Preparation, structural characteristics and catalytic properties of large-pore rare earth element (Ce,La)/Al-pillared smectites

Ce/Al- and La/Al-pillared smectites were prepared by cation exchange of bentonite, saponite and laponite with hydrothermally treated (130-160 degrees C for 16-136 h) solutions containing mixtures of aluminumchlorohydrate (ACH) and Ce3+-/and La3+ salts. After calcination at 500 degrees C, the pillared products are characterized by basal spacings between 24.8 and 25.7 Angstrom and surface areas of approximately 430 m(2) g(-1). The products are hydrothermally stable at 500 degrees C after 2 h in steam. The large basal spacings are due to the formation of a large Ce/La-bearing Al-polyoxocation, whose formation is favored by initially high Al concentrations greater than or equal to 3.7 M and an OH/Al molar ratio of approximately 2.5. The Ce/Al or La/Al molar ratios can be as low as 1/30. Al-27 nuclear magnetic resonance (NMR) spectroscopy has shown that the polyoxocation has a higher Al-tetrahedral/Al-octahedral ratio than the Keggin structure Al-13, which may partly explain the higher stability compared to normal Al-pillared clays. Hydroconversion of n-heptane indicated that the activity of the Pt-loaded pillared products is higher than that of a conventional Pt-loaded amorphous silica-alumina catalyst. Selectivity is strongly dependent on the type of starting clay and its acidity. In industrial hydrocracking of normal feedstock, a Ni/W-loaded Ce/Al-pillared bentonite catalyst showed rapid deactivation due to coke-formation reducing the surface area and the pore volume. Additionally, coke-formation is facilitated by the relatively high iron content of the pillared bentonite (3.43 wt% Fe2O3).