A catalytic system capable of reaching high performance in the hydrogenolysis of cellulose at low reaction temperature and short reaction times has been developed. Therefore, supported noble metal catalysts based on Pt, Pd and Ru have been combined with dilute mineral acids. A broad variable set in terms of type of noble metal, type of acid, acid concentration and reaction time could be evaluated based on chemical interpretation and supported by a Design of Experiment (DoE) approach. The variables significantly influenced conversion of cellulose, product range and selectivity towards sugar alcohol formation. Thus, at 160 • C, above 60% yield in sugars and sugar alcohols with 84% selectivity at a cellulose conversion of 72% could be reached. Besides, glycerol, propylene glycol, ethylene glycol and methanol were formed as additional valuable by-products leading to an overall carbon utilization above 89%. Furthermore, the concept was successfully transferred to real feedstocks in the form of spruce reaching close to 60% conversion in only one hour reaction time.
Cellulose and even spruce can be converted efficiently into valuable platform chemicals via combined hydrolysis and hydrogenation in the aqueous phase. Thereby, heteropoly acids together with supported ruthenium catalysts show not only high activity but also remarkable selectivity to sugar alcohols reaching up to 81% yield of C(4) to C(6) sugar alcohols in only 7 h at 160 °C.
A series of polyols, carbohydrates, and cellulose were tested in the aqueous, CuO/ZnO/Al2O3-catalyzed hydrogenolysis reaction at 245 °C and 50 bar H2. The compositions of liquid-phase products were analyzed; based on these results a unified reaction mechanism is proposed that accounts for the observed product distribution. Elementary transformations such as dehydration, dehydrogenation/hydrogenation, Lobry de Bruyn-van Ekenstein isomerization and retro-aldol cleavage were identified as most important for controlling the selectivity of simple polyols and carbohydrates. For cellulose the product distribution is considerably different than for glucose or sorbitol, indicating a change in the reaction pathway. Therefore, next to the traditional hydrolysis of the glycosidic bond, an additional depolymerization mechanism involving only the reducing ends of cellulose oligomers is proposed to account for this observation.
Noble causes: Cellulose is effectively converted into methanol, propylene, and ethylene glycol over Cu-based catalysts. Overall yields of above 93 %, together with 63 % yield of C1–C3 compounds, can be reached over simple noble-metal-free systems, opening new opportunities for the sustainable and cost-efficient valorization of cellulose
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