NPTEL – Chemical – Mass Transfer Operation 1

MODULE 5: DISTILLATION

LECTURE NO. 1

5.1. Introduction
Distillation is method of separation of components from a liquid mixture which
depends on the differences in boiling points of the individual components and the
distributions of the components between a liquid and gas phase in the mixture.
The liquid mixture may have different boiling point characteristics depending on
the concentrations of the components present in it. Therefore, distillation
processes depends on the vapor pressure characteristics of liquid mixtures. The
vapor pressure is created by supplying heat as separating agent. In the
distillation, the new phases differ from the original by their heat content. During
most of the century, distillation was by far the most widely used method for
separating liquid mixtures of chemical components (Seader and Henley, 1998).
This is a very energy intensive technique, especially when the relative volatility of
the components is low. It is mostly carried out in multi tray columns. Packed
column with efficient structured packing has also led to increased use in
distillation.

5.1.1. Vapor Pressure

Vapor Pressure: The vaporization process changes liquid to gaseous state. The
opposite process of this vaporization is called condensation. At equilibrium, the
rates of these two processes are same. The pressure exerted by the vapor at this
equilibrium state is termed as the vapor pressure of the liquid. It depends on the
temperature and the quantity of the liquid and vapor. From the following
Clausius-Clapeyron Equation or by using Antoine Equation, the vapor pressure
can be calculated.

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Clausius-Clapeyron Equation:
 p v     1 1 
ln  v       (5.1)
 p1   R  T1 T 
where p v and p1v are the vapor pressures in Pascal at absolute temperature T
and T1 in K. λ is the molar latent heat of vaporization which is independent of
temperature.
Antoine Equation:
B (5.2)
ln p v (Pascal)  A 
T C
Typical representative values of the constants A, B and C are given in the
following Table 5.1 (Ghosal et al., 1993)
Table 5.1: Typical representative values of the constants A, B and C

Components Range of A B C
Temperature (T),
K
Acetone 241-350 21.5439 2940.46 -35.93
Ammonia 179-261 21.8407 2132.50 -32.98
Benzene 280-377 20.7934 2788.51 -52.36
Ethanol 270-369 21.8045 3803.98 -41.68
Methanol 257-364 23.4801 3626.55 -34.29
Toluene 280-410 20.9063 3096.52 -53.67
Water 284-441 23.1962 3816.44 -46.13

Readers are suggested to revise the thermodynamics for more about vapor
pressure and boiling point.

5.1.2. Phase Diagram

For binary mixture phase diagram only two-component mixture, (e.g. A (more
volatile) and B (less volatile)) are considered. There are two types of phase
diagram: constant pressure and constant temperature.

5.1.3. Constant Pressure Phase Diagram

The Figure 5.1 shows a constant pressure phase diagram for an ideal solution
(one that obeys Raoult's Law). At constant pressure, depending on relative

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concentrations of each component in the liquid, many boiling point temperatures

are possible for mixture of liquids (solutions) as shown in phase disgram diagram
(Figure 5.1). For mixture, the temperature is called bubble point temperature
when the liquid starts to boil and dew point when the vapor starts to condense.
Boiling of a liquid mixture takes place over a range of boiling points. Likewise,
condensation of a vapor mixture takes place over a range of condensation
points. The upper curve in the boiling point diagram is called the dew-point curve
(DPC) while the lower one is called the bubble-point curve (BPC). At each
temperature, the vapor and the liquid are in equilibrium. The constant pressure
phase diagram is more commonly used in the analysis of vapor-liquid
equilibrium.

Figure 5.1: Phase diagram of binary system at constant pressure

5.1.4. Constant temperature (isothermal) phase diagram

The constant temperature phase diagram is shown in Figure 5.2. The constant
temperature phase diagram is useful in the analysis of solution behaviour. The
more volatile liquid will have a higher vapor pressure (i.e. pA at xA = 1.0)

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Figure 5.2: Binary Phase diagram at constant temperature

5.1.5. Relative volatility

Relative volatility is a measure of the differences in volatility between two
components, and hence their boiling points. It indicates how easy or difficult a
particular separation will be. The relative volatility of component ‘A’ with respect
to component ‘B’ in a binary mixture is defined as
y A / xA
 AB  (5.3)
y B / xB
where, yA = mole fraction of component ‘A’ in the vapor, xA = mole fraction of
component ‘A’ in the liquid. In general, relative volatility of a mixture changes with
the mixture composition. For binary mixture, xB = 1-xA. So Equation (5.3) can be
rearranged, simplifying and expressed by dropping subscript 'A' for more volatile
component as:
 ave x
y (5.4)
1  ( ave  1) x

The Equation (5.4) is a non-linear relationships between x and y. This Equation

can be used to determine the equilibrium relationship (y vs. x) provided the

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average relative volatility, ave is known. If the system obeys Raoult’s law, i.e
p A  Py A , pB  Py B , the relative volatility can be expressed as:
pA / xA
 AB  (5.5)
p B / xB
where pA is the partial pressure of component A in the vapor, pB is the partial
pressure of component B in the vapor and P is the total pressure of the system.
Thus if the relative volatility between two components is equal to one, separation
is not possible by distillation. The larger the value of , above 1.0, the greater the
degree of separability, i.e. the easier the separation. Some examples of optimal
relative volatility that are used for distillation process design are given in Table
5.2.
Table 5.2: Some optimal relative volatility that are used for distillation process design

More volatile component Less boiling component Optimal Relative

(normal boiling point oC) (normal boiling point, oC) volatility
Benzene (80.1) Toluene (110.6) 2.34
Toluene (110.6) p-Xylene (138.3) 2.31
Benzene (80.6) p-Xylene (138.3) 4.82
m-Xylene (139.1) p-Xylene (138.3) 1.02
Pentane (36.0) Hexane (68.7) 2.59
Hexane (68.7) Heptane (98.5) 2.45
Hexane (68.7) p-Xylene (138.3) 7.0
Ethanol (78.4) iso-Propanol (82.3) 1.17
iso-Propanol (82.3) n-Propanol (97.3) 1.78
Ethanol (78.4) n-Propanol (97.3) 2.10
Methanol (64.6) Ethanol (78.4) 1.56
Methanol (64.6) iso-Propanol (82.3) 2.26
Chloroform (61.2) Acetic acid (118.1) 6.15

5.1.6. Vapor-Liquid Equilibrium (VLE)

It is useful for graphical design in determining the number of theoretical stages
required for a distillation column. A typical equilibrium curve for a binary mixture
on x-y plot is shown in Figure 5.3. It can be plotted by the Equations (5.4) or (5.5)
as discussed earlier section. It contains less information than the phase diagram
(i.e. temperature is not included), but it is most commonly used. The VLE plot

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expresses the bubble-point and the dew-point of a binary mixture at constant

pressure. The curved line in Figure 5.3 is called the equilibrium line and it
describes the compositions of the liquid and vapor in equilibrium at some fixed
pressure. The equilibrium line can be obtained from the Equation (5.4) once the
relative volatility is known.

y = 0.671x3 - 1.883x2 + 2.211x + 0.003

R² = 0.999
Mole fraction of benzene in vapour, y

Equilibrium curve

45o diagonal line

Mole fraction of benzene in liquid , x

Figure 5.3: Equilibrium diagram for a benzene-toluene mixture at 1 atmosphere

This particular VLE plot (Figure 5.3) shows a binary ideal mixture that has a
uniform vapor-liquid equilibrium that is relatively easy to separate. On the other
hand, the VLE plots shown in Figure 5.4 represented for non-ideal systems.
These non-ideal VLE systems will present more difficult separation.

