CONTINUOUS DISTILLATION

UNIT-2
Distillation process, in its simplest form, can be represented in a block diagram as shown
in the Figure below:

It showed a mixture of 2 substances (components) in 1 feed stream is separated

into 2 product streams, distillate (top product or overhead product) and bottoms.
The more volatile component will vaporize more and is removed in the distillate stream
and the less volatile component will remain in the bottoms stream. The bottoms
stream is in liquid phase, while the distillate stream is produced by condensing the vapor
phase.
The Figure below showed the simplest set-up for continuous distillation operation: 1 feed
steam (F) and 2 product streams - Distillate (D) and Bottoms (B The overhead
condenser shown in a total condenser, i.e. all the overhead vapor is condensed into
liquid.

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Equipment for Continuous Distillation
The following is a brief discussions of the various equipment used in continuous
distillation:
Distillation column
This is the main equipment where the separation process described above is carried out.
In general, the distillation column is separated into 3 sections: rectifying (or enriching)
section, stripping (or exhausting) section and feed (or flashing) section. At the
rectifying section, the more volatile component is removed through contacting the rising
vapor with the down-flowing liquid. At the stripping section, the down-flowing liquid is
stripped of the more volatile component by the rising vapor.
The distillation can be equipped with trays or packing’s or both. See the Figure below.

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Overhead condenser
This is a heat exchange equipment for condensing the hot vapor leaving the top of the
distillation column. Either cooling water (e.g. using shell-and-tube heat exchanger) or air
(using fin-fan condensers) can be used as the cooling medium. In either case, partial or
total condensation may be achieved.
In the case of total condensation (as in the analysis above), all the vapor is converted into
liquid. For partial condensation, there remain in the vapor state the most volatile
components. The condensed liquid is partially returned to the distillation column as reflux
and partially withdrawn as distillate product
Overhead accumulator
This is a horizontal (usually) pressure vessel whereby the condensed vapor is collected.
Pumps
Pumps can be used for returning the reflux liquid back to the distillation column, or for
pumping out the bottoms product for storage, or for pumping the feed into the distillation
column.
Reboiler
The purpose of the reboiler is to produce the vapor stream in the distillation column, called
the reboiled vapor or the boil-up vapor. Reboilers can be both external and internal (stab-
in). Steam reboilers or fired reboilers can be used. Fired reboilers typically uses fuel gas
or fuel oil or combination of both.

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Feed/Bottom Exchanger
The heat exchanger is used for heat conservation: the hot bottoms stream is used to heat
up the feed stream before it enters the distillation column. As a result the bottoms product
is cooled and then rundown to storage. For better temperature control of the feed stream,
a separate preheater or charge heater (both not shown in the above diagram) may be
used. This is usually located downstream of the feed/bottom exchanger for final
temperature adjustment. Steam may be used for the preheater, and fuel gas-fuel oil is
used for the charge heater.
Charge Heater / Steam Preheater (not shown in Figure)
This can be a fuel gas/fuel oil-fired heater or steam-heated exchanger for final
temperature control before the feed enters the column.
NOTE: Other distillation columns may have slightly different set-ups. The specific
equipment used depends on the types of mixtures to be separated and the complexity of
the operation. Some operations may have more than 1 feed inlet, as well as one or more
side draws.
The McCabe-Thiele Method
This method uses the equilibrium curve diagram to determine the number of theoretical
stages (trays) required to achieve a desired degree of separation. It is a simplified
method of analysis making use of several assumptions, but nonetheless a very useful
tool for the understanding of distillation operation.
Analysis using the McCabe-Thiele Method
The following notations shall be used:
y : mole fraction of more volatile component in vapor phase
x : mole fraction of more volatile component in liquid phase
V : molar flow rate of vapor, mole/time
L : molar flow rate of liquid, mole/time
F : molar flow rate of feed (vapor or liquid or mixed), mole/time
Refer to the Figure below that shows several plates inside a distillation column. Assume
that the plates are numbered serially from the top down and that the plate under
consideration is the n-th plate from the top. Then the plate immediately above this plate
is plate (n-1) and the plate immediately below this plate is plate (n+1).

