Production of renewable long-chained cycloalkanes from biomass-derived furfurals and cyclic ketones

Abstract

Developing renewable long-chain cycloalkanes from lignocellulosic biomass is of significance because it offers huge resource storage, wide applications in aviation/diesel fuels and mitigation of CO2 emissions. In this paper, cycloalkanes with carbon chain lengths of 13-18 were produced from biomass-derived furfural species (furfural and 5-hydroxymethylfurfural) and cyclic ketones (cyclopentanone and cyclohexanone) via aldol condensation, followed by hydrogenation to saturate the CC and CO bonds, and hydrodeoxygenation to remove oxygen atoms. The aldol condensation of the furfural species with cyclic ketones was catalyzed by NaOH and the target condensation intermediates were obtained in yields of more than 90% at room temperature (30 °C) with a short reaction time (40 min). By using amorphous zirconium phosphate combined with Pd/C as the catalyst, liquid cycloalkanes were produced at the optimal conditions with a yield of 76%. When the combined solid catalyst was reused, the target products reduced after the second run but the initial yield could be largely recovered by recalcination of the spent zirconium phosphate. Considering that cyclopentanone and cyclohexanone can be easily produced from furfural (originating from hemicellulose) and phenol (originating from lignin), respectively, this condensation has the potential to achieve the integrated conversion of biomass-derived cellulose, hemicellulose and lignin to jet fuel and/or diesel additives.