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CONTENTS

1. ELECTROCHEMICAL WASTEWATER TREATMENT TECHNOLOGIES 1.1 What happens inside an electrochemical cell during the electrolysis of a wastewater? 1.2 Types of electrochemical wastewater treatment technologies 1.3 Advantages of electrochemical technologies in environmental remediation ELECTROCOAGULATION 2.1 What is coagulation? 2.2 The electrochemically-assisted coagulation: fundamentals
2.2.1 ANODE MATERIALS 2.2.2 ELECTRODISSOLUTION 2.2.3 ELECTROLYTIC GENERATION OF OXYGEN AND HYDROGEN 2.2.4 MAIN PROCESSES INVOLVED IN THE ELECTROCHEMICALLY ASSISTED TECHNOLOGIES FOR COLLOID-POLLUTED WASTES

2.

2.3 Electrochemical cells


2.3.1 TANK CELLS 2.3.2 FLOW CELLS 2.3.3. PROMOTION OF THE ELECTROFLOTATION PROCESS 2.3.4 OTHER PROCESSES

3.

2.4 Electrocoagulation of soluble organics and break-up of emulsions. Removal of phosphates 2.5 Advantages and disadvantages of electrocoagulation ELECTRO-OXIDATION 3.1 Fundamentals 3.2 Electrode materials 3.3 Electrochemical cell
3.3.1 IS IT RECOMMENDED THE USE OF DIVIDED CELLS? 3.3.2 STIRRED-TANK CELLS 3.3.3 SINGLE-FLOW CELLS 3.3.4 FILTER-PRESS CELLS 3.3.5 OTHER CELLS

3.4 Indirect electrochemical oxidation processes 3.5 Advantages of the electrooxidation technologies 3.6 Combined processes

1.1 What happens inside an electrochemical cell during the electrolysis of a wastewater?
Power supply

e-

e-

Ox influent
Anode

5. Migration of anions

Red
Cathode

1. Electrooxidation

2. Electroreduction

Red M

Ox
M Mn+

5. Migration of cations 3. Electrodissolution 4. Electrodeposition Mn+

effluent

Diluted solution

Anionic membrane

Cathionic membrane

Anionic membrane

Cathionic membrane

Concentrated solution

1.2 Types of electrochemical wastewatertreatment technologies

anode

cathode

Anions

electrodialysis

Feed solution

Cations

Electro-oxidation

electrocoagulation

Electrodeposition
metal

Rotational cathode

anode Electrolyte flux

1.3 Advantages of electrochemical technologies in environmental remediation

Environmental compatibility: the main reagent used is the electron No residues are formed.
Versatility: Many processes occur simultaneously in any electrochemical cell. Plethora of reactors, electrode materials, shapes, configuration can be utilized and allow to promote different kinds of treatment technologies. Point-of-use production of chemicals is facilitated by electrochemical technology Volumes of fluid from microliters to thousand of cubic meters can be treated

Processes work at room temperature and atmospheric pressure


Selectivity: the applied potentials can be controlled to selectively attack specific compounds. Easy operation. Amenability to automation. Cost effectiveness

2. ELECTROCOAGULATION
2.1 What is coagulation?
Pollutants size
100 micras 10 micras 1 micra 0.1 nm 100 nm 10 nm 1 nm 1 mm 1 cm

Dissolved comp. Colloids Suspended solids

influent

Diameter of the particle (mm) 10 1 0.1 10-2 10-3 10-4

Time needed to settle 1 m (aprox) 1s 10 s 2 min. 2h 8d 2 years

effluent

Typical hydraulic residence time of a settler for wastewater treatment

Sludge

Bulk solution

Interaction energy

Negatively charged particle

+ + + ++ + + + + + + + - + + + + + + + ++ ++ + + + + + +

Ea Ea+Eb

Diffuse layer -(electrostatic potential)

Surface potential

Eb

Distance between particles

Zeta potential
Distance from the surface

Electrostatic repulsion energy: Ea Van der Waals attraction energy: Eb Resulting energy : Ea+Eb

Coagulation is a chemical treatment which consists of the addition of chemical reagents to reduce the electrical repulsion forces that inhibit the aggregation of particles.

