Separation and Purification Technology 256 (2021) 117849

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

A facile and economical configuration for continuous generation and

separation of oil in water emulsions
Sunil Kumar , Aseem Pandey , Milana Trifkovic *, Steven L. Bryant *
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr. NW, Calgary, AB T2N 1N4, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: The development of a facile, compact, and inexpensive system for continuous liquid-liquid emulsification and
Emulsification separation, is a major engineering challenge in different industries such as petroleum, cosmetics, and food
Chitin nanocrystals production. Herein, we report a simple and scalable design strategy for continuous generation and separation of
Wettability
the oil in water emulsions. The inexpensive, abundantly available sand was utilized for the fabrication of porous
Porous medium
Demulsification
beds connected to process piping for continuous emulsion generation and separation. A mechanistic under­
standing of the governing parameters such as sand wettability, pore size, retention time, and energy dissipation
are discussed in detail. Building on this understanding, we are able to generate stable oil in water emulsions with
either nanoparticles or surfactants and achieve their complete demulsification by tuning the sand wettability,
pore size, and retention time. We show the industrial applicability of the designed system by generation and
separation of extremely viscous heavy crude oil in water emulsion, which would be suitable for pipeline
transportation. Our results show the new way for the development of a modular and economical process unit at
the industrial scale for liquid-liquid emulsification and separation.

1. Introduction
Emulsion based system have found interest in a wide variety of in­
dustries, such as drug delivery, pharmaceutical, cosmetics, food industry
and the petroleum industry [1,2]. Development of continuous mixing
process for the immiscible fluid phases towards more agile and modular
configuration remains one of the major challenges in these industries.
The oil and gas industries encounter emulsions in several form
throughout the value chain. The upstream petroleum operations
generally utilize emulsion for enhanced oil recovery operations [3–5] or
for transportation of highly viscous crude oil through pipeline as
emulsified oil droplets in water exhibiting optimum viscosity for pipe­
line transport [6,7]. However, such processes often require continuous
emulsion destabilization or demulsification to recover the constituent
phases, thereby enabling recycling of the expensive emulsion stabilizers.
Therefore, a paradigm shift, away from the batch type production to a
facile, continuous mixing configuration is the need of the hour for these
industries.
High shear mechanical mixing devices such as homogenizers or
ultra-sonicaters have become standard units for emulsification process.
However, these devices increase the overall size of the process unit and
are limited to a batch type processing [8–10]. Static mixers allow
continuous mixing of the immiscible phase to achieve emulsification at a
lower energy consumption than high shear mixing devices. To date
several studies have demonstrated the application(s) of static mixers for
continuous emulsification process as an attractive alternative at the in­
dustrial scale [11–13]. Unlike emulsification, development of a contin­
uous process for demulsification at the industrial scale is cumbersome
and has gained considerable attention by the scientists [14,15]. Several
demulsification techniques have been developed till date, such as,
chemical or biological, electrical, thermal and mechanical techniques
[16–18]. Novel approaches such as ultrasonic and microwave irradia­
tion have also been developed in the last decade [19–21]. However,
achieving high throughput at a low capital expenditure remains a
challenge for these technologies. Mechanical coalescers are attractive
because they satisfy both of the criteria for large scale applications. Li
and Gu [16] tested the coalescence efficiency for an oil-in-water (O/W)
emulsion, utilizing three different coalescing media, which include
polypropylene fibres and nylon fibres as the fibrous beds and poly­
propylene particles as the granular beds. They have examined the effect
of flow rate, inlet oil concentration, bed length, and fibre size on the
coalescence performance of the emulsion droplets. Ma and co-workers

* Corresponding authors.
E-mail addresses: mtrifkov@ucalgary.ca (M. Trifkovic), steven.bryant@ucalgary.ca (S.L. Bryant).

https://doi.org/10.1016/j.seppur.2020.117849
Received 22 July 2020; Received in revised form 29 September 2020; Accepted 3 October 2020
Available online 7 October 2020
1383-5866/© 2020 Elsevier B.V. All rights reserved.
S. Kumar et al.
investigated the efficiency of glass microfibers as a coalescing media to
remove oil phase from the emulsions [22]. They conducted a series of
experiments to investigate the effect of different parameters on oil
removal efficiency such as bed porosity, bed height, flow velocity and
influent oil concentration. The effect of coalescer geometry on the
coalescence efficiency has also been investigated [23]. The authors
estimated that the bed geometry alters the critical (interstitial) velocity
which depends upon the flow model and further affects the separation
efficiency. The development of filtrate materials with suitable wetta­
bility for oil water separation has been of particular interest. The super-
hydrophobic materials exhibit superior ability to block water, whereas
super-hydrophilic materials exhibit an oil blocking behaviour. Until
now, several reports have utilized these materials either for fabricating
membranes, porous sponge or foams for efficient oil–water separation
[24–28]. The complexity associated with the fabrication of such mate­
rials hindered their wide-spread utilization at the industrial scale.
Particle stabilized emulsions (Pickering emulsions) exhibit superior
stability in comparison to the surfactants, owing to their strong
adsorption to the oil–water interface [29–31]. The stability of Pickering
emulsions is highly influenced by the particle size, shape, surface
properties, and wettability [32,33]. In comparison to spherical particles,
anisotropic particles exhibit superior emulsion stability at lower particle
loadings [34–36]. Though Pickering emulsions can be formulated with
wide variety of particles, naturally occurring renewable biomaterials
such as cellulose and chitin have gained considerable attention in the
past decade as emulsion stabilizers [10,37–43]. Both cellulose nano­
crystals (CNCs) and Chitin Nanocrystals (ChiNCs) exhibit amphiphi­
licity, high aspect ratio (rod like morphology), high strength and
stiffness and excellent dispersibility in water which makes them excel­
lent emulsion stabilizers for industrial applications [10,37,43–46].
Herein, we propose such a facile and inexpensive process for
continuous emulsification and demulsification. This platform utilizes
the abundantly available sand to fabricate a porous sand packed bed and
ChiNCs or CNCs as emulsion stabilizers. The sand pack was used for
emulsification by co-injection of oleic and aqueous (nanoparticle
dispersion) phases continuously through the sand pack. For demulsifi­
cation, the emulsion was injected through another sand pack for
continuous oil–water separation. The sand surface wettability and size
were altered to elucidate its effect on the emulsification/demulsification
process. In addition, the emulsification and demulsification were opti­
mized by carefully investigating the underlying mechanisms. More
importantly, the developed process was also tested and investigated for
the surfactant-based emulsions to widen the scope of application. To the
best of our knowledge, this is the first comprehensive report on the
development of a facile, modular, and inexpensive process for contin­
uous emulsification and demulsification using an abundantly available
material such as sand. This versatile platform can be implemented for
applications such as large-scale formulation of heavy oil in water
emulsion for efficient pipeline transport and further demulsification at
the refinery gate.
2. Experimental section
2.1. Materials
Chitin powder used for the synthesis of ChiNCs was procured from
the Alfa Aesar. Dodecane (Sigma Aldrich) was used as received as the oil
phase. Tergitol NP 10 (non-ionic surfactant) was procured from Sigma
Aldrich and used as received. Quartz sand with different mesh sizes,
ASTM 16–30, 50–70, 100–140, 140–270 mesh was used to make a sand
pack as a porous media after acid washing and treating. SurfaSil
(Dichlorooctamethyltetrasiloxane) was obtained from Thermo Scientific
and used as a silanizing agent. Water was purified with a Milli-Q
apparatus (18.2 MΩ.cm at 25 ◦ C, pH – 6.5) and is referred to as puri­
fied or deionized (DI) water in the subsequent text. Spray dried CNCs
with an average length of 100–200 nm and width of 15 nm were
2
Separation and Purification Technology 256 (2021) 117849
supplied by Alberta Innovates Technology Futures (AITF) and were
desulfated using HCl as detailed in our previous work [47].
