Advanced Oxidation Processes(AOPs)

-An Emerging Treatment Technologies for

Industrial Wastewater treatment
AOP Engineering Laboratory
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 Structure of the Presentation

 Introduction
 Advanced Oxidation Processes
- Ozone based
AOP Engineering Laboratory

- Fenton
 Photochemical Oxidation Processes
- UV Photolysis
- H2O2/UV
- Ozone/UV
- TiO2 Photocatalysis Photocatalysis
- PhotoFenton
 Conclussions and Recommendations
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 INTRODUCTION

Advanced Oxidation Technologies or Processes (AOTs, AOPs) are efficient novel

methods for water treatment, which have afforded very good results in industrialized
countries and are beginning to be employed in developing regions

Conventional secondary (e.g., activated sludge process) and tertiary (such as filtration
and disinfection) treatments in urban wastewater treatment plants (WWTPs) are not
AOP Engineering Laboratory

effective in the removal of most Contaminants of Emerging Concern(CECs )entering

WWTPs.

The term “Advanced Oxidation Processes” for the first time defined in 1987 by
Glaze et al.

Glaze, William; Kang, Joon-Wun; Chapin, Douglas H. (1987). "The Chemistry of Water
Treatment Processes Involving Ozone, Hydrogen Peroxide and Ultraviolet
Radiation". Ozone: Science & Engineering. 9 (4): 335–352. doi:
10.1080/01919518708552148
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 AOP Engineering Laboratory
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 OH• Characteristics (redoxpotential)

Fluorine 2.23
Hydroxyl radical 2.06
AtomicOxygen(singlet) 1.78
Ozone 1.52
Hydrogenperoxide 1.31
AOP Engineering Laboratory

Perhydroxyl radical 1.25

Permanganate 1.24
Hypobromousacid 1.17
Chlorinedioxide 1.15
Hypochlorousacid 1.10
Hypoiodousacid 1.07
Chlorine 1.00
Bromine 0.80
Iodine 0.54

* very powerful oxidation compound (F2 > OH• > O3 > ........)
* oxidation power related to chlorine (Eº = 1.36 V)
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Rate constants of °OH radical with organics: 1-1000 x 107 mol-1 L s-1 5/77
 OH• Characteristics (no especific oxidant)

Compounds that can be oxididez by OH radicals

Acids Formic, gluconic, lactic, malic, propionic, tartaric
Benzyl, tert-butyl, ethanol, ethylene glycol, glycerol,
Alcohols
isopropanol, methanol, propenediol
Acetaldehyde, benzaldehyde, formaldehyde, glyoxal,
AOP Engineering Laboratory

Aldehydes
isobutyraldehyde, trichloroacetaldehyde
Benzene, chlorobenzene, chlorophenol, creosote,
Aromatics dichlorophenol, hydroquinone, p-nitrophenol, phenol,
toluene, trichlorophenol, xylene, trinitrotoluene
Aniline, cyclic amines, diethylamine, dimethylformamide,
Amines
EDTA, propanediamine, n-propylamine
Dyes Anthraquinone, diazo, monoazo
Ethers tetrahydrofuran
Ketones Dihydroxyacetone, methyl ethyl ketone
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 OH• Characteristics (no especific oxidant)

Compounds that can not be oxidized by hydroxyl

radicals
Acetic acid Acetone Carbon tetrachloride
Chloroform Maleic acid Malonic acid
Methylene chloride Oxalic acid n-paraffins
AOP Engineering Laboratory

Tetrachloroetane Trichloroetane

Brigda,J., Chem.Eng.Proc. (Dec 1995) pp 62-66

Scavenger effect (at high concentration)

Inorganic ions: Sulfate, chloride, carbonate,..
Alcohols: methanol, terbutanol,..
Hydrogen Peroxyde
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 Biodegradability enhancement by AOPs
mg/L
mg/L
8000 800

COD O3
WO 6000
BOD
600
COD
BOD
dyes
pulp&paper 4000 400
AOP Engineering Laboratory

2000 200

0 0
0 30 60 90 120 150 0 50 100 150 200
tiempo, min tiempo, min

Garcia-Molina et al., 2002. Liakou and Lyberatos, 1996.

mg/L
mg/L
1000
1000
COD COD
800
800 BOD BOD
600 600
Fenton
400 400 O3
textil 200 200
surfactants
0 0
0 150 300 450 600 0 1500 3000 4500
H2O2 dose mg/L ozone feed, mg

Bertanza et al., 2000. Beltran et al., 1999a.

