Journal of Membrane Science 452 (2014) 117126

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Application of thin lm composite membranes with forward osmosis

technology for the separation of emulsied oilwater
Phuoc H.H. Duong a, Tai-Shung Chung a,b,n
a
b

Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576, Singapore
Water Desalination & Reuse (WDR) Center, King Abdullah University of Science and Technology, 23955-6900 Saudi Arabia

art ic l e i nf o

a b s t r a c t

Article history:
Received 10 August 2013
Received in revised form
3 October 2013
Accepted 12 October 2013
Available online 28 October 2013

Large amounts of oily wastewater have been produced from various industries. The main challenge of
oily wastewater treatments is to separate the stable emulsied oil particles from water. Therefore, the
aim of this study is to investigate the effectiveness of forward osmosis (FO) processes to treat the stable
oilwater emulsions. The FO technique has been demonstrated successfully for the treatment of a wide
range of oilwater emulsions from a low to a very high concentration up to 200,000 ppm. The
dependence of separation performance on oily feed concentration and ow rate has been investigated.
Water can be separated from oily feeds containing 500 ppm or 200,000 ppm emulsied oil at a relatively
high ux of 16.57 1.2 LMH or 11.87 1.6 LMH respectively by using a thin lm composite membrane PANTFC and 1 M NaCl as the draw solution. Moreover, this membrane can achieve an oil rejection of 99.88%
to produce water with a negligible oil level. Due to the presence of emulsied oil particles in the oily feed
solutions, the membrane fouling has been addressed in this study. Better anti-fouling TFC FO membranes
are needed.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Oilwater
Emulsion
Membranes
Separations
Forward osmosis

1. Introduction
In many industries, water is often essential for product development. As a result, a large amount of contaminated wastewater
needs to be treated and recycled. Among the pollutants in the
industrial wastewater, oil is one of the most common pollutants
presented in a wide range of concentrations from 10 ppm up to
200,000 ppm [1]. With the rapid growth of oil and gas industries,
the urgency to treat oily wastewater has emerged. Oil exists in
several forms in oily wastewater as classied into free oil (oil
droplet size 4150 m), dispersed oil (20 m ooil droplet size
o150 m) and emulsied oil (oil droplet size o 20 m) [1]. Oily
wastewater has been treated by some conventional techniques
including gravity and skimming, dissolved air otation, de-emulsication, coagulant and occulation. However, these techniques
are mainly useful for free oil solutions and dispersed/unstable
emulsied oil. There is an urgent need to develop environmentalfriendly, practical and cost-effective technologies to treat stable
emulsied oily wastewater.
Membrane technology has been applied for treating oily wastewater by using microltration (MF) [2,3], ultra-ltration (UF)
[2,4,5], or reverse osmosis (RO) [6], electrocatalytic [7] and
n
Corresponding author at: Department of Chemical and Biomolecular Engineering,
National University of Singapore, 4 Engineering Drive 4, Singapore 117576, Singapore.
Tel.: 65 65166645; fax: 65 67791936.
E-mail address: chencts@nus.edu.sg (T.-S. Chung).

0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.10.030

recently by forward osmosis [8,9] methods. Although treatment

of oily wastewater by MF and UF methods can achieve high water
permeability, the membranes are not effective to reject small
stable emulsied oil particles and other small contaminants
presented in wastewater. While RO membranes can achieve high
rejections towards contaminants with 99.9% oil rejection, high
energy consumption and severe fouling [10,11] have been encountered. In addition, due to the use of extremely high hydraulic
pressure, the compacted and tightly held fouling layer on the RO
membrane surface cannot be cleaned easily [12]. Therefore, treating highly contaminated oily wastewater by RO still exhibits
serious limitations such as the short membrane life time and
low recovery rate due to the high membrane fouling propensity,
high operation and equipment costs. Hence, a more economical
and practical process should be searched for the treatment
of stable emulsied oily wastewater. Instead of employing external
hydraulic pressure, forward osmosis (FO) is a naturally driven
process that potentially separates clean water from contaminated
sources via a semi-permeable membrane by the osmotic gradient
across the membrane. Compared to pressure-driven membrane
techniques, FO processes can produce clean water with
the comparable quality to the RO process with the additional
advantages of no or low pressure operation, higher water ux
and recovery rate, less fouling propensity and easy cleaning [13
16]. Therefore, FO may be a promising technology to effectively
and economically recycle water from stable emulsied oily
wastewater.

