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Preparation and characterization of the tolerance

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to acid/alkaline and anti-oil-fouling of regenerated

Cite this: RSC Adv., 2016, 6, 114750
cellulose membranes for oil–water separation
Wanfa Zhang, Xu Chen, Jiefeng Pan, Congjie Gao and Jiangnan Shen*

Received 24th July 2016
Accepted 29th November 2016
DOI: 10.1039/c6ra18766h
www.rsc.org/advances
Novel regenerated cellulose (RC) membranes were fabricated using an immersion precipitation phase
inversion method from five non-derivative solvents (NaOH/urea/H2O, NaOH/thiourea/H2O, LiOH/urea/
H2O, NaOH/urea/thiourea/H2O and LiOH/urea/thiourea/H2O) for oil–water separation. The prepared RC
membranes exhibited a similar asymmetric and reticulated pore structure, with a pore diameter ranging
from 12.77 to 17.09 nm, which is similar to typical ultrafiltration membranes. The biggest pore diameter
was obtained using a NaOH/urea/H2O solvent and the best mechanical properties were obtained using
a LiOH/urea/H2O solvent, which indicated that by using different mixed solvents, different pore sizes and
mechanical properties can be obtained for fabricated cellulose membranes. Measurements of the flux
and the rejection using edible oil/water in this study showed that our prepared membranes possessed
excellent oil retention ratios of up to 98%; meanwhile the water flux recovery ratios were around 90%
through simple water flushing. Besides, after immersion in strong acid/alkaline solution for a week, the
pure water flux (J), dimensions and weight showed no obvious change, and there was no change in
filtration performance at room temperature with a pH from 1 to 14, indicating the advantage of high
tolerance to acid/alkaline.

excellent fouling resistance properties due to their high

1. Introduction
With the rapid growth of industry and the wide application of
oil, large amounts of oily wastewater are becoming an inevitable
challenge to the world; not only bringing many toxic
compounds to water, but also threatening the ecological envi-
ronment, and even human beings.1,2 In this context, different
oil–water separation technologies have emerged, such as
chemical emulsication, pH adjustment, gravity settling,
centrifugal settling, heat treatment, membrane ltration, etc.,
each with advantages and disadvantages.3–5 Among these,
membrane technology has proved to be one of the best strate-
gies, possessing higher oil removal efficiency, lower energy
costs, and smaller space requirements, without additives and
hence providing a reduction in environmental pollution.6 As the
core component, membranes play an important role in sepa-
ration. Many studies have been widely developed for oil/water
separation with different membranes.7–9 However, membrane
fouling is a key problem affecting the economic and techno-
logical viability of the membrane separation process. As one of
the most promising candidates, cellulose membranes exhibit
not only excellent oil/water separation selectivity, but also
Center for Membrane Separation and Water Science & Technology, Ocean College,
Zhejiang University of Technology, Hangzhou 310014, China. E-mail: shenjn@zjut.
edu.cn
hydrophilicity.10
Cellulose, a renewable chemical resource, is considered as
one of the most abundant organic polymers on the earth. It has
attracted much attention due to its outstanding properties,
such as excellent mechanical strength, biodegradability, high
hydrophilicity, and thermal and chemical stability. Therefore, it
is a desirable material source in a future biomaterial-based and
sustainable economy.11–13 However, cellulose applications are
limited because it is very difficult to dissolve in some conven-
tional solvents and form into the desired shape.14 The reasons
for this are the strong intra-molecular and inter-molecular
hydrogen bonds between cellulose chains.13 Traditionally,
cellulose is used to produce cellulose derivatives, such as
cellulose acetate (CA) and cellulose nitrate (CN), which damages
its ability to endure severe acid, alkaline and organic solvents,
as well as causing serious environmental problems. Conse-
quently, cellulose solvents have a profound effect on the utili-
zation of cellulose resources.
Recently, solvents that can dissolve cellulose have been
established, including N-methylmorpholine-N-oxide (NMMO),
DMAc/LiCl and ionic liquids, however the cost is too high.15–18
Nowadays, several economical and practical mixed solvents
have been developed, including NaOH/urea/H2O,13,19–28 NaOH/
thiourea/H2O,29–33 LiOH/urea/H2O,34–40 NaOH/urea/thiourea/
H2O41–44 and LiOH/urea/thiourea/H2O.45,46 These non-derivative
solvents can dissolve cellulose below
10  C, which makes

