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The treatment of very concentrated oil-water emulsions by electrocoagulation (EC) was experimentally investigated as a pre-treatment step prior to a membrane process. The oil-water emulsion was prepared from a cutting mineral oil B22 currently used for drilling and machining operations. The electrocoagulation progress was followed by the measurement of COD, turbidity and pH in a batch process with recirculation of the liquid. This study is mainly focused on the effects of operating parameters such as initial pH, current density, oil concentration and recirculation rate, on the de-emulsification efficiency. Kinetic curves showed that the EC process exhibits two phases: a "reactive phase" during which the COD and the turbidity removals increase with electrolysis, and a stationary phase for which further aluminium dissolution is useless in the pollution abatement. The results showed that the treatment efficiency increases with increasing current density, but decreases with oil concentration. It appears that treatment of the considered cutting oil is completed through dissolution of around 10mgAl/g oil, with a slight positive effect of the liquid flow rate. Best results are also obtained with initial pH near 7.
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Journal of Hazardous Materials 152 (2008) 423–430
Electrocoagulation of cutting oil emulsions using
aluminium plate electrodes
K. Bensadok a,, S. Benammar a, F. Lapicque b, G. Nezzal a
aLaboratoire de G´enie des Proc´ed´es et de l’Environnement, F.G.M.G.P., USTHB, B.P. 32,
El Alia, 35111 Algiers, Algeria
bLaboratoire des Sciences du G´enie Chimique, CNRS-ENSIC, BP 20451, F-54001 Nancy, France
Received 4 January 2007; received in revised form 29 June 2007; accepted 29 June 2007
Available online 7 July 2007
The treatment of very concentrated oil–water emulsions by electrocoagulation (EC) was experimentally investigated as a pre-treatment step prior
to a membrane process. The oil–water emulsion was prepared from a cutting mineral oil B22 currently used for drilling and machining operations.
The electrocoagulation progress was followed by the measurement of COD, turbidity and pH in a batch process with recirculation of the liquid.
This study is mainly focused on the effects of operating parameters such as initial pH, current density, oil concentration and recirculation rate, on
the de-emulsification efficiency. Kinetic curves showed that the EC process exhibits two phases: a “reactive phase” during which the COD and the
turbidity removals increase with electrolysis, and a stationary phase for which further aluminium dissolution is useless in the pollution abatement.
The results showed that the treatment efficiency increases with increasing current density, but decreases with oil concentration. It appears that
treatment of the considered cutting oil is completed through dissolution of around 10 mg Al/g oil, with a slight positive effect of the liquid flow
rate. Best results are also obtained with initial pH near 7.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Electrocoagulation; Cutting oil emulsions; Aluminium plate electrodes; Very high COD
1. Introduction
Cutting oils also called “soluble oils”, are used in particular
during mechanical operations of cutting and machining metals.
They combine the properties of cooling and lubrication. A cut-
ting fluid concentrate usually contains a mineral oil, a surfactant
mixture, in some cases water and various additives, which are
included to meet the specifications of commercial concentrates
such as resistance to bacterial growth and low corrosion capac-
ity [1]. During their use, cutting fluids loose their properties and
effectiveness because of their thermal degradation and the pro-
duction of suspended metal particles. The oils have therefore
to be replaced periodically and the organic wastes generated
have to be taken away and treated. This constitutes a danger
Corresponding author at: University of Sciences and Technology H. Boume-
diene, F.G.M.G.P., Laboratory of Process and Environmental Engineering, B.P.
32, El Alia, 35111 Algiers, Algeria. Tel.: +213 76 14 60 02;
fax: +213 21 24 79 19.
E-mail address: (K. Bensadok).
to the environment because these effluents are highly charged
in surface-active agents and other organic matters. Moreover,
because of their great capacity of penetration in the ground,
they constitute a very serious threat for groundwater. Sokovic
and mijanovic [2] give an analysis of the ecological parameters
of the cutting fluids. The significant developments of the formu-
lations of cutting oils as well as the preparation of the synthetic
or semi-synthetic emulsions complicate some more the issue of
the purification of these effluents. Because of the stability of
these emulsions, there is no universal solution for their treat-
ment, and it can be necessary to combine one or two treatment
processes for highly effective purification. Several techniques
have been applied to treat these types of oily wastewater, e.g.
chemical [3] and biological [4] destabilization, ultrafiltration [5]
and nanofiltration [6]. Adsorption on mixed Ca and Mg oxides
obtained by thermal decomposition of dolomite was studied to
remove exhausted oils [7].
Coagulation makes it possible to destabilize the suspended
particles which cannot settle naturally because of their submicro-
metric size. The destabilization of negatively charged particles
0304-3894/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
424 K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430
takes place upon addition of positively charges species, which
can be supplied either by addition of chemicals, e.g. iron chloride
or aluminium sulphate, for conventional chemical treatment, or
by the dissolution of anodes in the case of electrocoagulation
(EC). Electrocoagulation is initiated by the oxidation of sac-
rificial anodes out of aluminium or iron yielding, respectively
Al3+ and Fe2+ ions. The latter ions are rapidly oxidized to Fe3+
by air oxidation. The metal ions combine to the hydroxyl ions
produced by the water electrolysis at the cathode, to form the
corresponding metal hydroxides, which favor the formation of
the flocs by destabilisation of the contaminants or particulate
suspensions. The flocs formed can be recovered from the liquid
surface by scraping – when the bubbles of hydrogen produced at
the cathode allow flotation – or settle depending on their density.
The development of EC process has been hindered for
years by the high investment costs and severe competition with
the chemical processes. It started to regain importance with
improvement of electrochemical processes and promulgation of
more stringent environmental legislations on wastewater. This
new rise of electrocoagulation has also been due to the rela-
tive reduction in the operation and investment costs. EC has
the potential to be competitive with respect to both economical
and environmental criteria for treatment of wastewater and other
related water management issues [8]. This technique has been
applied for treatment of waters containing suspended solids [9],
oils and greases [10–13], dyes and textile wastewaters [14,15],
or industrial wastes containing heavy metals [16] and phosphate
[17]. EC was also applied for defluoridation of water [18] and
urban wastewaters [19].
The electrochemical reaction occurring at the anode and
involving metal M-aluminium in the present case, is written as
Al(s) Al(aq)3++3e(1)
Hydrogen evolution occurs at the cathode depending on pH.
2H2O(l) +2eH2(g) +2OH(aq)(2)
2H(aq)++2eH2(g) (3)
The generated Al(aq)3+ ions combine with water and hydroxyl
ions to form corresponding hydroxydes and/or polyhydroxides
[20–22] as follow:
monomeric species such as Al(OH)2+, Al(OH)2+, and
Al(OH)4by Eqs. (4), (5) and (7),
polymeric species such as Al2(OH)24+ and Al2(OH)5+,
amorphous and less soluble species such as Al (OH)3by Eq.
(6) and Al2O3.
Considering only mononuclear speciation, the concentration
of the various Al forms present in solution (α) was calculated
Fig. 1. Solubility diagram of aluminium hydroxide Al(OH)3(s) considering only
mononuclear aluminium species. Data from [26].
by Holt et al. [26] depending on pH. Fig. 1 provides the speci-
ation diagram obtained by the authors. Al complexes acting as
coagulants are adsorbed on the particles and thus neutralise the
colloidal charges, resulting in destabilization of the emulsion.
This phenomenon is similar to the action of chemical coagu-
lants in the conventional chemical treatment. Hydrogen bubbles
formed at the cathode can adsorb on the flocculated species and
induce their flotation. The bubbles formed also reduce fouling
of the cathode surface which could occur by the formation of
NaCl is usually employed to increase the conductivity of the
water or the wastes to be treated. The presence of the chloride ion
in solution has been reported to decrease passivation of the Al
surface and thereby increase the efficiency of electrocoagulation
processes [23,24]. All authors attributed the effect of chloride
ion to its role in the “pitting” corrosion of the metal surface.
Mameri et al.[18] postulated a mechanism for the reduction
in Al passivation by the oxide layer formed, and the overall
equations can be written as
2Al +6HCl 2AlCl3+3H2(8)
AlCl3+3H2OAl(OH)3+3HCl (9)
Because of EC complexity, previous researchers have
adopted a largely empirical approach to understand the various
processes involved[8,19,26]: the capability of removal the pollu-
tant by their technology was clearly demonstrated and analysed.
The published works have often resulted in various EC systems
whose design and operations were developed to meet the speci-
fication of the specific pollutants investigated. However most of
these contributions have failed to extract and to quantify the key
underlying mechanisms of pollutant removal.
The efficiency of EC processes is to be controlled by several
parameters, e.g. current density, pH, flow rate, electrode mate-
rials, and the amount of matter to be removed. In this study,
treatment of cutting oil emulsions was considered as a pre-
treatment step prior to a membrane process. The progress of
the treatment carried out in a batch system provided with recir-
culation of the flow, was followed by time variations of COD
and turbidity.
K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430 425
Table 1
Characteristics of the emulsions used
Oil concentration 2% 4% 6%
COD (mg O2/L) 60 282 108 208 116 128
Turbidity (NTU) 26 400 51 712 64 125
pH before NaCl addition 8.63 9.09 9.69
pH after NaCl addition 8.43 9 9.3
Conductivity before NaCl
addition (s/cm)
257 322 419
Conductivity after NaCl
addition (s/cm)
3 150 3 350 3 730
2. Materials and methods
2.1. Chemical and analytical techniques
The metal used for the cell electrodes was Al alloy AU4G
(2017-Al). It is mainly produced by recovery of aluminium
waste, which explains its very accessible cost. The alloy con-
tains Cu at 4%, Fe, Mg and Mn each at 0.7%, Si at 0.5% and
lower percentages of Zn and Cr.
