membranes
Article
Chemical Cleaning and Membrane Aging in MBR for Textile
Wastewater Treatment
Huarong Yu 1,2 , Siyuan Shangguan 1,2 , Chenyu Xie 3 , Haiyang Yang 1,2, * , Chunhai Wei 1,2 , Hongwei Rong 1,2
and Fangshu Qu 1,2, *
Citation: Yu, H.; Shangguan, S.; Xie,
C.; Yang, H.; Wei, C.; Rong, H.; Qu, F.
Chemical Cleaning and Membrane
Aging in MBR for Textile Wastewater
Treatment. Membranes 2022, 12, 704.
https://doi.org/10.3390/
membranes12070704
Academic Editors: Naresh Mameda
and Ganesh Koyyada
Received: 9 June 2022
Accepted: 6 July 2022
Published: 12 July 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Membranes 2022, 12, 704. https://doi.org/10.3390/membranes12070704
1 Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education,
Guangzhou 510006, China; huarongyu@gzhu.edu.cn (H.Y.); sgsy2112016210@163.com (S.S.);
weich@gzhu.edu.cn (C.W.); hwrong@gzhu.edu.cn (H.R.)
2 School of Civil Engineering, Guangzhou University, Guangzhou 510006, China
3 Foshan Nanhai Jinglong Investment Holding Co., Ltd., Foshan 528211, China; x591780374@163.com
* Correspondence: hityanghaiyang@163.com (H.Y.); qufangshu@163.com (F.Q.)
Abstract: Membrane bioreactors have been widely used in textile wastewater treatment. Intensive
chemical cleaning is indispensable in the MBR for textile wastewater treatment due to the severe mem-
brane fouling implied. This work investigated the aging of three different membranes, polyvinylidene
fluoride (PVDF), polyether sulfone (PES), and polytetrafluoroethylene (PTFE), in the MBRs for textile
wastewater treatment. Pilot-scale MBRs were operated and the used membrane was characterized.
Batch chemical soaking tests were conducted to elucidate the aging properties of the membranes. The
results indicated that the PVDF membrane was most liable to the chemical cleaning, and the PES and
PTFE membranes were rather stable. The surface hydrophobicity of the PVDF increased in the acid
aging test, and the pore size and pure water flux decreased due to the elevated hydrophobic effect; al-
kaline oxide aging destructed the structure of the PVDF membrane, enlarged pore size, and increased
pure water flux. Chemical cleaning only altered the interfacial properties (hydrophobicity and surface
zeta potential) of the PES and PTFE membranes. The fluoro-substitution and the dehydrofluorination
of the PVDF, chain scission of the PES molecules, and dehydrofluorination of the PTFE were observed
in aging. A chemically stable and anti-aging membrane would be of great importance in the MBR for
textile wastewater treatment due to the intensive chemical cleaning applied.
Keywords: membrane bioreactor; textile wastewater; membrane aging; chemical cleaning
1. Introduction
The textile industry has always been a water-consuming and pollution-intensive sec-
tor [1–3]. Textile wastewater treatment is quite challenging due to the complex composition
as well as the xenobiotic and non-biodegradable dyes, textile auxiliaries, and other chemi-
cals [1,4] used. On the other hand, the discharge limits imposed on the textile industry are
increasingly stringent, which forces plants to upgrade their wastewater treatment processes.
The high price of water also encourages the reuse of textile wastewater [2,5].
Membrane technology has become an attractive alternative for textile wastewater
treatment [6,7]. Membrane bioreactor (MBR) possesses the merits of small footprints, low
maintenance, low sludge production, and high removal of organic and recalcitrant pollu-
tants [1,8,9]. Nanofiltration (NF) or reverse osmose (RO) could intercept non-biodegradable
chemicals or dyes and, thus, enable recycling in textile wastewater treatment [2,10]. Many
research studies on MBR or NF/RO for textile wastewater treatment exist. However, most
of these works focused on the feasibility of membrane processes, among which membrane
fouling was the most concerning issue [1,2,5]. Due to the complex composition of tex-
tile wastewater and toxic compounds, membrane fouling has always been much more
severe than for municipal wastewater treatment. However, another important issue is
that membrane aging was rarely considered in the MBR for textile wastewater treatment.
https://www.mdpi.com/journal/membranes
Membranes 2022, 12, 704 2 of 13

Membrane aging is defined as the change observed in membrane properties over long-term
use [11,12]. These properties can be expressed either as the membrane’s physical and chem-
ical characteristics (e.g., chemical composition and pore size), or as performance factors
(e.g., fouling rate and membrane resistance). Therefore, the anti-aging property of the
membrane product was of great importance [13]. Moreover, besides the commonly used
polyvinylidene fluoride (PVDF) and polyether sulfone (PES), more stable membrane mate-
rial, such as polytetrafluoroethylene (PTFE), has also been examined for textile wastewater
treatment [14,15].
Chemical cleaning is indispensable in the application of the membrane process. Strong
acid, caustic, and hypochlorite are usually used in chemical cleaning [12,16]. Membrane
aging resulting from chemical cleaning compromises the membrane system and shortens
the life span of the membrane [17]. Membrane aging usually begins with the degradation
of hydrophilic additives, such as polyvinyl pyrrolidone, and then proceeds to corrode
the membrane material [18–20]. Due to heavy fouling in MBR for textile wastewater, the
membrane must be subjected to more frequent chemical cleaning to recover flux [21,22],
which leads to more severe aging. However, the anti-aging characteristics of membranes
fabricated with different materials under the intensive chemical cleaning of textile wastew-
ater treatment have not been systematically investigated. In particular, the aging of the
PTFE membrane has rarely been reported.
Therefore, this study aimed to investigate membrane aging in textile wastewater
treatment. Commercial membranes made of different materials were examined, i.e., PVDF,
PES, and PTFE. Three pilot-scale MBRs were operated for exploring aging characteristics,
and batch soaking tests were also carried out to probe long-term aging properties according
to the concentration × time (CT, gh/L) value calculation. Pore size, pure water flux, contact
angle, surface zeta potential, functional groups, and surface morphology were analyzed for
all pristine and aged membrane specimens.

2. Material and Methods

2.1. Polit-Scale MBRs for Textile Wastewater Treatment
Three pilot-scale MBRs were constructed for textile wastewater treatment. The MBRs
comprised post-treatment processes after an A/O process. The pilot-scale experiment was
operated for 80 days, during which different organic loadings were applied to MBRs by
pumping mixed liquor from different points in the aeration tank, e.g., high loading from
the inlet end of the aeration tank, medium loading from the middle of the tank, and low
loading from the exit end of the tank. The quality of the influent of the MBRs, i.e., the
supernatant from these three points, can be found in Table 1.

Table 1. Water quality of the influent of pilot-scale MBRs.

CODcr Ammonia Nitrogen Total Phosphorus

pH
(mg/L) (mg/L) (mg/L)
Low loading
From the exit end of the aeration 145 ± 23 0.26 ± 0.12 0.41 ± 0.31 7.98 ± 0.53
tank
Medium loading
From the middle of the aeration 187 ± 35 0.89 ± 0.26 1.94 ± 1.13 8.12 ± 0.29
tank
High loading
From the inlet of the aeration 560 ± 91 17.35 ± 3.84 6.10 ± 2.93 8.29 ± 0.65
tank

Polyvinylidene Fluoride (PVDF) membrane, polyethersulfone (PES) membrane, and

polytetrafluoroethylene (PTFE) membrane were used in the three MBRs. The parameters of
the three membrane modules can be found in Table 2. The PVDF membrane and PES mem-
brane are both flat sheet membranes, and the PTFE membrane is a hollow fiber membrane.
Membranes 2022, 12, 704 3 of 13

Table 2. Parameters of the membrane modules and the corresponding MBRs.

