Chemical Engineering Journal 304 (2016) 882889

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Chemical Engineering Journal

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

Polysulfone/sulfonated polysulfone alloy membranes with an improved

performance in processing mariculture wastewater
Di Song, Jia Xu , Yunpeng Fu, Lina Xu, Baotian Shan
Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao, Shandong 266100, China
College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100, China

h i g h l i g h t s

Hydrophilic SPSf was synthesized and blended into PSf membranes.

Improved hydrophilicity, porosity, charged property.

Improved separation performance in the fouling test (compared the pure PSf membrane).

Much higher permeation flux and stability in real mariculture wastewater treatment.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, hydrophilic sulfonated polysulfone (SPSf) was synthesized via direct sulfonation of polysul-
Received 17 April 2016 fone (PSf) and efficiently implemented as a hydrophilic additive to prepare the polysulfone/sulfonated
Received in revised form 23 June 2016 polysulfone alloy membranes. On a basis of a high compatibility of PSf and SPSf, the effect of SPSf content
Accepted 3 July 2016
in the casting solution on the structure and separation performance of the membranes was investigated.
Available online 4 July 2016
It was demonstrated that the SPSf incorporation could significantly change the hydrophilicity, porosity,
morphology and the charge characteristic of the resulting membranes. Compared the pure PSf mem-
Keywords:
brane, the membrane with SPSf 15% yielded an improved hydrophilicity (contact angle was lowered
Membrane
Ultrafiltration
by 23%), more porous structure and more negatively charged surface. It exhibited a high pure water per-
Polysulfone meability of 2521.6 L/m2h MPa, excellent steady-state flux of 118.0 L/m2h and HA rejection of 86.8%
Sulfonated polysulfone when filtrating 10 mg/L humic acid (HA) solution in dead-end mode under an operating pressure of
Mariculture wastewater 0.08 MPa. In a real treatment of mariculture wastewater for 8 h, this membrane exhibited a significant
improved steady-state permeation flux of 175.7 L/m2h, which was increased by 144% and 26% compared
to those of the homemade and commercial PSf membranes, without any deterioration of the permeate
quality. The current investigation indicated that the PSf/SPSf alloy membranes held a promise for the real
application.
2016 Elsevier B.V. All rights reserved.

1. Introduction wastewater contains mainly organic contaminants in soluble, col-

With increasing demand for seafood and the continuous reduc-
tion of its annual yield, mariculture industry consistently develop
in a more sustainable and more efficient way. Generation of large
quantities of solid waste and wastewater remains a challenge of
the commercial mariculture industry [1]. Because feed and addi-
tive chemicals are added into seawater as a nutrition and disinfec-
tant for the growth of aquaculture during the cultivation process,
Corresponding authors at: Key Laboratory of Marine Chemistry Theory and
Technology, Ministry of Education, Ocean University of China, Qingdao, Shandong
266100, China.
E-mail address: qdxujia@sina.com.cn (J. Xu).
loidal and particulate forms, which has to be treated properly
before discharge to avoid the deterioration of marine ecological
environment such as eutrophication and water pollution in the
coastal areas. The purified wastewater can also be reused as recir-
culated seawater in a large-scale marine aquaculture plant to
achieve zero-liquid-discharge and can efficiently prevent the
breakout of infectious disease.
Nowadays, the wastewater treatment for mariculture industries
has attracted many interests whether from academic or practical
points of view [2,3]. The existing major obstacles involve the com-
plexity of process and operation management, large footprint, low
retention efficiency and high operating cost. In particular, bio-
chemical methods such as conventional activated sludge (CAS),

