Desalination 353 (2014) 4856

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Investigation of submerged membrane photocatalytic reactor (sMPR)

operating parameters during oily wastewater treatment process
C.S. Ong, W.J. Lau , P.S. Goh, B.C. Ng, A.F. Ismail
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, Skudai, 81310 Johor, Malaysia
Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia, Skudai, 81310 Johor, Malaysia

H I G H L I G H T S

G R A P H I C A L

sMPR could achieve high TOC degradation and oil rejection under optimized
conditions.
Excessive TiO2 loading and module
packing density would deteriorate sMPR
performance.
Higher ABFR could reduce the severe
fouling impacts during high feed
concentration.

Schematic diagram of oily wastewater separation and degradation using PVDF-TiO2 hollow ber membrane
under UV irradiation.

a r t i c l e

a b s t r a c t

i n f o

Article history:
Received 2 August 2014
Received in revised form 4 September 2014
Accepted 6 September 2014
Available online xxxx
Keywords:
TiO2
Submerged membrane photocatalytic reactor
Air bubble ow rate
Oil concentration
Module packing density
Wastewater

The performance of a submerged membrane photocatalytic reactor (sMPR) consisted of polyvinylidene uoridetitanium dioxide (PVDF-TiO2) hollow ber membranes was evaluated for the separation and degradation of
synthetic oily wastewater under UV irradiation. The effects of operating parameters such as TiO2 catalyst loading,
membrane module packing density, feed oil concentration and air bubble ow rates (ABFR) on the permeate
ux, oil rejection and total organic carbon (TOC) degradation (in the bulk feed solution) were studied. The
comparison of TOC degradation based on direct photolysis, neat PVDF membrane and PVDF-TiO2 membrane
were determined. It was clearly observed that TOC degradation using PVDF-TiO2 membrane was remarkably
higher compared to neat PVDF membrane. Gas chromatographymass spectrometry (GC-MS) analyses showed
that oil components in the wastewater could be efciently degraded in the presence of TiO2 under UV irradiation.
The average ux of membrane was reported to be around 73.04 L/m2 h using PVDF membrane embedded
with 2 wt.% TiO2 at 250 ppm oil concentration with module packing density of 35.3% and ABFR of 5 L/min.
A remarkable TOC degradation and oil rejection as high as 80% and N 90%, respectively, could be reached
under these optimized conditions. The ndings shown in this work provide useful information for the research of simultaneous separation and degradation of oily wastewater and facilitate the development of hybrid
sMPR.
2014 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +60 75535926.

E-mail addresses: lwoeijye@utm.my, lau_woeijye@yahoo.com (W.J. Lau).

http://dx.doi.org/10.1016/j.desal.2014.09.008
0011-9164/ 2014 Elsevier B.V. All rights reserved.

