CHAPTER 1: DISTILLATION

 Part 1
 Definition & process description
 Physical concept of distillation
 Vapor-liquid equilibrium relationship
 Relative volatility
 Batch distillation –Part 2
 Continuous distillation –Part 3
 Azeotropic distillation -Part 4
 Multicomponent distillation –Part 5
1.1: Definition & process description
 Distillation is a process of separating various
components of a liquid solution by heating the liquid to
forms its vapors and then condensing the vapors to
form the liquid.
 It is use to separate 2 or more substances present in
the liquid OR for purification purpose.
 Distillation is a commonly used method for purifying
liquids and separating mixtures of liquids into their
individual components
 Allcomponents presents in both
phases
 Familiar examples include
1) distillation of crude fermentation broths
into alcoholic spirits such as gin and
vodka
2) fractionation of crude oil into useful
products such as gasoline and heating oil.
3) In the organic lab, distillation is used for
purifying solvents and liquid reaction
products.
1.1: Definition & process description

Other definition
 Distillation is done by vaporizing a definite fraction
of a liquid mixture in a such way that the evolved
vapor is in equilibrium with the residual liquid
 The equilibrium vapor is then separated from the
equilibrium residual liquid by condensing the vapor
Laboratory / Testing
1.2: Physical Concept of distillation
 Carried out by either 2 principal methods
 First method: based on the production of a
vapor by boiling the liquid mixture to be
separated and condensing the vapors without
allowing any liquid to return to the still - NO
REFLUX (E.g. Flash, simple distillation)
 Second method: based on the return part of
the condensate to the still under such
condition that this returning liquid is brought
into intimate contact with the vapors on
their way to the condenser – conducted as
continuous / batch process (E.g. continuous
distillation)
1.3:Vapor – liquid equilibrium
DEFINITION:
 EVAPORATION: The phase transformation
processes from liquid to gas/vapor phase
 VOLATILITY: The tendency of liquid to change
form to gas/vapor phase
a) VAPOR – LIQUID EQUILIBRIUM OF AN
ORDINARY BINARY LIQUID MIXTURE
b) PREDICTION OF VAPOR – LIQUID
EQUILIBRIUM COMPOSITIONS FOR
ORDINARY BINARY MIXTURES
a) VAPOR – LIQUID EQUILIBRIUM OF AN
ORDINARY BINARY LIQUID MIXTURE

 Equilibrium curve: shows the relationship

between composition of residual liquid and
vapor that are in dynamic phase equilibrium.
The curve will be very useful in calculations to
predict the number of stages required for a
specified distillation process.
VAPOR – LIQUID EQUILIBRIUM
CURVE
 b) Prediction of vapor-liquid equilibrium
compositions for ordinary binary mixtures
 Raoult’s Law for ideal solution & Dalton’s Law of
partial pressure can be manipulated in order to
calculate compostions of liquid and vapor, which are
in equilibrium.
 Raoult’s Law – 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 the temperature:
pA = xA · PAo
pA = partial pressure of A in a vapor phase
xA = mole fraction of A in liquid phase
PAo = vapor pressure of A at the temperature
Prediction of vapor-liquid equilibrium
compositions for ordinary binary mixtures
 For a mixture of the different gases inside a
close container, Dalton’s law stated that the
resultant total pressure of the container is the
summation of partial pressures of each of all
gases that make up the gas mixture:
PT = pA + pB
 Dalton also state that the partial pressure of gas
(pA) is:
pA = yA · PT
pA = partial pressure of A in vapor phase
yA = mole fraction of A in vapor phase
PT = total pressure of the system
Phase Rule
Example:
Calculate the vapor and liquid compositions in
equilibrium at 95oC (368.2K) for benzene-toluene
using the vapor pressure from Table 11.1-1 at
101.32 kPa. Table 11.1-1
Solution
 1.4: Relative volatility (α) of a mixture
 Separations of components by distillation
process depends on the differences in
volatilities of components that make up the
solution to be distilled.
 The greater difference in their volatility, the
better is separation by heating (distillation).
Conversely if their volatility differ only slightly,
the separation by heating becomes difficult.
Relative volatility (α) of a mixture
 The greater the distance between the equilibrium
line & 45o line, the greater the difference the
vapor composition and a liquid composition.
Separation is more easily made.
 A numerical measure of ‘how easy’ separation –
relative volatility, αAB
 αAB – relative volatility of A with respect to B in
the binary system
 Relative volatility – ratio of the concentration of A in
the vapor to the concentration of A in liquid divided by the
ratio of the concentration B in the vapor to the
concentration of B in the liquid:
Relative volatility (α) of a mixture
y A / xA y A / xA
 AB  
y B / xB (1  y A ) /(1  x A )
αAB – relative volatility of A with respect to B in the
binary system
 If the system obeys Raoult’s law for an ideal
system:
PA x A PB xB PA x A
yA  yB   AB  yA 
PT PT PB 1  (  1) x A

