Pervaporation sorption 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. 

Samdani AR, Mandal S, and Pangarkar VG. Role of and criterion for sorption selectivity in pervaporative removal of trace organics from aqueous solutions. Sep. Sci. Tech. 2003 38(5) 1069-1092. 

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. 

Figure VI - 25. Sorption selectivity fleft) and pervaporation selectivity (right) as a function of the...

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. 

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. 

Carboxylic Groups Pervaporation separation of toluene/i-octane mixmres using copolyimide membranes containing 3,5-diaminobenzoic acid (DABA) was investigated in Ref. [128]. It was established that introduction of diaminobenzoic acid into the 6FDA-TrMPD polyimide improves membrane selectivity. The sorption component of the separation factor /3s is hnearly correlated with the membrane solubility parameter and with DABA content in the copolymer (/3s = 3.2, 3.3,4.3, 5.2 for DABA contents 0%, 10%, 33%, 60%, respectively). 

All the above mentioned high perm-selectivity of zeolite membranes can be attributed to the selective sorption into the membranes. Satisfactory performance can be obtained by defective zeolite membranes. Xylene isomers separation by zeolite membranes compared with polymeric membranes are summarized in Table 15.4. As shown, zeolite membranes showed much higher isomer separation performances than that of polymeric membranes. Specially, Lai et al. [41] prepared b-oriented silicalite-1 zeolite membrane by a secondary growth method with a b-oriented seed layer and use of trimer-TPA as a template in the secondary growth step. The membrane offers p-xylene permeance of 34.3 x 10 kg/m. h with p- to o-xylene separation factor of up to 500. Recently, Yuan et al. [42] prepared siUcalite-1 zeolite membrane by a template-free secondary growth method. The synthesized membrane showed excellent performance for pervaporation separation of xylene isomers at low temperature (50°C). 

Table 3.6-2 Selectivity of a pervaporation membrane for ethyl hexanoate and isobutyl alcohol with respect to water sorption coeffi-...

The concentration in the membrane depends on the outside activity and the sorption or partition coefficient of the species, the mobifity on the nature of the membrane. The driving force for a component is a function of the process parameters, e.g. temperature, pressure, and concentration. In a pervaporation process usually the minor component is removed from a mixture. For the retained major component the driving force will always be higher than for the transported one. The selectivity of the membrane is then determined by the differences in the product of mobility and concentration and not by a difference in the driving force. 

Table VI. 14 summarises some of these systems as an example. It can be concluded from these results that the determining factor in selective transport in pervaporation is thermodynamic interaction or preferential sorption. On the other hand the flux can be cotielated to the overall sorption.

Poly (vinyl alcohol) (PVA) has also been applied to alcohol-water pervaporation. ZSM-5 was again utilized, and mixed-matrix enhancements resulted. The ZSM-5/PVA mixed-matrix membranes demonstrated increased selectivity and flux, compared to pure PVA, for the water-isopropyl alcohol separation. Membrane swelling and fluxes increase as the water concentration in the feed increases. " Sorption studies of ZSM-5/PVA systems indicate that this hybrid material is a good candidate for the extraction of water from alcohol. Modified poly (vinyl chloride) embedded with NaA zeolite has demonstrated both flux and selectivity enhancements for the ethanol-water separation at high zeolite loadings. Voids at the solid-polymer interface prevented seleetivity enhaneement at low zeolite loadings. ... 

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