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Chemical Engineering and Processing 47 (2008) 12111223

Electrocoagulation/electroflotation in an external-loop airlift

reactorApplication to the decolorization of
textile dye wastewater: A case study
A.H. Essadki a, , M. Bennajah a , B. Gourich a , Ch. Vial b , M. Azzi c , H. Delmas d
a Ecole Superieure de Technologie de Casablanca, BP 8012, Oasis Casablanca, Morocco
b Laboratoire de Genie Chimique et Biochimique, LGCB-UBP/ENSCCF, 24 avenue des Landais, BP 206, 63174 Aubiere Cedex, France
c Faculte des Sciences An Chock, Laboratoire dElectrochimie et Chimie de lEnvironnement, BP 5366 Maarif, Casablanca, Morocco
d Laboratoire de Genie Chimique, ENSIACET-INPT, 5 rue Paulin Talabot, 31106 Toulouse, France

Received 20 August 2006; received in revised form 28 March 2007; accepted 28 March 2007
Available online 19 April 2007

Abstract
A 20 L external-loop airlift reactor was used as an electrochemical cell in order to carry out water depollution using batch electrocoagulation
(EC) without mechanical agitation, pumping requirements or air injection. Mixing and complete flotation of the pollutants were achieved using
only the overall liquid recirculation induced by H2 microbubbles generated by water electrolysis. A red dye from the Moroccan textile industry
was used in a case study to validate this innovative application of airlift reactors. Experimental results showed that the axial position of the Al
electrodes and the residence time in the separator section were the key parameters to achieve good mixing conditions, to avoid bubbles/particles
recirculation in the downcomer and to prevent floc break-up/erosion by hydrodynamic shear forces. Such optimum conditions corresponded to
an optimum liquid overall recirculation velocity that was correlated to current, electrode position and dispersion height. Operation time required
to achieve 80% COD and 80% color removal efficiencies was modeled as a function of current density. Similarly, specific energy and electrode
consumptions were correlated to current, electrode gap and conductivity, which provided the necessary tools for scale-up and process optimization.
Operation time and removal efficiencies were similar to those reported in conventional EC cells, but specific energy and electrode consumptions
were even smaller without the need for mechanical agitation, pumping requirements and air injection, which could not be achieved in other kinds
of conventional gasliquid contacting devices.
2007 Elsevier B.V. All rights reserved.

Keywords: Electrocoagulation; Electroflotation; External-loop airlift reactor; COD removal; Decolorization

1. Introduction standards. This is a particularly critical problem in Morocco

Wastewater from dyeing and finishing processes in the tex-
tile manufacturing industry constitute a substantial source of
pollution which exhibits intense color, high chemical oxygen
demand, fluctuating pH and suspended particles. Indeed, the
textile industry utilizes about 10,000 pigments or dyes, but
most of them are toxic substances to human and aquatic life
[1] and it has been reported that up to 15% of the dyes used
are released into wastewaters [2]. These must therefore be
treated before final discharge to achieve legal and aesthetic
Corresponding author. Tel.: +212 60878671; fax: +212 22252245.
E-mail address: essadki@est-uh2c.ac.ma (A.H. Essadki).
where the textile industry is highly developed. Conventional
methods for removing dyes from industrial wastewater consist
mainly of biological and physicochemical treatments and their
various combinations [37]. Biological treatments are cheaper
than other methods, but dye toxicity usually inhibits bacterial
growth and limits therefore the efficiency of the decolorization
[7]. Physicochemical methods include adsorption (e.g. on active
carbon), coagulationflocculation (using inorganic salts or poly-
mers), chemical oxidation (chlorination, ozonisation, etc.) and
photodegradation (UV/H2 O2 , UV/TiO2 , etc.) [819]. However,
these technologies usually need additional chemicals which
sometimes produce a secondary pollution and a huge volume
of sludge [2,20,21]. Water treatments based on the electroco-
agulation technique have been recently proved to circumvent

