Lewis acid zeolites for tandem Diels-Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene

Chun Chih Chang, Hong Je Cho, Jingye Yu, Ray J. Gorte, Jason Gulbinski, Paul J Dauenhauer, Wei Fan

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

Lewis acid zeolites including Zr-, Sn-, and Ti-BEA were examined for tandem [4 + 2] Diels-Alder cycloaddition of 2,5-dimethylfuran (DMF) and ethylene to oxanorbornene with subsequent dehydration to produce biorenewable p-xylene. Zr-BEA (Si/Zr = 168) exhibited superior performance with improved recalcitrance to deactivation, which was attributed to its low activity for the hydrolysis of DMF to 2,5-hexanedione and subsequent condensation. Zr-BEA also achieved the highest selectivity to p-xylene of 90% at 99% conversion of DMF. For low catalyst loading within a three-phase reactor, the reaction rate to form p-xylene was linearly proportional to the number of Lewis acid sites, while high catalyst loading exhibited zero order dependence on Lewis acid sites. A maximum achievable reaction rate was shown to be consistent with a transition in rate-limiting reactions from dehydration of oxanorbornene, the Diels-Alder product, to the Diels-Alder cycloaddition of DMF and ethylene.

Original languageEnglish (US)
Pages (from-to)1368-1376
Number of pages9
JournalGreen Chemistry
Volume18
Issue number5
DOIs
StatePublished - Jan 1 2016

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Zeolites
Lewis Acids
Cycloaddition
xylene
Xylene
Dehydration
dehydration
ethylene
Ethylene
Biomass
reaction rate
Reaction rates
Acids
acid
biomass
catalyst
Catalysts
condensation
Condensation
hydrolysis

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Lewis acid zeolites for tandem Diels-Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene. / Chang, Chun Chih; Je Cho, Hong; Yu, Jingye; Gorte, Ray J.; Gulbinski, Jason; Dauenhauer, Paul J; Fan, Wei.

In: Green Chemistry, Vol. 18, No. 5, 01.01.2016, p. 1368-1376.

Research output: Contribution to journalArticle

Chang, Chun Chih ; Je Cho, Hong ; Yu, Jingye ; Gorte, Ray J. ; Gulbinski, Jason ; Dauenhauer, Paul J ; Fan, Wei. / Lewis acid zeolites for tandem Diels-Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene. In: Green Chemistry. 2016 ; Vol. 18, No. 5. pp. 1368-1376.
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