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Highly concentrated phenolic wastewater

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mechanism study by FTIR-ATR
Article in Chemosphere September 2001
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Chemosphere 44 (2001) 10171023

www.elsevier.com/locate/chemosphere

Highly concentrated phenolic wastewater treatment by the

Photo-Fenton reaction, mechanism study by FTIR-ATR
~a, E. Tello Rendo
n, J.M. Don
~a Rodrguez *, J.A. Herrera Meli
J. Aran
an,
O. Gonz
alez Daz, J. Perez Pe~
na
Departamento de Qumica, Universidad de Las Palmas de Gran Canaria, Campus de Tara, E-35017 Gran Canaria, Spain
Received 24 May 2000; accepted 22 August 2000

Abstract
Phenol degradation by Photo-Fenton reaction has been studied in highly concentrated wastewaters and most intermediate species have been identied by Fourier Transform IR-Spectroscopy with ATR device. During the photodegradation of highly concentrated phenol solutions, the formation of dissolved and precipitate tannin has been
observed. The possibility of a Fe3 -Pyrogallol complex formation, previous to the tannin formation, has been proposed
too. The complex formation involving Fe3 ions could be related to the observed Photo-Fenton activity decrease.
Tannin formation inhibits the complete mineralization of phenol because  OH radicals attack will produce further
condensation steps and the polymer size increase. This fact limits the applicability of the process for highly concentrated
phenolic wastes mineralization. However, the tannin precipitation allows its separation from the solution by conventional ltration, and reduction of the corresponding dissolved organic carbon. These observations have been proved
from the identication of primary degradation products, catechol and hydroquinone. Catechol is considered to be the
rst step for the formation of tannins. Degradation process for phenol, catechol and hydroquinone have been monitored by total organic carbon (TOC) measurements along the reaction time span. From these results, a global mechanism for the Photo-Fenton degradation of phenol is proposed. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Photo-Fenton reaction; FTIR; Mechanism; Photodegradation; Polymerization

1. Introduction
Phenol and its derivatives are considered one group
of dangerous and hard to eliminate organic pollutants,
when present at high concentrations. These substances,
including phenol, cresol and other substituted phenolic
compounds are the raw materials for one of the oldest
synthetic resins used in industry, the phenolformaldehyde resins. Usually a phenolformaldehyde resin is

*
Corresponding author Tel.: +34-928-45-44-37; fax: +34928-45-29-22.
E-mail address: jmd@cicei.ulpgc.es (J.M. Do~
na
Rodrguez).

prepared with formaldehyde 40% by volume. Then 750 l

of water is removed for each ton of nal product. When
solid formaldehyde is used, only 160 l of condensation
water are removed from the nal mixture. These phenolic residues contain between 6002000 mg/l of phenol
and between 5001300 mg/l of formaldehyde. Other
phenolic waste sources are summarized in Table 1.
Phenols are very toxic. The maximum inlet concentration for a biological water treatment plant (BWTP) is
12 mg/l. Lower phenol concentrations (110 lg/l) in
freshwater produce unpleasant odour/taste during the
chlorinating process. At present, these residues are diluted before been discharged to a BWTP or are incinerated (cost: 167 $/ton). Consequently, in the last few
years many studies have been focused to reduce phenol

0045-6535/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 0 ) 0 0 3 5 9 - 3

1018

J. Ara~na et al. / Chemosphere 44 (2001) 10171023

Table 1
Phenolic waste sources
No.

Chemicals

Process

Waste description

Quantity

Phenols and
formaldehyde

Phenolformaldehyde
resins

500 l/ton of phenolic

resin

Phenols

Storage tanks, ships,

lorries, piping

Condensation water containing

less than 2000 mg/l of phenols and
formaldehyde
Rinsing water containing less than
15,000 mg/l

Phenols

Phenols production

Spills, cleaning water

concentration in wastewaters (Augugliaro et al., 1990;

Tsong-Yang et al., 1990; Scheck and Frimmel, 1995;
Chen et al., 1997; Fajerwerg et al., 1997; Peralta-Zamora
et al., 1997).
Photocatalysis is nowadays one of the most ecient
methods for unspecic and total mineralization of dissolved organic pollutants, but its eciency is restricted
to low concentrated solutions.
Heterogeneous photocatalytic degradation consists
of the use of semiconductors such as TiO2 or ZnO, able
to interact with a photon and generate electrons and
holes that can give place to the formation of hydroxyl
radicals,  OH (Serpone and Pelizzetti, 1989). On the
other hand, in the Photo-Fenton reaction,  OH are
generated by the reaction of Fe2 with H2 O2 , and the
Fe3 reduction by UV-light (Kim et al., 1997). The
possibility of aromatic compounds degradation mediated by carboxylic and hydroxylic groups, through the
formation of complexes with Fe3 , has been proposed
too (Sun and Pignatello, 1993):
RCO2 Fe2 hm ! R CO2 Fe2

