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Abstract
to overcome gravity override and the channeling and fingering of the injected gas, which
arises due to the low density and viscosity of the injected fluid combined with the rock
heterogeneity. A major challenge; however, is the stability of the generated foam when
it contacts the oil. In this study we investigate the feasibility of using inexpensive
nanoparticles made of coal fly-ash,an abundantly available waste product of coal power
plants, as a foam booster. We investigate the viability of reducing the size of fly-ash
particles to 100-200 nm using high frequency ultrasonic grinding. We also study the
foaminess (foamability), strength, and stability of the foams made with minor concen-
trations of fly-ash nanoparticles and surfactant, both in bulk and porous media. The
effect of monovalent and divalent ion concentration on the foaminess of the nano-ash
suspension combined with very low concentrations of a commercial alpha olefin sul-
fonate (AOS) surfactant, in presence and absence of oil, is studied. We observe that
∗
To whom correspondence should be addressed
†
Delft University of Technology, The Netherlands
‡
University of Tübingen, Germany
¶
Shell Global Solutions International, The Netherlands
1
bulk foam that contains very small amounts of nano-ash particles shows a higher sta-
remarkably stronger foam with mixtures of nano-ash and surfactant, such that the
amount of produced liquids from the cores significantly increases. For first time we
show that nano-ash can be used to stabilize nitrogen foam in presence of crude oil at
high temperature and pressure. In presence of oil, the nano-ash-AOS foam shows a
higher stability, although crude oil tends to form stable emulsions in water in presence
of nano-ash.
Introduction
Gas injection is a widely used improved oil recovery mechanism 1–3 . The microscopic sweep
efficiency of gas is higher compared to water-flooding. However, lower viscosity of the gaseous
phase leads to viscous fingering, and enhances channeling in heterogeneous reservoirs. In
addition, the large difference between the density of gas and oil results in gravity override 4 .
The high mobility of the gas phase can be reduced by formation of foam, which can be
generated by co-injection or alternating injection of the gas with an aqueous surfactant
mixture 5,6 . The low mobility of foam in high permeability zones diverts the flow of gas to
the low permeable areas, which allows the injected gas to reach the poorly-wept sections of
the reservoir.
In the subsurface applications, the generated foam should have a long lifetime to deliver
the desired function. Depending on the purpose of the application, foam properties can be
tuned. For example, when foam is used to mitigate the liquid loading problem in gas wells,
generally it should be stable over the total length of the well (typically few kilometers) and
also to carry as much liquid as possible from downhole to the surface (slow drainage). If
condensates are produced together with brine, the foam should also be oil-tolerant. Similarly,
when foam is employed as a mobility-control agent in gas-enhanced-oil-recovery projects it
has to remain stable when contacts the residual oil.
2
There are several technical and economic challenges in front of a successful foam-flooding
project. The economic issues include the availability of gas, compression costs 7 , and the
adsorption of surfactant 8–11 on the rock surface. With an adsorption rate of one milligram
surfactant per gram rock, up to one third of the value of the recovered oil in the EOR stage
can be spent to cover the costs of the adsorbed surfactant 12 . A chemistry-related technical
issue is the limited instability of surfactant at high temperature and high salinity of the
hydrocarbon reservoirs. Anionic surfactants are known to precipitate in aqueous media with
high salinity, due to their reaction with multivalent ions 13,14 . Some of the surfactants do not
have high thermal stability and can undergo a relatively fast thermal degradation process
at typical temperatures of a deep reservoir, i.e., 100o C or at higher temperature that are
suitable for steam-flooding, i.e., 200-300o C 15 . In addition, foams stabilized by surfactants
have short life time in presence of oil 16 .
It has been experimentally shown that the addition of a co-surfactant to the main foam-
ing surfactant can lead to more stability of the generated foam against oil 17 . Moreover,
the core-flood experiments have revealed that when a co-surfactant is used in the foaming
solution, the oil recovery increases 18 . However, these surfactants, which are known as foam
boosters, are typically expensive and exhibit high adsorption on the rock. These shortcom-
ings necessitate finding an alternative to co-surfactants to boost the foamability and stability
of the surfactants.
Nanoparticles are widely used as foam booster for the bulk foam, e.g., in the food and per-
sonal care products 19,20 . Under certain conditions, hydrophilic nanoparticles can be adsorbed
at the gas liquid interface and behave like surfactant molecules, especially in foam/emulsion
stabilization 21 . Compared to surfactants, nanoparticles are usually not available in large
quantities and can be more expensive. In order to prevent adsorption and aggregation of
the particles, the particles need to be coated with special chemicals to change their surface
properties, e.g., wettability 22 .
