Catalytic dehydration of glucose to 5-hydroxymethylfurfural with a bifunctional metal-organic framework

Glucose conversion to 5-hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Brönsted acid. In this work, a sulfonic acid functionalized metal-organic framework MIL-101(Cr)-SO 3 H containing both Lewis acid and Brönsted acid sites, was examined as the catalyst for γ-valerolactone-mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second-order kinetics with an apparent activation energy of 100.9 kJ mol −1 . Continuous reaction in the fixed-bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass-derived carbohydrate to HMF with a bifunctional metal-organic framework. © 2016 American Institute of Chemical Engineers AIChE J , 62: 4403–4417, 2016