Hydrolysing metal salts (iron, aluminium)

Particles stabilized by electrostatic repulsion forces

Compression of the diffuse layer by an increase of the ionic strength

Neutralization of superficial charges by adsorption of ions

Precipitation Charge Neutralization

Interparticle bridging

Enmeshment in a precipitate

Conventional Chemical Coagulation consists of the direct dosing of a coagulant solution to the wastewater.

Chemical reagent

Outlet
Inlet

coagulation flocculation
Sludge

sedimentation

Flocculation is a physical treatment in which the collision of coagulated colloids is promoted in order to make possible the formation of larger particles. The result of both processes is a wastewater in which the size of the particles is enough to be separated by a settler or a flotation unit.

Coagulation by hydrolysing aluminium salts


Al3+

Log [Alx(OH)y 3x-y ] / mol dm-3

0 -2 -4 -6

Al(OH)2+
Al(OH)4-

Al(OH)2+

AlT

Al(OH)3

Concentration of monomeric hydrolysis products of Al(III) in equilibrium with the amorphous hydroxides at zero ionic strength at 25C

-8 -10 -12

10

12

14

pH pH

Typical titration curve for neutralization of aluminium salt solutions

9 8 7 6 5 4

z1

z2

z3

z4

Nitrate media Sulphate media

3 2
0.0 0.5 1.0 1.5 2.0 2.5 3.0

OH-/Al

100

monomers [Al13O4(OH)24]7+

80

Ali/AlT

60 40
[Al(OH)3]*

20 [Al2(OH)2]4+ 0
3 3,5
0,25 1

[Al2(OH)x](6-x)+

pH
4
2

4,5
2,2 2,25

h= OH/ AlT

Coagulation by hydrolysing iron salts

Log [Fe(OH)y 3x-y ] / mol dm-3

0 -2 -4 -6 -8 -10 -12
Fe3+ Fe(OH)2+ Fe(OH)2+ Fe(OH)4-

Fe(OH)3

Concentration of monomeric hydrolysis products of Fe(III) in equilibrium with the amorphous hydroxides at zero ionic strength at 25C

10

12

14

pH

2.2 The electrochemically assisted coagulation: fundamentals

Electrocoagulation
An alternative to the direct use of a solution containing the coagulant salts, is the in situ generation of coagulants by electrolytic oxidation of an appropriate anode material (e.g. iron or aluminium). This process is called electrocoagulation or electrochemically assisted coagulation.

M e-

Electrochemical processes involved: Electrodissolution Electrolytic generation of oxygen and hydrogen

Electro-dissolution Mn+
coagulation
Unstabilized small flocculation particles
colloids macromolecules emulsions

Aggregated particles

2.2.1 ANODE MATERIAL

Aluminium

M e-

Electro-dissolution Mn+ coagulation

Iron

2.2.2 ELECTRODISSOLUTION

12

Aluminium, mg dm-3

10 8 6 4 2 0 0 0,005 0,01
-3

20

Aluminium, mg dm

-3

15 10 5 0 0 2 4 6 pH 8 10 12 14

0,015

Specific electrical charge, A h dm

Faradays value Chemical dissolution Experimental

Influence of current density

Influence of pH

Faradaic Efficiencies can be over 100%

Electrochemical process

Chemical process

pH profile in the electrochemical cell

A n o d e

pH profile

Direction of electrolyte flux

C a t h o d e

2.2.3 ELECTROLYTIC GENERATION OF OXYGEN AND HYDROGEN

Anodic processes H2 0

Cathodic processes

e-

H2 O e-

O2

H2

Air-dissolved flotation

Bubbles diminish the overall density of the system and the particle floats

Oxygen and hydrogen bubbles

turbulence

adhesion

Promotes soft mixing conditions and improves flocculation processes

Gaseous microbubbles link to pollutant particles. Consequently, the density of the new species decreases and this promotes the flotation of the particle

