Ecotoxicology and Environmental Safety 121 (2015) 73–79

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Ecotoxicology and Environmental Safety

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

Fabrication of zirconia composite membrane by in-situ hydrothermal

technique and its application in separation of methyl orange
R. Vinoth Kumar, Aloke Kumar Ghoshal, G. Pugazhenthi n
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

art ic l e i nf o a b s t r a c t

Article history: The main objective of the work was preparation of zirconia membrane on a low cost ceramic support
Received 2 December 2014 through an in-situ hydrothermal crystallization technique for the separation of methyl orange dye. To
Received in revised form formulate the zirconia film on the ceramic support, hydrothermal reaction mixture was prepared using
4 May 2015
zirconium oxychloride as a zirconia source and ammonia as a precursor. The synthesized zirconia powder
Accepted 6 May 2015
Available online 14 May 2015
was characterized by X-ray diffractometer (XRD), N2 adsorption/desorption isotherms, Thermogravi-
metric analysis (TGA), Fourier transform infrared analysis (FTIR), Energy-dispersive X-ray (EDX) analysis
Keywords: and particle size distribution (PSD) to identify the phases and crystallinity, specific surface area, pore
Zirconia membrane volume and pore size distribution, thermal behavior, chemical composition and size of the particles. The
Methyl orange
porosity, morphological structure and pure water permeability of the prepared zirconia membrane, as
Hydrothermal treatment
well as ceramic support were investigated using the Archimedes’ method, Field emission scanning
Dye removal
electron microscopy (FESEM) and permeability. The specific surface area, pore volume, pore size dis-
tribution of the zirconia powder was found to be 126.58 m2/g, 3.54 nm and 0.3–10 mm, respectively. The
porosity, average pore size and pure water permeability of the zirconia membrane was estimated to be
42%, 0.66 mm and 1.44
10  6 m3/m2 s kPa, respectively. Lastly, the potential of the membrane was in-
vestigated with separation of methyl orange by means of flux and rejection as a function of operating
pressure and feed concentration. The rejection was found to decrease with increasing the operating
pressure and increases with increasing feed concentrations. Moreover, it showed a high ability to reject
methyl orange from aqueous solution with a rejection of 61% and a high permeation flux of
2.28
10  5 m3/m2 s at operating pressure of 68 kPa.
& 2015 Elsevier Inc. All rights reserved.

1. Introduction characteristics. Among several varieties of dyes, methyl orange

(MO) is considered as a model compound for ordinary water so-
The annual global productions of dyes are calculated to be more luble azo dyes, which is extensively utilized in chemical, textile
than ten thousand tons. In that, around 15% quantity is lost during and paper industries. Furthermore it is dangerous to the en-
the industrial processes, such as dyeing, textiles printing and dye vironment (Shiue et al., 2012). The majority of the azo dyes and
manufacturing (Forgacs et al., 2004). These industrial processes their breakdown products are toxic and carcinogenic to animals
utilize several synthetic chemical dyes for a variety of purposes. and humans (Weisburger, 2002). Hence, this effluent is necessary
Textile dyeing is among the most environmentally unfriendly in- to be treated before discharging from the industries. The con-
dustrial processes owing to the large quantities of water de- ventional methods employed for separation of dyes from colored
manded and the strongly colored wastewater produced, polluted wastewater are flocculation/coagulation (Zahrim and Hilal, 2013),
with dyes and other chemical auxiliaries. The highly colored ef- adsorption (Qiao et al., 2009), chemical oxidation (Turgay et al.,
fluents dye streams could pose serious detrimental effects to the 2011) and photocatalytic processes (Velusamy et al., 2014), reac-
environment and thus to human health (Zaghbani et al., 2007; tion with ozone (Sharma et al., 2013) and biological treatment
Jana et al., 2010). Specifically, Azo dyes can be toxic upon de- (Nilesh and Chaudhari, 2006). In flocculation, coagulation and
gradation and this class of dye is widely used in many industries adsorption treatment methods, effluents are converted from the
by virtue of present unique properties and technical liquid state to a solid state and this way creates secondary

n
Corresponding author. Fax: þ 91 361 2582291.
E-mail address: [email protected] (G. Pugazhenthi).