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P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

Besides some remarkable advantages, FO processes still face

some challenges due to the need to regenerate the diluted draw
solution for reuse. Thus, a FO process needs to be integrated with a
secondary system for constantly recycling draw solutions and
simultaneously producing clean water. Different secondary systems such as UF [17], NF [18], RO [19], membrane distillation (MD)
[20,21], heating [22], magnetic eld [23] or coupled crystallization/RO [24] have been demonstrated to re-concentrate draw
solutions based on the natural properties of the draw solutes. By
choosing an osmotic efcient draw solute and a suitable regenerating process, the total energy consumption of the hybrid
FO system can be equal [24] or lower than that of RO process.
Moreover, the hybrid FO system has additional advantages again
the RO process such as: less fouling, easy cleaning, low equipment
cost and potentially higher water ux.
The purpose of this project is to investigate the applicability of
FO process towards stable emulsied oilwater separation. Various
methods have been applied to design FO membranes such as
traditional cellulosic membranes [25,26], thin-lm composite
(TFC) membranes [2730], and recently technology called layerby-layer (LbL) membranes [3134]. The TFC FO membrane is
favorable in desalination and water reuse due to its high water
permeability and good rejection to sodium chloride. Therefore,
this study aims to investigate TFC FO membranes for the treatment
of emulsied oilwater solutions. The TFC FO membrane was
prepared by a well-known interfacial polymerization and characterized by difference techniques to reveal the intrinsic membrane properties. The water uxes of the FO process under various
oilwater emulsion concentrations in the feed were systematically
investigated and the inuence of feed ow rate to membrane
performance was also examined. In addition, long-term performance of the TFC membrane was studied to collect some preliminary fouling data. This work may provide useful insights for
the design of the FO process toward oilwater separation.

2. Experimental
2.1. Materials
Polyacrylonitrile (PAN) was kindly provided by Prof. Hui-An Tsai
from Chung Yuan Christian University (Taiwan) and was vacuumdried overnight at 60 1C to remove moisture prior to use. Sodium
hydroxide (NaOH), ethanol, dimethylformamide (DMF), anhydrous
lithium chloride (LiCl), solvent blue 35, m-phenylene diamine

(MPD), trimesoyl chloride (TMC) and Tween 80 non-ionic surfactant

were ordered from Sigma-Aldrich (USA). N-methyl-2-pyrrolidone
(NMP), n-hexane and sodium chloride (NaCl) were obtained from
Merck (Germany). Soybean oil was purchased from Fairprice supermarket (Singapore). The commercially available cellulose triacetate
FO membrane (HTI-FO) from Hydration Technologies Inc was
employed as one of FO membranes. Polyethylene glycol 35,000
(PEG, Mw35,000 gmol  1), polyethylene oxide 100,000, 200,000
and 600,000 (PEO, Mw 100,000 gmol  1, Mw200,000 gmol  1,
and Mw600,000 gmol  1) were purchased from SigmaAldrich (USA).
2.2. Membrane preparation
Porous support membranes were fabricated using a phase
inversion method as described previously [35]. The compositions
of the casting solution used in this study were PAN (16%), LiCl (4%),
ethanol (5%) and DMF (75%). Membranes were cast on a glass plate
using a 100 mm casting knife, followed by immediate immersion in
a NMP/water (50/50) coagulant bath at room temperature. The ascast membranes were gently peeled off from the glass plate and
kept in a water bath overnight for completely phase separation
and solvent removal. The thickness of the resultant membranes
was about 62 75 mm. To increase their hydrophilic property, the
membranes were hydrolyzed by 1.5 M NaOH using the previously
described method [34]. The hydrolyzed membranes were used for
all subsequent studies.
The PAN-TFC membranes were fabricated by the deposition of a
thin polyamide layer onto a hydrolyzed PAN support. Briey, the
support membranes were rstly immersed in an aqueous 1.5%
(w/v) MPD solution for 5 min. The membranes were then taken
out from the solution and followed by the removal of excess water
droplets from the membrane surfaces by tissue papers. Secondly,
the membranes were placed in a frame so that only their top
surfaces were exposed as illustrated in Fig. 1. A solution of 0.05%
(w/v) TMC in hexane was poured onto the top surface of the
supports for 1 min to form a thin TFC lm via the polymerization
reaction between MPD and TMC molecules. The freshly prepared
PAN-TFC membranes were dried in open air at room temperature
for 1 min and stored in water.
2.3. Pore size characterization of the PAN support
The pore size, pore size distribution and molecular weight cutoff (MWCO) of the hydrolyzed PAN support were characterized by

Fig. 1. Schematic diagram of the lab-scale FO set-up.