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There are four streams (2 vapor and 2 liquid) associated with this plate, each with its own
flow rate and concentration:

Total Molar Composition (Mole

Stream
Flow rate Fraction MVC)

Vapor leaving
Vn yn
plate

Liquid leaving
Ln xn
plate

Vapour entering
Vn+1 yn+1
plate

Liquid entering
Ln-1 xn-1
plate

An ideal plate is one where the vapor leaving the plate is in equilibrium with the
liquid leaving the same plate (see the equilibrium diagram: xn and yn are in equilibrium).
On each plate, the vapor rising to it and the liquid flowing down to it are not in equilibrium.
Thus there is a concentration difference (driving force) for mass transfer between
the two phases.
The system tends to reach equilibrium on each tray because
some of the less volatile component condenses from the rising vapor into the liquid,
thus increasing the concentration of the more volatile component in the vapor as it moves

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upwards, e.g. yn > yn+1.
some of the more volatile component is vaporized from the liquid on the tray, thus
decreasing the concentration of the more volatile component in the liquid as it moves
downwards, e.g. xn-1 > xn.
The changes in vapour and liquid phase mole fractions are shown in the Figure below
(left). The combined effect is a gradual increase in concentration of the more volatile
component in the vapor as it moves up the column, and a gradual increase in
concentration of the less volatile component in the liquid as it moves down the
column. See the right Figure below.

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The vapour and liquid streams inside the column are assumed to be saturated at their
respective dew points and bubble points corresponding to the position in the column.
The heat released by one mole of vapor upon condensation is approximately equal to
the heat required to vaporize one mole of the liquid: the number of molecules passing
from the vapor phase to the liquid phase and vice versa will be approximately the
same: equimolar counter-diffusion.
If the molar heats of vaporization are approximately constant, we can assume that the
flows of liquid and vapor are nearly constant in each section of the column, i.e.
L1 = L2 = L3 = ......... = Ln = constant
V1 = V2 = V3 = ......... = Vn = constant
This is the important concept of constant molal overflow. Separation is achieved with
the vapor rich in the more volatile component leaving the top of the column, and the
liquid rich in the less volatile component leaving the bottom of the column.
The temperature decreases as one moves up the column, i.e. T n+1 > Tn > Tn-1.
The VLE data must be available at the operating pressure of the column. Information
required are the feed condition (temperature, composition), distillate and bottom
compositions; and the reflux ratio, which, as we seen earlier, is defined as the ratio of
reflux liquid over the distillate product. This is shown in the Figure below.

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For example, a column is to be designed for the separation of a 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 3 straight
lines: the rectifying section operating line (ROL), the feed line (also known as the q-line)
and the stripping section operating line (SOL).
Each of these lines passes through the points representing the mole fractions of the more
volatile component in the distillate, bottoms and feed (xD, xB and xF) respectively. These
lines represent the relationship between the concentrations in the vapor phase (y)
and the liquid phase (x).
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.
To obtain the number of theoretical trays using the McCabe-Thiele Method, we shall use
the "Parts-Whole Relationship": analysis is first carried out by partitioning the column
into 3 sections: rectifying, feed and stripping sections as shown in left Figure below.
These sections are then represented on the equilibrium curve for the binary mixture in
question and re-combined to make a complete design, as shown in the right Figure

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In the simplest case, the McCabe-Thiele Method to determine the number of theoretical
stages follows the steps below:
1. Analysis of the Rectifying section, and determine the ROL using xD and R
2. Analysis of the Feed section, and determine the feed condition (q)
3. Determination of the feed line (q-line) using xF and q
4. Locate the intersection point between ROL and q-line
5. Analysis of the Stripping Section, and determine the SOL using (4) and xB
NOTE:

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 When R is unknown (but instead specified as a multiple of the minimum rate), we will
first determine the q-line. Usually the SOL is the last line to draw, after both ROL and q-
line are drawn. Fixing the ROL and the q-line automatically fixes the SOL.
On the completed design (equilibrium diagram): The number of triangles drawn =
Number of theoretical trays + 1 Reboiler (last triangle). As an example, see
the Figure below. The number of theoretical trays = 6 + 1 Reboiler

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The feed plate location can also be determined. In the example above, it is Tray #3.
The following flowchart - FChart1 - can be used to find the number of theoretical trays
required for a given separation.

