Trans. Ind. Ceram. Soc., vol. 73, no. 3, pp. 1-8 (2014).

2014 The Indian Ceramic Society

ISSN 0371-750X (Print), ISSN 2165-5456 (Online)
http://dx.doi.org/10.1080/0371750X.2014.882246

Preparation and Characterization of Single Layer

Ultra Filtration Alumina Membrane Directly over
Porous Clay-Alumina Tubular and Capillary
Support for Textile Effluent Treatment
Sandeep Sarkar*, Sourja Ghosh, Priya Banerjee, Andr Larbot1, Sophie Cerneaux1,
Sibdas Bandyopadhyay and Chiranjib Bhattacharjee2
CSIR-Central Glass and Ceramic Research Institute
196, Raja S. C. Mullick Road
Jadavpur, Kolkata 700 032, India
[MS received August 21, 2013; Accepted January 07, 2014]

Clay-alumina porous tubular supports of 8/6 mm for outside diameter/inside diameter (OD/ID) were prepared by
extrusion and sintering at 1450oC for 110 min to obtain an average pore size and porosity of 1 m and 40% respectively.
Slip casting slurry was prepared by peptization of boehmite (AlO(OH)) powder with 1.5 N nitric acid and mixing it
with -Al2O3 powder of 40 nm particle size along with PVA and PEG in determined weight percentage. Clay alumina
porous support tubes of 3.1/1.9 and 8/6 mm (OD/ID) were coated with the slip casting slurry and sintered at 550oC
for 60 min to obtain -alumina membrane directly over the supports in a single step. The membrane layer prepared
over both the support tubes were without any intermediate layer. The membranes presented a pore diameter
distribution centered at 7.0 nm on 3.1/1.9 mm (OD/ID) and 5.5 nm on 8/6 mm (OD/ID) supports, which was in
ultrafiltration (UF) range. The prepared UF membranes were studied for treatment of bio-treated synthetic and real
textile effluent in the side stream mode. About 98% decolorization of synthetic dye solution and 95.6% colour
removal of real textile effluent were obtained by the combined effect of UF membrane and bioreactor.
[Keywords: Crack-free, Single layer, Ultrafiltration, Clay-alumina, Support tube, Textile effluent]

Introduction
Ceramic membrane technology is known for its
applications in various fields such as chemistry, food,
biotechnology, wastewater treatment, 1 gas transport
system 2 and membrane bioreactor (MBR). 3 Ceramic
membrane has an edge over the polymeric membranes
due to the intrinsic properties of a ceramic material,4 i.e.
high resistance to chemical abrasion, bio-inertness,
excellent thermal stability, high-pressure resistance, long
life time5, 6 and stability over a wide range of pH.7
In spite of these advantages, ceramic membrane did
not find too much industrial applications due to its complex
preparation process and high cost as compared to the
application of polymeric membrane. 8 This has raised
interest to prepare defect free ceramic ultrafiltration (UF)
membrane at low cost.
Unlike polymeric membrane, microporous UF ceramic
membrane is prepared in a multilayered structure
with progressively decreasing pore sizes from the porous
outer support to the inner microporous filtration layer.9, 10
These membranes are being prepared by depositing
*Corresponding author; e-mail: sandeepsarkar123@gmail.com
1

Institut Europen des Membranes, UMR 5635 ENSCM-CNRS-UMII,

Place Eugene Bataillon CC47 34095 Montpellier Cedex 5, France

Depart m ent of Chem ic al Engineering, Jadavpur Uni versi ty,

Kolkata 700032, India

VOL. 73 (3) JULY SEPTEMBER 2014

inorganic materials viz. alumina,1117 silica,18, 19 zirconia20

or titania21, 22 through sol-gel process23 over a strong
macroporous tubular support prepared from high purity
alumina, usually sintered at a high temperature superior
to 1500oC.24, 25 Attempts have been made to prepare low
cost support with natural minerals like clay along with
alumina.24 However, the complexity and cost of preparing
UF membrane over the support remains high. The
preparation of ceramic UF membrane is a multi step
process. Several membrane layers, each with a particular
pore size, are prepared one over another to reduce the
pore size and achieve the required UF membrane. As a
result, processing of ceramic UF membrane becomes
complex and more expensive than processing polymeric
membrane. Due to this, industrial applications of UF
ceramic membrane are limited, which otherwise may
effectively be used in wastewater treatment including
various other separation applications, viz. MBR, gas
separation, water purification, contactor, etc considering
its advantages over polymeric membrane.47 Industrial
wastewater, such as textile effluent, is usually treated by
conventional activated sludge processes (CASPs), which
involve the natural biodegradation of pollutants by
heterotrophic bacteria (i.e. activated sludge) in aerated
bioreactors. The treatment efficiency is usually limited for
the difficulties in separating suspended solids (SS).
Ceramic UF membrane bioreactor has been used for

