water

Article
Effect of Membrane Type for the Treatment of
Organized Industrial Zone (OIZ) Wastewater with a
Membrane Bioreactor (MBR): Batch Experiments
Oktay Özkan and İbrahim Uyanık *
Erciyes University, Faculty of Engineering, Department of Environmental Engineering, Melikgazi, Kayseri 38039,
Turkey; ozkan@erciyes.edu.tr
* Correspondence: iuyanik@erciyes.edu.tr; Tel.: +90-352-207-6666-7498

Received: 11 July 2017; Accepted: 1 August 2017; Published: 4 August 2017

Abstract: Organized industrial zone (OIZ) wastewater is a mixed wastewater that is contributed
by both municipal use and from different industrial sectors. Since MBR has advantages over
conventional treatment plants, membrane types and fouling become the most important parameters
in the treatment of this kind of wastewater. In this study, six different membrane types were used to
find the most suitable membrane with the least resistivity to fouling. Three different microfiltration
(MF) and ultrafiltration (UF) membranes were operated to estimate their (i) membrane, (ii) cake,
(iii) pore, and (iv) total resistances. The highest total resistance was observed in a polyethersulfone
(PES) membrane (3.8 × 1010 m−1 ), while the lowest one was a UF polyvinylidene fluoride (PVDF)
membrane with approximately 20 times lower resistance than the highest one. PVDF membranes
showed lower total resistances than PES membranes. An MF or a 250 kDa UF membrane could be
operated long-term in a membrane bioreactor with the least fouling potential.

Keywords: MBR; membrane selection; resistance; membrane fouling

1. Introduction
Environmental management of the industrial activities could be better controlled when they are
organized in an isolated area in developing countries [1–3]. Centralized and organized industrial
zones are common in Turkey, the number of which exceeded 250 [4]. Only one third of these organized
industrial zones (OIZs) have their own wastewater treatment plant (WWTP) [4]. The characteristics of
the wastewater of OIZs are very different from each other, as their wastewater originates from different
sectors. However, the wastewater is similar to municipal wastewater in terms of biological degradation
in that their wastewater also comes from the daily water consumption of workers. Industrial water
contamination must be controlled, since it affects not only the health of living organisms but also
indirectly affects the economy [5,6].
Membrane bioreactors (MBRs) are needed for wastewater to conform to regulations that require
high-quality effluents in both developed and developing countries [7,8]. Regardless of the effluent
quality of the MBR, it is a good pre-treatment option before a reuse alternative. However, MBR
treatment has some technical issues or limitations in operations, and membrane fouling is one of
them [8,9].
The fouling problem has been investigated in several studies. Most of the studies are linked
with microbial community for the reason of the fouling [10,11]. In a study of MBR treating textile
wastewater, microbial composition has been found to be affected by reactor operating conditions [12].
The study further maintains that microbial community may have an impact on biofouling, and each
MBR has its own characteristics. Therefore, microbial community structure is the main reason for
fouling, regardless of biodegradable type of wastewater to treat. In another study, factors affecting

