photoactive tiles for drug removal in polluted...
TRANSCRIPT
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Micro-sized TiO2 as photoactive catalyst coated on industrial porcelain grès tiles
in water drug photodegradation
aspirin and paracetamol
14-16 September 2016 Athens, Greece
Prof. Claudia BianchiUniversità degli Studi di Milano
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European Union LegislationDIRECTIVE 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 September2013 develop a strategic approach to pollution of water by pharmaceuticalsubstances”.
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
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WastewaterremediationPhotoactive
porcelain grès tile
Emerging
pollutants
PhotocatalyticOxydation
Photocatalytic Oxydation: AOP
Photoactiveporcelain grès tiles:
Emerging pollutants: Aspirin ¶cetamol
TiO2 catalyst
Photodegradationtest
TiO2
semiconductor
World Legislation
World Legislation
14-16 September 2016 Athens, Greece
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Pharmaceutical compounds
Aspirin Paracetamol
acetoxy group (-O-C(=O)- CH3)
carboxylic acid group (-C(=O)-OH)
amide group (-NH -C(=O)-CH3)
hydroxylic group (-OH)
14-16 September 2016 Athens, Greece
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Background
Traditional Physical Techniques
Transfer Organic Compounds from Water to another phase
SECONDARY
POLLUTION
TiO2 Photocatalysis
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Industrially produced photoactive porcelain gres
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Photoactive porcelain gres ceramic tiles
1) Preparation
Mixing and grinding Milling of raw materials in water:
clay minerals, natural minerals (feldspar, silica)
Forming by automated presses P=7000 tons
Firing in a tunnel kiln at 1300°C for 60 min
2) Photoactive modifies tiles
Covering with a suitable micro-TiO2 based-ink via digital printing (new) or spray deposition (old)
Treatment at high temperature: 680°C for 80 min
Brushing to remove unfixed powder
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Photodegradation tests
Min
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lizat
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%
C
on
vers
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% 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 CO2 and H2O.
Aspirin, Paracetamol and their by-products are completely degraded over time
14-16 September 2016 Athens, Greece
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Photodegradation results: comparison between spray and digital printing coatings
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Aspirin Paracetamol mixed together (1:1)
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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
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Photodegradation Mechanisms
Paracetamol
Aspirin
Aromatic ring cleavage
and further oxidation to CO2 and H20
14-16 September 2016 Athens, Greece
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Photodegradation Mechanisms
Keto-enolic tautomericequilibrum between hydroquinone/benzoquinone [1]
Solvation phenomena by water molecules: Aspirin-5H20 complex [2]
Paracetamol
Aspirin [2] M.Karthika, K.Senthilkumar, R.Kanakaraju, Computational and Theoretical Chemistry 966 (2011) 167–179.
[1] A.G.Rincón, C.Pulgarin, N.Adler, P.Peringer, J. Photochemistry. and Photobiology A: Chem. 139 (2001) 233–241.
14-16 September 2016 Athens, Greece
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14-16 September 2016 Athens, Greece
[F-] <0.50 [Ca2+] 86 [Cl-] 34 [Mg2+] 19 [SO4
2-] 58 [Na+] 18 [NO3
-] 30 [K+] 2 [NO2
-] <0.2 [NH4+] <0.1
[HCO3-] 222 [Mn2+] <0.001
pH 7.7Hardness 31 °fSpecific Conductance 681 mScm-1 (a)
(a) at 20 °C
Milan Tap water composition (mg L-1) and
chemico-phisycal characteristics
Use of tap water
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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.
Photodegradation results: ink-jet printing. Tap water vs deionized water
14-16 September 2016 Athens, Greece
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CONCLUSIONS
• 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 ofphotocatalytic ceramics even in the water
In this work the following key concepts were proposed:
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Thank You for your kind attention