Porous membranes permeation

Finally, dense (i.e. non-porous) membranes permeate O2 or H2 only and so are important only in applications where these gases play a role such as in air... 

Another possibility of constructing a chiral membrane system is to prepare a solution of the chiral selector which is retained between two porous membranes, acting as an enantioselective liquid carrier for the transport of one of the enantiomers from the feed solution of the racemate to the receiving side (Fig. 1-5). This system is often referred to as membrane-assisted separation. The selector should not be soluble in the solvent used for the elution of the enantiomers, whose transport is driven by a gradient in concentration or pH between the feed and receiving phases. As a drawback common to all these systems, it should be mentioned that the transport of one enantiomer usually decreases when the enantiomer ratio in the permeate diminishes. Nevertheless, this can be overcome by designing a system where two opposite selectors are used to transport the two enantiomers of a racemic solution simultaneously, as it was already applied in W-tube experiments [171]. 

A limitation to the more widespread use of membrane separation processes is membrane fouling, as would be expected in the industrial application of such finely porous materials. Fouling results in a continuous decline in membrane penneation rate, an increased rejection of low molecular weight solutes and eventually blocking of flow channels. On start-up of a process, a reduction in membrane permeation rate to 30-10% of the pure water permeation rate after a few minutes of operation is common for ultrafiltration. Such a rapid decrease may be even more extreme for microfiltration. This is often followed by a more gradual... 

In Figure 10.10a, it can be seen that for porous membranes, the partial pressure and concentration profiles vary continuously from the bulk feed to the bulk permeate. This is not the case with nonporous dense membranes, as illustrated in Figure 10.10b. Partial pressure or concentration of the feed liquid just adjacent to the upstream membrane interface is higher than the partial pressure or concentration at the upstream interface. Also, the partial pressure or concentration is higher just downstream of the membrane interface than in the permeate at the interface. The concentrations at the membrane interface and just adjacent to the membrane interface can be related according to an equilibrium partition coefficient KM i. This can be defined as (see Figure 10.10b) ... 

In the third part of the chapter the solid state properties of our block copolymer are examined. The surface energies of these materials are characterized by contact angle measurements. The organization of the polymer chains in the solid state phase is investigated by small-angle X-ray scattering (SAXS) and the gas selectivity of porous membranes coated with these block copolymers is characterized by some preliminary permeation measurements. 

The main emphasis in this chapter is on the use of membranes for separations in liquid systems. As discussed by Koros and Chern(30) and Kesting and Fritzsche(31), gas mixtures may also be separated by membranes and both porous and non-porous membranes may be used. In the former case, Knudsen flow can result in separation, though the effect is relatively small. Much better separation is achieved with non-porous polymer membranes where the transport mechanism is based on sorption and diffusion. As for reverse osmosis and pervaporation, the transport equations for gas permeation through dense polymer membranes are based on Fick s Law, material transport being a function of the partial pressure difference across the membrane. 

The situation is somewhat different with porous membranes, where the permselectivities for all components do not equal zero but exhibit certain values determined in most cases by the Knudsen law of molecular masses. In general, when porous membranes are used as separators in a membrane reactor next to the catalyst or the reaction zone (Figure 7.2a), it has been shown experimentally (Yamada et al. 1988) and theoretically (Mohan and Govind 1986, 1988a, b, Itoh et al. 1984, 1985) that there is a maximum equilibrium shift that can be achieved. On the basis of simple mass balances one can calculate that this maximum depends on, besides the reaction mechanism, the membrane permselectivities (the difference in molecular weights of the components to be separated) and it corresponds to an optimum permeation to reaction-rate ratio for the faster permeating component (which is a reaction product). 

It is obvious from the above discussion that porous and dense membranes form two different cases, each with its own advantages and disadvantages. Dense membranes, (permeable only to one component) operating at optimum conditions, can be used to obtain complete conversions. However, because the permeation rate is low, the reaction rate has also to be kept low. Porous membranes (permeable to all components but at different permselectivities) are limited under optimum conditions to a maximum conversion (which is not 100%) due to the permeation of all the components. The permeation rates through porous membranes are, however, much higher than those through dense membranes and consequently higher reaction rates or smaller reactor volumes are possible. 