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 AOP classics

homogeneous heterogeneous
AOP Engineering Laboratory

Photolysis Fe+3/UV/H2O2 O3/UV TiO2/UV O3/H2O2 O3

sonolysis

electrochem

Radical ·OH
radiation
UV-VIS
(light conditions) atmospheric pressure and room temperature
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Glaze 1987.
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 AOP modern (hot AOP)
• ELECTRON BEAM
• CAVITATION
• WET OXIDATION
• SUPERCRITICAL WATER OXIDATION
AOP Engineering Laboratory
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 WET OXIDATION

* Wet oxidation is a flameless radical oxidation process brought about when

an organic and/or oxidizable inorganic-containing liquid is mixed thoroughly
with a gaseous source of oxygen at temperatures of 150 to 325 ºC and gauges
AOP Engineering Laboratory

pressures of 0.2 to 2.06 Mpa (2 – 20 atm).

- High Pressure High operating Need to optimize the
and Temperature costs process

* WO is a process specially suited to treat effluents that are too concentrated

to be treated biologically and too diluted to be incinerated. The common COD
level of the emissary effluent to be treated by WAO is between 20 g/L and 200
g/L.
* Advantage: During the process neither NO x, SO2, HCl, dioxides nor other
harmful products are generated.
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 Lab WO installation
thermostatic
bath

stirrer
AOP Engineering Laboratory

reactor

controller
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 Lab WO installation
PO2 = 5 - 20
bar stirrer = 700 rpm V = 0.3 L

T = 150-200 C
AOP Engineering Laboratory

1) power supply, 2) controller, 3) oxygen cylinder, 4) heater, 5) stirrer, 6)

reactor, 7) sample extraction, 8) gas draining
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 WO reactor

1) Drop band with

screw
AOP Engineering Laboratory

2) Split ring pair with

screws
3) Bomb head
4) Dip tube
5) Cooling loop
6) Stirrer
7) Bomb cylinder
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 Suitability of water treatment according to COD

Incineration
AOP Engineering Laboratory

Wet Oxidation

Classical AOP autothermic

2 20 200

0 10 100 1000
COD (g.L-1)

Andreozzi, R., Caprio, V., Marotta, R. (1999) Advanced Oxidation Processes (AOP)
for water purification and recovery”, Catalysis Today 53 (1) 51-59
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 Suitability of water treatment according to TOC
TOC (mg.L-1)
AOP Engineering Laboratory

Flow rate (m3.h-1)

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Hancock,F.E. (1999) “Catalytic strategies for industrial water reuse”

Cat. Today 53, 3-9 16/77
 COD removal - AOPs Applications
COD mg/L
AOPsapplication
AOPs applicationregions
regionswith
with
regardsto
regards toeconomic
economicconsideration
consideration

300000 Incineration
100000
AOP Engineering Laboratory

WAO

10000
Fenton, WPO
1000

100
AOPs : H2O2/UV, PhotoFenton, O3/H2O2
TiO2/UV...
10

1 10 100 1000 10000

Flow rate m3/h

Suty,H., Coste, M. “The AOPs tools in the treatment of waste water effluents”
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3rd European Meeting on Solar Chemistry and Photocatalysis :Environmental

Applications Barcelona, 30 June and 1, 2 July 2004 17/77
 Ozone

O3
- 1785: M. van Marun . Oxygen with electric discharges gives a
AOP Engineering Laboratory

peculiar odor (irritant).