0255-2701/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2007.03.013
1212 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
most of these problems, while being also economically attractive
[1,2,2125].
Electrocoagulation (EC) is an electrochemical method for
treating polluted water which has been successfully applied for
treatment of soluble or colloidal pollutants, such as wastewa-
ter containing heavy metals, emulsions, suspensions, etc., but
also drinking water for lead or fluoride removal [2628]. In EC,
coagulants are delivered in situ using the corrosion of sacri-
ficial anodes when a DC voltage is applied. Simultaneously,
electrolytic gases (typically H2 ) are generated at the cathode.
Aluminum and iron materials are usually used as anodes, the
dissolution of which produces hydroxides, oxyhydroxides and
polymeric hydroxides. These are usually more effective coag-
ulants than those used in chemical dosing: they are able to
destabilize colloidal suspensions and emulsions, to adsorb, neu-
tralize or precipitate dissolved polluting species, and finally to
form flocs that can be removed either by settling/filtration or
flotation. In EC, settling is the most common option, while
flotation may be achieved by H2 (electroflotation) or assisted
by air injection [28]. A typical EC unit includes therefore an
EC cell/reactor, a separator for settling or flotation, and often
a filtration step. EC was seen as a promising technology in the
19th century, but had nearly disappeared by the 1930s. How-
ever, EC has been experiencing a renaissance in the 1990s [28].
Indeed, the benefits of EC include simplicity, efficiency, envi-
ronmental compatibility, safety, selectivity, flexibility and cost
effectiveness [2131]. In particular, the main points involve the
reduction of sludge generation [1], the minimization of the addi-
tion of chemicals and little space requirements due to shorter
residence time [1,2025], especially when EC is compared to
biological treatments.
Although EC may be as cost-effective as chemical dosing
[21,32], its main deficiency is the lack of dominant reactor design
and modeling procedures. Mollah et al. [27] described six typical
configurations for industrial EC cells and report their respec-
tive advantages and drawbacks. However, the literature reveals
any systematic approach for these configurations for design and
scale-up purpose. This situation stems mainly from the com-
plex interactions between electrochemistry, colloidal forces and
hydrodynamics that govern the behavior of EC reactors. While
the recent literature focuses usually on the two first aspects (such
as electrode design [26,27], electrode material [2022], etc.), the
hydrodynamics of the three-phase gasliquidsolid flow is still
disregarded, the presence of gas being usually considered as an
unnecessary complication [33]. This stems mainly from the fact
that most papers use laboratory-scale EC cells in which mag-
netic stirring is adjusted experimentally and the separation step
by floatation/sedimentation is not studied.
The objective of this work is to demonstrate that airlift
reactors can be suitable EC units. Airlift reactors constitute a
particular class of bubble columns in which the difference in gas
hold-up between two sections (namely, the riser and the down-
comer) induces an overall liquid circulation without mechanical
agitation [34,35]. They have been extensively applied in the
process industry to carry out chemical and biochemical slow
reactions, such as chemical oxidation using O2 , Cl2 or aero-
bic fermentation, but never as EC cells, as far as the authors
know. Airlift reactors present two main designs: external-loop
and internal-loop configurations. External-loop airlift reactors
offer the advantage to allow various designs of the separator sec-
tion, which favors gas disengagement at the top of the reactor
and maximizes consequently the overall recirculation veloc-
ity at the expense of more complex reactor geometries. Their
hydrodynamics has also been extensively studied in two-phase
gasliquid [36] and three-phase gasliquidsolid flows [37,38].
In this study, the aim is to demonstrate that such reactors can
be used as an EC cell in which complete flotation can be achieved
without air injection and good mixing conditions can be obtained
without mechanical agitation. This means that pollutants should
be floated to the surface only by tiny bubbles of hydrogen
and oxygen gases generated from water electrolysis; similarly,
the overall liquid circulation responsible for mixing in airlift
reactors should result only from electrochemically-generated
bubbles. In this way, the removal of a commercial red dye used
in a Moroccan factory by electrocoagulation/electroflotation
(EC/EF) has been investigated to validate this innovative appli-
cation of external-loop airlift reactors.
2. Materials and methods
2.1. Reactor design
An external-loop airlift made of transparent plexiglas was
used for this study. The reactor geometry is illustrated by
Fig. 1. By definition, the riser is the section in which the gas
phase is sparged and flows upwards. The diameters of the
riser and the downcomer are respectively 94 mm and 50 mm in
this work. Consequently, the riser-to-downcomer cross-sectional
ratio (Ar /Ad ) is about 3.5. This is a typical value when reaction
takes place only in the riser section. Both are 147 cm height
(H2 + H3 ) and are connected at the bottom by a junction of 50 mm
diameter and at the top by a rectangular gas separator (also
denoted gas disengagement section) of HS = 20 cm height. The
distance between the vertical axes of the riser and the downcomer
is 675 mm, which limits the recirculation of bubbles/particles
from the riser into the downcomer. At the bottom, the curvature
radius of the two elbows is 12.5 cm in order to minimize friction
and avoid any dead zone. The liquid volume depends on the clear
liquid height (h) and can be varied between 14 L and 20 L, which
corresponds to a clear liquid level between 2 cm and 14 cm in
the separator section. All the experiments were conducted at
room temperature (20 1 C) and atmospheric pressure in the
semi-batch mode (reactor open to the gas, closed to the liquid
phase). Contrary to conventional operation in airlift reactors,
no gas phase was sparged at the bottom in the riser. Only elec-
trolytic gases induced the overall gas recirculation resulting from
the density difference between the fluids in the riser and the
downcomer.
Two readily available aluminum flat electrodes of rectangular
shape (250 mm 70 mm 1 mm) were used as the anode and
the cathode, which corresponds to S = 175 cm2 electrode surface
area (Fig. 1). The distance between electrodes was e = 20 mm,
which is a typical value in EC cells (see, e.g., [21,33]). They
were treated with a HCl aqueous solution for cleaning prior use
 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223 1213

Fig. 1. External-loop airlift reactor (1: downcomer section; 2: riser section; 3: conductivity probes; 4: conductimeter; 5: analog output/input terminal panel (UEI-
AC-1585-1); 6: 50-way ribbon cable kit; 7: data acquisition system; 8: electrodes; 9: separator; 10: electrochemically-generated bubbles).

