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Clays and Clay Minerals

, Volume 44, Issue 6, pp 774–782 | Cite as

Preparation, Structural Characteristics and Catalytic Properties of Large-Pore Rare Earth Element (Ce, La)/Al-Pillared Smectites

  • Ernst Booij
  • J. Theo Kloprogge
  • J. A. Rob Van Veen
Article

Abstract

Ce/Al- and La/Al-pillared smectites were prepared by cation exchange of bentonite, saponite and laponite with hydrothermally treated (130–160 °C for 16–136 h) solutions containing mixtures of aluminumchlorohydrate (ACH) and Ce3+-/and La3+-salts. After calcination at 500 °C, the pillared products are characterized by basal spacings between 24.8 and 25.7 Å and surface areas of approximately 430 m2 g−1. The products are hydrothermally stable at 500 °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 ≥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. 27Al nuclear magnetic resonance (NMR) spectroscopy has shown that the polyoxocation has a higher Altetrahedral/Aloctahedral ratio than the Keggin structure Al13, 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).

Key Words

Al13 Bentonite Hydroconversion Hydrocracking Laponite Montmorillonite Pillared Clays REE Saponite 

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Copyright information

© The Clay Minerals Society 1996

Authors and Affiliations

  • Ernst Booij
    • 1
  • J. Theo Kloprogge
    • 2
  • J. A. Rob Van Veen
    • 3
  1. 1.Faculty of Earth SciencesFree University of AmsterdamAmsterdamThe Netherlands
  2. 2.ZoetermeerThe Netherlands
  3. 3.Koninklijke/Shell Laboratorium AmsterdamAmsterdamThe Netherlands

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