Water 2017, 9, 582; doi:10.3390/w9080582 www.mdpi.com/journal/water

Water 2017, 9, 582 2 of 8

the biofouling mechanism were reviewed and fouling factors discussed [13]. Biofouling increases
as mixed liquor suspended solids (MLSS), organic loading rate (OLR), and food to microorganisms
(F/M) ratio are high, and dissolved oxygen concentration, hydraulic retention time (HRT), and sludge
retention time (SRT) are low [14]. High salinity and temperature also increase the soluble microbial
products and decrease membrane permeability. Although system parameters in MBR can be changed,
it still may not be easy to stabilize all the parameters in desired levels. Therefore, membrane fouling is
inevitable, but it could be minimized.
While MBR batch studies [15,16] were conducted for the removal of some micropollutants,
membrane types were investigated in other studies [17,18]. One study on natural organic matter (NOM)
removal investigated using hollowfiber (HF) membranes—two hydrophobic and one hydrophilic.
Hydrophobic ones fouled more quickly because hydrophilic compounds formed a gel layer on the
surface of the membrane [17]. Another study on membrane type and materials was conducted using
three different MF membranes with the same pore sizes. Track-etched polyester (PETE) membrane
was the worst one, while the other two were nearly the same in terms of flux decline [18].
The membrane type operated in MBR did not vary widely, since almost 50% of the membranes
used in commercial MBR products were polyvinylidene difluoride (PVDF) from among three
membrane configurations; namely, flat sheet (FS), hollowfiber (HF), and multitube (MT) [8].
Polyethersulfone (PES) membranes are the second-most-used membranes, and are used only for
FS modules. FS module was compared with HF module in a study showing that it could be operated
for 6 months without external cleaning compared to HF module (4 months) [19].
Membrane resistances of the MBR studies have been estimated only for specific resistances in
the literature for the prediction of fouling behavior [20–22]. One study shows that cake resistance
plays a major role in filtration efficiency [23]. Another one shows that the fouling is irreversible, as
the blocking resistance is the major one. Similarly, when cake resistance is the major one, fouling is
reversible [22]. However, a pre-study of the membrane resistances is not performed before a long-term
operation in MBR.
Selection of membrane type is a hard task for industrial wastewater, since fouling is one of
the most important parameters for long-term operations [8]. In this study, membrane types were
investigated according to their resistances to an organized industrial zone (OIZ) wastewater using six
different MF and UF membranes in MBR.

2. Materials and Methods

2.1. Membrane Bioreactor (MBR)

The reactor used in the study is made of plexiglass with a 20 L of active volume. Real wastewater
and activated sludge from the Kayseri organized industrial zone (KOIZ) WWTP were initially fed to
the reactor. Then, it was continuously monitored with a programmable logic control (PLC) system as
for the dissolved oxygen (DO), oxidation-reduction potential (ORP), pH, temperature, pressure, water
level, and flux. Basic influent and effluent parameters of the reactor for one month of operation with a
10 kDa ultrafiltration (UF) FS membrane are given in Table 1.
Wastewater fed to the MBR was from the primary sedimentation tank of the WWTP. Operational
parameters of the MBR were stable during each day when the modules were operated. MLSS was
7.2 ± 0.2 g/L, while hydraulic retention time (HRT) was 40 h. A peristaltic pump (Watson-Marlow,
Sci-Q 300) with constant speed was used in all experiments to vacuum the filtrate from the reactor.
Wastewater of KOIZ mainly comes from textile, paper, recycling, and metal industries, including
the wastewater of daily use of 7000 workers, which turns the character of the wastewater into a
high-strength domestic wastewater in terms of biodegradability.
Water 2017, 9, 582 3 of 8

Table 1. Membrane bioreactor (MBR) influent and effluent parameters.

Parameters Influent Effluent

pH 7.1 ± 0.36 7.9 ± 0.4
Electrical conductivity (EC) (ms/cm) 4.8 ± 0.92 5.1 ± 1.1
Chemical oxygen demand (COD) (mg/L) 471 ± 228 39.5 ± 22.3
Biochemical oxygen demand (BOD) (mg/L) 211 ± 75 0
NO2 -N (mg/L) 0 0
NO3 -N (mg/L) <0.01 3.5 ± 2.1

2.2. Membranes
Flat sheet membranes used in the study are given in Table 2. Membrane materials are PES
and PVDF (three of each), and membrane types were three microfiltration (MF) and three UF with
different pore sizes and molecular weight cutoff (MWCO) values. Membranes are given with increasing
pore sizes.

Table 2. Properties of microfiltration (MF) and ultrafiltration (UF) membranes. PES: polyethersulfone;
PVDF: polyvinylidene difluoride.