A B S T R A C T

C.S. Ong et al. / Desalination 353 (2014) 4856

1. Introduction
Emulsions of cutting uid are always used in the machining process
to aid the cutting process, to prevent corrosion, and to improve lubrication, cooling, surface cleaning and tool life [1]. A considerable amount of
oil-contaminated wastewater which contains high concentration of
aliphatic and aromatic compounds can be generated from the above
mentioned processes, causing detrimental and harmful effect to environment and aquatic life as well as groundwater sources [2]. Despite
their well acceptance in industry, those conventionally used treatment
methods such as electrocoagulation [3], membrane ltration [4,5], and
otation process [6,7] have been associated with high operating cost
and lack of capability in removing oil molecules below 10 m in size
[8,9]. Additionally, some harmful by-products are likely to be generated,
requiring additional treatment process to eliminate them. In view of
this, various kinds of advanced treatment methods have been proposed
by researchers to overcome the drawbacks of the existing treatment
processes. Among the methods proposed, advanced oxidation process
(AOP) has received great attention over the past decade, mainly
due to its high efciency to remove recalcitrant, toxic and nonbiodegradable organic micropollutants from wastewater [1012]. Nevertheless, most of the classical AOPs are limited by the large amount
of residual pollutants and the catalysts retained in the process which require additional treatment to eliminate them [1315]. To overcome this
problem, a heterogeneous photocatalyst integrated with membrane
process is proposed as this hybrid process could deal with a broad
range of organic pollutants via degradation followed by separation. Of
the photocatalysts available in the market, titanium dioxide (TiO2)
nanoparticle is the most popular one owing to its good thermal and
physical stability, cheapness, excellent photocatalytic, antibacterial
and antifouling properties [1620]. Many research efforts have been devoted to design a sustainable photocatalytic membrane reactor (PMR)
with high efciency and low energy consumption. In general, two
main congurations for PMR are being pursued, namely i) reactor
with catalysts suspended in the feed solution and ii) reactor with
catalysts immobilized in/on the membrane. The latter option is more favorable as the recovery process of TiO2 photocatalysts can be greatly
simplied, hence reduces the operational complexity and cost in practical application [10,2123]. Worth saying that the presence of unrecovered TiO2 nanoparticles might raise another concern to environmental
safety. Despite the large number of experimental studies showing that
the suspended-TiO2 photocatalysis process holds signicant advantages, this mode of photocatalytic water treatment is constrained
by some technical challenges, such as ineffective catalysts recovery
and difcult reuse of the catalyst particles to allow continuous water
treatment [10]. Therefore, a hybrid submerged membrane photocatalytic reactor (sMPR) is proposed by immobilizing TiO2 photocatalysts
in membrane matrix with vacuum pressure driving through permeate
side under UV irradiation. In this integrated treatment process,
membrane not only functions as the support for TiO2 photocatalyst
but also acts as a physical selective barrier for the degraded products. Although the performance of the membrane-photocatalysts integrated
process has been examined in various industrial wastewater treatment
processes [10], only little attention has been paid to the synthetic cutting oil wastewater. To the best of our knowledge, this is the rst attempt to investigate the inuence of operating parameters on the
simultaneous separation and degradation of synthetic cutting oil wastewater using TiO2 incorporated PVDF ultraltration (UF) membranes in
sMPR.
The major focus of this work is to assess the performance of sMPR for
synthetic cutting oil wastewater treatment based on several key operating parameters, i.e. TiO2 catalyst loading (embedded in membrane matrix), module packing density, initial feed concentration and air bubble
ow rate (ABFR). The identication of the chemical compounds before
and after photocatalytic degradation was studied by GC-MS. The comparison between direct photolysis, neat PVDF UF membrane and PVDF

49

membrane immobilized with TiO2 catalysts were also evaluated based

on TOC degradation.
2. Experimental
2.1. Materials
PVDF (Kynar 760) pellets purchased from Arkema Inc., Philadelphia,
USA were used as the main membrane forming material. N,Ndimethylacetamide (DMAc) (Merck, N99%) was used as solvent to dissolve polymer without further purication. Polyvinylpyrrolidone (PVP)
(Molecular weight: 40,000 g/mol) purchased from Sigma Aldrich and
titanium dioxide (TiO2) (Degussa P25, a mixture of 75% anatase and
25% rutile with BET surface area 50 m2/g, average particle size ~21 nm,
energy band gap 3.18 eV) from Evonik were used as the photocatalyst.
The cutting oil obtained from RIDGID, Ridge Tool Company, Ohio, USA
was used to synthesize oily wastewater of various concentration.
2.2. Preparation of membrane and membrane module
PVDF (18 wt.%) was added into pre-weighed DMAc solvent after
being dried for 24 h in oven at 50 C. The solution was then mechanically stirred at 600 rpm until all the polymeric pellets were completely dissolved. It was followed by the addition of 5 wt.% PVP and TiO2 catalyst
loading varying from 0 to 4 wt.%. Lastly, the dope solution was
ultrasonicated to remove any air bubbles trapped within the solution
prior to spinning process.
PVDF hollow ber membranes were fabricated using dry-jet wet
spinning method as described elsewhere [24]. The as-spun hollow bers were immersed into water bath for 2 days to remove residual solvent. Prior to air drying, the bers were post-treated by 10 wt.% glycerol
aqueous solution for 1 day to minimize ber shrinkage and pore collapse. At last, the hollow bers were dried at room temperature for
3 days before module fabrication.
A various number of bers (30, 60 and 90 bers) with the length of
approximately 28 cm were then potted into each PVC tube using epoxy
resin (E-30CL Loctite Corporation, USA). The membrane module was
then left for hardening at room temperature before its protruding
parts were cut and xed into a PVC adaptor to complete the module
preparation.
2.3. Preparation of synthetic wastewater
The synthetic cutting oil wastewater was prepared by mixing
distilled water with commercial cutting oil (RIDGID Nu-Clear Cutting
Oil, #70835, Ridge Tool Company). The emulsion was prepared by
mixing cutting oil in the range of 25010,000 ppm and sodium
dodecylbenzenesulfonate (SDS) at the ratio of 9:1. The solution was
then blended by a high speed blender (Model: BL 310AW, Khind) for
2 min with an agitation speed of 50 Hz at room temperature.
2.4. sMPR conguration and experimental procedures
A schematic diagram of sMPR is shown in Fig. 1. The dimension of
the sMPR is 18 cm (W) 20 cm (L) 40 cm (H). Two hollow ber membrane modules were placed at the bottom of sMPR containing approximately 14 L of synthetic cutting oil solution. An air compressor (Model:
2 HP single cylinder 24 L tank, Orimas) was used to generate air bubbles
within the submerged tank through air diffuser installed underneath
the membrane modules. To investigate the effect of ABFR, an air ow
meter was used to control the ow rate in the range of 15 L/min. An
8 W black light blue UV-A lamp with a maximum light intensity output
at 365 nm (Model: FL8BLB, Sankyo Denki Co., Ltd., Japan) was placed in
between two membrane modules. The UV light intensity was measured
using a UVX radiometer (UVP Inc., Upland, CA) with an UV-A sensor
(UVX-36, UVP Inc., Upland, CA) at the side wall of sMPR without feed