0.1% w/w of the total

production diluted in
60 volumes of water
Idem 2

and intermediate species participate. Experimental conditions for the degradation of those intermediates may
not be the same for all of them. This may be the reason
why in many cases the complete elimination of total
organic carbon (TOC) in not achieved.
In this article, the phenol degradation at high
concentrations (15 g/l of C from phenol) by the
Photo-Fenton reaction has been studied. Experimental
conditions, considering the intermediates species, have
been optimized in order to obtain a TOC reduction of
about 100%. The reaction process has been monitored
by FTIR spectroscopy, and most of the intermediate
species have been identied. From these results, a global
mechanism for the degradation of phenol is proposed.
The possibility of tannin precipitation makes this
process able to detoxicate high phenol concentrated
wastewaters by ltration and separation of the low toxic
tannin solid waste.

2. Experimental section
2.1. Chemicals

ROHFe3 hm ! RO H Fe2

Other authors have indicated the possible participation
of Fe3 by-product complexes in the Fe3 to Fe2 reduction, without coupled dissolved organic compounds
oxidation during the reduction step (Zepp et al., 1992):

The reagents used were Aldrich products: phenol

99:0 %, catechol 99:0 %, hydoquinone (99%),
hydogen peroxide (33%) and dihydrated ferrous sulphate. The pH control was maintained with 0.5 N nitric
acid solution.

Fe3 Ln hm ! Fe2

2.2. Equipments and analyses

Fe2 H2 O2 ! OH Fe3

Experiments were carried out in 200 ml glass vessels.

Sample solutions were continuously air bubbled. The
dissolved organic carbon concentrations were over 0.5
g/l in every experiment, because the FTIR technique is
unable to follow the process evolution for lower concentrations due to the low signal intensity. Samples' pH
was held at 3 during the whole experiment. An 800 W
UV-lamp (HPA 8068, ENCO) was employed as UV
light source. TOC was analyzed by a TOC Shimadzu
5000 A analyzer.
IR studies were made by a spectrophotometer FTIR
model RS/1 (UNICAM), equipped with an air and CO2

These complexes have been considered as possible process-accelerating species (Chen and Pignatello, 1997).
Many mechanisms for the phenol degradation by
heterogeneous photocatalysis have been proposed. It has
been suggested that phenol is oxidized by  OH radicals,
and converted in catechol and hydroquinone. These may
be degraded to aliphatic acids and nally to CO2
(Okamoto et al., 1985a,b; Mattews and McEvoy, 1992).
The global mechanism for the complete mineralization of phenol is very complex since many dierent steps

J. Ara~na et al. / Chemosphere 44 (2001) 10171023

purge unit. An internal reection device (Standard Circle Liquid Analyzer, Spectra-tech) has been employed
for the determination of water-dissolved substances. IR
spectra were made with 128 scans using a 4 cm 1 resolution. Reference water was subtracted to every spectra
shown in this article. KubelkaMunk units have been
employed.

3. Results and discussion

3.1. Phenol
In the rst assay (phenol-a) a 5 g/l test solution (200
ml) was employed for the Photo-Fenton reaction. 0.02
g/l of Fe2 and three doses of 2 g/l of H2 O2 each, were
added after 0, 2 and 4 h. Initially, when phenol-started
reaction promoted by Fe2 and H2 O2 , the solution became yelloworange and the progressive appearance of a
precipitate in the same color was observed.
Four hours after the reaction started, no important
degradation, as TOC reduction, was noticed (Fig. 1).
However, the phenol IR bands evolution with reaction
time showed the phenol degradation to other products.
After every H2 O2 dose addition, a sudden organic carbon mineralization took place, but it did not progress
with time, indicating that it is the Fenton reaction, independent on irradiation, which was taking place as the
initial step for the process (Peral et al., 1988).
On the other hand, the reaction monitoring by FTIR
measurements conrmed the progressive transformation
of phenol into catechol and hydroquinone. Fig 2(a)
shows the obtained spectra between 1000 and 1600
cm 1 , after 3 h of reaction and after subtracting the
initial phenol spectrum. Reference spectra for catechol
and hydroquinone are also shown. Absorption bands at
1519, 1480, 1385 and 1100 cm 1 may be attributable to
both catechol and hydroquinone, but bands at 1289,
1270 and 1020 cm 1 and those at 1230 and 1210 cm 1

Fig. 1. % Phenol-a degraded.

