1

CHE 312
SEPARATION PROCESSES 1
DISTILLATION
Distillation can be defined as the process of separating, concentrating or purifying liquid by boiling it and then
condensing the resulting vapour. It is the most widely used method of separating liquid mixtures into their vapour
components. It is one of the major operations in the process industries and the key operation in any oil refinery.
Distillation, in the industry, takes place in a distillation column. A distillation column is equipment for separating
liquid mixtures. It is a hollow vertical column, fitted with trays inside or packing material, in which liquid
mixtures are separated into their components by boiling the mixture and condensing the resulting vapour. The
vertical cylindrical column provides, in a compact form and with the minimum of ground requirements, a large
number of separate stages of vaporization and condensation. In engineering terms, distillation columns have to be
designed with a larger range in capacity than any other types of processing equipment, with single columns 0.3–
10 m in diameter and 3–75 m in height. Designers are required to achieve the desired product quality at minimum
cost and also to provide constant purity of product even though there may be variations in feed composition.
The separation of benzene from a mixture with toluene, for example, requires only a simple single unit as shown
in Figure 1 and virtually pure products may be obtained. A more complex arrangement is shown in Figure 2
where the columns for the purification of crude styrene formed by the dehydrogenation of ethyl benzene. In this
case, several columns are required and it is necessary to recycle some of the streams to the reactor.

Figure 1: Separation of a Binary Mixture

Figure 2: Multicomponent Separation

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VAPOUR–LIQUID EQUILIBRIUM
The composition of the vapour in equilibrium with a liquid of given composition is determined experimentally
using an equilibrium still. The results are conveniently shown on a temperature–composition diagram as shown in
Figure 3.In the normal case shown in Figure 3a, the curve ABC shows the composition of the liquid which boils
at any given temperature and the curve ADC the corresponding composition of the vapour at that temperature.
Thus, a liquid of composition x1 will boil at temperature T1, and the vapour in equilibrium is indicated by point D
of composition y1. It is seen that for any liquid composition x the vapour formed will be richer in the more volatile
component, where x is the mole fraction of the more volatile component in the liquid, and y in the vapour.
Examples of mixtures giving this type of curve are benzene–toluene, n-heptane–toluene, and carbon disulphide–
carbon tetrachloride. In Figures 3b and c, there is a critical composition xgwhere the vapour has the same
composition as the liquid, so that no change occurs on boiling. Such critical mixtures are called azeotropes.

Figure 3: Temperature - Composition Diagrams

For distillation purposes, it is more convenient to plot y against x at a constant pressure, since the majority of
industrial distillations take place at substantially constant pressure. This is shown in Figure 4 where it should be
noted that the temperature varies along each of the curves.

Figure 4: Vapour Composition as a Function of Liquid Composition at Constant Temperature

Partial Vaporization and Partial Condensation

If a mixture of benzene and toluene is heated in a vessel, closed in such a way that the pressure remains
atmospheric and no material can escape and the mole fraction of the more volatile component in the liquid, that is
benzene, is plotted as abscissa, and the temperature at which the mixture boils as ordinate, then the boiling curve
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is obtained as shown by ABCJ in Figure 5. The corresponding dew point curve ADEJ shows the temperature at
which a vapour of composition y starts to condense.

Figure 5: Effect of Partial Vaporization and Condensation at the Boiling Point

If a mixture of composition x2 is at a temperature T3 below its boiling point, T2, as shown by point G on the
diagram, then on heating at constant pressure the following changes will occur:
 When the temperature reaches T2, the liquid will boil, as shown by point B, and some vapour of
composition y2, shown by point E, is formed.
 On further heating, the composition of the liquid will change because of the loss of the more volatile
component to the vapour and the boiling point will therefore rise to some temperature T1. At this
temperature, the liquid will have a composition represented by point L, and the vapour a composition
represented by point N. Since no material is lost from the system, there will be a change in the proportion
of liquid to vapour, where the ratio is:

 On further heating to a temperature T1, all of the liquid is vaporized to give vapour D of the same
composition y1 as the original liquid. It may be seen that partial vaporization of the liquid gives a vapour
richer in the more volatile component than the liquid. If the vapour initially formed, as for instance at
point E, is at once removed by condensation, then a liquid of composition x3 is obtained, represented by
point C. The step BEC may be regarded as representing an ideal stage, since the liquid passes from
composition x2 to a liquid of composition x3, which represents a greater enrichment in the more volatile
component than can be obtained by any other single stage of vaporization.