50

C.S. Ong et al. / Desalination 353 (2014) 4856

where Cp and CF are the concentration of oil in the permeate (ppm) and
the feed (ppm), respectively.
The oil concentrations in permeate and feed were determined using
a UVvis spectrophotometer (Model: DR5000, Hach) with absorbance
measured at 294 nm which the maximum absorption occurs. The relation between absorbance and oil concentration is found to be linear as
shown in Fig. 2. The same relation has been used for measuring
unknown oil concentration in each permeate.
To measure zeta potentials of the membrane surface, streaming potential measurements were performed using a SurPASS electrokinetic
analyzer (Anton Paar, Graz, Austria). As only the outer surface of hollow
ber membrane was analyzed, adjustable gap cell was used. During
analysis, potassium chloride (1 mM) was used as electrolyte, whereas
0.1 M hydrochloric acid and 0.1 M sodium hydroxide were used for
pH titration. The detailed characterization of streaming potential measurements can be found elsewhere [25].
To determine the photocatalytic degradation efciency, TOC degradation (%) of feed was determined according to Eq. (4).

TOC degradation

Fig. 1. Schematic diagram of the sMPR system: (a) connection to UV lamp control panel,
(b) feed solution tank, (c) UV-A lamp, (d1, d2) membrane modules of different packing
density, (e) connection to peristaltic pump and permeate collection tank, (f) air diffuser,
(g) air ow meter and (h) air compressor.

solution in the tank and an intensity of approximately 0.333 mW/cm2

was recorded. Water permeate was then produced using peristaltic
pump (Model: 77200-60, Masterex L/S, Cole Parmer) by creating
vacuum pressure on permeate side.
The performance of sMPR was determined based on direct photolysis, neat PVDF UF membrane and PVDF-TiO2 UF membrane under UV
irradiation. The effect of different catalyst loading, module packing density, feed concentration and ABFR were studied. Membrane module
packing density () could be calculated according to Eq. (1):
n

OD2 fiber
ID2 module

where n is the number of bers for each module, OD is the outer diameter of the hollow ber membrane (1.15 mm) and ID is the inner diameter of PVC module (15 mm).

TOC t
TOC 0


 100

where TOCt and TOC0 are the TOC concentration of the permeate (ppm)
at reaction time t and initial feed (ppm), respectively and are measured
by TOC analyzer (Model: TOC-LCPN, Shimadzu Co.).
To describe the kinetics of photocatalytic reactions of aquatic organics, the LangmuirHinshelwood model as expressed in Eq. (5) was
employed [26,27]. This model basically relates the degradation rate (r)
(mg/L min) with the concentration of organic compound (C) (mg/L).

dC
kK C
r ad
dt 1 K ad C


ln

C
C0


kr K ad t kapp t:

where Q is the quantity of permeate (L), A is the effective membrane

area (m2), and t is time to obtain the quantity of Q (h). The membrane
oil rejection, R (%), was evaluated using the Eq. (3).
R



Cp
 100
1
CF

 
A plot of ln CC0 versus reaction time t yields a straight line, and
the slope is the kapp.