- 1840: Schönbein discovered Ozone, a different substance
based on Oxygen (from greek ozein, smell)
- 1856: Thomas Andrews demonstrate that Ozone is only
formed by Oxygen
- 1863: Soret found the relation Oxygen-Ozone (three volumes
of oxygen produces two volumes of ozone)

Thermodinamically unstable  have to be produced “in situ”

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3 O 2 ↔ 2 O3 ozone% explosion limit = 30%

18/77
 Ozone generation
 UV (185 nm) irradiation (air oxygen)

 Electric discharge
AOP Engineering Laboratory

O2 O2

 Electrolitic
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only 5-10% of electric energy leads to ozone production 19/77

 Ozone reactivity
O3 ───® 3/2 O2 DH°= - 34.61 kcal/mol
O3 + 2 H+ + 2 e- ───® O2 + H2O E° = 2.07 V

Moxidized
M
AOP Engineering Laboratory

O3 M’oxidized
M
Initiators
Promoters HO·

Inhibition

metallic ions oxidation

organics :direct and indirect attack
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 Ozone mass transfer

Generation (air, oxygen)

AOP Engineering Laboratory

Mass transfer
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water treatment with ozone

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 Ozone via hydroxyl radical

• Ozone at high pH
3 O 3  OH -  H  
 2 OH •  4 O 2
• Ozone /UV
AOP Engineering Laboratory

h
O 3  H 2O  2 OH   O 2
• Ozone /Hydrogen Peroxyde

H 2 O 2  2 O 3  2 OH  3 O 2

• Catalytic Ozonation
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C, TiO2, oxides and salts of Fe, Mn, Ce, Cu, Co..22/77

 Ozone Material & operating conditions
Catalytic
O3 gas analyzer Air vent
reduction

O3 liquid
analyzer

pH sensor
AOP Engineering Laboratory

P
P
P T Air vent
O3 gas analyzer

O2

O3 generator Traps of
Reactor NaOH 2M Trap of KI

Pressure valve
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 Ozone Material & operating conditions
 Ozonation Set-up
AOP Engineering Laboratory
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 Ozone/Hydrogen Peroxyde
(Peroxone)
AOP Engineering Laboratory

H 2 O 2  2 O 3  2 OH   3 O 2
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 Fenton = Fe+2- H2O2

* Developed 1894 by Henry John Horstman Fenton as an analytical

reagent
Fenton HJH (1894). "Oxidation of tartaric acid in Presence of iron" J.
Chem Soc, Trans. 65 (65): 899-911. doi : 10.1039/ct8946500899
AOP Engineering Laboratory

Fe 2 + + H 2 O 2 → Fe 3 + + OH· + OH-

Fe 3 + + H 2 O 2 → Fe 2 + + OOH· + H+

* Suggested by Haber and Weiss in the 1932

Haber, F. and Weiss, J. (1932). "Über die des Hydroperoxydes KATALYSE"
Naturwissenschaften . doi : 10.1007/BF0150471
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 Hydrogen Peroxide
H2O2
Discovered by Thenard 1818
by reacting barium peroxide with nitric acid
AOP Engineering Laboratory

Hydrogen peroxide is a clear liquid, slightly more viscous than water,

colorless. pure hydrogen peroxide have a pH of 6.2, pH can be as low as 4.5
when diluted at approximately 60%.
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 Fenton

Fenton = Fe+2- H2O2 pH mV T

AOP Engineering Laboratory

Fe2+  H 2 O 2  Fe3+  OH-  OH 

H
3 
 2


Fe  H 2 O 2 Fe  OH Fe 2  HO2 

(a )

 OH Fe3+ H2O2

Fe3  HO2   Fe 2  H   O 2 H2O2 Fe2+ O 2H

mechanism through de Fe(IV) ??

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 AOP Engineering Laboratory
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Fenton mechanism

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 Fenton like

• Fe+2- H2O2 at not acidic pH

AOP Engineering Laboratory

• Me+2- H2O2 at basic or neutral pH

• Heterogeneous Fenton by using solids

containing metalic oxids- H2O2

• …….
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 Fenton
Advantages Disadvantages

 Very cheap  Operation pH 2-4 (optimal =3)

Simplicity  (easy  Generation of sludge through the

AOP Engineering Laboratory


maintenance). Robustness. removal of iron ions.
Flexibility

Exploration of Fenton at different pH (neutral and

basic) under research (iron complexes, Cu,..)
Possibility of supporting Fe ions on a solid under
research
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 Photochemical Oxidation Processes

