abstract
Ordered porous silicates of the type TUD-1 and zeolite beta possessing zirconium and aluminium sites were evaluated as eco-friendly heterogeneous, multifunctional catalysts for the integrated reduction-acid conversion of furfural (Fur, industrially produced from hemicellulosic components of biomass) to useful bio-products, namely, furfuryl alcohol (FA), alkyl furfuryl ethers (FEs), alkyl levulinate esters (LEs), levulinic acid (LA), angelica lactones (AnLs), and gamma-valerolactone (GVL); the bio-products spectrum was obtained by GC x GC-ToFMS. Carrying out the one-pot conversion of Fur to bio-products using a multifunctional catalyst is challenging since various reactions are involved and it is difficult to control all of these to meet high reaction efficiencies and selectivities. Aiming at designing improved multifunctional catalysts for this reaction system, the TUD-1 and zeolite beta type silicates possessing zirconium and aluminium sites in different ratios were prepared and characterised on microstructural and molecular levels. Systematic characterisation, catalytic testing using 2-butanol as dual functional solvent-H-donor, and kinetic modelling studies were performed using the Zr,Al-containing micro- and mesoporous materials. Different steps of the overall reaction of Fur were studied separately starting from intermediate products using the same materials, which helped understand the influence of the material properties on reactivity of intermediates and reaction selectivity. Zr-sites of the silicate catalysts were essential for effectively initialising the overall process (reduction of Fur to FA), and for the reduction of LEs to GVL; the co-presence of Al-sites promoted acid-catalysed steps (FA to FEs, LEs, AnLs, LA). The good stability of the catalysts was verified by catalytic and characterisation studies of the spent catalysts. (C) 2015 Elsevier B.V. All rights reserved.
keywords
MEERWEIN-PONNDORF-VERLEY; ZR-ZEOLITE-BETA; N-BUTYL LEVULINATE; GAMMA-VALEROLACTONE; ETHYL LEVULINATE; EFFICIENT CONVERSION; ZIRCONIA CATALYSTS; N2O DECOMPOSITION; MESOPOROUS ALUMINOSILICATE; LIGNOCELLULOSIC BIOMASS
subject category
Chemistry; Engineering
authors
Antunes, MM; Lima, S; Neves, P; Magalhaes, AL; Fazio, E; Neri, F; Pereira, MT; Silva, AF; Silva, CM; Rocha, SM; Pillinger, M; Urakawa, A; Valente, AA
our authors
Ana Luísa Carvalho Magalhães
Post-doc Fellowship
Anabela Tavares Aguiar Valente
Principal Researcher
Carlos Manuel Silva
Associate Professor
Maria de Lourdes Gomes Pereira
Associate Professor with Aggregation
Maria Margarida Feitor Pintão Moreno Antunes
Junior Researcher
Martyn Pillinger
Principal Researcher
Patrícia dos Santos Neves
Assistant ResearcherGroups
G1 - Porous Materials and Nanosystems
G4 - Renewable Materials and Circular Economy
G5 - Biomimetic, Biological and Living Materials
acknowledgements
This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID /CTM /50011/2013) and QOPNA research Unit (FCT UID/QUI/00062/2013), financed by National funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement. The FCT and the European Union are acknowledged for grants to M.M.A. (SFRH/BPD/89068/2012), P.N. (SFRH/BPD/73540/2010), A.M. (SFRH/BPD/95393/2013) and A.F.S (SFRH/BD/101018/2014), cofunded by MCTES and the ESF through the program POPH of QREN. S.L. and A.U. thank MINECO for support through Severo Ochoa Excellence Accreditation 2014-2018 (SEV-2013-0319).