Membrane Membrane Membrane Flux Operation Mode MLSS in MBR

Material Module Area (m2 ) (LMH) (min) Tank (g/L)
MBR 1 PVDF Flat sheet 420 15 8 min on, 2 min off 12
MBR 2 PES Flat sheet 470 15 8 min on, 2 min off 12
MBR 3 PTFE Hollow fiber 360 15 8 min on, 2 min off 12

No hydraulic backwash was applied in MBR1 and MBR2, while it was used in MBR3
every 2 h at 20 LMH for 70 s, according to the supplier’s suggestion.
In order to examine the anti-aging nature of the membrane, an online chemical clean-
ing was applied to the three MBRs every week using backwashing sodium hypochlorite
(500 ppm) and hydrochloride acid (500 ppm) sequentially, each for 15 min at 15 LMH.
Offline chemical cleaning was conducted every month, and three offline chemical cleanings,
in total, were applied in each MBR. Offline chemical cleaning was operated by draining
the membrane tank, then filling it with sodium hydroxide at 40,000 ppm and sodium
hypochlorite at 3000 ppm (~300 total free chlorine), and soaking the membrane module for
12 h. Subsequently, the membrane tank was drained and filled with hydrochloride acid at
20,000 ppm and soaked for another 12 h.
After the pilot-scale experiment, membrane samples from five different points on the
membrane modules were collected, cleaned with tap water, and subjected to characteriza-
tions. The pristine membranes were also characterized for comparison.

2.2. Membrane Aging Batch Test

In order to further investigate the anti-aging property of the three membranes used,
they were subjected to batch aging tests in static soaking mode. The membrane specimens
were soaked in the chemical cleaning solution without stirring. Two batches of the mem-
brane were subjected to acid soaking (hydrochloric acid at 19,767 ppm) and alkaline-oxide
soaking (sodium hydroxide at 39,452 ppm and sodium hypochlorite at 3000 ppm). The
concentrations of the cleaning chemicals were adjusted to match the concentration × time
(CT, gh/L) value in the real MBR, as shown in Table 3. Membrane specimens at the soaking
time of 12.16 h, 36.48 h, 6.08 days, 12.16 days, 18.24 days, and 30.40 days were collected to
simulate aging durations of 1 month, 3 months, 1 year, 2 years, 3 years, and 5 years in the
chemical cleaning scenario in MBR operation. The aged membrane was collected, washed
with pure water, and subjected to the following characterizations.

Table 3. Calculation of CT values of cleaning frequency, cleaning duration, and chemical concentration.

Chemical Cleaning Procedures in Real CT Value

Batch Tests
MBR Operation (gh/L)

Chemical Soaking Time in a Continuous Batch-Test Matched with the CT Value in Real MBRs Clean
Offline Cleaning Online Cleaning
Chemical
(1 per Month for (1 per Week for 1 Month 1-Month 3-Months 1-Year 2-Years 3-Years 5-Years
Concentration
12 h) 15 min) Equivalent Equivalent Equivalent Equivalent Equivalent Equivalent

Sodium
Hypochlorite 3000 500 36.5 3000 12.16 h 36.48 h 6.08 days 12.16 days 18.24 days 30.40 days
(mg/L)
Sodium
hydroxide 40,000 480 39,452 12.16 h 36.48 h 6.08 days 12.16 days 18.24 days 30.40 days
(mg/L)
Hydrochloric
20,000 500 240.5 19,767 12.16 h 36.48 h 6.08 days 12.16 days 18.24 days 30.40 days
acid (mg/L)

2.3. Membrane Characterization

The pure water fluxes (L/m2 h) of the pristine and aged membranes were measured
at a pressure of 0.10 MPa. Prior to the test, 0.15 MPa pressure was applied for 30 min for
stabilization. The flat sheet membrane (PVDF and PES) was cut to 76 mm in diameter
(with a surface area of 45.34 cm2 ) to fit the UF cell (Amicon 8400, Millipore, Bedford, MA,
USA) for flux measurements [23]. The hollow fiber membrane was cut to 100 mm in
length, and 7 fibers were assembled into a module (with surface area of 43.96 cm2 ) using
epoxy resin [24].
 The pure water fluxes (L/m h) of the pristine and aged membranes were measured
at a pressure of 0.10 MPa. Prior to the test, 0.15 MPa pressure was applied for 30 min for
stabilization. The flat sheet membrane (PVDF and PES) was cut to 76 mm in diameter
(with a surface area of 45.34 cm2) to fit the UF cell (Amicon 8400, Millipore, Bedford, MA
USA) for flux measurements [23]. The hollow fiber membrane was cut to 100 mm in
Membranes 2022, 12, 704 length, and 7 fibers were assembled into a module (with surface area of 43.96 cm2) 4using of 13
epoxy resin [24].
Mean pore size and pore size distribution of the pristine and aged membrane were
measured
Mean by poreusing
sizeaandcapillary
pore sizeflowdistribution
porometer (Porometer
of the pristine3G,andAshland, VA, USA) [25].
aged membrane were
The contact
measured by using angle was measured
a capillary by using(Porometer
flow porometer a drop shape 3G, analyzer
Ashland, (DSA100,
VA, USA)KRUSS,[25].
Hamburg, Germany).
The contact angle Thewasaverage
measured andbystandard
using a deviation
drop shape of analyzer
5 measurements
(DSA100, were used
KRUSS,
to describeGermany).
Hamburg, the membrane sampleand
The average [26].standard deviation of 5 measurements were used to
Thethe
describe surface
membranezeta potential was measured using a solid surface analyzer (SurPASS 3,
sample [26].
The surface zeta potential
Anton Parr, USA). Potassium chloride was measured
measuring using a solid surface
1 mmol/L was used analyzer (SurPASS
as the test 3,
solution,
Anton
and allParr, Ashland,were
experiments VA, USA).
carried Potassium
out at room chloride measuring
temperature (24 1± mmol/L
2 °C) [27].was used as the
test solution,
Surface and all experiments
functional groups ofwere carried outwere
the membrane at room temperature
analyzed by using (24a ± 2 ◦ C) [27].
Fourier-trans-
formSurface
infrared functional
spectrometergroups of theNicolet
(FTIR, membrane iS50,were analyzed byWaltham,
ThermoFisher, using a Fourier-transform
MA, USA) with
infrared
a diamond spectrometer
attenuated(FTIR, Nicolet iS50,
total reflectance ThermoFisher,
(ATR) Waltham, MA, in
accessory. Wavenumbers USA) with afrom
the range dia-
mond attenuated total reflectance (ATR) accessory. Wavenumbers
4000 to 650 cm were analyzed with a resolution of 4 cm , and 64 scans for each sample
−1 −1 in the range from 4000
to cm−1 were
650acquired
were
−1
[28].analyzed with a resolution of 4 cm , and 64 scans for each sample
were Membrane
acquired [28]. specimens were also subjected to a focused ion beam scanning electron
Membrane
microscope specimens
(FIB-SEM, were
LYRA 3 also
XMU, subjected
TESCAN, to aWarrendale,
focused ion beam scanning
PA, USA) electronmor-
for surface mi-
croscope
phology (FIB-SEM,
analysis and LYRApore3 XMU, TESCAN, Warrendale, PA, USA) for surface morphology
size observation.
analysis and pore size observation.
3. Results and Discussion
3. Results and Discussion
3.1. Change of Membrane Properties in the Pilot-Scale MBR Experiment
3.1. Change of Membrane Properties in the Pilot-Scale MBR Experiment
Pilot-scale MBRs
Pilot-scale MBRs were were operated
operated for for 80
80days,
days,during
duringwhich
whichonline
onlinechemical
chemicalcleaning
cleaning
was carried
was carried outout 11 11 times,
times, and
andoffline
offlinechemical
chemicalcleaning
cleaningwaswascarried out
carried out3 times.
3 times.After the
After
experiments, the membranes in three MBRs were characterized
the experiments, the membranes in three MBRs were characterized and compared with and compared with the
new membrane. As shown in Figure 1a, the pore size of
the new membrane. As shown in Figure 1a, the pore size of all membranes decreased all membranes decreased after
beingbeing
after used.used.
ThisThismaymay be attributed
be attributed to fouling, which
to fouling, whichnarrowed
narrowed or or
blocked
blocked thethe
pores.
pores.It
should be noted that the intensive chemical cleaning adopted
It should be noted that the intensive chemical cleaning adopted in the experiment may in the experiment may de-
teriorate the
deteriorate themembrane
membranematerial material(the (themembrane
membraneaging)aging)and,
and,thus,
thus, enlarge
enlarge the pore size,
the pore size,
but it seems likely that membrane fouling was greater than
but it seems likely that membrane fouling was greater than membrane aging on varying membrane aging on varying
membranepore
membrane poresizes.
sizes.TheThe pure
pure water
water fluxes
fluxes of the
of the pristine
pristine membrane
membrane and used
and used mem-
membrane
brane also indicated membrane fouling
also indicated membrane fouling after the MBR experiment. after the MBR experiment.

