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Title: Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation

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 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Delaware State Univ., Dover, DE (United States). Catalysis Center for Energy Innovation
  2. Delaware State Univ., Dover, DE (United States). Catalysis Center for Energy Innovation, and Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470089
Alternate Identifier(s):
OSTI ID: 1412033
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 9; Journal 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; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); biofuels (including algae and biomass); bio-inspired; hydrogen and fuel cells; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Vasiliadou, Efterpi S., Gould, Nicholas S., and Lobo, Raul F. Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation. United States: N. p., 2017. Web. doi:10.1002/cctc.201701315.
Vasiliadou, Efterpi S., Gould, Nicholas S., & Lobo, Raul F. Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation. United States. doi:10.1002/cctc.201701315.
Vasiliadou, Efterpi S., Gould, Nicholas S., and Lobo, Raul F. Mon . "Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation". United States. doi:10.1002/cctc.201701315. https://www.osti.gov/servlets/purl/1470089.
@article{osti_1470089,
title = {Zeolite-Catalyzed Formaldehyde-Propylene Prins Condensation},
author = {Vasiliadou, Efterpi S. and Gould, Nicholas S. and Lobo, Raul F.},
abstractNote = {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.},
doi = {10.1002/cctc.201701315},
journal = {ChemCatChem},
number = 23,
volume = 9,
place = {United States},
year = {2017},
month = {11}
}

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