in water drug photodegradation aspirin and paracetamol Prof. - PowerPoint PPT Presentation

Micro-sized TiO 2 as photoactive catalyst coated on industrial porcelain grès tiles in water drug photodegradation aspirin and paracetamol Prof. Claudia Bianchi Università degli Studi di Milano 14-16 September 2016 Athens, Greece

European Union Legislation DIRECTIVE 2013/39/EU OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy “… .the Commission shall, as far as possible within two years from 13 September 2013 develop a strategic approach to pollution of water by pharmaceutical substances” . COMMISSION DIRECTIVE (EU) 2015/1787 of 6 October 2015 amending Annexes II and III to Council Directive 98/83/EC on the quality of water intended for human consumption Programs to plan: “monitoring, parameters and frequencies, risk assessment, sampling method and sampling points regulation 14-16 September 2016 Athens, Greece

Photodegradation  Emerging pollutants: test Emerging Aspirin &paracetamol pollutants World Legislation  Photocatalytic Wastewater Oxydation: AOP World Legislation Photoactive remediation TiO 2 catalyst porcelain grès tile  Photoactive porcelain grès tiles: Photocatalytic TiO 2 Oxydation semiconductor 14-16 September 2016 Athens, Greece

Pharmaceutical compounds hydroxylic group (-OH) carboxylic acid group (-C(=O)-OH) acetoxy group (-O-C(=O)- CH 3 ) amide group (-NH -C(=O)-CH 3 ) Aspirin Paracetamol 14-16 September 2016 Athens, Greece

Background Traditional Physical Techniques TiO 2 Photocatalysis Transfer Organic Compounds from Water to another phase SECONDARY POLLUTION

Industrially produced photoactive porcelain gres

Photoactive porcelain gres ceramic tiles 1) Preparation 2) Photoactive modifies tiles  Mixing and grinding  Covering with a suitable micro-  Milling of raw materials in water: TiO 2 based-ink via digital printing clay minerals, natural minerals (new) or spray deposition (old) (feldspar, silica)  Forming by automated presses  Treatment at high temperature: 680 ° C for 80 min P=7000 tons  Brushing to remove unfixed  Firing in a tunnel kiln at 1300 ° C for powder 60 min

Photodegradation tests Mineralization% Conversion% CONVERSION % : degradation of starting molecules into their by-products Aspirin and Paracetamol disappear over time MINERALIZATION % : degradation of all organic compounds into harmless inorganic compounds, as CO 2 and H 2 O. Aspirin, Paracetamol and their by-products are completely degraded over time 14-16 September 2016 Athens, Greece

Photodegradation results: comparison between spray and digital printing coatings Aspirin Paracetamol mixed together (1:1) Mineralization% Conversion% 100 100 100 Conversion (%) 80 80 80 Conversion (%) Conversion (%) 60 60 60 40 40 40 20 20 / 20 0 0 / 0 / 24 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 24 10 24 24 time (h) time (h) time (h) 80 80 80 Mineralization (%) Mineralization (%) 60 Mineralization (%) 60 60 40 40 40 20 20 20 / 0 / 24 0 0 1 2 3 4 5 6 7 8 9 10 0 / 0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 24 24 time (h) time(h) time (h) Comparison between spray deposition ( u ) and ink-jet printing ( p ) tiles . Aspirin (red) and Paracetamol (black) as single molecule and then in mixture (1:1) 14-16 September 2016 Athens, Greece

Photodegradation Mechanisms Paracetamol Aromatic ring cleavage and further oxidation to CO 2 and H 2 0 Aspirin 14-16 September 2016 Athens, Greece

Photodegradation Mechanisms Paracetamol Keto-enolic tautomeric equilibrum between hydroquinone/benzoquinone [1] [1] A.G.Rincón , C.Pulgarin, N.Adler, P.Peringer, J. Photochemistry. and Photobiology A: Chem. 139 (2001) 233 – 241. Solvation phenomena by water molecules: Aspirin-5H 2 0 complex [2] Aspirin [2] M.Karthika, K.Senthilkumar, R.Kanakaraju, Computational and Theoretical Chemistry 966 (2011) 167 – 179. 14-16 September 2016 Athens, Greece

Use of tap water Milan Tap water composition (mg L -1 ) and chemico-phisycal characteristics [F - ] [Ca 2+ ] <0.50 86 [Cl - ] [Mg 2+ ] 34 19 2- ] [Na + ] [SO 4 58 18 - ] [K + ] [NO 3 30 2 - ] + ] [NO 2 <0.2 [NH 4 <0.1 - ] [Mn 2+ ] [HCO 3 222 <0.001 pH 7.7 Hardness 31 ° f 681 mScm -1 (a) Specific Conductance (a) at 20 ° C 14-16 September 2016 Athens, Greece

Photodegradation results: ink-jet printing . Tap water vs deionized water Fig.6 . Photocatalytic tests of paracetamol (  ) and aspirin (  ) as single molecule a) and mixed (b). Conversion % (full symbol), mineralization % (empty symbol) performed with digital printing tile. Tap water. 14-16 September 2016 Athens, Greece

CONCLUSIONS In this work the following key concepts were proposed: • Evaluation of industrially prepared porcelain grés tiles’ photoactivity for the water purification • Comparison between two different coating methods, both industrially feasible • Study of the degradation of mixture of drugs, closer to the environmental reality • Use of tap water, closer to the environmental reality • Lack of deactivation of the photocatalytic materials and possible immediate reuse of the tiles • Need a thorough study on the best reactor configuration for a real use of photocatalytic ceramics even in the water

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