Chemical Engineering Science 61 (2006) 3602 – 3609

www.elsevier.com/locate/ces

Treatment of industrial liquid wastes by electrocoagulation:

Experimental investigations and an overall interpretation model
Mohamed Khemis, Jean-Pierre Leclerc, Gaëlle Tanguy, Gérard Valentin, François Lapicque ∗
Laboratoire des Sciences du Génie Chimique, CNRS-ENSIC-INPL, BP 20451, F-54001 Nancy, France

Received 29 August 2005; received in revised form 26 December 2005; accepted 26 December 2005
Available online 23 February 2006

Abstract
The paper presents the results of experimental investigations of treatment of concentrated wastes by electrocoagulation using sacrificial
aluminium (Al) anodes. Tests were carried out batchwise in an electrochemical cell with recirculation for various wastes of industrial significance:
the technique was shown to allow efficient abatement of the suspensions with concentrations of dissolved Al ranging from 150 to 500 mg l−1 .
Hydrogen evolution and Al dissolution occurred with current yields over unity. Besides, the time variation of the COD largely depended
on the nature of the waste treated: whereas the treatment proceeds regularly for latex suspensions, the COD abatement with oil and silica
suspensions starts only after sufficient accumulation of Al (III) species in the media. We proposed a phenomenological model for prediction
of the waste abatement in term of COD by complexation of the matter suspended by Al (III), and taking into account the “latency” period
observed experimentally. The values of the parameters involved are discussed in relation to the suspension treated.
䉷 2006 Published by Elsevier Ltd.

Keywords: Waste treatment; Industrial liquid wastes; Electrocoagulation; Suspensions; COD

1. Introduction The relationship between the removal yield of suspended

Electrocoagulation is an effective technique for the treatment
of liquid wastes of various origins, in particular in the presence
of suspended matter (Koren and Syversen, 1995; Nameri et al.,
1998; Jiang et al., 2002; Sanchez-Calvo et al., 2003; Kumar
et al., 2004; Holt et al., 2005). Cations generated by dissolu-
tion of sacrificial anodes induce flocculation of the dispersed
pollutants contained, by reduction in the zeta potential of the
suspended entities. The metal hydroxide formed acts to coag-
ulate the liquid impurities, and the hydrogen bubbles evolved
at the cathode allow flotation of foam containing the organic
matter. The aggregates formed can be removed by decantation
or flotation. The process usually consists of two stages often
achieved in distinct chambers: (i) electrogeneration of the metal
cations and their physical action on the pollutant, (ii) formation
of the flocs, flocculation and settling upon addition of floccu-
lating agents and under low stirring. Flocculation and settling
processes have not been investigated here.
∗ Corresponding author.
E-mail address: francois.lapicque@ensic.inpl-nancy.fr (F. Lapicque).
0009-2509/$ - see front matter 䉷 2006 Published by Elsevier Ltd.
doi:10.1016/j.ces.2005.12.034
matter and the amounts of aluminium (Al) dissolved and hy-
drogen generated at the electrodes was previously investigated
for oil suspensions (Khemis et al., 2005). The present study
deals with the treatment of various concentrated suspensions of
industrial significance, namely soluble oils, latex, and colloidal
ionic silica. Electrocoagulation runs conducted batchwise re-
vealed that the abatement of chemical oxygen demand (COD)
could start only in the presence of a sufficient amount of Al
(III) in the medium.
Modelling of electrocoagulation processes has been little in-
vestigated. Interactions between organic matter and aluminium
hydroxide complexes have been formerly studied (Kumar et
al., 2004; Inan et al., 2004). Recently Carmona et al. (2006) de-
veloped a model for prediction of treatment of oil suspensions,
and relying upon the adsorption equilibrium of oil on solid
Al hydroxide particles: various adsorption models were used
for this purpose. Although physically meaningful in particular
with concern to adsorption phenomena, this model does not
represent the “latency” period observed for COD abatement. In
addition to the experimental part mentioned above, we propose
here an alternative, phenomenological model for treatment of
 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609 3603

industrial wastes by electrocoagulation, taking into account the 150

latency period and based on global complexation equilibrium Soluble oil

Zeta potential (mV)

