Stability, liquid membrane

Schlosser, S. and Kossaczky, E. (1987) Liquid membranes stabilized by polymeric surfactants, in Synthetic Polymeric Membranes (ed. B. Sedlacek), W. de Gruyter, Berlin, p. 571. 

In the future, novel developments of liquid membranes for biochemical processes should arise. There are several opportunities in the area of fermentation or cell culture, for the in situ recovery of inhibitory products, for example. Another exciting research direction is the use of liquid membrane for enzyme encapsulation so that enzymatic reaction and separation can be combined in a single step. Chapter 6 by Simmons ial- (49) is devoted to this technique. The elucidation of fundamental mechanisms behind the liquid membrane stability is essential, and models should be developed for the leakage rate in various flow conditions. Such models will be useful to address the effect of parameters such as flow regime, agitation rate, and microdroplet volume... 

Supported liquid membrane stability and lifetime limit the industrial application of this separation technique. Therefore, the stability of these membranes needs to be enhanced drastically. A proper choice of the operating and membrane composition factors might improve the lifetime of SLM systems. 

Park, Y. (2006). Development and optimization of novel emulsion liquid membranes stabilized by non-Newtonian conversion in Taylor-Couette flow for extraction of selected organic and metallic contaminants. Ph.D. thesis, Georgia Institute of Technology, Atlanta, GA, USA. 

Liquid Membrane Stability. While studies of other investigators have indicated that the blood has good compatibility with the liquid fluorocarbon surface, they also indicate that fluorocarbon droplets should not be introduced to the bloodstream of animals (6, 7, 8). Liquid membrane rupture in the oxygenator apparatus could produce droplets from the fluorocarbon which had formed the liquid membrane. These droplets would be entrained and returned to a test animal with the oxygenated blood. As a preliminary test for liquid membrane rupture and droplet formulation, the oxygen flow into apparatus was momentarily stopped, and blood samples were withdrawn for examination. 

The specific rate of oxygen transfer per unit of liquid membrane area seems to be quite reasonable. However, methods to form and utilize effectively much smaller diameter liquid membranes, perhaps similar to those used in other liquid membrane applications, would be required to obtain enough membrane area per unit blood volume for a practical blood oxygenator. The stability of the liquid membranes does not seem to be a major problem however, more definitive liquid membrane stability information would be required before the blood oxygenator application. 

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]. 

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. 

An alternative description of membrane stability has been based on hydrodynamic models, originally developed for liquid films in various environments [54-56]. Rupture of the film was rationalized by the instability of symmetrical squeezing modes (SQM) related to the thickness fluctuations. In the simplest form it can be described by a condition [54] d Vdis/dh < where is the interaction contribution related to the dis-... 

In conclusion, it should be mentioned that extraction parameters (the equilibrium constants of exchange reactions and ion-pair stabilities) were introduced into the theory of ion-selective electrodes in [2, 31,33, 34, 35,69]. The theory of ISEs with a liquid membrane and a diffusion potential in the membrane was extended by Buck etal. [11, 13, 14, 73, 74] and Morf [54]. 

Fig. 7.3. Correlation between the selectivity coefficient and the ratio of stability constants in water for a liquid membrane ISE based on valinomycin dissolved in nitrobenzene. (After Morf [151].)...

In the supported liquid membrane process, the liquid membrane phase impregnates a microporous solid support placed between the two bulk phases (Figure 15.1c). The liquid membrane is stabilized by capillary forces making unnecessary the addition of stabilizers to the membrane phase. Two types of support configurations are used hollow fiber or flat sheet membrane modules. These two types of liquid membrane configuration will be discussed in the following sections. 

The emulsion liquid membrane (Fig. 15.1b) is a modification of the single drop membrane configuration presented by Li [2] in order to improve the stability of the membrane and to increase the interfacial area. The membrane phase contains surfactants or other additives that stabilize the emulsion. 

Clearly, in such systems, the nature and stability of the liquid membranes is a critical issue [57]. 

EMF-measurements are, therefore, a method for directly assessing the relative stability of the complexes of the valinomycin group antibiotics in water and water-like solvents (cf. Fig. 11 and Ref. (87)). The selectivity constants of the liquid membranes are in this case independent of the ion-selective behavior of the membrane solvents used. 

Fig. 11. Comparison of the electrochemical alkali ion selectivity of neutral antibiotics in liquid membranes (log for macrotetrolides (85), log K lM for valinomycin (86)) with the stability of the complexes (log K from Table 2) between these antibiotics and alkali cations in methanol...

In this paper an overview of the developments in liquid membrane extraction of cephalosporin antibiotics has been presented. The principle of reactive extraction via the so-called liquid-liquid ion exchange extraction mechanism can be exploited to develop liquid membrane processes for extraction of cephalosporin antibiotics. The mathematical models that have been used to simulate experimental data have been discussed. Emulsion liquid membrane and supported liquid membrane could provide high extraction flux for cephalosporins, but stability problems need to be fully resolved for process application. Non-dispersive extraction in hollow fib er membrane is likely to offer an attractive alternative in this respect. The applicability of the liquid membrane process has been discussed from process engineering and design considerations. 

In the early 1970s Li [13] proposed a method that is now called Emulsion (surfactant) Liquid Membrane (ELM) or Double Emulsion Membrane (DEM) (Fig. 3). The name reveals that the three liquid system is stabilized by an emulsifier, the amount of which reaches as much as 5 % or more with respect to the membrane liquid. The receiving phase R, which usually has a smaller volume than the donor solution, F of similar nature, is finally dispersed in the intermediate phase, M. In the next step the donor solution F is contacted with the emulsion. For this purpose, the emulsion is dispersed in the donor solution F by gentle mixing typically in a mixer-settler device. After this step, the emulsion is separated and broken. The enriched acceptor solution is further processed and the membrane liquid M is fed back for reuse. 

Fortunato, R. et al.. Supported liquid membranes using ionic liquids study of stability and transport mechanism, /. Membr. Sci., 242,197, 2004. 

More recently the use of membrane contactors to solve the stability problem of liquid membranes has been proposed [19-21], The concept is illustrated in Figure 11.4. Two membrane contactors are used, one to separate the organic carrier phase from the feed and the other to separate the organic carrier phase from the permeate. In the first contactor metal ions in the feed solution diffuse across the microporous membrane and react with the carrier, liberating hydrogen counter ions. The organic carrier solution is then pumped from the first to the second membrane contactor, where the reaction is reversed. The metal ions are... 

Kirch and Lehn have studied selective alkali metal transport through a liquid membrane using [2.2.2], [3.2.2], [3.3.3], and [2.2.C8] (146, 150). Various cryptated alkali metal picrates were transported from an in to an out aqueous phase through a bulk liquid chloroform membrane. While carrier cation pairs which form very stable complexes display efficient extraction of the salt into the organic phase, the relative rates of cation transport were not proportional to extraction efficiency and complex stability (in contrast to antibiotic-mediated transport across a bulk liquid membrane). Thus it is [2.2.Ca] which functions as a specific potassium ion carrier, while [2.2.2] is a specific potassium ion receptor (Table VI). 

Stabilized liquid membrane device (SLMD) A water-insoluble organic complexing mixture diffuses to the exterior surface of the sampler through a polymeric membrane Divalent metal ions Preconcentration, in situ sampling, determination of labile metal ions in grab samples Days to several weeks Extraction with acid 73... 

Brumbaugh, W.G., J.D. Petty, J.N. Huckins, and S.E. Manahan. 2002. Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water. Water Air Soil Pollut. 133 109-119. 

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