Jawaharlal Nehru Technological

University Kakinada

III Year B. Tech. Petrochemical Engineering

II Sem.
Mass Transfer Operation II
Azeotropes
Presentation by

Prof. K. V. Rao
Academic Advisor / Visiting Professor
School of Petroleum Courses

Azeotropes
The term azeotrope means nonboiling by any means (Greek:
a -non, zeo -boil, tropos -way/mean), and denotes a mixture of
two or more components where the equilibrium vapor and
liquid compositions are equal at a given pressure and
temperature .
It was Wade and Merriman who had first introduce the term
azeotrope in 1911 to designate mixtures that have a minimum
or maximum boiling point at constant pressure or,
equivalently, in the vapour pressure under isothermal
conditions. They define the azeotropy state as a stationary
point in the equilibrium T-x,y or P-x,y. The mixture whose
composition corresponds to an extremal point is called an
azeotrope.
If at the equilibrium temperature the liquid mixture is
homogeneous, the azeotrope is a homoazeotrope.
If the vapor phase coexists with two liquid phases, it is a
heteroazeotrope. Systems which do not form azeotropes are

Figure
1:
Graphical
representations of the VLE
for the most common types
of
binary
mixtures
at
constant pressure:
a) Non-azeotropic;
b) Minimum-boiling
homoazeotrope;
c) Minimum-boiling
heteroazeotrope;
d) Maximum-boiling
azeotrope. Left: boiling
temperature
Tbp
and
condensation
temperature Tdp and the
equilibrium
mapping
vectors in T - x; y space.

The formation of azeotrope is due to the differences in

the intermolecular forces of attraction among the
mixture components. There are 3 groups that
particularly deviate from the ideality that simply
explains the binary mixtures. They are :
1. Positive deviation from Raoults law: The
components dislike each other. The attraction
between identical molecules (A-Aand B-B) is
stronger than between different molecules (A-B).
This may cause the formation of a minimumboiling azeotrope and heterogeneity.
2.

Negative deviation from Raoults law: The

components like each other. The attraction
between different molecules(A-B) is the strongest.
This may cause the formation of a maximumboiling azeotrope.

3. Ideal mixture obeys Raoults law:

The
components
have
similar
physiochemical
properties. The intermolecular forces between
identical and different molecules (A-A, B-B and A-

The tendency a mixture to form an azeotrope

depends on 2 factors (Horsely, 1973; King, 1980):
1. The differences in the pure component boiling
point
2. The degree of nonideality.
Due to azeotrope and resulting phase behaviour,
there are profound effects on the feasibility and
technology for distillation-based operation.

Azeotropic Distillation & Extractive Distillation

Azeotropic distillation usually refers to the specific
technique of adding another component to generate a
new, lower-boiling azeotrope that is heterogeneous (e.g.
producing two immiscible liquid phases) to facilitate the
separation of components in the original mixture into
pure components or the desired compositions beyond
the azeotropic compositions.
A common historical example of azeotropic distillation is
its use in dehydrating ethanol and water mixtures. For
this, a near azeotropic mixture is sent to the final
column where azeotropic distillation takes place.
Several entrainers can be used for this specific process:
benzene, pentane, cyclohexane, hexane, heptane,
isooctane, acetone, trichloroethylene and diethyl ether
are all options as the mixture. Of these benzene and
cyclohexane have been used the most extensively.

Table: Some azeotropic mixtures

Mixture
1.
2.
3.
4.

Water-Ethanol
Pyridine-Water
Ethanol-Benzene
Acetic acid-Toluene

% Composition of
Boiling point
azeotrope
(pressure = 1 atm)
95.97 Ethanol
78.13oC
57.00 Pyridine
92.6oC
32.40 Ethanol
67.8oC
28.00 Acetic-acid
105.4oC

There are several liquid pairs which form maximum boiling

point azeotrope. Some examples are tabulated below:
Mixture
1.
2.
3.
4.

Nitric acid-Water
Acetic acid-Pyridine
Chloroform-Acetone
Hydrogen chloride-Water

% composition
of azeotrope
68% Nitric acid
65% Pyridine
80% Chloroform
79.8% Water

Boiling point (pressure

= 1 atm)
125.5C
139.0 C
65.0 C
108.6 C

Separation of Azeotropic Mixtures

Recall from previous lecture that an zoetrope is a
special class of liquid mixture that boils at a constant
temperature at a certain composition. It behaves as if
it were one component with one constant boiling
point. Such mixture cannot be separated using
conventional distillation methods.
Distillation of a mixture that exhibits azeotropic
behaviour begins similarly to conventional distillation.
The difference is that, as the process continues, a
temperature is reached at which the compositions of
the vapour phase and liquid phase become the same.
Once this happens an azeotrope has been formed,
and the individual components can no longer be
separated
by
conventional
distillation.
The
compositions of the liquid and vapour remain the
same until all of the liquid is eventually vapourised.

