Treatment of CECs by solar driven AOPs. Sixto Malato Plataforma Solar de Almería E:

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1 Treatment of CECs by solar driven AOPs Sixto Malato Plataforma Solar de Almería E:

2 Contents Solar photo-fenton. Design of the photoreactor. Adequate experiments and evaluation of CECs? Adequate experiments for plants design and economical approach? Other concepts: Fe-complexes Combination with other technologies. Economic assessment. Slide 2

3 I, W/m 2 m TiO 2 activity, l 39 nm Solar photocatalysis 12 1 O 3 Fe 3+ activity, l nm 8 H 2 O 6 O 3 O 2 H 2 O CO H 2 O Wavelength, µm µm Catalysis Today 147, 1 59, 29. Slide 3

4 Solar photocatalysis Source: Slide 4

5 Solar photo-fenton Ferric iron forms complexes with water and hydroxyl ligands, some of which photoactive. Fe 3+ reduction through a Ligand to Metal Charge Transfer... Different light absorption properties depending on L Slide 5

6 Ferric iron forms complexes with water and hydroxyl ligands, some of which photoactive. Solar photo-fenton Fe 3+ reduction through a Ligand to Metal Charge Transfer... Different light absorption properties depending on L Operational ph range and quantum efficiency of unmodified photo- Fenton (absence of organic ligands) limited to region around ph 3. Slide 6

7 Solar photo-fenton Advantages Highly oxidative HO can attack and degrade most organic structures. Very fast. Modest cost of reagents (iron, H 2 O 2, and acids/bases for ph control). Fe 3+ to Fe 2+ photoreduction possible with solar radiation. Disadvantages Requires strict ph control Use of ph controlling reagents (acids and bases) increases salinity of treated water. Some anions present in natural water (such as CO 3 2- /HCO 3 -, PO 4 3- ) scavenge HO, effectively stopping the process. Non selectivity of HO means that biodegradable components are also targeted. Slide 7

8 Design of the photoreactor 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) Slide 8

9 Design of the photoreactor Appl. Catal. B: Environ., 17, 9-123, 215. Slide 9

10 Design of the photoreactor Appl. Catal. B: Environ., 17, 9-123, 215. Slide 1

11 Design of the photoreactor Appl. Catal. B: Environ., 17, 9-123, 215. Slide 11

12 Design of the photoreactor Appl. Catal. B: Environ., 17, 9-123, 215. Slide 12

13 Design of the photoreactor Appl. Catal. B: Environ., 17, 9-123, 215. Slide 13

14 DOC( g/l) Parent compound (μg/l) Design of the photoreactor Highly polluted effluents (g/l or mg/l) Need of HO Aim: mineralisation Irradiance limitation Increase I, increase r Effluents containing micropollutants (μg/l) Less HO needed Aim: parent compound Irradiance limitation?? Q UV (kj/l) or t 3W (h) t (min) For micropollutant removal, there is photosaturation, so the process can be operated in photoreactors with wider optical lengths. NOT possible with CPCs!!! J. Hazar. Mat., 279, , 214. Appl. Catal. B: Environ., 178, , 215. Slide 14

15 Design of the photoreactor Extensive and non-concentrating solar photoreactors could be a good alter-native for working at high light path length, large volumes and short treatment time with low iron concentration. Micropollutants!! Raceway Pond Reactors (RPR) liquid depth can be easily varied Pay attention when using open photoreactors as wastewater should be completely confined in them and requiring treatment time should be in the range of minutes, for avoiding evaporation of water Chemosphere, 13, 73-81, 215 Catalysis Today, 287, 1 14, 217 Slide 15

16 Design of the photoreactor In Raceway Pond Reactors (RPR) liquid depth can be easily varied A (m 2 ) = /4 p 2 + pq V (m 3 ) = A D Microalgal cultures in RPR and TPBR. Almería. Applied for microalgal mass culture q 1 p Low cost materials, mainly plastic liners. Construction cost 1 /m 2 (CPC 1 /m 2 ) Slide 16

17 Concentration ( g/l) r = kc Adequate experiments for CECs? Model compounds at different realistic C in natural water. Fe (II),.1 mm, H 2 O 2, 25 mg L -1, natural ph Carbamazepine Correct C for kinetic studies? Sulfamethoxazole Flumequine t 3W (min) Fenton Photo-Fenton A Ofoxacin Sulfamethoxazole Carbamazepine Flumequine Ibuprofen B H 2 O 2 consumption C H 2 O 2 consumption (mg/l) Ibuprofen Ofloxacin t 3W (min) 5 Slide 17

18 Adequate evaluation of CECs? SOLID PHASE EXTRACTION (SPE) SPE Dry with N 2 1 ml ACN/water LC 1 ml AcOEt GC Dry with N 2 Slide 18

