Performance of rare earth modified faujasites in the process of toluene disproportionation

The purpose of the present paper is the study of the performances of some catalysts based on y-type faujasite exchanged with La (3+) and Ce (3+) cations in the process of toluene disproportionation to benzene and xylenes. In the first stage the crystallographic study by the X-rays diffraction method shows that the cation exchange causes 311 plane displacements in the zeolite structure, accompanied by a decrease of diffraction limit intensity. Further the faujasite pretreatment with NH4 (4+) ions plays some role in the protection of the crystallinity. Moreover the cation exchange seems to take an optimum value around 73% for which the toluene conversion is maximum. This phenomenon is probably due to a decrease of the internal free volume for a pronounced cation exchange. The best performances are obtained by the zeolite that has undergone a slow and programmed thermal activation after cation exchange. This is probably due to the slowness of ion rearrangement phenomena, and of the catalytic surface restructuration. In the second stage the realization of toluene disproportionation process shows that the cation exchange with such elements confers to the faujasite an appreciable catalytic activity in the temperature range of 350-500 degC. The catalysts obtained permit about 20-60% toluene conversions. The catalytic activity is slightly higher in La-modified samples, whereas those containing Ce (3+) present relatively a better selectivity to the main process. Nevertheless, both types of catalysts show approximately a similar behaviour, favourizing the p-xylene formation. The proportion of the latter exceeds that of thermodynamic equilibrium at temperatures less than 430 degC. The temperature increase affects this selectivity. This is probably due to dehydration phenomenon which are frequent around this value