Emerging Technologies

Received: 17 March 2009 Revised: 8 April 2009 Accepted: 14 April 2009 Published online in Wiley Interscience: 28 May 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2214

Contributions of electrochemical oxidation

to waste-water treatment: fundamentals
and review of applications
Ángela Anglada, Ane Urtiaga∗ and Inmaculada Ortiz

Abstract
OVERVIEW: This paper provides an overview of some fundamental aspects of electrochemical oxidation and gives updated
information on the application of this technology to waste-water treatment. In recent years, electrochemical oxidation has
gained increasing interest due to its outstanding technical characteristics for eliminating a wide variety of pollutants normally
present in waste-waters such as refractory organic matter, nitrogen species and microorganisms.

IMPACT: The strict disposal limits and health quality standards set by legislation may be met by applying electrochemical
oxidation. However, treatment costs have to be cut down before full-scale application of this technology. Deployment of
electrochemical oxidation in combination with other technologies and the use of renewable sources to power this process are
two steps in this direction.

APPLICATIONS: Effluents from landfill and a wide diversity of industrial effluents including the agro-industry, chemical, textile,
tannery and food industry, have been effectively treated by this technology. Its high efficiency together with its disinfection
capabilities makes electro-oxidation a suitable technology for water reuse programs.

c 2009 Society of Chemical Industry

Keywords: electrochemical oxidation; waste-water treatment; process development; advanced oxidation processes

NOTATION line of investigation due to the high energy requirement of

Q = specific electrical charge (kAh m−3 )
W = specific energy consumption (kWh m−3 )
I = current intensity (A)
J = current density (A m−2 )
V = cell potential (V)
A = electrode area (m2 )
F = Faraday constant (96 487 C mol−1 )
v = volume of electrolyte (L)
n = number of exchanged electrons (mole− mol−1
pollutant)
[P]t = concentration of pollutant (mol L−1 ) at time t
[P]t+
t = concentration of pollutant (mol L−1 ) at time t +
t
t = time (s)
INTRODUCTION
In recent years, the appearance of pollutants that are recalcitrant
to conventional biological and chemical treatments together with
the stricter restrictions imposed by new legislation have caused
much research work to focus on waste-water treatment by electro-
oxidation processes. Electrochemical oxidation has been found to
be an environmentally benign technology able to mineralize
completely non-biodegradable organic matter and to eliminate
nitrogen species. Two lines of investigation have been followed:
(1) replacement of conventional processes by electrochemical
oxidation and (2) integration of electrochemical oxidation into
electro-oxidation. As electricity is basically the only consumable in
electrochemical oxidation, the use of photovoltaic (PV) modules as
a power supply is also envisaged as a possible means of reducing
the operating costs,1 providing a sustainable solution. This paper
considers the fundamentals of electrochemical oxidation and gives
a short overview on the potential applications of this technology
in waste-water treatment. Special emphasis is put on the latest
developments and some of the challenges that have yet to be
faced are highlighted.
ELECTROCHEMICAL OXIDATION OF WASTE-
WATERS
Figure 1 shows a conceptual diagram of an electrochemical reactor
for waste-water electro-oxidation,2 which includes a power supply,
a cathode, an anode and the electrolyte.
Electrochemical oxidation of pollutants can take place through
two different oxidation mechanisms as shown in Fig. 2: (1) direct
anodic oxidation, where the pollutants are destroyed at the anode
∗
Correspondence to: Ane Urtiaga, Department of Chemical Engineering,
University of Cantabria, Avenida de los Castros s/n, 39005 Santander, Spain.
E-mail: urtiaga@unican.es
1747

Department of Chemical Engineering, University of Cantabria, Avenida de los

a treatment plant. Current research is focusing on the second Castros s/n, 39005 Santander, Spain

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c 2009 Society of Chemical Industry
 www.soci.org Á Anglada, A Urtiaga, I Ortiz

