Ankara 2 - Treatment by AOPs - Malato

Outlook
Waste water treatment by advanced oxidation processes (solar photocatalysis in degradation of industrial contaminants)
Sixto Malato Rodrguez (sixto.malato@psa.es) Plataforma Solar de Almera , TABERNAS-Almera SPAIN
Innovative Processes and Practices for Wastewater Treatment and Re-use. 8-11 October 2007, Ankara University, Turkey Re1/77
Introduction
Photocatalysis Photo-Fenton
Photoreactors
Compound Parabolic Collectors State of the art
Applications
Pesticides OMW Pharmaceutical WW
Introduction
Biodegradable substances:
Biofilter treatment/ activated sludge treatment
Introduction
Non-destructive
Non-viable
Non-biodegradable substances can show

Non-toxic / inert behaviour Acute toxicity Chronic toxicity
High costs Toxic by-products High energy consumption
High costs High energy consumption

Partial destruction
Activated carbon Air stripping
Bio-treatment
Ozone
OH
radicals
Alternative treatment
Incineration
Innovative Processes and Practices for Wastewater Treatment and Re-use. 8-11 October 2007, Ankara University, Turkey Re-
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Introduction
H2O2/Fe2+ (Fenton): Fe 2+ + H 2 O2 Fe 3+ + OH + OH H2 O 2 /Fe2+ (Fe3+ )/UV (Photo-Fenton): Fe
3+
Introduction
h Fe2+ + HO
+
Photochemical AOPs
AOP key reactions wavelength
h TiO2/h/O2 (Photocatalysis): TiO2 e + h + h + H 2O OH + H

O 3 / H2 O 2 :
+ H+ H 2 O2 HO + O3 O2 + HO2 HO2 + O3 HO2 + O3
UV/ H2O2 UV/ O3
H2O2 + h 2 OH
< 300 nm < 310 nm
O3 + h O2 + O (1D) O (1D) + H2O 2 OH
HO2 H + + O2 HO3 HO + O2
O2 + O3 O2 + O3
3 2 2
O3 + H + HO3
UV/H2O2/ O3 O3 + H2O2 + h O2 + OH + OH2 < 310 nm UV/ TiO2 TiO2 + h TiO2 (e- + h ) + TiO2(h ) + OH-ad TiO2 + OHad
+ + + H2O2 + Fe2 Fe3 + OH + OH-
O3/ UV:
O3
h H2O2/UV: H 2 O2 2OH
HO + O HO CATALYSIS + O + h O ( D) + O O ( D) + H O H O SUN
1 1 2 2 2
< 390 nm
hv H 2 O2 2 HO
photo-Fenton
Fe3 + H2O + h Fe2 + H + OH
< 580 nm
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Photocatalysis
2000
-1
Photocatalysis
Standard Solar Radiation Spectra Extraterrestrial 2000
Irradiance, W m m
1500
-2
Global 37 Air Mass 1.5
1500
G=
Material CdO CdS Fe2 O3 GaP SnO2 TiO2 WO3 ZnO ZnS
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1000
U=
0.6 1.2 1.8
hc
hc EG
band gap energy is the energetic separation between a semiconductor valence and conduction band
for e-/h+ formation (nm) 590 497 565 540 318 390 443 390 336
h
recombinacin recombination
Red1 Oxid1
recombination recombinacin
Oxid2 Red2
1000
Band gap (eV) 2.1 2.5 2.2 2.3 3.9 3.0 2.8 3.2 3.7
500
2.4 3.0 3.6 4.2
500
C + h C (e + h + ) h + + H 2 O OH + H +
e +O 2 O 2
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W avelength, m
Photocatalysis
The process takes place at ambient temperature. Oxidation of the substances into CO2 is complete. The oxygen necessary for the reaction is obtained from the atmosphere. The catalyst is cheap, innocuous and can be reused. The catalyst can be attached to different types of inert matrices.
Photocatalysis
1000
Source: Scopus (http://www.scopus.com), June 2007
800
Publications (TiO2)
600
400
200
0
88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06
Year
Photo-Fenton Photo-Fenton method

Intensity (W.m-2.nm-1)
1.2
Photo-Fenton
TiO2
1.2
Reactions Fe2+, Fe3+ and H2O2 in water

