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Water Research 37 (2003) 30613069

Fenton oxidation of cork cooking wastewateroverall kinetic


analysis
Anabela M.F.M. Guedes1, Luis M.P. Madeiraa,b, Rui A.R. Boaventuraa,c,
Carlos A.V. Costaa,b,*
a

Departamento de Engenharia Qu!mica, Faculdade de EngenhariaUniversidade do Porto. Rua Dr. Roberto Frias s/n,
4200465 Porto, Portugal
b
!
LEPAELaboratorio
de Engenharia de Processos, Ambiente e Energia, Portugal
c
!
LSRELaboratorio
de Processos de Separa@ao
* e Reac,cao,
* Portugal
Received 4 October 2001; accepted 13 March 2003

Abstract
In the present work, the possibility of using chemical oxidation through Fentons reagent for the pre-treatment of
cork cooking wastewaters was exploited. Aiming both the selection of the best operating conditions (pH, Fe2+:H2O2
ratio and initial H2O2 concentration) and the evaluation of the overall reaction kinetics, trials were performed in a batch
reactor. Operating at pH=3.2, H2O2 concentration=10.6 g/L and Fe2+:H2O2 ratio=1:5 (by weight), about 66.4% of
total organic carbon (TOC), 87.3% of chemical oxygen demand (COD) and 70.2% of biochemical oxygen demand
(BOD5) were removed and an increase of the BOD5/COD ratio from 0.27 to 0.63 was achieved. In the temperature
range 2050 C, the best performance was obtained at 30 C. The kinetic study was undertaken at different initial TOC
concentrations and temperatures. Overall kinetics can be described by a second-order followed by a zero-order rate
equation and the apparent kinetic constants at 30 C are k 2:3  104 L/mg min and k0 26:0 mg/L min, respectively.
The experiments performed at different temperatures conrmed the global kinetic model and allowed to calculate the
global activation energy for the second-order reaction (70.7 kJ/mol).
r 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Fentons reagent; Oxidation; Cork cooking wastewater; Kinetics

1. Introduction
The cork manufacturing industry faces an environmental problem concerning wastewaters disposal from
the cork cooking process, as they do not meet discharge

*Corresponding author. Departamento de Engenharia Qu!mica, LEPAE, Faculdade de Engenharia, Universidade do


Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal.
Tel.: +351-22-5081670; fax: +351-22-5081449.
E-mail address: ccosta@fe.up.pt (C.A. Costa).
1
Current address: Departamento de Engenharia Qu!mica,
Instituto Superior de Engenharia, Instituto Polit!ecnico do
!
Porto, R. Dr. Antonio
Bernardino de Almeida, 431, 4200-465
Porto, Portugal.

limits (Table 1). Moreover, cooking natural lignocellulosic materials often originates wastewater-containing
compounds (e.g., phenolic acids) in a concentration
inhibitory for conventional biological treatment. The
reduction of the organic load by a biological process is a
hard task due to the efuents toxicity and its low BOD5/
COD ratio, which is about 0.2 [1].
A possible strategy for overcoming this issue should
be the use of chemical oxidation as a pre-treatment step
in order to improve wastewater biodegradability. Such
processes have proved to be particularly effective for
eliminating organic impurities which are toxic, inhibitory or refractory for subsequent biological systems.
Recently, advanced oxidation processes (AOP) have
been developed and proposed for a number of situations

0043-1354/03/$ - see front matter r 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0043-1354(03)00178-7

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069

3062

Table 1
Parameter values (average) from analyses of cork cooking
wastewaters [1]
Analyzed parameter

Average valuea

Limit valueb

PH
Temperature ( C)

4.6
98

BOD5, 20 C (mg O2/L)


COD (mg O2/L)
TSS (mg/L)
Total copper (mg Cu/L)
Total iron (mg Fe/L)
Smell

1120
5090
1780
0.6
6.4
Not detectable in
the 1:20 dilution

Color

Not visible in the


1:20 dilution
0.6
151
13.0
860

6.09.0
Increase p3 C
in the receiving
stream
40
150
60
1.0
2.0
Not detectable
in the 1:20
dilution
Not visible in
the 1:20 dilution
0.5
2000
50
Not applicable

Phenols (mg/L)
Sulfates (mg/L)
Nitrates (mg/L)
Polyphenols (mg/L)
a
b

Number of samples analyzed=9.