Electrochemically assisted flocculation (electroflocculation)

Electrochemically assisted flotation (electroflotation)

2.2.4. MAIN PROCESSES INVOLVED IN THE ELECTROCHEMICALLY ASSISTED TECHNOLOGIES FOR COLLOID-POLLUTED WASTES
Anodic processes Cathodic processes

pollutants eElectrodissolution

Al(III) species
Electrocoagulation flocs Electroflocculation Electroflotation

e-

H2O H+ + O2

H2O H2 + OH-

e-

2.3 Electrochemical cells

purpose Only electrodissolution Type of cells

Electrocoagulation/electroflocculation
Electrocoagulation/electroflocculation electroflotation

2.3.1 TANK CELLS


Power supply

eInlet
Floated sludge

e-

Sludge

Flotation
M n+ M n+
hydrated H2O (Pollutant) H2 OH-

Outlet

Cathode

The process combines Sedimentation/flotation


Contrarily to electrooxidation processes, mass transport does not control the overall rate of the process

Anode

Precipitated

Settling
Settled sludge

Sludge

Mixing can be accomplished either by mechanical stirrers or by the evolved gases

Coagulation/flocculation

The activity of the anode can decrease with time due to the formation of insoluble hydroxides or sludge layer. These can be avoid by using motion electrodes or by using turbulence promoters

Power supply

eInlet M M n+
hydrated Floated sludge

e-

Sludge

Flotation
n+

H2O (Pollutant) H2 OH-

Outlet

Cathode

Anode

Precipitated

Settling
Settled sludge

Sludge

Hydrogen evolution can disturb the sedimentation process. For this reason, if possible, it is better to separate the cathodic process from the sedimentation

HydroShock ElectroCoagulation

2.3.2 FLOW CELLS

Normally, these cells do not promote the electroflocculation and the electroflotation processes except for especial designs. Hence its main goal is the electrodissolution and the electrocoagulation

The activity of the electrodes can be decreased by passivation. To solve this problem reverse of polarity (the anode acts as a cathode during a small period) are advised. This can be easily done in a cell designed with the only purpose of aluminium dosing
+ + + + -

+ + + + -

Multiple channels Single channel Electrode configuration in cells for aluminium dose

and both, monopolar and bipolar connections, allow this change of polarity!

Cathodes (-)
cathode

Bipolar electrodes +- +- +- + -

+ anode

Anodes (+)

However, it is more complex for cells that combine electrocoagulation and electroflotation in different compartments

The turbulence generated by the evolved gases can be used in both types of flow. However, vertical flow allows to improve the separation by electroflotation as compared with horizontal flow.

Horizontal flow

Vertical flow

2.3.3. PROMOTION OF THE ELECTROFLOTATION PROCESS

If electroflotation processes have to be promoted it has to be taken into account that:

e-

e-

Current density (j) influences on both: number of bubbles and the average size of bubbles

Flow rate can also be used to control the average bubble size

And also that the electroflotation can be carried out in the same or in a different cell

Power supply

Efluent

Divided electrocoagulation/ electroflotation

EF

EC

Separator

Power supply

Efluent

Combined electrocoagulation/ electroflotation

EF

EC

Separator

2.3.4 OTHER PROCESSES

influent

air

2.4 Electrocoagulation of soluble organics and break-up of emulsions. Removal of phosphates


Emulsion stabilized by electrostatic repulsion forces Compression of the diffuse layer by an increase of the ionic strength

Neutralization of superficial charges by adsorption of ions

Coalescence of phases Inter-droplet bridging

Dissolved organic matter


OH HO N N OH HO N N NO2 OH HO N N OH HO N N NO2 SO3 NO2 SO3 SO3 NO2 SO3 -

Binding of monomeric cationic species to anionic sites of the organic molecules, neutralising their charge and resulting in reduced solubility compounds

