Presentation is loading. Please wait.

Presentation is loading. Please wait.

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

Similar presentations


Presentation on theme: "Solar Photocatalysis for Urban and Industrial Waste Water Reclamation Sixto Malato Plataforma Solar de Almería (PSA-CIEMAT), Tabernas (Almería), Spain."— Presentation transcript:

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

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

3 driven by solar energy Solar Advanced Oxidation Processes near ambient temperature and pressure water treatment processes driven by solar energy which involve the generation of hydroxyl radicals in sufficient quantity to effective water purification Introduction 1/38

4 Introduction Wavelength, µm 2/38

5 Introduction CATALYSIS + SUN 3/38

6 Introduction 4/38

7 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) Introduction 5/38

8 Introduction 6/38

9 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 plants 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). 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: 7/38

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

11 AOP-BIO and BIO-AOP 9/38

12 WW characterization: TOC, COD, BOD, main inorganics, contaminants (LC-MS/GC-MS) Non-toxic or partially toxic (<50%) TOXICITY Toxic (>50%) EVALUATION OF BIODEGRADABILITY 2: Biodegradable. COD>Guideline AOP EVALUATION OF BIODEGRADABILITY DURING AOP 1: Partially or not biodegradable BIOLOGICAL TREATMENT COD and toxicity500 mg/L DILUTION AND EVALUATION OF BIODEGRADABILITY AOP EVALUATION OF BIODEGRADABILITY DURING AOP BIOLOGICAL TREATMENT AOP Biorecalcitrant compounds COD and toxicity

13 Combined photo-Fenton and biotreatment Biological treatment (IBR) Solar Photo-Fenton Industrial wastewater DOC 0 : 480 mg/L Non-biodegradable pesticides Biodegradable compounds Decontaminated water DOC: 75 mg/L 20 mg/L Fe / pH: % mineralization DOC f : 270 mg/L 21 mM H 2 O 2 consumed DOC 0 : 300 mg/L 1.5 days of biotreatment 75 % mineralization DOC residual : 75 mg/L AOP-BIO 11/38

14 Compound% Reduction combined system Final conc ( g/L) Imidacloprid Dimethoate99.45 Pyrimethanil81161 Thiacloprid Azoxystrobin99.43 Malathion100< 0.1 Carbofuran100< 0.1 Metalaxyl100< 0.1 Spinosyn a100< 0.1 Bupirimate100< 0.1 Fenamiphos100< 0.1 Tebufenozide100< 0.1 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 1. SPE extraction Oasis ® HLB LC-TOF-MS AOP-BIO 12/38

15 Real WW BIO-AOP 13/38

16 INITIAL CONDITIONS (photo-Fenton) Nalidixic acid: 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 H 2 O 2 ) 28% of the initial TOC was removed BIO-AOP 14/38

17 AOP-BIO and BIO-AOP % TOC reduction AOP BIO Biotr. time = 4 days BIO AOP t 30w = 350 min; H 2 O 2 = 65 mM (elim.NXA) t 30w = 21 min (elim. NXA) !!! H 2 O 2 = 12 mM (elim. NXA) !!! 15/38

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

19 Landfill leachate (COD: mg/L; DQO: mg/L) 3. Evaluation of toxicity and biodegradability 3.a Respirometry activated sludge 3.b Biodegradability by Zahn-Wellens 1.Pre-treatment (Coagulation/floculation) 2. Photo-Fenton (Fe 1 mM) Landfill leachate 17/38

20 Respirometry activated sludge Landfill leachate 18/38

21 Biodegradability by Zahn-Wellens Landfill leachate 19/38

22 1. Pre-treatment (Coagulation/floculation) 2. PHOTO-FENTON (<20 % mineralization) 3. BIOTREATMENT Landfill leachate TC= mg/L COD= mg/L DOC= mg/L Conduct.= 77.3 mS/cm /m 3 % M1M3M1M3 Chemicals (H ) Electricity Man power CPC + facilities Total (/m 3 ) /38

