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Understanding the reactions of heteroatomic cyclic compounds is essential for developing good catalysts for the upgrading of bio-oils into liquid fuels. The present study presents the reaction network of 2-methyltetrahydrofuran (2-MTHF, C5H10O), a bio-oil model compound, on silica-supported nickel phosphide at 0.1 MPa and 300 °C. Contact time experiments showed that 2-MTHF reacted to first form 1-pentanol and 2-pentanol, then n-pentanal, 2-pentanone, and 1- and 2-pentenes, and finally n-pentane. The observation is consistent with a reaction network in which adsorption of 2-MTHF is followed by rate-determining ring-opening steps on the more hindered side (path I) or the more open side (path II) to first produce adsorbed alcohols. The alcohols then transform into adsorbed aldehyde, ketone, and pentene species which can simply desorb or react to produce the final product n-butane (decarbonylation of adsorbed n-pentanal) or n-pentane (hydrogenation of adsorbed pentenes). Kinetic modeling of the proposed react...

The reactions of 2-methyltetrahydropyran (2-MTHP, C6H12O) on Ni2P/SiO2 provide insights on the interactions between a cyclic ether, an abundant component of biomass feedstock, with a transition-metal phosphide, an effective hydrotreating catalyst. At atmospheric pressure and a low contact time, conditions similar to those of a fast pyrolysis process, 70% of products formed from the reaction of 2-MTHP on Ni2P/SiO2 were deoxygenated products, 2-hexene and 2-pentenes, indicating a good oxygen removal capacity. Deprotonation, hydrogenolysis, dehydration, and decarbonylation were the main reaction routes. The reaction sequence started with the adsorption of 2-MTHP, followed by ring-opening steps on either the methyl substituted side (Path I) or the unsubstituted side (Path II) to produce adsorbed alkoxide species. In Path I, a primary alkoxide was oxidized at the α-carbon to produce an aldehyde, which subsequently underwent decarbonylation to 2-pentenes. The primary alkoxide could also be protonated to give a ...

2,5-Diformylfuran (DFF) was selectively synthesized from 5-hydroxymethylfurfural using a hydrotalcite-supported ruthenium catalyst (Ru/HT) by oxidation with molecular oxygen under mild reaction conditions. A combination of hydrotalcite, Amberlyst-15, and Ru/HT catalysts successfully afforded direct synthesis of DFF from hexoses such as fructose and glucose via isomerization, dehydration, and successive selective oxidation in one pot. Stepwise addition of catalyst improved DFF yield up to 49% from fructose and 25% from glucose, respectively.