http://dx.doi.org/10.1016/j.cej.2016.07.009
1385-8947/ 2016 Elsevier B.V. All rights reserved.
 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889
which is considered to be an efficient way for the wastewater
treatment, often fails to treat mariculture wastewater due to the
poor growth of activated sludge at a high salinity (seawater), lead-
ing to poor removal efficiencies of COD and NH3-N [46].
To overcome these challenges, membrane separation has been
proposed as a useful method for the mariculture wastewater treat-
ment to avoid the negative influence of the salinity effect of seawa-
ter [7]. A mineral tubular ultrafiltration (UF) membrane with
molecular weight cut-off (MWCO) of 15 kDa exhibited a flux of
97.7 L/m2h and a protein rejection of 26.0% at 0.4 MPa in process-
ing seafood wastewater [8]. Mameri et al. [9] also investigated the
UF performances of a ZrO2 membrane and a polysulfone (PSf)
membrane in treating seafood wastewater, exhibiting the high
protein rejections more than 70.2%, respectively. However, the
steady-fluxes decreased with the operating time, even lowered to
58 L/m2h after operation of 2 h [9]. It indicated that the mem-
branes suffered a severe membrane fouling due to the contaminant
accumulation on the membrane surface in processing mariculture
wastewater, resulting in a significant decline in the separation per-
formance. Therefore, the membranes with an improved separation
performance and anti-fouling property are urgently required.
Polysulfone (PSf) with high thermal, mechanical and chemical
stabilities [10,11] is now one of the commonly commercial ultrafil-
tration (UF) membrane materials. However, the hydrophobic nat-
ure of PSf makes membrane surface easily suffer from an
undesirable membrane fouling, especially organic fouling and
bio-fouling [12]. Consequently, a great deal of studies has focused
on the hydrophilic modification of membrane surface to improve
the anti-fouling property and separation performance, including
mainly surface grafting [13], surface coating [14] and blending
[15]. Compared to other techniques, blending method was advan-
tageous on the process simplification, easy industrialization and no
damage impact on the substrate.
Recently, membranes with high performance have been pre-
pared by incorporating a certain amount of hydrophilic sulfonated
polymers into the membrane matrix via blending-phase inversion,
involving PSf /sulfonated polysulfone (SPSf) [16], polyethersulfone
(PES)/ SPSf [17,18], PSf/sulfonated poly(ether ketone) (SPEK) [19]
and PSf/sulfonated polyphenylenesulfone (sPPSU) [20]. These
alloyed sulfonated polymers were proved that they not only adjust
the surface hydrophilicity and membrane morphology, but also
significantly enhance the separation performance [21,22] as well
as anti-fouling property [23]. Among the various sulfonated poly-
mers, SPSf is one of the most important hydrophilic sulfonated aro-
matic polymers, which exhibits the unique chemical and physical
properties involving high thermal and oxidation stabilities, adjus-
table hydrophilicity and excellent mechanical property [24,25],
which was usually blended into PSf or PES casting solution to fab-
ricate NF membranes [16,18] and serve as substrate of thin film
composite membranes [26]. Water transport and salt rejection
can be enhanced by the introduction of the hydrophilic SPSf into
the hydrophobic PSf substrates [16,26]. More important, on a basis
of similar dissolve mutually theory, SPSf is characteristic of high
compatibility with PSf due to the quite similar molecular chains
between them, which would facilitate the long-term stability and
durability of membranes. Therefore, we believe that the incorpora-
tion of SPSf in the PSf membrane can adjust the membrane struc-
ture, enhance the membrane hydrophilicity, and thus improve the
UF performance as well as the membrane durability in a real appli-
cation such as mariculture wastewater treatment.
In this work, a homemade water-soluble SPSf was synthesized
via direct sulfonation method using chlorosulfonic acid (CSA) as
sulfonating agent and used as part of membrane materials to fab-
ricate the hydrophilic PSf/SPSf UF membranes via phase inversion
method. The objectives of this study are (1) to investigate the
effects of SPSf content on the membrane formation, structure and
883
separation performance of the resulting PSf/SPSf membranes; (2)
to evaluate the separation performance in treating a model
organic-foulant solution as well as a real mariculture wastewater,
which holds promise for the treatment of mariculture wastewater
through an ultrafiltration process. As a benchmark, a homemade
non-sulfonated PSf membrane and a commercial PSf membrane
were also tested for comparison.
2. Experimental
2.1. Materials
Polysulfone (PSf, Udel P-1700, USA) was dried at 100 C for 24 h
prior to use. Chlorosulfonic acid (HSO3Cl, CSA, 99%) from Xiya
Reagent Research Center and chloroform (CHCl3) from the Iron
Pagoda Reagent were employed to synthesize SPS powders. N-
methyl-2-pyrrolidone (NMP) and polyethylene glycol 400 (PEG-
400) purchased from Sinopharm Chemical Reagent Co. Ltd were
used as the solvent and pore-former in the casting solution, respec-
tively. HA purchased from Sigma (St. Louis, USA) was applied as the
simulated organic foulant. Mariculture wastewater from offshore
fishing grounds was supplied by Huanghai Fisheries Research Insti-
tute (Qingdao, China). The commercial PSf membranes purchased
from Lanjing Membrane Co. Ltd. were used for comparison. Deion-
ized (DI) water used in all experiments was purified using a Milli-
pore water purification system to maintain a minimum resistivity
of 18.0 MX cm.
2.2. SPSf synthesis and characterization
SPSf was synthesized by direct sulfonation method using CSA as
the sulfonating agent similar to that described by Smitha and Tang
et al. [27,28]. Typically, the dried PSf was completely dissolved in
CHCl3 for 14 h at 50 C in a three-neck reaction flask. A certain
amount of CSA in CHCl3 was transferred into a dropper and then
added dropwise to the cooled polymer solution while stirring the
solution vigorously at 0 C. This reaction continued to form a slimy
mixture. Finally, the reaction mixture was poured into a large
amount of frozen ice water to precipitate in the acidic form of SPSf.
The product was filtered and washed with DI water repeatedly
until a neutral pH level and then the resulting SPSf powders were
finally obtained. The chemical structures of PSf and SPSf are illus-
trated in Fig. 1.
Degree of sulfonation (DS) is the average number of sulfonic
acid groups (-SO3H) in per repeating unit of SPSf polymer chain,
and it is often used to calculate the ion exchange capacity (IEC,
meq/g) which is defined as the number of moles of proton per
gram of dry powders [26]. DS and IEC were calculated by the fol-
lowing Eqs. (1) and (2), respectively [25]. The measurement proce-
dure was presented in Supporting Information.
0:442MV
DS  100% 1
W  0:08MV
Fig. 1. Chemical structures of PSf (a) and SPSf (b).
884 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889