Emission limit value according to Portuguese legislation.

[2], particularly oxidation by Fentons reagent [3,4]. This


is a very promising AOP wherein wastewater reacts with
hydrogen peroxide (H2O2) in a non-pressurized reactor,
at low temperatures, in the presence of a low-cost
catalyst (e.g., iron sulfate), yielding carbon dioxide and
water and/or other oxidation products [3].
The oxidation of many organic substances with H2O2
is improved by the addition of a catalyst (Fe(II) or more
rarely Cu(II) or other transition metal ions) to activate
the H2O2 molecule, leading to the formation of hydroxyl
radicals (OHd). These are the true oxidant species, which
exhibit a very high oxidation potential, 2.80 V [5], only
being surpassed by uorine.
Fenton oxidation is quite complex, as evidenced by
some of the proposed mechanisms found in the literature
[610]. Notwithstanding, it seems to be a general
agreement that the limiting step is the formation
of the hydroxyl radicals through the following reaction
[4,1113]:
Fe2 H2 O2 -Fe3 OH OHd :

Iron (II) is slowly regenerated through the so-called


Fenton-like reaction between Fe(III) and H2O2 [14,15]:
Fe3 H2 O2 2Fe  OOH2 H ;

Fe  OOH2 -HOd2 Fe2 ;

Fe3 HOd2 2Fe2 O2 H :

The OH species formed through Eq. (1) will then


attack the organic substrates present in the wastewater.

Nevertheless, numerous competitive reactions can also


occur, namely the following ones, which negatively
affect the oxidation process [11,12,16]:
Fe2 OHd -Fe3 OH ;

H2 O2 OHd -HOd2 H2 O:

This network of consecutive and parallel reactions


results in complex reaction kinetics. To overcome these
difculties, most of the kinetic studies focused on singlecomponent degradation [1719] or, in the case of
complex efuents, the overall kinetics was analyzed
instead.
The efciency of the Fenton oxidation process
depends on the H2O2:organic carbon ratio, organic
matter content, temperature and Fe(II) concentration
[3,20,21]. Depending on the efuent being treated,
different operating conditions should therefore be
employed to achieve high degradation efciencies. The
pH, Fe(II):H2O2 ratio and H2O2 concentration are also
crucial [8,16,20,21].
The rst goal of this work was to determine operating
conditions leading to high TOC removals from cork
cooking wastewaters using the Fentons reagent. Then, a
detailed kinetic study performed in a batch reactor using
the previously determined conditions was carried out.
This study allowed a better understanding of the process
and identication of practical aspects to consider in
future works.

2. Experimental
2.1. Analytical procedures
Total organic carbon (TOC) was measured by
catalytic oxidation/NDIR spectrometry [22] using an
Ionics analyzer, model 1258.
Chemical oxygen demand (COD) was determined by
colorimetric measurement after closed reux digestion
[22], carried out in a MERCK thermoreactor, model TR
300.
Biochemical oxygen demand (BOD5) was quantied
by the dilutions method [22]. The concentration of
dissolved oxygen was measured with an ORION oxygen
electrode, model 97-08-00.
Hydrogen peroxide concentration was determined by
photometry (MERCK photometer, model SQ 118, and
kit of reactants MERCK 14731 H2O2). Dissolved iron
concentration was assessed by AASdirect aspiration
method (ame)using a GBC spectrophotometer,
model 902.