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them easy to operate. The dissolution of cellulose at low
temperature is a fast dynamic self-assembly process between
solvent molecules and cellulose macromolecules.47 The disso-
lution mechanism of cellulose in solvents at low temperature
consists of two steps: (1) NaOH (or LiOH) “hydrates” are
attracted to cellulose chains through the formation of new
hydrogen-bonded networks, and are relatively stable, existing at
low temperatures; and (2) the urea (or thiourea, or urea and
thiourea) hydrates act as a shell, surrounding the NaOH (or
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LiOH) hydrogen-bonded cellulose to form an inclusion complex
(IC) with a sheath-like structure, and dissolve the cellulose.32,40,47
The mixed solvents used in the whole process are
environmentally-friendly; meanwhile, the dissolution process is
very fast, and a transparent solution is obtained in only a few
minutes.48 Regenerated cellulose solutions have been success-
fully prepared using the mixed solvent mentioned above, and
parts of them have been used for membrane preparation.20,35,49
In this work, a series of regenerated cellulose membranes
were prepared via a solution casting method using mixed
solvents. The membrane performance for oil–water separation
and its tolerance to acidic and alkaline (pH 1 and 14) conditions
was also studied. In addition, the morphology, and physical and
mechanical properties of the regenerated membranes were
investigated in detail. We hope to provide some useful infor-
mation on the structure of cellulose membranes from these
cellulose solvents at low temperature, and to promote the
further application of RC membranes.
2. Experimental
2.1 Materials
The cellulose (cotton pulp) was supplied by Shandong Silver
Hawk Chemical Fiber Co., Ltd (Gaomi, China) and the average
degree of polymerization (DP) was 600. It was dried at 70  C for
24 h before use. Bovine serum albumin (BSA) with a MW of
67 000 Da was purchased from Aladdin. Edible oil for the
preparation of an oil–water emulsion was supplied by Shanghai
Yi Hai Kerry Oil Co., Ltd (Pudong, China). All other chemical
reagents of analytical grade were purchased from commercial
sources in China.
2.2 Preparation of regenerated cellulose membranes
Five different cellulose directed solvents were employed to
dissolve the above mentioned cotton pulp. Firstly, aqueous
solutions of 7 wt% NaOH/12 wt% urea,20–22,24 9.5 wt% NaOH/4.5
wt% thiourea,31,32 5 wt% LiOH/12 wt% urea,34,35 4.6 wt% LiOH/
10 wt% urea/4.5 wt% thiourea,41–44 and 8 wt% NaOH/8 wt%
urea/6.5 wt% thiourea45,46 were precooled to
12  C in a freezer.
Then, a certain amount of cellulose was added immediately into
a solution and it was stirred vigorously for 5 min at ambient
temperature, and a transparent solution was obtained con-
taining 4 wt% cellulose. Aer that, the transparent cellulose
solution was centrifuged at 8000 rpm for 10 min at 10  C to
remove the slightly insoluble residuals and to degas the solu-
tion. The cellulose solution was immediately cast on a glass
