Enhanced Ethylene and Ethane Production with Free-Radical Cracking Catalysts

A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase.