Chapter 05

Distillatio
n

Dr. Amir
Muhammad
 Distillation

• Yellow bp = 100oC
• Blue bp = 80oC
• How do we get to Blue liquid out of the Green mixture?

2
 History
 The earliest known evidence of distillation comes
from a terracotta distillation apparatus dating to
3000 BC in the Indus valley of Pakistan.
 Distillation was known to be used by the
Babylonians of Mesopotamia. Initially, distillation
is believed to have been used to make perfumes.
 Distillation of beverages occurred much later.
The Arab chemist Al-Kindi distilled alcohol in 9th
century.
 Distillation of alcoholic beverages appears
common in Italy and China starting in the 12 th
century.
 European came to know of the techniques of
distillation by the 6th century AD after invasion by
Arabs December 3, 2024 3
 Introduction
 Distillation is the technique of preferential separation of the more
volatile component(s) from the less volatile ones in a feed solution by
partial vaporization of the feed followed by condensation.
 Distillation is a direct separation method as it employs no external
agents
 The vapor produced is richer in the more volatile component(s). The
distribution of the components in the two phases is governed by the
vapor–liquid equilibrium relationship.
 Only partial separation of the components can be achieved in this way.
 In order to have a larger degree of separation, multistage contact
between the vapor and the liquid phases is arranged in a suitable
device called a ‘distillation column

December 3, 2024 4
 Introduction

Distillation is the most widely used separation process in the

chemical industry.
It is normally used to separate liquid mixtures into two or more
vapor or liquid products with different compositions.
Distillation is an equilibrium stage operation. In each stage, a
vapor phase is contacted with a liquid phase and mass is
transferred from vapor to liquid and from liquid to vapor.
The less volatile, "heavy" or "high boiling", components
concentrate in the liquid phase; the more volatile, "light",
components concentrate in the vapor.
By using multiple stages in series with recycle, separation can
be accomplished.

December 3, 2024 5
Distillation

6
Distillation
Where is distillation used?

• Distillation is used to separate crude oil into

specific fractions, such as petrol or kerosene

• Water is distilled to remove impurities (e.g. salt

from seawater)

• Air is distilled to separate it into O2 and N2

• Distillation of fermented solutions has been used

since ancient times to produce beverages with a
high alcohol content 7
Distillation
Simple Laboratory distillation apparatus

8
Distillation
Industrial Distillation

9
Distillation

Large scale industrial distillation applications are

required for:

• petroleum refineries

• petrochemical and chemical plants

• natural gas processing plants

10
Distillation
The vertical cylindrical column provides, in a compact form and
with the minimum of ground requirements, a large number of
separate stages of vaporization and condensation.

December 3, 2024 11
Distillation

December 3, 2024 12
Advantages and Disadvantages of Distillation

• Advantages
1.It is an efficient method to obtain a pure substrate from a mixture of liquid.
2.This process is time efficient.
3.It is a reversible method, no permanent changes are made in the liquid
solution unless the reaction is stopped.
• Disadvantages
1.It does consume a huge amount of energy.
2.In some types of distillation it gives a slow output.
3.Higher operating costs
4.Unable to separate mixtures of close boiling points e.g Butadiene (268.4)
from butylene (268.2)
5.Not recommended for separation of heat sensitive materials
 5.2 VAPOUR–LIQUID EQUILIBRIA

Partial vaporisation and partial condensation

 Design or simulation of distillation collum

required as quantitative estimate of VLE
 Material balance to determine the amount of liquid
and vapor in mixture
minimum-boiling azeotrope maximum-boiling azeotrope
 Equilibrium Diagram
For distillation purposes it is more convenient to plot y against
x at a constant pressure, since the majority of industrial
distillations take place at substantially constant pressure.
Positive Azeotrope Negative Azeotrope

