Beruflich Dokumente
Kultur Dokumente
Abstract
The effective performance of electrocoagulation (EC) technique in the treatment of olive mill wastewater (OMW) has been investigated
using sacrificial aluminium electrodes. The optimum working pH was found to be in the range 46, allowing OMW to be treated directly
without pH adjustment. In addition, it is found that an increase in the current enhanced the speed of the treatment significantly. However,
simultaneous increase of electrode and energy consumption was observed. The optimum current density allowing the quickest treatment with
a low cost was found to be 75 mA cm2 . Therefore, a current density of 75 mA cm2 was selected as an optimum that allows fast and low cost
treatment.
Application of electrocoagulation procedure permitted high removal efficiencies of pollutants with both fresh and stored olive mill wastewater. The process produces a removal capacity of 76% of COD, 91% of polyphenols and 95% of dark colour, just after 25 min. The electrode
consumption was found to be 2.11 kg m3 of treated OMW. The results show that electrocoagulation could be considered as an effective
alternative solution for the treatment of OMW or may be combined with a classical biological process to achieve a high quality effluent water.
2004 Elsevier B.V. All rights reserved.
Keywords: Olive mill wastewater; Electrocoagulation; Aluminium electrode; Water treatment
1. Introduction
Olive mill wastewater (OMW) is a dark red to black effluent produced during olive oil extraction. It is estimated that
around 30 million cubic meter of OMW are generated annually in the Mediterranean area [1,2], during the seasonal
extraction of olive oil. This huge amount of wastewater
raised concerns about their possible negative effects on the
environment. In fact, OMW is characterised by high concentrations of several organic compounds including sugars,
tannins, pectins, lipids and phenolic substances [3,4] which
are responsible of their high COD and BOD. Their concentrations were generally in the range 80200 g l1 for
COD [5,6] and 1263 g l1 [7] for BOD. Specifically, it
has been reported that polyphenolic components of OMW
are responsible for its phytotoxicity [8,9] and antibacterial activity [2,10,11]. Therefore, the practice of spreading
OMW directly on agricultural soils must be accomplished
with great vigilance, since it may result in more damage
than beneficial effects on soil fertility. Moreover, OMW is
0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2003.12.001
1282
measured as COD. Other oxidising agents such as monosulphuric acid [19] and MnO2 [20] were also successfully used
for polyphenols removal from OMW. Another method was
recently applied to the treatment of OMW and consists of
the application of an integrated centrifugationultrafiltration
system [21] allowing an efficient reduction of pollution and
a selective separation of some useful products.
In a recent study, Galiatsatou et al. [22] investigated the
treatment of OMW using activated carbon produced from
olive pulp. Treatments of OMW by activated clay [23] or
lime [24] have also been reported to be effective for the
removal of phenolic compounds.
On the other hand, purification of industrial and urban
wastewaters by electrocoagulation (EC) is currently experiencing a renaissance. In this method, the coagulant is generated in situ by electrolytic oxidation of an appropriate anode
material that leads, at appropriate pH, to insoluble metal hydroxide able to remove pollutants by surface complexation
or electrostatic attraction. This technique characterised by
its simple equipment, easy operation and decreased amount
of sludge [25], was shown to be an effective and reliable
technology that provides an environmentally compatible
method for reducing a large variety of pollutants [2528].
In this study, electrocoagulation using aluminium electrodes was conducted to investigate the treatment of olive
mill wastewater. The removal efficiency of the treatment was
determined by monitoring the decrease of total phenol, COD
and dark colour intensity.
2. Experimental
2.1. Reagents and analytical procedures
Fresh olive mill wastewater was collected from a local
olive extraction plant which uses a classical process. OMW
was collected in a closed plastic container, diluted with tap
water (1:1) and stored at 0 C. Tap water was used for samples dilution because it is used in the extraction process.
OMW from the same sample was also stored for 3 months
at room temperature (>25 C) in an aerated vessel in order
to investigate the ageing effect. The main characteristics of
fresh and stored olive mill wastewater used in this work are
presented in Table 1.
Table 1
Physico-chemical characteristics of fresh and stored olive mill wastewaters
samples
Characteristics
pH
Total solid (g l1 )
COD (g l1 )
Polyphenol (g l1 )
OD (376 nm)
OD (280 nm)
Conductivity (ms cm1 )
Fresh OMW
Stored OMW
4.96
45.3
57.8
2.42
31.9
81.3
11.4
5.1
47
75.1
2.4
73
162
8.21
All used chemicals were of analytical grade. FolinCiocalteu reagent (FCR) (Flucka, England) was used at 1:10
dilution in distilled water. Determination of total polyphenols index was carried out with the official spectrophotometric procedure [29] in which FCR was used as a selective
reagent for polyphenols. Analysis of COD was determined
by the procedure described in the standard method [30]. The
total solid content was measured by drying a 100 ml aliquot
of OMW at 105 C until a constant mass was obtained.
The dark colour intensity was determined by measuring the
sample absorbance at 376 nm (UV-Vis spectrophotometer,
DR-5000). A digital calibrated pH-meter (Radiometer PHM
210) and a conductivity-meter (Radiometer CDM 230) were
used to measure the pH and the conductivity of the OMW
wastewater samples. The accuracies of COD, total polyphenols and colour intensity measurements were better than 4%.