2.2. Methods
2.2.1. Synthesis and characterization of Chitin nanocrystals
ChiNCs were synthesized in the laboratory by acid hydrolysis of
chitin powder using 3 M HCl [40]. 10 g of Chitin powder was added to 3
M HCl at 90 ◦ C and stirred for 90 min. The resulting mixture was sub­
jected to multiple cycles of washing with DI water and centrifuging at
4000 rpm for 30 min. The resulting suspension was then dialyzed
against DI water for 5 days. A probe sonicator (Q Sonica, 700 W) was
employed to break the aggregates in the ChiNC suspension with an
intermittent on off cycle for 10 min. Finally, the ChiNCs suspension was
filtered through a 5 µm and 1 µm filter to remove the residual debris. The
concentration of the ChiNCs suspension was then measured and the
suspension was kept in a 4 ◦ C fridge. ChiNC suspensions with different
loadings were prepared by diluting the stock ChiNCs suspension. The
ChiNC suspensions were then sonicated for 10 min using a probe soni­
cator (Q Sonica, 700 W) with an on–off cycle of 30 s. The prepared
suspension was then used for preparing the Pickering emulsion.
2.2.2. Dynamic light scattering (DLS) and zeta (ζ) potential measurements
The apparent hydrodynamic diameter of the ChiNC was measured
using a Malvern® Zetasizer Nano ZS instrument with a wavelength of
633 nm and scattering angle of 173◦ . DLS was performed on the dilute
suspensions (~1 mg/mL) and repeated a minimum of 15 times to obtain
the particle size distribution. The ζ-potential was measured using Mal­
vern® Zetasizer Nano ZS instrument with a disposable cuvette
(DTS1070). ChiNC dispersion of ~0.25 mg/mL in 10 mM NaCl were
prepared and measured a minimum of 3 times.
2.3. Atomic force microscopy (AFM)
AFM was performed on spin-coated films of ChiNC using an Asylum
MFP-3D instrument (Asylum Research, an Oxford Instrument Company,
Santa Barbara, CA, USA). Silicon substrates were cleaned in Piranha
solution for 30 min, followed by continuous rinsing with purified water
and drying with nitrogen gas. Suspensions of ~1 mg/mL were prepared
by dispersing freeze-dried ChiNC in purified water and ultra-sonicating.
ChiNC suspension were spin coated directly on silica substrate. AFM
images were collected in alternating current (AC) mode under air at­
mosphere using rectangular FMR cantilevers (NanoWorld) with normal
spring constants of 1.2–5.5 N/m and resonance frequencies of 60–90
kHz. The obtained images were processed in Igor Pro 6.0 running
Asylum Research AFM software (version 13.17) using a second order
flattening routine. The AFM size of the ChiNC was also determined by
selectively measuring the length and width of a minimum of 80 particles
where boundaries were distinguishable.
2.4. Optical microscopy
A Zeiss inverted microscope (Zeiss Axio Vert.A1) was used to obtain
images of the oil droplets. These images were processed in Image J
software to reveal the droplet size distribution of each sample. A mini­
mum of 100 droplets per sample was analyzed to ensure the accuracy of
the obtained distribution. The Sauter mean diameter (D3,2) of the
droplets was calculated and reported as average droplet size throughout.
2.5. Confocal laser scanning microscopy (CLSM)
CLSM was performed on filtrate immediatelty after the emulsion
separation tests. For confocal imaging, oleic phase was labelled with
perylene dye (0.01 mg/mL) and the nanocrystals were labelled with
rhodamine B isothiocyanate (RITC), as to enable direct viewing of both
the oil droplets and the nanoparticles within the filtrate as previouly
S. Kumar et al.
reported [47]. Filtrate was imaged using a Leica SP8 inverted CLSM
using exitiation wavelenght of 415 nm and 544 nm for perylene and
RITC respectively. Images were obtained using a 63x oil immersion
objective.
2.6. Emulsion preparation
For emulsion separation tests, different pre-generated oil in water
emulsions were prepared using a rotor stator homogenizer (PRO Sci­
entific PRO 250) with a 20 mm generator at 35,000 RPM for 1 min.
ChiNC was diluted to a concentration of 0.5 wt% from the stock solution
and 20 mM NaCl was added to the Chitin suspension to improve the
emulsification [40]. For tests carried out with desulfated CNCs, NaCl
was not added to aid emulsification [47]. Similar emulsification pro­
cedure was employed for emulsion prepared with Tergitol NP-10 sur­
factant in DI water. In one particular case, to obtain larger droplet size,
low energy mixing was employed for emulsification using a vortex mixer
(Fisher scientific digital vortex mixer) for 1 min.
2.7. Treatment of quartz sand and sand pack arrangements
The sand (quartz sand) used in the experiments was first washed with
2 M HCl. This acid washed sand is called as hydrophilic (HL) sand
throughout the manuscript. The surface wettability of the acid washed
sand was altered to hydrophobic using a silanizing agent. A mixture of
90% (V/V) Heptane and 10% (V/V) SurfaSil® was prepared for surface
treatment of sand. Sand was completely immersed in the mixture of
SurfaSil® and Heptane solution for 2 h. The solution was agitated every
15 min to ensure a uniform coating all over the sand. Silanized sand was
then rinsed with Heptane to remove unreacted SurfaSil®. After the
heptane rinse, the sand was further washed with methanol to ensure
complete removal of excess solvent/silanizing agent. Finally, the silan­
ized sand was dried for 12 h at 100 ◦ C in the oven. Dried sand was then
stored at ambient temperature before preparing the sand pack. The
treated sand is called as hydrophobic (HB) throughout the manuscript.
For emulsion generation and separation tests, different sand packs were
prepared with varying length, width and sand size (grain size). Ac­
cording to the sand size, suitable metallic meshes (screens) were inserted
at both the end caps of the sand pack to retain the sand in place and keep
it from flowing out of the sand pack. The corresponding sand sizes and
pore throat sizes (both for circular and tetrahedron arrangements) for
different ASTM sand sizes (mesh sizes) are tabulated somewhere in the
paper (supplementary Table ST1).
Fig. 1. Schematic representation of different setups for emulsion generation (a) and emulsion separation (b).
3
Separation and Purification Technology 256 (2021) 117849
2.8. Experimental setups for emulsion generation and separation
Dual piston pump(s) (VP-12 K, Vindum engineering) having flow
rate ranges from 0.0001 mL/min to 29 mL/min was used throughout the
experiments. All the tubing used in the setup had a pressure safety rating
of 2200 psi. The maximum pressure limit of the connected pressure
transducer was 2000 psi. To ensure safe operations, the pump was
operated with a safety interlock which would shut down the process
when the pressure reaches the set value of 1950 psi. The lab designed
emulsion generation (emulsification) setup consists of two pumps and
two transfer vessels for both the oleic phase and aqueous phase along
with one pressure transducer and one sand pack holder of varying di­
mensions. The set-up was designed to allow for simultaneous injection of
aqueous (nanoparticle suspension) and oleic phases through a sand pack
to generate emulsion. All the emulsion generation experiments involved
the aqueous and oleic phases meeting at a tee positioned just upstream
(before inlet) of the sand pack. From the tee, the two phases would enter
into the sand pack simultaneously. The schematic representation for the
emulsion generation setup is shown in Fig. 1(a). The calculation for
emulsion generation efficiency is mentioned in appendix SA1 in the
supplementary file.
The emulsion separation (demulsification) setup consists of one
pump and one transfer vessel (for emulsion) along with one pressure
transducer and one sand pack holder of varying dimensions. The pre­
pared emulsion was immediately poured into the transfer vessel con­
nected to the sand pack. Emulsion sample was collected through the
tubing before it enters the sand pack and kept untouched on the table
until the end of the test to see the effect of creaming. 150–300 mL of
emulsion was injected through a single sand pack system and collected
in 15 mL tubes/vials for further analysis like droplet size distribution
and oil separation efficiency. The schematics of emulsion separation
setup is shown in Fig. 1(b). The emulsion separation efficiency (oil
separation efficiency) was calculated based on the amount of initial oil
presence in the emulsion and the amount of free oil presence in the
effluent samples. The method is described in appendix SA2 in the sup­
plementary file. The tests were carried out at a lower flow rate of 1 mL/
min to avoid in-situ emulsification as well as to provide more contact
time (between emulsion droplets and sand surfaces) for adequate
demulsification.