 Separation is possible for > 1.0

Relative volatility (α) of a mixture
 Separation is possible for > 1.0
 For non-ideal solution, the values of change
with temperature.
 For ideal solution, the values of doesn’t
change with temperature.
 For solution that approaches ideal solution,
its would fairly constant.
Relative volatility (α) of a mixture
Example:
Using the data from table below, determine
the relative volatility for the benzene-
toluene system at 85°C and 105°C
Exercise 1
A liquid mixture is formed by mixing n-hexane (A) & n-
octane (B) in a closed container at constant pressure of 1
atm (101.3kPa).
i. Calculate the equilibrium vapor and liquid composition
of the mixture at each temperature
ii. Plot a boiling point diagram for n-hexane
iii. Plot an equilibrium diagram for the mixture
iv. Calculate the αAB at 100 °C
Use the following list of vapor pressure for pure n-heptane & n-octane
at various temperature.

Vapor Pressure

Temperature n-Hexane n-Octane

(°C) kPa mm Hg kPa mm Hg

68.7 101.3 760 16.1 121

79.4 136.7 1025 23.1 173

93.3 197.3 1480 37.1 278

107.2 284.0 2130 57.9 434

125.7 456.0 3420 101.3 760

Solution
Vapor Pressure

Temperature n-Hexane (A) n-Octane (B)

(°C) kPa XA YA kPa XB YB

68.7 101.3 1 1 16.1 0 0

79.4 136.7 0.6884 0.9290 23.1 0.3116 0.071

93.3 197.3 0.4007 0.7804 37.1 0.5993 0.2196

107.2 284.0 0.1920 0.5383 57.9 0.8080 0.4617

125.7 456.0 0 0 101.3 1 1

PART 2
Flash & batch distillation
 Flash (equilibrium) distillation
 Simple batch distillation
Flash (Equilibrium) Distillation
 Flash distillation – a single stage process because it has
only one vaporization stage (means one liquid phase is
expected to one vapor phase)
 The vapor is allowed to come to equilibrium with the liquid
 The equilibrium vapor is then separated from the
equilibrium residual liquid by condensing the vapor
 Flash distillation can be either by batch or continuous
Flash (Equilibrium) Distillation
 As illustrated in Figure 3, a liquid mixture feed, with
initial mole fraction of A at XF, is pre-heated by a
heater and its pressure is then reduced by an
expansion valve.
 Because of the large drop in pressure, part of liquid
vaporizes.
 The vapor is taken off overhead, while the liquid
drains to the bottom of the drum
 The system is called “flash” distillation because the
vaporization is extremely rapid after the feed enters
the drum.
 Now, we interested to predict the composition (x
and y) of these vapor and liquid that are in equilibrium
with each other.
Flash (Equilibrium) Distillation
Flash (Equilibrium) Distillation
Example
 A liquid mixture containing 70 mol% n-heptane
(A) and 30 mol % n-octane (B) at 30oC is to be
continuously flash at the standard atmospheric
pressure vaporized 60 mol% of the feed.
Determine
1) the compositions of vapor and liquid for n-
heptane
2) temperature of the separator for an equilibrium
stage?
The equilibrium data for n-heptane – n-octane
mixture at 1 atm and 30°C is given as follows:
T (K) xA yA
371.6 1 1
374 0.825 0.92
377 0.647 0.784
380 0.504 0.669
383 0.387 0.558
386 0.288 0.449
389 0.204 0.342
392 0.132 0.236
395 0.068 0.132
398.2 0 0
Solution
Basis = 100 moles of liquid feed (F)
Given, xF = 0.7
V = 0.6(100) = 60 moles f = V/F = 60/100 = 0.6

We want to fine the equilibrium composition of liquid and

liquid; y* & x*

The operating line: y* = (0.6-1)x* + 0.7

0.6 0.6
= -0.667x* + 1.167
From the intersection of the operating line & the equilibrium
curve as shown in the 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 ≈ 378oC
Determination of vapor-liquid equilibrium
composition for a flash distillation of n-heptane/n-
octane mixture
1.2

y, mol fraction of n-heptane in vapor

1

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
x, mol fraction of n-heptane in liquid

Figure: Equilibrium curve and operating line

Determination of equilibrium temperature for a flash
distillation of n-heptane-n-octane mixture

400 400

395 395
Temperature (K)

390 390

385 385 y

380 380

375 375

370 370
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x Mol fraction of n-heptane in vapor (y) and liquid (x)

Exercise 11.2-1 (page 752)
A mixture of 100 mol containing 60 mol%
n-pentane (A) and 40 mol% n-heptane (B) is
vaporized at 101.32 kPa abs pressure until 40
mol of vapor and 60 mol of liquid in
equilibrium with each other are produced.
This occur in a single stage system, and the
vapor and liquid are kept in contact with each
other until vaporization is complete.
Determine the composition of the vapor and
liquid.
The equilibrium data are as follows, where
x and y are mole fraction of n-pentane.
x (mol fraction of n- y (mol fraction of n-
pentane in liquid) pentane in vapor)

1.000 1.000
0.867 0.984
0.594 0.925
0.398 0.836
0.254 0.701
0.145 0.521
0.059 0.271
0 0
Answer:
xA = 0.430
yA = 0.854
Simple batch distillation
 Simple batch distillation which is also known as
differential distillation refer to a batch distillation in
which only one vaporization stage (or one exposed
liquid surface) is involved.
 Simple batch distillation is done by boiling a liquid
mixture in a stream-jacketed-kettle (pot) and the
vapor generated is withdrawn and condensed
(distillate) as fast as it forms.
 The first portion of vapor condensed will be richest in
the more volatile component A. As the vaporization
proceeds, the vaporized product becomes leaner in A.
Simple batch distillation
Simple batch distillation
1. Raleigh equation for ideal and non-ideal mixtures
 Consider a typical differential distillation at an
instant time, t1 as shown below:
Simple batch distillation
Now consider that the differential distillation at certain infinitesimal time
lapse,(dt), at t2 where t2=t1 + dt, after an infinitesimal amount of liquid has
vaporized as shown below:
Simple batch distillation

Applicable for ideal and

non-ideal solution
Simple batch distillation
The average composition of total material
distilled yav can be obtained by material
balance: (integrate from Rayleigh equation)

L1 x1  L2 x2  ( L1  L2 ) yav
L1 x1  L2 x2  Vyav
Simple batch distillation
2. Simplified Raleigh equation for ideal mixture

Consider a simple batch distillation process at

an initial time, t1, as shown below
Simple batch distillation

L1=no of moles of binary mixture

dL= dA + dB containing A and B at t1
y
A1= no of moles comp A in L1 at t1
B1= no of moles comp B in L1 at t1
x1= mol fraction of A in L1 at t1
dL= infinitesimal amount of liq that
L1= A1 + B1 has vaporized
X1
dA=infinitesimal amount of A that
has vaporized
dB = infinitesimal of B that has
vaporized
Simple batch distillation
 We know from definitions,
 dA   dB 
yA    yB   
 dA  dB   dA  dB 
 A   B 
xA    xB   
 A  B   A  B 
 Since  AB is constant for an ideal mixture,
dA B

 dA  dB A  B
y A / xA
 AB 
y B / xB dB A

dA  dB A  B
 After simplifying,
B  dA
 AB 
A  dB
 Rearranging,
dB dA
  AB 
B A
Simple batch distillation
 Integrating within the limits of t1 and t2,
B2 A2
dB dA

B1
B
  AB  
A1
A
 Since  AB is constant,
B2 A2
dB dA
 AB 
B1
B
 
A1
A
 AB ln B BB2  ln A AA2
1 1

 B2   A2 
 AB ln   ln   Eq.(5)
 B1   A1 
 Equation 5 known as simplified Raleigh
equation for simple batch distillation which
applicable for ideal solution.
Simple batch distillation
Example 1
A mixture of 100 mol containing 50 mol% n-pentane and 50
mol% n-heptane is distilled under differential (batch) conditions at
101.3 kPa until 40 mol is distilled. What is the average
composition of the total vapor distilled and the composition of
the n-pentane in the liquid left. The equilibrium data as follows,
where x and y are mole fractions of n-pentane: xA yA
1.000 1.000
0.867 0.984
0.594 0.925
0.398 0.836
0.254 0.701
0.145 0.521
0.059 0.271
0 0
Solution
xA yA 1/(yA –xA)