OH

HO N N

SO3 NO2

N N

NO2

Adsorption on a superficially charged precipitate

Enmeshment in a precipitate

OH

HO

SO3 -

OH

HO

SO3

NO2

NO2

HO

OH

OH

HO

SO3 -

SO3 -

Binding of polymeric cationic species to anionic sites of the organic molecules, neutralising their charge and resulting in reduced solubility compounds

NO2

OH

N HO

N SO3 -

NO2

Precipitation of phosphates

Log dissolved P
-2

FePO4
-4

AlPO4

-6

2
Electrodissolution cell

10

pH
Treated wastewater clarifier wastewater

2.5 Advantages and disadvantages of electrocoagulation

In literature some advantages are reported for electrocoagulation processes including: 1) A promotion in the flocculation process due to the movement of the smallest charged colloids inside the electric field generated in the electrochemical cell and also to the turbulence created by the bubbles (electroflocculation process) 2) A promotion in the separation process due to the hydrogen bubbles produced in the cathode during the electrolysis, which can carry the solids to the top of the solution, where they can be easily collected and removed (electroflotation process) 3) A more compact residue, as it is reported that the electrocoagulation process produces a smaller amount of sludge that the chemical coagulation, and that the solids produced are more hydrophobic 4) A more easy operation mode as no mixing of chemicals is required, the dosing of coagulants can be easily controlled by manipulating the cell voltage (or the current density), and thus the operating costs are much lower compared with most of the conventional technologies 5) Very simple. Suitable for small WWTP 6) Lower operating cost. However, higher investment

3.ELECTRO-OXIDATION
3.1 Fundamentals When can be applied? Wastewater polluted with soluble organic pollutants Is it possible the recovery of the pollutant as a valuable product? High calorific power? Biodegradable? no no Non AOP oxidation AOP oxidation Electrochemical oxidation

no

Electro-oxidation technologies: use of an electrolytic cell to oxidize the pollutants contained in a wastewater

pollutant
1. Direct electrolysis Oxidation of the pollutant on the electrode surface

H2 O eOH PO43-

pollutant

2. Advanced oxidation processes With some anode materials it is possible the generation of OH

3. Chemical oxidation

P2O84-

pollutant

On the electrode surface several oxidants can be formed from the salts contained in the salt

e-

Organic pollutant
intermediates (aromatics, carboxylic acids)

e+

...

CO2 H2 O

Direct electrolysis consists of the direct oxidation of a pollutant on the surface of the anode. To be oxidized the organic must arrive to the anodic surface and interact with this surface. This means that electrocatalytic properties of the surface towards the oxidation of organics can play an important role in the process. Likewise, it means that in certain conditions mass transfer can control the rate and the efficiency of the electrochemical process

O2
Cl-

Cl2

e-

Organic pollutant
intermediates (aromatics, carboxylic acids)

e+

...

CO2 H2 O
The potentials required for the oxidation of organics are usually high. This implies that water can be oxidized and the generation of oxygen is the main side reaction. This is a non desired reaction and it influences dramatically on the efficiencies

O2
Cl-

Cl2

e-

Organic pollutant
intermediates (aromatics, carboxylic acids)

e+

...

CO2 H2 O

O2
ClFrequently the potential is high enough to promote the formation of stable oxidants, through the oxidation of other species contained in the wastewater. This can have a beneficial effect on the efficiency as these oxidants can oxidize the pollutant in all the volume of wastewater

Cl2

e-

Organic pollutant
2. Mass transport, which can be promoted by a proper cell design

Organic pollutant

e+

...
CO2
1. Electrode material, which influences on the nature of the products and on the importance of theH side O reactions
2

O2
Cl-

3. The presence of compounds in the wastewater that can be transformed into oxidants, promoting mediated electrochemical oxidation processes

Cl2

3.2 Electrode material

DESIRABLE PROPERTIES

MECHANICAL STABILITY. CHEMICAL STABILITY MORPHOLOGY. ELECTRICAL CONDUCTIVITY CATALYTIC PROPERTIES RATIO PRICE/ LIFETIME.