Our objective is to examine the possibility of replacing the expensive foam boosters with
3
inexpensive nanoparticles made of abundantly available coal fly-ash. Coal fly-ash is a by-
product of coal power plants, and can be served as a source for the low-cost large-scale
production of hydrophilic nanoparticles. Recently, Singh et al. used fly-ash nanoparticles to
stabilize CO2 -foam in sandpacks and sandstone cores 23 . Here, we investigate the possibility
of reducing the size of fly-ash particles using high frequency ultrasonic grinding. The effec-
tiveness of the produced fly-ash nanoparticles (we will refer to them as nano-ash particles)
in stabilizing the foam generated from a low-concentration surfactant is studied in different
sets of test tube and core-flood experiments .
The structure of the paper is as follows. First, we discuss the theoretical aspects of
stabilizing foam with nanoparticles. Then, we describe the physical properties of the coal
fly-ash and whether it is possible to reduce the average size of the fly-ash particles in an
ultrasonic de-agglomeration process. In the next section, we perform test tube and core
flooding experiments to investigate the effect of nano-ash on the foaminess and the foam
stability in presence and absence of oil, for a foam generated in test tubes and in a porous
medium. We discuss the results and finish with conclusions.
The role of surfactants in stabilizing a foam film can be explained based on the equilibrium
between the capillary pressure and the disjoining pressure. Firstly, surfactants reduce the
gas–liquid interfacial tension, which results in a lower capillary pressure (reduced drainage)
and a lower level of surface energy. Secondly, presence of surfactant at the interface increases
the surface charge, which enhances the repulsive forces between the gas-liquid interfaces.
More details about the surfactant-stabilized foam and its properties can be found elsewhere 6 .
A surfactant molecule, which is dissolved in the liquid phase, moves to the gas-liquid interface
due to its thermal energy, kB T , where kB is the Boltzmann’s constant and T [K] is the
absolute temperature. The same amount of energy is required to detach a surfactant molecule
from the interface and move it to the bulk, until the concentration of surfactant at the
4
interface and the bulk of liquid reaches a thermodynamic equilibrium.
Figure 1: (a) Curvature of a gas–liquid interface for a contact angle 0<θ<90 24 ; (b) Surfactant
molecules at the gas–liquid interface; (c) Nanoparticle at the water-gas or water-oil interface;
contact angle and curvature of the interface 24
Particles can be adsorbed on the gas–liquid interface depending on the wettability and
contact angle 24 , as shown in Figure 1-a,c. A fully water–wet particle (θ=0) prefers to stay
in the liquid phase. A gas–wet particle (θ=180) prefers to stay in the gas phase. Particles
that are not fully hydrophilic or hydrophobic (0<θ<180) can be adsorbed on the gas–liquid
interface like a surfactant molecule. The difference between the adsorption of a particle
with the adsorption of a surfactant molecule is that for particles larger than a fraction of
a nanometer, the required energy to detach the particle from the interface is a few orders
of magnitude higher than the thermal energy of the particle. Therefore, the adsorption of
a particle on the interface is irreversible. The energy requirement for the detachment of
particles is calculated by
E = πa2 σgw (1 ± cos θ)2 , (1)
where a [m] is the diameter of the particle and σgw [N/m] is the surface tension. This implies
that the maximum stability of an adsorbed particle at the gas–liquid interface is obtained
for a contact angle of θ=90o . If the contact angle is less than 90o , the gas–liquid interface
5
curves around the gas phase and forms gas bubbles 24–26 , as shown in Figure 1-a. This
contact angle can be obtained by changing the surface properties of the solid particle via
altering the pH, concentration of electrolytes in the liquid phase, or by adding surfactants
to the suspension 27–29 . Kaptay used a simplified model that does not consider the presence
of surfactant at the interface 30 , and showed that the optimum contact angle for the stability
of particle-stabilized foam (for a monolayer of solid particles) is 70o 31 .
