Separation and Purication Technology 142 (2015) 137148

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Separation and Purication Technology

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

Effect of process parameters on fouling and stability of MF/UF TiO2

membranes in a photocatalytic membrane reactor
Sylwia Mozia a,, Kacper Szymanski a, Beata Michalkiewicz a, Beata Tryba a, Masahiro Toyoda b,
Antoni W. Morawski a
a
b

West Pomeranian University of Technology, Szczecin, Institute of Chemical and Environment Engineering, ul. Puaskiego 10, 70-322 Szczecin, Poland
Oita University, Department of Applied Chemistry, Dannoharu 700, Oita 870-1192, Japan

a r t i c l e

i n f o

Article history:
Received 20 October 2014
Received in revised form 19 December 2014
Accepted 20 December 2014
Available online 13 January 2015
Keywords:
Photocatalytic membrane reactor
Ceramic membrane
Ultraltration
Microltration
Fouling
Stability

a b s t r a c t
The investigations on the inuence of TiO2 photocatalyst (Aeroxide TiO2 P25) loading, feed cross-ow
velocity (vF) and transmembrane pressure (TMP) on the fouling and stability of ceramic membranes in
a photocatalytic membrane reactor are presented. Two ultraltration membranes with molecular weight
cut-off of 5 kDa (Filtanium 5) and 100 kDa (Filtanium 100), and one microltration membrane (Filtanium
0.2) with maximum pore size of 0.2 lm were used. Regardless of the applied vF (36 m/s), TMP (13 bar)
and TiO2 P25 loading (0.51.5 g/dm3) no permeate ux decline was observed when the UF membranes
were used. On the opposite, an increase of the ux for 510% compared to pure water ux due to abrasion
of the membranes separation layer by TiO2 P25 particles was found. In case of MF membrane a signicant
inuence of vF and TMP on permeate ux was observed. Application of vF = 3 m/s led to a signicant
membrane fouling while at vF = 6 m/s the permeate ux exceeded pure water ux in the whole range
of TMP. The ne UF Filtanium 5 membrane lost its separation properties due to abrasion by TiO2 P25 particles, whereas the performance of the ordinary UF Filtanium 100 membrane did not change during 100 h
of operation in the PMR. Additionally, the inuence of a commercial TiO2 ST01 (Ishihara Sangyo, Japan)
and laboratory made A700 (anatase) and A800 (rutile) on the permeate ux through Filtanium 100 membrane were assessed. The difference between the lowest and the highest values of the permeate uxes
measured for various TiO2 materials did not exceed 12%.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Every year huge amounts of wastewater containing toxic
organic pollutants are produced worldwide. Conventional water
and wastewater treatment technologies are usually ineffective in
removal of these chemicals and the pollutants enter the environment thus contaminating water sources. Therefore, numerous
attempts have been undertaken to develop new methods of water
and wastewater treatment. A very promising solution could be
application of photocatalytic membrane reactors (PMRs). PMRs
are hybrid systems coupling photocatalysis and a membrane process in one unit. Photocatalysis allows the organic pollutants to
be decomposed and mineralized to H2O, CO2 and mineral salts. A
membrane enables separation of the photocatalyst from the reaction medium and its further reuse. Additionally, the membrane
could serve as a barrier for the molecules present in the solution,

Corresponding author. Tel.: +48 91 449 47 30.

E-mail address: sylwia.mozia@zut.edu.pl (S. Mozia).
http://dx.doi.org/10.1016/j.seppur.2014.12.047
1383-5866/ 2015 Elsevier B.V. All rights reserved.

both initial compounds and products or by-products formed during the decomposition [1].
Two main types of PMRs can be differentiated: (i) with a photocatalyst in a suspension and (ii) with a photocatalyst immobilized
on the membrane surface or within its structure [1]. Most of the
PMRs described in literature are slurry reactors equipped with
polymer membranes [24]. However, polymer membranes have
some serious drawbacks when their application in PMRs is considered. The most important are low resistance to UV light and the
action of hydroxyl radicals. The limited stability of commercial
polymeric membranes under UV irradiation was conrmed by
Molinari et al. [5], whereas Chin et al. [6] reported the membranes
damage during their exposure to 200 mmol/dm3 H2O2 solution. To
increase the lifetime of the polymeric membranes in the hybrid
photocatalysis-membrane systems it is necessary to place them
separately from a photoreactor. Ceramic membranes exhibit properties that make them more appropriate for the application in the
PMRs, namely high chemical, pH, temperature and pressure resistance [7]. Ceramic membranes can be made of various materials,
including TiO2, Al2O3 or ZrO2. Particularly, the pure titania