December 3, 2024 17
 Dalton’s Law
The partial pressure PA of component A in a mixture of vapors is
the pressure that would be exerted by component A at the
same temperature, if present in the same volumetric
concentration as in the mixture.
By Dalton’s law of partial pressures,
P = ΣPA
that is the total pressure is equal to the summation of the partial
pressures. Since in an ideal gas or vapor the partial pressure is
proportional to the mole fraction of the constituent, then:
PA = yAP

December 3, 2024 18
 Raoult’s Law
Raoult's Law describes the behavior of vapors above a mixture of
liquids; in an ideal scenario the partial pressure of each component
present in the mixture is equal to its pure vapor pressure multiplied by
its mole fraction in solution.
For an ideal mixture, the partial pressure is related to the concentration
in the liquid phase by Raoult’s law which may be written as:
PA = P◦AxA
where P◦A is the vapor pressure of pure A at the same temperature.
This relation is usually found to be true only for high values of xA, or
correspondingly low values of xB, although mixtures of organic isomers
and some hydrocarbons follow the law closely.
For low values of xA, a linear relation between PA and xA again exists,
although the proportionality factor is Henry’s constant H, and not the
vapor pressure P0A of the pure material.
December 3, 2024 19
 For a liquid solute A in a solvent liquid B, Henry’s law takes
the form: PA = HxA
If the mixture follows Raoult’s law, then the vapour pressure of
a mixture may be obtained graphically from a knowledge of
the vapour pressure of the two components.
OA represents the partial pressure
PA of A in a mixture, and PB the
partial pressure of B, with the total
pressure being shown by the line
BA. In a mixture of composition D,
the partial pressure PA is given by
DE, PB by DF, and the total pressure
P by DG Figure : Partial pressures of ideal mixtures
December 3, 2024 20
 Applications of Raoult’s & Dalton’s Law

Over the range OC the mixture

follows Henry’s law, and over BA
it follows Raoult’s law

Although most mixtures show

wide divergences from ideality,
one of the laws is usually
followed at very high and very
low concentrations.
Figure : Partial pressures of non-ideal mixtures

December 3, 2024 21
 Applications of Raoult’s & Dalton’s Law

If the mixture follows Raoult’s law, then the values of yA for

various values of xA may be calculated from a knowledge of the
vapor pressures of the two components at various temperatures

Mole fraction of A in liquid

Mole fraction of A in Vapor

December 3, 2024 22
 Example 11.1

The vapour pressures of n-heptane and toluene at 373 K are

106 and 73.7 kN/m2 respectively. What are the mole fractions
of n-heptane in the vapour and in the liquid phase at 373 K if
the total pressure is 101.3 kN/m2?

December 3, 2024 23
 Volatility
Volatility is a measure of how easily a substance evaporates,
or how readily it changes from a liquid to a gas. A highly
volatile substance, like gasoline, evaporates quickly, while a
less volatile substance, like oil, evaporates more slowly.
It is defined as the ratio of partial pressure to the mole
fraction in the liquid:

The ratio of these two volatilities is known as the relative

volatility α given by: Volatility of A/Volatility of B

It tells us how much easier one component evaporates

compared to the other
December 3, 2024 24
 Relative volatility
Substituting PyA for PA, and PyB for PB:

or

This gives a relation between the ratio of A and B in the vapor to

that in the liquid and is useful in the calculation of plate
enrichment

December 3, 2024 25
 Relative volatility
Since with a binary mixture yB = 1 − yA, and xB = 1 − xA then:

Use for constructing

Equilibrium curve

This relation enables the composition of the vapor to be

calculated for any desired value of x, if α is known. For
separation to be achieved, α must not equal 1 and, considering
the more volatile component, as α increases above unity, y
increases and the separation becomes much easier
December 3, 2024 26
 Relative volatility

From the definition of the volatility of a component, it is seen

that for an ideal system the volatility is numerically equal to the
vapor pressure of the pure component. Thus
the relative volatility α may be expressed as:

This also follows by applying equation 11.1 from which

PA/PB = yA/yB, so that:

December 3, 2024 27
 Relative volatility
Whilst α does vary somewhat with temperature, it remains
remarkably steady for many systems, and a few values to
illustrate this point are given in Table

It may be seen that α increases as the temperature falls, so that

it is sometimes worthwhile reducing the boiling point by
operating at reduced pressure.
FRANK points out, this is valid if the relative volatilities at the top
and bottom of the column differ by less than 15 per cent.
If they differ by more than this amount, the equilibrium curve
must be constructed incrementally by calculating the relative
volatility at several points along the column
December 3, 2024 28
 Relative volatility

The figure shows several

equilibrium curves with
Increasing the pressure or different values of the
temperature, decreases the relative volatility. Note that
relative volatility. Q4 is high the greater the value of α,
temperature/pressure while the greater is the
it decreases towards Q1 separation area
December 3, 2024 29
Azeotropes

Minimum boiling azeotrope

Maximum boiling azeotrope
 METHODS OF DISTILLATION
TWO COMPONENT MIXTURES

Three main methods are used in distillation practice:

 Simple or Differential distillation.

 Flash or equilibrium distillation

 Rectification.

Of these, rectification is much the most important, and it differs

from the other two methods in that part of the vapor is
condensed and returned as liquid to the still, whereas, in the
other methods, all the vapor is either removed as such, or is
condensed as product
December 3, 2024 37
 Differential Distillation

Batch distillation without reflux is often called differential

distillation. Because there is no reflux, the vapor product is in
equilibrium with the liquid residue in the tank at any given time.

In this process the vapor

formed on boiling the
liquid is removed at
once from the system.
As this process consists
of only a single stage, a
complete separation is So ,XO
impossible unless the
relative volatility is
infinite.
December 3, 2024 38
 Differential Distillation

Since the vapor produced is richer in the more volatile component

than the liquid, it follows that the liquid remaining becomes steadily
weaker in this component, with the result that the composition of the
product progressively alters.

Thus, whilst the vapor formed over a short period is in equilibrium

with the liquid, the total vapor formed is not in equilibrium with the
residual liquid.

At the end of the process the liquid which has not been vaporized is
removed as the bottom product. The analysis of this process was first
proposed by RAYLEIGH

December 3, 2024 39
 Modelling Differential Distillation

If S is the number of moles of material in the still,

x is the mole fraction of component A
dS, is the amount which is vaporized, containing a mole fraction y of A

The rate of depletion of liquid is equal to the rate of distillate output:

Initial Amount in Still = Amount Vaporized + Amount left in Still

S = dS + (S - dS)

xS = ydS + (x - dx)(S - dS)

xS = ydS + xS – xdS – Sdx + dxdS

Neglecting the term dxdS: xS = ydS + xS – xdS – Sdx + dxdS

Sdx = ydS – xdS
December 3, 2024 40
 Modelling Differential Distillation

Sdx  ydS  xdS Numerical integration

dS ( y  x) Sdx

dS  dx 
 
S  y x

1/(y – x)
• •

Rayleigh equation x,final x xinitial

The integral on the right-hand side of this equation may be solved

graphically if the equilibrium relationship between y and x is available.

December 3, 2024 41
 Differential Distillation

In some cases a direct integration is possible Thus, if over the

range concerned the equilibrium relationship is a straight line of
the form y = mx + c, then:

= =

Multiplying and Divided by (m-1) =

December 3, 2024 42
 Differential Distillation

= -[

December 3, 2024 43
 Differential Distillation

= =

= =

From this equation the amount of liquid to be distilled in order to

obtain a liquid of given concentration in the still may be calculated,
and from this the average composition of the distillate may be
found by a mass balance.
December 3, 2024 44
 Differential Distillation
Alternatively, if the relative volatility is assumed constant over
the range concerned, then y = αx/(1 + (α − 1)x), may be
substituted in equation:

This leads to the solution:

As this process consists of only a single stage, a complete separation

is impossible unless the relative volatility is infinite.
Application is restricted to conditions where a preliminary separation
is to be followed by a more rigorous distillation, where high purities
are not required, or where the mixture is very easily separated
December 3, 2024 45
 Flash or Equilibrium Distillation

Flash or equilibrium distillation,

frequently carried out as a
continuous process, consists of
vaporizing a definite fraction of the
liquid feed in such a way that the
vapor evolved is in equilibrium
with the residual liquid
The feed is usually pumped through a fired heater and enters the still
through a valve where the pressure is reduced.
The still is essentially a separator in which the liquid and vapor
produced by the reduction in pressure have sufficient time to reach
equilibrium.
The vapor is removed from the top of the separator and is then
usually condensed, while the liquid leaves from the bottom.
December 3, 2024 50
 Modelling Flash or equilibrium distillation

In a typical pipe still where, for

example, a crude oil might enter at
440 K and at about 900 kN/m2, and
leave at 520 K and 400 kN/m2, some
15 per cent may be vaporized in the
process.
The vapor and liquid streams may contain many components in such
an application, although the process may be analyzed simply for a
binary mixture of A and B as follows:
If F = moles per unit time of feed of mole fraction xf of A,
D= moles per unit time of vapor formed with y the mole fraction of A
W = moles per unit time of liquid with x the mole fraction of A,
then an overall mass balance gives:
F=D+W
December 3, 2024 51
 Modelling Flash or equilibrium distillation

and for the more volatile component:

This is an "operating line" equation -- plotted on a graph whose

coordinates are vapor composition vs. liquid composition, it
yields a straight line. To plot the line, we only need to know the
fraction vaporized (to get the slope) and the feed composition
(to get the intercept).

December 3, 2024 52
Flash Distillation of Multicomponent Mixtures
Given a mixture of known overall composition zi at temperature T and pressure P, what is the fraction that is
vapour and what are the composition of the liquid and vapour phases in equilibrium?

The overall material balance for the system is

where F is the total number of moles of the initial mixture and D and W are the moles of vapour and
liquid products in equilibrium.

The relationship between the composition of the liquid and vapour phases in equilibrium is
described by means of the vaporisation equilibrium constant
Equation 5.54 or 5.56 can be utilized in an iterative procedure to estimate T, P or the fraction
of the initial mixture that is vaporised.
 5.7 Fractionation of Binary Mixtures
(Fractionating distillation/rectification/multistage
distillation)
• Single stage operation such as flash distillation is not very effective for separating
components of comparable volatilities; it is useful for separating components with widely
different boiling points.

• Fractionation, also known as rectification, is a distillation technique by which substantially

pure product can be separated even from mixtures with relative volatility very close to
unity.

• In fractionation, the vapours evolved by boiling the liquid are condensed and part of the
condensate called 'reflux’ is brought into intimate countercurrent contact with the rising
vapours

• The vapour gets enriched in more volatile component as it moves up in contact with the
liquid reflux that is flowing down and consequently a distillate product is obtained at the
top of the column which is very rich in more volatile component than the vapour obtained
from the flash distillation

• The liquid stream flowing down the column is stripped off the more volatile component
contacting it with a vapour that is generated by the partial vaporisation of the liquid.
 Concept/Principle Of Fractionation

Consider a mixture of benzene and toluene containing 30 mol%

benzene. Flash distillation of this mixture is represented on the
boiling-point diagram in Fig. 5.24.

• If the liquid is flashed at the bubble point of the feed

(represented by point A in the figure), distillate will have a
composition of 50 mol% benzene, which is the maximum
concentration that the vapour can attain by flash vaporisation at
101.3 kPa.

• Though the richest vapour is produced at this condition, the

quantity vaporised is infinitesimally small.

