Wastewater TreatmentAdvanced Oxidation

Processes
Assoc. Prof. Dr. Pakamas Chetpattananondh
Department of Chemical Engineering
Prince of Songkla University

Advanced oxidation
processes

Advanced oxidation processes (AOPs)

have been used for the treatment of wa
stewater containing recalcitrant organic
compounds such as pesticides, surfacta
nts, coloring matters, pharmaceuticals
and endocrine disrupting chemicals.
Moreover, they have been successfully
used as pretreatment methods in order
to reduce the concentrations of toxic or
ganic compounds that inhibit biological
wastewater treatment processes.

Electrochemical Oxidation
Potential

Advanced oxidation
processes

The main mechanism of AOPs function

is the generation of highly reactive
free radicals.
Hydroxyl radicals (HO) are effective
in
destroying
organic
chemicals
because they are reactive electrophile
s (electron preferring) that react rapidl
y and non-selectively with nearly all el
ectron-rich organic compounds.
They exhibit faster rates of oxidation
reactions comparing to conventional o
xidants such as O2.

Advanced oxidation
processes
A free radical is a molecule that has an

unpaired electron (represented by a dot

next to the chemical structure, e. g., A)
A radical needs to pair its unpaired
electron with another electron and will r
eact with another molecule in order to o
btain this missing electron.
If a radical achieves this by "stealing" an
electron from another molecule that
other molecule itself becomes a radical (
Reaction 1), and a self-propagating chai
n reaction is begun (Reaction 2).

Advanced oxidation
processes
A B A B

(Rxn 1)

B C B C

(Rxn 2)

If a radical pairs its unpaired electron by

reacting with a second radical, then the c
hain reaction is terminated, and both radi
cals "neutralize" each other (Reaction 3).

A B A B (Rxn 3)

Advanced oxidation
processes

Triplet oxygen can be transformed into a

reactive state if it is accepts a single elec
tron. The result of monovalent reduction
of triplet oxygen is called superoxide.
3

O2 e O

Ozone generator

Ozone generator
In the ozone generator, the corona-discharge element is present, which provides a
capacitive load.
In here ozone is produced from oxygen as a direct result of electrical discharge.
This corona-discharge ruptures the stable oxygen molecule and forms two oxygen
radicals.
These radicals can combine with oxygen molecules to form ozone.
To control and maintain the electrical discharge, a di-electric is present, carried
out in ceramic or glass.
The excessive heat of the electrodes is often cooled by cooling water, or by air.

Ozone

Ozone/Hydrogen
Peroxide
The peroxone process requires an ozone generation
system and a hydrogen peroxide feed system.
The process involves two essential steps:

Ozone dissolution and hydrogen peroxide addition.

Hydrogen peroxide can be added after ozone (thus
allowing ozone oxidation and disinfection to occur first
) or before ozone (using peroxide as a preoxidant, foll
owed by hydroxyl radical reactions) or simultaneously.
The most efficient operation is to add ozone first,
followed by peroxide for hydroxyl radical oxidation.

Ozone/Hydrogen
Peroxide

Ozone/UV

Ozone/UV

Fenton Reactions
In the Fenton reagent reaction superoxide donates an
electron to reduce Fe3+.

O Fe O 2 Fe
3

Fe2+ then catalyzes the breaking of the oxygenoxygen bond of hydrogen peroxide to produce a h
ydroxyl radical (OH)
ion (OH-):
2 and a hydroxide
3

Fe H 2 O 2 Fe HO OH

Titanium Dioxide/UV
Organic compounds can undergo oxidative
degradation through their reactions with valence
band holes, hydroxyl and peroxide radicals as wel
l as reductive cleavage through their reactions wi
th electrons.

Titanium Dioxide/UV
The key advantages of this process are the
operation at ambient conditions, the lack of mas
s transfer limitations when nanoparticles are use
d as photocatalysts and the possible use of solar
irradiation.
Moreover, TiO2 is a cheap, readily available
material and the photogenerated holes are highl
y oxidizing.
In addition, TiO2 is capable for oxidation of a
wide range of organic compounds into harmless
compounds such as CO2 and H2O.

Titanium Dioxide/UV
The major factors affecting TiO2/UV light process are:
initial organic load, amount of catalyst, reactors
design, UV irradiation time, temperature, solutions
pH, light intensity and presence of ionic species.
The use of excessive amounts of catalyst may reduce
the amount of energy being transferred into the
medium due to the opacity offered by the catalyst pa
rticles.
Reactors design should assure that uniform
irradiation of the catalyst surface is achieved.
For temperature values between 20 and 80C, a
minor effect of temperature has been noticed. Howe
ver, at temperature higher than 80C, a reduction of
the reaction rate has been reported.