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Solar Photocatalysis for Urban and Industrial Waste Water Reclamation

Solar Photocatalysis for Urban and Industrial Waste Water Reclamation. Sixto Malato Plataforma Solar de Almería (PSA-CIEMAT ), Tabernas (Almería), Spain . 1. 5. 6. 1. Central receiver technology. 2. Parabolic dishes + Stirling engines. 4.

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Solar Photocatalysis for Urban and Industrial Waste Water Reclamation

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  1. Solar Photocatalysis for Urban and Industrial Waste Water Reclamation Sixto Malato Plataforma Solar de Almería (PSA-CIEMAT), Tabernas (Almería), Spain.

  2. 1 5 6 1. Central receiver technology 2. Parabolic dishes + Stirling engines 4 3. Parabolic-trough technology (thermal oil) 4. Parabolic-trough technology (DSG) 1 5. Parabolic-troughs (gas) + Molten Salt TES 6. Linear Fresnel Collector 7 9 7. Solar furnaces 2 8 8. Water desalination 3 9. Water photocatalysis 10. Passive architecture 10

  3. Introduction Solar AdvancedOxidationProcesses “near ambient temperature and pressure water treatment processes driven by solar energywhich involve the generation of hydroxyl radicals in sufficient quantity to effective water purification” driven by solar energy 1/38

  4. Introduction Wavelength, µm 2/38

  5. Introduction CATALYSIS + SUN 3/38

  6. Introduction 4/38

  7. Introduction 1 Sun CPCs • Turbulent flow conditions • No vaporization of volatile compounds • No solar tracking • No overheating • Direct and Diffuse radiation • Low cost • Weatherproof (no contamination) 5/38

  8. Introduction 6/38

  9. Introduction The current lack of data for comparison of solar photocatalysis with other technologies definitely presents an obstacle towards an industrial application. Therefore, it is necessary: • Give sound examples of techno-economic studies. • Assessment of the environmental impact: life cycle analysis (LCA). • To lead to industry application it will be critical that the processes can be developed up to a stage, where the process: • can be compared to other processes. • is robust, i.e. small to moderate changes to the wastewater stream do not affect the plant’s efficiency and operability strongly. • is predictable, i.e. process design and up-scaling can be done reliably. • gives additional benefit to the industry applying the process (e.g. giving the company the image of being “green”). 7/38

  10. Examples of techno-economicstudies Sound examples of techno-economic studies: AOP-BIO and BIO-AOP Lanfill leachate Treatment of Ecs Combination NF/AOPs 8/38

  11. AOP-BIO and BIO-AOP 9/38

  12. AOP EVALUATION OF BIODEGRADABILITY DURING AOP AOP-BIO and BIO-AOP WW characterization: TOC, COD, BOD, main inorganics, contaminants (LC-MS/GC-MS) TOXICITY Non-toxic or partially toxic (<50%) Toxic (>50%) EVALUATION OF BIODEGRADABILITY 2 1 1 TOC>500 mg/L TOC<500 mg/L DILUTION AND EVALUATION OF BIODEGRADABILITY 2 EVALUATION OF BIODEGRADABILITY DURING AOP AOP 2 1 1 BIOLOGICAL TREATMENT 2 EVALUATION OF BIODEGRADABILITY DURING AOP BIOLOGICAL TREATMENT AOP BIOLOGICAL TREATMENT 1 2 COD and toxicity<Guideline DISCHARGE Biorecalcitrant compounds COD and toxicity<Guideline DISCHARGE AOP 2: Biodegradable. COD>Guideline 1: Partially or not biodegradable 10/38

  13. Non-biodegradable pesticides Biodegradable compounds AOP-BIO Combined photo-Fenton and biotreatment Industrial wastewater DOC0: 480 mg/L Decontaminated water DOC: 75 mg/L Biological treatment (IBR) Solar Photo-Fenton • 20 mg/L Fe / pH: 2.8 • 44 % mineralization • DOCf: 270 mg/L • 21 mM H2O2 consumed • DOC0: 300 mg/L • 1.5 days of biotreatment • 75 % mineralization • DOCresidual: 75 mg/L 11/38

  14. AOP-BIO 1. SPE extraction 1 2 3 4 2. LC-TOF-MS Oasis®HLB • Concentration of all pesticides decreased gradually throughout the process (mainly during the photo-Fenton process). • After the combined system: totally removed, except pyrimethanil and thiacloprid, found in range of g/L 12/38

  15. BIO-AOP Real WW 13/38

  16. BIO-AOP INITIAL CONDITIONS (photo-Fenton) • Nalidixicacid: 39 mg/L • Initial TOC: 822 mg/L • [NaCl] : 6.5 g/L • Total degradation of the nalidixic acid at 350 minutes (illumination time) (65 mM H2O2) • 28% of the initial TOC was removed 14/38

  17. 100 80 60 % TOC reduction 40 20 0 AOP-BIO and BIO-AOP t30w = 21 min (elim. NXA) !!! H2O2 = 12 mM (elim. NXA) !!! Biotr. time = 4 days Biotr. time = 4 days AOP BIO BIO  AOP t30w= 350 min; H2O2 = 65 mM (elim.NXA) 15/38