1.000 1.000 -

0.867 0.984 8.5470

0.594 0.925 3.0211

0.398 0.836 2.2831

0.254 0.701 2.2371

0.145 0.521 2.6596

0.059 0.271 4.7170

0 0 -
Solution
 Given L1 = 100 mol V (mol distilled) = 40 mol
 From material balance:
L1  L2  V L2  L1  V  100  40 L2  60 mol

 Substiting into Eq. (4)

x1 0.5
 L1   1   100   1 
ln  
 L2 
 
x 2
y  x
dx

ln
 60

  
x2 
y  x
dx

0.5
 1 
0.510   
x2 
dx
yx

 The unknown, x2 is the composition n of the liquid

L2 at the end of batch distillation.
Solution
 1 
0 .5
 1 
 By plotting versus x, the 
graph  y  x  
x2 
dx
yx
value is referring to the value of area under the
curve.
 From the graph, area under curve = 0.510 at x2
= 0.277. Composition of the liquid L2, x2 =
0.277.
 From material balance on more volatile
component:
x1L1  x 2L2 0.5  100  0.277  60
x1L1  x 2L2  y av V y av  y av 
V 40
y av  0.835
 Average composition of total vapor distilled, yav
= 0.835
 PART 3
Continuous distillation
Continuous / retrification distillation
Continuous / retrification distillation
 Retrification (fractionation) - or stage distillation with
reflux can be considered as 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.
 Continuous distillation - the process is more suitable for
mixtures of about the same volatility and the condensed
vapor and residual liquid are more pure (since it is re-
distilled)
 The fractionator consists of many trays which have holes
to permit the vapor, V which rises up from the lower tray
to bubble through and mixes with the liquid, L on the
upper tray and equilibrated, and V and L stream leaves in
equilibrium.
Continuous / retrification distillation
 During the mixing, the vapor will pick up more of
component A from the liquid while the liquid will richer
and richer in component B. As the vapor rises, it becomes
richer and richer in component A but poorer with
component B.
 Conversely, as the liquid falls further down, it becomes
poorer with A but richer in B. Thus we obtain a bottom
product and an overhead product of higher purity in
comparison to those obtained by single-stage simple
batch or flash distillation.
 NOTE: Fractionation refers to a process where a part or
whole of distillate is being recycled to the fractionator.
The recycled distillation (reflux) will supply the bulk of
liquid need to mix with vapor.
Continuous / retrification distillation
Continuous / retrification distillation
 The feed stream is introduced on some intermediate
tray where the liquid has approximately the same
composition as the feed.
 The system is kept steady-state: quantities (feed input
rate, output stream rates, heating and cooling rates, reflux
ratio, and temperatures, pressures, and compositions at
every point) related to the process do not change as
time passes during operation.
 With constant molal overflow assumption:
Ln 1  Ln  Ln 1  ....etc. Vn 1  Vn  Vn 1  ....etc.
 Conditions for constant molal overflow:
◦ Heat loses negligible (achieved more easily in industrial
column)
◦ Negligible heat of mixing
◦ Equal or close heats of vaporization
Continuous / retrification distillation
Number of plates required in a distillation column
 Four streams are involved in the transfer of
heat and material across a plate, as shown in
figure above:
Plate n receives liquid Ln+1 from plate n+1 above, and
vapor,Vn-1 from plate n-1 below.
Plate n supplies liquid Ln to plate n-1, and vapor Vn to
plate n+1
 Action of the plate is to bring about mixing
so that the vapor Vn of composition yn
reaches equilibrium with the liquid Ln of
composition xn.
Continuous / retrification distillation
 Design and operation of a distillation column
depends on the feed and desired products
 A continuous distillation is often a fractional
distillation and can be a vacuum distillation
or a steam distillation.
 Calculation for number of plates:
◦ Mc-Cabe & Thiele
◦ Lewis-Sorel Method
Continuous / retrification distillation
Mc-Cabe Thiele Method
The intersection of operating lines, q
 Feed enters as liquid at its boiling point that
the two operating lines intersect at point
having an x-coordinate of xF.
 The locus point of the intersection of the
operating lines is considerable importance
since it is dependent on the temperature and
physical condition of feed.
 The condition of the feed (F) determines the
relation between the vapor (Vm) in the
stripping section and (Vn) in the enriching
section, as well as between Lm and Ln.
The intersection of operating lines, q
heat needed to vaporize 1 mol of feed at entering conditions
q
molar latent heat of vaporizati on of feed
Hv  H F
q
Hv  H L
 q also as the no. of moles of saturated liquid produced
on the feed plate by each mole of feed added to tower.
 The relationship between flows above & below
entrance of feed: Lm  Ln  qF (1)
Vn  Vm  (1  q )F ( 2)

