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Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 83:13231338 (2008)

Review
An overview of the application of Fenton
oxidation to industrial wastewaters treatment
P Bautista, A F Mohedano, J A Casas, J A Zazo and J J Rodriguez
Ingeniera Qumica, Universidad Autonoma de Madrid, Crta. de Colmenar Km.15, 28049 Madrid, Spain

Abstract: This review provides updated information on the application of the Fenton process as an advanced
oxidation method for the treatment of industrial wastewaters. This technology has been used in recent decades
as a chemical oxidation process addressed to meet a variety of objectives including final polishing, reduction of
high percentages of organic load in terms of chemical oxygen demand or total organic carbon and removal of
recalcitrant and toxic pollutants thus allowing for further conventional biological treatment. The efficiency and
flexibility of this technology has been proven with a wide diversity of effluents from chemical and other related
industries or activities, including pharmaceutical, pulp and paper, textile, food, cork processing, and landfilling
among others.
2008 Society of Chemical Industry

Keywords: Fenton process; chemical oxidation; industrial wastewaters treatment; waste minimization; leachate

INTRODUCTION reaction of Fe3+ with intermediate organic radicals


Industrial activities generate wastewaters with a (Equations (3)(5)):2 6
wide variety of contaminants, such as phenol and
derivatives, hydrocarbons, halogenated sulphur and Fe2+ + H2 O2 Fe3+ + HO + HO
nitrogen-containing organic compounds, heavy metals
in the form of cyanides and other organic complexes. k = 76 L mol1 s1 (1)
+
Frequently these wastewaters contain a mixed pool Fe 3+
+ H2 O2 Fe 2+
+ HO2 + H
of pollutants in a wide range of concentrations. The
development of cost-effective technical solutions is k = 0.01 L mol1 s1 (2)
needed to successfully deal with the increasingly RH + HO R +H2 O (3)
complex problems arising in the field of industrial
wastewaters. R +Fe3+ R+ + Fe2+ (4)
+
In recent decades, chemical treatment methods R + HO R-OH (5)
involving the generation of hydroxyl radicals, known
as advanced oxidation processes (AOPs), have been Nevertheless, a number of competitive reactions
applied successfully for the removal or degradation can also occur (Equations (6)(9)), which negatively
of recalcitrant pollutants based on the high oxidative affect the oxidation process:
power of the HO radical.
Among these AOPs, the Fenton process is a widely Fe2+ + HO Fe3+ + HO
studied and used catalytic method based on the
k = 3.2 108 L mol1 s1 (6)
generation of hydroxyl radicals (HO) from hydrogen
peroxide with iron ions acting as homogeneous catalyst H2 O2 + HO HO2 +H2 O
at acidic pH and ambient conditions.1 The HO
k = 2.7 107 L mol1 s1 (7)
radical has a high standard oxidation potential (2.80 V)
and exhibits high reaction rates compared with other HO2 +HO O2 + H2 O (8)
conventional oxidants like Cl2 , O2 , O3 , hydrogen
HO +HO H2 O2
peroxide or KMnO4 . This radical reacts with most
organic and many inorganic solutes with high rate k = 5.2 109 L mol1 s1 (9)
constants.
The generally accepted mechanism of the Fenton The rate of the Fenton reaction should be
process proposes that hydroxyl radicals are produced strongly dependent on the presence of radical
in accordance with Equation (1), while the catalyst scavengers such as t-butanol or chlorine ions,
is regenerated through Equation (2), or from the but in some cases, a substantial decrease has

Correspondence to: J J Rodriguez, Ingeniera Qumica, Universidad Autonoma de Madrid, Crta. de Colmenar Km.15, 28049 Madrid, Spain
E-mail: juanjo.rodriguez@uam.es
(Received 14 March 2008; revised version received 25 April 2008; accepted 28 April 2008)
Published online 6 June 2008; DOI: 10.1002/jctb.1988

2008 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2008/$30.00


P Bautista et al.

not been observed even at high concentrations The reaction temperature is another crucial param-
of these species.7 This fact led some authors to eter in the Fenton process. In principle, increasing the
analyze the presence of additional oxidant species. temperature should enhance the kinetics of the pro-
Using electron paramagnetic resonance (EPR)-spin cess, but it also favours the decomposition of H2 O2
trapping techniques, experimental evidence has been towards O2 and H2 O, whose rate increases around 2.2
found for the existence of oxidizing intermediates times each 10 C in the range 20100 C.14
different from the hydroxyl radical,8 11 such as high- The dose of H2 O2 and the concentration of Fe2+
valent iron-complexes (e.g. ferryl species Fe(IV), are two relevant factors affecting the Fenton process,
denoted as Fe(OH)2 2+ ; Equation (10)). Depending being both closely related. The H2 O2 dose has to be
on the operating conditions (substrate, Fe/H2 O2 ratio, fixed according to the initial pollutant concentration. It
scavengers, etc.) one of them will predominate. is frequent to use an amount of H2 O2 corresponding
to the theoretical stoichiometric H2 O2 to chemical
Fe2+ + H2 O2 Fe(OH)2 2+ oxygen demand (COD) ratio,15 although it depends on
the response of the specific contaminants to oxidation
Fe3+ + HO +HO (10) and on the objective pursued in terms of reduction of
the contaminant load.
Whereas the hydroxyl radical reacts by hydrogen A schematic representation of the Fenton oxidation
abstraction, addition to double bonds or electron treatment is shown in Fig. 1. Typically a stirred batch
transfer, depending on the structure and especially reactor is used where the pH is controlled commonly
on the ionization potential of the organic pollutant, within the 33.5 range. Fe2+ is most frequently
the ferryl species are only able to oxidize organic added as ferrous sulphate and H2 O2 is usually fed
molecules by electron transfer. as 35% aqueous solution. The process usually works
The efficiency of the Fenton oxidation process at ambient temperature and pressure. The reactor
depends, among other factors, like temperature, pH, vessel must be coated with an acid-resistant material,
hydrogen peroxide and catalyst concentrations, on the because corrosion can be a serious problem. Addition
Fe3+ reduction to Fe2+ . Thus the presence of reaction of reactants is performed in the following sequence:
intermediates able to reduce Fe3+ and regenerate wastewater, followed by dilute sulphuric acid (for
the catalyst is crucial.3 However, there are reaction maintaining acidic conditions), the catalyst (Fe2+ salt)
intermediates that instead of reducing the Fe3+ remove in acidic solution, base or acid for pH adjustment
it from the Fe2+ /Fe3+ cycle, due to the generation and finally hydrogen peroxide. The discharge from
of iron complexes, delaying and/or inhibiting the the Fenton reactor passes to a neutralization tank
oxidation process. and after flocculant addition the Fe(OH)3 and other
Fenton reaction presents its maximum catalytic accompanying solids are separated by settling. If
activity at pH 2.83.0, which drastically diminishes necessary, a final sand-filtration stage can be used.
with an increase or a reduction of this pH value. At pH One of the advantages of the Fenton process with
higher than 3 Fe3+ starts precipitating as Fe(OH)3 and regard to other oxidation techniques is that no energy
breaks down the H2 O2 into O2 and H2 O preferently.12 input is necessary to activate hydrogen peroxide,
Besides, the formation of Fe(II) complexes at high pH because the reaction takes place at atmospheric
values leads to a drop of the Fe2+ concentration.13 On pressure and at room temperature. Furthermore, this
the other hand, Fe2+ regeneration by the reaction of method requires relatively short reaction times and
Fe3+ with H2 O2 is inhibited at more acidic pH values.4 uses easy-to-handle reagents. The main disadvantages

H2O2

Fe(SO4)7H2O Alkaline
agent Flocculant

pH adjusting
agent
pH pH
Raw wastewater control control

Treated wastewater

Oxidation Neutralization Flocculation


tank tank tank

Settling tank

Figure 1. Typical scheme for Fenton treatment.

