Mechanistic investigation of glycerol hydrogenolysis

    Research output: Research - peer-reviewArticle

    Abstract

    Mechanistic pathways for catalytic hydrogenolysis of glycerol to propylene glycol, ethylene glycol, and lactic acid over supported metal catalyst are proposed and substantiated by conversion studies, isotopic labeling, reaction studies of proposed intermediates, and computational molecular modeling. Contrary to the naïve expectation of hydrogenolysis as the simple replacement of -OH by -H, the first step of reaction is the dehydrogenation of glycerol to glyceraldehyde. This aldotriose then reacts further via one of two paths: (1) retroaldol cleavage to the enediol of hydroxyacetaldehyde, which, with or without tautomerization, is reduced to ethylene glycol, or (2) keto-enol tautomerization to the enediol, which then dehydrates and tautomerizes to pyruvaldehyde. Subsequent hydrogenation or water addition and rearrangement leads to propylene glycol or lactic acid, respectively. The presence of base promotes both pathways but favors enolization and dehydration of the glyceraldehyde, which leads to propylene glycol and lactate formation.

    LanguageEnglish (US)
    Pages735-742
    Number of pages8
    JournalRevue Roumaine de Chimie
    Volume60
    Issue number7-8
    StatePublished - Jul 1 2015

    Profile

    Propylene Glycol
    Hydrogenolysis
    Glycerol
    Lactic Acid
    Glyceraldehyde
    Ethylene Glycol
    Pyruvaldehyde
    Molecular modeling
    Dehydrogenation
    Dehydration
    Labeling
    Hydrogenation
    Metals
    Catalysts
    Water
    glycolaldehyde

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Mechanistic investigation of glycerol hydrogenolysis. / Kovacs, Dalila G.; Jackson, James E.; Miller, Dennis J.

    In: Revue Roumaine de Chimie, Vol. 60, No. 7-8, 01.07.2015, p. 735-742.

    Research output: Research - peer-reviewArticle

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