PHOTOCHEMICAL PROCESSES WAVELENGTH

UV (photolysis) < 190 nm
AOP Engineering Laboratory

H2O2/UV < 300 nm

O3/UV < 320 nm
O3/H2O2/UV < 320 nm
TiO2/UV (photocatalysis) < 400 nm
Fe+2/H2O2/UV (photoFenton) < 550 nm
Fe+2/e-/UV (photoelectroFenton) < 550 nm
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 AOP Engineering Laboratory
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PHOTOCHEMISTRY

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 PHOTOCHEMISTRY

Energy of photon with wavelength 

E = h.c/
h (Planck) = 6.656 10-34 J.s
c (light) = 3 108 m/s
AOP Engineering Laboratory

l= m
Einstein = 1 mol of photons
hc 0.1197
E  NA  J/Einstein
 

Quantum yield  (stoichiometric coefficient)

 = mol reacted/mol of photons absorbed
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 PHOTOCHEMISTRY
UV radiation ~ 100 - 400 nm
visible ~ 400 - 700 nm
near infrared ~ 700 - 1000 nm
far infrared 1000 - 10000 nm

UVA 320 – 400 nm

Engineering Laboratory

UVB 280 – 320 nm

UBC 100 – 280 nm

700

600

500
UV-VIS ENERGY ENERGY
E kJ/mol

400
AOP

300
200 nm 140 kcal.mol-1 588 kJ.mol-1
200
UV 700 nm 40 kcal.mol-1 168 kJ.mol-1
100
VISIBLE
0
OH 

200 300 400 500 600 700

long onda, nm
wavelength, nm 35/77
 SOLAR PHOTOCHEMISTRY

4 - 7% UV radiation ( <400 nm)

AOP Engineering Laboratory
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 PHOTOREACTOR DESIGN
mass balance

    v   0
global t
 R
AOP Engineering Laboratory

j componet  j  n j  M j   ijri
t i 1

momentum balance

 v    vv     p  g
t

energy balance

E  (Ev )   q  (pv )  ( v )
t
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 PHOTOREACTOR DESIGN
radiation balance

( U R )   q R   E   A  for every wavelength
t
1
 λw (x)  dΩ
AOP Engineering Laboratory


*
U Rλ (x)= I
c 4π

1
q Rλ (x)=   I*λw (x)  wdΩ
c 4π
I λ (x)= 
4π
I *
λw (x)  dΩ

UR = radiation internal energy , Einstein/m3

qR = radiant energy flux density vector , Einstein/(m2.s)
E = radiant energy emission , Einstein/(m3.s)
A = radiant energy absorption , Einstein/(m3.s)
c = light speed, m/s
Iw* = radiation intensity (escalar and by solid angle) in the vectorial
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direction w, Einstein/(m2.s.srad) 38/75

 PHOTOREACTOR DESIGN
for not emitting media

d  I*λw (x)  σλ
=-(λ +σλ )  I (x)  +   I*λw (x)  Pλ(w*,w)dΩ
*
λw
ds 4π 4π
AOP Engineering Laboratory

Iw* = radiation intensity (escalar and by solid angle) in the vectorial

direction w, Einstein/(m2.s.srad)
I = radiation intensity (escalar), Einstein/(m2.s)
x = position according the bundle moviment, m
s = lineal cordinate in w direction w (optical way),m
 = adsorption radiation coefficient, m-1
 = scattering coefficient, m-1
P(w*,w) = phase function of dispersion w*  w. Indicates the probability of a
bundle in the direction w* takes the direction w after dispersion.
 = solid angle, srad
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 PHOTOREACTOR DESIGN
photon balance
d  q 
    q 
dx
q =photon flow density vector, Einstein/(m2.s)
AOP Engineering Laboratory

m = absorbance, cm-1
x = position, cm x

 q    q  w exp(   x )
1 
 x  q  / q  w rad abs 0,8 0,1
0,01 0,9900 0,0100 1
0,6
q/qw 3
0,1 0,9048 0,0952 0,4 9
30
1 0,3679 0,6321 0,2
3 0,0498 0,9502 0
9 0,0001 0,9999 0 0,2 0,4 0,6 0,8 1 1,2
OH 

cm
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 AOP Engineering Laboratory
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Tubular Photoreactors

