Pervaporation diffusion selectivity

In comparison with adsorptive/absorptive techniques for aroma recovery from bioconversions, the disadvantage of pervaporation is the fact that both sorption and diffusion determine the overall selectivity. While the sorption selectivity is very high (equal to that of adsorptive/absorption), the diffusion selectivity favours water owing to the simple fact that water is a smaller molecule than aroma compounds and thus sterically less hindered during diffusion (Table 19.1). The overall (perm)selectivity P=SD) is therefore lower than in strictly sorption controlled processes, although it is still favourable compared with that for evaporation. This shortcoming compares, however, with operational advantages of pervaporation as outlined before. 

For illustration, rubbery polymeric membranes, whose polymeric network is sufficiently elastic and mobile to allow comparatively large organic compounds to diffuse through it (Table 3.6-2), are in general used for the recovery of organic compounds from aqueous solutions. Because of its small size, the bulk solvent, water, unfortunately diffuses through the membrane even better. This is why in organo-philic pervaporation the selectivity is mainly achieved and determined by the ratio of the solubility coefficients (sorption selectivity. Table 3.6-2). Membrane selectivity, as defined in Eq. (7), is an intrinsic parameter and can differ from the overall process selectivity, as wiU be shown later. 

A similar example of a promising application of solar heat for intensified process systems is pervaporation. In pervaporation, a selective membrane is used as barrier between two phases, the liquid feed and the vapour permeate. The process depends on the sorption equilibrium and the mobility of the components through the membrane and is rather independent of the vapour liquid equilibrium. The desired component, which is in liquid form in the feed, permeates through the membrane and evaporates while passing the membrane, because the partial pressure of the permeating component is kept lower than the equilibrium vapour pressure [21]. Permeabilities depend on the solubility and diffusion rates through the membrane. 

Hydrophilic pervaporation membranes can be very selective, mainly because the materials for this type of membrane show both sorption selectivity and diffusion selectivity much larger than unity. So they are widely utilized in the dehydration of organic solvents, whenever water is the minor component. 

We study first liquid separation through practically nonporous membranes and then we move on to porous membranes. Of the known techniques using nonporous membranes, (reverse osmosis, dialysis, liquid membrane permeation and pervaporation), we select the most common, reverse osmosis, to begin our study of integrated flux expression development. Pervaporation is considered next There is one feature which is, however, common to almost all nonporous membrane processes i.e. the additional phase, the membrane phase, is stationary in general (except in cases of rapid transient membrane swelling or emulsion liquid membranes). This is in contrast to molecular diffusion processes in a gas or liquid where all species can diffuse (they may or may not). 

Process Description Pervaporation is a separation process in which a liquid mixture contacts a nonporous permselective membrane. One component is transported through the membrane preferentially. It evaporates on the downstream side of the membrane leaving as a vapor. The name is a contraction of permeation and evaporation. Permeation is induced by lowering partial pressure of the permeating component, usually by vacuum or occasionally with a sweep gas. The permeate is then condensed or recovered. Thus, three steps are necessary Sorption of the permeating components into the membrane, diffusive transport across the nonporous membrane, then desorption into the permeate space, with a heat effect. Pervaporation membranes are chosen for high selectivity, and the permeate is often highly purified. 

The selectivity (amcm) of pervaporation membranes critically affects the overall separation obtained and depends on the membrane material. Therefore, membrane materials are tailored for particular separation problems. As with other solution-diffusion membranes, the permeability of a component is the product of the membrane sorption coefficient and the diffusion coefficient (mobility). The membrane selectivity term amem in Equation (9.11) can be written as... 

Pervaporation is a concentration-driven membrane process for liquid feeds. It is based on selective sorption of feed compounds into the membrane phase, as a result of differences in membrane-solvent compatibility, often referred to as solubility in the membrane matrix. The concentration difference (or, in fact, the difference in chemical potential) is obtained by applying a vacuum at the permeate side, so that transport through the membrane matrix occurs by diffusion in a transition from liquid to vapor conditions (Figure 3.1). Alternatively, a sweep gas can be used to obtain low vapor pressures at the permeate side with the same effect of a chemical potential gradient. 

