13C [formula omitted] n.m.r. study of coke formation on HZSM-5

Abstract

The carbonaceous residue (coke) formed on HZSM-5 during the conversion of methanol to gasoline was studied by 13C n.m.r. spectroscopy using cross-polarization and magic angle spinning and by e.p.r. spectroscopy. Measurements were made on samples with different coke contents and on samples from which some external coke had been removed by treatment with an oxygen plasma. It was found that the amount of carbon visible by n.m.r. differed from that expected from the measured coke contents and that the ratio of these amounts varied with the degree of coking. We concluded that the n.m.r.-visible carbon was most probably composed of methyl-substituted polycyclic aromatic hydrocarbons, the degree of methyl substitution and ring condensation changing with the coke content. It was inferred that these methyl-substituted polycyclic aromatics were present in the channels of the zeolite whereas the coke invisible to n.m.r. could be highly condensed polycyclic aromatics or “graphitic” structures on the external surfaces of the zeolite crystals. It appears that initial coke formation is internal and that external coke forms at latter stages in the deactivation process.