Adsorption separated single-molecular

Fig. 4.4 Pore-filling models for protein adsorption in a mesopore channel (a) separated single-molecularadsorption (b) separated double-molecular adsorption (c) separated triple-molecular adsorption (d) interdigitated triple-molecular adsorption where adjacent layers are interdigitated by 1/4 of the protein diameter through changing the relative orientation. Adapted from [37],...

Figures 6 and 7 illustrate the preposed mechanism in OC. Using the specific example of a separation of a styrene n-butyl methacrylate copolymer, the first SEC separates the copolymer according to molecular size in solution. At any desired retention time, the flow in the first instrument is stopped and an injection made into the second instrument of a single molecular size "slice" of the chrcoiatogram. The solvent running in the second instrument is a mixture of tetrahydrofuran (THF) and n-heptane. THF is a solvent for both styrene cuid n-butyl methacrylate portions of the polymer molecules. However, n-heptane is a nonsolvent for the styrene-rich portions. As a result, vrfien the injection is made into the second instrument, the styrene-rich molecules will shrink relative to the n-butyl methacrylate-rich molecules. An immediate size distribution will be present vrfiich will reflect the composition differences. The smaller styrene-rich molecules will enter more pores of the column packing than their n-butyl methacrylate-rich counterparts and so be fractionated. Furthermore, since the styrene-rich molecules "hate" the mobile phase, they should find the surface area of the packing more "sticky" than the n-butyl methacrylate-rich molecules. Thus, again the styrene-rich molecules should be retarded relative to the others. According to this picture, the mechanisms of size exclusion, adsorption and partition are thus able to act synergistic ally to accomplish a composition separation.

If a Type I isotherm exhibits a nearly constant adsorption at high relative pressure, the micropore volume is given by the amount adsorbed (converted to a liquid volume) in the plateau region, since the mesopore volume and the external surface are both relatively small. In the more usual case where the Type I isotherm has a finite slope at high relative pressures, both the external area and the micropore volume can be evaluated by the a,-method provided that a standard isotherm on a suitable non-porous reference solid is available. Alternatively, the nonane pre-adsorption method may be used in appropriate cases to separate the processes of micropore filling and surface coverage. At present, however, there is no reliable procedure for the computation of micropore size distribution from a single isotherm but if the size extends down to micropores of molecular dimensions, adsorptive molecules of selected size can be employed as molecular probes. 

A sharp separation results in two high purity, high recovery product streams. No restrictions ate placed on the mole fractions of the components to be separated. A separation is considered to be sharp if the ratio of flow rates of a key component in the two products is >10. The separation methods that can potentially obtain a sharp separation in a single step ate physical absorption, molecular sieve adsorption, equiHbrium adsorption, and cryogenic distillation. Chemical absorption is often used to achieve sharp separations, but is generally limited to situations in which the components to be removed ate present in low concentrations. 

Methane can be oxidatively coupled to ethylene with very high yield using the novel gas recycle electrocatalytic or catalytic reactor separator. The ethylene yield is up to 85% for batch operation and up to 50% for continuous flow operation. These promising results, which stem from the novel reactor design and from the adsorptive properties of the molecular sieve material, can be rationalized in terms of a simple macroscopic kinetic model. Such simplified models may be useful for scale up purposes. For practical applications it would be desirable to reduce the recycle ratio p to lower values (e.g. 5-8). This requires a single-pass C2 yield of the order of 15-20%. The Sr-doped La203... 

The other molecular probe method is the single-probe method (SP method), which is separately proposed by Avnir and Jaroniec,93 and Pfeifer et al.108-112 In the SP method, a single adsorption isotherm is analyzed using a modified FHH theory. The FHH model was developed independently by Frenkel,113 Halsey,114 and Hill,115 and describes the multilayer adsorption coverage. Since the SP method uses only one probe molecule, this method is more convenient than the MP method. However, there are many theoretical limitations in applying the SP method to determination of the surface fractal dimension. Therefore, it is really necessary to discuss whether the SP method is an adequate tool to investigate the surface fractal dimension or not before applying the SP method to certain system. 

For multi-component systems it seems intuitive that single-component diffusion and adsorption data would enable one to predict which component would be selectively passed through a membrane. This is only the case where molecular sieving is observed for all other separations where the molecules interact with one another and with the zeolite framework their behavior is determined by these interactions. Differences in membrane properties such as quahty, microstructure, composition and modification can also play a large role in the observed separation characteristics. In many cases, these properties can be manipulated in order to tailor a membrane for a specific apphcation or separation. 

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