Starting with superheated vapour represented by point H, on cooling to D condensation commences, and the first
drop of liquid has a composition K. Further cooling to T1 gives liquid L and vapour N. Thus, partial condensation
brings about enrichment of the vapour in the more volatile component in the same manner as partial vaporization.
The industrial distillation column is, in essence, a series of units in which these two processes of partial
vaporization and partial condensation are effected simultaneously.
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P a rtia l P res s ures , a nd Da lton’s , Ra o ult’s a nd Henry’s La ws

The partial pressure PA of component A in a mixture of vapours is the pressure that would be exerted by
component A at the same temperature, if present in the same volumetric concentration as in the mixture. Dalton’s
law of partial pressures states that the total pressure is equal to the summation of the partial pressures.

Since in an ideal gas or vapour the partial pressure is proportional to the mole fraction of the constituent, then:

= ………………………………………………………………………………………………….. (1)

For an ideal mixture, the partial pressure is related to the concentration in the liquid phase by Raoult’s law which
may be written as:
= ………………………………………………………………………………………………… (2)

Where is the vapour pressure of pure A at the same temperature.

This relation is usually found to be true only for high values of , or correspondingly low values of , although
mixtures of organic isomers and some hydrocarbons follow the law closely. For low values of , a linear relation
between and again exists, although the proportionality factor is Henry’s constant H, and not the vapour
pressure of the pure material.

For a liquid solute A in a solvent liquid B, Henry’s law takes the form:
= ………………………………………………………………………………………………….. (3)
If the mixture follows Raoult’s law, then the vapour pressure of a mixture may be obtained graphically from
knowledge of the vapour pressure of the two components. Thus, in Figure 6, OA represents the partial pressure
of A in a mixture, and CB the partial pressure of B, with the total pressure being shown by the line BA. In a
mixture of composition D, the partial pressure is given by DE, PB by DF, and the total pressure P by DG,
from the geometry of Figure 6.

Figure 6: Partial Pressures of Ideal Mixtures

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Figure 7 shows the partial pressure of one component A plotted against the mole fraction for a mixture that is not
ideal. It is found that over the range OC the mixture follows Henry’s law, and over BA it follows Raoult’s law.
Although most mixtures show wide divergences from ideality, one of the laws is usually followed at very high
and very low concentrations. If the mixture follows Raoult’s law, then the values of for various values of
may be calculated from knowledge of the vapour pressures of the two components at various temperatures.

Figure 7: Partial Pressures of Non-ideal Mixtures.

Thus,
= , = ,
∴ = , and = ………………………………………………………………………….(4)
But + = 1, + =1
∴ + =1
(1 − )
+ =1

+ (1 − )=

− + =

− = −
−
∴ = …………………………………………………………………………………………….(5)
−

Example 1: The vapour pressures of n-heptane and toluene at 373 K are 106 and 73.7 kN/m2 respectively. What
are the mole fractions of n-heptane in the vapour and in the liquid phase at 373 K if the total pressure is 101.3
kN/m2?

Solution: At 373 K, = 106 2 = 73.7 2 , = 101.3 2

− 101.3 − 73.7
∴ = = = 0.856
− 106 − 73.7

106 × 0.856
= = = 0.896
101.3
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One of the most widely used correlations of saturated vapour pressure is that proposed by Antoine. This takes the
form:
ln = 1 − 2 /( + 3 )………………………………………………………………………………(6)

This is only valid over limited ranges of both temperature and pressures.

