Solar Photocatalysis PDF

Outlook
Waste water treatment by advanced

Introduction
oxidation processes Photocatalysis
(solar photocatalysis in degradation of
Photo-Fenton
industrial contaminants)
Photoreactors
Compound Parabolic Collectors
Sixto Malato Rodríguez
State of the art
(sixto.malato@psa.es)
Applications
Pesticides
Plataforma Solar de Almería , TABERNAS-Almería
OMW
SPAIN
Pharmaceutical WW
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Innovative Processes and Practices for Wastewater Treatment Innovative Processes and Practices for Wastewater Treatment
and Re-
Re-use. 8-11 October 2007, Ankara University, Turkey and Re-
Re-use. 8-11 October 2007, Ankara University, Turkey
1
Introduction Introduction
Biodegradable substances:
¾ Biofilter treatment/ activated sludge treatment •High costs
Non-viable
Non-destructive •High energy
Non-biodegradable substances can show consumption
• High costs
¾ Non-toxic / inert behaviour • Toxic by-products Partial
• High energy destruction
¾ Acute toxicity consumption
¾ Chronic toxicity
Activated carbon
Air stripping Bio-treatment •OH radicals
Alternative
treatment Incineration Ozone
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Introduction Introduction
z H2O2/Fe2+ (Fenton): Fe 2+ + H 2 O2 → Fe 3+ + OH − + OH • Photochemical AOPs
z H2 O 2 /Fe2+ (Fe3+ )/UV (Photo-Fenton): Fe 3+
⎯⎯ν → Fe2+ + HO •
h⎯ AOP key reactions wavelength
z TiO2/hν/O2 (Photocatalysis): TiO2 ⎯⎯

ν → e− + h+
h⎯ UV/ H2O2 H2O2 + hν → 2 OH •
λ < 300 nm
+
h + H 2O→ OH + H • + O3 + hν → O2 + O (1D)
UV/ O3 λ < 310 nm
O 3 / H2 O 2 : H⎯+ − • •− O (1D) + H2O → 2 OH•
z H 2 O2 ←⎯ → HO − + O3 → O2 + HO2− HO2 + O3 → HO2 + O3
UV/H2O2/ O3 O3 + H2O2 + hν → O2 + OH• + OH2• λ < 310 nm
HO2• ⇔ H + + O2• − O2•− + O3 → O2 + O3•− O3•− + H + → HO3•
TiO2 + hν → TiO2 (e- + h )
CATALYSIS
• • +
HO3• → HO • + O2 HO + O → HO + O 3 2 2
UV/ TiO2 λ < 390 nm
TiO2(h ) + OH-ad → TiO2 + OHad•
+
ν → O ( D) + O O (+
h⎯ D) + H O ⎯
⎯→ H O
1 hv
⎯⎯ ⎯ 2 HO • H2O2 + Fe2 → Fe3 + OH• + OH-
1
O3/ UV: H 2 O2 ⎯⎯→ + +
SUN
z O3 2 2 2 2
photo-Fenton λ < 580 nm
+ + +
Fe3 + H2O + hν → Fe2 + H + OH•
ν → 2OH •
h⎯
z H2O2/UV: H 2 O2 ⎯⎯
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Photocatalysis Photocatalysis
“band gap” energy hν

2000 Standard Solar Radiation Spectra 2000
is the energetic
hc separation between
-1
λ G=
Extraterrestrial
Irradiance, W m µ m
recombinación
recombination
1500 Global 37º Air Mass 1.5 1500 a semiconductor

-2
EG valence and Red1 Oxid2

conduction band
hc Oxid1 Red2
U=
1000 1000
λ
recombination
recombinación
Material “Band gap” (eV) λ for e-/h+ formation“ (nm)
CdO 2.1 590
500 500 CdS 2.5 497
Fe2 O3
GaP
2.2
2.3
565
540 C + hυ →C (e − + h + )
SnO2 3.9 318
0 0 TiO2 3.0 390 h + + H 2 O → • OH + H +
0.6 1.2 1.8 2.4 3.0 3.6 4.2 WO3 2.8 443
W avelength, µ m ZnO 3.2 390
e − +O 2 →O 2• −
ZnS 3.7 336
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Photocatalysis Photocatalysis
•The process takes place 1000

