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

Phuong P. Bui, S. Ted Oyama, Atsushi Takagaki, Brad P. Carrow, Kyoko Nozaki

Research output: Contribution to journalArticle

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Abstract

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.

Original languageEnglish
Pages (from-to)4549-4558
Number of pages10
JournalACS Catalysis
Volume6
Issue number7
DOIs
Publication statusPublished - Jul 1 2016

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Nickel
Silicon Dioxide
Alcohols
Silica
Alkenes
Adsorption
Hydrogenolysis
Deprotonation
Cyclic Ethers
Aldehydes
Ketones
Dehydration
Feedstocks
Atmospheric pressure
Transition metals
Ethers
Biomass
Pyrolysis
Catalysts
Carbon

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran. / Bui, Phuong P.; Oyama, S. Ted; Takagaki, Atsushi; Carrow, Brad P.; Nozaki, Kyoko.

In: ACS Catalysis, Vol. 6, No. 7, 01.07.2016, p. 4549-4558.

Research output: Contribution to journalArticle

Bui, Phuong P. ; Oyama, S. Ted ; Takagaki, Atsushi ; Carrow, Brad P. ; Nozaki, Kyoko. / Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran. In: ACS Catalysis. 2016 ; Vol. 6, No. 7. pp. 4549-4558.
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