MEMBRANE REACTORS AND ADVANCED/HYBRID MEMBRANE PROCESSES IN GREEN CHEMISTRY APPLICATIONS R. Molinari, P. Argurio, C. Lavorato Dipartimento di Ingegneria per l'Ambiente e il Territorio e Ingegneria Chimica (DIATIC), Università della Calabria, Via P. Bucci, cubo 45/A, I-87036 Rende (CS) – Italy. Tel. +390984496699, Fax +390984496655; email: r.molinari@unical.it Membranes, thanks to their ability to discriminate at molecular level, are today applied or experimented in various processes and particularly in that ones involving chemical reactions thus making membrane reactors (MRs). The applications concern environmentally friendly processes operating under mild conditions including advanced energy conversion processes such as the photocatalytic ones with potentiality of using a renewable source like the solar energy. Novel applications such as: i) catalytic and photocatalytic production of phenol from benzene, ii) catalytic production of methanol from methane, iii) reduction reactions (e.g. phenylethanol from acetophenone), iv) photocatalytic water splitting and v) complexation –ultrafiltration (e.g. removal of arsenic from wastewater) will be described. The one-step Fenton reaction of benzene oxidation to phenol was studied in various reactor configurations and various catalysts. Vanadium(III) chloride was compared to vanadium(IV) acetyl acetonate as catalysts in a two-phase membrane reactor1. A recent approach is the use of two different three-compartment membrane contactors where phenol, produced in the aqueous reacting phase, was extracted in the organic phase and simultaneously stripped in the basic aqueous phase at 100% purity2. The one step synthesis of phenol and its simultaneous separation was also studied in a photocatalytic membrane contactor using benzene, both as reactant and extraction solvent3. Selective oxidation of hydrocarbons (CH4) in liquid phase in a membrane reactor was studied observing advantages such as enhanced methane concentration/dispersion in the liquid phase and increase of the gas-liquid contact area4. Photocatalytic hydrogenation of acetophenone to produce phenylethanol in a MR, under UV and visible light, using a pollutant such as formic acid as hydrogen and electron donors in aqueous solution, will be presented and discussed. Water splitting, by a Z-scheme system using Au/CeO2 as photocatalyst for oxygen generation, Au/TiO2 for hydrogen generation mediated by the Fe3+/Fe2+ redox couple in a two compartments cell separated by a nafion membrane, has been studied with encouraging results5. Polymer Assisted Ultrafiltration (PAUF), where a complexation reaction is coupled with a membrane separation already experimented in the selective recovery of metal ions from waters6, will be presented in the arsenic removal from aqueous matrices. 1) R. Molinari, P. Argurio, T. Poerio, Vanadium(III) and vanadium(IV) catalysts in a membrane reactor for benzene hydroxylation to phenol and study of membrane material resistance, APP. CAT. A-General, 437 (2012) 131-138. 2) R. Molinari, P. Argurio, T. Poerio, Benzene Hydroxylation and Simultaneous Extraction of Phenol in Two Membrane Contactors Made with Three-Compartment Cells, I&EC Res, 52(31) (2013) 10540-10548. 3) R. Molinari, A. Caruso, T. Poerio, Direct benzene conversion to phenol in a hybrid photocatalytic membrane reactor, Catalysis Today, 144 (2009) 81-86. 4) R. Molinari, P. Argurio, S.M. Carnevale, T. Poerio, Membrane contactors operating in mild conditions for liquid phase partial oxidation of methane, J. Membr. Sci. 366 (2011) 139-147. 5) T. Marino, A. Primo, A. Corma, R. Molinari, H. Garcìa, Photocatalytic overall water splitting by combining gold nanoparticles supported on TiO2 and CeO2, 2nd European Symposium on Photocatalysis, Bordeaux (France), 29th-30th September 2011, pp P. 1.6. 6) R. Molinari, T. Poerio, P. Argurio, Selective separation of copper(II) and nickel(I

