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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 electrogenerated hydrogen peroxide. In acidic solu-
toxic pollutants, there has been an increasing interest tions, the H2O2 is continuously provided by two-
in the treatment of industrial euents by electro- electron reduction of oxygen on the cathode surface
chemical methods as an alternative to traditional (Yeager, 1984):
biological treatments, in recent years. Many studies O2 2H 2e ! H2 O2 1
have been carried out on the direct anodic oxidation
of wastewater containing organic pollutants (Schar- Carbon is widely used as a cathode material for
ian and Kirk, 1986; Comninellis and Pulgarin, 1991; hydrogen peroxide generation because it exhibits a
Stucki et al., 1991; Feng et al., 1995). Several anode range of electrochemical activities towards oxygen
materials have been tested, but the complete miner- reduction, high overpotential for hydrogen evolution
alization of the pollutants has only been obtained and low catalytic activity for hydrogen peroxide
using high oxygen overvoltage anodes such as SnO2 decomposition:
(Cossu et al., 1998; Comninellis and Pulgarin, 1993), H2 O2 2H 2e ! 2H2 O 2
PbO2 (Belhadj and Savall, 1998; Bonfatti et al., 1999)
and boron-doped diamond (Fot et al., 1999; Perret These properties can be enhanced (Nagaoka et al.,
et al., 1999). 1986; Do and Chen, 1994) or decreased (Kinoshita,
Besides direct oxidation, organic pollutants can 1988) by chemical or electrochemical surface pre-
also be treated by an indirect electrolysis generating treatment depending on the nature of the electrode
in situ chemical agents such as hypochlorite ions surface.
(Panizza et al., 2000; Do and Yeh, 1995; Comninellis Hydrogen peroxide alone is not a strong oxygen-
and Nerini, 1995), ozone (Tatapudi and Fenton, transfer agent, but the oxidation of organics is
1993), and hydrogen peroxide (Sudoh et al., 1986). improved in the presence of Fe2+ ions because the
Several authors have reported on the removal of reaction leads to the formation of the highly
organic pollutants, such as formaldehyde (Do and oxidizing OH radicals, according to Fentons
Chen, 1993), aniline (Brillas et al., 1995), phenol 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): 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
3  2
Fe e ! Fe 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
In this paper the electrochemical treatment of a real (Kinoshita, 1988). After each treatment the cathode was
chemical wastewater, mainly containing naphtha- washed with distilled water and dried in air.
lene- and anthraquinone-sulphonic acids was studied, During the electrolysis the solution was saturated with
by electrogeneration of Fentons reagent using oxygen and its temperature was maintained at 358C. In fact,
a higher temperature would cause an increase in the
graphite cathodes. In particular, the eect of cathode
oxidation rate but the current eciency would decrease
potential, Fe2+ concentration and cathode surface due to the increase in the self-decomposition of hydrogen
pre-treatment were also analysed in order to nd the peroxide (Do and Yeh, 1996):
optimal operating conditions.
2H2 O2 ! 2H2 O O2 7
EXPERIMENTAL
During the electrolyses, the pH of the solution was
Euent continually adjusted to pH=4 by the addition of H2SO4
because it was found by other authors (Lin and Lo, 1997;
The wastewater used for the study was obtained from the
Lunar et al., 2000) that the degree of oxidation of organics
regeneration of ion-exchange resin towers by a chemical
with Fentons reagent is maximum when the pH lies in the
industry. These towers constitute the nal step in the
interval pH 35.
treatment plant. They receive the euent from a biological
The electrolyses were carried out by means of potentio-
treatment system and allow the lowering of the chemical
static methods using an EG&G mod. 273/A potentiostat.
oxygen demand (COD) value and colour, as they hold the
The amount of electricity was measured by a coulometer.
sulphonic compounds:
During the experiments samples were drawn from the cell
R OH C10 H7 SO   at dierent times and analysed. The COD and the lowering
3 ! R C10 H7 SO3 OH 5
of colour were chosen as parameters in order to evaluate the
As the resins lose eciency during their functioning, they progress of the oxidation. The COD was determined with
are regenerated: the open reux method according to standard methods
(APHA, 1989). As the residual H2O2 reacts with dichromate
R C10 H7 SO 
3 NaOH ! R OH C10 H7 SO3 Na and hence a higher COD would be obtained, its eect was
6 considered in the COD measurements. It was observed that
At this moment, naphthalene- and anthraquinone-sulphonic for 1 mg l1 residual H2O2, an additional 0.3 mg l1 COD is
acids are released, producing the dark coloured euent that generated. The hydrogen peroxide concentration was
is the object of this study. The composition and other determined by titration with potassium permanganate.
characteristics of the tested euent are reported in Table 1. The fading of colour was monitored by measuring the
Since no iron was present in the euent, dierent decrease of absorbance at 420 nm, the length of the
concentrations of FeSO4 were added to the solution, in maximum absorbance, using a spectrophotometer (Perkin-
order to promote Fentons reaction. Elmer Lambda 2).
The instantaneous current eciency (ICE) for the
organics oxidation was calculated as
Apparatus and procedure
The experiments were performed using an undivided cell
CODt  CODtDt
with a volume of 200 ml, supplied with a heat exchanger and ICE FV 10
a magnetic stirrer (Fig. 1). 8000 DQ
The reference electrode was a saturated calomel electrode
(SCE), placed in a glass-luggin capillary positioned 3 mm where (COD)t and (COD)tDt are the chemical oxygen
from the cathode surface. A platinum wire (area=3 cm2) demands at times t and t+Dt (in mg O2 dm3) respectively,
was used as the anode and a commercial graphite felt F is the Faraday constant (96,487 C mol1), V is the volume
(area=15 cm2, thickness=0.6 cm, BET51 m2/g) as the of electrolyte (dm3), and DQ is the charge passed between
cathode. The electric contact of the cathode was made by time t and t+Dt (C).
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

