Hydroxymethylation of Furfural to HMF with Aqueous Formaldehyde over Zeolite Beta Catalyst

Hydroxymethylation of 2-furaldehyde (furfural) toward 5-hydroxymethyl-2-furaldehyde (HMF) was examined in this work among various zeolites with an aqueous formaldehyde as a reagent in a batch and a flow reactor system. It was found that the zeolite beta gave high activity and good reusability with calcination treatment before each run for the target reaction in the batch system. The unique stability of the HMF yield in the liquid-flow system was also observed only in the case of zeolite beta. The effect of the SiO2/Al2O3 ratio in the zeolite beta suggested that hydrophobicity would be an important factor in faster hydroxymethylation with an aqueous formaldehyde reagent. The highest turnover frequency (TOF) for HMF production was found to be 2.4 h(-1) in the case of zeolite beta with SiO2/Al2O3 = 440 in the batch reactor system. An approximately 30% yield for HMF was achieved under optimum conditions for zeolite beta catalysts.