Studies in the field of hydrolysis of plant polysaccharides are ordinary classified according to protic reactions with diluted or concentrated acids. Such classification is based on the significant difference in the mechanisms of the reactions. The hydrolysis of polysaccharides of plant materials with the diluted acids is indicated by the concentrations of the mineral acids 0.5–10.0 % or happens by acid-free autohydrolysis, without any use of acids. Each of these reactions has considerably different kinetic and temperature-time parameters. They have both advantages and disadvantages. In particular, the hydrolysis using dilute acids is specified by a significant consumption of reagents and the presence of a large amount of carbohydrate degradation products in the hydrolysate. Autohydrolysis is characterized by a relatively low monosaccharide yield, high energy consumption for the process and the formation of many by-products. To date, studies regarding hydrolysis of polysaccharides of plant materials with acids in a concentration range of less than 0.5 % are absent. The reason for the lack of interest in research in this area, in our opinion, was the statement that acid in the process of hydrolysis is spent on the neutralization of ash components of plant materials at a flow rate of 5 to 20 g/kg of dry raw materials. Accordingly, when hydrolysis is carried out with ultra-low concentrations of acid, it is possible to completely neutralize it and switch the hydrolysis process from acid to acid-free autohydrolysis. The purpose of the work was to establish the efficiency of the hydrolysis process at ultra-low acid consumption. A study of the process of hydrolysis of hemicelluloses of birch wood at ultra-low concentrations of sulfuric acid was carried out. The possibility of almost complete hydrolysis of hemicelluloses with sulfuric acid with concentration of 0.10–0.25 % is shown. The process of hydrolysis of hemicelluloses with ultra-low acid concentrations is well described by the first order reaction. The general kinetic constants are calculated according to the experimental data. They show that the process occupies an intermediate position between acid-free autohydrolysis and traditional hydrolysis of hemicelluloses with sulfuric acid with a concentration of more than 0.5 %. The developed technique is advantageously different from the known methods of hydrolysis of hemicelluloses by low consumption of sulfuric acid (more than 5 times) and energy resources. Hemicellulose hydrolysates obtained by ultra-low acid concentration regimes have high benign properties and can be used in xylitol production.
Abstract. Microcrystalline cellulose (MCC) is a common product used in pharmaceutical, food and other industries. MCC is obtained by liquid-phase hydrolysis of cotton or wood bleached pulp with diluted 0.5–10.0 % mineral acids at a temperature of 100–140 °C. This process requires significant consumption of acid, water, and heat energy. Production of MCC in general is very expensive, which determines its high cost and the need to find alternative methods of cellulose hydrolysis. It is proposed to hydrolyze cellulose with concentrated hydrochloric acid produced by absorption of hydrogen chloride. We studied the processes of hydrogen chloride adsorption by bleached wood pulp with 8–18 % humidity. It is shown that adsorption of hydrogen chloride is determined by pulp humidity and is 3–5 % of the dry pulp mass. The sorption of hydrogen chloride leads to the formation of hydrochloric acid with a concentration of 25–40 % in the raw material moisture, significant heating of the mass and rapid hydrolysis of the amorphous cellulose fraction. It has been found that the use of pure hydrogen chloride for saturation causes strong darkening and humification of pulp. We recommend the use of hydrogen chloride gas-air mixtures to saturate the pulp, which will significantly reduce the sorption temperature and eliminate the strong darkening of the pulp during hydrolysis. The adsorption of hydrogen chloride by cellulose proceeds at an extremely high rate and is accompanied by the formation of a clearly visible sorption front at a temperature of 45–60 °C. Hydrolysis occurs for 15–30 min at 40–60 °C until the amorphous cellulose fraction is completely decomposed. A very small amount of monosaccharides is formed (4 % of dry pulp). The yield of MCC is high, more than 95 %. These circumstances are probably related to the recrystallization of a part of the amorphous fragments of cellulose macromolecules, which is a characteristic of hydrolysis with concentrated acids. The product obtained by cellulose hydrolysis is identical to MCC according to the data of IR spectroscopy, X-ray diffraction and viscometry. The article shows the high efficiency of cellulose hydrolysis with hydrogen chloride gas-air mixtures compared to traditional methods of MCC production.
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