plate to a given thickness of 360 mm and was then immersed
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into a 5 wt% H2SO4 coagulation bath to coagulate and regen-
erate for 5 min at 20  C, and the solutions were coded as RC-NU,
RC-NT, RC-LU, RC-LTU and RC-NTU, respectively. The resulting
RC membranes were washed with a large amount of running
water and deionized water until they reached pH ¼ 7, and they
were nally immersed into deionized water for the
characterization.
2.3 Characterization
2.3.1 X-ray diffraction (XRD). RC membranes were dried at
70  C for 6 h in a vacuum oven and were then ground into
powder. Samples were tested using a PANalytical (Netherlands)
X'Pert PRO, for X-ray diffraction (XRD) analysis. The X-ray
source is CuKa radiation (l ¼ 0.154056 nm), at a voltage of 40
kV, and a current of 40 mA, using as the detector an X'Celerator
super detector, over a 2q range from 5 to 50 degrees. The crys-
tallinity Xc (%) of the cotton pulp and RC membranes was
calculated using the following relationship:
Sc
Xc % ¼  100% (1)
Sc þ Sa
where Sc and Sa are the areas of the crystal and amorphous
diffraction peaks of the samples, respectively.
2.3.2 X-ray photo-electron spectroscopy (XPS). The N
content of the residual urea (or thiourea, or urea and thiourea)
in the cellulose membranes was measured with an elemental
analyser (XPS, Kratos AXIS Ultra DLD, Japan).
2.3.3 Scanning electron microscopy (SEM). The
morphology of the RC membranes was investigated using
a Hitachi S-4700(II) SEM operating at an acceleration voltage of
5 kV. The prepared RC membranes were frozen in liquid
nitrogen, and immediately snapped and sputtered with gold,
and then the morphology of the RC membranes was observed
and photographed.
2.3.4 Mechanical properties. The tensile strength (sb) and
elongation at break (3) of the membranes in both dry and wet
states were measured using a CTM2050 (Xin Qiang instrument
manufacturing Shanghai Co., Ltd) instrument at a strain rate of
5 mm min
1 at room temperature. A gauge length of 30 mm was
used. The specimens were cut into strips of 100 mm  10 mm.
The wet membranes were measured immediately aer soaking
in water for 30 min. The experiment was repeated at least three
times and average values were taken.
2.3.5 Filtration experiment. Water permeability (J)
measurements of the wet membranes were conducted in
a cross-ow manner and were carried out using miniature
ultraltration equipment at room temperature. All the
membrane samples were pre-compacted under a pressure of
0.2 MPa for 30 min in order to get steady ltration and were
tested at 0.1 MPa pressure. Aer that, an oil-in-water emulsion
containing edible oil at 800 mg L
1 in deionized water was used
to test the separation performance of the membrane. The oil-in-
water emulsion was generated through mixing edible oil with
water at over 3000 rpm for 30 min, which obtained a stable and
reproducible emulsion. The pH of the oily wastewater was
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adjusted using NaOH and H2SO4. The J value was calculated J2

