Liquid membranes supported

In general, high selectivities can be obtained in liquid membrane systems. However, one disadvantage of this technique is that the enantiomer ratio in the permeate decreases rapidly when the feed stream is depleted in one enantiomer. Racemization of the feed would be an approach to tackle this problem or, alternatively, using a system containing the two opposite selectors, so that the feed stream remains virtually racemic [21]. Another potential drawback of supported enantioselective liquid membranes is the application on an industrial scale. Often a complex multistage process is required in order to achieve the desired purity of the product. This leads to a relatively complicated flow scheme and expensive process equipment for large-scale separations. 

As the main disadvantage of liquid membrane systems is the instability over a longer period of time, another approach would be to perform separation through a solid membrane [22]. Enantioselective polymer membranes typically consist of a nonse-lective porous support coated with a thin layer of an enantioselective polymer. This 

A different approach is the use of an ultrafiltration membrane with an immobilized chiral component [31]. The transport mechanism for the separation of d,l-phenylalanine by an enantioselective ultrafiltration membrane is shown schematically in Fig. 5-4a. Depending on the trans-membrane pressure, selectivities were found to be between 1.25 and 4.1, at permeabilities between 10 and 10 m s respectively (Fig. 5-4b). 

I///1 L-amino acid condensate region I 1 polysulfone region, fixed L-Phe 

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Liquid-liquid extraction is a basic process already applied as a large-scale method. Usually, it does not require highly sophisticated devices, being very attractive for the preparative-scale separation of enantiomers. In this case, a chiral selector must be added to one of the liquid phases. This principle is common to some of the separation techniques described previously, such as CCC, CPC or supported-liquid membranes. In all of these, partition of the enantiomers of a mixture takes place thanks to their different affinity for the chiral additive in a given system of solvents. 

Fig. 5-2. Three types of the liquid membrane eonfiguration (a) emulsion liquid membrane (b) supported liquid membrane (e) elassieal bulk liquid membrane set-up.

In supported liquid membranes, a chiral liquid is immobilized in the pores of a membrane by capillary and interfacial tension forces. The immobilized film can keep apart two miscible liquids that do not wet the porous membrane. Vaidya et al. [10] reported the effects of membrane type (structure and wettability) on the stability of solvents in the pores of the membrane. Examples of chiral separation by a supported liquid membrane are extraction of chiral ammonium cations by a supported (micro-porous polypropylene film) membrane [11] and the enantiomeric separation of propranolol (2) and bupranolol (3) by a nitrate membrane with a A/ -hexadecyl-L-hydroxy proline carrier [12]. 

As described above, the application of classical liquid- liquid extractions often results in extreme flow ratios. To avoid this, a completely symmetrical system has been developed at Akzo Nobel in the early 1990s [64, 65]. In this system, a supported liquid-membrane separates two miscible chiral liquids containing opposite chiral selectors (Fig. 5-13). When the two liquids flow countercurrently, any desired degree of separation can be achieved. As a result of the system being symmetrical, the racemic mixture to be separated must be added in the middle. Due to the fact that enantioselectivity usually is more pronounced in a nonaqueous environment, organic liquids are used as the chiral liquids and the membrane liquid is aqueous. In this case the chiral selector molecules are lipophilic in order to avoid transport across the liquid membrane. 

ILs, on the other hand, are uniquely suited for use as solvents for gas separations. Since they are non-volatile, they cannot evaporate to cause contamination of the gas stream. This is important when selective solvents are used in conventional absorbers, or when they are used in supported liquid membranes. For conventional absorbers, the ability to separate one gas from another depends entirely on the relative solubilities (ratio of Henry s law constants) of the gases. In addition, ILs are particularly promising for supported liquid membranes, because they have the potential to be incredibly stable. Supported liquid membranes that incorporate conventional liquids eventually deteriorate because the liquid slowly evaporates. Moreover, this finite evaporation rate limits how thin one can make the membrane. This... 

The solubilities of the various gases in [BMIM][PFg] suggests that this IL should be an excellent candidate for a wide variety of industrially important gas separations. There is also the possibility of performing higher-temperature gas separations, thanks to the high thermal stability of the ILs. For supported liquid membranes this would require the use of ceramic or metallic membranes rather than polymeric ones. Both water vapor and CO2 should be removed easily from natural gas since the ratios of Henry s law constants at 25 °C are -9950 and 32, respectively. It should be possible to scrub CO2 from stack gases composed of N2 and O2. Since we know of no measurements of H2S, SO, or NO solubility in [BMIM][PFg], we do not loiow if it would be possible to remove these contaminants as well. Nonetheless, there appears to be ample opportunity for use of ILs for gas separations on the basis of the widely varying gas solubilities measured thus far. 