P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

solute separation experiments. Briey, aqueous feed solutions

contained 200 ppm neutral organic solutes (PEG or PEO) at various
molecular weights were utilized to determine the rejection of the
support towards different neutral solute sizes. The experiments
were carried at 5 bar under room temperature with an effective
membrane area of approximately 3.14 cm2. The solute rejection (R)
was calculated from the concentrations of the solute in the feed
and permeate that were analyzed by a total organic carbon (TOC)
analyzer (TOC-VCSH, Shimadzu, Japan).
From the known molecular weight (M) of a neutral solute, its
Stokes diameter (ds) was calculated in the following equations
[36]:
For PEG:
ds 33:46  10  12 M 0:557

For PEO:
ds 20:88  10  12 M 0:587

From the solute rejection and diameter, the mean effective pore
size (p) was determined at solute rejection R 50%, the geometric
standard deviation (sp) was dened as the ratio of ds at R 84.13%
over that at R 50%, and the MWCO was found at R90%. The pore
size distribution of the membrane was conducted using the
following equation:
"
#
ln dp  ln p 2
dRdp
1
p exp 

3
ddp
dp ln sp 2
2ln sp 2

2.4. Characterization of the membranes

The morphologies of membranes were observed under a eldemission scanning electron microscope (FESEM). The freeze-dried
samples were freeze-fractured in liquid nitrogen to maintain their
original structure. The samples were coated with platinum particles by a JFC 1300 auto ne coater (JEOL, Japan) before analyses.
The images were obtained with a FESEM JSM 6700 F (JEOL, Japan)
at an accelerating voltage of 5 kV.
The surface topologies of the selective layers of membranes
were examined under the area of 5 m  5 m by a Bruker
Dimension Icon atomic force microscope (AFM) (Bruker, USA)
under tapping mode in the air. The mean roughness (Ra) was
calculated using NanoScope Analysis software to qualitatively
compare the surface roughness of the membranes. The contact
angles () of the selective layers of membranes with DI water and
oilwater emulsion were determined by a Contact Angle Geniometer (Rame Hart, USA) at room temperature.
The functional groups formed on the PAN-TFC membranes
were analyzed under the attenuated total reectance (ATR) mode
using Fourier transform infrared spectroscopy (FTIR) FTS 135 (BioRad, USA) over the range of 8004000 cm  1. The number of scans
for each sample was 16. The changes in surface chemistry of PANTFC membranes compared with PAN membranes were further
characterized by X-ray photoelectron Spectrometry (XPS) Kratos
AXIS UltraDLD (Kratos Analytical, UK) using mono Al K
(h1486.71 eV, 5 mA, 15 kV) as the X-ray source over the scan
range of 1100 to  5 eV.
2.5. Preparation and characterizations of oilwater emulsions
The oilwater emulsions were prepared by a blender as
described previously [37] with slight modications. The mixture
of soybean oil and Tween 80 at the ratio of 9 to 1 respectively was
added into water to get a solution with a total organic

119

concentration (total oil and surfactant concentration) of

200,000 ppm. The solution was then blended by a high speed
blender (HGBTWTS3, Waring, Torrington, USA) for 3 min to
achieve a stable emulsied oilwater solution. This solution was
further diluted to obtain various solutions with the total organic
concentration ranging from 500 ppm to 200,000 ppm.
For clear visualization of the fouled emulsied oil particles that
formed on the membrane surface during the FO separation, dyed
oily solutions were used. First, the oil was dyed with solvent blue
35 at a concentration of 0.2 wt% to form the dark blue oil. Then the
dark blue oil was mixed with Tween 80 and water followed a
mixing process as described above to form blue emulsied oil
water solutions.
The size distribution of oil particles in the synthesized oil
water emulsion was determined by two techniques: (1) dynamic
light scattering (DLS) method which is favorable for detecting of
the small particles and (2) optical microscopy method which is
suitable for large particle measurements. DLS measurements were
carried out using a Malvern Instruments particle sizer (Zetasizer
Nano ZS, Malvern Instruments, UK) equipped with a HeNe laser
at 25 1C. Optical microscope images of the emulsions were conducted by an Olympus microscope (SZX16, Olympus, USA)
equipped with a ber optics light source (LG-PS2, Olympus, USA).
The viscosity of oilwater emulsions was measured by a
rotational cone and plate rheometer (AR-G2 rheometer, TA instruments, USA) at 23 1C under a steady-state mode using a 40 mm,
11 cone geometry.
2.6. Pure water permeability, salt rejection, salt permeability
and oil rejection tests
The water permeability (A, L m  2 h  1/bar, referred to as
LMHbar  1), salt rejection (Rs, %), salt permeability (B, L m  2 h  1,
referred to as LMH) and organic rejection (oil and surfactant
rejection) (Ro, %) of the membranes were determined by testing
the membranes using a lab-scale dead-end ltration set-up under
the RO mode. The tests were carried out at room temperature with
an effective membrane area of approximately 3.14 cm2. The A
values were obtained from the tests using DI water as the feed
under an applied pressure of 5 bar.
Rs values were determined by carrying out the tests using a
2000 ppm NaCl solution under the rapid stirring condition
(700 rpm) as the feed under a trans-membrane pressure of 5 bar.
Rs was calculated as the following equation:


