Separation processes Extraction

For selection of alternative solvents (non-ozone depleting) for separation processes (extraction and HPLC mobile phase optimisation) references [24,25] are very useful. 

Example 5.5 Equipartition principle in separation processes Extraction Since the minimization of entropy production is not always an economic criterion, it is necessary to relate the overall entropy production and its distribution to the economy of the process. To do this, we may consider various processes with different operating configurations. For example, by modifying an existing design, we may attain an even distribution of forces and hence an even distribution of entropy production. 

In contrast to other separation processes, extraction does not lead directly to pure key components. The feed phase after extraction (raffinate phase) contains not only the carrying substance which is inert to the solvent, hut also solvent, and valuable key components. The receiving or extract phase, consists essentially of the solvent and key components. Regeneration of the solvent and purification of the key components requires additional separation processes, for example, rectification. 

The species Dunaliella salina is rich in beta-carotene (up to 14% of its dry matter), which is present as a mixture of cis- and tra 5-isomers. For pharmaceutical applications, especially, it is important that no toxic organic solvents are used in the separation process. Extraction with SCCO2 improved the cis/trans ratio as compared to extraction with acetone. An optimum beta-carotene yield was attained at 30MPa and 40°C. " ... 

The foremost separation process is crude distillation and in second place, if deeper conversion is envisaged, solvent extraction (deasphalting). 

The thermospray process extracts sample molecules from a solvent and turns them into ions. Therefore, the system is both an inlet and an ion source, so a separate ion source is not necessary. 

Butadiene Separation. Solvent extraction is used in the separation of butadiene (qv) [106-99-0] from other C-4 hydrocarbons in the manufacture of synthetic mbber. The butadiene is produced by catalytic dehydrogenation of butylene and the Hquid product is then extracted using an aqueous cuprammonium acetate solution with which the butadiene reacts to form a complex. Butadiene is then recovered by stripping from the extract. Distillation is a competing process. 

Extraction of C-8 Aromatics. The Japan Gas Chemical Co. developed an extraction process for the separation of -xylene [106-42-3] from its isomers using HF—BF as an extraction solvent and isomerization catalyst (235). The highly reactive solvent imposes its own restrictions but this approach is claimed to be economically superior to mote conventional separation processes (see Xylenes and ethylbenzene). 

Alternative approaches are to be found in the hterature. Derivations of the above equations are given in numerous texts (2,10—12), which also describe graphical or analytical solutions to the problem. Many of these have direct analogues in other separation processes such as distillation (qv) and hquid—hquid extraction, and use plots such as the McCabe-Thiele diagram or Ponchon-Savarit diagram. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

An improved solvent extraction process, PUREX, utilizes an organic mixture of tributyl phosphate solvent dissolved in a hydrocarbon diluent, typically dodecane. This was used at Savannah River, Georgia, ca 1955 and Hanford, Washington, ca 1956. Waste volumes were reduced by using recoverable nitric acid as the salting agent. A hybrid REDOX/PUREX process was developed in Idaho Falls, Idaho, ca 1956 to reprocess high bum-up, fuUy enriched (97% u) uranium fuel from naval reactors. Other separations processes have been developed. The desirable features are compared in Table 1. 

The early developments of solvent processing were concerned with the lubricating oil end of the cmde. Solvent extraction processes are appHed to many usefiil separations in the purification of gasoline, kerosene, diesel fuel, and other oils. In addition, solvent extraction can replace fractionation in many separation processes in the refinery. For example, propane deasphalting (Fig. 7) has replaced, to some extent, vacuum distillation as a means of removing asphalt from reduced cmde oils. 

See Extraction High pressure thchnology Separations process synthesis. 

Solvent Extraction. Extraction processes, used for separating one substance from another, are commonly employed in the pharmaceutical and food processing industries. Oilseed extraction is the most widely used extraction process on the basis of tons processed. Extraction-grade hexane is the solvent used to extract soybeans, cottonseed, com, peanuts, and other oilseeds to produce edible oils and meal used for animal feed supplements. Tight specifications require a narrow distillation range to minimize solvent losses as well as an extremely low benzene content. The specification also has a composition requirement, which is very unusual for a hydrocarbon, where the different components of the solvent must be present within certain ranges (see Exthaction). 