For each permeate ux and its quality analysis, three samples (with
10 ml each) were taken and the remaining permeate was recycled back
to the tank. Three measurements were made for each sample and then
the average value was reported together with its standard deviation
(based on 95% condence level). To determine membrane water ux,
J (L/m2 h), the following equation was employed.

Q
At

where kr is the intrinsic rate constant (mg/L min) and Kad is the adsorption equilibrium constant (L/mg). When the adsorption is relatively
weak and/or the concentration of organic compound is low, Eq. (6)
can be simplied to the rst-order kinetics with an apparent rate constant kapp (min1):

2.5. Analytical methods and measurements

Fig. 2. Calibration graph between absorbance and oil concentration.

C.S. Ong et al. / Desalination 353 (2014) 4856

2.6. Solid phase extraction (SPE) and gas chromatographymass

spectrometry (GC-MS) analysis
The determination of oil in permeate sample involved a preconcentration by solid-phase extraction (SPE). Specically, oil extraction was performed with HyperSep C18 cartridges (500 mg resin/3 ml
cartridge volume). All samples were acidied to pH 2 with HCl and an
appropriate volume of methanol was added, equal to 2% of the sample
volume. Subsequent to acid and methanol addition, samples were
passed twice through C18 cartridges followed by HPLC-grade water,
using vacuum pump at a ow rate of 24 ml/min. The sample was
loaded directly on top of the cartridge and the same ow rate as the cartridge volume was used (equal to 3 ml/min). After sample loading, the
cartridges were washed with HPLC-grade water twice before pouring
10 ml of dichloromethane at ow rate of 1 ml/min. The eluted sample
was analyzed with HP 7890B/5977A GC-MSD (Agilent Technologies,
Palo Alto, CA, USA) operated at an electron impact (70 eV) and in a
full-scan mode. The HP Model 7890B GC was equipped with a HP5MS coated capillary column (30 m 0.25 mm ID 0.25 m lm thickness). Samples were injected in splitless mode with He as carrier gas.
The GC oven was programmed at 75 C and held 2 min, heated to
275 C at 6 C/min, and held at the maximum temperature for 35 min.
System control and data acquisition were achieved with the Agilent
MassHunter GC-MS Acquisition B.07.00.SP2 and MSD ChemStation
Enhanced Data Analysis F.01.00.1903. The identication of the photocatalysis degradation products was done by comparing the GC-MS spectra patterns with those of standard mass spectra in the National
Institute of Standards and Technology (NIST) library.

51

Table 1
Apparent rate constant (kapp) and correlation coefcient (R2) for TOC degradation at different UV operating conditions.
UV operating condition

kapp (103 min1)

R2

UV (photolysis)
UV with neat PVDF membrane
UV with PVDF-TiO2 membrane

1.50
3.10
5.20

0.9987
0.9351
0.8958

explanation is further supported by the higher value of apparent rate

constant (kapp) in the case of PVDF-TiO2 membrane as shown in
Table 1. To further conrm the degradation of the organic compounds,
the chromatograms of solution samples before and after photocatalysis
using PVDF-TiO2 membrane were compared and the results are shown
in Fig. 4. It can be clearly seen that signicant peak as shown in sample A
was decreased in sample B. The identication of possible organic compounds is summarized in Table 2. It is found that majority of identied
hydrocarbons can be associated to chemical compounds in the range
of C12C39. Among these compounds, C27 fractions had approximately
23.8% while C16 and C14 fractions were 18.7% and 14.7%, respectively.
This observation was analogous to that reported by Li et al. [28] in
which approximately 90% of hydrocarbon groups detected within oily
wastewater are C10C30 straight chain alkanes. In our study, the previous most abundant hydrocarbons (C27C39) were disappeared in sample B, most probably due to photocatalytic activity that breaks the
long-chained organic compounds into relatively smaller organic compounds (C12C16).
3.2. Effect of TiO2 catalyst loading

