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Most of our knowledge on kraft pulping comes from studies on dissolved lignin in the freely drainable black liquor and isolated residual lignin in pulp. However, entrapped liquor in the delignified chips has been shown to differ significantly from the free liquor. The present study has compared three liquor fractions: free, lumen and fiber wall liquor. The free liquor was obtained by draining the delignified chips, the lumen liquor was separated by centrifugation and the fiber wall liquor by subsequent leaching. The liquor in the fiber wall had the lowest concentration of lignin and hydrosulfide ions and the highest concentration of monovalent cations. The dissolved lignin in the fiber wall liquor had the highest molar mass and the highest content of xylan. The highest concentration of dissolved lignin was in the liquor filling the lumen cavities. The lignin in the free liquor had the lowest molar mass and the lowest content of lignin structures containing β-O-4 linkages and aliphatic hydroxyl groups. The lowest mass transfer rate of dissolved lignin was from the lumen liquor to the free liquor probably restricted by the tortuosity of the chip.

Analysis of entrapped and free liquor to gain new insights into kraft pulping