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Figure 5.4: Vapor-liquid equilibrium curve for non-ideal systems

The most challenging VLE curves are generated by azeotropic systems. An

azeotrope is a liquid mixture which when vaporized, produces the same
composition as the liquid. Two types of azeotropes are known: minimum-boiling
and maximum-boiling (less common). Ethanol-water system (at 1 atm, 89.4 mole
%, 78.2 oC; Carbon-disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1 atm) and
Benzene - water (29.6 mole% H2O, 69.25 oC, 1 atm) are minimum-boiling
azeotropes. Hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm); Acetone
- chloroform (65.5 mole% chloroform, 64.5 oC, 1 atm) are the examples of
Maximum-boiling azeotropes. The Figure 5.5 shows two different azeotropic
systems, one with a minimum boiling point (Figure 5.5a) and one with a
maximum boiling point (Figure 5.5b). The points of intersections of the
equilibrium curves with the diagonal lines are called azeotropic points. An
azeotrope cannot be separated by conventional distillation. However, vacuum
distillation may be used as the lower pressures which can shift the azeotropic
point.

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Figure 5.5: VLE curves for azeotropic systems: (a) for maximum boiling point, (b) for minimum
boiling point

Although most distillations are carried out at atmospheric or near atmospheric

pressure, it is not uncommon to distill at other pressures. High pressure
distillation (typically 3 - 20 atm) usually occurs in thermally integrated processes.
In those cases the equilibrium curve becomes narrower at higher pressures as

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shown in Figure 5.6. Separability becomes less at higher pressures.

Figure 5.6: Variation of equilibrium curve with pressure

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MODULE 5: DISTILLATION

LECTURE NO. 2

5.2. Distillation columns and their process calculations

There are many types of distillation columns each of which is designed to
perform specific types of separations. One way of classifying distillation column
type is to look at how they are operated. Based on operation, they are of two
types: batch or differential and continuous columns.

5.2.1. Batch or differential distillation columns and their process

calculation
In batch operation, the feed is introduced batch-wise to the column. That is, the
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. Consider a
binary mixture of components A (more volatile) and B (less volatile). The system
consists of a batch of liquid (fixed quantity) inside a kettle (or still) fitted with
heating element and a condenser to condense the vapor produced as shown in
Figure 5.7. The condensed vapor is known as the distillate. The distillate is
collected in a condensate receiver. The liquid remaining in the still is known as
the residual. The process is unsteady state. The concentration changes can be
analyzed using the phase diagram, and detailed mathematical calculations
carried out using the Rayleigh Equation. Readers are suggested to follow chapter
9 (Page 369) of text book “Mass-transfer operations” by R. E Treybal, third
edition. As the process is unsteady state, the derivation is based on a differential
approach to changes in concentration with time. Let L1 = initial moles of liquid

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originally in still, L2 = final moles of liquid remained in still, x1 = initial liquid

composition in still (mole fraction of A), x2 = final liquid composition in still (mole
fraction A). At any time t, the amount of liquid in the still is L, with mole fraction of
A in the liquid being x. After a small differential time (t + dt), a small amount of
vapor dL is produced, and the composition of A in the vapor is y (mole fraction).
The vapor is assumed to be in equilibrium with the residue liquid. The amount of
liquid in the still is thus reduced from L to (L - dL), while the liquid composition
changed from x to (x - dx). Then the material balance on A can be written as:

Figure 5.7: Simple batch or differential distillation process

Initial amount in still = Amount left in still + Amount vaporized

xL  ( x  dx)( L  dL)  ydL (5.6)

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or

xL  xL  xdL  Ldx  dxdL  ydL (5.7)

Neglecting the term (dx)(dL), the Equation (5.7) may be written as:

Ldx  ydL  xdL (5.8)

Re-arranging and Integrating from L1 to L2, and from x1 to x2, one can obtain the
following Equation which is called Rayleigh Equation:

L  x1 1
ln  1    dx (5.9)
x2 ( y  x )
 L2 

The integration of Equation (5.9) can be obtained graphically from the equilibrium
curve, by plotting 1/(y-x) versus x.

Example problem 5.1

A mixture of 40 mole % isopropanol in water is to be batch-distilled at 1 atm until
70 mole % of the charge has been vaporized. Calculate the composition of the
liquid residue remaining in the still pot, and the average composition of the
collected distillate. VLE data for this system, in mole fraction of isopropanol, at 1
atm are (Seader and Henley, 1998):
Temp.(K) 366 357 355.1 354.3 353.6 353.2 353.3 354.5
y 0.220 0.462 0.524 0.569 0.593 0.682 0.742 0.916
x 0.012 0.084 0.198 0.350 0.453 0.679 0.769 0.944

Solution 5.1:
Calculate 1/(y-x)
As per Rayleigh Equation

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L  1
ln  1   
x1
dx
2 ( y  x)
 L2  x

x1= 0.4
Feed L1 = 100
Distillate (D) = 70
Liquid residue as L2 = L1-D = 30
L  1
Find x2 by equating ln  1   
x1
dx
2 ( y  x)
 L2  x

The value of x2 = 0.067

L1 x1  L2 x2
yD   0.543
D

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MODULE 5: DISTILLATION
LECTURE NO. 3

5.2.2. Continuous distillation columns

In contrast, continuous columns process a continuous feed stream. No
interruptions occur unless there is a problem with the column or surrounding
process units. They are capable of handling high throughputs. Continuous
column is the more common of the two types.

Types of Continuous Columns

Continuous columns can be further classified according to the nature of the feed
that they are processing:
Binary distillation column: feed contains only two components
Multi-component distillation column: feed contains more than two
components the number of product streams they have
Multi-product distillation column: column has more than two product streams
where the extra feed exits when it is used to help with the separation,
Extractive distillation: where the extra feed appears in the bottom product
stream
Azeotropic distillation: where the extra feed appears at the top product stream
the type of column internals.
Tray distillation column: where trays of various designs are used to hold up the
liquid to provide better contact between vapor and liquid, hence better
separation. The details of the tray column are given in Module 4.
Packed distillation column: where instead of trays, 'packings' are used to
enhance contact between vapor and liquid. The details of the packed column are
given in Module 4.