Oil–water emulsions were prepared from a cutting mineral
oil B22 supplied by Naphtal (Sonatrach, Algeria) and currently
used for drilling and machining operations. The emulsions were
diluted in deionized water to form very stable emulsion with
mean diameter droplet and the zeta potential equal, respectively
to 112 nm and 30 mV. The zeta potential was measured using
a Malvern Zetasizer 3000HS. The diameter of the oil droplet
was measured using Malvern Mastersizer nano S. In all cases,
sodium chloride at 1.5gL
1concentration was added for suf-
ficient electrical conductivity of the emulsion to be treated, as
suggested by S´
anchez-Calvo et al. [13] and Chen et al. [27]. This
addition has negligible effect on the initial pH of the emulsion
(Table 1). Carmona et al. [28] observed that the characteristics
of these types of emulsions were not affected by the addition
of supporting electrolyte such as NaCl at low/moderate con-
centrations. COD and turbidity levels of the dilute emulsions
are very high (Table 1) and nearly proportional to their concen-
tration, as expected. The progress of electrocoagulation in the
batch process was followed by measurement of COD, turbid-
ity, conductivity and pH. The COD levels of the samples were
determined using the standardized colorimetric technique with
an excess of hexavalent chromium and subsequent measurement
of the optical density. Turbidity was measured by a Hanna Instru-
ment LP 2000 turbidimeter which measures the quantity of light
absorbed by the suspended particles in comparison with a stan-
dard solution. Accuracy of the two analytical techniques was
better than 5%. The pH was measured using a Hanna Instrument
pH 211 Microprocessor pH Meter. Conductivity was measured
using a Hanna Instrument Conductivity Meter EC 214. The main
features of the emulsions used are given in Table 1.
2.2. Set-up and protocol
The batch experimental set up is shown in Fig. 2. The
system consisted of an EC cell, a cylindrical reactor, a peri-
staltic pump for the recirculation of the effluent and a sampling
valve to collect the samples. The EC cell consisted of two
polymeric halves which were bolted to form the rectangu-
lar channel cell. An aluminium electrode with dimensions of
100 mm ×50 mm ×12 mm, was embedded in each of the two
valves: only one face was exposed to the solution and the
effective electrode area was 5.0×103m2. The electrode gap
was maintained constant at 20 mm. The electrodes were con-
nected to a digital dc power supply (P. Fontaine, MC4020C,
40 V, 2 A). Two digital multimeters (Multimetrix X1000) were
used to measure the current passing through the circuit and the
applied potential, respectively. The tank reactor with a capacity
of 1.5 ×103m3was made in PlexiglassTM and was provided
with inlet and outlet fittings for recirculation of the liquid.
Homogenisation of the effluent was ensured by magnetic stir-
ring at approximately 250 rpm. The gentle agitation allowed the
gases to be separated from the liquid, thus avoiding the formation
of foam which could affect the occurrence of electrocoagulation.
Fig. 2. Schematic diagram of experimental set-up. (1) dc power supply; (2) magnetic stirrer; (3) plexiglass reactor; (4) peristaltic pump; (5) electrochemical cell; (6)
aluminium electrodes; (7) conductimeter; (8) pH meter.
426 K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430
To avoid passivation of the electrodes, the electrochemical cell
was entirely cleaned after each experiment with detergent and
acetone, as described by Kobya et al. [15]. All experiments were
carried out at room temperature near 25 C.
One litre of fresh emulsion was introduced into the tank,
and after the NaCl was added, the selected current was applied
to the cell. At regular intervals, samples were collected and
pH was adjusted to 7 by the addition of aliquots of concen-
trated hydrochloric acid for optimal precipitation of aluminium
hydroxide as reminded in Fig. 1 [13]. The collected samples were
allowed to settle for 24 h, COD and turbidity were then deter-
mined from the clear fractions recovered. Contrary to previous
observations with others suspensions [29] the only adjustment
of pH did not result in visible COD abatement in the B22 oil sus-
pensions. It has to be mentioned that accidental entrainment of a
small sludge particle could occur drawing the clear liquid from
the settling tube, causing an unexpected additional error in the
analytical procedure. Replicates of most experiments were made
to overcome this experimental issue. Analysis of the results of
replicate experiments led to estimate that the global uncertainty
in determination of COD and turbidity was near 5%.
3. Results and discussion
3.1. General aspects
This study is mainly focused on the electrocoagulation treat-
ment of cutting oil emulsions with very high concentration for
investigation of the effects of the main operating parameters,
e.g. initial pH, current density, oil concentration and recircu-
lation rate. Turbidity and COD values were used to evaluate
the EC progress and the removal efficiency. For all cases, two
phases were observed during the discontinuous treatment: (i) a
“reactive” phase for which the abatement of COD and turbidity
increases regularly with time and (ii) a steady phase for which
further Al dissolution has no effect on the treatment efficiency.
The intercept between the two periods can be considered as the
minimum time required for the treatment, corresponding to the
minimum required concentration of dissolved Al.
The progress of electrocoagulation is to be linked to the
amount of dissolved aluminium. The theoretical concentration
of dissolved Al, CAl in g/L, can be expressed by Faraday’s law
as follows
CAl =eIt
nFV =eQ
nFV (10)
where M,I,t,n,Fand V, are, respectively the molecular weight
of aluminium (g/mol), the current (A), the electrolysis time (s),
metal valence (3 for Al), Faraday constant (96 500 C/mol) and
the emulsion volume in the overall circuit. Qis the electrical
charge passed during the galvanostatic runs and Φeis the current
yield. For appreciable change in the volume of the liquid in the
flow rig because of the repeated samplings, Eq. (10) had to be
modified accordingly. The current efficiency for Al dissolution
was previously found to be larger than unity [10,29], and the
actual concentration of Al can attain 150% of the theoretical
level, due to the chloride-induced dissolution mentioned above.