to avoid passivation. The electrodes were placed in the riser,
parallel to the main flow direction to minimize pressure drop
in the riser and maximize the recirculation velocity. The axial
position of the electrode could also be varied in the column.
The distance (H1 ) between the bottom of the electrodes and the
bottom of the riser ranged between 7 cm and 77 cm (Fig. 1).
EC was conducted in the intensiostat mode, using a digital DC
power supply (Didalab, France) and recording potential during
the experiments. The width of the electrodes was maximized by
taking into account riser diameter and electrode inter-distance.
Electrode length L should be maximized to enhance mixing of
dissolved Al and favor the formation of H2 microbubbles, but the
condition L < H2 /4 was retained to avoid limiting the possible H1
values. Current density values (j) between 5.1 and 51 mA/cm2
were investigated, which corresponds to current (I = jS) in the
range 1.010 A.
2.2. Chemicals and methods
The average liquid velocity in the downcomer (ULd ) was
measured using the conductivity tracer technique [39]. Two con-
ductivity probes placed in the downcomer section were used
to record the tracer concentration resulting from the injection
of 5 mL of a saturated NaCl solution at the top of the down-
comer using a data acquisition system based on a PC computer
equipped with RTI-815 A/D converter. The distance between
the probes was 90 cm (Fig. 1). Liquid velocity was estimated
using the ratio of the mean transit time between the tracer peaks
1214 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
Fig. 2. Example of experimental data from conductivity tracer experiments in
the downcomer section when current density j = 21.4 mA/cm2 .
detected successively by the two electrodes and the distance
between the probes. The superficial liquid velocity in the riser
(ULr ) was deduced from a mass balance on the liquid phase:
Ad
ULr = ULd (1)
Ar
An example of experimental data provided by the conductivity
tracer technique is reported in Fig. 2.
Experiments were carried out using a red dye solution consist-
ing of a mixture of 2-naphthoic acid and 2-naphtol (Fig. 3) with
a total concentration C0 = 20 mg/L. This mixture belongs to the
dispersive dye class [20]. This class groups organic, non-ionic
compounds nearly insoluble although they are applied in aque-
ous solution using simple immersion technique [20]. This dye
and its concentration are typical of wastewater from a Moroccan
textile factory. Synthetic solutions were prepared by dissolving
the dye in tap water. Solution conductivity and pH were mea-
sured using a CD810 conductimeter (Radiometer Analytical,
France) and a ProfilLine pH197i pHmeter (WTW, Germany).
Fig. 3. Molecular structure of the constituents of the red dye.
Fig. 4. UVvis absorption spectrum of the red dye.
Dye concentration was estimated from its absorbance charac-
teristics (Fig. 4) in the UVvis range at maximum wavelength
A450 (max = 450 nm) using a UVvis spectrophotometer (Pye
Unicam, SP8-400, UK). Chemical oxygen demand (COD) was
measured using the standard closed reflux colorimetric method.
Initial COD was about 2500 mg O2 /L. Initial pH was varied
between 5 and 10 using minute addition of 0.1 M H2 SO4 or
NaOH solutions [1,5,20,22]. The conductivity (i.e. the ionic
strength) of dye solutions was adjusted by sodium chloride addi-
tion in the range 1.029 mS/cm, which covers the range usually
explored in the literature (see, e.g., [21,31,33]). NaCl is a salt
exhibiting low toxicity at moderated level, reasonable cost, high
conductivity and high solubility, but it played also the role of sup-
porting electrolyte. This addition had a negligible effect on the
initial pH of the solutions. pH, absorbance and COD were mea-
sured over time on filtered samples recovered from two locations
in the downcomer section in order to check reactor homogene-
ity. Experimental values reported in this work correspond to
the average of these two samples. COD, color removal and tur-
bidity efficiencies (YCOD , YCOL and YABS ) were expressed as
percentage and defined as:
COD(t = 0) COD(t)
YCOD = (2a)
COD(t = 0)
A450 (t = 0) A450 (t)
YCOL = (2b)
A450 (t = 0)
YCOL and YABS were obtained using the same equation (Eq.
(2b)), but YCOL was based on absorbance measurements at
450 nm after filtration, while YABS was measured without fil-
tration/decantation. YABS was used to analyze qualitatively the
evolution of turbidity over time. This parameter shows whether
the flocs flotate or are destroyed and driven by the liquid flow.
The specific electrical energy consumption per kg dye
removed (Edye ) and the specific electrode consumption per kg
dye (Al ) were calculated as follows:
 
kWh UIt
Edye = (3)
kg dye 1000V (C0 YCOL )
 
kg Al 3600MAl ItAl 1
Al = (4)
kg dye 3F V (C0 YCOL )
 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223 1215

using initial dye concentration C0 (kg/m3 ), current intensity I does not circulate between the electrodes. As a result, it is com-
(A), cell voltage U (V), electrolysis time t (h), liquid volume V pulsory to reduce the circulation time (i.e. the time necessary for
(m3 ), molar weight of aluminum MAl = 0.02698 kg/mol, Fara- the liquid to accomplish one loop) and achieve perfect mixing
days constant F (96,487 C/mol e ) and the Faradic yield Al of as quickly as possible. This may be obtained easily by increas-
Al dissolution. Al was estimated as the ratio of the weight loss ing ULd . Conversely, the objective of complete flotation may
of the aluminum electrodes during the experiments mexp and be achieved only if hydrodynamic shear forces remain weak
the amount of aluminum consumed theoretically at the anode in the riser to avoid floc break-up and in the separator to limit
mth : break-up and erosion, which means low ULd values. A simple
solution would consist in increasing e, but this would reduce
mexp 3F electrode surface S at constant L. Additionally, electrical energy
Al = = mexp (5)
mth 3600MAl It supply is known to increase steeply with electrode distance (see,
This parameter depends upon the pH and the amount of other e.g., [41]). At constant electrode geometry, the solution consists
species present in solution, for example co-existing anions [40]. of an adequate selection of ULd resulting from a compromise
between mixing and floc stability. This can be obtained first by
optimizing the axial position of the electrodes using both the
3. Results and discussion
conductivity tracer technique for ULd estimation and turbidity
measurements to estimate the amount of dispersed Al particles
3.1. Airlift reactors as EC cells
in the downcomer.
Experimental results showed that no liquid overall circu-
In airlift reactors, the driving force of the overall liquid cir-
lation could be detected when the electrodes were placed in
culation results from the gas hold-up difference between the
the upper part of riser, for H1 approximately higher than
riser (r ) and the downcomer (d ), and also from the dispersion
60 cm (Fig. 1). For 7 cm < H1 < 60 cm, ULd decreased when H1
height. Gas hold-up is defined as the ratio of volume occupied
increased, as expected from Eq. (6). Overall liquid velocities in
by the gas phase over the total volume of the corresponding sec-
the downcomer for two axial positions are reported in Fig. 5
tion. Dispersion height (hD ) corresponds to the distance from
at various current densities. Using the fact that ULd hD I/2 ,
the surface in which a gas phase can be observed in the riser
a two-parameter model was used to fit the data using the
(Fig. 1). Conversely, wall friction effects oppose to the overall
LevenbergMarquardt method for parameter optimization. The
liquid circulation. They are usually taken into account by two
results are given in the following equation:
empirical coefficients KT (that takes the effects of pressure drop
 