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069

2.2. Oxidation runs and experimental setting


The tests were performed in a perfectly mixed 1 Lcapacity batch reactor (with an acrylic stopper) and the
reaction was followed by continuously monitoring the
oxidationreduction potential (ORP), pH and temperature of the medium. Two HANNA Instruments electrodes (models HI 2930 and HI 1912, respectively) and a
thermocouple were used, the electrodes being connected
to HANNA Instruments digital controllers and the
thermocouple to an HANNA Instruments digital
recorder. pH was kept constant through the addition
of NaOH 2 M or H2SO4 0.1 M solutions during the tests.
This is particularly important because as the reaction
proceeds, pH tends to decrease due to the formation of
organic acids [17,21,23].
After adjusting initial pH, solid iron sulfate (from
Riedel-deHa.en) was added to the wastewater followed
by hydrogen peroxide solution (commercial H2O2 with a
concentration of 11.6 M, from Sociedade Portuense de
Drogas, SA), with intermediate pH adjustment when
necessary. Finally, 23 drops of 50% diluted anti-foam
ER/18 (Eigemann & Veronelli SPA) was also added. As
experimentally determined, the effects of the anti-foam
agent over TOC and COD are negligible. In the runs,
time zero coincides with the H2O2 addition and in the
optimization experiments monitoring was stopped when
ORP no further changed, which is a possible indication
of the completion of the reaction, as already suggested
by Bigda [3].
At the end of each run, the reactor contents were
transferred to a glass ask and stored at 4 C. After a 20
24 h settling period, TOC, or even COD and BOD5,
were determined in vacuum ltered samples, using a
Whatman GF/C lter disk. Settling followed by ltration reduces TOC value around 7%.
After selecting the best experimental conditions, an
additional run was carried out to characterize the
supernatant (TOC, COD, BOD5, TSS) and to determine
the volume and water content of the sludge. The water
content was determined after drying the sludge for 2 h at
100 C. Residual H2O2 was also measured in the
supernatant to evaluate possible interference with
COD. As the obtained H2O2 concentrations (1.1 mg/L)
only increase the total COD of the treated wastewater by
about 0.5 mg/L [24], the interference is negligible.
In order to study the global kinetics of this reaction,
two sets of batch experiments were performed under
isothermal conditions. A volume of 750 mL of wastewater was used and the best operating conditions
dened in this study were employed, i.e., pH=3.2,
[H2O2]initial=10.6 g/L and Fe2+:H2O2 ratio=1:5
(by weight). In the rst set of experiments, at 30 C,
the initial TOC concentration varied between 753
and 1505 mg/L (obtained by diluting the raw wastewater with distilled water). In the second set, the

3063

temperature ranged between 20 and 50 C (with


[TOC]initial=1505 mg/L).
In the kinetic study, the samples were transferred to
small vials containing excess sodium sulte and immediately refrigerated. For TOC analysis, samples were
homogenized, without previous sedimentation and
ltration.

3. Results and discussion


3.1. Physicochemical characterization of cork cooking
wastewater
The cork cooking wastewater used here had intense
brownish color. To ensure a constant composition
during the experimental work, a sufcient volume of
wastewater was ltered after decantation during about
2 h. The relevant parameters were analyzed and the data
are shown in Table 2. The water exhibits high organic
content (TOC=1505 mg/L) and low biodegradability
(BOD5/COD=0.27).
3.2. Study and optimization of the operating conditions
Three sets of runs were performed in a batch reactor
to independently study the effect of the following
parameters: initial H2O2 concentration, Fe2+:H2O2
ratio and pH. Wastewater samples (200 mL) were heated
up to 30 C before starting the experiments. This
temperature was chosen based on some literature
references which point out a range of 2040 C as being
optimal for Fenton oxidation (e.g., [21]).
3.2.1. H2O2 concentration
In the rst set of experiments, the pH of the medium
and the Fe2+:H2O2 ratio (by weight) were kept constant
at 3.0 and 1:5, respectively, the values being chosen
based on Bigda [3] recommendations. The initial H2O2
concentration was changed between 3.9 and 13.8 g/L.
For the lower initial H2O2 concentration (3.9 g/L), the
water became completely turbid and brown and no
sludge was produced. In the other runs, a clear brown
colored sludge was produced, probably due to Fe

Table 2
Chemical characterization of the used cork cooking wastewater
after ltration
Analyzed parameter

Results

TOC (mg/L)
COD (mg O2/L)
BOD5 (mg O2/L)
PH

1505
5000
1340
4.3

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069

3.2.2. Iron:hydrogen peroxide ratio


In the second set of experiments pH and [H2O2] were
xed at 3.0 and 10.6 g/L, respectively, and the
Fe2+:H2O2 ratio was varied between 1:9 (0.11) and 1:2
(0.50), by weight. In all runs, a brown sludge (rust
colored) and a yellow supernatant were observed. For
iron:hydrogen peroxide ratios higher than 1:5 (i.e.,
between 1:2 and 1:4), the sludge volume increased with
the ratio. For lower ratios, the sludge volume was
practically constant (about 200 mL/L of wastewater).
The highest TOC removal (69.1%) corresponds to
Fe2+:H2O2=1:2 (Fig. 2). However, as it is only slightly
lower (65.4%) for Fe2+:H2O2=1:5, the use of the ratio
1:5 (by weight) is recommended because less catalyst is
required, without signicant decrease in TOC removal.
3.2.3. pH
The effect of pH was evaluated in the range 2.04.5,
whereas the H2O2 concentration and the Fe2+:H2O2
ratio were maintained at 10.6 g/L and 1:5, respectively.

