Ternary Azeotropic System

Up to this point we have looked at systems with fairly ideal vapor-liquid equilibrium behavior. The last separation system examined is a highly nonideal ternary system of methyl acetate (MeAc), methanol (MeOH), and water. Methyl acetate and methanol form a homogeneous minimum-boiling azeotrope at 1.1 atm with a composition of 

4 mol% methyl acetate and a temperature of 329 K. This means that the overhead product from the distillation column cannot have a composition greater than this azeotropic composition. 

Results indicate that the temperature on Stage 41 does not change for constant product impurities for aU of these feed composition disturbances. So there is a conflict between the SVD and the invariant-temperature criteria. One recommends Stage 38, while the other recommends Stage 41. 

The other control degree of freedom that is fixed in this figure is the reflux ratio. Unlike the other systems studied, the bottom three rows of Table 6.2 show that the required changes in reflux ratio are smaller than the required changes in the reflux flow rate in this multicomponent, nonideal system. The reflux ratio is fixed at 0.732. 

Closed-loop Multiplicity. One of the interesting features of nonlinear systems is the possible appearance of multiple steady states. Most researchers have explored open-loop multiplicity. We found that closed-loop multiplicity occurs in the methyl acetate/methanol/ water system. 

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Esters of medium volatility are capable of removing the water formed by distillation. Examples are propyl, butyl, and amyl formates, ethyl, propyl, butyl, and amyl acetates, and the methyl and ethyl esters of propionic, butyric, and valeric acids. In some cases, ternary azeotropic mixtures of alcohol, ester, and water are formed. This group is capable of further subdivision with ethyl acetate, all of the ester is removed as a vapor mixture with alcohol and part of the water, while the balance of the water accumulates in the system. With butyl acetate, on the other hand, all of the water formed is removed overhead with part of the ester and alcohol, and the balance of the ester accumulates as a high boiler in the system. 

Azeotropic compositions are rare for terpolymerization and Ham 14 has shown that it follows from the simplified eqs. 38-40 that ternary azeotropes should not exist. Nonetheless, a few systems for which a ternary azeotrope exists have now been described (this is perhaps a proof of the limitations of the simplified equations) and equations for predicting whether an azeotropic composition will exist for copolymerizations of three or more monomers have been formulated.20113 This work also shows that a ternary azeotrope can, in principle, exist even in circumstances where there is no azeotropic composition for any of the three possible binary copolymerizations of tire monomers involved. 

The VLB was also measured for binary and ternary systems of [ethanol + [C2Cilm][C2S04] and [ethanol + ethyl ferf-butyl ether + [C2Cilm][C2S04] at 101.3 kPa [151]. This ternary system does not exhibit a ternary azeotrope. The possibility of [C2Cilm][C2S04] use as a solvenf in liquid-liquid extraction or as an entrainer in extractive distillation for fhe separation of the mixture ethanol/ethyl fcrf-butyl ether was discussed [151]. 

Data of Azeotropes. The choice of azeotropic entrainer for a desired separation is much more restricted than that of solvents for extractive distillation, although many azeotropic data are known. The most extensive compilation is that of Ogorodnikov, Lesteva, and Kogan (Handbook of Azeotropic Mixtures (in Russian), 1971). It contains data of 21,069 systems, of which 1274 are ternary, 60 multicomponent, and the rest binary. Another compilation Handbook of Chemistry and Physics, 60th ed., CRC Press, Boca Raton, FL, 1979) has data of 685 binary and 119 ternary azeotropes. Shorter lists with grouping according to the major substances also are available in Lange s Handbook of Chemistry... 

In contrast, certain mixtures of two (binary) or three (ternary) components form constant boiling mixtures that cannot be separated by distillation. In such cases, each component contributes a fixed amount and the boiling point of the mixture is characteristic of the components. Such a system is called an azeotrope. The boihng point of an azeotrope may be higher or lower than that of the individual components. Common binary azeotropes are listed in Table 4.7 and ternary azeotropes are listed in Table 4.8. 

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... 

Schematic DRDs are particularly useful in determining the implications of possibly unknown ternary saddle azeotropes by postulating position 7 at interior positions in the temperature profile. Also note that some combinations of binary azeotropes require the existence of a ternary saddle azeotrope. As an example, consider the system acetone (56.4°C), chloroform (61.2°C), and methanol (64.7°C) at 1-atm pressure. Methanol forms minimum-boiling azeotropes with both acetone (54.6°C) and chloroform (53.5°C), and acetone-chloroform forms a maximum-boiling azeotrope (64.5°C). Experimentally there are no data for maximum- or minimum-boiling ternary azeotropes for this mixture. Assuming no ternary azeotrope, the temperature profile for this system is 461325, which from Table 13-18 is consistent with DRD 040 and DRD 042. However, Table 13-18 also indicates that the pure-component and binary azeotrope data are consistent with three temperature profiles involving a ternary saddle azeotrope, namely, 4671325, 4617325, and 4613725. All three of these temperature profiles correspond to DRD 107. Calculated residue curve trajectories for the acetone-chloroform-methanol system at 1-atm pressure, as...

As an example. Van Dongen (Ph.D. Thesis, University of Massachusetts, 1983) considered the separation of a methanol-methyl acetate mixture, which forms a homogeneous azeotrope, using n-hexane as an entrainer. The distillation boundaries for this system (Fig. 13-87a) are somewhat curved. A separation sequence that exploits this boundary curvature is shown in Fig. 13-87b. Recycled methanol—methyl acetate binary azeotrope and methanol-methyl acetate—hexane ternary azeotrope are added to the original feed FO to produce a net feed com-... 

This ternary azeotropic distillation program uses a special system of utility subroutines with programmed initialization. Eight main controls, KNTRL, are used with various options on each. Four parameter options are built into the program, but the values are changed by the user by using PRMTR cards. Twenty-one DATA cards allow the user to give the pertinent conditions and specifications for the separation to be calculated. 

In Region II, the high- and low-boiling nodes are MIPK and the MEK-water azeotrope, respectively. The more complicated cyclo-hexane-ethanol-water system (Fig. 13-58c) has three separatrices and three regions, all of which share the ternary azeotrope as the low-boiling node. 

As one last example of the separations system synthesis method, a process was being developed to produce the chemical diethoxymethane (DEM), the ethanol acetal of formaldehyde. The raw materials are paraformaldehyde and ethanol, and the reaction by-produces water. Diethoxymethane, ethanol, and water form a homogeneous ternary azeotrope that is readily removed from the reaction mass (the paraformaldehyde being relatively nonvolatile). The species allocation... 

Two of the three composition goals, pure DEM and pure water, have been met and by mass balance, sufficient water has been regenerated to serve as the mixing agent for dragging the ternary azeotrope into the two-phase region (actually, the extra water is first put in the system, then continually recycled as is the entrainer in the previous example). A third composition near the ethanol-... 

Surface of vaporization the constant T for a ternary liquid system A + B + C with an azeotrope M. 

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