Study on the structure and properties of xylan extracted from eucalyptus, sugarcane bagasse and sugarcane straw

Abstract: Lignocellulosic biomasses are an important source of chemical components such as cellulose, lignin and hemicelluloses, and can be used for a variety of purposes in both the pulp and paper and chemical conversion industries. Xylan, the main hemicellulose found in hardwood and grass plants, plays an important role during the pulping/pretreatment process reactions, including those used in 2nd generation bioethanol production. It may also play an important role in the production of certain novel materials.This thesis evaluates the composition of eucalyptus (Eucalyptus urophylla x Eucalyptus grandis), sugarcane bagasse and sugarcane straw, with a specific focus on the structure and properties of xylan. The chemical characterization of biomasses showed that sugarcane bagasse and straw contain larger amounts of extractives, ash and silica than eucalyptus. The large amount of silica leads to an overestimation of the Klason lignin content, if not corrected. By using a complete mass balance approach, sugarcane bagasse and straw were shown to contain smaller amounts of lignin (18.0% and 13.9%, respectively) than previously reported for these raw materials, and certainly a much smaller amount of lignin than was found in eucalyptus (27.4%). The hemicellulose content in sugarcane bagasse (28.7%) and straw (29.8%) was much higher than that in eucalyptus (20.3%).In order to investigate the structure of the xylan in greater detail, it was extracted with dimethyl sulfoxide from holocellulose, obtained by either peracetic acid or sodium chlorite delignification. The structure of the isolated xylans was confirmed by FTIR and 1H NMR analysis. In eucalyptus, the O-acetyl-(4-O-methylglucurono)xylan (MGX) was identified. This had a molar ratio of xylose units to branches of 4-O-methylglucuronic acid of 10:1.1 and a degree of acetylation of 0.39. All 4-O- methylglucuronic acid groups were attached to position O-2 of the xylose units, which had an acetyl group in position O-3. The acetyl groups were distributed in positions O-3 (64%), O-2 (26%) and O-2,3 (10%). The MGX had a molecular weight (Mw) of about 42 kDa.In bagasse and straw, arabinoxylan (AX) was identified. This had a molar ratio of xylose units to arabinosyl substitutions of 10:0.5 for bagasse and 10:0.6 for straw. A degree of acetylation was 0.29 and 0.08 for bagasse and straw, respectively. The arabinose units were attached preferentially to position O-3 in AX. In the xylan from bagasse, the acetyl groups were found in positions O-3 (60%), O-2 (13%) and O-2,3 (27%), while in the xylan from straw, the acetyl groups were distributed between positions O-3 (67%) and O-2 (33%). The AX had a molecular weight (Mw) of about 38 kDa and 30 kDa for bagasse and straw, respectively.The differences in the structure of xylan present in the various biomasses played an important role during hydrothermal pretreatment, which is often used as the first step in 2nd generation ethanol production. The varying amounts of uronic acid and acetyl groups resulted in different starting pH levels of liquor and, thus, affected the chemical transformation in the biomasses in different ways. The hydrothermal pretreatment resulted mostly in the removal and/or transformation of hemicelluloses, but also in the formation of a significant number of pseudo-lignin structures. In addition, in eucalyptus, pseudo-extractives structures were generated. The sugarcane straw showed the highest mass loss during the investigated pretreatment.