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abstract
Article history:
The electrochemical removal of a synthetic solution containing 120 mg L1 of alizarin red
has been studied by electro-Fenton process using a gas-diffusion cathode to produce in situ
hydrogen peroxide by oxygen reduction. The effect of operating conditions such as Fe2
14 October 2008
concentration, applied current, solution pH and temperature on the efficacy of the process
was investigated. It is shown that alizarin red and its products may be effectively degraded
by the OH radicals produced by the reaction between the Fe2 ions and the electro-
Keywords:
After 4 h of electrolysis COD removal was only 45% when no ferrous ions were added to the
Electro-Fenton
solutions, while the presence of ferrous ion greatly improved COD removal up to more than
Gas-diffusion electrode
90%. In particular 1.0 mM was the optimal concentration of ferrous ions and the single step
Alizarin red
or the stepwise addition of Fe2 ions enables the same COD removal. The oxidation rate
Dyes removal
increased with increasing of current density and temperature and with decreasing of pH.
generated H2O2.
The UVvis analysis indicated that the discoloration of the solution occurs simultaneous
with the destruction of aromatic rings and alizarin red is oxidised firstly to colourless
intermediates (mainly phthalic acid, small carbonyl species) and then to carbon dioxide.
2008 Elsevier Ltd. All rights reserved.
1.
Introduction
(1)
(2)
340
(3)
(4)
(5)
(6)
2.
Experimental
2.1.
COD0 CODt
F V 100
8 I t
(7)
1,2-Dihydroxyanthraquinone
C14H8O4
OH
OH
Chemical structure
O
Molecular Weight
Class
Colour index
240.2 g/mol
Anthraquinone
58055
341
2.2.
3.
3.1.
COD removal (
The electrochemical oxidation of alizarin red by electro-Fenton process was studied under different experimental conditions in order to investigate the influence of operative
parameters on COD and colour removal.
Fig. 1 shows the influence of Fe2 ions on the evolution of
COD during the treatment of 120 mg L1 of alizarin red solution at 200 mA and pH 3.
250
(8)
3.2.
(9)
75
50
250
25
0
0
0.5
1.5
200
150
200
100
100
50
Addition
150
100
50
0
0
Time (h)
Fig. 1 Influence of the Fe2D concentration on COD
evolution during the electrolysis of alizarin red.
Conditions: Na2SO4 0.05 M, pH [ 3; T [ 25 8C; I [ 200 mA;
Fe2D concentration: (,) 0 mM; (O) 0.25 mM; (B) 0.5 mM;
(>) 1.0 mM; (3) 2.0 mM. The inset shows the evolution of
COD removal after 4 h of treatment as a function of Fe2D
concentration.
0
0
Time (h)
Fig. 2 Effect of Fe2D feeding on COD evolution during the
electrolysis of alizarin red. Conditions: Na2SO4 0.05 M,
pH [ 3; T [ 25 8C; I [ 200 mA; Fe2D feeding: (,) 1.0 mM at
t [ 0 h; (O) 0.5 mM at t [ 0 h; (B) 0.5 mM at
t [ 0 h D 0.5 mM at t [ 2 h.
342
60
C.E. ( )
250
200
150
40
20
0
0
Q (Ah L-1)
100
50
0
0
Time (h)
Fig. 3 Influence of applied current on COD and current
efficiency (inset) evolution during the electrolysis of
alizarin red. Conditions: Na2SO4 0.05 M, pH [ 3; T [ 25 8C;
Fe2D [ 1.0 mM; applied current: (,) 100 mA; (O) 150 mA;
(B) 200 mA.
3.3.
Influence of pH
3.4.
Influence of temperature
(10)
3.5.
Oxidation mechanism
250
200
COD removal ( )
100
80
60
150
100
40
50
20
0
0
0
0
pH (-)
Fig. 4 Effect of pH on the COD removal during the
electrolysis of alizarin red. Conditions: Na2SO4 0.05 M;
T [ 25 8C; Fe2D [ 1.0 mM; applied current: 200 mA.
Time (h)
Fig. 5 Influence of temperature on the COD removal
during the electrolysis of alizarin red. Conditions: Na2SO4
0.05 M, pH [ 3; Fe2D [ 1.0 mM; I [ 200 mA; Temperature:
(B) 25 8C; (O) 35 8C; (,) 45 8C.
C / C (-)
Absorbance (a.u.)
5
0h
0.5 h
1.0 h
1.5 h
2.0 h
4
3
references
0.8
0.6
0.4
0.2
0
0
Time (h)
2
1
0
200
300
400
500
600
Wavelenght (nm)
Fig. 6 Changes in the UVvis spectra with the time passed
during electrolysis of alizarin red. Conditions: Na2SO4
0.05 M, pH [ 3; T [ 25 8C; Fe2D [ 1.0 mM; applied current:
200 mA. The inset shows the time evolution of the
normalised absorbance peak (ratio absorbance/initial
absorbance: C/C8) at (O) 420 nm and (B) 280 nm and
normalised COD (,).
with the same ratios during the treatment and faster than the
COD (Fig. 6, inset). This fact indicates that, in agreement with
the mechanism proposed by Liu et al. (Liu et al., 1999), the first
step in the oxidation of alizarin red is the cleavage of the
aromatic ring in the CC bond near the C]O group to form
colourless intermediates (mainly phthalic acid, small
carbonyl species) and finally these intermediates are mineralised to carbon dioxide.
4.
343
Conclusions
Acknowledgements
The authors gratefully acknowledge Dr. Paolo Granone for his
helpful discussion.
344
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