Extractive distillation vapor liquid equilibria

In all cases, the selective solvents (entrainers) have the task of altering the partition coefficients in a way that high separation factors and selectivities for the different phase equilibria (extractive distillation vapor-liquid equilibrium (VLE), extraction liquid-liquid equilibrium (LLE), absorption gas-liquid equilibrium (GLE)) are achieved, resulting in a separation of compounds. The required partition coefficients, separation factors and selectivities can be calculated with the help of thermodynamic models (g -models, equations of state). 

The topic covered in the 10 papers of the first section is commonly referred to as salt effect in vapor-liquid equilibrium and is potentially of great industrial importance. This salt effect leads to extractive distillation processes in which a dissolved salt replaces a liquid additive as the separating agent the replacement often results in a greatly improved separating ability and reduced energy requirements. Two papers in this volume, those by Sloan and by Vaillancourt, illustrate the use of such processing to concentrate nitric acid from its aqueous azeotrope. Nevertheless, the effect has not been exploited by industry to nearly the extent that would seem to be merited by its scientific promise. 

The effect of salts on the vapor-liquid equilibrium of solvent mixtures has been of considerable interest in recent years. Introduction of a salt into a binary solvent mixture results in a change in the relative volatility of the solvents. This effect can be used to an advantage where the separation of the solvents is of interest. Furter and co-workers have demonstrated the potential importance of salts as separating agents in extractive distillation (J, 2, 3). 

The use of a dissolved salt in place of a liquid component as the separating agent in extractive distillation has strong advantages in certain systems with respect to both increased separation efficiency and reduced energy requirements. A principal reason why such a technique has not undergone more intensive development or seen more than specialized industrial use is that the solution thermodynamics of salt effect in vapor-liquid equilibrium are complex, and are still not well understood. However, even small amounts of certain salts present in the liquid phase of certain systems can exert profound effects on equilibrium vapor composition, hence on relative volatility, and on azeotropic behavior. Also extractive and azeotropic distillation is not the only important application for the effects of salts on vapor-liquid equilibrium while used as examples, other potential applications of equal importance exist as well. 

The research programs on extractive distillation by salt effect and on salt effect in vapor-liquid equilibrium at the Royal Military College of Canada are supported by the Defence Research Board of Canada, Grant No. 9530-142. 

Separation processes which involve non-volatile salts arise in two situations. First, as an alternative to extractive or azeotropic distillation, salts may be added to a system to alter the vapor-liquid equilibrium behavior. Second, there are cases where a salt is generated in the process before final product purification. For example, product streams from processes involving esterification, etherification, or neutralization contain salts and are often fed to separation units such as distillation or stripping columns. 

Measurements of binary vapor-liquid equilibria can be expressed in terms of activity coefficients, and then correlated by the Wilson or other suitable equation. Data on all possible pairs of components can be combined to represent the vapor-liquid behavior of the complete mixture. For exploratory purposes, several rapid experimental techniques are applicable. For example, differential ebulliometry can obtain data for several systems in one laboratory day, from which infinite dilution activity coefficients can be calculated and then used to evaluate the parameters of correlating equations. Chromatography also is a well-developed rapid technique for vapor-liquid equilibrium measurement of extractive distillation systems. The low-boiling solvent is deposited on an inert carrier to serve as the adsorbent. The mathematics is known from which the relative volatility of a pair of substances can be calculated from the effluent trace of the elutriated stream. Some of the literature of these two techniques is cited by Walas (1985, pp. 216-217). 

A salt dissolved in a mixed solvent is capable, through such effects on the structure of the liquid phase as preferential association and others, of altering the composition of the equilibrium vapor. Hence salt effect on vapor-liquid equilibrium relationships provides a potential technique of extractive distillation. A review is presented of the use of dissolved salts, rather than liquid solvents, as separating agents for extractive distillation. 

Literature pertaining to salt effect in vapor-liquid equilibrium and to extractive distillation using salt effect was recently reviewed by Furter and Cook (10), and the theory and technical aspects were reviewed by Furter (II). Vapor-liquid equilibrium data for 188 systems containing salt were previously compiled by Ciparis (12), who has also published a recent book with Dobroserdov and Kogan on the theory and practice of extractive distillation by salt effect (13). 

The design of azeotropic or extractive distillation columns, as with con-A ventional columns, demands a knowledge of the vapor-liquid equilibrium properties of the system to be distilled. Such knowledge is obtained experimentally or calculated from other properties of the components of the system. Since the systems in azeotropic or extractive distillation processes have at least three components, direct measurement of the equilibrium properties is laborious and, therefore, expensive, so methods of calculation of these data are desirable. 

The vapor-liquid equilibrium (VLB) and liquid-liquid extraction (LLE) correlations in Aspen Plus are not always as accurate as possible. This can cause significant errors, particularly near pinch points in distillation columns. If data is available, Aspen Plus will find values of the parameters for any of the VLB or LLE correlations by doing a regression against the data you input. This is illustrated to obtain an improved fit for the non-random two-liquid (NRTL) VLB correlation for the binary system water and isopropanol (IPA). VLB data for water and isopropanol is listed in Table B-1. This system has a minimum boiling azeotrope at 80.46°C. The Aspen Plus fit to the data with NRTL is not terrible, but can be improved. 

Determination of stage requirements for extractive distillation follows the approaches discussed in Section 5.3. It is necessaiy to have vapor-liquid equilibrium data, and these are measured conventionally. A representative relation between solvent/nonsolvent ratio and relative volatility is shown in Rg. 5.5-4, taken from the papers of Oerster and Drickamer et al. From the figure it is clear that vatious combinations of solvent content and stage requirements are possible, and the optimum solvent ratio must be determined. Figure 5.5-4 deals with the separation of toluene fium methylcyclohexane using phenol as the solvem. The natural volatility of the binaiy mixture is shown as the bottom line (no phenol presem) and the enhancement of this volatility by phenol addition is significant. A ffow diagram of this separation process te shown in Fig. 5.5-5. 

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