Zougagh, M., Valcarcel, M., and Rios, A., Automatic selective determination of caffeine in coffee and tea samples by using a supported liquid membrane-modified piezoelectric flow sensor with molecularly imprinted polymer. Trends Anal. Chem., 23, 399, 2004. 

Classical LLEs have also been replaced by membrane extractions such as SLM (supported liquid membrane extraction), MMLLE (microporous membrane liquid-liquid extraction) and MESI (membrane extraction with a sorbent interface). All of these techniques use a nonporous membrane, involving partitioning of the analytes [499]. SLM is a sample handling technique which can be used for selective extraction of a particular class of compounds from complex (aqueous) matrices [500]. Membrane extraction with a sorbent interface (MESI) is suitable for VOC analysis (e.g. in a MESI- xGC-TCD configuration) [501,502]. 

The production process for (S)-phenylalanine as an intermediate in aspartame perpetuates the principle of reracemization of the nondesired enantiomer (Figure 4.5) in a hollow fiber/ liquid membrane reactor. Asymmetric hydrolysis of the racemic phenylalanine isopropylester at pH 7.5 leads to enantiopure phenylalanine applying subtilisin Carlsberg. The unconverted enantiomer is continuously extracted via a supported liquid membrane [31] that is immobilized in a microporous membrane into an aqueous solution of pH 3.5. The desired hydrolysis product is charged at high pH and cannot, therefore, be extracted into the acidic solution [32]. 

Huang, D.S., Huang, K.L., Chen, S.P. et al. (2008) Rapid reaction-diffusion model for the enantioseparation of phenylalanine across hollow fiber supported liquid membrane. Separation Science and Technology, 43 (2), 259-272. 

Alguacil, F. J. Coedo, A. G. Dorado, M. T. Padilla, I. Phosphine oxide mediate transport modelling of mass transfer in supported liquid membrane transport of gold(III) using Cyanex 923. Chem. Eng. Sci. 2001, 56, 3115-3122. 

Antico, E. Masana, A. Hidalgo, M. Salvado, V. Valiente, M. New sulfur-containing reagents as carriers for the separation of palladium by solid supported liquid membranes. Hydrometallurgy 1994, 35, 343-352. 

Several manufacturers introduced products amenable for this solid-supported LLE and for supported liquid extraction (SLE). The most common support material is high-purity diatomaceous earth. Table 1.8 lists some commercial products and their suppliers. The most widely investigated membrane-based format is the supported liquid membrane (SLM) on a polymeric (usually polypropylene) porous hollow fiber. The tubular polypropylene fiber (short length, 5 to 10 cm) is dipped into an organic solvent such as nitrophenyl octylether or 1-octanol so that the liquid diffuses into the pores on the fiber wall. This liquid serves as the extraction solvent when the coated fiber is dipped... 

In the past decade, several novel solvent-based microextraction techniques have been developed and applied to environmental and biological analysis. Notable approaches are single-drop microextraction,147 small volume extraction in levitated drops,148 flow injection extraction,149 150 and microporous membrane- or supported liquid membrane-based two- or three-phase microextraction.125 151-153 The two- and three-phase microextraction techniques utilizing supported liquid membranes deposited in the pores of hollow fiber membranes are the most explored for analytes of wide ranging polarities in biomatrices. This discussion will be limited to these protocols. 

The principle of a three-phase membrane extraction is illustrated in Figure 1.28. An organic solvent is immobilized in the pores of a porous polymeric support consisting of a flat filter disc or a hollow fiber-shaped material. This supported liquid membrane (SLM) is formed by treating the support material with an organic solvent that diffuses into its pores. The SLM separates an aqueous... 

FIGURE 1.34 Apparatus for liquid membrane extraction. (A) Manual off-line instrument based on peristaltic pump. (B) Instrument with online connection to HPLC for environmental studies. (C) Experimental set-up for supported liquid membrane HPLC determination of biomolecules in blood plasma or urine.153 (Reproduced with permission from the authors.)... 

Support coated open tubular (SCOT) columns, 4 615 6 379 Supported liquid membranes, 16 28 Support material, in fluidized-bed encapsulation, 11 540 affinity chromatography, 6 392-393 chromatography, 6 375 gas chromatography, 6 375 Supported metals... 

As discussed by Frankemfeld and Li(28) and del Cerro and Boey(29), liquid membrane extraction 28,29) involves the transport of solutes across thin layers of liquid interposed between two otherwise miscible liquid phases. There are two types of liquid membranes, emulsion liquid membranes (ELM) and supported liquid membranes (SLM). They are conceptually similar, but substantially different in their engineering. 

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