Cp  s
 100%
4
Rs 1 
Cf  s
where Cf  s and Cp  s are the NaCl concentrations of the feed and
the permeate, respectively. They were determined by conductivity
measurements using an 856 conductivity module (Metrohm,
Switzerland).
The B values of membranes were determined from the solutiondiffusion theory:
1  Rs
B

AP 
Rs

where P is the applied pressure and is the osmotic pressure

different across the membrane.
The Ro values were determined by carrying out the tests using a
200,000 ppm oilwater emulsion under the rapid stirring condition (700 rpm) as the feed under a trans-membrane pressure of
5 bar. Ro was calculated as the below equation:


Cp  o
Ro 1 
 100%
Cf  o
where Cf  o and Cp  o are the oilwater emulsion concentrations of

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P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

Probability density function, nm-1

0.07

the feed and the permeate respectively. The oilwater emulsion

concentration was determined using a TOC analyzer.

0.06
0.05

2.7. Forward osmosis tests

0.04

FO experiments were conducted on a lab-scale crossow FO

unit as illustrated earlier [7]. All experiments were carried out at
room temperature (23 72 1C) in the ow channels without any
spacer [25]. The system was operated with a draw solution and a
feed solution owing counter-currently on each side of the
membrane. The membranes were tested in the FO operation mode
which the selective layer faces against the feed solution (Fig. 1).
Performance of the membranes was evaluated by water ux
(Jv, L m  2 h  1, abbreviated as LMH), reverse salt ux (Js,
g m  2 h  1, abbreviated as gMH) and oil ux (Jo, gMH), which
were calculated using the following equations:

0.03
0.02
0.01
0

20

40

60

80

100

Pore size, dp (nm)

Jv

Fig. 2. Pore size distribution of the PAN support.

V
Aef f t

Table 1
Characteristics of the PAN support.
Mean pore diameter,
P (nm)

Geometric standard deviation,

rP

MWCO (kDa)

PWPa
(L m  2 h  1/bar)

Salt rejectionb,
Rs (%)

Water contact angle,

(deg)

24.2

2.03

693

87.2

0

58.2 7 1.8

a
b

Tested at 5 bar using DI water as the feed.

Tested at 5 bar using 2000 ppm NaCl as the feed.

Top surface (before IP)

Top surface (after IP)

100 nm

100 nm

Cross-section

10 m

Bottom

100 nm

100 nm

Fig. 3. FESEM images of the PAN at sheet membranes before and after interfacial polymerization.

P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

Js

C t  f V t  f
Aef f t

3. Results and discussion

3.1. Morphology and separation characteristics of the porous PAN
support

and
Jo

121

C t  d V t  d
Aef f t

where V (L) is the volume of water that has permeated across the
membrane in a predetermined time t (h) during the test. Aeff is
the effective membrane surface area (m2). Ct  f and Vt  f are the salt
concentration (g/L) and the volume of the feed (L) at the end of FO
tests, respectively. Ct  d and Vt  d are the oil concentration (g/L)
and the volume of the draw (L) at the end of FO tests, respectively.
The oil concentration in the draw solution was determined by a
UVvis spectrometer (Spectroquant Pharo 300, Merck, Germany)
at the wavelength of 265 nm.
The amount of emulsied oil particles that fouled onto the
membrane surfaces was determined by analyzing the amount of
carbon in the fouling layers. Briey, fouled membranes were
immersed into water under a shaking condition for 30 min to
de-adsorb the fouled particles from the membrane surfaces and to
re-suspend them into water. Subsequently, the concentrations of
oil in the water solutions were quantitatively measured by a TOC
analyzer.

