Hydrolysis of Wood Hemicelluloses at Ultra-Low Sulfuric Acid Concentrations

Anna V. Bakhtiyarova, Sergey D. Pimenov, A. Sizov
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Abstract

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.
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木材半纤维素在超低硫酸浓度下的水解研究
在植物多糖水解领域的研究通常根据与稀释或浓缩酸的质子反应进行分类。这种分类是基于反应机理的显著差异。用稀释后的酸水解植物多糖时,矿物酸的浓度为0.5 - 10.0%,或采用无酸自水解,不使用任何酸。每一种反应都有相当不同的动力学和温度-时间参数。它们既有优点也有缺点。特别地,使用稀酸的水解是由试剂的大量消耗和水解产物中大量碳水化合物降解产物的存在所指定的。自水解的特点是单糖产量相对较低,过程能耗高,形成许多副产物。迄今为止,关于在浓度范围小于0.5%的酸水解植物多糖的研究尚不存在。我们认为,对这一领域的研究缺乏兴趣的原因是,水解过程中的酸以5至20 g/kg干燥原料的流速消耗在中和植物材料的灰分成分上。因此,当用超低浓度的酸进行水解时,可以完全中和它,将水解过程从酸水解转变为无酸自水解。本工作的目的是确定在超低酸耗下水解工艺的效率。对桦木半纤维素在超低浓度硫酸条件下的水解过程进行了研究。用浓度为0.10 ~ 0.25%的硫酸几乎可以完全水解半纤维素。用一级反应很好地描述了半纤维素在超低酸浓度下水解的过程。根据实验数据计算了一般动力学常数。结果表明,该工艺介于无酸自水解和传统的半纤维素用浓度大于0.5%的硫酸水解之间。所开发的技术与已知的半纤维素水解方法相比,具有较低的硫酸消耗(5倍以上)和能源消耗的优点。超低酸浓度制得的半纤维素水解物具有良好的性能,可用于木糖醇生产。
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