Separation mechanisms molecular sieving 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. 

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 separation mechanism of inorganic membranes is even more complex than that of polymeric separating layers. Compared with polymeric pervapora-tion membranes these hydrophiHc inorganic ones are not dense, but porous. Molecular-sieving effects, caused by shape and size of molecules, and shape and size of the pores determine the separation. The surface of the membrane and the inside of the pore walls are highly hydrophiHc, so preferential sorption of water on the membrane and inside the pores and surface diffusion in the adsorbed layer play an additional very important role. 

The transport properties across an MIP membrane are controlled by both a sieving effect due to the membrane pore structure and a selective absorption effect due to the imprinted cavities [199, 200]. Therefore, different selective transport mechanisms across MIP membranes could be distinguished according to the porous structure of the polymeric material. Meso- and microporous imprinted membranes facilitate template transport through the membrane, in that preferential absorption of the template promotes its diffusion, whereas macroporous membranes act rather as membrane absorbers, in which selective template binding causes a diffusion delay. As a consequence, the separation performance depends not only on the efficiency of molecular recognition but also on the membrane morphology, especially on the barrier pore size and the thickness of the membrane. 

The adsorptive separation is achieved by one of the three mechanisms steric, kinetic, or equilibrium effect. The steric effect derives from the molecular sieving property of zeolites. In this case only small and properly shaped molecules can diffuse into the adsorbent, whereas other molecules are totally excluded. Kinetic separation is achieved by virtue of the differences in diffusion rates of different molecules. A large majority of processes operate through the equilibrium adsorption of mixture and hence are called equilibrium separation processes. 

When a separation can be effected by a purely adsorptive mechanism (GSC), various adsorbants and porous polymers are used. Commercially available adsorbants include silica gel, activated charcoal, and molecular sieve materials. These adsorbants are used mainly for the analysis of gases and low-molecular-weight, low-boiling compounds. ... 

To overcome these limitations, mixed matrix membranes (MMM) started to emerge as an alternative approach in membrane technology. In this approach, the superior gas separation properties of the molecular sieve materials combine with the desirable mechanical properties and economical processability of polymers (Moore et al. 2004). A mixed matrix is a blend of inorganic particles (such as nanoparticles) in a polymer matrix, which are well dispersed. The effect of the inorganic dispersed phase on the MMM properties is related to its chemical structure, surface chemistry, and the type of particles. The inorganic materials used... 

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