TY - JOUR
T1 - Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran
AU - Bui, Phuong P.
AU - Oyama, S. Ted
AU - Takagaki, Atsushi
AU - Carrow, Brad P.
AU - Nozaki, Kyoko
PY - 2016/7/1
Y1 - 2016/7/1
N2 - 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.
AB - 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.
KW - 2-methyltetrahydropyran
KW - contact time studies
KW - hydrodeoxygenation
KW - nickel phosphide
KW - reaction network
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U2 - 10.1021/acscatal.6b01033
DO - 10.1021/acscatal.6b01033
M3 - Article
AN - SCOPUS:84977118030
VL - 6
SP - 4549
EP - 4558
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 7
ER -