(111f) Aqueous-Phase Fructose Dehydration Using Zeolite Catalysts

Reactions producing of 5-Hydroxymethylfurfural (HMF) and levulinic acid from sugar molecules represent important steps in the conversion of biomass to useful chemical products.¹  The dehydration of glucose and fructose is catalyzed by acids, and previous researchers have used a variety of solvent and catalyst combinations to efficiently transform fructose and glucose into HMF.^2,3 Zeolite catalysts offer certain advantages over other acidic catalysts in sugar dehydration, including simple catalyst separation relative to homogeneous acid catalysts, stability in high-temperature aqueous systems, stability to thermal regeneration, and potential shape selectivity.⁴ Indeed, zeolite catalysts have been investigated for glucose and fructose dehydration reactions a number of times.^4-8 Although zeolite-water systems tend to give low yields of HMF without the addition of an extracting phase, production of levulinic acid over zeolites may be a more promising venture.  In this work, we offer some insight into why zeolites give low selectivity to HMF using an acidic BEA zeolite in aqueous solvent. In particular, we investigated sugar dehydration in aqueous suspensions of zeolites with HPLC, as well as MS, UV-Vis, and ATR/FTIR spectroscopies.  We show that side reactions of fructose, sequential reactions of HMF, and preferential adsorption of HMF on the zeolites play important roles in determining product selectivities.  By tuning reaction conditions and catalyst characteristics, we demonstrate that zeolites are promising candidates for the production of levulinic acid directly from C₆ sugars.

References

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