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Chemical Engineering Journal 148 (2009) 97–105

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Influence of the anodic material on electrocoagulation performance

Ivonne Linares-Hernández a , Carlos Barrera-Díaz a,∗ , Gabriela Roa-Morales a ,
Bryan Bilyeu b , Fernando Ureña-Núñez c
a
Universidad Autónoma del Estado de México, Facultad de Química, Paseo Colón intersección Paseo Tollocan S/N, C.P. 50120, Toluca, Estado de México, Mexico
b
Xavier University of Louisiana, Department of Chemistry, 1 Drexel Drive, New Orleans, LA 70125, USA
c
Instituto Nacional de Investigaciones Nucleares, A.P.18-1027, Col. Escandón, Delegación Miguel Hidalgo, C.P. 11801, México, D.F., Mexico

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

Article history: The removal of organic pollutants from a highly complex industrial wastewater by aluminum, iron
Received 31 October 2007 and aluminum + iron electrocoagulation systems was evaluated. Under optimal conditions of pH 8 and
Received in revised form 14 July 2008 45.45 A m−2 current density, the electrochemical method yields a very effective reduction of all organic
Accepted 10 August 2008
pollutants. The optimal treatment (aluminum + iron) reduced chemical oxygen demand (COD) by 69%,
biochemical oxygen demand (BOD5 ) by 71%, color by 83%, turbidity by 80% and total coliforms by 99%. The
Keywords:
raw and treated wastewater was characterized by UV–vis spectroscopy and cyclic voltammetry to confirm
Combined Al–Fe electrode system
the increase in water quality. Finally, the sludge produced during electrocoagulation was characterized
Electrocoagulation
Industrial wastewater
by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDS).
COD reduction © 2008 Elsevier B.V. All rights reserved.

1. Introduction trol only by adjusting current makes automation quite easy

[15–17].
Billions of liters of industrial wastewater are produced every day. Usually, aluminum or iron plates are used as anodes in the elec-
The presence of dyes and organic substances constitute a substan- trocoagulation process. When a direct current voltage is applied,
tial source of pollution which exhibits intense color, high chemical the anodes dissolve to produce Al3+ or Fe2+ ions. The electro-
and biochemical oxygen demand and suspended particles. Colored chemically generated metallic ions are good coagulants. They can
wastewater can cause environmental problems by absorbing light hydrolyze near the anodes to produce a series of activated inter-
and interfering with fundamental aquatic biological processes. Sev- mediates that are able to destabilize the finely dispersed particles
eral kinds of treatments have been used to remove pollutants from present in the wastewater. The destabilized particles then aggre-
these effluents; unfortunately, most are not very effective in the gate to form flocs. At the same time, hydrogen bubbles produced at
case of mixed industrial wastewater [1,2]. the cathode can float most of the flocs. Thus, the aggregates formed
Electrocoagulation processes are a promising technology that can be removed by decantation or flotation from wastewater [18].
can be used for the removal of both color and colloidal particles A number of electrocoagulation studies have been carried out
[2–8]. Electrocoagulation is an electrochemical method of treat- by different types of wastewater using either iron or aluminum
ing polluted water whereby sacrificial anodes dissolve to produce as anodes. However, it has been noted that iron electrodes intro-
active coagulant precursors (usually aluminum or iron cations) into duce a green color into treated water which then turns yellow
solution. Additionally, electrolytic reactions evolve gas (usually as and turbid. This effect is due to the presence of Fe2+ ions which
hydrogen bubbles) at the cathode that can enhance the process; oxidize to Fe3+ in acidic or neutral conditions. The formation of
this effect is known as electroflotation [9–14]. Fe(OH)3 as result of the reaction of Fe3+ with OH− ions gives yel-
Electrochemical methods offer some advantages over tradi- low color to the water and increases turbidity. This phenomenon
tional chemical treatment: less coagulant ion is required, less is the reason for choosing aluminum electrodes for electrocoagu-
sludge is formed, and electrocoagulation equipment is very com- lation processes [19]. However, in the case of arsenic removal and
pact; thus, suitable for installation where the available space colored wastewater, iron electrodes are much more effective than
is rather limited. Furthermore, the convenience of dosing con- aluminum. The reason for this special case is that the adsorption
capacity of hydrous aluminum oxide for As(III) is higher than ferric
oxides [16]. Therefore, for an evaluation of the best performance of
∗ Corresponding author. Tel.: +52 722 2173890; fax: +52 722 2175109. electrocoagulation, a laboratory treatment of pollutants is required
E-mail address: [email protected] (C. Barrera-Díaz). to obtain the best removal yields [20,21].