19 Adequate evaluation of CECs? SOLID PHASE EXTRACTION (SPE) SPE Dry with N 2 1 ml ACN/water LC 1 ml AcOEt GC Dry with N 2 Slide 19

20 SPE Adequate evaluation of CECs? SOLID PHASE EXTRACTION (SPE) Before the analysis, samples were prepared by a Solid Phase Extraction. Stop the reaction. Concentrate the sample. Separates interferences from the sample matrix. t, t1, t2, t3, t4, t5, t6, t7, t8, t9, t1, t11, t12, t13, t14, t15 Slide 2

21 Adequate evaluation of CECs? UPLC/UV-DAD HPLC/MS/MS Qtrap 55 15µg/L >1µg/L Ofloxacina Sulfametoxazol Carbamecepina Flumequina Ibuprofeno? ng/l Model CECs Carbamacepine Ibuprofen Flumequine Ofloxacin Sulphametoxazole Area Concentracion ( g/l) Slide 21

22 Adequate evaluation of CECs? UPLC/UV-DAD HPLC/MS/MS Qtrap 55 SPE (automatic) >1µg/L 15µg/L? ng/l Optimised method: micro-contaminants in MWTP effluent. Slide 22

23 Adequate evaluation of CECs? C/C iluminación Acetaminofen Cafeina Ofloxacin Antipirina Sulfamethoxazole Carbamazepina Flumequina Ketorolac Atrazina Isoproturon Hydroxybifenil Diclofenaco Ibuprofen Progesterona Triclosan t 3W [min] Degradation of 15 contaminants; 15 μg L -1 each in MWTP effluent evaluated by SPE and UPLC/UV- DAD. One could study the whole process. Conclusions later applied to MWTP effluent evaluated by LC-MS. Slide 23

24 Adequate experiments for plants design and economical approach? CHARACTERIZATION (QTRAP LC-MS/MS system) 29/62 Compounds with higher contribution in MWTP Effluent Wat. Res., 47, , 213. Slide 24

25 Adequate experiments for plants design and economical approach? Solar TiO Solar photo-fenton t 3W (min) I Contaminants Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4-Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-Ofloxacin; 9-Trimethoprim; 1-Gemfibrozil; 11-4-MAA; 12-Naproxen; 13-4-FAA; 14- C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine Concentration (ng/l) t 3W (min) Contaminants Contaminants > 1 ng L -1. C = rest of contaminants at less than 1 ng L Wat. Res., 47, , 213. J. Hazar. Mat., 323, , 217. Chem. Eng. J., 318, , 217. Slide 25 Concentration (ng/l)

26 Ozonation ) (min sts Solar photo-fenton t 3W ) in) mi(nm im(e t 3TW I Con Cce onnt ce rant tio ra ntio (nng/l) (ng/l) Solar TiO innatn ma tain nm CoCnota 1-Bisphenol A; 2-Ibuprofen; 3-Hydrochlorothiazide; 4-Diuron; 5-Atenolol; 6-4-AA; 7-Diclofenac; 8-Ofloxacin; 9-Trimethoprim; 1-Gemfibrozil; 11-4-MAA; 12-Naproxen; 13-4-FAA; 14- C; 15-4-AAA; 16-Caffeine; 17-Paraxanthine AOPs PhD School. 2nd summer school. Porto July 1-14, inants Contam Contaminants > 1 ng L-1. C = rest of contaminants at less than 1 ng L-1 Wat. Res., 47, , 213. J. Hazar. Mat., 323, , 217. Chem. Eng. J., 318, , 217. Slide 26 Concentration (n g/l) Adequate experiments for plants design and economical approach?

27 Adequate experiments for plants design and economical approach? Solar TiO2 Solar photo-fenton Ozonation Treatment time, min Accumulated solar Energy, kj L -1 Reagent Consumption - - H 2 O 2 54 mg L -1 Fe(II) 5 mg L -1 O mg L -1 LC-MS chromatogram. Ozonation. Photo-Fenton. t = t = 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 Slide 27

28 Other concepts: Fe-complexes Advantages of organic - iron complexes Maintain Fe 3+ soluble at wider ph range, enabling direct treatment at near-neutral ph values found in many natural waters Better absorbers in the UV-VIS region than ferric-aqua complexes Possible formation of additional oxidative species from Ligands via loss of electrons. [Fe 3+ L] + hv [Fe 3+ L]* Fe 2+ + L Complex photolysis L + O 2 O 2 + L HO 2 H + + O 2 Formation of superoxide radical species Superoxide/hydroperoxyl equilibrium Fe 3+ + O 2 Fe 2+ + O 2 Fe 3+ + HO 2 Fe 2+ +O 2 + H + Promotion of Fe 3+ reduction Slide 28