2.9. Energy dissipation calculation
Energy dissipation (Ed ) during the emulsification process was esti­
mated using Eq. (1) for different sand pack setups [48,49].
Ed = ΔP × Qnet × tr (1)
S. Kumar et al.
A×φ×L
tr =
Qnet
Where ΔP is the differential pressure across the sand pack (Pa), Qnet is
the net volumetric flowrate (m3/s), tr is residence time of injected fluids
in the sand pack (sec), A is the cross-sectional area (m2), L is length of
sand pack (m), andφ is the porosity of sand pack (dimensionless). The
numerator part of Eq. (2) is nothing but the pore volume available for
injected fluids to flow through. However, for convenience psi, mL/min,
cm2 and cm units are used for pressure, flowrate, area and length
respectively with a unit conversion factor of 6894.76 × 106 to keep the
energy in Joule throughout.
3. Results and discussions
The emulsions were prepared with the synthesized ChiNCs or cel­
lulose nanocrystals (CNCs). ChiNCs had a rod-shaped morphology with
an average length and width of 250 nm and 20 nm respectively (Fig. S1
(a)). The measured apparent hydrodynamic diameter for ChiNCs was
120 ± 40 nm and the zeta potential was 30 ± 4 mV as depicted in
supplementary Fig. S1(c). Cellulose nanocrystals (CNCs) have a similar
morphology but negative surface charge (zeta potential ¡14 ± 3 mV)
(Fig. S1(b,c)).
3.1. Emulsion generation by co-injection of aqueous and oleic phases
The emulsion generation tests were carried out by co-injecting an
oleic phase (dodecane (1.36 cP)) and dispersion of 0.5 wt% of ChiNCs in
water as an aqueous phase through the sand pack. The emulsion gen­
eration efficiency was calculated based on the amount of generated
emulsion and the amount of injected free phases. The calculation
method is described in appendix SA1 in the supplementary file. Sand­
packs prepared with both hydrophilic and hydrophobic sand were used
to examine the effect of sand surface wettability on emulsion generation
efficiency. The properties of both the hydrophilic and hydrophobic sand
such as contact angle and zeta-potential have already been reported
elsewhere [50–59] The results for emulsification by co-injecting ChiNCs
and dodecane through 7.6 cm long sand packs filled with 100–140
ASTM sands (pore size = 7.7–23.2 μm) (both hydrophilic and hydro­
phobic) are shown in Fig. 2. The water to oil ratio for this experiment
was kept 1:1 by keeping equal flow rates of both the aqueous and the
oleic phases. The net flow rate is the summation of flow rate for both
Fig. 2. Emulsion generation efficiencies and differential pressures (across sand
pack) of co-injection (1:1 ratio) of ChiNCs (0.5 wt%) suspension and dodecane
through hydrophilic and hydrophobic sand packs (bed length 7.6 cm, inner
diameter (ID) = 0.7747 cm, 3/8′′ tubing, A = 0.4713 cm2 and ASTM 100–140
sand with porosity, ϕ = 34.5%) at varying flow rate.
Separation and Purification Technology 256 (2021) 117849
phases. It was observed that hydrophilic sand packed bed was able to
(2) emulsify the oleic and aqueous phases completely at a threshold net flow
rate of 20 mL/min. However, hydrophobic sand packed bed was not able
to emulsify the oleic and water phases at all the flow rates tested. The
results shown in Fig. 2 indicates the importance of wettability of the
sand surface in emulsification process.
To examine the effect of sand size or the resulting pore throat size
(supplementary Table ST1), emulsion generation experiments were
carried out for 50–70 ASTM sand (pore size = 15.7–46.4 μm), which has
a larger pore throat size compared to 100–140 ASTM sand (pore size =
7.7–23.2 μm). The threshold net flow rate for 50–70 ASTM sand for
complete emulsification was 2.8 times higher than the 100–140 ASTM
sand (supplementary Table ST2 for emulsion efficiency). The results
obtained by utilizing CNCs as opposed to ChiNCs indicate that the par­
ticle surface charge does not alter the emulsification process (supple­
mentary Fig. S2). Note that both type of particles had interfacial affinity.
Surfactants are commonly employed as emulsifiers and to compare
surfactant-stabilized and nanoparticle-stabilized emulsion systems, we
used Tergitol NP10 as the emulsifier. When the aqueous phase (con­
taining 0.5 wt% of surfactant) and dodecane (the oleic phase) was co-
injected in the same sand pack, it was observed that emulsification ef­
ficiency was nearly zero and no emulsion was observed in the effluent.
Moreover, the differential pressure across the sand pack was signifi­
cantly lower (less than 10 psi) in comparison to the emulsification ex­
periments carried out with nanoparticles (100–300 psi). The lower
pressure differential across the sand pack can be attributed to the lower
capillary pressure required for the fluid(s) to enter into a pore space due
to the lower surface tension in presence of the surfactant [60]. Pressure
dissipation (or loss) in sand pack/porous beds (including static mixers)
is the combination of kinetic energy loss, viscous energy loss and energy
loss due to friction, which greatly depends on the flow rate, fluid(s)
properties, sand shape and size (hence pore throat size) and sand pack
dimensions [48,49,61]. Therefore, based on Eq. (1 and 2) to provide
more energy and enable proper mixing of the fluid phases sand pack
cross sectional area was varied. A sand pack of 0.4731 cm2 (3/8′′ tubing)
was replaced by one with a lower cross-sectional area of 0.1641 cm2 (1/
4′′ tubing). When 50–70 ASTM sand was packed in a 3.5 cm long sand
pack the emulsion generation efficiencies were 7, 23 and 54% with
differential pressure along the sand pack of 13, 22 and 32 psi at a given
flow rate of 10, 40 and 56 mL/min respectively (shown in supplemen­
tary Table ST2). However, when the sand pack was packed with
100–140 ASTM sand, the smaller pore throat resulted in an increase in
the capillary entry pressure requiring higher energy input to overcome
this flow restriction [60]. As a result, emulsion generation efficiency
increased significantly viz., 87.8, 89 and 96% with differential pressure
across the sand pack of 38, 59 and 156 psi corresponding to the flow
rates of 10, 30 and 56 mL/min respectively (shown in supplementary
Table ST2).
Since further reduction of the cross-sectional area/tubing diameter
was not feasible the length of the sand pack bed was increased from 3.5
cm to 10 cm to further increase the energy dissipation of the system (see
Eq. (1) and (2)). The 10 cm long sand pack enabled complete emulsifi­
cation, i.e. 100% emulsion generation efficiency at a threshold flow rate
of 20 mL/min for 100–140 ASTM sand. The corresponding energy
dissipated, the differential pressure at varying flow rates is reported in
supplementary table ST2.
The emulsion generation efficiency as a function of increase in the
dissipated energy for both the nanoparticle and surfactant systems are
shown in Fig. 3. Results demonstrate that the surfactant system was able
to achieve complete emulsification (100%) at a lower energy (threshold
energy of 0.378 J) as compared to the nanoparticle system (threshold
energy of 1.03 J). Beyond the threshold energy both the systems
(nanoparticle and surfactant) have achieved complete emulsification
(Supplementary Table ST2). Increasing energy dissipation leads to an
increase in change in interfacial Gibbs free energy (hence entropy)
which is the basic criteria for emulsification from a thermodynamic
4
S. Kumar et al.
Fig. 3. Emulsion generation efficiencies with increasing energy dissipation for
nanoparticle (ChiNCs (0.5 wt%))-dodecane and surfactant (Tergitol NP 10
(5000 ppm))-dodecane systems (1:1 phase ratio) (refer supplemen­
tary Table ST2).
point of view [62].