1385-8947/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2008.08.007
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98 I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105

Only a very few reports on the combined use of both aluminum

and iron electrodes in the same cell has been published [22–25].
Aluminum has been used as sacrificial anode and stainless steel
or iron as cathode for removal of carbon black, clay, and suspended
solids without changing polarity of electrodes. The use of combina-
tion electrodes of dissimilar metals and the frequent change of their
polarity has not yet been studied, which may provide an alternative
method for efficient removal of both organic materials and heavy
metals from water. Recently arsenic removal efficiency of the Al–Fe
combination electrode system has been described [26]. However,
the use of combined aluminum and iron anodes in the same elec-
trolytic cell for industrial wastewater has not been reported. Thus,
the goal of this research is to investigate the influence of anodic
material on the electrocoagulation process for treating highly pol-
luted industrial wastewater.
The anodic materials used in the electrocoagulation process
were aluminum, iron and aluminum + iron plates. The effective-
ness of aluminum, iron, and aluminum + iron electrocoagulation
systems was evaluated and the influence of different operating
parameters optimized. The physicochemical characteristics of the Fig. 1. A schematic diagram of the electrochemical reactors.
wastewater before and after applying the electrochemical treat-
ments are presented.
2.3. Methods of analysis

2. Materials and methods The initial evaluation of the electrochemical treatment was
determined by analysis of the chemical oxygen demand (COD) and
2.1. Wastewater samples the color (465 nm, Pt/Co scale) at different time intervals. How-
ever, once the optimal conditions were found the raw and treated
Samples of wastewater were collected from a treatment plant wastewater samples were analyzed for the BOD5 and COD, color,
located at the end of an industrial park. This facility receives the pH, total coliforms, turbidity, iron and aluminum content, as indi-
industrial discharge of 144 different factories. All of the indus- cated in the Standard Methods procedures [27].
trial effluents enter the wastewater treatment plant together [18].
The actual wastewater treatment plant consists of shredders, sand 2.3.1. Cyclic voltammetric measurements
separators, oil and grease separators, primary clarifiers, biological Cyclic voltammetry of crude and treated wastewater was per-
activated sludge reactors, secondary clarifiers and a chlorine disin- formed using a standard three-electrode cell. The waveforms were
fecting unit. This treatment only achieves a 60% reduction in COD, generated by a potentiostat model Epsilon-BAS The carbon paste
which does not comply with environmental discharge standards. electrodes (CPE) were circular with a surface area of about 3.5 mm2 .
Thus, additional treatment steps are required to improve the quality The CPE was prepared from a 1:1 mixture of 99.99% pure single
of the water. crystal graphite (Alfa AESAR) and nujol oil (Fluka). The paste was
Wastewater samples were collected at the inlet of the biological transferred into a PVC tube and compacted to eliminate trapped
activated sludge reactor in plastic containers and cooled to 4 ◦ C, air then a copper conductor was inserted before the paste set. The
then transported to the laboratory for analysis and electrochemical surface of the electrode was renovated after each potential scan
treatments. [28]. The scan rate was 100 mV s−1 . The reference electrode was
an Ag/AgCl saturated with KCl and the counter electrode was a
2.2. Electrochemical reactors platinum wire.

Three different electrochemical reactors were used in this study. 2.3.2. UV–vis spectrometry
The main difference among them is the anodic material. The alu- UV–vis spectra were obtained from samples of raw and treated
minum and iron reactors have the same characteristics; both of wastewater using a double beam PerkinElmer 25 spectropho-
them are batch monopolar electrochemical reactors which con- tometer. The scan rate was 960 nm s−1 within the 200–700 nm
tain an array of 10 parallel electrodes. Each electrode has 0.11 m wavelength range. The samples were scanned in quartz cells with
long and 0.06 m wide which gives an area of 0.0132 m2 each a 1 cm optical path.
and a total anodic area, Aa of 0.066 m2 . A 4 dm3 recipient served
as the supply vessel for the reactor. A dc power source sup- 2.3.3. Thermodynamic analysis
plied the system with 1–4 A at 8 V, corresponding to a current The existence of aluminum and iron complexes in aqueous
density of 15.15–60.60 A m−2 . The electrochemical reactor with solution has been reported [29,30]. Using this information the dis-
aluminum–iron anodes contains an array of 12 parallel electrodes; tribution diagrams of chemical species were calculated using the
6 aluminum and 6 iron electrodes, alternating the aluminum and MEDUSA program [31].
iron. Each electrode is 0.11 m long and 0.06 m wide for an area
of 0.0132 m2 each and a total anodic area, Aa of 0.0792 m2 . The 2.3.4. Sludge characterization
volume of the reactor is 4 dm3 , the dc power source supplied the The sludge generated by the electrochemical technique was ana-
system with 1–4 A at 13 V, corresponding to a current density of lyzed by scanning electron microscopy (SEM) and energy dispersive
12.62–50.5 A m−2 . After various elapsed times, samples were taken. X-ray microanalysis (EDS). The analysis was performed on a Phillips
A schematic diagram of the electrochemical reactors is shown in XL-30 microscope to observe the composition and configuration of
Fig. 1. the structure. SEM provides images of rough material with resolu-
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Table 1
Physicochemical characteristic of the raw industrial wastewater