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12
It covers various scenarios other than the general 5-step approach as shown above,
such as unknown R, unknown q, etc.
Rectifying Section Operating Line (ROL)
Consider the rectifying section as shown in the Figure below.
(System shows a total condenser and the reflux is at bubble point)

Material balance around the envelope shown:

IN = OUT

Overall Balance
Vn+1 = Ln + D
(Total):

Component
Vn+1 yn+1 = Ln xn + D xD
Balance (MVC):

Thus, we have
(Ln + D) yn+1 = Ln xn + D xD
Under constant molal overflow assumption:
L1 = L2 = .......... Ln-1 = Ln = Ln+1 = L = constant
V1 = V2 = .......... Vn-1 = Vn = Vn+1 = V = constant
The subscripts can be dropped. Thus, the equation simplifies to:
(L + D) yn+1 = L xn + D xD

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Re-arranging in the form y = f(x), we have

Introducing Reflux Ratio R = L / D,

This is the Operating Line Equation for the rectifying section, or ROL in short.
Characteristics: Straight Line Equation
Slope R/(R+1), constant for given value of R
Intercept (1/R+1) xD, constant for given R and purity of distillate xD
In addition, if xn = xD, then yn+1 = xD
Thus, the operating line passed through the point (xD , xD) on the 45o diagonal line.
The operating line connects the concentrations of the more volatile component in the
vapor and liquid between 2 adjacent phases. By plotting the operating line on the
equilibrium curve, we can graphically construct using the "staircase" construction to
determine the number of theoretical stages required for the separation in the rectifying
section. See the Figure below.

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The method starts off by identifying the point xD on the diagonal. Starting from (xD, y1) on
the diagonal (note: y1 = xD), draw a horizontal line to the left until it touches the equilibrium
curve: this gives the point (x1, y1).
From this point (x1, y1) draw a vertical line down to the ROL: this gives the point (x1, y2).
In this manner we had obtained one triangle (no.1) where the horizontal distance is (xD -
x1) and the vertical distance is (y1 - y2). One triangle is equivalent to one theoretical tray.
See the Figure below.

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The difference (xD - x1) represents the decrease in the concentration of the more volatile
component in the liquid phase as its moves down one tray, i.e. from tray 1 to tray 2. The
difference (y1 - y2) represents the increase in the concentration of the more volatile
component in the vapour phase as its moves up one tray, i.e. from tray 2 to tray 1. See
the Figure below:

Usually the subscripts "n+1" and "n" are not shown:

When the reflux ratio R changes, the ROL will change

Stripping Section Operating Line (SOL)
Analysis of the stripping section is not really required, as SOL can be automatically fixed
once ROL and q-line are drawn.
The SOL is the last line to draw, by connecting xB on the diagonal to the point of
intersection between the ROL and q-line. With ROL fixed, when the q-line changes the
SOL changes as well.
The Figure below shows 3 different SOL that correspond to 3 different q-lines, for a given
ROL (i.e. fixed R and xD).

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Analysis of Stripping Section
Analysis of SOL is presented below using the Figure below which shows the stripping
section of a distillation column. The reboiled vapour in equilibrium with bottoms liquid
leaving the column.

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Material balance : IN = OUT
Assuming constant molal overflow
L'm = L'm+1 = .... = L' = constant
V'm = V'm+1 = ..... = V' = constant
Material balance:
Overall : L' = V' + B'
MVC : L' xm = V' ym+1 + B xB
Substituting, and re-arrange in the form y = f(x), we obtain

Again, dropping the subscripts "m+1" and "m" we have:

Substituting V' = L' - B: we have the stripping operating line (SOL)

This is straight line with slope ( L' / L' - B) and intercept ( B xB / L' - B )
In addition, when x = xB , y = xB, i.e. the operating line passed through ( xB, xB ) on the
45o diagonal line.
Using the equilibrium diagram, the stripping section operating line can be drawn and the
number of theoretical stages in the stripping section can be done in the same manner.
Reminder: The last "stage" on the graphical construction represents the reboiler.
Introduction of Feed : the q-line
Consider the section of the distillation column (see the Figure below) at the tray where
the feed is introduced (known as the feed tray location), say tray f :

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The feed may consists of liquid, vapour or a mixture of both. The quantities of the liquid
stream and vapour stream in the rectifying and stripping sections may change abruptly
because of the addition of the feed stream.
Define:
q = The moles of liquid flow in the stripping section that results from the
introduction of each mole of feed.
The value of q can be controlled by adjusting the amount of preheat the feed stream is
subjected to before entering the column.
For different feed conditions, q has the following numerical limits:
· cold feed (below bubble point) q > 1
· feed at bubble point (saturated liquid) q = 1
· feed partially vapour 0 < q < 1
· feed at dew point (saturated vapour) q = 0
· feed superheated vapour q < 0
If the feed is a mixture of liquid and vapour, then q is the fraction of the feed that is liquid.
For example, if a feed is 25% liquid and 75% vapour, then q = 0.25.
Recall our analysis of Flash Distillation: by changing the fraction of feed vapourised, we
change the composition of the more volatile component in the vapour and liquid product
streams.
Feed Section Operating Line (q-line)
See the Figure below for a feed tray and consider F moles/hr of feed, with fraction q of
liquid; thus