Current supply Indirect oxidation

During indirect electrochemical oxidation, a strong oxidizing agent
+ - is electro-generated at the anode surface and then destroys the
pollutants in the bulk solution. The most common electrochemical
e- e-
oxidant is probably chlorine which is formed by the oxidation of
chloride at the anode. Although the role of active chlorine in the
oxidation of organic pollutants is not clear, ammonia oxidation is
usually acknowledged to take place through this mechanism.5,6
Anions The extensive use of active chlorine is due to the ubiquitous
presence of chloride in waste-waters and to its quite effective
Cations action. Other common oxidants that can be electrochemically
produced are hydrogen peroxide, peroxodisulfuric acid (H2 S2 O8 )
and ozone. Metal catalytic mediators (Ag+2 , Co+3 , Fe+3 , etc.) are
Anode Cathode
also employed for the generation of hydroxyl radicals, as occurs in
Oxidation Reduction
the electro-Fenton scheme. However, the use of metal ions may
processes processes
result in an effluent with a higher toxicity than that of the initial
Figure 1. Conceptual diagram of an electrochemical reactor. effluent. Thus, this approach requires a separation step to recover
the metallic species.7
surface; (2) indirect oxidation where a mediator (HClO, H2 S2 O8 and
others) is electrochemically generated to carry out the oxidation.
DESIGN OF AN ELECTROCHEMICAL OXIDATION
It has to be kept in mind that during electro-oxidation of aqueous
effluents, both oxidation mechanisms may coexist.3 PROCESS
In order to design an electrochemical oxidation system, the
electrode material, the configuration of the cell and the operating
Direct oxidation
conditions have to be taken into account.
Direct oxidation of pollutants takes place in two steps: (1) diffusion
of pollutants from the bulk solution to the anode surface and
(2) oxidation of pollutants at the anode surface. Consequently, Electrode material
the efficiency of the electrochemical process will depend on The choice of electrode material is of paramount importance as
the relationship between mass transfer of the substrate and it affects the selectivity and the efficiency of the process. The
electron transfer at the electrode surface. The rate of electron electrode material must have the following properties:
transfer is determined by the electrode activity and current
• High physical and chemical stability; resistance to erosion,
density.
corrosion and formation of passivation layers.
During anodic oxidation of organic pollutants, two different
• High electrical conductivity.
pathways can be followed:4
• Catalytic activity and selectivity.
• Electrochemical conversion. Organic compounds are only • Low cost/life ratio. The use of electrode materials that are
partially oxidized (Equation (1)). Therefore, a subsequent inexpensive and durable must be favoured.
treatment may be required.
In order to assess the selectivity of an anode material, competition
R −−−→ RO + e −
(1) between the oxidation of organics at the anode and the side
reaction of oxygen evolution must be considered:
• Electrochemical combustion. Organic compounds are trans-
formed into water, carbon dioxide and other inorganic 2H2 O −−−→ O2 + 4H+ + 4e− (3)
components:
The oxidation of water to oxygen occurs at approximately 1.2 V
R −−−→ CO2 + H2 O + Salts + e− (2) vs. NHE (normal hydrogen electrode). However, in fact, a higher

(a) (b)
Pollutants Mediator Pollutants

e- e- Oxidation
in the bulk

Destroyed Oxidant Destroyed

pollutants pollutants
Anode Anode
Electrolyte Electrolyte
surface surface
DIRECT OXIDATION INDIRECT OXIDATION
1748

Figure 2. Schemes for (a) direct and (b) indirect electrolytic treatment of pollutants.

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Contributions of electrochemical oxidation to waste-water treatment www.soci.org

