CHAPTER 1

DISTILLATION
 Distillation

Physical Single
VLE Multistage
concept of stage
relationship distillation
distillation distillation

VLE of
VLE (pure Flash Batch
binary
substance) distillation distillation
mixture

Open Close
system system

Boiling point
VLE diagram
diagram

VLE Relative
composition volatility
 PHYSICAL CONCEPT OF DISTILLATION
Separated components
obtained for vapour &
liquid

Common separation
Vapour rich with
technique, consume
volatile component
a lot of energy

Original mixture contain

less volatile compound
PHYSICAL CONCEPTS OF DISTILLATION
(APPROACH IN EVAPORATION)

WHAT IS EVAPORATION?

Process of phase transformation from liquid phase to gas

phase or vapor phase
Tendency of liquid to change form to gas is called volatility
EVAPORATION PROCESS

Molecular
separation needs
energy, &
Intermolecular supplied by
forces must be surrounding or
overcome, external heating
Molecules of pulled away
liquids are held resulting much
close by weaker
intermolecular
forces (hydrogen
bonding, van
der waal
VAPOR LIQUID EQUILIBRIUM OF PURE SUBSTANCE

http://www.learnthermo.com/T1-tutorial/ch02/lesson-D/pg01.php
VAPOR LIQUID EQULIBRIUM IN DIFFERENT SYSTEM

OPEN SYSTEM CLOSE SYSTEM

Evaporation occur continuously, Liquid evaporate & accumulate over

until all liquid transform into vapour the liquid surface, & transform back
phase to original liquid itself, while liquid still
evaporating

One way process only, evaporation Two way process. Until certain time,
rate is much higher than the rate of evaporation will be the same
condensation rate, depend on as condensation rate (dynamic
surrounding equilibrium state).
CONT
CLOSE SYSTEM OPEN SYSTEM
 BOILING POINT DIAGRAM
Boiling point of
liquid B Mixture entirely
vapour

Dew point
Saturated vapour
start to condense

Bubble point Boiling point of

Liquid start to boil liquid A

Mixture
completely
liquefied
 5 SEPARATE REGIONS IN B.P DIAGRAM
Region a
Superheated vapour region is a region where the vapours is not about to condense
(not a saturated vapour). A superheated vapour has a temperature greater than the
saturation temperature for the pressure.
Region b
Liquid phase region is the region that lies just beneath the bubble point line (sub-
cooled liquid mixtures exist). The temperature in this region is less than its bubble
point.
Region c
Equlibrium vapor-liquid region is a region enclosed in between upper dew point line
and lower bubble point line (vapour & liquid coexist in dynamic phase equilibrium).
Region d
Saturated liquid region lies along bubble point line. This is region where liquid
mixture is just about to bubble its first vapor bubble.
Region e
Saturated vapor region is lies along dew point line. In this region, all the vapours are
about to condense.
 VLE DIAGRAM
Mole fraction of
component 1 in vapour Curve line represented
phase > liquid phase equilibrium composition of
(component 1 more liquid & vapour at constant
volatile compare to P
component 2

Equilibrium curve shows

the relationship between
compositions of residual
liquid and vapour that are
in dynamic phase
equilibrium.
PREDICTION OF VLE COMPOSITION
FOR BINARY MIXTURE
 RAOULTS LAW
Raoults law states that; the partial pressure of a component in the
vapor phase is equal to the mole fraction of the component in the
liquid multiplied by its pure vapor pressure at that temperature.
Raoults law equation for component A as follows:
PA = xAPA

where PA = partial pressure of A in vapor phase

xA = mol fraction of A in liquid phase
PoA= vapor pressure of pure A at the temperature
 DALTONS LAW
Daltons law states that the resultant total pressure of the
container is the summation of partial pressures of each of all
the gases that make up the gas mixture.
PT = PA + PB
Dalton also states that the partial pressure of a gas (PA) is:
PA = yAPT
Where yA = mol fraction of A in vapor phase
PT = total pressure of the system
PA = partial pressure of A in vapor phase
PB = partial pressure of B in vapor phase
From those equations,
From Dalton law PT = P A + PB
Substitute PA = xAPA and PB = xBPB from Raoults law yield:
PT = xAPA + xBPB
= xAPA + (1- xA)PB