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4.2.2.1. A single-stage continuous distillation (Flash distillation):

A single-stage continuous operation occurs where a liquid mixture is partially

vaporized. The vapor produced and the residual liquids are in equilibrium in the
process are separated and removed as shown in Figure 5.8. Consider a binary
mixture of A (more volatile component) and B (less volatile component). The feed
is preheated before entering the separator. As such, part of the feed may be
vaporized. The heated mixture then flows through a pressure-reducing valve to
the separator. In the separator, separation between the vapor and liquid takes
place. The amount of vaporization affects the concentration (distribution) of A in
vapor phase and liquid phase. The relationship between the scale of vaporization
and mole fraction of A in vapor and liquid (y and x) is known as the Operating
Line Equation. Define f as molal fraction of the feed that is vaporized and
withdrawn continuously as vapor. Therefore, for 1 mole of binary feed mixture,
(1- f) is the molal fraction of the feed that leaves continuously as liquid. Assume,
yD = mole fraction of A in vapor leaving, xB = mole fraction of A in liquid leaving,
xF = mole fraction of A in feed entering. Based on the definition for f, the greater
the heating is, the larger the value of f. If the feed is completely vaporized, then f
= 1.0 Thus, the value of f can varies from 0 (no vaporization) to 1 (total
vaporization). From material balance for the more volatile component (A) one can
write

1.x F  fy D  (1  f ) x B (5.10)

Or,

fy D  x F  (1  f ) x B (5.11)

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Figure 5.8: Flash distillation process

The Equation (5.11) on rearranging becomes:

1 f  x
y D    x B  F (5.12)
 f  f

The fraction f depends on the enthalpy of the liquid feed, the enthalpies of the
vapor and liquid leaving the separator. For a given feed condition, and hence the
known value of f and xF, the Equation (5.12) is a straight line Equation with slope
- (1-f)/f and intercept xF/f as shown in Figure 5.9. It will intersect the equilibrium
line at the point (xB, yD). From this value, the composition of the vapor and liquid
leaving the separator can be obtained.

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Figure 5.9: Graphical presentation of flash veporization

5.2.2.2. Multi-stage Continuous distillation-Binary system

A general schematic diagram of a multistage counter-current binary distillation
operation is shown in Figure 4.10. The operation consists of a column containing
the equivalent N number of theoretical stages arranged in a two-section cascade;
a condenser in which the overhead vapor leaving the top stage is condensed to
give a liquid distillate product and liquid reflux that is returned to the top stage; a
reboiler in which liquid from the bottom stage is vaporized to give a liquid bottom
products and the vapor boil off returned to the bottom stage; accumulator is a
horizontal (usually) pressure vessel whereby the condensed vapor is collected;
Heat exchanger where the hot bottoms stream is used to heat up the feed stream

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before it enters the distillation column. The feed enters the column at feed stage
contains more volatile components (called light key, LK) and less volatile
components (called heavy key, HK). At the feed stage feed may be liquid, vapor
or mixture of liquid and vapor. The section above the feed where vapor is
washed with the reflux to remove or absorb the heavy key is called enriching or
rectifying section. The section below the feed stage where liquid is stripped of the
light key by the rising vapor is called stripping section.

Figure 5.10: Multi-stage binary distillation column

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MODULE 5: DISTILLATION

LECTURE NO. 4

5.2.2.3. Analysis of binary distillation in tray towers: McCabe-

Thiele Method
McCabe and Thiele (1925) developed a graphical method to determine the
theoretical number of stages required to effect the separation of a binary mixture
(McCabe and Smith, 1976). This method uses the equilibrium curve diagram to
determine the number of theoretical stages (trays) required to achieve a desired
degree of separation. It assumes constant molar overflow and this implies that: (i)
molal heats of vaporization of the components are roughly the same; (ii) heat
effects are negligible. The information required for the systematic calculation are
the VLE data, feed condition (temperature, composition), distillate and bottom
compositions; and the reflux ratio, which is defined as the ratio of reflux liquid
over the distillate product. For example, a column is to be designed for the
separation of a binary mixture as shown in Figure 5.11.

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Figure 5.11: Schematic of column for separation of binary mixture

The feed has a concentration of xF (mole fraction) of the more volatile

component, and a distillate having a concentration of xD of the more volatile
component and a bottoms having a concentration of xB is desired. In its essence,
the method involves the plotting on the equilibrium diagram three straight lines:
the rectifying section operating line (ROL), the feed line (also known as the q-
line) and the stripping section operating line (SOL). An important parameter in
the analysis of continuous distillation is the Reflux Ratio, defined as the quantity
of liquid returned to the distillation column over the quantity of liquid withdrawn as
product from the column, i.e. R = L / D. The reflux ratio R is important because
the concentration of the more volatile component in the distillate (in mole fraction
xD) can be changed by changing the value of R. The steps to be followed to
determine the number of theoretical stages by McCabe-Thiele Method:

 Determination of the Rectifying section operating line (ROL).

 Determination the feed condition (q).
 Determination of the feed section operating line (q-line).
 Determination of required reflux ratio (R).
 Determination of the stripping section operating line (SOL).

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 Determination of number of theoretical stage.

Determination of the Rectifying section operating line (ROL)

Consider the rectifying section as shown in the Figure 5.12. Material balance can
be written around the envelope shown in Figure 5.12:

Overall or total balance:

Vn1  Ln  D (5.13)

Component balance for more volatile component:

Vn1 y n1  Ln xn  DxD (5.14)

From Equations (4.13) and (4.14), it can be written as

( Ln  D) y n1  Ln xn  DxD (5.15)

Consider the constant molal flow in the column, and then one can write: L1 = L2 =
.......... Ln-1 = Ln = Ln+1 = L = constant and V1 = V2 = .......... Vn-1 = Vn = Vn+1 = V =
constant. Thus, the Equation (5.15) becomes:

( L  D) y n1  Lxn  DxD (5.16)

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Figure 5.12: Outline graph of rectifying section

After rearranging, one gets from Equation (5.16) as:

 L   D 
y n 1    xn    xD (5.17)
L D L D

Introducing reflux ratio defined as: R = L/D, the Equation (5.17) can be expressed
as:

 R   1 
y n 1    xn    xD (5.18)
 R 1  R  1

The Equation (5.18) is the rectifying section operating line (ROL) Equation having
slope R/(R+1) and intercept, xD/(R+1) as shown in Figure 5.13. If xn = xD, then
yn+1 = xD, the operating line passed through the point (xD, xD) on the 45o diagonal
line. When the reflux ratio R changed, the ROL will change. Generally the

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rectifying operating line is expressed without subscript of n or n+1. Without

subscript the ROL is expresses as:

 R   1 
y x    xD (5.19)
 R  1  R  1

Figure 5.13: Representation of the rectifying operating line

Determination the feed condition (q):

The feed enters the distillation column may consists of liquid, vapor or a mixture
of both. Some portions of the feed go as the liquid and vapor stream to the
rectifying and stripping sections. The moles of liquid flow in the stripping section
that result from the introduction of each mole of feed, denoted as ‘q’. The
limitations of the q-value as per feed conditions are shown in Table 5.3.

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Table 5.3: Limitations of q-value as per feed conditions

Feed condition Limit of q-value

cold feed (below bubble point) q>1
feed at bubble point (saturated liquid) q=1
feed as partially vaporized 0<q<1
feed at dew point (saturated vapor) q=0
feed as superheated vapor q<0
feed is a mixture of liquid and vapor q is the fraction of the feed that is liquid

Calculation of q-value

When feed is partially vaporized:

Other than saturated liquid (q = 1) and saturated vapor (q = 0), the feed condition
is uncertain. In that case one must calculate the value of q. The q-value can be
obtained from enthalpy balance around the feed plate. By enthalpy balance one
can obtain the q-value from the following form of Equation:

HV  H F
q (5.20)
HV  H L

where HF, HV and HL are enthalpies of feed, vapor and liquid respectively which
can be obtained from enthalpy-concentration diagram for the mixture.

