Bifunctional Catalysts With Improved Hydrothermal Stability for the Hydrolytic Hydrogenation of Cellulose

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The production of glucose and/or sorbitol from the hydrolytic hydrogenation of cellulose , offers the potential to be used as a renewable feedstock in a biorefinery for the production of fuels and value added chemicals. Here we report the results of the study of the effect of cellulose crystallinity , cellulose/catalyst ratio , reaction temperature and reaction time on the catalytic performance for the conversion of cellulose into sorbitol.  We studied a series of single , binary and ternary metal oxide supports with a range of surface acidity and phosphated niobic acid.  Ru was supported using evaporative deposition on the supports.  The catalytic materials were characterized using nitrogen adsorption , X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR).  Ruthenium supported on NbOPO4 displayed the best catalytic performance with hexitols yields of about 45% at 100% cellulose conversion.  All materials suffer a decrease in their surface areas after treatment in hot water.  However , treating Ru/NbOPO4 in water at 210°C and 230 °C and 35 bar H2 for 24 h or 48 h caused a slight decrease in cellulose conversion , but a significant increase in hexitol and hydrogenolysis products yield.  Ru/Nb2O5 (HY 340) and the equivalent amount of phosphoric acid present in Ru/NbOPO4 give essentially the same conversion as Ru/NbOPO4 but a lower yield to sugar alcohols and a higher yield to hydrogenolysis products.  Decreasing cellulose crystallinity and cellulose/catalyst ratio , increases the cellulose conversion and hexitols yield for Ru/NbOPO4.


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