Cell configuration
Table 1. Potential of oxygen evolution of different anodes, V versus
NHE8 One of the most important issues in cell design is to maintain
high mass transfer rates as the main reactions that take place
Anode Potential (V) Conditions in electrochemical oxidation processes take place on electrode
Pt 1.3 0.5 mol L−1 H2 SO4
surfaces. To improve mass transfer to the surface of the electrode,
Pt 1.6 0.5 mol L−1 H2 SO4
common methods such as gas sparging, high fluid velocity, use of
IrO2 1.6 0.5 mol L−1 H2 SO4 baffles and incorporation of various types of turbulence promoters
Graphite 1.7 0.5 mol L−1 H2 SO4 are employed. Sono-electrochemical processes have also been
PbO2 1.9 1 mol L−1 H2 SO4 tested to enhance mass transfer.8 Besides procuring a high mass
SnO2 1.9 0.5 mol L−1 H2 SO4 transfer rate, cell construction should account for easy access to
TiO2 2.2 1 mol L−1 H2 SO4 and exchange of cell components.11 In Fig. 3, an overview of the
Si/BDD 2.3 0.5 mol L−1 H2 SO4 various aspects that have to be considered in the design of an
Ti/BDD 2.7 0.5 mol L−1 H2 SO4 electrochemical reactor is shown.12
Two types of electrodes, mainly of two-dimensional and three-
dimensional construction exist. The latter guarantee a high value
of electrode surface to cell volume ratio. As can be seen in
voltage has to be applied for electrochemical oxidation of water Fig. 3, both types of electrodes can be classified into static
to occur at the anode. The difference between the value of the and moving electrodes. The use of moving electrodes leads
voltage at which the oxidation of water actually begins to take to increased values of the mass-transport coefficient due to
place, and the thermodynamic value is the oxygen evolution turbulence promotion. Among the two-dimensional electrodes,
overpotential.8 In Table 1, the oxygen evolution overpotential of static parallel and cylindrical electrode cells are used in the major
several electrode materials is presented. reactor designs in current studies of electrochemical oxidation of
Low O2 overvoltage anodes are characterized by a high elec- waste-waters. Cell designs using the parallel plate geometry in a
trochemical activity toward oxygen evolution and low chemical filter press arrangement are widely deployed due to the ease of
reactivity toward oxidation of organics. Effective oxidation of pol- scale-up to a larger electrode size, with more electrode pairs or an
lutants at these anodes may occur at low current densities; at high increased number of cell stacks.13
current densities, significant decrease of the current efficiency is Besides the electrode geometry and configuration, the configu-
expected due to the production of oxygen. In contrast, at high O2 ration of the cell (divided and undivided cells) has to be considered
overvoltage anodes, higher current densities may be applied with in the reactor design. In divided cells, the anolyte and catholyte
minimal contribution from the oxygen evolution side reaction. In are separated by a porous diaphragm or an ion conducting mem-
view of the afore mentioned facts, high O2 overvoltage anodes brane. For divided cells the choice of the separating diaphragm or
are usually preferred. In particular, boron-doped diamond (BDD) membrane is as important as the appropriate choice of electrode
anodes have been reported to yield higher organic oxidation rates materials for proper functioning of the electrolytic process. Over-
and greater current efficiencies than other commonly used metal all, the use of divided cells should be avoided whenever possible,
oxides such as PbO2 9 and Ti/SnO2 -Sb2 O5 .10 because separators are costly and tightening of a divided cell

Divided cell
Cell configuration
Undivided cell

Parallel plates

Static electrodes Concentric cylinders

2-dimensional Stacked discs

REACTOR DESIGN

electrodes
Parallel plates
Moving electrodes
Rotating electrodes
Electrode
configuration
Porous electrodes
Static electrodes
Packed bed electrodes
3-dimensional
electrodes
Active fluidized bed
Moving electrodes electrodes

Moving bed electrodes

Plug flow

Flow type
Perfect mixing
1749

Figure 3. Classification of electrochemical reactors in terms of cell configuration, electrode geometry and flow type.