Fe 2+ + H 2 O 2 Fe3+ + OH + OH
k = 53 76 M-1 s-1 k = 2.6 5.8108 M-1 s-1
Fe
2+
+ H 2O2 Fe
h
3+
+ OH + OH
2+
1.0
1.0
Fe 2+ + OH Fe3+ + OH
Fe 2+ + HO 2 Fe3+ + HO 2
k = 0.75 1.5106 M-1 s-1 k = 1 210-2 M-1 s-1 k = 0.33 2.1106 M-1 s-1 k = 0.05 1.9109 M-1 s-1
Fe
0.8
0.8
Optical Density
3+
+ H 2O Fe
+ H + OH
Fe3+ + H 2 O 2 Fe 2+ + HO 2 + H +
Fe3+ + HO 2 Fe 2+ + O 2 + H + Fe3+ + O 2 Fe 2+ + O 2

Solar Spectrum
0.6
Advantages
High reaction rates Cheap, non-toxic reagents (Fe, H2O2, acid, base)
0.6
Equilibriums
H 2O
2
OH + H 2 O 2 H 2 O + HO 2
k = 1.7 4.5107 M-1 s-1
HO 2 + H
K = 2.63 10-12 M
0.4
Fe3+ (0.25 mM, pH=2.8)
0.4
Radical reactions
2 OH H 2 O 2
2 HO 2 H 2 O 2 + O 2
[Fe]3+ + H 2 O 2 [Fe(HO2 )]2+ + H + [Fe(OH)] + H 2 O HO

2 2+ 2
K = 3.1 10-3 M
+ +
0.2
0.2
k = 5 8 109 M-1 s-1 k = 0.8 2.2 10 M s k = 1.4 1010 M-1 s-1

6 -1 -1
[Fe(OH)(HO 2 )] + H
K = 2 10-4 M K = 3.55 10-5 M K = 1.02 10-12 M
Disadvantages
pH adjustment necessary Iron removal necessary
O2 + H
0.0 300
400
500
0.0 600
HO 2 + OH H 2 O + O 2
OH O + H + HO + H
2 +
Wavelength (nm)
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H 2O 2
K = 3.16 3.98 10-12 M

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Photo-Fenton
Fenton reactions with organics
R +Fe R +Fe
3+ + 2+
Photo-Fenton
Photo-Fenton PhotopH [-]
1 1.5 2 2.5 3 3.5 4 4.5 5
[Fe3+ L] + h [Fe3+ L]* Fe 2+ + L [Fe(H 2 O)]3+ + h Fe 2+ + OH + H + [Fe(OH)]2+ + h Fe 2+ + OH [Fe(OOC R)]2+ + h Fe 2+ + CO 2 + R
R +Fe 2+ R +Fe3+ R +R R R R +HO RO 2 H 2
OH + RH R + H 2O R CH = CH 2 + OH R C H CH 2 OH
3+
-3 1.E-03 10
10 1.E-04
-4
c [M]
Fe + RO 2 H Fe + OH + OR
R + O 2 RO 2

2+
OH + RX RX + + OH
1.E-05 10
-5
Quantum yield
RO 2 + H 2 O ROH + HO 2
1.E-06 10-6
-7
Persistent complexes with Mono- y Dicarboxylic acids (L). Reaction is stopped before complete mineralisation
10 1.E-07
[Fe(H2O)6] aaaaaaaaaaaa [Fe(H2O)3(OH)3] ddddddddddddddd
3+
[Fe(H2O)5(OH)] bbbbbbbbbbbbbbb 4+ [Fe2(H2O)8(OH) eeeeeeeeeeee 2]
2+
[Fe(H2O)4(OH)2] ccccccccccccccccc
Fe 3+ + n L [FeL n ] x + H 2O 2 , no further reaction dark

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Photo-Fenton
Source: Scopus (http://www.scopus.com), June 2007
70 60 50 40 30 20 10 0 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06
Outlook
Publications (photo-Fenton)
Introduction
Photoreactors
Applications
Photoreactors
Photoreactors
Catalyst Mixer Chemical oxidant Oxygen (Air) Sun
Contaminated water
Pre-treatment (pH adjustment, filtering, etc)
Tank Pump Filter
Solar UV light
Contaminated water
Treated water
Post-treatment (catalyst recovering, pH adjustment, etc.)
Photoreactor (Solar Collector Field)
Batch process
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Photoreactors
100
Photoreactors
UV direct (tracking the Sun)
Reflectivity (%)
80 60
Al Rh Pt
40 20 0 300 100
Au Cu Ag
Reflectivity
320 340 360 380 400
Direct radiation: solar radiation that reaches ground level without being absorbed or scattered. Diffuse radiation: the radiation that has been dispersed but reaches the ground.
Wavelength (nm)
Quartz
Transmissivity (%)
80 Pyrex 60 PTFE 40 20 0 300

TM
Duran
TM
Standard Glass
Solar UV Spectra
Transmissivity
325 350 375 400 19/77
UV global horizontal
Global radiation: The sum of both.