23 (ng-μg/L) NATURAL WATERS Photochemical transformations TRANSFORMATION PRODUCTS EMERGING CONTAMINANTS Until recently unknown Commonly use Emerging risks (EDCs, antibiotics) Unregulated WWTPs INCOMPLETE REMOVAL CONTINUOUS INTRODUCTION INTO THE ENVIRONMENT Treatment of ECs 21/38

24 Treatment of ECs 22/38

25 CHARACTERIZATION 29/62 Compounds with higher contribution in MWTP Effluent LC-QLIT-MS/MS Treatment of ECs 23/38

26 75 L, 4.1 m 2, control T (35 ºC) 50 L, 0.69 g O 3 h -1 Treatment of ECs 24/38

27 Contaminants > 1000 ng L -1. C = rest of contaminants at less than 1000 ng L -1 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 Solar photo-Fenton Solar TiO 2. Ozonation Treatment of ECs 25/38

28 LC-MS chromatogram. Photo-Fenton. t = 0 t = 20 (t 30W = 14) min LC-MS chromatogram. Ozonation. t = 0 t = 60 min Toxicity assays during ozonation and photo- Fenton showed < 10% inhibition on V. fisheri bioluminescence and in respirometric assays with municipal activated sludge Solar TiO2 Solar photo-Fenton Ozonation Treatment time, min Accumulated solar Energy, kJ L Reagent Consumption ---- H 2 O 2 54 mg L -1 Fe(II) 5 mg L -1 O mg L -1 Treatment of ECs 26/38

29 H 2 O kg -1 Fe(II) 0.72 kg -1 H 2 SO kg -1 NaOH 0.12 Kg -1 Electricity 0.07 Kwh -1 O Kg -1 Labour 18.8 h kg O 3 Solar photo-FentonOzonation m3m3 90%98%90%98% Reagent Labour Electricity Investment Total Treatment of ECs Calculation basis: 90% or 98% degradation of micropollutants 5000 m 3 /day 27/38

30 Combination NF/AOPs 28/38

31 NF in parallel (5.2 m 2 ). 1.4 m 3 h -1 Combination NF/AOPs 29/38

32 Micropollutants at 15 µg L -1, each Ions mg L -1 Na + K + Mg 2+ Ca 2+ SO 4 2- Cl - HCO Combination NF/AOPs 30/38

33 Solar photocatalysis Inorganic ions R (%)C e, CF=4 (mg L -1 )C e, CF=10 (mg L -1 ) Na + K + Mg 2+ Ca 2+ SO 4 2- Cl - HCO Pharmaceuticals R (%)C e, CF=4 (mg L -1 )C e, CF=10 (mg L -1 ) Carbamazepine Flumequine Ibuprofen Ofloxacin Sulfamethoxazole Combination NF/AOPs 31/38

34 r = kC Fe (II), 0.1 mM H 2 O 2, 25 mg L -1 Natural pH Combination NF/AOPs 32/38

35 Fe(III)-L + hν [Fe(III)-L]* Fe(II) + L Fe (II), 0.1 mM 0.2 mM EDDS H 2 O 2, 25 mg L -1 Natural pH Ethylenediamine-N,N'-disuccinic acid (EDDS) Combination NF/AOPs 33/38

36 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. Combination NF/AOPs CF1410 Solar photo-Fenton H 2 O 2 consumed (gm -3 ) Q uv (kJ L -1 ) t(min) / CPC surface (1) / / /12.4 Solar photo-Fenton like Fe (III)-EDDS complex H 2 O 2 consumed (gm -3 ) Q uv (kJ L -1 ) t(min) / CPC surface (1) / / /2.7 34/38

37 Flow rate 20 L/min. CPC with pyrex glass tubes, m 2. Irradiated volume 9.79 L. Total volume 25 L. Catalyst loading g/L, Pt/(TiO 2 -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). Heterogeneous photocatalytic hydrogen generation in a solar pilot plant 35/38

38 Heterogeneous photocatalytic hydrogen generation in a solar pilot plant 36/38

39 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. Heterogeneous photocatalytic hydrogen generation in a solar pilot plant. Int. J. Hydrogen Energy, 38 (29), 2013, Heterogeneous photocatalytic hydrogen generation in a solar pilot plant 37/38

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


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

Similar presentations


Ads by Google