Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

Abstract

• The hydrogenation of HMF to furan diols was studied and optimized in flow reactor. • The commercial Ru/C was an efficient catalyst for the BHMF and BHMTHF synthesis. • The highest BHMF and BHMTHF yields were ascertained only tuning the contact time. • The catalyst was stable up to 6 h and easily reactivable through acetone washing. • Internal mass transfer limitations occurred and affected the overall reaction rate. 5-hydroxymethylfurfural (HMF), accessible from various feedstocks, represents an important renewable platform-chemical, precursor for valuable biofuels and bio-based chemicals. In this work, the continuous hydrogenation of an aqueous solution of HMF to give strategic monomers, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) was investigated in a continuous flow reactor adopting a commercial Ru/C (5 wt%) as catalyst. The influence of the main process variables on products yield and selectivity was studied and optimized. The highest BHMF and BHMTHF yields of 87.9 and 93.7 mol%, respectively, were achieved by tuning the catalyst contact time, keeping all other variables constant (temperature, pressure, hydrogen flow rate, initial HMF concentration). Intraparticle diffusion limitation for hydrogen and HMF was shown to occur at some of the tested conditions by performing the HMF hydrogenation with different catalyst particle sizes, confirmed by calculations. Constant catalyst activity was observed up to 6 h time-on-stream and then gradually reduced. Fresh and spent catalyst characterization showed no significant sintering and negligible leaching of ruthenium during time-on-stream. A decrease of the specific surface area was observed, mainly due to humin deposition which is likely the reason for catalyst deactivation. Catalyst performance could be restored to initial values by a thorough washing of the catalyst.