Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran

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• 作者：Phuong P. Bui ; S. Ted Oyama ; Atsushi Takagaki ; Brad P. Carrow ; Kyoko Nozaki
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：July 1, 2016
• 年：2016
• 卷：6
• 期：7
• 页码：4549-4558
• 全文大小：570K
• 年卷期：0
• ISSN：2155-5435

文摘

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 primary alcohol which could desorb or form the final product 2-hexene. In Path II, a secondary alkoxide was oxidized to produce a ketone or was protonated to a secondary alcohol that was dehydrated to give 2-hexene. The active sites for the adsorption of 2-MTHP and O-intermediates were likely to be Ni sites.