Advanced Oxidation Processes

(AOPs)

Presented by
Shangali Pius
Anagu Chidi Charles
Abang Roger
Hongwei Li
Tudor Zankov
 definition
• Advanced oxidation processes (AOPs) are used for the
destruction of synthetic organic chemicals (SOCs) in water,
apart from disinfection and deactivation of pathogenic
microorganisms that are difficult to degrade biologically.
• These processes include the application of ozone, hydrogen
peroxide, and ultraviolet light, either individually or in
combination O3/UV; H2O2/UV; and O3/H2O2/UV.

• These processes are mediated by free-radical reactions, and

are becoming increasingly complex from the standpoint of
scientific analysis.
• Oxidation processes based on generation of hydroxyl radical
(HO•) intermediates. Combinations based on H2O2, O3 and
UV have been investigate most heavily
All these AOP’s have an item in common: the generation of hydroxyl
radical, which is extremely reactive, and possesses a very high oxidation
potential. As a matter of fact, the hydroxyl radical shows an oxidation
potential over 3 Volts, surpassed only by the negative oxidation potential of
fluorine (see Table 1).
 Table 1: Comparison of various oxidising Potentials

Electrochemical
Oxidation
Potential, EOP relative to
Oxidizing agent (EOP)V Chlorine
Fluorine 3.06 2.25
Hydroxyl radical 2.80 2.05
Oxygen (atomic) 2.42 1.78
Ozone 2.08 1.52
Hdrogen Peroxide 1.78 1.30
Hypochlorite 1.49 1.10
Chlorine 1.36 1.00
Chlorine dioxide 1.27 0.93
Oxygen (Molecular) 1.23 0.90

Sources:
www-rcf.usc.edu/~pirbazar/group_homepage/resear/adv.html
www.iupac.org/publications/pac/1998/pdf/7012x2271.pdf
Examples of AOP Methods
 Theory of AOPs
• Involves the generation and use of the HO• as a strong oxidant to
destroy compounds that cannot be oxidized by conventional oxidants
such as O2, O3 and Cl

• HO reacts with dissolved constituents in a series of oxidation reactions

until the constituents are completely mineralized

• They are non selective in their mode of attack and are able to operate
at normal temperature and pressure

• Able to oxidize almost all reduced materials present in wastewater

without restriction to specific classes or groups of compounds

• AOP differs from other treatment processes because wastewater

compounds are degraded rather than concentrated or transferred into a
different phase
• Because no secondary materials are generated, there is no need to
dispose of or regenerate material
 Ultra Violet (UV)

• Ultraviolet light (UV) is a general term for electromagnetic radiation

emitted from the region of the spectrum lying beyond the visible light
(400 nm) and before x-rays (100 nm).

• UV is widely accepted as a reliable, environmentally friendly solution

for water disinfection.

UV disinfection system
• UV exhibits strong bactericidal and virucidal properties, and unlike
some chemical disinfection processes, UV does not produce any
harmful by-products.

• Innovative reactor design allows for optimal UV radiation efficiency.

• A broad range of equipment capabilities provides for best suited

solution depending on water quality and flow rate.
 Chlorine

• Chlorination is used for many reasons in wastewater treatment such as

in disinfection, taste and odor control, color removal, oxidation of
ammonia, iron, manganese and sulfide and BOD removal.

• Most common chlorine compounds used in waste water treatments are

chlorine gas ( Cl2), calcium hypochlorite [Ca(OCl2)], sodium
hypochlorite (NaOCl) and chlorine dioxide (ClO2).

• The rate and efficiencies of reactions when the chlorine is added to the
wastewater depends on temperature, pH, buffering capacity and the
form in which the chlorine is supplied.
• Chlorine in aqueous solution produces hypochlorus acid and
hypochlorite ion.
• Cl2 + H2O ⇔ HOCL + H+ + Cl- (hypochlorous acid)
• HOCL ⇔ H+ + OCL- (hypoclorite ion)
 Chlorine cont‘d
• Amount of HOCL and OCL- present in water called free chlorine
residual. The disinfection power of HOCL is 40 – 80 times greater
than that of OCL-.

• That is why wastewater at lower PH is easy to disinfect by

chlorination.

• While the chlorine gas lower the pH hypochlorite in solution raises the
pH and favors the formation of OCL-, which is less effective than
HOCL.