100 Latex
between Al (III) species and the suspended matter.
50 Anionic silica

2. Experimental details Cationic silica

0

2.1. Chemicals and analytical techniques -50

The metal used for the cell electrodes was an Al alloy A-
U4G (2017-Al) with a copper content at 4%. The following
suspensions were used:
• The oil suspension was a dispersion (Sol 1000姠, Molydal,
France) of current use for drilling and machining operations.
It consisted of a mixture of refined mineral oils (70%), glycol
ethers, amines and chlorinated alcanes.
• The latex emulsion was an aqueous dispersion of acryloni-
trile and 1–3 butadiene copolymer (Chemigum姠 Latex 248),
and was kindly offered by Hutchinson France. The original
emulsion with 55 wt% copolymer content was used after di-
lution.
• The inorganic emulsions were colloidal dispersions of silica
from Clariant, France: Klebosol姠 30R50 for the anionic sil-
ica, and Klebosol姠 30CAL50 for the cationic material. The
mother solution at a 50% weight concentration was diluted.
The emulsions were diluted in deionised water. The ranges of
dilution factor were chosen for the sake of representative con-
ditions of concentration under industrial practice. Latex emul-
sions had to be diluted tenfold or more to avoid blockage of
the Al surface by formation of a thick solid layer. The concen-
trations given here express the concentrations of the original
media in the solutions obtained before treatment.
The main features of the dispersions used are given in Table 1.
The liquid media were slightly alkaline, except for the cationic
suspension as expected. In all cases, sodium chloride at 1.5 g l−1
was added for sufficient electrical conductivity of the liquid
to be treated. Conductivity of the resulting media was ranging
from 0.35 to 0.38 mS cm−1 . Zeta potentials of the dispersions
were negative, ranging from −70 to −30 mV. The pH of zero
charge was near 2.5 for the two organic dispersions and the
cationic silica suspension, and near 9 for the anionic resins, as
shown in Fig. 1.
The organic media were dispersions of regular droplets of
a few
m, whereas the diameter of silica particles was of one
order of magnitude smaller. The COD levels of the dispersions
-100
0 2 4 6 8 10 12
pH
Fig. 1. Variations of the zeta potential of the various suspensions investigations
with the solution pH.
were determined using the standardised calorimetric technique
with an excess of hexavalent chromium and subsequent mea-
surement of the optical density. The organic suspensions were
highly concentrated, and the most concentrated dispersions had
COD contents of the order of 100 g l−1 . In contrast, COD levels
of the silica dispersions were 100-times lower.
Turbidity of inorganic suspensions was measured by an IR
beam at 890 nm and detection of the dispersed light, using a
Hanna Ins. LP 2000 spectrophotometer for this purpose. Data
were given in Formazide Turbidity Unit (FTU). The signifi-
cant turbidity measured indicated that silica nanoparticles were
likely agglomerated in the dispersions. Al concentrations in the
dispersion samples taken during the runs were determined by
potentiometric titration using EDTA after Sajo procedure re-
ported in Charlot (1961).
2.2. Set-up and protocol
The electrocoagulation cell was the parallel plate electro-
chemical cell described in Khemis et al. (2005), provided with
two facing 50 × 100 mm electrodes out of the Al-based alloy.
The electrode gap was maintained at 20 mm and the liquid was
driven at 6.2 cm3 s−1 in the cell. Experiments were conducted
batchwise with recirculation of the liquid in a circuit consist-
ing of a peristaltic pump and a 2 litre double-walled tank for
temperature control at 20 ◦ C and separation of the gas formed
at the electrode surfaces. The gas was collected in a graduated
vessel acting as a gas holder.
Aliquots of NaOH were introduced in dispersions of cationic
silica, so that the initial pH attained 6.5. One litre of fresh emul-
sion was introduced into the circuit tank, and the chosen current

