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


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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  1. Akitt JW, Greenwood NN, Khandelwahl BL, Lester GD. 1972. 27Al NMR studies of the hydrolysis and polymerization of the hexa-aquo-aluminum cation. J Chem Soc Dalton Trans:604–610.Google Scholar
  2. Barrer RM, MacLeod DM. 1955. Activation of montmorillonite by ion exchange and sorption complexes of tetraalkylammonium montmorillonites. Trans Faraday Soc 51: 1290–1300.CrossRefGoogle Scholar
  3. Bottero JY, Cases JM, Fiesinger F, Poirier JE. 1980. Studies of hydrolyzed aluminum chloride solutions: 1. Nature of aluminum species and composition of the aqueous solutions. J Phys Chem 84:2933–2934.CrossRefGoogle Scholar
  4. Bottero JY, Tchoubar D, Cases JM, Fiesinger F 1982. Investigation of the hydrolysis of aqueous solutions of aluminum chloride: 2. Nature and structure by Small Angle X-ray Scattering. J Phys Chem 86:3667–3672.CrossRefGoogle Scholar
  5. Brindley GW, Sempels RE. 1977. Preparation and properties of some hydroxy-aluminium beidellites. Clay Miner 12: 229–237.CrossRefGoogle Scholar
  6. Fu G, Nazar LF, Bain AD. 1991. Aging process of alumina sol-gels: Characterization of new alumina polyoxocations by 27A1 NMR spectroscopy. Chem Mater 3:602–610.CrossRefGoogle Scholar
  7. Gonzalez F, Pesquera C, Benito I, Mendioroz S, Poncelet G. 1992. High conversion and selectivity for cracking of n-heptane on cerium-aluminium montmorillonite catalysts. J Chem Soc: Chem Commun:491–493.Google Scholar
  8. Johansson G. 1960. On the structure of some basic aluminum salts. Acta Chem Scand 14:771–773.CrossRefGoogle Scholar
  9. Kloprogge JT. 1992. Pillared clays. Preparation and characterization of clay minerals and aluminum based pillaring agents [dissertation]. Utrecht, The Netherlands: Univ of Utrecht. 349 p.Google Scholar
  10. Kloprogge JT, Booij E, Jansen JBH, Geus JW. 1994. Synthesis of Al-pillared beidellite and its catalytic activity in the hydroconversion of n-heptane. Catalysis Lett 29:293–297.CrossRefGoogle Scholar
  11. Kloprogge JT, Breukelaar J, Geus JW, Jansen JBH. 1994. Characterization of Mg-saponites synthesized from gels containing amounts of Na+, K+, Rb+, Ca2+, Ba2+, or Ce4+ equivalent to the CEC of the saponite. Clays Clay Miner 42:18–22.CrossRefGoogle Scholar
  12. Kloprogge JT, Breukelaar J, Jansen JBH, Geus JW. 1993. Development of ammonium-saponites from gels with variable ammonium concentrations and water content at low temperatures. Clays Clay Miner 41:103–110.CrossRefGoogle Scholar
  13. Kloprogge JT, Geus JW, Jansen JBH, Seykens D. 1992. Thermal stability of basic aluminum sulfate. Thermochim Acta 209:265–276.CrossRefGoogle Scholar
  14. Kloprogge JT, Seykens D, Geus JW, Jansen JBH. 1993. The effects of concentration and hydrolysis on the oligomerization and polymerization of Al(III) as evident from the 27Al NMR chemical shifts and linewidths. J Non-Cryst Solids 160:144–151.CrossRefGoogle Scholar
  15. Kloprogge JT, Seykens D, Jansen JBH, Geus JW. 1992. A 27Al nuclear magnetic resonance study on the opfimalization of the Al13 polymer. J Non-Cryst Solids 142:94–102.CrossRefGoogle Scholar
  16. Kunwar AC, Thompson AR, Gutowski HS, Oldfield E. 1984. Solid state aluminum-27 NMR studies of tridecameric Al-oxo-hydroxy clusters in basic aluminum selenate, sulfate and the mineral Zunyite. J Magn Reson 60:467–472.Google Scholar
  17. Lahav N, Shani U, Shabtai J. 1978. Cross-linked smectites. I: Preparation and properties of some hydroxy-aluminum montmorillonite. Clays Clay Miner 26:107–115.CrossRefGoogle Scholar
  18. Lussier RJ, Magee JS, Vaughan DEW. 1980. Pillared interlayered clay catalysts preparation and properties. In: Wanke SE, Chakrabarty SK, editors. 7th Canadian symposium on catalysis. Preprint. Edmonton: Alberta, Canada, p 88.Google Scholar
  19. McCauley JR, inventor; Katalistiks International, assignee. 1988 Mar 4. Stable intercalated clays and preparation method. International patent PCT/US88/00567. 127 p.Google Scholar