at ambient temperature. Source: Scopus (http://www.scopus.com), June 2007
•Oxidation of the
substances into CO2 is
800
complete.
Publications (TiO2)
•The oxygen necessary 600
for the reaction is
obtained from the
atmosphere. 400
•The catalyst is cheap,

innocuous and can be
200
reused.
•The catalyst can be
attached to different 0
types of inert matrices. 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06
Year
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Photo-Fenton Photo-Fenton
Reactions Fe2+, Fe3+ and H2O2 in water
Photo-Fenton method 1.2 TiO2 1.2
Fe 2+ + H 2 O 2 → Fe3+ + OH − + OH • k = 53 – 76 M-1 s-1

2+ 3+ − •
Fe + H 2O2 → Fe + OH + OH 1.0 1.0 Fe 2+ + OH • → Fe3+ + OH − k = 2.6 – 5.8·108 M-1 s-1
Intensity (W.m-2.nm-1)
• −
Fe 2+ + HO 2 → Fe3+ + HO 2 k = 0.75 – 1.5·106 M-1 s-1
hν
•
3+ 2+ + • Fe3+ + H 2 O 2 → Fe 2+ + HO 2 + H + k = 1 – 2·10-2 M-1 s-1
+ H 2O ⎯⎯→ Fe + H + OH
Optical Density
Fe 0.8 0.8
•
Fe3+ + HO 2 → Fe 2+ + O 2 + H + k = 0.33 – 2.1·106 M-1 s-1
Solar Spectrum
•−
Fe3+ + O 2 → Fe 2+ + O 2 k = 0.05 – 1.9·109 M-1 s-1 Equilibriums
Advantages 0.6 0.6
OH • + H 2 O 2 → H 2 O + HO 2
•
k = 1.7 – 4.5·107 M-1 s-1
H 2O
⎯⎯⎯→ −
HO 2 + H +
K = 2.63 10-12 M
2 ←⎯⎯⎯
¾ High reaction rates 0.4 0.4

Radical reactions
⎯⎯⎯→
[Fe]3+ + H 2 O 2 ←⎯⎯⎯ [Fe(HO2 )]2+ + H + K = 3.1 10-3 M
Fe3+
¾ Cheap, non-toxic reagents (0.25 mM, pH=2.8) 2+
[Fe(OH)] + H 2 O
⎯⎯⎯→ +
[Fe(OH)(HO 2 )] + H +
K = 2 10-4 M
(Fe, H2O2, acid, base)
2 ←⎯⎯⎯
0.2 0.2 2 OH • → H 2 O 2 k = 5 – 8 109 M-1 s-1
• ⎯⎯⎯→ •− +
•
2 HO 2 → H 2 O 2 + O 2
6
k = 0.8 – 2.2 10 M s -1 -1 HO O2 + H K = 3.55 10-5 M
Disadvantages
2 ←⎯⎯⎯
0.0 0.0
•
HO 2 + OH • → H 2 O + O 2 k = 1.4 1010 M-1 s-1 ⎯⎯⎯→
OH • ←⎯⎯⎯ O •− + H + K = 1.02 10-12 M
300 400 500 600
¾ pH adjustment necessary
Wavelength (nm) •
HO + H
2
+ ⎯⎯⎯→
←⎯⎯⎯ H 2O 2
•+
K = 3.16– 3.98 10-12 M
¾ Iron removal necessary
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Photo-Fenton Photo-Fenton
Fenton reactions with organics “Photo-
Photo-Fenton”
• 3+ + 2+
R +Fe → R +Fe [Fe3+ L] + hν ⎯
⎯→ [Fe3+ L]* ⎯
⎯→ Fe 2+ + L•
pH [-]
R • +Fe 2+ → R − +Fe3+ 1 1.5 2 2.5 3 3.5 4 4.5 5 [Fe(H 2 O)]3+ + hν ⎯
⎯→ Fe 2+ + OH • + H +
-3
1.E-03
10 [Fe(OH)]2+ + hν ⎯
⎯→ Fe 2+ + OH •
R • +R • → R − R OH • + RH → R • + H 2O
[Fe(OOC − R)]2+ + hν → Fe 2+ + CO 2 + R •
R • +HO •2 → RO 2 H R − CH = CH 2 + OH • → R − C • H − CH 2 OH 10
1.E-04
-4
2+ 3+ − •
Fe + RO 2 H → Fe + OH + OR OH • + RX → RX •+ + OH −
c [M]
-5
• 1.E-05
10
R • + O 2 → RO 2
Quantum yield
• •
RO 2 + H 2 O → ROH + HO 2
10-6
1.E-06
Persistent complexes with Mono- y Dicarboxylic acids (L). 10

