Azeotropes residue curve maps

Fig. 3. Residue curve map for a ternary mixture with a distillation boundary mnning from pure component D to the binary azeotrope C.

Even though the simple distillation process has no practical use as a method for separating mixtures, simple distillation residue curve maps have extremely usehil appHcations. These maps can be used to test the consistency of experimental azeotropic data (16,17,19) to predict the order and content of the cuts in batch distillation (20—22) and, in continuous distillation, to determine whether a given mixture is separable by distillation, identify feasible entrainers/solvents, predict the attainable product compositions, quaHtatively predict the composition profile shape, and synthesize the corresponding distillation sequences (16,23—30). By identifying the limited separations achievable by distillation, residue curve maps are also usehil in synthesizing separation sequences combining distillation with other methods. 

Residue curve maps exist for mixtures having more than three components but cannot be visualized when there are more than four components. However, many mixtures of industrial importance contain only three or four key components and can thus be treated as pseudo-temary or quaternary mixtures. Quaternary residue curve maps are more compHcated than thek ternary counterparts but it is stiU possible to understand these maps using the boiling point temperatures of the pure components and azeotropes (31). 

Fig. 5. The acetone—2-propanol—water system where I represents the 2-propanol—water azeotrope, (a) Residue curve map (34) (b) material balance lines...

The overwhelming majority of all ternary mixtures that can potentially exist are represented by only 113 different residue curve maps (35). Reference 24 contains sketches of 87 of these maps. For each type of separation objective, these 113 maps can be subdivided into those that can potentially meet the objective, ie, residue curve maps where the desired pure component and/or azeotropic products He in the same distillation region, and those that carmot. Thus knowing the residue curve for the mixture to be separated is sufficient to determine if a given separation objective is feasible, but not whether the objective can be achieved economically. 

All extractive distillations correspond to one of three possible residue curve maps one for mixtures containing minimum boiling azeotropes, one for mixtures containing maximum boiling azeotropes, and one for nonazeotropic mixtures. Thus extractive distillations can be divided into these three categories. 

Minimum Boiling Azeotropes. AH extractive distillations of binary minimum boiling azeotropic mixtures are represented by the residue curve map and column sequence shown in Figure 6b. Typical tray-by-tray composition profiles are shown in Figure 7. 

Fig. 10. Residue curve map for separating a maximum boiling azeotrope using a high boiling solvent where (-----------------) represents the distillation boundary and...

As a starting point for identifying candidate solvents, all compounds having boiling points below that of any component in the mixture to be separated should be eliminated. This is necessary to yield the correct residue curve map for extractive distillation, but this process implicitly rules out other forms of homogeneous azeotropic distillation. In fact, compounds which boil as much as 50°C or more above the mixture have been recommended (68) in order to minimize the likelihood of azeotrope formation. On the other hand, the solvent should not bod so high that excessive temperatures are required in the solvent recovery column. 

Historically azeotropic distillation processes were developed on an individual basis using experimentation to guide the design. The use of residue curve maps as a vehicle to explain the behavior of entire sequences of heterogeneous azeotropic distillation columns as weU as the individual columns that make up the sequence provides a unifying framework for design. This process can be appHed rapidly, and produces an exceUent starting point for detailed simulations and experiments. 

Podebush Sequence forPthanol—Water Separation. When ethyl acetate is used as the entrainer to break the ethanol—water azeotrope the residue curve map is similar to the one shown in Figure 21d, ie, the ternary azeotrope is homogeneous. Otherwise the map is the same as for ethanol—water—benzene. In such... 

FIG. 13-58 (Continued) Residue curve maps, (h) MEK-MIPK-water system containing two minumum-hoiling binary azeotropes. 

Exploitation of Homogeneous Azeotropes Homogeneous azeotropic distillation refers to a flowsheet structure in which azeotrope formation is exploited or avoided in order to accomplish the desired separation in one or more distillation columns. The azeotropes in the system either do not exhibit two-hquid-phase behavior or the hquid-phase behavior is not or cannot be exploited in the separation sequence. The structure of a particular sequence will depend on the geometry of the residue curve map or distillation region diagram for the feed mixture-entrainer system. Two approaches are possible ... 