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Photoreactors
UV must be 2000 accurately measured!
1500
Photoreactors
Decembre
2000
-1
Standard Solar Radiation Spectra Extraterrestrial
Mximum UV (<400 nm) sunny days (37, N)

E(W m )
-2
50
40
Irradiance, W m m
30
UVdir
1500
-2
Global 37 Air Mass 1.5

1000
20
10
UVglo
W m-2 ?m-1
Espectros medidos en UV spectramomentos diferentes
0 8 10 12 14 16 18 20 22
1000
1000
500
Hora Local
June
500
0.0 0.30 0.35 0.40
500
Wavelenght, m
50
UVglo
40
E(W m )
0 0.6 1.2 1.8 2.4
0 4.2
-2
30
UVdir
W avelength, m
3.0
3.6
20
10
0 8 10 12 14 16 18 20 22
Hora Local
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State of the art

Sandia National Labs (Albuquerque, USA) developed in 1989 the first solar facility for water detoxification at pre-industrial level based on 1-axis Parabolic Trough Collectors (PTC). CIEMAT, in 1990, erected the second at CIEMAT Plataforma Solar de Almera (Spain), using 2axis PTCs.
State of the art

In the early nineties, the National Renewable Energy Laboratory, Sandia National Laboratories and the Lawrence Livermore National Laboratory addressed the Livermore experiment (USA). A Solar Detox Plant was olar installed using one-axis PTCs to treat TCEThis experiment constituted the first on-site groundwater test. Tests were successful but the economic contaminated during the figures not! Second World War.
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These pilot plants were the first step in the development of the solar technology.
12
State of the art
State of the art

One-sun (non-concentrating) One(nonconcentrating) collectors are cheaper than PTCs. An extensive effort in the PTCs. design of small non-tracking noncollectors, has resulted in the collectors, testing of several different nonnonconcentrating solar reactors. reactors. The design of a robust one-sun photoreactor is not trivial: weather-resistant, chemically inert and ultraviolettransmissive. Also, flow in nonconcentrating systems is usually laminar.
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State of the art
State of the art
DSSR-Pilotplant II in Wolfsburg DSSR-Pilotplant II

The Planning Concept:
Illuminated Reactor Area A = 30 m Flow Re 5000 (turbulent) Volumetric Flow Rate Vtot = 12 m /h Pressure Drop = 0.5 bar Treatment Capacity 0.9 m /d
3 3 2
Source: Prof. D. Bahnemann, Universitt Hannover

14
State of the art
State of the art
Thin-Film Fixed Bed Reactor (TFFBR)
Thin-Film Fixed Bed Reactor (TFFBR)
1995 in Almeria/Spain
2003 in Tunis/Tunisia

15
State of the art

PARABOLIC CONCENTRATORS
MAIN ADVANTAGES Turbulent flow No vaporization of compounds MAIN DISADVANTAGES Only Direct radiation High cost (Sun Tracking) Low optical efficiency Low Quantum efficiency (with TiO2) Overheating
Compound Parabolic Collectors
1 Sun COMPOUND PARABOLIC COLLECTORS

Turbulent flow conditions No vaporization of volatile compounds No tracking No Overheating Direct and Diffuse radiation Low cost Weatherproof (no contamination)
NON CONCENTRATING PHOTOREACTORS