http://dx.doi.org/10.1016/j.ecoenv.2015.05.006
0147-6513/& 2015 Elsevier Inc. All rights reserved.
74 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79

pollution. Chemical techniques such as photocatalytic and reaction 2. Materials and methods
with ozone method need bulk quantity of costly chemicals as well
as generating huge amount of waste slurry. The by-products from 2.1. Chemicals
chemical degradation are also colored and even toxic. Further-
more, biological degradation is inexpensive technique, harmless to Clays (ball clay, feldspar, kaolin, pyrophyllite and quartz) used
the environment and also not generates massive quantities of for synthesis of ceramic support were of mineral grade and ob-
sludge; however it is selective and time taking. Hence it is un- tained in the vicinity (Kanpur, India). Zirconium Oxychloride
suitable for many dyes (Tan et al., 2006). (ZrOCl2  H2O), Calcium Carbonate and Polyvinyl Alcohol (PVA)
Membrane separation process could be ecofriendly and an were supplied by Loba Chemie (Mumbai). Ammonium hydroxide
auspicious alternative for the separation of dyes. The pressure- solution (NH4OH, 25 wt%) and methyl orange (C14H14N3NaO3S)
driven membrane processes, especially reverse osmosis, nanofil- were procured form from Merck (I) Ltd. (Mumbai).
tration, ultrafiltration and microfiltration are being increasingly
utilized in the removal of dyes (Al-Bastaki, 2004; Kim et al., 2005; 2.2. Preparation of zirconia–ceramic composite membrane
Al-Aseeri et al., 2007; Mo et al., 2008). Within these techniques,
The procedure followed for the preparation of ceramic support
ceramic membranes are better than polymeric membranes due to
and its composition were explained in our earlier publication
excellent thermal, chemical and mechanical properties (Jedidi
(Monash and Pugazhenthi, 2011a). The zirconia–ceramic compo-
et al., 2009). However, nanofiltration and reverse osmosis techni-
site membrane was prepared through in-situ hydrothermal
ques are described by higher energy utilization. Therefore lower
synthesis by controlling growth of zirconia particle on the porous
pressure membrane techniques such as microfiltration and ultra-
ceramic support. The reaction mixture for hydrothermal reaction
filtration could be inexpensively more favorable for dye separa-
was prepared by dissolving 5 g of zirconium oxychloride in 100 mL
tion. Besides, ceramic membranes are made up of a composite of water. Then the pH was adjusted to 10.0 with addition of aqu-
formation with an active top layer, which typically decide its se- eous ammonia (25%) under stirring condition at room tempera-
paration characteristics. Mostly the active top layers are made by ture. After that the reaction mixture was stirred vigorously for
inorganic oxides fabricated via the sol–gel method, dip-coating, 5 min, and then transferred to Teflon coated stainless steel auto-
hydrothermal crystallization with a controlled particle size. In- clave reactor (capacity 200 mL) for in-situ hydrothermal crystal-
itially, the research on inorganic membranes was focused to the lization and a prepared porous ceramic support having 43 mm
fabrication of alumina membranes, which is of higher cost and diameter and 4.5 mm thickness was placed inside the reactor. The
used most widely (Yang et al., 1998). Nevertheless, in recent times, reaction mixture was subjected to hydrothermal crystallization at
various other porous membrane materials, such as zirconia, titania 90 °C for 60 h. After that, the membrane was recovered and wa-
and silica were used. Amongst these, zirconia is especially attrac- shed several times with Millipore water and dried at 90 °C for 24 h
tive material for making the ceramic membranes. The excellent followed by calcined at 400 °C for 6 h in air atmosphere.
characteristics of zirconia membrane are elevated chemical stabi-
lity and cleaning actions can be done in the range of 0–14 pH, 2.3. Methods for characterization
superior permeability and higher flux in separation owing to its
specific surface characteristics, and excellent thermal resistance 2.3.1. Characterization of zirconia powder
(Bhave, 1991). As-synthesized zirconia powder was collected from the bottom
In order to improve the flux of the membrane, the hydrophilic of the autoclave reactor. Then, the zirconia powder was washed,
adaptation in microfiltration is an excellent choice, which provides dried and calcined at the same condition adopted for the com-
an enhanced hydrophilic character to the membrane surface (Ko- posite membrane. Precise powder diffraction data of zirconia was
cherginsky et al., 2003). Nano-scale ZrO2, TiO2/Al2O3, Al2O3 and measured on a machine (Bruker AXS D8 advanced) with Cu Kα
SiO2 have been used to enhance the hydrophilic character and it (λ ¼1.5406 Å) radiation. The patterns were obtained in the 2θ
creates the charge on the surface of the membrane (Chang et al., range of 5–75° with a scan speed of 0.05° s  1. N2 adsorption/
2014). Several investigations on zirconia membrane have indicated desorption isotherm was computed at  196 °C in a surface area
its superior performance in the separation due to its special sur- analyzer (make: Beckman-Coulter; model: SA™ 3100). Thermo-
gravimetric (TGA) analysis of the zirconia powder (before calci-
face character (Zhou et al., 2010). These hydrophilic and charged
nation) was carried out in a instrument of Mettler Toledo with
membranes facilitate to attain a higher flux with good separation
model No.TGA/SDTA 851s in flowing nitrogen atmosphere at a
efficiency even though utilizing a realistically larger range of pore
heating rate of 10 °C min  1 from 25 to 900 °C. FTIR spectra were
size membranes. However, the difficulty of modification of ceramic
recorded using a Shimadzu IRAffinity-1 model Spectrometer in the
membranes leads in the way of adding nano-particles uniformly
wavenumber range of 4000–500 cm  1. The particle size dis-
into the porous ceramic membrane without blocking the mem-
tribution (PSD) of the zirconia powder was measured using a
brane pores. Several preparation methods have been developed,
machine Malvern Mastersizer 2000 (APA 5005s model, hydro
such as in situ hydrothermal synthesis, vapor phase transport MU) in wet dispersion mode.
method, secondary growth method for the deposition of nano-
materials on the ceramic matrix (Xu et al., 2004). Amongst these, 2.3.2. Characterization of zirconia ceramic composite membrane
hydrothermal technique has become basic route for the mod- The morphology of the prepared ceramic support and zirconia
ification of membrane surface by the deposition of nanomaterial composite membrane was investigated with an instrument FESEM
(Kalantari et al., 2015). (JEOL JSM-5600LV). Energy-dispersive X-ray (EDX) was carried out
In this present study, an inexpensive zirconia composite using SEM (LEO 1430 VPs Oberkochen, Germany). In order to
membrane on a porous ceramic support has been synthesized. The determine the porosity, the membrane was dried at 120 °C for 3 h
top layer of zirconia is prepared through in-situ hydrothermal and measured the dry weight of the membrane (MD). Then the
crystallization technique by controlling growth of zirconia particle membrane was placed in Millipore water for 24 h. After which, the
on the porous ceramic support. The separation potential of the wet weight (MW) of the membrane was determined after remov-
membrane is investigated with separation of methyl orange var- ing all visible water from the surface of the membrane with tissue
ious operating pressure and feed concentration. paper. Then the membrane was immersed in water, the pore filled
 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79 75