TOC removal (%)

80

60

40

20

0
0

10

12

14

[H2O2]initial (g/L)

Fig. 1. Effect of the initial H2O2 concentration on the TOC


removal (Fe2+:H2O2 ratio=1:5 and pH=3.0).

75
70

TOC removal (%)

precipitation. For higher H2O2 concentrations (corresponding to higher Fe loads), sludge became more clear
(rust colored) as H2O2 load increased. The supernatant
appearance also changed, being turbid and brown for
[H2O2] equal to 5.9 and 7.9 g/L and clear and yellow in
the other runs. The volume of produced sludge was
180 mL/L of wastewater for initial [H2O2]p10.6 g/L and
about 300 mL/L of wastewater for higher [H2O2].
The experimental data concerning TOC removal are
shown in Fig. 1. They evidence an increase in the
removal with increasing initial [H2O2]. However, for
H2O2 concentrations above 10.6 g/L such increase is not
signicant. Thus, for practical purposes, the use of
concentrations above 10.6 g/L is useless because it would
result in higher operation costs. Finally, it must be
stressed that the low TOC removal observed for [H2O2]
o7.9 g/L is in agreement with the above-mentioned
appearance of the wastewater after the oxidation runs.

65
60
55
50
0

0.1

0.2

0.3

0.4

0.5

0.6

Fe 2+:H2O2

Fig. 2. Effect of the initial Fe2+:H2O2 ratio (by weight) on the


TOC removal ([H2O2]initial=10.6 g/L and pH=3.0).
70

TOC removal (%)

3064

60

50

40

30
1.5

2.5

3.5

4.5

pH

Fig. 3. Effect of the pH of the reaction medium on the TOC


removal (Fe2+:H2O2 ratio=1:5 and [H2O2]initial=10.6 g/L).

The aspect and coloration of the supernatant varied,


being limpid and dark yellow in the runs at pH 2.0 and
2.5, limpid and light yellow in the runs at pH 3.0 and
3.5, and turbid and rust colored in the remaining ones.
The volume of produced sludge was 170 mL/L of
wastewater for pHp3.5, and 300 mL for pH>3.5.
The effect of pH in the TOC removal shows an
optimal range between 3.0 and 3.5 (Fig. 3). Such range is
clearly in accordance with that suggested in the
literature as being the ideal for Fenton oxidation of
many chemicals, i.e., 34 [3]. The drop in efciency at
high pH values may be due to the precipitation of
Fe(OH)3. In this form, iron decomposes H2O2 into
oxygen and water [6,21], and consequently the oxidation
rate decreases because less hydroxyl radicals are available. Besides, the formation of Fe(II) complexes must
also be taken into account at high pH values [25], which
leads to a decrease in Fe2+ concentration. On the other
hand, at very low pH values the reaction may be
inhibited. This is usually attributed to the formation of
the complex species [Fe(II) (H2O)6]2+, which reacts
more slowly with H2O2 (Eq. (1)) than [Fe(II) (OH)

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069


75
70

60

TOC removal (%)

TOC removal (%)

80

40

pH=3.2
pH=3.0

20

65

pH = 3.2

60

pH = 3.0
55
50

0
0

(A)

3065

10

12

14

[H2O2]initial (g/L)

0.1

0.2

0.3

0.4

0.5

0.6

Fe 2+:H2O2

(B)

Fig. 4. Effect of the initial H2O2 concentration (A) and of the Fe2+:H2O2 ratio (B) on the TOC removal for different pH values (A:
Fe2+:H2O2 ratio=1:5; B: [H2O2]initial=10.6 g/L).