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

membranes are widely used in microltration (MF) and ultraltration (UF) systems because they exhibit good fouling resistance due
to highly hydrophilic properties of their surface [8]. Despite
numerous advantages of ceramic membranes, the literature
reports on their application in PMRs are very limited [7,912].
Moreover, most of papers refer to a preparation of the membranes
with immobilized TiO2 layer and evaluation of their photocatalytic
efciency in the hybrid systems [9,10]. PMRs equipped with such
membranes were applied for decomposition of model dyes including Methyl Orange [9], Acid Orange 7 [10,12], Acid Red 4 [11] and
Rhodamine B [13]. The literature data on slurry PMRs equipped
with ceramic membranes is even much more scanty. A pilot scale
PMR with ceramic MF membranes and TiO2 in suspension was
applied for treatment of Colorado River water [14]. The authors
described mainly the efciency of the removal of pharmaceuticals
and endocrine disrupting compounds; however, did not present
any details on the permeate ux variations during the experiment.
Shi et al. [15] presented results of the treatment of waste seawater
from shrimp farms in a photocatalytic membrane reactor equipped
with a-Al2O3 membrane with pore size of 0.05 lm. Except from
TiO2 photocatalysis they examined combined systems, i.e. photocatalysis enhanced with H2O2 and photocatalysis in the presence
of Fenton reagent. The authors reported that the permeate ux
under 0.5 bar was 432 dm3/m2 h. Another researchers [16] studied
fouling and regeneration of two Al2O3 MF membranes with the
pores diameter of 0.2 and 1.0 lm for the recovery of ne TiO2 particles from acid wastes. It must be stressed, however, that the system was not a PMR but just an ordinary MF conguration. The
authors observed that the permeate ux increased with increasing
feed cross ow velocities (vF) in the range of 13.5 m/s. However,
at higher velocities it slightly decreased. That was explained by
the removal of larger particles by scouring action of the cross-ow
stream as the vF was increased. As a result, smaller particles were
deposited on a membrane which led to the formation of a more
dense ltration cake with a higher resistance. Application of backush was found to be an efcient method of the TiO2 cake removal
only in case of the 1 lm pore-size membrane [16].
The present state of the art in the area of PMRs with polymeric
membranes shows that application of TiO2 in a slurry contributes
to permeate ux decline due to deposition of TiO2 on a membrane
surface [1]. The severity of membrane fouling caused by TiO2
depends on process parameters such as photocatalyst loading,
transmembrane pressure and feed cross ow velocity [17]. Generally, the permeate ux improvement with increasing cross-ow
velocity was observed [17,18]. Moreover, it was found that when
the TiO2 concentration was increased from 0.001 to 3.0 g/dm3
the ux decline was proportional to TiO2 loading [1719].
The reports concerning membrane fouling caused by TiO2 particles in PMRs utilizing ceramic membranes are hardly to be found.
Moreover, there are no papers describing the stability of ceramic
membranes in PMRs. There is also lack of the papers presenting
thorough investigations on the inuence of process parameters
such as TiO2 amount, transmembrane pressure or feed cross-ow
velocity on the ceramic membranes performance in PMRs.
The present work describes the studies on the inuence of process parameters on the performance of TiO2 micro- and ultraltration membranes during ltration of TiO2 suspension under
conditions prevailing in a slurry photocatalytic membrane reactor.
Moreover, the effect of the photocatalyst type on the permeate ux
behavior was evaluated. Additionally, the membranes stability in
terms of separation properties was assessed during long term
operation in the PMR. The ceramic membranes made of titanium
dioxide were chosen due to the fact that they were made of a material (TiO2) exhibiting similar physico-chemical properties as the
photocatalysts used in the experiments. It should be noted, however, that the membranes were not the photocatalytic membranes.

The membrane module was separated from the photoreactor and

therefore the only role of a membrane in the system was separation of photocatalyst particles.
2. Experimental
2.1. Materials
Three single-channel tubular ceramic membranes with brand
name of Filtanium (TAMI Industries, France) were applied in the
experiments. Two of them were UF membranes with the molecular
weight cut-off, MWCO (according to manufacturer) of 5 kDa (Filtanium 5) and 100 kDa (Filtanium 100), and the third one was an MF
membrane with the maximum pore size of 0.2 lm (Filtanium 0.2).
The membranes were made of titanium dioxide. The membranes
length was 25 cm and the external/internal diameters amounted
to 10 mm/6 mm. The effective membrane area was 0.0047 m2. A
membrane was placed in a stainless steel housing having length
of 250 mm and diameter of 15 mm (TAMI Industries, France).
Before the experiments the brand new membranes were cleaned
chemically with application of NaOH and H3PO4 solutions according to the procedure recommended by the manufacturer.
During the rst part of the investigations TiO2 Aeroxide P25
(Evonik, Germany) was used as a photocatalyst. The TiO2 loading
amounted to 0.5, 1.0 or 1.5 g/dm3. In the second part of the
research three additional photocatalysts were applied: a commercially available ST-01 anatase-phase TiO2 (Ishihara Sangyo, Japan)
and the laboratory-made A700 (anatase) and A800 (rutile) samples. The A700 and A800 photocatalysts were prepared by calcination of the industrial grade TiO2, obtained by the sulfate technology
at the Chemical Factory Police S.A. (Poland). The calcination temperature amounted to 700 and 800 C, respectively. A detailed
characteristics of the photocatalysts can be found in our previous
works [20,21].
Polyethylene glycols (PEG) with an average molecular weight
(MW) of 4000 and 6000 g/mol (SigmaAldrich) and a series of dextrans with an average MW of 5000, 70,000, 110,000 g/mol (Polfa
Kutno) and 2,000,000 g/mol (SigmaAldrich) were used to determine the separation properties of the membranes. The concentration of the compounds in the feed was set at 1 g/dm3.
All solutions applied in the experiments were prepared using
pure water (0.066 lS/cm, Elix 3, Millipore).
2.2. Methods
Experimental setup of the photocatalytic membrane reactor is
presented in Fig. 1. The installation was equipped with two ow
through photocatalytic reactors (V = 0.84 dm3 each) containing
UV-C lamps (Philips TUV 16 W, kmax = 254 nm; UV light intensity:
1.54 W/m2). An air-operated double diaphragm pump SANDPIPER
S05 (WARREN RUPP, INC., Manseld, USA.) was applied to deliver
feed to the membrane module. At the beginning of each experiment the feed solution (7 dm3) was introduced to the feed tank.
After that the UV lamps were switched on and the pump was
started. During the process the solution in the feed tank was continuously mixed by a motorized mechanical stirrer. In the experiments in which the Filtanium 5 and Filtanium 100 membranes
were applied the transmembrane pressure (TMP) was changed
from 1 to 3 bar. In case of the Filtanium 0.2 the TMP was in the
range of 0.53 bar. The feed cross-ow velocity (vF) was set at 3,
4.5 or 6 m/s. The change of vF was achieved by changing the pump
delivery rate for a dened transmembrane pressure. The temperature of the feed was maintained at 20 1 C. The membrane was
working in the inside-out mode, i.e. the feed owed in the lumen
side of the membrane and the permeate was collected from the

S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

139

Fig. 1. Schematic diagram of the laboratory-scale photocatalytic membrane reactor used in the experiments (P1, P2, P3 manometers, R1, R2 rotameters, FT feed tank,
S stirrer, P pump, UV1, UV2 photoreactors with UV-C lamps, MM membrane module, H heater, C cooler).