with water saturated weight of the membrane (MA) was measured 3. Results and discussion
(A refers to Archimedes). The porosity of the membrane was es-
timated according to the below expression (Monash and Pug- 3.1. Characterization of zirconia powder
azhenthi, 2011b).
X-ray diffraction analysis of fumed zirconia powder shows the
MW−MD tetragonal phase along with some small peaks of the monoclinic
ε=
MW−MA (1) phase (Fig. 1). The patterns with a wide base line illustrate the
presence of amorphous zirconia. As a whole, zirconia powder is
packed with both amorphous and nano-crystals. Crystallite size of
the zirconia powder is calculated by Debye–Scherrer formula
2.3.3. Pure water permeability and microfiltration of methyl orange
(D ¼Kλ/β cos θ), in which K ( ¼0.90) stands for shape factor, λ
(MO)
(¼0.15406 nm) represents the wave length of X-rays, β is the full
The in-house made dead-end filtration setup with capacity of
width of diffraction peak at half-maximum intensity in radians,
250 ml was used to determine the water flux and pure water and θ is the Bragg angle. The crystallite size of the zirconia is found
permeability presented as supplementary data (see Fig. S1). It to be in the range of 5.54–14.31 nm. The bigger crystal size is due
consists of two parts, a cylindrical top part and a base plate with a to the thermally activated crystal growth. This result is in ac-
provision to keep a membrane. The membrane was placed on a cordance with previous results published in the literature (Wu and
perforated casing and then kept in the bottom compartment. The Cheng, 2000; Etienne et al., 1994; Gestel et al., 2006). N2 adsorp-
upper compartment of the batch cell was pressurized using ni- tion–desorption isotherm is depicted in Fig. 2(a). It clearly re-
trogen gas by setting a desired pressure through regulator at- presents type IV adsorption isotherm with H-2 hysteresis loop
tached with the nitrogen cylinder. The water flux was calculated at according to IUPAC classification and associated with capillary
various applied pressures. At every applied pressure, the collection condensation in the mesopores (Sangwichien et al., 2002). The
of first 50 mL of permeate was disposed and time taken for col- pore size distribution of the zirconia is calculated from desorption
branch of isotherm by BJH model. In Fig. 2(b), the distribution
lection of following 50 mL of permeate was noted for the de-
curve indicates that the most of the pores are present with a size
termination of flux. The following relations were used to calculate
smaller than 10 nm and the sample possesses a relatively narrow
the water flux and pure water permeability.
size distribution. BET surface area and pore diameter are estimated
Q to be 126.58 m2/g, and 3.54 nm, respectively.
JW = = L p ΔP Thermogravimetric analysis is carried out for the as-synthe-
A ΔT (2)
sized zirconia powder (figure not shown). The total weight loss is
where, JW is the water flux (ms  1), Q is the volume of water estimated to be approximately 21%. In general, the weight loss at
permeated (m3), A is the effective membrane area (m2), ΔT is the temperature below 150 °C is owing to elimination of weekly ad-
sampling time (s). LP is water permeability (ms  1 kPa  1) and ΔP is hered water molecule that was absorbed by the sample. The
applied pressure (kPa). weight loss at higher temperature is attributed to removal of
The average pore size was determined using Hagen Poiseuille structural hydroxyl groups. Moreover, the weight loss of the par-
expression assuming that pores are cylindrical in shape (Almandoz ticle after 450 °C is found to be insignificant. This justifies the
et al., 2004; Bowen et al., 1997; Kumar et al., 2015). selection of calcination temperature for the synthesis membrane.
Fig. 3 demonstrates the FTIR spectra of zirconia (both before and
εr 2ΔP after calcination). Before calcination, OH stretching and bending
JW = = L p ΔP band appear at around 3400 and 1600 cm  1, respectively. These
8μτl (3)
bands are related to adsorbed water, and illustrate the [ZrO(OH)2]n

