Detailed examination of the degradation of phenol derivatives under oxygen delignification conditions.
Several phenolic compounds were subjected to oxygen-alkali oxidations under oxygen delignification conditions, and their degradations were examined in detail by applying a novel formula. The formula was established on the basis of the two following considerations. The degradation of the phenolic compounds should be expressed by the sum of two types, each of which is caused by molecular oxygen and by highly reactive active oxygen species (HAOS). The degradation should be described by a mathematical equation to which a rate function, k(t), dependent on reaction time t, is applied instead of a rate constant. By rearrangements, the following formula was obtained: k(t) = A/(t + B) (A, B are constants). This is hyperbola, and the illustration of k(t) visualized the contribution of HAOS to the degradation of the phenolic compounds. HAOS did not contribute so much to the degradation, especially at 70 degrees C, which suggests the low energy supply for the HAOS generation at 70 degrees C. The extrapolation of k(t) to the beginning of the reaction gives its initial value, k(initial), which is the rate constant of the reaction between the phenolic compounds and molecular oxygen. As expected, k(initial) was dependent on the electronic property of their substituents. Quantification of the phenolic compounds degraded by HAOS showed that the contribution of HAOS to the degradation is not great. The maximum contribution was observed in the oxidation of 2,6-dimethylphenol at 85 degrees C. In this case, 5 and 95% of the compound were degraded by HAOS and molecular oxygen, respectively.
Yokoyama
Tomoya
T
Laboratory of Wood Chemistry, Department of Biomaterial Sciences, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan. yokoyama@woodchem.fp.a.u-tokyo.ac.jp
Matsumoto
Yuji
Y
Meshitsuka
Gyosuke
G
D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008031:Lignin / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010636:Phenols / Q000032:analysis / Q000737:chemistry*
D010636:Phenols; D008031:Lignin; D010100:Oxygen