domestic wastewater treatment.26 Ceramic membrane

remains chemically stable in a wide range of pH and
temperature.7 A MBR system associated with UF ceramic
membrane filtration is the most appropriate for treatment
of wastewater since it makes the in situ cleaning of
membrane easy and convenient as these inorganic
membranes highly resist chemical abrasion and
biodegradation as stated earlier.
The objective of this work is to prepare a cost effective
crackless -alumina UF membrane directly over porous
clay-alumina capillary support of 3.1/1.9 mm (OD/ID),
precisely for the first time and 8/6 mm (OD/ID) tubular
support without any intermediate layer by newly designed
coating slurry. The performance efficiency of crossflow UF
membrane bioreactor (UMBR) with the prepared tubular
UF membrane in comparison to capillary UF membrane
was studied for textile effluent reclamation.
The first step consisted of preparation of single layer
-alumina UF membrane over a low cost porous clayalumina tubular support and capillary tubes. Method of
preparation of capillary tubes has been discussed
elsewhere. 24 The tubular support was prepared by
extrusion of ceramic paste, composed of clay and alumina
powder, and then sintering at a temperature below the
sintering temperature of pure alumina porous support
(1700oC). 25 Newly developed slip casting slurry was
prepared from boehmite sol and -alumina powder along
with organic additives for coating both the tubular and
capillary porous supports by dip coating technique. The
coated tubes were then fired to obtain -alumina UF
membrane over the porous supports without any
intermediate layer. In the second step, the prepared UF
membranes were characterized and their applicability was
investigated by treating textile effluent in a side-stream
membrane bioreactor process.
Experimental
Raw Materials
Alpha alumina (-Al2O3; 99% purity), with a mean
particle size of 6 m was purchased from Hindalco India
Limited (Birla, India). Kaolin clay (China), mainly composed
of kaolinite (Al2O3.2SiO2.2H2O), with a mean particle size
of 7 m and an organic binder, Methocel (Dow Chemical
Company), were used along with the alumina in preparation
of porous capillary support tube as described elsewhere.24
Boehmite AlO(OH) powder (74% purity) with a specific
surface area of 250 m2.g1 (Pural SB, SASOL, Germany)
and -Al2O3 with mean particle size of 40 nm (Presi, France)
were used as starting raw materials for preparation of UF
coating slurry. Polyvinyl alcohol (PVA) (RHODOVIOL
25/140) was used as binder and polyethylene glycol with
300 Daltons molecular weight (Merck, India) was used as
plasticizer along with nitric acid (70% purity, Merck, India) as
peptizing agent in the slurry preparation. Dolapix C64 was
used as dispersing agent for dispersing -Al2O3 powder.
Polyethylene glycol (SRL, India) of various molecular
weights, starting from 8000 to 35000 Da was utilized to

execute the molecular weight cutoff (MWCO) experiment

of the membrane. Permeate and feed concentrations were
determined by liquid phase chromatography using an
optical differential refractometer, Waters R 401.
Stock solutions of commercially used textile reactive
dyes were prepared in distilled water and autoclaved at
121oC and 1 atm for 15 min. Reactive yellow dye supplied
by M/s Clariant Chemicals India Ltd was selected as a
model dye in this study. All the culture media, organic and
inorganic compounds, and reagents used were of
analytical grade obtained from Merck, Mumbai, India.
Preparation of Tubular Support Tubes
The ceramic paste was obtained by mixing clay and
alumina raw powders in 55:45 ratio along with organic
additives and water.24 The paste was extruded by single
screw extruder using an extrusion die leading to green
tube with dimensions of 10/7 mm (OD/ID). The extruded
tube was then dried and fired in air at 1450oC for 100 min
as per the schedule illustrated in Fig. 1 to obtain 8/6 mm
(OD/ID) tubular porous supports.

