Furanic jet fuels – Water-free aldol condensation of furfural and cyclopentanone

A method for the water-free, large-scale synthesis of bio-jet fuel precursors, distinct from traditional fossil-based sources, is introduced. This approach involves the aldol condensation of furfural with cyclopentanone, producing C₁₀-C₁₅ fuel precursors eligible for further hydrodeoxygenation to high-performance diesel and jet fuel hydrocarbons. In the context of process integration, aldol condensation reactions were conducted under water-free conditions, utilizing excess furfural as the solvent. Evaluation of various commercial catalysts confirmed the feasibility of running in excess furfural. Both basic and acidic catalysts demonstrated significant activity, with CaO and amorphous silica-alumina achieving ≥80 mol% conversion of cyclopentanone and yielding ≥80 mol% selectivity towards the desired fuel components within 5 h of reaction. However, an overlooked aspect is the notable formation of undesired heavy side products. Observations indicated that the high furfural concentration, combined with the use of strong acidic catalysts, were the primary cause of heavy side product formation. The strong base catalyst, CaO, significantly reduced the formation of these oligomers, but did not appear to stop it completely. Interestingly, water content did not appear to play a major role in byproduct selectivity. To further suppress the formation of oligomers, the use of process-owned intermediates as solvents is proposed.