Autohydrolysis of aspen milled wood lignin

Abstract

In order to obtain further understanding of the nature of lignin reactions during autocatalysed hydrolysis (autohydrolysis) of wood, milled wood lignin (MWL) was isolated from aspen (Populus tremuloides) and treated under autohydrolysis conditions. By this means reactions of the lignin itself could be distinguished from those taking place between lignin and the carbohydrate or other components of the wood. The material after the reaction was separated into a dioxane insoluble fraction (DI), a dioxane soluble but ether insoluble fraction (DSEI), and an ether soluble fraction (ES). Studies were carried out on the DI and DSEI fractions; no direct study was made of the small ES fraction.The formation of DI material increased linearly during the first 7.5 min at 170 °C and then levelled off. At the same time DSEI decreased and then levelled off. Gel permeation chromatography of the DSEI fraction suggested that during autohydrolysis there is an initial generation of low molecular weight fragments which recombine to form first a high molecular weight soluble fraction and from this the insoluble product. The DSEI fraction contained increased conjugated and unconjugated keto groups. Carboxylic acids were also detected; they have been attributed to the reincorporation of low molecular weight aromatic acids generated by the hydrolysis of the corresponding esters. The dioxane insoluble (DI) fraction had fewer unconjugated keto groups than the DSEI fraction, indicating that these groups participated in the condensation reactions leading to the formation of insoluble material. These probably involve position 6 of the aromatic ring.