2.

DISTILLATION

By: Taressa M.
Nov., 2022
 Introduction

Distillation: is a process/method in which a liquid or vapor

mixture of two or more substances is separated into its
component fractions of desired purity, by the application
and removal of heat.

What is the primary criteria to apply distillation process?

 Distillation is done on the basis of differences in their
volatilities in a boiling liquid mixture.
 What kind of separation process is it? Physical/chemical
 Distillation is a physical separation process, and not a
chemical reaction.(for our case)
 Principle: Separation depends on the differences in boiling
points of the individual components.
 On the vapor pressure characteristics of liquid mixtures.

Why a liquid boils? For any liquid, the individual

molecules within the liquid
Atmospheric pressure, P atm are continuously in motion
A small percentage of these
molecules attain enough
kinetic energy to leave the
liquid phase
This exerts an opposing pressure
Vapor on the atmosphere above the
Pressure, P solution known as the vapor
pressure, P
 It may also expressed as a method used to separate the
components of liquid solution, which depends upon the
distribution of these various components between a vapor
and a liquid phase.
 The vapor phase is created from the liquid phase by
vaporization at the boiling point.
 Distillation is concerned with solution where all
components are appreciably volatile such as:
 In ammonia-water or
 Ethanol-water solutions, where both components will be in
the vapor phase.

4
 Distillation in general provides the cheapest and best
method for separating a liquid mixture to its components,
except when:-
1. The difference of volatility b/n the components is small
2. A small quantity of high-boiling point components is to
be recovered from the feed. Distillation requires that the
whole feed be vaporized in order to recover this small
quantity.
3. A compound is thermally unstable even under vacuum
conditions.

4. The mixture is extremely corrosive or highly fouling.

Q.1 How do you explain the difference b/n Distillation and
Evaporation? 5
 2.1 Vapor and liquid equilibrium relationship
What is an Equilibrium?

 Distillation columns are designed based on boiling point properties

of the components in the mixture being separated.
 Thus, the sizes, particularly the height of distillation columns are
determined by the vapor-liquid equilibrium(VLE) data for mixtures.
 The composition of the vapor in equilibrium with a liquid of given
composition is determined experimentally using an equilibrium
still/separator.
 The vapor-liquid equilibrium for each pure substance of the mixture
is off course its vapor-pressure, temperature and mole fraction
relationships and this is represented graphically. 6
• Lets consider a binary mixtures A-B and component A is more volatile
one, i.e. the vapor pressure of pure A at any temperature is higher than
the vapor pressure of pure B.

A B
n1
A+B
nF
B n2
A

• For distillation purpose, the results more conveniently shown on

temperature-composition diagram plotted at constant pressure;
• And this is because the majority of industrial distillation take place at
substantially constant pressure.
 Constant pressure vapor-liquid Equilibrium

Figure 1 Temp.(T) vs( x, y) and Vapor vs liquid comp.

8
(boiling pt curve) (x vs y or (equilibrium curve)
 Thus from the above figure the two curves are:
 The lower curve: shows the composition of the liquid
which boils at any given temperature, and
 The upper curve: shows the corresponding composition of
the vapor at that temperature.
From the graph in which region separation takes place?
N.B:
 distillation separation can be made only in the region where
a looped curve is exist.
 The term boiling point for a solution ordinarily has no
meaning since vaporization occur over a temperature
range(b/n their B.Pt), i.e. from the bubble point to the dew
point.
9
If so what will happen as the shape of the graph varies
from diagonal (45o ) line??
• The greater the distance of the equilibrium curve from 45o
diagonal of x-y graph, the easier separation using
distillation.

10
 Boiling-Point Diagrams and x,y Plots

Boiling-point diagram for system benzene (A)-toluene (B) at a

total pressure of 101.32 kPa
If we start with a cold liquid
composition is xA1 = 0.318
(xB1 = ? and heat the mixture, it
will start to boil at
98ºC.
The first vapor composition in
equilibrium is yA1 = 0.53
(yB1 = 0.468).
Continue boiling, the
composition xA will move to
the left since yA is richer in11A.
 A common method of plotting the equilibrium data is
shown in Fig. 2 where yA is plotted versus xA for the
benzene-toluene system. The 45º line is given to show
that yA is richer in component A than is xA.