When feed is cold liquid or superheated vapor:

q can be alternatively defined as the heat required to convert 1 mole of feed from
its entering condition to a saturated vapor; divided by the molal latent heat of
vaporization. Based on this definition, one can calculate the q-value from the
following Equations for the case whereby q > 1 (cold liquid feed) and q < 0
(superheated vapor feed) as:

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For cold liquid feed:

C p , L (Tbp  TF )  
q (5.21)


For superheated vapor feed:

C p ,V (Tdp  TF )
q (5.22)


where Tbp is the bubble point,  is the latent heat of vaporization and Tdp is the
dew point of the feed respectively.

Determination of the feed section operating line (q-line):

Consider the section of the distillation column (as shown in Figure 5.11) at the
tray (called feed tray) where the feed is introduced. In the feed tray the feed is
introduced at F moles/hr with liquid of q fraction of feed and vapor of (1-f) fraction
of feed as shown in Figure 5.14. Overall material balance around the feed tray:

L  L  qF and V  V   (1  q) F (5.23)

Component balances for the more volatile component in the rectifying and
stripping sections are:

For rectifying section:

Vy  Lx  DxD (5.24)

For stripping section:

V y  Lx  Bx B (5.25)

At the feed point where the two operating lines (Equations (5.24) and (5.25)
intersect can be written as:

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(V  V ) y  ( L  L) x  DxD  Bx B (5.26)

Figure 5.14: Feed tray with fraction of liquid and vapor of feed

From component balance around the entire column, it can be written as

Fx F  DxD  Bx B (5.27)

Substituting L-L’ and V-V’ from Equations (5.23) and (5.24) into Equation (5.26)
and with Equation (5.27) one can get the q-line Equation after rearranging as:

 q   1 
y    x    x F (5.28)
1 q  1 q 

For a given feed condition, xF and q are fixed, therefore the q-line is a straight
line with slope -q / (1-q) and intercept xF/(1-q). If x = xF , then from Equation

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(5.28) y = xF. At this condition the q-line passes through the point (xF, xF) on the
45o diagonal. Different values of q will result in different slope of the q-line.
Different q-lines for different feed conditions are shown in Figure 5.15.

Figure 5.15: Different q-lines for different feed conditions

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MODULE 5: DISTILLATION

LECTURE NO. 5

Determination of the stripping section operating line (SOL):

The stripping section operating line (SOL) can be obtained from the ROL and q-
line without doing any material balance. The SOL can be drawn by connecting
point xB on the diagonal to the point of intersection between the ROL and q-line.
The SOL will change if q-line is changed at fixed ROL. The change of SOL with
different q-lines for a given ROL at constant R and xD is shown in Figure 5.16.

Figure 5.16: Stripping section operating line with different q-lines

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The stripping section operating line can be derived from the material balance
around the stripping section of the distillation column. The stripping section of a
distillation column is shown in Figure 5.17. The reboiled vapor is in equilibrium
with bottoms liquid which is leaving the column.

Figure 5.17: Schematic of the stripping section

Consider the constant molal overflow in the column. Thus L'm = L'm+1 = .... = L' =
constant and V'm = V'm+1 = ..... = V' = constant.

Overall material balance gives

L  V   B (5.29)

More volatile component balance gives:

Lxm  V y m1  Bx B (5.30)

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Substituting and re-arranging the Equation (5.30) yields

 L  B
y m1    xm    x B (5.31)
V   V  

Dropping the subscripts "m+1" and "m" it becomes:

 L   B 
y    x    xB (5.32)
V   V  

Substituting V' = L' – B from Equation (5.29), the Equation (5.32) can be written
as:

 L   B 
y x    xB (5.33)
 L  B   L  B 

The Equation (5.33) is called the stripping operating line (SOL) which is a straight
line with slope ( L' / L' - B) and intercept ( BxB / L' - B ). When x = xB , y = xB, the
SOL passes through (xB, xB ) on the 45o diagonal line.

Determination of number of theoretical stage

Suppose a column is to be designed for the separation of a binary mixture where

the feed has a concentration of xF (mole fraction) of the more volatile component
and a distillate having a concentration of xD of the more volatile component
whereas the bottoms having a desired concentration of xB. Once the three lines
(ROL, SOL and q-line) are drawn, the number of theoretical stages required for a
given separation is then the number of triangles that can be drawn between
these operating lines and the equilibrium curve. The last triangle on the diagram
represents the reboiler. A typical representation is given in Figure 5.18.

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Figure 5.18: A typical representation of identifying number of theoretical stages

Reflux Ratio, R

The separation efficiency by distillation depends on the reflux ratio. For a given
separation (i.e. constant xD and xB) from a given feed condition (xF and q), higher
reflux ratio (R) results in lesser number of required theoretical trays (N) and vice
versa. So there is an inverse relationship between the reflux ratio and the
number of theoretical stages. At a specified distillate concentration, xD, when R
changes, the slope and intercept of the ROL changes (Equation (5.19)). From the
Equation (5.19), when R increases (with xD constant), the slope of ROL becomes
steeper, i.e. (R/R+1) and the intercept (xD/R+1) decreases. The ROL therefore
rotates around the point (xD, xD). The reflux ratio may be any value between a
minimum value and an infinite value. The limit is the minimum reflux ratio (result
in infinite stages) and the total reflux or infinite reflux ratio (result in minimum
stages). With xD constant, as R decreases, the slope (R/R+1) of ROL (Equation

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(5.19)) decreases, while its intercept (xD/R+1) increases and rotates upwards
around (xD, xD) as shown in Figure 5.19. The ROL moves closer to the
equilibrium curve as R decreases until point Q is reached. Point Q is the point of
intersection between the q-line and the equilibrium curve.

Equilibrium line
Q

ROL
xD/(Rm+1)
y

q-line

xD/(R+1)
SOL

xF xD
xB

Figure 5.19: Representation of minimum reflux rtio

At this point of intersection the driving force for mass transfer is zero. This is also
called as Pinch Point. At this point separation is not possible. The R cannot be
reduced beyond this point. The value of R at this point is known as the minimum
reflux ratio and is denoted by Rmin. For non-ideal mixture it is quite common to
exhibit inflections in their equilibrium curves as shown in Figure 5.20 (a, b). In
those cases, the operating lines where it becomes tangent to the equilibrium
curve (called tangent pinch) is the condition for minimum reflux. The ROL cannot

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move beyond point P, e.g. to point K. The condition for zero driving force first
occurs at point P, before point K which is the intersection point between the q-
line and equilibrium curve. Similarly it is the condition SOL also. At the total reflux
ratio, the ROL and SOL coincide with the 45 degree diagonal line. At this
condition, total number of triangles formed with the equilibrium curve is equal
minimum number of theoretical stages. The reflux ratio will be infinite.

Figure 5.20 (a): Representation of minimum reflux ratio for non-ideal mixture

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Figure 5.20 (b): Representation of minimum reflux ratio for non-ideal mixture

Tray Efficiency

For the analysis of theoretical stage required for the distillation, it is assumed that
the the vapor leaving each tray is in equilibrium with the liquid leaving the same
tray and the trays are operating at 100% efficiency. In practice, the trays are not
perfect. There are deviations from ideal conditions. The equilibrium with
temperature is sometimes reasonable for exothermic chemical reaction but the
equilibrium with respect to mass transfer is not often valid. The deviation from the
ideal condition is due to: (1) Insufficient time of contact
(2) Insufficient degree of mixing. To achieve the same degree of desired
separation, more trays will have to be added to compensate for the lack of

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perfect separability. The concept of tray efficiency may be used to adjust the the
actual number of trays required.

