Zeolite catalytic synthesis of high‐performance jet‐fuel‐range spiro‐fuel by one‐pot Mannich–Diels–Alder reaction

A one‐pot Mannich–Diels–Alder reaction was developed for synthesis of high‐performance jet‐fuel‐range spirocycloalkane with an overall yield of 71.6% from biomass and petroleum derived cyclopentanone, formaldehyde, and cyclopentadiene. HZSM‐5 zeolite with Si/Al molar ratio of 130 exhibits much higher catalytic activity, along with good recycling ability. Over it, a high selectivity (81.6%) and yield (80.9%) of target adduct is achieved with almost complete conversion of cyclopentanone, attributed to the synergy effect of appropriate ratio of Lewis to Brønsted acid sites and mass transfer effect of porous zeolite. More importantly, after hydrodeoxygenation, the resultant spirocycloalkane has much higher density and volumetric neat heat of combustion (0.952 g·ml−1, 40.18 MJ L−1) than the wildly used JP‐10 fuel (0.936 g ml−1, 39.41 MJ L−1). This work provides a promising route to produce high‐performance jet‐fuel‐range hydrocarbons through co‐conversion of biomass and petroleum derivatives.