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NAME :- KATARIYA DHAVAL 160140105016

KATARIYA PRADIP 160140105017

KAYASTH DARSHAN 160140105018
KHASHI VISHAL 160140105019
LADUMOR HARSHAD 160140105020
SUBJECT :- Advance Separation Technique
TOPIC:- Pressure Swing Distillation
Mixture of two or more liquids wherein it's component
cannot be separated by simple distillation because they have
same boiling point and vaporize point.
Method of separate an azeotropic mixture:-
1. Extractive Distillation
2. Azeotropic Distillation
3. Vacuum Distillation
4. Pressure Swing Distillation
 some binary azeotrope mixtures lose azeotropic behaviour
when the system pressure is changed.
 Pressure swing Distillation(PSD) is the process to be utilized
to separate the pressure sensitive mixture with close
boiling point or forming azeotrope
 In this case, separation can be achieved without using an
additional entrainer.
 A simple change in pressure can alter relative volatility of
the mixture with close boiling point or forming azeotrop
Basically three types of Operation mode in
Pressure Swing Distillation.
1. Continuous Operation
2. Batch Operation
3. Semi Continuous Operation
 In continuous Operation the separation is
performed using two columns maintained at
different pressure
 The distillate which approach the azeotropic
composition at low and high pressure are
recycled between two columns.
 In Batch Operation single column is used for
 First feed charged to column operated at
pressure P1 and Bottom removed collected
distillate D1 approach to azeotropic
 Then column is recharged with distillate D1
and operated at pressure P2 to get bottom A
as pure product removed.
 In semi Continuous Operation single Distillation column is used but
column operated continuously and periodically it is not recharged or
 Liquid level are maintained, Reboiler and condenser in charged
 The advantage is lower the investment cost and shorter downtime
when the Mixture is to be separated is changed.
 Pressure swing distillation is a complex distillation technique
in which two distillation column, one operating at low
[pressure and another at a high pressure , are used to
separate homogeneous azeotropic mixture.
 for a successful separation , it is necessary that the azeotrope
composition at the high and low pressure be sufficiently
different. This demonstration consider a binary mixture is a
good candidate for PSD because it exihibits a pressure –
sensitive minimum boiling azeotrope.
• The total feed F1 to Column T-1 operating at the lower
pressure P1 is the sum of the fresh feed F at mole fraction
xF, and the recycled distillate D2 at mole fraction xD2
(close to azeotropic mole fraction xP2). The mole fraction
of the total feed F1 is xF1 , and it is richer in A than the
azeotropic mole fraction of xP1 at pressure P1. The
bottoms leaving column T-1 is almost pure A. The
distillate leaving T-1 is D1 , having the mole fraction xD1 .
This mole fraction is richer in A than the azeotropic mole
fraction of xP1, but less rich in A than the azeotrope mole
fraction of xP2 .
• Distillate D1 is sent to Column T-2 as feed F2 . Nearly
pure B is obtained from bottom of T-2, and the distillate
D2 is recycled to Column T-1.
 Here are several example which process comes under the
pressure swing distillation after the slight change of the
pressure of azeotropes and they lose their azeotropic
1) acetone / methanol
2) acetic acid / toluene
3) ethanol / ethyl acetate
4) phenol / butyl acetate
5) propanol / toluene
Azeotropic distillation is technique involves
addition of third component in homogeneous
azeotropes, called entrainer to form minimum
boiling hetero-azeotrope with at least one of
the components of feed carrying water and
leaves near dry(pure) product in bottom.

The overhead vapours are condensed to two

liquid phases :-
1.) Entrainer rich phase is refluxed.
2.) The aqueous phase is decanted.
 Azeotrope is then removed as either distillate
or bottoms.
 Azeotropic distillation also refers to those
processes in which a new component is
added to an original feed mixture to be break
an azeotrope that otherwise would be formed
by the feed components.
 The purpose of adding entrainer is either to
seprate one component of closely boiling pair
or to seprate one of azeotrope.
 As another example, consider the operation of the
azeotropic distillation of acetic acid-water mixture
using n-butyl acetate (a type of ester) as the
entrainer, as shown in the Figure above. The boiling
point of pure acetic acid is 118.1°C, and for water