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 Multitubular Photoreactors
AOP Engineering Laboratory
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 Multitubular Photoreactors
AOP Engineering Laboratory
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 Solar Photoreactors
AOP Engineering Laboratory
OH 

Helioman-PSA – Almeria 44/75

 Solar Photoreactors
AOP Engineering Laboratory

Parabolic
CPC-PSA – Almeria
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 Experimental
Devices

c0: 200
ppm
cp: 0 - 1 g/L
AOP Engineering Laboratory

pH: free
T: 30 ºC

VR: 1,26 - 0,078

L
L = 100 - 26 cm
d = 4 - 1,95 cm
VT: 6 - 1,5 L

Smirror: 2500 - 120cm2

41º inclination (Barcelona
Latitude) and faced
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South.
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 Experimental
Devices
6 tubes
Vtubo: 0,135 L
Ltubo = 60 cm
dtubo = 1,75 cm
VR = 0,808
AOP Engineering Laboratory

5 codos
VC = 0,034L
VTC = 0,170 L
VTR = 0,978 L

c0: 50 ppm
cp: 0,4 g/L
pH: free
VT: 10 L
T: 30 ºC
q: 1,95 L/min
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 WATER PHOTOLYSIS
H 2O  h  H  OH 
O-H bond strength in H2O: ca. 497 kJ mol -1
(corresponding wavelength = 240 nm)
AOP Engineering Laboratory

H2O + hν → °OH + H°
Φ = 0.42 at 172 nm
H° + O2 → HO2°

Termination reactions:
2 °OH → H2O2
2 H° → H2
HO2° + °OH → H2O + O2
2 HO2° → H2O2 + O2
OH 

240 nm
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 WATER PHOTOLYSIS
H 2O  h  H  OH 
AOP Engineering Laboratory

VCV lamps ( = 180 nm)

Excimer lamps

Advantage: no gaseous, liquid or solid additive

Disadvantage: very limited penetration depth of the photons
high cost of 180 nm radiation (Xe lamp)
ozone production
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Potential application: microelectronics, gas treatment 49/77

 UV/ H2O2 (WATER PHOTOLYSIS)
AOP Engineering Laboratory

h
H 2O 2  2 OH  380 kJ/mol or 90 kcal/mol
h
H 2O 2  H   O 2 H  210 kJ/mol or 50 kcal/mol
OH 

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AOP Engineering Laboratory
H2O2 PHOTOLYSIS

H2O2 + hν → 2 °OH

pKa = 11.6
HO2- + hν → °OH + O°-
O°- + H2O → °OH + OH-

ε254: 18.6 for H2O2 ; 240 L mol-1 cm-1 for HO2-

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 UV/ H2O2
photoreactor
UVC-lamps

tubular
photoreactor
AOP Engineering Laboratory

4 low-pressure
15 W mercury
lamps 253.7
nm

Volume 1.5 L

Went,
13.9
rotameter
Einstein.s-1

punp
OH 

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 AOP Engineering Laboratory
OH 
UV/ H2O2

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 H2O2 PHOTOLYSIS

Advantages Drawbacks
 handling/safety precautions
 no residues
 very weak absorption except at
AOP Engineering Laboratory

 H2O2 is miscible with H2O high pH (several tens of kW-lamps)

; inner filter effect by organics
 H2O2 is readily available,
 needs UVC (254 nm). Gemicidal
transportable, storable
 °OH scavenging by H2O2 (°OH +
H2O2 → HO2° + H2O)
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 OZONE/UV

Absorbs < 320 nm (UVB-UVC)

Relative absorbance

H 2 O  O 3  h 
 2 OH •  O 2
AOP Engineering Laboratory

H
O
2 
O
3 
h

O
2H
O
22

H
O
22
h

2
OH•

wavelength, nm

320 nm
OH 

ε254: 18.6 for O3 L mol-1 cm-1

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 OZONE/UV mechanism
h
O3 + H2 O   O2 + H2 O2

H2 O2 h 2 OH·
hydroxyl radical
H2 O2 
 H+ + HO2-
HO2 - + O3 
 O3 - + HO2 ·
AOP Engineering Laboratory