For a naturally water–wet or hydrophilic particle (a contact angle of zero degree), the
contact angle can be increased by increasing the hydrophobicity of the particle. The max-
imum hydrophobicity can be obtained at the point of zero charge, i.e., a zeta potential of
zero 29 . This can be achieved by changing the concentration of monovalent and divalent ions
in the liquid phase. However, the point of zero charge makes the nanoparticle suspension
unstable and increases the rate of coagulation of the particles. These large particles, when
injected into a porous medium, block the pore throats and reduce the injectivity (injection
rate for a fixed pressure drop). Here, the main challenge is to find a condition, i.e., nano-
ash and surfactant concentration, pH, temperature, salinity, etc., that can provide a stable
suspension with high injectivity that is able to generate a strong foam in porous media.
Fly-ash particles
6
of less than 8 µm. They also found that most of the iron content is in the relatively low
number of large ash particles. It was observed that the composition of SiO2 in the larger
particles (around 8 µm) is higher than the smaller particles (around 1 µm) 33 . Based on
the amount of calcium oxide (CaO), fly-ash is classified into Class F (less than 20% CaO)
and Class C (higher than 20% CaO). The Class C fly-ash, which is a product of combustion
of subbituminous or lignite coals, contains a considerable amount of cementitious material,
which makes it suitable for use in cement products. The Class F fly-ash, which is mostly a
product of bituminous coal, does not contain cementitious material and therefore does not
harden in presence of water 34 .
To summarize, Class F fly-ash, which contains a large fraction of micrometer and sub-
micrometer amorphous aluminum silicate, can be potentially converted to nano-ash particles
using an economic comminution process, i.e., grinding and de-agglomeration. Large particles
with high iron oxide content can be filtered out during the grinding and de-agglomeration
process to reduce the possibility of precipitation of anionic surfactants.
Nano-ash production
Various comminution technologies can be utilized to reduce the size of coal fly-ash particles 35 .
Grinding can be done in a dry or a wet medium. In practice, the finest product of a dry
grinding process is above a mean particle size of 2-20 µm, which can be de-agglomerated to
an average particle size of 1 µm. A finer product, i.e., around 0.5 µm can be obtained by
using wet grinding and a suitable surfactant, e.g., in a ball mill 36 . Usually, it is possible to
de-agglomerate the product of a wet grinding process to even smaller sizes by using high-
intensity ultrasound devices 37,38 . Nevertheless, breaking particles to less than 1 µm is highly
energy-intensive 39 and only possible in small scales, whereas separation of agglomerated
particles to the same size is more energy-efficient due to the absence of moving mechanical
parts. All in all, the minimum average particle size that can be reached in wet-grinding
processes is above 100 nm.
7
Ultrasonic devices are used to break the bond between the agglomerated small particles
and homogenize the suspension 36 . Continuous implosions in the liquid phase near the ul-
trasound probe results in the fast movement and collision of the particles in the suspension;
consequently, abrasion and breakage of the particles can occur. This process is called ul-
trasound milling (or grinding) 38 . High intensity ultrasound grinding is extensively used in
handling nanomaterials 40 . In the production of inorganic nanomaterial, e.g., nanotubes, the
inorganic compound is vaporized at high temperature and then deposited on a substrate
at a lower temperature followed by high-intensity ultrasound grinding of the deposited soot
in a solvent (usually an organic liquid, e.g., alcohols) 40 . Another important application of
ultrasonic devices is separation of agglomerated particles, which is sometimes referred to
as ultrasound grinding 37,38,40,41 . Ultrasonic devices can also be used to separate the large
agglomerated particles after grinding the material in a ball mill or a planetary mill. Figure
2 shows the SEM imgae of ash particles after only five minutes of ultrasonic treatment. It
can be observed that a considerable number of particles are in a sub-micrometer size range.
In the next section, we study the effectiveness of longer ultrasound milling in reducing the
average particle size of a coal fly-ash suspension.
Experiments
Ultrasound grinding
8
circulated to control the temperature at 15o C. Samples with a volume of 5 ml are taken from
the receiver vessel at different times. The samples are immediately diluted by adding 10
ml of 1.0 wt% AOS solution to stabilize the suspension. Each sample remains stagnant for
15 minutes to allow the large particles to precipitate. Then size distribution of the stable
portion of each sample is measured by a Malvern Zetasizer Nano instrument.
Bulk-foam experiments
9
Ultrasound
generator
Transducer
Sound box
Receiver
vessel
Booster
horn
Coolant
Sonotrode
outlet
Cylinder
Coolant inlet
Figure 3: Process flow diagram of the ultrasound grinding experimental set-up; small arrows
show the circulating path of the suspension
quantified due to the multiple steps of dilution and separation of the large particles, however
it is estimated to be less than 0.05 wt%. The active AOS concentration in each sample is
adjusted to 1 mM (0.0315 wt%). Predetermined amounts of concentrated NaCl and CaCl2
in demineralized water are added to each sample to adjust the salt concentration. The pH of
each sample is adjusted to 4.0 by adding 0.1 M HCl solution. Foam is generated by applying
10 standard handshakes to each tube, which contains 5 ml nano-ash–AOS suspension.