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 www.soci.org
(reduction of electrode gap) is difficult and encounters a host of
mechanical and corrosion problems.11
In the case of flow characteristics within a reactor, two types
of limiting hydrodynamic behaviour may be considered, namely,
plug flow and perfect mixing.
Operating conditions
Among the variables that are usually modified in electrochemical
oxidation processes, the current density (intensity per unit area of
electrode) may be the term most frequently referred to because it
controls the reaction rate. It should be highlighted that an increase
in current density does not necessarily result in an increase in the
oxidation efficiency or oxidation rate and that for a given anode
material, the effect of current density on the treatment efficiency
depends on the characteristics of the effluent to be treated.
However, the use of higher current densities usually results in
higher operating costs due to the increase in energy consumption.
In contrast to current density, the effect of temperature on
the overall efficiency of the electro-oxidation process has not
been widely studied. It is generally acknowledged that direct
oxidation processes remain almost unaffected by temperature
whereas mediated oxidation processes do not.14 An improvement
with increasing temperature of the mediated oxidation processes
by inorganic electrogenerated reagents (active chlorine, perox-
odisulfate) has been reported. Nevertheless, operation at ambient
temperature is usually preferred as it provides electrochemical
processes with lower temperature requirements than those of
the equivalent non-electrochemical counterparts (i.e. incineration,
supercritical oxidation).
The physico-chemical characteristics of the waste-water (nature
and concentration of electrolyte, pH value and concentration
of target pollutants) also affect the electrochemical oxidation
process. Although no agreement has been reached on the effect
of the nature and concentration of electrolyte on the overall
oxidation efficiency, it has to be kept in mind that the higher the
concentration of electrolyte, the higher the conductivity and
consequently the lower the cell voltage for a given current
density. For this reason, electrochemical oxidation treatment is
more convenient and cost effective when the waste-waters to be
treated already have high salinity.
The pH value, like temperature, affects mostly indirect oxidation
processes. However, a review of previous publications does
not allow a conclusion to be reached on whether increasing
or decreasing pH favours pollutant removal in electrochemical
1.0
0.8
TOC/TOC0
TOC/TOC0
0.6
0.4
J
0.2
0.0
0 2 4 6
Time (h)
Figure 4. TOC dimensionless concentration profiles during the electrochemical treatment of phenol at different current densities:
50 A m−2 ,
1750
300 A m−2 and  600 A m−2 . Initial conditions: [phenol] = 470 mg L−1 ; [Na2 SO4 ] = 5000 mg L−1 ; pH = 2.3; T = 20 ◦ C; v = 1 L; anode area = 70 cm2 .
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c 2009 Society of Chemical Industry
Á Anglada, A Urtiaga, I Ortiz
oxidation of waste-waters. In chloride mediated reactions, the
pH value may affect the oxidation rate because it determines
the primary active chloro species that is present in the effluent.
During indirect oxidation, chlorine evolution occurs at the anode
(Equation (4)). At pH values lower than 3.3, the primary active
chloro species is Cl2 while at higher pH values its diffusion away
from the anode is coupled to its disproportionation reaction
to form HClO at pH<7.5 (Equation (5)) and ClO− at pH>7.5
(Equation (6)). In principle, operation at strongly acidic conditions
would be considered to be the best option as chlorine is the
strongest oxidant followed by HClO.15 However, the system setup
usually employed in electrochemical oxidation of waste-waters
promotes its desorption, hindering its action as an oxidizing agent.
Consequently, higher pH values would theoretically enhance the
electro-oxidation of pollutants, as HClO and ClO− are almost
unaffected by desorption of gases and they can act as oxidizing
reagents in the total volume of waste-water.14
Cl− −−−→ 1/2 Cl2 + e− (4)
Cl2 + H2 O −−−→ HOCl + H+ + Cl− (5)
− +
HOCl −−−→ OCl + H (6)
MEASUREMENT OF PROCESS EFFICIENCY
In electrochemical oxidation of waste-waters, the technical
feasibility of the process is evaluated as usual, in terms of the
percentage removal of pollutant reached, while the economic
feasibility is determined by the specific energy consumption. The
decrease in pollutant concentration during electro-oxidation of
waste-waters, as well as the evolution of any other parameter
during the process, can be represented against time or as a
function of the specific electrical charge:
J·A·t
Q= (7)
v
The rate of oxidation is determined from the concentration of
pollutant vs. time plot whereas the representation against Q
is a measure of the efficiency of the electro-oxidation process.
Disparities between both types of graphs only arise when the
influence of the current density is studied. To illustrate this point,
the evolution of the total organic carbon (TOC) concentration with
time and with Q during electrochemical oxidation of phenol by
means of a BDD anode is given in Fig. 4. The effect of current
1.0
0.8
0.6
0.4
0.2
J
0.0
0 5 10 15 20 25 30
Q (Ah/l)
◦
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Contributions of electrochemical oxidation to waste-water treatment
density in the range 150–600 A m−2 is shown. It can be seen that
although an increase in current density results in higher oxidation
rates (plot versus t), the oxidation efficiency decreased when the
current density increased from 150 to 300 A m−2 . Moreover, it
should be pointed out that the plots against Q constitute a means
of comparing the efficiency of the process at different scales, where
different anode areas per volume of effluent (A/V) are employed.16
There are specific energetic parameters (instantaneous current
efficiency (ICE), average current efficiency (ACE), electrochemical
oxidation index (EOI) and specific energy consumption (W)) that are
used to assess the energy efficiency of the process.7,17,18 Among
these, ICE is often used and measures the amount of current
intensity used on the destruction of the target pollutants, and the
occurrence and importance of side reactions. The occurrence of
side reactions can have different effects on the value of the ICE:
whereas the evolution of oxygen leads to a reduction of the ICE
value, the formation of electro-generated oxidants will only result
in a reduction of the ICE value when they do not contribute to the
elimination of the target pollutant. An ICE value of 1 indicates that
the applied intensity is being used for the oxidation of the target
pollutant completely.