Membrane Type Brand Pore Size (µm) Membrane Material

MP005 Microdyn-Nadir 0.05 PES
UF 4 kDa Philos 0.07 PES
UF 10 kDa Philos 0.1 PES
MV02 Microdyn-Nadir 0.2 PVDF
MF Philos 0.24 PVDF
UF 250 kDa Philos 0.44 PVDF

2.3. Experimental Procedure

Flat sheet membrane modules used in the study were prepared in the laboratory with an area of
285 cm2 . Firstly, the modules were submerged into distilled water and vacuumed for 30 min while
recording flux and pressure at every min. Secondly, the modules were submerged into the MBR
and operated for one day (24 h) without relaxation/backwashing. Lastly, the modules were cleaned
only physically and vacuumed again for 30 min with new distilled water to calculate the membrane
resistances. Physical cleaning was performed by removing cake layer with a soft sponge and by
washing it externally under running tap water. The membrane resistance (R) for each of the resistances
can be calculated as:
R = ∆P·µ−1 ·Jss −1 (1)

where R is the filtration resistance (m−1 ), ∆P is the pressure difference between steady state and the
beginning (Pa), µ is the permeate viscosity (Pa·s), and Jss is the steady-state flux (m3 /m2 ·s). From the
above experimental procedure, Rm can be calculated as membrane resistance from the distilled water
filtration and Rt can be calculated as total resistance from MBR filtration. After cleaning the module
with deionized water, the resistance is Rm + Rp , where Rp is the pore resistance. The cake resistance,
Rc , can be calculated from the difference of steps 1 and 3 as Rt − (Rm + Rp ). All experiments were
conducted daily, with a total time of 6 days. Figure 1 is illustrated for an easy understanding of the
experimental procedure.
Water 2017, 9, 582 4 of 8
Water 2017, 9, 582 4 of 8

Figure 1. Flow diagram of the experimental procedure.

2.4. Analytical
2.4. Analytical Methods
Methods
All parameters
All parameters were
were analyzed
analyzed according
according to
to Standard
Standard Methods
Methods [24].
[24]. In
In the
the MBR,
MBR, all
all parameters
parameters
mentioned above
mentioned above are
aremeasured
measuredonline.
online.Permeate
Permeateanalysis waswas
analysis made
madeusing a HACH
using a HACHmultimeter (pH,
multimeter
temperature, electrical conductivity (EC)), while turbidity analysis was made with a HACH
(pH, temperature, electrical conductivity (EC)), while turbidity analysis was made with a HACH 2100AN
laboratory
2100AN turbidimeter.
laboratory ChemicalChemical
turbidimeter. oxygen demands (CODs) of(CODs)
oxygen demands the permeate samples were
of the permeate analyzed
samples were
using titrimetric
analyzed method (Standard
using titrimetric Methods 5220
method (Standard C). Membrane
Methods fluxes were
5220 C). Membrane measured
fluxes as L·m−2·has
were measured
−1

(LMH).
L ·m−2 ·h−1 (LMH).

3. Results and Discussion

Basic water quality parameters of the effluent of membranes operated in the MBR were not
significantly different
significantly differentfrom
fromeach
eachother,
other,
as as shown
shown in Table
in Table 3. The
3. The treated
treated waterwater had EC,
had high highlow
EC,COD,
low
COD,
and and
low low turbidity.
turbidity. Although
Although this wastewater
this wastewater had higher
had higher organicorganic and pollutant
and pollutant loading
loading rate,
rate, these
these values
values are consistent
are consistent withMBR
with other otherstudies
MBR studies
treatingtreating municipal
municipal wastewater
wastewater treatment
treatment plants in plants
terms
in average
of terms ofCODaverage COD and
and turbidity turbidity
removal removal
[25,26]. Since[25,26]. Since thearemembranes
the membranes MF and UFare MF and EC
membranes, UF
membranes,
values do notEC values
reduce as do not reduce as expected.
expected.
Table 3. Permeate analysis results after MBR operation.
Table 3. Permeate analysis results after MBR operation.

Membrane Effluent pH EC (ms/cm) COD (mg/L) Turbidity (NTU)

Membrane Effluent pH EC (ms/cm) COD (mg/L) Turbidity (NTU)
MP005 8.10 ± 0.12 4.06 ± 0.08 19 ± 7 0.42 ± 0.25
MP005 8.10 ± 0.12 4.06 ± 0.08 19 ± 7 0.42 ± 0.25
UF 4UF
k 4k 8.19 ± 0.24
8.19 ± 0.24
4.23 ± 0.06
4.23 ± 0.06
32 ± 11
32 ± 11
0.36 ± 0.18
0.36 ± 0.18
UF 10
UFk10 k 8.10
8.10±±0.09
0.09 4.62±±0.11
4.62 0.11 38±± 44
38 0.720.72 ± 0.09
± 0.09
MV02MV02 8.16
8.16±±0.17
0.17 4.41±±0.10
4.41 0.10 66±± 14
66 14 0.880.88 ± 0.13
± 0.13
MF MF 8.01±±0.05
8.01 0.05 5.02±±0.27
5.02 0.27 67±± 99
67 ± 0.07
0.960.96 ± 0.07
UF 250 k 8.41 ± 0.10 4.65 ± 0.18 21 ± 16 0.21 ± 0.16
UF 250 k 8.41 ± 0.10 4.65 ± 0.18 21 ± 16 0.21 ± 0.16

