SO2-ethanol-water (SEW) fractionation of lignocellulosics

Aalto University, P.O. Box 11000, FI-00076 Aalto www.aalto.fi Author Mikhail Iakovlev Name of the doctoral dissertation SO2-ethanol-water (SEW) fractionation of lignocellulosics Publisher School of Chemical Technology Unit Department of Forest Products Technology Series Aalto University publication series DOCTORAL DISSERTATIONS 95/2011 Field of research Biorefineries Manuscript submitted 9 May 2011 Manuscript revised 10 August 2011 Date of the defence 21 October 2011 Language English Monograph Article dissertation (summary + original articles) Abstract This study deals with SO2-ethanol-water (SEW) fractionation as a potential method for a Lignocellulosic Biorefinery to achieve high yield separation of the three important components of biomass; cellulose, hemicelluloses and lignin. Representatives of all principal biomass species were successfully treated by SEW fractionation at similar rates. The kinetics of delignification, polysaccharides removal and cellulose hydrolysis at different temperatures and SO2 concentrations are described and interpreted from the viewpoint of acid-catalysed degradation of the biomass polymers. The fractionation pattern is compared to that of commercial acid sulfite cooking. The kinetics of delignification, hemicelluloses removal and cellulose hydrolysis during SEW fractionation each follow a two phase behaviour. The delignification is first order in lignin and SO2. The observed lignin sulfonation and delignification patterns can be explained using Hägglund’s consecutive fast sulfonation-slow hydrolysis scheme. During the initial phase of fractionation, the hemicelluloses removal and cellulose hydrolysis rates are related to the delignification rate, while in the following bulk phase the former two processes proceed independently from the latter. It is proposed that during the initial phase the hemicelluloses are removed together with lignin in the form of lignocarbohydrate complexes, while cellulose is protected by lignin from hydrolytic attack leading to a lower hydrolysis rate. Most hemicellulose side units as well as acetyl groups are cleaved during the first phase, while the glucomannan and xylan backbone polymers are removed at a considerably lower rate in the second (bulk) phase following first order kinetics in the residual polysaccharides. The observed polysaccharides dissolution behaviour can be interpreted in terms of low glucomannan stabilisation by crystallisation on cellulose at the applied conditions. Minimal cellulose dissolution occurs during fractionation, but the cellulose degree of polymerisation decreases by hydrolysis following zero-order kinetics. The products include cellulosic fibres and a spent liquor containing lignin and hydrolysed hemicellulose sugars, the latter present up to 50% in monomeric form. The investigated overall and carbohydrate material balances show no carbohydrate losses as further supported by very low amounts of formed oxidation and dehydration products. The properties of the fibre products are evaluated and their potential applications are discussed. The amount of sulfur bound to lignin is 2-3 times lower than that in acid sulfite cooking, and accounts for less than 1.1% on wood. The rest of SO2 (95-97%) can be fully recovered by distillation.This study deals with SO2-ethanol-water (SEW) fractionation as a potential method for a Lignocellulosic Biorefinery to achieve high yield separation of the three important components of biomass; cellulose, hemicelluloses and lignin. Representatives of all principal biomass species were successfully treated by SEW fractionation at similar rates. The kinetics of delignification, polysaccharides removal and cellulose hydrolysis at different temperatures and SO2 concentrations are described and interpreted from the viewpoint of acid-catalysed degradation of the biomass polymers. The fractionation pattern is compared to that of commercial acid sulfite cooking. The kinetics of delignification, hemicelluloses removal and cellulose hydrolysis during SEW fractionation each follow a two phase behaviour. The delignification is first order in lignin and SO2. The observed lignin sulfonation and delignification patterns can be explained using Hägglund’s consecutive fast sulfonation-slow hydrolysis scheme. During the initial phase of fractionation, the hemicelluloses removal and cellulose hydrolysis rates are related to the delignification rate, while in the following bulk phase the former two processes proceed independently from the latter. It is proposed that during the initial phase the hemicelluloses are removed together with lignin in the form of lignocarbohydrate complexes, while cellulose is protected by lignin from hydrolytic attack leading to a lower hydrolysis rate. Most hemicellulose side units as well as acetyl groups are cleaved during the first phase, while the glucomannan and xylan backbone polymers are removed at a considerably lower rate in the second (bulk) phase following first order kinetics in the residual polysaccharides. The observed polysaccharides dissolution behaviour can be interpreted in terms of low glucomannan stabilisation by crystallisation on cellulose at the applied conditions. Minimal cellulose dissolution occurs during fractionation, but the cellulose degree of polymerisation decreases by hydrolysis following zero-order kinetics. The products include cellulosic fibres and a spent liquor containing lignin and hydrolysed hemicellulose sugars, the latter present up to 50% in monomeric form. The investigated overall and carbohydrate material balances show no carbohydrate losses as further supported by very low amounts of formed oxidation and dehydration products. The properties of the fibre products are evaluated and their potential applications are discussed. The amount of sulfur bound to lignin is 2-3 times lower than that in acid sulfite cooking, and accounts for less than 1.1% on wood. The rest of SO2 (95-97%) can be fully recovered by distillation.