29 Other concepts: Fe-complexes Limitations of using Fe (III)-complexes for the treatment of contaminated water at near-neutral ph Treatment of high concentrations of contaminants or achieving mineralization is difficult as continuing treatment requires adding more and more complexing agent. This leads to a non-sustainable process with increasing TOC instead. Rapid photolysis of Fe(III)-complexes doesn t allow long treatment times necessary for mineralization. Logistics costs would be limited, as the reused WW could be used locally at municipal wastewater treatment plants or local industries within a short radius of the production plants. Therefore adequate for CECs. Slide 29

30 Other concepts: Fe-complexes HOOC COOH HOOC NH NH COOH Ethylenediamine-N,N'-disuccinic acid (EDDS) Fe(III)-L + hν [Fe(III)-L]* Fe(II) + L J Phys Chem A 118, , 214. Slide 3

31 Other concepts: Fe-complexes Comparing Fe:EDDS at neutral ph with classical photo-fenton at ph 3 Fe(III)-EDDS: (+) Rapid degradation of contaminant. (-) Constant TOC (total loss of activity following the break-up of the Fe(III)-EDDS complex). Classical pf: Slower degradation, but reliable (Fe dissolved) for longer time. (+) TOC eventually starts to decrease. J. Photochem. Photobiol. A: Chem. 33, 1-7, 215. Slide 31

32 Combination with other technologies Water ECs and TPs Salts Macromolecules Virus Bacteria Suspended Solid Pore Size µm Combination NF/AOPs MF UF NF RO Multivalent Monovalent Q/4, 4C 3Q/4, C Q, C r = kc Slide 32

33 Combination with other technologies CF=1 CF=4 LC-Qtrap- 55-MS/MS Slide 33

34 Combination with other technologies H 2 O 2 consumption (mg/l) Combination NF/AOPs 1,,8 C = 45µg/L C = 4 x 45µg/L H 2 O S C/ S C,6,4 H 2 O ,2 25 r = kc, 9% Q UV (kj/l) Slide 34

35 Combination with other technologies Combination NF/AOPs CF 1 4 Solar photo-fenton at ph = 3 H 2 O 2 consumed (gm -3 ) Q uv (kj L -1 ) t(min) / CPC surface / /22.6 Solar photo-fenton like Fe (III)-EDDS complex H 2 O 2 consumed (gm -3 ) Q uv (kj L -1 ) t(min) / CPC surface 14/15 1/3.3 Operational requirements for attaining 95% of pharmaceuticals degradation present in NF concentrates (CF=4 ) when solar photo-fenton (ph = 3) and photo-fenton like Fe(III)-EDDS complex were applied. CF=1, no NF, only AOP. Catalysis Today 252, 61-69, 215. Slide 35

36 Economic assessment Solar photo-fenton treatment of 1 m 3 /day MWTP effluent. Elimination of CEC >9% Classic photo-fenton, ph 3 Fe-EDDS, circumneutral ph D C D C S CPC (m 2 ) 4,3 2,3 3,6 1,2 Amortization Costs, /year AC CPC 12, 7,1 9,9 47, AC mbm --- 4, ,6 Operation costs, /year Reagents 34,3 13,2 292,7 145,9 Electricity 3,1 25,2 2,1 22,7 Maintenance and personnel 28,2 27,6 23,5 2,3 Total OC 92,6 66, 336,3 188,9 Total costs TC, /year 194,6 176,7 427,2 276,5 TC, /m Chem. Eng. J., 318, , 217. Chem. Eng. J., 31, , 217. Slide 36

37 Economic assessment Fe(III):EDDS Ozonation Solar photo-fenton Ozonation D C D C Time, min Fe(III), mm H 2 O 2, mg/l Q UV, kj/l O 3, mg/l H 2 SO 4, mg/l AOPs PhD School. 2 nd summer school. Porto July 1-14, EDDS, 217 ml/l Slide 37

38 Economic assessment Treatment of 1 m 3 /day MWTP effluent. Elimination of CEC >9% Solar photo-fenton Ozonation D C D C /m 3 /m 3 /m 3 /m 3 AC AC mbm OC TC TC ( /m 3 ), excluding NF membrane system Flow (m 3 /day) Solar photo-fenton Ozonation /m 3 /m 3 /m 3 /m 3 /m 3 /m 3 D C excluding NF membrane system D C excluding NF membrane system , , , , , Environ. Sci.: Water Res. Technol. 2, , 216. Slide 38

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41 Thank you very much for your attention Questions? Sixto Malato Rodríguez