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Journal of Hazardous Materials 319 (2016) 69–77

Contents lists available at ScienceDirect

Journal of Hazardous Materials


journal homepage: www.elsevier.com/locate/jhazmat

Treatment of highly concentrated tannery wastewater using


electrocoagulation: Influence of the quality of aluminium used for the
electrode
S. Elabbas a,b , N. Ouazzani a,b , L. Mandi a,b , F. Berrekhis c , M. Perdicakis d , S. Pontvianne e ,
M-N. Pons e , F. Lapicque e , J-P Leclerc e,∗
a
Laboratoire d’Hydrobiologie, Ecotoxicologie et Assainissement (LHEA, URAC 33), Faculté de Sciences Semlalia, BP 2390, Université Cadi Ayyad, Marrakech,
Morocco
b
Centre National d’Etude et de Recherche sur l’Eau et l’Energie (CNEREE), Université Cadi Ayyad, BP 511, Marrakech, Morocco
c
Equipe de Physico-chimie des Matériaux, Ecole Normale Supérieure, Université Cadi Ayyad, BP 2400, 40000 Marrakech, Morocco
d
Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME) UMR 7564, Université de Lorraine—CNRS, 405 rue de Vandœuvre,
F-54602 Villers-lès Nancy Cedex, France
e
Laboratoire Réactions et Génie des Procédés (LRGP) UMR 7274, CNRS, Université de Lorraine, 1 rue Grandville, BP 20451, 54001 Nancy cedex, France

h i g h l i g h t s

• COD and Cr(III) species can be simultaneously removed by electrocoagulation.


• Cu-containing Al alloy is more efficient than pure Al as electrodes.
• Dilution of too concentrated tannery wastewater is required for efficient treatment.

a r t i c l e i n f o a b s t r a c t

Article history: This paper deals with the ability of electrocoagulation (EC) to remove simultaneously COD and chromium
Received 12 October 2015 from a real chrome tanning wastewater in a batch stirred electro-coagulation cell provided with two
Received in revised form aluminium-based electrodes (aluminium/copper/magnesium alloy and pure aluminium). Effects of oper-
21 December 2015
ating time, current density and initial concentration of Cr(III) and COD have been investigated. The
Accepted 30 December 2015
concentrations of pollutants have been successfully reduced to environmentally acceptable levels even
Available online 4 January 2016
if the concentrated effluent requires a long time of treatment of around 6 h with a 400 A/m2 current
density. The aluminium alloy was found to be more efficient than pure aluminium for removal of COD
Keywords:
Aluminium electrodes
and chromium. Dilution of the waste has been tested for treatment: high abatement levels could be
Chromium obtained with shorter time of treatment and lower current densities. Energy consumption of the electro-
Current density coagulation process was also discussed. The dilution by half of the concentrated waste leads to a higher
Electrocoagulation abatement performance of both COD and chromium with the best energy efficiency.
Tannery wastewater © 2016 Elsevier B.V. All rights reserved.

1. Introduction the residual meat, fat and hair from the skin, to deeply clean the
skin and to improve its aspect and its functional properties.
Leather production, associated to cloth and craft industries, is a Despite the existence of less pollutant treatments, chromium
very important activity in many countries since antiquity. It rep- tanning remains the most employed technique because of the
resents a large economic input in many developing countries but higher quality of the leather obtained. A report issued in 2003 has
is also unfortunately an important source of pollution. The tan- estimated the number of tanneries in Morocco to more than 60
ning process is a transformation of raw animal hides into leather. units, most of them using chromium [1]. Tannery wastewater rise
It involves various chemical and mechanical operations to remove important environmental problems because of their complex com-
position and high concentrations of various organic and inorganic
chemicals reflected in particular by high values of Chemical Oxygen
∗ Corresponding author. Fax: +33 3 73 32 29 75. Demand (COD) [2,3] and chromium concentration over 5 g/L [4,5].
E-mail address: jean-pierre.leclerc@univ-lorraine.fr (J.-P. Leclerc).

http://dx.doi.org/10.1016/j.jhazmat.2015.12.067
0304-3894/© 2016 Elsevier B.V. All rights reserved.
70 S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77