A membrane is usually seen as a selective barrier that is able to be permeated by some species present into a feed while rejecting the others. This concept is the basis of all traditional membrane operations, such as microfiltration, ultrafiltration, nanofil-tration, reverse osmosis, pervaporation, gas separation. On the contrary, membrane contactors do not allow the achievement of a separation of species thanks to the selectivity of the membrane, and they use microporous membranes only as a mean for keeping in contact two phases. The interface is established at the pore mouths and the transport of species from/to a phase occurs by simple diffusion through the membrane pores. In order to work with a constant interfacial area, it is important to carefully control the operating pressures of the two phases. Usually, the phase that does not penetrate into the pores must be kept at higher pressure than the other phase (Figure 20.1a and b). When the membrane is hydrophobic, polar phases can not go into the pores, whereas, if it is hydrophilic, the nonpolar/gas phase remains blocked at the pores entrance [1, 2]. 

Selective separation of hquids by pervaporation is a result of selective sorption and diffusion of a component through the membrane. PV process differs from other membrane processes in the fact that there is a phase change of the permeating molecules on the downstream face of the membrane. PV mechanism can be described by the solution-diffusion mechanism proposed by Binning et al. [3]. According to this model, selective sorption of the component of a hquid mixture takes place at the upstream face of the membrane followed by diffusion through the membrane and desorption on the permeate side. 

To increase the sorption component of the separation factor, homogeneously distributed tetracyanoethylene, a strong electron acceptor having high affinity for electron donors, was added to the polyimide matrix [77]. It can be seen from data presented in Table 9.12 that this is accompanied by an increase in the sorption component /3s (benzene/cyclohexane) by a factor of 1.5 probably as a result of selective sorption of aromatic compounds by tetracyanoethylene with a simultaneous increase in the diffusion component /3d. The prepared membranes showed good pervaporation properties with respect to benzene/cyclohexane, toluene/isooctane mixtures. For example, for a two-component 50/50 wt% benzene/cyclohexane mixture at 343 K, the flux was 2 = 0.44 kg p,m/m h, and /3p (benzene/cyclohexane) = 48 and for a two-component toluene/isooctane mixture, 45/55 wt%, at 343 K the flux was 2 = 1-1 kg p-m/m h, and /3p (toluene/wo-octane) = 330. 

Finally, it is important to notice the effect of the support in the pervaporation flux, analyzed by Bruijn et al. [117] who proposed a model and evaluated the contribution of the support layer to the overall resistance for mass transfer in the selected literature data. They found that in many cases, the support is limiting the flux the permeation mechanism through the support corresponds to a Knudsen diffusion mechanism, which makes improvements in the porosity, tortuosity, pore diameter, and thickness necessary for an increase in the pervaporation flux. 

As we have seen previously, the separation mechanism in pervaporation is explained by an adsorption-diffusion process. In this way, the selective adsorption of the components in the zeolite will be responsible for the selectivity in the separation. Adsorption is an exothermic nonactivated process. In general, the isotherm of adsorption on zeohtes follows a single site Langmuir-type isotherm [74]. 

The experimental procedures are quite similar to and often confused with pervaporation. The main difference between VMD and pervaporation is the nature of the membrane used, which plays an important role in the separations. While VMD uses a porous hydrophobic membrane and the degree of separation is determined by vapor-liquid equilibrium conditions at the membrane-solution interface, pervaporation uses a dense membrane and the separation is based on the relative perm-selectivity and the diffusivity of each component in the membrane material. 

Separation from mixtures is achieved because the membrane transports one component more readily than the others, even if the driving forces are equal. The effectiveness of pervaporation is measured by two parameters, namely flux, which determines the rate of permeation and selectivity, which measures the separation efficiency of the membrane (controlled by the intrinsic properties of the polymer used to construct it). The coupling of fluxes affecting the permeability of a mixture component can be divided into two parts, namely a thermodynamic part expressed as solubility, and a kinetic part expressed as diffusivity. In the thermodynamic part, the concentration change of one component in the membrane due to the presence of another is caused by mutual interactions between the permeates in the membrane in addition to interactions between the individual components and the membrane material. On the other hand, kinetic coupling arises from the dependence of the concentration on the diffusion coefficients of the permeates in the polymers [155]. 

Semi-permeable membranes are generally used to select the chemical species to be diffused towards the acceptor stream [253]. Alternatively, other restrictive media can be used in a similar way to gas diffusion, e.g., in pervaporation, membraneless gas diffusion and distillation, as discussed below. 

TABLE 8.4 Selected Applications of Dialysis, Gas Diffusion, Pervaporation, Filtration, Distillation and Precipitation... 

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