 Rewrite the equations of enriching & stripping without

the tray subscripts: Vn y  Ln x  Dx D (3 )
Vm y  Lm x  Wxw ( 4)

 Subtracting (3) from (4)

(Vm  Vn )y  (Lm  Ln )x  (Dx D  Wxw ) (5)
The intersection of operating lines, q
 Substituting: FxF  Dx D  Wxw , Eq. (1) & (2) into (5) will
produce:
q xF
y x (q  line equation )
q 1 q 1
 The equation – locus of the intersection of the two
operating lines
 Setting y = x in the equation, the intersection of the q-
line equation with the 45o line is y = x = xF, where xF is
the overall composition of the feed.
 Slope = q/(q-1).
 A convenient way to locate a stripping line operating
line is 1st to plot the enriching operating line and then
q-line.
The intersection of operating lines, q

•Depending on the state of

the feed, the feed lines will
have different slopes:
q = 0 (saturated vapour)
q = 1 (saturated liquid)
0 < q < 1 (mix of liquid and
vapour)
q > 1 (subcooled liquid)
q < 0 (superheated vapour)
Animation of the construction of
enriching, stripping & q operating lines

http://www.separationprocesses.com/Distillation/DT_Ani
mation/McCabeThiele.html
Exercise
1) 11.4-1
2) 11.4-2
Steps of McCabe Thiele Method
1. Plot equilibrium mole fraction for
component that more volatile. [ y(mole
fraction A in vapor) vs x(mole fraction A
in liquid)]
2. Make 45° line (x=y)
3. Plot enriching line;
4. Plot q line
5. Plot stripping line
6. Determine the stages
7. Feed tray location
Tutorial
11.4-5
Exercise 11.4-6
Repeat Problem 11.4-1 but use a feed that
is saturated vapor at dew point. Determine
(a) Minimum reflux ratio, Rm
(b) Minimum number of theoretical plates at
total reflux
(c) Theoretical number of trays at an
operating reflux ratio of 1.5Rm
Example
 A mixture of benzene and toluene containing 40
mole% benzene is to be separated to give a product
of 90 mole% benzene at the top, and a bottom
product with not more than 10 mole% of benzene.
The feed is heated so that it enters the column at
its boiling point, and the vapor leaving the column is
condensed but not cooled, and provides reflux and
product.
 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 stages needed and the
position of entry for the feed.
Example
Solution
 Feed, xF = 0.4
 Product, xD = 0.9
 Bottom, xw = 0.10
 Taking basis; 100 kmol of feed. A total mass
balance:
F = D +W hence; W = 100 – D (Eq. 1)
 A balance on MVC (benzene);
F  x F  D  x D  W  xw 100 (0.4)  D(0.9)  W (0.1)
40  0.9D  0.1W (Eq.2)

 From the calculations;

D = 37.5 kmol, W = 62.5 kmol
Solution
 Using notation from reflux:
Ln
R Ln  RD Ln  3D Ln  3(37 .5)
D
Ln  112 .5

 From material balance at the top stage;

Vn 1  Ln  D Vn 1  150 kmol

 Thus, the operating line equation:

Ln D 112 .5 D
y n 1  xn  xD y n 1  xn  xD
Vn 1 Vn 1 150 Vn 1
y n 1  0.75 x n  0.225
Solution
 Since the feed is all liquid at its boiling point,
it will all run down as increased reflux to the
plate below:
Lm  Ln  F Lm  112 .5  100 Lm  212 .5kmol

 The material balance at the bottom:

Lm  Vm1  W Vm  212 .5  62.5 Vm  150 kmol  Vn

 Bottom operating line equation:

Lm W 212 .5 62 .5
y m 1  xm  xw y m 1  xm  (0.1)
Vm 1 Vm 1 150 150
y m 1  1.417 x m  0.0417
Example
 11,200 kg/h of equal parts (in wt) of Benzene-Toluene
solution is to be distilled in a fractionating tower at
atmospheric pressure.
 The liquid is fed as a liquid-vapor mixture in which the
feed consist of 75% vapor. The distillate contains 94
wt% Benzene whereas the bottom products contains
98 wt% toluene. Determine;
◦ The flowrate of distillate and bottom product (kg/h)
◦ The minimum reflux ratio, Rm.
◦ The number of theoretical stages required if the
reflux ratio used is 1.5 times the minimum reflux
ratio
◦ The position of the feed tray
 The MW of Benzene = 78
 The MW of Toluene = 92
Solution
 xF = 0.5
 xD = 0.94
 Xw = 0.02
 From the total & component material
balance:
D = 5739.1 kg/h, W = 5260.9 kg/h
 Convert mass fraction to mol fraction. (Basis
of calculation = 100kg)
 Mol fraction: xF = 0.54, xD = 0.95, xw = 0.03
Solution
 Find q-line. Feed enters at 75% vapor.
q  0.75(qvapor )  0.25(q liquid )
q  0.75(0)  0.25(1.0) q  0.25

