Charge Density of Lignin Samples from Kraft Cooking of Birch Wood

Abstract

Black liquor, isolated dissolved lignin and residual lignin samples corresponding to different cooking times were obtained from flow-through kraft cooking of birch wood. Dissolved lignin was isolated from black liquor by acid precipitation and residual lignin was isolated from pulp by acid-dioxane extraction. The average mobility (μav) of the lignin-containing samples was determined by capillary zone electrophoresis. The lignin samples have a broad mobility distribution that reflects the charge-to-size ratio of the molecules. At pH 12, i.e. when lignin is completely dissociated, the μav of each type of sample increases during the cook, reflecting an increase in charge density of the lignin. For samples corresponding to the initial and beginning of the bulk delignification phases, the μav decreases in the order dissolved lignin>black liquor>residual lignin. The lower charge density of black liquor compared to dissolved lignin is proposed to be caused by associations between lignin and carbohydrate fragments dissolved in the black liquor. As from the middle of the bulk delignification phase, the μav of the three series of samples is quite similar. The decrease in mobility on lowering the pH is an indication of the degree of dissociation of the lignin phenol groups. At pH 10, i.e. about the pK_a of lignin, the μav of black liquor is highest throughout the cook. The relative order of μ_av is then black liquor>dissolved lignin≈residual lignin.