FFR% ¼  100% (7)
using the following equation J1
V
J¼ (2)
St The ux decline ratio (FDR) was calculated using eqn (8):
and the permeability coefficient (P) was calculated using the

J2
following equation FDR% ¼ 1
 100% (8)
J1
J
P¼ (3) where J1 is the pure water ux of the pristine membrane and J2
DP
is the pure water ux of the cleaned membrane aer oil-in-water
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where J (L h
1 m
2) is the permeate ux, t (h) is the time, V (L) is emulsion rejection experiments.
the permeated volume of water (or solution) for a given time, S
(m2) is the effective surface area of the membrane, P (L h
1 m
2
MPa
1) is the permeability coefficient, and DP (MPa) is the 3. Results and discussion
operating pressure.
3.1 Structure and morphology of the RC membranes
Solute concentration in the feed and permeated solutions
was determined using ultraviolet visible light spectroscopy (UV- The crystal structure of a cellulose membrane was usually
Vis) methods. The rejection of BSA or oil-in-water emulsion was closely related to its formation conditions and can reect the
dened through: mechanical performance of the membrane. Fig. 1 shows the

 crystalline structure of the RC membranes and cotton pulp. The
Cp
R¼ 1
 100% (4) RC membranes displayed three typical diffraction peaks at 2q ¼
Cf 0), (100) and
12.1 , 19.9 and 21.7 , which correspond to the (11
26,30
where Cp and Cf are the concentrations of the permeate and the (200) planes of cellulose II, respectively. These peaks were
feed, respectively. different from the three main peaks of the cotton pulp, whose
The porosity (Pr) of the RC membranes was calculated using special characteristic peaks at 2q ¼ 14.9 , 16.6 , 22.8 were
eqn (5):50 assigned to the (11 0), (110), and (200) planes of cellulose I,
 14
respectively. The XRD results indicate clearly that cellulose I
ðWw
Wd Þ rH2 O
Pr ¼   100% (5) (cotton pulp) is thoroughly converted to cellulose II (regen-
ðWw
Wd Þ rH2 O þ Ww =rc
erated cellulose) through the dissolution and regeneration
where Pr is the porosity of the wet membrane, Ww, and Wd are processes. Furthermore, the crystallinity of all the samples was
the wet and the dry membrane weights respectively, rH2O calculated based on the area under the curves of the diffraction
(0.998 g cm
3) is the density of water, and rc (1.528 g cm
3) is pattern (see eqn (1)) and this is shown in Table 1. The Xc (%)
the density of cellulose. values of all the RC membranes (32.73–45.32%) are lower than
The mean pore radius, rf (m), was evaluated by means of the that of cotton pulp (67.44%), suggesting that the crystal struc-
water-ow-rate method, using eqn (6):51 ture of the cotton pulp has been destroyed and reconstructed.
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Fig. 2 shows the whole XPS spectra of ve prepared membranes.
8hH2 OJL It is worth noting that there is no nitrogen element (no N peaks
rf ¼ (6)
Pr DP are present in Fig. 2) existing on the surface of the membranes,
which further suggests that residual urea (or thiourea, or urea
where rf (m) is the mean pore radius of the RC membrane, hH2O
and thiourea) in the membrane has been completely eluted
(N s m
2) is the viscosity of water, J (m3 m
2 s
1) is the pure
through water ushing.
water ux, L (m) is the thickness of the wet membrane, Pr is the
porosity of the wet membrane, and DP (Pa) is the trans-
membrane pressure.
The RC membrane was soaked in sulfuric acid aqueous
solution with a pH of 1 and sodium hydroxide aqueous solution
with a pH of 14, respectively, for a week at room temperature to
evaluate the tolerance to acid and alkaline conditions. The size
and distribution of emulsied oil droplets were measured using
a Malvern Zetasizer 3000 HAS particle size analyzer.
The antifouling properties of the RC membranes were eval-
uated using water–oil–water three stage ltration processes.
Aer oil-in-water emulsion rejection experiments, the
membranes were ushed with deionized water for 30 min, to
clean them. Then the pure water ux of the cleaned membranes
was measured at 0.1 MPa pressure. The ux recovery ratio (FRR)
was calculated using eqn (7):52
Fig. 1 XRD patterns of the RC membranes and cotton pulp.

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Table 1 Porosity (Pr), average pore size (2rf), crystallinity (Xc), and wet Fig. 4 shows SEM images of the RC membranes. All the
membrane thickness (L) for various regenerated cellulose membranes fabricated membranes display a similar asymmetric structure
and cotton pulp
and interconnected networks. The results indicate that the
Sample 2rf (nm) Pr% L (mm) Xc% porous structure of the membrane is well preserved through the
freeze-drying method. The porous structure of the membrane
Cotton pulp — — — 67.44 was ascribed to phase separation of the cellulose solution
RC-NU 15.55 91.46  0.49 0.171 45.32 during regeneration in 5% H2SO4 aqueous solution. When the
RC-NT 13.97 91.11  0.82 0.169 42.60
RC-LU 12.77 90.64  0.20 0.161 32.73
glass plate for casting the cellulose solution was immersed into
RC-LTU 17.09 91.84  0.42 0.183 37.21 the coagulation bath, diffusion between non-solvent and
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RC-NTU 15.21 90.39  0.06 0.180 33.17 solvent occurred. With a large amount of non-solvent diffusion
in the casting solution, polymer-rich and solvent-rich regions
were formed, and the solvent-rich regions contribute to the
formation of the pores.21 Simultaneously, from the cross-section
of the RC-LTU membrane, we can see the pore size near the free

Fig. 2 XPS whole spectra of the RC membranes.