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liquid flow = q F moles/hr
vapour flow = (1-q) F moles/hr
Overall material balance:
L' = L + q F
V = V' + (1-q) F
Component balance for the more volatile component - see the Figure below:

Rectifying section : V y = L x + D xD
Stripping section : V' y = L' x - B xB
At the feed point where the two lines operating lines intersect:
( V - V' ) y = ( L - L' ) x + D xD + B xB
we have:
V - V' = ( 1 - q ) F
L - L' = - q F
In addition, from component balance around the entire column:
F xF = D xD + B xB

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Thus, ( 1 - q ) F y = - q F x + F xF
Re-arranging in the form y = f(x), we have:

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 y = xF.
i.e. 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. See the Figure below.
Note that the q-line passes through the point (xF, xF) on the 45o diagonal for all values of
q.

Plotting of the q-line requires the q-value and the feed MVC mole fraction, xF. As shown
above, q = 1.0 for saturated liquid and q = 0.0 for saturated vapour. For vapour-liquid
mixture, q = fraction of feed that is liquid. For other conditions, we need to calculate the
q-values.

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The q-values
If the condition of the feed is known to be either saturated liquid or saturated vapour, then
the value of q is either 1 or 0. However, if we are not certain of the feed condition, then
we must calculate the value of q. We can do so by deriving a formula for q using
enthalpy balance around the feed plate f. This is shown in the Figure below:

With: Energy In = Energy Out, we have

F HF + L HL,f-1 + V' HV,f+1 = L' HL,f + V HV,f
where
HF = enthalpy of feed, evaluated at T F
HV = enthalpy of vapour, and
HL = enthalpy of liquid
Assume that HL,f-1 = HL,f = HL, and, HV, f+1 = HV,f = HV
Then,
F HF + L HL + V' HV = L' HL + V HV
F HF = (V - V') HV + (L' - L) HL
F HF = (1 - q ) F HV + q F HL
HF = HV - q HV + q HL
q (HV - HL) = HV - HF
We now have the equation for calculating q:

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Values of HF, HV and HL can be obtained from enthalpy-concentration diagram for the
mixture concerned.
Alternatives for calculating q
Not all mixtures have the enthalpy-concentration diagram conveniently available. Nor is
such information easily obtained. Thus, value of q cannot be calculated using the previous
formula. The equation for q can be re-written as:

Alternatively, from the formula, q can be interpreted as the heat required to convert 1
mole of feed from its entering condition to a saturated vapour; divided by the molal
latent heat of vaporization.
The feed tray location can be identified once the number of theoretical trays is
determined.
Feed Plate Location
Optimum location would be the one represented by the triangle that has one corner on
the rectifying line and the other corner on the stripping line.
In transferring from the rectifying section to the stripping section, the steps on the diagram
should be kept as large as possible, and the transition is made at the first opportunity
after passing the intersection point.
As can be seen from the Figure below, the optimum feed location is stage no.5 that results
in the least number of stages. Any other location would have resulted in more than 5
trays.

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As an example, see the Figure below whereby the "staircase" construction is continued
beyond tray 5. As we stepped-off along the ROL to tray 6 and tray 7, note that the triangles
had become smaller, which means that the driving force for mass transfer is smaller. As
a result, more trays will be required to achieve the desired separation

sep aration.
Comparing the 2 cases, we can clearly see that tray 6 for the first case is more effective
than that for the second case - the triangle is larger. And the Figure below showed the
case whereby the change to SOL is made too soon, at tray 4. Again the result is less
than optimum.

