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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.
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+
effluent
Diluted solution
Anionic membrane
Cathionic membrane
Anionic membrane
Cathionic membrane
Concentrated solution
anode
cathode
Anions
electrodialysis
Feed solution
Cations
Electro-oxidation
electrocoagulation
Electrodeposition
metal
Rotational cathode
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
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
influent
effluent
Sludge
Bulk solution
Interaction energy
+ + + ++ + + + + + + + - + + + + + + + ++ ++ + + + + + +
Ea Ea+Eb
Surface potential
Eb
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.
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.
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
9 8 7 6 5 4
z1
z2
z3
z4
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
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
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-
Electro-dissolution Mn+
coagulation
Unstabilized small flocculation particles
colloids macromolecules emulsions
Aggregated particles
Aluminium
M e-
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
Influence of pH
Electrochemical process
Chemical process
A n o d e
pH profile
C a t h o d e
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
turbulence
adhesion
Gaseous microbubbles link to pollutant particles. Consequently, the density of the new species decreases and this promotes the flotation of the particle
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-
Electrocoagulation/electroflocculation
Electrocoagulation/electroflocculation electroflotation
eInlet
Floated sludge
e-
Sludge
Flotation
M n+ M n+
hydrated H2O (Pollutant) H2 OH-
Outlet
Cathode
Anode
Precipitated
Settling
Settled sludge
Sludge
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+
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
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
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
EF
EC
Separator
Power supply
Efluent
EF
EC
Separator
influent
air
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
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
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
DESIRABLE PROPERTIES
MECHANICAL STABILITY. CHEMICAL STABILITY MORPHOLOGY. ELECTRICAL CONDUCTIVITY CATALYTIC PROPERTIES RATIO PRICE/ LIFETIME.
Metals
material
Carbon
oxides
phenol
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?
phenol
Carbon dioxide
e-
few intermediates Large conversion to carbon dioxide Large current efficiencies only limited by mass transfer +
BDD Ti/PbO2
OH generation?
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
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 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-
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
anode
cathode
OUTLET ANOLYTE
OUTLET CATHOLYTE
INLET ANOLYTE
INLET CATHOLYTE
Large electrode surfaces / volume ratios Small interelectrode gap Plane electrodes
Electrolyte flow
CATHODE
ANODE
e-
Electrodo
inert1 electroactive
inert2
Product
The oxidation is carried out in the whole reaction volume (not limited to the electrode surface)
higher efficiency
Power supply
Homogeneous reactions
V e
-
I A e
-
B e
-
A anode B e
-
D e Ccathode
Heterogeneous reactions
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
Treated waste
Dosing of reagent
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
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
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
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
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
Environmental compatibility: the main reagent used is the electron No residues are formed.
3500 3000
-3 COD / mg dm
2500 2000 1500 1000 500 0 0 500 1000 1500 2000 2500 3000 W / kWh m-3
NaOH Solution
H2
+ Filter
Electrochemical Reactor
S(S)
electrooxidation
biooxidation
b) post-treatment biooxidation
electrooxidation