In this study, ve kinds of regenerated cellulose (RC)

membranes were successfully fabricated using different mixed
solvents, but the same structure was exhibited from a macro-
scopic perspective. To minimize changes to the structure of the
membrane in the wet state, freeze-drying techniques were
adopted to obtain the dry membrane (
50  C, 2 Pa for 12 h).
Here, as an example, the RC-LTU membrane (diameter, 47 mm)
in the wet state and dry state (freeze-drying) is shown in Fig. 3.
Clearly, the dry or wet state of the RC membrane has
a tremendous inuence on the transparency; it exhibits
complete transparency under wet conditions, but seems like
a piece of white paper under dry condition. That is attributed to
different llers in the pores of the membrane under wet or dry
conditions. In wet conditions, the porous membrane (as shown
in Fig. 3a) is lled with water, which has a much lower refractive
index compared with air, so the membrane exhibits a trans-
parent state.

Fig. 4 SEM images of the RC membranes: (a–c) RC-NU, (d–f) RC-NT,

(g–i) RC-LU, (j–l) RC-LTU, and (m–o) RC-NTU; (a, d, g, j and m) the
free surface (in contact with the coagulant), and (b, e, h, k and n) the
back surface (in contact with glass); (c, f, i, l and o) a cross-section; and
Fig. 3 Digital photos of an RC membrane: (a) wet state; and (b) dry (p–r) a cross-section of the RC-LTU membrane: (p), near the free
state. surface; (q), the middle section; and (r), near the back surface.

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surface (in contact with the coagulant) is larger than that near
the back surface (in contact with glass) from the SEM images,
and the pore size was gradually reduced from the free surface to
the back surface. This could be explained in that coagulant
diffusion was much faster on the free surface than on the back
surface. As listed in Table 1, the pore diameter (2rf) ranges from
12.77 to 17.09 nm for different RC membranes, measured using
the water-ow-rate method, and the porosity (Pr) was very high,
between 90% and 92%, due to the excellent hydrophilicity of
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cellulose. The results indicate that cellulose membranes with
different pore sizes can be obtained through using different
mixed solvents.
3.2 Mechanical properties
The mechanical properties of membranes, including tensile
strength (sb) and elongation at break (3), are important
parameters in relation to their application in oil/water separa-
tion processes. Fig. 5 displays sb and 3 for the RC membranes
prepared from the different mixed solvents. It is clear that the sb
and 3 values for both the dry and wet prepared RC membranes
decrease with a decrease in the membrane crystallinity (shown
in Table 1). The RC-LU membrane prepared from a 5 wt% LiOH/
12 wt% urea system exhibits lower mechanical properties than
the others. For the ternary system (7 wt% NaOH/12 wt% urea,
9.5 wt% NaOH/4.5 wt% thiourea, 5 wt% LiOH/12 wt% urea), the
reason could be the fact that the LiOH/urea aqueous solvent has
Fig. 5 The tensile strength (sb) and elongation at break (3) of the five
prepared membranes under dry (a) and wet (b) conditions.
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stronger cellulose solubility than the NaOH/urea aqueous
solvent and NaOH/thiourea aqueous solvent.40 The results
indicate that cellulose membranes with different mechanical
properties can be obtained by using different mixed solvents.
The tensile strengths of all the membranes in the dry or wet
state were relatively low, due to the low degree of polymerization
of cellulose (DP 600) and low concentration of casting solution
(4 wt%) under the effective operating pressure (below 0.2 MPa),
as shown in part 3.3.
3.3 Permeation and rejection performance
In order to evaluate the permeation and rejection performances
of our prepared RC membranes, BSA rejection was taken as an
example. The experimental results, including water ux and
BSA rejection, are depicted in Fig. 6a. The pure water ux values
of the RC membranes are between 11.6 and 18.5 L h
1 m
2.
Interestingly, the pure water ux decreases with a decrease in
the crystallinity of the membranes, which is in contrast with
Table 1, for the RC membranes (RC-NU, RC-NT, and RC-LU)
fabricated in a three component solvent system. That is to
say, for a certain concentration of cellulose, the stronger the
dissolution system for membrane preparation, the smaller the
pore size of the membrane structure. The Xc value for RC-LU
Fig. 6 (a) Pure water flux and BSA rejection using the RC membranes;
and (b) pure water flux of the RC-LTU membrane under different
operating pressures.
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Table 2 RC membrane tolerance to acidic and alkaline conditions