1.E-07
-7
Reaction is stopped before complete mineralisation 3+

[Fe(H2O)6]
aaaaaaaaaaaa [Fe(H2O)5(OH)]
bbbbbbbbbbbbbbb
2+
[Fe(H 2O)4(OH)2]
ccccccccccccccccc
+
4+
[Fe(H2O)3(OH)3]
ddddddddddddddd [Fe2(H2O)8(OH)2]
eeeeeeeeeeee
Fe 3+ + n L → [FeL n ] x + ⎯H⎯2O⎯
2 ,⎯
dark
⎯→ no further reaction
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Photo-Fenton Outlook
Source: Scopus (http://www.scopus.com), June 2007

70
Introduction
Publications (photo-Fenton)
60
Photocatalysis
50 Photo-Fenton
40 Photoreactors
Compound Parabolic Collectors
30
State of the art
20
Applications
10 Pesticides
OMW
0
92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 Pharmaceutical WW
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Photoreactors Photoreactors
Catalyst Chemical Oxygen

oxidant (Air)
Mixer
Sun
Tank Solar UV
Pre-treatment
Contaminated (pH Pump light
water adjustment,
filtering, etc)
Filter
Contaminated
water
Photoreactor
(Solar Collector
Post-treatment Field)
Treated (catalyst
water recovering, pH
adjustment, etc.)
Batch process
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100
Al Direct radiation:
Reflectivity (%)
UV direct (tracking the Sun)

80
Rh solar radiation that
60
Pt reaches ground
40 Au level without being
absorbed or
Cu
20 Ag Reflectivity
0
scattered.
Diffuse radiation:
300 320 340 360 380 400
Wavelength (nm)
the radiation that
100
Quartz
Transmissivity (%)
80
Pyrex
TM has been dispersed
but reaches the
TM
Duran
60 Standard Glass
ground.
PTFE
40
Solar UV Spectra
20
Transmissivity
UV global horizontal Global radiation:
0
The sum of both.
300 325 350 375 400
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¡UV must be
Decembre
Máximum UV (λ<400 nm) sunny days

50
2000 Standard Solar Radiation Spectra accurately

2000
(37º, N)
40
measured!
-1
UVdir
Extraterrestrial
Irradiance, W m µ m
30
E(W m )
-2
1500 Global 37º Air Mass 1.5 1500
20
-2
1000 10
UVglo
Espectros medidos en
W m-2 ?m-1
UV spectramomentos
diferentes 0
8 10 12 14 16 18 20 22
Hora Local
1000 1000
500
June
500 500 50
UVglo
0.0 40
0.30 0.35 0.40

UVdir
Wavelenght, µm
E(W m )
30
-2
0 0
20
0.6 1.2 1.8 2.4 3.0 3.6 4.2

W avelength, µ m 10
0
8 10 12 14 16 18 20 22
Hora Local
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State of the art State of the art
Sandia National Labs (Albuquerque, USA) In the early nineties, the
developed in 1989 the first solar facility for
National Renewable
water detoxification at pre-industrial level
based on 1-axis Parabolic Trough Collectors Energy Laboratory,
(PTC). CIEMAT,
CIEMAT in 1990, erected the second at Sandia National
Plataforma Solar de Almería (Spain), using 2- Laboratories and the
axis PTCs. Lawrence Livermore
National Laboratory
addressed the “Livermore
experiment” (USA). A
These pilot plants were the Solar
olar Detox Plant was
first step in the installed using one-axis
development of the solar PTCs to treat TCE-
groundwater This experiment constituted the first on-site
technology. test. Tests were successful but the economic
contaminated during the figures not!
Second World War.
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One-
One-sun (non-
(non-concentrating)
concentrating)
collectors are cheaper than
PTCs.
PTCs. An extensive effort in the
design of small non-
non-tracking
collectors,
collectors, has resulted in the
testing of several different non-
non-
concentrating solar reactors.
reactors.
The design of a robust one-sun
photoreactor is not trivial:
weather-resistant, chemically
inert and ultraviolet-
transmissive. Also, flow in non-
concentrating systems is
usually laminar.
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DSSR-Pilotplant II in Wolfsburg
DSSR-Pilotplant II
The Planning Concept:
2
Illuminated Reactor Area A = 30 m
Flow Re 5000 (turbulent)

