Distillation

Topics
Vapor-liquid equilibrium
Types of Distillation
Mass Balance in a Distillation Column
Determination of Ideal Number of Plates –
McCabe –Thiele & Lewis Sorel Analysis.
Multicomponents Distillation
 Introduction
What is Distillation
Distillation is a process wherein a liquid or vapour mixture of two
or more substances is separated into its component fractions of
desired purity, by the application and removal of heat.

method of separating mixtures based on differences in their

volatilities in a boiling liquid mixture.

less volatile, "heavy" or "high boiling", components

concentrate in the liquid phase; the more volatile, "light",
components concentrate in the vapor.

used for many commercial processes, such as production of

gasoline, distilled water, alcohol, and many other liquids
 2.1: Vapor-Liquid Equilibrium
(VLE)
Equilibrium in Chemical Engineering

Chemical equilibrium
 rates of reaction in both directions are same.

Phase equilibrium
 the rate of changing from one phase to another is same to
the rate of the reverse change.

Vapor-liquid phase equilibrium: ??: ??

 Vapor-Liquid Equilibrium (VLE)

 Condition or state where the rate of evaporation (liquid changing

to vapor) equals the rate of condensation (vapor changing to
liquid).

 VLE data can be determined experimentally using an equilibrium

still.
or
 VLE data can be determined or approximated with the help of
certain theories such as Raoult's Law, Dalton's Law, and/or
Henry's Law.
 Binary system-VLE Data

 There are several different types of plots for binary system:

1. Pxy diagram: x and y as functions of pressure at constant

temperature.
2. Txy diagram: x and y as functions of temperature at constant
pressure.
3. xy diagram: x versus y at constant pressure (temperature is a
parameter along the curve).

 Since most applications require data at constant pressure,

Txy and xy diagrams are the most commonly used.
Txy Diagram (Phase Diagram
 Binary system-VLE Data

y Diagrams xy diagram for binary system

 xy diagram for a binary system,
relates the compositions of the liquid
and vapor phases in equilibrium with
each other.

 These diagrams be generated from

Constant pressure- boiling point
diagram
 Binary system-VLE Data
Temperature-composition diagram(Txy)
How to present
VLE data?
 Binary system-VLE Data
Step 1 VLE data is obtained from Boiling points diagram

T
Tb(B)
V
T1
T2

T3
T4

L Tb(A)

x1 x2 x3 y1 x4 y2 y3 y4
xA
 Binary system-VLE Data
Step 3 Plots x-y diagram

yA T4

T3

T2

T1

xA
 VLE at Low Pressures – Raoult’s Law

Consider a system with two phases (vapor and liquid) at given values of
pressure and temperature.

P What is the equilibrium

relationship between the
T
measurable variables P, T, yi,
V xi in this system?

L
 VLE Relationship
If experimental data are not available, estimation of VLE can still be
done. HOW?
 simplest method assumes ideal vapor and ideal liquid phases.
 Raoult’s law.

Raoult’s Law
Pyi  Pi xi
sat pi  Pi o xi
Where
pi= partial pressure of species i in the vapor
Pi o = the vapor pressure of pure species
xi=mole fraction of species i in the liquid

13
 VLE at Low Pressures – Raoult’s Law

Calculations Using Raoult's Law

Bubble-point pressure problem -- T,x given -- P,y unknown.

The vapor pressures are found at the given temperature, which allows direct
calculation of the pressure and vapor mole fractions:

 Py i  P   Pi sat xi
Pi sat xi
yi 
P
Where
P = total pressure of component A in the vapor.
Pi sat = vapor pressure of species i
xi =mole fraction of species i in the liquid
 VLE at Low Pressures – Raoult’s Law

Calculations Using Raoult's Law

Dew-point pressure problem -- T,y given -- P,x unknown.

No trial and error is needed, as P can be directly calculated.