 Addition of n-butyl acetate (boiling point 125 °C) will

result in the formation of a minimum-boiling
azeotrope with water (boiling point 90.2°C). The
azeotropic mixture therefore will be distilled over as
vapour product from the high-boiling acetic acid,
which leaves as bottoms product.
 When the overhead vapour is condensed and collected
in a decanter, it forms two insoluble layers:
1.) Top layer of nearly pure butyl acetate saturated
with water.
2.) A bottom layer of nearly pure water saturated with
butyl acetate.
 The liquid from the top layer is returned to the
distillation column as reflux and source of entrainer.
The liquid from the bottom layer is sent to another
column for the recovery of the entrainer by removing
the water using steam stripping.
 When binary mixture is heterogeneous , sepration of
the components is possible without addition of an
Extractive distillation can be 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
In simple terms, extractive distillation is a means of
separating two substances with similar boiling points by
adding a third substance to change the boiling point of one
of compounds, thus making them easier to separate.
Solvent is continuously added near the top of the column so
that an appreciable amount is present in the liquid phase
throughout the column. The component having the
greater volatility(not necessarily the lowest boiling point
component) is taken overhead as a relatively pure distillate.
The other component leaves with the solvent via the
column bottoms.
The solvent is then separated from the bottoms in second
distillation column. Selection of an extractive distillation
solvent is the most important step in developing a
successful extractive distillation solvent is the most
important step in developing a successful extractive
distillation sequence.
Important selection criteria of solvent are given below.
1. It should enhance the relative volatility of the key
component significantly.
2. Required solvent quantity to be added to the azeotropic
mixture should not be excessive.
3. It should be soluble in the feed components.
4. It should be easily separable from the bottom product.
5. It should be relatively inexpensive and easily available.
6. It should be stable at the operating condition of both the
7. It should be non reactive with the feed components.

8. It should have low latent heat of veporisation.

9. It should be non-corrosive and non-toxic
10. It should not from immiscible liquid mixtures at any point in
the column
Cyclohexane is manufactured from benzene. The mixture
from the reactor comes out with the desired product and also
a significant amount of unreacted benzene which is to be
recycled back to the reactor for economic reasons. Product
mixture contains nearly 45% cyclohexane and balance
It is desired to operate the distillation column at 150kPa a as
dictated by the process flow sheet.
At this pressure, cyclohexane and benzene boil at 94.3 C and 93.5
C, respectively. Binary homogenous azeotrope at this pressure is
formed at 91 C, containing 45.5% cyclohexane which is nearly the
same composition of reactor exit product mix.
In this case propylene glycol is selected as a solvent as benzene is
highly soluble in the solvent. Further the solvent has high boiling
point at 150kPa a and no new azeotropes are formed.
Distillate from the column is 99.3% pure cyclohexane. Bottoms
from the first column is feed to second column from which
distillate is 85% pure benzene which is recycled back to the reactor.
Bottoms from the second column is nearly pure solvent which
is recycled to the first column.
Apart form organic solvents, inorganic salts such as
potassium and sodium acetates, calcium chloride, calcium
nitrate, caustic soda, etc., can also be used to break the
Another well-known example of example of extractive
distillation is dehydration of nitric acid-water
azeotrope(containing 64.1% HNO3 by mass at 101.325 kPa a
and 122 C). In this case sulphuric acid is used as solvent.
Advantages of extractive distillation over azeotropic distillation:-
1. Choice of third components to be added is greater as selection
of third components does not depend upon an incident of
azeotrope formation.
2. Energy requirements is less as the third components or solvent
is not completely vaporised in principle column or in auxiliary
column .
Only small fraction of solvent is vaporized in both columns as the
same is obtained as bottom products.
While entire entrainer is to be vaporized in azeotropic distillation in
both columns as the same is coming out as one of the components
of overhead vapour from both the columns.
However, this advantage of the extractive distillation is lost if
volatilised components or the components to be taken out as
top product along with entertainer the azeotropic
mixture(containing 4.4% by mass water ), energy consumption
of azeotropic distillation using n-pentane as entrainer is less
as compared to the same by extractive distillation using
ethylene glycol as solvent .
Azeotropic and extractive distillations are techniques used in
the field of chemistry and engineering. Major industries,
especially pharmaceuticals, are making use of these
techniques to further improve their research.
Distillation is a very important process in separating certain
components from the mixture and is typically based on the
volatility of the components in the mixture of the boiling
liquid. Although these techniques are usually compared with
each other, many chemical engineering students are still
confused about the difference. Azeotropic and extractive
distillations have some similarities but they also have distinct
differences and these are observed on the processes.
Distillation is the most widely used separation technique in the
chemical process industries. Not all liquid mixtures can be
separated by ordinary fractional distillation, however. When the
components to be separated of system have relative volatilities
of close to 1.00 (i.e. close boiling mixture), separation becomes
difficult and expensive because a large number of trays and a
high reflux ratio are necessary.
Both the equipment and utility will costs increase markedly and
the separation by ordinary distillation can become
uneconomical. If the mixture forms azeotropes, a different
problem arises - the azeotropic composition can limit the
separation. In such a case, the azeotrope must be "broken" to
enable separation.
Azeotropic distillation is any of a range of techniques used
to break an azeotrope in distillation. In chemical
engineering, 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), such as the example below with the addition of
benzene to water and ethanol. This practice of adding an
entrainer which forms a separate phase is a specific sub-
set of (industrial) azeotropic distillation methods, or
combination thereof. In some senses, adding an entrainer
is similar to extractive distillation.