[P]t − [P]t+
t
ICE = nFv (8)
I
t
Finally, the energy consumption (W) is directly related to the
specific electrical charge (Q, kAh m−3 ) and the cell potential (v):
W (kW hm−3 ) = Q · V (9)
ADVANTAGES AND DISADVANTAGES
Electrochemical oxidation provides several advantages for the
prevention and remedy of pollution problems. The inherent
advantage is its environmental compatibility as it uses a clean
reagent, the electron, and there is little or no need for addition
of chemicals. Likewise, electrochemical oxidation is generally
characterized by simple equipment, easy operation and brief
retention time. Other advantages include:12
(1) Robustness: the reaction can be terminated easily in seconds
by cutting off the power and it can also be restarted quickly
after an operation problem.
(2) Versatility: these processes can deal with many pollutants and
treat quantities from microlitres to millions of litres.
(3) Electrochemical processes often have lower temperature
and pressure requirements than those of equivalent non-
electrochemical counterparts such as incineration and su-
percritical oxidation. As a consequence, volatilization and
discharge of un-reacted wastes is avoided.
(4) Amenability to automation: the electrical variables used
in electrochemical processes (I,v) are particularly suited to
facilitating data acquisition, process automation and control.
The main drawback of this process is its high operating cost due
to the high energy consumption. Additionally, potential for the
formation of chlorinated organics during indirect oxidation by
active chlorine needs to be considered. Also, in order to apply
this technology, the effluent has to be conducting. Unfortunately,
not all waste streams will have sufficient conductance and the
addition of an electrolyte may be necessary. Moreover, electrode
fouling may occur due to deposition of material on the electrode
surface.
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APPLICATIONS OF ELECTROCHEMICAL
OXIDATION
The feasibility of electrochemical oxidation was first tested with
a wide variety of synthetic waste-waters containing a diversity
of target compounds. However, in recent years, research work
focusing on the treatment of actual waste-waters has increased.
Overall, the aim of these studies was mainly, to eliminate non-
biodegradable and/or toxic organic pollutants and ammonia
nitrogen contained in the effluent. Elimination of nitrite and
nitrate from waste-waters has also been studied, although to a
less extent. Moreover, several attempts have been made recently
at removal of micro-contaminants such as pharmaceuticals and
endocrine disrupting chemicals.19,20 As these contaminants are
usually present in concentrations in the region µg L−1 , the
achievement of high mass transfer rates in the electrochemical cell
is of paramount importance and is one of the main issues that needs
to be tackled before electrochemical oxidation can be applied
successfully in this field. Last, but not least, microorganisms can
be inactivated electrochemically21 directly or via the generation
of ‘‘killer’’ agents such as ·OH. Coupling of elimination of refractory
pollutants with disinfection of waste-waters in a single treatment
step poses an attractive compact alternative, especially in the
field of water reclamation and reuse where effective elimination
of pathogens is crucial to protect public health. Reduction
of COD concentration from 3820 to 78 mg L−1 and complete
elimination of microorganisms (initial count of 180 CFU mL−1 )
during electrochemical oxidation of latex waste-water represents
an example of the versatility of this technique.22 Nevertheless,
although many experimental studies have been carried out in this
field, the majority have been performed at laboratory scale and
only lately have investigations begun at pilot scale.15,23,24
The efficiency and flexibility of this technology has been proven
with a wide diversity of effluents as shown in Table 2. The main
conclusion drawn from these is that electrochemical oxidation
represents a useful solution when the presence of recalcitrant
and toxic pollutants prevents the use of conventional biological
treatments. Under appropriate conditions complete elimination
of COD, colour, ammonia and microorganisms can be achieved. In
contrast to other advanced oxidation processes such as ozonation
and Fenton oxidation that have been proposed for the treatment
of refractory residues, electrochemical oxidation does not lead to
Table 2. Application of electrochemical oxidation in treatment of
waste-water
Type of wastewater Reference
Chemical Industry:
Fine chemical industry 14,31
Pulp and Paper industry 28,41
Petrochemical industry 23,42
Pharmaceutical industry 42
Textile Industry 43,44,45
Tannery Industry 39,46,47
Food Industry 48,49,50
