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CHE333

Simultaneous Heat & Mass


Transfer Operations

Lecture 4: Distillation
Dr. Abdul Razzaq
Assistant professor, CUI, Lahore Campus.

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Contents
 Introduction
 Vapor liquid equilibrium, x-y, T-x-y and H-x-y diagrams
 Partial vaporization and partial condensation
 Basic laws
 Binary distillation : McCabe-Thiele Method, Lewis-Sorel Method,
Ponchon-Saravit Method for calculation of trays
 Reflux ratio, minimum reflux ratio, Total Reflux ratio, their
calculations
 Plate efficiency

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Distillation
• Separation technique

• More volatile component(s) from the less volatile component(s)

• “Separation of mixtures into their several components according to


their volatility/boiling point is called distillation

• Multistage contact offers a larger degree of separation between tow


phases i.e. vapor-liquid phase

• The distribution is governed by vapor-liquid equilibrium relationship

• The arrangement/device is called as “distillation column”

• Separation, recovery, increasing purity.


Distillation
Advantages:
 It gives direct separation into pure products and no further processing is
usually required

 It can be used for separation of multicomponent mixtures

 May be carried out batch wise or continuously

Limitations:

 If components in a mixture have nearly same boiling point, they can not
be separated by normal distillation

 Heat sensitive liquids may degrade due to thermal effect


Distillation
Distillation

• Partial vaporization

• Partial condensation
Vapor Liquid Equilibrium
Vapor-Liquid Equilibrium:
 Composition of vapor in equilibrium with a liquid of given composition is
determined experimentally, and the results can be plotted on temp-composition
diagram
 Curve ABC shows the composition of the liquid which boils at any given
temperature.
 Curve ADC shows the corresponding composition of the vapor at that
temperature.
 It is seen that for any liquid composition, the vapor formed will be richer in
more volatile component.
 Benzene-Toluene, n-heptane-toluene, carbon disulfide-carbon tetrachloride are
the examples of mixture which will give this type of curve.
Vapor Liquid Equilibrium
Vapor Liquid Equilibrium

 At constant pressure
• Bubble point curve
(T vs. x)
• Dew point curve
(T vs. y)
Vapor Liquid Equilibrium
 For distillation purposes it is more convenient to plot y against x at a constant
pressure. T-x-y Data
x-y Data

Fig: Vapor composition as a


function of liquid composition at
constant pressure and selected
temperature.
Vapor Liquid Equilibrium
• Critical composition (xg ) / Azeotropic point
• Positive and Negative azeotrope
• Temperature minimum and maximum azeotrope
Vapor Liquid Equilibrium
Partial Vaporization and Partial Condensations:

Liquid to
Vapor ratio?

Fig: Effect of partial vaporization and condensation at the boiling point


Vapor Liquid Equilibrium
Partial Vaporization and Partial Condensations:
 Curve ABCJ is the boiling point curve

 Curve ADEJ shows the temperature at which a vapor of composition y


starts to condense.

 Consider a mixture of composition x2 at a temperature T3, upon heating


the following changes will occur:

 At temp T2, liquid will boil and vapors with composition y2 are formed.

 On further heating the composition of the liquid will change cause of the
loss of more volatile component to the vapor

 On further heating to a temperature T1, all of the liquid is vaporized to


give vapor D of the same composition y1 as the original liquid.
Vapor Liquid Equilibrium
Partial Vaporization and Partial Condensations:
 Partial vaporization of the liquid gives a vapor richer in the more volatile
component than the liquid.

 Starting with superheated vapor represented by point H, on cooling to D


condensation commences, and the first drop of liquid has a composition
K.
Basic Laws

 Daltons Law

• Partial pressure is related to the


 Raoults Law concentration in liquid phase.
• PAo is the vapor pressure of pure A at
same temperature
• True for higher concentrations

• For low values of concentration,


 Henrys Law Henerys constant is used instead of
partial pressures
Basic Laws

Mixture following Raoults law


Basic Laws
 Volatility

 Relative Volatility
Distillation
 Differential Distillation:

• Batch, Simple example

• No reflux

• Liquid boils the vapors formed is once removed

• The process end liquid which is not vaporized is removed a the


bottom product
Distillation
 Flash Distillation:

• Continuous process

• Vapors is already in equilibrium with the liquid

• Feed is pumped through a fired heater

• Feed enters through the valve where the pressure reduces and
sufficient time is provided to reach equilibrium
Distillation
 Rectification:

• Achieved by fractionating column

• Enrichment of the MVC

 Batch Distillation:

• MVC evaporated from the still continuously

• Distillation continued until the residue of the still contains material


with low content of MVC.
Distillation
 In order to develop a method for the design of distillation units it is
necessary to develop an analytical approach for

