The conversion of lignocellulosic biomass into valuable chemicals and fuels has received considerable attention owing to the issues related to global warming. 5-Hydroxymethylfurfural (HMF) is a versatile lignocellulose-derived platform chemical used in a wide range of high-value bioproducts. However, the HMF production is completed with polymerization by which humins are inevitably formed as a by-product. Recently, the potential of humins for various applications has been explored. In this study, a series of ZSM-5 zeolite catalysts modified with iron (Fe) and tungsten (W) were used to selectively control glucose dehydration to HMF and humins. The zeolite catalysts possessing tunable bifunctional Brønsted–Lewis acid characteristics were prepared through pretreatment using a diluted nitric acid solution, followed by metal impregnation. The impregnation of Fe into ZSM-5 induced the formation of highly dispersed extraframework isolated Fe3+ ions and Fe2O3 species, which increased the content of Lewis acid sites. The W species added to ZSM-5 existed in the form of Si–OH–W linkages and polytungstates with moderate-to-strong Brønsted acidity. The selective synthesis of HMF was efficiently performed over the Fe-modified ZSM-5 catalysts. Furthermore, the W-modified catalysts exhibited potential application as novel catalysts for the selective production of humins. The controlled selectivity to each product depended on the acidic properties and Lewis/Brønsted acidity ratio of the catalysts as well as the transition metal-dependent characteristics of the Brønsted and Lewis acid sites.
Read full abstract