  18. No DPs BIO-AOP LC-TOF-MS chromatograms Retention time (min) 16/38

  19. 2. Photo-Fenton (Fe 1 mM) 3. Evaluation of toxicity and biodegradability 3.a Respirometryactivatedsludge 3.b BiodegradabilitybyZahn-Wellens Landfillleachate Landfillleachate (COD: 15615 mg/L; DQO: 42630 mg/L) • Pre-treatment (Coagulation/floculation) 17/38

  20. Landfillleachate Respirometryactivatedsludge 18/38

  21. Landfillleachate BiodegradabilitybyZahn-Wellens 19/38

  22. Landfillleachate • Pre-treatment (Coagulation/floculation) 2. PHOTO-FENTON (<20 % mineralization) 3. BIOTREATMENT 20/38

  23. Treatment of ECs WWTPs NATURAL WATERS (ng-μg/L) EMERGING CONTAMINANTS • Untilrecentlyunknown • Commonly use • Emergingrisks (EDCs, antibiotics) • Unregulated INCOMPLETE REMOVAL Photochemicaltransformations CONTINUOUS INTRODUCTION INTO THE ENVIRONMENT TRANSFORMATION PRODUCTS 21/38

  24. Treatment of ECs 22/38

  25. Treatment of ECs LC-QLIT-MS/MS CHARACTERIZATION 29/62 Compoundswithhighercontribution in MWTP Effluent 23/38

  26. Treatment of ECs 75 L, 4.1 m2, control T (35 ºC) 50 L, 0.69 g O3 h-1 24/38

  27. Ozonation Treatment of ECs Solar TiO2. Solar photo-Fenton 1-Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4-Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-Ofloxacin; 9-Trimethoprim; 10-Gemfibrozil; 11-4-MAA; 12-Naproxen; 13-4-FAA; 14-∑C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine Contaminants > 1000 ngL-1. ∑C = rest of contaminants at less than 1000 ngL-1 25/38

  28. Treatment of ECs Toxicity assays during ozonation and photo-Fenton showed < 10% inhibition on V. fisheri bioluminescence and in respirometric assays with municipal activated sludge LC-MS chromatogram. Ozonation. t = 0 t = 60 min LC-MS chromatogram. Photo-Fenton. t = 0 t = 20 (t30W = 14) min 26/38

  29. Treatment of ECs Calculation basis: 90% or 98% degradation of micropollutants 5000 m3/day H2O2 1.1 € kg-1 Fe(II) 0.72 € kg-1 H2SO4 0.20 € kg-1 NaOH 0.12 € Kg-1 Electricity 0.07 € Kwh-1 O20.15 € Kg-1 Labour18.8 € h-1 23.1 € kg O3 27/38

  30. Combination NF/AOPs 28/38

  31. Combination NF/AOPs NF in parallel (5.2 m2). 1.4 m3h-1 29/38

  32. Combination NF/AOPs Micropollutants at 15 µg L-1, each 30/38

  33. Combination NF/AOPs Solar photocatalysis 31/38

  34. Combination NF/AOPs r = kC Fe (II), 0.1 mM H2O2, 25 mg L-1 Natural pH 32/38

  35. Combination NF/AOPs Fe (II), 0.1 mM 0.2 mMEDDS H2O2, 25 mg L-1 Natural pH Fe(III)-L + hν → [Fe(III)-L]* → Fe(II) + L• Ethylenediamine-N,N'-disuccinicacid (EDDS) 33/38

  36. Combination NF/AOPs Operational requirements for attaining 95% of pharmaceuticals degradation present in NF concentrates (CF=4 and 10) when solar photo-Fenton and photo-Fenton like Fe(III)-EDDS complex were applied. CF=1, no NF, only AOP. 34/38

  37. Heterogeneousphotocatalytichydrogen generation in a solar pilotplant Flow rate 20 L/min. CPC with pyrexglass tubes, 1.375 m2. Irradiated volume 9.79 L. Total volume 25 L. Catalyst loading 0.2-1 g/L, Pt/(TiO2-N) or Pt/(CdS-ZnS) Sacrificial agents: formic acid (0.05 M), glycerol (0.001 M) and a municipal wastewater (97.7 mg/L of DOC). 35/38

  38. Heterogeneousphotocatalytichydrogen generation in a solar pilotplant 36/38

  39. Heterogeneousphotocatalytichydrogen generation in a solar pilotplant 0.05 M formic acid Real wastewater, 98 mg/L of DOC Reaction conditions: 5 g of catalyst, 25 L of aqueous solution. Data corresponding to 5 hours of irradiation. K. Villa, X. Domènech, S. Malato, M. I. Maldonado, J. Peral. Heterogeneousphotocatalytichydrogengeneration in a solar pilotplant. Int. J. HydrogenEnergy, 38 (29), 2013, 12718-12724. 37/38

  40. Acknowledgements Unidad de Tratamientos Solares de Agua (Solar Treatment of Water Research Group) . Plataforma Solar de Almería (CIEMAT). 38/38

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