Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). We developed magnetically recoverable catalysts containing 2 nm Ru nanoparticles (NPs) in mesoporous Fe3O4-SiO2 with the Ru nominal loading of 1, 3, and 5 wt.%. XPS showed that the surface of Ru NPs contains an equimolar ratio of Ru0 and Ru4+ species. All three catalysts exhibited excellent activities in cellulose hydrogenolysis to EG and PG, independent of the Ru loading, revealing that for all three compositions the Ru NP surface is accessible to reagents. The EG and PG selectivities were shown to depend on temperature, reaction time, and Ru and Ca(OH)2 loadings. The highest selectivities to EG (19%) and PG (20%) were obtained for 50 min at 255 °C, 60 bar hydrogen pressure, 0.1167 mmol of Ru per 1 g of cellulose and 0.195 mole of Ca(OH)2 per 1 mole of cellulose. In these conditions the cellulose conversion was 100%. It is worth noting that the activities and selectivities of the Ru-Fe3O4-SiO2 catalysts described in this work significantly exceed those for the commercial Ru/C catalyst and Ru/MN-270 reported by some of us previously (table 1). To study the catalyst stability, 5 % Ru-Fe3O4-SiO2 was separated from the reaction medium using a neodymium magnet and then added to a fresh portion of cellulose, distilled water, and Ca(OH)2. The data presented in Table 2 indicate that the EG and PG selectivities at 100% conversion (~ 19 and 20%, respectively) and the activity do not change, revealing that the catalyst is stable in the cellulose hydrogenolysis.

Magnetically recoverable catalysts for cellulose conversion into ethylene- and propylene glycols

253rd National Meeting (2017)

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