in the riser and the separator section into account) and KB (that hD
ULd (cm/s) = 5.8 j 0.20 (7)
accounts for pressure drop in the downcomer and the junction). hD max
The overall liquid circulation velocity in the riser ULr can there-
fore be predicted from an energy balance using the following in which hDmax is the maximum dispersion height correspond-
Equation [34,35]: ing to H1 = 7 cm. A good agreement was obtained between
experiments and predictions (Fig. 5). This equation confirms
 0.5
2ghD (r d ) the key role of the axial position of the electrodes on reac-
ULr = (6) tor hydrodynamics and mixing properties, and the weaker
KT /(1 r )2 + (Ar /Ad )2 KB /(1 d )2
influence of current. The fitted parameter = 0.40 was a bit
When the clear liquid height h is high enough to achieve total lower than expected from theoretical considerations, but this
gas disengagement in the separator (this is often the case in
external-loop airlift reactors when recirculation velocity is not
too high), d remains negligible. In this work, the situation is
however more complex because the gas phase is not injected,
but electrochemically-generated. This means that both hD and
r depend on the axial position of the electrodes in the riser.
At constant current density, r should vary approximately as
dispersion height hD when electrode position H1 is modified,
provided r  1. One can deduce from Eqs. (1) and (6) that
ULd hD . At constant H1 , the evolution of dispersion height
due to gas flow should be negligible when r  1. On the basis
of empirical correlations from the literature [3436], r should
with between 0.5
vary with superficial gas velocity UGr as UGr
and 0.6 in external-loop airlift reactors. As gas flow rate should
be proportional to current (provided the evolution with I of the
Faradic yield for H2 formation remains negligible), this gives
ULd I/2 . Fig. 5. Influence of the axial position of the electrodes (H1 ) and current den-
As the distance between electrodes is e = 20 mm and the riser sity (j) on the overall liquid recirculation ULd (h = 14 cm; initial pH 8.3; initial
diameter 94 mm, it is obvious that a fraction of the liquid phase conductivity: = 2.4 mS/cm).
1216 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
result is however satisfactory when one considers the following
points:
The range of gas flow rates used to establish correlations from
the literature was widely different from that of this work;
The mechanisms of gas dispersion, the physicochemical prop-
erties of the gas phase (H2 in this work) and bubble size
differed;
The Faradic yield of H2 generation was not taken into account;
Other geometrical parameters, such as the distance between
riser and downcomer, were not directly accounted for.
Consequently, Eq. (7) is of utmost importance for scale-up
purpose at constant aspect ratio (Ar /Ad ) and L/H2 ratio. Nev-
ertheless, if Ar /Ad had to be varied, one can benefit from the
available know-how on external-loop airlift reactors to account
for this effect [36].
The corresponding turbidity data based on A450 without fil-
tration is reported in Fig. 6 for an electrolysis time of 10 min and
two axial positions of the electrodes. In all cases, flocs occupied
nearly 1 cm thickness at the free surface of the disengagement
section and no settling was reported in the junction and in the sep-
arator. Fig. 6 shows however that turbidity rose when H1 = 7 cm
for current density higher than 15 mA/cm2 . This corresponded
to ULd values in the range 910 cm/s in Fig. 5. Conversely,
complete flotation was always observed for H1 = 47 cm, as A450
remained low, about 0.06. As a result, electrode position must
be chosen in order to maintain ULd always lower than 9 cm/s,
regardless of current density in the range of j studied (Fig. 7).
Such a condition was achieved for H1 = 47 cm, as shown in
Fig. 5, which corresponds nearly to mid-height in the riser.
However, H1 = 47 cm is only a coarse approximation of the
optimum electrode height, but the simple way to optimize mix-
ing conditions does not consist in adjusting precisely H1 because
it is easier from a practical point of view to adjust the clear liq-
uid height h. Indeed, h affects simultaneously hD and hDmax in
Eq. (7), but its range (2 cm < h < 14 cm in this work) is usually
far smaller than H1 (between 7 and 77 cm). Its expected impact
Fig. 6. Evolution of absorbance A450 of non-filtered samples after 10 min oper-
ation with 1 cm of floc thickness already formed as a function of the axial
position of the electrodes (H1 ) and current density j (initial pH 8.3, conductivity:
= 2.4 mS/cm).
Fig. 7. Evolution of absorbance A450 of non-filtered samples after 10 min opera-
tion with 1 cm of floc thickness already formed as a function of superficial liquid
velocity ULd in the downcomer (initial pH 8.3, conductivity: = 2.4 mS/cm).
on ULd is therefore limited to 7% on the basis of Eq. (7) for
H1 = 47 cm, which imposes a preliminary determination of the
optimum H1 range. Additionally, h plays an important role on
gas disengagement and solid flotation. When h was equal to
2 cm, the sludge occupied almost the total volume of the disen-
gagement section, allowing the flocs to be driven by the liquid
flow. As far as h was increased, the flotation layer thickness at
the surface occupied a decreasing volume fraction of the disen-
gagement section. As ULd varies slightly, the residence time of
the liquid phase in the separator () should increase steeply with
h. This should reduce both the direct entrainment of solid parti-
cles from the riser into the downcomer, but also the erosion of
flotation layer by the overall liquid circulation in the separator.
Fig. 8 highlights the strong influence of the clear liquid height
on the evolution of turbidity at constant j and H1 . Experimental
data was plotted as a function of that is nearly proportional to
h. Initial A450 value was 0.25; in Fig. 8, absorbance after 10 min
was divided by three when increased from 20 s to 55 s. In this
work, it is difficult to quantify the respective effects of h and , as
depends also on the distance between the riser and the down-
Fig. 8. Influence of the residence time of the liquid phase in the separator
on turbidity A450 after 10 min operation (initial pH 8.3; current density:
j = 28.6 mA/cm2 ; conductivity: = 2.4 mS/cm).
 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223 1217

