Abstract
The rate of sorption of methanol (MeOH), propan-2-ol (i-PrOH), and 2-methyl-propan-2-ol (t-BuOH) onto a Wyoming montmorillonite saturated with Al3+-, Cr3+-, or Fe3+-cations has been studied by isothermal gravimetry in the temperature range 18°–105°C using samples of differing weights and grain-size distributions. The rate of sorption for all the alcohols increased with decreasing sample and grain size, demonstrating that inter-, rather than intraparticle mass transfer was the rate-limiting process. Optimization of the sample parameters (2 mg sample of < 45-μm grain size, pretreated at 120°C yielded integral diffusion coefficients at 18°C of 1.1 × 10−4 m2/s for t-BuOH for the Cr3+-form and 2.0 × 10−14 m2/s for MeOH and i-PrOH for the Al3+-form. In general, the rate of alcohol sorption decreased as MeOH ≥ i-PrOH > t-BuOH, but no temperature dependence of the sorption rate was observed. The alcohol sorption rate was dependent on the cation present, with Fe3+ < Cr3+ < Al3+.
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Adams, J. M., Ballantine, J. A., Graham, S. H., Laub, R. J., Purnell, J. H., Reid, P. I., Shaman, W. Y. M., and Thomas, J. M. (1978) Organic synthesis using sheet silicate intercalates: Low temperature conversion of olefin to secondary ether: Angew. Chemie. Int. Ed. 17, 282–283.
Adams, J. M., Breen, C., and Riekel, C. (1979a) The diffusion of interlamellar water in the 23.3-Å Na+-mont-morillonite:pyridine/H2O intercalate by quasielastic neutron scattering: Clays & Clay Minerals 27, 140–144.
Adams, J. M., Breen, C., and Riekel, C. (1979b) Deuterium/ hydrogen exchange in interlamellar water in the 23.3-0A Na+-montmorillonite pyridine/water intercalate: J. Colloid Interface Sci. 68, 214–220.
Adams, J. M., Clement, D. E., and Graham, S. H. (1981) Low temperature reactions of alcohols to form t-butyl ethers using clay catalysts: J. Chem. Res. (S), 254–255.
Adams, J. M., Clement, D. E., and Graham, S. H. (1982) Synthesis of methyl t-butyl ether from methanol and iso-butene using a clay catalyst: Clays & Clay Minerals 30, 129–134.
Adams, J. M., Reid, P. I., and Walters, M. J. (1977) The cation-exchange capacity of clays: School Sci. Review 59, 722–725.
Atkins, M. P., Smith, D. J. H., and Westlake, D. J. (1983) Montmorillonite catalyst for ethylene hydration: Clay Miner. 19, 423–430.
Barrer, R. M. (1978) Zeolites and Clay Minerals as Sorbents and Molecular Sieves: Academic Press, New York, 258–338.
Barrer, R. M. and Macleod, D. M. (1954) Intercalation and sorption by montmorillonite: Trans. Faraday Soc. 50, 980–989.
Bennet, H. and Reed, R. A. (1971) Chemical Methods of Silicate Analysis: Academic Press, London, 71–79.
Breen, C., Adams, J. M., and Riekel, C. (1985) Review of the diffusion of pyridine and water in the interlamellar space of montmorillonite: Relevance to kinetics of catalytic reactions in clays: Clays & Clay Minerals 33, 275–284.
Breen, C., Deane, A. T., and Flynn, J. J. (1987) The acidity of trivalent cation-exchanged montmorillonite. Temperature programmed desorption and infra-red studies of pyridine and n-butylamine: Clay Miner, (in press).
Carslaw, H. S. and Jaeger, J. C. (1959) Conduction of Heat in Solids: 2nd ed., Oxford University Press, Oxford, 330–331.
Crank, J. (1956) The Mathematics of Diffusion: Clarendon Press, Oxford, 1–84.
Doelle, H-J. and Riekert, L. (1979) Kinetics of sorption, desorption and diffusion in zeolites: Angew. Chemie. Int. Ed. Engl. 18, 266–272.
Eagan, J. D., Kindl, B., and Anderson, R.B. (1971) Kinetics of adsorption on A zeolites. Temperature effects: Adv. Chem. 102, 164–170.
Gregory, R., Smith, D. J. H., and Westlake, D. J. (1983) The production of ethyl acetate from ethylene and acetic acid using clay catalysts: Clay Miner. 18, 431–435.
Karger, J., Pfeifer, H., Rausch, M., and Walter, A. (1980) Self-diffusion of n-paraffins in NaX zeolite: J. Chem. Soc., Faraday Trans. I 16, 717–737.
Ilavsky, J., Brunovska, B., and Hlavacek, V. (1980) Experimental observation of temperature gradients occurring in a single zeolite pellet: Chem. Eng. Sci. 35, 2475–2479.
Lee, L.-P. and Ruthven, D. M. (1979) Analysis of thermal effects in adsorption rate measurements: J. Chem. Soc., Faraday Trans. 1 75, 2406–2422.
Moore, R. M. and Katzer, J. R. (1972) Counterdiffusion of liquid hydrocarbons in type Y zeolite: Effect of molecular size, molecular type, and direction of diffusion: J. Amer. Inst. Chem. Eng. 18, 816–824.
Ross, D. K. and Hall, P. L. (1980) Neutron scattering methods of investigating clay systems: in Advanced Chemical Methods for Soil and Clay Minerals Research, J. W. Stucki and W. L. Banwart, eds., D. Riedel, Dordrecht, Holland, 93–168.
Ruthven, D. M. (1984) Principles of Adsorption and Adsorption Processes: Wiley, New York, 124–165.
Tennakoon, D. T. B., Schogl, R., Rayment, T., Klinowski, J., Jones, W., and Thomas, J. M. (1983) The characterisation of clay organic systems: Clay Miner. 18, 357–371.
Thomas, J. M. (1982) Sheet silicate intercalates: New agents for unusual chemical conversions: in Intercalation Chemistry, M. S. Whittingham and A. J. Jacobson, eds., Academic Press, New York, 57–99.
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Breen, C., Deane, A.T., Flynn, J.J. et al. Vapor-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 (1987). https://doi.org/10.1346/CCMN.1987.0350502
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DOI: https://doi.org/10.1346/CCMN.1987.0350502