1019

are only attributable to catechol and hydroquinone, respectively. An absorption shift to higher wavenumbers
(1393 cm 1 ) due to OH tension is observed. This band
shift may be due to the presence of other species in the
solution. In fact, once the catechol and hydroquinone
reference spectra have been subtracted from this spectrum, remaining bands at 1393, 1310, 1287 and 1229
cm 1 may be observed.
Fig. 3(a) shows the spectrum acquired from the
precipitate obtained during the phenol degradation. This
solid sample showed the typical high solubility of
phenolic polymers (tannin) in water, alcohol and ketone,
and its low solubility in ether. This spectrum is quite
similar to the tannic acid one (Fig. 3(b)). The bands
observed in this spectrum at 1717, 1696, 1573, 1557,
1530, 1450, 1436, 1388, 1334, 1308, 1196 and 1077 cm 1
have been observed in experiments made with catechol,
pyrogallol, H2 O2 and Fe3 mixtures (Figs. 3(c) and (d)).
The literature conrms the high reactivity of this substance with Fe3 (Bruneton, 1986). The reaction with
Fe3 and the corresponding free Fe3 concentration
decrease may explain the low activity observed for the
photo-induced reaction.
Photo-Fenton reaction for phenol was studied in two
samples containing 1 g/l of the pollutant. The rst

Fig. 2. (a) IR spectrum phenol-a sample after 3 h Photo-Fenton reaction, (b) and (c) IR spectra reference samples catechol
and hydroquinone.

1020

J. Ara~na et al. / Chemosphere 44 (2001) 10171023

Table 3
Filtering and Fe2 + H2 O2 successive additions treatments
applied to phenol-c (1 g/l) samplea

Fig. 3. IR spectrum: (a) solid sample got after Photo-Fenton

study with phenol-a; (b) reference tannic acid; (c) solid sample
got after reaction of catechol with Fe3 and H2 O2 ; (d) solid
sample got after reaction of pyrogallol with Fe3 and H2 O2 .

sample (phenol-b) was ltered several times and dierent

additions of H2 O2 were made during the reaction. The
other sample (phenol-c) was ltered only once, 3 h after
the reaction start. The procedure for these studies is
schematically shown in Tables 2 and 3.
Fig. 4 shows TOC reduction during these studies for
samples phenol-b and phenol-c. It can be observed that
ltering enhances TOC reduction, but when a degradation of about 9095% is achieved, the process becomes
slower. This can be explained by the presence of dis-

Table 2
Filtering and Fe2 +H2 O2 successive additions treatments
applied to phenol-b (1 g/l) samplea

Time (h)

Fe2 g=l

H2 O2 g=l

0
0.5 f1
1 f2
2 f3

0.01

0.01
0.01

0.5

1
1

fn ) Solution ltered.

Time (h)

Fe2 g=l

H2 O2 g=l

0
3 f1c
6

0.03

0.02

2
1
1

(f1c ) Solution ltered.

Fig. 4. TOC degraded (%) during Photo-Fenton reaction with

phenol-b N) and phenol-c j).

solved polymers, that have not been removed from the

sample after successive ltering. The existence of an
initial degradation t 0, before the sample irradiation
is also remarkable. This shows the eect of Fenton reaction as an initiating step (Okamoto et al., 1985a,b):
Fe2 H2 O2 ! Fe3  OH OH
Since catechol and hydroquinone are primary products
observed in this study for the degradation of phenol, it
was considered interesting to carry out degradation experiments of these products.
3.2. Catechol
Catechol degradation experiments have been performed for solutions containing 2.5, 1, 0.5 and 0.1 g/l of
the compound. Fe2 concentration was 0.2 and 2 g/l of
H2 O2 were added. In samples with 2.5, 1 and 0.5 g/l a
precipitate showing similar chemical and spectroscopic
features to that observed in phenol samples was obtained. This may reveal the possible formation of polymers in catechol samples. As for the phenol degradation
studies, only just after H2 O2 addition at t 0 and t 2
h, a strong catechol degradation may be observed. Fig. 5

J. Ara~na et al. / Chemosphere 44 (2001) 10171023

Fig. 5. TOC degraded (%) during Photo-Fenton reaction with

dierent catechol concentrations (0.1 g/l r, 0.5 g/l ppm d, 1 g/l
N) and 1 g/l hydroquinone j.

shows degradation, as TOC reductions, for samples with

1, 0.5 and 0.1 g/l. It may be observed that when catechol
concentration is increased degradation is more dicult.

