Size molecular sieving effect

In addition, depending on the size of the adsorbate molecules, especially in the case of some organic molecules of a large size, molecular sieve effects may occur either because the pore width is narrower than the molecules of the adsorbate or because the shape of the pores does not allow the molecules of the adsorbate to penetrate into the micropores. Thus, slit-shaped micropores formed by the spaces between the carbon layer planes are not accessible to molecules of a spherical geomehy, which have a diameter larger than the pore width. This means that the specific surface area of a carbon is not necessarily proportional to the adsorption capacity of the activated carbon. Pore size distribution, therefore, is a factor that cannot be ignored. 

Adsorption. Although several types of microporous soHds are used as adsorbents for the separation of vapor or Hquid mixtures, the distribution of pore diameters does not enable separations based on the molecular-sieve effect. The most important molecular-sieve effects are shown by crystalline zeoHtes, which selectively adsorb or reject molecules based on differences in molecular size, shape, and other properties such as polarity. The sieve effect may be total or partial. 

Species separated by molecular sieving effects when kinetic diameters fall iato different zeoHte aperture size categories (standard molecular sieve diameters = 300, 400, 500, 800, 1000,1300 pm. 

Molecular sieving effect of the membrane has been evidenced using a mixture of two isomers (i.e. no Knudsen separation can be anticipated), n-hexane and 2-2 dimethylbutane (respective kinetic diameters 0.43 and 0.62 nm). Figure 10 shows the permeate contains almost only the linear species, due to the sieving effect of the zeolite membrane (pore size ca 0.55 nm). This last result also underlines that the present zeolite membrane is almost defect-fi ee. 

Jhung, S.H., Lee, J.H., and Chang, J. (2008) Crystal size control of transition metal ion-incorporated aluminophos-phate molecular sieves effect of ramping rate in the syntheses. Micropor. Mesopor. Mater., 112, 178-185. 

The dependence of Dt on gas molecular size has been found to be He > C02 > Ar > N2 > CH in four different polymers 23 25>26,39). This trend correlates smoothly with the minimum effective gas molecular diameter deduced from molecular sieving effects in zeolites 39). The corresponding trend of D2 is not so clearcut,... 

With respect to porous solids, the surface associated with pores may be called the internal surface. Because the accessibility of pores may depend on the size of the fluid molecules, the extent of the accessible internal surface may depend on the size of the molecules comprising the fluid, and may be different for the various components of a fluid mixture (molecular sieve effect). 

Molecular sieving Fig. 4(e) where, due to steric hindrance, only small molecules will diffuse through the membrane, seems to be a useful principle for achieving good separations. To ensure this molecular sieving effect, ultramicroporous membranes have to be prepared. Moreover, such membranes should not only be defect free but must also present a very narrow pore size distribution to avoid any other (less selective) permeation mechanisms defect-free zeolite membranes appear to be good candidates for this type of separation. 

Obviously the pore size determines which molecules can access the acidic sites inside the zeolite framework (molecular sieving effect) and is responsible for the shape selectivity observed with these materials (see later). The catalytic activity is also influenced by the acid strength of these sites which is determined by the Si/Al ratio (see above). The latter can be increased by post-synthesis removal of A1 atoms. Dealumination can be achieved by treatment with a... 

Zeolitic materials have been widely used in the last decades in the chemical and petrochemical industries. This increasing interest on these materials is based in their unique properties a uniform intra-crystalline microporosity that provides aceess to a large and well-defined surface, the molecular sieve effect, and the electrostatic field centered at zeolite cations. Furthermore, some properties of zeolites can be tailored by changing the nature of the compensating cation located in the inner part of the cavities by means of their ion-exchange capability. In this way, the pore accessibility of some zeolites used in gas separation processes, as well as the adsorbent-adsorbate interactions, can be tailored by the introduction of cations with different size and chemical nature. Similarly, different cations can be used to introduce new chemical properties (acid-base, redox, etc.), which are needed for a given application in catalytic processes. 

Mokiailnr probe method. When the membrane pores reach the molecular dimensions, the molecular sieving effect becomes operative and the membrane can discriminate gas molecules with a diameter difference as low as 0.02 nm. Some methods utilizing molecules of different sizes as molecular probes have been used to estimate the pore size of a membrane. In these cases, the membranes can be characterized by their permeabilities or accessible micropore volumes to different gases. The pore size can be inferred from the permeation rates or micropore volumes of different gases whose molecular dimensions are known or can be calculated. 

Molecular sieving and the interactions of gas molecules with the membrane are possible alternatives. As discussed in Chapter 4, if surface diffusion is operative on a gas but not the other, it can enhance the separation factor. Although surface diffusion contribution decreases with increasing temperature, it becomes more important as the pore diameter becomes smaller. Therefore, it is possible that as inorganic membranes with smaUer pore sizes become available their separation performance may increase not only due to molecular sieving effects but also surface diffusion or other transport mechanisms. 

In many studies the separation factor, which is indicative of the membrane s ability to separate two gases in a mixture, is predominantly governed by Knudsen diffusion. Knudsen diffusion is useful in gas separation mostly when two gases are significantly different in their molecular weights. In other cases, more effective uansport mechanisms are required. The pore size of the membrane needs to be smaller so that molecular sieving effects become operative. Some new membrane materials such as zeolites and other molecular sieve materials and membrane modifications by the sol-gel and chemical vapor deposition techniques are all in the horizon. Alternatively, it is desirable to tailor the gas-membrane interaction for promoting such transport mechanisms as surface diffusion or capillary condensation. 

The best answer to the permeability/permselectivity optimization would be to synthesize very thin layers of materials having a comparatively high porosity and pore sizes in the range 5-8 A so as to achieve molecular sieving effects. Instead of the modification of already available membranes, the synthesis of new membranes seems more appropriate to reach the above goal. The two most promising candidates in this context are carbon and zeolite membranes. 

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