Subtopics

Vapor-Liquid Equilibrium
Types of Distillation
Mass Balance in a Distillation Column
Determination of Ideal Number of
Plates using Mc-Cabe Thiele Method
Multi components 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 point",

components concentrate in the liquid phase; the more
volatile, "light“ or “low boiling point”,
components concentrate in the vapor.

used for many commercial processes, such as

production of gasoline, distilled water, alcohol, and
many other liquids
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: ????

 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.

 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

xy 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 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
Pyi  Pi xisat
pi  Pi xi
o

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

12
 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:

 Pyi  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 P0A= 155.7 kPa
For toluene P0B= 63.3 kPa Raoult’s Law

Refer to equation Dalton Law: pi=Pi o xi

PAo x A  PBo (1  x A )  P

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

Dalton’s Law
Liquid composition;
xA=0.411 and
pA  pB  P
xB= 1-0.411=0.589 kPa

Vapor composition:

PAo x A
yA 
P
yA= (155.7 x 0.411)/101.32 = 0.632
yB= 1-0.632=0.368
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.
y A / 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
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 Raoult’s law,

PA0 116.9
 AB  0   2.54
PB 46.0

Similarly at 105ºC,

204.2
  2.38
86.0
Types of distillation column

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
 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

Trays/plates Distillate D
and/or which is
packings which richer in the
are used to more
enhance
component volatile
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 equimolar 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
Material –balance diagram for plate n Plate n
Ln, Vn+1
xn yn+1
Plate n+1
Ln+1 Vn+2,
Xn+1 yn+2
 Material balances for two
components systems
1. Total material balance on the entire
column
F=D+B

2. Component material balance on

component A

F xF= D xD+ BxB

W=B

Fig 1.10: Material balance for

continuous fractionating column
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
Ln D
yn 1  xn  xD
Vn 1 Vn 1
 R   1 
y  x  xD
 R  1   R  1 
where
Ln
R  Reflux ratio = constant
28 D
 Ln
R  slope
D
L R
R n 
Vn 1 R  1

29
 Operating Line: Rectifying
y

R 1
yn 1  xn  xD slope=R/(R+1)
R 1 R 1

1
xD
R 1

x
xD

30
 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:

Since equimolar flow is assumed ,the

slop is
Rearranging the equation : Lm
Vm 1
 Feed Line

 The conditions of the vapor rate or the liquid rate may change
depending of the thermal condition of the feed.

 It is related to the heat to vaporize 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
y q=1 q>1

Feed partial vapor 0<q<1

Feed at saturated vapour q=0 x=xf

Feed superheated q<0 q xF

yq  xq 
q 1 q 1
x

35
 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.

 No of trays = No of steps– 1(reboiler)

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 q-line 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
yn 1  xn  xD y
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 q-line 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 vapor.
 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 xD

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

1
xD
R 1

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

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

Minimum number 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.

D=0
Total reflux R=L/D=∞
F=0 L/V=1
R 1
yn 1 
R 1
xn 
R 1
xD 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 theoretical steps
 Can use Fenske equation to calculate Nmin

 xD
log .
1  xB  

 1  xD  xB 
N min 
ln  av

 (Ref. Transport Process and Separation Process Principles,

Geankoplis 4th ed. Page:716)
 Sometimes a column is operated in total reflux at startup
 MULTI COMPONENT SYSTEMS

Separation of more than two components.

Base on the relative volatility i value of
each components, (light or heavy
components)
A
A, B
Key component:
-light key
A, 1 2 -Heavy key
B,C

C
B
MULTICOMPONENT SYSTEM
 For non ideal solution (hydrocarbons), the
equilibrium data can be described by K factors
(distribution coefficient)

yi  K i x i
yi
Ki 
xi
 “K”= ratio of mole fraction in vapor and liquid
phases at equilibrium
 The value of K are available from Depriester
Chart.
Raoult’s law
(ideal system)
K (for non ideal
system-
dependant on T
and P)

y A  K A xA
 Phase equilibrium in multicomponent
 For ideal solutions, the equilibrium data
can be calculated from the Raoult’s and
Dalton’s Law
pi
pi  x Pi i
o
yi 
P
(Raoult’s Law) (Dalton’s Law)

x i Pio Pio p A PA x A
Ki   yA    K A xA
Px i P P P
Phase equilibrium in multicomponent
 Relative volatility (αi) for each component in a
multicomponent can be defined similar with
binary mixture.
 If component C in a mixture of A, B, C and D is
selected as the base component,

Ki Pio
i   ij  o
KC Pj
Phase equilibrium in multicomponent
 K factor strongly temperature dependent
because of the change in vapor pressure.

 The ratio of K factor is the same as the relative

volatility of components:

o
yi / x i K i Pi
 ij    o
y j / x j K j Pj
MULTICOMPONENT SYSTEM

Bubble Point
 ….initial boiling point of a liquid mixture.
 Must satisfy the relation yi=1.0

 y  K x
i i i  1.0

 The temperature is assumed and values

of Ki are obtained from vapor pressure
data and the known total pressure.
MULTICOMPONENT SYSTEM

Bubble Point
 If the summation Kixi > 1.0, a lower
temperature is chosen and repeat the
calculation until the equation is satisfied.

