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Removal of Organic Pollutants From Industrial

Wastewater by Electrogenerated Fenton's
Reagent

ARTICLE in WATER RESEARCH DECEMBER 2001

Impact Factor: 5.53 DOI: 10.1016/S0043-1354(01)00135-X Source: PubMed

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 Wat. Res. Vol. 35, No. 16, pp. 39873992, 2001
# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(01)00135-X 0043-1354/01/$ - see front matter

RESEARCH NOTE
REMOVAL OF ORGANIC POLLUTANTS FROM INDUSTRIAL
WASTEWATER BY ELECTROGENERATED FENTONS
REAGENT
MARCO PANIZZA* and GIACOMO CERISOLA
Dipartimento di Ingegneria Chimica e di Processo, P.le J. F. Kennedy 1, 16129 Genova, Italy

(First received 5 June 2000; accepted in revised form 10 February 2001)

Abstract}This study was performed to investigate the treatment of an industrial wastewater mainly
containing naphthalene- and anthraquinone-sulphonic acids, by electrogenerated Fentons reagent. The
hydrogen peroxide was produced in situ by electrochemical reduction of oxygen on graphite-felt cathodes
and the Fe2+ ions were also regenerated by cathodic reduction of Fe3+. The inuence of cathode
potential, Fe2+ concentration and electrode surface pre-treatment on chemical oxygen demand (COD)
removal and colour fading were studied. Results indicated that the higher COD removal was obtained in
the presence of 3 mM of ferrous ions working at a constant potential of
1 V vs. SCE. Moreover, it was
shown that both chemical and electrochemical pre-treatments of the cathode surface resulted in a decrease
of COD depletion. # 2001 Elsevier Science Ltd. All rights reserved

Key words}wastewater treatment, hydrogen peroxide, COD removal, graphite electrodes, polyaromatic
compounds

INTRODUCTION (Alvarez-Gallegos and Pletcher, 1999), by in situ

As many industries produce wastewater containing
toxic pollutants, there has been an increasing interest
in the treatment of industrial euents by electro-
chemical methods as an alternative to traditional
biological treatments, in recent years. Many studies
have been carried out on the direct anodic oxidation
of wastewater containing organic pollutants (Schar-
ian and Kirk, 1986; Comninellis and Pulgarin, 1991;
Stucki et al., 1991; Feng et al., 1995). Several anode
materials have been tested, but the complete miner-
alization of the pollutants has only been obtained
using high oxygen overvoltage anodes such as SnO2
(Cossu et al., 1998; Comninellis and Pulgarin, 1993),
PbO2 (Belhadj and Savall, 1998; Bonfatti et al., 1999)
and boron-doped diamond (Fot et al., 1999; Perret
et al., 1999).
Besides direct oxidation, organic pollutants can
also be treated by an indirect electrolysis generating
in situ chemical agents such as hypochlorite ions
(Panizza et al., 2000; Do and Yeh, 1995; Comninellis
and Nerini, 1995), ozone (Tatapudi and Fenton,
1993), and hydrogen peroxide (Sudoh et al., 1986).
Several authors have reported on the removal of
organic pollutants, such as formaldehyde (Do and
Chen, 1993), aniline (Brillas et al., 1995), phenol
electrogenerated hydrogen peroxide. In acidic solu-
tions, the H2O2 is continuously provided by two-
electron reduction of oxygen on the cathode surface
(Yeager, 1984):
O2 2H 2e
! H2 O2 1
Carbon is widely used as a cathode material for
hydrogen peroxide generation because it exhibits a
range of electrochemical activities towards oxygen
reduction, high overpotential for hydrogen evolution
and low catalytic activity for hydrogen peroxide
decomposition:
H2 O2 2H 2e
! 2H2 O 2
These properties can be enhanced (Nagaoka et al.,
1986; Do and Chen, 1994) or decreased (Kinoshita,
1988) by chemical or electrochemical surface pre-
treatment depending on the nature of the electrode
surface.
Hydrogen peroxide alone is not a strong oxygen-
transfer agent, but the oxidation of organics is
improved in the presence of Fe2+ ions because the
reaction leads to the formation of the highly
oxidizing OH radicals, according to Fentons
mechanism (Brillas et al., 1998; Do and Yeh, 1996):

