Journal of Water Process Engineering 26 (2018) 124–130

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Journal of Water Process Engineering

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

Inorganic microfiltration membranes incorporated with hydrophilic silica T

nanoparticles for oil-in-water emulsion separation
⁎ ⁎
Ruochen Liu, Ashwin Kumar Yegya Raman, Imran Shaik, Clint Aichele , Seok-Jhin Kim
School of Chemical Engineering, Oklahoma State University, Stillwater, OK 74078, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Hydrophilic modification of alumina microfiltration membranes was achieved by incorporating silica nano-
Microfiltration particles into the alumina matrix. The alumina tubular membrane, incorporated with silica nanoparticles, was
Oil-in-water emulsion separation tested for cyclohexane-in-water emulsion separation. The incorporated silica nanoparticles increased the hy-
Silica nanoparticles incorporation drophilicity of the membrane surface with the oil contact angles changing from 155° to 165°. The alumina
Hydrophilic modification
membrane treated with a 0.5 wt.% silica-nanoparticle solution yielded a water flux greater than 350 L m−2 h-1
and oil rejection greater than 93%, which represented a 20.5% and 6.0% enhancement in water flux and oil
rejection compared with the pristine alumina membrane. Due to the hydrophilic silica nanoparticle in-
corporation, the cyclohexane concentration of the permeate was less than 40 ppm when the cyclohexane con-
centration of the feed was 500 ppm at 40 °C and feed pressure was 43.7 psia. This work represents a key ad-
vancement toward the use of inorganic membranes to treat marginal water that contains hydrocarbon
contaminants.

1. Introduction appropriate materials. Several studies have been performed on mem-

On a global scale, approximately three barrels of produced water, a
byproduct of oil and gas production containing such impurities as hy-
drocarbons, dissolved inorganic and organic particles, are produced for
every barrel of oil extracted [1,2]. The existence of oil droplets along
with surface-active agents eventually tends to form stable oil-in-water
emulsions. In order to meet the discharge requirements, < 40 ppm of
hydrocarbon in the water phase [3], there is a significant need for ef-
ficient, cost-effective strategies to remove hydrocarbons from produced
water.
The primary technology used by major producers to remove hy-
drocarbons from produced water relies upon the addition of chemical
demulsifiers to remove surface active agents from the oil-water inter-
face [4]. Chemical demulsifiers have to match with the specific che-
mical profile of the produced fluid. Due to the lack of a predictive
model for choosing appropriate demulsifiers, this process can only be
accomplished through inefficient trial-and-error serial testing [4,5]. In
addition, the chemical treatments may also result in the formation of
sludge, which can cause further pollution [6].
Ultrafiltration (UF) polymeric membranes with pore sizes ranging
from 0.01 μm to 0.1 μm are commonly selected to separate water from
oil-in-water emulsions by size exclusion. The membrane pore size and
membrane thickness can be relatively controlled by selecting
branes involving oil-in-water emulsions. Yang et al. [7] coated poly-
dopamine (PDA) and polyethyleneimine (PEI) on a polypropylene
membrane to control the pore size at around 0.2 μm. An oil rejection of
98% was obtained by optimizing surface structures and properties,
which in turn determined filtration performance. Some membranes that
were made from natural materials were also studied to realize effective
oil/water separations including a bioinspired diatomite membrane and
a mineral-coated polypropylene membrane [8,9]. However, the poly-
meric membrane fabrication process takes extensive time due to strict
control of temperature and pressure and complicated procedures such
as crosslinking, salt-induced fabrication, and nitrogen atmosphere
protection [10–12].
Fouling is a serious issue that causes flux losses of membranes be-
cause of contaminants blocking the membrane pores. A typical step for
removing foulants on a membrane surface is to wash out the remaining
oil from the membrane. Ahmad et al. [13] synthesized a polymeric
membrane by utilizing polysulfone, with SiO2 nanoparticles (NPs) for
modification. Based on their research, the hydrophilic SiO2 nano-
particles were found to be capable of enlarging pore size with a series of
interconnected surface pores. The bigger pores not only increased anti-
fouling properties, but also increased membrane permeability si-
multaneously. Rajasekhar et al. [14] proposed a similar method in-
volving the fabrication of poly-(vinylidene fluoride) (PVDF) and tri-

