Oxidation of linear alcohols with hydrogen peroxide over titanium silicalite 1

In this paper different parameters affecting the oxidn. of alcs. with hydrogen peroxide are described. The influence of the amt. and of the crystallite size of the catalyst, as well as the concns. of hydrogen peroxide and substrate have been studied. The influence of the reaction temp., the chain length of the alc. (C6, C7, C8 and C9) and the position of the alc. group (a, b or g) on the reaction rate has also been investigated. As a result of this study it can be reported that the reaction is first order with respect to the amt. of catalyst and the hydrogen peroxide concn., and zero order in alc. concn. The activation energy for the oxidn. of 2-octanol is 71 kJ/mol. The particle size has a considerable effect on the reaction rate; larger particles result in slower reaction. There is a remarkable effect of the chain length on the reaction rate (C6a>g). The crystallite size effect can be explained by means of diffusion limitations, as could be illustrated by Weisz modulus calcns. The obsd. difference in activity between b and g alcs. cannot be related to differences in diffusion (single component diffusion of b and g alcs. show little difference) and therefore transition state restrictions of the alcs. in the pores of the TS-1 may be a possible explanation for this effect. [on SciFinder (R)]