Pyi
xi  sat
Pi
x i 1

1
P
 yi / Pi sat 
Example 1: (Use of Raoult’s Law for boiling
point Diagram)
Use Raoult's Law and calculate the vapour and liquid compositions in
equilibrium at 95Co (368.2 K) (in mole fractions, y and x) for the benzene-
toluene system using vapour pressure data measure at a pressure of 101.32
kPa as shown in Table 1 below :

Table 1:
 from Table 1
For benzene PA=155.7 kPa
For toluene PB= 63.3 kPa
Refer to equation Dalton Law:
p A  pB  P
Raoult`s Law
PA ox A  PB o (1  x A )  P
pi=Pi o .xi
155.7(xA) + 63.3 (1-xA)=101.32 kPa
Liquid composition;
xA=0.411 and
Vapor composition:
xB= 1-0.411=0.589 kPa
PAo x A
yA 
P
yA= (155.7 x 0.411)/101.32 = 0.632
xy data
 Relative Volatility of Vapor-Liquid Systems

Relative volatility ( AB )
It 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.

yA / xA y A / 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 system.

PA0 x A PB0 x B
Raoult’s law: yA  yB 
P P
PA0
 AB  0
PB
 AB x A
yA 
1  ( AB  1) x A

19
when αAB is above 1.0, a separation is possible.
 Example: Using data from table 1 calculate the relative volatility for
the benzene-toluene system at 85ºC (358.2K) and 105ºC (378.2K)

Solution: At 85ºC, substituting into equation below for a system following

Raoutl’s law,
PA 116 .9
 AB    2.54
PB 46.0

Similarly at 105ºC,
204.2
  2.38
86.0

The variation in α is about 7%. Answer

20
 The types of distillation
There are 3 types in which the distillation may be carried out;

 Differential or batch distillation

 Flash Distillation or equilibrium distillation

 Continuous Distillation with reflux – Binary systems

Differential or Batch 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.
 Feed to the column is
introduced batch-wise.
 Column is charged with a batch
and then the distillation process
is carried out.
 When the desired task is
achieved, a next batch of feed is
introduced.
 Flash Distillation
 Flash distillation is used most for separating components that boil at
widely different temperatures. Example: separation of crude oil.
 The process involves heating a feed stream and then allowing it to
expand into a vessel maintained at low pressure.
 Partial vaporization then occurs, and a phase equilibrium is (ideally)
reached.
 May be represented in equilibrium curve, in terms of;
 x (concentration of liquid),
 y (concentration of vapor) and
 f ( molal fraction of feed that is vaporized and withdrawn
continuously as vapor)
1 f xf
y xf 
f f
 Flash Distillation
More volatile component will be
concentrated in the vapor stream – the
less volatile in the liquid stream

Feed is preheated before

entering the separator

It is “flashed” by throttling
the feed stream through a
nozzle or valve into the
chamber – the pressure
drops through the valve.

A feed stream is
“flashed” into flash drum
and the liquid and vapor
are allowed to separate
under equilibrium.
 Continuous Distillation with
Reflux

 It effective separating components of comparable volatility.

 This requires the column to be constantly fed with new raw

material and the reboiler drained of the bottoms product
 Feed – somewhere near the middle of column;
 Top of the feed – enriching/rectification
 Bottom of the feed – stripping

 Concentration of the more volatile component is being increased

in the vapor from each stage going upward and decreased in the
liquid from each stage going downward
 To hold the condensed
vapor so that liquid
To cool and condense the vapor leaving (reflux) can be recycled
the top of the column back to the column

Distillate D
Trays/plates
and/or which is
packings which richer in the
are used to more
enhance volatile
component
separations component
of mole
fraction,
xD.