Ja SA/SBb WA/WBc
Conditions pH (L h
1 m
2) (%) (%)

Untreated 7 18.5 100 100

Sulfuric acid 1 18.3 98.6 98.5
treatment
Sodium hydroxide 14 18.4 98.3 98.1
treatment
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a
Pure water ux. b Area of the membrane aer and before treatment
under acidic or alkaline conditions, respectively. c Weight of the
membrane aer and before treatment under acidic or alkaline
conditions, respectively.

(32.73%) is relatively close to the value for RC-NTU (33.17%),

but there is an obvious gap in the pure water ux between them;
and RC-LTU possesses the highest ux of 18.5 L h
1 m
2 with
an Xc value of only 37.21%. The reason is that the pores formed
by the four component system are larger than in the three
component system, as conrmed in Fig. 4. The permeate ux
variation under different operating pressure conditions was
also evaluated, as shown in Fig. 6b. With an increase in the
operating pressure, rstly, the permeate ux of the RC-LTU
membrane increased gradually, and then the permeate ux
gradually stabilized aer the operating pressure increased to
0.18 MPa. It is implied that the networked pores of the RC
membrane undergo a continuous compression process, which
reduces the porosity and increases the ux resistance to some
extent with an increase in the operating pressure. Therefore, all
the RC membranes were pre-compacted at 0.2 MPa for 30 min
before testing the ux.

3.4 Tolerance to acid and alkaline conditions

Long term alkaline and acid stability, for adapting to different pH
values of operating environments, is one of the anticipated
properties for membrane application to oil/water separation. As
a representative of the RC membranes, only the RC-LTU
membrane was tested, due to similar chemical properties across
all samples. In this study, the performance losses (J, S and W) were
evaluated aer immersion in a solution with a pH value of 1 and
14, and recorded one week later at room temperature. Table 2 Fig. 7 Size distribution of emulsified oil droplets in oil-in-water
demonstrates that the RC-LTU membrane exhibits only a slight emulsions with different pH values: (a) pH ¼ 1; (b) pH ¼ 7; (c) pH ¼ 14.
degradation in performance, including pure water ux, and area
or weight aer treatment. This implies that the membrane is
stable under both alkaline and acid conditions. droplet size is as small as 0.5 mm. Meanwhile, a similar
phenomenon occurs in the emulsions with different pH values
3.5 Characterization of oil-in-water emulsions (pH ¼ 1, 7 and 14), due to the excellent resistance to acid and
alkaline conditions.
Fig. 7 indicates the size distribution of emulsied oil droplets in
oil-in water emulsions with a pH of 1, 7 or 14. Digital photos are
depicted in Fig. 8. It can be seen that the sizes of oil droplets 3.6 Oil–water separation performance and anti-oil-fouling
range from 0.5 mm to 4 mm, complying with the normal distri- properties
bution law. Aer a separation process using a membrane of RC- Anti-oil-pollution abilities are also very important for oil-in-
LTU or RC-LT, all the solutions present a change from a turbid water emulsion separation, because trace amounts of oil drop-
solution to a clear and transparent one. These excellent sepa- lets can enter into pores of membrane and result in membrane
ration results for oil and water further prove the successful fouling. The RC-LTU and RC-LU membranes were employed to
preparation of oil/water separation membranes, even if the oil evaluate the anti-oil-fouling properties of the RC membranes

