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Sixto Malato, PhD (sixto.malato@psa.es)Isabel Oller, PhD (isabel.oller@psa.es)
CIEMAT- Plataforma Solar de AlmeríaTabernas (Almería), Spain
Wastewater treatment by solar driven AOPs: design and applications
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
1. Central receiver technology
7. Solar furnaces
4. Parabolic-trough technology (DSG)
2. Parabolic dishes + Stirling engines3. Parabolic-trough technology (thermal oil)
8. Water desalination 9. Water treatment
1
1
3
10. Passive architecture 10
8
97
2
4
6. Linear Fresnel Collector
6
5. Parabolic-troughs (gas) + Molten Salt TES
5
Plataforma Solar de Almería-CIEMAT
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
3
1. Using solar photocatalytic and photochemical processes as tertiary treatment of theeffluents from secondary treatment of MWTPs, for production of clean water. For this, theremoval of both emerging pollutants and pathogens are investigated.
2. Using solar photocatalytic and photochemical processes for the remediation of industrialwastewaters contaminated with several types of pollutants and water reclaim for differentapplications.
3. Combining Advanced Oxidation Technologies with other water treatment techniques suchas nano- and ultra-filtration, ozonation, biological treatments, etc., for improving the watertreatment efficiency and reducing operating costs.
4. Assessment of photocatalytic efficiency of new materials under real solar light conditions, andtheir use in solar CPC reactors.
5. Using solar photocatalytic and photochemical processes for water disinfection. Severaltypes of contaminated water sources with a number of water pathogens are under study.
6. Developing new solar photo-reactors for different purposes (drinking water, water reclamation,irrigation, etc.), either water decontamination or water disinfection.
Research activities of STW Unit at PSA
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction.
Technical and engineering aspects of solar photo-reactors for
photocatalytic applications.
Solar photocatalysis as tertiary treatment for MWTPs effluents.
Solar reactors for water disinfection.
Outlook
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
(ng-μg/L)
Photochemical transformations
TRANSFORMATIONPRODUCTS
EMERGING CONTAMINANTS
• Until recently unknown
• Commonly use
• Emerging risks (EDCs,
antibiotics)
• Unregulated
WWTPs
INCOMPLETEREMOVAL
CONTINUOUS INTRODUCTIONINTO THE ENVIRONMENT
Introduction
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Compound OxidationPotential
Fluorine 2.23Hydroxyl radical 2.06Atomic Oxygen 1.78
Hydrogen Peroxide 1.31Peroxyradical 1.25
Permanganate 1.24Chlorine dioxide 1.15
Chlorine 1.00Bromine 0.80Iodine 0.54
Advanced Oxidation Processes (AOPs) are a source of hydroxyl radicals (OH )
“near ambient temperature and pressure water treatment processes which involve the generation of hydroxyl radicals in sufficient quantity to
effective water purification”
Nevertheless, technical applications are still scarce. Process costs may be considered the main obstacle to their commercial application.
Introduction
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
98 99 00 01 02 03 04 05 06 07 08 09 10 11 12 13 140
1000
2000
3000
4000
5000
6000
7000
8000
9000
Num
ber o
f pub
licat
ions
Year of publication
PhotocatalysisSolar photocatalysis
source: www.scopus.com 2015
Introduction. Solar AOPs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Fe3+ activity, l540‐580 nm
0.2 0.4 0.8 1.0 1.2 1.40
200
400
600
800
1000
1200I, W/m
2m
O3 O2
O3
H2O
H2O
CO
H2O
0.60
200
400
600
800
1000
1200
Wavelength, µm
O3 O2
O3
H2O
H2O
2
H2O
TiO
2activ
ity, l3
90nm
Wavelength, µm
Introduction. Solar AOPs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
22
2
2h
2
OOe
HOHh
)he(TiOTiO
OH
TiO2/UVA (Carey et al., 1976)
Aquacomplexes Fe(III) + hѵ ●OH
(Mazellier et al., 1997a,b; Brand et al., 1998, 2000;
Mailhot et al., 1999)
Aquacomplexes Fe(II) + h ѵ ●OH (Benkelberg and Warneck,
1995)
Fe(III)-Fe(II)/UVA
H2O2 + h ѵ 2 ●OH for l<280 nm
(Goldstein et al., 2007)
H2O2/UVA
OHHFeOHFe 2h2
3
Photo-Fenton (several authors, early 90s)
OHOHFeOHFe 322
2
Fenton (J. Chem. Soc., 1894)
Introduction. Solar AOPs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Linearly dependent on the energy flux but only ~5% of
the whole solar spectrum is available for TiO2 band-
gap.
