MODELING OF PROCESSES OF HYDROPEROXIDE EPOXIDATION OF OLEFINS - REACTION OF BUTADIENE WITH TERT-AMYL HYDROPEROXIDE

An investigation has been made of the general relationships governing the epoxidation of butadiene by organic hydroperoxides (TAHP, TBHP, IP BHP, EBHP) with catalysis by molybdenyl propylene glycolate, and a det ailed study has been made of the kinetics of the reaction for tert-amy l hydroperoxide. A mathematical model of the process has been develope d, adequately describing the experiment with variation in [TAHP](0) fr om 0.5 to 1.5 mole/l and in [Cat](0) from 3 to 8 x 10(-4) mole/l at a temperature of 110 degrees C, and taking account of the change in acti vity of the catalyst as a function of [Cat] and [ROOH](0). The complex influence of additions of an alcohol, which inhibits the epoxidation rate, but at the same time increases the proportion of the active form of the catalyst, has been explained. The generality of the effects ob served for all the examined reactions of hydroperoxide oxidation has b een confirmed, and also the need to allow for change in the state of t he catalyst in the solution during modelling of these processes. (C) 1 996 Elsevier Science Ltd. All rights reserved.