(a) (b)

Figure 1. Cont.
Membranes 2022, 12,
Membranes 2022, 12, 704
x FOR PEER REVIEW 5 of 13

(c)
Figure 1.
Figure 1. (a)
(a) Pore
Pore size,
size, (b)
(b) pure
pure water
water flux,
flux, and
and (c)
(c) contact
contact angle
angle of
of the
the pristine
pristine membrane
membrane and
and used
used
membrane from the pilot
membrane from the pilot MBRs.MBRs.

The contact
contact angles
angles of of the
the pristine
pristine PVDF,
PVDF,PES, PES,andandPTFE
PTFEmembrane
membranewere were46.3
46.3°◦ ± 5.8◦ ,
± 5.8°,
66.7°◦
66.7 ±±6.4°, ◦
6.4 ,andand56.1° ◦
56.1 ± ±6.2°, ◦
6.2respectively.
, respectively. Usually, thethe
Usually, PESPESmembrane
membrane waswasmoremorehydro-
hy-
philic than
drophilic thethe
than PVDFPVDF andandPTFE
PTFE membranes.
membranes.The Therelatively
relativelylower
lowercontact
contact angles
angles of the
PVDF and
PVDF andPTFE
PTFEmembranes
membranesmay may bebe attributed
attributed to the
to the hydrophilic
hydrophilic modification
modification in theinman-
the
manufacture
ufacture of membranes,
of membranes, which whichwas was always
always carried
carried out out for enhancing
for enhancing anti-fouling
anti-fouling [29–
[29–32].
After use, the
32]. After use,contact angle of
the contact the PVDF
angle of the and
PVDF PTFEandmembranes to 81.3◦ ±to8.2
increasedincreased
PTFE membranes ◦ and
81.3° ±
89.4 ◦ ± 7.9◦ . Membrane aging due to chemical cleaning may undermine the hydrophilic
8.2° and 89.4° ± 7.9°. Membrane aging due to chemical cleaning may undermine the hy-
modification of the membrane’s
drophilic modification surface, and
of the membrane’s membrane
surface, and fouling
membrane alsofouling
made italsomuch more
made it
hydrophobic. The contact The
much more hydrophobic. angle of the angle
contact PES membrane
of the PES did not change
membrane did significantly (from
not change signifi-
66.7 ◦ ± 6.4◦ to 61.0◦ ± 7.6◦ , p-value = 0.14), which implied that the PES membrane may be
cantly (from 66.7° ± 6.4° to 61.0° ± 7.6°, p-value = 0.14), which implied that the PES mem-
fabricated
brane maywithout muchwithout
be fabricated hydrophilic muchmodification. The final contact
hydrophilic modification. angles
The final of theangles
contact three
membranes
of the three membranes followed a common trend, e.g., PTFE > PVDF > PES, which that
followed a common trend, e.g., PTFE > PVDF > PES, which also implied also
the hydrophilic
implied that themodification
hydrophilicofmodification
the PVDF and of PES
the membranes
PVDF and PES might be worn off.
membranes might be
wornItoff.
should be noted that the pure water fluxes of PVDF and PTFE decreased more
significantly,
It should while the pore
be noted thatsize
thechange of the fluxes
pure water PTFE membrane
of PVDF and wasPTFE
not very considerable.
decreased more
Since the porewhile
significantly, size ofthethe
porePTFE
sizewas much
change of smaller,
the PTFEmembrane
membranefouling,
was notinvery this considera-
case, may
primarily
ble. Since comprise
the pore sizeporeofblocking
the PTFE rather
was than
muchpore constriction.
smaller, membrane In fouling,
this case,inthethisfouled
case,
pores were completely blocked and the unfouled pores were still
may primarily comprise pore blocking rather than pore constriction. In this case, the open. Pore size analysis
could
fouledonlyporesmeasure the open pores;
were completely blocked thus,
andthe thepore size ofpores
unfouled the usedwerePTFEstill did
open.not change
Pore size
significantly. However, pore blocking significantly decreased the
analysis could only measure the open pores; thus, the pore size of the used PTFE did number of available pores;
not
thus,
change pure water flux However,
significantly. decreased pore correspondingly. For the PVDF
blocking significantly membrane,
decreased the pore’s
the number size
of avail-
was
able much
pores;larger; thus, water
thus, pure pore blocking and pore
flux decreased constriction may
correspondingly. occur
For concurrently.
the PVDF membrane, The
decline in pore size and the decrease in flux were both observed.
the pore’s size was much larger; thus, pore blocking and pore constriction may occur con- The fouling of the PES
membrane was much lower compared to the PVDF and PTFE membranes, possibly due to
currently. The decline in pore size and the decrease in flux were both observed. The foul-
the more hydrophilic nature of the PES membrane.
ing of the PES membrane was much lower compared to the PVDF and PTFE membranes,
The change of membrane properties in the pilot experiment results from both mem-
possibly due to the more hydrophilic nature of the PES membrane.
brane aging and membrane fouling, and identifying the sole effect of membrane aging on
The change of membrane properties in the pilot experiment results from both mem-
membrane properties is difficult, as shown in Figure 1. Thus, batch tests were conducted to
brane aging and membrane fouling, and identifying the sole effect of membrane aging on
elucidate the susceptibility of the different membranes towards chemical cleaning.
membrane properties is difficult, as shown in Figure 1. Thus, batch tests were conducted
to elucidate
3.2. Membrane theProperties
susceptibility
in the ofAcidtheAging
different
Test membranes towards chemical cleaning.
Acid soaking and alkaline oxide soaking were conducted separately. As shown in
3.2. Membrane Properties in the Acid Aging Test
Figure 2a,b, acid chemical cleaning induced a significant decline in pore size and a decrease
Acid
in pure soaking
water flux. and
Thisalkaline
may beoxide soaking
attributed were
to the conducted
loss separately.
of hydrophilicity [20].AsThe
shown in
pore’s
Figure
size was2a,b, acid chemical
determined cleaning
by using induced
capillary a significant
flow porometry, decline
which in porethe
measured size
gasand a de-
pressure
crease in pure water flux. This may be attributed to the loss of hydrophilicity [20]. The
pore’s size was determined by using capillary flow porometry, which measured the gas
pressure required to force a wetting liquid out of through pores. The pore’s size can be
calculated using the Washburn equation [33]:
Membranes 2022, 12, 704 6 of 13