The core flood experiments were performed in an experimental set-up shown schematically
in Figure 4. Nitrogen with a purity of 99.98% is supplied in 200 bar cylinders, which is
connected through a Swagelock manual pressure regulator to a calibrated Bronkhorst mass-
flow controller. A Quizix piston-pump (±0.001 ml/min) is used for the injection of the
surfactant solution. The injected gas-to-liquid ratio is controlled by adjusting the set-points
10
of the pump and the mass-flow controller. A Bentheimer core with a length of 0.17 m and
a diameter of 0.04 m is drilled out of an outcrop block and dried in oven for 48 hours.
The outer boundary of the cylindrical core is isolated using Araldite epoxy. The glued core
is placed into a PEEK (polyether ether ketone) core holder, which is suitable for CT-scan
analysis because of its low X-ray attenuation. Two holes are drilled in the core for the
internal differential pressure transducer connectors. The overall pressure drop of the core is
measured by connecting a differential pressure transducer to the input and output lines of
the core holder. The outlet of the core holder is connected to a back pressure valve. The
pressure on the valve is maintained by a nitrogen cylinder, and is adjusted by a manual
Swagelock pressure regulator. The outlet liquid stream from the back pressure is collected
in a glass vessel, where the weight is monitored by a Sartorius Precision balance (±0.01g).
All the measurement instruments are connected to an in-house data acquisition software via
an I/O box (National Instrument), where data is recorded every five seconds.
Anionic C14−16 Alpha Olefin Sulfonate (AOS BIO-TERGE AS-40, Stepan) surfactant is
used as received. Isopropyl alcohol (IPA) with a purity of 99.7% (Sigma-Aldrich) is used as
a foam-killer, for cleaning the core after each experiment.
Experimental procedure
First the set-up is filled with helium at 8 bar. All the connections are tested for leakage using
a helium detector. Then, the core is flushed with CO2 for a few minutes at atmospheric
11
pressure to remove helium and air from the system. The core is vacuumed for 12 hours to
remove CO2 . Afterwards, one pore volume of degassed water (or brine) with a flow rate
of 1.0 ml/min is injected. After the water breakthrough, the back pressure is increased
gradually to 25 bar, and 10 to 15 pore volumes of water is injected to dissolve and remove
the remaining traces of CO2 and fully saturate the core. The permeability is measured by
altering the water flow rate and measuring pressure drop across the core. Afterwards, a few
pore volumes of the surfactant solution is injected to satisfy the adsorption capacity of the
rock surface.
The surfactant-alternating-gas (SAG) injection experiments are performed by flooding
the surfactant-saturated core with nitrogen. Nitrogen is injected with a flow rate of 1.0
ml/min at the experimental temperature and pressure. The gas injection is continued until
no more liquid is produced from the core. After the dynamic gas-injection experiment, gas
and surfactant solution with different flow rates are co-injected into the core such that the
total flow rate (gas+liquid) is equal to 1.0 ml/min (equivalent to 5 ft/day Darcy velocity).
The injection of each gas/liquid ratio is continued until an steady-state pressure drop is
observed across the core.
The CT-scan instrument is a third generation SOMATOM Volume Zoom Quad slice
scanner from Siemens. The X-ray tube of the CT scanner is operated at a nominal voltage
of 140 keV and current of 250 mA. The core holder is installed vertically using a polymethyl
methacrylate stand at the front edge of the table 42 . Each scan contains four slices, which
cover a vertical 2.5 mm thick cross-section from the middle of the core. The resolution of
each image is 521 × 521 pixels, with a pixel size of 0.3 × 0.3 mm2 43 . The liquid saturation
is calculated by
HUf oam − HUdry
Sw = , (2)
HUwet − HUdry
where HU is the measured attenuation coefficient and the subscripts f oam, dry, and wet
stand for the foam-, nitrogen-, and surfactant-saturated core. The accuracy of the measured
saturation is within ±2% 42 .