where, ε is the porosity of the membrane, r is the pore radius of H2O polymer structure. A sharp band at 1000 cm  1 describes Zr¼ O
the membrane, l is the pore length, τ is the tortuosity factor and μ group stretching vibration, indicating that Zr¼ O bond is not
is the viscosity of water.
The separation potential of the membrane was evaluated by 50
undertaking the separation tests of methyl orange using the same
setup filled with 100 mL of the feed solution. In order to determine
the permeate flux at fixed operating pressure, initial 10 mL of the 40
collected permeate was disposed and the time needed to collect tetragonal- ZrO2

subsequent 10 mL of permeate was calculated. The observed re-

30
jection was evaluated by the following expression.
Intensity

Cf −CP tetragonal- ZrO2

R= × 100 20
Cf (4) monoclinic- ZrO2

where, R is the observed rejection (%), Cf is the concentration of

the feed solution and Cp is the concentration of the permeate so- 10
lution. After carrying out a preliminary calibration procedure, the
precise concentration of dye was determined by measuring the
absorbance of the dye at a wavelength of 472 nm using a UV–vis 0
spectrophotometer (Spectrascan, UV 2300) (Monash and Pug-
azhenthi, 2014). After every experimental run, the membrane was
10 20 30 40 50 60 70
thoroughly washed with Millipore water, followed by flushing
2θ (Degrees)
with Millipore water at higher pressure to regain the original pure
water flux. Fig. 1. XRD pattern of zirconia powder.
76 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79

9
Before calcination
100

8
Volume adsorbed [cc g (STP) ]

80
-1

Transmittance (a.u.)
7
60

40
16
After calcination

14
20
Adsorption Isotherm
Desorption Isotherm 12
0
0.0 0.2 0.4 0.6 0.8 1.0 10
Relative pressure P/Po

8
4000 3500 3000 2500 2000 1500 1000 500
0.035
Wavenumbers (cm-1)
0.030 Fig. 3. FTIR analysis of zirconia powder.