MAIN ADVANTAGES Direct & Diffuse radiation No heating Low cost High optical efficiency MAIN DISADVANTAGES Laminar flow (low mass transfer) Vaporization of reactants Reactants contamination
16

y

= r
for
1 C= sin a
a + 2
Part A-B Part B-C
+ a + 2 cos ( a ) =r 1 + sin ( a )
for a +
3 a 2
r
O
x
S
One Sun CPC collector manufacturing: a = 90 all direct and diffuse solar 90 photons can be collected and used (diffuse UV radiation is a very important very fraction of total solar UV)
If a = 90
C=1
17
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EU Project (1996-1999) (1996-
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A very simple one-sun CPC collector was designed, constructed and tested oneto 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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Slurry systems are the most efficient, resulting an important reduction in the final treatment cost. A process for catalyst recuperation has been patented. EP-1-101-737-A1 (2001).
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.
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Process evolution is monitored through the measuring and integration of UV light up to a fixed level.
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The SOLARDETOX Consortium (BriteEuram 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)
1ST ENVIRONMENTAL NORMATIVES
Introduction
PILOT PLANT PHOTOCATALYSIS SOLAR COLLECTORS DEVELOMENT

NEW ENVIRONMENTAL EU DIRECTIVES: IPPC (1996),WFD (2000),...
NEW RESEARCH GROUPS NEW PROCESSES (catalysts, oxidants, photo-Fenton,...)

TOO EXPENSIVE ALTERNATIVES: GAC, AIR STRIPPING, INCINERATION...
Photoreactors
Applications
ENVIRONMENTAL MARKETING
PRIVATE COMPANIES
2007
APPLICATIONS
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Applications
It has demonstrated that the solar photocatalytic technology is sufficiently developed for industrial use. A European industrial consortium has been created to the design and setup of turnkey SOLARDETOX plants. The technology developed can be used, without modification, to address solar Photo-Fenton and TiO2 degradation process.
Applications
Phenols, nitrophenols and halophenols. Phenols, halophenols. Pharmaceutical compounds (antibiotics, disinfectants...). antibiotics, disinfectants...). Water disinfection. disinfection. Gasoline additives (MTBE, ETBE,..). Chlorinated hydrocarbons (solvents, VOCs, etc). solvents, VOCs, Residues from textile industry (dyes). dyes). Agrochemical wastes (pesticides). pesticides).
APPLICATIONS
Organics concentration hundreds of mg L-1. Low-medium flow (< 10 m3/h). Contaminants present within complex mixtures of organics. Contaminants with no easy treatment by conventional technologies.
25
Pesticides
Small amounts of pesticide remaining in the empty containers (approx. 70 units/ha).
Pesticides
QUITE WELL SUITED TO SOLAR PHOTOCATALYTIC TREATMENT: TREATMENT: 1. The initial pesticide concentration can be controlled as a function, so the most appropriate concentration for optimum photocatalytic efficiency can be chosen. 2. Toxicity is extreme, low-volume and in a welllowwelldefined location. 3. Such point sources of pollution may be ideally treated in small-scale treatment units. small4. Intensive agriculture in greenhouses is usually concentrated in sunny countries.
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Pesticides
The intensive agriculture activity is a very important economical sector in Almera. There are more than 350 km2 of greenhouses.
Pesticides
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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Pesticides
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 average global Yearly UV irradiation (UVG), sunrise to sunset: 18.6 WUV m-2 d) Average solar energy needed to degrade the contaminants (QUV): 12 kJUV L-1
Pesticides
Plastic grains
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Pesticides
Pesticides
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 37-tilted platform (local latitude) c) total collectors surface: 150 m2 d) Total photoreactor volume: 1061 L e) Total volume per batch: 1500 to 2000 L
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Ar =
QUV Vt 12 x 10 x 1875 x 10 J L L = = 112 m 2 3000 x 3600 x 18.6 s W m 2 Ts UVG

3 3 1
Final selected plant dimensioning (solar collector area) was: 150 m2

Innovative Processes and Practices for Wastewater Treatment and Re-use. 8-11 October 2007, Ankara University, Turkey Re57/77 Innovative Processes and Practices for Wastewater Treatment and Re-use. 8-11 October 2007, Ankara University, Turkey Re-
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Pesticides
Operating procedure: a) The system is run in batch mode using a 2000 L recirculation tank The 4 rows are connected in parallel (independently operated) and the 14 modules of each row in series After treatment water is returned to the washing system and the tank is refilled with new contaminated water
OMW
Typical composition (only main parameters) of OMW:
COD: Dissolved Phenols: TOC: pH: Relevant anions:
100
b)
80000 mg/L 4500 mg/L 35000 mg/L 5.1 phosphate 700 mg/L, chloride 500 mg/L,sulphate 100 mg/L, nitrite 6 mg/L.
O OH
OH O HO NH2
O
HO
OH
2 mm cuvette (quartz)
80
H3C
O OH
CH3
OH HO OH
HO
1/100
O
60
%T
c)
1/50 1/25
OH
HO HO OH
OH
H3C O HO
O H
HO
HO O OH HO O
40
20
1/10
300 350 400 450 500 550 600
nm
Transmission spectra of OMW through 2, mm pathlength at different dilution ratios.