3.2. Effect of oil concentration
The experiences were followed at constant current density
(i= 100 A/m2), the initial pH of emulsion was adjusted to 7, and
the liquid velocity in the cell was 5.33 103m/s, corresponding
to 320 cm3min1through the 10 cm2cross-sectional area. We
observe in Fig. 3 that removal of COD and turbidity expressed
in %, are lower with higher oil concentration. This is can be
explained by the fact that higher amounts of Al ions are required
for the treatment of more concentrated oil suspensions. For a
2 vol.% emulsion, the treatment does not progress any further
after 35 min, the residual COD was equal to 1475mg O2/L, cor-
responding to 98% COD abatement. Final turbidity was near
507 NTU, corresponding to the same abatement. For higher
oil concentrations, the stationary plateau of COD and turbidity
was reached after more than 1 h. This result is not in agreement
with previous work [29] also conducted with suspensions of
machining oil, for which the abatement yield was observed to
be nearly independent of the amount of suspended matter. How-
ever, the dependence of the concentration was shown to largely
depend on the nature of the pollutant to be treated and latex
suspensions had been shown to behave like the present cutting
oil [29].
The above results were plotted on the basis of the specific
electrical charge per gram oil, Q/moil (Fig. 4). Such a plot shows
that the electrical charge required for the treatment of the inves-
tigated cutting oil – and the amount of dissolved aluminium –
is directly proportional to the concentration of oil in the emul-
Fig. 3. Time variations of COD (a) and turbidity (b) removal depending on the
oil concentration at i= 100 A/m2, initial pH 7, liquid flow rate = 320 cm3/min.
Oil concentrations: () 2%; (×) 4%; () 6%.
K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430 427
Fig. 4. Variations of COD (a) and turbidity (b) removal with the specific charge
(Q/moil) depending on the oil concentration at i= 100A /m2, initial pH 7, liquid
flow rate = 320 cm3/min. Oil concentrations: () 2%; (×) 4%; () 6%.
sion to be treated. Treatment conducted in the above conditions
appears to be completed upon application of 70 As/g oil.
3.3. Influence of the current density
Three current densities 100, 150 and 200 A m2were tested
for the treatment of 4 vol.% emulsions. The initial pH was the
natural pH of the diluted emulsion, around 9, and the flow rate
was 320 cm3min1. The results, expressed in the form of COD
and turbidity reduction versus time, are shown in Fig. 5. Dur-
ing the reactive phase, the reduction rate of COD and turbidity
were observed to increase with the current density. This can be
explained by the fact that the amount of Al3+ species formed
by dissolution of the anode, increases with the current den-
sity according to Faraday’s law (Eq. (10)) and previous results
[12,15,29]. Higher amounts of dissolved aluminium allowed
higher coagulation efficiency and more significant destabilisa-
tion of the emulsion. Moreover as shown by Khemis et al. [29],
higher production rates of hydrogen allowed by higher currents,
favors the flotation of the flocculated matter.
This is not true in the second phase of the treatment: during
this period the separation process is not controlled by coagula-
tion but by other phenomena, e.g. formation of solid, liquid/solid
aggregation and adsorption of destabilized particles onto solid
Al(OH)3formed. As done in Section 3.1, the data could be suc-
cessfully plotted versus the specific charge (Q/moil), as shown in
Fig. 6. For the initial pH considered, around 80 As/g are required
for the treatment of the emulsion whatever the current density.
Fig. 7 represents the variation of the emulsion pH during
the electrolytic run. The pH was observed to increase rapidly
during the reactive phase, then to stabilise at pH close to 11.
This progressive increase in pH is explained by the occurrence
of water electrolysis resulting in hydrogen evolution and pro-
duction of OHions which are partly buffered by the various
forms of Al-hydroxides. As can be expected from [20,21], and
demonstrated in Fig. 1, at pH equal or higher than 11, aluminium
hydroxide is mainly in the form of soluble forms, which is to
limit the efficiency of the flocculation process. The relative sta-
bilisation of the pH, for 80 As/g, corresponds to the end of the
3.4. Effect of liquid flow rate
The effect of the flow conditions on the electrocoagulation
efficiency of the liquid waste has been scarcely investigated. We
studied here the influence of this parameter for the treatment of
4 vol.% emulsions. As shown in Fig. 8, the EC progress observed
by the removal of COD and turbidity, was slightly better at high
flow rates. This result could be explained by the fact that more
steady convection allowed by higher flow rates are to improve the
rates of transport and transfer phenomena of the various species
in the electrochemical cell. In addition, higher flow velocity is
to induce a greater number of collisions between the particles
of Al(OH)3and the destabilized oil droplets, thus improving the
Fig. 5. Time variations of COD (a) and turbidity (b) removal depend-
ing on the current density; initial pH 9; oil concentration = 4%, liquid
flow rate = 320 cm3/min. Current density: () 100A/m2;(×) 150 A/m2;()
200 A/m2.
428 K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430
Fig. 6. Variations of COD (a) and turbidity (b) removal with the specific charge
(Q/moil) depending on the current density; initial pH 9, oil concentration = 4%,
liquid flow rate = 320 cm3/min. Current density: () 100 A/m2;(×) 150 A/m2;
() 200 A/m2.