Fig. 2 Equilibrium diagram for Ben.(A) &Tol.(B) at 101.32

kPa (1atm).
12
Temperature composition diagram for some typical binary compounds

Show the above diagram in in x vs y.

Figure 2 (T )vs (x,y) and (x vs y) graph for a typical compounds 13

From the above VLE plot which mixtures are easy to separate?
 Benzene-toluene is relatively easy,….
 Acetone-carbon disulphide &
 Acetone-chloroform present difficulties for separation using
distillation. How it could be separated?
An azeotrope: is a mixture of two or more liquids in such a ratio
that its composition cannot be changed by simple distillation
(i.e. constant-boiling mixture).
This occurs because, when azoetrope is boiled, the resulting
vapor has the same ratio of constituents as the original mixture.
The two VLE plots above(b&c), shows two different azeotropic
systems, one with a minimum B.Pt and one with a maximum
B.Pt.
In other words, azeotropic system give a rise to VLE plots
where the equilibrium curve crosses the diagonal. 14
E.g. 2.1 Equilibrium Contact of Vapor-Liquid Mixture
A vapor at the dew point and 101.32kPa containing a mole
fraction of 0.40 benzene (A) and 0.60 toluene (B) and 100 kg
mol total is contacted with 110 kg mol of a liquid at the
boiling point containing a mole fraction of 0.30 benzene and
0.70 toluene. The two streams are contacted in a single stage,
and the outlet streams leave in equilibrium with each other.
Assume constant molal overflow. Calculate the amounts and
compositions of the exit streams.
Solution: The given values are V2 = 100 kg mol, yA2 = 0.40,
L0=110 kg mol , and xA0 = 0.30.
V1 V2 For constant molal
overflow,
L0 L1 V2 = V1 and L0 = L1.
15
Equilibrium Data for B-T mixture
Material balance on component A,
L0 x A0  V2 y A2  L1 x A1  V1 y A1  Mx AM
110 (0.30)  100(0.40)  110 x A1  100 y A1
Draw the equilibrium curve to solve
First, we assume that xA1 = 0.20 and yA1.
Assuming that xA1 = 0.20 and solving yA1 = 0.51.
Next, assuming that xA1=0.30 and solving, yA1 = 0.40.
Next, assuming that xA1=0.40 and solving, yA1 = 0.29.
(These point are plotted on the graph.)
At the intersection of this line with the equilibrium curve,
17
 Equilibrium curve for Benzene.-Toluene

yA1 = 0.455 and xA1 = 0.25. Answer

Vapor-Liquid Equilibrium Relations
Raoult’s Law
An ideal law, Raoult’s law, can be defined for vapor-liquid phases in
equilibrium (only ideal solution e.g. benzene-toluene, hexane-heptane
etc.
Similarly, Daltons law of partial pressure is:
(1)
p A  PA x A
p A  Py A
Where **

pA is the partial pressure of component A in the vapor in Pa (atm)

PA is the vapor pressure of pure A in Pa (atm)
P is total pressure of mixture
xA is the mole fraction of A in the liquid.
(2)
Composition in liquid: 1  x A  xB (3)
Composition in vapor: 1  y A  yB 19
The boiling point diagram can be calculated from the pure
vapor-pressure data in the table below and the following
equations:
p A  pB  P (4)

PA x A  PB (1  x A )  P
(5)
p A PA x A
yA  
P P (6)

20
Ex 2.2 Use of Raoult’s Law for Boiling-Point Diagram

Calculate the vapor and liquid compositions in equilibrium at

95ºC (368.2K) for benzene-toluene using the vapor pressure
from the table 2.1 at 101.32 kPa.
Solution: At 95ºC from Table2.1 for benzene, PA = 155.7kPa
and PB = 63.3 kPa. Substituting into Eq.(5) and solving,
PA x A  PB (1  x A )  P

155.7(xA) + 63.3(1-xA) = 101.32 kPa (760 mmHg)

Hence, xA= 0.411 and xB= 1 – xA = 1 - 0.411 = 0.589. Substituting into
eqn.(6), p A PA x A 155.7(0.411)
yA     0.632
P P 101.32 21
 Relative Volatility of Vapor-Liquid Systems
Relative volatility ( AB )