Table 3
Analytical results of supernatant and sludge after Fenton
oxidation of cork cooking wastewatera
Analyzed parameter

Results

TOC (mg/L)
COD (mg O2/L)
BOD5 (mg O2/L)
Formed sludge (mL/L of wastewater)
Sludge water content (%)
TSS (mg/L)
TOC removal (%)
COD removal (%)
BOD5 removal (%)
BOD5/COD
Dissolved Fe (mg/L)

505
634
399
176
96
46
66.4
87.3
70.2
0.63
5.5

Initial operating conditions: [H2O2]=10.6 g/L, Fe2+:H2O2


ratio=1:5, pH=3.2 and T 30 C.

(H2O)5]+, thus producing less amount of OHd. In


addition, the scavenging effect of these radicals by
hydrogen ions becomes important at very low pH and
the reaction of Fe3+ with H2O2 is inhibited [15]. In order
to more precisely dene the optimal pH value, an
additional run was performed at pH=3.2, and an even
higher removal was recorded (66.4%). This is included
in Fig. 3.
Finally, the rst two sets of experiments were repeated
at pH=3.2. The results, as illustrated in Fig. 4, show a
slight increase in the TOC removal and thus the best
initial operating conditions, for practical purposes, are
[H2O2]=10.6 g/L, Fe2+:H2O2 ratio (by weight)=1:5
and pH=3.2. For such conditions, Table 3 shows the
results of the analysis performed with the supernatant.
Removals of 66.4%, 87.3% and 70.2% for TOC, COD
and BOD5, respectively, were achieved, as well as a
BOD5/COD ratio of 0.63, which is suitable for
subsequent biological treatment. The soluble iron

concentration (5.5 mg/L) is not inhibitory because


values up to 100 mg/L do not cause problems to
activated sludge systems [26]. Besides, the minimum
amount of iron (12  103 mg/mg BOD5) required for
the biological treatment is present in the treated water
(13.8  103 mg/mg BOD5). The very low COD/TOC
ratio (about 1.3) indicates that residual organic carbon is
mostly due to refractory organics. Volume and water
content of the produced sludge are also given in Table 3,
which are important for sludge treatment/disposal costs
estimation.
3.3. Global kinetics
It must be remarked that since we have a very
complex reaction mixture, the overall kinetics will be
analyzed by taking into account the total amount of
organic carbon present within the reactor.
3.3.1. Effect of the TOC content
Fig. 5 shows the data obtained during the rst 5 min
of reaction when departing from different TOC concentrations. This rst set of experiments is particularly
suitable for determination of apparent reaction orders.
It is evident, particularly when departing from higher
organic loads, that a more signicant decrease in the
total organic carbon content occurs in the rst minutes,
with a less pronounced decrease later on. This may
suggest a change in the global kinetics.
The mass balance on a constant-volume (liquid phase)
batch reactor, where an n-order reaction takes place,
yields
r kC n 

dC
;
dt

where r denotes the rate of consumption of a


reactant with concentration C (in this case it refers to
[TOC]) and k is the overall kinetic constant. From Fig. 5

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069

3066
1600

[TOC] (mg/L)

[TOC]o = 1505 mg/L


[TOC]o = 1204 mg/L

1400

[TOC]o = 1004 mg/L


[TOC]o = 753 mg/L

[TOC] (mg/L)

1200

800

600

400
1

1000

(B)

Tim e (min)

800

600

400
0

(A)

Time (min)

Fig. 5. (A) Evolution of the TOC concentration within the batch reactor for different initial TOC contents and (B) details of the zeroorder kinetic ttings to the last minutes of reaction ([H2O2]initial=10.6 g/L, Fe2+:H2O2 ratio=1:5, pH=3.2 and T 30 C).

6.5

3.8

ln r (mg/(L.min)

ln r (mg/(L.min))

6.0
5.5

5.0
4.5
4.0

3.4

3.2

3.0
6.4

(A)

3.6

6.6

6.8

7.0

ln [TOC]average (mg/L)

7.2

6.1

6.2

(B)

6.3

6.4

6.5

6.6

6.7

ln [TOC]average (mg/L)

Fig. 6. Logarithm of reaction rates vs. logarithm of average TOC concentrations within the batch reactor for the rst (A) and last (B)
minutes of reaction (data from Fig. 5).

it can be seen that although for different initial TOC


concentrations, the reaction rate is approximately
constant within the rst 2 min; it decreases with the
initial organic matter content. From the linear decrease
in each run, the reaction rates were computed for the
average TOC concentrations and the order n was
obtained after a linear regression analysis (Fig. 6A).
The straight-line slope (2.06) indicates that oxidation
proceeds in accordance with approximate second-order
kinetics. In addition to the differential method of data
analysis, the method of initial rates was also employed.
In this case, the representation of ln dc=dtt0 vs.
ln C0 (initial TOC concentration) gave a straight line
with slope (n) equal to 1.98, thus conrming secondorder kinetics. This was also veried through the use of
the integral method.