⁎
Corresponding authors.
E-mail addresses: clint.aichele@okstate.edu (C. Aichele), seokjhin.kim@okstate.edu (S.-J. Kim).

https://doi.org/10.1016/j.jwpe.2018.10.002
Received 31 May 2018; Received in revised form 25 September 2018; Accepted 4 October 2018
2214-7144/ © 2018 Elsevier Ltd. All rights reserved.
R. Liu et al.
Table 1
Summary of the literature data of ceramic membranes for oil-in-water emulsion separation.
Membrane Supplied pressure (bar)
Zeolite MCM-22 1.00
Nano-TiO2-coated ceramic 1.60
Mullite-TiO2 composite ceramic hollow fiber 0.25
ZrO2–Al2O3 1.60
Carbon nanotubes 1.00
Titania-coated alumina 3.00
Kaolin based ceramic 2.07
block copolymer (TBC), which are regarded as self-cleaning materials.
Different ratios of these two components were investigated with the
expectation that membrane properties such as flux, oil rejection and
fouling resistance would be enhanced. Yuan et al. [15] also used PVDF
membrane to realize a 99% oil rejection rate with the water flux of
higher than 650 L/m2-h for the oil-in-water emulsion separation. Al-
though new self-cleaning materials are currently used in polymeric
membranes [13,14,16], as high as 70–90% of oil droplets can be de-
posited and adsorbed on the surface of membrane. This can be coun-
teracted by washing, which can remove as much as 30–40% of oil
droplets deposited on the membrane. Polymeric materials however
cannot tolerate corrosive condition such as acidic and basic solutions,
high temperatures, and organic solvents [17–19]. In addition, swelling
due to capillary force or the combination of molecular diffusion and
convection in the water-filled pores [20] can make the polymeric
membranes ineffective under severe environmental conditions.
Because of the many issues involving polymeric membranes, re-
searchers have focused on ceramic materials in order to overcome the
material-based limitations of polymers, as shown in Table 1. Generally,
ceramic membranes are synthesized and coated on porous supports
such as alumina disks or mullite hollow fibers. Chang et al. [6] modified
a ceramic alumina membrane by coating nano-TiO2 on the membrane
surface. The pore size of a ceramic alumina membrane without mod-
ification was found to be appropriate for oil separation. In addition,
TiO2 can increase the membrane hydrophilicity thereby increasing the
number of water molecules that are allowed to pass through the
membrane, therefore increasing the membrane flux. In some cases,
materials are synthesized on the surface [21,22] or in the channel [23]
of the supports to enhance transport efficiency and separation se-
lectivity. Chen et al. [23] synthesized the carbon nanotubes in the
channels of an yttria-stabilized zirconia (YSZ) membrane to remove
tiny oil droplets from the water. Under optimal growth conditions for
carbon nanotubes, the oil rejection of ∼100% was obtained. For in-
dustrial applications, membrane processes operating under harsh con-
ditions has to be considered when improving the membrane separation
efficiency. Studies have been performed about the use of silica for
coating microfiltration membranes [24–26]. These silica-decorated
membranes not only improved hydrophilicity but also corrosion re-
sistance [27]. Conveniently, another benefit of this modification is that
a ceramic support can also protect a membrane by enhancing me-
chanical stability.