• The disinfection efficiency of chlorine depends on contact time,

chlorine dosage, temperature, pH, nature of liquid and suspended
matter and type of microorganism.
• Chlorine is cheap, effective, available in large quantities, non toxic in
low concentration to higher forms of life the basic disadvantage
include acid generation, build up of total dissolved salts and formation
of potentially carcinogenic halogenated organic compounds
 Hydrogen peroxide – H2O2
• A powerful, safe and effective oxidant that looks like water in its
appearance, chemical formula and reaction products
2 H2O2 ----> 2 H2O + O2
(hydrogen peroxide ----> water + oxygen)

• Application in odor control, BOD/COD removal, metal oxidation and

precipitation in wastewater treatment, flocculation and
disinfection/bio-control.

• Used mostly in combination with ozone and UV in AOPs

 Technologies – Hydrogen Peroxide/UV

• HO• formed when water containing H2O2 is exposed to UV

light (λ = 200 – 280nm)

• The photolysis of H2O2 given as

• H2O2 + UV (or hυ λ = 200 – 280nm) → HO• + HO•

• Applied in the oxidation of trace constituents found in

treated water such as
– Sex and steroidal hormones
– Human prescription and non-prescription drugs
– Veterinary and human antibiotics
– Industrial and household wastewater products
 Technologies – Ozone/UV
• Production of free radical HO with UV light by the photolysis of
ozone
– O3 + UV (or hυ, λ <310nm) → O2 + O(1D)
– O(1D) + H2O → HO• + HO • (in wet air)
– O(1D) + H2O → HO• + HO• → H2O2 (in water)
• The photolysis in wet air results in the formation of HO•
• In H2O the photolysis of ozone leads to the formation of hydrogen
peroxide
• This H2O2 is subsequently photolyzed to form HO•. The use of O3 in
this application is not cost effective
• In air, the O3/UV process can degrade compounds through direct
ozonation, photolysis or reaction with the HO•
• The O3/UV process is more effective when compounds of interest can
be degraded through the absorption of the UV irradiation as well as
through the reaction with the HO•
 Technologies – ozone/hydrogen peroxide

• For compounds that do not absorb UV, AOPs involving

ozone/H2O2 may be more effective
• Used to reduce compounds in water such as
Trichloroethylene (TCE) and Perchloroethylene (PCE)
• The reaction is:
– H2O2 + 2O3 → HO• + HO• + 3O2
 applications
• Combined AOPs are more effective than any of the individual agents
(eg ozone, UV, H2O2)

• Usually applied at low COD wastewaters because of the cost of ozone

•
and /or H2O2 required to generate HO radicals

• Usually applied for the disinfection of treated wastewater and

treatment of refractory organic compounds

Problems
• Because half-life of the HO• is short (microseconds) it is not possible
to develop high concentrations

• Extremely low concentrations, detention time for the microorganism

disinfection based on the CT concept prohibitive
 Operational problems

• High concentration of carbonate and bicarbonate in some

wastewater can reacct with HO• and reduce the efficiency
of Advanced oxidation treatment processes
• Other factors succh as suspended material, pH, type and
nature of residual TOC, and other wastewater constituents
can affect the treatment process.
 Oxidation of refractory organic compounds

• The HO• can attack organic molecules found in highly treated effluents
by radical addition, hydrogen abstraction, electron transfer, and radical
combination
• Radical addition
– Addition of HO• to an unsaturated aliphatic or aromatic organic
compounds (eg C6H6) results in the production of a radical organic
compound that can be oxidized further by compounds such as O2
or ferrous iron to producce stable oxidized end product
• R + HO• → ROH where R = reacting organic compound
• Electron transfer
– Results in the formation of ions of a higher valence
• Rn + HO• → Rn-1 + OH-
• Hydrogen abstraction
– HO• used to remove a H atom from organicc ccompounds resulting
in the formation of a radical organic compound, initiating a cchain
reaction where the radical organic ccompound reacts with O2,
producing a peroxyl radical which can react with other organic
compound and so on
• R + HO• → R• + H2O

• Radical combination
– 2 radicals can combine to form a stable product
• HO• + HO• → H2O2
•
• In general, the reaction of HO with organic compounds, at
completion, will produce H2O, CO2, and salts: this process is also
known as minera