Parameter Value Discharge limits

in Mexico

COD (mg dm−3 ) 2000–2500 No value

BOD5 (mg dm−3) 900–1050 150
Color (Pt–Co U) 2500–4750 No value
Turbidity (NTU) 1400–1800 No value
pH 8 5–10
Fecal coliforms, MPN (mg dm−3 ) 110,000 No value
Total solids (mg dm−3 ) 5360 125

tion down to fractions of a micrometer, while energy disperse X-ray

spectroscopy offers in situ elemental analysis.

3. Results and discussion

3.1. Wastewater characteristics

Fig. 3. Aluminum species distribution in wastewater as a function of pH. The con-
centration of aluminum is [Al3+ ]TOT = 9.0 mM.
Table 1 shows the physicochemical characteristic of the raw
industrial wastewater and the discharge limits indicated in the
Mexican legislation. is Al(OH)3(s) . However, it is interesting to note that at pH greater
than 10 a new aluminum complex forms: Al(OH)4 − . This ion is sol-
3.2. Electrocoagulation using the aluminum anodes uble and directly affects the pollutant removal [3,5]. These results
electrochemical reactor agree with previous research, which indicate that the maximum
COD removal in wastewater is observed around pH 7 [4,32,33].
Wastewater samples were taken from the inlet of the biological COD removal is quite similar from pH 4 to 8. Since the actual
treatment tank, then electrochemically treated using the aluminum initial pH of the wastewater is around 8, further experiments were
reactor, adjusting the pH (using NaOH or H2 SO4 ) and applying 3 A of performed at this condition.
direct current with a treatment time of 60 min. The COD reduction The current density not only determines the coagulant dosage
as a function of treatment time at different initial wastewater pH rate but also the bubble production rate and size of the flocs, which
values is shown in Fig. 2. can influence the treatment efficiency of electrocoagulation [9,13].
As shown in Fig. 2, the maximum COD reduction occurs in the pH Therefore, the effect of current on the pollutant removal was inves-
range of 6–8 (46–50%). While the COD is reduced at all pH values, tigated. Fig. 4 shows the variation of the COD as a function of
the least effective was at pH 12 (<37%). current density, note that the best removal rate is achieved under
It is important to note in Fig. 2 that the influence of the pH on 45.45 A m−2 (50%) and no further increase in the COD removal
the COD removal in the range of 4–8 is not significant. Chemical is observed when the current density is increased to 60.6 A m−2
species associated with the aqueous pH are presented in Fig. 3. At (50.6%).
a pH below 3.5 the aluminum ion is the predominant specie. How- Using the aluminum electrochemical treatment the total col-
ever, at a pH 4–9.5 the predominant aluminum chemical specie iforms concentration was reduced by 99%, color was also reduced
by 85% and an 83% reduction in turbidity was observed.
The Al concentration in the wastewater plays an impor-
tant role in pollutant removal. Concentration and pH define the

Fig. 2. Effect of pH on COD reduction by Al electrode reactor, applying 3 A of direct Fig. 4. COD removal from wastewater at different current densities by Al electrode
current with a treatment time of 60 min. reactor, wastewater pH of 8 and treatment time of 60 min.
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100 I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105

Fig. 5. COD reduction in wastewater as a function of treatment time by Fe electrode reactor at different initial pH, and applying 3 A of direct current with a treatment time
of 60 min. Before (a) and after (b) precipitation of iron hydroxides with NaOH.

