Fundamentals of chemical industries

Unit operations: Distillation

Lecture # 2
 DISTILLATION
• Distillation, a chemical process for separating the
components of a liquid mixture by boiling and collecting
condensed vapors.
• Chemists use distillation to purify compounds in solution or
to separate mixtures of solutes. For example, different
compounds have different boiling points. This property
means that a more volatile compound will evaporate at a
lower temperature than a less volatile compound.
• Distillation must be well known in the chemical industry for
separation of liquid mixtures; it accounts for about 95% of all
liquid separations.
• It is important to note that distillation is not a chemical reaction
but it can be considered as a physical separation process.
PRINCIPLE:
Distillation is based on fact that different substances have different boiling
points(difference in volatility) & vapour of a boiling mixture will be richer in more volatile
components. Therefore when vapour is cooled & condensed the condensate will contain
more volatile components while the original mixture will contain more of less volatile
material. Separation of components from liquid mixture via distillation depends on:
Difference in the boiling point of individual components.

Concentration of components in liquid mixture.

Liquid with high vap. Pressure boils at low temp. hence boiling point of liquid mixture

depends on relative amount of components in mixture.

 Vapor Pressure and Boiling
The vapor pressure of a liquid at a particular temperature is the equilibrium pressure exerted
by molecules leaving and entering the liquid surface. Here are some important points regarding
vapor pressure.
• energy input raises vapor pressure
• vapor pressure is related to boiling
• a liquid is said to ‘boil’ when its vapor pressure equals the surrounding pressure
• the ease with which a liquid boils depends on its volatility
• liquids with high vapor pressures (volatile liquids) will boil at lower temperatures
• the vapor pressure and hence the boiling point of a liquid mixture depends on the relative
amounts of the components in the mixture
• distillation occurs because of the differences in the volatility of the components in the liquid
mixture
 The Boiling Point Diagram
• The boiling point diagram shows how the equilibrium compositions of the
components in a liquid mixture vary with temperature at a fixed pressure. Consider
an example of a liquid mixture containing 2 components (A and B) -a binarymixture. This
has the following boiling point diagram.
• Dew-point: is the temperature at which the saturated vapor starts to
condense. Bubble-point: is the temperature at which the liquid starts to
boil.
• The region above the dew-point curve shows the equilibrium composition of
the superheated vapor while the region below the bubble-point curve
shows the equilibrium composition of the subcooled liquid.
For example, when a subcooled liquid with mole fraction of A=0.4 (point A)
is heated, its concentration remains constant until it reaches the
bubble-point(point B), when it starts to boil. The vapors evolved during the
boiling has the equilibrium composition given by point C, approximately 0.8
mole fraction A. This is approximately 50% richer in A than the original liquid.
This difference between liquid and vapor compositions is the basis for
distillation operations.
 Relative volatility:
Relative volatility is a measure of the differences in volatility between 2
components, and hence their boiling points. It indicates how easy or
difficult a particular separation will be. The relative volatility of component
‘i’ with respect to component ‘j’ is defined as