A similar analysis was employed for the data after the


rst 2 min of reaction. In this case, the obtained slope
was 0.04 (Fig. 6B), suggesting that the second phase of
the reaction can be described by a zero-order kinetic
equation.
For determination of the kinetic constants, the
integral method is more adequate than those previously
described. In fact, it is used most often when the reaction
order is known and it is desired to evaluate specic
reaction rate constants [27]. Thus, for a second-order
reaction, integration of Eq. (7) yields
1
1

kt:
C
C0

TOC concentration data corresponding to the secondorder reaction step were tted to Eq. (8) and the

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069


0.0008

3067

1600

T = 20C
T = 30C

1400

T = 40C
T = 50C

[TOC] (mg/L)

1/C-1/C0 (L/mg)

0.0006

0.0004

1200

1000

[TOC]o = 1505 mg/L


[TOC]o = 1204 mg/L

800

[TOC]o = 1004 mg/L

0.0002

[TOC]o = 753 mg/L

600

400

0.0

1.0

2.0

3.0

4.0

Time (min)

apparent kinetic constant obtained by linear regression


analysis, i.e., k 2:3  104 L/mg min (Fig. 7). The
pseudo-second-order apparent kinetic constant includes
the hydroxyl radical concentration
0

10

15

20

Time (min)

Fig. 7. Fitting of the experimental data (for different initial


TOC contents) to a second-order reaction kinetic model for the
rst minutes of reaction.

m
2
2
dC
r k COH
TOC EkCTOC :

Fig. 8. Evolution of the TOC concentration within the batch


reactor for different reaction temperatures ([H2O2]initial=10.6 g/
L, Fe2+:H2O2 ratio=1:5, pH=3.2 and [TOC]initial=1505 mg/
L).

[3]). This can also account for the decrease in the


reaction rate mentioned above.
3.3.2. Effect of the temperature

For the zero-order dependence, integration of Eq. (7)


yields a linear decrease of the TOC concentration with
time, whose slope is the apparent zero-order kinetic
constant k0 : Fittings of experimental data are shown in
Fig. 5B, leading to an average apparent kinetic constant
k0=26.0 mg/L min.
Very recently, Szpyrkowicz et al. [6] also found that a
second-order reaction model is adequate to describe the
overall COD removal in the case of disperse dyes, with
quick oxidation during the rst 2030 min followed by
much smaller reaction rates.
The evolution of the TOC concentration recorded in
this study can be explained as follows. In all the
experiments, oxidation was carried out with a large
excess of peroxide as compared to ferrous ion (initial
H2O2/Fe2+ molar ratio=8.2). Under these conditions,
hydroxyl radicals are produced very rapidly, leading to a
fast decrease of TOC. When most of iron(II) has been
oxidized, iron(III) reacts very slowly with residual
peroxide to regenerate iron(II) via the formation of
peroxo complexes and their very slow decomposition
into iron(II) (Eqs. (2) and (3)). These reactions explain
the slower decomposition of TOC in the second step.
Furthermore, the formation of other radicals, particularly perhydroxyl radicals through Eqs. (3) and (6),
decreases both the concentration of the hydroxyl species
and the oxidation power of the medium (the oxidation
potentialsrelative to chlorinefor hydroxyl and
perhydroxyl radicals are 2.06 and 1.25 V, respectively

In the second set of experiments, the reaction


temperature was varied with the purpose of both
investigating its effects on the overall kinetics and to
allow the determination of the Arrhenius-type dependence of the global kinetic constant k on the temperature:
k AeE=RT ;