Example 2: The constants in the Antoine equation are:

For benzene: 1 = 6.90565, 2 = 1211.033, 3 = 220.79
For toluene: 1 = 6.95334, 2 = 1343.943, 3 = 219.377
Where is in mmHg, T is in oC and 10 is used instead of .
Determine the vapour phase composition of a mixture in equilibrium with a liquid mixture of 0.5 mole fraction
benzene and 0.5 mole fraction of toluene at 338K. Will the liquid vaporize at a pressure of 101.3 2?
Solution: From Antoine’s equation, log10 = 1 − 2 /( + 3 )
where = saturation vapour pressure of benzene at 338K (65oC)
=saturation vapour pressure of benzene at 338K (65oC)
1211.033
log10 = 6.90565 − = 2.668157
65 + 220.70
Similarly,
1343.943
log10 = 6.95334 − = 2.22742
65 + 219.377

∴ = 102.668157 = 465.75 62.10 / 2

Similarly,
= 102.22742 = 168.82 22.51 / 2

But partial pressures in the mixtures are:

= = 62.10 × 0.5 = 31.03 / 2

2
= = 22.51 × 0.5 = 11.255 /

Total pressure, = + = 31.05 + 11.255 = 42.305 / 2

For the composition of the vapour phase:
= , =
= , =
= 31.05 42.305 , = 11.255 42.305
= 0.734 , = 0.266
The liquid will not vaporize at a pressure of 101.3 kN/m2.

Example 3:What is the boiling point of an equimolar mixture of benzene and toluene at 101.3 kN/m2?
Solution: The saturation vapour pressures are calculated as a function of temperature using the Antoine equation
and the constants for benzene and toluene. Using Raoult’s law, the actual vapour pressures are given by:

= and = .
2
Then, the temperature at which ( + ) = 101.3 / is determined by a process of trial and error. The
data with pressures in / 2 , are:
T (K) ( + )
373 180.006 74.152 90.003 37.076 127.079
353 100.988 38.815 50.494 19.408 69.902
363 136.087 54.213 68.044 27.106 95.150
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365 144.125 57.810 72.082 28.905 100.967

365.1 144.534 57.996 72.267 28.998 101.265
101.265 / 2 and hence, at this pressure, the boiling point or the bubble point of the equimolar mixture is
365.1 K which lies between the boiling points of pure benzene, 353.3 K, and pure toluene, 383.8 K.
Since the total pressure is 101.3 / 2 , = 50.65/ and = 50.65/ .
Then, the saturation vapour pressures are estimated as a function of temperature, using the data of Example 2.
Trial and error is now used to determine when ( + = 1.0. The data, with pressures in / 2 are:

T (K) ( + )
373.2 180.006 0.2813 74.152 0.6831 0.9644
371.2 170.451 0.2872 69.760 0.7261 1.0233
371.7 172.803 0.2931 70.838 0.7150 1.0081
371.9 173.751 0.29 71.273 0.7107 1.0021
372.0 174.225 0.2907 71.491 0.7085 0.9992

As 0.9992 is near enough to 1.0000, the dew point may be taken as 372.0 K.

Relative Volatility
The relationship between the composition of the vapour yA and of the liquid xA in equilibrium may also be
expressed in a way, which is particularly useful in distillation calculations. If the ratio of the partial pressure to the
mole fraction in the liquid is defined as the volatility, then:
= and = …………………………………………………….(7)
The ratio of these two volatilities is known as the relative volatility αgiven by: = =
But = and =

∴ = …………………………………………………………………………………………….(8)

=∝ ……………………………………………………………………………………………...(9)
This gives a relation between the ratio of A and B in the vapour to that in the liquid.
But + = 1 and + = 1, such that =1− and = 1 − , then:
1−
∝=
1−
∝
∴ = 1+ ∝ −1 ……………………………………………………………………………………(10)
Similarly,
= ∝− ∝ −1 ………………………………………………………………………………………(11)

For separation to be achieved, must not equal 1 and, considering the more volatile component, as increases and
the separation becomes much easier.
From the definition of the volatility of a component, it is seen that for an ideal system, the volatility is
numerically equal to the vapour pressure of the pure component. Thus, the relative volatility may be expressed as:

∝= ………………………………………………………………………………………………..(12)