Agro-Industry
Olive oil 25,51–55
Dairy manure 56
Landfill leachate 15,30,57
Urban wastewater 20,32,58
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Electrooxidation
Biological
MBR
MBR
Chemical
coagulation
Electroenzymatic
Figure 5. Flow sheets for electrochemical oxidation treatment of waste-waters.
Figure 6. View of BDD electro-oxidation pilot plant in landfill leachate
treatment facility at Meruelo (Cantabria, Spain).
the accumulation of oxidation-refractory organics. For example,
significant differences were observed in the percentage of COD
removal obtained by electrochemical oxidation by means of a
BDD anode, Fenton oxidation and ozonation of the effluent
of a fine chemical manufacturing plant. Although total COD
removal was obtained by electro-oxidation, 80% and 50% were
the highest COD removal percentages achieved by ozonation
and Fenton oxidation respectively.25 In this context, electro-
oxidation has been successfully applied as a post-treatment to
Fenton oxidation to eliminate residual organic matter16,25 and to
oxidize ammonia,16 as the Fenton process was ineffective in the
1752
abatement of this pollutant. This confirms that electrochemical
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Á Anglada, A Urtiaga, I Ortiz
Effluent
Biological
Effluent
Electrooxidation
Effluent
Electrooxidation
Effluent
RO Electrooxidation
Effluent
Electrooxidation MBR
Effluent
Electrooxidation
oxidation is a technically feasible alternative to eliminate organic
pollutants. However, partial oxidation of ammonia to nitrate ions
has been reported. Deployment of electrochemical oxidation in
combination with ion exchange26 or reverse osmosis27 as a post-
treatment step could be a possible solution to this issue. Also,
high energy consumption is usually required limiting the further
full-scale commercial application. Two steps have been taken
to cut down treatment costs; (1) the use of this technology in
combination with other techniques as either a pre-treatment or
as a polishing step; (2) the use of renewable energy sources to
power electrochemical oxidation. Several flow sheets reported
for electro-oxidation-based wastewater treatment schemes are
shown in Fig. 5.
In this line of investigation, great effort is being put into the
integration of electrochemical oxidation with conventional bi-
ological processes. This system takes advantage of coupling a
biodegradation (reduction of operating cost) and a physicochem-
ical process (shorter retention time). When the effluent is first
subjected to electrochemical oxidation, biodegradability of the
organic pollutants is enhanced, improving the performance of
the subsequent biological process.28 In contrast, application of
electrochemical oxidation as a polishing step has the object of
completely mineralizing the refractory organic matter remaining
in the effluent after biological treatment. Panizza et al.29 demon-
strated that integration of a biofilm airlift suspension (BAS) reactor
with electro-oxidation by BDD anodes as a polishing step was
an effective means of treating a mixture of naphtalenesulfonates
contained in the infiltration water of a contaminated industrial
site. A reduction in energy consumption from 80 to 61 kWh m−3
was obtained after coupling the two processes. Other treatment
schemes that have been evaluated include: (1) electroenzymatic
oxidation followed by electrochemical oxidation;23 (2) membrane
bioreactor (MBR) followed by electro-oxidation;30 (3) chemical
coagulation followed by electro-oxidation and MBR;31 (4) MBR,
reverse osmosis and final electrochemical oxidation of the RO
concentrate.32
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Contributions of electrochemical oxidation to waste-water treatment
The encouraging results obtained so far during the treatment of
industrial wastes by combined methods involving electrochemical
oxidation set the basis for future work. Development of a sustain-
able process based on the integration of efficient technologies is
one of the key obstacles that have to be overcome before full-scale
implementation of electrochemical oxidation. Optimal treatment
schemes will eventually be decided upon achieving discharge
limits set by national or international environmental regulations
at a reasonable cost.33
At any rate, the selection of the best option relies on a
thorough understanding of the behaviour of each technology,
described by means of suitable mathematical models and
parameters. In this context, several models have been developed
in recent years to describe the electrochemical treatment of
waste-water containing organic pollutants and ammonia. One of
the first models to describe the electrochemical oxidation of
organic pollutants with non-active electrodes was developed