1450oC
Free
cooling

2oC/min
1000oC
2oC/min
300oC
2oC/min
25oC

100 min

60 min

25 oC

5 min

Fig. 1 Firing schedule for 8/6 mm (OD/ID) tubular support

Preparation of Slip Casting Slurry

Three types of slip casting slurries, namely, -alumina
slip (S1), boehmite sol slip (S2) and mixture of boehmite
sol and -Al2O3 slip (S3), were prepared to coat the porous
tubular support for comparative study.
S1 slurry was prepared by dispersing -Al2O3 powder
of 40 nm average particle size in Dolapix C64 and water
solution (0.01 wt% in 18 M distilled water) by ultrasonic
bath for 15 min, where Dolapix acted as dispersant. PVA
solution (12 wt%; binder and pore former) and PEG
(plasticizer) were added to the dispersed solution by slow
stirring (100 rpm) in a magnetic stirrer for 30 min to obtain
a well dispersed -Al2O3 slip casting slurry.
The second slurry, S2, was prepared from boehmite
sol (-AlOOH sol). The sol was prepared by mixing 10 wt%
boehmite (-AlO(OH)) powder in 18 M distilled water by
slow stirring and adding 0.5% nitric acid of 1.5 N strength
until a translucent sol was obtained. An average sol particle
size of 14 nm (approx) was obtained after peptization with
nitric acid. The sol was then mixed with PEG 300 and PVA
solution and mixed for 30 min by slow stirring (100 rpm) to
obtain a uniform slip casting slurry from beohmite sol.

TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

The third slurry, S3, was prepared by adding -Al2O3

powder in boehmite sol (10 wt%) and stirring (150 rpm) it
for 10 min for even dispersion of powder in the sol.
Thereafter, PVA solution and PEG were added into the
mixture and stirred in a conical flux for 10 min at 100 rpm
to minimize bubble formation. Table I illustrates the
composition of three different slip casting slurries for
coating porous support tube.

Component

Boehmite sol
(10 wt%)

Natural
cooling

1oC/min

1 C/min
25oC

60 min

90 min

25oC

Coating slurry
S1
S2
S3
(-alumina) (boehmite sol) (mixture)

550oC

200oC

Table I : Composition of different slip casting

slurries in weight percentage

Sl.
no.

S2 and S3 slurries, were fired at 700o, 500o and 550oC

respectively. Figure 2 illustrates a typical firing schedule
of porous tube coated with S3 slurry.

66

64

- alumina

1.5

Dolapix C64 solution

(0.01 wt%)

59.5

PVA solution
(12 wt%)

35

30

30

PEG

Preparation of UF Capillary and Tubular Membrane

Clay-alumina porous tubular and capillary support
tubes were coated with the prepared UF coating slurry by
dip coating method. It is very difficult to coat the inside
wall of a porous tube with the viscous coating slurry by
conventional dip coating method especially with smaller
inner diameter such as 2 mm or less in case of capillary
support tube. Proper masking of the outer surface before
dipping the tube into the coating slurry is difficult for such
small diameter of capillary tube. Moreover masking may
hinder the required capillary suction pressure inside the
tube wall for cake formation during the tube dipping into
the slurry. Pouring the solution from the top to bottom of
the capillary tube may cause formation of unwanted
bubbles along the inner wall, which may form defects after
firing. Therefore, the tubes of 200 mm length and 3.1/1.9
and 8/6 mm (OD/ID) were coated by introducing the slurry
from bottom to top according to the communicating vessels
process based on the principle of inverted siphon, i.e. liquid
flows from higher to lower level due to lower potential
energy of lower location. The technique eliminated the
above said tube dip coating problems. Another advantage
of this technique is to trap the unwanted denser particle
of the slurry, such as undissolved coating powder, binder
or other organic additives which may create defects in the
membrane after firing. The coating time for both the support
tubes was 2 min. The tubes were then dried for 24 h at
room temperature before firing at a temperature depending
on their composition. The porous tube, coated with S1,