Although new tanneries use modern equipments with opti- others types of effluents often listed in the literature. Phosphates
mal adjustment of the chromium quantity, conventional chromium were also successfully removed from (surface or ground) water
bath tanning processes still use chromium salts in excess. Fahim using this technique [24]. Moreover the experimental data gained
et al. [5] estimated that the leather takes up only 60 to 80% in treatment tests could lead to physicochemical modelling of
of the introduced chromium. Depending on the efficiency of the electrocoagulation process [25]. or in scaling-up and economic con-
operation, wastewater contains chromium species, which must be siderations [26].
removed before disposal. Removal of chromium has been also stud- Electrocoagulation uses a direct current source between two
ied for drinking water but the concentrations are there far much metal electrodes immersed in polluted water. The electrical current
lower than in tannery wastewater [6]. causes the dissolution of anodes made of iron or aluminium into
Several methods have been attempted and a recent review sum- wastewater. The metal species released in solution, at an appro-
marizes the chemical and biological treatment technologies for priate pH, can form wide ranges of coagulated species and metal
leather tannery wastewaters and their efficiencies [7]. In com- hydroxides that destabilize and aggregate the suspended particles
parison between electrocoagulation and chemical precipitation to or precipitate and adsorb dissolved contaminants. In the case of alu-
remove metals from acidic soil leachate, Meunier et al. [8] have minium, Al3+ ions are generated at the anode and combine to OH−
reported chromium removal of more than 99% with an initial con- ions provided by the cathode to form various monomeric species,
centration of 100 mg/L by chemical precipitation in the presence which finally transform to solid Al(OH)3 (s). Freshly formed amor-
of NaOH and Ca(OH)2 . Keerthi et al. [9] have tested a hybrid mem- phous Al(OH)3 (s) “sweep flocs” have large surface areas, which are
brane bioreactor with a COD removal of 72.69% from wastewater beneficial for rapid adsorption of soluble organic compounds and
with an initial Cr concentration at 1600 mg/L. Using coagulation trapping of colloidal particles. These flocs are removed easily from
and flocculation, Song et al. [10] have obtained a COD removal of the aqueous medium by sedimentation or flotation. In addition to
30–37% with an initial concentration of 3300 mg/L. Adsorption has ref [25]. other groups attempted in better understanding EC pro-
also been used for treatment of tannery effluents [4,5,11,12]. Fab- cess [27,28] in view to its more efficient integration in overall water
bricino et al. [4] have reported 90% of Cr(III) removal from an initial treatment operations.
concentration of 6100 mg/L using adsorption in an environment Numerous papers have compared the effect of the electrodes
friendly cycle with recovery of the metal. However this last pro- nature (namely iron and aluminium) whereas the purity of the
cess may be not economically feasible in the treatment of tannery anodes was rarely investigated. Vasudevan et al. [29] pointed out
wastewater because of high costs and the expertise required to the lower efficiency of pure aluminium electrodes compared to
implement and sustain the operation of such processes. Fahim et al. aluminium alloys in the remediation of phosphate-contaminated
[5] reported absorption of nearly 99% of the chromium from tan- water. The lower efficiency of pure aluminium was explained by
nery waste water using activated carbon at an final concentration of passive film formation, lower dissolution efficiency, non-uniform
44 mg/L from the initial level at 5500 mg/L. The adsorbent can also dissolution and higher operating voltage with time. The direct oxi-
be a natural soil as explored by Tiglyene et al. [12] Use of a cation dation of dissolved substances is also affected by the nature of the
exchange resin was reported to remove 96% of Cr(III) from a waste electrode as pointed out by Kruthika et al. [30].
