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R. Molinari, P. Argurio, E. Curcio, G. Golemme

Research activities on membrane and membrane processes of the Group of Chemical Fundaments of Membrane Technologies. R. Molinari, P. Argurio, E. Curcio, G. Golemme S.S.D.: 03/B2 – Fondamenti Chimici delle Tecnologie (ex CHIM/07)

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R. Molinari, P. Argurio, E. Curcio, G. Golemme

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  1. Research activities on membrane and membrane processes of the Group of Chemical Fundaments of Membrane Technologies R. Molinari, P. Argurio, E. Curcio, G. Golemme S.S.D.: 03/B2 – Fondamenti Chimici delle Tecnologie (ex CHIM/07) Department of Environmental and Chemical Engineering, University of Calabria, Via P. Bucci, 44/A, I-87036 Arcavacata di Rende (CS)-Italy Ph. +39 0984 496699; Fax +39 0984 496655; E-mail: r.molinari@unical.it Presented to: XXXI PhD Course Welcome Day –SIACE Doctorate-Rende 26/11/2015

  2. Outline (1/2)(MOLINARI - ARGURIO) MEMBRANE REACTORS Selectiveoxidation of hydrocarbons in liquidphase in membrane reactors Benzene to phenol Methane to methanol Photocatalyticprocesses in membrane reactors Photodegradation of pollutants in water Photosynthesis of organic compounds Photocatalytichydrogen production fromWater-splitting Photocatalytic hydrogenation of organic compounds Membrane processes coupled with specific interactions in treatment of waters Supported and Stagnant Sandwich Liquid Membranes Polymer Assisted Ultrafiltration (PAUF)

  3. Outline (2/2) Integrated Membrane SystemsforDesalination and Water treatment (CURCIO) Some critical issue on membrane desalination Membrane Distillation Reverse Electrodialysis Advanced membrane materialsfor the separation of gaseousmixtures (GOLEMME) Block-copolymer membranes for the purification of natural gas Mixed matrix membranes for the treatment of natural gas Mechanism of gas transport in mixed matrix membranes

  4. MEMBRANE REACTORS (MOLINARI - ARGURIO)

  5. Catalytic membrane TC Feed Permeate Selective oxidation of hydrocarbons in liquid phase in membrane reactors The selectivity of direct oxidation is rather poor and over-oxygenated by-products as catechols, hydroquinones and benzoquinones are formed Case 1: Benzene to phenol Biphasic membrane reactor Flow-throughmembrane reactor Biphasic membrane reactor Advantage: Control of contact time of phenol with the catalyst avoiding by-products formation. The control of reactivity is obtained by inclusion of the catalysts in polymeric membranes and permeating the oxidant solution, containing the substrate, at different permeate flow rates. Disadvantage: Catalyst leaching (under study) Advantage: Phenol permeation across the membrane to organic phase permits to take shelter from over oxidation obtaining a phenol selectivity in organic phase = 98% Disadvantage: Permeation rate. Indeed, phenol that does not cross rapidly the membrane, reacts further to generate over-oxidation products as 1-4 benzoquinone, biphenyl and tars (black solid). • 1. R. Molinari, T. Poerio, P. Argurio, One-step production of phenol by selective oxidation of benzene in a biphasic system, Catalysis Today, 118 (2006) 52-56. • 2. R. Molinari, T. Poerio, P. Argurio, Preparation, characterisation and reactivity of polydimethylsiloxane membranes for selective oxidation of benzene to phenol, Desalination, 200 (2006) 673-675. • 3. R. Molinari, T. Poerio, P. Argurio, Italy Patent CZ 2006 A000029 (2006), University of Calabria. • R. Molinari, T. Poerio, Selectivity control of benzene conversion to phenol using dissolved salts in a membrane contactor, Applied Catalysis A-General 393 (2011) 340-347. • 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, Appl. Catal. A: Gen. (2012), http://dx.doi.org/10.1016/j.apcata.2012.06.027