12
Results and discussion
Ultrasonic results
Figure 5 shows the average particle size of the de-agglomerated fly-ash suspension versus
ultrasonic treatment time. The average particle size is reduced linearly with logarithm of
time. An average particle size of around 200 nanometer is reached after 24 hours of ultrasonic
treatment of the fly-ash suspension. Moreover, we observed that the concentration of sub-
micrometer-sized particles in the mixture increases with the treatment time. The treatment
time can be reduced by using more sonotrodes in series.
Figure 6 shows the particle size distribution of the fly-ash suspension after 24 hours of
ultrasonic treatment. The measurement is done using dynamic light scattering in a Malvern
Zetasizer Nano instrument. The result shows that 55 % of the particles are smaller than the
average particle size of 250 nm. Moreover, it shows that only 0.07% of particles are larger
than 1 micrometer. Given the pore size distribution of the Bentheimer sandstone, which
is in the range of few to few hundreds of micrometer 44,45 , if no agglomeration occurs, the
particles will easily flow through the pore throats.
2500
2000
Ave. particle size [nm]
1500
1000
500
0
10 -5 10 -3 10 -1 10 1 10 3 10 5
time [s]
Figure 5: Average particle size of the fly-ash suspension versus ultrasonic milling time
13
30
10
0
10 0 10 1 10 2 10 3 10 4
Particle size [nm]
Figure 6: Particle size distribution of the fly-ash suspension after 24 hours of ultrasonic
treatment.
The effect of pH on the zeta-potential of a 0.25 wt% nano-ash suspension in a 1mM AOS
mixture is shown in Figure 7. Extrapolating the curve to a zero zeta-potential reveals that
the point of zero-charge occurs at pH 3.0, which is close to the point of zero charge of
pure silica in water (pH=2). The plot also shows that near a neutral pH, the nano-ash
suspension has good stability, with a zeta-potential between -30 mV to -40 mV. For our test
tube experiment, we use pH=4.0 to increase the hydrophobicity of the nano-ash particles.
However, to have a better injectivity and avoid agglomeration of the nano-ash particles in
the core, we conduct the core flood experiments at a neutral pH.
Figure 8 shows the effect of NaCl concentration on the nano-ash–AOS foam. The concentra-
tion of NaCl increases from left to right from zero to 0.5 wt%, 1.0 wt%, and 5.0 wt%. The
foaminess of the mixture decreases with increasing monovalent ion concentration. However,
the foam texture at higher monovalent concentration shows smaller bubbles and a larger
bubble density, compared to relatively high number of large bubbles in the mixture with no
14
-10
Figure 7: Effect of pH on the surface charge of nano-ash particles; the suspension is stabilized
in a 1.0 mM AOS solution.
NaCl. This observation is in agreement with the zeta potential measurements, which shows
that the (absolute value of) zeta potential of the nano-ash–AOS is lower at higher NaCl
concentrations. It was previously explained that the contact angle approaches its optimum
value (regarding the foam stability) when zeta potential is near the point of zero charge.
This effect is observed in Figure 8 at NaCl concentrations of 1.0 wt% and 5.0 wt%.
15
Effect of CaCl2 on foamability
We study the stability of foam in the presence of oil by adding 1 ml of model oil to the
generated foam with 0.03 wt% AOS foam and a 0.03 wt% AOS with less than 0.05 wt%
nano-ash foam. Figure 10 shows that while the nano-ash foam stays stable (right figure)
after adding 1.0 ml of Ondina 919, the 0.03 wt% AOS foam breaks almost instantaneously
(left figure). The mechanism of the stability of the nano-ash foam in presence of oil is not
clear. It can be speculated that the presence of nano-ash particles at the gas-liquid interface
16
prevents or slows down the oil droplets from entering and breaking the lamellae 46 . We
regenerated the foam in presence of oil by shaking the tubes. We observe that the foaminess
of the nanosh-AOS-suspension is higher than the foaminess of AOS solution in presence of
Ondina 919.
Similar behavior is observed after adding 1.0 ml hexadecane to the generated foam (with
and without nano-ash), which is shown in Figure 11. However, when we tried to regenerate
the foam by shaking the mixture of nano-ash–AOS–hexadecane, a very stable emulsion was
created in the nano-ash-AOS-hexadecane tube. It was not possible to identify the type of
emulsion in this experiment. The interaction of surfactant-nano-ash-hydrocarbons requires
more investigations to identify whether the continuous phase in the emulsion is hexadecane
or water.