PAN-TFC

TFC,
C=O
TFC,
N-H
TFC,
H-bond

PAN

PAN,
COO2100

1900

1700

1500

1300

1100

900

Wave number (nm-1)

Fig. 4. FTIR spectra of the surfaces of the PAN support and the PAN-TFC membrane.

PAN

405

The at sheet PAN membrane was fabricated as a porous

support for the subsequent deposition of a TFC layer via interfacial
polymerization. To obtain a continuous and uniform PAN-TFC
membrane with good FO performance, the porous support must
exhibit suitable characteristics including a narrow pore size distribution, high porosity and hydrophlilicity [3032]. Fig. 2 shows
the pore size distribution of the fabricated PAN membrane, while
Table 1 tabulates the physicochemical properties. The pore size
distribution is relatively narrow with a mean pore diameter (mp) of
24.2 nm and a geometric standard deviation (sp) of 2.03. In
addition, the membrane exhibits a moderate low water contact
angle of o 601 and a reasonably good pure water permeability of
87.2 LMHbar  1. FESEM images (Fig. 3) show that the membrane
cross-section has a porous open-cell structure consisting of some
nger-like macrovoids. This type of substrate structure is suitable
for the fabrication of TFC FO membranes because it may have low
transport resistance and low internal concentration polarization
[27,38].
3.2. Characterizations of the PAN-TFC membrane
The original PAN support and the interfacial polymerized PANTFC membrane were characterized by ATR-FTIR to conrm the
formation of the TFC layer onto the PAN support via interfacial
polymerization. From Fig. 4, the absorption peak at 1560 cm  1 of
the FTIR spectrum of the PAN support indicates the stretching
vibrations of the COONa groups of the support [39,40]. However,
the intensity of this peak is reduced in the PAN-TFC membrane
compared to that of the original PAN support. It is due to the
presence of the TFC layer onto the PAN support. Moreover, by
comparison of the two spectra, the formation of the TFC layer is
evident by the presence of the additional peaks at 1548 cm  1 and
1660 cm  1 which correspond to the bending vibration of NH
(amide II peak) and the stretching vibration of CQO (amide I
peak) respectively. Furthermore, the new peak at 1608 cm  1 in the
FITR spectrum of the PAN-TFC membrane is attributed to the
aromatic ring breathing of the TFC layer [4143].
XPS was employed to examine the chemical changes after the
deposition of the TFC layer on the membrane. Compared to the
N1s spectrum of the PAN sample, there are additional N1s peaks
with binding energies of 400.1 eV and 401.3 eV in the PAN-TFC
sample (Fig. 5). The new peaks belong to the nitrogen element of

PAN-TFC

403

401

399

397

405

403

401

399

Fig. 5. XPS N1s spectra of the surfaces of the PAN support and the PAN-TFC membrane.

397

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P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

the amide group that conrms the success of the interfacial

polymerization. Moreover, the presence of the rough ridge-valley
morphology of the active layer on the PAN-TFC sample, as shown
in Fig. 3, also indicates the formation of a TFC layer onto the PAN
substrate.
Table 2 tabulates the basic transport properties of the fabricated PAN-TFC membrane under the RO tests. The membrane has

Table 2
Transport properties of the PAN-TFC membrane.
Water permeabilitya,
A (L m  2 h  1/bar)

Salt rejectionb,
Rs (%)

Salt permeabilityb,
B (L m  2 h  1)

Oil rejectionc,
Ro (%)

0.686

87.1

0.354

99.88

a
b
c

Tested at 5 bar using DI water as the feed.

Tested at 5 bar using 2000 ppm NaCl as the feed.
Tested at 5 bar using 200,000 ppm oilwater emulsion as the feed.

suitable characteristics to be used as a FO membrane. With the oil

rejection of 99.88%, this PAN-TFC membrane is further explored to
separate water from the stable oilwater emulsions.
3.3. Characterization of synthesized oilwater emulsions
As aforementioned, Tween 80 was used as an emulsier to
prepare oilwater emulsions at a weight ratio of 9:1 of oil to
emulsier. Fig. 6 shows the four emulsions with concentrations
from 500 ppm to 200,000 ppm, while Fig. 7 displays their emulsied oil sizes of smaller than 20 mm in diameter visualized under
an optical microscope. However, submicron oil particles cannot be
discerned. Hence, a DLS was employed to measure the hydrodynamic size of submicron particles. Fig. 8 shows that the labsynthesized oilwater emulsions have a wide distribution of
particles from 50 nm up to microns in diameter. Comparing to
oil particles in the real oily wastewater [2], the lab-synthesized
oilwater emulsions have similar size characteristics.
3.4. Performance of PAN-TFC membranes towards various emulsied
oilwater concentrations

0
ppm

500
ppm

5000
ppm

50,000
ppm

200,000
ppm

Fig. 6. Feed solutions at varied oilwater emulsion concentrations.