Membranes 2022, 12, x FOR PEER REVIEW 6 of 13

required to force a wetting liquid out of through pores. The pore’s size can be calculated
using the Washburn equation [33]:

4𝛾
4γ·∙cosθ
𝑐𝑜𝑠𝜃
𝐷=
D = P𝑃
(1)
(1)

where
whereD Disisthe
thepore
poresize,
size,PPisisthe
thepressure
pressuremeasured,
measured,γγisisthe
thesurface
surfacetension
tensionof
ofthe
thewetting
wetting
liquid,
liquid,and
andθθ is
is the
the contact
contact angle
angle of
of the
the wall
wall of
of the
the pore.
pore.

(a) (b)

(c) (d)
Figure
Figure2.2.(a)
(a)Pore
Poresize,
size,(b)
(b)pure
purewater
waterflux,
flux,(c)
(c)contact
contactangle,
angle,and
and(d)
(d)zeta
zetapotential
potentialof
ofthe
thepristine
pristine
membrane and aged membrane in the acid aging test.
membrane and aged membrane in the acid aging test.

According
Accordingto tothe
theWashburn
Washburnequation,
equation,as asthe
thecontact
contactangle
angleincreases
increases(becoming
(becomingmore more
hydrophobic), the pore size calculated will decrease. Figure
hydrophobic), the pore size calculated will decrease. Figure 2c shows that 2c shows that the contact an-
the contact
gle of the
angle membrane
of the membrane surface increased
surface in the
increased in acid aging
the acid procedure.
aging procedure. It should be noted
It should that
be noted
the
thatcontact angleangle
the contact shown in Figure
shown 2c corresponded
in Figure 2c correspondedto thetomembrane’s
the membrane’s surface, whichwhich
surface, was
different from from
was different the contact angle angle
the contact related to the to
related wall
theofwall
the of
pore
theinporeEquation (1). Due
in Equation to Due
(1). the
difficulty in determining contact angle of the inner wall, it may be
to the difficulty in determining contact angle of the inner wall, it may be reasonable to reasonable to assume
that the pore
assume wallpore
that the contact
wallangle may
contact experience
angle the samethe
may experience trend
sameas the
trendmembrane’s surface
as the membrane’s
contact
surfaceangle
contact in angle
aging.inInaging.
addition, the PTFEthe
In addition, membrane is similar
PTFE membrane is to a depth
similar to afilter,
depthwhile
filter,
PVDF
while and
PVDF PESandmembranes
PES membranes are surface filters filters
are surface [34]. The
[34].depth filter PTFE
The depth membrane
filter PTFE membranepos-
sessed
possessedhigher surface
higher roughness
surface roughnessand, thus,
and, may
thus, bebe
may more
more susceptible
susceptibletotochemical
chemicalaging.
aging.
The
The significant increases in
significant increases insurface
surfacecontact
contactangle
angleand
andsurface
surface zeta
zeta potential
potential observed
observed forforthe
the
PTFEPTFE membrane
membrane indicated
indicated thatthat
acidacid chemical
chemical cleaning
cleaning maymay aggravate
aggravate its fouling
its fouling ten-
tendency.
dency.The zeta potential of all membranes decreased initially and then increased gradually.
The The
initial decline
zeta in the
potential ofzeta potential may
all membranes be attributed
decreased to the
initially andloss
thenofincreased
functionalgradually.
groups in
aging.
The Thedecline
initial obvious inincrease
the zetain the zetamay
potential potential for PTFEtomay
be attributed the belossdueof to the re-formation
functional groups
of aging.
in macromolecular
The obvious cross-linking.
increase in the zeta potential for PTFE may be due to the re-for-
mation of macromolecular cross-linking.
Figure 3 shows how surface morphology changed before and after acid chemical
soaking. No obvious change in the surface morphology could be found for the three mem-
branes. It was determined that the pore size of the PVDF membrane was much larger than
Membranes 2022, 12, x FOR PEER REVIEW

Membranes 2022, 12, 704 7 of 13

that of the PES membrane, which was consistent with the results of the poromet
Figure (Figure
urement 3 shows how surface
2a). The morphology
PTFE membrane changed before and after
demonstrated acid chemical
a multi-layer thread-li
soaking. No obvious change in the surface morphology could be found for the three
ture. Although
membranes. the surface
It was determined thatpore sizesize
the pore of ofthethePTFE membrane
PVDF membrane waswas
much the largest, th
larger
layer
than depth
that of the filtration
PES membrane,structure
whichallowed it to with
was consistent intercept foulants
the results that were much
of the porometry
than the surface
measurement (Figurepore size.
2a). The PTFEThe pore size
membrane of the PTFE,
demonstrated determined
a multi-layer by a capill
thread-like
structure. Although the surface pore size of the PTFE membrane was
porometer, also indicated that its apparent pore size was smaller than the PVD the largest, the multi-
layer depth filtration structure allowed it to intercept foulants that were much smaller than
brane and is comparable to the PES membrane. In addition, the pore size of the
the surface pore size. The pore size of the PTFE, determined by a capillary flow porometer,
membrane
also indicated and aged
that its membrane
apparent pore sizedidwasnot change
smaller thansignificantly for all three
the PVDF membrane and ismembr
cording totothe
comparable SEM
the PES results. This
membrane. implies
In addition, thethat
pore the
size pore
of the size decline
pristine membrane for the
and PVDF a
aged membrane did not change significantly for all three membranes,
obtained by a capillary flow porometer as shown in Figure 2a, may be attribute according to the SEM
results. This implies that the pore size decline for the PVDF and PES, obtained by a capillary
loss of hydrophilicity.
flow porometer as shown in Figure 2a, may be attributed to the loss of hydrophilicity.