1000DS Table 2
IEC 2 Water quality of the mariculture wastewater.
442 81DS
Parameter COD (mg/L) NH3-N (mg/L) pH Conductivity (ms/cm)
where W, V and M are the mass of SPSf (g), concentration of NaOH
Index 4.03 1.02 7.20 59.6
(mol/L) and volume of NaOH (mL) reacted with SPSf, respectively.

2.3. Membrane preparation 2.5. Water transport property and separation performance

The PSf/SPSf blended membranes were prepared via the wet
phase inversion method and the composition of the casting solu-
tions was summarized in Table 1, where the pure PSf casting solu-
tion was the same as our previous study [29]. Casting solutions
with various SPSf contents were prepared at 50 C for 12 h and
then degassed for 24 h to form homogeneous solutions. After-
wards, the homogeneous solution was cast on a clean glass plate
using a casting knife with a gate height of 180 lm at ambient tem-
perature. Then, the casting film was immersed immediately into DI
water at room temperature, which was different with the NF mem-
brane preparation [16,18]. The formed membrane was peeled off
and washed thoroughly with DI water followed by being stored
in DI water prior to use.
2.4. Membrane characterization
Water uptake (WU) property and porosity were measured as
follows. Membrane sample was soaked in DI water for 24 h and
weighed after removing the excess water on the surface using tis-
sue paper. Then the wet sample was dried in a vacuum oven at
40 C for 24 h and weighed again. WU and porosity were calculated
by the following Eqs. (3) and (4).
Pure water permeability (Lp) which is used to characterize the
water transport property was measured using a homemade
cross-flow UF setup with an effective membrane area of 19.63
cm2. The membrane sample was pre-pressurized with DI water
at 0.15 MPa for 2 h until reaching a steady state of permeation.
Four trans-membrane pressures of 0.08, 0.1, 0.12 and 0.14 MPa
were applied to the membrane filtration system [12] and the pure
water flux was measured. Lp, calculated by Eq. (5), was determined
by the average value of the measurements at different transmem-
brane pressures.
Q
Lp 5
AtP
where Q is the quantity of the permeate sample collected over a
period of time (L); t is the time of permeation (h); A is the effective
membrane area for filtration (m2); P is the transmembrane pressure
(MPa).
A dead-end filtration system with humic acid (HA) as a repre-
sentative foulant feed solution [30] was employed to evaluate
the separation performance of the resulting membranes in terms
of permeation flux (J) and HA rejection (R). Each run was lasted
120 min in a constant-pressure (0.08 MPa) mode at room temper-
ature. J and R were calculated from Eqs. (6) and (7).