It is a measure of the differences in volatility between two components,

and hence their boiling points. It indicates how easy or difficult a
particular separation will be.
pB
Volatility of A :  A  p A and Volatility of B: B 
xB
x
y A / x AA yA / xA
 AB  
y B / xB (1  y A ) /(1  x A )

Where αAB is the relative volatility of A with respect to B in the binary

PA x A PB xB
system. y  y 
Raoult’s law: A P B
P
Thus, for ideal system, the volatility of components equal to the vapor
pressure of the pure components, so;  x
P yA  AB A
 AB  A 1  ( AB  1) x A
PB

when αAB is above 1.0, a separation is possible. But when αAB = 1, result
22
Azeotropic mixture
Ex 2.4 Using data from table 2.1 calculate the relative
volatility for the benzene-toluene system at 85ºC
(358.2K) and 105ºC (378.2K)

Answer  AB = 2.54, = 2.38, The variation in α is about 7%.

23
2.2 Method of distillation of two component mixture
Distillation has two main methods in practice.
1.Production of vapor by boiling the liquid mixture to be separated in a
single stage and recovering and condensing the vapors. No liquid is
allowed to return to the single-stage still to contact the rising vapors.
(Batch system)
2.Returning of a portion of the condensate to the still. The vapors rise
through a series of stages or trays, and part of the condensate flows
downward through the series of stages or trays countercurrently to the
vapors (“fractional distillation, distillation with reflux, or rectification”).
(Continuous system)

There are 3 important types of distillation that occur in a single stage or still:
3. Simple batch or differential distillation
4. Equilibrium or flash distillation,
5. Rectification 24
Simple Batch or Differential Distillation

The pot is filled with liquid mixture

and heated.

Vapor flows upwards though the

column and condenses at the top.

Part of the liquid is returned to the

column as reflux, and the remainder
withdrawn as distillate.

Nothing is added or withdrawn from

the still until the run is completed. 25
 2. Flash Distillation or Equilibrium

yA
Separator

heater
xA

Flash distillation is a single stage separation technique.

1. A liquid mixture is pumped through a heater to raise the temperature
and enthalpy of the mixture.
2. It then flows through a valve and the pressure is reduced, causing
the liquid to partially vaporize.
3. Once the mixture enters a big enough volume (the “flash drum”), the
liquid and vapor separate.
4. Because the vapor and liquid are in such close contact up until the
“flash” occurs, the product liquid and vapor phases approach
equilibrium. 26
 Total mass balance: F  V L

Component A balance: FxF  V y A  Lx A

Where,
F, V and L are flow rate of feed, vapor and liquid respectively.
xF, yA and xA are mole fraction of component A in feed, vapor and
liquid.

Material balance for more volatile component :

V F V
xF  ( ) y A  (  ) x A x F  f y A  (1  f ) x A
F F F
Where

f = V/F = molal fraction of the feed that is vaporized and withdrawn

continuously as vapor.
How much the mole fraction of liquid be? 27
Ex 2.4 A mixture of 50% mole normal heptane and 50% normal octane
at 30ºC is continuously flash distilled at 1 standard atmosphere so that 60
mol% of the feed is vaporized. What will be the composition of the
vapor and liquid products?

xA 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

yA 0.247 0.453 0.607 0.717 0.796 0.853 0.898 0.935 0.968

28
Solution: Given: xF = 0.5, f = 0.6

Find: xA, yA
Basis: F = 100 mole
Applying the mass balance yields:

F  V L
Since ,
f V / F
V  fF  0.6(100)  60

L  F  V  100  60  40

29
Material balance for more volatile component,
V F V
xF  ( ) y A  (  ) x A
F F F
x F  f y A  (1  f ) x A

0.5  0.6 y A  (1  0.6) x A

Subtituting value of f =0.6 and xF =0.5 we get, 0.5  0.6 y A  0.4 x A

Assuming that xA = 0.5 and solving yA = 0.5.

Next, assuming that xA=0 and solving, yA = 0.83.

(These point are plotted on the graph.)