After rearranging, we obtain:

xA = (PT - PB)/(PA - PB)
and, yA = xAPA/ PT
Normally the subscript A for mol fraction is dropped. For binary solution it
is understood that mol fraction x and y refer to xA and yA respectively.
Thus;
x = (PT - PB)/(PA - PB) .(1)
y = xAPA/ PT ...........(2)
RELATIVE VOLATILITY OF
MIXTURE
 RELATIVE VOLATILITY
Separations of components by distillation process depend on
the differences in volatilities of components
The greater the difference in their volatility, the better is the
separation by heating (distillation).
One way to measure the difference in volatility of components
is by calculating the relative volatility of component A to B;
AB.
Relative volatility of A to B (AB) measure how many times
component A is more volatile than component B.
 RELATIVE VOLATILITY CONT..
The value of AB = unity (1) means that component A is as volatile as B
and the separation by heating becomes impossible.
The greater the value of AB, the better and easier is the separation by
heating.
Relative volatility of A to B expressed mathematically as;
AB = yA/xA
yB/xB
= yA.xB
yB.xA
For non-ideal solution, the values of AB change with temperature. For an
ideal solution, the values of AB does not change with temperature. For a
solution that approaches ideal solution, its AB would be fairly constant.
 EXERCISE 1
A liquid mixture is formed by mixing liquid n-heptane and liquid n-octane
in a closed container at constant external pressure of 1 atm (101.3 kPa).
a) Calculate the equilibrium compositions of vapor and liquid.
b) Plot a boiling point diagram for the system.
c) Plot an equilibrium curve for the system.
d) Calculate the relative volatility for all temperature.
Use the following list of vapor pressures for pure liquids n-heptane and n-
octane at various temperatures forpressure
Vapour the calculation.
(kPa) of pure
T(K) n-heptane n-octane
371.6 101.3 -
374.0 110.8 56.9
377.0 122.6 62.3
380.0 134.4 67.6
383.0 146.2 73.0
386.0 158.0 78.4
389.0 169.8 83.8
392.0 181.5 89.1
395.0 193.5 94.5
398.0 - 101.3
 FLASH
DISTILLATION
SCHEMATIC DIAGRAM FOR CONTINUOUS
FLASH EQUILIBRIUM PROCESS

V moles/h
equilibrium vapor
V, vapor y*

F moles/h liquid L, liquid

mixture feed
xF
separator
heater Expansion
Steam in condense valve
out L moles/h equilibrium
residual liquid
x*

xF is the initial mol fraction of A in feed

y* is the equilibrium mol fraction of A in the vapor
x* is the equilibrium mol fraction of A in the residual liquid
CONTINUOUS FLASH EQUILIBRIUM
A liquid mixture feed, with initial mole fraction of A at xF , is
pre-heated by heater and its pressure is then reduced by an
expansion valve.
At lower P, the hot liquid will boil at lower temperature inside
a separator drum.
The evolved vapor is allowed to attain an equilibrium with the
remaining liquid inside the flash drum(separator).
EQUILIBRIUM COMPOSITION OF VAPOR &
LIQUID FOR FLASH DISTILLATION
Consider a binary liquid mixture is to be separated by a flash
distillation process.
The binary is composed of two components; A as a low boiler
(more volatile) and B as a high boiler.
When the system has attained its equilibrium, the material
balance equation for the system can be written as follows:
Total mass balance: F = V + L
Mass balance of A: xFF = y*V + x*L
xF = y* V/F + x* L/F -----(2.1)
* just denote at the state of equilibrium
 EQUILIBRIUM COMPOSITION OF VAPOR &
LIQUID FOR FLASH DISTILLATION CONT
Assign f to denote fraction of the feed which has been
vaporized. f is defined mathematically as: f = V/F
Substitute f in the total mass balance equation:
(divide by F) F=V+L
1 = V/F + L/F
1 = f + L/F
L/F = 1 f ------------(2.2)
Substituting 2.2 in 2.1 to obtain:
xF = y*f + x*(1-f)
y* = (f-1)x* + xF ----------(2.3)
f f
 OPERATING LINE
To obtain x* and y*, draw the operating line and the
equilibrium curve on the same graph as shown below.