  6. CH4 cylinder Gas-liquid membrane contactor TC Selective oxidation of hydrocarbons in liquid phase in membrane reactors Case 2: Methane to methanol The selectivity of direct oxidation is rather poor and over-oxygenated by-products as formic acid, formaldehyde and carbon dioxide are formed. Advantages: i) methane concentration/dispersion in the liquid phase is enhanced (e.g. by micro-bubbles dispersion), thus increasing the contact area between the liquid phase containing the oxidizing agents and the gaseous phase containing the methane substrate; ii) gaseuous reactant depletion is avoided. Disadvantages: i) blocking of membrane contactor caused by catalyst aggregation/precipitation; ii) degradation of polymeric membranes. Thus appropriate membranes (e.g. ceramic) have to be selected for membrane contactor assembling. 1. R. Molinari, P. Argurio, S.M. Carnevale, T. Poerio, Membrane contactors operating in mild conditions for liquid phase partial oxidation of methane, Journal of Membrane Science 366 (2011) 139-147. 2. R. Molinari, T. Poerio, A. Caruso, P. Argurio, S. M. Carnevale, Direct mild partial oxidation of benzene and methane in catalytic and photocatalytic membrane reactors, DGMK Tagungsbericht 2008-3, Preprints of the DGMK Conference “Future Feedstocks for Fuels and Chemicals”, September 29 – October 1, 2008, Berlin, Germany, Edited by. S. Ernst, A. Jess, F. Nees, U. Peters, M. Ricci, E. Santacesaria, DGMK German Society fro Petroleum and Coal Science and Technology, Hamburg, Germany, ISBN 978-3-936418-81-1, pp.217-224.

  7. O2 - O2 Conduction band e- hν Band Gap (Eg) UV light h+ Valence band H2O/OH- OH Photocatalytic processes in membrane reactors • Photocatalytic drawbacks • High and non-specific reactivity • Low selectivity • Recovery of the suspended catalyst • Photocatalytic Membrane Reactors (PMRs) • Recovery and reuse of the catalyst • Rejection of substrates and by-products • Separation of the products/by-products • Continuous process Photodegradation of pollutants in water Complete mineralization of pharmaceuticals and their metabolites is possible in PMRs able to maintain in the reaction environment the pollutants and the catalyst giving the purified solution as permeate. One of the major problems observed in the PMRs with suspended catalyst is membrane fouling. To solve this problem we introduce a different membrane module configuration, the submerged membrane system with oxygen bubbling, to control the hydrodynamic conditions near membrane surface thus preventing particle deposition on the membrane. • R. Molinari, F. Pirillo, M. Falco, V. Loddo, L. Palmisano. Photocatalytic degradation of dyes by using a membrane reactor, Chem. Eng. Process.2004, 43, 1103. • R. Molinari, F. Pirillo, V. Loddo, L. Palmisano. Heterogeneous photocatalytic degradation of pharmaceuticals in water by using polycrystalline TiO2 and a nanofiltration membrane reactor, Catal. Today2006, 118, 205. • R. Molinari, A. Caruso, P. Argurio, T. Poerio. Degradation of the drugs Gemfibrozil and Tamoxifen in pressurized and de-pressurized membrane photoreactors using suspended polycrystalline TiO2 as catalyst, J. Membrane Sci.2008, 319, 54.

  8. Scheme of the discontinuous photoreactive system and the hybrid membrane system • (A) valvola di serraggio ; (B) termocoppia; (C) serbatoio non reagente; (D) pompa; (E) valvola di regolazione; (F) manometro; (G) modulo membrana; (H) linea in pressione; (I) rotametro; (PFP) fotoreattore “plug flow” V. AUGUGLIARO, E. GARCI´A-LO´PEZ, V. LODDO, S. MALATO –RODRIGUEZ, I MALDONADO, G. MARCI`, R. MOLINARI, L. PALMISANO, Degradation of lincomycinin aqueous medium: coupling of solar photocatalysisand membrane separation, in SeriePonencias, The Improving Human Potential Programme. Access to research infrasctructuresactivity. Research results at plataformasolar de Almeriawithin the year 2003 access campaign. Editorial CIEMAT, Madrid,2004, pp. 43-52. ISBN 84-7834-474-8.

  9. Scheme of the continuous hybrid membrane system • (A) valvola di serraggio ; • (B) termocoppia; • (C) serbatoio non reagente; • (D) pompa; • (E) valvola di regolazione; • (F) manometro; • (G) modulo membrana; • (H) linea in pressione; • (I) rotametro; • (L) serbatoio alimentazione; • (PFP) fotoreattore “plug flow”

  10. TC Photocatalytic processes in membrane reactors Photo assisted fenton for degradation of drugs in water. Coupling Advanced Oxidation Processes (AOPs) with UV radiation permitted to obtain enhanced results because of the promotion of iron catalyst regeneration and production of additional OH radicals in one step Photosynthesis of organic compounds One step synthesis of phenol and its simultaneous separation in a Photocatalytic Membrane Contactors using benzene as both reactant and extraction solvent, is a Green Process able to use, in perspective, the solar light. Drugs degradation is possible by coupling (AOPs) and PMRs able to control the contact time of the organic substrates in the oxidant environment and to reuse the catalyst, thus realizing in a single step both the degradation and the recovery of the purified water. • R. Molinari, P. Argurio, T. Poerio, F. Bonaddio. Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water, Sep. Sci. Technol.2007, 42, 1597.