To evaluate the effect of energy input beyond the threshold on the
emulsion microstructure, the flowrate of both fluid phases was further
increased. It was observed that with an increase in the flowrate droplet
size for the generated emulsion was reduced (Fig. S3). As shown in
Fig. S1(c), ChiNCs have a broad zeta potential distribution which in­
dicates that numerous particles in suspension possess different surface
charges. This in turn results in distribution of interfacial particle
adsorption dynamics. The net force required for a particle to reach the
oil–water interface is the difference between the input energy (for
mixing) and the force which arises due to electrostatic repulsion, van der
Wall interactions, image charge repulsion [43,63]. With an increase in
the energy dissipated (Ed ) by increasing the net flowrate during the
emulsification process, particles were readily able to overcome the
repulsive barrier at the generated oil–water interface and higher surface
coverage was achieved. Contrary, at lower energy input some fraction of
the nanoparticles was not able to overcome the repulsive barrier at the
interface or faced significant repulsions from the already adsorbed
nanoparticles at the interface (Supplementary Fig. S3). The lower par­
ticle coverage of the oil–water interface results in the increase in the
droplet size [64]. Similar behaviour of emulsion droplet size with
increasing energy input has been observed previously when emulsion
generation was carried out by a static mixture [48].
The underlying mechanisms of emulsion generation in hydrophilic
Fig. 4. Schematic of underlying mechanism for oil in water emulsion generation in (a) hydrophilic and (b) hydrophobic pores.
5
Separation and Purification Technology 256 (2021) 117849
sand pack (or channel) against hydrophobic sand pack are demonstrated
using a schematic in Fig. 4. Typically, at the macroscale, the nature of
the emulsion formed is determined by the affinity of the stabilizer for the
oil or the water (Hydrophilic-lipophilic balance for surfactants and
contact angle for nanoparticles)[65,66]. The effect of wall wettability or
solid–liquid interfacial tension in the case mechanical stirrers, sonicaters
does not influence the emulsion type. However, with a decrease in di­
mensions of the emulsification devices to microscale, such as in micro­
fluidic devices or porous capillaries the effect of solid–liquid interfacial
tension on the emulsion type plays a significant role [67]. When two
immiscible phases (example oil and water) are in contact with a solid
surface, one phase preferentially adheres to the solid surface and is
defined as the wetting phase. The wetting phase thereby forms a thin
film on the solid surface. Eqs. (3) and (4) shows the minimum amount of
energy required for the generation of oil in water and water in oil
emulsion for hydrophilic pore channels.
ΔEo/w = 4πr2 σ S− w + 4π r2 σw− o (3)
ΔEw/o = 4πr2 σ S− w + 4π r2 σw− o + 4πr2 σo− w (4)
Where, σ is interfacial tension, r is droplet radius, s, w and o repre­
sent solid water and oleic phases, respectively.
From Eqs. (3) and (4) it can be inferred that for hydrophilic pore
walls, generation of an oil in water emulsion is energetically favorable
over a water in oil emulsion. For the generation of a water in oil
emulsion in hydrophilic pore walls, two interfaces are involved, i.e. the
interface between the adsorbed water phase on the solid surface and the
continuous oil phase and the interface between the continuous oil phase
and dispersed water phase. This results in a creation on an extra inter­
face which increases the minimum amount of energy required for
emulsification. For an oil in water emulsion only the interface between
the continuous water phase (wetting phase) and the droplet phase (oil)
is involved which results in lower amount of energy required for
emulsification. To put it into perspective, for hydrophilic pore walls
generation of oil in water emulsion is energetically favorable. Moreover,
ChiNCs have the ability to kinetically stabilize oil in water emulsions
(θ < 90 ) by readily adsorbing to the generated oil–water interface [40].
◦
Similarly, for the hydrophobic sand pack, oil in water emulsion is
energetically unfavorable as shown in Eqs. (5) and (6) below.
ΔEw/o = 4πr2 σ S− o + 4πr2 σo− w (5)
ΔEo/w = 4πr2 σ S− o + 4πr2 σo− w + 4πr2 σ w− o (6)
Moreover, the energetically favorable state for hydrophobic pore
walls, i.e. water in oil emulsion was not observed in our experiments due
to the inability of the ChiNC or Tergitol NP-10 to stabilize water in oil
emulsions. Therefore, emulsion generation was not achieved for the
hydrophobic sand pack in our system. Similar observations on the effect
S. Kumar et al. Separation and Purification Technology 256 (2021) 117849

of surface wettability have been reported earlier for the microfluidic agreement with previous work which showed that complete droplet
devices [68,69]. Therefore, in hydrophilic sand pack systems, variation deformation or breakup occurs after several passes through the series of
in oil–water ratio in the injected streams did not alter the type of nozzles (here pore throats) [75].
generated emulsions i.e., they remained oil-in-water emulsions (Figs. S4 Fig. 6 illustrates the effect of grain size on the emulsion separation
and S15). efficiency. The oil separation efficiency improved as the pore diameter
approached the diameter of the emulsion droplets, reaching 100% for
ASTM 140–270 sand (pore size = 3.9–19.2 μm). This is depicted in Fig. 6
3.2. Demulsification using sand pack (b) where the pore size envelope (shaded blue) completely overlaps the
droplet diameter envelope (shaded green) for ASTM 140–270 sand
The emulsions formed by rod shaped nanoparticles have outstanding resulting in 100% separation efficiency whereas for ASTM 100–140 sand
long-term stability as highlighted by previous work [10,35,43,70,71]. the smaller droplet diameter did not overlap the pore size envelope. The
Owing to this enhanced stability of particle-stabilized emulsion, incomplete coalescence for ASTM 100–140 sand (97% separation effi­
instantaneous and continuous demulsification without the addition of ciency) resulted in a small amount of emulsion in the collected effluent
any chemical or external stimuli (such as temperature) is a formidable samples. The microscopic image confirmed that the collected emulsion
task. Surfactant stabilized emulsions which have lower stability in contains droplets less than 10 μm in diameter (Fig. S6(b)) which is lower
comparison to the particle-stabilized emulsions [29] have previously than the smallest pore throat size for ASTM 100–140 (pore size =
been demulsified using fibrous or granular beds with varying geometry. 7.7–23.2 μm) sand. The confocal images of the filtrate (aqueous phase
However, these methods lacked the efficiency in terms of complete after separation process) in case of sand packs containing ASTM
demulsification, inability to handle large volumes, operational ease, and 100–140 sand and ASTM 140–270 sand are shown in Fig. S7(a, b).
high operating costs [16,23,72,73]. Chawaloesphonsiya and Painma­ Confocal images reveal negligible amount of oleic phase present in the
nakul [73] utilized polypropylene coalescer media of different shapes filtrate with a droplet size of less than 1.5 μm in case of sand packs
(viz., granule, fiber, and tube) to demulsify cutting oil emulsion and containing ASTM 100–140 sand. However, such droplets were not seen
achieved a maximum demulsification efficiency of 43% in their work.
In order to depict the effect of sand surface wettability on demulsi­
fication, emulsion stabilized with ChiNCs (Oil: water-50:50) was injec­
ted through sand packs (L = 7.6 cm, 3/8′′ tubing, cross-sectional area (A)
0.4713 cm2) prepared with hydrophilic and hydrophobic sand. Here,
initially ASTM 16–30 sand (pore size = 45–186.2 μm) was chosen to
provide higher residence time and avoid in-situ emulsification. Effect of
decreasing the pore throat side is explained later in the article. As shown
in Fig. 5, hydrophilic and hydrophobic sands packed beds resulted in
12.95% and 47.37% oil separation efficiencies, respectively. The
aforementioned results indicated the effect of sand surface wettability
on the demulsification efficiency.
To further elucidate the effect of bed length on the demulsification
efficiency, sand packs (hydrophobic sand) with three different lengths
viz. 7.6 cm, 20 cm and 40 cm were prepared. It is to be noted that all the
experiments hereafter were carried out with a concentrated emulsion
(O: W- 70:30) to minimize the effect of creaming [74] (supplementary
Table ST3). As shown in Fig. S5, oil separation efficiency increased from
33.65% to 46.03% on increasing the bed length from 7.6 cm to 20 cm.