by Comninellis’ group and only considered direct oxidation
of organic contaminants.34 The model, characterized by its
simplicity, has shown excellent agreement with experimental
results obtained in the electro-oxidation by boron doped diamond
anodes of synthetic solutions of single organic compounds.
However, the model shows deviations when dealing with complex
mixtures such as those found in landfill leachates,15 where the
presence of electrogenerated secondary oxidants also contributes
to the overall kinetics. In contrast, the model developed by
Szpyrkowiczs’ group was able to describe the decolouration of
textile wastewaters35 when mediated oxidation by active chlorine
occurred. Mathematical models that describe the combined
contribution of both mechanisms to the overall oxidation of
organic pollutants have also been developed.36
As far as ammonia oxidation is concerned, empirical instead
of mathematical models have been mostly developed. Ammonia
oxidation is generally believed to occur through indirect oxidation
by active chlorine37,38 although some authors have observed that
direct and indirect ·OH oxidation may contribute to the overall
oxidation of this pollutant.39,40 Nonetheless, many of these models
still have to be validated for real waste-waters with complex
and unknown detailed composition. During the treatment of
real waste-waters, competitive reactions are known to occur at
the anode surface3,39 and the different species interact creating
complex scenarios. Recent attempts have been made to describe
these complex scenarios15 but due to the extremely diverse
features of waste-waters and electrode materials, a universal
approach has yet to be found.
PROCESS SCALE-UP
Despite the very good results obtained in laboratory scale
tests, a practical large-scale implementation of electrochemical
treatment of waste-waters has yet to be achieved. Progress in the
development of consistent mathematical models that describe
the complex scenarios and reactions involved in the electro-
oxidation of multicomponent mixtures of various pollutants, and
its integration with knowledge about reactor hydrodynamics will
undoubtedly contribute to this field. In 2007, a BDD electro-
oxidation pilot plant (Fig. 6) was installed in the context of a
project focusing on the treatment of landfill leachates using
advanced oxidation technologies. The raw leachate contains
about 2.8 g L−1 of TOC and 1.2 g L−1 of ammonia. On-site tests
were performed combining aerobic treatment, Fenton process
and electro-oxidation. The latter consists of an electrochemical
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reactor with 1.05 m2 of boron-doped diamond anodes. The overall
efficiency in the combined system was 99% organic matter
mineralisation: 50% of the initial TOC was degraded in the aerobic
treatment, 35% in the Fenton process and the remaining 15% in
the electro-oxidation step. The ammonia removal efficiency was
greater than 90%, of which 50% was due to the electrochemical
treatment, since the Fenton process was unable to reduce the
ammonia concentration. The results were consistent with the
predictions obtained from tests previously performed at laboratory
scale, showing the robustness of the system.16
CONCLUSIONS
Enormous advances have taken place in the development of
electrochemical oxidation processes for waste-water treatment.
Electrochemical oxidation processes have proven to be an
efficient and versatile technology able to handle a wide variety
of waste-waters. Nevertheless, to achieve an efficient and cost
competitive treatment, the waste-water should have relatively
high conductivity. Moreover, the advantage of coupling electron-
driven reactions (direct oxidation) with in situ generation of
oxidants (indirect oxidation) makes this technique an interesting
treatment alternative. In contrast, other treatment processes
that are being considered as a possible means of dealing
with refractory pollutants involve transportation and storage of
reactants and may cause, consequently, a significant problem for
safe processing. The main obstacles to be overcome before the full-
scale implementation of electrochemical oxidation is the reduction
of operating cost and the development of efficient and stable
electrode materials. Another major area for future research is the
improvement of the electrocatalytic activity and electrochemical
stability of the electrode materials for the development of better
and more cost-effective electrodes, which will result in lower
operational and capital costs.
ACKNOWLEDGEMENTS
The authors are grateful for the financial support provided by
the MICINN under projects PET2007-0431, CTM2006-00317 and
CTQ 2008-00690/PPQ. A. Anglada also thanks the MEC for a FPU
research grant.
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