Ww  Wd Q
WU  100% 3 J 6
Wd At

Cf  Cp
Ww  Wd R  100% 7
Porosity  100% 4 Cf
dAh
where Cf and Cp are the HA concentrations in the feed and perme-
where Ww and Wd are the weights of wet and dry membranes,
ate, respectively, which were determined by a UVvis spectropho-
respectively; d is the density of DI water at 25 C (g/mL); A and h
tometer (UV-2450, Shimadzu, Japan) at the wavelength of 254 nm.
are the surface area (cm2) and the thickness (cm) of the wet mem-
branes, respectively.
2.6. Performance evaluation in treating mariculture wastewater
Hydrophilicity of the membrane surface was determined using
a contact angle analyzer (DSA 100, Kruss, Germany) at room tem-
After reaching steady-state permeation by pre-pressurization
perature. 10 different locations were selected randomly and the
with DI water at 0.15 MPa for 2 h, separation performance of the
average value was calculated and presented. Fourier-transform
resulting membranes was determined by a dead-end filtration sys-
infrared (FTIR) spectroscopy (TENSOR 27, Broker, Germany) with
tem at 0.08 MPa for 8 h during the filtration of mariculture
attenuated total reflectance (ATR) mode and X-ray photoelectron
wastewater. Characteristics of the wastewater were presented in
spectroscopy (XPS, Thermo ESCALAB 250 XI, USA) were performed
Table 2. For comparison, a commercial PSf membrane and a home-
to measure the chemical composition of the resulting PSf/SPSf
made PSf membrane were tested under the same operating condi-
blended membranes. Membrane morphology was visualized by
tions. The separation efficiency was evaluated in terms of the
scanning electron microscopy (SEM, S-4800, Hitachi, Japan) and
removals of CODMn and ammonia nitrogen (NH3-N), which were
the mechanical properties were measured using a universal testing
determined using potassium permanganate method based on
machine (AGS-J-10kN, Shimadzu, Japan). Charge characteristic of
Seawater Quality Standard (National standards of Peoples Repub-
the membrane surface was characterized by the streaming poten-
lic of China GB3097-1997) and the nutrient automatic analyzer (AA
tial using a tangential flow streaming potential setup [30].
3, BRAN + LUEBBE, Germany), respectively. Changes in solution pH
and conductivity were also recorded using pH Meter (YSI Model
Table 1 60) and Conductivity Analyzer (DDS-307 A).
Composition of the casting solutions.