Typical materials include


Platinum Stainless stell

Metals

material

Carbon

Grafite Doped diamond DSA Ti/SnO2 Ti/PbO2

oxides

low efficiency electrodes High efficiency electrodes

Low efficiency electrodes

phenol

SOFT OXIDATION CONDITIONS

Quinones, polymers, carboxylic acids

e-

Fouling by polymers

Many intermediates Small conversion to carbon dioxide Slow oxidation rates Small current efficiencies Formation of polymers from aromatic pollutants is favoured

Pt IrO2 Mediated oxidation by a higher oxidation state of the species that conforms the electrode surface?

High efficiencies electrodes

phenol

HARD OXIDATION CONDITIONS

Carbon dioxide

e-

few intermediates Large conversion to carbon dioxide Large current efficiencies only limited by mass transfer +

BDD Ti/PbO2

OH generation?

Confirmed for conductive-diamond Suggested for PbO2/SnO2

Active electrodes
Pt Stainless steel DSA

Non-active electrodes
Ti/SnO2 Ti/ PbO2 Doped diamond
Drawbacks of non-active electrodes: Conductive diamond: large price >6000 euros/sqm PbO2/SnO2: Dissolution of toxic species

ROLE OF THE HYDROXYL RADICALS

Direct oxidation process


Interfase

Mediated oxidation process


Interfase Electrolyte Interfase Electrolyte

Electrochemical oxidation

R eAnode (+)

R
Electrolyte

H2O eOH R

Cred eCox

R R Cox RO
Mass Transport

RO
Electrochemical Reaction Mass Transport

RO

Anode (+)

RO
Electrochemical Reaction Mass Transport

RO

Anode (+)

Electrochemical Reaction

Kinetic or mass transport controlled

Kinetic controlled

Cathodic material

The organic-oxidation processes that occur in an electrochemical cell are usually irreversible. Hydrogen evolution is the main cathodic reaction.
eee-

e-

H2 O 0.5H2+ OH-

Deposit of carbonates OH- + HCO3ee-

Increase in the cell potential

Increase in the energy consumption

H2 O 0.5 O2+ 2H+


Polarity reversal

3.3 Electrochemical cell

DESIRED CHARACTERISTICS FOR A ELECTROCHEMICAL CELL


SIMPLE MECHANICAL DESIGN. SMALL PRICE. EASY TO USE. LOW MAINTENANCE COST. ENHANCED MASS TRANSFER. HOMOGENEOUS CURRENT DISTRIBUTION ON THE ELECTRODES. LARGE DURABILITY SAFETY

3.3.1 IS IT RECOMMENDED THE USE OF DIVIDED CELLS?

Power supply + eTurbulence promoters Membrane e-

1. The membrane increases the cell potential and consequently the operating cost. 2. Most organic-oxidation processes are irreversible

Anolite

Catholite

hW
ea + h

Anode

Cathode

Cell potential

hdiff hW ea + h + hreaction hW

Electrolyte ANODE CATHODE

Direction of charge flux

3.3.2 STIRRED-TANK CELLS


Power supply + eTurbulence promoters e-

anode

cathode

ADVANTAGE: Simplest cell


DRAWBACK: Low mass transfer coefficients

3.3.3 SINGLE FLOW CELL


ANODE
TURBULENCE PROMOTER Membrane? CATHODE

OUTLET ANOLYTE

OUTLET CATHOLYTE

INLET ANOLYTE

INLET CATHOLYTE

3.3.4 FILTER PRESS CELL

Large electrode surfaces / volume ratios Small interelectrode gap Plane electrodes