0.025
d(V P )/d(D P ) (ml/g.nm)

and crack free. Fig. 4(b) shows the deposition of fumed zirconia on
to the surface of the membrane. It indicates that the film of zir-
0.020 conia is deposited on the pore of ceramic support. Hence it can be
concluded that the ziconia is formed on the surface of the mem-
0.015 brane support with smooth consistent surface. In addition, the
pore density of the membrane is estimated from SEM micrographs
0.010 using Image J software. In order to minimize errors of image
analysis, three SEM micrographs are analyzed for each sample. The
0.005 pore density of the ceramic support and zirconia membrane is
found to be 2.34
106 and 3.80
105 pore/mm2, respectively. The
0.000 decreased pore density for the zirconia membrane is due to the
blockage of pores by the formation of zirconia particles on the
10 100 surface of ceramic support.
Pore diameter (nm) Fig. 4(b) (inside) depicts an EDX spectrum, which quantitatively
detects the constituent elements. The spectrum shows Zr peaks
Fig. 2. (a) N2 adsorption–desorption isotherms and (b) BJH pore size distribution of
zirconia. signifying the existence of zirconia on the composite membrane.
Other peaks detected in the EDX spectrum include oxygen, which
also derived from the deposition of ziconia. Fig. 5 depicts the pure
converted into Zr–O bond. The calcined zirconia shows absorption water flux of ceramic support along with zirconia membrane. As
peak around at 800 cm  1, which is typically monoclinic zirconia. Zr– expected water flux increases linearly with an increase of applied
O bonds exhibit bands at 450–520 cm  1 whereas a broad infrared pressure and follows Darcy's law. It is observed that the water flux
band at 520 cm  1 exhibits tetragonal ZrO2 phase (Chandra et al., is lower than that of ceramic support, which is accredited by re-
2010; Wong et al., 2002). The particle size distribution analysis was duction in pore radius on hydrothermal treatment. As a result, the
measured for the synthesized zirconia powder. It is found that the pure water permeability of zirconia membrane reduces resulting
size of the particles is in the ranges of 0.3–10 mm as shown in sup- in lower flux. The pure water permeability (Lp) for support and
plementary data (see Fig. S2). Moreover, the volume median dia- zirconia membrane is found to be 3.63
10  6 and
meter (d0.5) is calculated to be 2.237 mm. 1.44
10  6 m3/m2 s kPa, respectively.
Table S1 (presented as supplementary data) summarizes the
3.2. Characterization of ceramic support and zirconia composite overall properties of the fabricated ceramic support and zirconia
membrane membrane. As stated above, the porosity, water permeability,
mean pore size and pore density of the zirconia membrane is
The porosity of the prepared ceramic support and zirconia decreased (see Table S1), which is obviously due to the in-
composite membrane is measured to be 44%, and 42%, respec- corporation of the zeolite particles on the ceramic support by
tively. The average pore size is estimated to be 0.969 mm and hydrothermal treatment.
0.66 mm for support and composite membrane, respectively. It is
inferred from these values that, the porosity and pore radius of the 3.3. Microfiltration of methyl orange
zirconia membrane are reduced after hydrothermal treatment
owing to the deposition of zirconia particles on the surface of the 3.3.1. Effect of operating pressure
support. Fig. 4(a), illustrates the FESEM image of fabricated sup- The flux and rejection trend of MO solution with different op-
port and it is apparent that the uniform surface is highly porous erating pressures (69–207 kPa) at a fixed concentration
 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79 77

Fig. 4. (a) FESEM image of ceramic support and (b) zirconia–ceramic composite membrane with EDX.

0.0010
Zirconia-ceramic membrane
Ceramic support
0.0008
Water flux (m3/m2s)

0.0006

0.0004

0.0002

0.0000
0 50 100 150 200 250 300 350
Applied pressure (kPa)

Fig. 5. Variation of water flux with applied pressure for support and zirconia
membrane.