However, we observed that the flow rate effect on the tur-
bidity abatement was more significant for the highest values of
current density (Fig. 8). This reveals the synergetic effect of: (i)
the anode dissolution, forming Al3+ and allowing coagulation,
(ii) the transfer phenomena by convective diffusion, and (iii) the
flocculation phenomena. However, the influence of the flow rate
on the COD abatement was more significant at low current den-
sities, and was hardly visible at 200 A m2. These observations
Fig. 7. Variation of the liquid pH with the specific charge (Q/moil) during the
electrocoagulation according to current density; initial pH 9, oil concentra-
tion = 4%, liquid flow rate = 320 cm3/min. Current density: () 100 A/m2;(×)
150 A/m2;() 200 A/m2.
Fig. 8. Time variation of COD (a) and turbidity (b) removal depending on the
flow recirculation, initial pH 9, i= 100 A/m2, oil concentration = 4%. Liquid flow
rate: () 130 cm3/min; () 320 cm3/min; (×) 520 cm3/min; () 750 cm3/min.
are illustrated in Fig. 9 which gives the influence of the flow
rate and the current density on the COD and turbidity abate-
ment, after 90 min of electrolysis, corresponding to maximum
treatment in all cases.
Fig. 9. Effect of the recirculation flow rate on removal efficiency, initial pH 9,
oil concentration = 4% and electrolysis time = 90 min.
K. Bensadok et al. / Journal of Hazardous Materials 152 (2008) 423–430 429
Table 2
Effect of the initial pH on efficiency removal after 60 min of electrolysis
Initial pH Final COD (mg O2/L) Final turbidity (NTU) COD removal (%) Turbidity removal (%) Final pH
3 10 036 24 587 91 52 6.8
5 9 856 20 083 91 61 7.8
6 8 652 630 92 99 8.0
7 10 058 610 91 99 8.4
9 28 516 19 024 74 63 10.5
11 43 251 23 581 60 54 10.6
Current density = 100 A/m2; oil concentration=4vol.%, i.e. (Q/moil) = 56.25 As/g; liquid flow rate = 750 cm3/min.
3.5. Effect of initial pH of emulsions
It has been established that the initial pH is an important
operating factor influencing the performance of EC process
[10,12,27]. To examine its effect, the pH of the emulsion to be
treated was adjusted to the desired value by aliquots of sodium
hydroxide or hydrochloric acid. The current density was fixed at
2and the oil concentration was 4 vol.%. Table 2 shows
the removal yields of COD and turbidity after 60 min of elec-
trolysis, depending on the initial pH. The maximum removals
of COD, and turbidity were observed at neutral pH 6–7, and this
is in agreement with many previous works related to EC using
aluminium electrodes [11,13,15]. For neutral or acidic pH, the
effect is less significant on the COD removal whose value is
higher than 90%. The drop in turbidity removal, in acid or basic
media, is in accordance with the amphoteric character of alu-
minium hydroxide Al(OH)3whose solubility increases as the
solution becomes either more acidic or alkaline (Fig. 1). Solid
precipitate of aluminium hydroxide formed at pH 6–7 is a pre-
cursor for oil removal by coagulation. Furthermore, as shown
in Table 2, the more acid the initial liquid is, the higher is the
increase in pH during the run. This phenomenon was ascribed
by Vik et al. [25] to hydrogen evolution at cathode and according
to reaction (2).
In alkaline medium (pH >7), the final pH does not vary very
much and a slight drop was recorded. However for initial pH over
10, ionic forms of Al-hydroxides predominate, which reduces
the efficiency of the treatment by electrocoagulation.
4. Conclusion
Electrocoagulation using aluminium electrodes is a feasible
process for treatment of very stable cutting oil emulsions, char-
acterized by high COD and turbidity. Whatever the operating
conditions, EC proceeds in two phases: a reactive phase in which
the removal efficiency increases regularly with time – and the
amount of dissolved Al – and a stationary phase for which fur-
ther energy consumption for solubilisation of aluminium anode
is useless. The reactive phase is as longer as the oil concentra-
tion is high, and can be reduced by using higher current density
and, to a lower extent by higher liquid recirculation rate. The
optimal initial pH was found equal to 6–7 and remain for which
the COD and turbidity removal correspond, respectively to 92
and 99%.
In spite of very important removal efficiency, the final val-
ues of COD (8652 mg O2/L) and turbidity (610 NTU) remain
higher than standard rejections (120 mg O2/L and 5 NTU). In
this fact, the EC process would be appropriate perfectly as pre-
treatment step prior to a membrane process. Besides, treatment
of the investigated cutting oil, although incomplete, consumes
from 60 to 80 As/g oil, corresponding to 5.6–7.4 mg Al/g oil
assuming a current efficiency at 100%. In reality, higher dissolu-
tion yields are to be expected, and the Al concentration required
would be of the order of 10 mg/g oil. This value is a positive
aspect of the technique, since the sludge to be produced by the
treatment is to have an Al content of 1 wt.%, which is satisfactory
in view to disposing the sludge in safe conditions.