different possible Al chemical species present in aqueous solu- experimental conditions of 3 A of current and 60 min of electroly-
tion. sis along with the Faraday constant and the charge on the cation
The chemical dissolution process corresponds to the oxidation (z = + 3), it is possible to calculate the maximum amount of Al, in
of the aluminum plates with the simultaneous reduction of water this case 0.036 mol or 972 mg:
to form hydrogen [34], as shown in Eq. (1):
It
n= (6)
2Al(s) + 6H2 O → 2Al 3+
(aq) + 3H2(g) + 6OH(aq) −
(1) zF
The Al concentration in solution can be calculated using Eq. (7):
On the other hand, the electrochemical processes that occur
on the anode and on the cathode surfaces are represented in Eqs. n
[M] = (7)
(2)–(4). On the anode, aluminum dissolution and oxygen evolu- V
tion can compete. On the cathode, hydrogen evolution is the main where n is the number of moles and V is the volume (4 dm−3 )
expected reaction. of the reactor. The maximum expected Al concentration is thus
242 mg dm−3 . A particular effect that has been recently noted is
Al(s) → Al3+ (aq) + 3e− (2)
the so-called “superfaradaic efficiencies”. This term describes the
+ − difference between the theoretical amount of aluminum in aqueous
2H2 O → O2(g) + 4H (aq) + 4e (3)
solution and the actual Al detected. The detected Al concentra-
H2 O + e− → (1/2)H2(g) + OH− (aq) (4) tion in aqueous solution in the mixed solution is 358 mg dm−3
(previous to settling). The theoretical calculation corresponds to
The cathode may also be chemically attacked by OH− ions gen-
242 mg dm−3 , which implies that there is an excess of 50%. A pos-
erated during H2 evolution at high pH.
sible explanation of this difference is that a chemical process takes
2Al + 6H2 O + 2 OH− → 2Al (OH)4 − + 3H2 (5) place at the cathode promoting aluminum dissolution. The electro-
chemical oxidation and reduction of water can modify the pH on
The aluminum and hydroxide ions generated by electrode reactions
react to form Al(OH)3(s) .
Using Faraday’s law to calculate the maximum amount of Al
produced in the electrochemical process in Eq. (6) and with the

Fig. 6. Iron(II) species distribution diagram in wastewater as a function of pH. The Fig. 7. COD removal from wastewater in time in Fe reactor at different current
concentration of iron is [Fe2+ ]TOT = 18.0 mM. densities, wastewater pH of 8 and treatment time of 60 min.
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I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105 101

Fig. 8. COD reduction in wastewater in time by Al + Fe electrode reactor at different initial pH, and applying 3 A of direct current with a treatment time of 60 min. Before (a)
and after (b) precipitation of iron hydroxides with NaOH.

the anode and cathode surfaces with respect to the bulk pH. This The total coliforms, color and turbidity concentration were
is especially important on the cathode, where the pH can become reduced by 99%, 81% and 80%, respectively.
strongly alkaline. This can justify the important contribution of the The iron concentration in wastewater plays an important role
aluminum chemical dissolution in the cathode to the total dissolu- in pollutant removal. Concentration and pH define the different
tion rate [6]. possible iron chemical species present in aqueous solution. Using
Faraday’s law to calculate the maximum amount of Fe2+ produced
in the electrochemical process in Eq. (6), with the experimental
3.3. Electrocoagulation using the iron anodes electrochemical conditions of 3 A of current and 60 min of electrolysis along with the
reactor Faraday constant and the charge on the cation (z = + 2), it is possible
to calculate the maximum amount of Fe2+ to be 0.056 mol or 3.12 g.
In the case of iron anodes, wastewater samples were taken at The iron concentration in solution can be calculated using Eq.
different treatment times, as shown in Fig. 5, the best conditions (7): where n is the number of moles and V is the volume (3 dm−3 )
to obtain insoluble chemical specie starts at pH 9. Therefore, we of the reactor. The maximum concentration is thus 1042 mg dm−3
present two figures to show how the COD removal rate can be Fe2+ . A particular effect that has been recently noted is the so-called
modified if the final pH is adjusted. “superfaradaic efficiencies”. The detected Fe concentration in aque-
Fig. 5a and b shows the COD removal as a function of treatment ous solution in the mixed solution is 1150 mg dm−3 (previous to
time at different initial wastewater pH values. After certain elapsed settling). The theoretical calculation corresponds to mg dm−3 ; this
times, samples were taken and the supernatant (Fig. 5a) analyzed. implies that there is an excess of 10%.
At the same time, another set of samples were adjusted to final pH Electrocoagulation of wastewater using iron electrodes takes
9.5 using NaOH for precipitating iron hydroxides (Fig. 5b). place according to the following reactions [38]:
Fig. 5a shows that the maximum COD removal occurs at
pH 8 (53%) and the lowest at pH 12. Fig. 5b shows that
if pH is adjusted to 9.5, increasing precipitation, COD reduc-
tion increases, with the maximum reduction still at pH 8
(70%).
It is generally accepted that iron hydroxyl complexes form
after the initial oxidation at the anode and the highly insolu-
ble compound Fe(OH)2 is the predominant specie over a wide
pH range [35]. These results agree with previous research [36,37]
that at pH 5–9, the majority of iron complexes (coagulants)
are formed and this is the optimum pH range for carrying out
electrocoagulation. The minimum COD reduction was at pH 2,
since hydroxide ions generated at the cathode were neutralized
by H+ ions, limiting the formation of iron hydroxide complexes
(Fig. 6).
As previously discussed, COD reduction is quite similar from
pH 4 to 8. Since the actual pH of the wastewater is around 8, fur-
ther experiments were performed in this condition but final pH is
adjusted to 9.5, to improve the hydroxide precipitation.
Fig. 7 shows the variation of the COD as a function of current den-
sity, note that the best removal rate is achieved under 45.45 A m−2
(70%) and no significant increase in the COD removal is observed Fig. 9. COD reduction in wastewater in an Al + Fe reactor at different current densi-
when the current density is increased to 60.6 A m−2 (73%). ties, wastewater pH of 8 and treatment time of 60 min.
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102 I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105