shell side of the module. The permeate ux was estimated by measuring the volume of permeate which passed through the membrane during a period of time. Both the retentate and permeate
were recycled to the feed tank in order to maintain constant concentration of the photocatalyst. The experiments were repeated
at least twice in order to conrm the reproducibility of the results.
In case of the MF membrane a backush procedure using permeate as a ushing medium was applied. The backush pressure
was 4 bar. The backush frequency was 30:1, which means that
the backpulse duration was 1 s and the backpulse interval
amounted to 30 s.
The morphology of the surface of the brand new membranes
and the TiO2 ltration cake was analyzed using the laser scanning
microscopy (LSM) and atomic force microscopy (AFM) techniques.
The LSM measurements were performed with application of
VK9700 microscope (Keyence, Japan). The LSM membrane roughness (LSM-Ra) was calculated using the VK Analyzer software.
The AFM analysis was performed using NanoScope V Multimode
8 scanning probe microscope (Bruker Corp.). The measurements
were carried out in the ScanAsyst mode using the silicon nitride
ScanAsyst Air probe. The AFM membrane roughness (AFM-Ra)
was calculated with application of the NanoScope Analysis
software.
The morphology of the membranes and the thickness of the
TiO2 ltration cake was examined using Hitachi SU8020 Ultra-High
Resolution Field Emission Scanning Electron Microscope (UHR FESEM) equipped with Energy Dispersive Spectroscopy system (EDS
NSS 312, Thermo Scientic).
The FTIR/DRS spectra were recorded using Jasco FTIR 4200 spectrometer (Japan) equipped with a diffuse reectance accessory
(Harrick, USA).
The XRD patterns were recorded using XPert PRO diffractometer with Cu Ka radiation (k = 1.54056 ). TiO2 anatase over rutile
ratio was calculated from [19]:

Anatase contentA 1=1 1:26IR =IA

where IA and IR are the diffraction intensities of the (1 0 1) anatase

and (1 1 0) rutile crystalline phases at 2h = 25.3 and 27.4,
respectively.
The average anatase crystallite diameter D (nm) was calculated
using Scherrers equation [19]:

D Kk=b cos h

where K = 0.9 is a shape factor for spherical particles, k is the wavelength of the incident radiation (k = 1.54056 ), h is half of the diffraction angle (rad) and b is the line width at half-maximum height.
The BrunauerEmmettTeller (BET) surface area of the powders
was determined on the basis of nitrogen adsorptiondesorption
measurements at 77 K conducted in Quadrasorb SI (Quantachrome,
USA) apparatus. The samples were degassed at 80 C prior to nitrogen adsorption measurement. The BET surface area was determined by multipoint BET method using the adsorption data.
The particle size distribution of the photocatalysts was analyzed
by LA-950 Laser Diffraction Particle Size Distribution Analyzer
(Horiba, Japan). During the measurement the samples were circulated without any sonication in order not to destroy aggregates
formed in water suspensions of the photocatalysts.
The concentrations of polyethylene glycol and dextrans in feed
and permeate were determined using high performance liquid
chromatograph (HPLC) LaChrom Elite (Hitachi, Japan) equipped
with refractive index (RI) detector L-2490 and the PolySep-GFCP4000 column. The mobile phase was ultrapure water. The rejection coefcient was calculated on a basis of the equation:

R% 1  C permeate =C feed  100%

where Cpermeate and Cfeed represent the concentrations of dextran or

PEG in permeate and feed, respectively. The rejection of the model
molecules was determined in the absence of TiO2 in the feed.
3. Results and discussion
3.1. Characterization of TiO2 photocatalysts
Table 1 presents selected physico-chemical parameters of the
photocatalysts applied in the experiments: the commercially available TiO2 Aeroxide P25 and ST-01 as well as laboratory made
A700 and A800. A detailed description of the A700 and A800 photocatalysts can be found in our previous works [20,21].
In Fig. 2 the particle size distribution (PSD) of the photocatalysts
is shown. During PSD determination the sonication of the samples
was not applied in order to avoid destruction of the aggregates
which are formed in water. The P25 and ST01 photocatalysts

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

Table 1
Selected physico-chemical parameters of the photocatalysts.
Photocatalyst

Specic surface
area SBET (m2/g)

Anatase over
rutile ratio (A:R)

Crystallite size of
anatase (nm)

A700
A800
P25
ST-01

30
6
51
252

94:6
2:98
80:20
100:0

32
51
22
8

Fig. 2. Particle size distribution of various photocatalysts: P25, ST01, A700 and
A800.

exhibited the most uniform particle size distribution among all of

the TiO2 materials used, with the mean particle size of 4.2 and
6.6 lm, respectively. The A700 contained a portion of particles
with the diameters being lower than those in case of P25 and
ST01, however, in the PSD graph a second peak corresponding to
much larger particles can also be observed. The mean particle sizes
calculated for both peaks amounted to 3.4 lm and 33 lm, respectively. Similarly, a bimodal particle size distribution was found in
case of A800. However, the diameters of the particles measured
for this material were much larger than those determined in case
of other samples. The mean particle size calculated for the rst
and the second peak amounted to 4.9 lm and 95.5 lm,
respectively.
The analysis of the FTIR-DRS spectra (Fig. 3) revealed signicant
differences in the intensity of the bands corresponding to OH
vibrations (a broad band between 3000 and 3700 cm1). The intensity of these bands decreased in the following order:

Fig. 3. FT-IR/DRS spectra of various photocatalysts.

ST01 > P25 > A700 > A800. Higher intensity of the bands can be
attributed to a higher hydrophilicity of a material. According to this
assumption, the ST01 was the most hydrophilic whereas A800
exhibited the lowest hydrophilicity from all of the materials used.