METHODS OF DISTILLATION
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For a binary mixture with a normal y-x curve, the vapour is always richer in the more volatile component than the
liquid from which it is formed. There are three main methods used in distillation practice which all rely on this
basic fact. These are:
(a) Differential distillation: In this process, the vapour formed, when a still pot initially full, is heated at constant
rate, on boiling the liquid, is removed at once from the system. At the end of the process, the liquid which has
not been vaporized is removed as the bottom product.
(b) Flash or equilibrium distillation: This is frequently carried out as a continuous process. It consists of
vaporizing a definite fraction of the liquid feed in such a way that the vapour evolved is in equilibrium with
the residual liquid. The feed is usually pumped through a fired heater and enters the still through a valve
where the pressure is reduced. The still is essentially a separation in which the liquid and vapour produced by
the reduction in pressure have sufficient time to reach equilibrium. The vapour is removed from the top of the
separator and is then usually condensed, while the liquid leaves from the bottom.
(c) Rectification: In the two processes considered, the vapour leaving the still at any time is in equilibrium with
the liquid remaining, and normally, there will be only a small increase in concentration of the more volatile
component. The essentially merit of rectification is that it enables a vapour to be obtained that is substantially
richer in the more volatile component (MVC) than is the liquid left in the still. This is achieved by an
arrangement known as a ‘fractionating column’ which enables successive vaporization and condensation to be
established in one unit.

THE FRACTIONATING COLUMN

The operation of a typical fractionating column may be followed by reference to Figure 8. The column
consists of a cylindrical structure divided into sections by a series of perforated trays which permit the upward
flow of vapour. The liquid reflux flows across each tray, over a weir and down a downcomer to the tray below.
The vapour rising from the top tray passes to a condenser and then through an accumulator or reflux drum or
reflux divider, where part is withdrawn as the overhead product D, and the remainder is returned to the top
tray as reflux R.
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Figure 8: Continuous Fractionating Column with Rectifying and Stripping Sections

The liquid in the base of the column is frequently heated, either by condensing steam or by a hot oil stream,
and the vapour rises through the perforations to the bottom tray. A more commonly used arrangement is with
an external reboiler where the liquid from the still passes into the reboiler where it flows over the tubes and
weir and leaves as the bottom product by way of a bottoms cooler, which preheats the incoming feed.
The feed stream is introduced on some intermediate tray where the liquid has approximately the same
composition as the feed. The part of the column above the feed point is known as the rectifying section and the
lower portion is known as the stripping section. The vapour rising from an ideal tray will be in equilibrium
with the liquid leaving.
In analyzing the operation on each tray, it is important to note that the vapour rising to it, and the reflux
flowing down to it, are not in equilibrium, and adequate rates of mass and heat transfer are essential for the
proper functioning of the tray. The tray as described is known as a sieve tray and it has perforations of up to
about 12 mm diameter, although there are several alternative arrangements for promoting mass transfer on the
tray, such as valve units, bubble caps and other devices. In all cases, the aim is to promote good mixing of
vapour and liquid with a low drop in pressure across the tray. On each tray, the system tends to reach
equilibrium because:
(a) Some of the less volatile component condenses from the rising vapour into the liquid thus increasing the
concentration of the MVC in the vapour.
(b) Some of the MVC is vaporized from the liquid on the tray thus decreasing the concentration of the MVC
in the liquid.
The number of molecules passing in each direction from vapour to liquid and in the reverse is approximately
the same since the heat given out by one mole of the vapour on condensing is approximately equal to the heat
required to vaporize one mole of the liquid. This is thus, a case of equimolecular counter-diffusion. If the
molar heats of vaporization are approximately constant, the flows of liquid and vapour in each part of the
column will not vary from tray to tray. This is the concept of constant molar overflow.
In the arrangement discussed, the feed is introduced continuously to the column and two products streams are
obtained, one at the top much richer than the feed in the MVC and the second from the base of the column
weaker in the MVC.
A complete unit will normally consist of a feed tank, a feed heater, a column with boiler, a condenser, an
arrangement for returning part of the condensed liquid as reflux, and coolers to cool the two products before
passing them to storage. The reflux liquor may be allowed to flow back by gravity to the top plate of the
column or, as in larger units, it is run back to a drum from which it is pumped to the top of the column. The
control of the reflux on very small units is conveniently effected by hand operated valves, and with the larger
units by adjusting the delivery from a pump.

