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

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 Bianchi

Università degli Studi di Milano

European Union Legislation

DIRECTIVE 2013/39/EU OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

• f 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

• f 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

Wastewater

remediation

Photoactive porcelain grès tile Emerging pollutants Photocatalytic Oxydation

• Photocatalytic

Oxydation: AOP

• Photoactive

porcelain grès tiles:

• Emerging pollutants:

Aspirin &paracetamol

TiO2 catalyst Photodegradation test

TiO2 semiconductor

World Legislation World Legislation

14-16 September 2016 Athens, Greece

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

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

TiO2 Photocatalysis

Industrially produced photoactive porcelain gres

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

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 CO2 and H2O. 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

20 40 60 80 100

1 2 3 4 5 6 7 8 9 10

Conversion (%) time (h)

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20 40 60 80

1 2 3 4 5 6 7 8 9 10

Mineralization (%) time(h)

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Mineralization% Conversion%

20 40 60 80 100

1 2 3 4 5 6 7 8 9 10

Conversion (%) time (h) 24

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20 40 60 80

1 2 3 4 5 6 7 8 9 10

Mineralization (%) time (h) 24

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20 40 60 80 100

1 2 3 4 5 6 7 8 9 10

Conversion (%) time (h)

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20 40 60 80

1 2 3 4 5 6 7 8 9 10

Mineralization (%) time (h)

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Aspirin Paracetamol mixed together (1:1)

/

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 Aspirin

Aromatic ring cleavage and further oxidation to CO2 and H20

14-16 September 2016 Athens, Greece

Photodegradation Mechanisms

Keto-enolic tautomeric equilibrum 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.

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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 7.7 Hardness 31 °f Specific Conductance 681 mScm-1 (a)

(a) at 20 °C

Milan Tap water composition (mg L-1) and chemico-phisycal characteristics

Use of tap 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.

Photodegradation results: ink-jet printing.

Tap water vs deionized water

14-16 September 2016 Athens, Greece

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 of

photocatalytic ceramics even in the water In this work the following key concepts were proposed:

Thank You for your kind attention