Equilibrium curve
y Operating line

y*
y =x

xF,xF

x
x*
OPERATING LINE EQUATION CONT
The point at the intersection of the operating line and the
equilibrium curve gives the value of x* and y* that we seek since it
satisfy both the operating and equilibrium conditions.
To draw operating line, we simply take any two points on the line
and connect them.
Lets find what happens if we substitute x* = xF in equation 2.3 to
obtain one point on the line:
y* = (f-1)x* + xF ----------(2.3)
f f
y* = xF
Thus, one point on the operating line is already known i.e. (xF,xF).
To find the other point, we simply pick any convenient value for x*
and substitute in equation 2.3 to obtain y*.
 EXAMPLE 1
A liquid mixture containing 70 mol % n-heptane (A) and 30
mol % n-octane at 30C is to be continuously flash-vaporized
at the standard atmospheric pressure to vaporize 60 mol % of
the feed. What will be the compositions of the vapor and
liquid and the temperature in the separator for an equilibrium
stage? The equilibrium data for n-heptane-n-octane mixture
at 1 atm and 30C is given as follows:
The equilibrium data for n-heptane-n-octane
Solution:
Basis: 100 moles of liquid feed (F)
Given, xF = 0.7
V = 0.6 (100) f = V/F
= 60 mols = 0.6
 EXAMPLE 1 CONT
We want to find equilibrium compositions of vapor and liquid;
y* and x*
The operating line: y* = (0.6 - 1) x* + 0.7
0.6 0.6
y* = -0.667x* + 1.167
From the intersection of the operating line and equilibrium
curve as shown in graph,
Equilibrium mol fraction of n-heptane in liquid, x* = 0.62
Equilibrium mol fraction of n-heptane in vapor, y* = 0.76
The temperature of the separator at equilibrium ~ 378C.
 EXAMPLE 2
A feed containing 0.482 mol fraction methyl alcohol (A) and
0.518 mol fraction water (B) is to be partially vaporized by
simple equilibrium distillation. How many moles of vapor
should be removed per 100 moles feed to give a vapor
composition of 0.729 methyl alcohol if the total vapor
pressure is 760 mm Hg? The equilibrium data for methyl
alcohol-water mixture at the conditions is given as follows:
x y x y
0.000 0.000 0.400 0.729
0.020 0.134 0.500 0.779
0.040 0.304 0.700 0.870
0.080 0.365 0.800 0.915
0.100 0.418 0.900 0.958
0.150 0.517 0.950 0.979
0.200 0.579 1.000 1.000
0.300 0.665 - -
 EXAMPLE 2 SOLUTION
Basis: 100 moles
Given:
xF = 0.482
y* = 0.729
We want to find f
Sine we know y*, we can obtain x* from the plotted
equilibrium curve: x* = 0.400
Substitute y* and x* in the operating line equation:
0.729 = (f-1)0.400 + 0.482
f f
f = 0.249
V = fF = 0.249(100) = 24.9 moles of vapor is
removed
BATCH DISTILLATION
 WHAT IS BATCH DISTILLATION?
Also call as
differential
distillation

Only one
Condensed vapor
BATCH vaporization
form as fast as it
DISTILLATION involve (one liquid
forms
surface)

Boiling L in pot,
withdrawn vapor
form
 RALEIGH EQUATION FOR IDEAL & NON-IDEAL
MIXTURES
Consider a typical differential distillation at an initial
time, t1 as shown below:
Steam jacket

Steam in
condenser
dx dL

L
x
distillate
Where, L = number of moles of liquid mixture in the pot
x = mol fraction of a more-volatile component (component A)
dx = infinitesimal change of mol fraction of A
dL =infinitesimal change of mol of liquid
 DIFFERENTIAL DISTILLATION AT CERTAIN
INFINITE TIME LAPSE (t)
Consider the differential distillation at certain infinitesimal time
lapse (t) at t2 where t2 = t1 + t , after an infinitesimal amount of
liquid has vaporized as shown below:
Steam jacket

