Catalytic production of tetrahydropyran (THP): a biomass-derived, economically competitive solvent with demonstrated use in plastic dissolution
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. Further, 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.
- Research Organization:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Organization:
- USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)
- Grant/Contract Number:
- AC36-08GO28308; EE0009285
- OSTI ID:
- 2418779
- Journal Information:
- Green Chemistry, Journal Name: Green Chemistry Journal Issue: 23 Vol. 24; ISSN GRCHFJ; ISSN 1463-9262
- Publisher:
- Royal Society of ChemistryCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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