1324 J Chem Technol Biotechnol 83:13231338 (2008)


DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment

are the high cost of hydrogen peroxide and the fact removal efficiency for organochlorinated was also fairly
that the homogeneous catalyst, added as iron salt, high (>90%), and the toxicity of the raw wastewater
cannot be retained in the process thus requiring further towards the bioluminescent bacteria Vibrio fischeri was
separation to prevent additional water pollution. In dramatically reduced.
order to avoid the continuous loss of catalyst and In a further work, Barbusinski70 studied the
the need of removing iron after the treatment, which application of Fenton process for treating four types
increases the cost, heterogeneous catalysts can be of industrial wastewaters collected from two chemical
used. Recent studies have shown that hydrogen factories in southern Poland. The wastewaters came
peroxide can oxidize organic pollutants in the presence from the production of maleic acid, maleic anhydride,
of Fe-bearing solid catalysts. Zeolites,16 23 pillared 2-ethylhexyl alcohol, urea-formaldehyde adhesives
clays,24 28 alumina,29 silica,30 mesostructured SBA- and pesticides. Although high removal efficiencies
15,31,32 mesoporous molecular sieves,33,34 niobia,35 were obtained in terms of COD, these were not
iron oxides,36,37 ion-exchange resin38 and activated always accompanied by a reduction of ecotoxicity
carbon39,40 have been used as supports to prepare the (Vibrio fischeri) to sufficiently low levels unless
catalysts. frankly high H2 O2 amounts and reaction times were
used.
A good example on the benefits of applying Fen-
APPLICATION OF FENTON OXIDATION TO ton oxidation to wastewaters from chemicals man-
INDUSTRIAL WASTEWATERS ufacturing is reported by Collivignarelli et al.71 The
Fenton oxidation has been tested with a variety of wastewaters from a detergents producing plant were
synthetic wastewaters containing a diversity of target formerly treated by coagulationflocculation and fil-
compounds, such as phenols,41 44 chlorophenols,45 48 tration, a solution which showed to be not capable
formaldehyde,49 2,4-dinitrophenol,50,51 2,4,6-trinitro- of reaching the purification requirements. A new
toluene,52,53 2,4-dinitrotoluene,54 chlorobenzene,55,56 system consisting in a discontinuous Fenton oxi-
tetrachloroethylene,57 halomethanes,58 amines,59 he- dation and neutralisation process, followed by floc-
xahydro-1,3,5-trinitro-1,3,5-triazine (RDX).60,61 culation and sedimentation was successfully imple-
However, there are many chemicals which are refrac- mented.
tory to Fenton oxidation, such as acetic acid, acetone, Wastewaters from petroleum extraction, refin-
carbon tetrachloride, methylene chloride, oxalic acid, ing and chemical processing have been success-
maleic acid, malonic acid, n-paraffins, trichloroethane, fully treated with the Fenton system under ambi-
etc.62 It has been demonstrated that these compounds ent conditions of pressure and temperature.72
are resistant under the usual mild operating conditions These authors tested the efficiency of this pro-
of Fenton oxidation.2,28,40,44 cess for the treatment of two different wastewa-
In addition to those basic studies, the process has ter samples, one from oil production operations
been applied to industrial wastewaters (such as chemi- and the other one from a petrochemical plants
cal, pharmaceutical, textile, paper pulp, cosmetic, cork complex. The treated contaminants, in harzadous
processing wastewaters, etc.), sludge and contamined concentrations, were the following: m-cresol, 2-
soils63 68 with the result of significant reductions of chlorophenol, methyl-tertbutyl-ether (MTBE) and
toxicity, improvement of biodegradability, colour and volatile aromatics (benzene, toluene, ethylbenzene
odour removal. and xylene). In all cases a significant mineraliza-
tion (namely, complete oxidation) of the contam-
Chemical industry inants was observed in relatively short periods of
The chemical industry is a major contributor to time.
the nowadays problem of industrial wastewaters, Acidizing, a technique for improving the permeation
not only in terms of discharge volumes, but also ability of rock layers of petroleum wells using diluted
looking at the hazardous nature of many of the inorganic acids such as HCl, has long been one of
pollutants found in the effluents. The increasingly the most common ways of stimulation to increase
stringent regulations have enforced the application of the production rate of oil and gas reservoirs. This
advanced technologies for complying the discharge operation gives rise to about 200500 m3 waste acidic
limits and allowing for water recycling. Among those liquid per well, containing high concentrations of HCl
technologies, Fenton oxidation has been gaining and ferrous ions in addition to a high organic load. Gao
interest in the last two decades. et al.73 analyzed the potential of the Fenton process
Barbusinski and Filipek69 analyzed the efficiency of for the simultaneous removal of total organic carbon
the Fenton technology in the treatment of the wastew- (TOC) and Fe2+ from these acidic waste liquors,
aters from pesticides production in southern Poland. by adding H2 O2 . The samples used in that study
Most of the pesticides were completely degraded using were collected from an acidic waste liquor pond in
a H2 O2 dose of 2.5 g L1 , corresponding to five times China, with main characteristics: pH = 1.4, 94 mg
the stoichiometric amount on a COD basis. The L1 TOC and 208 mg L1 Fe2+ . The optimum molar
best results were achieved for the organophospho- ratio of H2 O2 /Fe2+ for the removal of Fe2+ was
rous pesticides, which degraded at 97100%. The 0.720.76, which was determined from the oxygen

J Chem Technol Biotechnol 83:13231338 (2008) 1325


DOI: 10.1002/jctb
P Bautista et al.