VOL. 73 (3) JULY SEPTEMBER 2014

Fig. 2 Firing schedule applied to coated capillary and tubular

support to prepare UF membrane with S3 slurry

Membrane Characterization
Static Characterization
The UF 3.1/1.9 mm (OD/ID) and 8/6 mm (OD/ID)
membranes were characterized by different techniques.
The mechanical resistance of the prepared tubular support
was measured by three-point bending method (universal
LLOYD Instruments, LRX apparatus) using a span of
30 mm and a cross-head speed of 10 mm.min1. The pore
size of the support was examined by mercury porosimetry
(Micromeritics autopore) whereas the UF top membrane
layer pore size distribution was determined by nitrogen
sorption (Quantachrome Corp.) and the pore diameter was
estimated by the BJH (Barrett-Joyner-Halenda) method. The
structural morphology, surface quality and thickness of the
support and UF membrane layers were examined by
scanning electron microscopy (JEOL Microscope, Japan).
Dynamic Characterizations
All the dynamic characterizations were performed on a
laboratory experimental setup using a 200 mm long
membrane of both 3.1/1.9 mm (OD/ID) capillary and
8/6 mm (OD/ID) tubular supports. Determination of pure
water permeability of the membranes was performed with
deionized water (18 M.cm). The molecular weight cutoff
(MW CO) of the membranes was determined using
solutions containing polyethylene glycol with molecular
weights of 8000 to 35000 Da. The concentration of each
solution was fixed at 103 mol.L1 and all the experiments
were carried out at the room temperature (25o to 35oC) at
a fixed pressure of 5 bar, and a solution velocity of 1 cm.s1
for both the membranes. The retention rate (R) of each
solute was estimated by the classical relation below:
R(%) = 100(1 Cp/Cf)
Cp and Cf being the solute concentration in the permeate
and in the feed solution, respectively.
Application of the UF Membrane in MBR
The prepared UF membranes were applied in MBR for
waste water treatment. Activated sludge was collected from
a common effluent treatment plant in sterile collection

bottles. Biodegradation of textile effluent was studied in

two different systems: one was synthetic dye solution of
reactive yellow dye and the other was coloured textile
effluent collected from a local dyehouse. In the first step,
batch experiments were run at increasing concentration of
the synthetic dye solution as well as the industrial effluent
with variable pH in order to determine the optimum
conditions of attaining the maximum bacterial activity. In
the second step, the untreated effluent without dilution was
added directly to the bioreactor in order to study the
acclimatization time of the microorganisms. For the
synthetic dye solution, an initial concentration of 50 mg.L1
was selected for this purpose.
The pH range suitable for microbial growth was
determined, and the final pH was adjusted between 6 and
10. Bacterial growth was measured at 620 nm by a
spectrophotometer.27
To measure decolourization of dye solution and effluent
during biological treatment, sampling was done at 12 h
intervals from the inoculated synthetic solution as well as
from textile effluent. The samples were clarified by
centrifuging at 5000 rpm for 4 min in order to prevent the
absorbance interference from the cellular or other
suspended debris. Uninoculated culture media with and
without added dyes were used as negative controls. The
decolorization efficiency of different isolates was
expressed as:
Decolourization (%) = (A0A)/A0 100
where A0 is the initial absorbance and A is the absorbance
of medium after decolourization at the max (nm) of each
dye. The max was determined by scanning the solution in
the entire ultraviolet-visible (UV-Vis) range and identifying
the wavelength corresponding to maximum absorption.
The clarified samples from the decolourization media were
used for determining the possible changes in the
absorption spectra of the dye in the UV-Vis range against
a baseline defined by the absorbance of clarified samples
from dye free media.28
The prepared UF membranes were utilized to purify
the bio-treated synthetic and real textile effluents in the
home-made pilot unit. Figure 3 illustrates a schematic
drawing of the home-made pilot unit for treating the biotreated textile effluents. The flow rate and the pressure
were independently controlled by regulating the speed
(rpm) of the pump motor by variable frequency drive and
introducing nitrogen gas to the feed tank through nitrogen
inlet valve. The flow rate and pressure were maintained
at 1.5 L.min1 and 2 bar, respectively during all filtration
experiments. Permeate samples were collected at specific
intervals and analyzed in the spectrophotometer to observe
the decolourization efficiency of the MBR process.
The colour concentration of the treated and untreated
solutions were estimated by measuring the optical density
corresponding to max of 418.1 and 515 nm for reactive
yellow dye solutions and textile effluent respectively, with
a spectrophotometer (Cary 50 Bio, UV-visible
spectrophotometer of Varian).