3.1.
3.1. Resistances
Resistances
Membrane,
Membrane, pore, pore,andandcake resistances
cake of theofmembranes
resistances the membranes are given in Figure
are given 2. in PVDF
Figuremembranes
2. PVDF
showed lowest membrane (R ) and pore resistances (R ), while PES
membranes showed lowest membrane (Rm) and pore resistances (Rp), while PES membranes
m p membranes demonstrated high pore
resistance. The highest pore-sized membrane showed the lowest pore resistance.
demonstrated high pore resistance. The highest pore-sized membrane showed the lowest pore Membrane resistances
(R m ) of the Membrane
resistance. PVDF membranes were
resistances (Rmlower than
) of the PES membranes
PVDF membranes were because of the
lower thanhydrophobicity
PES membranes of
the membrane structure. An inverse relationship
because of the hydrophobicity of the membrane structure. An with the R of the PES membranes and their
m inverse relationship with the Rm of the pore
sizes may be originated
PES membranes frompore
and their the membrane
sizes may fabrication,
be originated as the
from contact angles differ.
the membrane The UF 10
fabrication, askDa
the
membrane with 0.1 µ pore size showed the highest membrane resistance with
contact angles differ. The UF 10 kDa membrane with 0.1 µ pore size showed the highest membrane distilled water.
MP005
resistance (PES)
with with the
distilled lowest pore-sized membrane indicated approximately 60% more cake
water.
resistivity
MP005 in (PES)
MBR. with
The hydrophobicity of this membrane
the lowest pore-sized membranecauses organic
indicated matter to form
approximately 60%a more
cake layer
cake
on the membrane surface. This type of membrane is not a good choice because of
resistivity in MBR. The hydrophobicity of this membrane causes organic matter to form a cake layer a very high potential
of
onathe
cakemembrane
layer beingsurface.
formed.This
Additionally, this cake layer
type of membrane is notmaya block
good the poresbecause
choice of the PES
of amembranes.
very high
potential of a cake layer being formed. Additionally, this cake layer may block the pores of the PES
membranes.
Water 2017, 9, 582 5 of 8
Water 2017, 9, 582 5 of 8
Water 2017, 9, 582 5 of 8