However, further increasing the bed length to 40 cm did not increase the
separation efficiency (47.74%) significantly. The obtained results are in

Fig. 5. Oil separation efficiencies of emulsion flow through hydrophilic and

hydrophobic sands packed beds, including differential pressure across the sand Fig. 6. (a) Effect of sand grain size on oil separation efficiencies. (b) Com­
packs (bed length 7.6 cm, inner diameter (ID) = 0.7747 cm, 3/8′′ tubing, A = parison of pore throat and emulsion droplet size. (sand pack’s length = 40 cm,
0.4713 cm2 and ASTM 16–30 sand, WOR = 1:1, flow rate 1 = ml/min, ChiNCs inner diameter (ID) = 0.7747 cm, 3/8′′ tubing, A = 0.4713 cm2 filled with
= 0.5 wt%). hydrophobic sands, WOR = 30:70, flow rate 1 = ml/min, ChiNCs = 0.5 wt%).

6
S. Kumar et al.
in case of sand pack containing ASTM 140–270 sand through confocal
microscope which further attributes to oil free filtrate (aqueous phase).
To elucidate the effect of pore wall wettability, demulsification
experiment was carried out with ASTM 140–270 hydrophilic sand. As
evident from Fig. S8, even though the pore throat matched the droplet
size, complete demulsification was not achieved. Based on these
experimental findings, we propose the mechanism of demulsifcation
through porous media with varying pore size and wettability (Fig. 7).
For a hydrophilic sand packed bed, the point-contact of emulsion droplet
with the pore wall does not result in its spreading over the pore surface
(Fig. 7a). As a result, the emulsion droplets pass through hydrophilic
pores and do not undergo coalescence (Fig. 7b). However, in case of
hydrophobic sand packed bed, when the emulsion droplet size and pore
throat size are similar, the oil droplets spread over the sand surface upon
contact with it (Fig. 7b). The strong adhesion of the oil phase with the
pore wall results in the draining of the continuous water phase,
detachment of ChiNCs from the interface and accumulation of oil phase
on the pore surface. The coalesced oil droplets increase in size as more
droplets undergo coalescence. If the emulsion droplets sizes are lower
than pore throat size (Fig. 7c), the droplet close to the pore surface may
undergo adhesion with the hydrophobic sand surface. This results in the
deformation of the drops adhered to the surface and creation of extra
surface that is not occupied by particles. This droplet will interact to the
surrounding droplets adhered to the hydrophobic sand surface and
further undergo induced coalescence through these “weak spots” in the
interface [76], resulting in an increase in the droplet diameter. The
droplet diameter after several coalescence stages will approach the pore
throat diameter eventually and will undergo complete phase separation
as shown in Fig. 7b.
Contrary to nanoparticle stabilized emulsion, the surfactant (Tergitol
NP 10) stabilized emulsion did not undergo demulsification at a flow
rate of 1 mL/min through the hydrophobic sand pack system (Fig. S9)
even when the sand pack was prepared with ASTM 140–270 sand
(corresponding pore throats: 3.9–19.2 μm). Note that for this set of ex­
periments, the emulsion was prepared with homogenizer and resulted in
average droplet size of 4 μm. However, when the flow rate was varied
between 0.2 mL/min to 5 mL/min, it was observed that at lower flow
rates or higher residence time resulted in partial demulsification
(Fig. S10). For the purpose of complete demulsification, surfactant sta­
bilized emulsion was prepared with a vortex mixer resulting in a larger
average droplet size of 11 μm. Similar to the nanoparticle stabilized
emulsion, complete demulsification was achieved at a flow rate of 1 mL/
min for the surfactant stabilized emulsion (Fig. S11). However, at a
higher flowrate of 5 mL/min, complete demulsification did not take
place. The prepared surfactant stabilized emulsion was also injected into
Fig. 7. Schematic of mechanisms involved during emulsion separation or
demulsification through hydrophilic pores (a), hydrophobic pores or channels
where pore size is similar to or less than emulsion drop diameter (b) hydro­
phobic pores or channels where pore size is bigger than emulsion drop diameter
(c) (not to scale).
7
Separation and Purification Technology 256 (2021) 117849
a hydrophilic sand pack. The hydrophilic sand pack did not result in any
demulsification as expected. Interestingly, the emulsion collected from
the outlet of the hydrophilic sand pack had an emulsion with average
droplet size of 6.5 μm which was smaller than the average droplet size of
the injected emulsion (12.84 μm). This inferred that hydrophilic sand
pack resulted in further emulsification under the applied shear
(Fig. S12).
The nanoparticle stabilized emulsions underwent complete demul­
sification (for similar pore and droplet size) regardless of the flow rate
(tested up to 5 mL/min). On the contrary, at higher flow rates surfactant
stabilized system did not undergo complete demulsification (Fig. S11).
We attribute this result to the difference in the elasticity of the emulsion
generated using surfactants in comparison to the nanoparticle stabilized
emulsions. Due to the elastic nature of the interface for surfactant-based
emulsion (Fig. S13), droplets squeeze and pass through the pores of sand
pack at higher flow rate (lesser residence or contact time) unlike Pick­
ering emulsions that possess a rigid interface. Fig. 8 depicts the gov­
erning mechanism of demulsification through hydrophobic sand pack
for the surfactant stabilized emulsions at low and high flow rate.
3.3. Emulsion generation and demulsification in case of heavy oil as an
oleic phase
After successful testing of the developed process for pure hydrocar­
bon (dodecane), the industrial applicability of the process was further
tested with a heavy crude oil of viscosity 22,000 cP. Since, the heavy
crude oil had a very low mobility due the high viscosity, the crude oil
was heated to a temperature 85⁰C to improve the mobility. Similarly, the
ChiNCs suspension (0.5 wt%) was also heated to 85⁰C to avoid sudden
temperature drop in the heavy crude oil during the emulsification pro­
cess in the sand pack. Furthermore, to minimize the heat loss to the
surroundings the connected tubing were reduced in length and were
properly insulated. The detail of the setup used for emulsion generation
with heavy crude oil is depicted in Fig. S14.
The emulsion generation test was carried out at different oil–water
ratios by adjusting the flow rates for the individual phases. Fig. S15
shows the collected emulsion samples and their microscopic images for
oil phase ratio (Φo) ranging from 0.2 to 0.35. Unlike the emulsion
generation tests with dodecane, it was not possible to increase the
oil–water ratio to 1 (or Φo = 0.5) due to the high differential pressure
across the sand pack. On increasing the oil flow rate to reach an oil–­
water ratio of 1, the encountered pressure differential was higher than
the safe working limit of the tubings (2000 psi). Using Eq. (1), the energy
dissipation for emulsification of the heavy crude oil at different flow
rates were found in range of 1.4 to 2.8 J.
For heavy oil transportation, the viscosity of the emulsion and sta­
bility are of prime importance. Therefore, emulsion (Φo = 0.35) viscosity
Fig. 8. Schematic of mechanisms involved during demulsification through
hydrophobic sands packed bed for surfactant-based emulsion at low flow rate
(a) and high flow rate (b) (not to scale).
S. Kumar et al.
and stability was measured using a parallel plate rheometer. As shown in
Fig. S16(a), emulsion viscosity was around 100 cP at shear rate of 10 sec-
1
which is significantly lower than the heavy oil viscosity of 22,000 cP.
Moreover, the emulsion was stable when subjected to a shear ramp
(1–100 sec-1) three times at a gap size of 1, 0.8 and 0.5 mm respectively.
The generated emulsion was flowed through 5 feet long 1/8′′ tubing to
observe the flow behaviour through conduits. It was observed that the
pump pressure required to pump an emulsion through the tubing was
significantly lower than the heavy crude oil (Fig. S16(b)).
The demulsification experiment was carried out with a heavy oil
emulsion (Φo = 0.35) prepared using a homogenizer. Similar to the
emulsification experiments, the generated emulsion was heated to a
temperature of 80⁰C to improve the heavy oil mobility after demulsifi­
cation inside the porous media. Prior to the experiment, emulsion sta­
bility was tested by preheating the emulsion at 80⁰C in the oven for one
hour. The generated emulsion was found to be stable and did not un­
dergo any phase separation after being heated to 80⁰C for one hour. The
setup used for this test is shown in Fig. S17. The aforementioned hy­
drophobic sand was used to carry out the demulsification. ASTM 50–70
sand was selected because the generated emulsion had an average
droplet size of around 60 µm. It was observed that the employed sand
pack system efficiently demulsified the heavy oil emulsion into the
constituent phases. The experiments were carried out at varying flow
rates. Samples collected at different flow rate are shown in supple­
mentary Fig. S18. Distinct oil and water along with the nanoparticle can
be seen in each vial (Fig. S18).