solution issued by tannery [13]. but the concentrated effluent of The aim of the present study was to investigate the treatment of
5480 mg/L was previously diluted 10-fold. Recent studies have been highly polluted traditional tannery wastewater by electrocoagula-
presented to facilitate the use of low chromium solutions by pos- tion with initial concentrations around 6 g/L COD and 7 g/L Cr(III).
sible effective chromium recycling through re-concentration using In comparison with pollutant levels usually encountered, these
nanofiltration [2]. Ouaissaa et al. [14] have obtained a 75% COD high concentrations of COD and Cr(III) are due to the nature of the
abatement of a low polluted tannery wastewater using an intensi- process involved: natural skin (inducing high organic pollution),
fied electrocoagulation process by addition of an adsorbent. Costa implication of various chemicals during the treatment and incom-
et al. [15] have reported a 40% TOC abatement using dimension- plete chromium absorption by the skin resulting in a high level
ally stable electrodes (DSA® ), however with the risk of oxidation of chromium in wastewater [31]. Another reason is that the liq-
of Cr(III) to Cr (VI). Sundarapandiyan et al. [16] have studied the uid released during this specific step is rejected directly with other
specific case of a very salty tannery wastewater (around 30 g/L of effluents of the tanning process. Removal of COD and Cr(III) was fol-
Cl− ): the high salinity was shown not to affect the efficiency of the lowed in discontinuous tests carried out with recirculation of the
treatment. Chromium from highly concentrated tannery wastew- electrolyte solution depending on the operating conditions, and in
ater (around 2.5 g/L) could be recovered at 99% using Pb anodes particular depending on the nature of the Al-based electrodes. First
and Cu cathodes after dilution of the effluent to less than 0.3 g/L tests conducted with the raw wastewater revealed moderate treat-
[17]. Isarain-Chávez [18] studied several electrochemical processes ment efficiency for both pollutants, presumably because of its high
to treat around 10 g/L of COD from tannery wastewater effluent contents in both Cr species and COD. It was then decided to dilute
but only the results concerning TOC were presented. Finally, for the wastewater prior to its treatment, for the sake of more efficient
treatment of a very concentrated effluent (COD 5470 mg/L and Cr operation. The optimal dilution factor was determined for the sake
6900 mg/L) ozonation could be used with COD abatement up to of high removal yield and acceptable energy consumption per m3
88% (Houshyar et al. [19]) but this treatment can oxidize Cr(III) of the original wastewater.
into Cr(VI), which generates another pollution issue. Finally, phy-
toremediation has investigated too for treatment of such waste, as
done by Mandi et al. [20]. 2. Mechanism of the electrocoagulation using aluminium
Electrocoagulation has been used in several of the above electrodes
mentioned results and it has been successfully applied to treat
numerous varieties of wastewater, of either industrial or urban In electrocoagulation processes, the coagulating species are pro-
origin. The main advantage of electrocoagulation is its ability to duced in situ and the overall process consists of three successive
treat simultaneously a wide range of type of pollutants includ- stages: (i) formation of coagulants by electrolytic oxidation of the
ing organic matter, heavy metals, dyes, and minerals. It was found sacrificial electrode (ii) destabilization of the contaminants, partic-
to be effective for the removal of dye [21,22], heavy metals from ulate suspension and breaking of emulsion and (iii) aggregation of
coal acid drainage wastewater [23], non-biodegradable organic pol- the destabilized phases to form flocs [25,27,28].
lution and arsenic from paper mill wastewater [22], and several The main reactions occurring at the electrodes are:
S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77 71