N2 inlet

Outlet Pressure valve

Gauge

Membrane

Permeate

Feed
Tank
Inlet
Pressure
Gauge
Positive
displacement
Pump

N2
Cylinder
Pressure
gauge

N2
Cylinder

Variable frequency
drive for Pump-motor
rpm control

Fig. 3 Schematic diagram of the home-made pilot unit

During the experimentation, analyses were carried out

on the most common control parameters of wastewater
treatment on raw textile effluents and synthetic dye
containing effluents, biotreated effluents, and permeate
samples of ultrafiltration. The chemical oxygen demand
(COD) and total suspended solids (TSS) contents were
determined according to the standard methods of APHA.
Total Kjeldhal nitrogen (TKN) concentration was evaluated
by a TKN analyzer (Kelplus, Pelican, India) and total
organic carbon (TOC) was measured by a TOC analyzer
(Shimadzu, Japan). pH, dissolved oxygen (DO) and total
dissolved solids (TDS) concentrations were measured
using respective meters (YSI, Model 55, USA). The number
of coliform organisms present was enumerated by the most
probable number (MPN) test. The MPN was estimated by
determining the number of tubes in each set of 5 tubes that
shows gas formation following the incubation period. This
test was carried out following APHA defined method.29
Results and Discussion
Clay-Alumina Support
Clay was used as a partial substitute of alumina for
the preparation of membrane support, which led to dual
benefits:

Firstly, clay being cheaper than alumina, it reduces the

raw material cost.

Secondly, clay contains fluxing impurities, which forms

a low melting phase for bringing down the sintering
temperature to below 1500oC, thereby reducing the
processing cost.

Tubular clay-alumina support (Fig. 4) prepared in this

work obtained a porosity of about 40% and an average
pore size of 1 m which is at par with the pore characteristic
of the capillary support.24 Figure 5 illustrates the pore size
distribution of tubular support determined by mercury
intrusion porosimetry. Porous tubular support prepared
from pure alumina sintered at 1600oC has a pore size of
more than 2 m (average).24 It is difficult to prepare UF

TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

membrane directly over such support without any

intermediate layer (micro filtration membrane) due to its
large pore size. Introduction of silica (clay) in the alumina
matrix of clay-alumina tubular support may reduce its
average pore size to 1 m, facilitating the preparation of
UF membrane directly over the support. The mechanical
resistance of the tubular support was found to be more
than 65 MPa by three-point bending method, which is
sufficient considering their use for ultrafiltration application
under pressure lower than 10 bar.

(b)

(a)
8.02 m

Fig. 6 SEM picture of S1 membrane over porous clay-alumina

support: (a) cross section, (b) top view exposing the microcracks

(a)

(b)
7.10 m

Fig. 4 Photographs of 8/6 and 3.1/1.9 mm (OD/ID) clay-alumina

supports

Single Layer UF Membrane

Both the capillary and tubular supports were coated
with S3 slip casting slurry. After sintering at 550oC for 90
min the crackless -Al2O3 layer (S3 membrane) presented
a pore diameter in the nanometer range (Figs. 8a and 8b)
and an average thickness of 7.3 m (Fig. 9a) for capillary
and 15.8 m for tubular supports (Fig. 9b). The variation

0,6
LOG
DIFFERENTIAL
INTRUSION
Log
Differential
intrusion
of OF
Hg
Hg

Fig. 7 Microcracks on S2 membrane over porous clay-alumina

tubular support (SEM picture): (a) cross section, (b) top view

0,5
0,4
0,3
0,2
0,1

(a)

0
-0,10,01

(b)
12.3 nm

0,1

10

100

PORE DIAMETER (m)

7.22 nm

6.94 nm

Pore size diameter / m

Fig. 5 Pore size distribution of 8/6 mm (OD/ID) support tube

Alumina Membrane over Clay-Alumina Support

The support tube was dip coated with S1, S2 and S3
slurry and fired as discussed earlier. Figure 6 illustrates
the SEM photograph of S1 membrane prepared over
porous support with S1 slurry. Though a membrane
thickness of 8 m (approx) was formed over the support
(Fig. 6a), a top view of the membrane (Fig. 6b) reveals
the occurrence of microcracks on the S1 membrane
surface. Hence the membrane is not suitable for UF
applications. Result was more severe for S2 membrane
prepared over porous support with S2 slurry. The
membrane (S2) was cracked as evident from the SEM
photograph (Fig. 7). A crackless membrane was prepared
with the S3 slip casting slurry. Probable reason for the
absence of cracks in S3 membrane is the presence of
-Al2O3 powder along with boehmite sol which may act as
a seeding agent during heat treatment.

