Simultaneous Conversion of C₅ and C₆ Sugars into Methyl Levulinate with the Addition of 1,3,5-Trioxane

The simultaneous conversion of C₅ and C₆ mixed sugars into methyl levulinate (MLE) has emerged as a versatile strategy to eliminate costly separation steps. However, the traditional upgrading of C₅ sugars into MLE is very complex as it requires both acid-catalyzed and hydrogenation processes. This study concerns the development of a one-pot, hydrogenation-free conversion of C₅ sugars into MLE over different acid catalysts at near-critical methanol conditions with the help of 1,3,5-trioxane. For the conversion of C₅ sugars over zeolites without the addition of 1,3,5-trioxane, the MLE yield is quite low, owing to low hydrogenation activity. The addition of 1,3,5-trioxane significantly boosts the MLE yield by providing an alternative conversion pathway that does not include the hydrogenation step. A direct comparison of the catalytic performance of five different zeolites reveals that Hβ zeolite, which has high densities of both Lewis and Brønsted acid sites, affords the highest MLE yield. With the addition of 1,3,5-trioxane, the hydroxymethylation of furfural derivative and formaldehyde is a key step. Notably, the simultaneous conversion of C₅ and C₆ sugars catalyzed by Hβ zeolite can attain an MLE yield as high as 50.4 % when the reaction conditions are fully optimized. Moreover, the Hβ zeolite catalyst can be reused at least five times without significant change in performance.