• Number of trays to be calculated

• Heat and material flows over the trays, the condenser, and the reboiler must be
established

• Thermodynamic data for how much mass transfer is needed to establish


equilibrium between the streams leaving each tray

• Required diameter of the column to accommodate the desired flowrates and to


operate within the available drop in pressure

• The desired degree of mixing of the streams on each tray


Distillation
 Four streams are involved in the transfer of heat and
material across a plate

 The action of the plate is to bring about mixing so that


the vapour Vn, of composition yn, approaches
equilibrium with the liquid Ln, of composition xn
 The streams Ln+1 and Vn−1 cannot be in equilibrium and,
during the interchange process on the plate, some of the
more volatile component is vaporised from the liquid
Ln+1, decreasing its concentration to xn, and some of the
less volatile component is condensed from Vn−1,
increasing the vapour concentration to yn
Distillation
 Assumptions for simplification

• Heat losses small and neglected, Ideal case the heat of mixing is zero

• Molar heat of vaporization, constant (Ind.of composition)

• One mole of Vn-1 liberates one mole of Vn (Vn=Vn-1), unless changes done

• Temperature change form one plate to another plate is small thus Hn+1 =

Hn

• Vn and Ln constant over the Rectifying section

• Vm an Lm are constant over the Stripping section


Distillation
 Material balance above plate „n‟

 Balance for more volatile component gives

 The above equation relates the


compositions of vapors rising to the plate to
the composition of liquid on any plate above
the feed plate.
 Since the molar liquid overflow is constant,
then
No. of plates: Lewis Sorel Method
Similarly, taking a material balance for
the total streams and for the more volatile
component from the bottom to above
plate „m‟

This eq gives the corresponding relation


b/w the composition of vapor rising to a
plate and the liquid on the plate for the
section below the feed plate.
No. of plates: Lewis Sorel Method

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No. of plates: Lewis Sorel Method
Example 11.7 (Coulson, vol-2)
No. of plates: Lewis Sorel Method
Example 11.7 (Coulson, vol-2)
No. of plates: Lewis Sorel Method
Example 11.7 (Coulson, vol-2)
No. of plates: Lewis Sorel Method
Example 11.7 (Coulson, vol-2)
No. of plates: Lewis Sorel Method
Example 11.7 (Coulson, vol-2)
No. of plates: McCabe & Thiele
 These equations are used in the Lewis–Sorel method to calculate the relation
between the composition of the liquid on a plate and the composition of the
vapour rising to that plate.

• If xn+1 = xd in equation, this equation represents a line passing through the point yn =
xn+1 = xd
• If xn+1 is put equal to zero, then yn = Dxd/Vn, giving a second easily determined point
• The top operating line is therefore drawn through two points of coordinates (xd, xd )
and (0, (Dxd/Vn))

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No. of plates: McCabe & Thiele
 These equations are used in the Lewis–Sorel method to calculate the relation
between the composition of the liquid on a plate and the composition of the
vapour rising to that plate.

• For the bottom operating line, if xm+1 = xw, then:


• Since Vm = Lm − W, it follows that ym = xw. Thus the bottom operating line passes
• through the point C, that is (xw, xw), and has a slope Lm/Vm

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No. of plates: McCabe & Thiele

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No. of plates: McCabe & Thiele
• Concentration in the still given by point 15 and point 16
• Similarly the concentration on the top is given by point 2 and point 1
• Condenser by completely condensing the vapor gives the liquid with
concentration at point A
• Still+ Condenser provides enrichment and is equal to 1 plate
• Hence actual number of plates is one less then ideal number of plates

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Intersection of operating lines: q-line
• The locus of the point of intersection of the operating lines is of considerable
importance and is dependent on the temperature and physical condition of the
feed

• This equation is commonly known as the equation of the q-line

• The line may thus be drawn through two easily determined points

• From the definition of q, it follows that the slope of the q-line is governed by the
nature of the feed as follows

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Intersection of operating lines: q-line

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Reflux ratio
 Reflux is altered, TOL is altered, hence number of plates
required varies

 If D = 0, under condition of total reflux R is infinity and


slope is 1

 TOL can be drawn between (xd,xd) and (0, xd/R+1)

 If reflux is reduced more stages are required to achieve


purity

 Further reduction of R will bring line to AE and infinite


number of stages is required from xd to xf

 Such condition is known as minimum reflux ration Rm

 A small increase in R beyond Rm will give a workable


system

 Line AG gives an impossible condition as couldn‟t reach


xf 38
Calculation of Minimum Reflux ratio
 Consider the conditions where q-line is vertical:

 Point E lies on equilibrium curve and has coordinates (xf, yf)

 The slope of the line AE is given by:


Calculation of Minimum Reflux ratio
 Consider the conditions where q-line is horizontal:

 The enrichment line for minimum reflux is given by AC, where Point C
has coordinates (xc, yc)
Calculation of Minimum Reflux
 Underwood and Fenske Equation

 For ideal mixtures or where relative volatility may be taken as constant,


Minimum reflux ratio may be calculated by using Fenske‟s equation
Plates at total reflux: Fenske’s method
 Fenske derived an equation for calculating the required number of
plates

 n is the required number of theoretical plates in the column


Plates at total reflux: Fenske’s method
For the separation of a mixture of benzene and toluene, considered in Example
11.7, xd = 0.9, xw = 0.1, and xf = 0.4. If the mean volatility of benzene relative to
toluene is 2.4, what is the number of plates required at total reflux?
Selection of Economic Reflux ratio
 The cost of distillation column includes:
a. Capital or fixed cost (such as those for purchase of distillation column, internals,
reboiler, condenser and other equipment)

b. Operating cost (such as utilities like condenser cooling water, reboiler steam etc)

 The steam required will be proportional to Vm, which may be taken as


Vn where the feed is liquid at its boiling point.

 From a material balance over the top portion of the column, Vn =D(R +
1) and hence the steam required per mole of the product is proportional
to R + 1.
Selection of Economic Reflux ratio
 The cost of the distillation column generally includes capital cost, operating cost and
depreciation cost

 There is no general relationship, however commonly practice displays it is usually 1.1-


1.5 times the minimum value
Selection of Economic Reflux ratio
Increasing the reflux ratio from Rm therefore affects
the capital and operating costs of a column as follows:
a) The operating costs rise and are approximately
proportional to (R + 1)
b) The capital cost initially falls since the number of
plates falls off rapidly at this stage
c) The capital cost rises at high values of R, since
there is then only a very small reduction in the
number of plates, although the diameter, and hence
the area, continuously increases because the vapor
load becomes greater. The associated condenser and
reboiler will also be larger and hence more
expensive
Murphree Plate Efficiency
 Theoretical, Ideal and Real plates
The ratio n/np of the number of ideal stages to the number of actual
trays represents the overall efficiency E of the column, which may be
30–100 percent
The proportion of liquid and vapour, and the physical properties of
the mixtures on the trays, will vary up the column, and conditions on
individual trays must be examined, as suggested by MURPHREE
Murphree Plate Efficiency
For a single ideal tray, the vapour leaving is in equilibrium with the
liquid leaving, and the ratio of the actual change in composition
achieved to that which would occur if equilibrium between
yn and xn were attained is known as the Murphree plate efficiency EM
Non Ideal Binary System: H-x diagram
 Previous case, constant molar overflow (CMO), constant molar heat content, no heat of
mixing
 For a non ideal system, where molar heat is no more constant molar heat content and
substantial heat of mixing exits, a method is developed using H-x diagram by
RUHEMANN, PONCHON and SAVARIT. PONCHON-SAVARIT Method
Non Ideal Binary System: H-x diagram
Non Ideal Binary System: H-x diagram
Non Ideal Binary System: H-x diagram
Non Ideal Binary System: H-x diagram
 PONCHON-SAVARIT Method
PONCHON-SAVARIT Method: Graphical procedure
1. Use R, xD, HD or hD to establish the location of common pole N with xD and hD‟ = hD –
QD or h = HD – QD
2. Use Equilibrium data alone to establish the point L1 at (x1, h1). Since L1 is assumed to
be a saturated liquid, x1 must lie on the saturated-liquid line.
3. Draw the operating line between L1 and N. This line intersects the saturated-vapor line
at V2 (y2, H2).
4. Repeat steps 2 and 3 until the feed plate is reached.
5. Draw a straight line passing through F and N.
6. Draw a vertical straight line at xw all the way down until it intersects the extension of
line F and M
7. Assuming the reboiler to be an equilibrium stage, the vapor VM+1 is in equilibrium with
the bottom stream.
8. Use equilibrium data alone to establish the value of ym+1 on the saturated-vapor line.
9. Draw the operating line between Lm(xm, hw‟) and VM+1.
10. Repeat steps 4 and 5 until the reboiler condition is reached and counte the number of
stages
 N (xd, hD’)

V4 V3 V2 V1
H or h

D
L2 L1
L3

x or y
VM1 VM VM1

hB LM LM-1
H or h

x or y

 Hw’, xw
V1

L1
H or h

y1

x1
35,000
N
30,000

25,000

20,000
H
15,000

10,000

5,000
F

1
0
0 0.2 0.4 0.6 0.8 1
0.9
0.8

0.7

0.6
M
y

0.5

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1
x
Thank You
for
Your Attention
email:
abdulrazzaq@cuilahore.edu.pk

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