3. Results and discussion

3.1. Role of TiO2 photocatalyst
Fig. 3 compares the TOC degradation performance of direct photolysis, neat PVDF UF membrane and PVDF-TiO2 UF membrane under UV irradiation. It is found that oil particles were barely photodegraded after
120 min of UV-A light exposure in the case of direct photolysis. In contrast, it is observed that the TOC degradation using PVDF-TiO2 membrane was remarkably higher compared to neat PVDF membrane,
conrming the important role of TiO2 catalyst in assisting oil degradation. The signicant oil degradation in the case of PVDF-TiO2 membrane
can be further explained by the generation of strong oxidants from the
TiO2 nanoparticles under UV irradiation that have consequently oxidized most of the organic compounds found in the feed solution. The

Fig. 5(a) shows the permeate ux and oil rejection with PVDF membrane made of different TiO2 loadings under UV irradiation. Owing to
the photoinduced-hydrophilicity effect of TiO2 catalyst embedded within membrane matrix, the permeate ux was reported to increase with
increasing TiO2 loading from 0 to 2 wt.%. Similar results have also
been reported by Vernardou et al. [29] and Risse et al. [30], where
they found that membrane hydrophilicity was remarkably increased
(i.e. lower water contact angle) with increasing TiO2 loading upon UV illumination. Excessive use of TiO2 (N 2 wt.%) however was found to negatively affect membrane permeate ux, mainly because of the TiO2
particle agglomeration which increases the water transport resistance
on membrane surface and results in lower ux [31]. Despite the ux
was declined with increasing TiO2 loading N2 wt.%, promising oil rejection (N 90%) was able to achieve throughout the entire experimental

(A)

(B)

Fig. 3. Comparison of TOC degradation between photolysis, neat PVDF membrane and
PVDF membrane in the presence of TiO2 catalyst (Operating condition: 8 W UV-A lamp,
temperature = 25 C and initial feed concentration = 1000 ppm).

Fig. 4. Comparison of chromatograms before (A) and after (B) photocatalytic degradation
in 240 min of UV irradiation (operating conditions: 8 W UV-A lamp, feed concentration =
1000 ppm and PVDF membrane immobilized with 2 wt.% TiO2).

52

C.S. Ong et al. / Desalination 353 (2014) 4856

Table 2
Identication of possible organic compounds before and after photocatalysis.
Photocatalytic
conditions

No.

Name

Chemical
formula

Before photocatalysis

1-Monolinoleoylglycerol trimethylsilyl ether

C27H54O4Si2

23.8

Octasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15hexadecamethyl-

C16H50O7Si8

18.7

Heptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13tetradecamethyl-

C14H44O6Si7

14.7

Hexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13tetradecamethyl-

C12H38O5Si6

8.03

Spirost-8-en-11-one, 3-hydroxy-,
(3, 5, 14, 20, 22, 25R)-

C27H40O4

8.03

Cholestan-3-one, cyclic 1,2-ethanediyl aetal, (5)-

C29H50O2

2.4

Oleic acid, 3-(octadecyloxy)propyl ester

C39H70O3

1.65

Cholestan-3-one, cyclic 1,2-ethanediyl acetal, (5)-

C29H50O2

1.39

9
10

Octadecane, 1,1'-[1,3-propanediylbis(oxy)]bisGlycine, N-[(3, 5, 7, 12)-24-oxo-3,7,12-tris

[trimethylsilyloxy]cholan-24-yl]

C39H80O2
C36H69NO6Si3

1.39
1.04

Octasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15hexadecamethyl36-

C16H50O7Si8

51

Heptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13tetradecamethyl-

C14H44O6Si7

36

Hexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13tetradecamethyl-

C12H38O5Si6

10.2

After photocatalysis

period, which can be attributed to the smaller pore size of membranes

than the mean diameter of oil particles, as reported in our previous
studies [32,33].
Fig. 5(b) on the other hand shows the TOC degradation of TiO2 incorporated PVDF composite membrane under UV irradiation. The TOC degradation increased when TiO2 loading increased from 1 to 2 wt.%, owing