Separation of Azeotropic Mixtures can be broadly

classified into the following methods:
by changing system pressure
by addition of an entrainer (azeotropic
distillation)
by combination with other processes (hybrid
systems)
Azeotropic Distillation - Separation
Azeotropes by Addition of Entrainer

of

Binary

Azeotropic distillation refers to processes whereby a new

component (called the entrainer) is added to the original
feed mixture to form (or nearly form) an azeotrope with one
(or more) of the feed components. The azeotrope is then
removed as either the distillate or the bottoms.
Azeotropic distillation also refers to those processes in which
a new component is added to an original feed mixture to
break an azeotrope that otherwise would be formed by the
feed components.
Thus, the purpose of deliberately adding the entrainer is
either to separate one component of a closely boiling pair or
to separate one component of an azeotrope.

To illustrate the basic concepts consider the set-up in the

Figure below for the separation of a mixture A-B that forms a
minimum-boiling azeotrope.
The entrainer E is a medium boiler (i.e. its boiling point in
intermediate between components A and B), or is a low
boiler that can form an intermediate boiling maximum

he feed (A and B) is mixed with the entrainer E before entering

column C1. Component B (which is essentially free of the
azeotrope A-E) is removed from the bottom of column C1, while
the overhead vapour from C1 is fed to column C2. Component
A is removed as overhead product and entrainer E as the
bottoms product. The entrainer is recycled back to column C1.
One example of such a separation is for the mixture acetoneheptane with benzene as the entrainer. The respective boiling
points are: A - acetone (56.2 oC), B - heptane (98.4 oC), E benzene (80.1 oC) and A-B Minimum-boiling azeotrope (55.6 oC).
Alternatively, component A can be separated first as overhead
from column C1. In such a process, the column C2 then splits
the bottoms from C1 into the entrainer E (as overhead product)
and component B (as bottoms product).
For a maximum-boiling azeotrope, the entrainer should either
be a medium boiler or a high boiler that forms an intermediateboiling azeotrope with component B.

Separation
by
Changing
(Pressure-Swing Distillation)

System

Pressure

Sometimes azeotropic distillation can be carried out

without the use of entrainer. Instead the distillation
columns are operated at different pressures, as it has
been known that the azeotropic concentration can be
shifted substantially by changing system pressure. This
method of separation is especially feasible for systems
with low-boiling azeotropes, as the azeotropic
concentration depends significantly on temperature,
which can be changed by changing the operating
pressure.
For example, as shown in the Figure, the system
tetrahydrofuran (THF) and water forms a minimumboiling azeotrope. In the first column, which operates at
lower pressure (1 bar), the high boiling component
(water) is removed as bottoms. The composition of the
overhead product is as close as possible to that of the
azeotrope at this pressure.

The pressure is increased to 8 bar in the second column. At

this higher pressure, the azeotrope forms at a lower
concentration of the low boiling component (THF), which can
then be removed as bottoms. The overhead product of the
second column is returned to the first column (in vapour
state) after pressure reduction.
In some systems, reducing the operation pressure can
eliminate azeotropic behaviour. For example, in the ethanolwater system, azeotropism disappears at a pressure below
70mm Hg.
Some other examples include:

PRESSURE SWING METHOD

USES PRESSURE TO SHIFT AZEOTROPE CONCENTRATIONS

Extractive distillation is defined as distillation in the

presence of a miscible, high boiling, relatively non-volatile
component, the solvent, that forms no azeotrope with the
other components in the mixture. The method is used for
mixtures having a low value of relative volatility, nearing unity.
Close boiling mixtures cannot be separated by simple
distillation, because the volatility of the two components in the
mixture is nearly the same, causing them to vaporize at nearly
the same temperature at a similar rate, making normal
distillation impractical.
This process is very similar to azeotropic distillation. Extractive
distillation refers to those processes in which a high-boiling
solvent is added alter the relative volatilities of components in
the feed.
The boiling point of the solvent is generally much higher than
the boiling points of the feed mixture that formation of new
azeotropes is impossible. The high boiling point will also
ensure that the solvent is will not appreciably vapourise in the

The separation of toluene (boiling point 110.8 oC) from isooctane (boiling point 99.3 oC) is difficult using conventional
distillation. Addition of phenol (boiling point 181.4 oC)
results in the formation of phenol-toluene mixture that
leaves the extractive distillation column as bottoms, while
relatively iso-octane is recovered as overhead product. The
phenol-toluene mixture is further separated in a second
column (solvent recovery column) whereby toluene appears
as distillate and the bottoms product, phenol, is recycled
back to the first column.
In the above example, when the solvent is added to the
original feed mixture it forms a new mixture with one of the
feed components by "absorbing" that component. This new
mixture has a much higher boiling point than the other feed
component that is not absorbed so that it leaves as bottoms
product from the extractive distillation column. The
unabsorbed feed component then leaves as the overhead
product.
The absence of azeotropes plus the fact that the solvent can