All FO experiments in this study were conducted for 30 min using

a 1 M NaCl draw solution and fresh PAN-TFC membranes. Five feed
concentrations were employed; namely, 0 ppm (DI water), 500 ppm,
5000 ppm, 50,000 ppm and 200,000 ppm (20 wt%). Table 3 summarizes water ux as a function of feed oil concentration. The water
ux drops from 19.671.0 LMH using DI water as the feed
to 16.571.2 LMH using a feed containing 500 ppm oil. The decrease
in water ux is probably due to the presence of emulsied oil particles
in the feed which causes viscosity increase and additional water

500 ppm

5000 ppm

50,000 ppm

200,000 ppm

20 m
Fig. 7. Optical microscopy images of oilwater emulsions at various concentrations.

P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

transportation resistance across the membrane because of the presence of emulsied oil particles. The water ux further decreases with
an increase in emulsied oil particle concentration from 500 ppm to
200,000 ppm. In addition to viscosity increase, the more precipitation
and adsorption of emulsied oil particles on the membrane surface
may be the other causes. As can be visualized clearly from Fig. 10A, a
higher concentration of emulsied oil particles in the feed creates a
thicker layer of adsorbed oil particles onto the membrane surface.
Furthermore, the amount of oil that fouled on the membranes was
quantitatively determined by a TOC analyzer. The results from Fig. 11A
further support the assumption that the membrane fouling is much
severer under a higher feed concentration condition.
3.5. Effect of feed ow rate to water ux for oilwater separation
The effect of feed ow rate to water ux was studied using 1 M
NaCl as the draw solution and oilwater emulsions with concentrations ranging from 0 ppm to 200,000 ppm as feeds under the FO

123

mode. Each experiment was conducted in 30 min by using a fresh

PAN-TFC membrane. The system was operated under the laminar ow
with a xed draw ow rate but various feed ow rates. As shown in
Fig. 9, water ux does not vary much by changing the feed ow rate
from 0.15 L/min to 1 L/min when oilwater emulsions of 0 ppm or
500 ppm are used. However, water ux is a function of feed ow rate
when the feed contains oil particles equal to or greater than 5000 ppm
possibly due to colloidal fouling. To understand more the effect of the
feed ow rate to water ux, additional experiments were conducted to
investigate the fouling behavior of the emulsied oil particles onto the
membrane surfaces under various feed conditions. As shown in
Figs. 10B and 11B, the higher feed ow rate (i.e., larger Re Number)
can reduce the fouling tendency of the emulsied oil particles onto the
membrane surface. The water ux is increased under higher feed ow
rate operations because of less fouling occurred [44]. Eventually, the
water ux reaches a plateau with increasing feed ow rate and the
plateau height is dependent on the concentration of oilwater emulsions. The higher the oil particle concentration, the higher the feed
ow rate and Re number are required to reach the plateau. This
phenomenon is probably due to the thicker and more compact cake
layer of oil particles formed on the membrane surface when the oil
concentration increases. Although the water ux of the 200,000 ppm

500 ppm

5000 ppm

50,000 ppm

0 ppm
10

100

1000

200,000 ppm

Re: 337

1000

Emulsion diameter (nm)

Fig. 8. Size distribution of the oilwater emulsion analyzed by a dynamic light

scattering.