PES PVDF
PES PVDF
Figure2.2.Membrane,
Figure Membrane, pore, and
and cake
cakeresistances
resistancesofofthe
themembranes.
membranes.
Figure 2. Membrane, pore, and cake resistances of the membranes.
Another significant result in Figure 2 is the pore resistances, which are very high in PES
Another
Another significant
significant result inin Figure
resultones. Figure 22 is the
the pore
isresistances
pore of resistances, which
resistances, which arevery veryhigh highininPES PES
membranes compared to PVDF The cake PDVF membranesare were higher than the
membranes
membranes compared
compared to PVDF
to PVDF ones. The
ones.that
Thethecake
cake resistances
resistances of PDVF membranes
of PDVF membranes were higher than thethe
than
pore resistances. This data indicates cake layer is removed by physical were washing.higher However,
pore resistances.
pore resistances. This data indicates that thethecake layer is removed by physical washing. However, pore
pore resistances This of PES data indicates
membranes thatare highercake layer
than istheremoved by physical
cake resistances, washing.
except forHowever, MP005
resistances of
pore resistances
membrane,
PES membranes
of PES membranes
which indicates
are higher
that the pores
than
are the
higher
of the
cake resistances,
than thefouled
membranes
except for
cake irreversibly. MP005
resistances, This membrane,
excepttypefor MP005
of fouling
which
indicates
membrane,
can that the pores
which indicates
only be cleaned of the
by chemical membranes
that the fouled
poresagents,
cleaning irreversibly.
of the membranes This type of
fouled irreversibly.
but not physically. fouling
This findingThis can only be
type of fouling
is consistent cleaned
with
byprevious
chemical
can cleaning
only studies.
be cleaned agents,
by but
chemical not physically.
cleaning agents, Thisbut finding
not is consistent
physically.
Pore blocking is found to be irreversible, while cake blocking is easily removed This with
findingprevious
is studies.
consistent withPore
by
blocking
previous is found
studies. to be
Pore irreversible,
blocking is while
found to cake
be blocking
irreversible, is
simple backwashing, and irreversible blocking may be formed due to the organic macromolecules easily
while removed
cake blocking by simple
is easily backwashing,
removed by
and simple
[22]. backwashing,
irreversible
However, blocking
in another andmay irreversible
study, PVDF blocking
be formed due to the
membranes may be formed
organic
showed due to the
macromolecules
a removable organic macromolecules
[22].character,
fouling However, in another
with flux
[22].PVDF
study,
being However, theinsame
nearlymembranes another study, the
asshowed
before PVDF membranes
a removable
operation fouling
[27]. showed
Other a removable
character,
studies with
of cake fouling
fluxand being character,
pore nearly
blocking with
the same
of flux
the as
being
before thenearly
operationthe same
[27]. as before
Other the
studies operation
of cake [27].
and Other
pore
membranes also showed that pore blocking and cake formation are the dominant fouling studies
blocking ofofthecake and
membranes pore blocking
also showed of the
that
poremembranes
blocking and
mechanisms also
in PES showed
cake that
formation[28].
membranes pore blocking and cake formation
are the dominant fouling mechanisms in PES membranes [28]. are the dominant fouling
mechanisms
Although
Although inthe
the PES
UFUF 4membranes
kDa4 kDamembrane[28]. showed
membrane showed the highest
the highest pore resistance,
pore resistance, it had total
it had lower lower total
resistance
(Figure Although
resistance
3) than thethe
(Figure MP005 UF 4membrane,
3) than thekDa membrane
MP005 both ofshowed
membrane, whichboth arethe highest
of which
the sameare pore
the resistance,
same
material material it(PES).
(PES). This had lower
couldThisbe total
could
due to
resistance
be due to (Figure
both the 3)
pore than the
sizes MP005
and the membrane,
manufacturing both of which
processes are
of
both the pore sizes and the manufacturing processes of different membrane suppliers. Total resistances the same
different material
membrane (PES). This
suppliers. could
Total
be due to both the pore sizes and the manufacturing processesto of different membrane suppliers. Total
of resistances
the membranes of the weremembranes
inverselywere inverselytoproportional
proportional their pore sizes. their pore
The lowest sizes. The
total resistancelowestwas total
seen
resistances
resistance was of the
seen membranes
in the UF 250 were
kDa inversely
membrane proportional
with the highest to their
pore pore
size. sizes.
However, Thethat lowest
alignment total
in the UF 250 kDa membrane with the highest pore size. However, that alignment was not reflected on
resistance was seen in thewaterUF 250 kDa membrane has with the highest pore size. However, that alignment
thewas
waternot quality,
reflected asonit the
has betterquality,
COD and as itturbidity better COD
removal and
thanturbidity
the other removal
membranes. than theThe other
effect
was not
membranes. reflected
The on
effect theof water
pore quality,
sizes is as it
discussed has inbetter
another COD study,and turbidity
which removal
suggested than
that the other
larger pore
of pore sizes is discussed in another study, which suggested that larger pore sizes exhibit faster flux
membranes.
sizes The effect
exhibit faster flux of pore sizes
decline, whileis having
discussed betterin another study, in
flux recovery which suggested
different that larger [21].
UF membranes pore
decline, while having
sizesstudy
exhibit faster better
flux flux recovery
decline, while having in different UFrecovery
membranes [21]. The study also showed
The also showed that hydrophobicity is better
the secondflux unwanted in property
different UF membranes
in terms of fouling.[21].
thatThehydrophobicity
study also showedis the second
that unwanted
hydrophobicity property
is the secondin terms
unwantedof fouling.
property Membranes
in terms ofwith lower
fouling.
Membranes with lower MWCO and high hydrophobicity demonstrated the worst performance, as
MWCOMembranesand high hydrophobicity demonstrated the worst performance, as in the current study, with
in the currentwith study, lowerwithMWCO and high hydrophobicity
the hydrophobic membrane (MP005) demonstrated the worst
with the smallest pore performance,
size. as
theinhydrophobic membrane (MP005) with the smallest pore
the current study, with the hydrophobic membrane (MP005) with the smallest pore size. size.