 If the summation Kixi = 1.0, the composition

of the vapor in equilibrium with liquid
Bubble Point
For a mixture of A, B, C and D with C as the base
component:
 Assume the temperature.
 Calculate the value of αi from the value of Ki at
this temperature.
 Calculate the value of KC from

K C  1.0
 x
i i

 Compare the temperature corresponding to

the calculated value of KC to the assumed
temperature.
Bubble Point
 If the values differ, the calculated temperature
is used for the next iteration.
 After the final temperature is known, the vapor
composition is calculated from

i x i
yi 
  i x i 
 Example 1
A liquid feed to a distillation tower at 405.3 kPa abs
is fed to a distillation tower.The composition in mole
fractions is as follows:
n-butane(xA=0.40),
n-pentane(xB=0.25),
n-hexane(xC=0.20),
n-heptane(xD=0.15).
Calculate the boiling point and the vapor in
equilibrium with the liquid. Let n-hexane will be the
base component.
Solution: Assume a temperature and find the K
values for all component.
Depriester Chart

T = 65oC
 Cont’
 Assuming T = 65oC

KC  1/ i xi  1/ 3.643  0.2745

Referring to figure 11.7-2,
at 0.2745, the T is 69oC.

Get the K value from Ki

from Depriester  ij 
Chart. Kj

For the second trial, use 69oC and follow the same procedure.
 MULTICOMPONENT SYSTEM
Dew Point
 ...initial condensation temperature
 Must satisfy the relation xi=1.0

 yi 
 xi      1.0
 Ki 
 Also trial and error calculation
 After final T is known, liquid composition calculated from

yi  i
xi 
  yi  i 
 EXAMPLE:
BOILING POINT,DEW POINT, AND FLASH
VAPORIZATION OF MULTICOMPONENT FEED
 A liquid feed to a distillation tower at 405.3 Kpa abs is fed to a
distillation tower. The composition in mole fractions is as follows:
 N-butane (xA=0.40)
 N-pentane (xB=0.25)
 N-hexane (xC=0.20)----------base component
 N-heptane (xD=0.15)
a) Calculate the boiling point of feed and composition of vapor in
equilibrium.
b) Calculate the dew point of feed and composition of liquid in
equilibrium.
SOLUTION

 a) Calculate the boiling point and composition of

vapor in equilibrium

 1) Assume 1st temperature = 650C

 2) Obtain value of K from Depriester Chart
 3) Construct temperature trial table
 4) Stop the iteration when the assumed temperature
gives same values with the exact temperature.
(means it is the bubble point)
 Trial 1 (Temperature = 650C)
Comp xi Ki αixi

A 0.40 1.68 6.857 2.743

B 0.25 0.63 2.571 0.643
C 0.20 0.245 1.000 0.200
D 0.15 0.093 0.380 0.057
Total 1.00 Σαixi = 3.643
Kc = 1/Σαixi = 1/3.643 = 0.2745 (690C)----get from
Depriester chart
* Since the final temperature is not same with the assume temperature,
do next trial using last temperature.
 Trial 2 (Temperature = 690C)
Comp xi Ki αixi

A 0.40
B 0.25
C 0.20
D 0.15
Total 1.00 Σαixi =
Kc = 1/Σαixi = 1/(……) = ……(….0C)----get from
Depriester chart
* Since the final temperature is not same with the assume temperature,
do next trial using last temperature.
 Trial 3 (Temperature = 700C)
Comp xi Ki αixi yi

A 0.40 1.86 6.607 2.643 0.748

B 0.25 0.710 2.522 0.631 0.178
C 0.20 0.2815 1.000 0.200 0.057
D 0.15 0.110 0.391 0.059 0.017
Total 1.00 Σαixi = 3.533 1.000
Kc = 1/Σαixi = 1/3.533 = 0.2830 (700C)----
get from Depriester chart
* Since the final temperature is same with the assume temperature, stop the iteration.
* The last value of temperature is called bubble point.
SOLUTION

 b) Calculate the dew point and composition of liquid

in equilibrium

 1) Assume 1st temperature = 1060C

 2) Obtain value of K from Depriester Chart
 3) Construct temperature trial table
 4) Stop the iteration when the assumed temperature
gives same values with the exact temperature.
(means it is the dew point)
 Trial 1 (Temperature = 1060C)
Comp yi Ki yi/αi

A 0.40 3.50 5.036 0.0794

B 0.25 1.54 2.216 0.1128
C 0.20 0.695 1.000 0.2000
D 0.15 0.330 0.4748 0.3159
Total 1.00 Σyi/αi = 0.7081
Kc = Σyi/αi = 0.7081 get temperature from
Depriester chart
* Since the final temperature is not same with the assume temperature,
do next trial using last temperature.
 Trial 2 (Temperature = 1070C)
Comp yi Ki yi/αi xi

A 0.40 3.55 4.931 0.0811 0.114

B 0.25 1.60 2.222 0.1125 0.158
C 0.20 0.720 1.000 0.2000 0.281
D 0.15 0.340 0.472 0.3178 0.447
Total 1.00 Σyi/αi =0.7114 1.000
Kc = yi/αi= 0.7114 -----Close to Kc actual
at (1070C)=0.720 (get from Depriester chart)
*Kc that have been calculated is close enough with Kc at 1070C from
Depriester Chart.
*Thus, the last value of temperature is called dew point.