Casting solution (wt%) PSf SPSf PEG-400 Deionized water NMP 3. Results and discussion
PSf 18 8 0.4 73.6
PSf/SPSf-5% 17.1 0.9 8 0.4 73.6 3.1. Characterization of the synthesized SPSf
PSf/SPSf-10% 16.2 1.8 8 0.4 73.6
PSf/SPSf-15% 15.3 2.7 8 0.4 73.6
As shown in Fig. 1, the sulfonic groups introduced in the sul-
PSf/SPSf-20% 14.4 3.6 8 0.4 73.6
fonation are likely localized at the ortho position relative to the
 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889
ether oxygen atom on an aromatic ring of the main chain, which is
attributed to the activation of ortho positions by the electron-
donating oxygen atoms via electron resonance [22]. According to
the Eqs. (1) and (2), DS and IEC of the synthesized SPSf equal to
approximately 30% and 0.60 meq/g, respectively, indicating that
ten repeating units of PSf polymer chain yield three sulfonic acid
groups (SO3H) in average [22,31].
To further verify the success of SPSf synthesis, TGA and FTIR
measurements of PSf and SPSf were conducted and the results
are shown in Fig. 2. In Fig. 2a, TGA curve shows that PSf exhibits
only one major weight loss starting from around 500 C due to
the decomposition of aromatic backbone of PSf, corresponding to
the significant negative peak at approximately 500 C in DTG curve
(Fig. 2a). It also shows the decomposition of aromatic backbone of
PSf is an endothermic reaction. For SPSf, three stages of weight loss
are observed in TGA curve. The initial weight loss appears in the
range of 100200 C due to the desorption of water bonded to
the sulfonic groups although the SPSf sample was dried in oven
overnight, demonstrating the strongly hydrophilic nature of SPSf.
The second stage occurs at the temperature of 200450 C, which
is contributed to the decomposition of SO3H [32], indicating the
existence of SO3H groups in SPSf. The final weight loss is observed
above 500 C which is in agreement with PSf, corresponding to the
decomposition of typical aromatic SPSf. DTG curve also shows
three obvious changes which are corresponding to the weight
losses in TGA curve. In Fig. 2b, FTIR measurements shows that
compared to PSf, SPSf exhibits more predicable absorption peaks
at approximately 3400 cm1 and 1057 cm1, which corresponds
to the OAH bond and S@O bond in the sulfonic acid groups. In
addition, compared to PSf, a new peak appears at about
1680 cm1 for SPSf, which corresponds to the stretching vibration
of benzene rings for the polarity of substituted groups. Further-
more, both the peaks at 1238 and 1166 cm1, ascribed to stretch-
ing vibrations of O@S@O moiety, and the peaks at 1379 and
1407 cm1, ascribed to the benzene rings in PSf are merged into
two relatively broad peaks at about 1230 cm1and 1404 cm1,
respectively. It is related to the substituent of sulfonic acid groups
on benzene ring. These characteristic bands confirm the successful
sulfonation of PSf.
3.2. Characterization of the PSf/SPSf blending membranes
When DI water is used as the non-solvent to induce the phase
inversion, pure SPSf fails to form a free-standing asymmetric mem-
brane in this study because the high hydrophilicity of SPSf leads to
a dramatically slow precipitation rate during the phase inversion.
Therefore, the PSf/SPSf blended membranes are fabricated from
120
100 (a) PSf
Weight (%)
80 SPSf
60 TGA
40
20
DTG
0
Derivative
-1
-2
0 200 400 600 800
0 -1
Temperature ( C)
Fig. 2. TGA, DTG (a) and FTIR spectra (b) of PSf and SPSf.
885
the various casting solutions consisting of PSf with a fixed content
and hydrophilic SPSf with varied contents. Photos of various cast-
ing solutions are shown in Fig. S1. It presents that the casting solu-
tions with a ratio of SPSf to PSf below 20:80 are homogeneous and
transparent due to the high compatibility of PSf and SPSf, which is
contributed to the quite similar polymer chains of SPSf and PSf.
However, with a further increase in the SPSf content, the casting
solution changes turbid (Fig. S1e) and even to separated layers
(Fig. S1f), indicating the low compatibility depending on the dis-
tinct difference in hydrophilicity between PSf and SPSf polymers.
Therefore, the ratios of SPSf to PSf from 0:100 to 20:80 are chosen
for the membrane fabrication.
As shown in Fig. 3, the incorporation of SPSf influences the sur-
face properties of the resulting membranes. A gradual reduction in
water contact angle from 75 to 58 indicates an improvement in
the surface hydrophilicity with an increasing SPSf content from
0% to 15%. Water uptake (WU) of the PSf/SPSf membranes
increases obviously compared to the pure PSf membrane and the
membrane with 15% SPSf yields a highest WU of 50%, which is
about 3.5 times of that of the pure PSf membrane. It can be
explained by the introduction of sulfonic acid groups in the
blended membranes, which can improve the water affinity via
the hydrogen bonds between water molecule and sulfonic acid
group, resulting in an increasing surface hydrophilicity and water
uptake. In addition, membrane porosity goes up first with an
increase in SPSf content (up to 15%) and then declines when SPSf
Fig. 3. Hydrophilic properties of the resulting membranes. (a) PSf, (b) PSf/SPSf-5%,