comer. One can however assume that when h is not too small, the
distance between riser and downcomer reduces mainly the direct
recirculation of the solid phase, while h acts more effectively on
floc erosion.
As a conclusion, experimental data showed that an overall
liquid circulation with good mixing conditions and complete
flotation could be achieved using only the electrochemically-
generated bubbles, provided:

The electrodes were adequately placed in riser: in this work,

this means that ULr should be close, but lower than 2.5 cm/s
in order to avoid floc break-up by the hydrodynamic shear
forces in the riser;
The clear liquid height was carefully selected in the separa-
tor in order to minimize solid recirculation in the downcomer
and floc erosion by the liquid phase, while maximizing solid
entrainment by the bubbles and the formation of a stable
flotation layer at the free surface of the reactor.
The second point must take two constraints into account: h
is limited both by the separator height (HS ) and by the increase
of ULr that should remain lower than 2.5 cm/s. This justifies the
choice of an external-loop airlift reactor because its geometry
permits large distances between riser and downcomer in order to
favor complete flotation, which is not possible in internal-loop
airlift reactors.
3.2. Application to decolorization of textile dye wastewater
The objective was to achieve A450 in the exhaust water
lower than 0.07. This gave a condition on color removal, but
also on turbidity removal. Additionally, 80% COD abatement
was requested to achieve the Moroccan limits for COD in tex-
tile wastewater. Using the optimized position of the electrode
defined in Section 3.1 (H1 = 47 cm and h = 14 cm), the respec-
tive influences of the operating conditions of EC (such as current
density operation time. . .) and of the physicochemical properties
of wastewater before treatment (such as initial pH and conduc-
tivity) were investigated in order to achieve the objectives by
complete flotation.
Fig. 9. Influence of the initial pH on COD removal and decolorization after 8 min
operation (conductivity: = 2.4 mS/cm, current density: j = 28.5 mA/cm2 ).
The effect of pH can be explained as follows. The main
reactions are during EC are:
Anode : Al0(s) Al3+ + 3e (8)
Cathode : 2H2 O + 2e H2(g) + 2OH (9)
At low pH, such as 23, cationic monomeric species Al3+
and Al(OH)2 + predominate. When pH is between 49, the
Al3+ and OH ions generated by the electrodes react to form
various monomeric species such as Al(OH)2 + , Al2 (OH)2 2+ ,
and polymeric species such as Al6 (OH)15 3+ , Al7 (OH)17 4+ ,
Al13 (OH)34 5+ that finally transform into insoluble amorphous
Al(OH)3(s) through complex polymerization/precipitation kinet-
ics [23]. When pH is higher than 10, the monomeric Al(OH)4
anion concentration increases at the expense of Al(OH)3(s) . In
addition, the cathode may be chemically attacked by OH ions
generated together with H2 at high pH values [1]:
2Al + 6H2 O + 2OH 2Al(OH)4 + 3H2 (10)
Two main mechanisms are generally considered: precipitation
for pH lower than 4 and adsorption for higher pH. Adsorp-
tion may proceed on Al(OH)3 or on the monomeric Al(OH)4

3.2.1. Inuence of initial pH

pH is known to play a key role on the performance of EC
[2,2125,27]. In this work, the influence of the initial pH on
COD and turbidity removals is illustrated in Fig. 9 at constant
current density and initial conductivity. An optimum was found
for the initial pH, which was between 7.0 and 8.0, although it dif-
fered slightly between COD and color removal yields. However,
the pH changed during batch EC, as already mentioned in the
above-mentioned papers. Its evolution depended on the initial
pH. EC process exhibits some buffering capacity because of the
balance between the production and the consumption of OH
[30], which prevents high change in pH (Fig. 10). The buffering
pH seems just above 7: when the initial pH is above this value,
pH decreases during EC; otherwise, the opposite behavior is Fig. 10. Evolution of pH values during EC for different values of initial pH
observed. (conductivity: = 2.4 mS/cm, current density: j = 28.6 mA/cm2 ).
1218 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223