MEMBRANE REACTORS AND ADVANCED/HYBRID MEMBRANE PROCESSES IN GREEN CHEMISTRY APPLICATIONS

MOLINARI, Raffaele;Lavorato C.
2013-01-01

Abstract

MEMBRANE REACTORS AND ADVANCED/HYBRID MEMBRANE PROCESSES IN GREEN CHEMISTRY APPLICATIONS R. Molinari, P. Argurio, C. Lavorato Dipartimento di Ingegneria per l'Ambiente e il Territorio e Ingegneria Chimica (DIATIC), Università della Calabria, Via P. Bucci, cubo 45/A, I-87036 Rende (CS) – Italy. Tel. +390984496699, Fax +390984496655; email: r.molinari@unical.it Membranes, thanks to their ability to discriminate at molecular level, are today applied or experimented in various processes and particularly in that ones involving chemical reactions thus making membrane reactors (MRs). The applications concern environmentally friendly processes operating under mild conditions including advanced energy conversion processes such as the photocatalytic ones with potentiality of using a renewable source like the solar energy. Novel applications such as: i) catalytic and photocatalytic production of phenol from benzene, ii) catalytic production of methanol from methane, iii) reduction reactions (e.g. phenylethanol from acetophenone), iv) photocatalytic water splitting and v) complexation –ultrafiltration (e.g. removal of arsenic from wastewater) will be described. The one-step Fenton reaction of benzene oxidation to phenol was studied in various reactor configurations and various catalysts. Vanadium(III) chloride was compared to vanadium(IV) acetyl acetonate as catalysts in a two-phase membrane reactor1. A recent approach is the use of two different three-compartment membrane contactors where phenol, produced in the aqueous reacting phase, was extracted in the organic phase and simultaneously stripped in the basic aqueous phase at 100% purity2. The one step synthesis of phenol and its simultaneous separation was also studied in a photocatalytic membrane contactor using benzene, both as reactant and extraction solvent3. Selective oxidation of hydrocarbons (CH4) in liquid phase in a membrane reactor was studied observing advantages such as enhanced methane concentration/dispersion in the liquid phase and increase of the gas-liquid contact area4. Photocatalytic hydrogenation of acetophenone to produce phenylethanol in a MR, under UV and visible light, using a pollutant such as formic acid as hydrogen and electron donors in aqueous solution, will be presented and discussed. Water splitting, by a Z-scheme system using Au/CeO2 as photocatalyst for oxygen generation, Au/TiO2 for hydrogen generation mediated by the Fe3+/Fe2+ redox couple in a two compartments cell separated by a nafion membrane, has been studied with encouraging results5. Polymer Assisted Ultrafiltration (PAUF), where a complexation reaction is coupled with a membrane separation already experimented in the selective recovery of metal ions from waters6, will be presented in the arsenic removal from aqueous matrices. 1) R. Molinari, P. Argurio, T. Poerio, Vanadium(III) and vanadium(IV) catalysts in a membrane reactor for benzene hydroxylation to phenol and study of membrane material resistance, APP. CAT. A-General, 437 (2012) 131-138. 2) R. Molinari, P. Argurio, T. Poerio, Benzene Hydroxylation and Simultaneous Extraction of Phenol in Two Membrane Contactors Made with Three-Compartment Cells, I&EC Res, 52(31) (2013) 10540-10548. 3) R. Molinari, A. Caruso, T. Poerio, Direct benzene conversion to phenol in a hybrid photocatalytic membrane reactor, Catalysis Today, 144 (2009) 81-86. 4) R. Molinari, P. Argurio, S.M. Carnevale, T. Poerio, Membrane contactors operating in mild conditions for liquid phase partial oxidation of methane, J. Membr. Sci. 366 (2011) 139-147. 5) T. Marino, A. Primo, A. Corma, R. Molinari, H. Garcìa, Photocatalytic overall water splitting by combining gold nanoparticles supported on TiO2 and CeO2, 2nd European Symposium on Photocatalysis, Bordeaux (France), 29th-30th September 2011, pp P. 1.6. 6) R. Molinari, T. Poerio, P. Argurio, Selective separation of copper(II) and nickel(I
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