DISTILLATION

Distillation is the method of separation of more

volatile component from the less volatile one of a
mixture by partial vaporization
Distillation
Distillation is a common separation method for
liquid mixtures
Some
Some of its areas of application include in
1. Organic process industries e.g separation of
aniline and nitrobenzene, ethanol-water
ethanol
separation
2. Petroleum refinery

Distillation Operation
Feed enters at some point on the tower
Reboiler heats up the liquid from
bottom of the tower and liquid
partially vaporizes
Vapour flows up through the trays
or packings
Vapor leaves at the top and enters
into a overhead condenser and
then to the reflux drum
Figure 1
Part of the condensate is withdrawn as top
product and rest is recycled into the column as reflux

An
An intimate contact between the
liquid and vapour occurs on each
tray or packing surface
More
More volatile component moves
from liquid to vapour phase
Less volatile component moves
from vapour to liquid
Concentration of less volatiles
increases in the liquid phase as it
flows down
Figure 1

High degree of separation of more volatiles from the less

volatiles is achieved
Top
Top product is rich in more volatile and bottom product is rich in
less volatile

Binary Distillation
Distillation is an equilibrium staged process
The feed mixture in binary distillation has two
components.
At equilibrium, the components in the mixture will
distribute themselves between the vapour phase and
liquid phase
Resulting in the feed being separated into two
products, an overhead distillate and a bottom product,
with compositions different from that of the feed.

Vapour-Liquid
Liquid Equilibrium

Vapour-liquid
liquid and physicochemical properties of the
system is required to solve the equilibrium stage process
problem
The equilibrium data can be obtained from:
1. experiments
2. thermodynamics

The data is usually shown with reference to the more

volatile component

For binary mixtures, VLE data is typically represented

by equilibrium diagram such as:
T-x-y diagram
P-x-y diagram
x-y diagram
H-x-y diagram

1.
2.
3.
4.

Features of Phase Diagram

bubble-point
point curve or saturated liquid line
dew-point
point curve or saturated vapour line
Subcooled liquid region
Superheated vapour region
vapour-liquid region
bubble-point and dew-point
point temperatures
The dew-point: is the temperature at which the
saturated vapour starts to condense.
The bubble-point: is the temperature at which the
liquid starts to boil.

Constant Pressure Phase Diagram

The T-x-yy diagram is also known as:

Constant-pressure
pressure phase diagrams
Boiling point-concentration diagram
commonly used for distillation calculations

Figure 2

Constant Pressure Phase Diagram

The distribution of components

in the liquid and vapour phases is
a function of temperature

Liquids of different composition

at the same pressure will boil at
different temperatures- bubble-point
point curve
Vapours of different composition
at the same pressure will condense
at different temperatures- dew-point
curve

boiling of a liquid mixture takes

place over a range of boiling points.
points
Condensation of a vapour mixture
takes place over a range of
condensation points

Figure 3

Changes in Distribution of Components in the

(a): At

Phases with Temperature.

temperature 86 oC;

Concentration of benzene Liquid: x = 0.40,

Vapour: y = 0.00,
Liquid-phase; no vapour.

(b): Temperature 95.2 oC;

Concentration of benzene Liquid: x = 0.40,
Vapour: y = 0.61,
Liquid-phase; first bubble of vapour produced,

(Bubble Point - solution about to boil).

(c): Temperature 98.0 oC
Concentration of benzene Liquid: x = 0.31;

Vapour: y = 0.52
Vapour-Liquid Mixture;
(continued vaporization of liquid as heat is added).

Figure 3

Changes in Distribution of Components in the

Phases with Temperature.

(d): Temperature 101.6 oC

Concentration of benzene Liquid: x = 0.21
Vapour: y = 0.40
Vapour-phase; last droplet of liquid
remains (dew point)
(e): Temperature 108 oC
Vapour-phase only, no liquid.
The process is unsteady-state
state in nature.

NOTE:
As heating continues,
vaporization occurs over a range of boiling points.
points
Figure 3
At any time when 2 phases - vapour and liquid - are present, the
concentration of benzene (more volatile component) in the vapour (y) is
always higher than that in the liquid (x).
(x) The reverse is true for toluene (less
volatile component).

x-yy Diagram
can be obtained from constant
pressure phase diagram
The plot expresses the bubblebubble
point and the dew-point
point of a
binary mixture at constant
pressure.
contains less information than
the constant pressure phase
diagram (i.e. temperature is not
included),
but it is most commonly used.