anion depending on the dye chemical structure. The formation

of Al(OH)3(s) is therefore optimal in the 49 pH range, which
corresponds to the optimum pH values investigated in this work.
Consequently, one can conclude that the key mechanism for dye
removal is adsorption in this work.
However, pH affects also bubble size [43]. Typical bubble
sizes in electroflotation always fall in the range of 2070 m
[44], far smaller than those observed in conventional air-
assisted flotation, which provides both sufficient surface area
for gasliquidsolid interfaces and mixing efficiency to favor
the aggregation of tiny destabilized particles. Hydrogen bubbles,
which obey usually to a lognormal size distribution, are known
to be the smallest about neutral pH [45]. The difference between
maximum pH for COD and turbidity confirms this result and can
be attributed to the formation of more stable flocs when pH is
about 7, although it does not correspond to the optimum for dye
removal.
As a conclusion, pH adjustment is compulsory before EC in
airlift reactors, as in conventional EC cells. pH may be adjusted
in the optimum range in order to achieve a compromise between
best coagulation and best flotation. The optimum range may
however vary as a function of electrode material and dye struc-
ture. In the following sections, initial pH will be fixed at about
8 to maximize COD removal efficiency.

3.2.2. Inuence of current density and operation time

The current density is expected to exhibit a strong effect on
EC [2131], especially on the kinetics of COD abatement and
color removal: higher the current, shorter the treatment. This is
ascribed to the fact that at high current density, the extent of Fig. 11. Evolution of COD (a) and turbidity removal efficiency (b) during EC
anodic dissolution of aluminum increases, resulting in a greater as a function of current density j (initial pH 8.3, conductivity: = 2.4 mS/cm).
amount of precipitate for the removal of pollutants. Moreover,
bubble generation rate increases and the bubble size decreases
between 100% and 160%; they decrease with increasing time
with increasing current density. These effects are both beneficial
in the first minutes of the run, but also with higher current den-
for high pollutant removal by H2 flotation [25].
sity. These trends have already been reported in the literature
Experimental results show that COD removal efficiencies
[46]. This mass overconsumption of aluminum electrodes may
increase faster when current density increases (Fig. 11a). Dye
be due to the chemical hydrolysis of the cathode (Eq. (10)), but
removal seems therefore more rapid, as expected. The curves
it also often explained by the corrosion pitting phenomenon
reach however the same asymptotic value as a function of time,
which causes holes on the electrode surface. The mechanism
around 83%, regardless of current density. As a result, the objec-
suggested for corrosion pitting involves chloride anions and
tive can be achieved on the whole range of current density, but
the minimum operation time tN for which YCOD > 80% decreases
from 36 min to 9 min when current increases from 1 A to 6 A.
Color removal curves follow exactly the same trends, which
was expected because the dyes constitute the only source of
pollution in this work (data not reported). Color removal pro-
ceeds during EC because the constituents responsible for the
red color (2-naphthoic acid and 2-naphtol) are adsorbed. For
turbidity (Fig. 11b), the behavior is identical to YCOL , except
when current is 6 A. In this case, when EC is carried out for a
too long time, YABS decreases probably because of the too rapid
generation of Al(OH)3 particles that seem to have difficulties to
flocculate and flotate. As a result, there is a maximum time for
optimum batch EC operation that is a function of current density.
As a first approximation, the amount of Al released is propor-
tional to the product Al It. The Faradic yield Al is reported in Fig. 12. Evolution of the Faradic yield Al as a function of current density j
Fig. 12 as a function of time and current density: the values are (initial pH 8.3, conductivity: = 2.4 mS/cm).
 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
can be summarized as follows [33]:
2Al + 6HCl 2AlCl3 + 3H2
AlCl3 + 3H2 O Al(OH)3 + 3HCl
This mechanism can therefore produce more aluminum hydrox-
ide flocs and H2 bubbles than the equivalent current supplied
should. However, the time tN necessary to achieve 80% removal
for COD and color did not follow a first-order kinetics [33].
The amount of pollution removed was not proportional to the
amount of Al released by the electrodes, as tN did not vary as
1/(Al I). Similarly, taking into account a minimum dissolved Al
concentration before EC starts [46] did not fit the data in the
range 16 A. This may be due to the complexity of dye removal:
the dye is formed by two constituents, the second one being an
oxidized form of the first one. Consequently, their affinity for
flocculation may differ and vary with current density. Addition-
ally, at high current density, other reactions may be encountered
at the anode, such as the direct oxidation of one or the two con-
stituents of the dye, but also oxygen formation at the anode,
which plays a negative role on EC:
4OH O2 + 2H2 O + 2e
Conversely, high current density allows the passivation of the
cathode to be reduced [26], but an increase in energy consump-
tion that induces heating by Joule effect. As a result, too high
current densities have generally to be avoided.
From an energetic point of view, energy consumption during
EC is known to vary as the product UIt. Energy requirements
per kg of dye removed (Edye ) to achieve 80% COD and color
removal efficiency are reported in Fig. 13 as a function of current
density. Energy requirements per kg COD removed can be esti-
mated approximately by dividing Edye by about 125 (2467 mg/L
O2 divided by 20 mg/L dye), as YCOL YCOD in this work. Edye
values in Fig. 13 are similar and even lower than those reported
by several authors [24,25]. Fig. 13 shows a continuous increase
of Edye with j, which has already been observed in the litera-
ture for textile dye wastewater [2,2125,27]. This means that the
decrease in tN does not compensate the impact of current density
increase on energy requirements (Edye I2 ). However, Edye rep-
resents only a fraction of the operating costs of EC, from 20% to
Fig. 13. Influence of current density j on electrode and energy consumption (Al
and Edye ) at minimum time tN for which YABS 80% and YCOD 80% (initial
pH 8.3, conductivity: = 2.4 mS/cm).
1219
(11a)
(11b)
Fig. 14. Influence of current density j on electrode and energy consumption
