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a,*
Department of Environmental Science and Engineering, Kwangju Institute of Science and Technology (K-JIST),
Kwangju 500 712, South Korea
b
Department of Chemistry, Anna University, Chennai 600 025, India
Received 22 February 2001; received in revised form 10 October 2001; accepted 26 October 2001
Abstract
Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A
solution containing 4 104 M dye was completely degraded in 24 h irradiation time. The intensity of the solar light
was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2 , SO2
4 ,
NO
3 , NH4 and H2 O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate inuenced
the photodegradation eciency. The rapidity of photodegradation of dye intermediates were observed in the presence
of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride
substantially aected the photodegradation eciency. High performance liquid chromatography and chemical oxygen
demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light
induced degradation of textile dye in wastewater is a viable technique for wastewater treatment. 2002 Elsevier
Science Ltd. All rights reserved.
Keywords: Titanium dioxide; Hydrogen peroxide; Potassium persulphate; Photomineralisation
1. Introduction
Textile mills are major consumers of water and consequently one of the largest group of industries causing
intense water pollution. The euent contains wide range
of chemicals of varying kind. Reactive dyes are not
amenable for ready biodegradation. The current treatment of dye waste in textile industries is focussed on the
removal of colour along with aesthetic issues. Several
physico-chemical and biological methods are available
for the treatment of textile wastewater. Unfortunately
these processes have high operating cost and are of
limited applicability. Strong colour is another important component of textile wastewater. If colour is not
0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 2 8 4 - 3
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CO2 , SO2
2 , NH4 and NO3 as end products were
tested by bubbling through lime water, turbidimeter
procedure and spectrophotometer methods respectively.
JanuaryFebruary
MarchApril
MayJune
JulyAugust
SeptemberOctober
NovemberDecember
95 000
101 750
105 000
102 400
92 200
89 710
Table 2
Eect of initial concentration of the dye on the degradation
eciency
Concentration of the
dye (104 M)
k 1 (min1 )
Degradation (%)
1
2
3
4
5
1:36 102
1:04 102
5:22 103
3:96 103
2:90 103
98
98
82
71
32
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Table 3
Eect of TiO2 loading on the degradation of the dye
Amount of TiO2 (g/l)
k 1 min1 103
Degradation (%)
1.0
2.0
2.5
3.0
4.0
2.89
3.96
5.22
5.41
5.70
60
71
82
82
82
1176
Table 4
Chemical structure and absorption maxima of reactive blue 4
dye
Dye
(commercial
name)
Chemical structure
Reactive
blue 4
kmax
(nm)
596, 253
were carried out during JanuaryApril and JuneSeptember. In tropical countries like India intense sunlight
is available almost through out the year and hence solar
light could be eectively used for photocatalytic degradation of pollutants in wastewater. In case of large
surface demanding photocatalytic degradation, sunlight
would be the ultimate source.
3.6. Mineralisation product of the dye
2
1177
Fig. 3. HPLC chromatograms (RB4) as a function of irradiation time: (a) 4 h, (b) 8 h, (c) 16 h and (d) 24 h.
1178
H2 O2 e ! OH OH
H2 O2 O
2 ! OH OH O2
H2 O2 ! 2 OH
H2 O2 ! O2
2 2H
The oxidising power of these radicals is strong enough to break azo groups of dyes adsorbed on the surface of TiO2 leading to the formation of ammonium and
nitrate ions. This shows that reactions involving ring
nitrogen compounds are more complex and there are
many signicant reaction paths leading to nitrate ions
in addition to ammonium ions (Pelizzetti and Minero,
1994). The HPLC chromatograms of reactive blue 4 dye
is presented in Fig. 5. The chromatograms indicate the
existence of small amount of parent dye without their
fragments even after longer irradiation, which suggests
that the mineralisation of the fragments is tremendously
faster in the presence of hydrogen peroxide.
2
S2 O2
8 eaq ! SO4 SO4
2
S2 O2
8 ecb ! SO4 SO4
Fig. 5. HPLC chromatograms (RB4) as a function of hydrogen peroxide (8:80 103 M): (a) 4 h, (b) 6 h, (c) 8 h and (d) 12 h.
Fig. 6. Inuence of potassium persulphate: initial concentration of the dye 4 104 M, initial COD 108 mg/l and irradiation time 8 h.
modes of reactions with organic compounds: (i) by abstracting a hydrogen atom from saturated carbon, (ii) by
adding hydrogen to unsaturated or aromatic carbon
and (iii) by removing one electron from the carboxylate
anion and from certain neutral molecules (Nasr et al.,
1997). In addition, it can trap the photogenerated electrons and/or generate hydroxyl radical (Nasr et al., 1997;
Pelizzetti et al., 1991; Minero et al., 1993).
SO
4
SO
4
e
cb
SO2
4
H2 O ! OH
9
SO2
4
10
11
intermediates
SO
4 dye
SO2
4
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OH CO2
3 ! OH CO3
OH
HCO
3
! H2 O
CO
3
13
14
This type of trend was also observed in the photocatalytic degradation of reactive dyes (Nansheng et al.,
1996). Behar et al. (1970) reported the possibility of
generating carbonate radical anions (CO
3 ) with the
help of hydroxyl radicals. Thus the free hydroxyl radical
which is a primary source (oxidant) for the photocatalytic degradation decreases gradually with increase in
carbonate ions and ultimately signicant decrease in the
percent degradation of reactive blue 4.
3.10. Inuence of sodium chloride
12
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tion and washing the catalyst. Hence the photodegradation of textile dyes employing solar energy may
emerge as a viable method because of its eco-friendliness
and cost eective.
Acknowledgements
This work was supported partially by Brain Korea 21
project 2000. The authors are grateful to the research
grant from the Ministry of Education, South Korea.
References
Fig. 8. Inuence of sodium chloride: initial concentration of
the dye 4 104 M, initial COD 108 mg/l and irradiation
time 8 h.
15
Cl h
vb ! Cl
16
Cl Cl !
Cl
2
17
4. Conclusion
It is evident that TiO2 catalysed photodegradation
using solar irradiation is a suitable technique for removal of dyes in wastewater from textile industries. The
intermediates formed during the course of degradation
give strong evidence for the destruction of the dye into
smaller fragments. The oxidising agents such as hydrogen peroxide and persulphate ion have major role in the
degradation eciency of the dye. The additives such as
sodium carbonate and sodium chloride are hindering the
rate of photocatalytic degradation but it can be removed
by diluting the dye solution to appropriate concentra-
1181