Bottoms B
-richer in the
less volatile
component,
where the mole
fraction of the
more volatile
component is,
xB provide the necessary vaporization for
the distillation process
Distillation with reflux and
McCABE-THIELE method
 Rectification (fractionation )or
stage distillation with reflux ;
can be considered to be a process in
which a series of flash-vaporization
stages are arranged in a series in such
a manner that the vapor and liquid
products from each stage flow
counter current to each other
Hence in each stage , a vapor V and
a liquid stream L enter, are contact
and mixed and equilibrated , and a
vapor and a liquid stream leave in
equilibrium
 At each stage of the column
Lin,xin Vout,yout
two phases come in contact
with each other, mix, approach
thermal and composition
Lout,xout Vin,yin equilibrium to the extent which
depends on the efficiency of
the contact stage

Streams leaving the stage are in thermodynamic

equilibrium with each other

Streams coming to the stage are not in equilibrium

McCabe-Thiele method of calculation
for Number of theoretical Stages

 It is a mathematical graphical method for determining the number of

theoretical trays or stages needed for a given separation of a binary
mixture of A and B.
 The main assumption in this method is that There must be an
equi-molar flow through the tower between the feed inlet and the top
tray and the feed inlet and the bottom tray
 Action on an Ideal Plate
 By definition, a vapour and liquid leaving a plate are brought into
equilibrium.
 Assume that the plates are numbered serially from top down and
that the plate under consideration is the nth plate from the top.
 Then the immediately above plate n is plate n-1, and the
immediately below is n+1. Vn-1
Ln-2
yn-1
Xn-2
Plate n-1
Ln-1 Vn

Xn-1 yn
Plate n
Ln, Vn+1
xn yn+1
Plate n+1
Ln+1 Vn+2,
Material –balance diagram for plate n
Xn+1 yn+2
 3.0 Material balances for two
components systems

1. Total material balance on the entire column

F=D+W

2. Component material balance on component A

F xF= D xD+ W xW

Fig 1.10: Material balance for

continuous fractionating column
. Material Balances (top section)
3
 Material Balances (top section)
 Material balance around condenser:
V  LD
 Overall material balance over the Fig 1.11:
Vn 1  Ln  D
 Components material balance over the Fig 1.11:
Vn 1 y n 1  L n x n  D x D
L D
yn 1  n xn  xD
Vn 1 Vn 1
 R   1 
y  x    xD
 R 1  R 1
where
Ln
R  Reflux ratio = constant
33 D July 2012
Material Balances (top section)
Ln
R  slope
D
L R
R n 
Vn 1 R  1

34 July 2012
Operating Line: Rectifying
y

slope=R/(R+1)

1
xD
R 1

x
R 1 xD
yn 1  xn  xD
35
R 1 R 1 July 2012
 4. Material Balances (bottom section- Stripping)

Vm 1  Lm  W

Vm 1 y m 1  Lm x m  WxW

Lm Wx w
y m 1  xm 
Vm1 Vm 1

liquid flow to plate m+1 = Vapour flow from plate m+1 + Bottom
product withdrawn

Overall components material balance over plate m+1:

Rearranging the equation : Since equi-molar flow is assumed ,the

slop is
Lm
Vm 1
 Feed Line
 The conditions of the vapour rate or the liquid rate may change
depending of the thermal condition of the feed.

 It is related to the heat to vaporise one mole of feed divided by molar

latent heat (q)
 It is the locus of the intersection of the two operating lines

 Its intersection with the 450 line is y=x=xf where xf is the overall
composition of the feed.
Feed Line Equation
 If xq = xF, and yq =xF then;
 The point of intersection of the two operating lines lies on the
straight line of slope (q/q -1) and intercept (xF, yF)

q xF
yq  xq 
q 1 q 1

the heat needed to vaporize 1 mole of feed entering conditions

q
molar latent heat of vaporization of feed
 Feed line behavior
Feed at saturated liquid Cold feed

x
y=
y q=1 q>1

Feed partial vapor 0<q<1

Feed at saturated q=0 x=xf

vapour

Feed superheated q<0 q xF

yq  xq 
q 1 q 1
x

40 July 2012
 THEORETICAL STAGES
 Starting at xD and stepping of
the plate xW

 Since reboiler is considered a

theoretical step, the no of
theoretical trays in a tower is
equal to the number of the
theoretical step, minus 1.