Steam in y
condenser

L - dL
x - dx
distillate

Mass balance of component A will yield:

xL = (x-dx)(L-dL) + y(dL)
 DIFFERENTIAL DISTILLATION AT CERTAIN
INFINITE TIME LAPSE (t) CONT
xL = xL x.dL L.dx + dx.dL + y.dL
L.dx = -x.dL + y.dL
L.x = (y-x)dL
dL = dx
L (y x)
Integrating both sides within limit initials (t1) to final (t2)
x1
In (L L ) = (1/y-x)dx .(3.1)
1/ 2
x2

Where, L1 = number of moles of liquid at t1

L2 = number of moles of liquid residue at t2
x1 = mol fraction of A in liquid at t1
x2 = mol fraction of A in liquid at t2
 RALEIGH EQUATION
Equation 3.1 is known as the Raleigh equation which
is applicable for both and ideal solution ( constant)
and non-ideal solution ( non-constant).
x1
The term (1/y-x)dx
x2

must be evaluated graphically by determining area

under the graph of (1/y-x) versus x between the
limit x1 and x2.
 EXAMPLE 1
A liquid mixture containing 50 mol % n-heptane (A) and 50
mol % n-octane (B) was subjected to a differential distillation
at atmospheric pressure with 60 mol % of the liquid being
distilled. Compute the composition of the distillate and the
residue. The vapor-liquid equilibrium data for n-heptane-n-
octane mixture is given as follows:
x y
1.000 1.000
0.655 0.810
0.487 0.674
0.312 0.492
0.157 0.279
0.000 0.000
GRAPH 1/(y-x) VS x FOR n-heptane-octane
SYSTEM
 EXAMPLE 2
100 moles of ethanol-water solution containing
18% by mole ethanol is subjected to a batch
distillation to reduce the ethanol content to 6%.
Determine the fraction of the liquid that has
been distilled, and the average composition of
the distillate. Ethanol forms a non-ideal solution
with water.
 x y
0.0000 0.0000
0.0190 0.1700
0.0721 0.3891
0.0966 0.4375
0.1238 0.4704
0.1661 0.5089
0.2337 0.5445
0.2608 0.5580
0.3273 0.5826
0.3965 0.6122
0.5079 0.6564
0.5198 0.6599
0.5732 0.6841
0.6763 0.7385
0.7472 0.7815
0.8943 0.8943
1.0000 1.0000
GRAPH 1/(y-x) VS x FOR CH3CH2OH-H2O
SOLUTION
 SIMPLIFIED RALEIGH EQUATION FOR
IDEAL MIXTURES
For an ideal solution ( constant), the Raleigh can be
simplified.
Consider a simple batch distillation process at an
initial time, t1 as shown below:
Steam jacket

Steam in dL = dA + dB
y condenser
L 1 = A1 + B1
x

distillate
 SIMPLIFIED RALEIGH EQUATION FOR
IDEAL MIXTURES CONT
Where,
L1 = number of moles of a binary liquid mixture containing A and B
at time t1
A1 = number of moles of component A in L1 at time t1
B1 = number of moles of component B in L1 at time t1
x1 = mol fraction of component A in L1 at time t1
dL = infinitesimal amount of liquid that has vaporized
dA = infinitesimal amount of component A that has
vaporized
dB = infinitesimal amount of component B that has
vaporized
 SIMPLIFIED RALEIGH EQUATION FOR
IDEAL MIXTURES CONT
From definitions,
dA dB
yA = yB =
dA + dB dA + dB

A B
xA = xB =
A +B A + B

Since is constant for an ideal mixture:

dA B
yA/xA x
dA + dB A + B
AB = =
dB A
yB/xB x
dA + dB A + B
 SIMPLIFIED RALEIGH EQUATION FOR
IDEAL MIXTURES CONT
B.dA
After simplifying, AB =
A.dB

Rearranging, dB dA
.AB =
B A
Integrating within limits of t1 to t2,

dB dA
.AB =
B A
 SIMPLIFIED RALEIGH EQUATION FOR
IDEAL MIXTURES CONT
Since AB is constant,
B2 A2 ________ (3.2)
AB.ln ( )= ln ( )
B1 A1
Equation 3.2 is known as the simplified Raleigh
equation for simple batch distillation which is
applicable only for ideal solutions.
 EXAMPLE 1