Chemical structure

Probability
(%)

to photoinduced-hydrophilicity on the membrane surface by TiO2 catalyst upon UV illumination. Photo-induced electrons are generated during UV illumination and large amount of OH radicals is formed due to
dissociation of water molecules through oxygen vacancies. However,
further increase in TiO2 loading was detrimental to the oil degradation
as TiO2 agglomeration might lead to inefcient adsorption of UV energy

C.S. Ong et al. / Desalination 353 (2014) 4856

53

Fig. 5. Effect of TiO2 catalyst loading on (a) permeate ux and oil rejection and (b) TOC degradation of PVDF-TiO2 composite membrane in the sMPR system (operating conditions:
temperature = 25 C, vacuum pump ow rate = 15 ml/min and pH = 7).

Table 3
Apparent rate constant (kapp) and correlation coefcient (R2) for TOC degradation with
PVDF-TiO2 composite membranes at different TiO2 catalyst loading.
TiO2 (wt.%)

kapp (103 min1)

R2

0
1
2
3
4

0.20
0.80
2.80
2.10
1.30

0.9298
0.8522
0.9355
0.8633
0.8961

nanoparticles as a result of TiO2 agglomeration [35,36]. This trend is exactly the same as those observed in permeate ux and TOC degradation,
revealing that membrane surface charge does to some extent govern
membrane performance in this study. Based on the results obtained
here, it can be said that the membrane separation performance and
the photocatalytic activity are not favored at excessive TiO2 loading
and 2 wt.% TiO2 was therefore selected as optimal catalyst loading in
the following studies.
3.3. Effect of module packing density

and consequently caused the deterioration of photocatalytic activity

and less OH radicals generated on membrane surface. This phenomenon was supported by the decreased value of kapp in the PVDF membrane embedded with 3 and 4 wt.% TiO2 in comparison to the
membrane with 2 wt.% TiO2 (see Table 3).
In order to better understand the effect of TiO2 loading on membrane performance, surface charge of each membrane with respect to
zeta potential was determined. The zeta potential measured for the origin PVDF membrane and PVDF membranes modied with 1, 2, 3 and
4 wt.% TiO2 were 3.5, 8, 8.9, 8 and 3.5 mV, respectively, at
pH 7. It can be clearly seen that the zeta potential of the modied
PVDF membranes with 12 wt.% TiO2 loading was signicantly higher
than that of the origin PVDF membrane, conrming the role of the negative charged TiO2 nanoparticles in inducing membrane charge properties [34]. However, the use of excessive loadings of TiO2 (N2 wt.%) for
PVDF membrane tended to reduce negative surface charges, owing
to the enhancement of electrostatic attractive force among TiO2

To further investigate the performance of PVDF-TiO2 membrane

during sMPR process, the membrane module packing density also
needs to be considered. As reported in literature [3741], mass transfer
was able to be enhanced with higher membrane module packing density, which contributed to greater membrane ux. Yet the effect of module packing density on the corresponding photocatalytic degradation
has not been reported so far. Thus, an attempt has been made in this
work to investigate the permeate ux, oil rejection and TOC degradation
as a function of module packing density. It can be clearly seen from
Fig. 6(a) that permeate ux increased with increasing module packing
density from 17.6% to 35.3%, owing to the enhanced mass transfer between the water molecules and membrane surface [38]. However,
when further increased the module packing density to 52.9%, the bers
were likely to attach to each other and resulted in the limited spaces
available between adjacent bers, causing both the effective mass transfer area and membrane ux to decrease [37]. The experimental work
conducted by Kiat et al. [42] showed that severe inter-ber fouling

Fig. 6. Effect of module packing density on (a) permeate ux and oil rejection and (b) TOC degradation of PVDF-TiO2 composite membrane in the sMPR system (operating conditions:
temperature = 25 C, membrane type: PVDF with 2 wt.% TiO2, vacuum pump ow rate = 15 ml/min and pH = 7).

