Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by 27Al 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Sisingle bondOsingle bondAl bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)xAl(OP)4−x species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Sisingle bondOsingle bondAl bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by 31P MAS NMR spectra.