VOL. 73 (3) JULY SEPTEMBER 2014

Fig. 8 SEM images of (a) defect-free UF -alumina membrane

over macroporous clay-alumina tubular support and
(b) UF -alumina membrane revealing the void (pore) in the
nanometer range

(b)

(a)

7.34 m

15.8 m

Fig. 9 SEM cross sections of UF -alumina membrane over

macroporous (a) 3.1/1.9 mm (OD/ID) capillary and (b) 8/6 mm (OD/ID)
tubular clay-alumina support revealing its membrane thickness

DESORPTION
(log
d) (cm 3.g 1)
Desorption Dv
Dv(log
d) [cc/g]

0.020

4000

3.1/1.9 mm (OD/ID) support

2 1
FLUX
(L.m 2
.h )
Flux (L/m
/hr)

3500
8/6 mm (OD/ID) support

3000
2500
2000
1500
1000
500
0
0

Fig. 11 Pure water flux of the 3.1/1.9 (OD/ID) capillary and

6/8 mm (OD/ID) tubular clay-alumina

140
120
100
80
60
8/6 mm (OD/ID) UF membrane

40
20

0.018

3.1/1.9 mm (OD/ID) UF membrane

3.1/1.9mm (OD/ID) membrane tube

8/6mm (OD/ID) membrane tube

0.016

PRESSURE
(bar)
Pressure (Bar)

2
FLUX
.h 1)
Flux(L.m
(L/m 2/h)

in the formation of UF membrane layer thickness found in

capillary and tubular clay-alumina supports with the same
coating slurry and process (including the coating time)
depends on the thickness of the support. This may be
due to the higher capillary forces occurring in a larger pore
volume concerning the tubular support than the capillary
support. Higher capillary force increases the formation of
cake thickness during the dip coating process. The
-alumina membrane layer obtained by the sol-gel process
presents a pore diameter distribution centered at 7.0 nm
for capillary and 5.5 nm for tubular supports, respectively
(Fig. 10). These values, determined by nitrogen adsorptiondesorption isotherms, confirm the prepared membrane as
a low UF membrane. The resulting crack-free single layers
UF membrane were achieved by adjusting the slip
composition, particularly the boehmite sol to -alumina
powder in 32:1 weight ratio and maintaining the coating
time of 2 min for both clay-alumina supports with similar
pore morphology.

0
0

0.014

Pressure (Bar)
PRESSURE
(bar)

0.012
0.010

Fig. 12 Pure water flux of the 3.1/1.9 (OD/ID) capillary and

6/8 mm (OD/ID) tubular UF membrane

0.008
0.006
0.004
0.002
0.000
-0.002
10

100

1000

Diameter ()()
DIAMETER

Fig. 10 Nitrogen adsorption-desorption isotherms of UF

-alumina membrane on 3.1/1.9 (OD/ID) capillary and 8/6 mm
(OD/ID) tubular supports

the cutoff. The cutoff of both the UF membrane, determined

at 90% rejection, was found to be 35 KDa (Fig. 13) at
room temperature. The home-made pilot unit (Fig. 3) was
also utilized to carry out membrane flux, MWCO and MBR
side stream filtration studies.
100
90

80
REJECTION
(%)
Rejection (%)

Pure Water Flux and MWCO

The pure water flux of the support was found to be
different for different support configurations as shown in
Fig. 11. At 5 bar pressure, the pure water flux of capillary
and tubular supports were 2514 and 2104 L.m 2.h1,
respectively. This small variation in flux for the two supports
may be explained by the fact that their supports have
different wall thicknesses, which leads to different
membrane resistances. The capillary support has higher
flux than the tubular support due to its lower wall thickness.
Similar trend has been found in the flux characteristics of
the UF membrane also (Fig. 12). The pure water flux of
the UF capillary and tubular membrane was found to be
107 and 95 L.m2.h1 at 5 bar pressure, respectively.
The MW CO of both UF capillary and tubular
membranes were evaluated at 5 bar pressure using a
home-made pilot by administrating nitrogen gas for
increasing the pressure. The feed flow rate was maintained
at 1.5 L.min1. PEG solution (1 g in 1 L water) of different
molecules was utilized as the polymer solution to obtain

70
60
50
40

3.1/1.9 mm (OD/ID) UF membrane

30
20

8/6 mm (OD/ID) UF membrane

10
0
0

10000

20000

30000

40000

PEG
(Da)
Mol.MOL.
Wt. WT.
of PEG

Fig. 13 PEG rejection percentage of UF tubular membrane over

3.1/1.9 (OD/ID) capillary and 8/6 mm (OD/ID) tubular support

Textile Effluent Treatment by UF Membrane

Table II illustrates the characterization of untreated
textile effluent samples and treated samples using both
the UF membranes (capillary and tubular) based
bioreactor. Samples 1 to 4 denote simulated textile effluent
prepared with synthetic reactive yellow dye solutions

TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

Table II : Characterization of various samples obtained from the MBR study

Sl.
no.

