Relative volatility extractive distillation

Selectivity. The relative separation, or selectivity, Ot of a solvent is the ratio of two components in the extraction-solvent phase divided by the ratio of the same components in the feed-solvent phase. The separation power of a hquid-liquid system is governed by the deviation of Ot from unity, analogous to relative volatility in distillation. A relative separation Ot of 1.0 gives no separation of the components between the two liquid phases. Dilute solute concentrations generally give the highest relative separation factors. 

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. 

Separation Factor The separation factor in extraction is analogous to relative volatility in distillation. It is a dimensionless factor that measures the relative enrichment of a given component in the extract phase after one theoretical stage of extraction. For cosolutes i andj,... 

The dissociation extraction efficiency is measured in terms of a separation factor, a, which is defined in an analogous manner to that of relative volatility in distillation ... 

The importance of good selectivity for extraction processes parallels that of relative volatility for distillation. Practical processes require that S exceed unity, the more so the better. Selectivities close to unity will result in large plant equipment, large numbers of extraction contacts or stages, and in general, costly investment and operation. If j3 = 1, separation is impossible. 

Mixtures with low relative volatility or which exhibit azeotropic behavior. The most common means of dealing with the separation of low-relative-volatility and azeotropic mixtures is to use extractive or azeotropic distillation. These processes are considered in detail later. Crystallization and liquid-liquid extraction also can be used. 

As with azeotropic distillation, the separation is possible in extractive distillation because the extraneous mass-separating agent interacts more strongly with one of the components than the other. This in turn alters in a favorable way the relative volatility between the key components. 

Extractive distillation and. salt distillation. Methods that primarily modify liquid-phase behavior to alter the relative volatility of the components of the mixture. 

In normal applications of extractive distillation (i.e., pinched, closeboiling, or azeotropic systems), the relative volatilities between the light and heavy key components will be unity or close to unity. Assuming an ideal vapor phase and subcritical components, the relative volatility between the light and heavy keys of the desired separation can be written as the produc t of the ratios of the pure-component vapor pressures and activity-coefficient ratios whether the solvent is present or not ... 

The variable that has the most significant impact on the economics of an extractive distillation is the solvent-to-feed (S/F) ratio. For closeboiling or pinched nonazeotropic mixtures, no minimum-solvent flow rate is required to effect the separation, as the separation is always theoretically possible (if not economical) in the absence of the solvent. However, the extent of enhancement of the relative volatihty is largely determined by the solvent concentration and hence the S/F ratio. The relative volatility tends to increase as the S/F ratio increases. Thus, a given separation can be accomplished in fewer equihbrium stages. As an illustration, the total number of theoretical stages required as a function of S/F ratio is plotted in Fig. 13-75 7 for the separation of the nonazeotropic mixture of vinyl acetate and ethyl acetate using phenol as the solvent. 

Liquid-liquid extraction is used primarily when distillation is imprac-tic or too costly to use. It may be more practical than distillation when the relative volatility for two components falls between 1.0 and 1.2. Likewise, liquid-liquid extraction may be more economical than distillation or steam-stripping a dissolved impurity from wastewater when the relative volatility or the solute to water is less than 4. In one case discussed by Robbins [Chem. Eng. Prog., 76 (10), 58 (1980)], liquid-liquid extraction was economically more attractive than carbon-bed or resin-bed adsorption as a pretreatment process for wastewater detoxification before biotreatment. 

Recoverability. The extrac tion solvent must usually be recovered from the extract stream and also from the raffinate stream in an extraction process. Since distillation is often used, the relative volatility of the extraction-solvent to nonsolvent components should be significantly greater or less than unity. A low latent heat of vaporization is desirable tor a volatile solvent. 

As mentioned earlier the ease or difficulty of separating two products depends on the difference in their vapor pressures or volatilities. There are situations in the refining industry in which it is desirable to recover a single valuable compound in high purity from a mixture with other hydrocarbons which have boiling points so close to the more valuable product that separation by conventional distillation is a practical impossibility. Two techniques which may be applied to these situations are azeotropic distillation and extractive distillation. Both methods depend upon the addition to the system of a third component which increases the relative volatility of the constituents to be separated. 

