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Influence of exchange cation and layer charge on the isomerization of α-pinene over SWy-2, SAz-1 and Sap-Ca

Published online by Cambridge University Press:  09 July 2018

C. Breen*
Affiliation:
Materials Research Institute, Sheffield Hallam University, Sheffield S1 1WB, UK
A. J. Moronta
Affiliation:
Materials Research Institute, Sheffield Hallam University, Sheffield S1 1WB, UK
*

Abstract

SWy-2 (Wyoming), Sap-Ca saponite (California) and SAz-1 (Cheto, Arizona) were exchanged with different cations (Al, Ni, Mg, Ca and Na). The catalytic activity of these ionexchanged clays was measured directly using the isomerization of α-pinene at 80°C for 2 h to yield camphene, limonene and other minor products. The order of activity for the different cationexchanged forms was Al > Ni > Mg > Ca > Na, which correlated well with the known polarizing power of these cations and the resulting interlayer acidity. Catalysts derived from Sap-Ca were the most active followed by SWy-2, with SAz-1 the least active by a considerable margin. The greater activity of Sap-Ca over SWy-2 was attributed to the high tetrahedral charge in the former. Reduction of the layer charge of SAz-1 using Li fixation caused a significant improvement in the catalytic activity of the Al-exchanged reduced-charge SAz-1.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2001

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Footnotes

Current address: Centro de Superficies y Catálisis, Facultad de Ingeniería, Universidad del Zulia, P.O. Box 15251, Maracaibo 4003A, Venezuela

