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Synthesis of Highly Microporous and Hydrophilic Alumina-Pillared Montmorillonite: Water-Sorption Properties

Published online by Cambridge University Press:  02 April 2024

P. B. Malla  and
S. Komarneni
P. B. Malla
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802
S. Komarneni
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802
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Abstract

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A montmorillonite exchanged with large hydroxy-Al cations was thermally treated to convert the hydroxy cations to oxide pillars and to generate permanent microporosity in the interlayers. The pillared clay products were characterized by X-ray powder diffraction (XRD) and water-sorption measurements to delineate the effect of aging of the pillaring solutions, the methods of drying and concentration of clay-water suspensions, and the temperatures of calcination on micropore volumes. Although samples prepared at different conditions gave d(001) reflections of 17–17.5 Å, at least to 500°C, the concentrations of clay-water suspensions and the temperatures of calcination significantly changed the pore-size distribution and the volume of micropores present in the sample, as calculated from the water-sorption isotherms. A narrow pore-size distribution having little or no macroporosity or external surface condensation was observed in samples prepared by the addition of the pillaring solution directly to the clay (solid) without first making a clay-water suspension and calcining the sample at ≥400°C. About 87% of the total volume was found to be micropores of ≤14–17 Å in the sample calcined at 600°C. Aging the pillaring solution, however, did not influence either the water-sorption isotherms or the XRD patterns significantly under the conditions specified. Essentially the same results were obtained for samples prepared from both hydroxy-Al polymer (OH/Al = 2) and aluminum chlorohydrol (ACH) solutions.

Although alumina-pillared clays exhibited an extreme type-I isotherm (Langmuir type) for nitrogen adsorption, the sorption of water vapor gave an isotherm of unusual shape that fit neither a BET nor a Langmuir equation. This latter behavior has previously been attributed to a unique pore size and hydrophobicity and is apparently common to all pillared montmorillonite materials. The hydrophobicity of the pillared clay apparently developed on calcination by the migration of protons from the interlayers to the octahedral sheets, in which sites of cationic substitution (negative charge) were located. Protons migrated back to the interlayers by treatment with NH3, which subsequently converted to NH4+ in the interlayers. The exchange of the NH4+ by Ca2+ introduced hydrophilicity to the alumina-pillared clay, which was reflected both in the shape of the water isotherm (close to moderate Brunauer type I), the heat of sorption, and the total sorption capacity.

Keywords

HydrophobicityMontmorillonitePillared interlayer complexPorositySurface condensationThermal treatmentX-ray powder diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 38 , Issue 4 , August 1990 , pp. 363 - 372
Copyright
Copyright © 1990, The Clay Minerals Society

Footnotes

1

Also with the Department of Agronomy.

