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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l
Ceramic Membrane Division, Central Glass and Ceramic Research Institute, 196, Raja S.C. Mullick Road, Kolkata-700032, India
Department of Chemical Engineering, Heritage Institute of Technology, Kolkata-700107, India
a r t i c l e
i n f o
Article history:
Received 22 September 2009
Received in revised form 14 May 2010
Accepted 17 May 2010
Available online 9 June 2010
Keywords:
Sulphur black efuent
Crossow microltration
Ceramic membrane
Biosorbent
Chemical pretreatment
Permeate ux
a b s t r a c t
Crossow microltration (CMF) using ceramic membrane, developed from a low cost composition of alumina and clay in the tubular multichannel conguration with ltration area of 0.045 m2 was used alone, and
in combination with different physicochemical techniques, viz. adsorption and chemical coagulation for
treatment of wastewater collected from the sulphur dyeing process of a garment processing industry. The
concentrated efuent was enriched with sulphur black dye, with turbidity 5912 NTU and COD of 3910 mg/l.
Adsorptive treatment was carried out using a biosorbent prepared from the roots of an aquatic weed, E.
Crassipes. Chemical pretreatment was carried out using different inorganic coagulants. Effect of different
transmembrane pressures (TMP) in the range of 0.41.2 kg/cm2 was observed and constant pressure ltration
was conducted at 1 kg/cm2 TMP. Performance of the single stage CMF process was compared with that of twostage processes in terms of the permeate quality, viz. COD, color, turbidity and TSS etc. and permeate ux.
Encouraging result was found after microltration of the biosorbent treated feed as well as, efuent pretreated
with aluminium sulphate. Dye removal was about 99%, with 80% reduction of COD. The chemical pretreatment
process considerably increased the permeate ux compared to the single stage process.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Different types of dyes are used in the textile industries. The chemical
structures of dyes vary enormously, and some have complicated aromatic
structures that resist degradation in conventional wastewater treatment
processes because of their stability under exposure to sunlight, oxidizing
agents and microorganisms. Dye containing wastewater usually consists
of a number of contaminants including acids, bases, dissolved solids, high
chemical oxygen demand (COD), toxic compounds, xing compounds
and color. The conventional treatments of wastewater containing dyestuff
include biological oxidation [1], chemical coagulation [24] and adsorption [5,6]. Biological methods are although cheap and simple to apply,
however, dyeing wastewater cannot be readily degraded by the
conventional biological processes. This is due to the complex structures
of most commercial dye compounds and their non-biodegradability. The
other treatment methods include ozonation [7], UV, UV/H2O2 decoloration [8], Fenton's reagent oxidation [9], chemical precipitation and ion
exchange [10] etc. Some of these methods are relatively expensive and
each has its merits and limitations in application. Membrane based
separation processes are gradually emerging as attractive alternative to
the conventional separation processes. However, one of the major
Corresponding author. Tel.: +91 33 2473 3469/76; fax: +91 33 2473 0957.
E-mail address: sourja@cgcri.res.in (S. Ghosh).
0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.05.029
68
Table 1
Characterization of the untreated sulphur black efuent.
pH
Table 2
Characterization of the biosorbent (WHR).
Conductivity TDS
Turbidity Dye concentration COD
TSS
(mS/cm)
(mg/l) (NTU)
(mg/l)
(mg/l) (mg/l)
12.07 36.9
20,200
5912
890
3910
5550
Properties
Quantitative value
Raw material
Bulk density (kg/m3)
Moisture content (%)
Ash content (%)
Surface area (m2/g)
Average particle size (mm)
Roots of E. Crassipes
133
9.6
44
81
0.038
69
reduction also (Fig. 4). Reduction of TSS decreased with the increase of
solution pH, at acidic pH TSS removal was 94% which decreased to 84%
at pH 12. Again, turbidity removal was found as pH independent and
over 98% reduction was obtained in the entire pH range studied. Based
on these results, pH 4 was selected as optimum pH for the further
study.
In Fig. 5, the effect of WHR dose on the removal of dye and COD
reduction (%) is shown, solution pH was adjusted at 4. At 0.5 g/l dose,
dye adsorption was over 99% which remained constant with increased
doses of WHR. Removal of COD gradually increased with increase of
adsorbent dose and at 1 g/l dose COD reduction was about 68%. This
could be attributed to the increased surface area with availability of
more effective sites for adsorption. However, with further increase of
adsorbent doses no improvement in the COD reduction was observed.