Figure 4

x-yy Diagram
It is useful for graphical design in
determining the number of
theoretical stages required for a
distillation column
The curved line is called the
equilibrium curve and describes
the compositions of the liquid and
vapour in equilibrium at fixed
pressure.
below the equilibrium line is the
45 degree line or diagonal line
where y=x
Figure 4

Equilibrium Curve from Phase Diagram

Figure 5

By drawing horizontal lines (constant T) like DF and HJ on the phase

diagram
Obtain the corresponding mole fractions x and y at the intersections with the
horizontal lines.
With a set of x-y
y values, a graph of y vs. x can be plotted i.e. the
equilibrium curve

Constant temperature (isothermal)

phase diagram
The constant
temperature phase
diagram is as shown.
It is useful in the analysis
of solution behaviour.
The more volatile liquid
will have a higher vapour
pressure (i.e. pA at xA =
1.0)
Figure 6

 The following can be used to obtain a suitable

relationship distillation process parameters:
1. Raoults law
2. Relative volatilities
3. Equilibrium coefficients

Raoults Law
For ideal gases or vapors, the partial pressure is proportional to the
mole fraction of the constituents.
PA= yAPT
[1]
For ideal mixtures, the partial pressure is related to the
concentration in the liquid phase by Raoults law
PA = PA xA
[2]
Where PA is vapor pressure of pure species A at same
temperature.
combining [1] and [2];
similarly,
[3]
But for a binary mixture,

and

[4]

Combining [3] and [4];

From [5a] & [1] respectively;
equilibrium relation
And

[5a]
are
[5b]

Table 1: Vapour Pressure Data for Benzene Toluene

Toluene System at 101.32 kPa

Using the vapour pressure from table 1, calculate the vapour and liquid compositions in
equilibrium at 95oC (368.2K) and 101.32 kPa

Table 2: Vapour Pressure and Equilibrium Data for Benzene Toluene System at 101.32 kPa

Relative Volatility
Relative
Relative volatility is a measure of separability of A and B.
It
It is defined as ratio of the concentration of more volatile
component (A) in vapour phase to its concentration in liquid
phase, divided by the ratio of the less volatile component (B),
in vapour phase to its concentration in the liquid phase.
[7a]

[8]

For systems that obey Raoults law, [7a] can be

written as:
[7b]
Relative
Relative volatility is not a strong function of
temperature
Relative
Relative volatility can be assumed constant over a
temperature range and composition
The higher the value of relative volatility, the higher the
separation
If

then, separation is not possible

This is because when

components A and B have the same volatility and will

vapourise together when heated

y=x

i.e. vapour and liquid will have the same composition.

y = x is represented by the straight line through the origin of the

VLE diagram
If relative volatility is constant it can be used to obtain the
equilibrium curve data
Substituting values of x between 0 and 1will yield the equilibrium
curve predictions

Example
Using data from table 1 calculate the relative volatility for the
benzene-toluene system at 85oC (358.2K) and 105oC (378.2K)

VLE of Real Solutions

Most
Most solutions, at least to some extent, deviate from
ideality
This
This mean they may not exactly obey Raoult law
The deviation from Raoult's law may either be positive
or negative deviation
A
A liquid mixture exerting an equilibrium total vapour
pressure more than that calculated by [5b]
[5b is said to
exhibit positive deviation from ideality.
If the total vapour pressure is less than that calculated by
[5b], the deviation is called negative
n
deviation.

If the deviation from ideality are large, the mixture may have
either a maximum or a minimum vapour pressure when boiling
at constant temperature
or correspondingly, have a minimum or a maximum
temperature when boiling at constant pressure.
At this point, the composition of vapour phase equals that of
liquid phase and is called minimum boiling or maximum boiling
azeotrope.
The azeotropic point is a function of total pressure and can for
some mixtures be shifted, or even disappear, by changing the
total pressure.
Azeotropic mixtures cannot be separated by standard
distillation, but there are methods that may still be used to
separate such mixtures

Deviations from ideal behaviour in the liquid phase are taken

into account by modifying Raoult's law by introducing a liquid
phase activity coefficient i
[9]

[10]
[11]

The activity coefficient i is a function of temperature T and

composition of component i in the liquid phase.

