Liquid phase oxidation of xylenes: Effects of water concentration and alkali metals

A facile and precise batch oxidation reaction system allows continuous monitoring of the oxidation rate and cumulated oxygen conversion of xylenes, and the side reactions to carbon monoxide and carbon dioxide may also be studied. The oxidation reaction can be analyzed precisely with the rate and amount of oxygen consumed. The reaction reveals that 4-carboxybenzaldehyde is an unstable intermediate of p-xylene oxidation as the reaction proceeds instantaneously from p-toluic acid to TPA (terephthalic acid). The alkali metals accelerate oxidation, even though they retard the reaction initially. The oxidation rate increases with decreasing water concentration. However, in the later part of reaction, the reactivity decreases a bit if the water concentration is very low. This retarding effect of water can be overcome partly by the addition of potassium. The oxidation of o-xylene, compared with the oxidation of p-xylene and m-xylene, proceeds quite fast initially, however, the oxidation rate of xylene isomers in the later stage of reaction is in the order of p-xylene > m-xylene > o-xylene.