3.2. Characterization of brand new membranes

Fig. 4 presents SEM cross sections of the membranes applied in
the study. All the membranes were made of TiO2. The Filtanium 5
consisted of 4 layers: a porous support with a thickness of ca.
2 mm, two intermediate layers: the rst one built of larger TiO2
particles (thickness of ca. 40 lm), and the second one consisting
of smaller particles (thickness of ca. 15 lm), and the top layer composed of ne particles (thickness of ca. 1.5 lm). The Filtanium 100
membrane was also composed of 4 layers, with approximate thickness of 2.2 mm, 50 lm, 10 lm and 1.5 lm, respectively. The TiO2
particles forming the skin layer were, however, much larger in case
of Filtanium 100 (Fig. 4d) compared to Filtanium 5 (Fig. 4b). The
Filtanium 0.2 was built of 3 layers: the porous support exhibited
thickness of ca. 2.3 mm, the intermediate layer was ca. 30 lm thick
and the separation layer thickness was ca. 10 lm.
The brand new membranes were also characterized by the surface roughness (LSM-Ra) determined on a basis of LSM measurements. The highest LSM-Ra value was observed in case of the MF
membrane (0.165 lm, S.D. = 0.016 lm). That was associated with
the large diameter of the pores on the membrane surface. The
LSM roughness of Filtanium 5 membrane amounted to 0.082 lm
(S.D. = 0.022 lm), whereas the LSM-Ra calculated for Filtanium
100 was 0.051 lm (S.D. = 0.008 lm).
Figs. 57 present changes of permeate ux during ltration of
pure water through the membranes. In case of Filtanium 5 membrane the experiment was carried out for 16 h, divided for 2 days
(Fig. 5). The ux measured during the rst day was lower than that
observed during the last 8 h of UF when it stabilized at a level of
142 dm3/m2 h. In case of Filtanium 100 membrane (Fig. 6) the
ultraltration of pure water was carried out for 25 h. A continuous
decrease of the permeate ux was observed in the initial 12 h of
the experiment. During this time the ux was lowered for ca.
50%, i.e. from 1000 dm3/m2 h to ca. 500 dm3/m2 h. The permeate
ux got stabilized at a level of 494 dm3/m2 h.
The longest time necessary for the permeate ux stabilization
was observed in case of Filtanium 0.2 membrane (Fig. 7). MF of
pure water through this membrane was conducted for 34 h. At
the beginning of the process the permeate ux rapidly decreased
from ca. 6600 dm3/m2 h to 4250 dm3/m2 h just within 1 h. The stable permeate ux was found to be 2196 dm3/m2 h.
A signicant decrease of PWF through a ceramic membrane
during conditioning stage was also reported by Chevereau et al.
[22]. The authors observed that the ux was decreasing for about
500 h until it reached a stable value. They concluded that the surface hydration of TiO2 is a very slow process, during which the formation of hydroxyl groups and adsorption of molecular water on
the membrane occurs. Mendret et al. [10] also found that the pure
water ux through a brand new ceramic membrane was decreasing in the initial step of ltration. However, it got stabilized much
faster than in the previously described example, i.e. after 4 h of the
process. The authors reported also that when they used the same
membrane, but rstly immersed in water for 30 days, the permeate
ux during ltration of pure water was stabilized just at the beginning of the process. They concluded that the membrane that was
kept dry gave higher permeate ux than the membrane immersed
for a long time in pure water because in the former case the feed
solution must ow for a dened time to assure the wetting of
membrane pores. The authors also stressed that this phenomenon
is not often described and explained in literature [10].

S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

(a)

(b)

(c)

(d)

(e)

(f)

141

Fig. 4. SEM cross sections of (a and b) Filtanium 5, (c and d) Filtanium 100 and (e and f) Filtanium 0.2 membranes (1 support, 2, 3 intermediate layers, 4 top layer).

Fig. 5. Changes of permeate ux during UF of pure water through Filtanium 5

membrane at TMP of 3 bar. Insert: dependence of stabilized pure water ux (PWF)
on TMP.

Fig. 6. Changes of permeate ux during UF of pure water through Filtanium 100

membrane at TMP of 3 bar. Insert: dependence of stabilized pure water ux (PWF)
on TMP.

Based on the analysis of the results shown in Figs. 6 and 7

another explanation for the permeate ux decline can also be
found. During ltration the unbound TiO2 particles present in the
surface layer of the membranes were being moved under the
action of the pressure and the owing feed. That led to a higher
membrane rigidity and decreased porosity. As a result the permeate ux decline was observed. During the night the membrane was

kept wet but was no longer under the action of the pressure. Therefore, at the beginning of the second day of water ltration the permeate ux was a bit higher than at the end of the rst day of the
experiment, what is especially visible in case of Filtanium 100
and Filtanium 0.2 (Figs. 6 and 7). Such an increase of the ux might
be explained by the membrane decompression.
A linear dependence between PWF and transmembrane pressure was observed for all the examined membranes (Figs. 57).

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

3.3. Inuence of TiO2 loading on permeate ux through UF membranes

in the PMR

Fig. 7. Changes of permeate ux during UF of pure water through Filtanium 0.2

membrane at TMP of 3 bar. Insert: dependence of stabilized pure water ux (PWF)
on TMP.

The permeance in case of Filtanium 5 amounted to 47 dm3/m2 h

bar, in case of Filtanium 100 it reached 165 dm3/m2 h bar and for
the Filtanium 0.2 membrane it amounted to 732 dm3/m2 h. The
stable PWF values were used as a reference in further discussion.
The separation properties of the membranes were determined
using PEG and dextrans solutions. The rejection of PEG with an
average molecular weight (MW) of 4000 and 6000 g/mol by the Filtanium 5 membrane reached 97% and 99%, respectively. The rejection coefcient (R%) of dextran having MW of 5000 g/mol was
lower and amounted to 83%. In case of Filtanium 100 membrane
the efciency of separation of dextrans having 70,000 g/mol and
110,000 g/mol was equal to 95% and 99%, respectively. The separation properties of the MF Filtanium 0.2 membrane were evaluated
with application of dextran with MW of 2,000,000 g/mol. The R%
value in this case was equal to 17%.
The rejection coefcients determined for the brand new membranes served as a point of reference during assessment of the
degree of the membranes damage by the abrasive action of TiO2
particles.