Figure
Figure SEM
3. 3. photograph
SEM photographof theof
pristine membrane
the pristine and aged and
membrane (five-years
aged equivalent)
(five-yearsmembrane
equivalent) mem
inthe
theacid
acid aging
aging test. (a) Pristine PVDF membrane, (b) prestine PES membrane,
test. (a) Pristine PVDF membrane, (b) prestine PES membrane, (c) pristine(c)
PTFE
pristine PT
membrane, (d) aged PVDF membrane, (e) aged PES membrane, (f) aged PTFE membrane.
brane, (d) aged PVDF membrane, (e) aged PES membrane, (f) aged PTFE membrane.
The ATR-FTIR spectra of the pristine and aged membranes are shown in Figure 4.
For theThe
PVDF ATR-FTIR
membrane,spectra of the pristine
the characteristic and
peaks (at aged
1400, membranes
1280, 1180, and 1072 −1 )
arecmshown in F
did not change significantly in acid aging, while two new peaks at 2850 and 2920 cm −1 ,
For the PVDF membrane, the characteristic peaks (at 1400, 1280, 1180, and 1072 c
representing C-H2 and C-H3 bonds, appeared in the aged specimen. This indicated that
not change significantly in acid aging, while two new peaks at 2850 and 2920 cm
a fluoro-substitution reaction may occur [35]. These two peaks also appeared in the aged
senting
PES C-H2
and PTFE and C-H3
membrane bonds,
specimen, appeared
which indicatedin the aged
a similar specimen.
substitution This indicate
of functional
fluoro-substitution
groups reaction
on the carbon chain. For themayPESoccur [35]. the
membrane, These two peaks
intensities also appeared
of the aromatic ring in
−1 ), C-S bond on the sulfonic group (1413 cm−1 ), C-O group (1299 cm−1 ), sulfuryl
PES and PTFE membrane specimen, which indicated a similar substitution of fu
(1590 cm
group
groups (Ar-SO -Ar, 1160
on 2the cm−chain.
carbon
1 ), and C-H bond on the benzene ring (860 cm−1 ) decreased in
For the PES membrane, the intensities of the arom
the aging procedure. This may be attributed to the chain scission−1of PES molecules [17].
(1590 cm ), C-S bond on the sulfonic group (1413 cm ), C-O group (1299 cm−1),
−1
For the PTFE membrane, an extra peak at 1680 cm−1 appeared in the aged membrane, and
group
this peak(Ar-SO 2-Ar,
represented 1160 C=C
alkenyl cm−1stretch,
), and which
C-H bond on the
may result frombenzene ring (860 cm−1) decr
the dehydrofluorination
the aging
reaction [35]. procedure. This may be attributed to the chain scission of PES molecu
For the PTFE membrane, an extra peak at 1680 cm−1 appeared in the aged membr
this peak represented alkenyl C=C stretch, which may result from the dehydrofluo
reaction [35].
Membranes 2022, 12, x FOR PEER REVIEW
Membranes 2022, 12, 704 8 of 13

Figure
Figure 4. The
4. The FTIRFTIR of pristine
of pristine and
and aged aged (five-years
(five-years equivalent) equivalent)
membranes inmembranes
the acid aging in the
test. acid agi
3.3. Membrane Properties in the Alkaline Oxide Aging Test
3.3.Sodium
Membrane Properties in the Alkaline Oxide Aging Test
hydroxide and sodium hypochlorite were used together to conduct the al-
Sodium
kaline oxide aginghydroxide
test for theirand sodium
strong hypochlorite
cleaning performance.were used together
This combination to conduct
has been
widely used to clean severe membrane fouling, e.g., in textile wastewater
line oxide aging test for their strong cleaning performance. This combination treatment [1]. As
shown in Figure 5a, with aging, the membrane’s pore size increased to different extents
widely used to clean severe membrane fouling, e.g., in textile wastewater treat
for different membranes, e.g., 2.13 µm to 14.73 µm for PVDF, 0.188 µm to 0.360 µm for
As shown
PES, and 0.414inµmFigure 5a,µm
to 0.478 withforaging, the membrane’s
PTFE. This may be attributed poreto size increased
the oxidation of to
thedifferen
for different
membrane membranes,
additives e.g., 2.13
(such as polyvinyl μm to 14.73
pyrrolidone, PVP)μmor tofor
thePVDF, 0.188ofμm
deterioration the to 0.36
membrane’s material [17]. The pure water flux of all membranes
PES, and 0.414 μm to 0.478 μm for PTFE. This may be attributed to the oxidati increased after aging
tests (Figure 5b), e.g., from 14,520 LMH to 456,600 LMH for the PVDF membrane, from
membrane additives (such as polyvinyl pyrrolidone, PVP) or to the deteriorati
642 LMH to 1164 LMH for the PES membrane, and from 1640 LMH to 2420 LMH for the
membrane’s
PTFE membrane.material
Pure water [17].
fluxThe pureconsistently
changed water fluxwith of pore
all membranes increased
size variations. The aft
tests (Figure 5b), e.g., from 14,520 LMH to 456,600 LMH for
PVDF membrane was the most susceptible to alkaline oxide aging; the pore’s size increased the PVDF membra
by 5.92LMH
642 folds and flux increased
to 1164 LMH for bythe
30.45 folds
PES [36]. The PTFE
membrane, and membrane
from 1640 was LMH
rather stable
to 2420 LM
against caustic oxide aging, with pore size increases by 15.46% and
PTFE membrane. Pure water flux changed consistently with pore size variati flux increases by 47.56%.
This trend is different from acid aging, which induced decreases in pore size and flux. In
PVDF membrane was the most susceptible to alkaline oxide aging; the pore’s
acid aging, the structure of the membrane and pore remains intact, and interfacial inter-
creased
action mayby 5.92major
be the foldsfactor
andthat
fluxdetermined
increasedthe bypore’s
30.45size
folds
and[36].
flux, The
whilePTFE membran
in caustic
ther stable against caustic oxide aging, with pore size increases by 15.46% and
oxide aging, serious erosion and pore enlargement may occur [36,37].
creases by 47.56%. This trend is different from acid aging, which induced dec
pore size and flux. In acid aging, the structure of the membrane and pore remai
and interfacial interaction may be the major factor that determined the pore’s
flux, while in caustic oxide aging, serious erosion and pore enlargement may occu
Membranes
Membranes 2022,
2022, 12,
12, x704
FOR PEER REVIEW 99 of
of 13
13

(a) (b)

(c) (d)
Figure
Figure 5.
5. (a)
(a) Pore
Pore size,
size, (b)
(b) pure
pure water
water flux,
flux, (c)
(c) contact
contact angle,
angle, and
and (d)
(d) zeta
zeta potential
potential of
of the
the pristine
pristine
membrane and aged membrane in the alkaline oxide
membrane and aged membrane in the alkaline oxide aging test.aging test.