The above results demonstrate the application of a simple and low-
cost process, utilizing abundantly available sand for continuous gener­
ation and separation of the oil in water emulsion for industrial appli­
cations. Specific to heavy crude oil transportation through pipelines,
traditional methods such as heating, dilution, core annular flow, and oil
upgrading have limitations in terms of cost, operational ease, and sus­
tainability [77]. Transportation of heavy crude in the form of an
emulsion is considerably one of the most effective methods. However,
the separation of the constituent phases (oil and water) remains a
formidable task due to the associated cost of the demulsifier and addi­
tional treatment of the aqueous phase before discharge/reuse [6,7]. To
address these challenges, the designed set up in this study enables
continuous generation and separation of heavy oil in water emulsion
using naturally occurring nanoparticles and sand. The produced emul­
sion emulsions can significantly improve the flowability of heavy oil
without changing the composition and properties of the heavy oil. The
developed first and foremost lab-scale prototype has the potential to
transport heavy oil with a lower environmental footprint while maxi­
mizing the return on every barrel of heavy oil produced.
4. Conclusion
In summary, a process for continuous generation of an oil in water
emulsion and demulsification was successfully developed. The key
components of the developed process are i) a class of nanomaterials
tailored for interfacial activity and emulsion stability, and ii) a porous
medium whose pore size and wettability are chosen depending on
application: emulsification of co-injected oil and aqueous nanoparticles
dispersion, or demulsification of the previously generated emulsion. For
emulsification, sand wettability is of utmost importance. Hydrophilic
sand pack is required for complete emulsification. Furthermore, the
emulsion droplet size is a function of energy dissipated during the
emulsification process. Contrary to the emulsification process, demul­
sification required hydrophobic sand. Along with the sand wettability,
pore to droplet size ratio governed the complete demulsification of the
emulsion. Additionally, the developed process displayed excellent
applicability to surfactant-stabilized emulsions. The surfactant-based
system required lower energy for emulsification in comparison to
nanoparticles. Contrary, to nanoparticle-based emulsions where
demulsification was independent of the flow rate, complete
8
Separation and Purification Technology 256 (2021) 117849
demulsification for surfactants was only achieved at low flow rates/high
residence time, due to the elasticity of the surfactant-stabilized inter­
face. In addition, the process, generated heavy crude emulsion with a
viscosity suitable for pipeline transportation. The recyclability of the
nanoparticles after demulsification, would make this process a low-cost
alternative to the current process of heavy oil/bitumen dilution. Utili­
zation of this facile, inexpensive design strategy developed herein can be
further extended for food and pharmaceutical applications.
Notes
The manuscript was written through contributions of all authors. All
authors have given approval to the final version of the manuscript.
CRediT authorship contribution statement
Sunil Kumar: Conceptualization, Methodology, Validation, Formal
analysis, Investigation, Writing - original draft. Aseem Pandey:
Conceptualization, Methodology, Validation, Formal analysis, Investi­
gation, Writing - original draft. Milana Trifkovic: Conceptualization,
Formal analysis, Investigation, Resources, Supervision, Writing - review
& editing, Project administration. Steven L. Bryant: Conceptualization,
Formal analysis, Investigation, Resources, Supervision, Writing - review
& editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the Canadian Excellence Research Chair
in Materials Engineering for Unconventional Reservoirs, and Alberta
Innovates-Technology Futures. The help of Dr. Stephanie Kedzior for
AFM imaging of Chitin Nanocrystals is highly appreciated.
References
[1] S. Kokal, Crude-oil emulsions: A state-of-the-art review, SPE Prod. Facil. 20 (2005)
5–12, https://doi.org/10.2118/77497-PA.
[2] D.J. McClements, Food Emulsions: Principles, Practices, and Techniques, CRC
Press, 2015.
[3] A. Bera, A. Mandal, Microemulsions: a novel approach to enhanced oil recovery: a
review, J. Pet. Explor. Prod. Technol. 5 (2015) 255–268, https://doi.org/10.1007/
s13202-014-0139-5.
[4] S. Kumar, A. Mandal, Studies on interfacial behavior and wettability change
phenomena by ionic and nonionic surfactants in presence of alkalis and salt for
enhanced oil recovery, Appl. Surf. Sci. 372 (2016) 42–51, https://doi.org/
10.1016/j.apsusc.2016.03.024.
[5] A. Pandey, A. Telmadarreie, M. Trifkovic, S. Bryant, Cellulose Nanocrystal
Stabilized Emulsions for Conformance Control and Fluid Diversion in Porous
Media, in: SPE Annu. Tech. Conf. Exhib., Society of Petroleum Engineers, 2018: p.
18. https://doi.org/10.2118/191609-MS.
[6] D.P. Rimmer, A.A. Gregoli, J.A. Hamshar, E. Yildirim, Pipeline Emulsion
Transportation for Heavy Oils, in: Emulsions, American Chemical Society, 1992:
pp. 295-312 SE–8. https://doi.org/doi:10.1021/ba-1992-0231.ch008.
[7] J. Salager, M.I. Briceño, C.L. Bracho, Heavy Hydrocarbon Emulsions . Making use
of the State of the Art in Formulation Engineering, 2001. https://doi.org/10.1201/
9781420029581.ch20.
[8] T. Huppertz, Other Types of Homogenizer (High-Speed Mixing , Ultrasonics ,
Microfluidizers, Membrane Emulsification), (2011) 761–764.
[9] J. Zhang, S. Xu, W. Li, High shear mixers: A review of typical applications and
studies on power draw, flow pattern, energy dissipation and transfer properties,
Chem. Eng. Process. Process Intensif. 57–58 (2012) 25–41, https://doi.org/
10.1016/j.cep.2012.04.004.
[10] L. Bai, S. Huan, W. Xiang, L. Liu, Y. Yang, R.W.N. Nugroho, Y. Fan, O.J. Rojas, Self-
Assembled Networks of Short and Long Chitin Nanoparticles for Oil/Water
Interfacial Superstabilization, ACS Sustain. Chem. Eng. 7 (2019) 6497–6511,
https://doi.org/10.1021/acssuschemeng.8b04023.
[11] N. Kiss, G. Brenn, H. Pucher, J. Wieser, S. Scheler, H. Jennewein, D. Suzzi,
J. Khinast, Formation of O/W emulsions by static mixers for pharmaceutical
S. Kumar et al.
applications, Chem. Eng. Sci. 66 (2011) 5084–5094, https://doi.org/10.1016/j.
ces.2011.06.065.
[12] F. Theron, N. Le Sauze, Comparison between three static mixers for emulsification
in turbulent flow, Int. J. Multiph. Flow. 37 (2011) 488–500, https://doi.org/
10.1016/j.ijmultiphaseflow.2011.01.004.
[13] L. Fradette, B. Brocart, P.A. Tanguy, Comparison of mixing technologies for the
production of concentrated emulsions, Chem. Eng. Res. Des. 85 (2007) 1553–1560,
https://doi.org/10.1205/cherd06015.
[14] L. Hu, S. Gao, Y. Zhu, F. Zhang, L. Jiang, J. Jin, An ultrathin bilayer membrane
with asymmetric wettability for pressure responsive oil/water emulsion separation,
J. Mater. Chem. A. 3 (2015) 23477–23482, https://doi.org/10.1039/c5ta03975d.
[15] S. Yan, G. He, D. Ye, Y. Guo, W. Fang, Amphiphilic hyperbranched
polyethyleneimine for highly efficient oil-water separation, J. Mater. Chem. A. 8
(2020) 2412–2423, https://doi.org/10.1039/c9ta09640j.
[16] J. Li, Y. Gu, Coalescence of oil-in-water emulsions in fibrous and granular beds,
Sep. Purif. Technol. (2005), https://doi.org/10.1016/j.seppur.2004.05.006.