In order to evaluate the inuence of TiO2 loading on the permeate ux through Filtanium 5 and Filtanium 100 membranes a set of
experiments in which photocatalyst concentration amounted to
0.5, 1.0 or 1.5 g/dm3 was performed. The experiments were conducted at TMP of 3 bar and the feed cross-ow velocity of 3 m/s.
During the process the UV lamps were switched on. No signicant
differences between the permeate uxes measured under the
applied conditions were observed. The ux in case of the Filtanium
5 membrane was about 150155 dm3/m2 h, whereas in case of Filtanium 100 membrane it was in the range of 530550 dm3/m2 h,
regardless of TiO2 doses. It was also noticed that the permeate
uxes during the PMR operation were higher than those measured
for pure water (Figs. 5 and 6).
The literature data on PMRs utilizing polymeric membranes
show that when the photocatalyst concentration increases, the
permeate ux decrease takes place as a result of a cake layer
build-up on the membrane surface [1719]. The results obtained
in the present work are in disagreement with these data, i.e. no
permeate ux decline through the UF membranes due to the presence of TiO2 was observed. This might lead to a conclusion that the
conditions applied in the discussed experiments prevented from
TiO2 cake deposition on the membrane surface even at higher photocatalyst loadings. To verify this supposition the samples of membranes after PMR operation at TMP of 3 bar and vF of 3 m/s were
analyzed using SEM. The TiO2 P25 concentration was 1.5 g/dm3.
The SEM microphotographs of the membranes cross sections are
shown in Fig. 8. It can be observed that in case of both membranes
the surface was covered with a ltration cake layer which means
that the supposition was wrong. The TiO2 cake had a similar thickness in case of both UF membranes, i.e. 37 lm (S.D. = 3 lm) for Filtanium 5 and 45 lm (S.D. = 3 lm) for Filtanium 100.
Thus, other explanation for the obtained results should be
found. Taking into account that the experiments were realized
under the conditions prevailing in PMRs, i.e. in the presence of

Fig. 8. SEM microphotographs of cross-sections of the Filtanium 5 and Filtanium 100 membranes after experiments in the PMR (process parameters: vF = 3 m/s, TMP = 3 bar,
1.5 g TiO2P25/dm3).

S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

UV irradiation, the superhydrophilicity of TiO2 was taken into consideration. During UV irradiation TiO2 particles gain superhydrophilic properties [23] and this phenomenon can last even a few
hours after the end of the exposition to UV light [24]. Since in
the experiments performed in this study the TiO2 suspension was
continuously circulated between the photoreactors and the membrane module, the photocatalyst was able to maintain its superhydrophilic properties. The positive inuence of the superhydrophilic
effect on the permeate ux was previously reported by other
researchers [25,26]. Ma et al. during their investigations [25] found
that Si-doped TiO2/Al2O3 composite UF membrane after irradiation
with UV light exhibited higher pure water permeability than the
membrane kept in the dark. Moustakas et al. [26] suggested that
superhydrophilic properties of TiO2 could restrict from deposition
of the photocatalyst particles on a membrane surface. Instead, a
thin layer of superhydrophilic TiO2 particles could be formed on
a membrane thus increasing its hydrophilicity which further leads
to the improvement of the permeability.
In order to verify the hypothesis that the increase of the permeate ux observed during PMR operation was associated with the
superhydrophilic effect of TiO2, the additional experiments without the presence of UV irradiation were carried out. The obtained

143

data revealed that the permeate uxes measured in the presence

and in the absence of UV light were very similar. Taking this into
account it can be concluded that the superhydrophilic effect of
TiO2 was not the reason for the observed permeate ux increase.
Nonetheless, considering the results obtained during ltration
of the photocatalyst, it can be stated that the TiO2 cake layer should
exhibit a porous structure. Otherwise, the resistance of the ltration cake might be so high that the ux decline instead of improvement could be observed. Indeed, the SEM analysis conrmed the
porous structure of the cake (Fig. 8). The separation layer of both
Filtanium 5 and Filtanium 100 membranes was built of much ner
particles (Fig. 4b and d) than the TiO2 cake (Fig. 8). The PSD analysis (Fig. 2) revealed that the diameter of TiO2 aggregates was in the
range of 0.717.4 lm with the mean size of 4.2 lm. The resistance
of the layer comprising large TiO2 aggregates and exhibiting low
thickness (45 lm) was signicantly lower than the membrane
resistance and therefore the presence of the deposit did not cause
the permeate ux decrease during the ltration.
On a basis of LSM analysis (Fig. 9) it was found that the roughness of the TiO2-covered membranes was higher than that of the
unused ones. However, no signicant differences between the
roughness of the ltration cake calculated for both UF membranes

Fig. 9. LSM images of the surface of the Filtanium 5 (a) and Filtanium 100 (b) membranes before (left image) and after (right image) the experiments in the PMR (process
parameters: vF = 3 m/s, TMP = 3 bar, 1.5 g TiO2P25/dm3).

