Catalysis Today, Vol.31, No.3-4, 275-292, 1996
Aromatization of Propane over Gahmfi Catalysts - Reaction Scheme, Nature of the Dehydrogenating Species and Mode of Coke Formation
The kinetic modelling of propane aromatization over a Ga/HMFI catalyst and the comparison of Ga2O3-HMFI mixtures with different compositions has allowed us to specify the respective roles of dehydrogenating species and of protonic sites. Propane aromatization over Ga/HMFI catalyst occurs mainly through a conventional bifunctional reaction scheme (with desorbed intermediates) in which the dehydrogenating gallium species are responsible for dehydrogenation of propane, of oligomers and of cyclic olefins and diolefins while protonic sites are responsible for oligomerization, cyclization and cracking. This bifunctional transformation is kinetically limited by propane dehydrogenation. Unfortunately, gallium species also catalyze alkane cracking and hydrogenolysis as well as alkene hydrogenation with formation of the undesired products methane and ethane. From the comparison of the catalytic properties of MFI gallosilicates calcined under air flow at various temperatures, it can be concluded that tetrahedral gallium is inactive in dehydrogenation reactions. Dehydrogenation occurs through a bifunctional mechanism involving the joint participation of gallium oxide (extra framework species) and of protonic sites. Coke formed during propane aromatization causes a blockage of the access to the protonic sites of the zeolite which is responsible for deactivation. Ga decreases the coking/aromatization rate ratio of HMFI and facilitates the coke removal through oxidative treatment, both effects being more pronounced after Ga/HMFI pretreatment at high temperature under hydrogen because of the better dispersion of the Ga species.
Keywords:SHORT-CHAIN ALKANES;ZEOLITE CATALYSTS;GA/HZSM-5 CATALYSTS;ZSM-5 CATALYSTS;LIGHT ALKANES;GALLIUM;CONVERSION;HZSM-5;HYDROCARBONS;AROMATICS