Lignin Sulfonation - A different Approach

The research on sulfite pulping has been characterized by the attempts to explain its chemistry. The. different approach presented is incited by perceptions about the (still) unsolved problem of the ultrastructural features of lignin in wood. A simple kinetic model has been chosen to describe the reaction order of lignin as "concentration" (weight) in the dissolution kinetics, the cooking liquor being used in substantial excess. Three states of lignin were used: in wood as sawdust (W), in milled. wood (MW) and as milled wood lignin (MWL). Cooks were performed at pH 1.5, and 6. (measured at room temperature). The lignin was also modified chemically in two ways: alkaline borohydride reduction and diazomethane methylation. The reaction order (with the kinetics used) was found to be about 2/3, which is the value to be expected for particles of equal size reacting, at the particle surface. The cooks were carried onto completion, defined as the maximum amount of dissolved lignin. Depending on the state of lignin, apart dissolved more or less "immediately". The kinetic results are presented in dissolution/time and Arrhenius diagrams. Some experiments were made to ensure that counterfeit results were evaded. It was found that lignin is very reactive, that is why the sulfonation chemistry alone does not necessarily determine its dissolution rate. It became evident that the ultrastructure dispersion of lignin in wood is beneficial for its dissolution. For W, the rate was much higher at pH 1.5 than at 6. MW lignin and MWL dissolved (after extraction of the "immediate" lignin) at higher rates than W lignin. For MWL, the rate difference between pH 1.5 and 6 was moderate, compared to W lignin. Borohydride reduction did not affect the lignin dissolution from W, but gave a large decrease of sulfonation rate for MWL. Methylation had also a small rate effect for W, but again a large decrease for MWL.