At the intersection of this line with the equilibrium curve,

yA = 0.58 and xA = 0.39. Answer

30
 x=0
y-intercept= 0.834

yA

xA
3th xA =0.39 xF =0.5
1st
yA = 0.58 yF = 0.5

31
 3. Rectification
 Rectification (fractionation) or stage distillation with reflux is
a series of flash-vaporization stages are arranged in a series which the
vapor and liquid products from each stage flow counter-currently to
each other.
 The liquid in a stage is conducted or flows to the stage below and the
vapor from a stage flow upward to the stage above.

V1 V2 V3 V2 Vn Vn+1

L0 L1 L2 L1 Ln-1 Ln

Vn 1  Ln 1  Vn  Ln
A total material balance:
Vn 1 y n 1  Ln 1 x n 1  Vn y n  Ln x n
A component balance on A: 32
 2.3 Binary Fractional Distillation
In a distillation column the stages (referred to as sieve plates or trays) in
a distillation tower are arranged vertically, as shown schematically in
figure below.
1. Feed enters the column somewhere
in the middle of the column.

2. Feed is liquid, it flows down to a

sieve tray or stage.

3. Vapor enters the tray and bubbles

through the liquid on this tray as the
entering liquid flows across.

6. The concentration of the more volatile 4. The vapor and liquid leaving the tray
component is being increased in the vapor are essentially in equilibrium.
form each stage going upward and 5. The vapor continues up to the next
decreased in the liquid from each stage tray or stage, where it is again
going downwards. contacted with a down flowing liquid.
33
 7. The final vapor product coming
overhead is condensed in a condenser
and a portion of the liquid product
(distillate) is removed, which contains a
high concentration of A.
8. The remaining liquid from the
condenser is returned (refluxed) as a
liquid to the top tray.

9. The liquid leaving the bottom tray

enters a re-boiler, where it partially
vaporized, and the remaining liquid,
which is lean in A or rich in B, is
10. The vapor from the re- withdrawn as liquid product.
boiler is sent back to the bottom
stage or trays is much greater. 34
 Exercise No.1

1. The vapor-pressure data are given below for the system hexane-
octane.
(a) Using Raoult’s law, calculate and plot the xy data at a total pressure
of 101.32 kPa.
(b) Plot the boiling-point diagram.

T(ºF) T(ºC) Vapor Pressure

n-Hexane n-Octane
kPa mmHg kPa mmHg
155.6 68.7 101.3 760 16.1 121
175 79.4 136.7 1025 23.1 173
200 93.3 197.3 1480 37.1 278
225 107.2 284.0 2130 57.9 434
258.2 125.7 456.0 3420 101.3 760

35
Exercise No.2 (continue)

2. A mixture of 50 g mol of liquid benzene and 50 g mole water. Determine the

boiling at 101.32 kPa pressure. Liquid benzene is immiscible in water.
Determine the boiling point of the mixture and the composition of the vapor.
Which component will first be removed completely from the still? Vapor
pressure data of the pure components are as follows:
Temperature Pwater Pbenzene
(mm Hg) (mm Hg)
K ºC