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... In any case this trade-off warrants additional research. [42] Such a membrane treatment would effectively increase the cation retention of the system, while the permeate may be suitable for onsite reuse. Increased cation concentrations in the middle electrochemical cell compartment will also result in a more resilient system, as periodic increases in current demand will not result in complete depletion of cations in the Period VIII Period I -VII, IX middle compartment. ...
... This was likely due to the pH dependent solubility of some metal sulfides such as ZnS, NiS and FeS [40,41]. Al showed significant resolubilization, which most likely can be explained by the pH dependent solubility behavior of Al(OH)3 [42]. Such a resolubilization can be avoided by implementing a solid removal step after the bioreactor [37][38]. ...
Metallurgical wastewaters are characterized by a low pH (<4), high concentrations of sulfate (15 gSO42− L−1), and metal(loid)s. Current treatment requires the consumption of chemicals such as alkali and high levels of waste sludge generation. In this study, we have shown that combining water electrolysis and sulfate reducing bioreactors enables the in-situ generation of base and H2, eliminating the need for base and electron donor addition, resulting in the near-zero treatment of metallurgical wastewater. By extracting cations from the effluent of the system to the bioreactor, the bioreactor pH could be maintained by the in-situ production of alkali. The current for pH control varied between 112 – 753 mol electrons per m³ wastewater or 5 – 48 A m−2 electrode area. High concentrations of sulfate in the influent and addition of CO2 increased the current required to maintain a steady bioreactor pH. On the other hand, a high sulfate reduction rate and increased influent pH lowered the current required for pH control. Moreover, the current efficiency varied from 14% to 91% and increased with higher pH and cation (Na+, NH4+, K+, Mg2+, Ca2+) concentrations in the middle compartment of the electrochemical cell. The salinity was lowered from 70 – 120 mS cm−1 in the influent to 5 – 20 mS cm−1 in the system effluent. The energy consumption of the electrochemical pH control varied between 10 and 100 kWh m−3 and was affected by the conductivity of the wastewater. Industrial wastewater was treated successfully with an average energy consumption of 39 ± 7 kWh m−3, removing sulfate from 15 g SO42− L−1 to 0.5 ± 0.5 g SO42− L−1 at a reduction rate of 20 ± 1 gSO42− L−1 d−1..Metal(loid)s such as As, Cd, Cu, Pb, Te, Tl, Ni and Zn were removed to levels of 1 – 50 µg L−1.
... Other experimental conditions were consistent with the experimental conditions: distance between electrodes was 1.8 cm, magnetic stirring speed was 550 rpm, current density was 4.5 mA m 2 , experimental electrode was aluminum electrode, concentration of polymers in sewage is 800 mg/L. The change curves for the oil removal rate and turbidity data that were obtained under the experimental conditions of different values of initial pH (pH = 5, 6,7,8,9) are shown in Figs. 3 and 4, respectively. ...
... Indeed, Chloride ions significantly reduce the negative effects of other coexisting ions such as CO3 2and SO4 2which can form an insulating layer on the electrode surface and increase the resistance of the electrochemical cell [27]. In this study, we added 0.5 g/L of NaCl to the synthetic fluoride solution in order to assess its effect on removal efficiency. ...
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The present work has been focused on the removal of fluoride from aqueous solutions through the electrocoagulation process. This work aimed to assess the efficiency of electrodes and electrocoagulation process in fluoride removal from aqueous solutions. Batch experiments were carried out using monopolar Iron and Copper electrodes as anode and cathode. Fluoride removal were influenced by operating variables such as current density, nature of electrodes, initial fluoride concentration and NaCl amount which have significant effects on removal efficiency. Indeed, the increase of current density from 0.18 to 27.8 mA/cm 2 , fluoride removal efficiency increased from 61 to 98% using Fe electrodes while 57 to 63% using Cu electrodes during the electrolysis time indicating the high capacity of Fe electrodes for fluoride removal. The addition of NaCl solution increased the fluoride removal efficiency from 65% to 70% using Fe electrodes. Kinetics modelling revealed that Fluoride was removed on the surface of Fe electrodes following a pseudo-second order kinetic while pseudo-first order kinetic using Cu electrodes. Maximum energy consumption was 70 kWh/m 3 with water containing 0.5 g/L of NaCl while an energy of 45 kWh/m 3 for water without NaCl. Consequently, electrocoagulation technology is a promising method for defluoridation of water using iron electrodes.
... Different from the dosage experiment, the highest removal was determined for the Cd 2+ ions. At higher pH conditions, the solubility of Al 3+ decreases due to the formation of hydroxides and precipitation [39], interfering with its adsorption by Alg/CSPPh 2 beads. Therefore, pH 6.0 was selected as the optimal condition for further experiments. ...