10

where A is the pre-exponential (or frequency) factor and


E is the global activation energy.
Fig. 8 shows the experimental data at temperatures
between 20 C and 50 C. TOC concentration decreases
more markedly in the rst minutes of reaction, with a
subsequent smaller reaction rate. This is in agreement
with the change in the global kinetics mentioned above.
The time after which this change occurs decreases when
increasing the temperature. Moreover, the nal TOC
content within the reactor is smaller at 30 C (thus a
higher efciency is attained), suggesting that this can be
the optimal temperature for the reaction, which is in
agreement with other results found in the literature
[20,21]. At a lower temperature (20 C), the reaction rate
is smaller and at temperatures above 4050 C hydrogen
peroxide decomposition into oxygen and water becomes
very signicant [21]. This rapid H2O2 decomposition at
high temperatures is a common behavior in the Fenton
process [20,28], leading to a decline in the overall
efciency. Possible losses of TOC by volatilization were
evaluated by stirring and heating the wastewater at
temperatures up to 50 C for 20 min. In these conditions,

A.M.F.M. Guedes et al. / Water Research 37 (2003) 30613069

3068

unavoidably arise from H2O2 decomposition via nonproducing OHd reactions, reaction of the OHd species
with non-target chemicals (scavenging) or even other
well-known reactions reported in the literature that
reduce the amount of H2O2 available for Fenton
reaction [17,23].
For implementation of Fenton oxidation at an
industrial level, other reactor congurations (continuous
or semi-continuous) have to be tested. For predicting the
performance of such reactors, the knowledge of the
kinetics, reaction rate-law and rate constants obtained in
this work are crucial.

T = 20C

0.0005

T = 30C
T = 40C

0.0004

1/C-1/C0 (L/mg)

T = 50C
0.0003

0.0002

0.0001

0
0

Time (min)

4. Conclusions

ln k (L.mg-1.min-1)

Fig. 9. Fitting of the experimental data (for different reaction


temperatures) to a second-order reaction kinetic model for the
rst minutes of reaction.

Fenton oxidation of cork cooking wastewater, performed in a batch reactor, led to the following
conclusions:

-5

-7

-9

-11
0.003

0.0031

0.0032

0.0033

0.0034

0.0035

1/T (K-1)
Fig. 10. Arrhenius-type plot of the apparent second-order
kinetic constants.

i.e., in the absence of Fenton reaction, TOC only


decreased by about 0.3%. Volatilization losses are then
negligible.
To analyze the experimental data, the integral method
was used for the first step. The results shown in Fig. 9
clearly evidence a good agreement with Eq. (8). From
the slopes of the lines, the apparent second-order kinetic
constants were obtained and from the corresponding
Arrhenius-type plot (Fig. 10) we got A 2:5  108 L/
mg min and E 70:7 kJ/mol. For the zero-order reaction rate data no correlation could be established. This is
probably due to the decomposition of H2O2, which
strongly increases with temperature (approximately 2.2
times for each 10 C rise in the range 20100 C [21]).
This work shows that the use of the Fentons reagent
requires a very ne control of the operating conditions
to achieve high performances. Otherwise, limitations will

The initial H2O2 concentration to be used should be


10.6 g/L (7 g H2O2/g wastewater TOC). Higher
concentrations only slightly increase TOC removal
and imply higher operation costs.
Oxidation efciency increases with Fe2+:H2O2 ratio
but a maximum ratio of 1:5 (by weight) is proposed.
Higher ratios originate greater oxidation but are not
proportionate.
Maximum TOC removal was observed for pH=3.2.

For the selected conditions, TOC, COD and BOD5


removals of 66.4, 87.3 and 70.2% were obtained at
30 C, respectively. The BOD5/COD ratio was increased
from the initial value of 0.27 to 0.63, suggesting that the
sequential use of a biological treatment process could
further reduce BOD5 level.
For initial TOC concentrations between 753 and
1505 mg/L, the overall reaction can be described by two
steps: second-order followed by a zero-order reaction
rate with respect to TOC. The apparent kinetic
constants at 30 C were: k=2.3  104 L/mg min and
k0 26:0 mg/L min, for the second and zero-order
kinetic equations, respectively. The experiments carried
out at the temperature range 2050 C showed an
optimum TOC removal at 30 C and allowed computation of the global activation energy for the second-order
reaction (70.7 kJ/mol).
The results obtained with this preliminary study
suggest that Fenton oxidation is a promising pretreatment process for cork cooking wastewater.

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