Overall Efficiency

The overall tray efficiency, EO is defined as:

No. of theoratica l trays

Eo  (5.34)
No. of actual trays

It is applied for the whole column. Every tray is assumed to have the same
efficiency. The overall efficiency depends on the (i) geometry and design of the
contacting trays, (ii) flow rates and flow paths of vapor and liquid streams, (iii)
Compositions and properties of vapor and liquid streams (Treybal, 1981; Seader
and Henley, 1998). The overall efficiency can be calculated from the following
correlations:

The Drickamer-Bradford empirical correlation:

Eo  13.3  66.8 log(  ) (5.35)

The corrrelation is valid for hydrocarbon mixtures in the range of 342 K < T <
488.5 K, 1 atm < P < 25 atm and 0.066 < µ < 0.355 cP

The O'Connell correlation:

Eo  50.3( ) 0.226 (5.36)

Murphree Efficiency

The efficiency of the tray can also be calculated based on semi-theoretical

models which can be interpreted by the Murphree Tray Efficiency E M. In this case
it is assumed that the vapor and liquid between trays are well-mixed and have
uniform composition. It is defined for each tray according to the separation

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achieved on each tray based on either the liquid phase or the vapor phase. For a
given component, it can be expressed as:

Based on vapor phase:

y n  y n 1
E MV  (5.37)
y n*  y n 1

Based on liquid phase:

x n  x n 1
E ML  (5.38)
x n*  x n 1

Example problem 5.2:

A liquid mixture of benzene toluene is being distilled in a fractionating column at
101.3 k Pa pressure. The feed of 100 kmole/h is liquid and it contains 45 mole%
benzene (A) and 55 mole% toluene (B) and enters at 327.6 K. A distillate
containing 95 mole% benzene and 5 mole% toluene and a bottoms containing 10
mole% benzene and 90 mole% toluene are to be obtained. The amount of liquid
is fed back to the column at the top is 4 times the distillate product. The average
heat capacity of the feed is 159 KJ/kg mole. K and the average latent heat 32099
kJ/kg moles.
Calculate
i. The kg moles per hour distillate, kg mole per hour bottoms
ii. No. of theoretical stages at the operating reflux.
iii. The minimum no. of theoretical stages required at total reflux
iv. If the actual no. of stage is 10, what is the overall efficiency increased
at operating condition compared to the condition of total reflux?
The equilibrium data:
Temp.(K) 353.3 358.2 363.2 366.7 373.2 378.2 383.8
xA (mole fraction) 1.000 0.780 0.580 0.450 0.258 0.13 0
yA(mole fraction) 1.000 0.900 0.777 0.657 0.456 0.261 0

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Solution 5.2:

F=D+B
100 = D + B
F xF = D xD + B xB
Therefore, D = 41.2 kg mole/h, B = 58.8 kg mole/h
y = [R/(R+1)] x + xD/(R+1) = 0.8 x +0.190
q = 1+ cpL (TB-TF)/Latent heat of vaporization
TB = 366.7 K from boiling point of feed, TF = 327.6 K ( inlet feed temp)
Therefore q = 1.195
Slope of q line = 6.12
From the graph (Figure E1), Total no of theoretical stages is 8 at operating reflux
(Red color)
From the graph (Figure E1), Total no of theoretical stages is 6 at total reflux
(Black color)
Overall efficiency at operating conditions: Eo (Operating) = No of ideal stage/ No
of actual trays = 7.9/10 = 0.79
Overall efficiency at total reflux conditions: Eo (total relux) = No of ideal stage/ No
of actual trays = 5.9/10=0.59
Overall efficiency increased: 0.79-0.59 = 0.20

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Figure E1: Graph representing the example problem 5.2.

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MODULE 5: DISTILLATION

LECTURE NO. 6

5.2.2.4. Analysis of binary distillation by Ponchon-Savarit

Method

Background Principle:

The method is concerned with the graphical analysis of calculating the theoretical
stages by enthalpy balance required for desired separation by distillation process
(Hines and Maddox, 1984). In this method, the enthalpy balances are
incorporated as an integral part of the calculation however it is not considered in
the analysis separation by distillation process by McCabe-Thele method. This
procedure combines the material balance calculations with enthalpy balance
calculations. This method also provides the information on the condenser and
reboiler duties. The overall material balance for the distillation column is as
shown in Figure 5.11:

F  DB (5.39)

For any component the material balance around the column can be written as:

Fx F  DxD  Bx B (5.40)

Overall enthalpy balance for the column yields

FH F  QR  DH D  BH B  QC (5.41)

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where H is the enthalpy of the liquid stream, energy/mol, Q R is the heat input to
the reboiler, J/s and QC is the heat removed from condenser, J/s. The heat
balance on rearrangement of Equation (5.41) gives

 Q   Q 
FH F  D H D  C   B H B  R  (5.42)
 D   R 

The Equation (5.41) is rearranged as Equation (5.42) for the convenience to plot
it on the enthalpy-concentration diagram. The points represented by the feed,
distillate and bottom streams can be plotted on the enthalpy-concentration
diagram as shown in Figure 5.21.

Figure 5.21: Representation of feed, distillate and bottom streams on the enthalpy-concentration

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Substituting the Equation (5.39) into the Equation (5.40) and (5.42) we get

( D  B) x F  DxD  Bx B (5.43)

 Q   Q 
( D  B) H F  D H D  C   B H B  R  (5.44)
 D   R 

From the Equations (5.43) and (5.44) one can write

QR
H F  (H B  )
D xF  xB R
  (5.45)
B xD  xF Q
(H D  C )  H F
D

The Equation (5.45) can also be written on rearrangement as:

xF  xB xD  xF
 (5.46)
Q Q
H F  (H B  R ) (H D  C )  H F
R D

Comparing the Equation (5.46) with the points plotted on Figure (5.21), it is found
that the left hand side of the Equation (5.46) represents the slope of the straight
line between the points (xB, HB-QR/B) and (xF, HF). The right hand side of the
Equation (5.46) represents the slope of the straight line passing through the
points (xF, HF) and (xD, HD-QC/D). From this it can be said that all three points are
on a same straight line. The amount of distillate as per Equation (5.45) is
______
proportional to the horizontal distance x F x B and the amount of bottoms is
______
proportional to the horizontal distance x D x F , then from the overall material
balance it can be interpreted that the amount of feed is proportional to the
______
horizontal distance x D x B . This leads to the inverse lever rule. Based on this
principle, the analysis of distillation column is called Enthalpy-composition
analysis or Ponchon-Savarit analysis of distillation column.

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Analysis of tray column

Consider the theoretical stage shown in Figure 5.12 and the principle by which it
operates is described in the enthalpy-composition diagram as shown in Figure
5.22.

