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Introduction:

All liquid mixtures have forces of intermolecular attraction. The molecular


interactions when two or more components are mixed may cause the mixture to
form certain “inseparable” compositions where the vapor and liquid compositions
at equilibrium are equal within a given pressure and temperature range. These
specific mixture compositions are called azeotrope. Azeotropes have sometimes
been mistaken for single components because they boil at a constant temperature
The components that form the azeotrope and need to be separated. There are
various types of azeotrope that can exist

• Binary azeotrope: Azeotrope formed by two components


• Ternary azeotrope: Azeotrope formed by three components
• Heterogeneous azeotrope: Azeotrope where the forming components are
immiscible
• Homogeneous azeotrope: Azeotrope where the forming components are
miscible
• Minimum boiling azeotrope: Azeotrope with lower boiling point than its
constituent components
• Maximum boiling azeotrope: Azeotrope with higher boiling point than its
constituent components
Txy and Pxy diagrams:

Components:

Water/ethanol

Water/isopropanol

Water/butanol

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Graphs:

Azeotrope formation= x=0.15, y=78.2℃

Figure 1: Txy diagram for water ethanol system

Azeotrope formation= x=0.1, y=0.0792bar

Figure 2: Pxy diagram for water ethanol system

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Azeotrope formation= x=0.282, y=80.2℃

Figure 3: Txy diagram for water isopropanol system

Azeotrope formation= x=0.322, y=0.0643bar

Figure 4: Pxy diagram for water isopropanol system

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Azeotrope formation= x=0.614, y=87.5℃

Figure 5: Txy diagram for water butanol system

Azeotrope formation= x=0.709, y=0.0434bar

Figure 6: Pxy diagram for water butanol system

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Methods:

The azeotrope can be separated by various techniques. One measure of the degree of
enrichment, or, the ease of separation, is the relative volatility between pair of the components.
The tendency of a mixture to form an azeotrope depends on two factors:

(i) The difference in the pure component boiling points


(ii) The degree of nonideality

The closer the boiling points of the pure components and the less ideal mixture, the greater the
likelihood of an azeotrope. There are various methods by which the separation can be achieved.
The methods are mentioned below.

• Pressure swing distillation


• Homogeneous azeotropic (homoazeotropic) distillation
• Heterogeneous azeotropic (heteroazeotropic) distillation
• Extractive distillation
• Membrane-distillation hybrids
Pressure swing distillation:

The basic principle is that to overcome the azeotropic composition by changing the system
pressure. By increasing or decreasing the operating pressure in individual columns we can
move distillation boundaries in the composition space or even make azeotropes appear or
disappear. One of the key factor is that azeotrope is sensitive to pressure changes and recycle
ratio which increases costs. The smaller the change in azeotropic composition with pressure,
the larger is the recycle

Figure 7: Pressure swing distillation

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Heterogeneous azeotropic distillation:

Entrainer is immiscible and forms azeotrope with at least one of the original azeotropic
components. The distillation is carried out in a combined column-decanter column. Entrainer
is recovered and recycled to the first column. The major principle on which it works involves
Liquid-liquid immiscibilities are used to overcome azeotropic compositions. It found wide
range of application in industry.

Figure 8: Heterogeneous azeotropic distillation

Homogeneous azeotropic distillation

The entrainer is completely miscible with the components of the original mixture. It may form
homoazeotropes with the original mixture components. The distillation is carried out in a
conventional single-feed column.

Figure 9: Homogeneous azeotropic distillation

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Extractive distillation:

The entrainer has a boiling-point that is substantially higher than the original mixture
components and is selective to one of the components. Distillation is carried out in a two-feed
column with a heavy entrained added continuously at the top. The main part of the entrainer is
removed as bottom product. There are other methods that may also be called entrainer-addition
distillations e.g. Reactive distillation, chemical drying and Distillation in the presence of salts
etc. The principle on which it works is that the entrainer alters the relative volatility of the
original components. The entrainer has a substantial higher affinity to one of the original
components and extracts it downwards the azeotropic column.

Figure 10: Extractive distillation

Membrane-distillation hybrids :

The separation of liquid and gas mixtures with membranes as separating agents are used in this
process. The membrane itself acts as the mass separating agent, preferentially absorbing and
diffusing one of the azeotrope-forming components. The feed mixture is partially separated by
means of a semipermeable barrier (the membrane) into a retentate and permeate is that part of
the feed that does pass through the membrane. The most commonly used membrane technology
for liquid azeotropic mixtures is pervaporation with low pressure on the permeate side of the
membrane so as to evaporate the permeate.

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Figure 11: Membrane-distillation hybrid

Conclusion:

The selection of the method depends on the application and economic aspects. Any of above
method can be used. The basic advantages of distillation are listed as: potential for high
throughput, any feed concentration, and high purity. But major disadvantage is that distillation
tends to use large amounts of energy and process complexity. The other methods that can be
used in per-vaporization. The per-vaporation can simplify the overall process structure, reduce
the energy consumption and avoid entrainers. The main benefit of using membranes as mass
separating agents is that the selectivity is independent of the vapor-liquid equilibria, but the
problem is that membrane units only handle relatively pure feeds, that is, liquid mixtures dilute
in one component and without heavy contaminants like salts and tar and less flexibility to
variations in feed composition.

A combined system of pervaporation and pressure-swing distillation was found to be


economically favorable in many cases.

References:

1. Ahmad, B.S., Y. Zhang and P.I. Barton (1998). Product Sequences in Azeotropic Batch
Distillation. AIChE J. 44(5), 1051–1070.
2. Andersen, H.W., L. Laroche and M. Morari (1995). Effect of Design on the Operation
of Homogeneous Azeotropic Distillation. Comp. Chem. Eng. 19(1), 105–122.
3. Baburina, L.V., V.M. Platonov and M.G. Slin’ko (1988). Classification of Vapor-
Liquid Equilibrium Diagrams for Homogeneous Azeotropic Mixtures. Theor. Found.
Chem. Eng. 22(4), 390–396 [535–542].