308.5 35.3 43 150

325.9 52.7 106 300

345.8 72.6 261 600

353.3 80.1 356 760

36
2.4 Design of distillation column for binary mixtures

Components of distillation column

Fig. Continues fractionating column with rectifying and stripping sections

37
 Number of plates required in a distillation column
i. In order to develop a method for the design of distillation
units to give the desired fractionation,
 it is necessary, in the first instance, to develop an analytical
approach which enables the necessary number of trays to be
calculated.
 First the heat and material flows over the trays, the
condenser, and the re-boiler must be established.
 Thermodynamic data are required to establish how much
mass transfer is needed to establish equilibrium between the
streams leaving each tray( i.e. VLE).
 The required diameter of the column designed to
accommodate the desired flow rate to operate within the
available drop in pressure, while at the same time for the
desired degree of mixing of the streams on each tray. 38
 Material & Energy balance over a plate
 Let’s take 4 streams involved in the transfer of heat and material
across the nth plate, as shown below.
 Here, plate n receives liquid Ln+1 from plate n + 1 above, and vapor
Vn-1 from plate n-1 below.
 Similarly Plate n supplies liquid Ln to
plate n-1, and vapor Vn to plate n+1
M.B: V n+ L n = Vn-1 + Ln+1,
Here the action of the plate is to bring
about mixing so that the vapor
Stream V n, approaches equilibrium
with the liquid stream Ln
Where as the streams Ln+1 and Vn-1,
cannot be in equilibrium,.
39
Heat balance over a plate:
Ln+1 HLn+1 + Vn-1Hvn-1 = VnHvn + LnHLn + losses + Heat of mixing
Where: HL n : is the enthalpy per mole of the liquid on plate n, and
HV n is the enthalpy per mole of the vapor rising from plate n.
This equation is difficult to handle for majority of mixtures, some
simplifying assumptions are usually made; like
 the heat loss will be small and may be neglected
 Heat of mixing is zero ,assuming ideal system
 Molar heat of vaporization of this mixture may be taken as constant
& independent of composition.
• For these conditions there are two basic methods for determining the
number of plates required:
1. Lewis-Sorel Method
2. McCabe – Thiele Method
40
1. Lewis–Sorel method
If a unit is operating as shown below, so that a Loop 1
binary feed F is distilled to give a top product D
and a bottom product W, with x f, x d ,and x w as the
corresponding mole fractions of the more volatile
component, and the vapor Vt rising from the top
plate is condensed, and part is run back as liquid at
its boiling point to the column as reflux, the
remainder being withdrawn as product.
M.B Above plate n: V n = Ln+1 + D Loop 2
Expressing this balance for the more volatile component gives:
YnVn = Ln+1 Xn+1 + DXd Thus : Y n = (Ln+1/V n)Xn+1 + (D/V n)X d

This equation relates the composition of the vapor rising to the plate to the composition of
the liquid on any plate above the feed plate.

Since the molar liquid over flow is constant, L n may be replaced by Ln+1 and: Yn = (L

n /V n)Xn+1 + (D/V n)X d 41

 Similarly, taking a material balance for the total streams
and for the more volatile component from the bottom to
above plate m, and noting that Lm= Lm+1 gives:
Lm = V m + W
YmVm = Lm Xm+1 – WXw
Ym = (Lm/Vm)Xm+1 – (W/Vm)Xw
• These two equations, gives the corresponding relation
between the compositions of the vapor rising to a plate and
the liquid on the plate, for the section above and below the
feed plate.
• These two equations are the equations of the operating
lines.
42
2. The method of McCabe and Thiele

 McCabe and Thiele (1925) developed a graphical method to determine the

theoretical number of stages required to affect the separation of the binary
mixture.

The simplifying assumptions of :

 Constant molar heat of vaporization, no heat losses, and no heat of mixing, lead
to a constant molar vapour flow and a constant molar reflux flow in any section
of the column, that is Vn= Vn+1 , Ln= L , and so on.

 Using these simplification, the two enrichment equations are obtained:

Yn = (Ln/Vn)xn+1 + (D/Vn) xd (i)

Y m = (Lm/Vm)xm+1 – (W/Vm)xw (ii)

 These equations are used in the Lewis–Sorel method to calculate the
relation between the composition of the liquid on a plate and the
composition of the vapour rising to that plate.

The information required for the systematic calculation are

 The VLE data
 Feed condition (temperature, composition)
 Distillate and bottom compositions and
 The reflux ratio, which is defined as the ratio of reflux liquid over the
distillate product.
For example, a column is to be designed for the separation of a
binary mixture
44
 McCabe and Thiele pointed out that, since these equations represent
straight lines connecting y n with xn+1 and y m with xm+1, they can be
drawn on the same diagram as the equilibrium curve to give a simple
graphical solution for the number of stages required.

 If xn+1= xd in equation (i), then

 Yn = (Ln/Vn)Xd + (D/Vn) Xd = Xd((Ln+D)/Vn) = Xd and this equation

represents a line passing through the point Yn=Xn+1 = Xd. If Xn+1 is put

equal to zero, then yn= Dxd/Vn , giving a second easily determined

point.
The top operating line is therefore drawn through two points of
coordinates (xd, xd) and (0, (Dxd/Vn))

For the bottom operating line, equation (ii),

if xm+1= xw, then: Ym = (Lm/Vm)Xw - (W/Vm) Xw = Xw((Lm-W)/Vw) = xw

Thus the bottom operating line passes through the point C, that is
(xw,xw), and has a slope Lm/Vm.