3
Volumetric Flow Rate Vtot = 12 m /h
Pressure Drop = 0.5 bar

3
Treatment Capacity 0.9 m /d
Source: Prof. D. Bahnemann, Universität Hannover
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Thin-Film Fixed Bed Reactor (TFFBR) Thin-Film Fixed Bed Reactor (TFFBR)
1995 in Almeria/Spain 2003 in Tunis/Tunisia

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State of the art Compound Parabolic Collectors
PARABOLIC CONCENTRATORS
MAIN ADVANTAGES MAIN DISADVANTAGES
Turbulent flow Only Direct radiation
No vaporization of compounds High cost (Sun Tracking)
Low optical efficiency
Low Quantum efficiency (with TiO2) 1 Sun COMPOUND
Overheating PARABOLIC COLLECTORS
NON CONCENTRATING PHOTOREACTORS
9 Turbulent flow conditions
9 No vaporization of volatile
MAIN ADVANTAGES MAIN DISADVANTAGES compounds
Direct & Diffuse radiation Laminar flow (low mass transfer) 9 No tracking
No heating Vaporization of reactants
9 No Overheating
9 Direct and Diffuse radiation
Low cost Reactants contamination 9 Low cost
High optical efficiency 9 Weatherproof (no contamination)
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Compound Parabolic Collectors Compound Parabolic Collectors
y
1
ρ = rθ for θ ≤θa + π 2 Part A-B
C=
sinθ a θ + θ a + π 2 − cos (θ − θ a ) π 3π
θΑ ρ=r
1 + sin (θ − θ a )
for θ a +
2
≤θ ≤
2
−θ a Part B-C
R C
r
O θΑ x
θ
If θa = 90 B C = 1
A B
One Sun CPC collector manufacturing: θa = 90º

90º ⇒ all direct and diffuse solar
photons can be collected and used (diffuse UV radiation is a very
very important
fraction of total solar UV)
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EU Project (1996-
(1996-1999)
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A very simple one-

one-sun CPC collector was designed, constructed and tested
to optimize the manufacturing process (modularity), on site installation
installation
(minimum interconnecting pieces and not illuminating zones) and cost
saving
Additional system advantages:

• Easy manufacturing
• Low investment cost
• Simple operation and
supervision
• Low maintenance requirements
• No sun tracking devices are
needed
• UV diffuse radiation can be
profited
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The plant is designed with full automatic

systems. A Programmable Logic Controller
receives all plant data signals (flow-rate,
tanks level, temp, solar UV-A irradiation, etc)
and control pumps and system valves.
Slurry systems are the most efficient, resulting an
important reduction in the final treatment cost. A
process for catalyst recuperation has been
Process evolution is monitored through the measuring and
patented. EP-1-101-737-A1 (2001). integration of UV light up to a fixed level.
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The SOLARDETOX
Consortium (Brite-
Euram III Program,
Contract No.
BRPR-CT97-0424)
has installed during
1999 the first
European Solar
Detoxification
Plant. Main plant
characteristics are:
•CPC surface: 100
m2
•Treatment
volume: 800 L.
•Batch Operation
•Automatic
operation
•cost of the plant:
100000 €
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Outlook Applications
1976 PHOTOCATALYSIS AT LAB SCALE (BASIC RESEARCH)
Introduction 1ST ENVIRONMENTAL NORMATIVES
Photocatalysis PILOT PLANT NEW RESEARCH

PHOTOCATALYSIS GROUPS
Photo-Fenton
Photoreactors SOLAR COLLECTORS NEW PROCESSES (catalysts,
Compound Parabolic Collectors DEVELOMENT oxidants, photo-Fenton,...)
NEW ENVIRONMENTAL EU TOO EXPENSIVE ALTERNATIVES:
State of the art DIRECTIVES: IPPC (1996),WFD GAC, AIR STRIPPING,
(2000),... INCINERATION...
Applications
ENVIRONMENTAL
Pesticides PRIVATE COMPANIES
MARKETING
OMW
2007 APPLICATIONS
Pharmaceutical WW
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Applications Applications
9It has demonstrated that the solar photocatalytic technology − Phenols,