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Among the many strategies utilized to improve the adsorption capacity of adsorbent materials, the modification of their chemical nature has been widely exploited, especially considering the polysaccharide-based adsorbents. Based on this, a phosphine-functionalized chitosan derivative (CSPPh 2) was associated with alginate (Alg), resulting in beads that were utilized to adsorb Cd 2+ and Al 3+ from water. After a complete characterization [Fourier transformed infra-red (FTIR), X-ray diffraction (XRD), thermogravimetric analyses (TGA/DTG), scanning electron microscopy (SEM), swelling analysis, and pH of point of zero charge (pH PZC)], adsorption experiments were performed to determine the optimal operational conditions. Under similar conditions, the Alg/CSPPh 2 showed superior adsorption performance compared to the beads prepared using raw chitosan. Moreover, the maximum adsorption capacities for Cd 2+ (78.2 mg/g) and Al 3+ (81.5 mg/g) were computed to Alg/CSPPh 2 beads under mild conditions (pH 6.0, 25 °C, 50 mg of adsorbent). The adsorption process for both metals was well-fitted by the pseudo-first-order kinetics and Freundlich isotherm model. Overall, the adsorption of these metals on Alg/ CSPPh 2 occurred via physical interaction forces, and the functional groups on the beads, including the-PPh 2 groups, have a pivotal role as binding sites. The post-utilized beads could be regenerated and reused up to 5 times consecutively with a slight decrease in their removal capacity. This study demonstrated that these original beads containing phosphine-functionalized chitosan are enhanced adsorbents to remove metal ions of different valences from the water environment.
Electrocoagulation with electrical polarity inversion was used to treat oil in water emulsions (145 ± 5 mg dm^(−3)) using a cylindrical 4.8 dm3 reactor in continuous mode. The effects of spatial time and time between polarity inversion were explored using a three-level full factorial design (3^2), followed by Spearman correlation (ps), which has shown that the aluminum concentration in the treated effluent is not directly dependent on the mass of aluminum released by the electrodes. Nonetheless, the loss of mass of the electrodes is correlated (ps = 0.6970) to oil removal and to less electric power consumption (ps = −0.6909). Surface response analysis revealed that increasing the number of inversion cycles reduces electrode degradation. The treatment reduced the effluent's chemical oxygen demand by over 92.8%. Regarding environmental impact, there is an inverse statistical correlation between aluminum in the treated effluent and oil removal (ps = −0.7426), indicating that removing more oil with less environmental impact is possible. The better condition, considering oil removal and lower electrode consumption, was obtained with a spatial time of 36 min and a polarity inversion time of 10 s; for this condition, oil removal reached 87.0% with an energy expenditure of about 7.21 kW h.m^(−3).
Municipal wastewater can include many pollutants that have an effect on the environment, so treatment is very necessary before discharge into water bodies and for further recycling in recreation and agriculture. As a result, in this study, municipal wastewater is treated using Electro Coagulation (EC) and Chemical Coagulation (CC), with comparisons of both processes. For EC, aluminum electrodes and iron electrodes were used at different voltages and times. Aluminum sulphate and ferric chloride were used in the CC, along with coagulant dosage and contact time. After treating the municipal wastewater for electrocoagulation, the maximum removal efficiency of COD, TOC, TDS, and BOD is 85%, 87%, 82%, and 81% for the aluminum electrode, respectively and 92%, 92%, 84%, and 88% for the iron electrode, respectively. For chemical coagulation, the maximum removal efficiency of COD, TOC, TDS, and BOD is 81.66%, 80.09%, 84.67%, and 77.08% for aluminum sulphate as a coagulant, and 86%, 83.90%, 87.73%, and 81.8% for ferric chloride as a coagulant. Electrocoagulation was found to be superior to chemical coagulation in this study. And Fe is a very promising electrode compared to Al.
α$\alpha $‐alumina production has been industrialized since many years ago. Nevertheless, there are still challenges in the efficient synthesis of α$\alpha $‐alumina with subtle specifications for high‐tech applications, specifically on large scales. So, here, we investigated the large‐scale synthesis of α$\alpha $‐alumina by the precipitation method and with industrial‐grade poly aluminum chloride (PAC) as the aluminum precursor, for the first time. The synthesis procedure was optimized in terms of synthesis yield and facilitation of α$\alpha $‐alumina formation by adjusting the concentration of the precursor (PAC) and precipitant (NaOH) solutions. The samples were characterized by conducting several analyses, including XRD, XRF, FE‐SEM, TEM, EDS, DLS, and gas adsorption (BET). The results indicated the significant effects of PAC and NaOH concentrations on the synthesis yield and facilitation of the α$\alpha $‐alumina formation. According to the results and process considerations, working at higher levels of PAC (0.75 gr/ml) and NaOH (1.0 M) concentrations was found to be the optimum synthesis conditions. Also, the potential of the optimized sample as the abrasive material and the catalyst support was evaluated. The results confirmed the high potential of the optimized sample in these applications. This study therefore introduces a promising and cost‐effective method for the large‐scale synthesis of versatile α$\alpha $‐alumina. This article is protected by copyright. All rights reserved
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Different industries such as petroleum refineries, food processing, restaurants, marine produce oily wastewaters with widely variable compositions and high pollutant levels. Studies have shown that efficient oil removal is achieved with electrocoagulation, EC, which is considered a new and effective wastewater treatment method that combines coagulation, flotation, sedimentation, and electrochemistry. During the EC process, metal ions are dissociated by applying an electric current, which hydrolyzes them and generates flocs to remove pollutants from the wastewater. The current study provides an overview of emerging electrochemical technology for oil-containing wastewater treatment with an overview of the origin and characteristics of oily wastewater. The treatment techniques for oily wastewater established thus far are briefly discussed. This review focuses on oil removal from polluted water by the EC process. Additionally, EC process efficiency, statistical research, and present challenges were discussed and reviewed. Some recommendations for future improvement trends of the EC method are presented.