Fe2 H2 O2 ! Fe3 OH
OH 3

*Author to whom all correspondence should be addressed.
Tel.: +39-010-353-6032; fax: +39-010-353-6028; e-mail: The propagation of Fentons reaction can also be
ici-corr@unige.it enhanced by electrochemical regeneration of Fe2+
3987
3988 Marco Panizza and Giacomo Cerisola

ions on the cathode surface (Brillas et al., 1996):
3
2
Fe e ! Fe
In this paper the electrochemical treatment of a real
chemical wastewater, mainly containing naphtha-
lene- and anthraquinone-sulphonic acids was studied,
by electrogeneration of Fentons reagent using
graphite cathodes. In particular, the eect of cathode
potential, Fe2+ concentration and cathode surface
pre-treatment were also analysed in order to nd the
optimal operating conditions.
EXPERIMENTAL
Euent
The wastewater used for the study was obtained from the
regeneration of ion-exchange resin towers by a chemical
industry. These towers constitute the nal step in the
treatment plant. They receive the euent from a biological
treatment system and allow the lowering of the chemical
oxygen demand (COD) value and colour, as they hold the
sulphonic compounds:
R OH
C10 H7 SO



3 ! R C10 H7 SO3 OH 5
As the resins lose eciency during their functioning, they
are regenerated:
R C10 H7 SO


3 NaOH ! R OH C10 H7 SO3 Na
At this moment, naphthalene- and anthraquinone-sulphonic
acids are released, producing the dark coloured euent that
is the object of this study. The composition and other
characteristics of the tested euent are reported in Table 1.
Since no iron was present in the euent, dierent
concentrations of FeSO4 were added to the solution, in
order to promote Fentons reaction.
Apparatus and procedure
The experiments were performed using an undivided cell
with a volume of 200 ml, supplied with a heat exchanger and
a magnetic stirrer (Fig. 1).
The reference electrode was a saturated calomel electrode
(SCE), placed in a glass-luggin capillary positioned 3 mm
from the cathode surface. A platinum wire (area=3 cm2)
was used as the anode and a commercial graphite felt
(area=15 cm2, thickness=0.6 cm, BET51 m2/g) as the
cathode. The electric contact of the cathode was made by
a platinum wire isolated from the solution. The surface of
the graphite felt was modied by electrochemical or
chemical pre-treatment. The former was executed by
anodization in a phosphate buer (pH=6.88) at 1.8 V vs.
SCE for 5 min, followed by cathodization at
1.5 V vs. SCE
4 for 1 min (Nagaoka et al., 1986). The latter consisted of
dipping the graphite in a solution 0.5 M of H2SO4 for 30 min
(Kinoshita, 1988). After each treatment the cathode was
washed with distilled water and dried in air.
During the electrolysis the solution was saturated with
oxygen and its temperature was maintained at 358C. In fact,
a higher temperature would cause an increase in the
oxidation rate but the current eciency would decrease
due to the increase in the self-decomposition of hydrogen
peroxide (Do and Yeh, 1996):
2H2 O2 ! 2H2 O O2 7
During the electrolyses, the pH of the solution was
continually adjusted to pH=4 by the addition of H2SO4
because it was found by other authors (Lin and Lo, 1997;
Lunar et al., 2000) that the degree of oxidation of organics
with Fentons reagent is maximum when the pH lies in the
interval pH 35.
The electrolyses were carried out by means of potentio-
static methods using an EG&G mod. 273/A potentiostat.
The amount of electricity was measured by a coulometer.
During the experiments samples were drawn from the cell
at dierent times and analysed. The COD and the lowering
of colour were chosen as parameters in order to evaluate the
progress of the oxidation. The COD was determined with
the open reux method according to standard methods
(APHA, 1989). As the residual H2O2 reacts with dichromate
and hence a higher COD would be obtained, its eect was
6 considered in the COD measurements. It was observed that
for 1 mg l
1 residual H2O2, an additional 0.3 mg l
1 COD is
generated. The hydrogen peroxide concentration was
determined by titration with potassium permanganate.
The fading of colour was monitored by measuring the
decrease of absorbance at 420 nm, the length of the
maximum absorbance, using a spectrophotometer (Perkin-
Elmer Lambda 2).
The instantaneous current eciency (ICE) for the
organics oxidation was calculated as
CODt
CODtDt
ICE FV 10
8000 DQ
where (COD)t and (COD)tDt are the chemical oxygen
demands at times t and t+Dt (in mg O2 dm
3) respectively,
F is the Faraday constant (96,487 C mol
1), V is the volume
of electrolyte (dm3), and DQ is the charge passed between
time t and t+Dt (C).