Thus if the relative volatility between 2 components is very close to one, it is

an indication that they have very similar vapor pressure characteristics. This
means that they have very similar boiling points and therefore, it will
be difficult to separate the two components via distillation.
 Role of Raoult’s Law and Dalton’s Law
• The temperature at which the vapor pressure of a liquid becomes equal to the pressure of the surrounding
area is known as the boiling point of that liquid. At this temperature point, the liquid is converted into its
vapor form via the formation of vapor bubbles at its bulk.
• It is important to note that the boiling point of the liquid changes with the surrounding pressure. For
example, the boiling point of water at sea level is 100oC but its boiling point at an altitude of 1905 meters is
93.4oC (since the atmospheric pressure is relatively lower at high altitudes).
• For a mixture of liquids, the distillation process is dependent on Dalton’s law and Raoult’s law. As
per Raoult’s law, the partial pressure of a single liquid component in an ideal liquid mixture equals the
product of the vapor pressure of the pure component and its mole fraction. According to Dalton’s law of
partial pressures, the total pressure exerted by a mixture of gases is equal to the sum of the partial
pressures of all the constituent gases.
• When a mixture of liquids is heated, the vapor pressure of the individual components increases, which in
turn increases the total vapor pressure. Therefore, the mixture cannot have multiple boiling points at a
given composition and pressure.
 Why is it Impossible to Completely Purify a Mixture by
Distillation?
• At the boiling point of a mixture of liquids, all the volatile constituents boil.
However, the quantity of a constituent in the resulting vapor is based on its
contribution to the total vapor pressure of the mixture. This is why the
compounds with higher partial pressures can be concentrated in the vapors
whereas the compounds having low partial pressures can be concentrated
in the liquid.
• Since a component in the mixture cannot have zero partial pressure, it is
impossible to obtain a completely pure sample of a component from a
mixture via distillation. However, samples of high purity can be obtained
when one of the components in the mixture has a partial pressure which is
close to zero.
 TYPES OF DISTILLATION
According to the differences in boiling points between
the liquids, distillation process classified into four types:
• Simple distillation.
• Fractional distillation.
• Vacuum distillation.
• Steam distillation
• Simple distillation may be used when the boiling points of two liquids are significantly different
from each other or to separate liquids from solids or non- volatile components. In distillation, the
mixture is heated to change the volatile compounds from liquid material to vapors. The vapor
rises and passes into a condenser. Usually, the condenser is cooled to promote condensation of
the vapor, which is collected.
• Fractional distillation is used for the boiling points of the components of a mixture are close to
each other as determined using Raoult's law. A fractionating column is used to discrete the
components used a sequence of distillations called rectification. In fractional distillation mixture
is heated, vapor rises and enters the fractionating column. Then vapor cools and condenses on
the packing material of the column. The heat of rising vapor causes this liquid to vaporize again,
moving it along the column and yielding a higher purity sample of the more volatile component
of the mixture.
• Steam distillation is used for temperature sensitive materials. It is popular for laboratory method
for purification of organic compounds but has become less common due to the proliferation of
vacuum distillation. Steam distillation is important in certain industrial sectors.
• Vacuum distillation is used for separate that components which have high boiling points.
Lowering the pressure of the apparatus also lowers boiling points. Vacuum distillation is used for
normal boiling point exceeds decomposition temperature of a compound.
• Azeotropic Distillation: In the distillation of mixture of liquids, the liquid can be heated to
convert them to gaseous state. Since they have different boiling points, they condense back at
different rate and can easily separate. Some of the mixtures exhibit the same concentration in the
vapor phase and the liquid phase. They are called as azeotropes. Azeotropes cannot be separated
by simple distillation method as in contrast to ideal solutions with one component typically more
volatile than the other, if the mixture forms an azeotrope than vapor and liquid concentrations
will be same that prevents the separation through simple approach.
• Azeotropic mixture cannot be separated by normal distillation method. Therefore addition of a
foreign substance which is called as entrainer decreases the boiling point of azeotropic solution
and separates the components of mixture at different boiling points. • Example of azeotropic
distillation is separation of ethanol with water from its aqueous solution. The boiling point of
water is 100 °C and boiling point of ethanol is 78.3°C. • By addition of benzene to the azeotropic
mixture as entrainer, ethanol can be separated out from the solution.
• Benzene breaks the mixture of water and ethanol and forms a new azeotrope between benzene
and ethanol • The volatility of water (more polar liquid) is enhanced. • On distillation, water distills
at 65.85 ̊C leaving alcohol and benzene behind. • The boiling point of this binary mixture is 68.2 ̊C
and benzene gets distilled leaving pure alcohol behind. It can be distilled off at 78.3 ̊C. • The
benzene can be recycled. • Thus using fractional distillation method, absolute alcohol can be
prepared.
• Extractive Distillation 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.
