Synergism in the actions of a transition metal cation and a Lewis acid in the liquid- and gas-phase catalytic conversion of alkanes over modified ZSM-5 zeolites under mild conditions

Bimetallic catalysts have been prepared by successively modifying the high-silica zeolite ZSM-5 with cobalt and aluminum salts. The performance of these catalysts in the conversion of higher alkanes at medium temperatures (130–190°C) depends on whether the reaction is conducted in the liquid or gas phase. In both cases, the transition metal and surface-anchored aluminum chloride act synergetically. In the liquid-phase reactions of n-heptane and n-dodecane, the activity of the bimetallic systems is more than one order of magnitude higher than the activity of the hydrogen form of the initial zeolite. New adsorption and catalytic sites resulting from the introduction of the two modifiers into the zeolite have been discovered by diffuse reflectance IR spectroscopy. In particular, the modifiers generate a new state of cobalt in which the transition metal atoms are linked with aluminum atoms through chlorine or oxygen atoms. The liquid-phase conversion of alkanes over the modified zeolites is unlikely to proceed via a carbocationic mechanism.