Figure
Figure 5c 5c shows
shows thethe contact
contact angle of the pristine and aged membranes. The The rapid
rapid
increase
increase in in the
the contact
contact angle
angle inin the
the beginning
beginning may may be be attributed
attributed to to the
the wash
wash outout ofof the
the
hydrophilic coating or
hydrophilic coating orgrafting.
grafting.TheThesubsequent
subsequentdecrease
decrease in in contact
contact angle
angle for for
the the
PVDF PVDFand
and
PTFEPTFE membrane
membrane couldcould be attributed
be attributed to the to the oxidation
oxidation or erosionor erosion of the membrane
of the membrane material
material (e.g., dehydrofluorination
(e.g., dehydrofluorination process),process), which resulted
which resulted in a more in hydrophilic
a more hydrophilic
surface.surface.
For the
For
PESthe PES membrane,
membrane, the contact
the contact angle experienced
angle experienced a decline
a decline followedfollowed by a gradual
by a gradual rise. rise.
The
The initial
initial decrease
decrease couldcould be ascribed
be ascribed to the
to the formation
formation of phenol
of phenol groups
groups andand hydrolysis
hydrolysis of
thethe
of sulfonyl
sulfonyl group,
group, andandthethe
subsequent
subsequent increase
increase may
may bebeattributed
attributed to to
thethedegradation
degradation of
hydrophilic
of hydrophilic additives
additives(such
(suchas as
PVP)PVP)[38].
[38].
The zeta
The zeta potential
potential of of all
all membranes
membranes showed showed aa down-and-up
down-and-up trend. trend. TheTheinitial
initialde-
de-
crease in
crease in zeta
zeta potential
potential maymay be be attributed
attributed to to the
the dehydrofluorination
dehydrofluorination reaction reaction in in PVDF
PVDF
and PTFE
and PTFE aging
aging and and the
the formation
formation of of phenol
phenol group
group andand sulfonic
sulfonic acid
acid functions
functions in in PES
PES
aging. The
aging. The subsequent
subsequentincrease
increasein in the
the zeta
zeta potential
potential maymay result
result from
from thethe reformation
reformation of of
macromolecular cross-linking.
macromolecular cross-linking.
The surface
The surface morphology
morphology of of the
the aged
aged membrane
membrane is is shown
shown in in Figure
Figure 6. The PVDF
6. The PVDF
membrane was seriously eroded, with an appearing fiber-like supporting layer. could
membrane was seriously eroded, with an appearing fiber-like supporting layer. This This
also explain
could the drastic
also explain increases
the drastic in porein
increases size andsize
pore fluxand
in the
fluxPVDF
in themembrane.
PVDF membrane.No obvious No
change could
obvious changebecould foundbefor the for
found PESthe and
PESPTFE
and membranes.
PTFE membranes. Photos of pristine,
Photos acid-aged,
of pristine, acid-
and alkaline
aged, oxide-aged
and alkaline membranes
oxide-aged are shown
membranes in Figure
are shown 7. The7.alkaline
in Figure oxide-aged
The alkaline PVDF
oxide-aged
membrane turned red and brittle, which indicated severe aging
PVDF membrane turned red and brittle, which indicated severe aging and dysfunction. and dysfunction. The
susceptibility of PVDF to alkaline oxide chemicals has also
The susceptibility of PVDF to alkaline oxide chemicals has also been reported been reported [17,20,35,36].
[17,20,35,36].
 Membranes2022,
Membranes
Membranes 2022,12,
2022, 12,704
12, xxFOR
FORPEER
PEERREVIEW
REVIEW 1010of
10 of13
of 13
13

Figure6.6.6.SEM
Figure
Figure SEMphotograph
SEM photographof
photograph ofthe
of thepristine
the pristinemembrane
pristine membraneand
and aged
andaged (five-years
aged(five-years equivalent)
(five-yearsequivalent) membrane
equivalent)membrane
membrane in
in
inthe
thethealkaline
alkaline
alkaline oxide
oxide
oxide aging
aging
aging test. (a)
test.
test. Aged PVDF
(a) Aged
(a) Aged membrane,
PVDF
PVDF membrane,
membrane, (b) aged PES
(b) aged
(b) aged membrane,
PES membrane,
PES membrane, (c) aged PTFE
(c) aged
(c) aged PTFE
membrane.
membrane.
PTFE membrane.

Figure7.7.Photographs
Figure Photographs of thepristine
pristineand
andaged
aged(five-years
(five-yearsequivalent)
equivalent)membrane
membranein
inthe
thebatch
batchaging
aging
Figure 7. Photographsofofthe
the pristine and aged (five-years equivalent) membrane in the batch
test.
test. test.
aging
Accordingtoto
According
According tothethe
the FTIR
FTIR
FTIR analysis
analysis
analysis (Figure
(Figure
(Figure 8),
8),8), the
thetheC-H C-H
C-H (2850
22(2850 cm
cmcm−1−1 −1) and C-H3 (2920 cm−1
) andC-H C-H 3 (2920 cm−1−1)))
2 (2850 ) and 3 (2920 cm
stretching peaks
stretching peaks
stretching appeared
peaks appeared
appeared in in the
in the alkaline
the alkaline
alkaline oxide oxide
oxide aging aging
aging for for all
for all three
allthree membranes,
threemembranes,
membranes, which which
which
couldbe
could
could beattributed
attributedto
attributed to the
tothe substitution
thesubstitution
substitution reaction
reaction
reaction and
and and thethe
the formation
formation
formation ofalkane.
of alkane. Forthe
For
of alkane. the
For PVDF
PVDF
the
membrane,
membrane, the
the peak
peak appeared
appeared at
at 1430
1430 cm
cm −1,,indicating
−1 indicating
− 1
PVDF membrane, the peak appeared at 1430 cm , indicating the generation of C-OH the
the generation
generation of
of C-OH
C-OH bending
bending in
in
carboxylic
carboxylic
bending acid,
in acid, and
and the
carboxylic the
acid,peak
peakand that
thatthe appeared
appeared
peak that at 1560
at appeared
1560 cm atcm −1 peak (C=C−bond)
−1 peak
1560(C=Ccm bond)1 evidenced
peakevidenced
(C=C bond) de-
de-
hydrofluorination
hydrofluorination
evidenced reactions.These
reactions.
dehydrofluorination These reactions
reactions
reactions. These enhanced
enhanced
reactionsthe the hydrophilicity
hydrophilicity
enhanced andelectroneg-
and
the hydrophilicityelectroneg-
and
ativity of
ativity of the
the membrane.
electronegativity membrane.
of the membrane. For the
For the For
PESthe
PES membrane,
membrane,
PES membrane, the scission
the scission of (Ph-SO2-Ph-O)
of
the scission (Ph-SO2-Ph-O)
of (Ph-SO2-Ph-O) chain
nn chainn
could be
couldcould
chain verified
be verified by the
by theby
be verified downward
downward
the downward trend
trend of of all characteristic
all characteristic
trend peaks
peaks of
of all characteristic of PES [38].
PES [38].
peaks of PES For the
For[38].
the
PTFE
For
PTFE membrane,
themembrane,
PTFE membrane, peaksat
peaks at 1210cm
peaks
1210 cm1210
at
−1 and 1155
−1 andcm −1 and
1155 cm−1−11155
cm ,,representing
representing theCF
cm−1 , representing
the CF22bond,
bond,
the CFdecreased,
2 bond,
decreased,
while peaks
decreased, at
while 1430
peaks cm at−1 and
1430 1580
cm −1 cmand −1 , representing
1580 cm the
−1 , representing
while peaks at 1430 cm and 1580 cm , representing the C=C bond, increased, indicating
−1 −1 C=C bond,
the increased,
C=C bond, indicating
increased,
aadehydrofluorination
dehydrofluorination
indicating reaction. reaction.
a dehydrofluorination
reaction.
Membranes
Membranes2022, 12,12,
2022, 704x FOR PEER REVIEW 1111
ofof
1313

Figure
Figure 8.8.The
TheFTIR
FTIRof
ofpristine
pristine and
and aged
aged (five-years
(five-years equivalent)
equivalent) membranes
membranesin
inthe
thealkaline
alkalineoxide
oxide
aging test.
aging test.

Unlikeacid
Unlike acidcleaning,
cleaning,which
whichonly
onlyaltered
alteredthe
theinterfacial
interfacialproperty
propertyofofmembranes,
membranes,al- al-
kalineoxide
kaline oxidecleaning
cleaninginduced
inducedmuchmuchmoremoresevere
severemembrane
membraneagingagingoror erosion.Sodium
erosion. Sodium
hydroxide
hydroxide andand sodium
sodium hypochlorite
hypochlorite are chemicals
are the the chemicals
most most commonly
commonly used
used in in the re-
the removal
moval of organic fouling. Particularly for MBR for textile wastewater treatments,
of organic fouling. Particularly for MBR for textile wastewater treatments, frequent frequent
alka-
alkaline
line oxide oxide cleaning
cleaning may bemay be indispensable.
indispensable. Therefore,
Therefore, special
special anti-aging
anti-aging modifications
modifications for
for membranes
membranes susceptible
susceptible to chemical
to chemical cleaning
cleaning (such(such as PVDF)
as PVDF) would would be necessary
be necessary for thefor
the MBR
MBR for textile
for textile wastewater
wastewater treatment;
treatment; otherwise,
otherwise, membranesmembranes
that arethat arestable
rather ratherunder
stable
intensive chemicalchemical
under intensive cleaningcleaning
(like PES(like
or PTFE)
PES orshould
PTFE)be chosen.
should be chosen.

4.4.Conclusions
Conclusions
This
Thiswork
workinvestigated
investigatedthetheaging
agingofofthree
threedifferent
differentmembranes—PVDF,
membranes—PVDF,PES, PES,andand
PTFE—used in MBR for textile wastewater treatment. Pilot-scale MBRs were
PTFE—used in MBR for textile wastewater treatment. Pilot-scale MBRs were carried out, carried
out,
andand
thethe used
used membrane
membrane waswas studied
studied to investigate
to investigate fouling
fouling andand aging.
aging. Batch
Batch aging
aging tests
tests were conducted to elucidate the aging process of three membranes. The following
were conducted to elucidate the aging process of three membranes. The following conclu-
conclusion
sion couldcould be drawn:
be drawn:
1.1. The
ThePVDF
PVDFmembrane
membranewaswasmost
mostsusceptible
susceptibletotochemical
chemicalcleaning.
cleaning.InInthe
theacid
acidaging
aging
test,
test, the surface hydrophobicity of PVDF increased, and the pore size andthe
the surface hydrophobicity of PVDF increased, and the pore size and thepure
pure
water flux decreased due to the elevated hydrophobic effect. Alkaline oxide
water flux decreased due to the elevated hydrophobic effect. Alkaline oxide aging aging
destructed the PVDF membrane’s structure, enlarged pore size, and increased pure
destructed the PVDF membrane’s structure, enlarged pore size, and increased pure
water flux. The fluoro-substitution reaction and the dehydrofluorination reaction may
water flux. The fluoro-substitution reaction and the dehydrofluorination reaction
occur in the aging.
may occur in the aging.
2. The PES and PTFE membranes were rather stable. Chemical cleaning barely changed
2. The PES and PTFE membranes were rather stable. Chemical cleaning barely changed
the surface structure of the membrane specimens, although the interfacial properties
the surface structure of the membrane specimens, although the interfacial properties
(hydrophobicity and surface zeta potential) were altered. The chain scission of PES
(hydrophobicity and surface zeta potential) were altered. The chain scission of PES
molecules and the dehydrofluorination of the PTFE were observed in aging.
molecules and the dehydrofluorination of the PTFE were observed in aging.
3. Membrane aging in the MBR for textile wastewater treatment should be carefully
3. Membrane aging in the MBR for textile wastewater treatment should be carefully
considered due to the possible intensive chemical cleaning process.
considered due to the possible intensive chemical cleaning process.
Membranes 2022, 12, 704 12 of 13

Author Contributions: Conceptualization, H.Y. (Huarong Yu) and F.Q.; methodology, H.Y. (Huarong
Yu) and H.Y. (Haiyang Yang); validation, H.R. and C.W.; resources, H.R. and C.X.; data curation, S.S.;
writing—original draft preparation, S.S. and H.Y. (Huaorng Yu); writing—review and editing, F.Q.
and H.Y. (Haiyang Yang); supervision, H.R.; funding acquisition, H.R. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was jointly supported by the National Natural Science Foundation of China
(52070045, 52170072), Natural Science Foundation of Guangdong Province (2022A1515011909), the
Fundamental Research Program of Guangzhou (202102010496), and the Department of Education of
Guangdong Province (2020KTSCX095, 2019KQNCX109).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are available on demand to the authors.
Acknowledgments: The authors acknowledge the scientific-technical services of the Guangdong
University of Technology for the SEM and FTIR measurements.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Jegatheesan, V.; Pramanik, B.K.; Chen, J.; Navaratna, D.; Chang, C.-Y.; Shu, L. Treatment of textile wastewater with membrane
bioreactor: A critical review. Bioresour. Technol. 2016, 204, 202–212. [CrossRef]
2. Brik, M.; Schoeberl, P.; Chamam, B.; Braun, R.; Fuchs, W. Advanced treatment of textile wastewater towards reuse using a
membrane bioreactor. Process. Biochem. 2006, 41, 1751–1757. [CrossRef]
3. Hai, F.I.; Yamamoto, K.; Nakajima, F.; Fukushi, K. Bioaugmented membrane bioreactor (MBR) with a GAC-packed zone for high
rate textile wastewater treatment. Water Res. 2011, 45, 2199–2206. [CrossRef]
4. Paździor, K.; Bilińska, L.; Ledakowicz, S. review of the existing and emerging technologies in the combination of AOPs and
biological processes in industrial textile wastewater treatment. Chem. Eng. J. 2019, 376, 120597. [CrossRef]
5. De Jager, D.; Sheldon, M.; Edwards, W. Colour removal from textile wastewater using a pilot-scale dual-stage MBR and subsequent
RO system. Sep. Purif. Technol. 2014, 135, 135–144. [CrossRef]
6. Keskin, B.; Ersahin, M.E.; Ozgun, H.; Koyuncu, I. Pilot and full-scale applications of membrane processes for textile wastewater
treatment: A critical review. J. Water Process. Eng. 2021, 42, 102172. [CrossRef]
7. Tavangar, T.; Jalali, K.; Shahmirzadi, M.A.A.; Karimi, M. Toward real textile wastewater treatment: Membrane fouling control
and effective fractionation of dyes/inorganic salts using a hybrid electrocoagulation—Nanofiltration process. Sep. Purif. Technol.
2019, 216, 115–125. [CrossRef]
8. Yang, X.; López-Grimau, V. Reduction of Cost and Environmental Impact in the Treatment of Textile Wastewater Using a
Combined MBBR-MBR System. Membranes 2021, 11, 892. [CrossRef]
9. Cinperi, N.C.; Ozturk, E.; Yigit, N.O.; Kitis, M. Treatment of woolen textile wastewater using membrane bioreactor, nanofiltration
and reverse osmosis for reuse in production processes. J. Clean. Prod. 2019, 223, 837–848. [CrossRef]
10. Ćurić, I.; Dolar, D.; Bošnjak, J. Reuse of textile wastewater for dyeing cotton knitted fabric with hybrid treatment: Coagula-
tion/sand filtration/UF/NF-RO. J. Environ. Manag. 2021, 295, 113133. [CrossRef]
11. Robinson, S.; Abdullah, S.Z.; Bérubé, P.; Le-Clech, P. Ageing of membranes for water treatment: Linking changes to performance.
J. Membr. Sci. 2016, 503, 177–187. [CrossRef]
12. Regula, C.; Carretier, E.; Wyart, Y.; Gésan-Guiziou, G.; Vincent, A.; Boudot, D.; Moulin, P. Chemical cleaning/disinfection and
ageing of organic UF membranes: A review. Water Res. 2014, 56, 325–365. [CrossRef]
13. Zhang, Y.; Wang, J.; Gao, F.; Chen, Y.; Zhang, H. A comparison study: The different impacts of sodium hypochlorite on PVDF and
PSF ultrafiltration (UF) membranes. Water Res. 2017, 109, 227–236. [CrossRef]
14. You, S.-J.; Damodar, R.A.; Hou, S.-C. Degradation of Reactive Black 5 dye using anaerobic/aerobic membrane bioreactor (MBR)
and photochemical membrane reactor. J. Hazard. Mater. 2010, 177, 1112–1118. [CrossRef]
15. Miyoshi, T.; Nguyen, T.P.; Tsumuraya, T.; Tanaka, H.; Morita, T.; Itokawa, H.; Hashimoto, T. Energy reduction of a submerged
membrane bioreactor using a polytetrafluoroethylene (PTFE) hollow-fiber membrane. Front. Environ. Sci. Eng. 2018, 12, 1.
[CrossRef]
16. Meng, F.; Zhang, S.; Oh, Y.; Zhou, Z.; Shin, H.-S.; Chae, S.-R. Fouling in membrane bioreactors: An updated review. Water Res.
2017, 114, 151–180. [CrossRef]
17. Li, K.; Su, Q.; Li, S.; Wen, G.; Huang, T. Aging of PVDF and PES ultrafiltration membranes by sodium hypochlorite: Effect of
solution pH. J. Environ. Sci. 2021, 104, 444–455. [CrossRef]
18. Abdullah, S.Z.; Bérubé, P.R. Assessing the effects of sodium hypochlorite exposure on the characteristics of PVDF based
membranes. Water Res. 2013, 47, 5392–5399. [CrossRef]
Membranes 2022, 12, 704 13 of 13

