Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

Vasiliadou, Efterpi S.; Gould, Nicholas S.; Lobo, Raul F.

doi:10.1002/cctc.201701315

Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

Journal Article · Mon Nov 13 00:00:00 EST 2017 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201701315· OSTI ID:1470089

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Delaware State Univ., Dover, DE (United States). Catalysis Center for Energy Innovation
Delaware State Univ., Dover, DE (United States). Catalysis Center for Energy Innovation, and Dept. of Chemical and Biomolecular Engineering

Prins condensation of formaldehyde with propylene to form 3-buten-1-ol is investigated using microporous solid acid catalysts. Zn/H-beta shows high conversion but leads to a broad product distribution composed primarily of pyrans. Mechanistic studies revealed that 3-buten-1-ol reacts via Prins cyclization or dehydrate to 1,3-butadiene that further reacts with formaldehyde via a hetero-Diels–Alder reaction. These secondary reactions are suppressed over ZSM-5 catalysts: 3-buten-1-ol is the predominant product over H-ZSM-5 zeolite under all conditions investigated. 3-Buten-1-ol selectivity of up to 75 % is achieved. In a second step 3-buten-1-ol dehydrates at temperatures as low as 423 K, forming 1,3-butadiene. Although Brønsted acid sites are the primary catalytic sites, ion exchange of ZnII increases the overall rate and 3-buten-1-ol selectivity. H-ZSM-5 showed significant differences in reactivity and selectivity as a function of the Si/Al ratio; optimal catalytic properties were observed within Si/Al=40–140.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001004

OSTI ID:: 1470089

Alternate ID(s):: OSTI ID: 1412033

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 23 Vol. 9; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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