2,5-Bis(hydroxymethyl)furan (BHMF) is a bio-derived building block for polyester production, obtained via the hydrogenation of 5-hydroxymethylfurfural (HMF). First-principles thermodynamic equilibrium calculations indicate that this reaction is not thermodynamically limited under relevant conditions (e.g., 100 °C and high H2 partial pressure). In this work, crude HMF was employed as the feedstock for BHMF synthesis. Initially, acidic impurities and humins were removed from unrefined HMF through filtration using a packed bed of γ-alumina. A comprehensive study of the filtration process is presented, including filtration kinetics, breakthrough curve analysis, and mathematical modeling. The purified HMF was subsequently hydrogenated over a 10 wt% CuZrO2 catalyst, using ethanol as the reaction solvent. Batch reactions were first performed for collection of kinetic data to guide the transition to continuous flow operation. Kinetic data was collected in a fixed bed reactor at varying contact time, time on stream, temperature, and HMF concentration. This data was used to develop a kinetic model for HMF hydrogenation. Maximum BHMF production rates were achieved at 130 °C, accompanied by minor formation of byproducts from BHMF ring-opening reactions. The BHMF selectivity was 100 % at 100 °C although with lower reaction rates. Furthermore, catalyst stability tests revealed a loss of up to 50 % in catalytic activity within the first 24 h, likely due to the adsorption of HMF-derived oligomers that are not easily removed by filtration.
Chavarrio, Javier E., et al. "Catalytic hydrogenation of HMF to BHMF over copper catalysts." Applied Catalysis. B, Environmental, vol. 383, Oct. 2025. https://doi.org/10.1016/j.apcatb.2025.126101
Chavarrio, Javier E., Votava, Erick, Mavrikakis, Manos, & Huber, George W. (2025). Catalytic hydrogenation of HMF to BHMF over copper catalysts. Applied Catalysis. B, Environmental, 383. https://doi.org/10.1016/j.apcatb.2025.126101
Chavarrio, Javier E., Votava, Erick, Mavrikakis, Manos, et al., "Catalytic hydrogenation of HMF to BHMF over copper catalysts," Applied Catalysis. B, Environmental 383 (2025), https://doi.org/10.1016/j.apcatb.2025.126101
@article{osti_3000177,
author = {Chavarrio, Javier E. and Votava, Erick and Mavrikakis, Manos and Huber, George W.},
title = {Catalytic hydrogenation of HMF to BHMF over copper catalysts},
annote = {2,5-Bis(hydroxymethyl)furan (BHMF) is a bio-derived building block for polyester production, obtained via the hydrogenation of 5-hydroxymethylfurfural (HMF). First-principles thermodynamic equilibrium calculations indicate that this reaction is not thermodynamically limited under relevant conditions (e.g., 100 °C and high H2 partial pressure). In this work, crude HMF was employed as the feedstock for BHMF synthesis. Initially, acidic impurities and humins were removed from unrefined HMF through filtration using a packed bed of γ-alumina. A comprehensive study of the filtration process is presented, including filtration kinetics, breakthrough curve analysis, and mathematical modeling. The purified HMF was subsequently hydrogenated over a 10 wt% CuZrO2 catalyst, using ethanol as the reaction solvent. Batch reactions were first performed for collection of kinetic data to guide the transition to continuous flow operation. Kinetic data was collected in a fixed bed reactor at varying contact time, time on stream, temperature, and HMF concentration. This data was used to develop a kinetic model for HMF hydrogenation. Maximum BHMF production rates were achieved at 130 °C, accompanied by minor formation of byproducts from BHMF ring-opening reactions. The BHMF selectivity was 100 % at 100 °C although with lower reaction rates. Furthermore, catalyst stability tests revealed a loss of up to 50 % in catalytic activity within the first 24 h, likely due to the adsorption of HMF-derived oligomers that are not easily removed by filtration.},
doi = {10.1016/j.apcatb.2025.126101},
url = {https://www.osti.gov/biblio/3000177},
journal = {Applied Catalysis. B, Environmental},
issn = {ISSN 0926-3373},
volume = {383},
place = {United States},
publisher = {Elsevier},
year = {2025},
month = {10}}