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Cross-Linked Smectites. V. Synthesis and Properties of Hydroxy-Silicoaluminum Montmorillonites and Fluorhectorites

Published online by Cambridge University Press:  02 April 2024

Johan Sterte  and
Joseph Shabtai
Johan Sterte*
Affiliation:
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112
Joseph Shabtai*
Affiliation:
Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112
*
1Research associate on leave from Chalmers University of Technology, Gothenburg, Sweden.
2To whom correspondence should be addressed.
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Abstract

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Solutions containing hydroxy-SiAl (HSA) oligocations were prepared by two procedures: (1) treatment of a mixture of orthosilicic acid and AlCl3 with aqueous NaOH, followed by aging of the product; and (2) preliminary preparation and aging of hydroxy-Al13 oligocations followed by reaction of the latter with orthosilicic acid. Ion exchange of Na,Ca-montmorillonite with HSA oligocations yielded pillared, cross-linked montmorillonites (designated as HSA-CLM) showing a maximum d(001) value of 19.5 Å for air-dried samples, and maximum surface areas of ~500 m2/g after outgassing at 250°C/10−3 torr. Corresponding ion exchange of Li-fluorhectorite yielded HSA fluorhectorites (HSA-CLFH) showing a maximum d(001) value of 19.0 Å and a surface area of 355 m2/g. Calculated structural formulae for the HSA-CLM and HSA-CLFH products, based on elemental analysis, showed a gradual increase in the Si/Al ratio in the intercalated HSA oligocations with increasing Si/Al ratio in the pillaring solution. Optimum d(001) values and surface areas of HSA-CLM and HSA-CLFH products were obtained using method 2 and applying a ratio of 1.6–2.5 mmole (Si)Al/g smectite.

The thermal stabilities of HSA-CLM and HSA-CLFH products were determined by heat treatment between 250° and 700°C and subsequent measurement of the d(001) values and surface areas. HSA-CLFH products showed the unusual behavior of increase of d(001) with increase in temperature from 400° to 500°C, and essential constancy of d(001) from 500° to 600°C. The HSA-CLM products showed a gradual decrease in surface area, whereas the HSA-CLFH products prepared with a Si/Al ratio of 1.04–2.18 in the pillaring solution showed constant surface areas with increasing temperature from 250° to 600°C. HSA-CLM and HSA-CLFH show sharply higher acidities compared with those of reference Al-CLM and Al-CLFH samples obtained by pillaring with hydroxy-Al13 oligocations. This increased acidity is probably due to the presence of acidic, surface silanol groups in the HSA oligocations.

Keywords

Cross-linked smectiteFluorhectoriteHydroxy-SiAl oligocationsPillared montmorilloniteThermal stability
Type
Research Article
Information
Clays and Clay Minerals , Volume 35 , Issue 6 , December 1987 , pp. 429 - 439
Copyright
Copyright © 1987, The Clay Minerals Society

