Behavior Of Calcium,Magnesium and Manganese Compounds During Oxygen Bleaching of Kraft Pulps

During oxygen bleaching of kraft pulps manganese compounds can, depending on their amounts, the charges of sodium hydroxide and of magnesium protector, and on the presence of trace amounts of catalytically active transition metals retard or promote the depolymerization of the cellulose. The present report deals with pulps pretreated with 2 % nitrogen dioxide. As shown in forthcoming papers similar results were obtained with pulps without pretreatment with nitrogen compounds.

Pretreatment with nitrogen dioxide at 80°C followed by washing with water removed about 95 % of the magnesium and manganese from kraft pulps. Subsequent oxygen bleaching for 180 min removed 40–90 % of the calcium remaining in the pretreated pulps. Produced hydroxycarboxylate ions gave rise to low molecular complexes of calcium and of magnesium, added as protector. Competition for complexing ligands contributed to a decreased dissolution of calcium with increasing addition of magnesium. When magnesium was applied large amounts of colloids of polynuclear magnesium species were produced. These contained lignin fragments and less abundant metal compounds such as manganese and calcium.

Wet oxidation of both low molecular complexing agents and of organic fragments of larger size contributed to a decreased or unchanged concentration of low molecular metal complexes and metal compounds linked to the colloids with hydrated magnesium oxide as the main constituent. The conditions which favored the wet oxidation were similar to those which led to an increased attack on the lignin and carbohydrates in the fibers and thus promoted the dissolution of low molecular metal complexes and the formation of metal ions containing colloids. Under certain conditions precipitation of sparingly soluble manganese compounds of oxidation states higher than +2 had a predominant influence on the concentration of manganese in the liquor.