2. Experimental
2.1. Membrane synthesis
Hydrophilic silica NPs (16 nm, A200, AEROSIL) were added into
deionized water (resistivity of 18 mΩ cm−1) and stirred for 2 h to
prepare a homogeneous silica-NPs containing solution at the weight
percentage of 0.05%, 0.5%, and 5%. The α-alumina tubular membrane
(70 mm length, 11 mm outer diameter, 8 mm inner diameter, 0.2 μm
pore size, CoorsTek) was washed with ethanol and water successively,
and dried in 60 °C overnight. The dried membrane was then immersed
into the silica NPs containing solution for a 15 s pre-wetting to
Journal of Water Process Engineering 26 (2018) 124–130
Feed temperature (℃) Flux (L/m2-h) Oil rejection rate Reference
– 9 100% [21]
40 385 99% [6]
– 150 97% [28]
30 441 97.8% [29]
– 36 100% [23]
60 108 100% [22]
– 79.7 98.5% [30]
incorporate silica NPs onto the surface. After drying at 60 °C overnight,
the above membrane was immersed in the same solution for 15 min
with ultra-sonication to uniformly incorporate the silica NPs on the
membrane surface. Finally, after drying overnight at 60 °C, the mem-
brane was calcined at 350 °C for 30 min with the ramping rate of 30 °C/
h to integrate the silica NPs firmly onto the membrane surface. The
alumina membranes immersed in solutions containing 0.05%, 0.5%,
and 5% silica NPs were named as M0.05, M0.5, M5, and the pristine
membrane was named M0.
2.2. Oil-in-water emulsion synthesis
For preparation of oil-in-water emulsions, cyclohexane (+99%
purity, Alfa Aesar) was used as the dispersed oil phase and DI water was
used as the continuous aqueous phase. Sodium Dodecyl Sulphate (SDS),
a water soluble, anionic surfactant with an HLB [31] value of 40 (as
stated by the vendor) was used as the surfactant. The oil-in-water
emulsions were prepared using an Ultra-Turrax digital homogenizer
operating at 10,000 rpm for 5 min. Initially, the surfactant was added to
the aqueous phase followed by vigorous shaking to aid in complete
mixing of SDS with the aqueous phase. The dispersed oil phase was
added in a drop wise manner to aid in homogenous distribution of
water droplets [32–34]. The cyclohexane-in-water emulsion consisted
of 500 ppm of cyclohexane, and 0.13 wt.% SDS.
An Olympus BX53 cross-polarized optical microscope equipped with
a high-speed camera was used for measuring the droplet size of cyclo-
hexane-in-water emulsions. The schematic of the microscope stage and
the procedure to determine the droplet size of the emulsions using
Image J from the microphotographs can be found elsewhere [35]. Fig. 1
shows the droplet size distribution of the cyclohexane-in-water emul-
sion. The average droplet size of the emulsion was 2.5 ± 0.7 μm. Bottle
tests confirmed that no phase separation of this emulsion occurred and
the emulsion was stable at the investigated temperatures.
2.3. Emulsion separation experiment
In order to investigate the separation capability of the prepared
membranes, the modified membrane was sealed into the stainless steel
module of a once-through system with epoxy resin (Fig. 2).
300 mL of the emulsion was added to the sample cylinder. A pres-
sure of 43.7 psia was then supplied from compressed Ar on the feed side
Fig. 1. Droplet size distribution of cyclohexane-in-water emulsion.
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of the membrane. The separation efficiency is defined according to the

