Abstract
Aluminum phosphates (APO-5s) were synthesized and evaluated as heterogeneous catalysts for the valorization of furfural to furfuryl acetals (FAs) and furfuryl alcohol ethers (FAEs). Weakly acidic APO-5 (Al/P = 1) exhibited excellent catalytic performance with 96 % FA yield in ethylene glycol, and analysis of the acetalization reaction supported that adsorption and acidic catalyst sites co-catalyzed the reaction. In addition, the catalyst was stable and reusable though with some deactivation after five recycles. Oppositely, more acidic APO-5 (Al/P = 1.5) catalyzed the one-pot synthesis of FAE with 55 % yield in 2-propanol with unchanged performance in three successive reactions after intermediate calcination. The reaction pathway for the direct hydrogenolysis of acetal into ether by catalytic transfer hydrogenation and etherification was promoted by the co-solvent 1,4-dioxane, possibly by hydrogen bonding. The study demonstrates a simple approach to design APO catalyst systems allowing very efficient and highly selective valorization of furfural to fuel bio-additives.
Highlights
In the last century, the World’s energy demand has predominantly been covered by nonrenewable carbon-based fossil fuels, which are gradually becoming exhausted
Acidic APO-5 (Al/P = 1) exhibited excellent catalytic performance with 96 % furfuryl acetals (FAs) yield in ethylene glycol, and analysis of the acetalization reaction supported that adsorption and acidic catalyst sites co-catalyzed the reaction
Bio-additives derived from FF by acetalization and reductive etherification have attracted attention due to their potential as blending high-octane gasoline components [6,7,8,9,10]
Summary
The World’s energy demand has predominantly been covered by nonrenewable carbon-based fossil fuels, which are gradually becoming exhausted. This has led to severe environmental problems such as global warming, and uncertainty about future supply safety. Zr-Montmorillonite catalyzed the conversion of FF in different C2-C6 diols to the corresponding cyclic FAs with yields above 75 %, and the products with ethylene glycol (EG) and 1,5-pentanediol were shown to exhibit high miscible in commercial diesel obtaining improved density, cloud point and flash point [15]. Riisager reusability of the spent catalysts was examined by catalytic as well as characterization studies
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