100 Ib moles of a liquid solution is charged into a

distillation unit. This solution contains 0.20 mol fraction
of A and 0.80 mol fraction of B. If the mixture is
subjected to a simple batch distillation, what will the
residual liquid and distillate composition be after 8 Ib
moles of component A has been removed with the
vapor. Assume that AB is constant at 1.414.
 EXAMPLE 1 SOLUTION
Basis: 100 Ib moles liquid solution feed (L1)
A1 = 20 Ib moles
B1 = 80 Ib moles
A2 = 20-8 = 12 Ib moles
We want to find x2
The Raleigh equation, AB.ln(B2/B1) = ln(A2/A1)
1.414 ln (B2/80) = ln (12/20)
B2 = 55.76 Ib moles
x2 = A2/ (B2 + A2) = 12/(55.76 + 12) = 0.177
 EXAMPLE 1 SOLUTION CONT...
Thus, the composition of the residual liquid is 17.7
mol % A and 82.3 mol% B.
y2 = 8/(8 + 80 -55.76) = 0.248
Thus, the composition of the distillate is 24.8 mol% A
and 75.2 mol % B.
MULTI-STAGES DISTILLATION
 RECTIFICATION

DEFINITION
Vapor and the liquid are repeatedly and continuously
heated to obtain much pure bottom and overhead
products.
 DISTILLATION COLUMN
Va moles/h vapour
ya moles/moles A

Vapour rise up
and bubbles
through the liquid

Condenser
Distillate

Enriching
section
Liquid falls down
F moles/h

xF moles/h Accumulator
LR moles/h Reflux
xR moles/moles A
Stripping
Reflex
section D moles/h overhead product
pump
xD moles/moles A
Vb moles/h vapour
yb moles/moles A
Trays/Plates
Lb moles/h liquid B moles/h Bottom product
Reboiler
x moles/moles A xB moles/moles A
 DISTILLATION COLUMN
COMPONENTS
REBOILER -> Heats the liquid
ACCUMULATOR -> Accumulate all condense liquid
STRIPPING SECTION -> More volatile component (MVC)
is vaporised
ENRICHING/ENRICHING SECTION -> Less volatile component (LVC)
is condensed
TRAYS/PLATES -> Encourage vapour liquid contact
PACKING -> Alternative to trays
CONDENSER -> Vapour from column is cooled to liquid
REFLUX PUMP-> Condensed vapour can be returned to column
TOP PRODUCT -> From condenser
BOTTOM PRODUCT -> From reboiler
PRINCIPLE OPERATION
Vapour and liquid are bought in continuous &
counter-current

Vapour rise from lower tray & bubble through ,

mixes with the liquid on the upper tray

Vapour will pick up more A from liquid while liquid

will be richer with B

As the vapour rises up, it becomes richer with A but

poor with B

As the liquids falls down, it becomes poorer A with

but richer with B

Finally, we obtain a bottom product and an overhead

product of higher purity
 ENRICHING SECTION
A. ENRICHING FLOW
Part of distillation tower called
enriching section.
Condenser at the top of the
column cools the vapour,
collected in the accumulator.
A portion is returned to the
column as reflux.
Remainder is removed as Reflux ratio (R) =
Distillate or Top Product. number of mole of liquid returned back to
Mass balance on flowrates : the tower (L)

Vapour = Liquid + Distillate number of mole of liquid removed as

distillate (D)
 STRIPPING
STRIPPINGSECTION
SECTION
A. STRIPPING FLOW
Built up from the bottom up of the fractionator tower
to the feed plate.
Feed flows down column to reboiler.
Reboiler heats liquid to boiling point & vapour rises.
Liquid that does not vaporise is removed as Bottoms.
Vapour rises & is forced into contact with falling liquid.
On the trays, some liquid reboils & some vapour
condenses due to heat transfer between phases, more
stages created.
 CONT.

F moles/h feed
in Stripping section
xF mol/mol A
plate m 1

CU
plate m CU
T T

Vm + 1, ym + 1 Lm ,
xm

plate m + 1

Vb moles/h vapour B moles/h bottom

yb mol/mol A product
xB mol/mol A
Lb moles/h liquid Reboiler
xb mol/mol A Reboiler
boundary
MAC-CABE THIELE METHOD

A simple graphical method to determine

the number of ideal stages which are
required in order to obtain a specified
separation by a multi-stages continuous
distillation.
 MAC-CABE THIELE
ASSUMPTIONS
Sensible heat is negligible relative to heat
of vaporization.
All components have approximately
equivalent molal heat of vaporization.
Heat losses from the fractionator is
negligible.
Heat of mixing between vapor and liquid
is negligible.
 MAC-CABE THIELE METHOD
To determine the ideal (real) stages, we need to draw the enriching line, the
stripping line, the feed line, and the equilibrium curve on the same graph.

