Journal article
Sulfurous zeosils for dehydra-decyclization of tetrahydrofuran to renewable butadiene
Green chemistry : an international journal and green chemistry resource : GC, Vol.26(3), pp.1430-1442
02/05/2024
DOI: 10.1039/d3gc03090c
Abstract
Renewable 1,3-butadiene (1,3-BD, C4H6) was synthesized from the tandem decyclization and dehydration of biomass-derived tetrahydrofuran (THF) on weak Br & oslash;nsted acid zeolite catalysts. 1,3-BD is a highly solicited monomer for the synthesis of rubbers and elastomers. Selective conversion of THF to 1,3-BD was recently measured on phosphorus-modified siliceous zeolites (P-zeosils) at both high and low space velocities, albeit with low per-site catalytic activity. In this work, we combined kinetic analyses and QM/MM calculations to evaluate the interaction of THF with the various Br & oslash;nsted acid sites (BAS) of Boric (B), Phosphoric (P), and Sulfuric (S) acid modified silicalite-1 catalysts toward a dehydra-decyclization pathway to form 1,3-BD. Detailed kinetic measurements revealed that all three catalysts exhibited high selectivity to 1,3-BD ca. 64-96% in the order of S-MFI > P-MFI > B-MFI at a given temperature (360 degrees C). Notably, the S-MFI maintained a selectivity >90% for all evaluated process conditions. The computational results suggested that the nature of the Br & oslash;nsted acid sites and the adsorption energetics (relative THF-acid site interaction energies) are distinct in each catalyst. Additionally, the protonation of THF can be improved with the addition of a water molecule acting as a proton shuttle, particularly in S-MFI. Overall, S-containing zeosils exhibited the ability to control reaction pathways and product distribution in dehydra-decyclization chemistry optimization within microporous zeolites, providing another alternative weak-acid catalytic material.
Details
- Title: Subtitle
- Sulfurous zeosils for dehydra-decyclization of tetrahydrofuran to renewable butadiene
- Creators
- Raisa Carmen Andeme Ela - University of MinnesotaJorge Barroso - University of South DakotaGaurav Kumar - University of MinnesotaKaivalya Gawande - University of Massachusetts AmherstSophie A. Brauer - University of MinnesotaManish Shetty - Texas A&M UniversityXinyu Li - University of MinnesotaWei Fan - University of Massachusetts AmherstBess Vlaisavljevich - University of South DakotaPaul J. Dauenhauer - University of Minnesota
- Resource Type
- Journal article
- Publication Details
- Green chemistry : an international journal and green chemistry resource : GC, Vol.26(3), pp.1430-1442
- Publisher
- Royal Soc Chemistry
- DOI
- 10.1039/d3gc03090c
- ISSN
- 1463-9262
- eISSN
- 1463-9270
- Number of pages
- 13
- Grant note
- OAC-1626516 / NSF; National Science Foundation (NSF) NSF MRSEC; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) CHE-1901635 / National Science Foundation (NSF), Center for Sustainable Polymers; National Science Foundation (NSF) Farm families of Minnesota Mistletoe Research Fellowship (Momental Foundation)
- Language
- English
- Date published
- 02/05/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984618506402771
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