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

was observed. The LSM-Ra in case of Filtanium 5 amounted to

0.220 lm (S.D. = 0.012 lm) and in case of Filtanium 100 it was
0.252 lm (S.D. = 0.021 lm).
To sum up, the obtained results revealed that despite the presence of the TiO2 ltration cake on the surface of Filtanium 5 and
Filtanium 100 membranes no permeate ux decrease took place.
Instead, an increase of the ux compared to PWF was found. However, the increase cannot be explained in terms of the superhydrophilic effect of TiO2. In view of the above, the most probable
explanation for the permeate ux improvement is the abrasion of
a membrane skin layer by the photocatalyst particles. As a result
some new pores were formed or some existing pores were
enlarged. A more detailed discussion on the abrasion of the membranes by the photocatalyst particles will be presented later.
3.4. Inuence of feed cross-ow velocity on permeate ux in the PMR
During the investigations on the inuence of feed cross ow
velocity on the permeate ux through the UF and MF membranes
the vF of 3, 4.5 or 6 m/s was applied. Since no effect of TiO2 loading
on permeate ux was observed in case of both UF membranes (Section 3.3), the concentration of 1.5 g/dm3 was applied in the discussed experiments. The UV lamps remained switched on during
the whole process in order to assure the conditions prevailing in
PMRs. For both Filtanium 5 and Filtanium 100 membranes there
was no signicant effect of the velocity on the permeate ux. The
mean permeate ux in the experiments with Filtanium 5 membrane was about 150 dm3/m2 h. For Filtanium 100 membrane the
permeate ux ranged from 545 to 570 dm3/m2 h and was insignificantly higher at vF = 6 m/s. It was also observed that under all the
conditions applied in the study the permeate uxes were higher
than PWF values, similarly as in the experiments described in the
previous section.
Different results were obtained in case of the MF Filtanium 0.2
membrane (Fig. 10). Since that membrane had much larger pores
than the UF ones, what created a danger of pore blockage by
TiO2 particles, the additional experiments with application of backushing (BF) were realized except from the standard ltration. The
backushing frequency was set at 30:1, which means that after
30 s of ltration a 1 s backush with permeate was applied. As
can be seen in Fig. 10, in case of the Filtanium 0.2 the feed crossow velocity had a signicant inuence on the permeate ux. In
general, the ux was decreasing with a decrease of vF. Moreover,
at cross ow velocities of 4.5 and 6 m/s the permeate ux was
higher than PWF, whereas at 3 m/s the ux decreased signicantly
below the value measured for pure water. It is well noticeable that
the increase of the ux in case of the higher vF values was much
more signicant than the increase observed for the UF membranes.
At the feed cross ow velocity of 6 m/s the permeate ux was

Fig. 10. Inuence of the feed cross-ow velocity on the permeate ux through
Filtanium 0.2 membrane (process parameters: TMP = 3 bar, 1.5 g TiO2P25/dm3,
backushing (BF) frequency 30:1).

higher than the PWF for ca. 1650 dm3/m2 h, whereas at 4.5 m/s
for ca. 510 dm3/m2 h (Fig. 10). In case of the lowest vF a decrease
of the ux for ca. 770 dm3/m2 h below the PWF value was
observed. The signicant increase of the permeate uxes at vF of
4.5. and 6 m/s compared to PWF can be attributed to the abrasion
of the surface of Filtanium 0.2 membrane by the photocatalyst particles, similarly as it was found in case of the UF membranes. As
can be seen in Fig. 4f the top layer of Filtanium 0.2 was built of particles with a non-uniform distribution. It can be assumed that during ltration the particles having ner sizes underwent erosion
what led to the opening of new pores or enlargement of the existing ones. As a result the permeate ux increase was found. The
abrasion cannot be also excluded in case of vF = 3 m/s. However,
at this cross ow velocity a signicant fouling of the membrane
by the photocatalyst particles occurred and therefore the ux
increase caused by the abrasive action of TiO2 particles cannot be
seen. Moreover, taking into consideration that the increase of the
ux was more signicant at vF = 6 m/s compared to that at 4.5 m/
s it can also be concluded that at the latter cross ow velocity
the membrane fouling took place as well. However, the severity
of this phenomenon in that case was not as high as at vF = 3 m/s
since the ux remained higher than PWF.
The application of the backush was found to be ineffective in
the discussed experiments. Although the BF frequency was high,
the permeate ux was similar to the ux measured during the
experiments without membrane backushing. No signicant inuence of BF on permeate ux restoration during MF of processing
acid wastewater containing ne TiO2 particles through a 0.2 lm
pore-size a-Al2O3 membrane was also found by Zhao et al. [16].
On the opposite, the authors observed a high efciency of backushing in case of a membrane with nominal pore size of 1 lm. The
differences in the results were attributed to the lower ux decline
and higher resistances of the membrane and fouling layer in case of
the membrane with 0.2 lm pores compared to that with 1 lm
pores.
The data presented in Fig. 10 show that selection of a proper
feed cross ow velocity is a more efcient way of improvement
of permeate ux than the application of the membrane backush.
Figs. 11 and 12 present SEM and LSM images of the cross section
and the surface of the Filtanium 0.2 membrane after the experiments realized at vF = 3 m/s in the PMR. Similarly as in case of both
UF membranes a formation of a TiO2 cake was also observed for the
MF membrane (Fig. 11a). However, the cake thickness was signicantly lower (14 lm, S.D. = 1 lm) in case of MF compared to UF
membranes. An explanation of these results needs further investigations. Nonetheless, based on the present data it might be concluded that in case of the Filtanium 0.2 membrane the
photocatalyst particles were not only deposited on the membrane
surface but also entered its pores what affected the ltration cake
thickness. Such a conclusion can be drawn on a basis of the SEM
cross section of the membrane taken at higher magnication
(Fig. 11b). In this microphotograph the presence of small TiO2 particles, probably P25, between the larger TiO2 particles forming the
membrane structure can be seen. However, it must be remembered that due to the fact that both materials, i.e. the membrane
and the photocatalyst were made of TiO2 the unequivocal differentiation of the particles origin is difcult.
The surface roughness (LSM-Ra) of the TiO2 cake formed on the
membrane surface was similar to that measured for both UF membranes and amounted to 0.233 lm (S.D. = 0.010 lm). The LSM
images presented in Figs. 9 and 12 show the samples after the
experiments realized at the same process parameters, i.e. at
vF = 3 m/s, TMP = 3 bar and with application of 1.5 g TiO2/dm3. Taking this into consideration, it might be concluded that the roughness of the surface of TiO2 cake formed under the same process
conditions is independent of the membrane type.

S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

145

(a)

Fig. 13. Inuence of transmembrane pressure on permeate ux during experiments

realized with Filtanium 5 and Filtanium 100 membranes (process parameters:
vF = 3 m/s; 1.5 g TiO2P25/dm3).

