A perturbation chromatography technique using radiotracer gases has been developed to determine the adsorption equilibrium constants and diffusivities in molecular sieves. The ethane and ethylene 13X molecular sieve systems were studied in regions of high concentration. The data obtained by this technique are shown to be in agreement with equilibrium data obtained by static methods and with kinetic data obtained by adsorption uptake and chromatographic methods, but not with kinetic data obtained using NMR techniques. The tracer-pulse chromatographic technique is much more efficient for obtaining gas adsorption equilibria and intraparticle diffusivities and is considerably easier to adapt to wide pressure and temperature ranges than the conventional methods.
S. H. HYUN and R. P. DANNER
Department of Chemical EngineeringThe Pennsylvania State Unlversity University Park, PA 16802
SCOPEDespite the obvious industrial importance of adsorption equilibria and kinetics in porous materials such as molecular sieves, reliable information in this area is still quite limited. This condition is the result of experimental difficulties and, in part, of the lack of a complete model to describe the complex adsorption kinetic process in porous solids. The adsorption kinetic or intraparticle diffusivity data reported in the literature have frequently shown discrepancies of several orders of magnitude among different investigators using different techniques of measurement.Ruthven (1983) recently reviewed methods for determining diffusivities in zeolites. Most earlier studies used direct measurement of the adsorption uptake on an exposed layer of adsorbent. A chromatographic method is also being used which is based on the analysis of response of an adsorption bed to a concentration pulse or step change at the inlet. More recently NMR methods have been used to measure adsorption diffusivities. The chromatographic techniques are easier to operate, more efficient in producing data, and more suitable for higher temperature and pressure ranges. Conventional chromatographic methods, however, have been limited to infinitely dilute adsorbed phase concentrations with only one adsorbable component. Furthermore, Karger and Ruthven (1981) have raised doubts about the micropore diffusivities determined by adsorption uptake and chromatographic techniques. Use of NMR for the study of adsorption diffusivities involves an extension of the methods originally developed to study self-diffusion in liquids. Application of NMR is restricted to molecules which contain a sufficiently high density of atoms with impaired nuclear spins, such as found with the hydrogens in hydrocarbons.The objective of this work was to develop a tracer-pulse chromatographic technique (i,e., perturbation chromatography technique) which can be used for both pure and multicomponent systems over the entire concentration range. A mathematical model using bidispersed pore structure, which is more realistic in pelletized particles, has been developed to describe the chromatographic behav...