Azeotropic Distillation

 The presence of azeotrope in a binary system presents a limit (a distillation boundary) for the
product compositions achievable in a single distillation column.
( For example , the ethanol-water system at atmospheric pressure has a homogeneous azeotrope at
351 K of composition 90 mol% ethanol. A typical mixture from a fermentation process has very
low ethanol concentrations (4-6 mol%). If this mixture is fed to a distillation column operating at
atmospheric pressure, high-purity water can be produced out from the bottom but the ethanol purity
of the distillate cannot exceed 90 mol%).
 Sometimes, binary azeotropic mixtures can be separated by using two columns that operate at
different pressures. This flowsheet is effective if the composition of the azeotrope shifts
significantly with pressure. This method has the important advantage of not introducing other
components , which can present problems because of small traces of impurities in the final products.
 Involves adding a third volatile component, called entrainer, which forms a ternary azeotrope with
the two components to be separated and thus changes their relative volatilities and finally alters
their separation factor (activity coefficients) in the distillation system.
 The Azeotropic Distillation system typically consists of two distillation columns for dehydration
of 92.4 wt% ethanol solution from the Ordinary Distillation Column:
(1) A dehydration column (azeotropic column) for further concentration in the presence of the
entrainer
(2) An entrainer recovery column (stripping column) for separation of entrainer from the product
stream
 For the process:
 The feed is an ethanol/ water mixture with composition that is near the binary azeotrope, which
has been produced in an upstream binary distillation column.
 The process consists of two columns in which the addition of benzene (entrainer) takes the
water out of the top of the first column, producing high-purity ethanol out the bottom.
 The overhead vapor is then condensed and forms two liquid phases: the ethanol-entrainer
(organic phase) and the water-entrainer (aqueous phase).
 The organic phase provides reflux to the first column
 The aqueous phase is fed to a second distillation column that produces high-purity water out
the bottom and recycles the distillate back to the first column

 In the dehydration column, ethanol (>99 wt%) exits from the bottoms while water vapor,
solvent, and small amounts of ethanol exit from the tops. The top stream enters a separator,
called decanter, and splits into ethanol-entrainer (organic phase) and water-entrainer (aqueous
phase) streams.
 The organic phase is refluxed back into the first column, while the latter is processed in the
entrainer recovery column.

Entrainer
Azeotropic Decanter
Recovery
Column
Column
- The commonly used entrainers for breaking binary ethanol-water azeotropes by heterogeneous
azeotropic distillation are benzene, toluene, and cyclohexane. A mixed solvent, e.g., a mixture of
benzene and n-octane can also be used.
 Benzene is a traditional entrainer in heterogeneous azeotropic distillation for ethanol
dehydration. For many years, however, benzene has been substituted by other solvents
because of its carcinogenic effect. Currently, cyclohexane is one of the most used entrainers
for this separation. However, cyclohexane also has the disadvantage of flammability.