Anodic reaction:

Fe(s) → Fe2+ (aq) + 2e− (8)

Cathodic reaction:

2H2 O(l) + 2e− → 2OH− (aq) + H2(g) (9)

Solution reaction

Fe2+ (aq) + 2OH− (aq) → Fe(OH)2(s) (10)

Overall reaction:

Fe(s) + 2H2 O(l) → Fe(OH)2(s) + H2(g) (11)

3.4. Electrocoagulation using the aluminum + iron anodes

electrochemical reactor

In the cases of the reactor with both aluminum and iron anodes,
wastewater samples were taken at specific treatment times as
shown in Fig. 8. The best conditions for forming the insoluble iron
complex starts at pH 9. Since final pH affects iron complex pre-
cipitation, analysis was done both straight out of reactor and after Fig. 10. Cyclic voltammograms recorded at the 3.5 mm2 CPE over a potential win-
treatment with NaOH as shown in Fig. 8a and b. dow of −1.5 to 1.45 V of the raw, aluminum, iron, and aluminum + iron treated
wastewater.
As shown in Fig. 8, minimal COD reduction occurs when the
initial pH is 2 or 12 and the maximum is at pH 8. In addition, post-
The reactions that are taking place are show below:
treatment addition of NaOH to encourage precipitation of the iron
hydroxides, increases the maximum COD removal from 50% to 69%.
Anodic reactions:
The distribution diagram of aluminum and iron chemical species
calculated from the MEDUSA program gives the same results as Al(s) → Al3+ (aq) + 3e− (12)
shown in Figs. 3 and 6. At low pH the aluminum ion is the predom-
inat specie in solution, from pH 3.3 to 10.0 Al(OH)3(s) is the most Fe(s) → Fe2+ (aq) + 2e− (13)
abundant chemical specie in the solution; however, above pH of 10 Cathodic reaction:
the soluble Al(OH)4 −1 appears in the solution causing the rediso-
lution of sludge. The iron species are: Fe2+ dominates up to pH 7.5, 2H2 O(l) + 2e− → 2OH− (aq) + H2(g) (14)
after which Fe(OH)2(s) remain. Solution reactions:
Since the COD reduction is quite similar from pH 4 to 8 and
the actual pH of the wastewater is around 8, the experiments were Fe2+ (aq) + 2OH− (aq) → Fe(OH)2(s) (15)
performed at that pH, but afterwards adjusted to about 9–10 to
Al3+ (aq) + 3OH− (aq) → Al(OH)3(s) (16)
improve the iron hydroxide precipitation.
The variation of the COD as a function of current density is shown Overall reaction:
in Fig. 9. The optimum reduction is achieved at 37.87 A m−2 (69%)
Fe(s) + Al(s) + 2H2 O(l) → Fe(OH)2(s) + Al(OH)3(s) + H2(g) (17)
with only a slight increase when the current density is increased to
50.5 A m−2 (71%).
The aluminum + iron combined electrochemical treatment
reduces total coliforms, color and turbidity by 99%, 83% and 80%,
respectively.
Using Faraday’s law in Eq. (6), with the experimental conditions
of 3 A of current and 60 min of electrolysis along with the Faraday
constant and the charge on the cation (z = + 3), the calculated max-
imum amount of Al is 0.036 mol or 972 mg. The Al concentration in
solution is calculated using Eq. (7) to be 242 mg dm−3 .
Likewise, the calculated maximum amount of Fe2+ is 0.056 mol
or 3.12 g and the corresponding maximum concentration is
782 mg dm−3 Fe2+ .
The detected Fe and Al concentration in aqueous solution in
the mixed solution were found to be quite similar to the expected
theoretical values.

Table 2
COD reduction kinetics, using first- and second-order equations

Electrode First-order model Second-order model

K (min−1 ) r2 K × 10−5 (dm3 mg min−1 ) r2

Aluminum 0.026 0.984 2 0.997

Fig. 11. UV–vis spectra of the raw, aluminum, iron, and aluminum + iron treated
Iron 0.050 0.985 4 0.999
wastewater, The scan rate was 960 nm s−1 within the 200–700 nm wavelength range.
Aluminum + iron 0.044 0.958 3 0.991
The samples were scanned in quartz cells with a 1 cm optical path.
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I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105 103

Table 3
A comparative results obtained by the three anodic experiments.