(c) PSf/SPSf-10%, (d) PSf/SPSf-15%, (e) PSf/SPSf-20%.
PSf SPSf (b)
-1
1407cm -1
1379cm
Transmittance (%)
-1
1238cm
-1
1166cm
-1
1680cm
-1
1404cm
-1
1230cm 1057cm
-1
3600 3000 2400 1800 1200 600
Wavenumber (cm )
886 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889
content is beyond 20%, similar to the tendency of WU, which
depends on the membrane swelling. High hydrophilicity results
in an increase in the membrane swelling, leading to a higher mem-
brane thickness, and an excessive swelling might occur with the
SPSf content of more than 20% to shrink the effective pore volume
so as to lower the membrane porosity. These results demonstrate
that SPSf is indeed incorporated into the membranes and a satis-
factory surface property can be achieved by adjusting the ratio of
SPSf to PSf in the casting solutions.
To further verify the successful incorporation of SPSf in the
membranes, ATR-FTIR and XPS measurements for the PSf/SPS-
15% membrane were conducted and the results are illustrated in
Fig. 4 and Fig. S2. In Fig. 4a, for the PSf/SPSf-15% membrane, a char-
acteristic peak at 1047.8 cm1 is observed due to the stretching
vibrations of the S@O bond in sulfonic acid groups. Compared to
the PSf membrane, the PSf/SPSf-15% membrane exhibits a peak
at approximately 1680.0 cm1, corresponding to the stretching
vibration of benzene rings, whose intensity can be enhanced with
the increasing amount of substituted polar groups and the higher
polarity of substituted groups on the benzene rings [28]. In
Fig. 4b and c, measurements of sulphur element show an obvious
increase in S content in terms of S@O and SAO bonds after SPSf
blending, indicating the existence of sulfonic acid groups in the
PSf/SPS-15% membrane surface.
Effect of the SPSf content on the membrane structure was inves-
tigated using SEM measurements, as shown in Fig. 5. There is no
obvious difference in the top surface morphology, where no dis-
tinct pore structure is observed. However, SPSf content has a sig-
nificant impact on the bottom surface morphology. More porous
structure is obtained with an increase in the SPSf content, which
might be explained by consideration that the improved
hydrophilicity can decrease the solvent exchange rate between
non-solvent (water) and organic solvent (NMP) in the casting film
so as to induce a delayed demixing during the phase inversion
[22,33]. The much greater affinity of SPSf to water makes the poly-
mer dope of PSf/SPSf tolerate a higher water content in the casting
Absorbance
2100
eV Area(%)
S=O 167.8 1127.2
S-O 168.9 579.2
Intensity (a.u.)
172 170 168
Binding energy (eV)
Fig. 4. FTIR spectra (a), XPS spectra of PSf membrane (b) and PSf/SPSf-15% membrane (c).
film and leads to a longer time for the solvent exchange [30,34]. In
addition, delayed demixing favors to not only the more porous
structure but also the higher membrane thickness as expected
[30]. We found that it is the case (Fig. 5ko) and the membrane
becomes thicker with the SPSf content. Moreover, from cross-
sectional SEM images, the finger-like macrovoids tend to be bulkier
and more fully developed, which is also attributed to the delayed
demixing process.
Mechanical property plays an important role in a real applica-
tion of the membrane system, such as cleaning efficiency and life
span of the membranes. Fig. 6a shows the mechanical stress of
the PSf/SPSf blended membranes and it was found that the
mechanical property is lowered with the SPSf content from 0% to
20%. It can be explained that the introduction of the strong polar
sulfonic acid groups into the polymer chains reduces the aggrega-
tive state and expands the polymer matrix, giving rise to the chain
movements so as to make the plastic material more flexible
[35,36].
To evaluate the charge characteristic of the resulting mem-
branes, zeta potentials for the PSf and PSf/PSf-15% membranes
were determined as a function of pH in a tangential flow mode
(independent of the membrane pore size). The results are shown
in Fig. 6b. PSf/SPSf-15% membrane exhibits a negatively charged
property in all the testing range of pH from 3.5 to 6.0 and shows
a much lower zeta potential compared to PSf membrane, ascribing
to the dissociation of sulfonic acid groups in the SPSf-containing
membrane. In addition, the PSf/SPSf-15% membrane shows a slow
decrease in zeta potentials from 21 mV to 25 mV with an ele-
vated pH from 4.0 to 6.0. It might partially depend on the mem-
brane hydrophilicity [30], which leads to an increase in the
swelling layer thickness and thus decreases the Coulomb attrac-
tion for the adsorption of hydroxide ions by increasing the dis-
tance from ion to swelling layer surface. Therefore, for the PSf/
SPSf-15% membrane, zeta potential is retarded by the more hydro-
philic surface and the corresponding plateau curve is shown in
Fig. 6b.
PSf/SPSf-15% PSf (a)
1800 1500 1200 900 600
-1
W avenum ber (cm )
(b) eV Area(%) (c)
S=O 167.8 2891.7
S-O 168.9 2160.2
Intensity (a.u.)
166 172 170 168 166
Binding energy (eV)
 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889 887