Table 1
Physicochemical features of the suspensions treated

Effluent 5% oil suspension 5% latex 10% anionic silica 10% cationic silica

COD (mg l−1 ) 147 000 88 000 1200 1200

TOC (mg l−1 ) 34 000 14 000 — —
Turbidity (FTU) — — 1800 2200
Particle size (
m) 5±2 2 ± 0.5 0.2 0.3
Initial pH 9.1 8.4 9.4 4.8
3604 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609
was applied to the cell. The pH of the medium attained rapidly
a steady level, near 9.3 within 0.2 for the slightly alkaline dis-
persions, and near 8.5 for the cationic silica. From six to eight
10-cm3 samples were taken at regular intervals without addition
of fresh liquid. pH of the samples was adjusted to 6.5 ± 0.5
upon addition of hydrochloric acid for optimal precipitation of
Al(OH)3 (Bard et al., 1985). Al content was analysed from
a fraction of the sample, and the rest was allowed to settle
for 6–24 h, depending on the suspension considered. COD and
turbidity were determined from the clear fractions recovered.
Analysis of the collected gas by chromatography revealed the
exclusive presence of hydrogen. The mole number of hydrogen
produced at t, nH2 , was deduced straightforward.
3. Generation of species at the Al electrodes
Dissolution of Al leads to Al (III) species:
Al = Al3+ + 3e. (1)
Depending on the pH, the trivalent ion combines with OH−
ions to form aluminium hydroxides, and the neutral, insoluble
form Al(OH)3 predominates for pH near 6.5. In addition to the
reduction of dissolved oxygen, hydrogen is formed by water
reduction:
2H2 O + 2e = H2 + 2OH− . (2)
Besides, the presence of chloride ions catalyses Al corrosion
producing hydrogen, according to the overall stoichiometry:
2Al + 3H2 O = 2Al3+ + 6OH− + 3H2 . (3)
The cell electrodes were changed every 10 runs and the ageing
of the electrodes was observed to affect only little the treatment
efficiency (Khemis et al., 2005).
The current efficiencies of Al dissolution and H2 evolution
were calculated using Faraday’s law from the amount produced
and taking into account the number of electrons involved:
zAl F mAl

Al = , (4)
MAl Q
zH2 F nH2

H2 = , (5)
Q
where Q is the electrical charge passed, mAl is the weight
of dissolved Al, and MAl its molar weight. Coefficients zAl
and zH2 are, respectively equal to 3 and 2, after reactions (1)
and (2).
Current yields for the two reactions were larger than unity
in all cases, all along the runs, indicating the occurrence of the
chemical overall reaction (3). For the treatment of oil dispersion
and anionic silica, the current yield of Al dissolution exhibited a
significant decrease with time, in particular in the first minutes
of the run, whereas an increasing tendency was observed with
the latex suspensions. The yields of hydrogen evolution were
less subject to variation along time.
Yield
Al generally attained lower levels with more concen-
trated suspensions than with dilute media, suggesting the pos-
sible blockage of the electrode surface by the organic matter.
For oil and silica dispersions, the dissolution yield was ranging
from 1.4 to 1.9, depending on the conditions, whereas the vari-
ation range was 1.0–1.6 for latex. The effect of the current den-
sity on
Al depended on the suspension nature:
Al decreased
markedly with the current density for oil suspensions, whereas
a positive effect was observed with anionic silica; no clear ef-
fect was evidenced for latex-containing media. As a matter of
fact the inhibition of the electrode surface observed with high
suspension contents appeared to be reduced with high current
densities, which indicated the positive effect of the electrogen-
erated gas.
The yields for hydrogen evolution were less influenced by the
concentration of suspensions (Khemis, 2005). Current yields
varied from 1.6 to 2.2 but no marked effect of the operating
conditions could be evidenced, except the positive effect of the
current density with the most concentrated wastes, whatever
their nature. Reactions (1)–(3) indicate that 3 mol hydrogen are
formed for 2 mol Al (III), corresponding to molar H2 /Al ratio
of 1.5. Experiments led to values for this ratio ranging from
1.5 to 2.2.
4. Treatments of the suspension
4.1. Treatment rates
As explained in a previous paper (Khemis et al., 2005), ad-
justing the pH of the oil dispersion samples to 6.5 allowed
visible settling of the pollutant: the abatement yield of COD
induced by the change in pH of the initial oil suspension was
near 13%. This effect was hardly visible for latex emulsions and
was not observed for the silica. Treatment of the dispersions
was generally efficient, with COD abatement ranging from 92%
to 97%.
Profiles of the time variations of COD depended on the dis-
persion nature, as shown in Fig. 2. For oil and silica disper-
sions (Fig. 2(a) and (b), respectively), treatment consisted of
three phases: (i) a “latency” period in which Al (III) species
accumulates in the circuit and contributes to reduction of the
zeta potential of the surface of the dispersed matter; (ii) a rise
of COD abatement, likely due to low values of the zeta po-
tential and possible agglomeration of the Al (III)-complex dis-
persion; (iii) a plateau, for which further addition of Al (III)
species does not allow further treatment. The first phase was
not observed with latex emulsions, and the dispersed droplets
appeared to be more continuously complexed by electrogen-
erated Al (III) species (Fig. 2(c)). Treatment of concentrated
silica and latex dispersions required longer periods (Fig. 2(b)
and (c)). The effect of concentration on the treatment rate was
not observed with oil dispersion, except for the 15% emul-
sion which was less stable, then more prone to coagulation
(Fig. 2(a)).
Analysis of samples of silica dispersions showed that tur-
bidity increased in the first minutes of the treatment, due to
accumulation of aluminium hydroxide particles formed by the
 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609 3605

