Advanced treatments for elimination of pollutants in using solar irradiation

Transcription

1 Advanced treatments for elimination of pollutants in using solar irradiation Sixto Malato Rodríguez Plataforma Solar de Almería (CIEMAT), Tabernas (Almería), Spain.

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

3 Introduction Solar Advanced xidation 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 3

4 Introduction CATALYSIS + SU 4

5 I, W/m 2 m Ti 2 activity, l 39 nm Introduction Fe 3+ activity, l nm 8 H H 2 C H Wavelength, µm 5

6 Introduction

7 Introduction 1 Sun CPCs Turbulent flow conditions o vaporization of volatile compounds o solar tracking o overheating Direct and Diffuse radiation Low cost Weatherproof (no contamination)

8 Introduction

9 Introduction

10 Introduction

11 Introduction

12 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 ).

13 Examples of techno-economic studies Sound examples of techno-economic studies. AP-BI and BI-AP Sound examples of techno-economic studies. Landfill leachate Sound examples of techno-economic studies. Treatment of ECs Sound examples of techno-economic studies. Combination F/APs

14 AP-BI and BI-AP

15 AP-BI and BI-AP Industrial WW characterization: TC, CD, BD, main inorganics, contaminants (LC-MS/GC-MS) 1 AP Toxic (>5%) EVALUATI F BIDEGRADABILITY DURIG AP TXICITY on-toxic or partially toxic (<5%) EVALUATI F BIDEGRADABILITY 1: Partially or not biodegradable TC>5 mg/l 2: Biodegradable. CD>Guideline TC<5 mg/l DILUTI AD EVALUATI F BIDEGRADABILITY 2 BILGICAL TREATMET 1 AP 2 1 EVALUATI F BIDEGRADABILITY DURIG AP 2 BILGICAL TREATMET 1 AP 2 EVALUATI F BIDEGRADABILITY DURIG AP BILGICAL TREATMET CD and toxicity<guideline DISCHARGE Biorecalcitrant compounds AP CD and toxicity<guideline DISCHARGE

16 AP-BI and BI-AP Combined photo-fenton and biotreatment Industrial wastewater DC : 48 mg/l on-biodegradable pesticides Solar Photo-Fenton 2 mg/l Fe / ph: % mineralization DC f : 27 mg/l 21 mm H 2 2 consumed Biodegradable compounds Biological treatment (IBR) DC : 3 mg/l 1.5 days of biotreatment 75 % mineralization DC residual : 75 mg/l Decontaminated water DC: 75 mg/l

17 AP-BI and BI-AP 1 Combined photo-fenton and biotreatment 8 Industrial wastewater DC : 48 mg/l % BIDEG. 6 4 on-biodegradable pesticides 2Solar Photo-Fenton Biodegradability limit Biodegradable compounds S1 (DC : 49 mg/l) S2 (DC : 46 mg/l) S5 (DC : 345 mg/l) Biological treatment (IBR) S6 (DC : 255 mg/l) S3 (DC : 44 mg/l) S7 (DC : 17 mg/l) 2 mg/l Fe / ph: S4 2.8 (DC : 4 mg/l) DC : S8 3 (DC mg/l : 145 mg/l) 44 % mineralization 1.5 days of biotreatment DC f : 27 4 mg/l % mineralization 21 mm H 2 2 consumed Time (days) DC residual : 75 mg/l Decontaminated water DC: 75 mg/l

18 AP-BI and BI-AP C (mg/l) Industrial wastewater DC : 48 mg/l on-biodegradable pesticides 5 25 Combined photo-fenton and biotreatment Photo-Fenton Solar Photo-Fenton 2 mg/l Fe / ph: % mineralization DC f : 27 mg/l Biodegradable compounds DC CD H 2 2 consumed AS Biological treatment (IBR) DC : 3 mg/l IBR 1.5 days of biotreatment 75 % mineralization 21 mm H 2 2 consumed DC 2 residual : 754mg/L Illumination time (hours) Treatment time (hours) AS Decontaminated water DC: 75 mg/l

19 AP-BI and BI-AP Compound % Reduction combined system Final conc ( g/l) Imidacloprid Dimethoate SPE extraction Pyrimethanil Thiacloprid Azoxystrobin Malathion 1 <.1 Carbofuran 1 <.1 Metalaxyl 1 <.1 Spinosyn a 1 <.1 Bupirimate 1 <.1 Fenamiphos 1 <.1 Tebufenozide 1 <.1 asis HLB 2. LC-TF-MS 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

20 AP-BI and BI-AP Real WW H Parameter Amount ph 3.98 Conductivity 7 ms.cm -1 TC 775 mg.l -1 CD 342 mg.l -1 alidixic acid 45 mg.l -1 TSS.47 g.l -1 Cl g.l P 4.1 g.l -1 S g.l -1 a + 2 g.l -1 Ca 2+.2 g.l -1

21 AP BI BI AP AP-BI and BI-AP 1 8 t 3w = 21 min (elim. XA)!!! % TC reduction Biotr. time = 4 days t 3w = 35 min; H 2 2 = 65 mm (elim.xa) APPRACH 1 Biotr. time = 4 days APPRACH 2 H 2 2 = 12 mm (elim. XA)!!!

