The kinetics of the heterogeneous catalytic gas-phase oxychlorination of ethylene to 1,2-dichloroethane was investigated, using a copper chloride on alumina catalyst at 180°C. The reaction rate increased with increasing partial pressures of ethylene and oxygen, but was independent of hydrogen chloride partial pressure. A reaction rate model based on the surface reaction of ethylene and oxygen to form an ethylene oxide intermediate as the rate-determining step provided the best fit of the experimental data. Mechanisms based on the Deacon reaction were not consistent with the data. The energy of activation for the rate expression was 24.5 kcal per mole. A study of the effect of process variables on chlorocarbon selectivity indicated that decreasing the hydrogen chloride partial pressure decreased side reactions to other chlorocarbons.
SummaryTwo kinds of mathematical models have been developed for batch penicillin fermentations: (1) general models, b a d on averaged, nondmensionalized cell and penicillin synthesis curves from plant scale fermentom and (2) particular models developed from specific sets of experimental data from two sources. Parameter-temperature functions used with the general models were assumed to have general shapes which could apply to many fermentations, i.e., they were bssed on the familiar temperature response of enzyme-catalyzed reactions. Parameter-temperature functions for the particular models were determined from experimental data for batch runs at various temperatures.
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