Fig. 1. Various unit processes and operations in leather processing.

At aluminium anode: This tank is a large wooden cylinder (3.5 m high and with a radius
of 1.56 m) placed horizontally. The effective volume of the tank
Al → Al3+ + 3e− (1)
was 17.14 m3 . The barrel can rotate on two hollow metal shafts for
At aluminium cathode: possible introduction of raw hides, chemicals, dyestuff and water
through the square-shaped hatch of the tank. A gear wheel fixed
2H2 O + 2e− → H2 + 2OH− : (2) on the flange of the barrel allows transmission of rotation. Large
Moreover in the presence of chloride ions, aluminium from the grab samples (10 L) were collected in polyethylene containers and
cathode can dissolve and form hydrogen: stored at 4 ◦ C in the dark until use. Their average characteristics are
given in Table 1.
Al + 3 H2 O → Al3+ + 3OH− + 3/2 H2 (3) Sub-samples of 2 L liquid were used for each electrocoagula-
In the solution: tion test. The effluent was characterized by very high chromium
content near 7 g/L and about 6 g/L of COD. The composition of
Al 3+
+ 2OH− → Al(OH)3 (4) tannery wastewater is strongly depending on the level of optimiza-
tion of the factory. If the modern industry releases less polluted
Because of the standard potential of the Al/Al3+ couple near
wastewater, the majority of semi-traditional industries used very
−1.8 V/NHE, occurrence of side reactions e.g. oxygen evolution
concentrated solutions of chromium to guaranty the quality of the
or Cr(III) oxidation to Cr(VI) with standard potentials at 1.23 and
treatment. Several publications have shown the efficiency of the
1.33 V respectively, is very unlikely and have not been considered
treatment of tannery wastewater, however most of the papers have
here. Two types of aluminium electrodes were employed, namely
focused their interest on the organic pollution characterized by TOC
the aluminium alloy (duralumin) and pure aluminium aiming to
or COD [9,32]. and the papers including the follow-up of chromium
assess the effect of the chemical composition of the electrodes on
are based on low chromium concentrations, generally lower than
the treatment effectiveness. For both electrodes, operating time,
100 mg/L [33,34].
current density and dilution rate have been investigated to deter-
mine the optimal conditions for chromium and organic matter
removal and electrical energy consumption but also to point out 3.2. Electrode materials
the effect of aluminium electrodes composition on efficiency and
super-faradaic charge yields. Two types of aluminium electrode have been used in this
present study. Aluminium alloy (duralumin) A-U4G (2017-Al) had
the following metal contents: Cu (4%), Fe (0.7%), Mg (0.7%), Mn
3. Materials and methods
(0.7%), Si (0.5%), Zn (0.25%) and Cr (0.1%). The “pure” aluminium
(1050) electrodes contained actually impurities but to a low level as
3.1. Tannery effluent samples
listed below: Si (0.25%), Fe (0.4%), Cu (0.05%), Ti(0.05%), Mn(0.05%),
Zn(0.07%).
Leather processing involves a number of unit operations as
shown in Fig. 1. The pre-tanning operation includes successively
the following steps: soaking, liming, removal of extraneous tissues Table 1
(unhairing), deliming and bating. Furthermore chromium tanning Main characteristics of the wastewater.
treatment involves degreasing, pickling by acidification, pressing Parameter Value
and drying. Finally the shaving, dyeing and other operations –
pH 3.8
depending on the final use of the leather – are conducted for obtain Conductivity (mS/cm) 54.2
a finished leather. COD (g O2 /L) 5.8
The samples were obtained from the tank used for chromium Cl− (g/L) 23.3
tanning step in a small traditional tannery in Marrakech city SO4 2− (g/L) 1.3
Cr(III) (g/L) 7.0
(Morocco) having a capacity of treatment of about 500 hides/day.
72 S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77

Fig. 2. Experimental set-up for electrocoagulation tests.

3.3. Experimental set-up

Electrocoagulation treatment was carried out in a discontinuous


system under solution recirculation functioning. The electrocoagu-
lation cell used, consisted of two identical polymethylmethacrylate
(Perspex) halves being 20 cm long, 10 cm wide and 5 cm thick.
Metal plates with an area of (15 × 7 cm2 ) acting as facing elec-
trodes were embedded in the polymeric halves, as described in [35].
The active electrode surface was first mechanically polished under
water with abrasive paper, rinsed with ultra-pure water and dried
prior to immersion in the wastewater. The area of each electrode
was 105 cm2 . The gap between anode and cathode was maintained
at 2 cm. The electrodes were connected to a DC power supply (AFX
2930 SB, China) providing current intensities up to 5 A. The current
was ranging from 2.1 to 4.2 A (200–400 A m−2 respectively) in the
present investigation. The current was kept constant during each
run and the cell voltage was monitored. The schematic diagram of
Fig. 3. Effect of current density on the chromium concentration versus time (a)
the complete electro coagulation system is shown in Fig. 2. duralumin (b) pure aluminium.

