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Adsorption: Journal of the International Adsorption Society (v.3, #4)
Adsorption of normal and branched paraffins in faujasite zeolites NaY, HY, Pt/NaY and USY by Joeri F. M. Denayer; Gino V. Baron (pp. 251-265).
The effect of chain length and branching of paraffins (from C6 to C12) on adsorption and diffusion in zeolites NaY, Pt/NaY, HY and USY has been investigated using the chromatographic method at 275–400°C. The Henry constants of the paraffins increase exponentially with the chain length (with a factor two per extra carbon group), the heats of adsorption increase with circa 7 kJ/mol per extra carbon group. Multicomponent sorption experiments reveal that longer chains are adsorbed preferentially over shorter chains, even at higher loadings. The multicomponent adsorption can be reasonably well described by an extended Langmuir adsorption isotherm, in which the stronger adsorption of the longer chains is reflected by their higher Henry constants. The molecular shape and zeolite type within this FAU group has only a small influence on the adsorption properties. Mass transfer in the pellets as used in catalytic conditions seems to be limited by macropore diffusion, rather than by micropore diffusion, which cannot be measured with the chromatographic method. Increasing the Si/Al-ratio of the zeolite reduces the adsorption capacity, but does not influence the relative adsorption properties.
Keywords: multicomponent equilibrium; zeolite; chromatography; paraffins; heat of adsorption
Equilibria and kinetics characterisation of two different structured nutshell-derived activated carbons by K. Wang; A. Ahmadpour; D. D. Do (pp. 267-275).
Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
Keywords: characterisation; equilibria; kinetics; micropore size distribution; n-butane; nutshell
Influence of analysis conditions on low pressure adsorption measurements and its consequences in characterization of energetic and structural heterogeneity of microporous carbons by Y. Bereznitski; M. Jaroniec; K. P. Gadkaree (pp. 277-282).
Nitrogen adsorption isotherms on nonporous and microporous carbons were thoroughly studied at low relative pressures. For nonporous carbons low pressure measurements seem to be unaffected by analysis conditions. However, these measurements on microporous solids may be affected by analysis conditions at relative pressures below 10−4. It was shown that selection of proper equilibration time is crucial for correct measurements of equilibrium pressures during adsorption on microporous carbons. The isotherm shift induced by insufficient equilibration of the system may affect the surface heterogeneity and microporosity analysis. A comparison of the adsorption energy and pore volume distribution functions calculated from low pressure nitrogen adsorption isotherms measured at different equilibration times on a microporous carbon shows that this effect is smaller than it was expected.
Keywords: surface heterogeneity; nitrogen adsorption; micropore analysis; microporous carbon; low pressure adsorption
Review of time lag permeation technique as a method for characterisation of porous media and membranes by S. W. Rutherford; D. D. Do (pp. 283-312).
The time lag permeation technique has proven to bean effective method for characterisation. Because of the simple nature of the permeation experiment, transport parameters can be directly obtained from experimental data hence avoiding the intensive mathematical treatment required by other techniques. The method has historically been applied to diffusion and adsorption in porous membranes and diffusion in polymer membranes. Since its origins in 1920, interest in the time lag method has expanded because of its value in characterising simple permeation processes and also complex systems of diffusion with simultaneous adsorption and surface diffusion. This review focuses on presenting the asymptotic solution of the mass balance diffusion equations and includes applications of time lag analysis, in order to give a critical and broad perspective of this method as a tool for characterisation. It includes much of the previously published literature in order to show that for most cases the asymptotic solution of the transport equations is simple, and for more complex cases that an analytical solution is possible hence avoiding cumbersome numerical techniques.
Keywords: time lag; porous media; membrane; Frisch's method; permeation