(b)

Fig. 11. SEM micrographs of the cross-section of the Filtanium 0.2 membrane after
the experiments in the PMR (process parameters: vF = 3 m/s, TMP = 3 bar, 1.5 g
TiO2P25/dm3).

3.5. Inuence of transmembrane pressure on permeate ux in the PMR

Fig. 13 presents the inuence of transmembrane pressure on
the permeate ux measured for both UF membranes during PMR
operation. For comparison purpose the PWF values are also shown.
As was already discussed in the previous sections, in case of the UF

membranes no signicant inuence of the feed cross ow velocity

on the permeate ux was observed, therefore, in Fig. 13 the data
collected at vF of 3 m/s are only presented.
The increase of TMP during the experiments realized in the PMR
led to a linear increase of the permeate ux for both UF membranes, despite application of the lowest cross ow velocity from
all the examined values. However, the slope of the observed relationship was different from the one representing the correlation
determined for pure water. The uxes measured during the experiments with TiO2 were slightly higher (ca. 510%) than PWF for all
the examined pressures. The observed increase of the ux can be
explained by the abrasion of the skin layer of the membranes as
mentioned earlier.
The inuence of the transmembrane pressure on the permeate
ux during experiments realized with application of MF Filtanium
0.2 membrane is shown in Fig. 14. In case of this membrane the vF
value had a signicant inuence on the permeate ux, therefore
the results obtained at various cross ow velocities are shown. At
the lowest TMP applied (i.e. 0.5 and 1 bar) the permeate uxes
measured during PMR operation were higher than PWF. However,
at the lowest vF (i.e. 3 m/s) an increase of the pressure up to 2 bar
resulted in a decline of the ux compared to pure water ux. Moreover, in case of that cross ow velocity the uxes measured at TMP

Fig. 12. LSM images of the surface of the Filtanium 0.2 membrane before (left image) and after (right image) experiments in the PMR. Process parameters:
TMP = 3 bar, 1.5 g TiO2P25/dm3.

vF = 3 m/s,

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

Fig. 14. Inuence of transmembrane pressure on permeate ux during experiments

realized with Filtanium 0.2 membrane (process parameters: vF = 36 m/s; 1.5 g
TiO2P25/dm3).

of 2 and 3 bar were almost the same. On the opposite, a linear

increase of the permeate ux with increasing TMP was found when
the vF of 6 m/s was applied. In case of the medium cross ow velocity used (i.e. 4.5 m/s) the permeate ux increased almost linearly
up to TMP of 2 bar. However, further rise of the pressure contributed only insignicantly to the ux improvement. The observed
results can be explained in terms of the critical ux phenomenon.
The critical ux, in brief, corresponds to the permeate ux below
which fouling is not promptly observed [27]. The data presented
in Fig. 14 show that only in case of the highest cross ow velocity
the critical ux was not reached in the investigated system.

3.6. Stability of ceramic membranes during PMR operation

In general, ceramic membranes are known to exhibit very good
resistance to the harmful action of oxidative species or very low/
very high solution pH. However, it must be considered that the ltration of a photocatalyst suspension at high feed cross-ow velocities, usually applied in ceramic membrane systems, creates a risk
of destruction of the membrane surface due to abrasion. This could
result in a loss of separation properties of the membrane thus contributing to shortening of its lifetime.
The stability of the UF membranes used in the experiments was
determined on a basis of changes of their separation properties in
terms of dextran and polyethylene glycol (PEG) rejection after 50,
70 and 100 h of PMR operation. The results are summarized in
Fig. 15.
In case of Filtanium 5 the rejection of both dextran (5000 g/mol)
and PEG (6000 g/mol) was continuously decreasing in time. The
efciency of dextran separation decreased from 83% at the beginning of the process to 58% after 100 h of experiments realized in

Fig. 15. Changes of separation properties of Filtanium 5 and Filtanium 100

membranes during their operation in PMR.

the presence of TiO2. What is interesting, after the same time of

operation the Filtanium 5 membrane completely lost the separation properties towards PEG. It is remarkable that in case of the Filtanium 100 membrane much higher stability towards TiO2 action
was observed. In fact, no decrease of the efciency of dextran
(70,000 g/mol) rejection in time was found.
The Filtanium 5 membrane is dened by the manufacturer as a
ne-UF membrane, in contrast to the Filtanium 100 which is an
ordinary UF membrane. The Filtanium 5 exhibited more dense skin
layer built of smaller particles than the Filtanium 100 (Fig. 4) in
order to assure lower MWCO value. The results shown in Fig. 15
indicate that the resistance of such a separation layer to the
destruction by abrasive TiO2 is very low.
In order to investigate whether the structure of the surface of
the Filtanium 5 membrane changed after its application in the
PMR the AFM images of the as-received and the destroyed samples
were compared (Fig. 16). Before the measurement the sample of
the membrane taken from the PMR was cleaned gently with a
sponge in order to remove TiO2 particles. However, despite this
operation some remains of the ltration cake were still present
on the membrane surface as can be observed in Fig. 16b. The
AFM images were taken at the scanned area of 5 lm  5 lm and
1 lm  1 lm, respectively. It can be observed that the topography
of the membrane surface changed signicantly after its operation
in the PMR. Namely, the surface became much more rough. The
average roughness of the brand new membrane amounted to
3.5 nm (S.D. = 0.5 nm) and 2.0 nm (S.D. = 0.2 nm) for the scanned
areas of 5 lm  5 lm (AFM-Ra5) and 1 lm  1 lm (AFM-Ra1),
respectively. In case of the used membrane the AFM-Ra5 amounted
to 14.9 nm (S.D. = 1.4 nm) whereas the AFM-Ra1 was equal to
10.7 nm (S.D. = 1.2 nm). It can be seen that the calculated roughness values were dependent on the scanned area. An increase of
the membrane surface roughness with increasing scanned area
was already discussed by Boussu et al. [28] and Johnson et al.
[29]. The authors [28] stressed that it is crucial that the same scan
size range is used when comparing the surface roughness for different samples.
The observed increase in the Filtanium 5 roughness after the
experiment in the PMR compared to the brand new membrane
(Fig. 16) might lead to a conclusion that the gentle skin layer present on this membrane surface (Fig. 4) was scraped by the TiO2 P25
particles during the ltration process. As a result, the membrane
lost its separation properties (Fig. 15).
The loss of separation properties due to the gradual abrasion of
the membrane skin layer can explain the increase of the permeate
ux through Filtanium 5 observed during the experiments discussed earlier. However, in case of the other UF membrane, Filtanium 100, although the permeate ux was also higher than PWF the
separation properties did not deteriorate. Therefore, it might be
supposed that only some ner particles building the membrane
skin layer were eroded. That led to opening of some new pores
with diameters so small that they contributed to the value of the
permeate ux but did not change the separation characteristics
of the membrane.
In order to characterize the separation properties of the MF Filtanium 0.2 membrane the model solution of 2,000,000 g/mol dextran was used. As expected, the retention of the model compound
by the brand new membrane was very low and amounted to 17%
only. However, the efciency of dextran separation increased in
time of the process and after 50 h of operation amounted to 34%.
The results lead to a conclusion that during the process the deposition of TiO2 particles in the membrane pores occurred, which
conrms the supposition stated earlier on a basis of Fig. 11b.
Taking into consideration the obtained results it was concluded
that the most promising membrane for the application in the PMR
is Filtanium 100. The usage of the ultrane ceramic membrane is

