Chemical aspects of kraft pulping

Summary

Kraft pulping is interpreted in chemical terms on the basis of results from extensive qualitative and quantitative model experiments. In essence, the behavior of lignin is explained as a competition between degradation reactions, mainly involving aryl ether cleavage with participation of neighboring groups, and condensation reactions, comprising conjugate addition of carbanions to quinone methide intermediates. The initial phase of technical delignification is tentatively ascribed to the cleavage of α- and β-aryl ether bonds in phenolic lignin units, whereas the cleavage of β-aryl ether bonds in non-phenolic lignin units is considered to be the rate-determining reaction of the bulk phase. The residual phase may possibly be attributed to the rupture of C-C linkages and to aryl ether cleavage without neighboring group participation. Experimental support for these correlations is provided. The interplay of the various lignin reactions, illustrated in a summarizing scheme, explains some known observations in kraft pulping.

Attention is drawn to analogies between reactions involved in the degradation of carbohydrates and those reponsible for the degradation of lignin. From the chemical standpoint, therefore, the selectivity of delignification is due to differences in the reactivity of the wood polymers, rather than to differences in the mechanisms of the degradation reactions. This fact explains the limitations of selective delignification.