Module:3

Dr. N. K. Patel
Lecture:14 Absolute alcohol

Module: 3
Lecture: 14
ABSOLUTE ALCOHOL

INTRODUCTION

In chemistry, azeotropic distillation is a technique which is used to break

an azeotrope in distillation. Azeotropic distillation is the specific technique of
adding another component to generate new, lower-boiling azeotrope that is
heterogenous. 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.

An azeotrope can be either homogeneous or heterogeneous.

Homogeneous azeotrope contains one liquid phase, while heterogeneous
azeotrope contains two liquid phase. Heterogeneous azeotrope easily
separated by distillation while homogenous azeotrope are pressure sensitive
and it can be separated by pressure swing distillation.

Solvent selection for azeotropic distillation is more difficult than for

extractive distillation. There are fewer solvents that will form azeotropes that
boil at a low temperature to be easy to remove in the distillate or boil at high
temperature to be easy to remove in the bottoms.

The binary or ternary azeotrope formed must be separated. In practice

this requirement is met by heterogeneous azeotrope and by azeotrope that
are easy to separate with water wash.

Importance and industrial relevance of azeotropic distillation

 In chemical industry, it is required for efficient recovery and recycle of

organic solvents
 Most liquid mixtures of organic solvents form azeotropes that
complicate the synthesis and conceptual design of recovery processes
 Azeotropes can be also utilized to separate mixtures not ordinarily
separable by normal distillation

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Dr. N. K. Patel
Lecture:14 Absolute alcohol

 Distillation is the most common unit operation in recovery processes

because of its ability to produce high purity products
 Azeotropic mixtures may often be effectively separated by distillation
by adding a third component, called entrainer

Azeotrope is classified in following class

 Binary azeotrope: Azeotrope formed by two components

 Ternary azeotrope: Azeotrope formed by three components
 Homogeneous azeotrope: Azeotrope where the forming components
are miscible
 Heterogeneous azeotrope: Azeotrope where the forming components
are immiscible

Azeotropic mixture can be separated by using following distillation

method
1. Pressure swing distillation
2. Hybrid methods
3. Homogeneous azeotropic distillation
4. Heterogeneous azeotropic distillation
5. Extractive distillation

First two methods not required any entrainer and remaining methods
required entrainer.

1. Pressure swing distillation

In this method pressure is changed to overcome the azeotropic
composition.

2. Hybrid methods
In this method membrane is used as the mass separating agent by
absorbing and diffusing one of the azeotrope forming component.

3. Homogeneous azeotropic distillation

In this method entrainer is added to form tertiary phase. Entrainer is
miscible with the original components.

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Dr. N. K. Patel
Lecture:14 Absolute alcohol

4. Heterogeneous azeotropic distillation

In this method entrainer forms heteroazeotrope with one of the
original azeotrope component. The distillation is carried out in a
combined column-decanter column.

5. Extractive distillation
In this method entrainer is added which, alters the relative volatility
of the original components. The distillation is carried out in a two-
feed column with a heavy entrainer added continuously in the top
stages.

An entrainer was added to separate homogeneous azetropic mixture

by distillation. Entrainer are also used to enable the separation of non-
azeotropic mixtures were the direct separation is either not feasible due to
process constraints or highly uneconomical. An entrainer facilitates the
separation by selectively altering the relative volatilities of the component in
azeotropic mixture.

The choice of an entrainer determines the separation sequence and

hence the overall economics of the process, entrainer selection is a critical
step in the synthesis and conceptual design of azeotrope distillation process.
Entrainers are commonly selected based in on prior experience with the
same or a similar process.

Selection of entrainer

For selection of entrainer following properties are desirable.

 It should boil within limited range of the hydrocarbon to be separated
 Should form azeotrope, on mixing with the hydrocarbon, a large
deviation from Raoult’s law to give a minimum azeotrope with one or
more of the hydrocarbons types in the mixture
 It should be soluble in hydrocarbons
 It should be easily separable from the azeotrope
 It should be inexpensive and easily available
 It should be stable at distillation temperature
 It should be nonreactive with the hydrocarbon being separated and
with the material of construction of the equipment

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Dr. N. K. Patel
Lecture:14 Absolute alcohol

MANUFACTURE

Raw material

Ethyl alcohol (96%)

Water (4%)

Manufacture process

C2H5OH 96.0%, H2O 4.0%

C2H5OH 18.5%, C6H6 74.1%, H2O 7.4%

Water Condenser

Water Condenser
Water

Benzene
make up Water
Column C

Column D
Rich in
C2H5OH benzene
96.0%
H2O 4.0%
Column A Steam Steam
Seperator
Steam

Aqueous
alcohol
Water
100%
C2H5OH
Figure: Manufacture of Absolute alcohol from 96% alcohol

Block diagram of manufacturing process

Diagram with process equipment

Animation

Azeotropic distillation of 95-96% industrial alcohol results into absolute

alcohol. Azeotropic distillation was carried out at 101kPa using benzene as
third component. 95% alcohol was fed into column (A). The ternary
azeotrope was taken overhead in this column and absolute alcohol was
obtained as a bottoms product. The overhead vapours are condensed and

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Dr. N. K. Patel
Lecture:14 Absolute alcohol

passed to separator (decanter) (B), in which two liquid layer form. The upper
layer rich in benzene was returned to column (A) as reflux, and the lower
layer was fed to column (C). In column (C) ternary azeotrope is produced as
the overhead product and benzene - free aqueous alcohol as the bottoms
product. The simple distillation of benzene - free aqueous alcohol produces
an overhead product of 95% alcohol and a bottom product of nearly pure
water. The benzene is recycled continuously in this system and it is necessary
only to make up the benzene losses from the system. This withdrawing agent
is used over and over again with a loss that should not exceed 0.5% of the
volume of the anhydrous alcohol produces.

PROPERTIES

 Boiling Point : 780C

 Melting Point : -1140C
 Flash Point : 120C
 Vapour pressure : 44.6mmHg (200C)
 Auto ignition temperature : 361.60C

USES

 As a solvent in ultraviolet-visible spectroscopy

 As a solvent for laboratory and industrial applications
 As a fuel alcohol
 As a biofuel additive for gasoline
 For the purification and precipitation of biomolecules like proteins and
nucleic acids
 To prepare staining and destaining reagents
 For dehydrating tissues prior to embedding

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