  20. Mendioroz S., González F, Pesquera C, Benito I, Blanco C, Poncelet G. 1993. Preparation of thermalstable pillared clays. In: Guczi L et al., editors. New frontiers in catalysis. Proceedings of the 10th International Congress on Catalysis; Budapest, Hungary. Amsterdam: Elsevier Science, p. 1637–1640.CrossRefGoogle Scholar
  21. Occelli ML. 1986. New routes to the preparation of pillared montmorillonite catalysts. J Mol Catal 35:377–395.CrossRefGoogle Scholar
  22. Occelli ML, Landau SD, Pinnavaia TJ. 1984. Cracking selectivity of a delaminated clay catalyst. J Catal 90:256–260.CrossRefGoogle Scholar
  23. Occelli ML, Lester JE. 1985. Nature of active sites and coking reactions in a pillared clay mineral. Eng Chem Prod Res Dev 24:27–32.CrossRefGoogle Scholar
  24. Occelli ML, Lynch JL, Senders MV. 1987. TEM analysis of pillared and delaminated hectorite catalysts. J Catal 107: 557–565.CrossRefGoogle Scholar
  25. Occelli ML, Tindwa RM. 1983. Physicochemical properties of montmorillonite interlayered with cationic-oxyaluminum pillars. Clays Clay Miner 31:22–28.CrossRefGoogle Scholar
  26. Rausch WV, Bale HD. 1964. Small Angle X-ray Scattering from aluminum nitrate solutions. J Phys Chem 40:3391–3394.CrossRefGoogle Scholar
  27. Schönherr S, Görz H, Bertram R, Müller D, Gessner W 1983. Vergleichende Untersuchungen an unterschiedlich dargestellten basischen Aluminiumchlorid-lösungen. Z Anorg Allg Chem 502:113–122.CrossRefGoogle Scholar
  28. Schutz A, Stone WEE, Poncelet G, Fripiat JJ. 1987. Preparation and characterization of bidimensional zeolitic structures obtained from synthetic beidellite and hydroxy-aluminum solutions. Clays Clay Miner 35:251–261.CrossRefGoogle Scholar
  29. Sterte J. 1991a. Preparation and properties of large pore RE/Al-pillared montmorillonite. A comparison of RE-cations. In: Ponceler G, Jacobs PA, Grange P, Delmon B, editors. Preparation of catalysts V. Amsterdam, The Netherlands: Elsevier Science, p 301–310.Google Scholar
  30. Sterte J. 1991b. Preparation and properties of large pore La-Al-pillared montmorillonite. Clays Clay Miner 39:167–173.CrossRefGoogle Scholar
  31. Tokarz M, Shabtai J. 1985. Cross-linked smectites IV: Preparation and properties of hydroxyaluminum-pillared Ceand La-montmorillonites and fluorinated NH4+-montmorillonites. Clays Clay Miner 33:89–98.CrossRefGoogle Scholar
  32. Trillo JM, Alba MD, Alvero R, Castro MA, Muñoz A, Poyato J, Tobías MM, Lagaly G. 1993. Montmorillonite intercalated with Al(III), La(III) and alumina pillars: structural aspects and reactivity. Solid State Ionics 63–65:457–463.Google Scholar
  33. Tsai PR. Hsu PH. 1985. Aging of partially hydrolyzed aluminum solutions of sodium hydroxide/aluminum ratio = 2. 2. Soil Sci Soc Am J 49:1060–1065.CrossRefGoogle Scholar
  34. Turner RC. 1976. Effects of aging on properties of polynuclear hydroxy aluminum cations. Can J Chem 54:1528–1534.CrossRefGoogle Scholar
  35. Vaughan DEW. 1988. Pillared clays—a historical perspective. Catal Today 2:187–198.CrossRefGoogle Scholar
  36. Vaughan DEW, Lussier RJ, Magee JS, inventors. 1979 Nov 27. Pillared interlayer clay materials useful as catalysts and sorbents. US patent 4,176,090.Google Scholar
  37. Vaughan DEW, Magee JS. 1980. Preparation of molecular sieves based on pillared interlayer clays (PILC). In: Rees LVC, editor. Proceedings of the 5th International Conference on Zeolites; Naples, Italy. London: Heyden Pr. p 94–101.Google Scholar
  38. Vogels JMJ, Breukelaar J, Kloprogge JT, Jansen JBH, Geus JW. 1997. Hydrothermal crystallization of ammonium- saponite at 200 °C and autogeneous water pressure. Clays Clay Miner: In press.Google Scholar
  39. Wang W, Hsu PH. 1994. The nature of polynuclear OH-Al complexes in laboratory-hydrolyzed and commercial hydroxyaluminum solutions. Clays Clay Miner 42:356–368.CrossRefGoogle Scholar
  40. Yamanaka S, Brindley GW. 1979. High surface area solids obtained by reaction of montmorillonite with zirconyl chloride. Clays Clay Miner 27:119–124.CrossRefGoogle Scholar

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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