When the two operating lines have been drawn in, the number of stages

required may be found by drawing steps between the operating line

and the equilibrium curve starting from point A.

46
 This method is one of the most important concepts in chemical
engineering and is an invaluable tool for the solution of distillation
problems. The assumption of constant molar over flow is not limiting
since in very few systems do the molar heats of vaporization differ by
more than 10 per cent. The method does have limitations, however,
and should not be employed when the relative volatility is less than
1.3 or greater than 5, when the re-flux ratio is less than 1.1 times the
minimum, or when more than twenty-five theoretical trays are
required.

47
 The steps to be followed to determine the number of theoretical stages
by McCabe-Thiele Method:
1. Determination of the Rectifying section operating line (ROL).

2. Determination the feed condition (q).

3. Determination of the feed section operating line (q-line).
4. Determination of required reflux ratio (R).
5. Determination of the stripping section operating line (SOL).
6. Determination of number of theoretical stage.

48
 Effect of feed conditions
The condition of feed stream is represented by the quantity q,
which is the mole fraction of liquid in feed.
Lm  Ln  qF (0)
(1)
Vn  Vm  (1  q ) F

The enriching and striping operating-line

equations on an x-y diagram can be
derived as follows:
Vn y  Ln x  Dx D (2)

Vm y  Lm x  Wx w (3)

Where the y and x values are the point of

intersection of the two operating lines.
Subtracting eqn.(2) from eqn.(3),
(Vm  Vn ) y  ( Lm  Ln ) x  ( DxD  Wxw ) (4)
49
 Cont’d
Substituting eqn. and into eqn.(4) and rearranging,

FxF  DxD  Wxw Lm  Ln  qF Vn  Vm  (1  q) F

q x
y x F Vn  Vm  (1  q) F
q 1 q 1 (5)

c pL (Tb  TF ) c pV (TF  Td )
q  1 q  1
 

Cold-liquid feed Superheated vapor

where
C pL , CpV = specific heats of liquid and vapor, respectively
TF = temperature of feed
Tb, Td = bubble point and dew point of feed respectively
50
λ = heat of vaporization
Location of the feed tray in a tower and number of trays.
From eqn.(15), the q-line equation and is the locus of the intersection
of the two operating lines. Setting y = x in eqn(15), the intersection of
the q-line equation with the 45º line is y=x=xF, where xF is the overall
composition of the feed.
In given below the figure, the q line is plotted for various feed
conditions. The slope of the q line is q/(q-1).

q = 0 (saturated vapor)
q = 1 (saturated liquid)
q > 1(sub-cooled liquid)
q < 0 (superheated vapor)
0 < q < 1 (mix of liquid and vapor)

51
Number of stages and trays

1st point

2nd point

3rd point
n = 7 =number of tray + reboiler
Number of tray = 6 52
Using Operating Lines and the Feed Line in McCabe-Thiele Design

Slope = R/(R+1)

Slope = q/(1-q)

Slope = Lm/ Vm

53
Total and Minimum Reflux Ratio for McCabe-Thiele Method
A Total flux

One limiting values of reflux ratio is that of total reflux, or R = ∞.

Since R = Ln/D and, by eqn.(16).
Vn 1  Ln  D (i)

Then Ln is very large, as is the vapor flow Vn. This means that the slope
R/(R+1) of the enriching operating line becomes 1.0 and the operating
lines of both sections of the column coincide with the 45º diagonol line,
as shown in Fig below.

Minimum number of trays can be obtained by returning all the overhead

condensed vapor V1 from the top of the tower back to the tower as
reflux, i.e., total reflux. Also, the liquid in the bottoms is re-boiled.

