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Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid-treated Wyoming bentonite

Published online by Cambridge University Press:  09 July 2018

C. Breen*
Affiliation:
Chemistry Division, School of Science, Sheffield City Polytechnic, Pond Street, Sheffield S1 1WB, UK

Abstract

Four 15 g samples of an unsedimented Wyoming bentonite were treated with 200 cm3 of 0·025, 0·050, 0·100 and 0·250 mol dm−3 H2SO4 for 1 h at room temperature (samples I–IV, respectively). Three further 15 g samples were treated with 200 cm3 of 50% (v/v) H2SO4 for 1 h at 20°C (sample V), and 1 and 2 h under reflux (samples VI and VII, respectively). X-ray fluorescence and diffraction studies revealed that only samples VI and VII suffered any substantial structural attack. The resulting acidity of the clays, determined by cyclohexylamine desorption, indicated that sample V contained the largest number of protons at 0·59 mmol H+ (g clay)−1. Sample V was also the most efficient catalyst for the dehydration and etherification of hexan-1-ol, giving a combined product yield of 17·0% after 2 h reflux in neat reactant. The parent bentonite and samples I and II showed no discernible catalytic activity despite measured acidities of 0·1, 0·24 and 0·34 mmol H+ (g clay)−1. In contrast samples III and IV gave combined product yields of 4·5 and 11·0%, respectively, which correlated well with the measured acidities of 0·38 and 0·48 mmol H+ (g clay)−1. Samples VI and VII, prepared by reflux in acid, contained 0·3 and 0·1 mmol H+ (g clay)−1, respectively, and gave combined product yields of 13·0 and 6·0%.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1991

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References

Adams, J.M. (1987) Synthetic organic chemistry using pillared, cation-exchanged and acid-treated montmorillonite catalysts—A review. Appl. Clay ScL, 2, 309–342.Google Scholar
Adams, J.M., Ballantine, J.A., Graham, S.H., Laub, R.J., Purnell, J.H., Reid, P.I., Shaman, W.Y.M. & Thomas, J.M. (1979) Selective chemical conversion using sheet silicates: low temperature addition of water to 1-alkenes. J. Catal., 58, 238–252.Google Scholar
Atkins, M.P., Smith, D.J.H. & Westlake, D.J. (1983) Montmorillonite catalysts for ethylene hydration. Clay Miner., 18, 423429.CrossRefGoogle Scholar
Ballantine, J.A., Davies, M., Patel, I., Purnell, J.H., Rayanakorn, M., Williams, K.J. & Thomas, J.M. (1984) Organic reactions catalysed by sheet silicates: Ether formation by intermolecular dehydration of alcohols and by addition of alcohols to alkenes. J. Mol. Catal., 26, 37–56.Google Scholar
Ballantine, J. A. (1986) The reactions in clays and pillared days. Pp. 197-212 in: Chemical Reactions in Organic and Inorganic Constrained Systems(Button, R., editor). Reidel, Dordrecht.Google Scholar
Ballantine, J.A., Graham, P., Patel, I., Purnell, J.H., Williams, K. & Thomas, J.M. (1987) New differential thermogravimetric method using cyclohexylamine for measuring the concentration of interlamellar protons in clay catalysts. Proc. Int. Clay Conf. Denver,, 311318.Google Scholar
Banin, A. & Shaked, D. (1969) Particle size and surface properties of acidic montmorillonite. Proc. Int. Clay Conf. Tokyo, 1, 669–682.Google Scholar
Breen, C., Deane, A.T. & Flynn JJ. (1987) The acidity of trivalent cation-exchanged montmorillonite. Temperature programmed desorption and infrared studies of pyridine and n-butylamine. Clay Miner., 22, 169–178.Google Scholar
Breen, C. (1991) Thermogravimetric and infrared study of the desorption of butylamine, cylohexylamine and pyridine from Ni- and Co-exchanged montmorillonite. Clay Miner., 26, 487–496 Google Scholar
El-Akkad, T.M., Flex, N.S., Guindy, S.R., El-Massry, S.R. & Nashed, S. (1982) Thermal analyses of mono- and divalent montmorillonite cationic derivatives. Thermochim. Acta, 59, 9–17.CrossRefGoogle Scholar
Fahn, R. & Fenderl, K. (1983) Reaction products of organic dye molecules with acid-treated montmorillonite. Clay Miner., 18, 447458.CrossRefGoogle Scholar
Farmer, V. C. & Mortland, M.M. (1966) An infrared study of the co-ordination of pyridine and water to exchangeable cations in montmoriUonite and saponite. J. Chem. Soc. Sect. A, 344351.CrossRefGoogle Scholar
Granquist, W.T. & Gardner-Sumner, G. (1959) Acid dissolution of a Texas bentonite. Clays Clay Miner., 6, 292–308.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
Hirokawa, A. (1980) Characteristics and applications of the acid-treated iacid-clay\ Nendo Kagaku, 20, 99–106. Hojabri, F. (1971) Dimerisation of propylene and its uses for isoprene manufacture. J. App. Chem. Biotech., 21, 8789.Google Scholar
Horvath, I. & Gaukova, L. (1979) Mechanism of the H2O(g) release during a dehydroxylation of montmorillonite. Chem. Zvesti., 33, 604–611.Google Scholar
Kaplan, H. (1966) One step process of acid activating mineral clays and alkylating phenolic compounds with an alkene hydrocarbon. U.S. Patent 3,287,422, 4pp.Google Scholar
Loeppert, R.H. & Mortland, M.M. (1979) The influence of heat-stable intercalate on the rate of dehydroxylation of smectite. Clays Clay Miner., 27, 373–376.Google Scholar
Mills, G.A., Holmes, J. & Cornelius, E.B. (1950) Acid activation of some bentonite days. J. Phys. Colloid Chem., 54, 1170–1185.Google Scholar
Morgan, D.A., Shaw, D.B., SidebottomM.J., Soon, T.C. & Taylor, R.S. (1985) The function of bleaching earths in the processing of palm, palm kernel and coconut oils. J. Am. Oil Chem. Soc., 62, 292–299.CrossRefGoogle Scholar
Novak, I. & Gregor, M. (1969) Surface area and decolorizing ability of some acid-treated montmorillonites. Proc. Int. Clay Conf. Tokyo, 851857.Google Scholar
Osthaus, B. (1956) Kinetic studies on montmorillonite and nontronite by the acid-dissolution technique. Clays Clay Miner., 4, 301–321.Google Scholar
Parry, E.P. (1963) An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity, J. Catal. 2,, 371379. Google 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, 125–128.CrossRefGoogle Scholar
Tanabe, K. (1970) Solid Acids and Bases—their Catalytic Properties. Academic Press, New York.Google Scholar
Thomas, C.L., Hickey, J. & Stecker, G. (1950) Chemistry of day cracking catalysts. Ind. Eng. Chem., 42, 866–871.Google Scholar
Vasil'ev, N.G. & Ovacharenko, F.D. (1977) The chemistry of the surfaces of the acid forms of natural layer silicates. Russ. Chem. Rev., 46, 775–788.Google Scholar
Ward, J.W. (1968) A spectroscopic study of the surface of zeolite Y: the adsorption of pyridine. J. Coll. Interf. Sci., 28, 269–277.Google Scholar
Yariv, S. & Heller, L. (1970) Sorption of cyclohexylamine by montmorillonites. Israel J. Chem., 8, 935–945.Google Scholar