References

Atkins, M. P. and Ashton, A. G. (1985) Novel pillared interlayered clays, processes for their production and uses thereof: European Patent Appl. 85300040.4, Aug. 7, 1985, 20 pp.Google Scholar
Barrer, R. M. and Jones, D. L., 1970 Chemistry of soil minerals. Part VIII. Synthesis and properties of fluorhectorites J. Chem. Soc. (A) 1531 – 1537.CrossRefGoogle Scholar
Bottero, J. V., Cases, J. M., Fiessinger, F. and Poirier, J. E., 1980 Studies of hydrolyzed aluminum chloride solutions. 1. Nature of aluminum species and composition of aqueous solutions J. Phys. Chem. 84 2933 – 2939.CrossRefGoogle Scholar
Edelman, C. H. and Favejee, J. C. L., 1940 On the crystal structure of montmorillonite and halloysite Acta Crystallogr. 102 417 – 431.Google Scholar
Endo, T., Mortland, M. M. and Pinnavaia, T. J., 1980 Intercalation of silica in smectite Clays & Clay Minerals 28 105 – 110.CrossRefGoogle Scholar
Grim, R. E., 1968 Clay Mineralogy New York McGraw-Hill 278 – 352.Google Scholar
Gunnarsson, L. and Nilsson, R., 1983 Polyaluminumsulfat-ett redskap for pappersmakaren Cellulosa 2 22 – 25.Google Scholar
Hodges, S. C. and Zelazny, L. W., 1983 Interactions of dilute, hydrolyzed aluminum solutions with clays, peat and resin Soil Sci. Soc. Amer. J. 47 206 – 212.CrossRefGoogle Scholar
Holy, N. L. and Pignolet, L. H., 1983 Polymer-bound phosphine catalysts Homogeneous Catalysis with Phosphine Complexes New York Plenum Press 447 – 448.Google Scholar
Johansson, G., 1960 On the crystal structures of some basic aluminum salts Acta Chem. Scan. 14 771 – 773.CrossRefGoogle Scholar
Lahav, N., Shani, U. and Shabtai, J., 1978 Cross-linked smectites. I. Synthesis and properties of hydroxy-aluminum montmorillonite Clays & Clav Minerals 26 107 – 115.CrossRefGoogle Scholar
Lewis, R. M., Ott, K. C and Van Samen, R. A. (1985) Silica-clay complexes: U.S. Patent 4,510,257, Apr. 9, 1985, 10 pp.Google Scholar
Luciuk, G. M. and Huang, P. M., 1974 Effect of monosilicic acid on hydrolytic reactions of aluminum Soil Sci. Soc. Amer. Proc. 38 235 – 244.CrossRefGoogle Scholar
Occelli, M. L., 1986 New routes to the preparation of pillared montmorillonite catalysts J. Mol. Catal. 35 377 – 389.CrossRefGoogle Scholar
Pinnavaia, T. J., 1983 Intercalated clay catalysts Science 220 365 – 371.CrossRefGoogle ScholarPubMed
Pinnavaia, T. J., Landau, S. D., Tsou, M. S. and Johnson, I. D., 1985 Layer cross-linking in pillared clays J. Amer. Chem. Soc. 107 7222 – 7224.CrossRefGoogle Scholar
Pinnavaia, T. J., Mortland, M. M. and Endo, T. (1983) Silica-clay complexes: U.S. Patent 4,367,163, Jan 4, 1983, 9 pp.Google Scholar
Pinnavaia, T. J., Raythatha, R., Guo-Shuh Lee, R., Halloran, L. J. and Hoffman, J. F., 1979 Intercalation of catalytically active metal complexes in mica-type structures. Rhodium hydrogenation catalysts J. Amer. Chem. Soc. 101 6891 – 6897.CrossRefGoogle Scholar
Pinnavaia, T. J., Tsou, M. S. and Landau, S. D., 1985 New chromia-pillared clay catalysts J. Amer. Chem. Soc. 107 4783 – 4785.CrossRefGoogle Scholar
Pinnavaia, T. J., Tsou, M. S., Landau, S. D. and Raythatha, R. H., 1984 On the pillaring and delamination of smectite clay catalysts by polyoxocations of aluminum J. Mol. Catal. 27 195 – 212.CrossRefGoogle Scholar
Plee, D., Borg, F., Gatineau, L. and Fripiat, J. J., 1985 High-resolution solid-state 27A1 and 29Si nuclear magnetic resonance study of pillared clays J. Amer. Chem. Soc. 107 2362 – 2369.CrossRefGoogle Scholar
Shabtai, J., 1979 Zeolites and cross-linked silicates as media for selective catalysis Chim. Ind. 61 734 – 741.Google Scholar
Shabtai, J. and Fijal, J. (1986) A novel class of hydropro-cessing catalysts and preparation methods: U.S. Patent 4,579,832, Apr. 1, 1986, 12 pp.Google Scholar
Shabtai, J. and Lahav, N. (1980) Cross-linked montmorillonite molecular sieves: U.S. Patent 4,216,188, 6 pp.Google Scholar
Shabtai, J., Massoth, F. E., Tokarz, M., Tsai, G. M. and McCauley, J., 1984 Characterization and molecular shape selectivity of cross-linked montmorillonite (CLM) catalysts Proc. 8th Internat. Congress Catal., Berlin, 1984, Vol. IV Weinheim Verlag-Chemie 735 – 745.Google Scholar
Shabtai, J., Rosell, M. and Tokarz, M., 1984 Cross-linked smectites. III. Synthesis and properties of hydroxy-aluminum hectorites and fluorhectorites Clays & Clay Minerals 32 99 – 107.CrossRefGoogle Scholar
Sterte, J., 1986 Synthesis and properties of titanium oxide cross-linked montmorillonite Clays & Clay Minerals 34 658 – 664.CrossRefGoogle Scholar
Tokarz, M. and Shabtai, J., 1985 Cross-linked smectites. IV. Preparation and properties of hydroxyaluminum-pil-lared Ce- and La-montmorillonites and fluorinated NH4 +-montmorillonites Clays & Clay Minerals 33 89 – 98.CrossRefGoogle Scholar
Turner, R. C. and Ross, G. J., 1969 Conditions in solution during the formation of gibbsite in dilute aluminum salt solutions. III. Hydroxyaluminum products of reactions during the neutralization of aluminum chloride solutions with sodium hydroxide Can. J. Soil Sci. 49 389 – 396.CrossRefGoogle Scholar
Vaughan, D. E. W. Lussier, R. J. and Rees, L. V. C., 1980 Preparation of molecular sieves based on pillared interlayered clays (PILC) Proc. 5th Internat. Conf. Zeolites, Naples, 1980 London Heyden 94 – 101.Google Scholar
Wada, S. I. and Wada, K., 1980 Formation, composition and structure of hydroxy-aluminosilicate ions J. Soil Science 31 457 – 467.CrossRefGoogle Scholar
Ward, J. H. and Rabo, J. A., 1976 Infrared studies of zeolite surfaces and surface relations Zeolite Chemistry and Catalysis 118 – 284.Google Scholar
Yamanaka, S., Doi, T., Sako, S. and Hattori, M., 1984 High surface area solids obtained by intercalation of iron oxide pillars in montmorillonite Mat. Res. Bull. 19 161 – 168.CrossRefGoogle Scholar