HO2 · 
 H+ + O2 -
O2 - + O3 
 O3 - + O2
OH· + O3 
 HO2 · + O2
HO2 · + O3 
 OH· + 2O2
hydroperoxyl radical H+ + O3 - 
 HO3
HO3 
 OH· + O2
2OH· 
 H2 O2
scavenger HO2 · + HO2 · 
 OH· + 2O2
HO2 · + O2 - 
 O2 + HO2 -
OH 

H2 O2 + OH· 
 HO2 · + H2 O
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 Ozone/UV

h
O 3  H 2O  2 OH   O 2
AOP Engineering Laboratory
OH 

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 Ozone/Hydrogen Peroxyde/UV
AOP Engineering Laboratory

h
O 3  H 2O  2 OH   O 2

H 2 O 2  2 O 3  2 OH   3 O 2
OH 

58/77
 OZONE/UV

Advantages Disadvantages

 no residues  need to produce O3 (but bactericidal use

of O3)
 easy O3 dosification
AOP Engineering Laboratory

 necessity of destroying residual gaseous

 UV absorption higher than
that of H2O2 (0.1 kW-
lamps)
O3
 efficiency limited by O3 hydrosolublity,
gas-liquid transfer and scavenging of
°OH (°OH + O3 → HO2° + O2)

Problems

 Unwanted stripping of VOCs

 Br- + 3 O3 → BrO3- + 3 O2 (overall reaction)

OH 

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 Photocatalysis

Heterogeneous photocatalysis
Semiconductor based catalyst:
* TiO2 , ZnO, ...
AOP Engineering Laboratory

* CdS

Homogeneous photocatalysis
Photosensitizers
(ruthenium(II) poly(pyridyl),...)

PhotoFenton
Fe+3/UV/H2O2
OH 

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 Zeolite with photosensitizers

Zeolite
N N
AOP Engineering Laboratory

2,2‘ - bipiridin (bpy)

N N

N Fe2+ N

N N

[Fe(bpy)3]2+ (1 nm)
OH 

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 Zeolite with photosensitizers

14
Zeolita Y
12 ZeoY-Fe(III)
ZeoY-Fe(II)bpy3
AOP Engineering Laboratory

10
ZeoY-Fe(II)bpy3-TiO2
Absorbància
Absorbance

4
2

0
200 300 400 500 600 700 800
 [nm]
OH 

UV Visible 62/77
 TiO2/UV
h
Ti O2  e  h
Ti O2 • 

good UV absorption
AOP Engineering Laboratory

low quantum yield (  < 0.03)

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 TiO2/UV
Advantages Disadvantages

 No consumable additive  Separation of the catalyst from the

solution
Use of Solar UV
AOP Engineering Laboratory


 UV irradiation is poorly utilized by
TiO2 despite high absorption
 Simplicity  (easy
maintenance). Robustness.
Flexibility  Poisoning of catalyst by organic
matter.
 Much lower sensitivity to pH
than UV-AOPs based on  Low quantum yield
H 2O 2 , O 3

 Reduction of some pollutants:

Mn+, CCl4
OH 

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 PhotoFenton

Fe+3/UV/H2O2 H2O2 Fe2(SO4)3

Fe(III) in the presence of UV :

AOP Engineering Laboratory

Fe3+(aq) + H2O + hn OH· + Fe2+ +H+

UV lamps
quantum yield for the formation of Fe(II) (360 nm)
0.14 at 313 nm
0.017 at 360 nm
Faust, B. C.; Hoigne, J., Atmos.
Environ. 24A (1990) pp. 79-89

Magnetic
Stirrer
OH 

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 PhotoFenton
Fe(III) in the presence of UV :

Fe3+(aq) + H2O + hn OH· + Fe2+ +H+

Fenton
AOP Engineering Laboratory

Fe2+  H 2 O 2  Fe3+  OH-  OH 

H
3 
 2

 2
Fe  H 2O 2 Fe  OH Fe  HO2 

(a )



Fe3  HO2   Fe2  H   O 2

OH 

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 PhotoFenton
Additional reactions in Photo-Fenton