Electrolyte flow

3.3.5. OTHER CELLS


+ +

Steel cathode polyuretane Activated carbon Steel anode

Packed bed cell

Cell with continuous regeneration of the adsorbent

Rotating electrode cell

CATHODE

ANODE

3.4 Indirect electrochemical oxidation processes


Power supply

e-

pollutant a) Direct electrolysis product

Electrodo

inert1 electroactive

inert2

pollutant Product b) Indirect electrolysis

inert pollutant electroactive

Product

The oxidation is carried out in the whole reaction volume (not limited to the electrode surface)

No mass transfer control

higher efficiency

Both direct and indirect electro-oxidation develop simultaneously in the cell

Power supply

Homogeneous reactions
V e
-

I A e
-

B e
-

A anode B e
-

D e Ccathode

Heterogeneous reactions

Types of mediated electrochemical oxidation processes

Without addition of reagents: changes in the pH and temperature to promote the generation of oxidants from the direct oxidation of salts present in the wastewater (in some cases throught hydroxyl radicals) With additions of reagents: in addition to changes in pH and temperature, some salts are added to promote the generation of oxidants

Production of reagents and treatment of the waste in the same cell Production of reagents and treatment of the waste in different cells

Dosing of reagent
Electrosynthesis of the oxidant

wastewater

Oxidation and electroxidation of the pollutants

Separation of the oxidant or of its reduction product

Treated waste

Dosing of reagent

Electrosynthesis of the oxidant

Separation of the oxidant or of its reduction product

Oxidation and electrooxidation of the pollutants

wastewater

Treated waste

To take in mind The potential at which the electrogenerated oxidants are produced must not be near the potential for water oxidation, since then a large portion of the current will be employed in the side reaction The rate of generation of the electrogenerated oxidant should be large The rate of oxidation of pollutant by the electrogenerated oxidant must be higher than the rates of any competing reactions. The electrogenerated oxidant must not be a harmful product

Ag(I) / Ag(II) Reversible oxidant


The oxidant can be reduced in the cathode. A divided cell may be considered

Co(II) / Co(III)

Ce(III) / Ce (IV)
Fe(II) / Fe (III) SO4 2- / S2O8 2PO4 3- / S2O8 4These oxidants are generated from anions typically present in a wastewater It can be formed by a cathodic process. Extra oxidation efficiency!

Irreversible (killers)
The oxidant is not reduced on the cathode. Non-divided cells are used for their production

Cl2 O3 H2O 2

Ag(I) / Ag(II)
Ag Ag2 e

E 0 1.98Vvs.SHE
Ag2 e Ag

Some pollutants efficiency removed by this technology: Ethylene glycol, isopropanol, acetone, organic acids, benzene, kerosene

Main drawbacks

R CO 2

H 2 O OH O 2

ions Ag+ are harmful products chlorides can reduce the efficiencies due to precipitates formation silver is very expensive

Co(II) / Co (III)
Co (II) Co (III ) e E 0 1.82Vvs.SHE Co (III ) e Co (II)
Main drawback This process has to be carried out in divided cells (Co can be electrodeposited on the cathode surface) Some pollutants successfully treated: Organic radioactive waste materials, dichloropropanol, ethylene glycol

R CO 2

H 2 O OH O 2

Sulphate/peroxodisulphate
Large efficiencies with diamond electrodes

Its presence is very common: Sulphate salts are frequently present in industrial wastewaters. Very powerful oxidant (non selective oxidation) It decomposes at temperatures above 60C

2 1 S2O8 H 2O 2 SO2 4 2H

2 SO4

S 2 O8

2 e

E 0 2.06Vvs.SHE

2 S2O8 H2O SO5 SO2 4 2H 2 SO5 H2O H2O2 SO2 4

O2

Phosphate/peroxodiphosphate
Large efficiencies with diamond electrodes

2 PO4

P2O8 2 e

E 0 2.01Vvs.SHE

Its presence is very common: Phosphate salts are frequently present in industrial wastewaters Powerful oxidant (more selective than persulphate). The oxidation carried out by this reagent depends importantly on the pH Less sensitive to temperature