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Fig. 8 Digital photos of the rejection results using RC membranes
before and after separation (F: feed emulsion, P: permeate solution):
(a) different RC membranes; (b) the RC-LTU membrane at different
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pHs.
(Fig. 9a). Oil rejection ratios were all above 98%, with the RC-
LTU membrane showing 98.34%, and the RC-LU membrane
99.02%. Particularly, the initial ux of the RC-LTU membrane
was 18.5 L (m2 h)
1 and it dropped to 17.1 L (m2 h)
1 aer the
ltration of the oil-in-water emulsion, while the pure water ux
could recover up to 16.8 L (m2 h)
1 following simple water
ushing, with a ux recovery ratio of 91.0% and a ux decline
ratio of 7.5%. For the RC-LU membrane, the initial ux was
11.6 L (m2 h)
1, which declined to 10.0 L (m2 h)
1 aer oil-in-
water emulsion ltration, while the ux could recover to
10.5 L (m2 h)
1 following simple water ushing with a ux
recovery ratio of 90.3% and a ux decline ratio of 13.6%, which
Fig. 9 Permeate flux, oil-in-water rejection and flux recovery ratio for
the RC membranes; (a) with different RC membranes, and (b) for the
RC-LTU membrane at different pHs.
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revealed the excellent anti-oil-fouling properties of the RC
membranes.
RC membranes in acid, neutral, and alkaline oil-in-water
emulsions, with pH values of 1, 7, and 14, were also employed
to evaluate the anti-oil-fouling properties (Fig. 9b). The initial
ux of the RC-LTU membrane was 18.5 L (m2 h)
1, which
declined to 16.4 L (m2 h)
1, 17.1 L (m2 h)
1, and 15.8 L (m2 h)
1
for oil-in-water emulsion ltration at a pH of 1, 7, and 14,
respectively. The ux could recover to 16.6 L (m2 h)
1, 16.8 L (m2
h)
1, and 16.5 L (m2 h)
1 following simple water ushing, with
a ux recovery ratio of 89.7% at pH 1, 91.0% at pH 7, and 89.1%
at pH 14. Although the RC membrane exhibited a slightly lower
ux recovery ratio at pH 1 and 14, the anti-oil-fouling properties
of the RC membrane were also competitive under a harsh acidic
or basic environment. The rejection ratios of the emulsions at
different pH values were higher than 98% at a pH of 1 (98.08%),
7 (98.31%) and 14 (98.14%), respectively. This further revealed
the excellent anti-oil-fouling properties of the RC membranes.
The above results indicate that the RC membranes have
potential application in the treatment of oily wastewater.
4. Conclusions
Novel regenerated cellulose oil–water separation membranes
were developed using immersion precipitation phase inversion
strategies, with ve kinds of mixed solvent (7 wt% NaOH/12
wt% urea, 9.5 wt% NaOH/4.5 wt% thiourea, 5 wt% LiOH/12
wt% urea, 4.6 wt% LiOH/10 wt% urea/4.5 wt% thiourea, 8
wt% NaOH/8 wt% urea/6.5 wt% thiourea). Their similar struc-
tures and morphologies were conrmed using SEM and X-ray
diffraction. Pore diameters ranging from 12.77 to 17.09 nm,
measured using the water-ow-rate method, indicated that the
RC membranes belong to a typical ultraltration membrane
class. Measurements with an edible oil/water emulsion indi-
cated that the prepared membranes possessed excellent oil
retention ratios of up to 98% and a ux of up to 18.5 L h
1 m
2
under a pressure of 0.1 MPa, with water ux recovery ratios of
around 90% following simple water ushing. Meanwhile, our
membranes also showed excellent stability under acidic and
alkaline conditions with no obvious change in the pure water
ux (J), dimensions and weight aer immersion at different pH
values (pH ¼ 1 or 14) for a week.
Acknowledgements
The research was supported by the National High Technology
Research and Development Program 863 (No. 2015AA030502),
and the Natural Science Foundation of Zhejiang Province (No.
LY16B060013).
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