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A Biorefinery Cascade Conversion of Hemicellulose-Free Eucalyptus Globulus Wood: Production of Concentrated Levulinic Acid Solutions for γ-Valerolactone Sustainable Preparation

1
Chemical Engineering Department, Polytechnical Building, University of Vigo (Campus Ourense), As Lagoas, 32004 Ourense, Spain
2
CITI (Centro de Investigación, Transferencia e Innovación)—University of Vigo, Tecnopole, San Cibrao das Viñas, 32901 Ourense, Spain
3
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Giuseppe Moruzzi 13, 56124 Pisa, Italy
*
Authors to whom correspondence should be addressed.
Catalysts 2018, 8(4), 169; https://doi.org/10.3390/catal8040169
Received: 14 March 2018 / Revised: 18 April 2018 / Accepted: 19 April 2018 / Published: 21 April 2018
(This article belongs to the Special Issue Catalytic Transformation of Lignocellulosic Platform Chemicals)
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Abstract

Eucalyptus globulus wood samples were subjected to preliminary aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid (mainly made up of cellulose and lignin) was employed as a substrate for converting the cellulosic fraction into mixtures of levulinic and formic acid through a sulfuric acid-catalyzed reaction. These runs were carried out in a microwave-heated reactor at different temperatures and reaction times, operating in single-batch or cross-flow modes, in order to identify the most favorable operational conditions. Selected liquid phases deriving from these experiments, which resulted in concentrated levulinic acid up to 408 mmol/L, were then employed for γ-valerolactone production by levulinc acid hydrogenation in the presence of the commercial 5% Ru/C catalyst. In order to assess the effects of the main reaction parameters, hydrogenation experiments were performed at different temperatures, reaction times, amounts of ruthenium catalyst and hydrogen pressure. Yields of γ-valerolactone in the range of 85–90 mol % were obtained from the hydrogenation of the wood-derived solutions containing levulinic acid, obtained by single-batch operation or by the cross-flow process. The negative effect of co-produced formic acid present in crude levulinic acid solutions was evidenced and counteracted efficiently by allowing the preliminary thermal decomposition of formic acid itself. View Full-Text
Keywords: Eucalyptus globules; levulinic acid; γ-valerolactone; single batch and cross-flow processes; acid catalysis; ruthenium Eucalyptus globules; levulinic acid; γ-valerolactone; single batch and cross-flow processes; acid catalysis; ruthenium
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Rivas, S.; Raspolli Galletti, A.M.; Antonetti, C.; Licursi, D.; Santos, V.; Parajó, J.C. A Biorefinery Cascade Conversion of Hemicellulose-Free Eucalyptus Globulus Wood: Production of Concentrated Levulinic Acid Solutions for γ-Valerolactone Sustainable Preparation. Catalysts 2018, 8, 169.

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