References

Ballantine, J.A., Davies, M., O'Neil, R.M., Patel, I., Purnell, H., Rayankorn, M. & Williams, K.J. (1984) Organic reactions catalysed by sheet silicates: Ester production by the direct addition of carboxylic acids to alkenes. J. Mol. Catal. 26, 5777.CrossRefGoogle Scholar
Boyd, S.A. & Jaynes, W.F. (1994) Role of the layer charge in organic contaminant sorption by organoclays. Pp. 4877 in. Layer Charge Characteristics of 2:2 Silicate Clay Minerals (Mermut, A.R., editor). CMS Workshop Lectures, 6. Clay Minerals Society, Boulder, CO, USA.Google Scholar
Breen, C. & Moronta, A.J. (1999) Influence of layer charge on the catalytic activity of mildly acidactivated tetramethylammonium-exchanged bentonites. J. Phys. Chem. B, 103, 56755680.CrossRefGoogle Scholar
Breen, C. & Moronta, A.J. (2000) Characterisation and catalytic activity of aluminum- and aluminum/ tetramethylammonium-exchang ed bentonites. J. Phys. Chem. B, 104, 27022708.Google Scholar
Breen, C. & Watson, R. (1998) Acid-activated organoclays: preparation, characterisation and catalytic activity of polycation-treated bentonites. Appl. Clay Sci. 12, 479494.Google Scholar
Breen, C., Watson, R., Madejová, J., Komadel, P. & Klapyta, Z. (1997) Acid-activated organoclays: Preparation, characterisation and catalytic activity of acid-treated tetramethylammonium-exchan ged smectites. Langmuir, 13, 64736479.Google Scholar
Brown, D.R. & Rhodes, C.N. (1997) Br€ nsted and Lewis acid catalysis with ion-exchanged clays. Catal. Lett. 45, 3540.Google Scholar
Chiche, B., Finiels, A., Gauthier, C. Geneste, P., Graille, J. & Pioch, D. (1987) Acylation over cation-exchanged montmorillonite. J. Mol. Catal. 42, 229235.Google Scholar
Clementz, D.M. & Mortland, M.M. (1974) Properties of reduced charge montmorillonite: Tetra-alkylammonium ion exchange forms. Clays Clay Miner. 22, 223229.Google Scholar
De Stefanis, A., Perez, G., Ursini, O. & Tomlinson, A.A.G. (1995) PLS versus zeolites as sorbents and catalysts. II. Terpene conversions in alumina-pillared clays and phosphates and medium pore zeolites. Appl. Catal. 132, 353365.Google Scholar
Gregory, R., Smith, D.J.H. & Westlake, D.J. (1983) The production of ethyl acetate from ethylene and acetic acid using clay catalysts. Clay Miner. 18, 431435.Google Scholar
Janek, M. & Komadel, P. (1993) Autotransformation of H-smectites in aqueous solution. The effect of octahedral iron content. Geol. Carpath. Ser. Clays, 44, 5964.Google Scholar
Jaynes, W.F. & Bigham, J.M. (1987) Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites. Clays Clay Miner. 35, 440448.CrossRefGoogle Scholar
Kaviratna, H. & Pinnavaia, T.J. (1994) Acid hydrolysis of octahedral Mg2+ sites in 2:1 layered silicates: An assessment of edge attack and gallery access mechanisms. Clays Clay Miner. 42, 717723.Google Scholar
Kukkadapu, R.K. & Boyd, S.A. (1995) Tetramethylphosphonium- and tetramethylammonium-smectites as adsorbents of aromatic and chlorinated hydrocarbons: Effect of water on adsorption efficiency. Clays Clay Miner. 43, 318323.Google Scholar
Lee, J.F., Mortland, M.M. & Boyd, S.A. (1989) Shapeselective adsorption of aromatic molecules from water by tetramethylammonium-smectit. . J. Chem. Soc. Faraday Trans. 85, 29532962.Google Scholar
Mendioroz, S. & Pajares, J.A. (1987) Texture evolution of montmorillonite under progressive acid treatment: Change from H3 to H2 type of hysteresis. Langmuir, 3, 676681.Google Scholar
Mokaya, R. & Jones, W. (1995) Pillared clays and pillared acid-activated clays: A comparative study of physical, acidity, and catalytic properties. J. Catal. 153, 7685.CrossRefGoogle Scholar
Mortland, M.M. & Raman, K.V. (1968) Surface acidity of smectites in relation to hydration, exchangeable cation and structure. Clays Clay Miner. 16, 393398.Google Scholar
Novak, I. & Čičel, B. (1978) Dissolution of smectites in hydrochloric acid: II. Dissolution rate as a function of crystallochemical decomposition. Clays Clay Miner. 26, 341344.Google Scholar
Nzengung, V.A., Voudrias, E.A., Nkedi-Kizza, P., Wampler, J.M. & Weaver, C.E. (1996) Organic cosolvent effects on sorption equilibrium of hydrophobic organic chemicals by organoclays. Environ. Sci. Technol. 30, 8996.Google Scholar
Pinnavaia, T.J., Tzou, M.S., Landau, S.D. & Raythatha, R.H. (1984) On the pillaring and delamination of smectite clay catalysts by polyoxo cations of auminum. J. Mol. Catal. 27, 195212.CrossRefGoogle Scholar
Purnell, J.H., Thomas, J.M., Diddams, P., Ballantine, J.A. & Jones, W. (1989) The influence of exchangeable aluminium ion concentration and of layer charge on the catalytic activity of montmorillonite clays. Catal. Lett. 2, 125128.CrossRefGoogle Scholar
Rhodes, C.N. & Brown, D.R (1994) Catalytic activity of acid-treated montmorillonite in polar and non-polar reaction media. Catal. Lett. 24, 285291.Google Scholar
Taylor, D.R. & Jenkins, D.B. (1986) Acid-activated clays. Soc. Min. Eng. AIME Trans. 282, 19011910.Google Scholar
Tennakoon, D.T.B., Schlögl, R., Rayment, T., Klinowski, J., Jones, W. & Thomas, J.M. (1983) The characterization of clay-organic systems. Clay Miner. 18, 357371.Google Scholar
Vaccari, A. (1998) Preparation and catalytic properties of cationic and anionic clays. Catal. Today, 41, 5371.CrossRefGoogle Scholar
Vicente, M.A., Suárez, M., López-González, J.D. & Bañares-Muñoz, M.A. (1996) Characterization, surface area, and porosity analyses of the solids obtained by acid leaching of a saponite. Langmuir, 12, 566572.CrossRefGoogle Scholar
Yu, J.Q., Zhou, P. & Xiao, S.D. (1995) Highly selective hydration reaction of α-pinene over H-mordenites prepared with quaternary ammonium-salts. Chin. J. Chem. 13, 280283.Google Scholar