54

C.S. Ong et al. / Desalination 353 (2014) 4856

Table 4
Apparent rate constant (kapp) and correlation coefcient (R2) for TOC degradation with
PVDF-TiO2 composite membranes at different module packing density.
Module packing density (%)

kapp (103 min1)

R2

17.6
35.3
52.9

0.09
2.30
1.00

0.9678
0.9589
0.9576

tended to occur when the packing density of the module exceeded a

critical value, i.e. 30.8% reported in their work. However, the critical
packing density might vary, depending on feed solution properties,
module dimension and membrane material. Yeo et al. [39] on the
other hand also reported that high membrane packing density could
lead to enhanced permeability, provided the packing density was not
excessive. It is because excessive packing density would cause foulant
accumulation to occur inside the ber bundle.
As illustrated in Fig. 6(b), TOC degradation increased when the module packing density was increased to 35.3%, but decreased with further
increased the module packing density to 52.9%. This can be explained by
the fact that when large amount of bers is packed in a module, they are
tended to attach to each other, reducing the active surface sites for UV
irradiation and photocatalysis. Because of this, lower value of kapp was
obtained (see Table 4). Despite the deterioration of ux and photocatalytic activity at high packing density, high rejection rate could be consistently achieved throughout the experiment. Based on these ndings, it
can be concluded that high packing density might adversely affect
both ltration performance and TOC degradation, hence, module packing density of 35.3% was selected as optimal module scale to apply in the
subsequent studies.
3.4. Effect of feed concentration
To deal with industrial oily wastewater of various oil concentrations,
the membrane performance and oil photodegradation at different initial
feed concentration in the range of 25010,000 ppm were also investigated based on the optimum TiO2 loading (embedded in membrane matrix)
and module scale as reported in previous sections. As shown in Fig. 7(a),
membrane ux was found to decrease signicantly with the increase of
feed concentration. The average ux of membrane was decreased from
around 73 L/m2 h at 250 ppm to b62 L/m2 h at 1000 ppm and further
to approximately 22 L/m2 h and 15 L/m2 h for concentration of
5000 ppm and 10,000 ppm, respectively. These results serve as the compelling evidence that thicker oil layer is formed on the membrane surface at high feed concentration, leading to increased water transport
resistance and decreased membrane permeability [43]. Additionally, at
low oil concentration, the ux decline rate was not as severe as that of
observed at high oil concentration. At 250 ppm, the membrane ux

F1

F2

F3

F4

P1

P2

P3

P4

Fig. 8. Feed and permeate solution at varied concentration (a) feed oil concentration of
250 ppm (F1), 1000 ppm (F2), 5000 ppm (F3) and 10,000 ppm (F4) and (b) their respective permeate sample (P1-4).

declined by around 8% in 480 min compared to 43%, 51% and 56% recorded for 1000 ppm, 5000 ppm and 10,000 ppm of oily solution, respectively. This increasing pattern was similar to the ndings reported in our
previous work [32,33], where the ux of PVDF-TiO2 membrane tested
under non-UV irradiation declined with increasing oil concentration.
However, this experimental results show that membrane ux with UV
irradiation was higher compared to those operated without UV irradiation. It is because of the photoinduced-hydrophilicity effect on the
PVDF-TiO2 surface under UV illumination as discussed in the previous
section.
Although membrane ux tended to decrease at higher oil concentration, promising oil removal rate was still able to obtain irrespective of oil
concentration (see sample illustrations in Fig. 8). Furthermore, as observed in Fig. 7(b), the degradation of oil under UV irradiation was highly efcient at low concentrations. The formation of thicker oil layer is the
main cause for this phenomenon, because it adversely affects the UV
light penetration on the membrane surface which in turn reduces the
active surface sites for UV irradiation and results in drastic reduction
in photocatalytic degradation of oil [28,44]. Fig. 9 shows that kapp declined with increasing initial feed concentration and the reaction rate
at 250 ppm was remarkably higher compared to 10,000 ppm. This indicates that photocatalytic degradation was seriously deteriorated at high
oil concentration.

Fig. 7. Effect of feed concentration on (a) permeate ux and oil rejection and (b) TOC degradation of PVDF-TiO2 composite membrane in the sMPR system (operating conditions: temperature = 25 C, membrane type: PVDF with 2 wt.% TiO2, module packing density = 35.3%, vacuum pump ow rate = 15 ml/min and pH = 7).