Oil at100 A/m2 5% Cationic silica

1 1
COD abatement

0.8 0.8

COD abatement
0.6 5% 0.6 100 A /m2

0.4
7% 150 A/ m2
0.4
10% 200 A/ m2
0.2 15% 0.2 300 A/ m2
0
0 20 40 60 80 100 120 0
(a) 0 100 200 300 400 500
Time (mn)
(a) Al conc. (mg/l)
Anionic silica at 100 A/m2
1 5% Cationic silica
4000
0.8
COD abatement

Turbidity (FTU)
0.6 3000 100 A/m2
5%
10% 150 A/m2
0.4 2000
15% 200 A/m2
0.2
1000 300 A/m2
0
0 10 20 30 40 50 60 0
(b) Time (mn) 0 100 200 300 400 500
Latex at150 A/m 2 (b) Al conc. (mg/l)
1
Fig. 3. Treatment of 5% cationic silica with various current densities versus
COD abatement

0.8
0.6
0.4
0.2
0 Examination of the above data indicates two characteristic
0 10 20 30 40
(c) Time (mn)
Fig. 2. Time variation of COD abatement depending on the suspension
concentration: (a) top, oil at 100 A m−2 ; (b) anionic silica at 100 A m−2 ; (c)
latex at 150 A m−2 .
dissolution. Turbidity exhibited a well-defined maximum be-
fore decreasing rapidly down to 0 FTU.
The current density had a large effect on the kinetics of the
waste treatment for both COD and turbidity variations: higher
current densities allowed shorter latency periods, and the treat-
ment is globally carried out within shorter periods. The ef-
fect of current density is linked to the production rate of Al
(III) species. The experimental COD and turbidity data were
plotted versus the amount of dissolved Al: Fig. 3 illustrates
the efficiency of the plot for the example of 5% cationic sil-
ica. The first period of the treatment, with increasing turbidity
and constant COD was observed for Al (III) concentrations be-
low 100 mg l−1 . The rise in COD abatement corresponded to
the maximum turbidity and its sudden decay, whereas the fi-
nal plateau with constant abatement yield was observed for nil
turbidity, with Al (III) concentrations over 140 mg l−1 for the
example treated. This last observation clearly shows that the
COD of the liquid fractions sampled after treatment was only
due to the presence of soluble compounds or to dispersed par-
ticles which could not agglomerate.
the concentration of dissolved Al: (a) COD abatement; (b) turbidity.
3.3%
5%
7% 4.2. Amount of Al salts required
10%
50 60 concentrations of dissolved Al for the treatment: (i) the occur-
rence of the rise of COD abatement, i.e., the end of the first
latency period, Cmin , and (ii) the minimal time required for
maximal treatment of the wastes considered, at the beginning
of the abatement plateau, Cmax .
The minimum concentration Cmin largely depends on the dis-
persion treated: Cmin was below 30 ppm for latex, ranged from
70 to 160 ppm for silica dispersions, and was of the order of
200–300 ppm for oil dispersions (Fig. 4). The low effect of the
current density confirms the fact that a minimum amount of Al
(III) is required to initiate coagulation. Moreover, the concen-
tration of dispersed matter has a moderate influence on Cmin ,
depending on the dispersion nature: for silica and latex suspen-
sions, Cmin slightly increases with the dispersion concentration,
whereas the most concentrated oil suspensions are less stable
