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The Al Pillaring of Clays. Part I. Pillaring with Dilute and Concentrated Al Solutions

Published online by Cambridge University Press:  28 February 2024

Robert A. Schoonheydt
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
J. van den Eynde
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
H. Tubbax
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
H. Leeman
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
M. Stuyckens
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
I. Lenotte
Affiliation:
Centrum voor Oppervlaktechemie en Katalyse, Materials Research Center, K. U. Leuven, K. Mercierlaan, 92, 3001 Heverlee, Belgium
W. E. E. Stone
Affiliation:
Section Physico-Chimie Minérale (MRAC), UCL, Place Croix du Sud, 2 Boite 18, 1348 Louvain-La-Neuve, Belgium

Abstract

Saponite, hectorite, and laponite have been pillared with cationic Al clusters, and special attention has been given to the solution chemistry or Al. Pillared saponite is obtained after exchange with refluxed Al solutions; while for hectorite, Al solutions treated with ammonium acetate give a pillared product with 1.8–1.9 nm spacing and thermal stability up to 873 K. In both types of solutions, the Keggin ion Al cluster is a minority species or totally absent. The typical 1.8–1.9 nm spacing is only obtained after washing. The quality of the pillared material can be judged from its thermal stability, its surface area, and the width of the d001 line before and after pillaring. The width should not exceed 0.3 nm before calcination and 0.5 nm after calcination. The latter criterion reflects the importance of the crystallinity of the parent clay for successful pillaring. Pillaring in concentrated conditions occurs by a combination of ion exchange and precipitation of Al and gives materials that exhibit poor thermal stability.

