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1)Pressure swing distillation

Principle
Diagram of operation
How operating conditions are manipulated
Ethanol water mixture
Show difference of Homogeneous and heterogeneous azeotropic. Give example to
show difference.

1) Pressure swing distillation

Some binary azeotrope mixtures lose its azeotropic behavior when the system pressure is
changed. In this case, this binary azeotrope mixture can be separated using pressure swing
distillation without using entrainer. Two distillations operate in series both at different pressure.
However, Pressure-swing distillation can only separate a pressure-sensitive azeotrope. For
example, ethanol-water mixture forms binary azeotrope at composition of 95.6 % Ethanol and
4.4% Water at ambient pressure.

Figure 1 : T-x-y diagram at different pressure P1 and P2


The azeotrope point moves towards the right side at high pressure at shifts to the left at lower
pressure. Assume that at point XP1 = 30% of component A is at azeotrope at pressure P 1. If the
pressure is raised to P2 , distillation can continue until point XP2. Again, if point XP2 is subjected to
low pressure P1, distillation will continue, therefore 100% of component A can be removed.

Diagram of operation

Let A= Water,
B = Ethanol
As the pressure decreases from P2 to P1, the azeotropic composition shifts to the left, towards a
smaller percentage of A as shown in figure. The feed F 1 with composition XF1 enters the first
column at low pressure P1. Feed F1 is the sum of fresh feed, F and recycled distillate, D 2 from
the second column. The fresh feed is richer in component A than the azeotrope mixture, while
recycled distillate, D2 has composition close to the azeotrope at pressure P2.
The feed F1 is richer in A than the azeotrope at P1, therefore it now can be separated by
distillation. The bottom product from the first column is almost pure A. The distillate, D 1, is
slightly richer in A than the azeotrope at P1 but less rich in A than the azeotrope at P 2. The second
column operates at higher pressure P 2. The bottom product is almost pure B and the distillate is
the recycled distillate,D2.

2) Homogeneous and heterogeneous azeotropes

Figure 1: a) minimum boiling homogeneous azeotrope, b) heterogeneous azeotrope


Azeotrope is a mixture of liquid that at certain proportion the boiling point of two components
are constant and cannot be separated by simple distillation. A heteroazeotrope is an azeotrope
where the vapour phase coexists with two liquid phases. At the azeotropic point, the
homogeneous vapor mixture condenses into a liquid system with two different phases of
composition equilibrium with each other. A homogeneous azeotrope exists when at equilibrium
condition the liquid mixture is homogeneous. The mixtures of homogeneous azeotrope are fully
miscible, while the mixtures of heterogeneous azeotrope are not completely miscible.

Method of separation
Homogeneous azeotropic distillation: The entrainer (used to alter the boiling point of mixture)
is completely miscible with the components of the mixture. It may form homogeneous
azeotropes with the original mixture components. The distillation is carried out in a conventional
single-feed column, such as extractive distillation/pressure swing distillation.
Heterogeneous azeotropic distillation: 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.

Figure 2.2: Heterogeneous azeotropic distillation of ethanol and water


A stripping column: column 1
A liquid-liquid settler (decanter) to separate the two liquid phases a and b
A distillation column: column 2
An example is ethanol water mixture with benzene as entrainer. The entrainer forms a
heterogeneous azeotrope with the orginal component.
The stripping column receives the liquid phase of composition x a from the settler. In column 1
the phase a is more volatile than the water (component A), which is then found almost pure at the
bottom of this column. The vapor phase of composition x a is accumulated at the top of column 1
and sent into the liquid-liquid settler, from where it is recycled back into the same column 1.
In the column 2 the liquid phase of composition x b constitutes the reflux of the distillation
column 2. The phase b is less volatile than the ethanol which is found at the bottom of this
column 2. The vapor coming from column 2 is sent into the settler where it split again into the
two liquid phases, where the azeotropes are broken.

Homogeneous azeotropic distillation can be carried out using pressure swing distillation, as
already shown in question 1.

Distillation condition
Homogeneous azeotropic distillation
The entrainer alters the relative volatility of the two azeotropic constituents without inducing
liquid-liquid separation. Some homogeneous azeotropic pressure sensitive component can be
separated using pressure-swing distillation, where two or more distillation columns operating at
different pressures with a recycle stream to achieve the desired separation. However, if the
change in azeotrope composition is small, the pressure-swing distillation will have very large
recycle flowrates, making the process inefficient and uneconomical process. Separation recycle
reflux reaches maximum for some mixture, and it can achieve with the same specifications with
a larger number of trays and requires a larger reflux. At infinite reflux, no separation is achieved.
For some mixture, the only separation yields the intermediate component as a pure distillate,
while the bottom product contains the light and heavy components. Sometimes the separation
yields the intermediate component as a pure bottom product while the distillate contains the light
and heavy components. For a minimum boiling azeotrope, the entrainer selection rules state that
one should use a component that introduces no distillation boundary between the azeotropic
constituents, and either a low or high boiling component that introduces no additional azeotrope
or a component which introduces new minimum boiling azeotropes.

Heterogeneous azeotropic distillation


The entrainer alters the relative volatility of the two azeotropic constituents and induces liquidliquid separation. Heterogeneous azeotropes can be easily separated using a decanter coupled
with one or more distillation columns, which follows the principle of both vapor-liquid and
liquid-liquid equilibrium driving forces. Many heterogeneous azeotropic distillation systems are
very sensitive to small changes in the operating conditions,

Small changes in bottoms products purity specs can significantly impact the column

temperature profile.
Small changes in the reflux ratio can significantly change the temperature profile.
Small deviation in pressure can move the overhead composition outside the
heterogeneous region, which can cause column failure.

Heterogeneous azeotropic distillation is used to separate close-boiling or azeotropic systems.


This type of distillation can be used as an alternative to extractive distillation, pressure swing
distillation, or homogeneous azeotropic distillation.

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