(1000 ppm) is shown in Fig. 6(a). The permeate flux increases with
increasing operating pressure, due to the increase of driving force
across the membrane. However, the permeate flux is lesser than
that of pure water flux. This may be due to various aspects such as
adsorption of dye particles on the surface of membrane and pores,
and concentration polarization. The dye particles are settled on the
membrane surface or into the pores, which raise membrane
fouling and resulting in reduction in permeate flux (Benitez et al.,
2009). The observed rejection slightly decreases with an increase
of applied pressure. It means that the membrane properties have
little effect on the dye removal with operating pressure. The re-
moval of MO dye is perhaps due to the surface charge of zirconia
membrane. The isoelectric point (IEP) of zirconia is reported to be
4 (Seshadri et al., 1998; Tsuru et al., 1998). It signifies that the
zirconia membrane is positively charged at pHo 4 and negatively
charged at pH 44. Therefore the prepared composite membrane is
negatively charged as the natural pH of dye solution used in this Fig. 6. (a) Effect of operating pressure and (b) feed concentration on methyl orange
work is 5.7. It can be clarified that the repulsion between mem- separation.
brane surface and the anionic dye molecule in the aqueous solu-
tion causes the removal of MO in the permeate. the permeate flux and rejection was investigated at a constant
pressure of 69 kPa and the obtained results are depicted in Fig. 6
3.3.2. Effect of feed concentration (b). As anticipated, the flux decline is high at higher concentration
The effect of feed concentrations (1000–3000 ppm) of MO on as the feed concentration raises the membrane fouling severely.
78 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79

