility Control. Presented
at the SPE Annual Technical Conference and Exhibition, San Antonio,
Texas, 8–10 October. SPE-159282-MS. http://dx.doi.org/10.2118/
159282-MS.
Saint-Jalmes, A. 2006. Physical Chemistry in Foam Drainage and Coars-
ening. Soft Matter 2 (10): 836–849. http://dx.doi.org/10.1039/
B606780H.
Sharma, M. K., Shah, D. O., and Brigham, W. E. 1985. The Influence of
Temperature on Surface and Microscopic Properties of Surfactant Sol-
utions in Relation to Fluid Displacement Efficiency in Porous Media.
AIChE J. 31 (2): 222–228. http://dx.doi.org/10.1002/aic.690310208.
Singh, R. and Mohanty, K. K. 2014. Foams Stabilized by In-Situ Surface-
Activated Nanoparticles in Bulk and Porous Media. Presented at the
SPE Annual Technical Conference and Exhibition, Amsterdam, 27–29
October. SPE-170942-MS. http://dx.doi.org/10.2118/170942-MS.
Wellington, S. L. and Vinegar, H. J. 1988. Surfactant-Induced Mobility
Control for Carbon Dioxide Studied with Computerized Tomography.
In Surfactant-Based Mobility Control, ed. D. H. Smith, Vol. 373,
Chap. 17, 344–358. Washington, DC: American Chemical Society.
Worthen, A., Bagaria, H., Chen, Y. et al. 2012. Nanoparticle Stabilized
Carbon Dioxide in Water Foams for Enhanced Oil Recovery. Pre-
sented at the SPE Improved Oil Recovery Symposium, Tulsa, 14–18
April. SPE-154285-MS. http://dx.doi.org/10.2118/154285-MS.
Worthen, A., Taghavy, A., Aroonsri, A. et al. 2015. Multi-Scale Evalua-
tion of Nanoparticle-Stabilized CO2-in-Water Foams: From the
Benchtop to the Field. Presented at the SPE Annual Technical Confer-
ence and Exhibition, Houston, 28–30 September. SPE-175065-MS.
http://dx.doi.org/10.2118/175065-MS.
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Stage: Page: 8 Total Pages: 8
Worthen, A. J., Bryant, S. L., Huh, C. et al. 2013. Carbon Dioxide-in-
Water Foams Stabilized With Nanoparticles and Surfactant Acting in
Synergy. AIChE J. 59 (9): 3490–3501. http://dx.doi.org/10.1002/
aic.14124.
Yu, J., An, C., Mo, D. et al. 2012. Foam Mobility Control for Nanopar-
ticle-Stabilized Supercritical CO2 Foam. Presented at the SPE
Improved Oil Recovery Symposium, Tulsa, 14–18 April. SPE-
153336-MS. http://dx.doi.org/10.2118/153336-MS.
Jingshan San is a technologist at Solvay in Bristol, Pennsylvania.
His research focuses on nanoparticle-stabilized CO2-foam
generation and foam-flow behavior in porous media and
proppant-suspension preparation and evaluation. San is a
member of SPE. He holds a master’s degree in petroleum engi-
neering from the New Mexico Institute of Mining and
Technology.
Sai Wang is a PhD-degree candidate in the Petroleum Engi-
neering Department at the University of North Dakota. His
research interests include CO2 foam for EOR and CO2 monitor-
ing in CO2 storage. Wang has authored or coauthored more
than 10 technical papers. He is a member of SPE. Wang holds
a master’s degree in petroleum engineering from the New
Mexico Institute of Mining and Technology.
Jianjia Yu is a research scientist in the Petroleum Recovery
Research Center at the New Mexico Institute of Mining and
Technology. His research interests include CO2-foam EOR,
CO2 capture, and produced-water remediation. Yu has auth-
ored or coauthored more than 35 technical papers and holds
one US patent. He is a member of SPE. Yu holds a PhD degree
in petroleum engineering from the New Mexico Institute of
Mining and Technology.
Ning Liu is an assistant professor in the Petroleum Engineering
Department at the University of Louisiana at Lafayette. Previ-
ously, he worked as a research scientist in the Petroleum Re-
covery Research Center at the New Mexico Institute of Mining
and Technology. Liu’s research interests include CO2-foam
EOR, CO2 monitoring in CO2 storage, and produced-water
remediation. He has authored or coauthored more than 27
peer-reviewed papers. Liu is a member of SPE. He holds a PhD
degree in materials engineering from the New Mexico Institute
of Mining and Technology.
Robert Lee is a professor emeritus at the New Mexico Institute
of Mining and Technology. His research interests include natu-
ral gas, produced water, and CO2 EOR. Lee has authored or
coauthored more than 200 technical papers. He is a member
of SPE. Lee holds a bachelor’s degree in chemistry from
Chung-Yuan Christian College, Taiwan; a master’s degree in
chemical engineering from Oregon State University; and a
PhD degree in chemical engineering from the University of
Michigan, Ann Arbor.