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Photo-Fenton Treatment of Water Containing Natural (2003)
Photo-Fenton Treatment of Water Containing Natural (2003)
www.elsevier.com/locate/chemosphere
b,*
Institute of Physical and Theoretical Chemistry, Vienna University of Technology, Veterinarplatz 1, A-1210 Vienna, Austria
b
CIEMATPlataforma Solar de Almera, P.O. Box 22, E-04200 Tabernas, Almera, Spain
c
Pesticide Residue Research Group, University of Almera, 04071 Almera, Spain
Received 10 December 2001; received in revised form 15 July 2002; accepted 15 July 2002
Abstract
Phenolic compounds are known to be present in high concentrations in various types of agro-industrial wastes. As
they are highly biorecalcitrant, the possibility of treatment by advanced oxidation processes should be investigated.
In this work, six model phenolic compounds (vanillin, protocatechuic acid, syringic acid, p-coumaric acid, gallic acid
and L -tyrosine) were chosen for a demonstration of degradation by photo-Fenton reaction, under articial light in
laboratory experiments in Vienna and under sunlight in pilot-plant experiments at the Plataforma Solar de Almera in
Spain.
All compounds were completely mineralised. No non-degradable intermediates were produced, either in experiments
with single substances or in a more complex matrix of a mixture of phenolic compounds. The expected selectivity of the
photo-Fenton reaction for aromatic compounds was proven by comparison of the decrease in total organic carbon with
the removal of total phenolic content.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Phenols; Photocatalysis; Photochemical treatment; Photo-Fenton; Water detoxication
1. Introduction
Various natural phenols and their condensation
products, such as tannins or lignins, are present in several types of agro-industrial wastes. Examples of such
wastewater originate in wood-processing industries, as
for instance, paper mills, masonite (fabrication of breboard), debarking of wood (Tello, 2001) or the cork
industry (Moreno, 1994), from tanneries using natural
tannins that still exist in great numbers (Bruneton,
1986), from grape pressing in the wine industry (vinasse)
0045-6535/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 4 0 3 - 4
72
2. Methods
2.1. Analysis
Ferrous sulphate FeSO4 7H2 O and sulphuric acid
were analytical grade (Merck). Hydrogen peroxide (30%
w/v) was analytical grade (Merck) for laboratory purposes and technical grade for the pilot-plant experiments. Total organic carbon (TOC) and inorganic
73
y
vw
Cu Hv Nw Ox Ox ! uCO2
H2 O wHNO3
2
2
1
1
1
y 2u m w x
2
5
74
Table 1
Experiments performed
Experiment
Performed
Reactor
Volume (l)
Substance
H2 O2 (mM)
Iron [mM]
E1
E2
E3
E4
E5
E6
E7
E8
E9
E10
E11
E12
E13
E14
Vienna
Vienna
Vienna
Vienna
Vienna
Vienna
PSA
PSA
PSA
PSA
PSA
PSA
PSA
PSA
Flask
Flask
Flask
Flask
Flask
Flask
FFR
FFR
FFR
FFR
FFR
FFR
FFR
FFR
2
2
2
2
2
2
19
19
19
19
19
19
19
19
17
12
13
19
23.5
18
17
17
17
12
13
19
23.5
85
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.2
1.0
0.2
0.2
0.2
0.2
0.2
E15
E16
E17
PSA
PSA
PSA
CPC
CPC
CPC
35
35
35
Vanillin
Gallic acid
Protocatechuic acid
Coumaric acid
L -Tyrosine
Syringic acid
Vanillin
Vanillin
Vanillin
Gallic acid
Protocatechuic acid
Coumaric acid
L -Tyrosine
Mixture of vanillin, gallic,
protocatechuic, coumaric acid
and L -tyrosine
Vanillin
Gallic acid
Protocatechuic acid
17
12
13
0.05
0.05
0.05
Initial concentration of phenolic compounds was 1 mM in all tests (1 mM each in the mixture).
Fig. 2. Degradation of p-coumaric acid and carbon mass balance (Experiment E4) in laboratory reactor.
Fig. 3. Phenol index: gallic vs. syringic acid in laboratory reactor (Experiments E2 and E6).
75
The reaction rate is a crucial parameter for evaluation of the application costs, because it determines the
size of the photoreactor required for treatment of a
given wastewater and, therefore, signicantly inuences,
not only the investment, but also the operating costs.
Consequently faster reaction rates are usually desirable
(Goswami et al., 1997) and, depending on the iron
concentration, the reaction has a maximum rate.
Fig. 4 shows the degradation of TOC for vanillin
with three dierent iron concentrations (Experiments
E7, E8 and E9, cf. Table 1). By approximately quadrupling the iron concentration from 0.05 to 0.2 mM, the
incident UV-radiation per litre necessary to achieve almost complete mineralisation was halved. A similar effect was reached by quintupling the iron concentration
to 1 mM. This shows the potential for increasing reaction rates with higher iron concentrations than used in
76
Dtn UVGN A
1000 V
77
4. Conclusions
78
Acknowledgements
The authors wish to thank the EC-DG Research
Improving Human Potential Programme (number of
contract HPR I-CT-1999-00013) and the LAGAR
Project (EC Fourth Framework Programme, number of
contract FAIR-CT98-3807, DG12-SSMI). The authors
also thank Mrs. Deborah Fuldauer for the correction of
the English.
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