reduction potential (ORP), used as a parameter develop new techniques for a more efficient cleaning
to indicate the transformation of the Fe3+ /Fe2+ . of this type of wastewaters. A possible strategy can
Under this optimal H2 O2 dose, the minimum Fe2+ be the use of chemical oxidation as a previous treat-
final concentration (1.21.3 mg L1 ) occurred at ment in order to reduce the toxicity and improve the
45 min at 3.34.5 pH. TOC removal was affected by biodegradability of the organic matter in these wastew-
oxidation as well as adsorption by ferric hydroxides aters. The removal of organic matter (TOC and COD)
being dominated by adsorption at a molar ratio by Fenton oxidation from two samples of wastewaters
H2 O2 /Fe2+ of 0.75, and by oxidation at a molar generated in a cosmetic industry in Madrid (Spain)
ratio H2 O2 /Fe2+ of 3.0. In this latter case (380 mg has been evaluated by Bautista et al.76 These two
L1 H2 O2 ), more than three-quarters of the TOC effluents contained significantly different values of
removal was due to oxidation, for a total TOC COD (4730 and 2660 mg L1 ). The corresponding
reduction of 65% in 120 min, at room temperature TOC values were 1215 and 785 mg L1 and the
and pH = 3.25. BOD5 /COD ratio was 0.133 and 0.169, respectively,
Leather tanning effluents are a source of severe indicative in both cases of a low biodegradability.
environmental impacts, since this industry generates The best results, TOC conversion higher than 45%
an alkaline wastewater with high concentrations of at 25 C and 60% at 50 C, were obtained using an
organic matter, sulfides, suspended solids and salts, initial pH equal to 3, a Fe2+ dose of 200 mg L1
which shows high toxicity values. The treatment of and an initial H2 O2 /COD weight ratio corresponding
these industrial wastewaters by combined chemical to the theoretical stoichiometric value. Application of
and biological oxidation was evaluated by Vidal et al.74 Fenton oxidation allowed compliance with the COD
In that study Fenton oxidation was used as batch pre- regional limit for industrial wastewaters discharges to
treatment. The H2 O2 /Fe2+ and H2 O2 /COD ratios the municipal sewer system. The overall kinetics of
were 9 and 4, respectively, reaching a COD reduction the process was adjusted to a second-order kinetic
close to 90%. Subsequently, the oxidized effluent was equation with respect to TOC. This simple equa-
fed to an activated sludge unit, reaching 3560% and tion described well the rate of TOC reduction over a
6070% of COD and BOD removal, respectively. wide range covering up to 8090% of the maximum
Therefore, this combined treatment increased the achievable TOC removal.
overall COD removal up to more than 95% versus A comparison of several AOPs was carried out with
the 60% attained without pre-treatment. Bioassays a cosmetic industrial effluent by Coste et al.77 After
with D. magna and D. pulex showed that this kind of a complete biological treatment by membrane biore-
treatment achieves only a partial toxicity removal of actor (BIOSEP) refractory COD still remained. Six
the tannery effluent. oxidation treatments were compared for COD reduc-
Dantas et al.75 evaluated the efficiency of Fenton tion: Fenton reagent, direct photolysis with a low
and photo-Fenton processes for the treatment of pressure UV lamp, O3 at acidic pH and pH 6.25,
wastewaters from the leather industry, investigating UV/O3 , UV/H2 O2 , O3 /H2 O2 and O3 /UV/H2 O2 . The
the reduction of COD, ammonia-N and toxicity. results obtained seem to indicate that the compo-
The results obtained showed that the degradation nents of the pre-treated effluent were removable by
process involves two stages: an initial fast one, radical mechanism, but a fraction needed UV pho-
where approximately 70% of the COD reduction tolysis to be completely oxidized. Fenton reagent
takes place, followed by a slow step, where after offered a maximum COD reduction of 80%, pre-
4 h reaction time the COD removal reached 90%. senting a fraction that may be more refractory to free
The efficiency of the Fenton and photo-Fenton radicals oxidation perhaps due to scavengers competi-
reactions increased from 65 to 90%, since the tion.
concentration of HO radicals increases in the second Wastewaters from phenolic resins manufacture have
process. The toxicity (using Artemia salina) decreased a high concentration of phenol and derivatives, which
upon COD reduction but the residual H2 O2 at are extremely toxic and refractory. Thus, treating
the end of the reaction had to be controlled phenolic wastewaters up to harmless level is an ardu-
because it affects negatively to the final toxicity ous task for many biological and chemical processes.
values. Kavitha and Palanivelu78 evaluated the efficiency of
The cosmetic industry generates wastewaters char- different Fenton-related processes, such as Fenton,
acterized by high levels of COD, suspended solids, fats solar-Fenton and UV-Fenton, for the degradation of
and oils and detergents. The reduction of the organic phenol in simulated and industrial wastewaters. The
load of these effluents by conventional biological pro- real effluent was taken from a resin-manufacturing
cesses is not likely due to its low biological oxygen facility in India and contained 2904 mg L1 COD,
demand (BOD5 )/COD ratio and thus they are fre- 933 mg L1 dissolved organic carbon (DOC) and
quently treated by means of coagulation/flocculation 1215 mg L1 phenol. Increased degradation and min-
with pressure-flotation to separate the resulting sludge. eralization efficiencies were observed in photo-Fenton
This leads to an important reduction of COD. Never- processes as compared to conventional Fenton oxi-
theless, the introduction of more stringent regulations dation. The optimum conditions were: room tem-
concerning public waste disposal makes necessary to perature, pH = 3, H2 O2 /COD weight ratio of 2.2

1326 J Chem Technol Biotechnol 83:13231338 (2008)


DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment

and Fe2+ /H2 O2 molar ratio of 0.026 for Fenton based on hydroxyl radicals were less selective but
and 0.013 for solar-Fenton. In both oxidation pro- considerably more effective in COD degradation. This
cesses phenol was removed effectively within 5 min explains why the combined methods H2 O2 /UV and
of reaction time. However, the degradation (COD) O3 /UV led both to complete destruction of AOX
and mineralization (DOC) efficiency of the Fenton and high removal of COD. Using Fenton oxidation
process were 82 and 41%, respectively, whereas in both AOX and COD could be removed almost
solar-Fenton almost complete degradation and 97% completely, being the reaction time needed for this
mineralization were achieved within 120 min of reac- treatment fairly low compared with the other two
tion time. AOPs.
Park et al.79 investigated the feasibility of Fen- Kulik et al.82 applied modified Fenton oxidation
ton oxidation for the removal of colour and the (H2 O2 /Fe2+ system without pH adjustment) in com-
non-biodegradable organics from a wastewater from bination with lime coagulation for the treatment of
pigment production. Batch tests were performed three rinsing wastewater samples from a pharmaceuti-
in order to determine the optimum conditions cal plant formulating medical ointments. All samples
for plant operation, such as pH, H2 O2 dosage, were pre-treated by adsorption/flocculation/filtration
H2 O2 /Fe2+ molar ratio and contact time. The ini- processes with bentonite, but the quality of effluents
tial organic pollution of the raw wastewater was did not comply with the regulations for wastewater
2700 mg L1 of COD and it was found that the discharge to local sewerage, since the organic matter
removal efficiencies reached more than 90% and content of the three effluents in terms of COD was
around 50% for colour and COD, respectively. In 4000, 5400 and 13 130 mg L1 . The application of
addition, the biodegradability of the effluent was sig- Fenton-like oxidation with subsequent iron(III)/lime
nificantly improved by means of Fenton oxidation coagulation substantially improved the quality and the
since BOD5 /COD ratio was increased from 0.04 to biodegradability of the pharmaceutical effluents with
0.36. different chemical characteristics allowing to meet the
discharge limits. The rapid pH decrease to acidic val-
Pharmaceutical industry ues 3 during the initial stage of the process for all the
Treatment of pharmaceutical wastewaters has always effluents suggested that pH adjustment was unneces-
been troublesome owing to the wide variety of chem- sary. Under the most favourable treatment conditions
icals used in drug manufacturing, which leads to (H2 O2 /COD weight ratio of 2:1, H2 O2 /Fe2+ molar
wastewaters of variable composition and fluctua- ratio of 10:1 and 2 h reaction time), COD removal of
tions in pollutant concentrations. The substances 87%, 94% and 96% and BOD7 removal of 79%,
synthesized by the pharmaceutical industry are in 92% and 95% were achieved for the three efflu-
most cases structurally complex organic chemicals ents.
that are resistant to biological degradation. For this
Another example of industrial application of the
reason, conventional methods are usually inappropri-
Fenton process for the treatment of pharmaceutical
ate for the treatment of pharmaceutical wastewaters
effluents is reported by Tekin et al.83 In their study
and advanced oxidation processes can be considered
Fenton oxidation is applied as a pre-treatment for
good candidates for providing feasible technical solu-
the wastewaters generated by a drug manufacturing
tions.
plant in Turkey, leading to an improvement of the
Fenton oxidation has proved to be a suitable pre-
wastewater biodegradability and a reduction of the
treatment for an extremely polluted pharmaceutical
wastewater with 362 000 mg L1 COD, mostly due to toxicity of these effluents. Treatability studies were
recalcitrant compounds, as indicated by a BOD5 /COD conducted at lab scale with synthetic aqueous solutions
ratio as low as 0.008.80 The results reported by of each chemical produced in the factory in order
these authors show that during the first 10 min of to establish the operating conditions for the full-
Fentons reaction more than 90% of the total COD scale treatment plant. Optimum pH was found to
removal (5560%) can be achieved. This finding is be 3.5 and 7.0 for the first (oxidation) and second
of special interest for the industrial application of (coagulation) stage of the Fenton process, respectively.
Fenton technology, because it proves that it permits The effect of temperature on COD removal was
a significant COD reduction in a fairly short period tested at room temperature and at 50 C, and no
of time. This advantage of the Fenton process with significant differences were observed. Similar results
respect to other advanced oxidation processes was were found by San Sebastian et al.80 with this type
also pointed out by Hofl et al.81 , who compared of wastewater. The industrial treatment plant using
the efficiency of three AOPs (H2 O2 /UV, O3 /UV and Fenton oxidation followed by aerobic degradation
Fenton) for the removal of adsorbable organic halogen in sequencing batch reactors (SBR), provided an
(AOX) and COD from a pharmaceutical wastewater. overall removal efficiency of 98% for both COD
The results showed that the three methods are suitable and BOD5 , complying with the discharge regional
for the degradation of AOX and COD. UV irradiation limits. The COD removal efficiency attained in the
involved a high selectivity for the degradation of AOX Fenton oxidation unit ranged between 45% and
compared to COD. On the other hand, processes 50%.