 i.e. No of trays = No of steps - 1

4 stages + reboiler
 Construction for the McCabe-Thiele
Method
1. equilibrium  2. equilibrium 
Step 1: Plot equilibrium curve and 45 degree line.
curve curve
45° line Step 2: Plot given compositions (xF, xB, and xD)
y y Step 3: Draw q­line from xF and yF
Step 4: Determine Rmin from intersection of the
rectifying section OL and the equilibrium curve.
45° line Step 5: Determine R from R/Rmin
Step 6: Draw OL for Rectifying section
Step 7: Draw OL for Stripping section
xB x=zF xD
x

5. and 6. 7.
3. 4.
equilibrium  equilibrium  equilibrium 
equilibrium 
curve curve curve
curve

y y y y

xB xD xB x=zF xD xB x=zF xD xB x=zF xD

x=zF

Rmin/(Rmin+1) R/(R+1)
 Complete picture McCabe Thiele

R 1 y
y n 1  xn  xD
R 1 R 1 y1

q xF
y x
q 1 1 q
zf
Lm Wx w
y m 1  xm 
Vm 1 Vm 1
1 yB
xD
R 1
xB xN zf xD
x
 Complete picture McCabe Thiele
Step 1: Plot equilibrium curve(VLE) data.
Step 2: Plot 45 degree line(diagonal line. y=x)
Step 3: Plot given compositions (xF, xB, and 
xD)
Step 4: Draw q­line from xF and yF y
Step 5: Draw OL for Rectifying section y1
Step 6 : Draw OL for Stripping section
Step 7: Start stepping off from the distillate 
end until 
the intersection of the two operating lines is 
passed.
Step 8: Continue stepping but use the  zf
stripping operating line.
Step 9: Count the number of stages.
Step 10: Subtract one for the reboiler to give 
the number of theoretical trays yB

xB xN zf xD
x
 Reflux Ratio

 The analysis of fractionating columns is facilitated by the

use of a quantity called reflux ratio.
 Two ratios are used, one is the ratio of the reflux to the
overhead product and the other is the ratio of the reflux to
the vapour.
 Both ratios refer to quantities in the rectifying section.
The equations for those ratios are

L V D L L
RD   and RV  
D D V LD
 Minimum Reflux Ratio Rm

• Reflux ratio, R that will require an infinite number of plate for the
given desired separation of xd and xb

• at any reflux less than total, the number of plates needed is larger
than at total reflux and increases continuously as the reflux ratio
decreased.
• This corresponds to the minimum amount of liquid return in the
tower, and hence the minimum reboiler duty and condenser cooling
capacity
If R is decreased, the slope of the (ROL) 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 450 line and closer to the equilibrium line.

To achieve separation, the number of steps required to give a fixed x D

and xW increases. Separation more difficult when driving
force of mass transfer is zero
(operation at equilibrium point)
Minimum Reflux
Min Reflux happens when the two operating lines intersect
on equilibrium curve
1.0

0.9

0.8

0.7

0.6
Ya

0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

XB Xa
XD
Minimum Reflux
Don’t forget the q line. Min reflux occurs at intersection with
equilibrium curve because all three lines should intersect
1.0

0.9

0.8

0.7

0.6
Ya

0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

XB Xa
XD
Calculation of Minimum Reflux
Ratio Rm
 Based on the previous figure, the slope of the line is
given by
R 1
y n 1  xn  xD
R 1 R 1

At this point: xn=x* and yn+1=y*

Rmin 1
y*  x* xD
Rmin  1 Rmin  1
xD  y *
Rmin 
y * x *
 Minimum Reflux Ratio Rm

Rmin 1
y*  x* xD
Rmin  1 Rmin  1 slope=R/(R+1)
xD  y * y*
Rmin 
y * x *

1
xD
R 1

xF xD
xB
x* x
Feed –liquid at bubble point Feed –partially
(saturated liquid feed) q=1 vapour( 0<q<1)

Feed –cold liquid (q>1) Feed –saturated vapor (q=0)

 Minimum num of plates or Total
Reflux
 If no product is withdrawn from the still (D=0), the column is
said to operate under conditions of total reflux and, as seen from
equation , the top operating line has its maximum slope of unity,
and coincides with the line x=y.