Table 3
Water uxes of PAN-TFC FO membranes to separate water from various oily water
solutions.
Feed concentration (ppm)

Viscositya (cP)

Draw

Water uxb (LMH)

0
500
5000
50,000
200,000

0.933
0.933
0.938
1.091
1.822

1M
1M
1M
1M
1M

19.6 7 1.0
16.5 7 1.2
15.5 7 1.1
13.17 0.6
11.8 7 1.6

a
b

NaCl
NaCl
NaCl
NaCl
NaCl

Re: 337

Re: 898

Re: 1123

25

25

20

0 ppm

500 ppm
5,000 ppm
50,000 ppm
200,000 ppm

15
10
5

0.2

0.4

0.6

0.8

Flow rate (L/min)

1.2

1.4

Water flux (LMH)

20

Water flux (LMH)

Re: 674

Re: 449

Fig. 10. Images of PAN-TFC membranes after 30 min testing: (A) at different feed
concentrations from 0 ppm to 200,000 ppm, and (B) with the 200,000 ppm feed
under different feed ow rates (Reynolds numbers). Blue color presented on the
membrane's surfaces indicates the fouled emulsied oil particles. (For interpretation of the references to color in this gure legend, the reader is referred to the web
version of this article.)

At 23 1C.
Under FO operation mode, feed ow rate at 1 L/min.

Re: 898

Control

15
10
5
0

500

1000

1500

2000

2500

Re Number

Fig. 9. Water ux as functions of feed ow rate and feed concentration under the FO mode using 1 M NaCl as the draw. The reverse salt ux values were o 10 gMH for all
the tests. (A) Water ux vs. Feed ow rate and (B) Water uf vs. Feed Re number.

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P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

100

Normalized amount of fouled oil (%)

Normalized amount of fouled oil (%)

100

80

60
Re: 337

40

20
Re: 898
0
500000

50000

5000

500

80

60

40

20
Feed concentration: 200,000 ppm
0

500

1000

1500

Re Number

Feed concentration (ppm)

100

1 L/min (Re: 1123)

0.6 L/min (Re: 674)

80

Normalized water flux (%)

Normalized water flux (%)

Fig. 11. The normalized amount of fouled oil onto the PAN-TFC membrane surface after the rst 30 min of oilwater separation as functions of (A) feed concentration, and
(B) feed Reynolds number.

0.4 L/min (Re: 449)

60
40
20
0

10

100
80
60

Oil-water emulsion as
the feed

40
20
0

12

DI water as the feed

Top: Initial draw solution conc. = 0.5M NaCl

Botttom: Initial draw sol ution conc. = 1.0M NaCl
0

Time (h)

10

12

Time (h)

Normalized water flux (%)

Normalized water flux (%)

Fig. 12. Normalized water ux as functions of time and feed ow rate for PAN-TFC
membranes using an oilwater emulsion of 200,000 ppm as the feed and 1 M NaCl
as the draw solution under the FO mode.

100
80
60
40

20
0

100
80

10

20

30

40

50

60

70

Water recovery (%)

Fig. 13. Normalized water ux as a function of water recovery for oilwater
separation using an oilwater emulsion of 200,000 ppm as the feed and 1 M NaCl
as the draw solution under the FO mode.

oilwater feed increases from 6.4 to 11.8 LMH when the feed ow rate
increases from 0.4 L/min (Re of 449) to 1 L/min (Re of 1123) as shown
in Fig. 9, the declines of their normalized uxes follow a very similar
pattern regardless of operation conditions as illustrated in Fig. 12. It is
because of the rapid formation of the oil cake layer on membrane
surface. As soon as the cake layer forms, the fouling is less sensitive to
the change in feed ow rate [45].

Oil-water emulsion as
the feed

60
40
20
0

DI water as the feed

Top: Initial draw solut ion conc. = 1.5M NaCl

Botttom: Initial draw solution conc. = 4.0M NaCl
0

10

12

Time (h)
Fig. 14. Normalized water ux as a function of time for PAN-TFC and HTI-FO
membranes under FO tests using an oilwater emulsion of 200,000 ppm and DI
water as feeds. All the tests had a similar initial water ux (  11 LMH). (A) PAN-TEC
membrane and (B) HTI-FO membrane.

Fig. 13 shows the normalized water ux as a function of water

recovery for the emulsied oily water with an extremely high
concentration of 200,000 ppm. The water recovery rate is more
than 60% while the water ux still maintains half of the initial
water ux. Hence, the water recovery rate of this process can
achieve higher than 90% when treating a 5000 ppm oily feed
which is more commonly discarded from many industries. The
water recovery rate of this treatment process mainly depends on
the feed conditions (such as oil concentration, viscosity,

P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

125

Fig. 15. Characteristics of PAN-TFC and HTI-FO membranes and their interactions with emulsied oil particles.

