Advanced Oxidation Technologies

(AOPs)
Alternative to biological treatment systems.
Used for the treatment for industrial wastewater
containing recalcitrant organic compounds.
As pretreatment method to biological treatment
systems.
Mechanism
Generation of highly reactive free radicals, .OH
Oxidation potential = 2.33v
Attack
organic
R +on
HO
ROHchemicals by,(1)
R + HO R + H2O
Rn + HO Rn-1 + OH-

(2)
(3)

AOPs
Technologies
1.
2.
3.
4.
5.

Titanium dioxide/UV light process

Hydrogen peroxide/UV light process
Fentons reactions
Wet Air Oxidation Technology
Cavitation

1. Titanium dioxide/UV light process

TiO2 + h ecb + h+
(4)
ecb + O2 O2-
(5)
h+ + H2O H+ + HO
(6)
Oxidative degradation as well as reductive
cleavage of organic compounds.
Doping of TiO2 lattice eg. Silver doped TiO2
Key advantages

Process operation at ambient conditions.

Lack of mass transfer limitations.
Possible use of solar radiations.
TiO2 cheap and readily available.
capable for oxidation of a wide range of organic
compounds.

 Major factors affecting TiO2/UV light process

initial organic load

amount of catalyst
reactors design
UV irradiation time
temperature
solutions pH
light intensity
presence of ionic species

Photocatalytic oxidation of olive oil

(1/100) times dilution of olive oil mill waste water.
1 g/l TiO2 removed 22% COD and 94% phenols

Photocatalysis with TiO2 for phenol containing

wastewater
99% of target compound removed in 4 hr. with 15W
light intensity and 1 g/l TiO2 conc.

 Heterogeneous TiO2 assisted photo catalytic

degradation of wastewater from a thermoelectric
power station.
Cynide and formate removal analysis
solar/H O /TiO system
Under optimum conditions pH=6, T=40oC, H2O2=6.5g/l,
TiO2=1.5g/l, after 3 hr
2

Pollutant

Influent (mg/l)

After treatment
(mg/l)

CN-

10

NH3

150

22

COD

1240

50

TOC

980

14

2. Hydrogen peroxide/UV light process

H2O2 + h 2 HO (7)
H2O2 + HO 2 + 2 (8)
H2O2 + 2 HO + 2 + 2
2 HO H2O2
(10)
2 2 H2O2 + 2
(11)
HO + 2 H2O + 2
(12)

(9)

Eq 7 is rate limiting reaction.

Optimal H2O2 concentration.
Major factors affecting the process
Amount of H2O2
Wastewater pH
dilution should be done at an optimum level

UV/H2O2 process has been widely used for dyes

removal
C.I Acid Orange 7 (a commonly detected dye in textile wastewater)
decolorization of Reactive blue 19

 US/UV/H2O2 processes
malachite green, contaminant from textile industry

3. Fentons reactions
Fe2+ + H2O2 Fe3+ + OH- + HO (13)
Fe2+ + HO Fe3+ + OH(14)
HO + RH H2O + R (15)
R + Fe3+ R+ + Fe2+ (16)
As a pretreatment to biological treatment
major parameters affecting Fenton process

solutions pH(2-4)
amount of ferrous ions
concentration of H2O2
initial concentration of the pollutant
presence of other ions

drawbacks that Fenton processes

requirement for acidic conditions
interference by substances that complex iron ions
production of iron oxide sludge

 photo Fenton process (H2O2/Fe2+/UV)

(17)
Fe3+ + H2O Fe2+ + H+ + HO
treatment of olive mill wastewater

COD removal from oil recovery industry

wastewater
86% COD removal for H2O2/Fe2+ = 8.7
81% COD removal for photo fenton process with
H2O2/Fe2+=168

4. Wet Air Oxidation Technology (WAO)

Aqueous phase process.
formation of carboxylic acids in addition to the
primary end-products, CO2,H2O and off-gases.
T=100 to 320oC at elevated pressures.
low (100-200C) operation
medium (200-260C) operation
high temperature (260-3 20C) operation

Spent Caustic treatment

ethylene spent caustic
refinery spent caustic
sulfidic caustic (caustic washing of LPG for sulfur removal)
Naphthenic caustic (high COD, TOC)(low T foaming hence high T
operation )
cresylic spent caustic