Type
Research Article
Copyright
Copyright © 1993, The Clay Minerals Society

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References

Akitt, J. W., and Elders, J. M., (1988) Multinuclear magnetic resonance studies of the hydrolysis of aluminium (III). Part 8. Base hydrolysis monitored at very high magnetic field: J. Chem. Soc. Dalton Trans., 13471355.Google Scholar
Akitt, J. W., Greenwood, N. N., Khandelwal, B. L., and Lester, G. D., (1972) 27Al nuclear magnetic resonance studies of the hydrolysis and polymerisation of the hexa-aquo-al-uminium (III) cation: J. Chem. Soc. Dalton, 604610.CrossRefGoogle Scholar
Akitt, J. W., and Milic, N. B., (1984) Aluminium-27 nuclear magnetic resonance studies of the hydrolysis of alumini-um(III). Part 6. Hydrolysis with sodium acetate: J. Chem. Soc. Dalton, 981984.Google Scholar
Bottero, J. Y., Axelos, M., Tchoubar, D., Cases, J. M., Fripiat, J. J. and Fiessinger, F., 1987 Mechanism of formation of aluminium hydroxide from Keggin Al13 polymers J. Colloid Interface Sci. 117 4757 10.1016/0021-9797(87)90166-4.CrossRefGoogle Scholar
Bottero, J. Y., Tchoubar, D., Cases, J. M. and Fiessinger, F., 1982 Investigation of the hydrolysis of aqueous solutions of aluminium chloride. 2. Nature and structure by small-angle X-ray scattering J. Phys. Chem. 86 36673673 10.1021/j100215a034.CrossRefGoogle Scholar
Chariot, G., 1957 L’Analyse Qualitative et les Réactions en Solution Paris Masson.Google Scholar
Chevalier, S., Franck, R., Lambert, J. F., Barthomeuf, D. and Suquet, H., 1992 Stability of Al-pillared saponites: Evidence for disorganization during storage in air Clay Miner. 27 245248 10.1180/claymin.1992.027.2.08.CrossRefGoogle Scholar
Figueras, F., 1988 Pillared clays as catalysts Catal. Rev. Sci. Eng. 30 457 199 10.1080/01614948808080811.CrossRefGoogle Scholar
Figueras, F., Klapyta, Z., Auroux, A. and Gueguen, C., 1990a Influence of the structure of the original clay on the properties of pillared clay materials Sci. Geol. Mem. 86 2532.Google Scholar
Figueras, F., Klapyta, Z., Massiani, P., Mountassir, Z., Tichit, D., Fajula, F., Gueguen, C., Bousquet, J. and Auroux, A., 1990b Use of competitive ion exchange for intercalation of montmorillonite with hydroxy-aluminium species Clays & Clay Minerals 38 257264 10.1346/CCMN.1990.0380304.CrossRefGoogle Scholar
Furrer, G., Ludwig, C. and Schindler, P. W., 1992 On the chemistry of the Keggin All3 polymer J. Colloid Interface Sci. 149 5667 10.1016/0021-9797(92)90391-X.CrossRefGoogle Scholar
Hem, J. D., and Robertson, C. E., (1967) Forms and stability of aluminium hydroxide complexes in dilute solution: U.S. Geological Survey Water-Supply Paper 1827-A, A1-A55.Google Scholar
Maes, A., Peigneur, P., Cremers, A. and Bailey, S. W., 1975 Thermodynamics of transitions metal ion exchange in montmorillonite Proc. Int. Clay Conf. 1975 Wilmette Applied Publishing 319329.Google Scholar
Mitchell, I. V., 1990 Pillared Layered Structures London Elsevier Applied Science.Google Scholar
Occelli, M. L., Landau, S. L. and Pinnavaia, T. J., 1987 Physicochemical properties of delaminated clay cracking catalyst J. Catal. 104 331338 10.1016/0021-9517(87)90365-4.CrossRefGoogle Scholar
Pinnavaia, T. J., Landau, S. D., Tzou, M. S. and Johnson, I. D., 1985 Layer cross-linking in pillared clays J. Am. Chem. Soc. 107 72227224 10.1021/ja00310a102.CrossRefGoogle Scholar
Pinnavaia, T. J., Tzou, M. S., Landau, S. D. and Raythatha, R. H., 1984 On the pillaring and delamination of smectite clay catalyst by polyoxo cations of aluminium J. Mol. Catal. 27 195212 10.1016/0304-5102(84)85080-4.CrossRefGoogle Scholar
Plee, D., Borg, F., Gatineau, L. and Fripiat, J. J., 1985 High resolution solid-state 27 Al and 29Si nuclear magnetic resonance study of pillared clays J. Am. Chem. Soc. 107 23622369 10.1021/ja00294a028.CrossRefGoogle Scholar
Plee, D., Gatineau, L. and Fripiat, J. J., 1987 Pillaring processes of smectites with and without tetrahedral substitution Clays & Clay Minerals 35 8188 10.1346/CCMN.1987.0350201.CrossRefGoogle Scholar
Schönherr, S., Görz, H., Müller, D. and Gessner, W., 1981 Uber basische Aluminiumsalze und ihre Losungen. VI. Darstellung und Charactersierung eines wasserlöslichen Al13O40-chlorides Z. Anorg. Aug. Chem. 476 188194 10.1002/zaac.19814760522.CrossRefGoogle Scholar
Schoonheydt, R. A. and Leeman, H., 1992 Pillaring of saponite in concentrated medium Clay Miner. 27 249252 10.1180/claymin.1992.027.2.09.CrossRefGoogle Scholar
Schutz, A., Stone, W E E Poncelet, G. and Fripiat, J. J., 1987 Preparation and characterisation of bidimensional zeolite structures obtained from synthetic beidellite and hydroxyl-aluminium solutions Clays & Clay Minerals 35 251268 10.1346/CCMN.1987.0350402.CrossRefGoogle Scholar
Sterte, J. P., 1988 Hydrothermal treatment of hydroxycat-ion precursor solutions Catal. Today 2 219231 10.1016/0920-5861(88)85005-3.CrossRefGoogle Scholar
Sterte, J. P., Otterstedt, J. E., Delmon, B., Grange, P., Jacobs, P. A. and Poncelet, G., 1987 Aluminium-oxide-pillared montmorillonite: Effect of hydrothermal treatment of pillaring solution on the product structure Preparation of Catalysts IV Amsterdam Elsevier 631646.Google Scholar
Thompson, A. R., Kunwas, A. C., Gutawsky, H. S., and Old-field, E., (1987) Oxygen-17 and aluminium—27 nuclear magnetic resonance spectroscopic investigations of aluminium (III) hydrolysis products: J. Chem. Soc. Dalton Trans., 23172319.CrossRefGoogle Scholar
Urabe, K., Sakurai, H., and Izumi, Y., (1988) On efficiency determining factors in pillared clay catalysts: in Proc. 9th Intern. Cong. Catalysis 1988, Phillips, M. J., and Ternan, M., eds., The Chemical Institute of Canada, 18651885.Google Scholar
Van Olphen, H. and Fripiat, J. J., 1979 Data Handbook for Clay Minerals and Other Non-metallic Minerals London Per-gamon Press.Google Scholar
Vaughan, D E W Lussier, R. J. and Rees, L. V., 1980 Preparation of molecular sieves based on pillared interlayered clays (PILC) Proc. Fifth Int. Conf. on Zeolites 1980 London Heyden 94101.Google Scholar