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Reflux Ratio, R
We have seen that, for a given reflux ratio, and using the McCabe-Thiele method, one
can determine the number of theoretical trays required for a given separation. We now
turn our analysis to the importance of reflux ratio. As we recall, the importance of the
reflux ratio is that it can affects the separation efficiency, i.e. xD (mole fraction of MVC in
distillate).
For a given separation (i.e. constant xD and xB) from a given feed condition (xF and q),
using a higher reflux ratio (R) will results in lesser number of theoretical trays (N) required,
and vice versa. In other words, there are many possible combination of reflux ratio R
and number of theoretical trays, N. We therefore have a trade-off between R and N,
as shown in left Figure (higher R, lower N), middle Figure (high R, low N) and right
Figure (low R, high N) below:

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:

Analysis of Reflux Ratio Changes

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There is an inverse relationship between the reflux ratio and the number of theoretical
stages. For a new design, of course the reflux ratio and number of theoretical stages can
both be varied to achieve an optimum balance.For an existing column, the number of
trays used is fixed, hence higher distillate concentration (mole fraction xD) can only be
obtained by increasing the reflux ratio.Recall the operating line equation for
the rectifying section:

At a specified distillate concentration (i.e. constant xD), when R changes, the slope
and intercept of the ROL changes. The ROL therefore rotates around the point (xD,
xD).When the required separation is clearly defined - with a given feed condition (i.e.
xF and q fixed), and a specified product compositions (i.e. xD and xB fixed) - increasing
R will results in lesser number of theoretical stages required.From the ROL equation,
we can see that when R increases (with xD constant), the slope of ROL becomes steeper,
i.e. (R/R+1) and the intercept (xD/R+1) decreases. This is shown in the Figure below.

Thus, as R increases, the ROL rotates downwards around (xD, xD). The SOL also
moved down accordingly. The area between the equilibrium curve and ROL is now larger,
and we can draw larger triangles between the operating lines. This means that there are
now greater driving force for separation, which in turns mean that lesser number of
theoretical stages are required. The reverse is true when R decreases.

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The reflux ratio can assume any number between a minimum value and an infinite
value, and the number of theoretical stages required for separation changes accordingly.
In the next sections, we will first look at two extremes of the reflux ratios, and then an
analysis of how the most suitable reflux ratio is determined. At one end of the limit is
the minimum reflux ratio (that results in infinite stages) and at the other end is the total
reflux or infinite reflux ratio (which results in minimum stages).
Minimum Reflux Ratio for Ideal Solution
Note in this instance when R is originally unknown (it may simply be specified as
multiples of the minimum reflux ratio, Rmin). We must first find out the value of Rmin.Since
R is unknown, the ROL cannot be plotted first. Therefore the first operating line to be
drawn is the q-line, using known values of xF and q. Refer to the flowchart FChart1 for
more information.We then look at the methodology of finding Rmin. This requires the
analysis of ROL when R decreases. Refer to the ROL equation. With xD constant, as R
decreases, the slope of ROL becomes less steep, i.e. (R/R+1) decreases, while its
intercept (xD/R+1) increases. As R decreases, the ROL therefore rotates
upwards around (xD, xD). The ROL moves closer to the equilibrium curve. Separation
thus becomes more difficult as the driving force for mass transfer decreases. To achieve
any separation, more theoretical stages are required.R can be decreased until point N
is reached. Point N is the point of intersection between the q-line and the equilibrium
curve. See the Figure below.

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At point N, the ROL crosses the equilibrium for the first time. This is the point where
the driving force for mass transfer is zero (operation at equilibrium condition). Point N is
also known as the Pinch Point. Separation is not possible at thispoint.We cannot
reduce R beyond this point. The value of R at this point is known as the minimum reflux
ratio and is designated Rmin. Thus, the condition for Rmin occurs when the ROL (from xD)
joins a point on the equilibrium curve (such as point N).With minimum reflux ratio, we are
returning the minimum amount of liquid to the column. Thus, this point also corresponds
to the minimum reboiler heat duty and condenser cooling capacity required for the
separation.
In the above analysis, the pinch point occurred at the intersection of the ROL and q-line
and the equilibrium curve. This type of pinch is also known as the feed pinch, and it
corresponds to infinite number of stages in the column on each side of the pinch point
(i.e. in both rectifying and stripping sections of the column).Minimum relfux is determined
by the feed pinch in the case of equilibrium curves with no inflections ("distortions"),
such as that in the Figure above, which is typical for ideal solutions or solutions
with approximately constant relative volatilities.
Total Reflux @ Infinite Reflux Ratio
As noted previously, as R increases, the ROL rotates downward around (xD, xD), and
the number of theoretical stages required for separation decreases. At very large
value of R ( as R approaches infinity), the slope approaches 1.0 and the intercept
apraoches 0. The ROL (thus the SOL as well) coincides with the 45 o diagonal line. This
is shown in the Figure below.