As mentioned previously, ternaiy mixtures can be represented by 125 different residue curve maps or distillation region diagrams. However, feasible distillation sequences using the first approach can be developed for breaking homogeneous binaiy azeotropes by the addition of a third component only for those more restricted systems that do not have a distillation boundaiy connected to the azeotrope and for which one of the original components is a node. For example, from... 

The transformed variables describe the system composition with or without reaction and sum to unity as do Xi and yi. The condition for azeotropy becomes X, = Y,. Barbosa and Doherty have shown that phase and distillation diagrams constructed using the transformed composition coordinates have the same properties as phase and distillation region diagrams for nonreactive systems and similarly can be used to assist in design feasibility and operability studies [Chem Eng Sci, 43, 529, 1523, and 2377 (1988a,b,c)]. A residue curve map in transformed coordinates for the reactive system methanol-acetic acid-methyl acetate-water is shown in Fig. 13-76. Note that the nonreactive azeotrope between water and methyl acetate has disappeared, while the methyl acetate-methanol azeotrope remains intact. Only... 

Figure 12.10 A residue curve map with three binary azeotropes and one ternary azeotrope.

Thus, distillation line and residue curve maps are excellent tools to evaluate feasibility of azeotropic separations, with just one exception, namely, the use of high-boiling entrainers for separation. In such cases, the equi-volatility curves discussed in this chapter are a better way of determining separation feasibility. 

Process synthesis and design of these non-conventional distillation processes proceed in two steps. The first step—process synthesis—is the selection of one or more candidate entrainers along with the computation of thermodynamic properties like residue curve maps that help assess many column features such as the adequate column configuration and the corresponding product cuts sequence. The second step—process design—involves the search for optimal values of batch distillation parameters such as the entrainer amount, reflux ratio, boiler duty and number of stages. The complexity of the second step depends on the solutions obtained at the previous level, because efficiency in azeotropic and extractive distillation is largely determined by the mixture thermodynamic properties that are closely linked to the nature of the entrainer. Hence, we have established a complete set of rules for the selection of feasible entrainers for the separation of non ideal mixtures... 

For the synthesis of heterogeneous batch distillation the liquid-liquid envelope at the decanter temperature is considered in addition to the residue curve map. Therefore, the binary interaction parameters used in predicting liquid-liquid equilibrium are estimated from binary heterogeneous azeotrope or liquid-liquid equilibrium data [8,10], Table 3 shows the calculated purity of original components in each phase split at 25 °C for all heterogeneous azeotropes reported in Table 1. The thermodynamic models and binary coefficients used in the calculation of the liquid-liquid-vapour equilibrium, liquid-liquid equilibrium at 25 °C and the separatrices are reported in Table 2. 

Nitromethane shows the simplest residue curve map with one unstable curved separatrix dividing the triangle in two basic distillation regions. Methanol and acetonitrile give rise two binary azeotropic mixtures and three distillation regions that are bounded by two unstable curved separatrices. Water shows the most complicated residue curve maps, due to the presence of a ternary azeotrope and a miscibility gap with both the n-hexane and the ethyl acetate component. In all four cases, the heteroazeotrope (binary or ternary) has the lowest boiling temperature of the system. As it can be seen in Table 3, all entrainers except water provide the n-hexane-rich phase Zw as distillate product with a purity better than 0.91. Water is not a desirable entrainer because of the existence of ternary azeotrope whose n-hexane-rich phase has a water purity much lower (0.70). Considering in Table 3 the split... 

Residue curve maps of the THF system were predicted for reactive distillation at different reaction conditions (Fig. 4.29). The topology of the map at nonreactive conditions (Da = 0) is structured by a binary azeotrope (unstable node) between water and THF. Pure water and pure THF are saddle nodes, while the 1,4-BD vertex is a stable node. 

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