54
Minimum number of theoretical steps Nm
 x 1  xw  (ii)
log  D 
when a total condenser is used (α is  1  x D xw 
Nm 
constant). log  av
(iii)
For small variations in α,  av  1 w 
1/ 2

where α1 is the relative volatility of the overhead vapor

55
αw is the relative volatility of the bottoms liquid.
 Minimum reflux ratio
The minimum reflux ratio (Rm) will require an infinite number of
trays for the given separation desired of xD and xW.
If R is decreased, the slope of the enriching operating line R/(R+1)
is decreased, and the intersection of this line and the stripping line
with the q line moves farther from the 45º line and closer to the
equilibrium line.
Two operating lines touch the
equilibrium line (“pinch point”) at y’
and x’ (number of steps required
becomes infinite).
The line passes through the points
x’, y’ and x D (y = x D):

Rm x  y
 D (19)
Rm 1 xD  x 56
 Operating and optimum reflux ratio

Total reflux = number of plates is a minimum, but the tower

diameter is infinite.
This corresponds to an infinite cost of tower and steam and cooling
water. This is the limit in the tower operation.
Minimum reflux = number of trays is infinite, which again gives an
infinite cost. These are the two limits in operation of the tower.
Actual operating reflux ratio to use is in between these two limits.
The optimum reflux ratio to use for lowest total cost per year is
between the minimum Rm and total reflux (1.2Rm to 1.5Rm).

57
Tray Efficiency
It is assumed that the vapor leaving each tray is in equilibrium with the
liquid leaving the same tray and the trays are operating at 100%
efficiency.

In practice, the trays are not perfect. There are deviations from ideal
conditions.

The deviation from the ideal condition is due to:

(1) Insufficient time of contact

(2) Insufficient degree of mixing.

To achieve the same degree of desired separation, more trays will have to
be added to compensate for the lack of perfect separability.

Tray efficiency may be used to adjust the actual number of trays required
The overall tray efficiency, EO is defined as:
It is applied for the whole column.
Every tray is assumed to have the same efficiency.

The overall efficiency depends on the:

(i) Geometry and design of the contacting trays,
(ii) Flow rates and flow paths of vapor and liquid
streams,
(iii) Compositions and properties of vapor and liquid
streams
 when the composition of the vapour equals that of the liquid, and no further
enrichment occurs.
 This mixture is called an azeotrope, and it cannot be separated by
straightforward distillation.
 A condition is shown in the y − x curves that the equilibrium curve crosses
the diagonal, indicating the existence of an azeotrope.
 A large number of azeotropic mixtures have been found, such as water-nitric
acid, water-hydrochloric acid, and water-alcohols.
 When the activity coefficient is greater than unity, giving a positive
deviation from Raoult’s law, the molecules of the components in the system
repel each other and exert a higher partial pressure. This leads to the
formation of a “minimum boiling” azeotrope.
 For values of the activity coefficient less than unity, negative deviation from
Raoult’s law results in a lower partial pressure and the formation of a
“maximum boiling” azeotrope.
 The principle of azeotropic and of extraction distillation lies in the
addition of a new substance to the mixture so as to increase the relative
volatility of the two key components, thus make separation relatively easy.
 In azeotropic distillation the substance added forms an azeotrope with one
or more of the components ,
 With extractive distillation the substance added is relatively non-volatile
compared with the components to be separated, and fed continuously near
the top of the column.
 This extractive agent runs down the column as reflux and is present in
appreciable concentrations on all the plates.
 The third component added to the binary mixture is sometimes known as
the entrainer or the solvent.
• if benzene is added to the ethanol–water azeotrope, then a ternary
azeotrope is formed
• This requires the use of three atmospheric pressure fractionating
columns, and a continuous two-phase liquid separator or decanter.
 An azeotrope is a liquid mixture when vaporized , produces the
same composition as the liquid
 Starting with a mixture containing a lower proportion of ethanol, it
is not possible to obtain a product richer in ethanol than this by
normal binary distillation.
 Near azeotropic conditions exist at points marked A in Figure 11.44.
 The addition of the relatively non-polar benzene entrainer serves to
volatilise water, a highly polar molecule, to a greater extent than
ethanol, a moderately polar molecule, and a virtually pure ethanol
product may be obtained.
 The first tower in Figure 11.44 gives the ternary azeotrope as an
overhead vapour, and nearly pure ethanol as bottom product.
 The ternary azeotrope is condensed and splits into two liquid
phases in the decanter.
 The benzene-rich phase from the decanter serves as reflux, while
the water–ethanol-rich phase passes to two towers, one for benzene
recovery and the other for water removal.
 The azeotropic overheads from these successive towers are
returned to appropriate points in the primary tower.
Extractive Distillation
• It is the presence of a miscible, high-boiling, relatively non-volatile component, the
solvent, that forms no azeotrope with the other components in the mixture.
• The method is used for mixtures having a low value of relative volatility, nearing
unity.
• To a binary mixture which is difficult or impossible to separate by ordinary means, a
third component, termed a solvent, is added, thus permitting the separation.
• The added solvent is low volatility and itself not appreciably vaporised