C.S. Ong et al. / Desalination 353 (2014) 4856

3.5

4
2.9

2.5
2

2
1.5

1
0.5
0

3.5

3.5

kapp ( 10-3 min-1)

kapp ( 10-3 min-1)

55

1000

5000

Oil concentration (ppm)

Fouling is always more signicant when membrane is used to treat

oily wastewater of relatively high concentration. Therefore, in order to
effectively alleviate this problem, the effect of ABFR on the membrane
performance and oil degradation during sMPR process was investigated
and the results are presented in Fig. 10. As can be seen from Fig. 10(a),
the average membrane ux was found to increase with increasing
ABFR from zero to 5 L/min. The ux improvement at higher ABFR is likely due to the generation of circulation ow in the sMPR which limits the
oil adsorbed onto the membrane surface and further reduces the membrane fouling tendency [45].
Fig. 10(b) shows the enhancement of TOC degradation when higher
ABFR was applied in sMPR system. The detailed mechanism can be explained by the following pathways (Eqs. (7)(10)). The formation of
more OHradicals is prompted with larger number of oxygen bubbles resulted from higher ABFR (Eqs. (7)(8)). Meanwhile, large amount of
OH radicals is formed due to dissociation of water molecules upon UV
illumination (Eq. (9)). These OHradicals will mineralize those hydrocarbon groups in the oily wastewater to become CO2 and H2O (Eq. (10)).
With air ow (O2 ~ 78%) under 365 nm irradiation [46]:
hv

OzoneO3 O day H2 O2OHformation of hydroxyl radicals

8
hv

H2 O H  OH
Oil 3OH xCO2 yH2 Omineralization:

1.5

1.3

ABFR (L/min)

3.5. Effect of air bubble ow rate (ABFR)

hv

1.9

10000

Fig. 9. Apparent rate constant (kapp) for TOC degradation at different feed oil
concentrations.

Oxygen bubbles Dissolved oxygen Ozone O3

2.5

0.5

0.2

250

2.8

9
10

Fig. 11. Apparent rate constant (kapp) for TOC degradation at different ABFR.

The enhanced TOC degradation at higher ABFR was further conrmed by kapp shown in Fig. 11. Based on these ndings, it can be concluded that air bubbling under UV irradiation was crucial for the
enhancement of TOC degradation. It is worth mentioning that high oil
rejection was consistently achieved regardless of ABFR, indicating that
smaller membrane pore size is the dominant factor in ensuring excellent oil separation process.

4. Conclusion
A laboratory-scale sMPR exhibited remarkably improved performances not only in degrading synthetic cutting oil wastewater but
also in producing permeate of high quality at relatively low operating
cost. The results showed that TOC degradation using PVDF-TiO2 membrane was remarkably higher compared to neat PVDF membrane. Furthermore, GC-MS analyses showed that synthetic oily wastewater
could be efciently degraded using PVDF-TiO2 composite membrane
under UV irradiation. The inuence of several key operating parameters,
such as TiO2 loading, membrane module packing density, initial feed
concentration and ABFR on membrane performances were investigated
based on permeate ux and its quality. It was found that both TOC degradation and membrane ux were seriously deteriorated when excessive TiO2 loading and module packing density were used. Although
thicker oil layer tended to form at high feed concentration which adversely affected photocatalytic degradation and water ux, the introduction of higher ABFR could reduce the impacts to certain extent.
With respect to TOC degradation and oil rejection, the in-house made
membrane could achieve 80% TOC degradation and N 90% rejection
when it was operated under optimized conditions. Overall, this study
not only provides some useful information for the simultaneous

Fig. 10. Effect of ABFR on (a) permeate ux and oil rejection and (b) TOC degradation of PVDF-TiO2 composite membrane in the sMPR system (operating conditions: temperature = 25 C,
membrane type: PVDF with 2 wt.% TiO2, module packing density = 35.3%, initial feed concentration = 1000 ppm, vacuum pump ow rate = 15 ml/min and pH = 7).

56

C.S. Ong et al. / Desalination 353 (2014) 4856

separation and degradation of oily wastewater, but also facilitates the

development of hybrid sMPR in real oily wastewater industry.
Acknowledgments
The authors gratefully acknowledge the nancial support by the
LIMPID FEP-7 Collaborative European Project Nanocomposite Materials
for Photocatalytic Degradation of Pollutants (Project number: NMP3SL-2012-310177) and Fundamental Research Grant Scheme (Project
number: 4F306).
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