Figure 5.22: Operation principle of stage-wise binary distillation on enthalpy-concentration diagram

The vapor entering to the tray (n), Vn+1 is a saturated vapor of composition yn+1
wheras the liquid entering to the tray is Ln-1 of composition xn-1. The point P in the
Figure 5.22 represents the total flow to the tray. The point P lies in a straight line
______
joining xn-1 and yn+1. The distance y n1 P is proportional to the quantity Ln-1 and
______
the distance x n1 P is proportional to the quantity Vn+1 as per lever rule. So

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______
Ln 1 y n 1 P
 ______ (5.47)
Vn 1
x n 1 P

The sum of the liquid and vapor leaving the plate must equal the total flow to the
plate. So the tie line must pass through the point P which represents the addition
point of the vapor Vn and liquid Ln leaving the tray. The intersection of the tie line
with the enthalpy-composition curves will represent the compositions of these
streams.

Around the tray n, the material balances can be written as:

Vn1  Ln  Vn  Ln1 (5.48)

Vn1 y n1  Ln xn  Vn y n  Ln1 xn1 (5.49)

The enthalpy balance around the tray gives

Vn1 H V ,n1  Ln H L,n  Vn H V ,n  Ln1 H L,n1 (5.50)

Where HV is the enthalpy of the vapor and HL is the enthalpy of the liquid. From
the material and enthalpy balance Equations above mean that the stream that
added to Vn+1 to generate Ln is same to the stream that must be added to V n to
generate Ln-1. In the Figure 5.22, Δ represents the difference point above and
below the tray. This point of a common difference point can be extended to a
section of a column that contains any number of theoretical trays.

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MODULE 5: DISTILLATION

LECTURE NO. 7

Stepwise procedure to determine the number of theoretical trays:

Step 1: Draw the equilibrium curve and the enthalpy concentration diagram for
the mixture to be separated

Step 2: Calculate the compositions of the feed, distillate and bottom products.
Locate these compositions on the enthalpy-concentration diagram.

Step 3: Estimate the reflux rate for the separation and locate the rectifying
section difference point as ΔR as shown in Figure 5.23. Point y1 is the intersection
point of line joining point xD and ΔR and HV-y curve.

Step 4: Locate the stripping section difference point Δs. The point Δs is to be
located at a point where the line from ΔR through xF intersects the xB composition
coordinate as shown in Figure 4.23.

Step 5: Step off the trays graphically for the rectifying section. Then the point of
composition x1 of liquid of top tray is to be determined from the equilibrium
relation with y1 of vapor which is leaving the tray and locate it to the HL-x curve.
Then the composition y2 is to be located at the point where the line of points Δ R
and x1 intersects HV-y curve. This procedure is to be continued until the feed plate
is reached.

Step 6: Similarly follow the same rule for stripping section. In the stripping
section, the vapor composition yB leaving the reboiler is to be estimated from the
equilibrium relation. Then join the yB and ΔS to find the xN. The vapor composition

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yN is to be determined by extending a tie line to saturated vapor curve HV-y. The

procedure is to be continued until the feed tray is attained.

Determination of the reflux rate:

The reflux rate can be calculated from the energy balance around the condenser
as:

V1 H V ,1 LD H D  DH D  QC (5.51)

By substituting V1 = LD + D into Equation (5.51) and rearranging, it can be written

as:

_________
LD ( H D  QC / D)  H V ,1  R H V ,1
  _________ (5.52)
D H V ,1  H D
H V ,1 H D

________ ________
Where  R H V ,1 and H V ,1 H D are the lengths of lines between points ΔR and HV,1

and HV,1 and HD. The internal reflux ratio between any two stages in rectifying
section can be expressed as:

_________
Ln ( H D  QC / D)  H V ,n 1  R H V ,n 1
  _________ (5.53)
Vn 1 ( H D  QC / D)  H L ,n
 R H L ,n

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Figure 5.23: Representation of estimation of no of stages by Ponchon-Savarit Method

Whereas in the stripping section it can be expressed as:

Lm1 H V , m  ( H B  QR / B)
 (5.54)
Vm H L ,m1  ( H B  QR / B)

The relationship between the distillate and bottom products in terms of

compositions and enthalpies can be made from the material balance around the
overall column which can be written as:

FH F  QR  DH D  BH B  QC (5.55)

Overall material balance F = D + B combining with Equation (5.55) yields

_________
D H F  ( H B  QR / B) xF  S
  _________ (5.56)
B ( H D  QC / D)  H F
xF  R

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Minimum number of trays

In this method, if D approaches zero, the enthalpy coordinate (HD +QC/D) of the
difference point approaches infinity. Other way it can be said that Qc becomes
large if L becomes very large with respect to D. Similarly enthalpy coordinate for
stripping section becomes negative infinity as B approaches zero or liquid
loading in the column becomes very large with respect to B. Then the difference
points will locate at infinity. In such conditions, the trays required for the desired
separation is referred as minimum number of trays. The thermal state of the feed
has no effect on the minimum number of trays required for desired separation.

Minimum reflux

The minimum reflux for the process normally occurs at the feed tray. The
minimum reflux rate for a specified separation can be obtained by extending the
tie line through the feed composition to intersect a vertical line drawn through xD.
Extend the line to intersect the xB composition line determines the boilup rate and
the reboiler heat duty at minimum reflux.

Example problem 5.3:

A total of 100 gm-mol feed containing 40 mole percent n-hexane and 60 percent
n-octane is fed per hour to be separated at one atm to give a distillate that
contains 92 percent hexane and the bottoms 7 percent hexane. A total
condenser is to be used and the reflux will be returned to the column as a
saturated liquid at its bubble point. A reflux ratio of 1.5 is maintained. The feed is
introduced into the column as a saturated liquid at its bubble point. Use the
Ponchon-Savarit method and determine the following:
(i) Minimum number of theoretical stages
(ii) The minimum reflux ratio
(iii) The heat loads of the condenser and reboiler for the condition of
minimum reflux.

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(iv) The quantities of the diustillate and bottom streams using the actual
reflux ratio.
(v) Actual number of theoretical stages
(vi) The heat load of the condenser for the actual reflux ratio
(vii) The internal reflux ratio between the first and second stages from the
top of tower.

VLE Data, Mole Fraction Hexane, 1 atm

x 0 0.1 0.3 0.5 0.55 0.7 1

y 0 0.36 0.7 0.85 0.9 0.95 1

Enthalpy-Concentration Data

Mole fraction,
Hexane 0 0.1 0.3 0.5 0.7 0.9 1
Sat.
Liquid 7000 6300 5000 4100 3400 3100 3000
Enthalpy, Sat.
Cal/gm-mol Vapor 15,700 15,400 14,700 13,900 12,900 11,600 10,000

Solution 5.3:

(i) The minimum number of stages can be obtained by drawing vertical operating
lines that intersects as R tends to infinity. As shown in Figure E2, three stages
required.

(ii) Using Equation (5.52), the minimum reflux is

_________
LD ( H D  QC / D)  H V ,1  R H V ,1 19000  11500
  _________   0.88
D H V ,1  H D 11500  3000
H V ,1 H D

(iii) From the Figure E2, H B  QR / B =-5000

QR / B = 5000+7000 = 12000

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H D  QC / D = 19000

QC / D = 19000-11500 =7500

(iv) The distillate and bottom flowrates are obtained by solving the overall and
component material balances simultaneously

100 = D + B

0.4 (1000 = 0.92 D + 0.04 B

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Figure E2: Minimum reflux and minimum stages for example problem 4.3

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Figure E3: Actual stages for Example problem 4.3.