19. Abdullah, S.Z.; Bérubé, P.R. Filtration and cleaning performances of PVDF membranes aged with exposure to sodium hypochlorite.
Sep. Purif. Technol. 2018, 195, 253–259. [CrossRef]
20. Puspitasari, V.; Granville, A.; Le-Clech, P.; Chen, V. Cleaning and ageing effect of sodium hypochlorite on polyvinylidene fluoride
(PVDF) membrane. Sep. Purif. Technol. 2010, 72, 301–308. [CrossRef]
21. Lebron, Y.A.R.; Moreira, V.R.; da Costa, P.R.; Alkmin, A.R.; Neta, L.S.D.F.; Cerqueira, A.C.; Amaral, M.C.S. Chemical cleaning
procedures on permeability recovery and lifespan of MBR membranes treating petroleum refinery wastewater: From bench- to
pilot-scale applications. J. Water Process. Eng. 2021, 44, 102411. [CrossRef]
22. Bagheri, M.; Mirbagheri, S.A. Critical review of fouling mitigation strategies in membrane bioreactors treating water and
wastewater. Bioresour. Technol. 2018, 258, 318–334. [CrossRef]
23. Qu, F.; Yang, Z.; Li, X.; Yu, H.; Pan, Z.; Fan, G.; He, J.; Rong, H. Membrane fouling control by UV/persulfate in tertiary wastewater
treatment with ultrafiltration: A comparison with UV/hydroperoxide and role of free radicals. Sep. Purif. Technol. 2020,
257, 117877. [CrossRef]
24. Yu, H.; Du, C.; Qu, F.; He, J.; Rong, H. Efficient biostimulants for bacterial quorum quenching to control fouling in MBR.
Chemosphere 2021, 286, 131689. [CrossRef]
25. Tanis-Kanbur, M.B.; Peinador, R.I.; Calvo, J.I.; Hernández, A.; Chew, J.W. Porosimetric membrane characterization techniques: A
review. J. Membr. Sci. 2021, 619, 118750. [CrossRef]
26. Li, B.; Ke, X.-X.; Yuan, Z.-H.; Zhong, L.-B.; Zhao, Q.-B.; Zheng, Y.-M. High performance electrospun thin-film composite
forward osmosis membrane by tailoring polyamide active layer with polydopamine interlayer for desulfulrization wastewater
desalination. Desalination 2022, 534, 115781. [CrossRef]
27. Liu, J.; Cui, H.; Zhang, T.; Liu, X.; Wang, L. Application of the quorum sensing inhibitor to improve ARGs removal by membrane-
based household drinking water treatment process. Sep. Purif. Technol. 2021, 285, 120352. [CrossRef]
28. Yan, Z.; Lu, Z.; Chen, X.; Jiang, Y.; Huang, Z.; Liu, L.; Fan, G.; Chang, H.; Qu, F.; Liang, H. Membrane distillation treatment of
landfill leachate: Characteristics and mechanism of membrane fouling. Sep. Purif. Technol. 2022, 289, 289. [CrossRef]
29. Wang, S.; Li, J.; Suo, J.; Luo, T. Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation
treatment. Appl. Surf. Sci. 2010, 256, 2293–2298. [CrossRef]
30. Fu, C.; Liu, S.; Gong, T.; Gu, A.; Yu, Z. Investigation on surface structure of potassium permanganate/nitric acid treated
poly(tetrafluoroethylene). Appl. Surf. Sci. 2014, 317, 771–775. [CrossRef]
31. Yang, L.; Wei, J.F.; Zhao, K.Y.; Luo, Z.A. Preparation of a Hydrophilic PVDF Membranes by Electron Beam Induced Grafting
Polymerization of Acrylic Acid. Adv. Mater. Res. 2013, 625, 273–276. [CrossRef]
32. Zhang, M.; Nguyen, Q.T.; Ping, Z. Hydrophilic modification of poly (vinylidene fluoride) microporous membrane. J. Membr. Sci.
2009, 327, 78–86. [CrossRef]
33. Cai, J.; Jin, T.; Kou, J.; Zou, S.; Xiao, J.; Meng, Q. Lucas–Washburn Equation-Based Modeling of Capillary-Driven Flow in Porous
Systems. Langmuir 2021, 37, 1623–1636. [CrossRef]
34. Xiao, K.; Sun, J.; Mo, Y.; Fang, Z.; Liang, P.; Huang, X.; Ma, J.; Ma, B. Effect of membrane pore morphology on microfiltration
organic fouling: PTFE/PVDF blend membranes compared with PVDF membranes. Desalination 2014, 343, 217–225. [CrossRef]
35. Rabuni, M.; Sulaiman, N.N.; Aroua, M.; Chee, C.Y.; Hashim, N.A. Impact of in situ physical and chemical cleaning on PVDF
membrane properties and performances. Chem. Eng. Sci. 2015, 122, 426–435. [CrossRef]
36. Ren, L.; Yu, S.; Yang, H.; Li, L.; Cai, L.; Xia, Q.; Shi, Z.; Liu, G. Chemical cleaning reagent of sodium hypochlorite eroding
polyvinylidene fluoride ultrafiltration membranes: Aging pathway, performance decay and molecular mechanism. J. Membr. Sci.
2021, 625, 119141. [CrossRef]
37. Wu, Q.; Zhang, X.; Cao, G. Impacts of sodium hydroxide and sodium hypochlorite aging on polyvinylidene fluoride membranes
fabricated with different methods. J. Environ. Sci. 2018, 67, 294–308. [CrossRef]
38. Hanafi, Y.; Szymczyk, A.; Rabiller-Baudry, M.; Baddari, K. Degradation of Poly(Ether Sulfone)/Polyvinylpyrrolidone Membranes
by Sodium Hypochlorite: Insight from Advanced Electrokinetic Characterizations. Environ. Sci. Technol. 2014, 48, 13419–13426.
[CrossRef]