Liquid immobilized membranes structure

In Section 5.4.4, we studied a variety of chemical reaction facilitated separation where the reaction was taking place in a thin liquid layer acting as the liquid membrane Figure 5.4.4 illustrated a variety of liquid membrane permeation mechnisms. Here we will identify first the structural configuration of the liquid membranes as they are used in separators with countercurrent flow pattern (as well as for the cocurrent flow pattern). There are three general classes of liquid membrane structures emulsion liquid membrane (ELM) supported liquid membrane (SLM) or immobilized liquid membrane (ILM) hollow fiber contained liquid membrane (HFCLM). Each will be described very briefly. 

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]. 

Vrakas, D., Giaginis, C., Tsantili-Kakoulidou, A. Different retention behavior of structurally diverse basic and neutral drugs in immobilized artificial membrane and reversed-phase high performance liquid chromatography ... 

There are reports of numerous examples of dendritic transition metal catalysts incorporating various dendritic backbones functionalized at various locations. Dendritic effects in catalysis include increased or decreased activity, selectivity, and stability. It is clear from the contributions of many research groups that dendrimers are suitable supports for recyclable transition metal catalysts. Separation and/or recycle of the catalysts are possible with these functionalized dendrimers for example, separation results from precipitation of the dendrimer from the product liquid two-phase catalysis allows separation and recycle of the catalyst when the products and catalyst are concentrated in two immiscible liquid phases and immobilization of the dendrimer in an insoluble support (such as crosslinked polystyrene or silica) allows use of a fixed-bed reactor holding the catalyst and excluding it from the product stream. Furthermore, the large size and the globular structure of the dendrimers enable efficient separation by nanofiltration techniques. Nanofiltration can be performed either batch wise or in a continuous-flow membrane reactor (CFMR). 

A novel polymeric bicontinuous microemulsion (PBM) membrane, consisting of an interconnecting network of nanometer pore size water channels, was employed as liquid membrane support [13] for the immobilization of new porphyrin carrier [14] for facilitated oxygen transport. Although the membrane resulted to be stable due to the nanoporous structure, a modest (2.3-2.4) O2/N2 selectivity was achieved. 

Way, Noble and Bateman (49) review the historical development of immobilized liquid membranes and propose a number of structural and chemical guidelines for the selection of support materials. Structural factors to be considered include membrane geometry (to maximize surface area per unit volume), membrane thickness (<100 pm), porosity (>50 volume Z), mean pore size (<0.1)jm), pore size distribution (narrow) and tortuosity. The amount of liquid membrane phase available for transport In a membrane module Is proportional to membrane porosity, thickness and geometry. The length of the diffusion path, and therefore membrane productivity, is directly related to membrane thickness and tortuosity. The maximum operating pressure Is directly related to the minimum pore size and the ability of the liquid phase to wet the polymeric support material. Chemically the support must be Inert to all of the liquids which It encounters. Of course, final support selection also depends on the physical state of the mixture to be separated (liquid or gas), the chemical nature of the components to be separated (inert, ionic, polar, dispersive, etc.) as well as the operating conditions of the separation process (temperature and pressure). The discussions in this chapter by Way, Noble and Bateman should be applicable the development of immobilized or supported gas membranes (50). 

Criteria for immobilized liquid membrane (ILM) support selection can be divided into two categories structural properties and chemical properties. Structural properties include geometry, support thickness, porosity, pore size distribution and tortuosity. Chemical criteria consist of support surface properties and reactivity of the polymer support toward fluids in contact with it. The support thickness and tortuosity determine the diffusional path length, which should be minimized. Porosity determines the volume of the liquid membrane and therefore the quantity of carrier required. The mean pore size determines the maximum pressure difference the liquid membrane can support. The support must be chemically inert toward all components in the feed phase, membrane phase, and sweep or receiving phase. 

Immobilized Liquid Membranes. Facilitated transport liquid membranes for gas separations can be prepared In several configurations. The complexatlon agent solution can be held between two nonporous polymer films (2j1), Impregnated Into the pore structure of a micro-porous polymer film (25), or the carrier can be exchanged for the counterion In an Ion exchange membrane (it). 

However, Immobilized liquid membranes supported with porous substrates have two prlmeu y experimental problems loss of solvent and loss or deactivation of the carrier. Matson et al. ( ) prevented evaporative loss of liquid by maintaining the relative humidity of the gas streams in the range of 60 to 90%. Another problem may arise when humidification is used. If solvent condenses out of the feed gas stream onto the ILM and a pressure gradient between the feed and sweep gas stream exists, solvent may flow through the support pore structure leaching the carrier out of the membrane. 

Carrier Chemistry. The use of structurally modified macrocycllc polyethers (crown ethers) as CcU rlers In bulk, emulsion, and Immobilized liquid membranes Is the subject of the chapter by Bartsch et al. (111). They discuss the use of lonlzable crown ethers for the coupled transport of alkali metal cations. The lonlzable carboxylic and phosphonlc acid groups on the macrocycles eliminate the need for an anion to accompany the catlon-macrocycle complex across the liquid membrcuie or for an auxiliary complexlng agent In the receiving phase. The influence of carrier structure on the selectivity and performance of competitive alkali metal transport across several kinds of liquid membranes Is presented. 

Immobilized Liquid Membranes. A pilot plant study of the recovery of ethylene and propylene from a polypropylene reactor off-gas stream was presented by Hughes et al. (23). Aqueous solutions of Ag Ion were Immobilized In the pore structure of commercial reverse osmosis hollow fiber modules. The pilot plant operated at feed pressures of 414-827 kPa, feed flow rates of 1.42-4.25 m /h at STP, and sweep flow rates of 3.79 10" - 0.114 m /h hexane. Permeate streams with propylene concentrations In excess of 98 mole % were observed in pilot plant operation with modules containing 22.3 to 37.2 m membrane area. 

Facilitated transport of gases has been the subject of numerous Investigations which are summarized in recent review articles (2 2). Immobilized liquid membranes (ILMs) were prepared for the majority of these studies by Impregnating the pore structure of very thin, microporous polymeric substrates with a solution of a solvent and a complexatlon agent (). Such ILMs have two primary experimental problems loss of solvent phase and loss or deactivation of the com-... 

Thus, the major difference between our ILM structure to that utilized by previous workers lies In the fact that we have a single-ply structure wherein the liquid membrane is Immobilized within the pores of a mlcroporous hydrophobic support as compared to the two-ply structure of GE workers discussed above. To be noted also Is that moisture condensation on the hydrophobic supports does not automatically lead to flooding due to the hydrophobic nature of the surface (unlike that with hydrophilic membranes). 

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