Separation techniques extraction

Every single regeneration problem has to be analysed individually, however, the following case study demonstrates how a selection of separation techniques, extraction and phase separation, can successfully be applied to regenerate a spent ionic liquid based electrolyte satisfactorily. As a case study the electrolyte 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ([BMP]Tf2N) was chosen, which is used for electrodeposition of aluminum as described in the literature [137, 138],... 

Immunoassay plays an important role in clinical analysis. It is followed by electrometric techniques polarography and electrometric sensors (ion-selective membrane electrodes, or ISME, and biosensors). Because of the complexity of the matrix, spectrometric techniques must precede the separation technique (extraction or chromatographic techniques). The best reliability for clinical analysis is achieved by using immunoassay methods and electrochemical sensors. Because of the possibility of assaying the activity of the ions continuously and without any prior separation, electrochemical... 

Extraction chromatography (formerly called reversed-phase partition chromatography) combines the best features of solvent extraction and chromatographic separation techniques. Extraction chromatographic systems consist of a mobile liquid phase and a stationary liquid phase on an inert support. Separations are achieved by taking advantage of the difference in the distribution of ions between the two liquid phases. 

The element may be obtained by separating neodymium salts from other rare earths by ion-exchange or solvent extraction techniques, and by reducing anhydrous halides such as NdFs with calcium metal. Other separation techniques are possible. 

Extraction Between Two Phases When the sample is initially present in one of the phases, the separation is known as an extraction. In a simple extraction the sample is extracted one or more times with portions of the second phase. Simple extractions are particularly useful for separations in which only one component has a favorable distribution ratio. Several important separation techniques are based on simple extractions, including liquid-liquid, liquid-solid, solid-liquid, and gas-solid extractions. 

In Chapter 7 we examined several methods for separating an analyte from potential interferents. For example, in a liquid-liquid extraction the analyte and interferent are initially present in a single liquid phase. A second, immiscible liquid phase is introduced, and the two phases are thoroughly mixed by shaking. During this process the analyte and interferents partition themselves between the two phases to different extents, affecting their separation. Despite the power of these separation techniques, there are some significant limitations. 

Traditionally, chiral separations have been considered among the most difficult of all separations. Conventional separation techniques, such as distillation, Hquid—Hquid extraction, or even some forms of chromatography, are usually based on differences in analyte solubiUties or vapor pressures. However, in an achiral environment, enantiomers or optical isomers have identical physical and chemical properties. The general approach, then, is to create a "chiral environment" to achieve the desired chiral separation and requires chiral analyte—chiral selector interactions with more specificity than is obtainable with conventional techniques. 

Until separation techniques such as chromatography (28,29) and counter-current extraction had advanced sufficientiy to be of widespread use, the principal alkaloids were isolated from plant extracts and the minor constituents were either discarded or remained uninvestigated. With the advent of, first, column, then preparative thin layer, and now high pressure Hquid chromatography, even very low concentrations of materials of physiological significance can be obtained in commercial quantities. The alkaloid leurocristine (vincristine, 22, R = CHO), one of the more than 90 alkaloids found in Catharanthus roseus G. Don, from which it is isolated and then used in chemotherapy, occurs in concentrations of about 2 mg/100 kg of plant material. 

Phase Separation. Microporous polymer systems consisting of essentially spherical, intercoimected voids, with a narrow range of pore and ceU-size distribution have been produced from a variety of thermoplastic resins by the phase-separation technique (127). If a polyolefin or polystyrene is insoluble in a solvent at low temperature but soluble at high temperatures, the solvent can be used to prepare a microporous polymer. When the solutions, containing 10—70% polymer, are cooled to ambient temperatures, the polymer separates as a second phase. The remaining nonsolvent can then be extracted from the solid material with common organic solvents. These microporous polymers may be useful in microfiltrations or as controlled-release carriers for a variety of chemicals. 

Absorption. As a separation technique, absorption (qv), also called extractive distillation, starts with an energy deficit because the process mixes in a pure material (solvent) and then separates it again. This process is nevertheless quite common because it shares most of the advantages of distillation. Additionally, because it separates by molecular type, it can be tailored to obtain a high a. The following ratios are suggested for equal costs (7) ... 

The use of separation techniques, such as gel permeation and high pressure Hquid chromatography interfaced with sensitive, silicon-specific aas or ICP detectors, has been particularly advantageous for the analysis of siUcones in environmental extracts (469,483—486). Supercritical fluid chromatography coupled with various detection devices is effective for the separation of siUcone oligomers that have molecular weights less than 3000 Da. Time-of-flight secondary ion mass spectrometry (TOF-sims) is appHcable up to 10,000 Da (487). 