Parameter Raw wastewater Aluminum Iron Aluminum–iron

Concentration % Removal Concentration % Removal Concentration % Removal

−3
COD (mg dm ) 2202 1107 50 660 70 687 69
BOD5 (mg dm−3) 1030 552 46 315 70 300 71
Color (Pt–Co U) 3525 535 85 650 81 600 83
Turbidity (NTU) 1975 320 83 388 80 388 80
Total coliforms, MPN (mg dm−3 ) 1.1 × 105 <3 >99 <3 >99 <3 >99
Sludge (kg m−3 ) NA 11 NA 20 NA 9.6 NA
Al and/or Fe (mg dm−3 ) <1.0 21.37 NA 0 NA 9.0 NA

3.5. COD reduction velocity (Eq. (18)):

dCCOD
The COD reduction velocity can be obtained using a kinetic = −k[CCOD ]2 (18)
dt
model. Recent research describes that the kinetic constant can
be obtained using the drop of the pollutant and discarding the where CCOD represents the COD (mg dm−3 ), t represents the time,
points that remain constant in wastewater [39]. The COD reduction and k the rate constant or the velocity at which the pollutant is
kinetics was evaluated using the first and second-order equations being removed from wastewater (dm3 mg min−1 ).
(Table 2) through a final electrolysis time of 60 min, pH 8 and 3 A. Recent research indicates that this model represents the COD
The second-order model best fits the decrease in COD with time is reduction kinetics for electrocoagulation treatment [33].

Fig. 12. Micrographs and elemental analysis of the sludge generated by aluminum (a), iron (b), and aluminum + iron and (c) electrocoagulation process.
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104 I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105