than dilute media.
Al concentrations for maximal treatment of the dispersions,
Cmax , are given in Fig. 5 for two dispersions investigated.
Contrary to Cmin , concentrations Cmax are of the same order
of magnitude for all the dispersions studied, in the following
ranges: from 260 to 560 ppm for oil suspensions, 120–240 ppm
for latex-containing media, 100–160 ppm for cationic sil-
ica, and 120–260 ppm for anionic silica. As discussed above,
coagulation of oil suspensions and silica dispersions—when
initiated—was carried out upon addition of little amounts of
Al (III) species, whereas coagulation of latex proceeded more
regularly. As for Cmin , the current density had a low effect on
3606 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609

400 requires higher amounts of coagulant than for dilute media

Oil (Fig. 5(b)), however without a linear relationship between the
300 two variables. The loss of stability of dispersions upon electro-
5%
Cmin (mg/l)

7% generation of Al (III) has been interpreted by the phenomeno-

200
10% logical model presented below.
100 15%
5. Model for treatment of the wastes by electrocoagulation
0
0 100 200 300 400
(a) Current density (A/m2) 5.1. Development of the model

300 The model developed for representation of the COD profiles

Anionic silica
relies upon the following assumptions:
Cmin (mg/l)

200 5%
10% 1. Treatment of suspensions by electrocoagulation occurs only
15% for coagulant concentrations, CAl , over the threshold level
100
Cmin (Fig. 6), as observed experimentally. The concentration
of active Al salts is equal to the difference (CAl − Cmin ).
0 Time tmin was defined as the time at which CAl = Cmin .
0 100 200 300 400 Regardless of this assumption, concentration CAl measured
(b) Current density (A/m2)
by analysis of the sampled fractions, was deduced from (4):
Fig. 4. Concentrations of dissolved Al required to allow start-up of COD
t
MAl I 0
Al dt
abatement versus the current density: (a) top, oil dispersions; (b) bottom, CAl (t) = , (6)
anionic silica. zAl F V
where V is the volume of treated liquid.
2. The organic or mineral matter contained in the suspensions
800
Oil is expressed in the model in terms of COD level, S. S was
600 considered to be the sum of three contributions (Fig. 6): S1
Cmax (mg/l)

5%
represents the amount of suspended matter that can be re-
400 7%
moved by the pH change made before analysis (see Section
10%
200 4.1); S2 expresses the matter concentration which can be
15%
treated by electrocoagulation after addition of coagulant; S3
0 corresponds to the amount of matter which cannot be treated
0 100 200 300 400
(a) by the electrochemical technique. Concentrations [S1 ], [S2 ],
Current density (A/m2)
and [S3 ] were expressed in mg O2 per litre. Only concen-
300
trations [S] and [S2 ] varied with time.
The intrinsic COD level of the investigated suspension, [S0 ],
5%
Cmax (mg/l)

200 was written as

10%

100 15% [S0 ] = [S1 ] + [S2,t=0 ] + [S3 ]. (7)

Anionic silica

0
0 100 200 300 400 S0
(b) Current density (A/m2) S1
COD (mgO2 /l)