Fig. 5. SEM images of the resulting membranes. (a), (f), (k) and (p) PSf; (b, g, l, q) PSf/SPSf-5%; (c, h, m,r) PSf/SPSf-10%; (d, i, n, s) PSf/SPSf-15%; (e, j, o, t) PSf/SPSf-20%.

Fig. 6. Mechanical properties (a) and Zeta potentials (b) of the resulting membranes.
Pure water permeability (L/m hMPa)

3000
3.3. Water transport property of the PSf/SPSf blended membrane
2500
2

Pure water permeability was measured to evaluate the water

transport property of the resulting membranes and the results 2000
are shown in Fig. 7. The membranes apparently tend to be much
1500
more permeable with an increase in SPS content from 0% to 15%.
For example, the membrane with blending 15% SPSf exhibits 3 1000
times higher pure water permeability compared to the pure PSf
membrane. It is attributed to the increasing membrane 500
hydrophilicity and the more porous structure with the SPSf con-
0
tent, as shown in Fig. 3 and Fig. 5. However, a further increase in a b c d e
the SPSf content beyond 15% cannot lead to a higher pure water Membrane type
permeability, which is in agreement with the membrane thickness Fig. 7. Pure water permeability of the resulting membranes. (a)PSf, (b) PSf/SPSf-5%,
and porosity shown in Fig. 3. (c) PSf/SPSf-10%, (d) PSf/SPSf-15%, (e) PSf/SPSf-20%.
888 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889

3.4. Separation performance of the PSf/SPSf blended membrane 3.5. Real application in mariculture wastewater treatment

Filtration experiments in dead-end mode are carried out using Filtration experiments with real mariculture wastewater as feed
10 mg/L HA solution to evaluate the separation performance of were conducted to investigate the separation efficiency of the PSf/
the resulting membranes. As presented in Fig. 8a, the initial perme- SPSf blended membranes, and both homemade and commercial
ation flux is significantly enhanced from 90.0240.0 L/m2h with an PSf membranes were tested under the same operating conditions
increase in SPSf content from 0% to 15%, while there is no signifi- for comparison. For evaluate the stability of membrane perfor-
cant difference in the initial permeation flux when SPSf content mance, the experiment period was prolonged to 8 h. The results
is increased to 20%, similar to the trend of pure water permeability are shown in Fig. 9. It can be seen that the PSf/SPSf-15% membrane
(Fig. 7). With the operating time for each run, a decrease in the per- exhibits the significantly enhanced initial and steady-state perme-
meation flux is observed due to the concentration polarization, HA ation fluxes of 220.0 and 175.7 L/m2h, respectively, which are
adsorption and pore blockage until approaching a relatively steady much higher than the steady-state fluxes of the homemade and
state within 60 min. Although the membrane with SPSf blending commercial PSf membranes (72.0 and 140.1 L/m2h, respectively).
yields a more serious flux decline than the pure PSf membrane dur- It is attributed to the improvement of surface hydrophilicity and
ing the HA filtration, a higher steady-state permeation flux is pore structure of the alloy membranes. Moreover, the relatively
achieved for the PSf/SPSf blended membranes. For example, the long-term filtration experiments demonstrate that the SPSf swel-
steady-state permeation flux of the membrane with blending ling behavior has little impact on the separation performance
15% SPSf grows up 2 times compared to the pure PSf membrane. and durability of the resulting membranes.
The more serious flux decline, which was consistent with the pre- In addition, all the membranes yield the similar permeate qual-
vious literature [37], might ascribe to the much higher initial per- ities. The membranes exhibit a CODMn removal efficiency of above
meation flux in dead-end mode for the PSf/SPSf membrane which 50% and the CODMn in the permeate can meet the Seawater Quality
can bring more foulant to the membrane surface although it yields Standard (GB3097-1997, China, <3.0 mg/L). Meanwhile, the pH
an improved hydrophilicity. In Fig. 8b, although HA rejection ranged in 7.27.3 and salinity ranged in 5559 ms/cm (conductiv-
slightly decreases with an increase in SPSf content due to the more ity) are obtained in the permeate, which shows that the mem-
porous structure formed, all the membranes exhibit HA rejections branes have little impact on the pH and salinity of the
still more than 85%. In consideration of both separation perfor- wastewater, and thus the permeate from the UF membranes can
mance and membrane structure, the PSf/SPSf-15% membrane satisfy the requirement of reuse for the growth of some halophilic
seems appropriate and is applied in a real mariculture wastewater marine organisms. Although NH3-N concentration in the permeate
treatment. is in the range 0.70.8 mg/L, which is not enough to achieve