This might be due to overlapping of adsorption sites as a result of
overcrowding of adsorbent particles [17].
In Fig. 6, reduction of turbidity and TSS with variation of the
adsorbent dose is shown. It may be observed that turbidity reduction
was about 99% irrespective of the adsorbent dose. TSS reduction was
maximum (94%) at 1 g/l dose, thereafter it decreased. From these
results optimum dose was selected as 1 g/l which was used in the
further comparison study.
Fig. 3. Effect of pH on dye removal and COD reduction (WHR dose: 1 g/l).
Fig. 5. Dye removal and COD reduction with variation of adsorbent dose.
70
Fig. 7. Dye removal with variation of the coagulant dose in the chemical pretreatment
study.
71
Fig. 9. Particle size distribution of the different samples of sulphur black efuent.
quality and permeate ux. Five types of feed were treated by CMF:
Feed 1: efuent treated with biosorbent (WHR, 1 g/l, pH 4); Feed 2:
efuent treated with aluminium sulphate (1 g/l); Feed 3: efuent
pretreated with ferric chloride (3 g/l); Feed 4: efuent pretreated
with ferrous sulphate (1 g/l) and lime (1 g/l) and Feed 5: untreated
sulphur black efuent. Removal of dye after CMF of untreated and the
pretreated efuents with time was studied (Fig. 10). In CMF study at
constant TMP of 1.0 kg/cm2, the similar trend like that of batch scale
pretreatment study was found. As expected, maximum dye removal
(N99%) was obtained for the WHR treated feed (Feed 1) within 15 min
of ltration. For the aluminium sulphate treated feed (Feed 2) also,
9899% removal of dye was found. For Feed 3, 90% removal of dye was
observed and for Feed 4 it was about 81%. For the pretreated feeds,
steady state was achieved within a short time of CMF and dye removal
was almost constant with time. However, removal of dye was
signicantly less for the direct CMF of efuent. After 15 min, 51%
removal was observed which gradually decreased to about 46% after
120 min.
The removal of COD from permeate samples for the different feeds
of sulphur black efuent was shown (Fig. 11). For Feed 1, COD
removal was initially 74% which gradually increased to 80% within 1 h
of ltration. For Feed 2, COD reduction was increased from 66% at
15 min to 79% within 1 h. Unlike dye removal, COD reduction was
higher for the ferrous sulphate and lime treated feed (Feed 4)
compared to the ferric chloride treated feed (Feed 3). For Feed 3 COD
reduction varied from 44 to 53% which was about 5160% for the Feed
4. For the direct microltration of efuent (Feed 5) about 2224%
reduction in the COD was found.
The ceramic microltration membrane was highly efcient for
turbidity removal, irrespective of the types of feed (Fig. 12). It can be
observed that turbidity removal was 98.5% for the untreated efuent,
Fig. 10. Dye removal with time in the microltration study of sulphur black efuent
(Feed volume: 5.5 l; Filtration area: 0.045 m2; TMP: 1.0 kg/cm2).
which reached to near 100% with time for the different types of
treated feed. For these feeds, turbidity of most of the permeate
samples was below 1 NTU.
Reduction in TSS during CMF study of the various types of feed is
shown in Fig. 13. Here for Feed 1, TSS removal was within 9498% in
the range of the ltration time used in the study. TSS reduction was
maximum (N99%) for the aluminium sulphate treated feed (Feed 2).
Fig. 11. COD reduction (%) with time in the microltration study of sulphur black
efuent (Feed volume: 5.5 l; Filtration area: 0.045 m2; TMP: 1.0 kg/cm2).
Fig. 12. Turbidity reduction (%) with time in the microltration study of sulphur black
efuent (Feed volume: 5.5 l; Filtration area: 0.045 m2; TMP: 1.0 kg/cm2).
72
Fig. 13. TSS reduction (%) with time in the microltration study of sulphur black
efuent (Feed volume: 5.5 l; Filtration area: 0.045 m2; TMP: 1.0 kg/cm2).
Fig. 14. Permeate ux prole with time during cross ow microltration of sulphur
black efuent (Feed volume: 5.5 l; Filtration area: 0.045 m2; TMP: 1.0 kg/cm2).