Fig. 5. Concentrations of dissolved Al required to allow maximum treatment

of the solutions versus current density: (a) top, oil dispersions; (b) bottom,
anionic silica.
S2(t=0)
S2(t)
Cmax , except with latex dispersions for which more Al (III)
was required when higher current densities were applied.
Concentrations Cmax determined for oil dispersions were lit- S3
tle affected by the dispersion concentration in the range 5–10% 0 Cmin Cmax
(Fig. 5(a)), as observed in Section 4.1. However, treatment of
Al (III) dissolved (mg/l)
15% oil suspensions was carried out with a lower Al amount,
because of the reduced stability of such a suspension. In con- Fig. 6. Schematic variation of the COD level with the concentration of
trast, treatment of concentrated silica and latex dispersions dissolved Al.
 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609 3607

Table 2
Values of the model parameters for the four dispersions investigated

Oil Dispersion conc. 5% 7% 10% 15%

K = 5.0 × 10−4 l/mg n (mg Al/mg O2 ) 1.0 × 10−3 7.0 × 10−4 5.0 × 10−4 4.0 × 10−4
Cmin (mg/l) 200 200 200 0
Latex Dispersion conc. 3.3% 5% 7% 10%
K = 4.5 × 10−4 l/mg n (mg Al/mg O2 ) 1.9 × 10−3 1.7 × 10−3 1.65 × 10−3 1.23 × 10−3
Cmin (mg/l) 0 0 0 0
Anionic silica Dispersion conc. 5% 10% 15%
K = 6.0 × 10−3 l/mg n (mg Al/mg O2 ) 0.031 0.030 0.032
Cmin (mg/l) 80 80 110
Cationic silica Dispersion conc. 5% 10% 15%
K = 8.0 × 10−3 l/mg n (mg Al/mg O2 ) 0.051 0.031 0.022
Cmin (mg/l) 95 48 70

Values for [S1 ] and [S3 ] were drawn from the experimental
COD variation.
3. Electrocoagulation proceeds by complexation of suspended
matter by Al (III) species: chemical equilibrium was postu-
lated:
Al + nS 2 → Al-S,
 
(CAl − Cmin )
− 1+K − [S0 ]
n n
[S2 ] =
where n is an overall coefficient, expressed in mg Al (III)/ mg
O2 . Because of the dimension of n, (8) cannot be considered
as a real chemical process, but simply as the phenomenolog-
ical description of complexation of suspende matter by Al
species. Subscript 2 was mentioned in (8) since only frac-
tion S2 can be treated upon Al dissolution. Al-S corresponds
to the complexed particles, prone to flocculation by their
low zeta potential; for the sake of simplicity coefficient n
does not appear in the written form of the complexed form.
Overall equilibrium constant, K, was defined as
CAl-S CAl-S
K= = (9)
[Al][S2 ] CAl,free [S2 ]
where CAl,free is the concentration of free Al species, CAl-S ,
the concentration of Al in complexed form. Since (8) can-
not be considered as an elementary process in equilibrium,
coefficient n was not included in the expression for K in the
present model.
For t > tmin mass balance on dissolved Al led to:
CAl = Cmin + CAl,free + CAl-S .
Moreover, mass balance on the suspended matter which can be
treated by electrocoagulation, was written as
[S2,t=0 ] = [S2 ] +
1
CAl-S .
n l mg−1 for the organic dispersions, and around 6 × 10−3 l mg−1
Eqs. (9), (10) and (11) linked with variables [S2 ], CAl-S and
CAl,free . Rearrangement of the equations led to the equation:
   