  11. Au/TiO2 550 nm PHOTOCATALYTIC HYDROGEN PRODUCTION FROM WATER-SPLITTING Hydrogen is widely considered one of the most attractive and environmentally friendly fuels of the future. The growing interest in hydrogen has resulted from the increasing need to develop new technologies, like photocatalysis, which is based on the utilization of solar light. However, powdered photocatalysts always produce a gas mixture of hydrogen and oxygen and thus, a separation process for the gas mixture is required before the hydrogen can be effectively utilized. Construction of a photocatalytic membrane-system1 enabling the separate evolution of hydrogen and oxygen from water under visible light irradiation is, therefore, of vital interest. TiO2 is by far the most studied photocatalyst, but it has a limited response for wavelenghts longer than 390 nm. We have been involved in developing titania materials with response for visible light depositing gold nanoparticles on the TiO2 surface (Au/TiO2) and employed this material to generate hydrogen from water splitting2. 1T. Marino, A. Primo, A. Corma, R. Molinari, H. Garcìa, submitted to Chemical Communications, 2011. 2C. Gomes Silva, R. Juàrez, T. Marino, R. Molinari and H. Garcìa, J. Am. Chem. Soc., 2011, 133 (3), pp 595-602. References:

  12. Photocatalytic hydrogenation of organic compounds in a membrane reactor • Photocatalytic hydrogenation using hydrogen donors for the reduction in liquid phase of selected organic compounds: • hydrogenation of intermediates from biomass for the production of liquid fuels • hydrogenation of ketones to their corresponding alcohols intermediates in the pharmaceutical industry • Disadvantages: • Recombination of photo-generated electron/hole pairs • Difficulty to utilize visible light • Advantages: • Reduction of organic compounds without the direct addition of H2 avoiding the costs associated with storing and transporting of hydrogen. • Reactions conducted in a photocatalytic system that allows to carry out the reactions under mild experimental conditions with potentiality of using renewable solar energy. • Combination with other physical and chemical technologies (e.g. membrane reactor).

  13. Membrane processes coupled with specific interactions in treatment of waters Raffaele Molinari, Pietro Argurio

  14. Goals of separation processes • recovery of metals and pharmaceuticals from contaminated wastewater; • detoxification of wastewater; • water recycling and reuse.

  15. SLM: transport Advantages A LM phase (organic solvent + selective carrier) is immobilized in the pores of a hydrophobic microfiltration membrane. • high separation factors; • very high selectivity by using an appropriate carrier molecule, • uphill concentration and separation, • use of little amount of expensive extractants, • low capital and operating costs, • high flexibility and easy scale up. Feed phase Membrane phase Strip phase AC A A BC B B Disadvantage Counter transport mechanism A + BC D AC + B feed side AC + B D BC + A strip side A: target component, B: counter ion The low system stability does not yet allow large scale application of SLMs.

  16. Stagnant Sandwich LM A possible alternative to minimize these problems is the use of stagnant sandwich liquid membranes (SSwLMs), where the liquid membrane phase is confined between two hydrophilic membranes that separates the feed and strip phases. Hydrophilic membranes Liquid Membrane with Carrier The SSwLM system was tested in the removal of the inorganic ion copper(II)* and of the organic drug Gemfibrozil**. In both cases the SSwLM gave better fluxes and better stabilities with respect to the traditional SLM configuration. *R. Molinari, P. Argurio, T. Poerio, Flux enhancement of stagnant sandwich compared to supported liquid membrane systems in the removal of Gemfibrozil from waters, J. Membr. Sci. 340 (2009) 26-34 **R. Molinari, P. Argurio, T. Poerio, Studies of various solid membrane supports to prepare stable sandwich liquid membranes and testing Copper(II) removal from aqueous media, Sep. Pur. Technol. 70 (2009) 166-172.

  17. Possible applications • SLM technique is today largely employed in the field of environmental analysis as a sample preparation technique. • Treatment of wastewaters coming from the metal finishing industry. E.g. the selective recovery of Ni ions from wastewater of stainless steel industry. • The treatment of spent etching solution of the electronic industry, with the SLM technique, has been proposed and technically validated in literature as possible large scale application. • Remediation of nuclear waste.