following equation:

η = (1−Ci/ C0) × 100% (1)

where Ci is the cyclohexane concentration in the effluent; C0 is the

cyclohexane concentration in the feed before separation. The permea-
tion flux J was calculated as:

J = V /(A × t ) (2)
Fig. 2. Schematic of once-through membrane filtration system.
V (L) is the volume of the permeate; A (m2) is the membrane area; t
(h) is the separation time.

Fig. 3. SEM images of (a–c) M0, (e–g) M0.5, and (i–k) M5 under different magnification and cross-section SEM images of (d) M0, (h) M0.5, and (l) M5 showing silica
film in the membrane channels.

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Fig. 4. SEM images of (a, b) M0, (c, d) M0.5, and (e, f) M5, respectively, before and after oil-in-water emulsion separation at supplied pressure of 43.7 psia and room
temperature.

Table 2 this technique, an automatic liquid sampler with injections of 1 μl was

Elemental surface composition of M0, M0.5, and M5 before and after cyclo- used for injection of all the samples. The wettability was measured
hexane-in-water emulsion separation, respectively. The atomic percentage va- using a contact angle goniometer (Core Laboratories IFT-10) at room
lues are on an oxygen-free basis. temperature and atmospheric pressure.
EDX atomic % Si/Al

Si Al 3. Results and discussion

M0 Before separation 0 100 0 3.1. Characterization of the membrane

After separation 0 100 0
M0.5 Before separation 0.59 99.41 0.0059
After separation 0.45 99.55 0.0045 The morphology of the membranes after silica NPs were in-
M5 Before separation 16.62 83.38 0.1993 corporated on the alumina membrane is shown in Fig. 3. The silica NPs
After separation 7.89 92.11 0.0857 were incorporated on the surface and in the pore channels of the alu-
mina membrane. When the alumina membrane was treated with a 0.5%
solution, the silica NPs were incorporated on the membrane surface
2.4. Characterization
(Fig. 3e-g) which resulted in minimal blocking of membrane channels
(Fig. 3h). However, when the 5% solution was used, a continuous layer
Micro-morphological images were obtained by FEI Quanta 600
of silica NPs was formed on the membrane surface (Fig. 3i-k) and ag-
Field-Emission Gun Environmental Scanning Electron Microscope
gregated in membrane channels (Fig. 3l) which narrowed the mem-
(SEM) with an Evex EDS X-ray microanalysis system and HKL EBSD
brane pores.
system. Cyclohexane that was extracted from the permeate using
Fig. 4 shows the morphology of membranes (M0, M0.5 and M5)
chloroform (CHCl3) was measured using a gas chromatography-mass
before and after oil-in-water emulsion separation. EDX elemental ana-
spectrometry system [36] (Shimadzu, GC/MS QP2010 (EI/CI sources)
lysis (1–2 μm depth) was performed on the membranes to compare
(PS-313) - Capillary column GC with quadrupole mass analyzer). For
surface composition changes before and after the separations. From the

Fig. 5. (a) Photographs of cyclohexane droplets (cyclohexane) on the membrane surface; (b) Cyclohexane contact angle as a function of increasing silica NP
concentration.

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Fig. 6. Microphotographs of the (a) feed and (b) permeate before and after microfiltration with M0.5 under the supplied pressure of 43.7 psia and the feed tem-
perature of 20 °C.

Table 4
Permeate cyclohexane concentration (in mass fraction) and cyclohexane re-
jection rates of M0.5.
Supplied Feed cyclohexane Permeate Oil Initial
pressure concentration cyclohexane rejection average flux
(psia) (ppm) concentration rate (%) (0-5 min) (L
(ppm) m−2 h-1)

29.2 500 2.04 99.59 596

43.7 500 33.89 93.22 784
58.2 500 42.91 91.82 1032

Fig. 7. Comparisons of the silica NPs concentration on the permeate flux over
time with the supplied pressure of 43.7 psia and the feed temperature of 20 °C.

Table 3
Permeate cyclohexane concentration (in mass fraction) and cyclohexane re-
jection rates of M0, M0.05, M0.5, and M5.
Membrane Feed cyclohexane Permeate Oil Initial
concentration cyclohexane rejection average flux
(ppm) concentration rate (%) (0-5 min) (L
(ppm) m−2 h-1)

M0 500 60.42 87.92 640 Fig. 9. Impact of the feed temperature on the permeate flux over time with the
M0.05 500 64.98 87.00 761 supply pressure equal to 43.7 psia (M0.5).
M0.5 500 33.89 93.22 784
M5 500 35.91 92.82 672
Table 5
Permeate cyclohexane concentration (in mass fraction) and cyclohexane re-
jection rates of M0.5 under different feed temperature.
Feed Feed Permeate Oil Initial
temperature cyclohexane cyclohexane rejection average
(oC) concentration concentration rate (%) flux (0-
(ppm) (ppm) 5 min) (L
m−2 h-1)

20 500 33.89 93.22 784

40 500 28.38 94.32 1149
60 500 39.54 92.09 1337

EDX measurements in Table 2, it was found that the atomic % of Si for

Fig. 8. Impact of the supply pressure on the permeate flux over time with the
feed temperature equal to 20 °C (M0.5).
M0.5 reduced from 0.59 to 0.45 and the atomic % of Si for M5 reduced
from 16.62 to 7.89 during separations. These data show that for the
optimal membrane (M0.5), the majority of the silica that was originally
added to the membrane remained on the membrane during the oil/
water separation and yielded an improvement in the oil rejection rate.
For the M5 membrane, the silica NPs aggregated due to the higher NP
concentration which decreased the interaction between the silica NPs
and the alumina surface [37,38]. The larger aggregates on the M5