(CAl − Cmin )
K[S2 ]2 + [S2 ] 1 + K − [S0 ] − [S0 ] = 0.
n
(12)
(8)
The expression for [S2 ] was easily deduced:
   2
CAl − Cmin
+ 1+K − [S0 ] + 4K[S0 ]
. (13)
2K
The abatement yield of COD was deduced straightforward:
[S0 ] − [S1 ] − [S2 ]
X= . (14)
[S0 ]
5.2. Results
The experimental variations of X were plotted versus CAl .
Model parameters n, K and Cmin were obtained by best fitting
of the data for each concentration value of the considered dis-
persion, and the various currents applied. Preliminary simula-
tions showed that parameter K was little dependent on the dis-
persion concentration, as expected. It was therefore preferred
for the final fitting to fix K at an average value for all disper-
sion concentrations, and the values obtained represent physico-
chemical features of the treated dispersions. The accuracy in the
parameter determination was evaluated by simulation around
the optimal point: it was found at 10% for parameters n and K;
Cmin was estimated within 10 mg l−1 for all suspensions, ex-
cept for concentrated suspensions of cationic silica, for which
the confidence interval attained 20–30 mg l−1 . Parameter val-
ues are summarised in Table 2. As exemplified by Fig. 7, ex-
perimental data are well represented by the model, in spite of
(10) noticeable dispersion with concentrated silica dispersions.
The predicted values for Cmin were perfectly consistent with
those observed experimentally, as shown by examination of
Table 2 and Fig. 4. No clear dependence of the suspension
concentration on Cmin could be established.
(11) Equilibrium constant K was far below unity, near 5 × 10−4
3608 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609

Oil 5% 0.1

Parameter n (mg Al/mg O2)

1

0.8
COD abatement

0.01
0.6 100 A/ m2 140 A/ m2 Oil
170 A/ m2 200 A/ m2 Latex
0.4 260 A/ m2 300 A/ m2
0.001 Anion.silica
0.2 Model
Cation.silica

0
0 200 400 600 800 1000 0.0001
(a) 1 10 100
Al concentration (mg/l)
Suspension concentration (%)
Latex 7%
1 Fig. 8. Variation of the overall coefficient n of the coagulation process with
the concentration of dispersion.
COD abatement

0.8
100 A/ m 2
0.6 150 A/ m 2

0.4
200 A/ m 2 The dependence of the suspension concentration on param-
300 A/ m 2 eter n is shown in Fig. 8. For latex suspensions and anionic
0.2 Model silica dispersion, n varied little with the concentration of sus-
0 pended matter, appearing as a sort of stoichiometric coeffi-
0 100 200 300 400 500 600 cient. The higher was the content of suspension, the higher the
(b) Al concentration (mg/l)
amount of Al to be dissolved. Data for cationic silica were not
5% anionic silica accurate enough for definitive conclusions on the coagulation
1
process. In contrast, parameter n varied with the reciprocal of
0.8 the oil concentration (Fig. 8): this fact is consistent with the
COD abatement

100 A/m2
0.6 150 A/m2 experimental observation of the nil dependence of the oil con-
200 A/m2 centration on Cmax (Section 4.2). In this case, the coagulation
0.4 300 A/m2
mechanism cannot be written as the simple equilibrium (8), and
Model
0.2 additional phenomena are to occur. For oil suspensions, synergy
0
in the flocculation–coagulation process seems to occur: falling
0 100 200 300 400 500 particles formed in a primary coagulation step would entrap
(c) Al concentration (mg/l) surrounding small micelles of pollutants—in accordance with
the multilayer model used by Carmona et al. (2006), resulting
Fig. 7. COD abatement of dispersions versus the concentration of dissolved in the formation of larger flocs of easier settling.
Al: (a) 5% oil; (b) 7% latex; (c) 5% anionic silica.

