Methanol-water ternary azeotropes

Properties Colorless liquid etherlike odor. Fp -88.68C, bp 63.2-65.6C, d 0.913 (20/4C), refr index 1.4320 (20C), flash p -22F (-30C). Insoluble in water 0.3 g/100 g water. Miscible with most organic solvents. Forms a binary azeotrope with methanol, a ternary azeotrope with methanol-water. 

Isoprene [78-79-5] (2-methyl-1,3-butadiene) is a colorless, volatile Hquid that is soluble in most hydrocarbons but is practically insoluble in water. Isoprene forms binary azeotropes with water, methanol, methylamine, acetonitrile, methyl formate, bromoethane, ethyl alcohol, methyl sulfide, acetone, propylene oxide, ethyl formate, isopropyl nitrate, methyla1 (dimethoxymethane), ethyl ether, and / -pentane. Ternary azeotropes form with water—acetone, water—acetonitrile, and methyl formate—ethyl bromide (8). Typical properties of isoprene are Hsted in Table 1. 

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... 

Surprisingly, there is limited nonproprietary experimental data on methanol esterification with acetic acid (29). Studies have been confined to liquid-phase systems distant from equilibrium (30), in regions where hydrolysis is unimportant. A physical study of the ternary methanol—methyl acetate—water system is useful for design work (31). Methyl acetate and methanol form an azeotrope which boils at 53.8°C and contains 18.7% alcohol An apparent methanol—water azeotrope exists, boiling at 64.4°C and containing about 2.9% water. These azeotropes seriously complicate methyl acetate recovery. Methyl acetate is quite soluble in water, and very soluble in water—methanol mixtures, hence two liquid phases suitable for decanting are seldom found. 

The use of a polar and a nonpolar solvent to separate acetone and methanol from a mixture of tetramethylene oxide and other oxides has been described by Hopkins and Fritsch.17 A schematic drawing of this purification process is shown in Fig. 6-1. The ternary azeotrope of acetone, methanol, and tetramethylene, a cyclic ether, may be broken by an extractive distillation using the highly polar solvent, water. The volatility of the methanol is lowered by the water to such an extent that the azeotrope of acetone and tetramethylene oxide may be distilled overhead in the extractive distillation column, and the methanol is withdrawn with the water from the bottom of the column. A second column is used to separate the azeotropic mixture of acetone and tetramethylene oxides by use of the relative nonpolar solvent, pentane. An azeotrope of pentane and acetone boiling at 32°C, is removed from the top of the column. The azeotrope is broken by adding water which results in the formation of two phases, a pentane phase and an acetone-water phase. 

Figure 9.13 gives a ternary diagram for the isopentane-methanol-TAME system at 4 bar. The phase equilibrium of this system is complex because of the existence of azeotropes. The UNIFAC physical property package in Aspen Plus is used to model the VLB in all units except the methanol/water column where the van Laar equations are used because of their ability to accurately match the experimental data. 

The ternary system of methyl acetate, methanol, and water illustrates the occurrence of a distillation boundary. Figures 1.27 and 1.28 give the binary azeotropes of the system at 20psia using NRTL physical properties. Figure 1.29 shows the ternary diagram with a distillation boundary. 

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... 

Water and 1-butanol form a heterogeneous azeotrope and an immiscibility gap over a limited region of ternary compositions exists. The stability of the stationary points of the system and the distillation line map modeled by UNIQUAC are shown on Figure 3a. One distillation boundary, miming from methanol (unstable node) to the binary heteroazeotrope (saddle) divides the composition space in two regions. The system belongs to Serafimov s topological class 1.0-2 (Hilmen, 2002). 

The TAME reactive distillation system with a two-column methanol recovery system was successfully simulated in Aspen Dynamics. The system features two recycles (methanol and water) and three feedstreams (C5, methanol, and water). The system is essentially a ternary system with inerts, but the complex vapor-liquid equilibrium results in the formation of azeotropes that result in losses of methanol out of the top of the reactive column with the inerts. Therefore, a methanol recovery system must be included in the plant design and control. 

---