Inert competitive adsorption for the inhibition of oligomerization of alkenes during alcohol dehydration

Katherine P. Vinter, Paul J Dauenhauer

Research output: Contribution to journalArticle

Abstract

Inhibition of secondary chemistries in a linear series of reactions remains a catalytic challenge, particularly when targeting the selective synthesis of intermediate chemicals. In this work, the inhibition of cyclohexene oligomerization following cyclohexanol dehydration with H-BEA zeolite catalyst was achieved with the addition of 2,5-dimethylfuran (DMF). Suppression of undesired olefin oligomerization occurred with the competitive adsorption of the hydrolysis product of DMF, 2,5-hexanedione, thereby preventing cyclohexene adsorption onto Brønsted acid sites. Activation energies were measured for cyclohexanol dehydration both with and without DMF and were found to be the same within experimental error, suggesting that DMF does not alter the catalytic mechanism of cyclohexanol dehydration. Adsorption models were generated to investigate the general case of adding inert chemicals to inhibit product side reactions. Allowable differences in free energies of adsorption between reactant, product, and inert necessary to promote inhibition of product adsorption, while allowing for reactant surface saturation, were quantitatively determined. Reactions that might benefit from the addition of inert chemicals were proposed including linear alcohol dehydration and benzyl acylation and alkylation.

Original languageEnglish (US)
Pages (from-to)3901-3909
Number of pages9
JournalCatalysis Science and Technology
Volume8
Issue number15
DOIs
StatePublished - Jan 1 2018

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Oligomerization
Alkenes
Dehydration
Olefins
Cyclohexanols
Alcohols
Adsorption
Zeolites
Acylation
Alkylation
Free energy
Hydrolysis
Activation energy
Catalysts
Acids

Cite this

Inert competitive adsorption for the inhibition of oligomerization of alkenes during alcohol dehydration. / Vinter, Katherine P.; Dauenhauer, Paul J.

In: Catalysis Science and Technology, Vol. 8, No. 15, 01.01.2018, p. 3901-3909.

Research output: Contribution to journalArticle

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