Effects of the Addition of Chlorohydrocarbons on the Oxidation of Propylene; A Consideration of the Negative Temperature Coefficient

Abstract

Abstract A small amount of allyl chloride, 1,1-dichloroethane, or chloroform was added to the reactant in the oxidation of propylene in an inert fluidized-bed reactor. A negative temperature coefficient is observed in the conversion of propylene and in the formation of various products, but not propylene oxide, in the experiments with allyl chloride or 1,1-dichloroethane added. The results of the chloroform-adding experiments show a positive temperature coefficient in the conversion of propylene and in the formation of gaseous products. The results of the work described here are discussed on the basis of the probable reaction scheme. The results of the chloroform-adding experiments support the proposed catalytic effect of the chlorocarbene on the decomposition of acetaldehyde. It is concluded that the negative temperature coefficient is attributable to the apparent inactivity of acetaldehyde (the branching agent) in the high-temperature region in this reaction atmosphere.