Studies of the processes of the hydrolytic oxidation of disaccharides are the first step towards the development of technologies for the direct conversion of plant polysaccharides, primarily cellulose, into aldonic and aldaric acids, which are widely used in chemical synthesis and various industries. In this study, heterogeneous catalysts based on a porous matrix of hypercrosslinked polystyrene (HPS) and noble metals (Pt, Au, Ru, and Pd) were proposed for the hydrolytic oxidation of cellobiose to gluconic and glucaric acids. The catalysts were characterized using low-temperature nitrogen adsorption, hydrogen chemisorption, electron microscopy, and other methods. In particular, it was shown that the Pt-containing catalyst contained, on average, six times more active centers on the surface, which made it more promising for use in this reaction. At a temperature of 145 °C, an O2 pressure of 5 bars, and a substrate/catalyst weight ratio of 4/1, the yields of gluconic and glucaric acids reached 21.6 and 63.4%, respectively. Based on the data obtained, the mathematical model of the cellobiose hydrolytic oxidation kinetics in the presence of 3% Pt/HPS MN270 was developed, and the parameter estimation was carried out. The formal description of the kinetics of cellobiose hydrolytic oxidation was obtained.
A new type of Ru-containing magnetically recoverable catalyst based on a polymer matrix of hypercrosslinked polystyrene (HPS) for the reaction of the hydrogenolysis of microcrystalline cellulose to ethylene and propylene glycol (EG and PG) is proposed. The catalyst is synthesized sequentially in two stages. At the first stage, by means of thermal decomposition of iron (III) salts in the presence of polyols, magnetite particles (Fe3O4) are formed in the pores of the HPS. At the second stage, Ru-containing nanoparticles of the active phase of the catalyst are synthesized on the surface of Fe3O4/HPS. Samples of the original HPS, Fe3O4/HPS and Ru-Fe3O4/HPS were characterized using various physicochemical methods. In particular, it was shown that the synthesized samples of catalysts have a high specific surface area (450 - 750 m2/g, depending on the magnetite content), retain the micro-mesoporous nature of the original polymer, and have a high saturation magnetization (4.0 ± 0.5 emu /g), which makes them easy to separate from the reaction mass by an external magnetic field. According to the results of transmission electron microscopy (TEM), the average diameter of the nanoparticles of the active phase Ru was 2.0 ± 0.5 nm. The hydrogenolysis of cellulose to glycols was carried out under the following conditions: 255 °C; 60 bar H2; 55 min; 0.3 g of cellulose; 0.07 g of catalyst 3% Ru-Fe3O4/HPS; 30 ml of H2O; 0.07 g of Ca(OH)2. Under these conditions, the selectivities for EG and PG were 22.6 % and 20.0 %, respectively. The degree of cellulose conversion reaches 100 %. The catalyst showed good stability under hydrothermal reaction conditions, is easily separated from the reaction mass by an external magnetic field, and can be used in the processes of cellulose-containing biomass conversion.
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