[17] R. Zolfaghari, A. Fakhru’l-Razi, L.C. Abdullah, S.S.E.H. Elnashaie, A. Pendashteh,
Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum
industry, Sep. Purif. Technol. (2016). https://doi.org/10.1016/j.
seppur.2016.06.026.
[18] M.A. Saad, M. Kamil, N.H. Abdurahman, R.M. Yunus, O.I. Awad, An overview of
recent advances in state-of-the-art techniques in the demulsification of crude oil
emulsions, Processes. 7 (2019) 1–26, https://doi.org/10.3390/pr7070470.
[19] S. Nii, S. Kikumoto, H. Tokuyama, Quantitative approach to ultrasonic emulsion
separation, Ultrason. Sonochem. (2009), https://doi.org/10.1016/j.
ultsonch.2008.07.005.
[20] A.H. Nour, S.F. Pang, A.H. Nour, M.S. Omer, Demulsification of water-in-crude oil
(W/O) emulsion by using microwave radiation, J. Appl. Sci. (2010), https://doi.
org/10.3923/jas.2010.2935.2939.
[21] S.A. Issaka, Review on the Fundamental Aspects of Petroleum Oil Emulsions and
Techniques of Demulsification, J. Pet. Environ. Biotechnol. (2015), https://doi.
org/10.4172/2157-7463.1000214.
[22] S. Ma, Y. Kang, S. Cui, Oil and Water Separation Using a Glass Microfiber
Coalescing Bed, J. Dispers. Sci. Technol. (2014), https://doi.org/10.1080/
01932691.2013.767209.
[23] R.M. Sokolovic, D.D. Govedarica, D.S. Sokolovic, Separation of oil-in-water
emulsion using two coalescers of different geometry, J. Hazard. Mater. (2010),
https://doi.org/10.1016/j.jhazmat.2009.10.109.
[24] W. Zhang, N. Liu, Y. Cao, X. Lin, Y. Liu, L. Feng, Superwetting Porous Materials for
Wastewater Treatment: from Immiscible Oil/Water Mixture to Emulsion
Separation, Adv. Mater. Interfaces. 4 (2017), https://doi.org/10.1002/
admi.201700029.
[25] J. Ge, J. Zhang, F. Wang, Z. Li, J. Yu, B. Ding, Superhydrophilic and underwater
superoleophobic nanofibrous membrane with hierarchical structured skin for
effective oil-in-water emulsion separation, J. Mater. Chem. A. 5 (2017) 497–502,
https://doi.org/10.1039/c6ta07652a.
[26] G. Wang, Y. He, H. Wang, L. Zhang, Q. Yu, S. Peng, X. Wu, T. Ren, Z. Zeng, Q. Xue,
A cellulose sponge with robust superhydrophilicity and under-water
superoleophobicity for highly effective oil/water separation, Green Chem. 17
(2015) 3093–3099, https://doi.org/10.1039/c5gc00025d.
[27] J. Gu, P. Xiao, Y. Huang, J. Zhang, T. Chen, Controlled functionalization of carbon
nanotubes as superhydrophobic material for adjustable oil/water separation,
J. Mater. Chem. A. 3 (2015) 4124–4128, https://doi.org/10.1039/c4ta07173e.
[28] W. Zhang, Z. Shi, F. Zhang, X. Liu, J. Jin, L. Jiang, Superhydrophobic and
superoleophilic PVDF membranes for effective separation of water-in-oil emulsions
with high flux, Adv. Mater. 25 (2013) 2071–2076, https://doi.org/10.1002/
adma.201204520.
[29] B.P. Binks, Particles as surfactants_similarities and differences, Curr. Opin. Colloid
Interface Sci. 7 (2002) 21–41.
[30] J.H.C. Robert Aveyard, Bernard P. Binks, Emulsions stabilised solely by colloidal
particles, Adv. Colloid Interface Sci. (2002) 503–546.
[31] E. Dickinson, Food emulsions and foams: Stabilization by particles, Curr. Opin.
Colloid Interface Sci. 15 (2010) 40–49. https://doi.org/10.1016/j.
cocis.2009.11.001.
[32] B.P. Binks, S.O. Lumsdon, Influence of particle wettability on the type and stability
of surfactant-free emulsions, Langmuir. 16 (2000) 8622–8631, https://doi.org/
10.1021/la000189s.
[33] J. Wu, G.H. Ma, Recent Studies of Pickering Emulsions: Particles Make the
Difference, Small. 12 (2016) 4633–4648, https://doi.org/10.1002/
smll.201600877.
[34] S.V. Daware, M.G. Basavaraj, Emulsions Stabilized by Silica Rods via Arrested
Demixing, Langmuir. (2015), https://doi.org/10.1021/acs.langmuir.5b00775.
[35] B. Madivala, S. Vandebril, J. Fransaer, J. Vermant, Exploiting particle shape in
solid stabilized emulsions, Soft Matter. 5 (2009) 1717–1727, https://doi.org/
10.1039/B816680C.
[36] V.R. Dugyala, S.V. Daware, M.G. Basavaraj, Shape anisotropic colloids: Synthesis,
packing behavior, evaporation driven assembly, and their application in emulsion
stabilization, Soft Matter. 9 (2013) 6711–6725, https://doi.org/10.1039/
c3sm50404b.
[37] M.V. Tzoumaki, T. Moschakis, V. Kiosseoglou, C.G. Biliaderis, Oil-in-water
emulsions stabilized by chitin nanocrystal particles, Food Hydrocoll. 25 (2011)
1521–1529, https://doi.org/10.1016/j.foodhyd.2011.02.008.
[38] I. Kalashnikova, H. Bizot, B. Cathala, I. Capron, Modulation of cellulose
nanocrystals amphiphilic properties to stabilize oil/water interface,
Biomacromolecules. 13 (2012) 267–275, https://doi.org/10.1021/bm201599j.
9
Separation and Purification Technology 256 (2021) 117849
[39] I. Capron, B. Cathala, Surfactant-free high internal phase emulsions stabilized by
cellulose nanocrystals, Biomacromolecules. (2013), https://doi.org/10.1021/
bm301871k.
[40] E. Perrin, H. Bizot, B. Cathala, I. Capron, Chitin nanocrystals for Pickering high
internal phase emulsions, (2014). https://doi.org/10.1021/bm5010417.
[41] S. Fujisawa, E. Togawa, K. Kuroda, Nanocellulose-stabilized Pickering emulsions
and their applications, Sci. Technol. Adv. Mater. 18 (2017) 959–971, https://doi.
org/10.1080/14686996.2017.1401423.
[42] S. Varanasi, L. Henzel, L. Mendoza, R. Prathapan, W. Batchelor, R. Tabor,
G. Garnier, Pickering Emulsions Electrostatically Stabilized by Cellulose
Nanocrystals, Front. Chem. 6 (2018) 1–9, https://doi.org/10.3389/
fchem.2018.00409.
[43] A. Pandey, M. Derakhshandeh, S.A. Kedzior, B. Pilapil, N. Shomrat, T. Segal-Peretz,
S.L. Bryant, M. Trifkovic, Role of interparticle interactions on microstructural and
rheological properties of cellulose nanocrystal stabilized emulsions, J. Colloid
Interface Sci. (2018), https://doi.org/10.1016/j.jcis.2018.08.044.
[44] Y. Zhang, Z. Chen, W. Bian, L. Feng, Z. Wu, P. Wang, X. Zeng, T. Wu, Stabilizing oil-
in-water emulsions with regenerated chitin nanofibers, Food Chem. 183 (2015)
115–121, https://doi.org/10.1016/j.foodchem.2015.03.030.
[45] M.V. Tzoumaki, T. Moschakis, E. Scholten, C.G. Biliaderis, In vitro lipid digestion
of chitin nanocrystal stabilized o/w emulsions, Food Funct. 4 (2013) 121–129,
https://doi.org/10.1039/c2fo30129f.
[46] W.T. Goodrich, J.D. Winter, Alpha-chitin nanocrystals prepared from shrimp shells
and their specific properties, Biomacromolecules (2007) 252− 257.