75% of solar collector efficiency and 1% for the catalyst
means 0.04% original solar photons are efficiently used.
This is a rather inefficient process.
0.25 0.30 0.35 0.40 0.45
TiO2
Arb
itrar
yU
nits
Wavelength, µm
Solar Spectrum
0.25 0.30 0.35 0.40 0.45
TiO2
Arb
itrar
yU
nits
Wavelength, µm
Solar Spectrum
Mild catalyst working under mild conditions with mild oxidants.
As concentration of contaminants and water ionic strength increase: slow kinetics and unpredictable
mechanisms need to be solved.
TiO2 efficiency improved with the addition of powerful oxidants or when doped (with iron, nitrogen…)
to undertake practical applications.
Pure TiO2 can utilize only UV and new catalysts able to work with the visible component of the solar
spectrum are needed.
Introduction. Solar photocatalysis with TiO2
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
L Fe L][Fe hν L][Fe 2*33
HOHFe hνO)][Fe(H 232
OHFe hν[Fe(OH)] 22 RCOFehνR)][Fe(OOC 2
22
Sola
r ir
radi
ance
[W.m
-2.n
m-1
]
300 400 500 6000
500
1000
1500
2000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Solar Spectrum
Fe3+
(0.25 mM, pH=2.8)
ε[M
-1.c
m-1
]Wavelength [nm]
Sola
r ir
radi
ance
[W.m
-2.n
m-1
]
300 400 500 6000
500
1000
1500
2000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Solar Spectrum
Fe3+
(0.25 mM, pH=2.8)
ε[M
-1.c
m-1
]Wavelength [nm]
OHOHFeOHFe 322
2 OHFeOHFe 32
Introduction. Solar photo-Fenton process
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Widely applied for wastewater treatment under different operating conditions.
Several aspects may also greatly contribute to market introduction upon achieving
maturity:
Catalysts based on immobilized iron. Heterogeneous photo-Fenton for working at
natural wastewaters pH.
Additives which enhance the process performance, either regarding kinetics or pH
operation range.
Optimization of treatment taking into account the wastewater specific characteristics.
Ways to minimize hydrogen peroxide consumption, which is the main factor regarding
operating costs.
Introduction. Solar photo-Fenton process
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction. Solar photocatalysis pilot plant
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
QUV (J l-1): cumulative UV energy during exposure time per unit of volume of treated water.
UV Dose (J m-2): UV energy received per unit surface during exposure time.
UV Energy (J): total UV energy received during exposure time.
, , ∙
∙
∙
Introduction. Evaluation and measurement of irradiance
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction.
Technical and engineering aspects of solar photo-reactors for
photocatalytic applications.
Solar photocatalysis as tertiary treatment for MWTPs effluents.
Solar reactors for water disinfection.
Outlook
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Technical and engineering aspects of solar photo-reactors
Concentrating or non-concentrating collectors
Sandia National Labs
(Albuquerque, USA)
developed in 1989 the first
solar facility for water
detoxification at pre-
industrial level based on
One-axis Parabolic Trough
Collectors (PTC).
These pilot plants were
the first step in the
development of the solar
technology.
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
CIEMAT, in 1990, erected the second at Plataforma Solar de Almería
(Spain), using 2-axis PTCs.
Initially, it consisted of two-axis HELIOMAN collectors with a total collector area of 384 m2.
It has been widely used during the 90s by manyEuropean research groups (supported by EU)resulting in a continuous contribution of newideas about the process and technology.
Technical and engineering aspects of solar photo-reactors
Concentrating or non-concentrating collectors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Concentrating or non-concentrating collectorsOne-sun (non-concentrating) collectors are cheaper than PTCs. An extensiveeffort in the design of small non-tracking collectors, has resulted in the testing of several different non-concentrating solar reactors.
The design of a robust one-sun photoreactor isnot trivial: weather-resistant, chemically inertand ultraviolet-transmissive. Also, flow in non-concentrating systems is usually laminar.