Fe(II) / Fe (III)
Fe2 Fe3 e E 0 0.77Vvs.SHE Fe(VI ) Fe3 e Fe2

Some pollutants treated by this technology: Celluloid materials, fats, urea, cattle manure, sewage sludge, meat packing wastes, ethylene glycol

R CO 2

R RO

H 2 O OH O 2

selectivity depends on operating conditions. Carbon dioxide can be the final product in the oxidation of organics good efficiencies are obtained for high temperatures and low current densities Electrocoagulation can occur simultaneously

Chloride/ Chlorine

2 Cl - Cl 2 2e

Its presence is very common: chloride salts are frequently present in industrial wastewaters. The chlorine speciation depends on the pH It can lead to the formation of organochlorinated compounds
hypochlorite Dosing in channel

Cl 2 H 2O HCl HClO

NaCl -

% HClO
1.0 0.8 0.6 0.4 0.2 0.0 5.0 6.0 7.0 8.0 9.0 10.0

Electrochemical cell NaCl


Dosing in pipe

hypochlorite

pH Electrochemical cell

Hydrogen peroxide
It can be formed on the cathode by reduction of oxygen
O 2 2H 2O 2e HO OH 2

E0=-0.065 V

However, the main drawback is the decomposition of the hydroperoxide anion that it is favoured at alkaline conditions.
HO 2 OH O2 2

To promote the efficiencies it is required : a cathode material with a high overpotential for the reduction of the hydroperoxide anion to water (graphite) Good oxygen transfer rates to the cathode surface
ee-

Combination of electrooxidation with cathodic generation of hydrogen peroxide allows to obtain current efficiencies over 100%. It is the best way of obtaining a valuable compound from the cathodic reaction in wastewater treatment processes

O2 H2 O 2

Anodic oxidation processes

Ozone
The oxidation of water to ozone can occur on the electrode surface but it is less favoured than that of oxygen

O 3 6H 6e 3H 2 O

E0=1.51 V E0=1.23 V

O 2 4H 4e 2H 2 O

To promote the formation of ozone: Use of anode material with large overpotentials for oxygen evolution Use of very high current densities Use of an adsorbate to block the oxygen evolution process (f.i.F-, BF4-, BF6-)

Some examples of electrochemical generation of ozone anode electrolyte current density B-PbO2 HPF6 (2M) 750 mA cm-2 Active carbon HBF4 (7.3 M) 600 mA cm-2 Active carbon HBF4 (62% w/w) 200 mA cm-2

yield 21% 35% 45%

3.5. Advantages of the electro-oxidation technology

Environmental compatibility: the main reagent used is the electron No residues are formed.

Can be a complementary treatment or a final treatment


Operation at room temperature and atmospheric pressure High efficiency if proper anode material is used.

The efficiency can be easily increased by promoting indirect processes


Easy operation. Amenability to automation.

3500 3000
-3 COD / mg dm

Lower operating cost compared with other AOP


Energy consumption during the treatment of an actual industrial waste. Electrochemical oxidation j:30 mA cm-2; natural pH; T: 25C ; Ozonation pH 12; T: 25C

2500 2000 1500 1000 500 0 0 500 1000 1500 2000 2500 3000 W / kWh m-3

3.6. Combined processes Treatment of gaseous effluents


Poor Gas H2S

NaOH Solution

H2

Rich Gas H2S Comportment of adjust of the pH Absorber


Solution

+ Filter

Electrochemical Reactor

S(S)

Combination of electrochemical oxidation with bio-oxidation


a) pre-treatment

electrooxidation

biooxidation

b) post-treatment biooxidation

electrooxidation

Main drawback: When to change?

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