Figure 3. Total resistances of the membranes.

Figure3.3.Total
Figure Totalresistances
resistances of
of the
the membranes.
membranes.
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3.2. Flux Pressure Profiles
3.2. Flux
3.2. Flux Pressure
Pressure Profiles
Profiles
Flux pressure profiles of the membranes are shown in Figures 4 and 5 for only MP005 and UF
250 kDa, Flux pressure
respectively. profiles
Flux pressure profiles These of of the membranes
membranes
membranes
the showed are the
are shown in Figure
highest
shown in Figure 44 and
and lowest and Figure
Figure 55 for
for only
total resistances,only MP005
MP005 and
respectively.
and
UF
ForUF 250
the250MP005 kDa, respectively.
kDa, membrane,
respectively.flux These membranes
rapidly
These showed
declinedshowed
membranes in 15 min the
the inhighest
MBR (Step
highest and lowest
and lowest2), while total resistances,
totalit was stable in
resistances,
respectively.
distilled water For
respectively. For
beforethe MP005
the MP005
and after membrane,
the operation
membrane, flux rapidly
flux rapidly declined
in the declined
MBR. Almost in 15
in 15 min
min in MBR
MBR (Step
no pressure
in (Step 2),
rise 2),
was while it was
observed
while it was in
stable
distilled
stable in in
waterdistilled water
filtration
distilled water(Step before
before and
1).and after
However, the
after the operation
it reached in
operationsteady the MBR.
in the state Almost
MBR.atAlmost 0.8 barno no pressure
forpressure
both therise rise
MBR was
was and
observed
observed
after in distilled
in distilled
the cleaning water
water(Step
operation filtration
filtration (Step
3). A(Step 1). However,
rapid1).rise
However, it reached
it reached
in pressure indicated steady
steady state
thatstate
the atat 0.8 bar for both
0.8 bar forsurface
membrane both thethe
was
MBR and
MBR and after
after the
the cleaning
cleaning operation
operation (Step
(Step 3).3). A
A rapid
rapid rise
rise inin pressure
pressure indicated
indicated that that the
the membrane
membrane
clogged by soluble foulants such as soluble microbial products (SMPs). This was also indicated in a
surface was
surface was clogged
clogged by by soluble
soluble foulants
foulants suchsuch asas soluble
soluble microbial
microbial products
products (SMPs).
(SMPs). This This waswas also
also
fouling study conducted in a submerged MBR [29].
indicated in
indicated in a fouling
fouling study
study conducted
conducted in in a submerged
submerged MBR MBR [29].[29].
However,a flux was almost recoveredaafter simple physical cleaning of the MP005 membrane.
However,
However, flux was almost recovered after simple physical cleaning of of the
the MP005
MP005 membrane.
membrane.
This is due to the flux
cakewaslayeralmost
formed recovered after simple
on the membrane physical
surface cleaning
in MBR operation, as shown in Figure 2
This is
This is due
due toto the
the cake
cake layer
layer formed
formed on on the
the membrane
membrane surface
surface in in MBR
MBR operation,
operation, as as shown
shown in in Figure
Figure
(MP005
2 (MP005
membrane
membrane
has has
the highest
the
cakecake
highest
resistance).
resistance).
Fouling
Fouling
of this
of
membrane
this membrane
cancanbe berelated
related
to high
to
2 (MP005 membrane has the highest cake resistance). Fouling of this membrane can be related to
pressure
high during
pressure filtration
during caused
filtration by
caused cake
by formation.
cake formation.Cake layer
Cake layer on onthe membrane
the membrane surface
surface acts
acts as
high pressure during filtration caused by cake formation. Cake layer on the membrane surface acts
another filter
as another layer
another filter to
filter layer increase
layer to
to increase the
increase the pressure
the pressure and
pressure and the resistance.
and the
the resistance. The
resistance. The easier
The easier cleaning
easier cleaning
cleaning ofof the
of the cake
the cake layer
cake layer
layer can
as
be can
related
be to the hydrophobic
related to the hydrophobicnature of the membrane.
nature of the In a membrane
membrane. In a fouling fouling
membrane study, itstudy,
is suggested
it is
is
can be related to the hydrophobic nature of the membrane. In a membrane fouling study, it
that increasing
suggested that surface
that increasing hydrophilicity
increasing surface cannot
surface hydrophilicity mitigate
hydrophilicity cannot membrane
cannot mitigate
mitigate membranefouling
membrane foulingin MBRs
fouling in [29].
in MBRs High
MBRs [29]. zeta
[29].
suggested
potential
High andpotential
zeta roughness and of membranes
roughness of alleviate membrane
membranes alleviate fouling, asfouling,
membrane stated as earlier
stated [29]. Therefore,
earlier [29].
High zeta potential and roughness of membranes alleviate membrane fouling, as stated earlier [29].
theTherefore,
PES membranes
Therefore, the PESused
the PES in this study
membranes
membranes usedare
used in not
in thisproper
this study for
study arean
are not
notMBR filtration
proper
proper for an
for anofMBR
OIZ wastewater,
MBR filtration of
filtration of as
OIZ
OIZthey
show high
wastewater, potential
as they of fouling.
show high potential
wastewater, as they show high potential of fouling. of fouling.