J Chem Technol Biotechnol 83:13231338 (2008) 1327


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Pulp and paper industry of chemicals used throughout the different opera-
The pulp and paper industry is known to generate tions. The environmental problems associated with
considerable volumes of wastewaters, about 80 m3 t1 textile effluents are in a great part due to colour.
of paper on average. More than 250 chemicals The biorefractory nature of textile wastewaters from
have been identified in the effluents resulting the dyeing and finishing stages is mainly attributable
from the different stages of papermaking. Whereas to the extensive use of various dyestuffs and chem-
some of these pollutants are naturally occurring ical additives (such as polyvinyl alcohol, surfactants,
wood extractives (tannins, resin acids, lignin, etc.), etc.). Therefore, the wastewaters are characterized by
others are xenobiotic compounds that are formed a high organic matter content (COD, BOD5 ), sus-
mostly in pulp manufacture (chlorinated lignins, pended solids, colour and pH values up to 2 in the
phenols, dioxins and furans, among others). These acid range and as high as 12 in the basic.12 Differ-
effluents are highly coloured and contain high organic ent treatments have been used for the wastewaters
loads, which in some cases can reach more than generated from textile dyeing. These include acti-
10 000 mg L1 of COD.84 Primary clarification is vated carbon adsorption, coagulationflocculation,
the most frequently used treatment for this type of biological degradation (activated sludge), electro-
wastewaters, sometimes followed by secondary or chemical treatment, ozonation, etc., which often
biological treatment. However, some drawbacks are produce final effluents still exceeding the discharge
associated with these methods, such as the large area limits.
required for aerobic biological treatment, the difficulty Several authors have successfully applied the
of controlling the population of microorganisms Fenton process for this kind of industrial effluents.
and the rigorous control of pH, temperature and In this way, Flaherty and Huang89 evaluated the
nutrients. Also, the presence of toxic or recalcitrant
efficiency of Fenton oxidation for the treatment
compounds seriously limits the efficiency of biological
of four refractory dyeing wastewaters from a US
treatments.
textile facility. Batch and continuous flow oxidation
The combination of Fenton and photo-Fenton
experiments were carried out, resulting in a 60%
oxidation has proved to be highly effective for the
and 30% COD reduction, respectively. A significant
treatment of pulp bleaching effluents.85,86 Solar photo-
colour reduction was achieved in all the cases. In
Fenton reduced TOC as much as 93% after 15 min
addition, these authors performed some experiments
according to the results of these last authors.
using Fe3+ (Fenton-like reaction) instead of Fe2+ ,
As indicated before, Fe3+ can also be used to
decompose H2 O2 giving rise to oxidative radicals in the concluding again that Fe3+ has a catalytic effect
so-called Fenton-like process. For most applications comparable to the traditionally used Fe2+ . They
no significant differences have been observed when suggested that FeCl3 or Fe2 (SO4 )3 would be the
Fe2+ or Fe3+ ions were used to catalyze the reaction, most practical catalysts for industrial applications
although Pera-Titus et al.87 suggested that if low of Fenton-like oxidation, due to their strong acidic
doses of Fentons reagent are used, ferrous ions may character.
be preferable. Tambosi et al.88 evaluated a Fenton- Badawy and Ali90 analyzed the effectiveness of Fen-
like process (involving oxidation and coagulation) ton oxidation for the combined treatment of industrial
for the treatment of a wastewater generated by a wastewaters generated from textile, chemical, food
Brazilian paper mill with the objective of reducing and metal finishing industries and domestic efflu-
COD, colour, odour and aromatic compounds. Batch ents from an Egyptian city. They compared the
experiments were carried out in order to determine efficiency of a conventional treatment based on coag-
the optimum operating conditions, which led to 75% ulationflocculation with the results obtained by the
COD removal. Based on these optimum conditions, use of Fenton oxidation. The industrial wastewaters
pilot-scale experiments were conducted and revealed contained 17503323 mg L1 of COD, 9003000 mg
a high efficiency in terms of mineralization, namely L1 of SS and 13.295.5 mg L1 of oil and grease
complete oxidation. Some terpenes identified in the in addition to heavy metals. The organic pollutants
starting wastewater were completely removed by the included refractory, non-biodegradable and toxic com-
Fenton-like treatment. pounds, such as the dyestuffs used by the textile indus-
Perez et al.85 evaluated the efficiency of several try. The authors found that coagulationflocculation
AOPs for colour and organic matter removal from has a poor effect on the removal of soluble organic
a cellulose bleaching effluent. The costs of the compounds such as reactive dyes. The best results
different technologies per unit of TOC reduction were were obtained with the Fenton process, reaching
compared. Fenton, Fenton-like and photo-Fenton as much as 100% colour removal and more than
achieved higher levels of TOC reduction and at lower 90% reduction of COD. The results proved that
costs than photocatalytic treatments. Fenton oxidation could be used for the treatment
of such industrial wastewaters without further treat-
Textile industry ment, since the final effluent complies with the
Textile industry is particularly known for its high Egyptian law for water reuse under a restricted cate-
water consumption as well as the amount and variety gory.

