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Thermogravimetric, infrared and mass-spectroscopic analysis of the desorption of methanol, propan-1-ol, propan-2-ol and 2-methylpropan-2-ol from montmorillonite

Published online by Cambridge University Press:  09 July 2018

C. Breen ,
J. J. Flynn  and
G. M. B. Parkes
C. Breen
Affiliation:
School of Chemical Sciences, Dublin City University‡, Glasnevin, Dublin 9, Ireland
J. J. Flynn
Affiliation:
School of Chemical Sciences, Dublin City University‡, Glasnevin, Dublin 9, Ireland
G. M. B. Parkes
Affiliation:
Catalysis Research Unit, Leeds Polytechnic, Calverley Street, Leeds LS1 3HE, UK
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Abstract

The desorption of methanol (MeOH), propan-1-ol (n-PrOH), propan-2-ol (i-PrOH) and 2-methylpropan-2-ol (t-BuOH) from Na+-, Ca2+-, Al3+-, Cr3+- and Fe3+-exchanged montmorillonite has been studied using variable temperature infrared (IR) spectroscopy and thermogravimetric analysis (TGA). Alcohol-saturated trivalent cation (M3+) exchanged samples exhibit maxima in the derivative thermograms at 20 and 110°C (MeOH), 30 and 160°C (n-PrOH), 20 and 110°C (i-PrOH) and 20, 55 and 80°C (t-BuOH). Alcohol-saturated Na+ and Ca2+-exchanged montmorillonite samples exhibit maxima at higher temperatures in the i-PrOH (20 and 140°C) and t-BuOH (30, 90 and 110°C) desorption profiles but at the same temperatures for MeOH and n-PrOH. Mass spectroscopic analysis of the vapours desorbed from the alcohol-treated samples show that the low-temperature maxima in the alcohol desorption from the M3+-exchanged clays are due to unchanged alcohol, whilst those occurring at 80°C (t-BuOH), 110°C (i-PrOH) and 160°C (n-PrOH) are due, in the main, to alkene produced from the intramolecular dehydration of the respective alcohol. Changes in the IR spectra of the adsorbed alcohols occur at temperatures which are in accord with the mass spectral data. No mass spectral evidence was found for the formation of dialkylethers via the competing intermolecular process but dimerisation and oligomerisation of t-BuOH were observed.

Type
Research Article
Information
Clay Minerals , Volume 28 , Issue 1 , March 1993 , pp. 123 - 137
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1993

