To achieve the separation of an azeotropic mixture by using pressure-swing distillation, the manipulation of the column pressure is required, e.g.

, by utilizing a second distillation column working under vacuum conditions (Figure 8.2). This type of distillation makes use of the change of the vaporliquid phase equilibrium at lower pressures than atmospheric (vacuum) leading to the disappearance of the azeotrope. The pressure required to eliminate the azeotrope in an ethanol water mixtures is less than 6 kPa. But to obtain a high purity product, distillation columns with a large number of plates (above 40) and a high reflux ratio are needed. These conditions imply significant capital costs (large column diameters) and increased energy costs due to the maintenance of vacuum in distillation towers with many plates. This configuration has no fluxes or refluxes connecting the two columns. In general, pressure-swing distillation cannot always be employed; its utilization is limited to mixtures with azeotropes susceptible to be displaced with small changes of pressure, which is not exactly the case in ethanolwater systems.

Most methods involving distillation for ethanol dehydration utilized in the industry comprise at least three steps: (1) distillation of dilute ethanol until it reaches a concentration near the azeotropic point, (2) distillation using a third component added that allows the ethanol removal, and (3) distillation to recover the third component and reutilize it in the process (Montoya et al., 2005). The azeotropic distillation corresponds to this scheme. This technology consists of the addition of an entrainer to the ethanolwater mixture to form a new azeotrope. The azeotrope formed is ternary (involves three components) and allows a much easier separation in schemes involving two or three distillation columns. Among the substances most used as entrainers for separation of ethanolwater mixtures are benzene, toluene, n-pentane, and cyclohexane. In the case of benzene, the process comprises one dehydration (azeotropic) column, which is fed with the mixture containing 90 to 92% ethanol from rectification column (Figure 8.3). The benzene is added in the upper plate. From the lower part of the azeotropic column, ethanol is removed with water content below 1%, while the overhead vapors in the column top, which correspond to a mixture with a composition equal or near to the composition of the ethanolwaterbenzene ternary azeotrope, are condensed and sent to a liquidliquid separator (decanter). Due to the mixture properties, the ternary azeotrope is located in the immiscibility zone of the ethanolwater benzene system (Figure 8.4), so once condensed, it is separated into two liquid phases: one phase with high benzene content that is recirculated as a reflux to the azeotropic column, and the another phase with higher water content that is fed to a smaller column for entrainer recovery (stripping column). The distillate from the stripping column has a significant benzene concentration and, for this reason, this stream is recycled back to the azeotropic column or to the decanter. The bottoms of the stripping column contain mostly water. If these bottoms have an important amount of ethanol, they are recirculated to the concentration column; in this way, the separation of water and ethanol is attained and the entrainer is recovered. As the process is operated in continuous regime, the benzene is permanently recirculating within the system. Nevertheless, small amounts of this compound leave the scheme along with the ethanol or water streams, thus a make-up stream is required. This latter stream is fed to the first plate (from the top) of the azeotropic column or is mixed with the reflux stream coming from the decanter to this same column.

The phase equilibrium properties are crucial for the design of an azeotropic distillation scheme. This equilibrium can be represented in the ternary diagram shown in Figure 8.4 for the case of benzene. The principles of topologic thermodynamics can be applied to the analysis of this diagram (Pisarenko et al., 2001). To provide more clarity, molar fractions are employed through the analysis are identical for compositions expressed in mass fractions. The feeding of the starting ethanolwater mixture is indicated by the straight line FBand is accomplished in such a way that the point M representing the pseudo-starting state of the system is located inside the distillation region I. This region is delimited by the two distillation boundaries, which coincide in the ternary azeotrope with the minimum boiling point. The distillation boundaries define the process constraints because any distillation operation (indicated by straight lines of mass balances) cannot have distillates and bottoms whose compositions are in different regions. When drawing a balance line corresponding to the indirect distillation for the point M(the prolongation of the straight line EMuntil the distillation boundary represented by the curve AC), bottoms with a composition corresponding to pure ethanol Eand distillate with a composition near to the ternary azeotrope represented by the point Nare obtained. The composition of this distillate corresponds to the immiscibility zone of the system so it is separated into two liquid phases indicated by the points Rand Sthat are determined following the tie lines of the liquidliquid equilibrium plot (bimodal plot). The point Rrepresents the liquid phase with higher water content (the raffinate) and the point S represents the liquid phase with higher benzene content (the extract) that is evidenced by its higher proximity to the vertex B(pure benzene) compared to point R. The stream with the composition of the point Sis recirculated as the reflux to the azeotropic column. The raffinate stream, in turn, undergoes distillation in the stripping column, which is represented by the balance line WRP that is located in the distillation region II. The composition of point P corresponds to the composition of the distillate stream from the stripping column that is recycled back to either the azeotropic column or the decanter. This type of analysis allows one to predict the behavior of the system without carrying out a rigorous assessment (shortcut method). These short-cut methods allow one to obtain valuable information for the subsequent rigorous modeling of the system. In particular, the application of these methods facilitates the specification of the operating conditions in the distillation columns when commercial process simulators employing rigorous methods are used. The above-described distillation receives the name hetero-azeotropic distillation considering that the entrainers form azeotropes located within the immiscibility zone of the system. This implies its separation into two liquid phases. The utilization of n-octane as a co-entrainer along with benzene has been proposed in order to decrease the energy costs of the traditional process (Chianese and Zinnamosca, 1990). The simulation and optimization accomplished based on a mass-transfer model (nonequilibrium model) for this process show that if the values of operating parameters of the column are adjusted to minimize the amount of plates in the azeotropic column, it is possible to reduce the capital costs, but increasing the heat flow rates required implies an increase of the energy costs. In terms of energy costs, the most influencing process parameters are the reflux ratio

and flow rate of the stream recirculated from the stripping column to the azeotropic column. For these parameters, their optimum values have been obtained according to economic considerations (Mortaheb and Kosuge, 2004). However, the utilization of benzene as an entrainer is not desirable due to its carcinogenic properties. In addition, the azeotropic distillation using this compound leads to the appearance of multiple steady states and the occurrence of a parametric sensibility related to small changes in column pressure (Wolf Maciel and Brito, 1995). Taking into account these drawbacks, the use of less contaminant entrainers has been attempted. In particular, some new ethanol-producing facilities in Brazil employ cyclohexane as the entrainer for ethanol dehydration by hetero-azeotropic distillation. Significant efforts to reduce the elevated energy consumption of the azeotropic distillation using such entrainers, such as benzene, cyclohexane, diethyl ether, and n-pentane, have been made. Under real conditions, distillation columns are configured in such a way that the dehydration process is operated using the heat recovered from the primary distillation system (concentration and rectification columns). Alternatively, rectification and stripping columns can be operated using the heat released in the azeotropic column. For fuel ethanol industry in the United States, the consumption of thermal energy during the separation and dehydration steps employing the azeotropic distillation is about 4.73 MJ/L ethanol on average (Madson and Monceaux, 1995).