[47] A. Pandey, M. Derakhshandeh, S.A. Kedziora, B. Pilapil, S. Neta, T. Segal-Peretz, S.
L. Bryant, M. Trifkovic, Role of interparticle interactions on microstructural and
rheological properties of cellulose nanocrystal stabilized emulsions, J. Colloid
Interface Sci. (2018), https://doi.org/10.1016/j.jcis.2018.08.044.
[48] J.P. Gingras, L. Fradette, P. Tanguy, J. Bousquet, Inline bitumen emulsification
using static mixers, Ind. Eng. Chem. Res. 46 (2007) 2618–2627, https://doi.org/
10.1021/ie0611913.
[49] U. Eberhard, H.J. Seybold, M. Floriancic, P. Bertsch, J. Jiménez-Martínez, J.
S. Andrade, M. Holzner, Determination of the effective viscosity of non-Newtonian
fluids flowing through porous media, Front. Phys. 7 (2019) 1–9, https://doi.org/
10.3389/fphy.2019.00071.
[50] M. Elimelech, M. Nagai, C.H. Ko, J.N. Ryan, Relative insignificance of mineral
grain zeta potential to colloid transport in geochemically heterogeneous porous
media, Environ. Sci. Technol. (2000), https://doi.org/10.1021/es9910309.
[51] S. Maaref, A. Kantzas, S. Bryant, Investigating sweep efficiency improvement in oil-
wet porous media by the application of functionalized nanoparticles, Fuel. (2020),
https://doi.org/10.1016/j.fuel.2020.117263.
[52] R.S. Sanders, R.S. Chow, J.H. Masliyah, Hydrophobic Interactions in Silane-Treated
Silica Suspensions and Bitumen Emulsions, Can. J. Chem. Eng. (2008), https://doi.
org/10.1002/cjce.5450810105.
[53] J. Foroozesh, S. Kumar, Nanoparticles behaviors in porous media: Application to
enhanced oil recovery, J. Mol. Liq. (2020), https://doi.org/10.1016/j.
molliq.2020.113876.
[54] A.M. Atta, M. Abdullah, H.A. Al-Lohedan, N.H. Mohamed, Coating sand with new
hydrophobic and superhydrophobic silica/paraffin wax nanocapsules for desert
water storage and transportation, Coatings. 9 (2019) 124.
[55] Y. Deng, L. Xu, H. Lu, H. Wang, Y. Shi, Direct measurement of the contact angle of
water droplet on quartz in a reservoir rock with atomic force microscopy, Chem.
Eng. Sci. (2018), https://doi.org/10.1016/j.ces.2017.12.002.
[56] J. Takeuchi, W. Sumii, H. Tsuji, M. Fujihara, ESTIMATION OF PERMEABILITY OF
POROUS MEDIA WITH MIXED WETTABILITIES USING PORE-NETWORK MODEL
11 (2016) 2241–2247.
[57] H.T. and M.F. Junichiro Takeuchi, MODELING OF PERMEABILITY OF POROUS
MEDIA WITH, 12 (2017) 1–7.
[58] H. Huang, W. Wang, L. Wang, Theoretical assessment of wettability on silane
coatings: From hydrophilic to hydrophobic, Phys. Chem. Chem. Phys. (2019),
https://doi.org/10.1039/c9cp01232j.
[59] S. Karmakar, A. Sane, S. Bhattacharya, S. Ghosh, Mechanics of a granular skin,
Phys. Rev. E. (2017), https://doi.org/10.1103/PhysRevE.95.042903.
[60] J.O. Helland, S.M. Skjœveland, Physically based capillary pressure correlation for
mixed-wet reservoirs from a bundle-of-tubes model, SPE J. 11 (2006) 171–180,
https://doi.org/10.2118/89428-PA.
[61] S. Ergun, Che Eng Pro 48, 89.pdf, Chem. Enfineering Prog. (1952) 89–94.
[62] Z. Wang, X. Lin, Z. Rui, M. Xu, S. Zhan, The role of shearing energy and interfacial
Gibbs free energy in the emulsification mechanism of waxy crude oil, Energies. 10
(2017), https://doi.org/10.3390/en10050721.
[63] H. Wang, V. Singh, S.H. Behrens, Image charge effects on the formation of
pickering emulsions, J. Phys. Chem. Lett. 3 (2012) 2986–2990, https://doi.org/
10.1021/jz300909z.
[64] S. Arditty, C.P. Whitby, B.P. Binks, V. Schmitt, F. Leal-Calderon, Some general
features of limited coalescence in solid-stabilized emulsions, Eur. Phys. J. E. 11
(2003) 273–281, https://doi.org/10.1140/epje/i2003-10018-6.
[65] W.C. Griffin, Classification of surface-active agents by “HLB”, J. Soc. Cosmet,
Chem, 1946.
[66] Y. Chevalier, M.A. Bolzinger, Emulsions stabilized with solid nanoparticles:
Pickering emulsions, Colloids Surfaces A Physicochem. Eng. Asp. 439 (2013)
23–34, https://doi.org/10.1016/j.colsurfa.2013.02.054.
[67] L. Shui, A. Van Den Berg, J.C.T. Eijkel, Interfacial tension controlled W/O and O/W
2-phase flows in microchannel, Lab Chip. 9 (2009) 795–801, https://doi.org/
10.1039/b813724b.
[68] L. Li, Z. Yan, M. Jin, X. You, S. Xie, Z. Liu, A. Van Den Berg, J.C.T. Eijkel, L. Shui,
In-Channel Responsive Surface Wettability for Reversible and Multiform Emulsion
S. Kumar et al. Separation and Purification Technology 256 (2021) 117849

Droplet Preparation and Applications, ACS Appl. Mater. Interfaces. (2019), https://
doi.org/10.1021/acsami.9b03160.
[69] W.A.C. Bauer, M. Fischlechner, C. Abell, W.T.S. Huck, Hydrophilic PDMS
microchannels for high-throughput formation of oil-in-water microdroplets and
water-in-oil-in-water double emulsions, Lab Chip. (2010), https://doi.org/
10.1039/c004046k.
[70] I. Kalashnikova, H. Bizot, B. Cathala, I. Capron, New Pickering emulsions stabilized
by bacterial cellulose nanocrystals, Langmuir. 27 (2011) 7471–7479, https://doi.
org/10.1021/la200971f.
[71] R.G. Alargova, D.S. Warhadpande, V.N. Paunov, O.D. Velev, Foam
superstabilization by polymer microrods, Langmuir. 20 (2004) 10371–10374,
https://doi.org/10.1021/la048647a.
[72] S. Ma, Y. Kang, S. Cui, Oil and Water Separation Using a Glass Microfiber
Coalescing Bed, J. Dispers. Sci. Technol. 35 (2014) 103–110, https://doi.org/
10.1080/01932691.2013.767209.
[73] N. Chawaloesphonsiya, P. Painmanakul, Study of Cutting-Oil Emulsion Separation
by Coalescer Process in Terms of Medium Characteristics and Bed Packing, Sep.
Sci. Technol. 49 (2014) 2960–2967, https://doi.org/10.1080/
01496395.2014.943768.
[74] E. Dickinson, 2 - Hydrocolloids and emulsion stability, in: G.O. Phillips, P.A.
Williams (Eds.), Handb. Hydrocoll. (Second Ed., Second Edi, Woodhead
Publishing, 2009: pp. 23–49. https://doi.org/10.1533/9781845695873.23.
[75] T. Benedikt, Experimental and numerical investigation of porous media flow with
regard to the emulsion process, 2002. http://e-collection.ethbib.ethz.ch/eserv/eth
:26305/eth-26305-02.pdf.
[76] C.P. Whitby, E.J. Wanless, Controlling pickering emulsion destabilisation: A route
to fabricating new materials by phase inversion, Materials (Basel). 9 (2016),
https://doi.org/10.3390/ma9080626.
[77] A. Hart, A review of technologies for transporting heavy crude oil and bitumen via
pipelines, J. Pet. Explor. Prod. Technol. (2014), https://doi.org/10.1007/s13202-
013-0086-6.

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