Fe3+ + H2O2 → H+ + Fe(HO2)2+

AOP Engineering Laboratory

Fe(HO2)2+ + hν → Fe(HO2)2+*

Fe(HO2)2+* → FeIII-O° ↔ FeIV=O + °OH

Fe(HO2)2+* → FeII + HO2°

°OH radicals are not the only active species

UV-visible photodegradable compounds

hν
RCO2Fe(III)   R   CO2  Fe(II)
OH 

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 Solar PhotoFenton
1.2 1.2
TiO2
1.0 1.0
-1

0.8 0.8
AOP Engineering Laboratory

W m min

Espectro solar
Solar spectrum

O.D.
-2

0.6 0.6

0.4 0.4

3+ -1
(0.25 mmol.L )
Fe 3+
0.2 0.2

0.0 0.0
300 400 500 600
Wavelength, nm
OH 

parabolic CPC PSA – Almeria 68/77

 PhotoFenton
Advantages Disadvantages

 Very cheap  Operation pH 2-4 (optimal =3)

Simplicity  (easy  Generation of sludge through the

AOP Engineering Laboratory


maintenance). Robustness. removal of iron ions.
Flexibility
 Cost of UV-visible lamps
 Increase mineralization (TOC
reduction)  Waters with suitable UV light
transmission
 Use of visible radiation
 Fouling of the surface of UV tubes
OH 

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 Strategy to combine AOPs with Biological treatments

* Decrease the treatment cost

* Increase biodegradability

* Eliminate toxicity
AOP Engineering Laboratory

CHEM BIOL

BIOL CHEM

DOMESTIC WASTEWATER
Biodegradability (BODn/COD) = 0.4 - 0.8
Metcalf and Eddy (1985)
OH 

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 Strategy to combine AOPs with Biological treatments
 

 
Wastewater

Non-biodegradable
 
Partially biodegradable
AOP Engineering Laboratory

Biodegradability
Biodegradability
 
Chemical
 
process   Organic
  Biodegradable
 
Low
High   Low
level
 

 
NO Yes
 
Chemical
 
 
Biodegradability Biological process
  process
 
OH 

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 Coupling Ozone with Biological and Menbrane Treatments

SOSTAQUA (http://www.sostaqua.com)
NOVEDAR (http://www.novedar.com)
AOP Engineering Laboratory

MBR
Reverse
activated sludge
Ultrafiltration Osmosis
Bioreactor
etc..

AOPs AOPs
(ozonation,UV/H2O2) (ozonation,UV/H2O2)
OH 

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 Ozone/UV with Biological treatment

ozone
UV Lamp
AOP Engineering Laboratory

Volcanic
stones

27ºC

Neutralizing
O3 stage
killer

1.5L Vessel Thermostatic

Stirrer Air Bath
OH 

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 sequencing photoreactor + bioreactor

H2O2 FeSO4
Volcanic
AOP Engineering Laboratory

stones

UV lamps

UV
27ºC

Neutralizing
stage

Thermostatic
Magnetic Bath
Stirrer
Air
OH 

74/77
 sequencing photoreactor + bioreactor
AOP Engineering Laboratory

Photoreactor 1.5 L
Black blue lamps (3 x 8W, 360 nm) = 6 Einstein/s
OH 

75/77
 SUMMARY
Chemical Oxidation Processes

Advantadges
- High oxidizing power
- Not selective oxidant
- No residues (except homogeneous Fenton and O3 catalytic)
AOP Engineering Laboratory

- Increase biodegradabilty
- Decrease toxicty

Disadvantages
- Cost of UV-Visible radiation and chemicals (H2O2, O3)
- Mass Transfer control for ozone
- UV light transmission of waters
- Rate decreases due to °OH scavenging by the
 sensitizer (H2O2, O3)
 products (HCO3-/CO32-, SO42-, HxPO43-x)
 reactant (Fe2+)
OH 

Good chance for coupling AOP with biological treatment

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 AOPs application fields

Drinki
ng
water
Domestic Well-
wastewat
ers waters
AOP Engineering Laboratory

Coolin
g
AOP
waters s

Abandon
ed-
Site
waters
Agricultu
re
wastewat
OH 

ers

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 AOP Engineering Laboratory
OH 

Th a nk
you
 AOP Engineering Laboratory
OH 

Th a nk
you

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