Mechanism and kinetics of 1-dodecanol etherification over tungstated zirconia

Rorrer, Julie; He, Ying; Toste, F. Dean; Bell, Alexis T.

doi:10.1016/j.jcat.2017.08.001

Mechanism and kinetics of 1-dodecanol etherification over tungstated zirconia

Journal Article · Wed Aug 23 00:00:00 EDT 2017 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2017.08.001· OSTI ID:1571085

Rorrer, Julie ^[1]; He, Ying ^[2]; Toste, F. Dean ^[2]; Bell, Alexis T. ^[1]

Univ. of California, Berkeley, CA (United States). Energy Biosciences Inst., and Dept. of Chemical and Biomolecular Engineering
Univ. of California, Berkeley, CA (United States). Energy Biosciences Inst., and Dept. of Chemistry

Growing interest in finding renewable alternatives to conventional fossil fuels and petroleum-derived specialty chemicals has motivated the investigation of biomass-derived alcohols to make ethers as diesel additives or lubricants. To optimize the direct etherification of long chain alcohols in the liquid phase, it is necessary to develop an understanding of the kinetics and mechanism of etherification and dehydration reactions. In this study, tungstated zirconia was identified as a selective solid-acid catalyst for the liquid-phase etherification of 1-dodecanol. Investigations of the mechanism and kinetics of this reaction suggest that cooperation between Brønsted- and Lewis-acid sites on tungstated zirconia enhances the selectivity to ether by increasing the surface concentration of adsorbed alcohol, thereby promoting bi-molecular ether formation relative to unimolecular alcohol dehydration. The suggested rate limiting step for etherification is the formation of a C–O bond between two adsorbed alcohol molecules, and the suggested rate-limiting step for dehydration is the cleavage of the C–H bond of the β-carbon atom in an adsorbed alcohol. Measurements of the kinetic isotope effects for etherification and dehydration support the proposed mechanism. Finally, a microkinetic model based on the proposed mechanism for dodecanol etherification and dehydration over tungstated zirconia accurately describes the observed effects of alcohol concentration and product inhibition.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1571085

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 354; ISSN 0021-9517

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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