Kinetic studies of hydrodeoxygenation of 2-methyltetrahydrofuran on a Ni2P/SiO2 catalyst at medium pressure

Ayako Iino, Ara Cho, Atsushi Takagaki, Ryuji Kikuchi, S. Ted Oyama

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

Bio-oil obtained by the pyrolysis of woody biomass contains many oxygenated organic compounds which degrade the product quality and make necessary upgrading for its use as a liquid fuel. Hydrodeoxygenation (HDO) is a catalytic hydrotreating process for the removal of the problematic oxygen functionalities and is promising for bio-oil upgrading. In this work, 2-methyltetrahydrofuran (2-MTHF) was chosen as a model oxygenated compound, and its HDO reaction mechanism was studied on a silica-supported nickel phosphide catalyst (Ni 2P/SiO2) at a medium pressure of 0.5 MPa. The temperature dependency of the catalyst activity was determined and it was found that at 350 C Ni2P/SiO2 showed 100% conversion and 85% selectivity to n-pentane, with higher oxygen removal activity and less CC bond cracking activity than commercial noble metal Ru/C and Pd/Al2O3 catalysts based on the same amount of active sites. A contact time study allowed the determination of a reaction sequence for 2-MTHF HDO on Ni 2P/SiO2 and it was found that CO bond cleavage of the furanic ring to generate either 2-pentanone or 1-pentanal was the rate-determining step. This was followed by hydrogen transfer steps to produce oxygen free compounds, n-pentane or n-butane. A partial pressure analysis of 2-MTHF and H2 was consistent with a rate equation derived using a Langmuir-Hinshelwood (L-H) mechanism. This suggested that adsorption of 2-MTHF and hydrogen occurred competitively and that these species reacted on the Ni2P/SiO2 surface. Although high partial pressure of H2 was favorable for hydrogenation, too much H2 competed with 2-MTHF adsorption, which caused lower conversion.

Original languageEnglish
Pages (from-to)17-27
Number of pages11
JournalJournal of Catalysis
Volume311
DOIs
Publication statusPublished - Mar 1 2014
Externally publishedYes

Fingerprint

upgrading
pentanes
catalysts
Partial pressure
Catalysts
Kinetics
Oxygen
partial pressure
kinetics
oxygen
oils
pentanone
Adsorption
liquid fuels
Hydrogen
phosphides
Time and motion study
adsorption
Liquid fuels
Butane

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Kinetic studies of hydrodeoxygenation of 2-methyltetrahydrofuran on a Ni2P/SiO2 catalyst at medium pressure. / Iino, Ayako; Cho, Ara; Takagaki, Atsushi; Kikuchi, Ryuji; Ted Oyama, S.

In: Journal of Catalysis, Vol. 311, 01.03.2014, p. 17-27.

Research output: Contribution to journalArticle

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abstract = "Bio-oil obtained by the pyrolysis of woody biomass contains many oxygenated organic compounds which degrade the product quality and make necessary upgrading for its use as a liquid fuel. Hydrodeoxygenation (HDO) is a catalytic hydrotreating process for the removal of the problematic oxygen functionalities and is promising for bio-oil upgrading. In this work, 2-methyltetrahydrofuran (2-MTHF) was chosen as a model oxygenated compound, and its HDO reaction mechanism was studied on a silica-supported nickel phosphide catalyst (Ni 2P/SiO2) at a medium pressure of 0.5 MPa. The temperature dependency of the catalyst activity was determined and it was found that at 350 C Ni2P/SiO2 showed 100{\%} conversion and 85{\%} selectivity to n-pentane, with higher oxygen removal activity and less CC bond cracking activity than commercial noble metal Ru/C and Pd/Al2O3 catalysts based on the same amount of active sites. A contact time study allowed the determination of a reaction sequence for 2-MTHF HDO on Ni 2P/SiO2 and it was found that CO bond cleavage of the furanic ring to generate either 2-pentanone or 1-pentanal was the rate-determining step. This was followed by hydrogen transfer steps to produce oxygen free compounds, n-pentane or n-butane. A partial pressure analysis of 2-MTHF and H2 was consistent with a rate equation derived using a Langmuir-Hinshelwood (L-H) mechanism. This suggested that adsorption of 2-MTHF and hydrogen occurred competitively and that these species reacted on the Ni2P/SiO2 surface. Although high partial pressure of H2 was favorable for hydrogenation, too much H2 competed with 2-MTHF adsorption, which caused lower conversion.",
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