A new look at the kinetics of oxygen delignification of softwood kraft pulp

Abstract

Abstract Using a Berty-type CSTR reactor, Ji (2007. Kinetics and mechanism of oxygen delignification, Ph.D. thesis. The University of Maine) obtained oxygen delignification kinetics first order in lignin when neglecting the higher initial delignification phase. In the present study the same Berty/CSTR reactor with an improved temperature control was used to determine the oxygen delignification kinetics of Southern Pine kraft pulp, with the kinetics now corrected for lignin removed by oxygen-free alkaline leaching. This removes the initial high delignification rate peak so that the kinetics over the entire lignin range can be modelled as first order in “reactive” lignin, which is lignin corrected for a small amount of unreactive lignin. It suggests that softwood pulp oxygen delignification consists of two contributions; phenolic delignification and alkaline leaching. The initial alkaline leaching phase is mathematically described by semi-infinite alkaline diffusion of dissolved lignin trapped in the cell wall after pulp washing. For phenolic delignification, the reaction orders in alkali concentration and oxygen of the power law delignification equation are 0.3 and 0.44 respectively, while the activation energy is 63 kJ/mol. Taking into account the unreactive HexA, the small amount of unreactive lignin, and the lignin removed by alkaline leaching, the kappa number is well predicted by the new delignification kinetics.