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

Published online by Cambridge University Press:  28 February 2024

Ernst Booij ,
J. Theo Kloprogge  and
J. A. Rob Van Veen
Ernst Booij
Affiliation:
Faculty of Earth Sciences, Free University of Amsterdam, De Boelelaan 1085, 1081 HV, Amsterdam, The Netherlands
J. Theo Kloprogge
Affiliation:
Hoevenbos 299, 2716 PZ Zoetermeer, The Netherlands
J. A. Rob Van Veen*
Affiliation:
Koninklijke/Shell Laboratorium Amsterdam, Badhuisweg 3, PO Box 3003, 1003 AA Amsterdam, The Netherlands
*
†Present address: SRTCA, PO Box 38000, 1030 BN Amsterdam, The Netherlands.
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Abstract

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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).

Keywords

Al13BentoniteHydroconversionHydrocrackingLaponiteMontmorillonitePillared ClaysREESaponite
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 6 , December 1996 , pp. 774 - 782
Copyright
Copyright © 1996, The Clay Minerals Society

References

Akitt, J.W., Greenwood, N.N., Khandelwahl, B.L. and Lester, G.D.. 1972. 27Al NMR studies of the hydrolysis and polymerization of the hexa-aquo-aluminum cation. J Chem Soc Dalton Trans: 604–610.CrossRefGoogle Scholar
Barrer, R.M. and MacLeod, D.M.. 1955. Activation of montmorillonite by ion exchange and sorption complexes of tetra-alkylammonium montmorillonites. Trans Faraday Soc 51: 1290–1300.CrossRefGoogle Scholar
Bottero, J.Y., Cases, J.M., Fiesinger, F. and Poirier, J.E.. 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
Bottero, J.Y., Tchoubar, D., Cases, J.M. and 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
Brindley, G.W. and Sempels, R.E.. 1977. Preparation and properties of some hydroxy-aluminium beidellites. Clay Miner 12: 229–237.CrossRefGoogle Scholar
Fu, G., Nazar, L.F. and Bain, A.D.. 1991. Aging process of alumina sol-gels: Characterization of new alumina polyoxocations by 27Al NMR spectroscopy. Chem Mater 3: 602–610.CrossRefGoogle Scholar
González, F., Pesquera, C., Benito, I., Mendioroz, S. and Poncelet, G.. 1992. High conversion and selectivity for cracking of n-heptane on cerium-aluminium montmorillonite catalysts. J Chem Soc: Chem Commun: 491–493.CrossRefGoogle Scholar
Johansson, G.. 1960. On the structure of some basic aluminum salts. Acta Chem Scand 14: 771–773.CrossRefGoogle Scholar
Kloprogge, J.T.. 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
Kloprogge, J.T., Booij, E., Jansen, J.B.H. and Geus, J.W.. 1994. Synthesis of Al-pillared beidellite and its catalytic activity in the hydroconversion of n-heptane. Catalysis Lett 29: 293–297.CrossRefGoogle Scholar
Kloprogge, J.T., Breukelaar, J., Geus, J.W. and Jansen, J.B.H.. 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
Kloprogge, J.T., Breukelaar, J., Jansen, J.B.H. and Geus, J.W.. 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
Kloprogge, J.T., Geus, J.W., Jansen, J.B.H. and Seykens, D.. 1992. Thermal stability of basic aluminum sulfate. Thermochim Acta 209: 265–276.CrossRefGoogle Scholar
Kloprogge, J.T., Seykens, D., Geus, J.W. and Jansen, J.B.H.. 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
Kloprogge, J.T., Seykens, D., Jansen, J.B.H. and Geus, J.W.. 1992. A 27Al nuclear magnetic resonance study on the opfimalization of the Al13 polymer. J Non-Cryst Solids 142: 94–102.CrossRefGoogle Scholar
Kunwar, A.C., Thompson, A.R., Gutowski, H.S. and 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
Lahav, N., Shani, U. and Shabtai, J.. 1978. Cross-linked smectites. I: Preparation and properties of some hydroxy-aluminum montmorillonite. Clays Clay Miner 26: 107–115.CrossRefGoogle Scholar
Lussier, R.J., Magee, J.S. and Vaughan, D.E.W.. 1980. Pillared inter-layered clay catalysts preparation and properties. In: Wanke, S.E., Chakrabarty, S.K., editors. 7th Canadian symposium on catalysis. Preprint. Edmonton: Alberta, Canada. p 88.Google Scholar