q  line equation
 q   x 
y q    x q   f 
 q  1  q  1
 0.25   0.54 
yq    xq    y q  0.333 x q  0.72
 0.25  1   0.25  1 
Let x  0.3, y q  0.333 (0.3)  0.72 y q  0.62
Plot (0.54, 0.54 ) and (0.3, 0.62 ) forq  line
Solution
 From the graph, y intercept for q-line = 0.36
xD 0.95
 0.36  0.36 Rm 1.64
Rm  1 Rm  1
 The number of theoretical stages required if
the reflux ratio used is 2 times the minimum
reflux ratio
R  2Rmin  2(1.64 ) R  3.28
R 1
y n 1  xn  xD
R 1 R 1
3.28 1
y n 1  xn  (0.95 )
3.28  1 3.28  1
y n 1  0.766 x n  0.222
At x  0.5, y n 1  0.766 (0.5)  0.222 y n 1  0.605
Plot (0.95, 0.95 ) and (0.5, 0.605 ) for enriching OL
Solution
 The number of theoretical stages required =
10.5 stages including boiler
 Feed plate location: 5 from top.
Q1 Final Exam Jan 2012
A distillation column with a total condenser
and partial reboiler is used to separate an
ethanol-water mixture. The feed containing
20 mole% ethanol enters the column at feed
rate 1000 kg.moles/hr. A distillate composition
of 80 mole% ethanol and bottom composition
of 2.0 mole% ethanol are desired. The external
reflux ratio is 5/3 and it is returned as a
saturated liquid. It is assumed the condition is
at constant molal overflow.
Given;
Enthalpy of feed at dew point, Hv =485 kJ/kg.mol
Enthalpy of feed at boiling point, HL =70 kJ/kg.mol
Enthalpy of feed at entrance condition, HF =15 kJ/kg.mol
The equilibrium curve of ethanol-water is provided in
Appendix 1.
Determine;
i) The minimum number of tray
ii) The total number of equilibrium tray
iii) The feed location
Q2, Final Exam Jan 2013
A total feed of 500 kmol/hr having an
overall composition of 55 mol% heptane
and 45mol% ethyl benzene is to be
fractionated at 1.0 bar to give a distillate
containing 95 mol% heptane and bottom
containing 2 mol% heptane. The feed enters
the tower at equimolar vapor and liquid.
The molecular weight of heptane = 100.2
kg/kmol and ethyl benzene =106.6 kg/kmol.
Equilibrium data for heptane-ethylbenzene
Determine
a) The flowrates of distillate and bottom
product in kg/hr
b) The minimum reflux ratio
c) The number of theoretical stages if the
reflux ratio used is 1.3 times the
minimum reflux ratio.
Table 1: Equilibrium data for heptane
ethylbenzene
Temperature Mole fraction
(°C)
XH YH
98.3 1.00 1.00
102.8 0.79 0.90
110.6 0.49 0.73
119.4 0.25 0.51
129.4 0.08 0.23
136.1 0.00 0.00
AZEOTROPIC DISTILLATION
 Azeotrope mixtures
 Minimum boiling point
 Maximum boiling point
 Azeotropic Distillation
Azeotrope mixtures
 Liquid and vapor are exactly the same at a
certain temperature
 It is a special class of liquid mixture that boils at
a constant temperature at a certain
composition
 Cannot be separated by a simple/conventional
distillation
Azeotropic Distillation
 An introduction of a new component called
entrainer is added to the original mixture to
form an azeotrope with one or more of feed
component
 The azeotrope is then removed as either the
distillate or bottoms
 The purpose of the introduction of entrainer is
to break an azeotrope from being formed by
the original feed mixture
 Function of entrainer:
◦ To separate one component of a closely boiling point
◦ To separate one component of an azeotrope
Azeotropic Distillation
 Azeotropic distillation is a widely practiced process
for the dehydration of a wide range of materials
including acetic acid, chloroform, ethanol, and many
higher alcohols.
 The technique involves separating close boiling
components by adding a third component, called an
entrainer, to form a minimum boiling.
 Normally ternary azeotrope which carries the
water overhead and leaves dry product in the
bottom.
 The overhead is condensed to two liquid phases;
the organic, "entrainer rich" phase being refluxed
while the aqueous phase is decanted.
Azeotropic Distillation
 A common example of distillation with an
azeotrope is the distillation of ethanol and water.
 Using normal distillation techniques, ethanol can
only be purified to approximately 89.4%
 Further conventional distillation is ineffective.
 Other separation methods may be used are
azeotropic distillation or solvent extraction
Azeotropic Distillation
 The concentration in the vapor phase is the same
as the concentration in the liquid phase (y=x)
 At this point, the mixture boils at constant
temperature and doesn’t change in composition
 This is called as minimum boiling point (positive
deviation)
Azeotropic Distillation
 The characteristic of such mixture is boiling
point curve goes through maximum phase
diagram
 Example: Acetone-chloroform
Azeotropic Distillation
 The most common examples:
◦ Ethanol-water (89.4 mole%, 78.25 oC, 1 atm)
◦ Carbon Disulfide-acetone (61 mol% CS2, 39.25oC,
1 atm)
◦ Benzene-water (29.6 mol% water, 69.25 oC, 1
atm)
Azeotropic Distillation
 Let say binary mixture: A-B formed an azeotrope
mixture
 Entrainer C is added to form a new azeotrope with
the original components, often in the LVC, say A
 The new azeotrope (A-C) is separated from the
other original component B
 This new azeotrope is then separated into
entrainer C and original component A.
 Hence the separation of A and B can be achieved
Azeotropic Distillation
Example: Acetic acid-water using entrainer n-
butyl acetate
 Boiling point of acetic acid is 118.1 oC, water is 100 oC
& n-butyl acetate is 125 oC
 The addition of the entrainer results in the formation
of a minimum boiling point azeotrope with water with
a boiling point = 90.2 oC.
 The azeotropic mixture therefore be distilled over as a
vapor product & acetic acid as a bottom product
 The distillate is condensed and collected in a decanter
where it forms 2 insoluble layers
 Azeotropic Distillation
Example: Acetic acid-water using entrainer n-
butyl acetate
 Top layer consist of nearly pure n-butyl acetate in
water, whereas bottom layer of nearly pure water
saturated with butyl acetate
 The liquid from top layer is returned to column as
reflux and entrainer
 The liquid from bottom layer is sent to another column
to recover the entrainer (by stream stripping)
Determination of Boiling Point Temperature in
multi component distillation
The calculation is a trial and error process
where
1. T is assumed
2. Value of relative volatility of each
component are then calculated using K
values at the assume T.
3. Then calculate value of Kc where
Kc= 1/(∑relative volatility x liq mole
fraction)
4. Find the T that corresponds to the
calculated value of Kc
5. Compare with T value read from table that
corresponds to the Kc.
6. If value is differ, the calculated T is used for
the next iteration.
7. After the final T is known, the vapor
composition is calculated from
Yi= (relative volatility x liq mole
fraction)/∑(relative volatility x liq mole
fraction)
Example 11.7-1
Bubble point@boiling point
Bubble point@boiling point
=temperature at which liquid begins to
vaporize
Dew point
=temperature at which liquid begins to
condense out of the vapor