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The depletion of fossil resources is driving forward the search for new and alternative renewable feedstocks in the production of renewable chemicals, which could replace the petroleum-based ones. One such feedstock is pine (Pinus sylvestris) sawdust, which is generated enormous amounts in Finnish sawmills yearly. However, prior to the utilization in high-value applications, it needs to be fractionated into its constituents. In this work, the objective was to produce monomeric hemicellulose sugars from pine sawdust without degrading cellulose or lignin simultaneously. The influence of the reaction temperature and time, as well as acid type and concentration, was studied. Based on the results, the temperature was the main distinguishing feature between cellulose and hemicellulose hydrolysis. Promising results were achieved with acid mixtures consisting of 0.5% sulfuric acid and 5.5 or 10% formic acid. At 120°C with the reaction time of 2 h, the mixtures produced hemicellulose sugars with the yields of 62%. These yields were comparable to the yields achieved in similar conditions with 1.5% sulfuric acid or 40% formic acid. Therefore, by using an acid mixture, the concentration of a single acid could be reduced significantly. The solid fractions remaining after the hydrolysis consisted mainly of cellulose and lignin, which verified the selectivity of the hemicellulose hydrolysis. Also, the fractionation of the remaining solids confirmed that the utilization of all the sawdust components is feasible.

One-step absolute solvent-free acid-catalyzed mechanical depolymerization of pine sawdust (PSD) and commercially available α-cellulose to water-soluble sugars was carried out using ball milling. For comparison purposes, the commonly reported "solventfree" mechanocatalytic depolymerization of lignocellulose method, which normally involves three steps (acid impregnation in solvent, vacuum drying, and mechanical depolymerization of lignocellulose), was performed. The 3,5-dinitrosalicylic acid (DNS) method was used to measure the total reducing sugar (TRS) of the obtained sugar solution, and major monosaccharides in the solution were analyzed by capillary electrophoresis (CE). More than 90% of the PSD became water-soluble through milling. Furthermore, most of the PSD was converted into TRS in approximately 30 min, and the highest TRS yield obtained was 31%, based on the dry mass. Interestingly, the TRS solutions obtained from the processed PSD were much darker than those obtained from α-cellulose due to the chromophores that formed during the depolymerization of lignin.

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