1021

In fact, the sample with 2.5 g/l almost did not show any
degradation.
Fig. 6 shows the spectrum for the sample with 2.5 g/l
at dierent reaction times. From this graphic it is apparent that absorptions at 1618, 1573, 1557, 1536, 1510,
1467, 1390, 1335, 1273, 1227, 1194, and 1098 cm 1 are
progressively enhanced. This set of bands can be attributable to the presence of dissolved Fe3 pyrogallol
or Fe3 catechol complexes, due to its resemblance to
the spectra showed in Figs. 3(c) and (d). In catechol
solutions at low concentration (0.1 g/l) degradation occurs without the formation of polymers. An important
increment in band width and intensity is observed between 1715 and 1680 cm 1 after 30 min in reaction. This
could be due to tensions in carboxylic groups when
joined to an aromatic ring or to an aliphatic group with
double bonds in a positions.
3.3. Hydroquinone
The Photo-Fenton degradation of hydroquinone was
attempted under the same conditions, in aqueous solutions of hydroquinone containing 2.5 and 1 g/l of the
compound. Fig. 5 shows the results for the sample with 1
g/l. In contrast with the sample of 1 g/l of TOC from
catechol, total hydroquinone degradation was achieved
after 2 h. Precipitates were only observed in solutions
containing 2.5 g/l and showed the same features of those
obtained for phenol and catechol.
4. Conclusions

Fig. 6. IR spectra from catechol sample (2.5 g/l) after PhotoFenton reaction: (a) 15 min; (b) 30 min; (c) 2 h.

From the previously exposed results, a global mechanism for highly concentrated phenol degradation by a
Photo-Fenton reaction is proposed (Scheme 1).
Phenol degradation by Photo-Fenton reaction begins
with the formation of catechol and hydroquinone. These
intermediates have been identied by IR spectroscopy
when present at high concentrations. On other hand,
catechol may be degraded to pyrogallol and 1,2,4 benzenetriol. These two compounds have been proposed as
intermediates in studies on phenol/TiO2 -photocatalytic
degradation (Okamoto et al., 1985a,b). Catechol and
pyrogallol, as it has been observed in this work, could
react with Fe3 giving place to a complex species, producing the correspondent Fe3 free concentration decrease and the consequent Photo-Fenton reaction
activity decrease. In these conditions, high concentration
of catechol and pyrogallol may produce tannin-like
polymers.
The observed Photo-Fenton activity decrease for
high phenol and catechol concentrations may be due to:
(a) The scattering eect of the precipitated solid
which gives place to a sharp solution darkness, producing a diminution of the UV light penetration.

1022

J. Ara~na et al. / Chemosphere 44 (2001) 10171023

Scheme 1. Global mechanism proposed for phenol high concentrated aqueous solutions degradation by the Photo-Fenton reaction.

(b) The Fe3 free concentration decrease due to

complex species formation produces its relative
red-ox potential variation.
These eects have been found to be reversible when the
solution is ltered or, without ltration treatment, when
the H2 O2 dose is increased. The solution ltration eliminates the suspended solid diminishing the scattering eect
and increasing the UV source penetration and ecacy.
On the other hand, H2 O2 successive additions promote
the  OH generation increase, which favors complex and
intermediate species degradation and the corresponding
progressive generated solids disappearance.
The proposed phenol degradation pathway by the
Photo-Fenton process indicates that dissolved phenol
and its toxic derivatives could be eliminated this way,
through its condensation as polymers, relatively nontoxic and easily removable from the solution by simple
ltration, during the initial times of the process. Once
the sample dissolved TOC has been diminished long
enough, the polymers formation is avoided and the
process continues until the complete mineralization of
the remaining toxic dissolved phenol derivatives.
Furthermore, the formation of these tannin-like
polyphenolic compounds, may be interesting as part of a
pretreatment wastewater treatment. As it is well known,
highly concentrated phenolic derivatives wastewater, as
the subproducts of the olive industries are not biodegradable. However, by means of this method, the pretreatment of these waste produces no TOC reduction
but its transformation to biodegradable substances as
tannins. In fact, this kind of substances are intermediate
compounds in the pathway of the natural biodegradation of biomass wastes.
Acknowledgements
This work has been supported by the Consejera de
Educaci
on y Cultura del Gobierno de Canarias (Proy-

ecto de Investigaci
on PI1998-071A), the Ministerio de
Educaci
on y Cultura de Espa~
na (Proyecto de Investigaci
on PB98-0739), the Spanish Agency for International Cooperation (AECI) and by the Fundaci
on
Universitaria de Las Palmas.
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