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 9 in which
plate n receives liquid from plate Vn-1 above, and vapour from plate n-1 below plate n supplies Ln to plate
n-1, and vapour Vn to plate n+1. The action of the plate is to bring about mixing so that the vapour Vn, 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 MVC is vaporized from the liquid Ln+1, decreasing its concentration to xn, and some of the
less volatile component (LVC) is condensed from Vn-1, increasing the vapour concentration to yn. The heat
required to vaporize the MVC from the liquid is supplied by partial condensation of the vapour Vn-1. Thus, the
resulting effect is that the MVC is passed from the liquid running down the column to the vapour rising up,
while the LVC is transferred in the opposite direction.
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Figure 9: Material Balance Over a Plate

Heat Balance Over a Plate

A heat balance across a plate n may be written as:

+1 −1 + −1 −1 = + + + ………………….(13)

where = Enthalpy per mole of the liquid on plate n.

= Enthalpy per mole of the vapour rising from plate n.

This equation is difficult to handle for the majority of mixtures, and some simplifying assumptions are
usually made. Thus, with good lagging, the heat losses will be small and may be neglected, and for an
ideal system, the heat of mixing is zero. For such mixtures, the molar heat of vaporization may be taken
as constant and independent of the composition. Thus, one mole of vapour Vn-1 on condensing releases
sufficient heat to liberate one3 mole of vapour Vn. It follows that Vn = Vn-1, so that the molar vapour flow
is constant up the column unless material enters or is withdrawn from the section. The temperature
change from one plate to the next will be small and may be taken as equal to +1 . Thus, = +1 ,
so that the moles of liquid reflux are also constant in this section of the column. Thus, Vn and Ln are
constant over the rectifying section, and Vm and Lm are constant over the stripping section. For these
conditions, there are two basic methods for determining the number of plates required.

Calculation of Number of Plates Using the Lewis–Sorel Method

A material balance above plate n, indicated by the loop I in Figure 10 gives:

= +1 + ………………………………………………………………………………(14)
Expressing this balance for the MVC gives:

= +1 +1 +
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Figure 10: Material Balances at Top and Bottom of Column

+1
= +1 + ……………………………………………………………………………(15)

This equation relates the composition of the vapour rising to the plate to the composition of the liquid on
any plate above the feed plate. Since the molar liquid overflow is constant, may be replaced by +1
and:

= +1 + ………………………………………………………………………………(16)

Similarly, taking a material balance for the total streams and for the MVC from the bottom to above plate
m, as indicated by the loop II in Figure 10, and noting that = +1 gives:

+1 = + ……………………………………………………………………………………..(17)
= +1 −
∴ = +1 − …………………………………………………………………………(18)

This equation, which is similar to equation (16), gives the corresponding relation between the
composition of the vapour rising to a plate and the liquid on the plate, for the section below the feed plate.
These two equations are the equations of the operating lines.

Example 4: A mixture of benzene and toluene containing 40 mole percent benzene is to be separated to
give a product containing 90 mole percent benzene at the top, and a bottom product containing not more
than 10 mole percent benzene. The feed enters the column at its boiling point, and the vapour leaving the
column which is condensed but not cooled, provides reflux and product. It is proposed to operate the unit
with a reflux ratio of 3 kmol/kmol of product. It is required to find the number of theoretical plates
needed and the position of entry for the feed. Pressure is at 100 kN/m2.