The choice of solvent determines which of the two components

in the original feed is removed predominantly in the distillation.
For example, if the fresh feed to the distillation is a mixture of 83
mole% ethanol and 17 mole% water, and ethylene glycol (boiling
point 197.35 oC) is the solvent; the volatility of ethanol is
increased more than that of water. Therefore, ethanol is removed
as the distillate from the extractive distillation column, and water
is separated in the solvent recovery column.
On the other hand, if a high-boiling hydrocarbon such as isooctane (boiling point 99.3 oC, vs. n-octane with boiling point
125.6 oC) is used as solvent, the volatility of water is enhanced
relative to that of ethanol, and water now becomes the distillate
in the extractive distillation column.
The number of possible solvents available for separation by
extractive distillation is usually much larger than for an
azeotropic distillation because of less severe volatility
restrictions. A general approach is to chose a compound that is
more similar to the higher-boiling component in the original feed,
and then go up the homologous series for that compound until a

Comparison between Azeotropic and Extractive

Distillation
Many of the entrainers used in azeotropic distillation are
either proven or suspected carcinogens or otherwise
classified as hazardous pollutants. Using the example of
ethanol-water from previous section, noted that benzene
is the entrainer. Ethanol is removed as the bottoms
product from the column. Benzene is too hazardous for
various reasons ranging from workplace to product to
environmental safety.
An alternative to recover ethanol is to use extractive
distillation. The solvent used is Propylene Glycol. Recall
also that ethanol forms a minimum-boiling azeotrope
with water at approximately 89.4 mole% (96 wt%)
ethanol.
A process schematic for the process is shown in the
Figure below:

For this separation, propylene glycol meets all the

requirements of an ideal extractive solvent:
It is miscible with water at all concentrations
It has a higher boiling point than water (187 0C
at 1 atm)
It does not form an azeotrope with water
It has a molecular affinity for water (the
hydroxyl -OH group forms a weak bond with
water molecule)
It is a relatively safe workplace material
.

In the above system, the first column is the

ordinary azeotropic distillation that produces an
ethanol-water azeotrope as the distillate and
nearly pure water as the bottoms. The distillate
is fed to the second column for extractive
distillation, where propylene glycol is added.
Ethanol is produced as the distillate, leaving the
top of the column.
This column can be conceptually divided into 3
sections. The middle section is the rectifying
section where ethanol is purified by the removal
of water. Bonding of the water molecules with
glycol raises ethanol's relative volatility with
respect to water, thus facilitating separation.
The following table shows the change in relative
volatility in the columns

The top section reduces the concentration of

propylene glycol in the ethanol distillate to
negligible level. The bottom section strips ethanol
from water. The bottoms from the second column is
sent to the third column, a glycol stripper, where
the glycol is recovered. The propylene glycol leaves
the stripper as a bottoms product and is recycled
back to the extraction column as the source of
solvent. The overhead from the glycol stripper
(containing mainly water and some ethanol) is sent
back to the first column where it combined with
fresh feed.

addition based distillation methods depending on the

properties and role of the entrainer and the organization
(scheme) of the process:
1. Homogeneous
azeotropic
distillation
(ordinary
distillation of homoazeotropic mixtures): 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.
2. Heteroazeotropic distillation
(decanter-distillation
hybrids that involve heteroazeotropes): The entrainer
forms a heteroazeotrope with at least one of the original
mixture components. The distillation is carried out in a
combined column and decanter system.
3. 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.
The distillation is carried out in a two-feed column
where the entrainer is introduced above the original

and reversibly with one of the original mixture

components. The reaction product is distilled out from
the non-reacting component and the reaction is
reversed to recover the initial component. The
distillation and reaction is usually carried out in one
column (catalytic distillation).
5. Chemical drying (chemical action and distillation): The
volatility of one of the original mixture components is
reduced by chemical means. An example is
dehydration by hydrate formation. Solid sodium
hydroxide may be used as an entrainer to remove
water from tetra hydro furan (THF). The entrainer and
water forms a 35-50 % sodium hydroxide solution
containing very little THF.
6. Distillation in the presence of salts: The entrainer (salt)
dissociates in the mixture and alters the relative
volatilities sufficiently so that theseparation becomes
possible. A salt added to an azeotropic liquid mixture
will reduce the vapor pressure of the component in
which it is more soluble. Thus extractive distillation can
be applied using a salt solution as the entrainer. An

Thank You