3.6. Comparative results iron was more effective in reducing COD, therefore the optimum
practice is to combine aluminum + iron for obtaining high COD and
Once the optimal conditions were found the raw and treated color removal efficiencies.
wastewater samples were analyzed using the BOD5 and COD, total
coliforms and turbidity. Table 3 shows the efficiencies obtained. Acknowledgements
Both aluminum and iron are almost equally effective in reducing
fecal coliforms and turbidity. However, aluminum was found to be The authors wish to acknowledge support given by the Uni-
more effective in removing color than iron. versidad Autónoma del Estado de Mexico, especially the Facultad
However, aluminum was found to be more effective in remov- de Química (projects 2452/2007 and 2425/2007) and the SNI for
ing color than iron and iron was more effective in reducing COD. supporting research.
The effluent treated with iron as the sacrificial anode appeared yel-
low, then turned brown. This behavior is attributed to the excess of References
iron ions generated during the electrolysis. The charge of Al (3+ ) is
greater than Fe (2+ ), so the removal capability of Al is greater than [1] J.G. Ibanez, M.M. Singh, Z. Szafran, Laboratory experiments on electrochemical
Fe. COD is a measure of oxidizable components of solution including remediation of environment. IV. Color removal of simulated wastewater by
electrocoagulation–electroflotation, J. Chem. Educ. 75 (1998) 1040–1041.
organics (dye, etc.) and inorganics (Fe (2+ ), among others). So, the [2] A.H. Essadki, M. Bennajah, B. Gourich, Ch. Vial, M. Azzi, H. Delmas, Electrocoag-
oxidation capability of Fe increases the COD removal value while for ulation/electroflotation in an external-loop airlift reactor—Application to the
determination of correct COD removal value of the solution, the Fe decolorization of textile dye wastewater: a case study, Chem. Eng. Process. 47
(2008) 1211–1223.
must be removed from solution because Fe (2+ ) was oxidized to Fe [3] M. Bayramoglu, M. Eyvaz, M. Kobya, Treatment of the textile wastewater by
(3+ ) and increases the COD removal value. Indeed, aluminum + iron electrocoagulation economical evaluation, Chem. Eng. J. 128 (2007) 155–161.
was combined to gain the advantages of both. [4] M. Kobya, E. Demirbas, O.T. Can, M. Bayramoglu, Treatment of levafix orange
textile dye solution by electrocoagulation, J. Hazard. Mater. 132 (2006) 183–188.
[5] N. Daneshvar, H. Ashassi Sorkhabi, M.B. Kasiri, Decolorization of dye solution
3.7. Cyclic voltammetry measurements containing acid red 14 by Electrocoagulation with a comparative investigation
of different electrode connections, J. Hazard. Mater. 112 (2004) 55–62.
[6] P. Cañizares, F. Martínez, M. Carmona, J. Lobato, M.A. Rodrigo, Continuos elec-
Cyclic voltammetry of raw and treated wastewater was per-
trocoagulation of synthetic colloid-polluted wastes, Ind. Eng. Chem. Res. 44
formed using a standard three-electrode cell. A chemically (2005) 8171–8177.
irreversible oxidation peak at a potential lower than that corre- [7] C. Tsouris, D.W. DePaoli, J.T. Shor, M.Z.-C. Hu, T.-Y. Ying, Electrocoagulation for
magnetic seeding of colloidal particles, Colloids Surf. 177 (2001) 223–233.
sponding to oxygen evolution is seen in Fig. 10 indicating the
[8] S.S. Vaghela, A.D. Jethva, B.B. Mehta, S.P. Dave, S. Adimurthy, G. Ramachandra-
reduction in COD. iah, Laboratory studies of electrochemical treatment of industrial azo dye
effluent, Environ. Sci. Technol. 39 (2005) 2848–2855.
3.8. UV–vis spectrometry [9] P.K. Holt, G.W. Barton, C.A. Mitchell, The future of electrocoagulation as a local-
ized water treatment technology, Chemosphere 59 (2005) 355–367.
[10] X. Chen, G. Chen, P.L. Yue, Investigation on the electrolysis voltage of electro-
The UV–vis spectra of the raw, Al, Fe and Fe + Al electrochemi- coagulation, Chem. Eng. Sci. 57 (2002) 2449–2455.
cally treated wastewater are shown in Fig. 11. There is a continuous [11] M. Khemis, J.P. Leclerc, G. Tanguy, G. Valentin, F. Lapicque, Treatment of indus-
trial liquid wastes by electrocoagulation: experimental investigations and an
signal curve in the region around 200–700 nm in the spectra cor- overall interpretation model, Chem. Eng. Sci. 61 (2006) 3602–3609.
responding to components of the wastewater. It is interesting [12] X. Chen, G. Chen, P.L. Yue, Separation of pollutants from restaurant wastewater
that the intensity of the curves decrease by anodic effects. These by electrocoagulation, Separ. Purif. Technol. 19 (2000) 65–76.
[13] N. Adhoum, L. Monser, Decolourization and removal of phenolic compounds
results indicate that there is a significant color reduction of the raw from olive mill wastewater by electrocoagulation, Chem. Eng. Process. 43
wastewater when the electrochemical treatments are applied. (2004) 1281–1287.
[14] G. Chen, Electrochemical technologies in wastewater treatment, Separ. Purif.
Technol. 38 (2004) 11–41.
3.9. Sludge characterization
[15] J.Q. Jiang, N. Graham, C. André, G.H. Kelsall, N. Brandon, Laboratory study
of electro-coagulation-flotation for water treatment, Water Res. 36 (2002)
SEM and EDS provides information about the morphology and 4064–4078.
elemental composition of the sludge generated by aluminum, iron, [16] P. Ratna Kumar, S. Chaudhari, K.C. Khilar, S.P. Majan, Removal of arsenic from
water by electrocoagulation, Chemosphere 55 (2004) 1245–1252.
and aluminum + iron electrocoagulation process. Fig. 12 shows dif- [17] C. Barrera-Díaz, M. Palomar-Pardavé, M. Romero-Romo, S. Martínez, Chemi-
ferent morphological images of the sludge. Fig. 12a shows the cal and electrochemical considerations on the removal process of hexavalent
aluminum sludge flocs composed primarily of aluminum com- chromium from aqueous media, J. Appl. Electrochem. 33 (2003) 61–71.
[18] I. Linares-Hernández, C. Barrera-Díaz, G. Roa-Morales, B. Bilyeu, F. Ureña-Nuñez,
pounds. Fig. 12b shows the iron treatment sludge composed mainly A combined electrocoagulation–sorption process applied to mixed industrial
of iron compounds. Fig. 12c shows the aluminum + iron treatment wastewater, J. Hazard. Mater. 144 (2007) 240–248.
sludge with both aluminum and iron present in the structure. [19] C. Barrera-Díaz, F. Ureña-Núñez, E. Campos, M. Palomar-Pardavé, M. Romero-
Romo, A combined electrochemical-irradiation treatment of highly colored and
Previous research indicates that when combined Fe and Al elec- polluted industrial wastewater, Rad. Phys. Chem. 67 (2003) 657–663.
trodes where used in a single electrochemical cell for As removal, [20] A. Vlyssides, E.M. Barampouti, S. Mai, Degradation of methylparathion in aque-
the sludge seem to be amorphous/poorly crystalline phases for ous solution by electrochemical oxidation, Environ. Sci. Technol. 38 (2004)
6125–6131.
aluminum hydroxide/oxyhydroxides (bayerite (Al(OH)3 ), diaspore [21] Z. Zaroual, M. Azzi, N. Saib, E. Chainet, Contribution to the study of electro-
(AlO(OH)), and iron oxyhydroxides (lepidocrocite (FeO(OH)), mag- coagulation mechanism in basic textile effluent, J. Hazard. Mater. 131 (2006)
netite (Fe3 O4 ), iron oxide (FeO)) [26]. 73–78.
[22] D.P. Avetisyan, A.S. Tarkhanyan, L.N. Safaryan, Electrofloatationcoagulation
removal of carbon black from acetylene production wastewaters, Sov. J. Water
4. Conclusions Chem. Technol. 6 (1984) 345–346.
[23] P.K. Holt, G.W. Barton, M. Wark, C.A. Mitchell, Aquantitative comparison
between chemical dosing and electrocoagulation, Colloids Surf. A 211 (2002)
The use of iron or aluminum as sacrificial electrodes in the treat-
233–248.
ment of wastewater by electrocoagulation has been found to be [24] A.I. Ivanishvili, V.I. Przhegorlinskii, T.D. Kalinichenko, Comparative evaluation
dependent on both pH and current density. Under the same opera- of the efficiency of electrocoagulation and reagent methods of clarifying waste
tional conditions aluminum and iron electrodes are almost equally water, Sov. J. Water Chem. Technol. 9 (1987) 468–469.
[25] V.K. Syrbu, R.V. Drondina, A.M. Romanov, A.I. Ershov, Combined electroflotoco-
effective in reducing fecal coliformes and turbidity. However, alu- agulation apparatus for water purification, Elektronnaya Obrabotka Materialov
minum was found to be more effective in removing color, while (Electron Treat. Met.) (1986) 57–59.
 Author's personal copy