(Al and Edye ) at constant operation time of 8 min (initial pH 8.3, conductivity:
= 2.4 mS/cm).
50% according to Bayramoglu et al. [23]. For these authors, the
main cost is generally electrode material. As a result, the specific
electrode consumption Al (kg Al required per kg dye removed)
has been also reported in Fig. 13. This parameter is roughly pro-
portional to It and exhibits a maximum for I about 5 A, which is
due to the counterbalancing effects of the decrease of tN when
(12)
current increases. When one considers Al at a constant time
(8 min), regardless of YCOL and YCOD , an abrupt change appears
between 1 A (5.7 mA/cm2 ) and higher current densities (Fig. 14)
that is probably characteristic of a change in EC mechanisms
described above. The fact that Al (t = 8 min) is nearly constant
and independent of j when j is higher than 10 mA/cm2 means
that dye removal is nearly proportional to the amount of alu-
minum released, but only when j > 15 mA/cm2 . The amount of
Al released can be estimated as follows [46]:
t
MAl I 0 Al dt
CAl (t) = (13)
3 3600FV
For the red dye, the following relation has been established:
0.80C0 V 2
tN = k (R = 0.995) (14)
I
with k = 17.2 104 (A min)/(kg dye removed).
As a conclusion, the influence of current density on EC in
airlift reactors is similar to that observed in conventional EC
cells. For the application studied in this work, one can distinguish
four key points:
from the point of view of operating costs that account both
for specific energy and electrode consumption, the best con-
ditions correspond to a low current and a high operation time,
such as I = 1 A and tN = 36 min;
considering investment costs, it may be interesting to limit
the size of the equipment and therefore operation time by
increasing current density;
considering scale-up procedure, it is preferable to operate at
j > 15 mA/cm2 (about 2 A), as a simple model tN 1/I may be
applied;
to avoid unnecessary Al(OH)3 release in wastewater, it is
finally compulsory to avoid too high current density and to
operate at j lower than 30 mA/cm2 .
1220 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
3.2.3. Inuence of wastewater conductivity
The increase of the conductivity by the addition of sodium
chloride is known to reduce the cell voltage U at constant current
density due to the decrease of the ohmic resistance of wastew-
ater [2,23,25]. Energy consumption, which is proportional to
UI, will therefore decrease. Chloride ions could significantly
reduce the adverse effects of other anions, such as HCO3 and
SO4 2 , for instance by avoiding the precipitation of calcium
carbonate in hard water that could form an insulating layer
on the surface of the electrodes and increase the ohmic resis-
tance of the electrochemical cell [2,41]. Chloride anions can also
be oxidized and give active chlorine forms, such as hypochlo-
rite anions, that can oxidize dyes. The main mechanism is as
follows:
Cl2 + 2e 2Cl (15a)
Cl2 + H2 O Cl + ClO + 2H+ (15b)
However, an excessive amount of NaCl (higher than 3 g/L)
induces overconsumption of the aluminum electrodes due to
corrosion pitting described above (Eq. (11)); Al dissolution
may become irregular [42]. Additionally, it is important to mon-
itor how the presence of NaCl affects COD and color removal
efficiencies. YCOD and YCOL usually increase with the addi-
tion of NaCl [2], but this result is not general [23,25]. In this
work, Fig. 15 shows an increase of YCOD and YCOL with
for the red dye between 2 and 28 mS/cm. YCOL enhancement
becomes however slight when is higher than 15 mS/cm in
Fig. 15.
The decrease in specific energy consumption Edye due to
the increase of conductivity is illustrated by Fig. 16. This fig-
ure indicates that Edye can be divided roughly by a factor 13
when conductivity is multiplied by a factor 12. However, high
chloride content exceeds usually the maximum concentration
tolerated in waters destined for further reuse. As a conclusion, a
value of 5 mS/cm seems a reasonable compromise because it
offers a moderate value of electrical consumption by Joule effect,
while preventing a rapid degradation of the electrode surface
[1,42].
Fig. 15. Influence of conductivity on COD and color removal efficiencies
(initial pH 8.3; current density: j = 28.6 mS/cm).
3.2.4. Complementary rules for scale-up and process
optimization
The position of the electrodes in the airlift reactor can be
optimized as a function of hydrodynamic parameters and cur-
rent density using Eq. (7). The necessary time to achieve 80%
removal efficiencies can be estimated using Eq. (14), though it
is valid only for the red dye used in this work in a limited range
of j values. Complementary rules should include the influences
of electrode gap and operating conditions on voltage (and con-
sequently on energy consumption). The measured potential is
the sum of three contributions, namely the kinetic overpotential,
the mass transfer overpotential and the overpotential caused by
solution ohmic resistance. Kinetic and mass transfer overpoten-
tials increase with current density, but mass transfer is mainly
related to mixing conditions: if mixing is rapid enough, mass
transfer overpotential should be negligible. In this case, the
model described by Chen et al. [41] is often recommended for
non-passivated electrodes [27]:
e
U = 0.76 + j + 0.20 ln(j) (16)
This equation is compared to experimental U values (with
e = 0.02 m) in Fig. 17. It exhibits a good agreement with exper-
imental data, both as a function of conductivity and current
density. This result shows that the overall liquid circulation
induced by hydrogen bubbles in the external-loop airlift reac-
tor achieves good mixing conditions and makes mass transfer
overpotential negligible, but without the need for mechanical
stirring, which corresponds to additional energy savings.
As a result, Eq. (16) seems able to estimate quantitatively the
effect of inter-electrode distance. Energy savings and heating by
Joule effect could therefore be optimized by decreasing this gap.
However, a small gap could hinder transport and suspension of
solid particles that are currently found in textile dye wastewater
[42] and it could also induce short-circuits [33]. As already men-
tioned in Section 2, electrode gap must obey a compromise for
the regular flow of the multiphase media and acceptable energy
dissipation. The value e = 0.02 m corresponds to this compro-
mise and should maintained in a scale-up procedure. This is
confirmed by the fact that this value has already been used in
Fig. 16. Influence of conductivity on energy consumption Edye at constant
current density j and operation time (initial pH 8.3).
 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223 1221