3.4. Experiments
of Al dissolution has been defined as the ratio of the weight amount
of Al present in the solution or in the flocs at time t, mAl , over that
The experiments were conducted at ambient temperature
produced by anodic dissolution according to Faraday’s law, with
(≈20 ◦ C) with 2 L wastewater gently stirred at 200 rpm in the tank.
three electrons exchanged per Al ion formed:
The solution was continuously circulated in the flow circuit by
means of a peristaltic pump at 50 mL/min. Ten cm3 fractions were mAl
˚Al = (6)
sampled at regular time intervals (every 10 min during the first MAl x 60It
3F
hour and every 30 min later), allowed to settle for 24 h, then fil-
tered (0.45 ␮m pore size) before any analysis to determine effluent where I is the applied current (A), time t is in minutes, F is the
COD, Cr(III) and Al(III) concentrations. Experiments with diluted Faraday constant and MAl is the molar weight of aluminium.
wastewater (1/2, 1/3, 1/4 and 1/6) were also conducted in order
to study the influence of the pollutant concentrations and because 4. Results and discussion
the treatment of highly concentrated effluents was sometimes very
difficult and energy consuming. 4.1. Effect of current density and electrolysis time on treatment
The pH was continuously measured with a multi-parameter
instrument (Consort C931, Turnhout, Belgium). COD was measured Cell current and electrolysis time are two important parame-
by the dichromate method [36] and subsequent measurement of ters in electrochemical processes. The value of the current density
the optical density using a HACH 2400 spectrophotometer (Love- determines the coagulant production rate, adjusts the rate and
land, Colorado). Chromium and aluminium concentration were size of the bubble production, and is hence to affect the growth
analysed by atomic absorption spectrometry after appropriate dilu- of flocs. These parameters were varied in the range 200–400 A/m2
tion in nitric acid solution. The removal efficiency of each pollutant and 5–360 min respectively. The cell voltage varied typically from
(R) was calculated using the following equation: 2 to 3 V depending on the operating conditions: the moderate cell
voltage is primarily due to the high conductivity of the waste to be
C0 − Ct
R(%) = x100 (5) treated, in particular in the treatment of the original wastewater
C0
(Table 1).
where C0 and Ct represent, respectively, the initial and the final Fig. 3 shows the effect of current density on Cr(III) removal
concentrations of COD or chromium. Moreover current efficiency versus time using both types of electrodes: aluminium alloy (dura-
S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77 73

Fig. 5. pH versus time (a) duralumin, (b) pure aluminium.

Fig. 4. Effect of current density on the COD concentration versus time (a) duralumin a large amount of electricity consumed is due to particular interac-
(b) pure aluminium. tions between the organic matter and Cr(III), or simply to the high
concentrations of the substances to be removed. With pure alu-
lumin) (Fig. 3a) and pure aluminium (Fig. 3b) respectively. The minium electrodes, Zongo et al. [37] noticed that the presence of
chromium removal efficiency increased with the current density Cr(VI) at 200 ppm does not affect COD abatement, but there are rel-
and electrolysis time but in different proportions depending on atively few papers dealing with the competition between different
the nature of the electrodes. With duralumin electrodes chromium types of pollutant at high concentrations.
removal yields of 93%, 95.4 and 99.7% were achieved after 360 min
at current densities of 200, 300, and 400 A/m2 , respectively. When 4.2. Effect of the electrode nature on the process
aluminium electrodes were used, the abatement was lower at
200 A/m2 (75%) but similar 93 and 99% at 300 and 400 A/m2 respec- Initial pH plays an important role in performance of the electro-
tively. coagulation process and its change during the treatment is linked
Fig. 4 shows the effect of current density versus time on COD to the efficiency [38]. The pH increase is mainly attributed to the
removal using both types of electrodes. An increase in current den- production of hydroxide ions (OH− ) that are continuously gener-
sity from 300 to 400 A/m2 yields to improved efficiency of COD ated from water reduction at the cathode as given by equation (3).
removal from 81 to 95% for the duralumin electrode after 360 min of However, the various equilibria between the Al hydroxide forms
treatment (Fig. 4a). Likewise what has been observed for chromium, depending on the pH medium provide the system buffer proper-
duralumin electrodes are also more efficient than pure aluminium ties. The pH of the waste under treatment can then attain a steady
electrodes to remove COD (Fig. 4b). level after sufficient Al dissolution. It is known that the formation
From the data shown in Figs. 3 and 4, it can be observed that of solid Al(OH)3 is optimal for pH ranging from 6–8.
the treatment consumes an electrical charge ranging from 2.27 104 Fig. 5 shows the variations of the tannery wastewater pH using
to 4.54 104 A s L−1 , which is really large in comparison with usual both types of electrodes: duralumin (Fig. 5a) and pure aluminium
charges in other electrocoagulation processes which often range (Fig. 5b). In both cases, the pH increased continuously with time
between 0.2 104 and 104 A s L−1 : assuming a 100% current efficiency for the three current density values considered. With duralumin
for Al dissolution is to result in Al(III) concentration up to 4.23 g L−1 electrodes, the final pH was between 6.5 and 7.0 depending on the
at the end of the run. At this point it can be wondered whether such current density, whereas with pure aluminium electrodes, a lower
74 S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77

Fig. 7. Chromium removed versus Al(III) produced at 200 A m−2 for several dilution
factors: (a) duralumin, (b) pure aluminium.
Fig. 6. Al(III) concentration versus the electrical charge: (a) duralumin, (b) pure
aluminium electrode.