References

Aylmore, L. A. G. and Quirk, J. P., 1967 The micropore size distributions of clay mineral systems J. Soil. Sci. 18 2 – 17.CrossRefGoogle Scholar
Barrer, R. M. and Bratt, G. C., 1959 Non-stoichiometric hydrates—II: Some heats and entropies or water and ammonia in ion-exchanged fujasites J. Phys. Chem. Solids 12 146 – 153.CrossRefGoogle Scholar
Ben Rhaiem, H., Pons, C. H., Tessier, D., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Factors affecting the microstructure of smectites: Role of cation and applied history of stresses Proc. Internat. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 292 – 297.Google Scholar
Brindley, G. W. and Semples, R. E., 1977 Preparation and properties of some hydroxy-aluminum beidellites Clay Miner. 12 229 – 236.CrossRefGoogle Scholar
Brindley, G. W. and Yamanaka, S., 1979 A study of hydroxy-chromium montmorillonites and the form of the hydroxy-chromium polymers Amer. Miner. 64 830 – 835.Google Scholar
Colier, R. K., Cole, T. S. and Lavan, Z., 1986 Advanced desiccation materials assessment—Final report Chicago, Illinois Gas Research Institute.Google Scholar
El-Akkad, T. M., Flex, N. S., Guindy, N. M., El-Massry, S. R. and Nashed, S., 1982 Nitrogen and water vapor adsorption on monovalent and divalent montmorillonite derivatives and their heats of immersion in polar liquids Surface Tech. 17 69 – 77.CrossRefGoogle Scholar
Gregg, S. J. and Sing, K. S. W., 1982 Adsorption, Surface Area and Porosity 2nd ed. New York Academic Press.Google Scholar
Hagymassy, J Jr. and Brunauer, S., 1970 Pore structure analysis by water vapor adsorption. II. Analysis of five silica gels J. Colloid Interface Sci. 33 317 – 327.CrossRefGoogle Scholar
Hagymassy, J Jr. Brunauer, S. and Mikhail, R Sh, 1969 Pore structure analysis by water vapor adsorption. I. t-curves for water vapor J. Colloid Interface Sci. 29 485 – 491.CrossRefGoogle Scholar
Malla, P. B., Yamanaka, S. and Komarneni, S., 1989 Unusual water vapor adsorption behavior of montmorillonite pillared with ceramic oxides Solid State Ionics 32/33 354 – 362.CrossRefGoogle Scholar
Occelli, M. L., 1983 Catalytic cracking with an interlayered clay, a two-dimensional molecular sieve Ind. Eng. Chem. Prod. Res. Dev. 22 553 – 559.CrossRefGoogle Scholar
Occelli, M. L., 1986 New routes to the preparation of pillared montmorillonites catalysts J. Molecular Catalysis 35 377 – 389.CrossRefGoogle Scholar
Occelli, M. L., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Surface and catalytic properties of some pillared clays Proc. Int. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 319 – 323.Google Scholar
Occelli, M. L. and Innes, R. A., 1985 Sorption and catalysis on sodium-montmorillonite interlayered with aluminum oxide clusters Appl. Catal. 14 69 – 82.CrossRefGoogle Scholar
Occelli, M. L., Parulekar, V. N. and Hightower, J. W., 1984 Sorption of normal paraffins in a pillared clay minerals Proc. 8th Int. Cong, on Catalysis, Berlin, 1984, Part IV Weinheim, Federal Republic of Germany G. Ertl, chrm., Verlag Chemie 725 – 733.Google Scholar
Pinnavaia, T. J., Tzou, M. and Landau, S. D., 1985 New chromia pillared clay catalysts J. Amer. Chem. Soc. 107 4783 – 4785.CrossRefGoogle Scholar
Pinnavaia, T. J., Tzou, M., Landau, S. D. and Raythatha, H., 1984 On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum J. Mol. Catal. 27 195 – 212.CrossRefGoogle Scholar
Stacey, M. H., 1988 Alumina-pillared clays and their adsorptive properties Catal. Today 2 621 – 631.CrossRefGoogle Scholar
Sterte, J., 1986 Synthesis and properties of titanium oxide cross-linked montmorillonite Clays & Clay Miner. 35 658 – 664.CrossRefGoogle Scholar
Tennakoon, D. T. B. Jones, W. and Thomas, J. M., 1987 Characterization of clay and pillared clay catalysts Solid State Ionics 24 205 – 212.CrossRefGoogle Scholar
Tennakoon, D. T. B. Jones, W. and Thomas, J. M., 1986 Structural aspects of metal-oxide-pillared sheet silicates J. Chem. Soc., Faraday Trans. 1 82 3081 – 3095.CrossRefGoogle Scholar
Tessier, D., 1984 Etude experimentale de l’organisation des matriaux argileu Paris Docteur es Sciences, Thesis, Institut Nationale de Recherches Agronomique.Google 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 Rees, LVC, 1980 Preparation of molecular sieves based on pillared interlayered clays (PILC) Proc. 5th Internat. Conf. Zeolites, Naples, 1980 London Heyden 94 – 101.Google Scholar
Vaughan, D. E. W., Lussier, R. J. and Magee, J. S. (1981) Pillared interlayered clay products: U.S. Patent 4, 271, 043, 6 pp.Google Scholar
Yamanaka, S. and Brindley, G. W., 1979 High surface area solids obtained by reaction of montmorillonite with zirconyl chloride Clays & Clay Minerals 27 119 – 124.CrossRefGoogle Scholar
Yamanaka, S. and Hattori, M., 1988 Iron oxide pillared clay Catalysis Today 2 261 – 270.CrossRefGoogle Scholar
Yamanaka, S., Malla, P. B. and Komarneni, S., 1990 Water adsorption properties of alumina pillared clay J. Colloid Interface Sci. 134 51 – 58.CrossRefGoogle Scholar
Yamanaka, S., Numata, K., Hattori, M., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Hydroxy-copper interlayering in montmorillonite by the titration method Proc. Int. Clay Conf, Denver, 1985 Bloomington, Indiana The Clay Minerals Society 273 – 276.Google Scholar
Yamanaka, S., Nishihara, T. and Hattori, M., 1987 Preparation and properties of titania pillared clays Materials Chemistry Physics 17 87 – 101.CrossRefGoogle Scholar
Yamanaka, S., Nishihara, T. and Hattori, M., 1988 Adsorption and acidic properties of clays pillared with oxide sols Microstructure and Properties of Catalysts, Proc. Materials Research Society, Boston, Massachusetts, 1987 111 283 – 288.Google Scholar