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membrane were easier to wash away during the microfiltration com-
pared with the smaller, non-aggregated silica NPs on M0.5. In order to
further estimate the membrane stability, the permeate solution through
the M0.5 was centrifuged at 2000 rpm for 5 min. No observable parti-
cles were found at the bottom of the centrifuge tube, which indicated
that M0.5 could be regarded as a promising candidate for further oil-in-
water emulsion separation.
The oil contact angles were measured to investigate the wettability
of the membranes at room temperature and atmospheric pressure
(Fig. 5a). The contact angle measurements were performed for 1 h. The
existence of the silica NPs increased the contact angle between cyclo-
hexane droplets and the membrane incorporation surface, indicating
that silica NPs enhanced hydrophilicity of the membrane (Fig. 5b).
3.2. Membrane performance on the oil-in-water emulsion separation
3.2.1. Effect of silica-NPs concentration
Membranes modified with three different concentrations of silica
NP solutions were used to separate the oil-in-water emulsion. Fig. 6
shows the microphotographs of the feed and permeate. No droplet was
observed in the permeate, which indicated the separation of cyclo-
hexane droplets from the oil-in-water emulsion.
As shown in Fig. 7, silica NP modified membranes yielded higher
fluxes compared with the unmodified alumina membranes. This can be
explained by the fact that the silica NPs enhanced the membrane hy-
drophilicity by strongly adsorbing the hydroxyl groups to the surface of
the silica NPs, thereby allowing more water molecules to be absorbed
and passed through the membrane, which is consistent with recent
literature [25,26]. As shown in Table 3, when the concentration of the
precursor solution was 0.5 wt.%, the permeate cyclohexane con-
centration decreased approximately 50% compared with the one in-
corporated with lower concentrations, indicating the effects of silica
NPs on repelling oils. Although more silica NPs provide higher hydro-
philicity, when the concentration of the silica NPs precursor solution
was 5 wt.%, the membrane channel was narrowed (Fig. 3) due to the
presence of agglomerated silica NPs. Thus, the flux of M5 was lower
than those of M0.05 and M0.5. M0.5 exhibited high flux and high cy-
clohexane rejection and was therefore selected for further experiments.
3.2.2. Effect of feed pressure
Fig. 8 shows the effect of trans-membrane pressure on the flux.
According to Shokrkar et al. [39], flux normally increases with in-
creasing trans-membrane pressure. When feed pressure was increased
from 29.2 to 58.2 psia, the driving force increased on the feed side
resulting in a higher water flux (Table 4).
3.2.3. Effect of feed temperature
Fig. 9 illustrates the effect of feed temperature on the flux over time.
Literature studies on the use of ceramic membranes for membrane
distillation applications show that an increase in temperature leads to
an increase in flux while maintaining a constant rejection rate [40–42].
Also, water permeability increases with an increase in temperature. In
accordance with the literature [43], the flux in our work increased at
higher feed temperatures (Fig. 9). As shown in Table 5, the cyclohexane
rejection rates varied less than 2% across the temperature range
20 °C–60 °C, thereby indicating that temperature did not affect the oil
rejection performance of M0.5, which is in accordance with the lit-
erature [40–42].
4. Conclusion
We demonstrated a novel method to incorporate hydrophilic silica
NPs into an α-alumina microfiltration tubular membrane for oil-in-
water emulsion separation. After treating the alumina membrane with a
0.5 wt.% silica NPs precursor solution, the water flux was greater than
350 Lm−2 h-1 and the oil rejection was greater than 93%. This
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Journal of Water Process Engineering 26 (2018) 124–130
represents a 20.5% and 6.0% enhancement in the flux and the oil re-
jection compared with the unmodified membrane. The contact angles of
oil on the modified membranes ranged from approximately 155° to
165°. The M0.5 membrane yielded a permeate cyclohexane con-
centration lower than 40 ppm with an average water flux of approxi-
mately 1000 Lm−2 h-1 at 43.7 psia and 40 °C. These data demonstrate
the utility of hydrophilic silica NPs on enhancing the separation po-
tential of inorganic membranes for oil-in-water emulsion separation.
Additional scaffolds, surface functionalization, and process configura-
tions are currently being investigated.
Funding
This work was supported by Oklahoma State University; the
National Energy Solutions Institute – Smart Energy Source (NESI-SES);
and the Technology and Business Development Program (TBDP).
Conflicts of interest
None.
Acknowledgement
We thank Dr. Nicholas Materer and Dr. David Jacobs from the
Department of Chemistry, Oklahoma State University, for granting us
access to the GC/MS and for their help with the GC/MS experiments.
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