An increase in dye adsorption on the membrane surface and Chandra, N., Singh, D.K., Sharma, M., Upadhyay, R.K., Amriphale, S.S., Sanghi, S.K.,
concentration polarization might be the responsible factors for this 2010. Synthesis and characterization of nano-sized zirconia powder synthe-
sized by single emulsion-assisted direct precipitation. J. Colloid Interface Sci.
observation (Cassano et al., 2008). The obtained rejection data at 342, 327–332.
these concentrations demonstrate that the rejection slightly in- Chang, Q., Zhou, J., Wang, Y., Liang, J., Zhang, X., Cerneaux, S., Wang, X., Zhu, Z.,
creases with increasing the feed concentration. At higher con- Dong, Y., 2014. Application of ceramic microfiltration membrane modified by
nano-TiO2 coating in separation of a stable oil-in-water emulsion. J. Membr. Sci.
centration, the transportation of MO through the membrane is 456, 128–133.
reduced due to the retention of MO in the deposit on the mem- Etienne, J., Larbot, A., Julbe, A., Guizard, C., Cot, L., 1994. A microporous zirconia
brane surface. MO agglomerates more rapidly when the con- membrane prepared by the sol–gel process from zirconyl oxalate. J. Membr. Sci.
86, 95–102.
centration of MO in the feed solution is high (Monash et al., 2010);
Forgacs, E., Cserhati, T., Oros, G., 2004. Removal of synthetic dyes from wastewaters:
as a result, concentration of MO in the permeate declines. a review. Environ. Int. 30, 953–971.
Gestel, T.V., Kruidhof, H., Blank, D.H.A., Bouwmeester, H.J.M., 2006. ZrO2 and TiO2
membranes for nanofiltration and pervaporation Part 1. Preparation and
characterization of a corrosion-resistant ZrO2 nanofiltration membrane with a
4. Conclusions MWCOo300. J. Membr. Sci. 284, 128–136..
Jana, S., Purkait, M.K., Mohanty, K., 2010. Removal of crystal violet by advanced
The zirconia–ceramic composite membrane has been success- oxidation and microfiltration. Appl. Clay Sci. 50, 337–341.
Jedidi, I., Saidi, S., Khemakhem, S., Larbot, A., Elloumi-Ammar, N., Fourati, A., Charfi,
fully prepared by in-situ hydrothermal crystallization with con- A., Salah, A.B., Amar, R.B., 2009. Elaboration of new ceramic microfiltration
trolled growth of zirconia particle on the porous ceramic support. membranes from mineral coal fly ash applied to waste water treatment. J.
XRD analysis of zirconia powder calcined at 450 °C reveals the Hazard. Mater. 172, 152–158.
Kalantari, N., Vaezi, M.J., Yadollahi, M., Babaluo, A.A., Bayati, B., Kazemzadeh, A.,
presence of tetragonal phase along with some small peaks of the 2015. Synthesis of nanostructure hydroxy sodalite composite membranes via
monoclinic phase of zirconia. EDX spectrum demonstrates the hydrothermal method: support surface modification and synthesis method
presence of the zirconia in the membrane FESEM image verifies effects. Asia–Pac. J. Chem. Eng. 10, 45–55.
Kim, T.H., Park, C., Kim, S., 2005. Water recycling from desalination and purification
that the zirconia particles adhere on the surface of the membrane. process of reactive dye manufacturing industry by combined membrane fil-
Moreover, porosity, average pore size and pure water permeability tration. J. Clean. Prod. 13, 779–786.
of the zirconia membrane is estimated to be 42%, 0.66 mm and Kocherginsky, N.M., Tan, C.L., Lu, W.F., 2003. Demulsification of water-in-oil
emulsion via filtration through a hydrophilic polymer membrane. J. Membr. Sci.
1.44
10  6 m3/m2 s kPa, respectively. Separation potential of the
220, 117–128.
prepared membrane is investigated on the effect of parameters Kumar, R.V., Basumatary, A.K., Ghoshal, A.K., Pugazhenthi, G., 2015. Performance
such as operating pressure and feed concentration and its influ- assessment of an analcime–C zeolite–ceramic composite membrane by removal
ences on both permeate flux and MO removal is discussed. of Cr(VI) from aqueous solution. RSC Adv. 5, 6246–6254.
Mo, J.H., Lee, Y.H., Kim, J., Jeong, J.Y., Jegal, J., 2008. Treatment of dye aqueous so-
Moreover, the highest separation (61%) is obtained with the lutions using nanofiltration polyamide composite membranes for the dye
permeate flux of 2.28
10  5 m3/m2 s at 68 kPa for the feed con- wastewater reuse. J. Dyes Pigm. 76, 429–434.
centration of 3000 ppm. Monash, P., Majhi, A., Pugazhenthi, G., 2010. Separation of bovine serum albumin
(BSA) using γ-Al2O3–clay composite ultrafiltration membrane. J. Chem. Technol.
Biotechnol. 85, 545–554.
Monash, P., Pugazhenthi, G., 2011. Development of ceramic supports derived from
Acknowledgment low-cost raw materials for membrane applications and its optimization based
on sintering temperature. Int. J. Appl. Ceram. Technol. 8, 227–238.
Monash, P., Pugazhenthi, G., 2011. Effect of TiO2 addition on the fabrication of
We would like to thank the Central Instrument Facility, IIT ceramic membrane supports: a study on the separation of oil droplets and
Guwahati for helping us to perform FESEM analysis. This work was bovine serum albumin (BSA) from its solution. Desalination 279, 104–114.
Monash, P., Pugazhenthi, G., 2014. Utilization of calcined Ni-Al layered double hy-
