Azeotropic mixture separation pressure swing distillation

J.-U. Repke, F. Fomer, A Klein, 2006, Separation of Homogeneous Azeotropic Mixtures by Pressure Swing Distillation - Analysis of the Operation Performanee, Chem. Eng. Techn., vol. 28, 1151-1557. 

Distillation is still the most common unit operation to separate liquid mixtures in chemical and petroleum industry because the treatment of large product streams and high purities with a simple process design is possible. Despite of this the separation of azeotropic mixtures into pure components requires complex distillation steps and/or the use of an entrainer. Industrial applied processes are azeotropic, extractive or pressure swing distillation (Stichlmair and Fair, 1998). Another sophisticated method for the separation of binary or multicomponent azeotropic mixtures is the hybrid membrane process, consisting of a distillation column and a membrane unit. 

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. 

The composition of many azeotropes varies with the system pressure (Horsley, Azeotropic Data-Ill, American Chemical Society, Washington, 1983 Gmehling et ah. Azeotropic Data, VCH Publishers, Deerfield Beach, Fla., 1994). This effect can be exploited to separate azeotropic mixtures by so-called pressure-swing distillation if at some pressure the azeotrope simply disappears, such as does the ethanol-water azeotrope at pressures below 11.5 kPa. However, pressure sensitivity can still be exploited if the azeotropic composition and related distillation boundary change sufficiently over a moderate... 

Azeotropic distillation and pressure-swing distillation. Methods that cause or exploit azeotrope formation or behavior to alter the boiling characteristics and separability of the mixture. 

Owing to the non-ideality of binary or multicomponent mixtures, the liquid phase composition is often identical with the vapor phase composition. This point is called an azeotrope and the corresponding composition is called the azeotropic composition. An azeotrope can not be circumvented by conventional distillation since no enrichment of the low-boiHrig component can be achieved in the vapor phase. Separating azeotropic mixtures therefore requires special processes, e.g. azeotropic or extractive distillation or pressure swing distillation. Azeotropic information is available in literature (Gmehling et al., 2004). 

Except for pressure swing distillation, which makes use of the pressure dependence of the azeotropic composition, all technologies require an entrainer to separate azeotropic mixtures. For some systems the azeotrope vanishes at certain pressures. This means that ordinary distillation at a different pressure (pressure or vacuum distillation) may circumvent the azeotrope. Although pressure swing distillation does not require an additional component in the process, it is not necessarily environmentally advantageous when compared to the alternatives, since additional... 

When a multicomponent fluid mixture is nonideal, its separation by a sequence of ordinaiy distillation columns will not be technically and/or economically feasible if relative volatiK-ties between key components drop below 1.05 and, particularly, if azeotropes are formed. For such mixtures, separation is most commonly achieved by sequences comprised of ordinary distillation columns, enhanced distillation columns, and/or liquid-liquid extraction equipment. Membrane and adsorption separations can also be incorporated into separation sequences, but their use is much less common. Enhanced distillation operations include extractive distillation, homogeneous azeotropic distillation, heterogeneous azeotropic distillation, pressure-swing distillation, and reactive distillation. These operations are considered in detail in Perry s Chemical Engineers Handbook (Perry and Green, 1997) and by Seader... 

Knapp, J. R, Doherty, M. F. (1992). A New Pressure-Swing Distillation Process for Separating Homogeneous Azeotropic Mixtures. Ind. Eng. Chem. Res., 31, 346-57. 

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