22 AP-BI and BI-AP LC-TF-MS chromatograms Initial wastewater IBR IBR + photo-fenton H H Cl P17 H P5 H P2 XA H H H H H H P3 H H P11 P34 P22 H H H H H P4 P27 P7 H H H H P9 H P14 H H P12 H H P15 H H H P6 H P1 H P13 H Retention time (min) Time (min) o DPs

23 Landfill leachate Landfill leachate (CD: mg/l; DQ: 4263 mg/l) TC = mg/l CD = 4263 mg/l IC = 5.9 mg/l Conduct. = 77.3 ms/cm DC = 1561 mg/l Cl - = 4.2 g/l ph = 7.4 a + = 32 g/l S 2-4 = 15.7 g/l K + = 5.7 g/l + H 4 = 445 mg/l

24 Landfill leachate Landfill leachate (CD: mg/l; DQ: 4263 mg/l) 1. Pre-treatment (Coagulation/floculation) 2. Photo-Fenton (Fe 1 mm) 3. Evaluation of toxicity and biodegradability 3.a Respirometry activated sludge 3.b Biodegradability by Zahn-Wellens

25 Landfill leachate SAMPLE 6 Respirometry activated sludge Respiration (mg 2 /L h) SAMPLE 4 SAMPLE 2 SAMPLE Time, s

26 Landfill leachate Biodegradability by Zahn-Wellens 1 8 D, % 6 BIDEGRADABILITY, 7% D t Ct - C B 1-1 CA - CBA 4 2 M M2 M4 M6 REF time, days M1 M3 M5 M7

27 Landfill leachate TC = mg/l CD= 4263 mg/l DC = 1561 mg/l Conduct. = 77.3 ms/cm 1. Pre-treatment (Coagulation/floculation) 2. PHT-FET (<2 % mineralization) 3. BITREATMET /m 3 % M1 M3 M1 M3 Chemicals (H 2 2 ) Electricity Man power CPC + facilities Total ( /m 3 )

28 Treatment of ECs LC-QLIT-MS/MS CHARACTERIZATI 29/62 Compounds with higher contribution in MWTP Effluent

29 Treatment of ECs 75 L, 4.1 m 2, control T (35 ºC) 5 L,.69 g 3 h -1

30 Treatment of ECs Solar photo-fenton inants Contam 1-Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-floxacin; 9Trimethoprim; 1-Gemfibrozil; 11-4-MAA; 12-aproxen; 13-4-FAA; 14- C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine ) (min ) (min t 3W t 3W I Concentration (n g/l) Solar Ti inants Contam Contaminants > 1 ng L-1. C = rest of contaminants at less than 1 ng L-1

31 Treatment of ECs inants Contam 1-Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-floxacin; 9Trimethoprim; 1-Gemfibrozil; 11-4-MAA; 12-aproxen; 13-4-FAA; 14- C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine ) (min ) (min t 3W Time Solar photo-fenton Concentration (n g/l) zonation inants Contam Contaminants > 1 ng L-1. C = rest of contaminants at less than 1 ng L-1

32 Treatment of ECs 1 Solar Ti 2 Solar photo- Fenton zonation Treatment time, min Accumulated solar energy, kj L Reagent Consumption LC-MS chromatogram. zonation. Photo-Fenton. t t = - H 2 2 Fe(II) 3 54 mg L -1 5 mg L mg L -1 t = 2 (t 3W = 14) min t = 6 min Toxicity assays during ozonation and photo- Fenton showed < 1% inhibition on V. fisheri bioluminescence and in respirometric assays with municipal activated sludge

33 Treatment of ECs Calculation basis: 9% or 98% degradation of micropollutants 5 m 3 /day H kg -1 Fe(II).72 kg -1 H 2 S 4.2 kg -1 ah.12 Kg -1 Electricity.7 Kwh Kg -1 Labour 18.8 h -1 Solar Photo-Fenton zonation m -3 9% 98% 9% 98% Reagent Labour Electricity Investment Total kg 3

34 Permeate Permeate Combination F/APs Water ECs and TPs Salts Macromolecules Virus Bacteria Suspended Solid Pore Size µm MF.1-1 UF F R Multivalent Monovalent r = kc WW+ECs AP For reuse WW + ECs AP For reuse UF Concentrate + ECs CAS Concentrate + ECs MBR Effluent +ECs F/R Effluent Pre-treatment F/R

35 Combination F/APs F in parallel (5.2 m 2 ). 1.4 m 3 h -1

36 Combination F/APs Ions mg L -1 a K Mg Ca S Cl HC Micropollutants at 15 µg L -1, each Carbamazepine (anticonvulsant) Flumequine (broadspectrum antibiotic) Ibuprofen (nonsteroidal antiinflammatory) floxacin (gramnegative antibiotic) Sulfamethoxazole (bacteriostatic antibiotic)

37 Combination F/APs Inorganic ions MF UF F R Water ECs and TPs Salts Macromolecules Virus Bacteria Suspended Pore Size Solid µm R (%) C e, CF=4 (mg L -1 ) C e, CF=1 (mg L -1 ) a K Mg Ca Multivalent 2- S Cl Monovalent - HC Pharmaceuticals R (%) C e, CF=4 (µg L -1 ) C e, CF=1 (µg L -1 ) C F = V i /V f Carbamazepine Flumequine Ibuprofen floxacin Sulfamethoxazole

38 Combination F/APs t 3W (min) Photo-Fenton A 2 CF = 1 CF = 4 Concentration ( g/l) CF = Fenton foxacin Sulfamethoxazole Carbamazepine Flumequine Ibuprofen B H 2 2 consumption C H 2 2 consumption (mg/l) r = kc CF H 2 2 H 2 S 4 (98%) consumption (g m -3 ) (g m -3 ) t 3W (min)

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

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