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The entire area between the equilibrium curve and diagonal line is used for separation,
with the largest possible driving force. This condition of infinite reflux ratio is known as
the Total Reflux, and for a specified separation (i.e. fixed xD and xB), the number of
theoretical stages required is a minimum.
In practice, the total reflux can be achieved by reducing the feed to zero, returning all
the overhead product back to the column as reflux and reboiling all the bottoms
product. Alternatively, such a condition can be interpreted as requiring infinite reboiler
heat duty and condenser cooling capacity for a given feed rate.
The minimum reflux ratio and the infinite reflux ratio place a constraint on the range of
separation operation. Any reflux ratio between R min and Total R will produce the desired
separation, with the corresponding number of theoretical stages varying from infinity at
Rmin to the minimum number (Nmin at Total R). The relationship between R and N is shown
in the Figure below. The choice of reflux ratio to use is governed by cost considerations.

The choice of reflux ratio to use is governed by cost considerations.

Optimum Reflux Ratio
As we had seen in the previous section, we will use neither the minimum nor
the infinite reflux ratio for actual design. Nonetheless, these 2 numbers are useful in
helping us to identify the lower and upper limits of "useable" reflux ratio. Intuitively, the
reflux ratio to be used should fall in-between the minimum and infinite reflux ratios. See
the Figure below.

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We must therefore evaluate the trade-off between reflux ratio R, and number of theoretical
trays N. For new design, the reflux ratio to be used should be the optimum, or the most
economical, for which the total cost will be the least. This is shown in the Figure below.
Note that there are 2 components of total cost: fixed costs (such as those for purchase
of the distillation column and internals, reboiler, condenser, and other equipment)
and operating costs (costs associated with operation of the plant, e.g. utilities like
condenser cooling water, reboiler steam, pump horsepower, etc).

At minimum reflux ratio, the fixed cost is infinite (due to infinite number of stages
required), but the operating cost is at a minimum, because minimum amount of liquid
is to be handled (e.g. consuming lesser pump horsepower, lesser cooling capacity, etc).
As reflux ratio increases, less stages are required but larger equipment are now needed
to handle the increased reflux liquid and reboiled vapour load. Thus the fixed cost
initially decreased but eventually increase again when the reflux ratio approaches
total reflux. The fixed cost this falls through a minimum and then rise again to infinity.
As for the operating cost, it will continue to increase with increasing reflux ratio.

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The total cost, which is the sum of fixed cost and operating cost, must therefore passes
through a minimum. The reflux ratio at this minimum total cost is the optimum (or
economical) reflux ratio. Typically the optimum reflux ratio is approximately 1.2 to 1.5
times Rmin.
Tray Efficiency
In the previous analysis, we have assumed that the vapor leaving each tray was
in equilibrium with the liquid leaving the same tray. This analysis assumed that the trays
are operating at 100% efficiency. However, in actual practice, the trays are not perfect,
i.e. there are deviations from ideal conditions.
Except when temperature changes significantly (for example, in presence of exothermic
chemical reaction) from tray to tray, the assumption that vapour and liquid leaving the
trays are at the same temperature is often reasonable. The equilibrium with respect to
mass transfer, however, is not often valid. This can be due to:
(1)In sufficient time of contact
(2) insufficient degree of mixing
Recall: When we used the McCabe-Thiele Method for continuous distillation operation,
we already noted that not all triangles are of the same size.
Therefore in actual operation the vapor and liquid streams leaving a tray are not in
equilibrium. To achieve the same degree of separation desired, more trays will have to
be added to compensate for the lack of perfect separability. The actual number of trays
required can be adjusted using the tray efficiency.
We will look at 2 types of tray efficiency: Overall Efficiency and Murphree Efficiency.
Overall Efficiency
We define the overall tray efficiency EO as:

EO is applied throughout the whole column, i.e. every tray is assumed to have the same
efficiency. The advantage is that it is simple to use, but it must be bear in mind that in
actual practice, not all the trays have the same efficiency.
The advantage is that it is simple to use, but it must be bear in mind that in actual practice,
not all the trays have the same efficiency.
The overall efficiency has been found to be a complex function of the following:

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Murphree Efficiency
The Murphree Tray Efficiency EM , is based on a semi-theoretical models that assumes
that the vapour between trays is well-mixed (uniform composition), that the liquid in the
down comers is well-mixed (uniform composition), and that the liquid on the tray is well
mixed and is of the same composition as the liquid in the down comer leaving the tray.
It is defined for each tray according to the separation achieved on each tray. This can
be based on either the liquid phase or the vapor phase. For a given component, it is equal
to the change in actual concentration in the phase, divided by the change predicted by
equilibrium condition. Referring to the Figure below, we have:

Vapor phase:

Liquid phase:

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Separation of Azeotropic Mixtures
Azeotropic mixtures cannot be easily separated by ordinary distillation methods. For
example, in the case of ethanol-water, one cannot recover more than 89.4 mole% ethanol
using ordinary distillation, as the mixture becomes azeotropic at this point. Other
separation techniques (such as azeotropic distillation) must be used. Often the equipment
and set-up used is unique for each mixture.
Distillation of a mixture that exhibits azeotropic behaviour begins similarly to conventional
distillation. The difference is that, as the process continues, a temperature is reached at
which the compositions of the vapour phase and liquid phase become the same.
Once this happens an azeotrope has been formed, and the individual components can
no longer be separated by conventional distillation. The compositions of the liquid and
vapour remain the same until all of the liquid is eventually vapourised.
Separation of Azeotropic Mixtures can be broadly classified into the following methods:
 by changing system pressure
 by addition of an entrainer (azeotropic distillation)
 by combination with other processes (hybrid systems)
Azeotropic Distillation - Separation of Binary Azeotropes by Addition of Entrainer
Basic Concepts
Azeotropic distillation refers to processes whereby a new component (called
the entrainer) is added to the original feed mixture to form (or nearly form) an
azeotrope with one (or more) of the feed components. The azeotrope is then removed
as either the distillate or the bottoms.
Azeotropic distillation also refers to those processes in which a new component is added
to an original feed mixture to break an azeotrope that otherwise would be formed by the
feed components.
Azeotropic distillation
The technique of addition of another component to form a new low boiling point
azeotropic solution such as benzene can be added to the solution of ethanol and water
in azeotropic distillation.

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 The azeotropic distillation unit consists of a container to feed the azeotrope, decanter
and steamer. For example; the mixture of acetic acid and water can be separate out with
the addition of an ester like n- butyl acetate. Remember the boiling point of acetic acid is
118.1 0C and water is 100 0C. Addition of ester whose boiling point is 125 0C forms a
minimum- boiling azeotrope with water with boiling point 90.2 0C. Hence azeotropic
mixture will be distilled over as vapor and leave acetic acid at bottoms. The overhead
vapor is condensed and collected in a decanter. Here it forms two insoluble layers in
which the top layer contains pure butyl acetate with water, and a bottom layer contains
pure water saturated with butyl acetate. The top layer is returned to the distillation column
and bottom layer is sent to another column for the recovery of the ester by steam stripping.
How Azeotropic Distillation Works
The entrainer decreases the boiling point of azeotropic solution and separates the
components of mixture at different boiling points. When azeotropic mixture is heated with
entrainer, the condensed overhead vapor forms two liquid phases and collects in the
decanter. In decanter, the top layer contains ester whereas bottom layer contains water.
The top layer of ester again back to first column as reflux and source of entrainer whereas
bottom layer of water back to 2nd column. The bottom of 2nd column contains mixture
of ethanol and water which transfers to 3rd column for distillation. Third column contains
pure water at bottom and distillate is returned to the 1st column for recycling.

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Heterogeneous azeotropic distillation:
The heterogeneous azeotrope contains the vapor phase with two liquid phases. Some
common examples of heterogeneous azeotropic mixtures are benzene with water,
butanol with water and dichloromethane with water. In the heterogeneous azeotropic
distillation, the liquid phase of the mixture is immiscible.
Extractive Distillation
This process is very similar to azeotropic distillation. Extractive distillation refers to those
processes in which a high-boiling solvent is added alter the relative volatilities of
components in the feed. The boiling point of the solvent is generally much higher than
the boiling points of the feed mixture that formation of new azeotropes is impossible.
The high boiling point will also ensure that the solvent is will not appreciably vapourise in
the distillation process. As an illustration, consider the simplified system shown in
the Figure below for separation of toluene and iso-octane using phenol as the solvent.