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DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment

The effectiveness of Fenton and ozone oxidation including Fenton oxidation. Perez et al.93 investi-
have been compared with a coagulationflocculation gated the simultaneous use of Fenton, Fenton-like
process to remove toxicity as well as colour and COD and photo-Fenton for the treatment of textile wastew-
from the wastewater generated by a textile finishing aters generated from a hydrogen peroxide bleaching
industry located in Istanbul (Turkey).91 The operat- unit in Spain. The combination of these processes
ing conditions for each process were established on was proved to be highly effective for the treatment
the basis of complete removal of the toxicity to Daph- of this type of wastewaters. Lin and Peng94 stud-
nia magna. The results obtained indicate that Fenton ied the treatment of textile wastewaters from a large
oxidation removes COD to a major extent (59%) dyeing and finishing mill by a continuous process
rather than O3 (33%), while colour removal was of combined coagulation, Fenton oxidation and acti-
similar (89% and 91%, respectively). The coagula- vated sludge. An economic evaluation of the process
tionflocculation treatment yielded COD and colour was carried out and the optimum operating condi-
removal close to those of Fenton oxidation, but it tions were selected, the removal of COD reaching
produces a higher volume of sludge containing recal- almost 90% in those conditions. Fongsatitkul et al.95
citrant compounds (dyes, additives, etc.). Although investigated the potential of biological degradation
the Fenton process was operated at a higher tem- in association with Fenton oxidation for treating the
perature (40 C), this was not a drawback since the wastewaters from a textile factory in Central Thailand.
temperature of the effluent to be treated was above The authors compared the efficiency of different tech-
70 C. nologies: biological treatment in a sequencing batch
Papadopoulos et al.92 examined the effectiveness reactor (SBR) as a single process, Fenton oxidation
of Fenton oxidation for the reduction of the prior to that biological treatment and SBR followed
organic content of the wastewater generated from by Fenton oxidation. The best results were obtained
a textile industry in Athens (Greece). The ini- by the second arrangement, which attained more than
tial organic pollution of the raw wastewater was 90% and close to 80% reduction of COD and colour,
respectively.
1200 mg L1 of BOD, 8100 mg L1 of COD and
3010 mg L1 of TOC. The low BOD/COD ratio,
0.148, indicates that this organic matter is non- Food industry
biodegradable. The experimental results showed that The Fenton technology has also proved to be
the COD decreased by about 45% within 4 h effective for the treatment of wastewaters generated
and a higher reaction time did not lead to fur- by the food industry. This includes wastewaters from
ther significant COD reduction (48% overall reduc- olive oil extraction plants, commonly named olive
tion after 6 h). The maximum colour removal was mill wastewaters96 98 and wastewaters generated
by the table olive producing industry.99 In the
71.5%.
former case, the oily juice is extracted from the
As indicated before, heterogeneous Fenton oxida-
fruit through simple milling or, more recently,
tion is an interesting alternative to the traditional
by centrifugation. Table olive production requires
homogeneous Fenton process. In this way, Dantas
a previous treatment in order to eliminate the
et al.39 studied the treatment of a textile wastewa-
bitterness of the fruit, due to the presence of
ter (COD = 1000 mg L1 ) in Santa Catarina State
polyphenolic compounds. For this purpose, the olives
(Brazil) by adsorption and simultaneous catalytic
are treated with a 2% sodium hydroxide solution,
wet hydrogen peroxide oxidation using composites
followed by consecutive water rinsings. The high
of iron oxide and activated carbon (Fe2 O3 /carbon). contaminant load of the wastewaters generated in
They pointed out that no iron was leached to the these processes includes polyphenols among the
aqueous phase, indicating that the homogeneous Fen- most important pollutants. Moreover, the chelating
ton reaction was not significant and the catalyst is character of some compounds present in these
fairly stable at pH above 3.0. Besides, a lower hydro- effluents leads to the presence of some toxic heavy
gen peroxide consumption than in the homogeneous metals in solution. Anaerobic digestion has been
Fenton process was needed, achieving 71% COD the most frequently used method for treating these
removal at room temperature with a H2 O2 dose lower wastewaters. However, phenolic compounds inhibit
than 1000 mg L1 (less than half the stoichiometric biological treatment to a great extent since phenols
amount). are toxic to methanogenic bacteria at relatively low
Collivignarelli et al.71 described the application concentrations.
of Fenton technology to the wastewaters of a Beltran de Heredia and Dom nguez99 applied
textile factory in substitution of the previously Fenton oxidation to the treatment of the liquor
used coagulationflocculation treatment, which did resulting from black olive pickling, characterized by
not allow compliance with the discharge lim- high COD content (6700 mg L1 ) and the presence
its. of polyphenolic compounds. After 515 min reaction
Due to the complexity and high organic mat- time 73% of COD and 90% of polyphenols were
ter content of textile effluents several authors have removed. The colour of these wastewaters was also
suggested the application of combined treatments almost completely eliminated. Rivas et al.96 analyzed

J Chem Technol Biotechnol 83:13231338 (2008) 1329


DOI: 10.1002/jctb
P Bautista et al.

the treatment of an olive oil mill wastewater (CODo = and 0.60.9 g L1 , respectively, as well as an acidic
12.8 g L1 ) from a southwestern Spain factory by pH, around 5.
means of the Fenton technology. These authors Several authors have proposed different technical
studied the influence of some operating variables solutions for cork processing wastewaters, involving
and proposed a kinetic model for the process. The mainly physical-chemical methods. Guedes et al.103
reaction between Fe3+ and H2 O2 was suggested to used Fenton oxidation as a pre-treatment step in order
be the controlling step. The simultaneous inefficient to improve biodegradability. The starting wastewater
decomposition of hydrogen peroxide into water had a high organic pollution (COD = 5000 mg L1 ,
and oxygen was believed to play an important TOC = 1505 mg L1 ) with a low biodegradability
role. (BOD5 /COD = 0.27). The authors accomplished a
An integrated Fentoncoagulation/flocculation pro- kinetic study of the process and selected the opti-
cess, using Ca(OH)2 , was applied by Beltran de mal operating conditions, achieving a COD reduction
Heredia et al.100 to wine distillery wastewaters, com- of 87.3%. A rapid decrease of TOC was observed
monly known as vinasses. The experimental variables within the initial 2 min, followed by a significantly
studied were H2 O2 and Fe doses, [H2 O2 ]o to [Fe2+ ]o slower degradation. The oxidation proceeds through
molar ratio, the effluent dilution and the way the an approximate second-order kinetics during the first
reagents were added (splitting the reagent doses into 2 min of reaction, while the second phase of the
different fractions). The optimal operating condi- reaction can be described by a zero-order kinetic
tions of the integrated process were established at equation.
17 g L1 of H2 O2 and a [H2 O2 ]o to [Fe2+ ]o ini- Due to the complexity of these wastewaters, com-
tial molar ratio of 15. The H2 O2 dose was below bined techniques have frequently been suggested
one-half the stoichiometric amount relative to COD. to treat them. Peres et al.104 compared coagula-
Under these conditions a COD removal of 74% was tion/flocculation with Fenton oxidation followed by
attained. coagulation/flocculation. The second arrangement
Horng et al.101 evaluated the treatment of the reduced COD, total polyphenols and aromatic com-
wastewater from a brewery plant containing high pounds by 74, 99 and 98%, respectively, representing
COD and SS concentrations. The treatment included a considerable improvement compared with coagu-
biological (anaerobic and aerobic) processes and lation/flocculation alone. Beltran de Heredia et al.105
Fenton oxidation. The resulting effluent satisfied the also checked these two methods, reaching similar con-
existing local discharge standards. Fenton oxidation clusions. From a kinetic study based on the initial
was applied to simultaneously remove COD and SS rate method they reported that the rate of COD
from the aerobic effluent so that a stable effluent removal upon Fenton oxidation is maximum when
quality and increasingly stringent local discharge the H2 O2 /Fe2+ initial molar ratio is equal to 10.
limits in the future could be addressed. The In addition, these authors analyzed the effect of
operating conditions were set at COD/H2 O2 = 1, the way of adding the reagents and observed that
Fe2+ /H2 O2 = 2 (molar ratio), pH = 23 and 1 h the amount of organic matter (as COD) removed
reaction time. by Fenton oxidation is increased by distributing
Gomec et al.102 reported on the improvement the H2 O2 and ferrous salt feeding in several addi-
of an existing treatment for olive mill wastew- tions.
aters by including a Fenton oxidation step. Another combined process for the treatment of
COD removal increased from 74 to almost cork boiling wastewater has been investigated by
90%. Dias-Machado et al.106 These authors applied Fenton
oxidation as a pre-treatment, followed by biologi-
cal treatment. The use of this chemicalbiological
Cork processing industry combined solution increases the bioavailability of the
The main source of pollution in the cork processing polyphenols present in the wastewater since these com-
industry comes from the cork boiling step. After har- pounds are partially oxidized into simpler molecules,
vest from the producer tree, Quercus suber L., the cork improving their biodegradability. TOC reduction by
is stabilized by drying in open air for approximately Fenton oxidation was very fast within the early stage
3 months. One of the first stages of industrial prepara- of the process (XTOC = 79% after 6 min), confirm-
tion of cork consists in its immersion for approximately ing the previous conclusion of Guedes et al.103 in the
1 h in boiling water. This process improves cork sense that the first 35 min are sufficient to achieve
textural and plastic properties, making this mate- a high degree of chemical degradation. The results
rial more homogeneous, flat and elastic. The same obtained by Dias-Machado et al.106 showed that Fen-
water may be repeatedly used up to 2030 times, ton oxidation, using small amounts of oxidant and
reaching temperatures of about 100 C during boiling, catalyst combined with a biodegradative inoculum,
with variable periods of cooling. The high volumes added almost simultaneously, allows TOC reduc-
of wastewaters produced (400 L t1 of cork) are tions above 90%, a 20% better than the obtained
characterized by high COD, BOD and polyphenols by chemical oxidation alone. The main advantage
content, in the range of 4.55.5 g L1 , 1.11.8 g L1 of this integrated method is that small amounts of