Figure 4. Flux
Flux pressure profileofof
ofMP005
MP005membrane.
membrane. LMH:
LMH: L
L·m −·h
2 −1 −1
·h·−1h.. .
−2
Figure 4. Flux
Figure 4. pressure profile
pressure profile MP005 membrane. LMH: ·m−2
L·m

Figure 5.
Figure 5. Flux
Flux pressure
pressure profile of UF 250
250 kDa membrane.
membrane.
Figure 5. Flux pressure profile of UF
UF 250kDa
kDa membrane.
Water 2017, 9, 582 7 of 8

The UF 250 kDa membrane, with the best performance in the current study, showed little or no
pressure rise in all steps. This membrane also had little or no flux decline when operated in the MBR
(Figure 5). MBR flux of this membrane reached as high as 25 LMH, while the worst one (MP005)
declined from about 12 LMH to 6 LMH.
Resistances and flux-pressure profiles of PVDF membranes showed less resistivity to OIZ
wastewater than PES membranes. Both membrane types are known to be hydrophobic; however,
the PVDF membranes used in this study seem to be less hydrophobic than PES membranes.
The membrane with the best performance was a UF membrane (MWCO of 250 kDa), which has
hydrophobic nature and PVDF material. Therefore, hydrophobicity may not be a fouling parameter in
the MBR filtration of OIZ wastewater.

4. Conclusions
MBR treatment of industrial wastewater is not a novel subject; however choosing the right
membrane in a long-term operation is essential for maintenance, investment, and operation costs.
Membrane resistivity is the key parameter for the treatment of mixed industrial wastewater in terms
of fouling for operation. This study showed that for a high-strength industrial zone wastewater,
membranes with high pore size showed low resistance with PVDF membranes. A UF membrane which
had a 250 kDa MWCO value and highest pore sized membrane demonstrated the best performance in
terms of resistance. Water quality of this permeate was also much better than other types of membranes.
Tertiary treatment of this wastewater for reuse will be investigated with different nanofiltration (NF)
and reverse osmosis (RO) membranes in our further studies.

Acknowledgments: This study was funded by The Scientific and Technological Research Council of Turkey
(TUBITAK) (Project Number: 114Y521). We also thank the Istanbul Technical University National Research Center
on Membrane Technologies (ITU-MEMTEK).
Author Contributions: Oktay Özkan conceived and designed the experiments; İbrahim Uyanık performed the
experiments, analyzed the data, provided membrane materials, and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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