Table 1. Characteristics of the exchange regeneration euent

Parameter Value

Naphthalene sulphonic acid 26.1 mg l1


Naphthalene disulphonic acid 95.1 mg l1
Hydroxy naphthalene disulphonic acid 176.1 mg l1
Anthraquinone sulphonic acid 34.5 mg l1
Anthraquinone disulphonic acid 138.3 mg l1
Aminoanthraquinone 24.6 mg l1
Phenol 16.5 mg l1
Chlorides 5 mg l1
Carbonates 4100 mg l1
Absorbance (420 nm) 1.266
COD 1361 mg l1
Conductivity 7450 mS cm1
Fig. 1. Schematic diagram of the experimental set-up.
Removal of pollutants from wastewater 3989

RESULTS AND DISCUSSION On the basis of the current/potential curves,


therefore, the electrolysis of the wastewater was
In order to choose the correct potential at which carried out at a constant potential of 1 V vs. SCE,
the electrochemical generation of hydrogen peroxide using both unmodied and pre-treated graphite as a
takes place, some current/potential curves were cathode. In fact, at potentials more negative than
recorded. Figure 2 shows the results of these 1 V vs. SCE the current eciency drops due to the
experiments performed in aerated and deaerated secondary reaction of hydrogen evolution (Fig. 2,
euent. curve b).
In aerated solution, with unmodied graphite, a The evolution of COD during a preliminary
plateau at about 1 V vs. SCE was observed, curve electrolysis carried out in a deaerated solution,
(a). This plateau was attributed to the reduction of showed that the anodic oxidation of organics on
dissolved oxygen to H2O2, according to reaction (1). platinum anode can be disregarded (Fig. 3). Figure 3
This assumption was conrmed by the fact that in also shows the inuence of Fe2+ ions on the COD
nitrogen purged solution, the current was lower evolution during the electrolyses carried out with
because oxygen reduction was avoided (curve b). unmodied graphite in aerated solution. In the
However, for a potential more cathodic than 1.2 V absence of ferrous ions, only a low COD depletion
vs. SCE the side reaction of hydrogen evolution was obtained, after 15 h of electrolyses, because H2O2
commenced. alone is a bad oxidant for organic compounds.
Curves (c) and (d) illustrate the inuence of On the contrary, in the solution containing Fe2+
electrode surface modication on oxygen reduction ions, organics oxidation was accelerated because of
in aerated solution. Replacing the unmodied gra- the formation of OH radicals, according to Fentons
phite with electrochemical pre-treated graphite as reaction (equation (3)). The COD removal increased
cathode material, curve (d), resulted in an increase of from 51% to 87% when the concentration of Fe2+
the plateaux and consequently in an increase of the ions increased from 0 to 3 mM. With a further
oxygen reduction activity. In fact, anodic pre- increase of Fe2+ concentration to 4 mM, no sig-
treatment caused an increase of quinone-like groups nicant changes in COD removal were observed.
on graphite surface which are active functional This fact was probably due to the consumption of
groups involved in oxygen reduction to hydrogen OH radicals by an excess of ferrous ions:
peroxide (Do and Chen, 1994).
Fe2 OH Fe3 OH 8
On the contrary, the plateau reduction current
3+
decreased when chemically modied graphite was In addition, at pH=4, we observed that Fe also
used as cathode, curve (c). This behaviour, in reacted with H2O2 and precipitated as Fe(OH)3.
accordance with results obtained by Pakula et al. During the electrolyses the cell potential remained
(1995) may be explained by the decrease in specic almost constant at DE=2.9  0.1 V.
surface area (SBET ) caused by chemical oxidation. Figure 4 shows that, in the rst 5 h of electrolysis,
Curves (c) and (d) also indicate that the potential the COD depletion is a pseudo-rst-order reaction,
where oxygen reduction and hydrogen evolution and it is well described by the equation
commenced were not signicantly inuenced by COD0
surface pre-treatment. ln kt 9
CODt

Fig. 2. I2E curves on graphite-felt electrodes (thickness=6 mm, area=15 cm2). Conditions: pH=4, scan
rate=5 mV s1. (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.
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 Comninellis Ch. and Pulgarin C. (1993) Electrochemical


oxidation of phenol for wastewater treatment using SnO2
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organic compounds producing in situ hydrogen Renoldi F. (1998) Electrochemical treatment of landll
leachate: oxidation at Ti/PbO2 and Ti/SnO2 anodes.
peroxide by oxygen reduction on graphite cathodes. Environ. Sci. Technol. 32, 35703573.
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and electrode surface pre-treatment on the treatment formaldehyde with electrogenerated hydrogen peroxide.
performances are investigated. Experimental results J. Electrochem. Soc. 140, 16321637.
Do J. S. and Chen P. (1994) In situ oxidative degradation of
showed that: formaldehyde with hydrogen peroxide electrogenerated
on the modied graphite. J. Appl. Electrochem. 24,
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concentration of 3 mM for the electro-Fenton degradation of phenol with in situ electrogenerated
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Italian National Research Program entitled Leghe e Kinoshita K. (1988) Carbon. Electrochemical and Physico-
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