Samples

MPN Residual
COD
DO
index/
colour (mg.L1) (mg.L1)
100 mL
(%)

pH Turbidity
(NTU)

TSS
(mg.L1)

TDS
TOC
TKN
(g.L1) (mg.L1) (mg.L1)

Membrane
flux
(L.m2.h1)
(P = 2 bar)

Synthetic dye
solution (simulated)

100

2750

2.3

7.6

9.8

73.3

10.6

12.0

1.5

Biotreated synthetic
dye solution

920

96.8

400

4.6

7.4

2.3

400

10.2

17.6

1.3

Permeate of
bio-treated synthetic
dye solution by UF
tubular membrane

97.2

60.6

6.3

7.5

0.8

53.3

9.9

9.5

0.9

78.6

Permeate of
bio-treated synthetic
dye solution by UF
capillary membrane

98

50

7.2

7.2

0.6

43.3

9.9

8.1

0.8

84.5

Real textile effluent

46

100

3700

1.7

11.6

44.3

1593.3

79.5

170.0

2.4

Biotreated
real effluent

1600

7.3

500

3.9

7.3

16.6

2103.4

12.3

14.2

1.3

Permeate of
bio-treated real
effluent by UF
tubular membrane

6.8

99.4

5.9

7.2

0.8

72.8

12.3

8.3

0.7

50.9

Permeate of
bio-treated real
effluent by UF
capillary membrane

4.4

65.7

6.8

7.2

0.5

62.6

12.1

7.9

0.7

58.8

having initial dye concentration of 50 mg.L1 with a salt

concentration of 10 g.L1, biotreated synthetic dye solution,
permeate of biotreated synthetic dye solution collected
using UF 8/6 tubular and 3.1/1.9 capillary membranes,
respectively. While samples 5 to 8 denote untreated textile
effluent, biotreated effluent, permeate of biotreated effluent
collected using UF tubular and capillary membranes,
respectively.
The results indicated that 98% decolorization of
reactive yellow dye solution was achieved starting from
an initial dye concentration of 50 mg.L1 in the membrane
bioreactor treatment.
For textile effluent, about 95.6% colour removal was
obtained by the combined effect of UF and bioreactor.
Permeate samples in both the cases were free from
coliforms. The process resulted in considerable removal
of COD and TSS. The separation efficiency of both the
membranes was found acceptable for reuse purpose. The
flux was found to be slightly better for 3.1/1.9 capillary
membrane than 8/6 tubular membrane for both the
synthetic dye solutions and the real effluent. As stated
earlier, this may be due to the higher membrane resistance
of 8/6 tubular membrane owing to higher membrane
thickness than the 3.1/1.9 capillary membrane.
Batch scale setup of ultrafiltration coupled membrane
bioreactor was run for 6 days till collection of adequate
quantity of permeate for chemical analysis. During this
VOL. 73 (3) JULY SEPTEMBER 2014

operation, flux was measured at every 12 h. A decline in

flux was obtained after 48 h which may have occurred
due to fouling or clogging by sediments. Keeping other
parameters unaltered, flux levels were restored by
providing a backwash whenever necessary.
Conclusions
The 8/6 mm (OD/ID) porous tubular support was
prepared by extrusion of a ceramic paste made with
clay and alumina powders after firing at 1450oC. The
support had an average pore size of 1 m and 40%
porosity, which were similar to the reported values of
clay-alumina capillary supports.

The defect-free UF -alumina membrane layer was

successfully deposited directly over the clay-alumina
capillary and tubular support. The UF membrane layer
was prepared from S3 slip casting slurry composed of
beohmite sol and -alumina powder inside the support
tube by communicating vessels dip coating technique
in one-step.

Though the pore size and porosity of both the capillary

and the tubular support were similar, coating thickness
of the UF ceramic membranes was different due to
different wall thicknesses, which generated different
capillary forces in cake formation during coating of the
tubes.

The membrane obtained was a -alumina membrane

with a MWCO of 35 KDa directly over low cost clayalumina capillary and tubular supports. This eliminates
the requirement of intermediate layer between the
support and the actual membrane, which further
reduces the cost and complexity in development of UF
ceramic membrane, which can be utilized in various
gas and liquid filtration applications. The next part of
the work will be devoted to the preparation of cost
effective multichannel UF membrane for filtration
applications.
The UF capillary and tubular membranes were
effectively used in MBR process for textile wastewater
purification; UF capillary membrane obtained better flux
due to smaller membrane thickness.