The value of activity coefficient i approaches unity as the

liquid concentration xi approaches unity, and the highest value
of occurs as the concentration approaches zero

Many equations have been suggested for the calculation of

the activity coefficient, and the simplest versions are the
van Laar, Margules, or Wilson equations.
equations
The van Laar equations for a binary mixture of component
A (more volatile) and component B (less volatile) are given
by the following equations,
where the constants
and are different and can be
found estimated from experimental values in reference
literature
(12)
(13)

Batch Distillation
There are many types of distillation columns
Each type of distillation column is designed to perform
specific types of separations.
One way of classifying distillation column type is based on
their mode of operation.
Based on operation, the two types of distillation columns
are batch (or differential) and continuous columns.
In
In batch operation, the feed is introduced batch-wise
batch
to the
column and then the distillation process is carried out; and
when the desired task is achieved, a next batch of feed is
introduced

Consider a distillation process

involving binary mixture of
components A (more volatile) and
B (less volatile) as shown.
The
The system consists of a batch of
liquid (fixed quantity) inside a
kettle (or still) fitted with heating
element and a condenser to
condense the vapour produced
The condensed vapour is known
as the distillate.
The distillate is collected in a
condensate receiver.
Figure 7

The
The liquid remaining in the still is
known as the residual.
The process is unsteady state.
The concentration changes can
be analyzed using the phase
diagram.
Detailed mathematical
calculations can be carried out
using the Rayleigh Equation.

As a result of the unsteady

nature of the process, the
derivation is based on differential
approach to changes in
concentration with time.

Figure 7

Derivation of Rayleigh Equation

Let L1 = initial moles of liquid originally in still;
L2 = final moles of liquid remained in still;
x1 = initial liquid composition in still (mole fraction of A);
x2 = final liquid composition in still (mole fraction A);
At any time t, let:
L= the amount of liquid in the still;
x= mole fraction of A in the liquid.

After a small differential time (t + dt), a small amount of vapour

dL is produced, and the vapour is assumed to be in equilibrium
with the residue liquid.
Let y = the vapour composition of A (mole fraction).
The amount of liquid in the still is thus reduced from L to (L - dL),
while the liquid composition changed from x to (x - dx).
Then the material balance on A can be written as:
Initial amount in still = Amount left in still + Amount vaporized
xL = (x-dx)(L-dL) + ydL
xL = xL xdL Ldx + dxdL + ydL

[14]
[15]

Neglecting the term dxdL,, the Equation (2) may be written as:
Ldx = ydL - xdL
[16]
Re-arranging
arranging and Integrating from L1 to L2, and from x1 to x2,
one can obtain the following Equation which is called Rayleigh
Equation:
[17]
This is to avoid a negative as there is less material at the end
than at the start
The integration of Equation (17) can be obtained graphically
from the equilibrium curve, by plotting 1/(y-x)
1/(y versus x.

Example
A mixture of 40 mole % isopropanol in water is to be batchdistilled at 1 atm until when the mole fraction of isopropanol in
the still reaches 6.7 mole % . Calculate the amount of distillate
collected and its average composition.
composition VLE data for this system,
in mole fraction of isopropanol,
isopropanol at 1 atm are (Seader and
Henley, 1998):

Calculate 1/(y-x)
Rayleigh Equation is given by:

Given;
Feed L1 = 100
x1= 0.4 , x2= 0.067
then;

Find L2 by equating
Trapezoid formula:
The amount of distillate is obtained by D= L1 - L2
Average composition of distillate by

Continuous distillation columns

Unlike batch distillation columns, continuous columns process
a continuous feed stream.
Continuous columns are capable of handling high
throughputs; as such, they are more commonly used
compared to batch columns.
Continuous columns can be further classified according to the
nature of the feed that they are processing, hence we have:
Binary distillation
components

column:

feed

contains

only

two

Multi-component distillation column: feed contains more

than two components

Multi-product
product distillation column: column has more than
two product streams
Extractive distillation: where the extra feed appears in the
bottom product stream
Azeotropic distillation: where the extra feed appears at the
top product stream