1330 J Chem Technol Biotechnol 83:13231338 (2008)


DOI: 10.1002/jctb
Fenton oxidation to industrial wastewaters treatment

reagents are required for the Fenton oxidation, less The final effluent was free of solids, colour and
than half that previously recommended as optimal for Fe, and the COD reduction reached 80%. This
these wastewaters. combination of Fenton with membrane filtration
showed highly efficient for the removal of recalcitrant
Landfill leachates pollutants.
Although landfill leachates have been proved to be The Fenton-like process (Fe3+ -H2 O2 ) has also
toxic and recalcitrant, landfilling still remains one shown to be an efficient treatment for the oxidation
of the main systems for municipal and industrial of landfill leachate.110 It has been demonstrated that
solid waste disposal. The composition of landfill the oxidation state of the catalyst does not affect to
leachates varies greatly depending on the type of the efficiency of the process in terms of COD removal.
wastes and the age of the landfill. Biological treatments Working temperatures above 30 C did not lead to
including anaerobic and aerobic processes have shown additional COD reduction and a less efficient use
to be very effective in the early stages when dealing of H2 O2 was observed. A rough economic analysis
with domestic wastes because the BOD/COD ratio of the process indicates that this treatment can be
of the leachate has a high value. However, this a suitable alternative to deal with this type of liquid
ratio generally decreases as the age of landfill wastes.
increases, due to the presence of pollutants that
inhibit biomass activity and/or are recalcitrant to
biological treatments. To treat these aged or refractory SUMMARY
landfill leachates different methods have been used, Fenton oxidation has been demonstrated in full-
such as flocculationprecipitation, adsorption on scale applications as a feasible technology for the
activated carbon, evaporation, chemical oxidation and treatment of a wide diversity of industrial wastewaters.
incineration. Among them, growing interest has been It represents a useful solution in many cases where
focused on advanced oxidation processes, which can the presence of recalcitrant and toxic pollutants
achieve a substantial reduction of COD and improve discards the use of conventional biological treatments.
the biodegradability. Plant design and construction is simple and the
Kang and Hwang107 studied the effectiveness process does not imply any operating problem
of Fenton oxidation against the non-biodegradable other than controlling a safety handling of hydrogen
organic substances present in a leachate from peroxide. In general it has low energy consumption
Kimpo metropolitan landfill in Korea (CODo = as it commonly works at ambient temperature and
1500 mg L1 ). The overall COD removal efficiency pressure. The main economic drawback derives
(by oxidation and coagulation) was maximum around from the consumption of oxidizing reagent (H2 O2 )
a pH of 3.5 in the oxidation step and drastically when dealing with high organic loads. Nevertheless,
decreased beyond pH = 5. Both the overall COD this can be adapted to the case needs using this
removal efficiency and the efficiency by oxidation technique as a conditioning treatment previous to
itself were increased by increasing the H2 O2 dose. a biological process or in combination with some
Otherwise, a dose of ferrous sulphate beyond 500 mg other techniques, like coagulationflocculation or
L1 did not increase the percentage of COD elimi- membrane systems.
nated. The cases described throughout the text are
Lopez et al.108 evaluated the application of the collected in Table 1, which summarizes the state of
Fenton process as pre-treatment for the leachate the art on the application of Fenton technology to
from a municipal landfill located in southern the treatment of industrial wastewaters. The economy
Italy (CODo = 10 540 mg L1 ) with the objective of of this technology is very dependent on the H2 O2
improving its overall biodegradability (BOD5 /COD consumption and in this respect the information
ratio) up to a level compatible with a biologi- compiled from the literature reveals that a wide
cal treatment (BOD5 /COD 0.5). The maximum range of H2 O2 to COD ratios have been used in
amount of COD that could be removed by the Fen- practice.
ton pre-treatment was about 60%, using reagent As indicated before, Fenton oxidation has been
dosages of 10 000 mg L1 of H2 O2 and 830 mg used in connection with other techniques in integrated
L1 of Fe2+ . The H2 O2 dose represented less than wastewater treatments. Table 2 collects a representa-
one-half the stoichiometric amount with respect tive list of examples.
to COD.
Primo et al.109 investigated the treatment of a
mature municipal landfill leachate from Cantabria ACKNOWLEDGEMENTS
(Spain) in an integrated system pilot facility which The authors greatly appreciate financial support
operated in batch and continuous mode. The sequence from the Consejera de Educacion y Ciencia of
of stages was: Fenton oxidation, neutralization of the CM through the project REMTAVARES (S-
Fenton effluent and ultrafiltration with submerged 0505/AMB/0395) and the Spanish MEC through
membranes. The initial COD of the leachate averaged the project CONSOLIDER-TRAGUA (CSD2006-
2100 mg L1 and the BOD5 /COD ratio was 0.08. 0044).

J Chem Technol Biotechnol 83:13231338 (2008) 1331


DOI: 10.1002/jctb
1332
Table 1. Summary on the application of Fenton oxidation to industrial wastewaters
P Bautista et al.

