Liquid membrane separations using different extractants

LIQUID MEMBRANE SEPARATIONS USING DIFFERENT EXTRACTANTS 8.3.1 Neutral donor ligands... 

There are a number of different membrane techniques which have been suggested as alternatives to the SPE and LLE techniques. It is necessary to distinguish between porous and nonporous membranes, as they have different characteristics and fields of application. In porous membrane techniques, the liquids on each side of the membrane are physically connected through the pores. These membranes are used in Donnan dialysis to separate low-molecular-mass analytes from high-molecular-mass matrix components, leading to an efficient cleanup, but no discrimination between different small molecules. No enrichment of the small molecules is possible instead, the mass transfer process is a simple concentration difference over the membrane. Nonporous membranes are used for extraction techniques. 

Most of the chiral membrane-assisted applications can be considered as a modality of liquid-liquid extraction, and will be discussed in the next section. However, it is worth mentioning here a device developed by Keurentjes et al., in which two miscible chiral liquids with opposing enantiomers of the chiral selector flow counter-currently through a column, separated by a nonmiscible liquid membrane [179]. In this case the selector molecules are located out of the liquid membrane and both enantiomers are needed. The system allows recovery of the two enantiomers of the racemic mixture to be separated. Thus, using dihexyltartrate and poly(lactic acid), the authors described the resolution of different drugs, such as norephedrine, salbu-tamol, terbutaline, ibuprofen or propranolol. 

The use of liquid membranes in analytical applications has increased in the last 20 years. As is described extensively elsewhere (Chapter 15), a liquid membrane consists of a water-immiscible organic solvent that includes a solvent extraction extractant, often with a diluent and phase modifier, impregnated in a microporous hydrophobic polymeric support and placed between two aqueous phases. One of these aqueous phases (donor phase) contains the analyte to be transported through the membrane to the second (acceptor) phase. The possibility of incorporating different specific reagents in the liquid membranes allows the separation of the analyte from the matrix to be improved and thus to achieve higher selectivity. 

Nondispersive solvent extraction is a novel configuration of the conventional solvent extraction process. The term nondispersive solvent extraction arises from the fact that instead of producing a drop dispersion of one phase in the other, the phases are contacted using porous membrane modules. The module membrane separates two of the immiscible phases, one of which impregnates the membrane, thus bringing the liquid-liquid interface to one side of the membrane. This process differs from the supported liquid membrane in that the liquid impregnating the membrane is also the bulk phase at one side of the porous membrane, thus reducing the number of liquid-liquid interfaces between the bulk phases to just one. 

Partitioning of components between two immiscible or partially miscible phases is the basis of classical solvent extraction widely used in numerous separations of industrial interest. Extraction is mostly realized in systems with dispergation of one phase into the second phase. Dispergation could be one origin of problems in many systems of interest, like entrainment of organic solvent into aqueous raffinate, formation of stable, difficult-to-separate emulsions, and so on. To solve these problems new ways of contacting of liquids have been developed. An idea to perform separations in three-phase systems with a liquid membrane is relatively new. The first papers on supported liquid membranes (SLM) appeared in 1967 [1, 2] and the first patent on emulsion liquid membrane was issued in 1968 [3], If two miscible fluids are separated by a liquid, which is immiscible with them, but enables a mass transport between the fluids, a liquid membrane (LM) is formed. A liquid membrane enables transport of components between two fluids at different rates and in this way to perform separation. When all three phases are liquid this process is called pertraction (PT). In most processes with liquids membrane contact of phases is realized without dispergation of phases. 

Membrane extraction encompasses a class of liquid-phase separations where the primary driving force for transport stems from the concentration difference between the feed and extractant liquids rather than a pressure gradient, as is the case with most of the other processes discussed above. A microporous membrane placed between the feed and the extractant liquids functions primarily as a phase separator. The degree of separation achievable is determined by the relative partition coefficients among individual solutes. This operationx is known as membrane solvent extraction. If a nonporous, permselective membrane is used instead, however, the selectivity of the membrane would be superimposed on the partitioning selectivity in this case the process may be referred to as perstraction. These process concepts are illustrated in Fig. 34. 

Promising results are shown by recently developed integrated SLM-ELM [84, 85] systems. These techniques are known as supported liquid membrane with strip dispersion (SLMSD), pseudo-emulsion-based hollow fiber strip dispersion (PEHFSD), emulsion pertraction technology (EPP), and strip dispersion hybrid Hquid membrane (SDHLM). AH techniques are the same the organic phase (carrier, dissolved in diluent) and back extraction aqueous phase are emulsified before injection into the module and can be separated at the module outlet. The difference is only in the type of the SLM contactors hoUow fiber or flat sheet and in the Hquid membrane (carrier) composition. These techniques have been successfuUy demonstrated for the removal and recovery of metals from wastewaters. Nevertheless, the techniques stiU need to be tested in specific apphcations to evaluate the suitabUity of the technology for commercial use. 

There are several processes for the separation of liquid mixtures using porous membranes or asymmetric polymer membranes. With porous membranes, separation may depend just on differences in diffusivity, as is the case with dialysis, where aqueous solutions at atmospheric pressure are on both sides of the membrane. For liquid-liquid extraction using porous membranes, the immiscible raffinate and extract phases are separated by the membrane, and differences in the equilibrium solute distribution as well as differences in diffusivity determine the extract composition. 

We have continued to pioneer in the development and application of many separation techniques from heatless drying (the removal of moisture by intermittent absorption and desorption at different pressure levels), through the use of molecular sieve absorbers, advanced lube oil extraction media, and CO2 absorption promoters, to the use of liquid membranes (containing an encapsulated absorbing phase) and lasers to activate only specific molecules. 

The recuperation of metal ions is carried out by different types of processes such as solvent extraction [47], membrane separation [48], and chemical absorption [49]. Among these processes, solvent extraction is the most widely adopted type for the removal of metals, where the extraction agent (such as di(2-ethylhexyl) phosphoric acid, trw(2-ethylhexyl)amine, liquid phosphine oxides) is dissolved in an organic solvent (kerosene, toluene, etc.) that is used as the diluents [50,51]. 

Apart from the work conducted by Li et al. at Exxon which is fully reported in the proceedings of a seminar on Liquid Membrane Applications in Waste Water Treatment and Metals Recovery held at UMIST in May 1980, investigations on applications of liquid membranes to metals recovery are conducted at a number of other places. Thus, extraction of copper is studied at UMIST (11, 12), Graz (13-15) and Bend Research (16). The last place is also active in the use of membranes for the extraction of uranium (17), whereas work on the extraction of copper, zinc, cadmium and lead is conducted by Boyadzhiev et al. (18). Extraction of different metals has also been studied by Stelmaszek (19) and Strzelbicki (20, 21) and of zinc alone at Imperial College (7). All the accumulated data point towards membrane extraction as a promising process for the solution of separation problems, particularly in dilute solutions. 

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