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References

Adams, J.M. & Clapp, T.V. (1985) Infrared studies of 1-hexene adsorbed onto Cr3+-exchanged montmorillonite. Clays Clay Miner. 33, 15–20.Google Scholar
Adams, J.M., Clapp, T.V. & Clement, D.E. (1983) Catalysis by montmorillonites. Clay Miner. 18, 411–421.CrossRefGoogle Scholar
Adams, J.M., Clement, D.E. & Graham, S.H. (1981) Low temperature reaction of alcohols to form t-butyl ethers using clay catalysts. J. Chem. Res. 254-255Google Scholar
Adams, J.M., Reid, P.I. & Walters, M.J. (1977) The cation exchange capacity of clays. School Sci. Rev. 59,722-724.Google Scholar
Al-Oswais, A.A., Ballantine, J.A., Purnell, J.H. & Thomas, J.M. (1987) Thermogravimetric study of the intercalation of acetic acid and water by Al3+-exchanged montmorillonite. J. Mol. Catal. 35, 201–212.Google Scholar
Annabi-Bergaya, F., Cruz, M.I., Gatineau, L. & Fripiat, J.J. (1980) Adsorption of alcohols by smectites. II Nature of the bonds. Clay Miner. 15, 225–237.Google 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 the intermolecular dehydration of alcohols and by addition of alcohols to alkenes. J. Mol. Catal. 26, 37–56.CrossRefGoogle Scholar
Ballantine, J. A., Graham, P., Patel I,, Purnell, J.H. & Williams, K.J. (1987) New differential thermogravimetric method using cyclohexylamine for measuring the concentration of interlamellar protons in clay catalysts. Proc. Int. Clay Conf. Denver, 311-318.Google Scholar
Bennet, H. & Reed, R.A. (1971) Chemical Methods For Silicate Analysis, pp. 71-79. Academic Press, London.Google Scholar
Breen, C. (1991a) Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid-treated Wyoming bentonite. Clay Miner. 26, 473–486.Google Scholar
Breen, C. (1991b) Thermogravimetric and infrared study of the desorption of butylamine, Cyclohexylamine and pyridine from Ni and Co exchanged montmorillonite. Clay Miner. 26, 487–496.Google Scholar
Breen, C. & Deane, A.T. (1987) The adsorption of 1,4-dioxan, Tetrahydrofuran and tetrahydropyran from binary solution with methanol on Al3+- and Cr3+-exchanged montmorillonite. Clay Miner. 22, 199–205.Google Scholar
Breen, C., Deane, A.T. & Flynn, J.J. (1987a) Vapour phase sorption kinetics for tetrahydrofuran, Tetrahydropyran and 1,4-dioxan by A13+-, Cr3+- and Fe3+-exchanged montmorillonite. Clays Clay Miner. 35, 343–346.Google Scholar
Breen, C., Deane, A.T. & Feynn, J.J. (1987b) The acidity of trivalent cation-exchanged montmorillonite. Temperature programmed desorption and infrared studies of pyridine and n-butylamine. Clay Miner. 22, 169–178.CrossRefGoogle Scholar
Breen, C., Deane, A.T., Flynn, J.J. & Reynolds, D. (1987c) Vapour phase sorption kinetics for methanol, Propan-2- ol and 2-methylpropan-2-ol on Al3+-, Cr3+- and Fe3+-exchanged montmorillonite. Clays Clay Miner. 35, 336–342.CrossRefGoogle Scholar
Datka, J. (1980) Transformations of but-1-ene molecules adsorbed in NaHY zeolites studied by infrared spectroscopy. J. Chem. Soc. Faraday Trans. 1. 76, 2437–2447.CrossRefGoogle Scholar
Dowdy, R.H. & Moreland, M.M. (1967) Alcohol water interactions on montmorillonite surfaces. I. Ethanol. Clays Clay Miner. 15, 25-271.Google Scholar
Farmer, V.C. & Russell, J.D. (1971) Interlayer complexes in layer silicates. The structure of water in lamellar solids. Trans. Faraday Soc. 67, 2737–2749.Google Scholar
Grady, M.C. & Gorte, R.J. (1985) Adsorption of 2-propanol and propene on H-ZSM-5: evidence for stable carbenium ion formation. J. Phys. Chem. 89, 1305–1308.Google Scholar
Ison, A. & Gorte, R.J. (1984) The adsorption of methanol and water on H-ZSM-5. J. Catal. 89, 150–158.Google Scholar
Nguyen, T.T., Raupach, M. & Janik, L.J. (1987) Fourier transform infrared study of ethylene glycol monoethyl ether adsorbed on montmorillonite: implications for surface area measurements of clays. Clays Clay Miner. 35, 53–59.Google Scholar
Noller, H. & Ritter, G. (1984) Temperature programmed desorption of methanol, Ethanol, Propan-1-ol and propan-2-ol on silica-magnesia mixed oxides. J. Chem. Soc. Faraday Trans. 1. 80, 275–283.Google Scholar
Rochester, C.H., Graham, J. & Rudham, R. (1984) Infrared study of the adsorption of propan-2-ol on rutile at the solid/vapour and solid/heptane interface. J. Chem. Soc. Faraday Trans. 1. 80, 2459–2466.Google Scholar
Ross, P.F., Busca, G., Lorenzelli, V., Saur, O. & Lavallev, L.-C. (1987) Microcalorimetric and FT-IR spectroscopic study of the adsorption of isopropyl alcohol and hexafluoroisopropyl alcohol on titanium dioxide. Langmuir, 3, 52–58.Google Scholar
Russell, J.D. & Farmer, V.C. (1964) Infra-red spectroscopic study of the dehydration of montmorillonite and saponite. Clay Miner. Bull. 5, 443–464.Google Scholar
Schutz, A., Stone, W.E.E., Poncelet, G. & Fripiat, J.J. (1987) Preparation and characterisation of bidimensional zeolitic structures obtained from synthetic beidellite and hydroxy-aluminium solutions. Clays Clay Miner. 35, 251–261.Google Scholar
Shuali, U., Steinberg, M., Yariv, S., Muller-Vonmoos, M., Kahr, G. & Rub, A. (1990) Thermal analysis of sepiolite and palygorskite treated with butylamine. Clay Miner. 25, 107–119.Google Scholar
Shuali, U., Yariv, S., Steinberg, M., Muller-Vonmoos, M., Kahr, G. & Rub, A. (1991) Thermal analysis of pyridinetreated sepiolite and palygorskite. Clay Miner. 26, 497–506.Google Scholar
Suda, Y., Morimoto, T. & Nagao, M. (1987) Adsorption of alcohols on titanium dioxide (rutile) surface. Langmuir 3, 99–104.CrossRefGoogle Scholar
Tennakoon, D.T.B., Schlogl, R., Rayment, T., Klinowski, J., Jones, W. & Thomas, J.M. (1983) The characterisation of clay-organic systems. Clay Miner. 18, 357–371.Google Scholar