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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
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
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
1120
5090
1780
0.6
6.4
Not detectable in
the 1:20 dilution
Color
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
H2 O2 OHd -HOd2 H2 O:
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.
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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
80
60
40
20
0
0
10
12
14
[H2O2]initial (g/L)
75
70
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
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60
50
40
30
1.5
2.5
3.5
4.5
pH
60
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
dC
;
dt
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1600
[TOC] (mg/L)
1400
[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).
TOC concentration data corresponding to the secondorder reaction step were tted to Eq. (8) and the
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
800
0.0002
600
400
0.0
1.0
2.0
3.0
4.0
Time (min)
10
15
20
Time (min)
m
2
2
dC
r k COH
TOC EkCTOC :
10
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)
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.
References
[1] Costa C. Personal communication. Faculty of Engineering, University of Porto, 1995.
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