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Enginyeria de Processos d'Oxidació Avançada

Santiago Esplugas

Departament Enginyeria Química Universitat de Barcelona

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Barcelona June 2nd, 2010

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Structure of the Presentation

- Research Group

-- Research fields

- Projects in development

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Our research group

Professors:

Santiago Esplugas

Jaime Gimenez

Carme Sans

Esther Chamarro

Assistant Professor

Bernardi Bayarri

Renato Falcao Dantas

Óscar González

Pilar Marco

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Our research groupResearchers

Ana Justo

Simone Vendramel

PhD candidates

Angel Cruz

Natalia de la Cruz

Antonella de Luca

Bruno Domenjoud

Maria del Mar Mico

Ywann Penru

Joao Pereira

Violette Romero

Bruno Santos

Ramiro Vallejo

Master Thesis

Final Project

Anna Barrabida

Marco Bonadies

Raquel Santos

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Research fields

-Water reuse

-Micro-pollutants removal

-Coupling AOP-Biological treatment

-Biomass characterization

-Solar Photo-catalysis applied to environment

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Projects in development

-Advanced Oxidation as pos-treatment for water reuse (Consolider)

-Advanced oxidation for organic matter control in effluents from WWTP(Cenit)

-Advanced oxidation for organic matter control in Sea Water(Cenit)

-Coupled AOP-Biological reactors for pesticides removal in greenhouses (Cenit)

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-Removal of Emerging Pollutants by advanced oxidation processes (CICYT 2009-SPAIN)

-Engineering of Advanced Oxidation Processes (CIRIT 2009-SPAIN)

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Projects in development

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CollaborationsUniversidade Federal do Rio de Janeiro – Brazil

Universidad de Santiago de Compostela – Spain

Wageningen Univ & Research – Netherlands

EPFL, Lausanne – Switzerland

University of Salerno – Italy

North Carolina State Unievrsity - USA

Colorado State University – USA

University of Porto – Portugal

INTEC - Argentina

…………………Companies:

-Acciona agua – Spain

-Suez Degremont – France

-AGBAR - Spain

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AOPREMOVAL OF POLLUTANTS FROM WATER

*PHYSICAL METHODS (non destructive ):Mechanical separationSedimentationFiltrationAdsorption and ion exchangeReverse osmosis

*CHEMICAL METHODS (destructive ):PrecipitationIon exchangeChemical Oxidation (and reduction):

biochemical oxidationchlorinehydrogen peroxideozonehydroxyl radical (OH •) AOPs

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•Oxygen: moderate oxidant with small solubility in water that needs high investments in installations, but its low operation costs may do the process attractive.•Chlorine: strong oxidant and cheap. Possibility of producing chlorinated organic compounds, more toxic than the initial ones. It has good enough solubility in water.•Permanganate: strong enough oxidant, but expensive. It is selective, no easy to handle and not desirable manganese is added to the treated water. •Hydrogen peroxide: multipurpose oxidant soluble in water that could be applied directly or with a catalyst (without it some organic compounds are not attacked).•Ozone: strong oxidant that as oxygen and hydrogen peroxide does not introduce new ions to the medium. It is more soluble in water than oxygen. Its difficult handling. Necessary to generate it on-site. Process, normally, is controlled by mass transfer.

Classical Oxidants

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OH• Characteristics (redoxpotential)

Fluorine 2.23 Hydroxyl radical 2.06 Atomic Oxygen (singlet) 1.78 Ozone 1.52 Hydrogen peroxide 1.31 Perhydroxyl radical 1.25 Permanganate 1.24 Hypobromous acid 1.17 Chlorine dioxide 1.15 Hypochlorous acid 1.10 Hypoiodous acid 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)Rate constants of °OH radical with organics: 1-1000 x 107 mol-1 L s-1

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OH• Characteristics (no especific oxidant)

Compounds that can be oxididez by OH radicals

Acids Formic, gluconic, lactic, malic, propionic, tartaric

Alcohols Benzyl, tert-butyl, ethanol, ethylene glycol, glycerol, isopropanol, methanol, propenediol

Aldehydes Acetaldehyde, benzaldehyde, formaldehyde, glyoxal, isobutyraldehyde, trichloroacetaldehyde

AromaticsBenzene, chlorobenzene, chlorophenol, creosote, dichlorophenol, hydroquinone, p-nitrophenol, phenol, toluene, trichlorophenol, xylene, trinitrotoluene

AminesAniline, cyclic amines, diethylamine, dimethylformamide, 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 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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AOP classics

homogeneous heterogeneous

Radical ·OH

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

electrolysis

sonolysis

(light conditions) atmospheric pressure and room temperature

O3 O3/H2O2

radiation UV

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Photochemical Oxidation Processes

PHOTOCHEMICAL PROCESSES WAVELENGTH

UV (photolysis) < 190 nm

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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Biodegradability enhancement by AOPs

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

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

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pulp&paper

Fenton

textil

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dyes

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surfactants

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* COD removal

* BOD increase

* contaminants removal

* TOC removal

WASTEWATER CONTAMINANTS

AOPs