6. Conclusion

The performance of electrocoagulation technique for treat-

for the silica. The order of magnitude of K was discussed in
relation to the COD level: as a matter of fact, the concentration
ratio of complexed Al over free Al species, CAl-S /CAl,free , is
equal to product (K[S2 ]). Although varying along the treatment,
concentration [S2 ] was of the order of magnitude of the initial
COD level. For [S2 ] equal to 105 , 5 × 104 , and 500 mg/l, re-
spectively for oil, latex and silica suspensions, the correspond-
ing values of product (K[S2 ]) attained 50, 25 and 4. These
estimates clearly show that, in the major course of electroco-
agulation process, dissolved Al was mainly in the form of a
complex with the suspended matter, in particular for the two
organic suspensions.
Besides, n was of the order of 10−3 mg Al (III)/mg O2 for
the organic suspensions, expressing the high efficiency of Al
(III) species in the COD abatement, since 200 g l−1 COD—i.e.,
nearly 40 g l−1 TOC—can be treated by dissolution of a few
10−1 g l−1 Al. The overall coefficient n is far lower for the silica:
COD values for inorganic dispersions are little significant, and
the efficiency of the technique should be better discussed in
terms of abatement of turbidity or suspended matter.
ment of various concentrated dispersions has been shown. The
concentrations of coagulant required for maximal treatment are
little dependent on the current density. The nature of the dis-
persed phase appears to govern the mechanism of electroco-
agulation. With oil and silica dispersions, electrocoagulation
observed by the COD level, occurs after a latency period for
which Al (III) accumulates; in contrast treatment of latex pro-
ceeds more regularly. Moreover electrocoagulation of concen-
trated oil emulsions can be carried out with Al amounts very
similar to those with diluted emulsions, whereas for the other
dispersions, the concentration of Al (III) required varies with
the dispersion concentration.
The various dispersions can be treated with Al concentra-
tion ranging from 120 to 560 ppm: the sludge to be produced
by flocculation and dehydration has low Al contents, which
is of large interest for disposal or reuse in industry. Previ-
ous works showed that the energy consumption could range
from 2 to 4 kWh m−3 (Sanchez-Calvo et al., 2003): the pro-
cess seems competitive in comparison to incineration or water
evaporation.
 M. Khemis et al. / Chemical Engineering Science 61 (2006) 3602 – 3609
A simple model based on an overall equilibrium between
the dispersed matter, S, and dissolved Al provided satisfac-
tory interpretation of the experimental data. The values of the
equilibrium constant showed that Al species is mainly in com-
plex form (Al-S) for the major part of the batch run. The
dependence of the dispersion concentration on the required
amount of Al hydroxide is governed by the dispersion nature.
The interpretation model proposed could be applied to treat-
ment of various dispersed wastes, provided the parameters in-
volved have been determined in preliminary investigations: the
model could be used in designing the process and its opera-
tion. Besides, more thorough investigations should be carried
out to support more complex mechanism, allowing a closer
description of the synergy in the coagulation for particular
wastes.
Notation
CAl concentration of dissolved Al, mg l−1
CAl,free concentration of free Al (III) species, mg l−1
CAl-S concentration of Al in complexed form, mg l−1
Cmin minimal value of Al concentration to allow start-up
of electrocoagulation, mg l−1
Cmax Al concentration required for maximum treatment
of the waste, mg l−1
F Faraday’s constant, 96487 A.s eq−1
I current, A
K equilibrium constant of the coagulation process,
l mg−1
m weight amount of Al dissolved, kg
M molecular weight, kg mol−1
n overall coefficient of the coagulation process, mg
Al (III)/ mg O2
nH2 number of mole of hydrogen, mol
Q electrical charge passed, A.s
S COD of the suspension at time t, mg O2 l−1
S0 intrinsic COD of the suspension to be treated, mg
O2 l−1
S1 COD variation of the suspension induced by pH
change, without Al dissolution, mg O2 l−1
S2 COD of the suspension which can be removed by
electrocoagulation, mg O2 l−1
S3 final COD level of the treated suspension, with an
excess of dissolved Al, mg O2 l−1
X COD abatement
z number of electrons involved in the electrode
reaction

Faradaic yield
3609
Subscripts
Al related to aluminium
H2 related to hydrogen evolution
t =0 start of the electrochemical run
Acknowledgments
The authors would like to thank G. Paternotte for his valuable
assistance in the analytical part, the staff of the mechanical
workshop for the precise construction of the cell and the flow
rig, and J.F. Remy for the zeta potential measurements and
SEM observations. Thanks are also due to Prof. Can Vu and
M.L Pérard (Clariant France), and N. Carniol (Hutchinson) for
supplying the wastes and their composition.
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