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

Abstract

a 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 CO 2 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 C]C and C]O 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 biomassderived cellulose, hemicellulose and lignin to jet fuel and/or diesel additives.

Synthesis of Jet Fuel Range Cycloalkanes with Cyclopentanone and Furfural

“…In addition, gas products including C1–C5 light alkanes (mostly CH 4 , C 2 H 6 ,C 3 H 8 , trace butane, and pentane) were observed, and a total C1–C5 light alkane yield of 13% was obtained. These gas products were produced from an HZSM-5-catalyzed cracking reaction. , Based on complete conversion of the condensation and detected products, more than 90% of the carbon balance was obtained.…”

New synthetic approaches to biofuels from lignocellulosic biomass

“…Similar high yield of derived C 9 and C 10 alkanes (gasoline) were after hydrogenation and HDO obtained of the aldol condensation products over Pd/C and Pd-FeO x /SiO 2 catalysts, respectively. In an analogous study, Liu et al [23] reported the aldol condensation of various furfural species with cyclic ketones over a NaOH catalyst and obtained high yield (>90%) of the target condensation intermediates under mild conditions (30 °C; 40 min). Afterwards, amorphous zirconium phosphate combined with Pd/C catalyzed HDO of the condensation intermediates to cycloalkanes (gasoline) in good yield (76%) at optimized reaction conditions.…”

Chemical Transformations of Biomass-Derived C6-Furanic Platform Chemicals for Sustainable Energy Research, Materials Science, and Synthetic Building Blocks

“…The obtained adducts usually act as substrates for hydrogenolysis in the synthesis of biobased fuels. Simple ketones like acetone, methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone are used as enolate components . The main idea of this process is lengthening the carbon backbone of the molecule to obtain higher hydrocarbons.…”

“…Simple ketones like acetone, methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone are used as enolate components. 155 The main idea of this process is lengthening the carbon backbone of the molecule to obtain higher hydrocarbons. Various bases like CaO 156 or piperidine 157 can be applied.…”