Batch and Continuous-Flow Preparation of Biomass-Derived Furfural Acetals over a TiO Nanoparticle-Exfoliated Montmorillonite Composite Catalyst.

Furfural acetals with high octane value, high calorific value and high oxidation resistance are considered promising biofuels or fuel precursors with huge potential demand. However, there are few studies on efficient scalable catalyst systems, including continuous-flow catalyst systems, for their preparation. In this work, TiO nanoparticles supported on exfoliated montmorillonite, with strong Lewis acid sites and abundant accessible Brønsted acid sites, is used to catalyze the acetalization reactions of biomass-derived furfural and alcohols. Low dosage of the catalyst made the reaction reach equilibrium in a very short time (TOF=690-1305 min ) at room temperature with the acetal as the only product. In continuous-flow reactions, the catalyst showed a stable product output with conversion close to that for the batch reaction with a short catalyst-reactant contact time of 150 s. Contrast experiments revealed that both Lewis and Brønsted acid sites on the catalyst were indispensable for maximizing the catalytic performance, and simultaneously activating both furfural and alcohol on the adjacent Lewis and Brønsted acid sites was proposed to be responsible for the high catalytic performance.