Summary A direct and rapid method for determining the average molecular weight (MW) and content of lignin and hemicelluloses in spent cooking liquor by high performance size-exclusion chromatography (HPSEC) using a cartridge glass column and 2.5 mM NaOH as an eluent was developed. A Uv290 detector in line with a RI detector was applied to characterise lignin and hemicelluloses, respectively, from liquor during the kraft cooking of grey and black alder wood. During the main delignification stage, the concentration of high-MW wood components in liquor changed through the maximum. The MW values of hemicelluloses in the liquor decreased to DPn = 30 ± 5 and DPw = 55 ± 5. The M̄ n and M̄ w of lignin in spent kraft cooking liquor during the main and final delignification stages did not exceed 3000 and 5000, respectively.

The influence of wood chips impregnation with modelled green liquor at a liquor-to-wood ratio of 0.7:1 and 4:1, marked further by 0.7M and 4M, respectively, on the extended kraft delignification of pine chips has been investigated. It was shown that the dynamics of delignification and hemicelluloses removal after the pretreatment was significantly changed, in comparison to conventional kraft cooking. The lignin, xylan and mannan removal rate constants in the initial, bulk and final phases of the second stage of cooking were calculated. It has been found that, after the pretreatment at 0.7 M and 4 M, the delignification rate increased by 12 and 5% at the initial phase and by 10 and 6% at the bulk phase, respectively. The selectivity of delignification was higher in the case of a low liquor-to-wood ratio at the impregnation stage.

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Summary An approach to a chromophore composition study using the direct size-exclusion chromatography (SEC-UV) analysis of an alkaline extract of pulp fibre walls is described. Absorbance in the 290–405 nm range of 2% and 18% NaOH extract from unbleached pulps obtained by conventional and extended kraft delignification of black alder wood is compared. The effect of cooking conditions on the localisation and accessibility of chromophores is elucidated. The alkali-soluble lignin from pulp produced by extended cooking was less oxidised, less conjugated, and less coloured as compared with the conventional kraft lignin. A chromophore accessibility index is proposed. The chromogenic structures in pulps obtained by extended cooking were more resistant to alkali solutions than those in conventional kraft pulps.

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