Table 1. Characteristics of the exchange regeneration euent

Parameter Value

Naphthalene sulphonic acid 26.1 mg l
1

Naphthalene disulphonic acid 95.1 mg l
1
Hydroxy naphthalene disulphonic acid 176.1 mg l
1
Anthraquinone sulphonic acid 34.5 mg l
1
Anthraquinone disulphonic acid 138.3 mg l
1
Aminoanthraquinone 24.6 mg l
1
Phenol 16.5 mg l
1
Chlorides 5 mg l
1
Carbonates 4100 mg l
1
Absorbance (420 nm) 1.266
COD 1361 mg l
1
Conductivity 7450 mS cm
1
Fig. 1. Schematic diagram of the experimental set-up.
 Removal of pollutants from wastewater
RESULTS AND DISCUSSION
In order to choose the correct potential at which
the electrochemical generation of hydrogen peroxide
takes place, some current/potential curves were
recorded. Figure 2 shows the results of these
experiments performed in aerated and deaerated
euent.
In aerated solution, with unmodied graphite, a
plateau at about
1 V vs. SCE was observed, curve
(a). This plateau was attributed to the reduction of
dissolved oxygen to H2O2, according to reaction (1).
This assumption was conrmed by the fact that in
nitrogen purged solution, the current was lower
because oxygen reduction was avoided (curve b).
However, for a potential more cathodic than
1.2 V
vs. SCE the side reaction of hydrogen evolution
commenced.
Curves (c) and (d) illustrate the inuence of
electrode surface modication on oxygen reduction
in aerated solution. Replacing the unmodied gra-
phite with electrochemical pre-treated graphite as
cathode material, curve (d), resulted in an increase of
the plateaux and consequently in an increase of the
oxygen reduction activity. In fact, anodic pre-
treatment caused an increase of quinone-like groups
on graphite surface which are active functional
groups involved in oxygen reduction to hydrogen
peroxide (Do and Chen, 1994).
On the contrary, the plateau reduction current
decreased when chemically modied graphite was
used as cathode, curve (c). This behaviour, in
accordance with results obtained by Pakula et al.
(1995) may be explained by the decrease in specic
surface area (SBET ) caused by chemical oxidation.
Curves (c) and (d) also indicate that the potential
where oxygen reduction and hydrogen evolution
commenced were not signicantly inuenced by
surface pre-treatment.
Fig. 2. I2E curves on graphite-felt electrodes (thickness=6 mm, area=15 cm2). Conditions: pH=4, scan
rate=5 mV s
1. (a) and (b) are for unmodied graphite in aerated and deaerated solution, respectively.
(c) and (d) are for chemical and electrochemical pre-treated electrode in aerated solution.
3989
On the basis of the current/potential curves,
therefore, the electrolysis of the wastewater was
carried out at a constant potential of
1 V vs. SCE,
using both unmodied and pre-treated graphite as a
cathode. In fact, at potentials more negative than

1 V vs. SCE the current eciency drops due to the
secondary reaction of hydrogen evolution (Fig. 2,
curve b).
The evolution of COD during a preliminary
electrolysis carried out in a deaerated solution,
showed that the anodic oxidation of organics on
platinum anode can be disregarded (Fig. 3). Figure 3
also shows the inuence of Fe2+ ions on the COD
evolution during the electrolyses carried out with
unmodied graphite in aerated solution. In the
absence of ferrous ions, only a low COD depletion
was obtained, after 15 h of electrolyses, because H2O2
alone is a bad oxidant for organic compounds.
On the contrary, in the solution containing Fe2+
ions, organics oxidation was accelerated because of
the formation of OH radicals, according to Fentons
reaction (equation (3)). The COD removal increased
from 51% to 87% when the concentration of Fe2+
ions increased from 0 to 3 mM. With a further
increase of Fe2+ concentration to 4 mM, no sig-
nicant changes in COD removal were observed.
This fact was probably due to the consumption of
OH radicals by an excess of ferrous ions:
Fe2 OH Fe3 OH
8
3+
In addition, at pH=4, we observed that Fe also
reacted with H2O2 and precipitated as Fe(OH)3.
During the electrolyses the cell potential remained
almost constant at DE=2.9  0.1 V.
Figure 4 shows that, in the rst 5 h of electrolysis,
the COD depletion is a pseudo-rst-order reaction,
and it is well described by the equation
COD0
ln kt 9
CODt
3990 Marco Panizza and Giacomo Cerisola

Fig. 3. Inuence of ferrous ion concentration on COD removal eciency using unmodied electrodes.
Conditions: area of cathode=15 cm2, thickness=0.6 cm, applied potential=
1 V vs. SCE, pH=4,
T=358C, volume=200 ml.

