Journal of Siberian Federal University. Chemistry / Dechlorinative Oligomerization of Multiply Chlorinated Methanes Catalyzed by Activated Carbon Supported Pt-Co

Full text (.pdf)
Issue
Journal of Siberian Federal University. Chemistry. 2012 5 (1)
Authors
Kovalchuk, Vladimir I.; Rhodes, William D.; McDonald, Mark A.
Contact information
Kovalchuk, Vladimir I. : Department of Chemical and Petroleum Engineering , University of Pittsburgh, Pittsburgh, PA 15261, United States , e-mail: ; Rhodes, William D. : Department of Chemical and Petroleum Engineering , University of Pittsburgh, Pittsburgh, PA 15261, United States; McDonald, Mark A. : National Energy Technology Laboratory (NETL) , United States Department of Energy, Pittsburgh, PA 15236, United States
Keywords
hydrodechlorination; chloromethanes; dehalogenative oligomerization; Fischer-Tropsch synthesis; reaction mechanism; platinum; cobalt
Abstract

The hydrodechlorination of dichloromethane, trichloromethane, and their mixtures catalyzed by a Pt- Co/C catalyst has been investigated in an effort to elucidate the chemistry associated with the generation of hydrocarbon oligomerization products. In the reaction of dichloromethane with hydrogen, the catalyst did not exhibit deactivation and maintained the steady-state activity within 18 h on stream at 523 K; whereas, when trichloromethane was added or converted in the absence of dichloromethane, significant deactivation occurred within the first 5 h on stream. Hydrocarbon oligomerization products were observed with all three reaction mixtures; the selectivity followed the order dichloromethane + dihydrogen < trichloromethane + dihydrogen < dichloromethane + trichloromethane + dihydrogen. The generation of ethane and propane was virtually independent of the reaction mixture composition. However, selectivity toward ethylene and propylene was significantly greater with the trichloromethane + dihydrogen and dichloromethane + trichloromethane + dihydrogen mixtures compared to the dichloromethane + dihydrogen feed. It was concluded that the saturated hydrocarbon products are formed by means of the alkyl mechanism of hydrocarbon chain growth; whereas, the alkenyl mechanism is responsible for the formation of the unsaturated hydrocarbons.

Pages
3-17
Paper at repository of SibFU
https://elib.sfu-kras.ru/handle/2311/2854