Issue 23, 2022

Catalytic production of tetrahydropyran (THP): a biomass-derived, economically competitive solvent with demonstrated use in plastic dissolution

Abstract

Tetrahydropyran (THP) is a five-carbon heterocyclic ether that is non-carcinogenic, non-peroxide forming, biodegradable, and economically competitive with tetrahydrofuran (THF) as a solvent. In this work, THP has been synthesized from renewable biomass at >99.8% selectivity and 98% yield via hydrogenation of furfural-derived 3,4-dihydropyran (DHP) over Ni/SiO2 in a continuous flow reactor at 150–200 °C. The apparent activation energy of THP formation is 31 kJ mol−1, and the reaction orders with respect to the partial pressures of H2, DHP, and THP are: 2, 1, and −0.3. The kinetic data has been fitted to a Hougen–Watson model where the rate limiting step is the hydrogenation of adsorbed DHP. Ni/SiO2 is shown to have a low deactivation rate constant of 0.012 h−1 over 100 h time on stream and can be regenerated in situ. As a performance advantage, THP is shown to be resistant to ring opening polymerization under strongly acidic conditions that THF is not, revealing it to be a superior solvent. The minimum selling price of THP is competitive with the market price of THF ($900–1400 per ton) at a DHP feedstock cost of $1000 per ton. Conductor-like Screening Model for Real Solvents (COSMO-RS) and molecular dynamics (MD) simulations with 1008 solvents and 8 common plastics have demonstrated that THP can serve as an alternative solvent to THF, 2-methyltetrahydrofuran (MeTHF), and cyclopentyl methyl ether (CPME) for plastic dissolution, especially low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS) and polyvinyl chloride (PVC). This work establishes THP as a green solvent with excellent thermal, chemical and peroxidative stability that can be used for numerous applications, including waste plastic recycling.

Graphical abstract: Catalytic production of tetrahydropyran (THP): a biomass-derived, economically competitive solvent with demonstrated use in plastic dissolution

Supplementary files

Article information

Article type
Paper
Submitted
14 Sept. 2022
Accepted
31 Okt. 2022
First published
08 Nov. 2022

Green Chem., 2022,24, 9101-9113

Author version available

Catalytic production of tetrahydropyran (THP): a biomass-derived, economically competitive solvent with demonstrated use in plastic dissolution

R. G. Dastidar, M. S. Kim, P. Zhou, Z. Luo, C. Shi, K. J. Barnett, D. J. McClelland, E. Y.-X. Chen, R. C. Van Lehn and G. W. Huber, Green Chem., 2022, 24, 9101 DOI: 10.1039/D2GC03475A

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