financially supported by a research grant under the Fast Track droxide (LDH) as an adsorbent for removal of methyl orange dye from aqueous
Scheme (SR/FTP/ETA-44/2010) from Department of Science and solution. Environ. Prog. Sustain. Energy 33, 153–159.
Technology (DST), Government of India. Nilesh, P.T., Chaudhari, S., 2006. Degradation of azo dyes by sequential Fenton’s
oxidation and aerobic biological treatment. J. Hazard. Mater. B 136, 698–705.
Qiao, S., Hu, Q., Haghseresht, F., Hu, X., Lu, G.Q., 2009. An investigation on the ad-
sorption of acid dyes on bentonite based composite adsorbent. Sep. Purif.
Appendix A. Supplementary information Technol. 67, 218–225.
Sangwichien, C., Aranovich, G.L., Donohue, M.D., 2002. Density functional theory
predictions of adsorption isotherms with hysteresis loops. Colloids Surf. A 206,
Supplementary data associated with this article can be found in 313–320.
the online version at http://dx.doi.org/10.1016/j.ecoenv.2015.05. Seshadri, K.S., Ahamed, J., Kesavamoorthy, R., Srinivasan, M.P., Krishnasamy, V.,
1998. Estimation of pore charge on zirconia membrane prepared by sol–gel
006.
route using zeta potential measurement. J. Mater. Sci. Technol. 14, 425–428.
Sharma, S., Buddhdev, J., Patel., M., Ruparelia, J.P., 2013. Studies on degradation of
reactive red 135 dye in wastewater using ozone. Procedia Eng. 51, 451–455.
References Shiue, A., Ma, C., Ruan., R., Chang, C., 2012. Adsorption kinetics and isotherms for
the removal methyl orange from wastewaters using copper oxide catalyst
prepared by the waste printed circuit boards. Sustain. Environ. Res. 22,
Al-Aseeri, M., Bu-Ali, Q., Haji, S., Al-Basataki, N., 2007. Removal of acid red and 209–215.
sodium chloride from aqueous solutions using nanofiltration. Desalination 206, Tan, X., Kyaw, N.N., Teob, W.K., Li, K., 2006. Decolorization of dye-containing aqu-
407–413. eous solutions by the polyelectrolyte-enhanced ultrafiltration (PEUF) process
Al-Bastaki, N., 2004. Removal of methyl orange dye and Na2SO4 salt from synthetic using a hollow fiber membrane module. Sep. Purif. Technol. 52, 110–116.
waste water using reverse osmosis. Chem. Eng. Process. 43, 1561–1567. Tsuru, T., Takezoe, H., Asaeda, M., 1998. Ion separation by porous silica–zirconia
Almandoz, M.C., Marchese, J., Pradanos, P., Palacio, L., Hernandez, A., 2004. Pre- nanofiltration membranes. AIChE J. 44, 765–768.
paration and characterization of non-supported microfiltration membranes Turgay, O., Ersoz, G., Atalay, S., Forss., J., Welander., U., 2011. The treatment of azo
from aluminosilicates. J. Membr. Sci. 241, 95–103. dyes found in textile industry wastewater by anaerobic biological method and
Benitez, F.J., Acero, J.L., Real, F.J., Garcia, C., 2009. Removal of phenyl-urea herbicides chemical oxidation. Sep. Purif. Technol. 79, 26–33.
in ultrapure water by ultrafiltration and nanofiltration processes. Water Res. 43, Velusamy, P., Pitchaimuthu, S., Rajalakshmi, S., Kannan, N., 2014. Modification of the
267–276. photocatalytic activity of TiO2 by b-cyclodextrin in decoloration of ethyl violet
Bhave, R.R., 1991. Inorganic Membranes Synthesis, Characteristics and Applications. dye. J. Adv. Res. 5, 19–25.
Van Nostrand Reinhold, New York. Weisburger, J.H., 2002. Comments on the history and importance of aromatic and
Bowen, W.R., Mohammad, A.W., Hilal, N., 1997. Characterisation of nanofiltrtation heterocyclic amines in public health. Mutat. Res. Fundam. Mol. Mech. Mutagen.
membranes for predictive purposes-use of salts uncharged solutes and atomic 506–507, 9–20.
force microscopy. J. Membr. Sci. 126, 91–105. Wong, M.S., Huang, H.C., Ying, J.Y., 2002. Supramolecular-templated synthesis of
Cassano, A., Mecchia, A., Drioli, E., 2008. Analyses of hydrodynamic resistances and nanoporous zirconia–silica catalysts. Chem. Mater. 14, 1961–1973.
operating parameters in the ultrafiltration of grape must. J. Food Eng. 89, Wu, J.C., Cheng, L., 2000. An improved synthesis of ultrafiltration zirconia mem-
171–177. branes via the sol–gel route using alkoxide precursor. J. Membr. Sci. 167,
 R.V. Kumar et al. / Ecotoxicology and Environmental Safety 121 (2015) 73–79 79

253–261. Zahrim, A.Y., Hilal, N., 2013. Treatment of highly concentrated dye solution by
Xu, X., Bao, Y., Song, C., Yang, W., Liu, J., Lin, L., 2004. Microwave-assisted hydro- coagulation/flocculation–sandfiltration and nanofiltration. Water Resour. Ind. 3,
thermal synthesis of hydroxy-sodalite zeolite membrane. Microporous Meso- 23–34.
porous Mater. 75, 173–181. Zhou, J., Chang, Q., Wang, Y., Wang, J., Meng, G., 2010. Separation of stable oil–water
Yang, C., Zhang, G., Xu, N., Shi, J., 1998. Preparation and application in oil–water emulsion by the hydrophilic nano-sized ZrO2 modified Al2O3 microfiltration
separation of ZrO2/α-Al2O3 MF membrane. J. Membr. Sci. 142, 235–243. membrane. Sep. Purif. Technol. 75, 243–248.
Zaghbani, N., Hafiane, A., Dhahbi, M., 2007. Separation of methylene blue from
aqueous solution by micellar enhanced ultrafiltration. Sep. Purif. Technol. 55,
117–124.