Acetonitrile serves to greatly enlarge the spread of relative volatilities so that reasonably sized distillation equipment can be used to separate butadiene from the other components in the C4 fraction. The polar ACN acts as a very heavy component and is separated from the product without much difficulty.The feed stream is carefully hydrogenated to reduce the acetylene level rerun, and then fed to the single stage extractive distillation unit. Feed enters near the middle of the extractive distillation tower, while (lean) aqueous ACN is added near but not at the top. Butenes and butanes go overhead as distillate, with some being refluxed to the tower and the rest water washed for removal of entrained ACN. 

Since most of the C, hydrocarbons boil extremely close to isoprene, simple distillation of the C, cut would not produce high purity isoprene. Two stages of extractive distillation with acetonitrile are used where the ACN modifies the relative volatilities of the hydrocarbons and thus enables the separation to be made. 

The first stage does the bulk of the separation, and the second is used to remove other dienes and acetylenes from the isoprene. In the extractive distillation tower of each stage, the ACN solvent is introduced near the top, and being the highest boiling component, travels downward. The effective relative volatility of the less unsaturated hydrocarbons is increased with respect to isoprene. Thus most of the impurities go overhead and the isoprene is carried down with the solvent. 

Equilibrium data correlations can be extremely complex, especially when related to non-ideal multicomponent mixtures, and in order to handle such real life complex simulations, a commercial dynamic simulator with access to a physical property data-base often becomes essential. The approach in this text, is based, however, on the basic concepts of ideal behaviour, as expressed by Henry s law for gas absorption, the use of constant relative volatility values for distillation and constant distribution coeficients for solvent extraction. These have the advantage that they normally enable an explicit method of solution and avoid the more cumbersome iterative types of procedure, which would otherwise be required. Simulation examples in which more complex forms of equilibria are employed are STEAM and BUBBLE. 

One final point regarding extractive distillation is illustrated in Figure 12.28. The order in which the separation occurs depends on the change in relative volatility between the two components to be separated. Figure 12.28 shows both the residue curves and the equi-volatility curve for the system A-B-entrainer. This equi-volatility curve shows where the relative volatility between Components A and B is unity. On either side of the equi-volatility curve, the order of volatility of A and B changes. In Figure 12.28a, if the equi-volatility curve intersects the A-entrainer axis, then Component A should be recovered first. However, if the equi-volatility curve intersects the B-entrainer axis,... 

The principle of azeotropic and of extraction distillation lies in the addition of a new substance to the mixture so as to increase the relative volatility of the two key components, and thus make separation relatively easy. Benedict and Rup,in(43) have defined these two processes as follows. In azeotropic distillation the substance added forms an azeotrope with one or more of the components in the mixture, and as a result is present on most of the plates of the column in appreciable concentrations. With extractive distillation the substance added... 

Extractive distillation is a method of rectification similar in purpose to azeotropic distillation. To a binary mixture which is difficult or impossible to separate by ordinary means, a third component, termed a solvent, is added which alters the relative volatility of the original constituents, thus permitting the separation. The added solvent is, however, of low volatility and is itself not appreciably vaporised in the fractionator. 

The solvent added to the mixture in extractive distillation differentially affects the activities of the two components, and hence the relative volatility, a. 

The usual procedures of fractional, azeotropic, or extractive distillation under inert gases, crystallization, sublimation, and column chromatography, must be carried out very carefully. For liquid, water-insoluble monomers (e.g., styrene, Example 3-1), it is recommended that phenols or amines which may be present as stabilizers, should first be removed by shaking with dilute alkali or acid, respectively the relatively high volatility of many of these kinds of stabilizers often makes it difficult to achieve their complete removal by distillation. Gaseous monomers (e.g., lower olefins, butadiene, ethylene oxide) can be purified and stored over molecular sieves in order to remove, for example, water or CO2. 

Recovery Constraints Distillation is a primary means of solvent recovery. In a separation process the chosen solvent must be easily distilled from the extracted solute. The relative volatility should be large to ensure easy separation. The enthalpy of vaporization should be low for reduced energy consumption. 

Vapor Phase Absorption. Absorption is closely related to extractive distillation, in that a solvent is used for the separation of one or more constituents from a gaseous mixture. In absorption, however, the mixture to be treated is comprised of compounds having relatively large differences in volatility and condensation cannot be conveniently used. The various absorption processes differ primarily in the means used to separate product and absorber oil. A typical example of the application of vapor phase absorption in the petroleum industry is the recovery of gasoline from natural gas. 

Distillation. At different pressures with an added volatile azeotrope-forming substance (for azeotropic distillation) with an added relatively nonvolatile selective solvent (for extractive distillation). 

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