1. If not given, the equilibrium curve should be drawn first using the data
supplied. Then, draw the line y = x.
2. Draw the enriching operating line (ROL) by locating and joining the
points (xD,xD) and (0,xD/(R+1)). Note that the point (xD,xD) is on y=x line.
3. Determine the value of q and then draw the feed line (q-line);
y=(q/(q-1))x xF/(q-1) by joining point (xF,xF) to any other point which is
convenient to you.
4. Draw the stripping line by joining the point (xB,xB) to the interception
point where the enriching line across the feed line.
5. The number of ideal stages can be determined graphically by drawing
steps joining points (xB,xB) with (xD,xD). Each step represent one ideal
stage.
 OVERALL PLATE EFFICIENCY

Overall efficiency (%) = number of theoretical (ideal) plates 1 x 100%

number of real plates

0.8 = 3 1/number of real plates

0.8 = 2/number of real plates

Number of real plates = 2/0.8 =

 THE q LINE

To show the feed condition on the x-y

diagram.
Obtained by writing the two operating lines
at their intersection, at plate n and plate m
(the feed plate).
An enthalpy balance on the feed plate :

q = (Cp(Tb Tf)) + ) /
THE q LINE EQUATION
THE q LINE & FEED
CONDITION
 EXAMPLE 1
A mixture of benzene and toluene is fed to an intermediate
point of a continuous fractionating column. The feed
contains 45 mole % benzene (A) and 55 mole % toluene. A
distillate containing 92 mole % benzene and 8 mole %
toluene is obtained while the bottom contains 15 mole %
benzene and 85 mole % toluene. One mole of distillate is
removed for every 4 moles returned to the unit as reflux. The
feed enters at 131 oF and the unit operates at atmospheric
pressure.

a) Draw the enriching and stripping operating lines and the

feed line.
b) Determine the number of ideal plates required for the
 CONT
The following data for benzene-toluene mixture at 1 atm can
be used:

Molal heat capacity of the liquid mixture (Cp)= 40

Btu/(lbmoloF)
Molal heat of vaporization of the mixture () = 13700
Btu/lbmole
The atmospheric boiling point (Tb) = 210oF
The temperature of feed enter (Tf) = 131oF
The equlibrium data (mole fraction of benzene) is given as
follows:
 CONT

x y
1.000 1.000
0.773 0.897
0.659 0.831
0.555 0.757
0.459 0.678
0.370 0.591
0.288 0.496
0.211 0.393
0.141 0.281
0.075 0.161
0.013 0.031
0.000 0.000
McCABE-THIELE DIAGRAM

Feed
plate
location =
4
 LIMITING OPERATING
CONDITIONS
A. INFINITE REFLUX
As the reflux ratio (R)
increased, by reducing
D, the y-intercept
xD/R+ 1 of the enriching
line approaches zero
(the enriching line
approaches y = x line),
number of ideal plates
also reduced.
 CONT.

B. MINIMUM REFLUX RATIO

As the reflux ratio (R)
decreased, by increasing
D, the operating lines
(enriching & stripping)
move towards the
equilibrium curve, number
of required theoretical
plates increases
 EXAMPLE 2

A continuous distillation column is required to

separate a mixture containing 0.695 mole fraction
heptane (A) and 0.305 mole fraction octane to give
products of 95 % purity. The feed is liquid at its
boiling point.

a) Determine the minimum of reflux ratio.

b) Calculate the number of theoretical plates if
R = 2Rmin.
EQUILIBRIUM DATA (MOLE
FRACTION n-heptane)

x y
0.1 0.188
0.2 0.343
0.3 0.475
0.4 0.588
0.5 0.686
0.6 0.767
0.7 0.840
0.8 0.901
0.9 0.955
END OF CHAPTER 3