Phenols, nitrophenols and halophenols.
halophenols.
is sufficiently developed for industrial use. A European
industrial consortium has been created to the design and set- − Pharmaceutical compounds (antibiotics,
antibiotics, disinfectants...).
disinfectants...).
up of turnkey SOLARDETOX plants.
− Water disinfection.
disinfection.
9The technology developed can be used, without modification,
to address solar Photo-Fenton and TiO2 degradation process. − Gasoline additives (MTBE, ETBE,..).
APPLICATIONS − Chlorinated hydrocarbons (solvents,

solvents, VOCs,
VOCs, etc).
¾ Organics concentration ≤ hundreds of mg L-1.
− Residues from textile industry (dyes).
dyes).
¾ Low-medium flow (< 10 m3/h).
¾ Contaminants present within complex mixtures of organics.
¾ Contaminants with no easy treatment by conventional − Agrochemical wastes (pesticides).
pesticides).
technologies.
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Pesticides Pesticides
QUITE WELL SUITED TO SOLAR PHOTOCATALYTIC

Small amounts of pesticide TREATMENT:
TREATMENT:
remaining in the empty
containers (approx. 70 1. The initial pesticide concentration can be controlled
units/ha). as a function, so the most appropriate concentration
for optimum photocatalytic efficiency can be
chosen.
2. Toxicity is extreme, low-
low-volume and in a well-
well-
defined location.
3. Such point sources of pollution may be ideally
treated in small-
small-scale treatment units.
4. Intensive agriculture in greenhouses is usually
concentrated in sunny countries.
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The intensive agriculture activity is a very important economical sector

in Almería. There are more than 350 km2 of greenhouses. These greenhouses yearly consume 5.200 tons of phytosanitary
products (1.5 million of bottles; 1.9 L average volume).
A process has been designed to recycle the plastic of these bottles. The
recycling process needs a washing of the plastic. This produces a water
with hundreds of mg/L of persistent toxic compounds.
Proposed Solution : Solar Photocatalytic

Treatment
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Plant design data:

a) Total yearly volume of
water to be treated
(Vt): 1875 m3
b) Yearly operating hours
of solar facility (Ts):
3000 h
c) Yearly
Yearly average global
UV irradiation (UVG),
sunrise to sunset: 18.6
WUV m-2
d) Average solar energy
needed to degrade the
contaminants (QUV): 12 Plastic
kJUV L-1
grains
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Solar field figures:

a) Individual CPC modules
formed by 20 parallel
tubes (surface: 2.7
m2/module)
b) 4 parallel rows with 14
modules each mounted
on a 37º-tilted platform
(local latitude)
c) total collectors surface:
150 m2
QUV Vt 12 x 10 x 1875 x 10 ⎡ J L L ⎤
3 3 −1
Ar = = = 112 m 2
Ts UVG 3000 x 3600 x 18.6 ⎢⎣ s W m −2 ⎥⎦ d) Total photoreactor
volume: 1061 L
Final selected plant dimensioning e) Total volume per batch:
(solar collector area) was: 150 m2 1500 to 2000 L
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Pesticides OMW
Operating procedure: Typical composition (only main parameters) of OMW:
a) The system is run in COD: 80000 mg/L
batch mode using
Dissolved Phenols: 4500 mg/L
a 2000 L
TOC: 35000 mg/L
recirculation tank
pH: 5.1
b) The 4 rows are Relevant anions: phosphate 700 mg/L, chloride 500 mg/L,sulphate
connected in 100 mg/L, nitrite 6 mg/L.
parallel O OH O OH
(independently 100
OH O
HO
O
OH
operated) and the 2 mm cuvette (quartz) H3C
O O
CH3
HO
NH2
HO
HO
14 modules of 80
1/100
OH
OH
each row in series O OH