• Extractive distillation is usually more desirable than azeotropic distillation since no

large quantities of solvent have to be vaporised.
• It is important to note that the solvent must not form an azeotrope with any of the
components
• The solvent to be used is selected on the basis of selectivity, volatility, ease of
separation from the top and bottom products, and the cost
STEAM DISTILLATION
• Steam distillation is a special type of distillation (a separation process) for
temperature sensitive materials like natural aromatic compounds.
• It once was a popular laboratory method for purification of organic compounds,
• Where a material to be distilled has a high boiling point, and particularly where
decomposition might occur.
• If direct distillation is employed, the process of steam distillation may be used.
• Steam is passed directly into the liquid and the solubility of the steam in the liquid
must be very low.
• Steam distillation also is an important means of separating fatty acids from mixtures
• Steam distillation is perhaps the most common example of differential distillation.
PLATE COLUMNS
• Distillation may be carried out in plate columns in which
each plate constitutes a single stage, or in packed
columns
• where mass transfer is between a vapour and liquid in
continuous counter current flow.
In actual design the following factors should be considered:
(a) The type of plate or tray.
(b) The vapour velocity, which is the major factor in
determining the diameter of the column.
(c) The plate spacing, which is the major factor fixing the
The three Layout of trays :
(a) Cross-flow
Normal and giving a good opportunity for mass transfer.

Cross-flow arrangement is much the most frequently used.

(b) Reverse
Down comers are much reduced in area, and there is a very long liquid
path.
This design is suitable for low liquid–vapour ratios.
(c) Double-pass

The liquid flow splits into two directions, s/m will handle high liquid–
vapour ratio.
There are three types of trays:
1)The bubble-cap tray
• This is the most widely used tray because of its range

of operation.
• The individual caps are mounted on risers and have

rectangular or triangular slots cut around their sides.

• The caps are held in position by some form of spider,

• The areas of the riser and the annular space around the riser should
be about equal.
• With small trays, the reflux passes to the tray below over two or
three circular weirs, with the larger trays through segmental down
2) Sieve or perforated trays
• These are much simpler in construction, with
small holes in the tray.
• The liquid flows across the tray and

down the segmental down comer.

3) Valve trays
• These may be regarded as a cross between a bubble-cap and a sieve tray.
• The construction is similar to that of cap types, although there are no risers and no
slots.
• It may be noted that with most types of valve tray the opening may be varied by
the vapour flow, so that the trays can operate over a wide range of flow rates.
• Because of their flexibility and price, valve trays are tending to replace bubble-cap
trays.
Homework No.3

1. A saturated liquid feed of 200 mol/h at the boiling point containing

42 mol% heptane and 58% ethyl benzene is to be fractionated at
101.32kPa abs to give a distillate containing 97 mol% heptane and a
bottoms containing 1.1 mol% heptane. The reflux ratio used is 2.5:1.
Calculate the mol/h distillate, mol/h bottoms, theoretical number of
trays, and the feed tray number. Equilibrium data are given below at
101.32kPa abs pressure for the mole fraction n-heptane xH and yH.

Temperature Temperature

K ºC xH yH K ºC xH yH

409.3 136.1 0 0 383.8 110.6 0.485 0.730

402.6 129.4 0.08 0.23 376.0 102.8 0.790 0.904

392.6 119.4 0.25 0.514 371.5 98.3 1.000 1.000

73
Understand the following
i. What is a multi component mixtures and multiple Column
Systems
ii. How to calculate the number of plates required for a Multi
component mixture separation?
iii. Azeotropic and Extractive distillation
iv. How to find theoretical stage using Ponchon Savarit
Method using enthalpy diagram.

74
End!