Solution: For 100 kmol of feed, an overall mass balance gives:

F=D+W
100 = D + W………………………………………………………………………………….…....(i)
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A balance on the MVC, benzene, gives:

= +

100 x 0.4 = 0.9D + 0.1W……………………………………………………………………….…(ii)

From equation (i), D = 100 – W
Substitute D in equation (ii), 40 = 0.9(100 - W) + 0.1W
W = 62.5 kmol and D = 37.5 kmol

But = → = =3 = 3 × 37.5 = 112.5

= + = 112.5 + 37.5 = 150

Thus, the top operating line is: = +1 +

∴ = 0.75 +1 + 0.225………………………………………………………………………(iii)

Since the feed is all liquid at its boiling point, this will all run down as increased reflux to the plate below.
Thus: = + = 112.5 + 100 = 212.5
Also, = − = 212.5 − 62.5 = 150
∴ = +1 −
212.5 62.5
+1 − = × 0.1
150 150
= 1.415 +1 − 0.042……………………………………………………………………....(iv)

Equilibrium data is given below:

Mole fraction of benzene in liquid 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Mole fraction of benzene in vapour 0 0.22 0.38 0.51 0.63 0.70 0.78 0.85 0.91 0.96

With the two equations (iii) and (iv) and the equilibrium curve, the composition on the various
plates may be calculated by working either from the still up to the condenser, or in the reverse
direction. Since all the vapour from the column is condensed, the composition of the vapour
from the top plate must equal that of the product , and that of the liquid returned as reflux .
The composition of the liquid on the top plate is found from the equilibrium curve and, since
it is in equilibrium with vapour of composition, = 0.90, = 0.79.
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Figure 11: Calculation of the Number of Plates by the Lewis–Sorel Method for Example 4.

The value of −1 is obtained from equation (iii) as:

−1 = (0.75 × 0.79) + 0.225 = (0.593 + 0.225) = 0.818, −1 is obtained from the equilibrium curve as 0.644
−2 = (0.75 × 0.644) + 0.225 = (0.483 + 0.225) = 0.708, −2 from equilibrium curve = 0.492

−3 = (0.75 × 0.492) + 0.225 = (0.369 + 0.225) = 0.594, −3 from the equilibrium curve = 0.382
This last value of composition is sufficiently near to that of the feed for the feed to be introduced on plate
(t − 3). For the lower part of the column, the operating line equation (iv) will be used.
Thus: −4 = (1.415 × 0.382) − 0.042 = (0.540 − 0.042) = 0.498, −4 from the equilibrium curve = 0.298
−5 = (1.415 × 0.298) − 0.042 = (0.421 − 0.042) = 0.379, −5 from the equilibrium curve = 0.208

−6 = (1.415 × 0.208) − 0.042 = (0.294 − 0.042) = 0.252, −6 from the equilibrium curve = 0.120

−7 = (1.415 × 0.120) − 0.042 = (0.169 − 0.042) = 0.127, −7 from the equilibrium curve = 0.048
This liquid −7 is slightly weaker than the minimum required and it may be withdrawn as the bottom product.
Thus, −7 will correspond to the reboiler, and there will be seven plates in the column.

Calculation of Number of Plates Using the McCabe and Thiele Method

The simplifying assumptions of constant molar heat of vaporization, no heat losses, and no heat of mixing, lead to
a constant molar vapour flow and a constant molar reflux flow in any section of the column, that is = +1 .
= +1 , and so on. Using these simplifications, the two enrichment equations are obtained:
= +1 + …………………………………………………………………………….(16)

= +1 − ………………………………………………………………………….(18)

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. McCabe and Thiele pointed out that, since
these equations represent straight lines connecting with +1 and with +1 , they can be drawn on the
same diagram as the equilibrium curve to give a simple graphical solution for the number of stages required. Thus,
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the line of equation (16) will pass through the points 2, 4 and 6 shown in Figure 11, and similarly the line of
equation (18) will pass through points 8, 10, 12 and 14.