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This contribution gives an analysis of the ecological parameters of the cutting fluids and its influence on the machinability parameters. Evaluation of quality parameters of the cutting fluids is based on output parameters of production process considering also ecological norms. Some results of machinability tests, which were done in tapping threads into standard reference steel C 45 E4 and Al-alloy AlMgSiPbBi for free cutting show how it is possible to achieve acceptable machinability parameters by use of new environment-friendly cutting fluid. The cutting parameters were chosen from the technological database with respect to particular machined material/cutting tool combinations. This approach has been used to quantify the performance of the existing products, compare products in the marketplace, and search for novel cutting aid additives.
Oily wastewater generated by steel and metal-finishing industries form emulsions which typically contain 100 to 30 000ppm of emulsified oil. Data on the breaking of O/W emulsions of commercial soluble oils using CaCl2 and AlCl3 as coagulants are reported. Demulsification rates were studied in a temperature range of 20 to 80°C and electrolyte concentrations of 5 to 40gl−1. The emulsion breaking efficiency study was followed by turbidity measurements. The process is controlled by droplet–droplet collisions.Droplet size distribution was measured by photon correlation spectroscopy and the effect of CaCl2 on the droplet size distributions is reported. The size increase of the droplets after the addition of the electrolyte indicates that the coalescence in an aggregate occurs instantaneously; therefore, the process could be described by the Smoluchosky's model of fast flocculation.The effect of electrolyte concentration and ionic charge on the zeta potential of soluble oils is also reported. The system shows good agreement with the electric double layer theory and the Schulze–Hardy rule.
The efficiency of electro‐coagulation as a turbidity removal process has been investigated using bentonite as a turbidity source. The influence of certain operational parameters such as current input, contact time, electrolyte concentration, and initial turbidity on the coagulation efficiency were studied. The process was found to achieve excellent turbidity removals. The lowest residual turbidities were 0.5 and 0.75 NTU for the samples with initial turbidities of 112 and 52 NTU, respectively. This was obtained at a current of 0.5 A, a contact time of 5 minutes, and a calculated dissolved iron concentration of 10.8 mg/l. At a constant current of 0.5 A, a reduction in the contact time from 5 to 2 minutes in the case of turbidity level 1 (52 NTU) and from 5 to 1 minute in the case of turbidity level 2 (112 NTU) resulted in better turbidity removals. The optimal operational parameters for turbidity level 1 are a current of 0.5 A, a contact time of 2 minutes and an NaCl concentration of 2 g/l resulting in a calculated amount of iron generated of 4.3 mg/1. However, for the case of turbidity level 2, the optimal values are a current of 0.5 A, a contact time of 1 minute and an NaCl concentration of 5 g/l with a calculated iron amount generated of 2.2 mg/l.
In spite of abundant literature on the topic, the efficiency of electrocoagulation for a specific effluent cannot be predicted in advance. Prior to designing an industrial wastewater treatment unit, preliminary treatment tests have to be done using different soluble oil wastes with a very high chemical oxygen demand (COD). The influence of various parameters can then be assessed. Coagulant dose, linked to the electrical charge passed and the nature of the waste, seem to be the controlling parameters of process efficiency. The results obtained at the laboratory-scale have been confirmed in a small pilot cell, and an industrial unit has been designed. A preliminary economic study shows that electrocoagulation may be competitive with current treatment technologies. From knowledge gained at bench-scale, we concluded that electrocoagulation appears to be a suitable process for treatment of soluble oily wastes with high COD.
The electrocoagulation of kaolinite and bentonite suspensions was studied in a pilot electrocoagulation system at the Western Research Center of CANMET to assess the operating cost and efficiency of the process. Factors affecting the operating cost such as, the formation of passivation layers on electrode plates, flow velocity and concentration of sodium chloride in the suspension were examined. The operating costs investigated in this paper were the power cost of the electrocoagulation cell and the material cost due to the consumption of the aluminum electrode. Comparison was based on the settling properties of the treated product: turbidity, settling rate, and cake height. Higher concentration of sodium chloride resulted in greater amount of aluminum dissolved chemically and electrochemically into the suspension and thus a better clarity of the supernatant of the treated product. Increased flow velocity could reduce significantly the operating cost while improving both clarity of the supernatant and the compactness of the sludge volume. The passivation layers developed quickly with time during the electrocoagulation process and more energy became wasted on the layers.
In waste water treatment, the use of a physico-chemical process by flotation would present some advantages compared to a separation by settling. However like each physico-chemical process, a separation by flotation needs a chemical destabilization. We have studied the use of an electrochemical destabilization coupled to a process of flotation (DAF). This paper presents the results obtained on an urban waste water treated by electrocoagulation and dissolved air flotation (DAF). To show the interest of coupling flotation and electrocoagulation, we have studied each process separately. Then we have combined the two processes. The role of each operation on pollution removal is presented. An effect of synergism between the two processes on the pollution abatement is shown. A reduction of 75% of the global COD is obtained. The results of the coupling are compared to the performance of an intensive treatment by flocculation-lamellar settler.