Industry Wastewater characteristics Operating conditions Main results Ref


1
Chemical Pesticides production: CODo = 235 mg L ; pH = 3.03.5; H2 O2 /COD = 21.2 (w/w); XCOD = 58.787.1%; Xorganophosphorous = 97100%; 69
organophosphorouso = 140158 g L1 ; H2 O2 /Fe2+ = 35 (molar); treaction = 2 h. Xorganochlorine > 90%
organochlorineo = 1657.5 g L1
Four types of industrial wastewater: CODo = 13 400, pH = 3.03.5; H2 O2 /COD = 0.37, 2.49, 2.68 and 21.37 XCOD = 71.788.6%; Xtoxicity (to Vibrio fischeri) = 70
2005, 1494 and 234 mg L1 (w/w); H2 O2 /Fe2+ = 35 (molar); treaction = 1.5 h. 1252%
Detergents production: CODo = 10 g L1 Industrial scale. H2 O2 /COD = 0.25 (w/w); XCOD = 90% 71
H2 O2 /Fe2+ = 2 (molar).
Petrochemical industry: TOCo = 94 mg L1 T = 20 C; pH = 3.25; [H2 O2 ]o = 380 mg L1 ; XTOC = 65% 73
H2 O2 /Fe2+ = 3 (molar) treaction = 2 h.
Cosmetic industry: CODo = 2395 and 4255 mg L1 ; T = 2550 C; pH = 3.0; H2 O2 /COD = 2.12 (w/w); XTOC = 4560%; XCOD = 69% 76
TOCo = 705 and 1090 mg L1 ; H2 O2 /Fe2+ = 4274 (molar); treaction = 4 h;
BOD5o /CODo = 0.133 and 0.169 Vreaction = 50 mL.
Phenolic resins manufacture: CODo = 2904 mg L1 ; Fenton or photo-Fenton (solar). Room temperature; Effective removal of phenol within 5 min. Fenton: 78
DOCo = 933 mg L1 ; phenolo = 1215 mg L1 pH = 3; H2 O2 /COD = 2.2 (w/w); H2 O2 /Fe2+ = 38.5 XCOD = 82%; XDOC = 41%. Photo-Fenton:
(Fenton) and 77 (photo-Fenton) (molar); treaction = 2 h. XCOD = 97%; XDOC = 97%
Pigment production: CODo = 2700 mg L1 ; T = 20.8 C; pH = 5; H2 O2 /COD = 1.85 (w/w); XCOD = 54.2%; BOD5 /COD = 0.36; Xcolour = 91.2% 79
BOD5o /CODo = 0.04; Colouro (454 nm) = 1.479 AU H2 O2 /Fe2+ = 10 (molar). Batch: treaction = 0.5 h;
Vreaction = 500 mL.
Pharmaceutical CODo = 362 g L1 ; BOD5o /CODo = 0.008 T = 40 C; pH = 4; H2 O2 /COD = 0.28 (w/w); XCOD = 56.4% 80
H2 O2 /Fe2+ = 10 (molar); treaction = 1.5 h;
Vreaction = 100 mL.
Pulp and paper CODo = 1384 mg L1 ; TOCo = 441 mg L1 Fenton or photo-Fenton. T = 25 and 70 C; pH = 2.8; Fenton: XTOC = 82%; Photo-Fenton: XTOC = 91% 85
H2 O2 /COD = 7.22 (w/w); H2 O2 /Fe2+ = 41 (molar);
treaction = 2 h; Vreaction = 100 mL; Solar or Xe light.
CODo = 1250 mg L1 ; TOCo = 537 mg L1 ; Fenton or photo-Fenton. T = 30 C; pH = 3; Fenton: XTOC = 90%; Photo-Fenton: XTOC = 93% 86
Colouro (Pt) = 649 mg L1 H2 O2 /COD = 5.76 (w/w); H2 O2 /Fe2+ = 26 (molar);
treaction = 15 min; Vreaction = 100 mL; Solar light
irradiation.
CODo = 964 mg L1 ; BOD5o /CODo = 0.4; Total Fenton-like. Batch: room temperature; pH = 2.5; XCOD = 75%; Xcolour = 98%; Xaromatics = 95%; 88
solidso = 1396 mg L1 ; H2 O2 /COD = 1.04 (w/w); H2 O2 /Fe3+ = 4 (molar); BOD5 /COD = 0.7; Treated wastewater toxic to
Colouro (PtCo) = 4236 mg L1 ; treaction = 1 h; Vreaction = 300 mL; Coagulation at Artemia salina
Odouro = 31 473 UO m3 pH = 5.

DOI: 10.1002/jctb
J Chem Technol Biotechnol 83:13231338 (2008)
Table 1. Continued

Industry Wastewater characteristics Operating conditions Main results Ref

DOI: 10.1002/jctb
Pilot scale (continuous flow): tR = 1 h; Vreaction = 50 L (a Xodour = 96%; XVOCs (terpernes) = 80%
series of 2 reactors); Q = 100 L h1 .
Textile Four wastewaters: CODo = 3600, 1030, 1970 and T = 25 C; pH = 3.5; H2 O2 /COD = 0.194.7, XCOD = 60% (batch); XCOD = 30% (continuous flow). 89
3160 mg L1 0.6616.5, 0.358.63 and 0.225.38 (w/w); Significant colour reduction.
H2 O2 /(Fe2+ /Fe3+ ) = 125 (molar). Batch:
treaction = 2 h; Vreaction = 300 mL; Continuous flow:
tR = 1 h; Vreaction = 1 L.
Textile Combined industrial and domestic wastewater: Room temperature; pH = 3; H2 O2 /COD = 0.34 (w/w); XCOD = 95%; Xcolour = 100%; BOD5 /COD = 0.625 90
CODo = 1596 mg L1 ; BOD5o /CODo = 0.31; H2 O2 /Fe2+ = 2 (molar).
TSSo = 320 mg L1 ; oil and greaseo = 5.8 mg L1 ;

J Chem Technol Biotechnol 83:13231338 (2008)


heavy metalso = 18.32 mg L1
CODo = 910 mg L1 ; BOD5o /CODo = 0.16; T = 40 C; pH = 3.5; H2 O2 /COD = 0.88 (w/w); XCOD = 59%; Xcolour = 89%; Complete removal of the 91
Colouro (PtCo) = 1570 mg L1 H2 O2 /Fe2+ = 12 (molar). toxicity to Daphnia magna
CODo = 8100 mg L1 ; BOD5o /CODo = 0.148; Room temperature; pH = 3; H2 O2 /COD = 0.0037 (w/w); XCOD = 45%; XTOC = 40%; Xcolour = 71.5%; 92
TOCo = 3010 mg L1 H2 O2 /Fe2+ = 1.2 (molar). Batch: treaction = 46 h; BOD5 /COD = 0.097
Vreaction = 2 L.
CODo = 1669 mg L1 ; TOCo = 605 mg L1 ; Fenton or photo-Fenton. T = 70 C; pH = 3; Fenton: XTOC = 75%; Photo-Fenton: XTOC = 79% 93
Colouro (Pt) = 40 mg L1 H2 O2 /COD = 6 (w/w); H2 O2 /Fe2+ = 41 (molar);
treaction = 2 h; Vreaction = 100 mL; Xe light.
CODo = 1000 mg L1 T = 25 C; pH = 3; H2 O2 /COD = 0.5 (w/w); XCOD = 71% 39
[Fe2 O3 /carbon] = 300 mg L1 . Batch: treaction = 1 h;
Vreaction = 400 mL.
CODo = 800 mg L1 Industrial scale. H2 O2 /COD = 1.25 (w/w); XCOD = 55% 71
H2 O2 /Fe2+ = 1.2 (molar).
Food Olive oil mill wastewater: CODo = 12.8 g L1 T = 2050 C; pH = 2.8; H2 O2 /COD = 2.66 (w/w); XCOD = 6585% 96
H2 O2 /Fe2+ = 100 (molar); treaction = 8 h.
Food Olive oil mill wastewater: CODo = 167181 g L1 ; T = 25 C; pH = 4; H2 O2 /COD = 0.05 (w/w); XCOD = 56%; Xpolyphenols = 99.5%; Xcolour = 35%; 98
TSSo = 3639 g L1 ; Total polyphenolso = 5.2 g L1 ; H2 O2 /Fe2+ = 8.33 (molar); treaction = 4 h. Xaromatics = 33%
Turbidityo = 14.614.8 NTU
Table olive producing industry: CODo = 6700 mg L1 ; T = 30 C; pH = 4; H2 O2 /COD = 4 (w/w); XCOD = 73%; Xpolyphenols = 2690%; 99
BOD5o /CODo = 0.64; TSS = 5.2 g L1 ; Total H2 O2 /Fe2+ = 10 (molar); treaction = 1.5 h; Xaromatics = 3594%
polyphenolso = 0.12 g L1 ; Vreaction = 0.5 L.
Aromaticityo (254 nm) = 17.0 AU