60
1/50 HO
OH O
HO
c) After treatment
O
%T
O HO
H3C H
1/25 HO
water is returned 40
OH HO HO O
OH
to the washing 20
system and the 1/10
Transmission spectra of OMW
tank is refilled with 0 through 2, mm pathlength at
new contaminated 300 350 400 450 500 550 600
different dilution ratios.
nm
water
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OMW OMW
OMW Dissolved Phenols behaviour with

different photocatalytic treatments
4000
Dissolved Phenols (mg/L)
Only TiO2
2-
TiO2 + S2O8 20 mM
3000
Fe 1mM+ H2O2 20 g/L
Fe 5mM+ H2O2 20 g/L
Fe 1mM+ H2O2 5 g/L
2000
1000
t30W=14.1 h
0
0 50 100 150 200 250 300 350
Q (kJ/L)
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OMW OMW
Treatment of OMW in the FFR. Fe = 5mM

20 40
1.4
20 h-sunny days-March
35
1.2
Installed and
COD and TOC (g/L)

15 30
H 2O 2 Consumed, (g/L)
COD
tested in a
1.0
25
Phenols (g/L)
TOC
Olive Mill at
0.8
10 20
Kivery Phenols
0.6
15
(ARGOS, 5 H 2O 2 0.4 10
Greece). 0.2 5
0 0.0 0
0 20 40 60 80 100 120
Q (kJ/L)
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OMW OMW
Pot experiment performed in

greenhouse because of:
-Protection from environment (wind, rain,
insects)
-Controled irrigation
-Additional light
TOC: 16000 ppm 8000 ppm 0 ppm

Tot.Phenols: 3200 mg/L 1600 mg/L 0 mg/L
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OMW OMW
Substrate: Olive production
Earth
- Bacteria ⇒ conversion of Use as fertilizer
Pressing
TOC
- Unknown disposal of Photocatalytic Olive oil
nutrients treatment + OMW
Perlita Neutralization
- Aluminium silicate, porosity
of 95%
- Inert substrate Pretreatment
Pots: Mud to
- 12 L volume, PVC, fair grey compostation
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Pharmaceutical WW Pharmaceutical WW
Composition of wastewater (seawater) containing

Femac (α-methylphenilglycine, C9H11NO2)
mg L-1 mg L-1 mg L-1
Femac 500-600 Susp. 20-100 COD 1500-

solids 1800
TOC 400-500 NH4+ 0-40 NO3- 200-600
Installed at DSM-DERETIL
Villaricos (ALMERIA)
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1000+400 L contact column, 5 – 10 h of contact

Æ Continuous flow 140 – 280 L·h-1 O2
PH
IBR
OUT
BIOLOGICAL
LOOP
FI
CONDITIONER
FI
OUT
BLOWER
NEUTRALIZATION OUT
TANK
SOLAR
LOOP
PH
OUT
FI
700 L IBR H2O2
3000 L total volume

BUFFER
1260 L illuminated volume

4000 L total volume Re-circulation flow 1.2 m3·h-1 O2
Recirc. Flow 11 m3·h-1 Continuous flow 40-80 L·h-1

PH
OUT
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Local time, h
12 14 16 18 20
600 40
500 30
40
35
-2
UV, W m
400 MPG, Fe= 20 mg/L
H2O2,CONS, mM
C, mg/L
T, ºC
Vi = 1260 L 20 TOC
300 VT = 3700 L H2O2,CONS , mM
30
20 T, ºC
200 UV, W m-2
10
25
100
0 0 0
0 50 100 150
t30W , min
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Overview coupling Photo-

Photo-Fenton/Biotreatment
IBR during 75 days
of continuous mode TOC treated
Bioreactor: Inlet vs. Outlet operation. 900
360
TOC Inlet Continuous operation 800 photo-Fenton
IBR
showed the stability
TOC Outlet 700
TOC (mg L-1)

300
TOC (mg L-1)
600 TOC outlet

and permanent
240
500
180
120 activity of the 400

300
60 immobilised biomass 200
0 with an influent, 100
which originates
25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105
0
Day
64 68 70 74 76 78 82 84 88 90 92 94 96 98 100 102
from the AOP pre-
pre- day
treatment (photo-
(photo-
Fenton)
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Pharmaceutical WW ACKNOWLEDGEMENTS
Total cost per m3 of treated effluents containing 1 kg/m3 of