Figure 10: 0.03 wt% AOS foam with (right) and without (left) nano-ash (<0.05 wt%) after
adding of 1 ml of Shell Ondina 919 to the generated foam
17
Figure 11: 0.03 wt% AOS foam with (right) and without (left) nano-ash (<0.05 wt%) after
adding of 1 ml of hexadecane
The measured pressure drop in foam-flood experiments is reported as the apparent foam
viscosity, which is calculated by
kA ∆p
µf oam = , (3)
qg + qw L
where k [m2 ] is the permeability of the core, A [m2 ] is the cross-sectional area of the core,
qg [m3 /s] and qw [m3 /s] are the injection rates of gas and liquid, ∆p [Pa] is the measured
pressure drop, and L [m] is the length of the core. The foam quality (or the gas fractional
flow) is defined by
qg
fg = . (4)
q g + qw
The transition foam quality is defined as the foam quality, at which the maximum apparent
viscosity is observed.
Figure 12 shows the liquid saturation profile during the injection of N2 with a flow rate of
1.0 ml/min (at 6 bar back pressure and 22o C) into a 0.03 wt% AOS-saturated core (top) and
18
0.03 wt% AOS-0.25wt% nanoash-saturated core (bottom). From left to right, the CT-images
show the movement of the gas front (blue area) in the liquid-saturated core (yellow area).
First, we can observe that the gas breakthrough occurs earlier, i.e., after the injection of 0.7
PV nitrogen in the core saturated with only surfactant solution, whereas in the core with
the nano-ash the breakthrough occurs after the injection of 0.78 PV nitrogen. It means that
the sweep efficiency of the nano-ash foam is higher than the surfactant foam. This can also
be observed in the darker blue color of the foam region in Figure 12-bottom, which indicates
a lower liquid saturation. Secondly, the gas front looks sharper and flatter for the nano-ash
foam, which shows a better conformance improvement.
0.00PV 0.012PV 0.13PV 0.24PV 0.36PV 0.48PV 0.59PV 0.71PV 0.83PV 0.94PV 1.1PV 4.7PV
0.00PV 0.062PV 0.19PV 0.32PV 0.45PV 0.57PV 0.7PV 0.83PV 0.96PV 1.1PV 1.2PV 1.3PV
Figure 12: liquid saturation profile during the injection of nitrogen into a 0.03 wt% AOS-
saturated core (top) and 0.03 wt% AOS-0.25wt% nanoash saturated core (bottom).
Figure 13 shows the foam apparent viscosity (i.e., scaled pressure gradient across the
core) during the gas injection. The maximum value of apparent viscosity which is normally
observed after the injection of one pore volume of gas is 25% higher for the surfactant without
nano-ash. However, surfactant foam becomes quickly unstable after the injection of 2.3 PV
of nitrogen. The nano-ash foam stays stable for a longer time (4.0 PV of nitrogen), as shown
19
by the lower slope of the tail of the apparent viscosity curves in Figure 13. To summarize,
the SAG experiments show that compared with the surfactant foam, the nano-ash foam is
more stable, has higher sweep efficiency, and provides a better conformance improvement.
0.025
AOS 0.03 wt%
AOS-Nanoash
Apparent viscosity [Pa.s]
0.02
0.015
0.01
0.005
0
0 1 2 3 4 5
Injected pore volume [#]
Figure 13: Apparent viscosity of foam during the injection of nitrogen (at 22o C and 6
bar back pressure) into the surfactant-saturated (solid blue line) and surfactant-nanoash-
saturated core (dash-dot red line)
Figure 14 shows the results of the core flooding experiments in absence of oil. The dotted-
dashed line curve with triangular markers shows the apparent viscosity of a foam generated
by the co-injection of different fractions of nitrogen and 1 mM AOS (0.03 wt%) into a 2.0
Darcy Bentheimer sandstone core. The solid and dashed line curves show the apparent
viscosity for the co-injection of nitrogen and a suspension of 0.03 wt% AOS-0.25 wt% nano-
ash. These two curves are obtained in different Bentheimer cores with similar permeability,
which shows the repeatability of the experimental results. The maximum apparent viscosity
of 0.03 wt% AOS foam is 0.25 Pa.s and is observed at a transition foam quality of 20%. By
adding nano-ash, the transition foam quality is shifted to 60% with a maximum apparent
viscosity of 0.95 Pa.s. This value is comparable to the maximum apparent viscosity of a
1.0 wt% AOS-nitrogen foam at the same foam quality (shown in Figure 14). This result
shows that in the presence of nano-ash, stronger foam is generated by using only 1/30 of the
surfactant that is required to generate the same foam in the absence of nano-ash.