The separation of toluene (boiling point 110.8 oC) from iso-octane (boiling point 99.3 oC)
is difficult using conventional distillation. Addition of phenol (boiling point 181.4 oC) results
in the formation of phenol-toluene mixture that leaves the extractive distillation column as
bottoms, while relatively iso-octane is recovered as overhead product. The phenol-
toluene mixture is further separated in a second column (solvent recovery column)
whereby toluene appears as distillate and the bottoms product, phenol, is recycled back
to the first column.
In the above example, when the solvent is added to the original feed mixture it forms a
new mixture with one of the feed components by "absorbing" that component. This new
mixture has a much higher boiling point than the other feed component that is not

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absorbed so that it leaves as bottoms product from the extractive distillation column. The
unabsorbed feed component then leaves as the overhead product.
The absence of azeotropes plus the fact that the solvent can be recovered by simple
distillation makes extractive distillation a less complex and more widely useful process
than azeotropic distillation.
Extractive Distillation
Selection of A Solvent
The choice of solvent determines which of the two components in the original feed is
removed predominantly in the distillation. For example, if the fresh feed to the distillation
is a mixture of 83 mole% ethanol and 17 mole% water, and ethylene glycol (boiling point
197.35 oC) is the solvent; the volatility of ethanol is increased more than that of water.
Therefore, ethanol is removed as the distillate from the extractive distillation column, and
water is separated in the solvent recovery column. On the other hand, if a high-boiling
hydrocarbon such as iso-octane (boiling point 99.3 oC, vs. n-octane with boiling point
125.6 oC) is used as solvent, the volatility of water is enhanced relative to that of ethanol,
and water now becomes the distillate in the extractive distillation column.
The number of possible solvents available for separation by extractive distillation is
usually much larger than for an azeotropic distillation because of less severe volatility
restrictions. A general approach is to choose a compound that is more similar to the
higher-boiling component in the original feed, and then go up the homologous series for
that compound until a homolog is found that boils high enough to make the formation of
azeotrope impossible.
Multicomponent System
Many of the Industry involve more than two components while the principles established
for binary solutions generally apply to such distillation, new problems are introduced
which require special consideration.
Consider the continuous separation of a ternary solution consisting of components A, B
and C whose relative volatilities are in that order A most volatile.
In order to obtain the three substances in substantially pure form either of schemes of
following figure can be used.

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 Figure Separation of a ternary system
Scheme (a)
According to scheme (a) the first column is used to separate C as a residue from the rest
of the solution.
The residue is necessarily contaminated at least a small amount of B and with an even
smaller amount of A although if relative volatilities are reasonably large.
The distillate which is necessarily contaminated at least a small amount of C, then
fractionated in a second column to provide nearly pure A and B.
Scheme (b) and (c)
According to scheme (b), the first tower provides nearly pure A directly, and the residue
is separated in the second.
Still a third scheme © is as shown in the above figure
Which of these schemes is used as a matter of cost and that may depend upon the
relative difficulties of the separations.
Generally scheme (b) will be more economical than (a) since it requires only one
vaporization of substance A.
Scheme © will generally be more economical then either of the others.

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Use of Open Steam

When an aqueous solution of a more volatile non aqueous substance is

fractionated, the non-aqueous substance being more volatile is collected as distillate and
water leaves at the bottom as residue. In such cases, the heat required can be provided
by introducing open steam directly to the bottom of the tower and the reboiler can be
eliminated. For a given distillate composition and reflux ration , the number of plates
required may be slightly more ,but the additional cost involved will be more than
compensated by savings in cost of the reboiler and its maintenance.
The enriching section of the column remains unaffected by the use of open steam and
hence, the operating line in this section remains unchanged. But the operating line in the
stripping section changes. The material balance equation for the more volatile component
in the stripping section becomes
L̅xm + G̅ (0) = G̅ ym+1 + WxW
Since there is no reboiler
L̅ = W and L̅xm = G̅ym+1 + L̅xw
Or L̅/G̅ = ym+1/ xm - xw
Above equation provides the slope of the lower operating line.
Open steam can also be used when there is chance of partial condensation of the vapor
in the upper part of the column.

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Fenske’s Equation
This equation can be used to theoretically calculate the minimum number of trays if the
relative volatility remains reasonably constant. Let Nm be the minimum number of trays in
the column. Besides there is a total reboiler. If αw is the relative volatility of A at the reboiler
temperature and pressure and xw and yw are the equilibrium liquid and vapor
concentrations in the reboiler, then we calculate the minimum number of trays by this
equation
Nm + 1 = [log xD (1-xw) /xw (1-xD)] / [log αw ]
Here αw is the average relative volatility of the more volatile component . The above
equation is called Fenske’s equation, which is useful for the calculation of the minimum
number of trays.

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