Isolation. Isolation procedures rely primarily on solubiHty, adsorption, and ionic characteristics of the P-lactam antibiotic to separate it from the large number of other components present in the fermentation mixture. The penicillins ate monobasic catboxyHc acids which lend themselves to solvent extraction techniques (154). Pencillin V, because of its improved acid stabiHty over other penicillins, can be precipitated dkecdy from broth filtrates by addition of dilute sulfuric acid (154,156). The separation process for cephalosporin C is more complex because the amphoteric nature of cephalosporin C precludes dkect extraction into organic solvents. This antibiotic is isolated through the use of a combination of ion-exchange and precipitation procedures (157). The use of neutral, macroporous resins such as XAD-2 or XAD-4, allows for a more rapid elimination of impurities in the initial steps of the isolation (158). The isolation procedure for cephamycin C also involves a series of ion exchange treatments (103). 

The fiber extraction (milling) process must be chosen so as to optimize recovery of the fibers in the ore, while minimizing reduction of fiber length. Since the asbestos fibers have a chemical composition similar to that of the host rock, the separation processes must rely on differences in the physical properties between the fibers and the host rock rather than on differences in their chemical properties (33). 

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. 

Di- and Triisobutylcncs. Diisobutylene [18923-87-0] and tnisobutylenes are prepared by heating the sulfuric acid extract of isobutylene from a separation process to about 90°C. A 90% yield containing 80% dimers and 20% trimers results. Use centers on the dimer, CgH, a mixture of 2,4,4-trimethylpentene-1 and -2. Most of the dimer-trimer mixture is added to the gasoline pool as an octane improver. The balance is used for alkylation of phenols to yield octylphenol, which in turn is ethoxylated or condensed with formaldehyde. The water-soluble ethoxylated phenols are used as surface-active agents in textiles, paints, caulks, and sealants (see Alkylphenols). 

Separation Processes. Separation of the catalyst from the products is a significant expense the process flow diagram and the processing cost are often dominated by the separations. Many soluble catalysts are expensive, eg, rhodium complexes, and must be recovered and recycled with high efficiency. The most common separation devices are distiUation columns extraction is also appHed. 

Recovery Process. Boron values are recovered from brine of Seades Lake by North American Chemicals Corp. In one process the brine is heated to remove some water and burkeite. The remaining brine is cooled to remove potassium chloride. This cooled brine is then transferred to another crystallizer where borax pentahydrate, Na2B40y 5H20, precipitates (18). In a separate process, boron is removed by Hquid—Hquid extraction followed by stripping with dilute sulfuric acid (19). Evaporator-crystallizers are used to recover boric acid [10043-35-3] H BO. In a third process, borax is recovered by refrigerating a carbonated brine. 

Skelland and Tedder, Extraction—Organic Chemicals Processing in Rousseau, Handbook of Separation Process Technology, Wiley, 1987, pp. 405 66. 

Deviations from Raonlt s law in solution behavior have been attributed to many charac teristics such as molecular size and shape, but the strongest deviations appear to be due to hydrogen bonding and electron donor-acceptor interac tions. Robbins [Chem. Eng. Prog., 76(10), 58 (1980)] presented a table of these interactions. Table 15-4, that provides a qualitative guide to solvent selection for hqnid-hqnid extraction, extractive distillation, azeotropic distillation, or even solvent crystallization. The ac tivity coefficient in the liquid phase is common to all these separation processes. 

In the last few years, Idemitsu commercialized a 5000 metric ton/year integrated reaction and separation process in SCR isobutene, as shown in Rig. 22-24. The reaction of isobutene and water takes place in the water phase and is acid catalyzed. The product, sec-butanol, is extracted into the isobutene phase to drive the reversible reaction to the right. The. s c-butanol is then recovered from the isobutene by depressurizing the SCR phase, and the isobutene is recompressed and recycled. 

The common impurities found in amines are nitro compounds (if prepared by reduction), the corresponding halides (if prepared from them) and the corresponding carbamate salts. Amines are dissolved in aqueous acid, the pH of the solution being at least three units below the pKg value of the base to ensure almost complete formation of the cation. They are extracted with diethyl ether to remove neutral impurities and to decompose the carbamate salts. The solution is then made strongly alkaline and the amines that separate are extracted into a suitable solvent (ether or toluene) or steam distilled. The latter process removes coloured impurities. Note that chloroform cannot be used as a solvent for primary amines because, in the presence of alkali, poisonous carbylamines (isocyanides) are formed. However, chloroform is a useful solvent for the extraction of heterocyclic bases. In this case it has the added advantage that while the extract is being freed from the chloroform most of the moisture is removed with the solvent. 

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