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
1 Sun CPCs
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
1,1,, ;
nnnnGnnUVnUV tttVAUVtEE
E, kJ L-1
Con
tam
inan
te, m
gL-
1
E, kJ L-1
Con
tam
inan
te, m
gL-
1
Experimental results evaluation and comparison
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
MAIN DISADVANTAGESMAIN ADVANTAGESPARABOLIC CONCENTRATORS
MAIN DISADVANTAGESMAIN ADVANTAGES
Chemically inertNo heatingLow cost
Laminar flow (low mass transfer)Direct & Diffuse radiation
High optical efficiency
NON CONCENTRATING PHOTOREACTORS
OverheatingLow Quantum efficiency (with TiO2)
Low optical efficiency
High cost (Tracking)Vaporization of volatile compounds Only Direct radiationTurbulent flow
MAIN DISADVANTAGESMAIN ADVANTAGESPARABOLIC CONCENTRATORS
Concentrating or non-concentrating collectors
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Colina-Márquez , Machuca-Martínez , Li Puma. Env. Sci. Technol., 43, 2009
LVRPA* distribution in a CPC in sunny (a) and cloudy (b) day.
*LVRPA= local volumetric rate of photon absorption, W/m3
Considerations:• I Constant = 30 W/m2
• Direct/diffuse = Constant
• 75% UV trasmittance by clouds
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Compound Parabolic Collectors (CPC)
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Connections
(elbow joints)
Compound Parabolic Collectors (CPC)
Technical and engineering aspects of solar photo-reactors
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Solar photocatalysis demonstration plants
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction.
Technical and engineering aspects of solar photo-reactors for
photocatalytic applications.
Solar photocatalysis as tertiary treatment for MWTPs effluents.
Solar reactors for water disinfection.
Outlook
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
CHARACTERIZATION
29/62 Compounds with
higher contribution in MWTP
Effluent
LC-QLIT-MS/MS
AOPs for tertiary treatment. ECs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
9.55.0
2.31.5
1.00.60
2000
4000
6000
8000
10000
12000
14000
16000
18000
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Con
cent
ratio
n ( n
g/L)
Emerging ContaminantsO
3 (mg/L)
Ozonation475290
280175
10085
450I
2000
4000
6000
8000
10000
12000
14000
16000
18000
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Emerging Contaminants
Con
cent
ratio
n (n
g/L)
t30W (m
in)
Mild Solar photocatalysis
with TiO2
2,281,12
0,560,050
2000
4000
6000
8000
10000
12000
14000
16000
18000
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Con
cent
ratio
n (n
g/L)
Emerging Contaminants
Quv (K
J/L)
Mild Solar photo-Fenton
Bisphenol A Ibuprofeno Hidrochlorothiazide Diuron Atenolol 4-AA Diclofenac Ofloxacin Trimethoprim Gemfibrozil 4-MAA Naproxen 4-FAA EC <1000ng/L 4-AAA Caffeine Paraxanthine
) Water characteristics and Micro-
contaminants concentration change depending on the day
that were taken.
AOPs for tertiary treatment. ECs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
LC-MS chromatogram. Photo-Fenton.t = 0
t = 20 (t30W = 14) minLC-MS chromatogram. Ozonation.t = 0 t = 60 min
AOPs for tertiary treatment. ECs
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
TiO2 based materials (immobilised, modified with graphene, several morphologies) and iron based materials like clays etc.
pH 3 pH 5 pH 7
New materials for solar photocatalysisapplications
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Introduction.
Technical and engineering aspects of solar photo-reactors for
photocatalytic applications.
Solar photocatalysis as tertiary treatment for MWTPs effluents.
Solar reactors for water disinfection.
Outlook
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Comisión Nacional de Energía AtómicaLos Pereira, Tucumán, Argentina
Makerere University, Uganda
Solar reactors for water disinfection
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Phytophtora after 5 h of solar exposure without TiO2.
Phytophtera after 5 h of solar exposure with TiO2.
Solar photocatalytic disinfection
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
0 1 2 3 4 510
100
1000
10000
100000
Fixed TiO2 (19,3 g/m 2)
Fixed TiO2 reused
C, C
FU
/mL
Q UV, kJ/L
Slurry TiO2 (50 mg/L)
No catalyst
Solar photocatalytic disinfection
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Solar photocatalytic disinfection
1st Summer School on Environmental applications of Advanced Oxidation ProcessesUniversity of Salerno, Fisciano (Italy), June 15-19, 2015.
Acknowledgments
Unidad de Tratamientos Solares de Agua (Solar Treatment of Water Research Group).
Plataforma Solar de Almería (CIEMAT).
http://www.psa.es/webeng/areas/tsa/index.php
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