Distillation solvent selection

T xtractive and azeotropic distillation in different types of chemical industry has become more important as more separations of close-boiling mixtures and azeotropic ones are encountered. Extractive distillation is used more because it is generally less expensive, simpler, and can use more solvents than azeotropic distillation. Solvent selection for azeotropic distillation has recently been discussed by Berg (I). Therefore, solvent screening for extractive distillation is discussed here. 

Highly Nonideal Systems. Highly nonideal systems are of principal concern the nonideality may be caused by the components present and/or by the operating conditions. This category includes subjects like critical phenomena, extractive/azeotropic distillation, solvent selection guidelines, salt effects, high molecular... 

Extraction and Extractive Distillation. The choice of an extraction or extractive distillation solvent depends upon its boiling point, polarity, thermal stabiUty, selectivity, aromatics capacity, and upon the feed aromatic content (see Extraction). Capacity, defined as the quantity of material that is extracted from the feed by a given quantity of solvent, must be balanced against selectivity, defined as the degree to which the solvent extracts the aromatics in the feed in preference to paraffins and other materials. Most high capacity solvents have low selectivity. The ultimate choice of solvent is deterrnined by economics. The most important extraction processes use either sulfolane or glycols as the polar extraction solvent. 

Extractive distillation works by the exploitation of the selective solvent-induced enhancements or moderations of the liquid-phase nonidealities of the components to be separated. The solvent selectively alters the activity coefficients of the components being separated. To do this, a high concentration of solvent is necessaiy. Several features are essential ... 

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. 

Affinity for solute the selectivity, which is a measure of the distribution of the solute between the two solvents (concentration of solute in feed-solvent divided by the concentration in extraction-solvent). Selectivity is analogous to relative volatility in distillation. The greater the difference in solubility of the solute between the two solvents, the easier it will be to extract. 

S Entropy (kJ-K-1, kJkg-1-K-1, kJkmol-1-K-1), or number of streams in a heat exchanger network (-), or reactor selectivity (-), or reboil ratio for distillation (-), or selectivity of a reaction (-), or slack variable in optimization (units depend on application), or solvent flowrate (kg s-1, kmol-s-1), or stripping factor in absorption (-)... 

The styrene concentrate is fed to a solvent recovery process or an extractive distillation process. The solvent selectively pulls the styrene out of the hydrocarbon mixture. The styrene raffinate, sans styrene, is sent back to be mixed with the pygas (although it can also be fractionated to pull out a high quality mixed xylene.)... 

Activity coefficients at infinite dilution, of organic solutes in ILs have been reported in the literature during the last years very often [1,2,12,45,64, 65,106,123,144,174-189]. In most cases, a special technique based on the gas chromatographic determination of the solute retention time in a packed column filled with the IL as a stationary phase has been used [45,123,174-176,179,181-187]. An alternative method is the "dilutor technique" [64,65,106, 178,180]. A lot of y 3 (where 1 refers to the solute, i.e., the organic solvent, and 3 to the solvent, i.e., the IL) provide a useful tool for solvent selection in extractive distillation or solvent extraction processes. It is sufficient to know the separation factor of the components to be separated at infinite dilution to determine the applicability of a compound (a new IL) as a selective solvent. 

Solvents used for extractive distillation vary considerably, but in almost all cases solvent selection presents a trade-off between its selectivity and solvency (194). The effectivity of the solvent can sometimes be improved by the addition of a salt (195). 

Caprolactam, adipic acid, and hexamethylenediamine (HMDA) are all made from cyclohexane. Almost all high-purity cyclohexane is obtained by hydrogenating benzene, although some for solvent use is obtained by careful distillation of selected petroleum fractions. 

Based on its ability to enhance solvating power by increasing fluid density, supercritical fluid extraction offers an attractive alternative for fractionation of fats and oils. It works by the phenomena of selective distillation and simultaneous extraction, as has been shown by many researchers [3-5]. While the use of supercritical fluids in the extraction of numerous biomaterials has been reported, its commercialization has been limited to the decaffeination of coffee and tea and to the extraction of flavors from hops and spices. The chemical complexity of most food ingredients and their tendency to react and degrade at elevated temperatures, emphasize the difficulties of supercritical solvent selection. Carbon dioxide is the preferred supercritical solvent (its properties have previously been cited [6]). 

GTC Aromatics C6-C8 hydrocarbon mixture Extractive distillation with selective solvents separates BTX from nonaromatic hydrocarbons 1 1995... 

In conclusion, recent developments in solvent selection, phase nonideality description, and tray-to-tray calculation schemes have greatly facilitated the design of extractive and azeotropic distillation schemes, and use of salts give new methods for extractive distillation separations. Finally, the work of Gerster (30), Black and Ditsler (29), and Black et al. (25) compare these two schemes. 

Extractive distillation is evaluated as an alternative to ordinary distillation for the separation of propylene-propane mixtures. Particular attention is given to the necessary compromises between different design factors solvent concentration within the primary column, solvent selectivity, solvent loss, etc. A major expense is associated with the sensible heat requirements of the circulating solvent process modifications so as to minimize this expense are discussed. The process analysis explores combinations of solvent selectivity and other solvent properties which might make extractive distillation attractive. It appears that in almost all cases extractive distillation offers no advantage compared with ordinary distillation. Only in special cases may circumstances warrant extractive distillation. External factors favoring the use of extractive distillation are identified. 

The costs of separating paraffin-olefin mixtures by extractive distillation are greatly affected by the solvent selectivity, the paraffin activity coefficient, and the solvent volatility they depend mostly upon solvent characteristics. For a solvent to be effective to separate key components A and B, the solvent must have a high value of y A/y B while it must also have a low y°V Further, the solvent vapor pressure should be lower, but not several orders of magnitude lower, than that of the less volatile hydrocarbon. 

Keywords solvent-based separation, solvent selection, extractive distillation, CAMD... 

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