250 100
(a) (b)

200 90
Rejection (%)
J (L/m h)

150 80
2

100 70
PSf
50 PSf 60 PSf/SPSf-5% PSf/SPSf-10%
PSf/SPSf-5% PSf/SPSf-10% PSf/SPSf-15% PSf/SPSf-20%
0 PSf/SPSf-15% PSf/SPSf-20% 50
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)

Fig. 8. Separation performance of the resulting membranes in filtrating HA solution. (a) Permeation flux and (b) HA rejection.

300 80
COD / NH3-N concentration (mg/L)

H-PSf PSf/SPSf-15% (a) COD (b)

60
Permeation flux (L/m h)

C-PSf NH3-N
250
2

Removal efficiency (%)

40
200 20

150 7 0
4
100 3
2
50
1
0 -80
0 100 200 300 400 500 Feed H-PSf PSf/SPSf-15% C-PSf
Time (min) Membrane type

Fig. 9. Separation performance (8 h) of the membranes in filtrating mariculture wastewater. Permeation flux (a) and concentrations of COD and NH3-N in the permeate with
removal efficiencies (b).
 D. Song et al. / Chemical Engineering Journal 304 (2016) 882889
Seawater Quality Standard (<0.5 mg/L), the removal efficiency of
NH3-N of approximately 25.0% is achieved. It might be explained
considering by the adsorption of ammonium onto the contami-
nants such as colloids and suspended solids in the mariculture
wastewater. According to the low removal efficiency of NH3-N,
another process such as ozone oxidation should be integrated with
the membrane technology, which will show a tremendous poten-
tial in wastewater treatment to meet wastewater recycling
standards.
4. Conclusion
In summary, we fabricated a hydrophilic and negatively
charged polysulfone/sulfonated polysulfone (PSf/SPSf) blended
membrane for the mariculture wastewater treatment. As demon-
strated, the resulting PSf/SPSf membranes exhibit good perfor-
mance including high flux and excellent rejection in the UF
process. For example, a high pure water permeability of 2521.6 L/
m2h MPa, excellent steady-state permeation flux of 118.0 L/m2h
and HA rejection of 86.8% were achieved when filtrating 10 mg/L
humic acid (HA) solution in dead-end mode under an operating
pressure of 0.08 MPa. For the practical mariculture wastewater
treatment, the resulting membrane exhibits a significant improved
steady-state permeation flux of 175.7 L/m2h without any deterio-
ration of the permeate quality. This membrane has the potential
for application in important environmental areas, such as wastew-
ater reclamation, dye purification, drug extraction, and so forth.
Acknowledgment
This work was supported by Shandong Province Key Project
(2014GHY115033), NSFC (No. 21306178), Qingdao applied basic
research project (No. 15-9-1-21-jch) and Fundamental Research
Funds for the Central Universities (No. 201564015).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2016.07.009.
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