References
1. K. K. Cham and A. M. Brownstein, Am. Ceram. Soc. Bull.,
70, 703-707 (1991).
2. R. S. A. de Lange, K. Keizer and A. J. Burggraaf, J. Membr.
Sci., 104, 81-100 (1995).
3. C. H. Xing, E. Tardieu, Y. Qian and X.-H. Wen, J. Membr.
Sci., 177, 73-82 (2000).

12. A. F. M. Leenaars and A. J. Burggraaf, J. Colloid Interf. Sci.,

105, 27-40 (1985).
13. M. A. Anderson, M. J. Gieselmann and Q. Xu, J. Membr.
Sci., 39, 243-258 (1988).
14. T. Okubo, M. W atanabe, K. Kusakabe and S. Morooka,
J. Mater. Sci., 25, 4822-4827 (1990).
15. T. Okubo, K. Haruta, K. Kusakabe and S. Morooka, J. Membr.
Sci., 59, 73-80 (1991).
16. M. I. D. de Albani and C. P. Arciprete, J. Membr. Sci., 69,
21-28 (1992).
17. A. Larbot, J. E. Fabre, C. Guizard and L. Cot, J. Membr.
Sci., 39, 203-212 (1988).
18. A. Kaiser and H. Schmidt, J. Membr. Sci., 22, 257-268 (1985).
19. L. C. Klein and D. Gallagher, J. Membr. Sci., 39, 213-220 (1988).
20. J. Etienne, A. Larbot, A. Julbe, C. Guizard and L. Cot,
J. Membr. Sci.,86, 95-102 (1994).
21. M. A. Anderson, M. J. Gieselmann and Q. Xu, J. Membr.
Sci., 39, 243-258 (1988).
22. N. Seffaj, S. Alami Younsi, M. Persin, M. Cretin, A. Albizane
and A. Larbot, Ceram. Int.,31, 205-210 (2005).

4. M. R. Weir, E. Rutinduka, C. Detellier, C. Y. Feng, Q. Wang,

T. Matsuura and R. LeVan Mao, J. Membr. Sci., 182, 41-50
(2001).

23. X. R. Huang, G. L. Meng, Z. T. Huang and J. M. Geng,

J. Membr. Sci., 133, 145-150 (1997).

5. K. A. DeFriend and A. R. Barron, J. Membr. Sci., 212, 29-38

(2003).

24. S. Sarkar, S. Bandyopadhyay, A. Larbot and S. Cerneaux,

J. Membr. Sci., 392-393, 130-136 (2012).

6. B. Elyassi, M. Sahimi and T. T. Tsotsis, J. Membr. Sci., 316,

73-79 (2008).

25. I. Voigt, G. Fischer, P. Puhlfur, M. Schleifenheimer and

M. Stahn, Sep. Purif. Technol., 32, 87-91 (2003).

7. D. A. White and M. Asaadi, Fouling Behavior in Inorganic

Tubular Membranes, p. 143 in: Proc. Int. Technical Conf.
Membrane Separation Process, Brighton, UK (1989).

26. X. Wen, Tsinghua Sci. Technol., 5, 283-287 (2000).

8. S. Khemakhem, A. Larbot and R. Ben Amar, Ceram. Int.,

35, 55-61 (2009).

28. S. As ad, M. A. Amoozegar, A. A. Pourbabaee, M. N.

Sarbolouki and S. M. M. Dastgheib, Bioresour. Technol.,
98, 2082-2088 (2007).

9. K. Li, Ceramic Membrane for Separation and Reaction,

p. 1, John Wiley& Sons, Chichester, UK (2007).
10. T. Van G es tel, C. Vandecasteele, A. Buekenhoudt,
C. Dotremont, J. Luyten, R. Leysen, B. Van der Bruggen
and G. Maes, J. Membr. Sci., 207, 73-89 (2002).

11. A. F. M. Leenaars, K. Keizer and A. J. Burggraff, J. Mater.

Sci., 19, 1077-1088 (1984).

27. A. Gopal, N. P. Shah and H. Roginski, Milchwissenschaft,

51, 619-622 (1996).

29. A. D. Eaton, L. S. Clesceri, E. W. Rice and A. W. Greenberg,

Standard M ethods for the Es timation of Water and
Wastewater, Americ an Public Health As s oc iation
Publications, Washington, USA (2005).

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