Femac (i.e. 700 mg TOC/L) for different scenarios.
Depreciation: 10 years Local Organizing Committee.
photo-Fenton/ Biol (Demo 2
photo-Fenton/Biol (1000 m photo-Fenton/Biol (10000 Ankara University.
plant) CPC) m2 CPC)
2300 m3 year 23000 m3 year 230000 m3 year Faculty of Engineering
€/m3 % €/m3 % €/m3 %
4.26 14.6 4.26 40.9 4.26 58.8
Reagents European Commission (Research DG):
INNOVA-MED Project
Electric power 0.43 1.5 0.21 2.0 0.21 2.9
Manpower 17.11 58.6 2.67 25.6 0.36 5.0 Contract No. INCO-CT-2006-517728.
Capital costs 1.96 6.7 1.52 14.6 1.52 21.0
(solar field)
Capital costs 5.43 18.6 1.75 16.8 0.89 12.3
(others)
Total (€ m-3) 29.2 10.4 7.2
77/77 78/77
and Re-
39
SPECIAL ISSUES ABOUT SOLAR PHOTOCATALYSIS
Catalysis Today, Vol. 54(2-
54(2-3), 1999.
Catalysis Today, Vol. 76(2-
76(2-4), 2002.
Catalysis Today, Vol. 101 (3-
(3-4), 2005.
Catalysis Today (SPEA-
(SPEA-4 Conference), in press 2007.
Solar Energy, Vol. 77(5). 2004.
Solar Energy, Vol. 79 (4). 2005.
Journal of Solar Energy Engineering, Vol. 129. FEBRUARY 2007
79/77
Innovative Processes and Practices for Wastewater Treatment
and Re-
40

Solar Photocatalysis PDF

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Outlook

Waste water treatment by advanced

z TiO2/hν/O2 (Photocatalysis): TiO2 ⎯⎯

“band gap” energy hν

1500 Global 37º Air Mass 1.5 1500 a semiconductor

EG valence and Red1 Oxid2

•The process takes place 1000

•The catalyst is cheap,

Fe 2+ + H 2 O 2 → Fe3+ + OH − + OH • k = 53 – 76 M-1 s-1

¾ High reaction rates 0.4 0.4

Persistent complexes with Mono- y Dicarboxylic acids (L). 10

Reaction is stopped before complete mineralisation 3+

Source: Scopus (http://www.scopus.com), June 2007

Catalyst Chemical Oxygen

UV direct (tracking the Sun)

Máximum UV (λ<400 nm) sunny days

2000 Standard Solar Radiation Spectra accurately

0.30 0.35 0.40

0.6 1.2 1.8 2.4 3.0 3.6 4.2

The Planning Concept:

Flow Re 5000 (turbulent)

Pressure Drop = 0.5 bar

1995 in Almeria/Spain 2003 in Tunis/Tunisia

One Sun CPC collector manufacturing: θa = 90º

A very simple one-

Additional system advantages:

The plant is designed with full automatic

1976 PHOTOCATALYSIS AT LAB SCALE (BASIC RESEARCH)

Introduction 1ST ENVIRONMENTAL NORMATIVES

Photocatalysis PILOT PLANT NEW RESEARCH

9It has demonstrated that the solar photocatalytic technology − Phenols,

APPLICATIONS − Chlorinated hydrocarbons (solvents,

QUITE WELL SUITED TO SOLAR PHOTOCATALYTIC

The intensive agriculture activity is a very important economical sector

Proposed Solution : Solar Photocatalytic

Plant design data:

Solar field figures:

each row in series O OH

OMW Dissolved Phenols behaviour with

Treatment of OMW in the FFR. Fe = 5mM

COD and TOC (g/L)

Pot experiment performed in

TOC: 16000 ppm 8000 ppm 0 ppm

Substrate: Olive production

Composition of wastewater (seawater) containing

Femac 500-600 Susp. 20-100 COD 1500-

1000+400 L contact column, 5 – 10 h of contact

700 L IBR H2O2

3000 L total volume

1260 L illuminated volume

Recirc. Flow 11 m3·h-1 Continuous flow 40-80 L·h-1

Overview coupling Photo-

TOC (mg L-1)

600 TOC outlet

120 activity of the 400

Total cost per m3 of treated effluents containing 1 kg/m3 of

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