Hydrodeoxygenation of model compounds on sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts; Role of sulfur-containing groups in reaction networks

Andrea Gutierrez, Eeva Maija Turpeinen, Tuula Riitta Viljava, Outi Krause*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

34 Citations (Scopus)

Abstract

Hydrodeoxygenation reactions were studied with model compounds on sulfided hydrotreating CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts with and without adding a sulfur-containing compound into the reaction mixtures. Clear differences were observed in the behaviour of the model compounds. The addition of H2S improved the reactivity of methyl heptanoate and guaiacol with the formation of methanethiol but decreased that of phenol. The presence of sulfur compounds in the gas phase affected also the selectivities reducing the hydrogenation activity of the catalysts and shifting the C7/C6 hydrocarbon distribution from methyl heptanoate. Thus sulfur groups present on the catalyst surface form the key components for the reactions. The reaction network of methyl heptanoate can be described with two types of reactions: reactions with only hydrogen addition and reactions with the contribution of the surface SH- groups. We propose that the ability of the nucleophilic SH- groups to interact with model compounds is a primary factor influencing the initial overall reactivity of the starting compounds. Furthermore, the increasing amount of SH- groups directed the distribution of hydrocarbons towards C6 instead of C7 hydrocarbons from methyl heptanoate by accelerating the decarbonylation/decarboxylation reaction and the 1-hexanethiol formation.

Original languageEnglish
Pages (from-to)125-134
Number of pages10
JournalCatalysis Today
Volume285
Early online dateFeb 2017
DOIs
Publication statusPublished - May 2017
MoE publication typeA1 Journal article-refereed

Keywords

  • Hydrodeoxygenation
  • Model compounds
  • Reaction networks
  • Role of sulfur
  • Sulfided catalysts
  • Sulfur-containing compounds

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