• Batch distillation refers to the use of distillation in batches. A mixture is distilled to separate it
into its component fractions before the distillation still is again charged with more mixture and
the process is repeated. Batch distillation is versatile and commonly employed for producing
biochemical, biomedical and/or pharmaceutical products, in which the production amounts are
small but a very high purity and an ultra-clean product is needed.
• Continuous distillation,
1. a form of distillation, is an ongoing separation in which a mixture is continuously
(without interruption) fed into the process and separated fractions are removed
continuously as output streams as time passes during the operation.
2. In a continuous distillation, each of the fraction streams is taken simultaneously
throughout operation; therefore, a separate exit point is needed for each fraction. In
practice when there are multiple distillate fractions, each of the distillate exit points are
located at different heights on a fractionating column.
3. The bottoms fraction can be taken from the bottom of the distillation column or unit, but
is often taken from a reboiler connected to the bottom of the column
 Simple Distillation
• The most common process used to separate two liquids whose boiling point differs at least
by about 50 °C.
Example:
Separation diethyl ether (B.P=34°C), from dioxane (B.P=101°C).
Separation chloroform (B.P=60°C), from an oil (B.P=220°C).
• Separation of a liquid substances from the solid substances in a mixture. Example:-Separation
H2O (B.P=100°C), KMnO4 (B.P ≥ 240°C).
• Simple distillation components:-
Any simple distillation system composed from the following main parts:-
1-Heating source.
2-Distillation flask.
3- Thermometer.
4- Condenser.
5- Receiving flask
• Separation of mixture by simple distillation:-
1- A mixture composed from A&B with boiling point (70 & 140) °C respectively is heated.
2- The lowest boiling point (A) will vaporized and ascended (elevated) from the solution till
it reach the top of the system, with recording its real b.p. with the help of thermometer.
3- The ascended vapor will converts to the liquid form by the action of the condenser, then
collect at the receiver.
4- Finally the highest boiling point will remain at the distillation flask.
 Fractional Distillation:
• Second technique of the distillation process, used to separate two liquids having close (near)
boiling points (Lower than 25 °C).
Example:
Separation of ethanol (78) °C from water (100) °C.
• Fractional distillation components:-
Fractional distillation system composed from the following main parts:-
1- Heating source.
2- Distillation flask.
3- Fractional column.
4- Thermometer.
5- Condenser.
6- Receiving flask .
 How It Works
• Vapors from a boiling solution are passed along a tall column,
called a fractionating column. The column is packed with plastic or
glass beads to improve the separation by providing more surface
area for condensation and evaporation. The temperature of the
column gradually decreases along its length. Components with a
higher boiling point condense on the column and return to the
solution; components with a lower boiling point (more volatile)
pass through the column and are collected near the top.
• Theoretically, having more beads or plates improves the
separation, but adding plates also increases the time and energy
required to complete a distillation.
 Vacuum Distillation
 Vacuum distillation is a method of distillation whereby the pressure
above the liquid mixture to be distilled is reduced to less than its vapor
pressure (usually less than atmospheric pressure) causing evaporation of
the most volatile liquid(s) (those with the lowest boiling points). This
distillation method works on the principle that boiling occurs when the
vapor pressure of a liquid exceeds the ambient pressure. Vacuum
distillation is used with or without heating the solution.
 Temperature sensitive materials (such as beta carotene) require vacuum
distillation to remove solvents from the mixture without damaging the
product. Vacuum distillation is sometimes referred to as low temperature
distillation. This type of distillation is in use in the oil industry.
 Steam Distillation:
• It is used for temperature sensitive materials.
• It is popular for laboratory method for purification of organic compounds but has become less
common due to proliferation of vacuum distillation.
• It is important in certain industrial sectors.
 Industrial distillation
• Industrial distillation is typically performed in large, vertical
cylindrical columns known as distillation towers or distillation
columns with diameters ranging from about 65 centimeters to
16 meters and heights ranging from about 6 meters to 90
meters or more. When the process feed has a diverse
composition, as in distilling crude oil, liquid outlets at intervals
up the column allow for the withdrawal of different fractions or
products having different boiling points or boiling ranges. The
"lightest" products (those with the lowest boiling point) exit
from the top of the columns and the "heaviest" products (those
with the highest boiling point) exit from the bottom of the
column and are often called the bottoms.
Some important applications of distillation are listed below.
• Distillation plays an important role in many water purification techniques. Many
desalination plants incorporate this method in order to obtain drinking water from
seawater..
• Many fermented products such as alcoholic beverages are purified with the help of this
method.
• Many perfumes and food flavorings are obtained from herbs and plants via distillation.
• Oil stabilization is an important type of distillation that reduces the vapor pressure of the
crude oil, enabling safe storage and transportation.
• Air can be separated into nitrogen, oxygen, and argon by employing the process of
cryogenic distillation.
• Distillation is also employed on an industrial scale to purify the liquid products obtained
from chemical synthesis.