  18. CP-UF principle Concentrate Feed solution + Particles formation Membrane Permeate Particles forming additive • low energy requirements (UF) with respect to RO • modularity • high removal efficiency and selectivity • optimal quality of treated water Advantages:

  19. Polymer regeneration The CP-UF process appears to be economically feasible if the polymer could be regenerated by the release of the metal or its chelate and reused. Ultrafiltration I Complexation Permeate Feed Ultrafiltration II Decomplexation By-product to dispose Retentate Recycle

  20. Potential application 1Modular integrated membrane process for the removal of metal chelates from soil washing solutions (5) (1) Soil Washing (6) (7) (3) • Citric acid solution at pH 5.5; • Soil washing solution; • Treated water for recycle; • Concentrated PEI-citric acid- copper solution; • Purge of treated water excess; • Concentrated PEI solution representing polymer recycle (chemically regenerated); • Water make-up; • Copper-citric acid diafiltrate; • Free copper concentrate. (2) Complexation pH 5.5 UF DF (4) (8) Decomplexation pH 2 (9) Membrane filtration 0.45 mm Photocatalysis pH 5.5 TiO2 Soil washing – Ultrafiltration (UF)– Diafiltration (DF)– Photocatalysis Performance achieved: water recovery (98 %) – polymer recycle – free metal recovery (99%) R. Molinari, T. Poerio, P. Argurio, Chemical and operational aspects in running the Polymer Assisted Ultrafiltration for separation of Copper(II)-Citrate Complexes from Aqueous Media, J. Membr. Sci. 295 (2007) 139-147.

  21. Potential application 2 Selectivity is an important feature of the CP-UF process. We investigated the possibility to use the CP-UF process for the selective separation of copper(II) and nickel(II) both contained in the same solution. Obtained results showed that the CP-UF methodology can be efficiently used to obtain selective separation of metals by means of their binding to water soluble polymers. R. Molinari, T. Poerio, P. Argurio, Selective separation of copper(II) and nickel(II) from aqueous media using the complexation–ultrafiltration process, Chemosphere, 70 (2008) 341–348.

  22. Integrated Membrane Systems for Desalination and Water treatment (CURCIO)

  23. SOME CRITICAL ISSUES IN MEMBRANE DESALINATION • Relatively low water recovery factor (50%) • Environmental impact related to the huge volume of brine discharged from SWRO • Relatively high energy consumption (3-4 kWh/m3) with respect to the theoretical value (1.1 kWh/m3) 0.5 m3 BRINE SWRO 1 m3 FEED 0.5 m3 PERM 26 - 29 July 2015 | Singapore

  24. MEMBRANE DISTILLATION Tdistillate, inlet = 20°C Fdistillate = Fretentate = 300 l/h Total membrane area = 0.35 m2

  25. REVERSE ELECTRODIALYSIS (RE) CEM: cation exchange membrane AEM: anion exchange membrane HCC: high concentration compartment LCC: low concentration compartment PLANCK-HENDERSON eq: R.A. Tufa, E. Curcio,   W. van Baak,  J. Veerman, S. Grasman,  E. Fontananova, G. Di Profio, RSC Adv., 2014,4, 42617-42623   MELPRO – 18-21 May 2014, Prague (Czech Republic)

  26. POWER DENSITY

  27. Advanced membrane materialsfor the separation of gaseousmixtures (GOLEMME)

  28. MMM Mixed Matrix Membranes (MMMs) for Gas Separation G. Golemme SBS-28 90% SBA-15-NH2 10% + = DoubleNanoMem NMP3-SL-2009-228631 MMM PIM-1 64.5% MFI 35.5% MMM CO2/N2 = 52 CH4/N2 = 7.3 (CO2/N2 = 30) (CH4/N2 = 4.0) + = CCS CO2/N2 = 30 M. G. Buonomenna, et al., Adv. Funct. Mater., 22 1759-1767 (2012) M. G. Buonomenna, et al, J. Mater. Chem. A, 111853-11866 (2013) (CO2/N2 = 22) CR Mason, MG Buonomenna, G Golemme, PM Budd, F. Galiano, A Figoli, K Friess, V Hynek, Polymer, 54 (2013) 2222-2230 PON 01_01840 MicroPerla

  29. HyflonAD60X 65 v% SAPO-34 (CHA) 35% CO2 CH4 MMM = + CO2/CH4 = 40 (CO2/CH4 = 22) CH4 G. Golemmeet al., EP2668995A1 (2013)

  30. Barriers to transport in porous materials Surfacetreatmentsremovinghydrophilic ≡Si-OH surfacegroupsspeed up H2sorption / desorption Frozenmoisture on silicalite-1 slows down H2diffusion O H H O O O H H H O H H H O H O O H O H H H H H O H O H O H O H H H H H O H O H O H G.N. Kalantzopoulos, A. Policicchio, E. Maccallini, I. Krkljus, F. Ciuchi, M. Hirscher, R.G. Agostino, G. Golemme, MicroporousMesoporous Mater., in press, DOI: 10.1016/j.micromeso.2015.08.039

  31. Thank you

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