If +1 = in equation (16), then: = + = …………………………………………..(19)

and this equation represents a line passing through the point = +1 = . If +1 is put equal to zero, then,
= / , giving a second easily determined point. The top operating line is therefore drawn through two
points of coordinates ( , ) and (0, ).
For the bottom operating line, equation (18), if +1 = , then:
= − ……………………………………………………………………………………(20)

Since = − , it follows that = . Thus the bottom operating line passes through the point C, that
is ( ), and has a slope . When the two operating lines have been drawn in, the number of stages
required may be found by drawing steps between the operating line and the equilibrium curve starting from point
A. This method is one of the most important concepts in chemical engineering and is an invaluable tool for the
solution of distillation problems. The assumption of constant molar overflow is not limiting since in very few
systems do the molar heats of vaporization differ by more than 10 per cent. The method does have limitations,
however, and should not be employed when the relative volatility is less than 1.3 or greater than 5, when the
reflux ratio is less than 1.1 times the minimum, or when more than twenty-five theoretical trays are required. In
these circumstances, the Ponchon–Savarit method should be used.

Example 5:The McCabe-Thiele Method

Example 4 is now worked using this method. Thus, with a feed composition, = 0.4, the top composition, is
to have a value of 0.9 and the bottom composition, is to be 0.10. The reflux ratio, = 3.

Solution
From a material balance for a feed of 100 kmol,
= = 150; = 112.5; = 212.5; D = 37.5 and W = 62.5 kmol
The equilibrium curve and the diagonal line are drawn in as shown in Figure 12.
The equation of the top operating line is: = 0.75 +1 + 0.225
Thus, the line AB is drawn through the two points A (0.9, 0.9) and B (0, 0.225).
The equation of the bottom operating line is: = 1.415 +1 − 0.042
This equation is represented by the line CD drawn through C (0.1, 0.1) at a slope of 1.415.
Starting at point A, the horizontal line is drawn to cut the equilibrium line at point 1. The vertical line is dropped
through 1 to the operating line at point 2 and this procedure is repeated to obtain points 3–6.
A horizontal line is drawn through point 6 to cut the equilibrium line at point 7 and a vertical line is drawn
through point 7 to the lower enrichment line at point 8. This procedure is repeated in order to obtain points 9–16.
The number of stages is then counted, that is points 2, 4, 6, 8, 10, 12, and 14 which gives the number of plates
required as 7.
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Figure 12: Determination of Number of Plates by the McCabe–Thiele Method for Example 5

Enrichment in Still and Condenser

Point 16 in Figure 12 represents the concentration of the liquor in the still. The concentration of the vapour is
represented by point 15, so that the enrichment represented by the increment 16–15 is achieved in the boiler or
still body. Again, the concentration on the top plate is given by point 2, but the vapour from this plate has a
concentration given by point 1, and the condenser by completely condensing the vapour gives a product of equal
concentration, represented by point A. The still and condenser together, therefore, provide enrichment (16 – 15)
+ (1 − A), which is equivalent to one ideal stage. Thus, the actual number of theoretical plates required is one
less than the number of stages shown on the diagram. From a liquid in the still, point 16 to the product, point A,
there are eight steps, although the column need only contain seven theoretical plates.

The Intersection of the Operating Lines

It is seen from the example shown in Figure 12 in which the feed enters as liquid at its boiling point that the two
operating lines intersect at a point having an X-coordinate of . The locus of the point of intersection of the
operating lines is of considerable importance since, as will be seen, it is dependent on the temperature and
physical condition of the feed. If the two operating lines intersect at a point with coordinates ( , ), then from
equations 16 and 18:

= + ………………………………………………………………………………………(21)
and: = − …………………………………………………………………………….…(22)
or − = − − ( )………………………………………………………………..(23)
A material balance over the feed plate gives,

+ + = +
or:
− = − − ………………………………………………………………………………(24)
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To obtain a relation between and , it is necessary to make an enthalpy balance over the feed plate, and to
consider what happens when the feed enters the column. If the feed is all in the form of liquid at its boiling point,
the reflux Lm overflowing to the plate below will be + . If however the feed is a liquid at a temperature ,
that is less than the boiling point, some vapour rising from the plate below will condense to provide sufficient
heat to bring the feed liquor to the boiling point. If is the enthalpy per mole of feed, and is the enthalpy of
one mole of feed at its boiling point, then the heat to be supplied to bring feed to the boiling point is ( - ),
and the number of moles of vapour to be condensed to provide this heat is ( - )/ , where λ is the molar
latent heat of the vapour. The reflux liquor is then:

= + + ( - )/ = + ( + - )/ = + ……………………………….(25)
ℎ 1
where = ℎ ℎ
Thus, − = − ……………………………………………………………………………….(26)

A material balance of the more volatile component over the whole column gives:

= +
Thus, from equation 23: −1 = −

or: = − ………………………………………………………………………….......(27)
−1 −1

This equation is commonly known as the equation of the q-line. If xq = xf, then yq = xf . Thus, the point of
intersection of the two operating lines lies on the straight line of slope q/(q − 1) passing through the point (xf , xf ).
When yq = 0, xq = xf /q. 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.

(a) Cold feed as liquor q > 1 q line /

(b) Feed at boiling point q = 1 q line |
(c) Feed partly vapour 0 < q < 1 q line \
(d) Feed saturated vapour q = 0 q line —
(e) Feed superheated vapour q < 0 q line /

These various conditions are indicated in Figure 13.

Altering the slope of the q-line will alter the liquid concentration at which the two operating lines cut each other
for a given reflux ratio. This will mean a slight alteration in the number of plates required for the given separation.
Whilst the change in the number of plates is usually rather small, if the feed is cold, there will be an increase in
reflux flow below the feed plate, and hence an increased heat consumption from the boiler per mole of distillate.

The Importance of the Reflux Ratio

Influence on the Number of Plates Required
The ratio Ln/D, that is the ratio of the top overflow to the quantity of product, is denoted by R, and this enables
the equation of the operating line to be expressed in another way, which is often more convenient. Thus,
introducing R in equation 16 gives:
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Figure 13: Effect of the Condition of the Feed on the Intersection of the Operating Lines
for a Fixed Reflux Ratio

= +1 + …………………………………………………………………………..(28)
+ +

= +1 + ………………………………………………………………………….……..(29)
+1 +1

Any change in the reflux ratio R will therefore modify the slope of the operating line and, as may be seen from
Figure 11.15, this will alter the number of plates required for a given separation. If R is known, the top line is
most easily drawn by joining point A (xd, xd ) to B (0, xd/(R + 1)) as shown in Figure 14. This method avoids the
calculation of the actual flow rates Ln and Vn, when the number of plates only is to be estimated.
If no product is withdrawn from the still, that is D = 0, then the column is said to operate under conditions of total
reflux and, as seen from equation 11.47, the top operating line has its maximum slope of unity, and coincides with
the line x = y. If the reflux ratio is reduced, the slope of the operating line is reduced and more stages are required
to pass from xf to xd, as shown by the line AK in Figure 14. Further reduction in R will eventually bring the
operating line to AE, where an infinite number of stages is needed to pass from xd to xf . This arises from the fact
that under these conditions the steps become very close together at liquid compositions near to xf , and no
enrichment occurs from the feed plate to the plate above. These conditions are known as minimum reflux, and the
reflux ratio is denoted by Rm. Any small increase in R beyond Rm will give a workable system, although a large
number of plates will be required. It is important to note that any line such as AG, which is equivalent to a smaller
value of R than Rm, represents an impossible condition, since it is impossible to pass beyond point G towards xf.
Two important deductions may be made. Firstly that the minimum number of plates is required for a given
separation at conditions of total reflux, and secondly that there is a minimum reflux ratio below which it is
impossible to obtain the desired enrichment, however many plates are used.
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Figure 14: Influence of Reflux Ratio on the Number of Plates Required for a Given Separation

Calculation of the Minimum Reflux Ratio

Figure 14 represents conditions where the q-line is vertical, and the point E lies on the equilibrium curve and has
co-ordinates (xf , yf ). The slope of the line AE is then given by:
−
=
+1 −
−
= −
……………………………………………………………………………………….....(30)

If the q -line is horizontal as shown in Figure 11.18, the enrichment line for minimum reflux is given by AC,
where C has coordinates (xc, yc). Thus:

−
=
+1 −

or, since yc = xf:

− −
= = ………………………………………………………………………….....(31)
− −
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