The C4 stream from steam crackers, unlike its counterpart from a refinery, contains about 45% butadiene by weight. Steam crackers that process significant amounts of Hquid feedstocks have satellite faciUties to recover butadiene from the stream. Conventional distillation techniques are not feasible because the relative volatihty of the chemicals in this stream is very close. Butadiene and butylenes are separated by extractive distillation using polar solvents. 

Separation Techniques. Current methods for separating fatty acids are by solvent crystaUi2ation or by the hydrophili2ation process. Other methods that have been used in the past, or perhaps could be used in the future, are panning and pressing, solvent extraction, supercritical fluid extraction, the use of metal salts in assisting in separation, separations using urea complexes, and adsorption/desorption. 

Of these five methods all but pressure-swing distillation can also be used to separate low volatiUty mixtures and all but reactive distillation are discussed herein. It is also possible to combine distillation and other separation techniques such as Hquid—Hquid extraction (see Extraction, liquid-liquid), adsorption (qv), melt crystallization (qv), or pervaporation to complete the separation of azeotropic mixtures. 

Robbins ( Oquid-Liquid Extraction, in Schweitzer, Handbook of Separation Techniques for Chemical Engineers, McGraw-Hill, New York, 1979, sec. 1.9) reported that most liquid-liquid extrac tion systems can be treated as having either (A) immiscible solvents, (B) partially miscible solvents with a low solute concentration in the extract, or (C) partially miscible solvents with a high solute concentration in the extract. 

ON-LINE COUPLING OF SUPERCRITICAL FLUID EXTRACTION WITH CAPILLARY ELECTRODRIVEN SEPARATION TECHNIQUES (SFE-CESTs)... 

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

One example of normal-phase liquid chromatography coupled to gas chromatography is the determination of alkylated, oxygenated and nitrated polycyclic aromatic compounds (PACs) in urban air particulate extracts (97). Since such extracts are very complex, LC-GC is the best possible separation technique. A quartz microfibre filter retains the particulate material and supercritical fluid extraction (SPE) with CO2 and a toluene modifier extracts the organic components from the dust particles. The final extract is then dissolved in -hexane and analysed by NPLC. The transfer at 100 p.1 min of different fractions to the GC system by an on-column interface enabled many PACs to be detected by an ion-trap detector. A flame ionization detector (PID) and a 350 p.1 loop interface was used to quantify the identified compounds. The experimental conditions employed are shown in Table 13.2. 

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. 

Solvent extraction is probably the separation technique which is most widely used in conjunction with AAS. It often allows the extraction of a number of elements in one operation and, because of the specific nature of AAS, non-selective reagents such as the thiocarbamate derivatives (e.g. APDC) may be used for the liquid-liquid extraction (see Section 6.18). 

Separation techniques may have to be applied if the given sample contains substances which act as interferences (Section 21.10), or, as explained above, if the concentration of the element to be determined in the test solution is too low to give satisfactory absorbance readings. As already indicated (Section 21.10), the separation methods most commonly used in conjunction with flame spectrophotometric methods are solvent extraction (see Chapter 6) and ion exchange (Chapter 7). When a solvent extraction method is used, it may happen that the element to be determined is extracted into an organic solvent, and as discussed above it may be possible to use this solution directly for the flame photometric measurement. 

Natural products, such as enzymes and vitamins, are almost invariably extracted from mixtures. To analyze the composition of any sample that we suspect is a mixture, we first separate its components by physical means and then identify each individual substance present (Fig. G.5). Common physical separation techniques include decanting, filtration, chromatography, and distillation. 

Despite its widespread application [31,32], the kinetic resolution has two major drawbacks (i) the maximum theoretical yield is 50% owing to the consumption of only one enantiomer, (ii) the separation of the product and the remaining starting material may be laborious. The separation is usually carried out by chromatography, which is inefficient on a large scale, and several alternative methods have been developed (Figure 6.2). For example, when a cyclic anhydride is the acyl donor in an esterification reaction, the water-soluble monoester monoacid is separable by extraction with an aqueous alkaline solution [33,34]. Also, fiuorous phase separation techniques have been combined with enzymatic kinetic resolutions [35]. To overcome the 50% yield limitation, one of the enantiomers may, in some cases, be racemized and resubmitted to the resolution procedure. 

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