Fig. 4. Kinetic analysis for pseudo-rst-order COD removal using unmodied graphite cathodes.
Conditions: area of cathode=15 cm2, thickness=0.6 cm, applied potential=
1 V vs. SCE, pH=4,
T=358C, volume=200 ml.

where COD0 and CODt are chemical oxygen Table 2. Kinetic results for COD removal with dierent
demands at the beginning and at time t. This gure concentrations of ferrous ions, using unmodied graphite cathodesa

also shows that a pseudo-rst-order reaction might Fe2+ concentration (mM) k (s 103) t1/2 (min.) k0 (s 103)
describe the behaviour of the system also for the nal
stage. However, in this case the values of k were 0 0.823 830 0.266
about 1 order of magnitude lower than in the rst 5 h 1 2.06 340 0.316
2 3.635 192 0.326
of the electrolysis (Table 2). This was probably due to 3 4.557 130 0.320
the fact that during oxidation there is a formation of 4 4.995 144 0.332
intermediates that are more dicult to remove. A a
k: pseudo-rst-order kinetic during the rst 5 h, k0 : pseudo-rst-
similar behaviour was observed both by Cossu et al. order kinetic during the nal part of electrolyses. Conditions:
(1998) during the electrochemical oxidation of a area of cathode=15 cm2, thickness=0.6 cm, applied potential
=
1 V vs. SCE, pH=4, T=358C, volume=200 ml.
landll leachate and by Ribordy et al. (1997) during
the electrochemical treatment of an industrial waste-
water. Figure 6 shows the inuence of Fe2+ ions on
The formation of more stable compounds and the colour disappearance, expressed as a ratio between
decreasing of organic concentration in the bulk the initial absorbance and the absorbance at time t.
solution caused a decrease of current eciency and As expected from the measurement of COD,
an increase of side reactions (Fig. 5). increasing ferrous ion concentration from 0 to
 Removal of pollutants from wastewater 3991

Fig. 5. Trend of current eciency during the electrolysis with unmodied graphite. Conditions: area of
cathode=15 cm2, thickness=0.6 cm, applied potential=
1 V vs. SCE, pH=4, T=358C, volume=200 ml,
[Fe2+]=3 mM.

Fig. 6. Eect of Fe2+ concentration on colour fading, expressed as a ratio between the absorbance at time
t and the initial absorbance, during the electrolysis with unmodied graphite. Conditions: area of
cathode=15 cm2, thickness=0.6 cm, applied potential=
1 V vs. SCE, pH=4, T=358C, volume=200 ml.

3 mM resulted in an increase of colour removal. A

further increase of Fe2+ concentration had only a
slight inuence on colour elimination.
Further experiments were carried out on a solution
containing 3 mM FeSO4 using unmodied and pre-
treated graphite cathodes. As illustrated in Fig. 7,
after 15 h of treatment, the maximum COD removal
eciency (87%) was achieved with unmodied
graphite. According to the current/potential curves,
the COD removal decreased to 75% employing
chemical pre-treated graphite, owing to a decrease
in specic surface area. However, the COD removal
was not aected by electrochemically treated graphite
replaced unmodied graphite, although the anodized
one showed a higher limiting current plateau (Fig. 2). Fig. 7. Inuence of graphite surface pre-treatment on COD
We speculate that this behaviour may be due to an removal eciency. (a) Unmodied graphite, (b) chemically
pre-treated graphite and (c) electrochemically pre-treated
increase in the side reactions, such as hydrogen graphite. Conditions: area of cathode=15 cm2, thick-
peroxide decomposition, on an electrochemically ness=0.6 cm, applied potential=
1 V vs. SCE, electrolysis
modied surface. time=15 h.
3992 Marco Panizza and Giacomo Cerisola
CONCLUSION
This work has considered the electrochemical
treatment of a wastewater containing polyaromatic
organic compounds producing in situ hydrogen
peroxide by oxygen reduction on graphite cathodes.
The eects of cathode potential, Fe2+ concentration
and electrode surface pre-treatment on the treatment
performances are investigated. Experimental results
showed that:
(1) The reduction of oxygen to H2O2 on graphite felt
occurs at
1 V vs. SCE.
(2) The maximum COD removal (87%) and colour
fading (89%) were obtained with a Fe2+
concentration of 3 mM for the electro-Fenton
treatment process.
(3) The COD removal kinetic followed a pseudo-
rst-order reaction.
(4) Chemical or electrochemical surface pre-treat-
ments had no benecial inuence in organics
oxidation.
Acknowledgements}The partial nancial support of the
Italian National Research Program entitled Leghe e
composti intermetallici: stabilita e, termodinamica, proprie-
ta siche e reattivita of MURST is gratefully acknowl-
edged.
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