Valeric Biofuel Production from γ‐Valerolactone over Bifunctional Catalysts with Moderate Noble‐Metal Loading

Abstract

SiO2‐Al2O3‐supported Ru, Ir and Pt‐based catalysts with moderate metal loading (1 %) were tested for the first time in the production of pentyl valerate (PV) in liquid phase from γ‐valerolactone, pentanol (in excess) and H2. The acidity of these bifunctional catalysts, plays a key role in the one‐pot process comprising two consecutive acid‐catalyzed reactions and a metal‐catalyzed one. Metal dispersion also shown to be relevant for the conversion of the pentyl pentenoate intermediate into PV by hydrogenation over the metal sites. Pt/SA catalyst with the highest surface acidity and metal dispersion reached optimal GVL conversion with a PV yield of 90.0 % after 10 h, exhibiting a PV productivity of 300 mmol/gM.h, i. e. a value between three and four times higher than the best result reported until now (91.8 mmol/gM.h). These findings highlight the potential that noble metal‐based catalyst with moderate metal loading have in the valorization of biomass‐derived platform molecules such as γ‐valerolactone.

Production of pentyl valerate from γ-valerolactone, pentanol and H2 using Pd and Rh-based bifunctional catalysts

“…This effect was also observed when Ru, Ir and Pt-based catalysts of similar metal loading are considered. 21 On the other hand, the overall GVL conversion after 8 h of reaction showed a better activity for Rh/SA and Pd/SA compared to the SA support. Although in the case of Rh/ SA the GVL conversion (60.5%) was only slightly higher than that with SA (58.0%), the reagent conversion over Pd/SA reached a significantly higher value (81.1%).…”

“…H 2 consumption was quantified by mass spectrometry (MS) in a Baltzers Omnistar unit. 21 The reduced and calcined samples were analysed by X-ray diffraction (XRD) using a PANalytical Empyrean diffractometer and Ni-filtered Cu-Kα radiation (40 kV and 45 mA) in the range of 2θ = 10-70°and scanning at a speed of 2°min −1 .…”

“…CO chemisorption via volumetric adsorption experiments at room temperature was performed in a conventional vacuum apparatus using a method described elsewhere. 21 Transmission electron microscopy (TEM) was performed using a JEOL 2100 plus microscope. For each sample, more than 130 particles randomly taken from at least ten TEM images were measured and the distribution of particle sizes was estimated.…”

“…More details about quantitative GC analysis can be found in previous studies. [20][21][22] The reactant conversion (X GVL , mol of GVL reacted/mol of GVL fed) was calculated as…”

Exploring the Zn-regulated function in Co–Zn catalysts for efficient hydrogenation of ethyl levulinate to γ-valerolactone

“…4,5 GVL is a kind of five-carbon cyclic lactone with stable physical and chemical properties, and can be widely used as a fuel, a food additive, a green solvent, an intermediate, etc. [6][7][8] However, due to the subsequent side reactions, the hydrogenation of EL to GVL usually suffers from low selectivity. 9,10 For example, GVL will undergo further hydrogenolysis and dehydration reactions to produce 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF).…”