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OMW
OMW Dissolved Phenols behaviour with different photocatalytic treatments
OMW
4000
Dissolved Phenols (mg/L)
Only TiO2
3000
TiO2 + S2O8 20 mM Fe 1mM+ H2O2 20 g/L Fe 5mM+ H2O2 20 g/L Fe 1mM+ H2O2 5 g/L
2-
2000
1000
0 0 50 100 150 200
t30W=14.1 h
250 300 350
Q (kJ/L)
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OMW
OMW
Treatment of OMW in the FFR. Fe = 5mM
20 40
20 h-sunny days-March
1.4 35 1.2 30
Installed and tested in a Olive Mill at Kivery (ARGOS, Greece).
COD and TOC (g/L)
COD TOC
10
1.0 0.8 0.6
Phenols (g/L)
25 20 15 10 5 0
Phenols H 2O 2
0.4 0.2
0 0 20 40 60 80 100
0.0 120
Q (kJ/L)
H 2O 2 Consumed, (g/L)
15
32
OMW
OMW Pot experiment performed in greenhouse because of:

-Protection from environment (wind, rain, insects) -Controled irrigation -Additional light
TOC: 16000 ppm Tot.Phenols: 3200 mg/L
8000 ppm 1600 mg/L
0 ppm 0 mg/L
33
OMW Substrate: Earth

- Bacteria conversion of TOC - Unknown disposal of nutrients - Aluminium silicate, porosity of 95% - Inert substrate
OMW
Olive production Use as fertilizer Photocatalytic treatment + Neutralization Pretreatment Mud to compostation
Pressing Olive oil OMW
Perlita
Pots:
- 12 L volume, PVC, fair grey
34
Pharmaceutical WW
Pharmaceutical WW
Composition of wastewater (seawater) containing Femac (-methylphenilglycine, C9H11NO2)
mg L-1 Femac TOC 500-600 400-500 Susp. solids NH4+ mg L-1 20-100 0-40 COD NO3mg L-1 15001800 200-600
Installed at DSM-DERETIL Villaricos (ALMERIA)

35
Pharmaceutical WW
1000+400 L contact column, 5 10 h of contact Continuous flow 140 280 Lh-1
Pharmaceutical WW
PH O2 IBR OUT
BIOLOGICAL LOOP
FI FI CONDITIONER OUT BLOWER
NEUTRALIZATION TANK
OUT
SOLAR LOOP
PH
OUT
1260 L illuminated volume 4000 L total volume Recirc. Flow 11 m3h-1

700 L IBR 3000 L total volume Re-circulation flow 1.2 m3h-1 Continuous flow 40-80 Lh-1
OUT
FI H2O2
BUFFER
O2 PH
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Pharmaceutical WW
Pharmaceutical WW
Local time, h
12 600 500 30 40 14 16 18 40 20
UV, W m
-2
35
300 200 100 0 0 50
Vi = 1260 L VT = 3700 L
20
30
20 10 25
t , min 30W
100
0 150
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H2O2,CONS, mM
C, mg/L
T, C
400
MPG, Fe= 20 mg/L TOC H2O2,CONS , mM T, C UV, W m-2
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Pharmaceutical WW
IBR during 75 days of continuous mode operation. Continuous operation showed the stability and permanent activity of the immobilised biomass with an influent, which originates from the AOP prepretreatment (photo(photoFenton)
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Pharmaceutical WW
Overview coupling Photo-Fenton/Biotreatment PhotoTOC treated
900 800 700 600 500 400 300 200 100 0 64 68 70 74 76 78 82 84 88 90 92 94 96 98 100 102
Bioreactor: Inlet vs. Outlet