180 min. Figs. 7 and 8 illustrate the amounts of chromium and COD
pH increase was observed up to 5.3 at the end of the run. These pH removed versus aluminium produced for both electrode materials,
variations appear greatly dependent on the nature of the electrode for reaction times limited to 70 min. For the sake of clarity in the
materials. illustration, the results have been zoomed on the first part of the
Fig. 6 shows the concentration of aluminium dissolved versus treatment, i.e. for amount of COD and Cr(III) removed below 3 g/L.
the charge passed per liquid volume unit for the two electrode In all cases, the amount of removed species increased obviously
materials, for all values of the current density. As expected, the with the amount of Al(III) generated. For the highest dilution fac-
amount of dissolved Al species increases along time; interpreta- tors (3 or more), a plateau in the removed amounts can be observed,
tion of the data show that Al dissolution proceeds with current corresponding to nearly complete treatment. In spite of significant
efficiency ranging from 1.2 to 3, depending on the operating con- dispersion all data for low abatement degree below 50% converge
ditions. The high concentration of chloride ions allows significant in a regular variation with the amount of Al dissolved. Generation
chemical dissolution of aluminium after Reaction (3). Moreover the of Al(III) is little affected by the dilution in spite of lower con-
amount of Al(III) species is globally slightly higher with duralumin centration of sodium chloride, as exemplified for the case of pure
electrodes than for pure Al, as shown by comparison of Fig. 6a and aluminium in Fig. 9, also in the first part of the runs: NaCl concen-
b. As a matter of fact Cu-containing Al electrodes are known to be tration remained actually at a sufficient level even in 1:6 dilution to
more prone to pitting corrosion than pure aluminium. Chromium promote Al dissolution, and the current efficiency in Al(III) varied
removal using duralumin was enhanced by the higher formation from nearly 3 in the first minutes, down to 1.1 within 0.2 during the
rate of Al(OH)3 whose flocs behave as an adsorbent for chromium last hour. Comparable observation was done with duralumin (data
ions. When the pH ranges between 4 and 7 co-precipitation of not shown).
chromium hydroxides such as Cr(OH)3 can occur. The COD removal Table 2 shows the removal efficiency at the end of the treatment
is also slightly higher using duralumin due to the affinity of the depending on the dilution factor. Depending on this factor, the ini-
organic material to Al(III) species. tial concentrations of chromium and COD varied between 915 and
6672 mg/L, and 928 AND 5864 mg O2 /L respectively. The removal
4.3. Effect of pollutant concentration on treatment efficiency and efficiency of COD is very high for the two Al-based materials when
energy consumption the dilution factor is higher than 1/2. On the contrary the abate-
ment is lower for the concentrated effluents. For chromium, the
The effluent has been diluted from 1 to 1/6, corresponding abatement is lower but at acceptable level for the diluted effluents.
to conductivities of 60, 43, 31, 23 and 16 mS/cm respectively However, as expressed above, it appears that Cr(III) and COD can
and treated by electrocoagulation at 200 A/m2 current density for be removed by adsorption of Al(III), therefore more diluted wastes
S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77 75

Fig. 10. Energy consumed for the treatment of 1 m3 diluted waste along the run for
Cr(III) removal. Duralumin electrodes were used at 200 A m−2 .

can be efficiently treated with moderate amounts of coagulant,


contrary to the original wastewater.
The energy consumption was calculated in terms of kWh per m3
of wastewater to analyse the possible positive effect in this specific
case of very concentrated effluents. The following relation has been
used:

UIt103
EEC = (7)
60(C0 − Ct )V

where U is the cell voltage measured during the electrolysis (V), I


the applied electrical current (A), t the current time of treatment
(min), and V the reactor volume (L). C0 and Ct represent the initial
pollutant concentration and the concentration at time t (in mg/L).
Fig. 8. COD removed versus Al(III) produced at 200 A m−2 for several dilution fac- As exemplified in Fig. 10 for the example of Cr(III) removal
tors: (a) duralumin, (b) pure aluminium. using duralumin electrode, the specific energy increases along
the run. Efficient treatment of the raw waste requires more than
20 kWh m−3 : this value is high in comparison to usual energy
demand in electrocoagulation processes but this is probably due
to the high amounts of both COD and Cr(III). Dilution of the waste
allows significant reduction of the energy demand per m3 of liq-
uid treated in the cell: taking into account the dilution made, this
would correspond to values ranging from 10 to 35 kWh m−3 raw
waste depending on the dilution factor.
As a matter of fact the energy demand was calculated per kg of
pollutant removed: Figs. 11 and 12 show the energy consumption
per kg of Cr(III) and COD removed, respectively, for both types of
electrode (duralumin in Figs. Fig. 1111a and Fig. 1212a, pure alu-
minium Figs. Fig. 1111b and Fig. 1212b). For both electrodes the
energy consumption globally increased with an increase in Cr(III)
and COD removal efficiency – with exception of a few data with Al
electrodes for unknown reasons -: abatement of the last percents
from waste is often more energy consuming. In spite of apprecia-
ble scattering of the data, energy consumption appears to be higher
Fig. 9. Concentration of Al(III) produced versus the electrical charge with pure alu- for the highly diluted solution (1:4 and 1:6). This is mainly due to
minium electrodes. Current density = 200 A m−2 .
the reduced conductivity, resulting in higher resistances of the cell
[39] as confirmed by the cell voltage which attained 3.2 V for the 1:6
Table 2
diluted waste. Comparing Table 2 and Fig. 11 show that a limited
Effect of effluent dilution on the maximum COD and chromium removal efficiency
using duralumin and pure aluminium electrodes; operation at 200 A/m2 for 180 min. dilution allows considerable reduction in the chromium concen-
tration in the effluent with very reasonable energy consumption:
Dilution factor
twofold dilution appears as the best compromise, allowing Cr(III)
Removal efficiency (%) 1:1 1:2 1:3 1:4 1:6 removal with an energy consumption near 1 kWh/kg, in compari-
COD Duralumin 58.1 97.6 100 100 100 son to nearly the double from the raw waste.
Pure Al 43.7 100 100 100 100 The removal of COD in comparison with chromium was found
to be very effective and less energy-demanding for both types of
Cr(III) Duralumin 73.3 91.7 94.5 96.2 98.1
Pure Al 57.2 91.2 92.9 97.9 98.1 electrodes (Fig. 12). The effect of the dilution factor is less visible
than for Cr(III) removal because of the data scattering but diluting
76 S. Elabbas et al. / Journal of Hazardous Materials 319 (2016) 69–77

Fig. 12. Effect of effluent dilution on the energy consumption per kg of COD removal
Fig. 11. Effect of effluent dilution on the energy consumption per kg of chromium versus COD removal efficiency; current density = 200 A m−2 ; (a) duralumin, (b) pure
removed versus chromium removal efficiency; current density = 200 A m−2 ; (a) aluminium.
duralumin, (b) pure aluminium.

noticeable differences we noticed between electrodes made of pure


two times the waste issued from the tannery plant allowed energy aluminium and the Al alloy show the necessity to deeply investi-
consumption near 0.7 kWh/kg COD removed. gate the influence of the nature of the electrode materials for other
Electrocoagulation process is very acceptable from the energy types of effluents.
consumption point of view. For the sake of comparison, data
reported in [40] revealed 3.8 kWh/kg COD removed with a 58% Acknowledgements
of abatement when treated tannery wastewater using an electro-
Fenton process. Strong variations of the energy consumption can The authors would like to acknowledge the France–Morocco
be expected: Daneshvar et al. [41] reported energy consumption cooperation for the financial support of this work in the frame-
between 4.7 and 7.57 kWh/kg COD under optimized conditions to work of the “Water and Environment Competency Pole” project.
remove dyes by electrocoagulation but it rose to more than 15 kWh In addition, the authors greatly thank the manager for the leather
for nearly complete abatement. A trade-off between abatement industry Mr. Slaissi Abd Aljalil for his help.
degree and energy consumption should be made.
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