Integrated reduction and acid-catalysed conversion of furfural in alcohol medium using Zr,Al-containing ordered micro/mesoporous silicates

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
nationality	International
journal	APPLIED CATALYSIS B-ENVIRONMENTAL
author keywords	Furfural; Integrated conversion; Multifunctional catalysts; Porous silicates; Reduction-acid catalysis
keywords	MEERWEIN-PONNDORF-VERLEY; ZR-ZEOLITE-BETA; N-BUTYL LEVULINATE; GAMMA-VALEROLACTONE; ETHYL LEVULINATE; EFFICIENT CONVERSION; ZIRCONIA CATALYSTS; N2O DECOMPOSITION; MESOPOROUS ALUMINOSILICATE; LIGNOCELLULOSIC BIOMASS
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.
publisher	ELSEVIER SCIENCE BV
issn	0926-3373
year published	2016
volume	182
beginning page	485
ending page	503
digital object identifier (doi)	10.1016/j.apcatb.2015.09.053
web of science category	Chemistry, Physical; Engineering, Environmental; Engineering, Chemical
subject category	Chemistry; Engineering
unique article identifier	WOS:000365050700052