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Thus D = 40.9 gmmol/h

B = 100 – 40.9 = 59.1 gmmol/h

L  L 
(v)  D   1.5 D   1.5(0.88)  1.32
 D  act  D  min

Using Equation (5.52) gives a new value for R :

( H D  QC / D)  11500
1.32  Or, H D  QC / D  22750
11500  3000

A new R is located in Figure E3 and the actual number of theoretical stages is

found as 5.

(vi) From the Figure E3

H D  QC / D  22750

So QC / D  22750 – 11500 = 11250

(vii) Reading enthalpies for the points (a) and (b) and using Equation (5.53) gives

Ln ( H D  QC / D)  H V ,n1 22750  12050

   0.563
Vn 1 ( H D  QC / D)  H L,n 22750  3750

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MODULE 5: DISTILLATION

LECTURE NO. 8

5.3. Introduction to Multicomponent Distillation

In industry, most of the distillation processes involve with more than two components.
The multicomponent separations are carried out by using the same type of distillation
columns, reboilers, condensers, heat exchangers and so on. However some
fundamental differences are there which is to be thoroughly understood by the designer.
These differences are from phase rule to specify the thermodynamic conditions of a
stream at equilibrium. In multicomponent systems, the same degree of freedom is not
achieved because of the presence of other components. Neither the distillate nor the
bottoms composition is completely specified. The components that have their distillate
and bottoms fractional recoveries specified are called key components. The most
volatile of the keys is called the light key (LK) and the least volatile is called the heavy
key (HK). The other components are called non-keys (NK). Light no-key (LNK) is
referred when non-key is more volatile than the light key whereas heavy non-key (HNK)
is less volatile than the heavy key. Proper selection of key components is important if a
multicomponent separation is adequately specified. Several short-cut methods are used
for carrying out calculations in multicomponent systems. These involve generally an
estimation of the minimum number of trays, the estimation of minimum reflux rate and
number of stages at finite reflux for simple fractionators. Although rigorous computer
methods are available to solve multicomponent separation problems, approximate
methods are used in practice. A widely used approximate method is commonly referred
to as the Fenske-Underwood-Gilliland method.

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5.3.1. Estimation of Minimum number of trays: Fenske Equation

Fenske (1932) was the first to derive an Equation to calculate minimum number of trays
for multicomponent distillation at total reflux. The derivation was based on the
assumptions that the stages are equilibrium stages. Consider a multicomponent
distillation column operating at total reflux as shown in Figure 5.24.

Equilibrium relation for the light key component on the top tray is

y1  K1 x1 (5.57)

For total condenser, y1 = xD then

x D  K1 x1 (5.58)

An overall material balance below the top tray and around the top of the column can be
written as:

V2  L1  D (5.59)

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Figure 5.24: Multicomponent column at minimum trays

Under total reflux condition, D = 0, thus, V2 = L1. The component material balance for
the light key component around the first plate and the top of the column is

V2 y 2  L1 x1  DxD (5.60)

Then under the conditions of the minimum trays, the Equation (5.60) yields y 2 = x1. The
equilibrium relation for plate 2 is

y 2  K 2 x2 (5.61)

The Equation (5.61) becomes at y2 = x1

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x1  K 2 x2 (5.62)

Substituting Equation (5.62) into Equation (5.58) yields

x D  K1 K 2 x 2 (5.63)

Continuing this calculation for entire column, it can be written as:

x D  K1 K 2 ...........K n K B x B (5.64)

In the same fashion, for the heavy key component, it can be written as:

xD  K1K 2 ...........K n K B xB (5.65)

Equation (5.64) upon Equation (5.65) gives

x D K1 K 2 ...........K n K B x B
 (5.66)
x D K1K 2 ...........K n K B x B

The ratio of the K values is equal to the relative volatility, thus the Equation (5.66) can
be written as

xD x
  1 2 ........... n B B (5.67)
x D x B

If average value of the relative volatility applies for all trays and under condition of
minimum trays, the Equation (5.67) can be written as

xD N min x B
  avg (5.68)
x D x B

Solving Equation (5.68) for minimum number of trays, Nmin

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 x x 
ln  D B 
x x
N min   D B  (5.70)
ln  ave

The Equation (5.70) is a form of the Fenske Equation. In this Equation, N min is the
number of equilibrium trays required at total reflux including the partial reboiler. An
alternative form of the Fenske Equation can be easily derived for multi-component
 ( DxD )( Bx B ) 
ln  
 ( Dx D )( Bx B ) 
calculations which can be written as N min 
ln  ave
(5.71)

The amount of light key recovered in the distillate is ( DxD ) . This is equal to the fractional
recovery of light key in the distillate say FR D times the amount of light key in the feed
which can be expressed as:
DxD  ( FRD ) Fx LK (5.72)
From the definition of the fractional recovery one can write
Bx B  (1  FRD ) Fx LK (5.73)
Substituting Equations (5.72) and (5.73) and the corresponding Equations for heavy key
into Equation (5.71) yields

 ( FR D )( FRB ) 
ln  
 (1  FR D )(1  FRB ) 
N min  (5.74)
ln  ave

Once the minimum number of theoretical trays, Nmin is known, the fractional recovery of
the non-keys can be found by writing Equation (5.74) for a non-key component and
either the light or heavy key. Then solve the Equation for FR NK,B or FRNK,D. If the key
component is chosen as light key, then FRNK,D can be expressed as

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 NK
N min

FR NK , D   LK
(5.75)
FRB
  NK
N min
 LK
1  FRB

4.3.2. Minimum Reflux: Underwood Equations

For multi-component systems, if one or more of the components appear in only one of
the products, there occur separate pinch points in both the stripping and rectifying
sections. In this case, Underwood developed an alternative analysis to find the
minimum reflux ratio (Wankat, 1988). The presence of non-distributing heavy non-keys
results a pinch point of constant composition at minimum reflux in the rectifying section
whereas the presence of non-distributing light non-keys, a pinch point will occur in the
stripping section. Let us consider the pinch point is in the rectifying section. The mass
balance for component i around the top portion of the rectifying section as illustrated in
Figure 5.24 is
Vmin yi ,n1  Lmin xi ,n  Dxi , D (5.76)

The compositions are constant at the pinch point then

xi ,n1  xi ,n  xi ,n1 (5.77)

and
yi ,n1  yi ,n  yi ,n1 (5.78)

The equilibrium relation can be written as

yi ,n1  mi xi ,n1 (5.79)

From the Equations (5.76) to (5.79) a balance in the region of constant composition can
be written as
Lmin
Vmin yi ,n 1  yi ,n 1  Dxi , D (5.80)
mi
Defining the relative volatility αi=mi/mHK and substituting in Equation (5.80) one can
express after rearranging as

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 i Dxi , D
Vmin y i ,n 1  (5.81)
Lmin
i 
Vmin m HK

The total vapor flow in the rectifying section at minimum reflux can be obtained by
summing Equation (5.81) over all components as:
 i Dxi , D
Vmin  Vmin yi ,n 1   (5.82)
Lmin
i i
i 
Vmin m HK

Similarly after analysis for the stripping section, one can get
 i , st Bx i , B
 Vst ,min   (5.83)
Lst ,min
i
 i , st 
Vst ,min m HK , st