McCauley, J.R., inventor; Katalistiks International, assignee. 1988 Mar 4. Stable intercalated clays and preparation method. International patent PCT/US88/00567. 127 p.Google Scholar
Mendioroz, S., González, F., Pesquera, C., Benito, I., Blanco, C. and 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
Occelli, M.L.. 1986. New routes to the preparation of pillared montmorillonite catalysts. J Mol Catal 35: 377–395.CrossRefGoogle Scholar
Occelli, M.L., Landau, S.D. and Pinnavaia, T.J.. 1984. Cracking selectivity of a delaminated clay catalyst. J Catal 90: 256–260.CrossRefGoogle Scholar
Occelli, M.L. and Lester, J.E.. 1985. Nature of active sites and coking reactions in a pillared clay mineral. Eng Chem Prod Res Dev 24: 27–32.CrossRefGoogle Scholar
Occelli, M.L., Lynch, J.L. and Senders, M.V.. 1987. TEM analysis of pillared and delaminated hectorite catalysts. J Catal 107: 557–565.CrossRefGoogle Scholar
Occelli, M.L. and Tindwa, R.M.. 1983. Physicochemical properties of montmorillonite interlayered with cationic-oxyaluminum pillars. Clays Clay Miner 31: 22–28.CrossRefGoogle Scholar
Rausch, W.V. and Bale, H.D.. 1964. Small Angle X-ray Scattering from aluminum nitrate solutions. J Phys Chem 40: 3391–3394.CrossRefGoogle Scholar
Schönherr, S., Görz, H., Bertram, R., Müller, D. and Gessner, W. 1983. Vergleichende Untersuchungen an unterschiedlich dargestellten basischen Aluminiumchlorid-lösungen. Z Anorg Allg Chem 502: 113–122.CrossRefGoogle Scholar
Schutz, A., Stone, W.E.E., Poncelet, G. and Fripiat, J.J.. 1987. Preparation and characterization of bidimensional zeolitic structures obtained from synthetic beidellite and hydroxy-aluminum solutions. Clays Clay Miner 35: 251–261.CrossRefGoogle Scholar
Sterte, J.. 1991a. Preparation and properties of large pore RE/Al-pillared montmorillonite. A comparison of RE-cations. In: Ponceler, G., Jacobs, P.A., Grange, P., Delmon, B., editors. Preparation of catalysts V. Amsterdam, The Netherlands: Elsevier Science. p 301–310.Google Scholar
Sterte, J.. 1991b. Preparation and properties of large pore La-Al-pillared montmorillonite. Clays Clay Miner 39: 167–173.CrossRefGoogle Scholar
Tokarz, M. and Shabtai, J.. 1985. Cross-linked smectites IV: Preparation and properties of hydroxyaluminum-pillared Ce-and La-montmorillonites and fluorinated NH4+-montmorillonites. Clays Clay Miner 33: 89–98.CrossRefGoogle Scholar
Trillo, J.M., Alba, M.D., Alvero, R., Castro, M.A., Muñoz, A., Poyato, J., Tobias, M.M. and Lagaly, G.. 1993. Montmorillonite intercalated with Al(III), La(III) and alumina pillars: structural aspects and reactivity. Solid State Ionics 63–65: 457–463.CrossRefGoogle Scholar
Tsai, P.P. and Hsu, P.H.. 1985. Aging of partially hydrolyzed aluminum solutions of sodium hydroxide/aluminum ratio = 2.2. Soil Sci Soc Am J 49: 1060–1065.CrossRefGoogle Scholar
Turner, R.C.. 1976. Effects of aging on properties of polynuclear hydroxy aluminum cations. Can J Chem 54: 1528–1534.CrossRefGoogle Scholar
Vaughan, D.E.W.. 1988. Pillared clays—a historical perspective. Catal Today 2: 187–198.CrossRefGoogle Scholar
Vaughan, D.E.W., Lussier, R.J. and Magee, J.S., inventors. 1979 Nov 27. Pillared interlayer clay materials useful as catalysts and sorbents. US patent 4,176,090.Google Scholar
Vaughan, D.E.W. and Magee, J.S.. 1980. Preparation of molecular sieves based on pillared interlayer clays (PILC). In: Rees, L.V.C., editor. Proceedings of the 5th International Conference on Zeolites; Naples, Italy. London: Heyden Pr. p 94–101.Google Scholar
Vogels, J.M.J., Breukelaar, J., Kloprogge, J.T., Jansen, J.B.H. and Geus, J.W.. 1997. Hydrothermal crystallization of ammonium-saponite at 200 °C and autogeneous water pressure. Clays Clay Miner: In press.CrossRefGoogle Scholar
Wang, W. and Hsu, P.H.. 1994. The nature of polynuclear OH-Al complexes in laboratory-hydrolyzed and commercial hydroxyaluminum solutions. Clays Clay Miner 42: 356–368.CrossRefGoogle Scholar
Yamanaka, S. and Brindley, G.W.. 1979. High surface area solids obtained by reaction of montmorillonite with zirconyl chloride. Clays Clay Miner 27: 119–124.CrossRefGoogle Scholar