Total reflux
D=0
R 1 R=L/D=∞
yn 1  xn  xD F=0
R 1 R 1 L/V=1
Ln  D  Vn1
If R=L/D= ∞ then R/(R+1)=1; also L=V
Ln  Vn1
yn 1  xn B=0
Total Reflux

 All vapour is condensed and returned as liquid

 Minimum number of plates
 Can use Fenske equation to calculate N min

 x D 1  x B  
ln 
 x B 1  x D  
N min  1
ln 
 (Ref. Unit Operations, McCabe Smith, 6 th ed. p666)
 Sometimes a column is operated in total reflux at
startup
McCabe - Thiele
Construction the operation lines:
 Locate the feed line
 Calculate the y-axis intercept xD/(RD + 1) of the rectifying line
and plot that line through the intercept and the point
(xD, xD)
 Draw the stripping line through point (xB,xB) and the
intersection of the rectifying line with the feed line.
 After the location of the feed plate the construction of the
number of ideal trays is found by the usual step-by-step
construction.
 The process can begin at the top and also a total condenser is
used.
Example 1
A mixture of benzene and toluene containing 40 mol % of benzene is to
be separated to give a product of 90 mol % of benzene at the top and
bottom product with not more than 10 mol % of benzene. It is
proposed to operate the unit with a reflux ratio of 3 kmol/kmol
product. It is required to find the number of theoretical plates needed
and the position of entry for the feed by Mccabe Thiele method.
Feed enter at its boiling points The equilibrium data are as follows:

x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

y 0.22 0.38 0.51 0.63 0.7 0.78 0.85 0.91 0.96
By using McCabe-Thiele Method:

1. Plot the equilibrium curve for benzene.

2. The equation for the rectifying line is:
yn1  0.75 xn  0.225
3. Draw the rectifying line through two points
(xd, xd) (0.9, 0.9)
(0,xd/R+1) (0, 0.225)
4. Draw the feed line intersect with the rectifying line
5. Draw the stripping line through point
(xb, xb) (0.1, 0.1)
and the intersection of rectifying line and feed line
6. Starting at point A, draw the horizontal line to cut the equilibrium
curve on point 1. Drop the vertical through 1 to the operating line
at point 2. Proceed in this way to obtain points 3-6
7. Draw horizontal line through 6 to cut equilibrium curve on point 7
and vertical through 7 to lower enrichment line at point 8.
Proceed to get point 9 – 16.
8. Count the number of plates + reboiler =7 stages.
9.Number of theoretical plates for separation,n-1=6stages
 Lewis Sorel Method

 calculate equation for rectifying line:

R 1 or yn1 
Ln
xn 
D
xd
yn 1  xn  xD Vn1 Vn1
R 1 R 1
Calculate equation for Stripping line:
Lm B
ym 1  xm  xb
Lm  B Lm  B
or
Lm B
ym 1  xm  xb
Vm 1 Vm 1

Calculate value Lm, Vm+1,VN+1 and LN and

subsitute inside rectifying & stripping
eqn.
Determination of number of plates by McCabe-Thiele Method
Example 2
A mixture of benzene and toluene containing 40 mol % of benzene is to
be separated to give a product of 90 mol % of benzene at the top and
bottom product with not more than 10 mol % of benzene. It is
proposed to operate the unit with a reflux ratio of 3 kmol/kmol
product. It is required to find the number of theoretical plates needed
by using Lewis Sorel Method.
Feed enter at its boiling points The equilibrium data are as follows:

x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

y 0.22 0.38 0.51 0.63 0.7 0.78 0.85 0.91 0.96
 Answer: Lewis Sorel Method
1. Draw VLE equilibrium data
2. Draw diagonal line 45 oC.
3. Composition of distillate x D given represents the composition of vapour yt,
4. From the vapour composition (y –axis), yt = xD .Find the liquid composition,
xt from equilibrium diagram.
5. Substitute xt value inside rectifying line equation to get yt-1
6. Find xt-1 from equilibrium diagram corresponding to yt-1
7. Calculate yt-2 and proceed with rectifying eqn till reach the point when
liquid phase composition equal to or less than xf.
8. Substitute value liquid phase composition equal to or less than xf inside
stripping eqn.
9. Continue step 8 until value liquid phase composition equal to or less than
xB.

62 July 2012
Basis: 100 mol of feed
Overall mass balance:
F  DB
100  D  B
100  B  D

Component mass balance on benzene:

x f F  xd D  xb B

(0.4)(100)  (0.9) D  (0.1) B

63 July 2012
  Substitute equation 1 into equation 2:

40  90  0.9 B  0.1B
40  0.9(100  B )  0.1B
B  62.5mol

 From equation 1,

100  B  D
D  100  62.5
D  37.5mol

64 July 2012
  We know that,

Ln
R
D
L
3.0  n
37.5
Ln  112 .5mol

 From equation ,

Vn1  Ln  D
Vn1  112 .5  37.5
Vn1  150mol

65 July 2012
  For rectifying section,

Ln D
yn1  xn  xd
Vn1 Vn1
112 .5 37.5
yn1  xn  (0.9)
150 150
yn1  0.75 x n  0.225

R 1
yn1  xn  xd
R 1 R 1
OR 3 1
yn1  xn  (0.9)
3 1 3 1
yn1  0.75 x n  0.225

66 July 2012
  For stripping section,

Ln
F

Lm

F  Ln  Lm
Lm  100  112 .5
Lm  212.5mol

67 July 2012
  From equation

Vm 1  Lm  B
Vm 1  212.5  62.5
Vm 1  150mol

Lm B
ym 1  xm  xb
Vm 1 Vm 1
212.5 62.5
ym 1  xm  (0.1)
150 150
ym 1  1.416 x m  0.042

68 July 2012
  Since all the vapor from the column is
condensed, the composition of the vapor yt
from the top plate must be equal that of the
product xd and that of the liquid returned as
reflux xt
 The composition of xt of the liquid on the top
plate is found from the equilibrium curve, so y t
= 0.90, xt = 0.79
 The value of yt-1 is obtained from equation for
rectifyingysection:
t 1  0.75 x t  0.225

yt 1  0.75(0.79)  0.225  0.818

 Xt-1 is obtained from equilibrium curve as 0.644

69 July 2012
 yt 2  0.75(0.644)  0.225  0.708

 Xt-2 is obtained from equilibrium curve as 0.492

yt 3  0.75(0.492)  0.225  0.594

 Xt-3 is obtained from equilibrium curve as 0.382

 This last value of composition is sufficiently

near to the feed for the feed to be introduced
on plate t-3 (xf = 0.4)
 For the lower part of the column, the
operating line for stripping will be used.

70 July 2012
 ym 1  1.416 x m  0.042
yt  4  1.416(0.382)  0.042  0.498

 Xt-4 is obtained from equilibrium curve as 0.298

yt 5  1.416(0.298)  0.042  0.379

 Xt-5 is obtained from equilibrium curve as 0.208

yt 6  1.416(0.208)  0.042  0.252

 Xt-6 is obtained from equilibrium curve as 0.120

yt 7  1.416(0.120)  0.042  0.127

 Xt-7 is obtained from equilibrium curve as 0.048
 The number of theoretical plates are 7 plates
in the column
71 July 2012
Determination of Number of
Plates using Lewis Sorel Method

72 July 2012
 END
Summary