Defining
Lmin Lst ,min
1  and 2  (5.84)
Vmin m HK Vst ,min m HK , st

Equations (5.82) and (5.83) then become

 i Dxi , D
Vmin   (5.85)
i i  1

 i Bx i , B
and  Vst ,min   (5.86)
i i  2

For constant molar overflow and constant relative volatilities, 1  2   that satisfies

both Equations (5.86). The change in vapor flow at the feed stage ( VF ) is then written
as by adding the Equations (5.86)
 i Dxi , D  i Bx i , B 
VF  Vmin  Vst ,min    
 i   
(5.87)
i  i  

Combining (5.87) with the overall column mass balance for component i can be
expressed as
 i Fx f , i 
VF     (5.88)
i  i   

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Again if the fraction q is known, the change in vapor flow at the feed stage can be
expressed as
VF  F (1  q) (5.89)
Comparing Equation (5.88) and (5.89)
  i x f ,i 
(1  q)     (5.90)
i  i   

Equation (5.90) is known as the first Underwood Equation which is used to calculate
appropriate values of λ. whereas Equation (5.86) is known as the second Underwood
Equation which is used to calculate Vm. From the mass balance Lm can be calculated as
L min  Vmin  D
(5.91)

4.3.3. Estimation of Numbers of Stages at Finite Reflux: Gilliland

Correlation
Gilliland (1940) developed an empirical correlation to relate the number of stages N at a
finite reflux ratio L/D to the minimum number of stages and to the minimum reflux ratio.
Gilliland represented correlation graphically with ( N  N min ) /( N  1) as y-axis and

( R  Rmin ) /( R  1) as x-axis. Later Molokanov et al. (1972) represented the Gilliland

correlation as:

( N  N min )  1  54.4( R  Rmin ) /( R  1)  ( R  Rmin ) /( R  1)  1 

 1  exp   
0.5 
(5.92)
N 1  11  117.2( R  Rmin ) /( R  1)  [( R  Rmin ) /( R  1)] 
According to Seader and Henley (1998), an approximate optimum feed-stage location,
can be obtained by using the empirical Equation of Kirkbride (1944) as
0.206
 x  xLK , B 
2 
NR
 
HK , F    B 
  x    (5.93)
NS
 xLK , F  HK , D   D 
 
where NR and NS are the number of stages in the rectifying and stripping sections,
respectively.

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Example problem 5.4:

A feed 100 kmoles/h of saturated liquid containing 10 mole % LNK, 55 mole % LK, and
35 mole % HK and is to be separated in a distillation column. The reflux ratio is 1.2 the
minimum. It is desired to have 99.5 % recovery of the light key in the distillate. The mole
fraction of the light key in the distillate should be 0.75. Equilibrium data: LNK = 4.0, LK
= 1.0, HK = 0.75.
Find
(i) Minimum number of stages required by Fenske method
(ii) Minimum reflux ratio by Underwood method
(iii) Number of ideal stages at R = 1.2 Rmin by Gilliland method
(iv) Also find the number of ideal stages at rectifying section and the stripping
section at the operating reflux ratio and location of feed stage.
Solution 5.4:
(i) Feed F = 100 kmol/s, xLNK,F = 0.1, xLK,F = 0.55, xHK,F = 0.35, xLK,D = 0.75, FRLK,D =
0.995, HK = 0.75, LNK = 4.0, LK = 1.0.
From the material balance
F .x LK , F FR LK , D
D  72.967 kmole/h
x LK , D

Therefore W = F-D = 27.033 kmole/h

The amount of kmoles of different component in distillate:
nLND = F.xLNK,F.FRLK,D = 54.725 kmole/h
nLNK,D = F.xLNK,F = 10 kmole/h
nHK,D = D- nLK,D – nLNK,D = 8.242 kmole/h
The amount of kilo moles of different component in bottoms:
nLK,B = F. xLK,F (1- FRLK,D) = 0.275 kmole/h
nLNK,B = 0
nHK,B = B-nLK,B –nLNK,B = 26.758 kmole/h
 = 1/HK
xHK,D = nHK,D/D = 0.113
xLK,B = nLK,B/B = 0.0102
Then as per Equation (5.71)

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Nmin = 22.50
(ii) To find the minimum reflux at the condition of saturated liquid, q = 1, 1 = 2 = ,
using Equation (5.90)
(4.0)(0.1) (1.0)(0.55) (0.75)(0.35)
0  
4.0   1.0   0.75  
gives  = 0.83
Then from Equation (5.85)
Vmin = 253.5 kmole/h
And Lmin = Vmin – D = 180.53 kmole/h
Rmin = Lmin/D = 2.47

(iii) Now using the Gilliland correlation (Equation (5.92) to determine number of ideal
stages at R = 1.2 Rmin =2.97 one can get N = 48.89
(iv) Using Kirkbride Equation
0.206
 x  xLK , B 
2 
NR
 
HK , F    B 
  x     0.275
NS
 xLK , F  HK , D   D 
 
Again NR + NS = N = 48.89
So by solving the above two Equations one get NR = 10.56 and NS = 38.34 and feed at
stage 11
Nomenclature

B Moles of bottoms F Moles of feed

BPC Bubble point curve f Molal fraction of feed
D Moles of distillate H Enthalpy
DPC Dew point curve K Equilibrium constant
Eo Overall tray efficiency L Moles of liquid
Emv Tray efficiency based on vapor L’ Moles of liquid in stripping section
phase N, n Number of tray
EmL Tray efficiency based on liquid P Pressure, Pinch point
phase Q Rate of heat transfer

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R Reflux ratio
V Moles of vapor
V’ Moles of vapor in stripping
section
x mole fractions in liquid
y mole fractions in vapor
T Temperature
 Relative volatility
µ Viscosity

Subscripts
B Bottom
C Condenser
D Distillate
F Feed
HK Heavy key
i 1, 2, 3, …., n
L Liquid
LK Light key
min Minimum
NK Non key
R Rectifying section
S Stripping section
V Vapor

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References
Ghosal, S.K., Sanyal, S.K. and Dutta, S., Introduction to Chemical Engineering,
Tata McGraw Hill Book Co. (2004).

Gilliland, E. R., Multicomponent Rectification: estimation of number of theoretical

plates as a function of reflux ratio, Ind. Eng. Chem., 32, 1220-1223 (1940).

Hines, A. L.; Maddox, R. N., Mass Transfer: Fundamentals and Applications,

Prentice Hall; 1 Edition (1984).

Kirkbride, C. G., Petroleum Refiner 23(9), 321 (1944).

McCabe, W. L., Thiele, E. W., Graphical Design of Fractionating Columns, Ind.

Eng. Chem. 17, 605 (1925).

McCabe, W. L. and Smith, J. C., Unit Operations of Chemical Engineering, (3rd

ed.), McGraw-Hill (1976).

Molokanov, Y. K., Korabline, T. R., Mazuraina, N. I. And Nikiforov, G. A., An

Approximate Method for Calculating the Basic Parameters of Multicomponent
Fractionation, International Chemical Engineering, 12(2), 209 (1972).

Seader, J.D. and Henley, E.J., Separation Process Principles, Wiley, New York
(1998).

Treybal R.E, “Mass Transfer Operations”, McGraw – Hill International Edition, 3rd
Ed., (1981).

Wankat, P. C., Equilibrium Staged Separations: Separations for Chemical

Engineers, Elsevier (1988).

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