Phenol binary azeotropes

Phenol, 13 747-756, 757. See also Phenols alkylation, 2 196—197 analytical methods for, 18 753—754 antimicrobial used in cosmetics, 7 831t from benzene, 3 620 from benzoic acid oxidation, 3 631 binary azeotrope with benzaldehyde, 3 591t... 

Such a process depends upon the difference in departure from ideally between the solvent and the components of the binary mixture to be separated. In the example given, both toluene and isooctane separately form nonideal liquid solutions with phenol, but the extent of the nonideality with isooctane is greater than that with toluene. When all three substances are present, therefore, the toluene and isooctane themselves behave as a nonideal mixture and then-relative volatility becomes high. Considerations of this sort form the basis for the choice of an extractive-distillation solvent. If, for example, a mixture of acetone (bp = 56.4 C) and methanol (bp = 64.7°Q, which form a binary azeotrope, were to be separated by extractive distillation, a suitable solvent could probably be chosen from the group of aliphatic alcohols. Butanol (bp = 117.8 Q, since it is a member of the same homologous series but not far removed, forms substantially ideal solutions with methanol, which are themselves readily separated. It will form solutions of positive deviation from ideality with acetone, however, and the acetone-methanol vapor-liquid equilibria will therefore be substantially altered in ternary mixtures. If butanol forms no azeotrope with acetone, and if it alters the vapor-liquid equilibrium of acetone-methanol sufficiently to destroy the azeotrope in this system, it will serve as an extractive-distillation solvent. When both substances of the binary mixture to be separated are themselves chemically very similar, a solvent of an entirely different chemical nature will be necessary. Acetone and furfural, for example, are useful as extractive-distillation solvents for separating the hydrocarbons butene-2 and a-butane. 

As an example of such an operation, consider the process of Fig. 9.54, The separation of toluene (bp 110.8 C) from paraffin hydrocarbons of approximately the same molecular weight is either very difficult or impossible, due to low relative volatility or azeotropism, yet such a separation is necessary in the recovery of toluene from certain petroleum hydrocarbon mixtures. Using isooctane (bp = 99.3°C) as an example of a paraffin hydrocarbon, Fig. 9.54a shows that isooctane in this mixture is the more volatile, but the separation is obviously difficult. In the presence of phenol (bp = 181.4 C), however, the isooctane relative volatility increases, so that, with as much as 83 mole percent phenol in the liquid, the separation from toluene is relatively easy. A flowsheet for accomplishing this is shown in Fig. 9.546, where the binary mixture is introduced more or less centrally into the extractive distillation tower (1), and phenol as the solvent is introduced near the top so as to be present in high concentration upon most of the trays in the tower. Under these conditions isooctane is readily distilled as an overhead product, while toluene and phenol are removed as a residue. Although phenol is relatively high-boiling, its vapor pressure is nevertheless sufficient for its appearance in the overhead product to be prevented. The solvent-recovery section of the tower, which may be relatively short, serves to separate the phenol from the isooctane. The residue from the tower must be rectified in the auxiliary tower (2) to separate toluene from the phenol, which is recycled, but this is a relatively easy separation. In practice, the paraffin hydrocarbon is a mixture rather than the pure substance isooctane, but the principle of the operation remains the same. 

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