2.2. Electrocoagulation procedure
The electrocoagulation experiments were conducted in
a home-made Plexiglas cell, with a special cover supporting a series of aluminium electrodes. Three electrodes
were connected as anodes and four as cathodes. A small
hole was drilled into the cover to serve as sampling port.
The electrodes having an immersed area of 60 cm2 each
(length 5 cm height 6 cm 2 faces) were fixed on the cover
and disposed vertically in the cell at a distance of 1 cm
from each other and there was a 2 cm distance between the
bottom of the electrodes and the bottom of the cell which
allowed easy stirring. The volume of the OMW treated each
time was 500 cm3 . A metrix (model AL 898 A) dc source
was used to supply the system with 0100 V and 20 A. In
preliminary tests, the effects of working parameters such
as electrode material, initial pH and current density were
studied in an attempt to achieve a more efficient treatment
of OMW. The optimised parameters were then applied for
the treatment of fresh and stored olive mill wastewater to
validate the treatment efficiency.
In a typical experiment, the specified volume of wastewater was poured into the cell, an initial sample was taken and
the current was then applied under regular magnetic stirring.
Different samples of 5 ml were taken at 10 min intervals for
up to 1 h and filtered before being analysed to determine the
residual polyphenol index, dark colour intensity and COD.
A gentle stirring rate of about 200 rpm was applied to
allow the chemical precipitate to grow large enough for
removal [25].
(anode)
3H2 O + 3e 23 H2 + 3OH
(1)
(cathode)
(2)
If the anode potential is sufficiently high, secondary reactions may occur at the anode, such as direct oxidation of organic compounds and of H2 O or Cl present in wastewater.
2Cl Cl2 + 2e
(3)
2H2 O O2 + 4H+ + 4e
(4)
(5)
HClO ClO + H+
(6)
(7)
100
Iron
90
Aluminium
Removal efficiency, %
80
70
60
50
40
30
20
10
0
Polyphenol index
1283
COD
Dark colour
Fig. 1. Effect of electrode material on the treatment efficiency (initial pH 4.96, current density 30 mA cm2 , electrolysis time 30 min).
1284
90
COD
Removal efficiency, %
80
Dark colour
70
60
50
40
30
20
10
0
0
12
10
Initial pH
Fig. 2. Effect of initial pH on the removal efficiencies of polyphenol, COD and dark colour (current density 30 mA cm2 , electrolysis time 30 min).
11
10
9
Final pH
8
7
6
5
4
3
2
1
1
10
11
Initial pH
Fig. 3. The pH change of OMW after electrocoagulation as a function of initial pH (current density 30 mA cm2 , electrolysis time 30 min).
90
i = 15 mA cm-2
Table 2
Effect of current density on electrode consumptiona
80
i = 30 mA cm-2
70
i = 45 mA cm-2
60
i = 75 mA cm-2
50
i = 120 mA cm-2
15
30
45
75
120
1.96
1.81
2.08
2.11
3.36
100
40
30
20
10
0
10
20
30
40
50
60
70
Time, min.
100
90
i = 15 mA cm-2
80
i = 30 mA cm-2
70
i = 45 mA cm-2
60
i = 75 mA cm-2
50
i = 120 mA cm-2
40
30
20
10
0
0
10
20
30
(b)
(a)
40
50
70
60
Time, min.
100
90
i = 15 mA cm-2
80
i = 30 mA cm-2
70
i = 45 mA cm-2
60
i = 75 mA cm-2
50
i = 120 mA cm-2
40
30
20
10
0
0
(c)
1285
10
20
30
40
50
60
70
Time, min.
the treatment efficiency of the electrocoagulation. Therefore, the effect of current density on the pollutants removal
was investigated. Fig. 4 shows COD, polyphenol index and
dark colour removal upon electrolysis time, when current
density was varied from 15 to 120 mA cm2 . As expected,
it appears that for a given time, the removal efficiency
increased significantly with increase of current density.
The highest currents (75 and 120 mA cm2 ) produced the
quickest treatment with 80.6% COD, 91% polyphenol and
96% colour reduction occurring after only 30 min. This is
ascribed to the fact that at high current, the amount of aluminium oxidised increased, resulting in a greater amount of
precipitate for the removal of pollutants. In addition, it was
demonstrated that bubbles density increases and their size
decreases with increasing current density [35], resulting in a
ItM
zF
(8)
1286
100
90
Removal efficiency, %
80
70
60
50
40
Fresh OMW
30
Polyphenol
20
COD
10
Dark colour
0
0
10
20
(a)
30
40
50
60
Time, min.
100
90
Removal efficiency, %
80
References
70
60
50
40
Stored OMW
30
Polyphenol
20
COD
10
Dark colour
0
0
(b)
10
20
30
40
50
60
Time, min.
Fig. 5. Polyphenol, COD and colour removal rates from (a) fresh OMW;
(b) stored OMW (current density 75 mA cm2 ).
4. Conclusion
In this work it was shown that electrocoagulation treatment achieves a fast and effective reduction of pollutants
(76% of COD, 91% of polyphenol and 95% of dark
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