I. Linares-Hernández et al. / Chemical Engineering Journal 148 (2009) 97–105 105

[26] A.G. Jewel, Gomesa, A Praveen Daida, a Mehmet Kesmez, A Michael Weir, H. [34] T. Picard, G. Cathalifaud-Feuillade, M. Mazet, C. Vandensteendam, Cathodic
Morenoa, R. Jose, B. Parga, C. George Irwin, D. Hylton McWhinney, D. Tony Grady, dissolution in the electrocoagulation process using aluminium electrodes, J.
A. Eric Peterson, L. David, Cocke, Arsenic removal by electrocoagulation using Environ. Monit. 2 (2000) 77–80.
combined Al–Fe electrode system and characterization of products, J. Hazard. [35] D. Ryan, A. Gadd, J. Kavanagh, M. Zhou, G. Barton, A comparison of coagulant
Mater. B139 (2007) 220–231. dosing options for the remediation of molasses process water, Separ. Purif.
[27] APHA, AWWA, Standard Methods for the Examination of Water and Wastewa- Technol. 58 (2008) 347–352.
ter, 19th edition, American Public Health Association, Washington, DC, 1995. [36] M.Y.A. Mollah, P. Morkovsky, J.A.G. Gomes, M. Kesmez, J. Parga, D.L. Cocke, Fun-
[28] G. Roa-Morales, L. Galicia, M.T. Ramírez-Silva, Evidence of ternary inclusion damentals, present and future perspectives of electrocoagulation, J. Hazard.
complexes formation using factorial design and determination of constant, J. Mater. B 114 (2004) 199–210.
Incl. Phenom. 46 (2003) 139–145. [37] N. Daneshvar, A.R. Khataee, A.R. Amani Ghadim, M.H. Rasoulifard, Decoloriza-
[29] M.R. Smith, A.E. Martell, Critical Stability Constants, Plenum Press, USA, 1974. tion of C.I. Acid Yellow 23 solution by electrocoagulation process: investigation
[30] C. Baes, R. Mesmer, The Hydrolysis of Cations, Robert E. Kriegeer, Malabar, FL, of operational parameters and evaluation of specific electrical energy consump-
1986. tion (SEEC), J. Hazard. Mater. 148 (2007) 566–572.
[31] I. Puigdomenech, Hydrochemical Equilibrium Constants Database (MEDUSA), [38] M. Bayramoglu, M. Kobya, O.T. Can, M. Sozbir, Operating cost analysis of elec-
Royal Institute of Technology, Stockolm, 1997. trocoagulation of textile dye waste water, Separ. Purif. Technol. 37 (2004)
[32] G. Mouedhen, M. Feki, M. De Petris Wery, H.F. Ayedi, Behavior of Aluminium 117–125.
electrodes in electrocoagulation process, J. Hazard. Mater. 150 (2008) 124–135. [39] B. Boye, M. Dieng, E. Brillas, Degradation of herbicide 4-chlorophenoxyacetic
[33] M. Kobya, H. Hiz, E. Senturk, C. Aydiner, E. Demirbas, Treatment of potato acid by advanced electrochemical oxidation methods, Environ. Sci. Technol. 36
chips manufacturing wastewater by electrocogulation, Desalination 190 (2006) (2002) 3030–3035.
201–211.