Microporous membranes (pore radius less than 10 A) are ideal materials to be used as separators in membrane reactor processes. Microporous membranes also combine the high selectivities to certain components with high permeation rates. The high selectivities mean that maximum conversions (and thus equilibria shifts) higher than those achieved by porous membranes can be attained, while the high permeation rates allow for high reaction rates... 

It has been mentioned earlier that using porous membranes for product separation during the course of an equilibrium reaction, maximum attainable conversions are limited because of reactant permeation. This is the case where the membrane forms the wall of the reactor in which a catalyst is packed. It has also been mentioned that in this mode equilibrium conversions for some slow reactions could be increased by factors ranging between 1.3 and 2.3. Another important operation mode arises when the membrane is inherently catalytic or when the catalytically active species are placed within the membrane pores (catalytically active membrane as shown in Figure 7.2b and 7.2c). In this case, reaction and separation take place simultaneously and are combined in parallel rather than in series as was the case in the previous mode. 

Reverse osmosis" is the popular name of a general process for the separation of substances in solution. The process consists in letting the solution flow under pressure through an appropriate porous membrane (called the "reverse osmosis membrane") and withdrawing the membrane permeated product generally at atmospheric pressure and surrounding temperature. 

As a result of Internal concentration polarization, the effective osmotic pressure difference across the membrane can be significantly below the osmotic pressure difference between the bulk solutions. The effective osmotic pressure can be calculated from the salt permeation coefficient and the salt diffusion resistance in the porous membrane substrate. The highest power output for a membrane is obtained at an operating pressure equal to about one half of the effective osmotic pressure. 

It has recently been demonstrated that solutes can be extracted from ionic liquids by perevaporation. This technique is based on the preferential partitioning of the solute from a liquid feed into a dense, non-porous membrane. The ionic liquids do not permeate the membrane. This technique can be applied to the recovery of volatile solutes from temperature-sensitive reactions such as bioconversions carried out in ionic liquids (34). 

Pervaporation is a membrane separation process in which a dense, non-porous membrane separates a liquid feed solution from a vapour permeate (Fig. 19.2c). The transport across the membrane barrier is therefore based, generally, on a solution-difliision mechanism with an intense solute-membrane interaction. It... 

Figure 9.7 shows the interface between the electrochemical cell and the mass spectrometer. The porous membrane (e.g. Teflon) plays an important role, permeating gases but not liquids through it. 

Figure 19.4. The spiral wound membrane module for reverse osmosis, (a) Cutaway view of a spiral wound membrane permeator, consisting of two membranes sealed at the edges and enclosing a porous structure that serves as a passage for the permeate flow, and with mesh spacers outside each membrane for passage of feed solution, then wound into a spiral. A spiral 4 in. dia by 3 ft long has about 60 sqft of membrane surface, (b) Detail, showing particularly the sealing of the permeate flow channel, (c) Thickness of membranes and depths of channels for flows of permeate and feed solutions.

Cross-section structure. An anisotropic membrane (also called asymmetric ) has a thin porous or nonporous selective barrier, supported mechanically by a much thicker porous substructure. This type of morphology reduces the effective thickness of the selective barrier, and the permeate flux can be enhanced without changes in selectivity. Isotropic ( symmetric ) membrane cross-sections can be found for self-supported nonporous membranes (mainly ion-exchange) and macroporous microfiltration (MF) membranes (also often used in membrane contactors [1]). The only example for an established isotropic porous membrane for molecular separations is the case of track-etched polymer films with pore diameters down to about 10 run. All the above-mentioned membranes can in principle be made from one material. In contrast to such an integrally anisotropic membrane (homogeneous with respect to composition), a thin-film composite (TFC) membrane consists of different materials for the thin selective barrier layer and the support structure. In composite membranes in general, a combination of two (or more) materials with different characteristics is used with the aim to achieve synergetic properties. Other examples besides thin-film are pore-filled or pore surface-coated composite membranes or mixed-matrix membranes [3]. 

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