concentration of other contaminants), membrane properties and

the osmotic efciency of the draw solution.
3.6. A comparison of polyamide and cellulose triacetate membranes
for emulsied oilwater separation
For a fair comparison, the PAN-TFC and the HTI-FO membranes
were operated at a similar initial water ux of approximately
11 LMH by adjusting the draw solution concentration. Separate
experiments were carried using DI water as the feed in order to
obtain the baselines for the oily water feed of 200,000 ppm. Draw
solutions of 0.5 M NaCl and 1.5 M NaCl were used for baseline
experiments of PAN-TFC and HTI-FO membranes, respectively.
As illustrated in Fig. 14, the two membranes show baseline
declines over time. This decline of water ux has been observed
in typical batch FO processes because of (1) the lower osmotic
driving force across the membrane owing to the diluted draw
solution (2) the increase of feed salinity due to reverse salt ux,
and (3) the effect of concentration polarization [14,15,27,46,47].
Draw solutions of 1 M NaCl and 4 M NaCl were employed to
study water ux declines for PAN-TFC and HTI-FO membranes,
respectively, using oily water as the feed. Compared to the HTI-FO
membrane, the PAN-TFC membrane shows a faster decline in
water ux overtime. This is due to the fact that the latter has
greater fouling of emulsied oil particles on the membrane surface. Interestingly, no severe fouling was observed for the HTI-FO
membrane under a similar feed condition. The difference in
fouling propensity may arise from their differences in physicochemical properties. Fig. 15 displays the surface roughness of these
two membranes measured by AFM, the PAN-TFC membrane has a
much higher surface roughness than the HTI-FO membrane (Ra:
21.4 72.6 nm vs. 4.2 7 2.1 nm). Even though a rougher active
surface may attribute to a higher water permeability due to a
larger surface area with water [48], it is also easily fouled because
of more contact opportunities between emulsied oil particles and
the large membrane surface [12,49]. As a result, the higher surface
roughness, the easier the attachment of foulant particles onto the
membrane surface. Thus the PAN-TFC membrane has more fouling
and a faster ux decline.
In addition, the differences in their molecular structures of
active layers may contribute to the variance in their anti-fouling
behaviors. As illustrated in Fig. 15, the CTA active layer of the HTIFO membrane only contains the hydroxyl (OH) groups which
generate weak hydrogen bonds between water/emulsied oil

particles and the membrane surface, while the active layer of the
PAN-TFC membrane is an aromatic polyamide layer that contains a
cross-linked portion of amide linkages (NHCO) and a linear
portion of carboxylic groups (COOH) [48]. Although both groups
(NHCO and COOH) help lower the contact angle and assist
water permeation by the formation of hydrogen bonds between
these functional groups and water molecules, they also facilitate
the hydrogen bonds between the OH groups around the emulsied
oil particles and the TFC layer [50]. This would result in fast fouling
of oil particles onto the PAN-TFC membrane surface. Therefore,
future works should aim to develop TFC layers with less fouling
propensity for oilwater separation.

4. Conclusions
This is the rst study that investigates the application of TFC FO
membranes for the purication of extremely high concentration
(up to 200,000 ppm) oily solutions. The effects of emulsied oil
water concentration and hydrodynamic operating conditions such
as feed ow rate or Re Number on separation performance via FO
have been investigated. Experimental data show that water ux is
getting lower at higher emulsied oilwater feed concentrations.
The feed ow rate plays an important factor in determining the
water ux when the feed contains high concentrations of oil
particles (Z5000 ppm). This work has demonstrated that FO
would be a feasible method to produce high quality pure water
with less than 0.12% residual oil from various oilwater emulsions.
By combining the PAN-TFC membrane with the FO technique, pure
water can be recycled from the 200,000 ppm oily wastewater at a
reasonable ow rate of 11.871.6 LMH using 1 M NaCl as the draw.
Although the PAN-TFC membrane exhibits much better performance compared to the HTI-FO membrane, the former tends to
foul faster than the latter. Therefore, further modications of TFC
membranes would be carried out in the future to improve their
long term performance in FO systems.

Acknowledgments
The authors would like to thank the Singapore National
Research Foundation under its Competitive Research Program for
the project entitled Advanced FO Membranes and Membrane
Systems for Wastewater Treatment, Water Reuse and Seawater

126

P.H.H. Duong, T.-S. Chung / Journal of Membrane Science 452 (2014) 117126

Desalination: Module designs and integrated systems for sustainable processes (Grant no. R-279-000-339-281). We specially
thank Miss S. Chen, Miss X. Fu, Dr. P. Li and Dr. S. Zhang for their
valuable suggestions.
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