20
1.5
AOS 1.0%
np-AOS 0.03% I
0.5
0
0 0.2 0.4 0.6 0.8 1
Foam quality [-]
Figure 14: Apparent viscosity of 1.0 wt% AOS (thick line with circle markers), 0.03 wt%
AOS foam in presence (circle and square markers) and absence (triangular markers) of 0.25
wt% nano-ash; no oil and no salt.
Figure 15 shows the effect of nano-ash on the liquid saturation. The average liquid saturation
in the Bentheimer sandstone core during the core flooding with a nano-ash foam is below
0.10 for foam qualities above 0.4. The co-injection of nitrogen with the same surfactant
concentration (0.03 wt%) without nano-ash generates a foam with an average saturation
of 40% in the Benthemer core. This observation can be explained by the fact that the
measured pressure drop in in nano-ash foam flow is higher, which is an indication of larger
viscous forces. This higher viscous force fights against the capillary forces, which results in
a better sweeping efficiency and a lower liquid saturation for the nano-ash foam.
We study the effect of remaining oil saturation on the steady-state apparent viscosity of the
nano-ash foam. We conduct experiments at room temperature and 6 bar back pressure with
two different model oils, i.e., hexadecane and n-Ondina 15 (with a viscosity of 0.015 Pa.s
at 40o C and 0.0033 Pa.s at 100o C), and one experiment at 80o C and 80 bar back pressure
with a north sea crude oil. To reach the remaining oil saturation, we fill the core with water,
inject two pore volumes of oil, and produced the oil by injection of 10 pore volumes of CO2
21
0.5
0.4
0.1
0
0 0.2 0.4 0.6 0.8 1
Foam quality [-]
Figure 15: Liquid saturation of foam in presence (triangular markers) and absence (circular
markers) of nano-ash.
followed by 15 pore volumes of water. The CO2 injection was performed at 3 bar to minimize
the CO2 dissolution in oil and quickly reach the residual oil saturation. It was followed by a
long water-injection step to remove the remaining CO2 from the core. Finally, we inject 10
pore-volumes of 0.25 wt% nano-ash in 0.03 wt% AOS suspension to satisfy the surfactant
adsorption capacity of the core and oil. At this stage, we reach a remaining oil saturation of
0.45 for the hexadecane and 0.57 for the n-Ondina 15 (we skip the CO2 flooding for n-Ondina
15). At the beginning of the nano-ash-nitrogen co-injection, denoted by upper triangular
markers in Figure 16, we changed the foam quality from 0.9 to 0.7 and 0.5. This increases
the observed apparent viscosity from 0.008 Pa.s to 0.04 and finally a maximum value of 0.18
Pa.s. At this point, we produce another 2.0 ml of hexadecane. When we switch back to 0.7
foam quality, the apparent viscosity of the foam increases to 0.55 Pa.s. This sudden increase
of the foam strength, denoted by ’*’ markers in Figure 16, can be explained by the lower oil
saturation in the core after the production of 2.0 ml of hexadecane. Another contributing
factor could be the adsorption of surfactant on the solid and oil phase. We have previously
observed that more than 15 pore volumes of 0.03 wt% AOS solution should be injected
to reach thermodynamic equilibrium between the surfactant solution and the rock surface.
Therefore, some surfactant and nano-ash could be lost to the surface of the rock at the early
stages of the nano-ash foam flooding. The maximum apparent viscosity is observed at 0.60
22
foam quality, which shows that the transition foam quality is not affected by the presence
of hexadecane. However, the apparent viscosity is reduced by a factor of 10%. The results
of the nano-ash foam flooding in presence of the remaining Ondina 15 is shown in Figure 16
(lower triangular markers). The apparent viscosity of nano-ash foam in presence of Ondina
15 decreases by a factor of 1/3 compared to the apparent viscosity of nano-ash foam (circular
and square markers) in absence of oil. The transition foam quality is between 50% to 70%
foam quality, with a maximum apparent viscosity of 0.28 Pa.s.
Figure 16: Steady-state apparent viscosity of AOS-foam with and without nanoparticle in
different gas fractional flow.
The effect of crude oil on the strength of nano-ash foam is studied by conducting an ex-
periment at 80 bar and 80o C. We chose crude oil and high temperature and pressure to
demonstrate the application of nano-ash-stabilized-foam for EOR at near field condition.
