Abstract

Liquid-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was investigated over Metal–Organic Framework- and zeolite-supported ruthenium catalysts in aqueous media at low reaction temperature. Ru/MIL-101(Cr) showed the highest activities over Ru/MIL-100(Cr) and the investigated Ru/zeolite catalysts in terms of both turn over frequencies (TOFs) for LA-to-GVL transformation and GVL formation rate. The catalytic activity of Ru/MIL-100(Cr) was comparable to Ru/HY-zeolite (Si/Al ≥ 5.2). The Ru/MIL-101(Cr) provided a combination of both high acidity of MIL-101(Cr) support and high dispensability of metallic sites, which promotes LA hydrogenation to 4-hydroxypentanoic acid and subsequent esterification of 4-hydroxypentanoic acid to GVL via a simultaneous access of LA into the both sites. Under the investigated mild reaction conditions, both GVL selectivity and yield exceeding 99 % with a full conversion of LA were obtained by using Ru/MIL-101(Cr) catalyst at a reaction temperature of 70°C after 5 h under H2 pressure of 1.0 MPa. Moreover, Ru/MIL-101(Cr) can be easily reused at least for four times. Ruthenium immobilized on Metal–Organic Frameworks is efficiently used as recyclable catalyst for levulinic acid hydrogenation to biomass-based γ-valerolactone.

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