adequate selection of the axial position of the electrodes (H1 ) and

the liquid height in the separator section (h) in order to avoid
floc break-up in the riser and floc erosion at the free surface.
A limiting value of the liquid velocity in the downcomer was
defined, while ULd was correlated to dispersion height hD and
current density j (Eq. (7)). These can be used at constant j and
Ar /Ad ratio for scale-up purpose.
Batch EC experiments on a red dye from the textile industry,
with 80% COD and color removal as the objectives, confirmed
that external-loop airlift reactors behaved as a conventional
EC cells. However, specific energy and electrode consumptions
seemed even lower than in the literature on treatment of textile
dye wastewater. As expected, a preliminary pH adjustment was
compulsory and the respective influences of current density and
conductivity exhibited trends similar to those reported in the lit-
erature for conventional EC cells. Simple models for predicting
the impact of operation time (Eq. (14)), current density and con-
ductivity (Eq. (16)) were derived in order to estimate voltage
and operating costs. and optimize process conditions. As this
study was carried out in pilot-scale airlift reactor (20 L), scale-
up seems easier on the basis of above-mentioned equations using
both the available know-how on EC and airlift reactor design.
In the future, the use of airlift reactors for EC under steady-
state conditions seems also promising. The main disadvantage
of airlift devices is however that their behavior is close to that
of a perfectly mixed reactor, which implies larger volumes and
longer residence time than in most conventional EC cells [27].
This will however avoid systems with an external recycle [24]
because of the internal liquid recirculation of airlift reactors.

Appendix A

Fig. 17. Validation of theoretical models relating potential, current and conduc-
tivity: (a) j = 28.6 mA/cm2 , initial pH 8.3; (b) = 2.4 mS/cm, initial pH 8.3. A450 absorbance measured at 450 nm (AU)
Ad cross-sectional area of the downcomer (m2 )
many other works on the economical evaluation of treatment of Ar cross-sectional area of the riser (m2 )
textile wastewater [21], oil recovery in O/W emulsions [46] and C0 dye concentration (kg/m3 )
more generally in industrial electrochemical processes [33] at CAl concentration of dissolved aluminum (kg/m3 )
several scales, both under batch and continuous conditions. COD chemical oxygen demand (mg O2 /L)
e electrode gap (m)
4. Conclusions Edye specific energy consumption (kWh/kg dye removed)
EC electrocoagulation
Electrocoagulation is already known as an efficient process EF electroflotation
for color removal in dye textile wastewater, but also for the F Faradays constant (96,487 C/mol e )
removal of soluble and colloidal pollutants in wastewater and g acceleration of gravity (m/s2 )
drinking water. In this work, external-loop airlift reactors have h liquid height in the separator section (m)
been shown to be versatile tools to carry out EC with complete hD dispersion height in Fig. 1 (m)
flotation, using only electrochemically generated H2 bubbles hDmax maximum dispersion height (m)
to achieve an overall liquid circulation and good mixing condi- H1 axial position of the electrodes in Fig. 1 (m)
tions. Consequently, the use of mechanical agitation, pumping or H2 , H3 , HS geometrical characteristics of the reactor in Fig. 1
compressed air was not necessary. This could not be achieved in (m)
other kinds of conventional gasliquid contacting devices than I current (A)
airlift reactors. External-loop devices are particularly adapted j current density (A/m2 )
because they offer specific designs for the disengagement sec- k constant in Eq. (14) (min A/(min kg dye removed))
tion that allow large distance between riser and downcomer. KB , KT friction factors in Eq. (6)
This improves flotation by minimizing the recirculation of Al L electrode length (m)
particles in the downcomer. These results were obtained by the mexp experimental weight loss of Al electrode (kg)
1222 A.H. Essadki et al. / Chemical Engineering and Processing 47 (2008) 12111223
mth theoretical weight loss of Al electrode (kg)
MAl molar mass of aluminum (0.02698 kg/mol)
R2 correlation coefficient
S electrode surface area (m2 )
t time (h)
tN necessary time to achieve the objectives (min)
U measured potential (V)
UGr
superficial gas velocity in the riser (cm/s)
ULd overall liquid recirculation in the downcomer (cm/s)
ULr overall liquid recirculation in the riser (cm/s)
V reactor volume (m3 )
YABS turbidity removal efficiency (%)
YCOD COD removal efficiency (%)
YCOL color removal efficiency (%)
Greek letters
d gas hold-up in the downcomer
r gas hold-up in the riser
wastewater conductivity (S/m)
max maximum wavelength of the absorption spectrum (nm)
Al specific consumption of the anode (kg Al/kg dye
removed)
liquid residence time in the separator (s)
Al Faradic yield of Al dissolution
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