Issue 3, 2024

Sulfurous zeosils for dehydra-decyclization of tetrahydrofuran to renewable butadiene

Abstract

Renewable 1,3-butadiene (1,3-BD, C4H6) was synthesized from the tandem decyclization and dehydration of biomass-derived tetrahydrofuran (THF) on weak Brønsted 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 Brønsted 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 °C). Notably, the S-MFI maintained a selectivity >90% for all evaluated process conditions. The computational results suggested that the nature of the Brønsted 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.

Graphical abstract: Sulfurous zeosils for dehydra-decyclization of tetrahydrofuran to renewable butadiene

Supplementary files

Article information

Article type
Paper
Submitted
17 avq 2023
Accepted
21 dek 2023
First published
22 dek 2023

Green Chem., 2024,26, 1430-1442

Sulfurous zeosils for dehydra-decyclization of tetrahydrofuran to renewable butadiene

R. C. Andeme Ela, J. Barroso, G. Kumar, K. Gawande, S. A. Brauer, M. Shetty, X. Li, W. Fan, B. Vlaisavljevich and P. J. Dauenhauer, Green Chem., 2024, 26, 1430 DOI: 10.1039/D3GC03090C

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