S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

Fig. 16. AFM images of the brand new Filtanium 5 membrane (a and c) and the membrane after the experiments in PMR (b and d). Process parameters:
TMP = 3 bar, 1.5 g TiO2 P25/dm3.

147

vF = 3 m/s,

not recommended due to its low resistance to the destruction by

harsh factors such as abrasive TiO2 particles. The MF Filtanium
0.2 membrane could be possibly used on condition that the optimum cross ow velocity and TMP are selected; however, it must
be taken into account that TiO2 particles deposition in the membrane pores might occur and this would affect its separation
characteristics.
3.7. Inuence of the type of photocatalyst on the permeate ux in the
PMR
In order to determine the inuence of the photocatalyst type on
the performance of ceramic membranes in the PMR a set of experiments with application of P25, ST01, A700 and A800 titanium
dioxide was realized. The Filtanium 100 membrane was selected
for these investigations due to its high resistance to fouling and
abrasion by P25 TiO2 particles. Based on the results described in
the previous sections the vF of 3 m/s and TiO2 concentration of
1.5 g/dm3 were applied. The obtained results are summarized in
Fig. 17. It can be seen that despite various properties of the TiO2
materials (Section 3.1) the photocatalyst type had a negligible
inuence on the permeate ux. The percentage difference between
the lowest and the highest ux at various TMP values was similar
and amounted to 1012% for 13 bar, respectively. An explanation
for the obtained results can be the high cross ow velocity applied
in the experiments. As was observed in case of TiO2 P25 photocatalyst (Fig. 8) the ltration cake formed under such conditions was

Fig. 17. Inuence of the type of a photocatalyst on permeate ux through Filtanium

100 membrane (process parameters: TMP = 13 bar, vF = 3 m/s, 1.5 g TiO2/dm3).

thin (45 lm) and very porous, therefore its contribution to the
overall ltration resistance was insignicant. It is also worth noting
that regardless of the TiO2 type used all the measured permeate
uxes were above the PWF.

4. Conclusions
The obtained results revealed that the performance of ceramic
UF membranes in a photocatalytic membrane reactor differed signicantly from that observed in case of a ceramic MF membrane.

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S. Mozia et al. / Separation and Purication Technology 142 (2015) 137148

During the experiments realized with application of UF membranes no inuence of feed cross ow velocity and TiO2 P25 photocatalyst concentration on the permeate ux was found in a range of
investigations. In case of Filtanium 0.2 MF membrane a deterioration of permeate ux with decreasing feed cross-ow velocity was
observed. At cross ow velocity of 3 m/s the ux decreased significantly below the value measured for pure water. That was attributed to the membrane pore blockage by photocatalyst particles. It
was concluded that selection of a proper feed cross ow velocity
was a more efcient way of improvement of permeate ux through
the MF membrane than the application of the membrane
backush.
An increase of permeate ux during PMR operation compared
to pure water ux (PWF) was found in case of both UF membranes,
regardless of process conditions. When the MF membrane was
applied such an increase was observed at feed cross ow velocities
vF P 4.5 m/s. It was concluded that the most probable explanation
for the permeate ux improvement was the abrasion of a membrane skin layer by the photocatalyst particles. Nonetheless, the
abrasion affected the separation characteristics only in case of
the ne UF Filtanium 5 membrane. That membrane lost completely
its separation properties towards PEG after 100 h of operation. No
signicant changes of dextran rejection by Filtanium 100 was
observed after 100 h of experiment. In case of the MF membrane
an increase of dextran rejection in time was found which was
attributed to the deposition of TiO2 particles in the membrane
pores.
The inuence of the photocatalyst type on the permeate ux
through Filtanium 100 membrane was found to be insignicant.
The results can be explained in terms of the high cross ow velocity applied in the experiments. Under such conditions the ltration
cake formed on the membrane was thin and porous thus its contribution to the overall ltration resistance was negligible.
A particular attention should be paid to the selection of membranes for PMRs not only with reference to their resistance to damage by oxidative species or UV radiation but also in terms of the
resistance to abrasion by photocatalyst particles. It should be taken
into consideration that ceramic membranes can also be damaged
by abrasive action of photocatalyst particles.
Acknowledgements
This research was supported by The National Science Center
(Poland) under Project No. 2011/03/B/ST5/01053.
The authors would like to thank Dr. Katarzyna Wilpiszewska
from Polymer Institute, WPUT, Szczecin for her assistance in LMS
analyses.
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