1333
Fenton oxidation to industrial wastewaters treatment
1334
Table 1. Continued
P Bautista et al.

Industry Wastewater characteristics Operating conditions Main results Ref


1
Cork processing CODo = 5000 mg L ; BOD5o /CODo = 0.27; T= 30 C; pH = 3.2; H2 O2 /COD = 2.12 (w/w); XCOD = 87.3%; XTOC = 66.4%; 103
TOCo = 1505 mg L1 H2 O2 /Fe2+ = 8.2 (molar); Vreaction = 200 mL. BOD5 /COD = 0.63
CODo = 3702 mg L1 ; BOD5o /CODo = 0.19; T = 30 C; pH = 3.5; H2 O2 /COD = 1.84 (w/w); XCOD = 65% 105
TSSo = 13901700 mg L1 ; Total H2 O2 /Fe2+ = 10 (molar); treaction = 2.5 h;
polyphenolso = 500620 mg L1 ; Vreaction = 0.5 L.
Aromaticityo (254 nm) = 0.961.17 AU (1/50 diluted
samples)
Landfill leachates CODo = 1500 mg L1 ; BOD5o /CODo = 0.02 T = 25 C; pH = 3.5; H2 O2 /COD = 1.1 (w/w); XCOD = 70% 107
H2 O2 /Fe2+ = 14.7 (molar); treaction = 3 h;
Vreaction = 1 L.
CODo = 10 540 mg L1 ; BOD5o /CODo = 0.22; Room temperature; pH = 3; H2 O2 /COD = 0.31 (w/w); XCOD = 25%; BOD5 /COD = 0.5 108
TOCo = 3900 mg L1 H2 O2 /Fe2+ = 19.7 (molar); treaction = 2 h.

Table 2. Application of Fenton oxidation in integrated wastewaters treatments

Industry Wastewater characteristics Operating conditions Main results Ref

Chemical Leather tannery industry: CODo = 319716797 mg L1 ; Combined Fenton and activated sludge system. XCOD 96% (Fenton: XCOD = 90%; Biological 74
BOD5o /CODo = 0.25 H2 O2 /COD = 4 (w/w); H2 O2 /Fe2+ = 9 (molar). treatment: XCOD = 3560%; XBOD = 6070%)
Pharmaceutical Three wastewater samples: CODo = 4000, 5400 and Lab scale. Fenton-like + lime coagulation. Room XCOD = 8796%; XBOD7 = 7995% 82
13 130 mg L1 ; BOD7o /CODo = 0.33, 0.45 and temperature. H2 O2 /COD = 2 (w/w); H2 O2 /Fe2+ = 10
0.54 mg L1 (molar); treaction = 2 h; Vreaction = 200 mL.
CODo = 3540 g L1 ; BOD5o /CODo = 0.06 Industrial scale. Fenton + SBR (V = 8 m3 ; 24 h/cycle). XCOD = 98%; XBOD = 98%. Fenton unit: 83
Room temperature; pH = 3.5; XCOD = 4550%; BOD5 /COD = 0.23
H2 O2 /COD = 0.260.29 (w/w); H2 O2 /Fe2+ = 150
(molar); Vreaction = 2 m3 .
Textile CODo = 697 mg L1 ; Transparencyo = 3.7 cm Continuous process of combined coagulation, Fenton XCOD = 88%; Transparency = 28.2 cm. 94
and activated sludge. pH = 4; H2 O2 /COD = 0.14
(w/w); H2 O2 /Fe2+ = 4.5 (molar);
[PAC]o = 100 mg L1 . Fenton: tR = 1 h;
Q = 1 mL min1 .

DOI: 10.1002/jctb
J Chem Technol Biotechnol 83:13231338 (2008)
DOI: 10.1002/jctb
Table 2. Continued

Industry Wastewater characteristics Operating conditions Main results Ref

CODo = 1047 mg L1 ; BOD5o /CODo = 0.42; Comparison of SBR, Fenton + SBR and SBR + Fenton. Best option: Fenton + SBR : XCOD = 91%; 95
Colouro = 544 ADMI units Lab.scale. Batch. Fenton: T = 2832 C; pH = 3; Xcolour = 80%
H2 O2 /COD = 0.0030.03 (w/w); H2 O2 /Fe2+ = 1
(molar); treaction = 0.5 h; Vreaction = 5 L. SBR: Three
reactors in parallel mode; T = 2832 C; V = 10 L;
24 h/cycle; STR = 60 days

J Chem Technol Biotechnol 83:13231338 (2008)


Food Wine distillery industry: CODo = 18.5 g L1 ; Integrated Fentoncoagulationflocculation process XCOD = 74% 100
TSSo = 13 g L1 (using Ca(OH)2 ). H2 O2 /COD = 0.92 (w/w);
H2 O2 /Fe2+ = 15 (molar).
Brewery industry: CODo = 16.3 g L1 Biological treatment (anaerobic and aerobic processes) Anaerobic process (UASB): XCOD = 90%; 101
and Fenton (pH = 23; H2 O2 /COD = 1 (w/w); Aerobic process: XCOD = 80%; Fenton:
H2 O2 /Fe2+ = 0.5 (molar); treaction = 1 h). XCOD = 35% and XSS = 40%
Cork processing CODo = 4250 mg L1 ; BOD5o /CODo = 0.19; Integrated Fentoncoagulation/flocculation process. XCOD = 74%; Xpolyphenols = 99%; 104
TSSo = 1720 mg L1 ; Total polyphenolso = 994 mg L1 ; T = 35 C; H2 O2 /COD = 4 (w/w); H2 O2 /Fe3+ = 81 Xaromatics = 98%; BOD5 /COD = 0.50
Aromaticityo (254 nm) = 2.16 AU (1/25 diluted samples) (molar); treaction = 5 h; Vreaction = 150 mL.
CODo = 23004600 mg L1 ; BOD5o /CODo = 0.150.21; Fenton oxidation + Biological treatment. T = 30 C; XTOC = 92% 106
TOCo = 12202000 mg L1 ; Total pH = 3.5; H2 O2 /COD = 1.092.17 (w/w);
polyphenolso = 660780 mg L1 H2 O2 /Fe2+ = 8.2 (molar); treaction = 0.5 h;
Vreaction = 1 L.
Landfill leachates CODo = 2100 mg L1 ; BOD5o /CODo = 0.08 Integrated system (Fenton + membrane filtration). Pilot XCOD = 80% (batch); XCOD = 83% (continuous); 109
plant. Room temperature; pH = 3; Batch: BOD5 /COD = 0.36
H2 O2 /COD = 4 (w/w); H2 O2 /Fe2+ = 13.8 (molar);
treaction = 1 h; Vreaction = 100 L. Continuous:
H2 O2 /COD = 3.3 (w/w); H2 O2 /Fe2+ = 11.4 (molar);
tresidence = 2 h.

1335
Fenton oxidation to industrial wastewaters treatment
P Bautista et al.

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