• The concentration of the distillate depends on the extent of

vaporisation. If the extent of vaporisation is say, 50%, the
concentration of the benzene in the distillate would be about 38
mol% as shown by point B in Fig. 5.24.
 Let us now consider flash vaporisation of the mixture at 372.6
K so that about 10% of the feed is vaporised.

Assume that the operation is carried out on a device

designated as the 'stage' represented by min Fig. 5.25.

• The distillate vapour has a composition 47 % mole percent

benzene and residue 28 % benzene.
• From 100 moles of a reed mixture containing 30 mol% benzene, we
could produce about 10 moles of distillate containing 47% benzene
by a single stage flashing operation.

• It is possible to obtain a vapor rich than G by partially condensing

the vapor rising form stage m on stage m-1 and so on

• Last stage m-3 produce about 0.93 moles of vapor with 80 % purity

• So by successive condensation on a series of separate devices we

get a distillate product which is richer than the product that Would
be obtained by a single-stage flashing
This process cannot be carried out commercialy because of following reasons

• Only very small quantities of the final products are obtained by this process
• Intermediate products - both liquid and vapour - available at different stages are not
subject to enrichment and are not utilized.
• Condensation of the vapour requires cooling by external means and vaporisation
requires heaters. This means that all the stages are to be maintained at their
operating temperatures byexternal means.
Let’s do it another way
By this scheme, distillate product which is almost pure A and bottom product which is almost B can be produced in
sufficiently large quantities from a given binary mixture of any composition. devices are required to maintain the
plates at the desired temperatures; in continuous operation, plates will attain steady state temperature
automatically and will remain at these temperatures, the operating conditions are altered.
 Fractionation in plate columns
• Fractional distillation can be carried out as multi stage countercurrent operation in
plate columns
• Plates used for distillation may be the sieve, bubble-cap plates, valve plates
• The feed is admitted on the feed plate which is located generally in the middle of the
column.
• The column is connected at the top to' condenser in which the overhead vapours are
condensed.
• A portion of the condensate is recycled at top of the column which is called the reflux.
The ratio of the moles of liquid returned as reflux to that moles of distillate product
withdrawn is designated as reflux ratio.
• The liquid leaving the bottommost plate is admitted to a reboiler. The vapour produced
in the reboiler is returned to the column as vapour boil up and the liquid leaving the
reboiler is the bottom product. The ratio of the moles of vapour sent back to the
column to the mole of bottom product is designated as the boil-up ratio.
Fractionation/rectification in plate
columns
The fractionating process

https://www.youtube.com/watch?v=BaBMXgVBQKk&t=157s

https://www.youtube.com/watch?v=OQv-Tr-k5Ic
December 3, 2024 72
Enrichment and stripping on an ideal plate of column
 Condenser of column
• The vapour leaving the top plate is taken to a
condenser which is usually a conventional tubular
heat exchanger.

• The condensers are generally arranged horizontally

near the ground because of the convenience in
construction and cleaning.

• In smaller columns, the condenser can be placed

near the top of the column, in which case, the reflux
flows to the top plate by gravity.

Condenser can be
(a) Total condenser
(b) Partial condensers

When it is desired to withdraw the distillate as vapor or

complete condensation is expensive then partial
condensers are preferred
Reboilers of plat columns

Internal reboilers
• They are integrated part of the column.
• They limited vapor capacity
• Cleaning requires shutdown of the unit

External reboilers
• Not integrated part of column.
• Can be arrange with spares which facilitate cleaning
(a) Kettle type reboiler
• Common in use
• Vapor and liquid are in equilibrium. Reboiler act as
theoretical plate
• Heating medium flow through the tube and liquid in
the tubes
(a) Vertical Thermosyphon reboiler with liquid withdrawn
from bottom sump
https://www.youtube.com/watch?v=E6fO3o-BGZw
(b) Vertical Thermosyphon reboiler with liquid withdrawn
from downcomer of last plate https://www.youtube.com/watch?v=YcptyuuGAwc