360 300
TOC Inlet TOC Outlet
240 180 120 60 0 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105
Day
TOC (mg L-1)
TOC (mg L-1)
photo-Fenton IBR TOC outlet
day
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Pharmaceutical WW
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
photo-Fenton/ Biol (Demo plant) 2300 m3 year photo-Fenton/Biol (1000 m CPC) 23000 m3 year
2
ACKNOWLEDGEMENTS
Local Organizing Committee. Ankara University. Faculty of Engineering European Commission (Research DG): INNOVA-MED Project Contract No. INCO-CT-2006-517728.
photo-Fenton/Biol (10000 m2 CPC) 230000 m3 year
/m3 4.26
% 14.6
/m3 4.26
% 40.9
/m3 4.26
% 58.8
Reagents
Electric power Manpower Capital costs (solar field) Capital costs (others) Total ( m-3) 0.43 17.11 1.96 5.43 29.2 1.5 58.6 6.7 18.6 0.21 2.67 1.52 1.75 10.4 2.0 25.6 14.6 16.8 0.21 0.36 1.52 0.89 7.2
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SPECIAL ISSUES ABOUT SOLAR PHOTOCATALYSIS

Catalysis Today, Vol. 54(2-3), 1999. 54(2Catalysis Today, Vol. 76(2-4), 2002. 76(2Catalysis Today, Vol. 101 (3-4), 2005. (3Catalysis Today (SPEA-4 Conference), in press 2007. (SPEASolar Energy, Vol. 77(5). 2004. Solar Energy, Vol. 79 (4). 2005. Journal of Solar Energy Engineering, Vol. 129. FEBRUARY 2007
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Outlook

Non-biodegradable substances can show

High costs Toxic by-products High energy consumption

High costs High energy consumption

Activated carbon Air stripping

h TiO2/h/O2 (Photocatalysis): TiO2 e + h + h + H 2O OH + H

UV/ H2O2 UV/ O3

< 300 nm < 310 nm

O3 + h O2 + O (1D) O (1D) + H2O 2 OH

Fe3 + H2O + h Fe2 + H + OH

Global 37 Air Mass 1.5

2.4 3.0 3.6 4.2

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

Photo-Fenton Photo-Fenton method

Reactions Fe2+, Fe3+ and H2O2 in water

k = 53 76 M-1 s-1 k = 2.6 5.8108 M-1 s-1

k = 1.7 4.5107 M-1 s-1

Fe3+ (0.25 mM, pH=2.8)

[Fe]3+ + H 2 O 2 [Fe(HO2 )]2+ + H + [Fe(OH)] + H 2 O HO

k = 5 8 109 M-1 s-1 k = 0.8 2.2 10 M s k = 1.4 1010 M-1 s-1

K = 2 10-4 M K = 3.55 10-5 M K = 1.02 10-12 M

K = 3.16 3.98 10-12 M

R +Fe 2+ R +Fe3+ R +R R R R +HO RO 2 H 2

[Fe(H2O)6] aaaaaaaaaaaa [Fe(H2O)3(OH)3] ddddddddddddddd

[Fe(H2O)5(OH)] bbbbbbbbbbbbbbb 4+ [Fe2(H2O)8(OH) eeeeeeeeeeee 2]

Fe 3+ + n L [FeL n ] x + H 2O 2 , no further reaction dark

Pre-treatment (pH adjustment, filtering, etc)

Tank Pump Filter

Post-treatment (catalyst recovering, pH adjustment, etc.)

Photoreactor (Solar Collector Field)

80 Pyrex 60 PTFE 40 20 0 300

Global radiation: The sum of both.

Standard Solar Radiation Spectra Extraterrestrial

Mximum UV (<400 nm) sunny days (37, N)

Global 37 Air Mass 1.5

Espectros medidos en UV spectramomentos diferentes

0 0.6 1.2 1.8 2.4

State of the art

State of the art

State of the art

State of the art

State of the art

State of the art

DSSR-Pilotplant II in Wolfsburg DSSR-Pilotplant II

Source: Prof. D. Bahnemann, Universitt Hannover

State of the art

State of the art

Thin-Film Fixed Bed Reactor (TFFBR)

Thin-Film Fixed Bed Reactor (TFFBR)

Source: Prof. D. Bahnemann, Universitt Hannover

State of the art

Compound Parabolic Collectors

1 Sun COMPOUND PARABOLIC COLLECTORS

NON CONCENTRATING PHOTOREACTORS

Compound Parabolic Collectors

Compound Parabolic Collectors

Part A-B Part B-C

Compound Parabolic Collectors

Compound Parabolic Collectors

Compound Parabolic Collectors

Compound Parabolic Collectors

Compound Parabolic Collectors

Compound Parabolic Collectors