Carbon molecular sieves diffusion

Fig. 8. Variation of activation energy with kinetic molecular diameter for diffusion in 4A 2eohte (A), 5A 2eohte (0)> carbon molecular sieve (MSC-5A) (A). Kinetic diameters are estimated from the van der Waals co-volumes. From ref. 7. To convert kj to kcal divide by 4.184.

Fig. 9. Uptake curves for N2 in two samples of carbon molecular sieve showing conformity with diffusion model (eq. 24) for sample 1 (A), and with surface resistance model (eq. 26) for example 2 (0)j LDF = linear driving force. Data from ref. 18.

Nitrogen production using carbon molecular sieves is the only known commercial process using differences In lntrapartlcle diffusivity, rather than inherent adsorbent selectivity or selective molecular exclusion, as the basis for the separation ... 

The primary requirement for an economic adsorption separation process is an adsorbent with sufficient selectivity, capacity, and life. Adsorption selectivity may depend either on a difference in adsorption equilibrium or, less commonly, on a difference in kinetics. Kinetic selectivity is generally possible only with microporous adsorbents such as zeolites or carbon molecular sieves. One can consider processes such as the separation of linear from branched hydrocarbons on a 5A zeolite sieve to be an extreme example of a kinetic separation. The critical molecular diameter of a branched or cyclic hydrocarbon is too large to allow penetration of the 5A zeolite crystal, whereas the linear species are just small enough to enter. The ratio of intracrystalline diffusivities is therefore effectively infinite, and a very clean separation is possible. 

Y.D. Chen, R.T. Yang, and P. Uawithya, Diffusion of oxygen, nitrogen and their mixtures in carbon molecular sieve, AlChE Journal. 40(4) 511 (1994). 

Y.D. Chen and R.T. Yang, Preparation of carbon molecular sieve membrane and diffusion of binary mixtures in the membrane, Ind. Eng. Chem. Res. 55 3146 (1994). 

Van Den Broeke and Krishna [56] compared the calculated and the experimental breakthrough curves of single components and of mixtures containing methane, carbon dioxide, propane, and propene on microporous activated carbon and on carbon molecular sieves. They ignored the external mass transfer kinetics and assumed that there is local equilibrium for each component between the pore surface and the stagnant fluid phase in the macropores. They also assumed that the surface-diffusion contribution is much larger than that of pore diffusion and they neglected pore diffusion. They used in their calculations three different... 

The main focus of this volume is on imderstanding the transport of molecules in microporous solids such as zeolites and carbon molecular sieves, and the kinetics of adsorption/desorption. This subject is of both practical and theoretical interest, since the performance of zeohte-based catalysts and adsorbents is strongly influenced by resistances to mass transfer and intracrystalline diffusion. However, at an even more basic level, the performance of microporous catalysts and adsorbents depends on favorable adsorption equilibria for the relevant species, so a general imderstanding of the fundamentals of adsorption equilibrium is a necessary prerequisite for understanding kinetic behavior. This chapter is intended to provide a concise summary of the general principles of adsorption equiHbriiun and of the main features of sorption kinetics in microporous solids, which generally depend on a combination of both equilibriiun and kinetic properties. 

Molecular sieves such as zeolites or carbon molecular sieves show a much higher selectivity for many gas mixtures than polymeric membranes due to their very defined pore sizes. For example it can be calculated from reported sorption and diffusivity data that zeolite 4A has an oxygen permeability of 0.77 Barter and an O2/N2 selectivity of approximately 37 at 35 °C [308]. 

For the carbon molecular sieving catalysts, thoe is clear evidence that the global rate is intonally transport limited. Consistent with this, a reduction of particle size of the Fe/SiOi CMS ca yst increased the global reaction rale by decreasing the diffusion length to the active metal sites. Using first-wder kinetics in the Thiele analysis, to consider the conversion ratios of the intemal-transport limited CMS catalyst particles at modest convositxis, leads to the result ... 

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