Changes in the lignincarbohydrate complex in softwood kraft pulp during kraft and oxygen delignification

Three kraft pulps in the kappa number range between 50 and 20 and the same pulps oxygendelignified to similar lignin contents (kappa approximately 6) were analyzed for lignincarbohydrate complexes (LCC) by a method based on selective enzymatic hydrolysis of the cellulose, and quantitative fractionation of the LCC. Between 85 and 90% of residual lignin in the unbleached kraft pulp and all residual lignin in the oxygendelignified pulps were isolated as LCC. Three types of complexes were found; viz., xylanlignin, glucomannanligninxylan and glucanlignin complexes. After pulping to a high kappa number, most of the residual lignin was linked to xylan. Different delignification rates were observed so that most of the residual lignin was linked to glucomannan when the pulping was extended to a low kappa number. With increasing degree of oxygen delignification, a similar trend in the delignification rates of LCC was observed so that the residual lignin was increasingly linked to glucomannan. Complex LCC network structures seemed to be degraded into simpler structures during delignification. The differences in delignification rates are discussed with reference to the solubility properties and structural differences of LCC, and to morphological aspects of the pulp.