Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

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

doi:10.1002/cctc.201701315

Title: 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

Abstract 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 Zn ^II 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.

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

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

Grant/Contract Number:: SC0001004

OSTI ID:: 1470089

Alternate ID(s):: OSTI ID: 1412033

Journal Information:: ChemCatChem, Vol. 9, Issue 23; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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