Abstract
Stricter environmental demands have increased the need to replace conventional C/D bleaching sequence by chlorine-free sequence. Permanganate is well known as a powerful oxidant and have been used industrially in variable fields. However, it has considered to be difficult to use permanganate as a bleaching reagent because of its strong oxidative effect decreasing the viscosity of pulps extremely. We have tried to use permanganate as a bleaching reagent for KP under the mild condition and it was clear that pernanganate oxidized lignin remained in pulps selectively and increased pulp brightness decreasing K number of pulps with small degradation of cellulose. We have employed the neutral condition in the permanganate bleaching process in this study. In this case, permanganate was converted to manganese dioxide after bleaching reaction. The manganese dioxide is remained in the treated pulp fibers because of its insolublity in water. So it was required to reduction the manganese oxide to manganese ion by using reductants with acid. In this paper, we proposed to use oxalic acid as a reducing reagent converting manganese oxide to manganese ion after bleaching reaction. Oxalic acid plays the role as a reductant and a acid, so post-treatment after bleaching became to be easy by using oxalic acid. On the study using lignin model compounds, it was clear that permaganate react with phenols firstly, after that oxalic acid reduce the manganese oxide to manganese ion in the mixture of permanganate, phenols and oxalic acid. Several lignin model compounds ($\textit{p}$-hydroxybenzaldehyde, vanillin, syringaldehyde, veratraldehyde) are selected to elucidate the effect of substituents on reaction rate and its mechanism with permanganate including oxalic acid in this study. Except for veratraldehyde, the rate of oxidative degradation of phenolic compounds by permanganate with oxalic acid are higher than neutral condition. Especially, the degradation rate of $\textit{p}$-hydroxybenzaldehyde are strongly dependent on pH of reaction mixture. On the other hand, the degradation rate of veratraldehyde are decreased with decreasing pH and main degradation product is veratric acid. This result indicate that pH of bleaching liquor should be kept over 2 to degrade of non-phenolic lignin in the pulps effectively in permanganate bleaching.