The crude oil with a viscosity of 0.23 Pa.s at 25o C and 0.059 Pa.s at 50o C, was obtained
from a north sea field. The Bentheimer sandstone core is saturated with water and flushed
with two pore volumes of crude oil. Then oil is produced by the injection of water, nitro-
gen, 1.0 wt% surfactant, and 0.03 wt% surfactant. At least 5 pore volumes of each agent is
23
injected into the core until no more oil is produced in each flooding stage. At the end, we
reach a remaining oil saturation of 23%. Then, we co-inject nitrogen and 0.03 wt% AOS and
measure the apparent viscosity of foam in different foam qualities. The result is shown in
Figure 17 with ’+’ markers. The surfactant foam reaches its maximum strength at the tran-
sition foam quality of 0.35, with an apparent viscosity of 0.01 Pa.s. No production of oil was
observed at this stage. After the surfactant foam flooding, we inject 10 pore volumes of 0.25
wt% nano-ash in 0.03 wt% AOS suspension into the core. After that, we co-inject nitrogen
and nano-ash-AOS suspension with different foam qualities, and measure the steady-state
apparent viscosity of the nano-ash foam. The apparent viscosity of the nano-ash foam in
presence of crude oil is shown with ’o’ markers in Figure 17. The first data point is obtained
at 0.7 foam quality, with an apparent viscosity of 0.01 Pa.s, slightly higher than the apparent
viscosity of the surfactant foam. However, after co-injecting a few pore volumes at a foam
quality of 0.5, crude oil was produced in the form of a dark-brown stable emulsion and the
apparent viscosity of foam gradually increased to 0.05 Pa.s. None of the measurements could
be reproduced because of the continuous production of the emulsified oil, i.e., the system
never reached a real steady state. This observation is showed particularly by the last ob-
tained data point at a foam quality of 0.4, which shows an apparent viscosity of 0.065 Pa.s
(top left corner of Figure 17). Although the higher foam strength at lower oil saturation can
explain the above experimental results, it is also possible that a higher observed apparent
viscosity is the direct result of plugging. To examine this hypothesis, we switch back to
the co-injection of nitrogen and 0.03 wt% surfactant (without nano-ash). We repeat the
measurements at 0.7, 0.8, 0.5, and 0.4 foam qualities. The measured apparent viscosities are
only slightly higher than the values previously obtained during the coinjection of nitrogen
and AOS solution. This result rules out the possibility of plugging and proves that the higher
apparent viscosity of nano-ash foam in presence of oil is indeed due to the stabilizing effect
of nano-ash on the generated foam. The formation of stable crude oil-surfactant emulsion in
presence of nano-ash and its contribution to the observed higher apparent viscosity requires
24
more investigation.
Figure 17: Effect of crude oil on the strength of 0.03 wt% AOS-nitrogen (’+’ markers) and 1
mM AOS-0.25wt% nano-ash-nitrogen (’o’ markers) at 80o C and 80 bar. The solid lines are
only guide lines and not an actual model fit.
Conclusions
We study the production of nano-ash particle from coal fly-ash, stability of the nano-ash-AOS
suspension, foaminess and foam stability of nano-ash-AOS-nitrogen foam, and its behavior
in porous media in presence and absence of oil. We demonstrate that nano-ash particles
with an average particle size of 100-200 nm can be produced in a scalable ultrasonic de-
agglomeration process. Our test-tube results show that the monovalent and divalent ions
have an adverse effect on the foaminess of nano-ash-AOS suspension. Bulk foam that contains
nano-ash particles shows a higher stability in presence of hexadecane and ondina 919. Our
core flooding experiments in the Bentheimer sandstone show that the nano-ash-AOS-nitrogen
foam is remarkably stronger than the AOS-nitrogen foam with the same AOS concentration.
The amount of produced liquid with mixture of nano-ash and AOS is significantly larger
than the mixture without nano-ash. For first time we show that nano-ash can be used to
25
stabilize nitrogen foam in presence of crude oil at high temperature and pressure. We also
observed that crude oil tends to form stable emulsions in water in presence of nano-ash.
Acknowledgement
We thank Shell Global Solutions International for financial support and permission to publish
this work. We are grateful to Dr. S. Vincent-Bonnieu for his comments on the draft of the
manuscript. We would like to thank Michiel Slob (TU Delft) for his technical support, Ellen
Meijvogel-de Koning (TU Delft) for her assistance with the CT-scan instrument, and Markus
Herrmann and Elsa Arefaine (NMI) for their help with the bulk experiments.
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