Distillation

Principles of Distillation
Distillation is a method used to separate the components of a liquid mixture that
depends on the distribution of these various components between a vapour phase
and a liquid phase. This requires that the components in the liquid mixture
have different boiling points. Another way of putting it is that the components in the
mixture must have different volatilities. Volatility is a measure of the readiness of a
liquid to vaporize.

A liquid with a low boiling point is said to be volatile, or having a high volatility, and
is known as the more volatile component (MVC). A high boiling point liquid has a low
volatility, and is known as the less volatile component (LVC).

The vapour phase is created by boiling of the liquid phase using steam or electrical
heating element. The MVC will distribute more in the vapour phase than the LVC and
the reverse is true in the liquid phase.

Relative Volatility
In order to separate a binary mixture using distillation process, there must be a
difference in volatilities of the components. The greater the difference, the easier it is
to do so. A measure for this is termed the relative volatility.
We define volatility of component-i as: partial pressure of component-i divide by
mole fraction component-i in liquid
For a binary mixture of A and B, therefore:

Volatility of A = pA / xA

Volatility of B = pB / xB

where p is the partial pressure of the component and x is the liquid mole fraction.

Relative volatility is the ratio of volatility of A (MVC) over volatility of B (LVC):

Relative volatility is therefore a measure of separability of A and B.

Since xB = 1 - xA , we have:

Replace with pA = yA PT ; pB = ( 1 - yA ) PT so as to express everything in MVC:

Dropping subscript 'A' for more volatile component, and simplifying: we obtain the
equation for relative volatility:

When a = 1.0, no separation is possible: both component-A and component-B are

equally volatile. They will vapourise together when heated. Solving the above
equation for a = 1.0, we obtain: y = x.
The larger the value of a above 1.0, the greater the degree of separability, i.e. the
easier the separation. Recall that when a system has reached equilibrium, no further
separation can take place - the net transfer rate from vapour to liquid is exactly
balanced by the transfer rate from liquid to vapour. Therefore, separation by
distillation is only feasible within the region bounded by the equilibrium curve and
the 45o diagonal line. From the equilibrium curve, we see that the greater the
distance between the equilibrium curve and the diagonal line (where y = x), the
greater the difference in liquid and vapour compositions and thereforethe easier the
separation by distillation. This is shown in the Figure. However, it is important to
note that in general, relative volatility of a mixture changes with the mixture
composition.

Ideal Solution & Raoult's Law

Raoult's Law states that, for an ideal solution, the equilibrium partial pressure of a
component at a fixed temperature T equals the product of its vapour pressure (when
it is pure) and its mole fraction in the liquid:

p* = Pvp x

Ideal solution has certain characteristics.

For component-A:

where

pA = equilibrium partial pressure of component-A in the gas at temperature T

Pvp,A = vapour pressure of pure liquid A at temperature T

xA = liquid-phase mole fraction of component-A at temperature T

Hence, from the equation, we see that Raoult's Law predicted a linear equilibrium
relationship between p and x.

Azeotrope / Azeotropic Mixture

Very large deviations from ideality lead to a special class of mixtures known
as azeotropes, azeotropic mixtures, or constant-boiling mixtures. Azeotrope is a
special class of liquid mixture that boils at a constant temperature at a certain
composition. At this condition, it behaves as if it was one component with one
constant boiling point.

A boiling liquid mixture at the azeotropic composition produces a vapour of exactly

the same composition, and the liquid does not change its composition as it
evaporates.

Two types of azeotropes are known: minimum-boiling and maximum-boiling (less

common). One of the best known minimum-boiling azeotrope is the ethanol-water
system which at 1 atm occurs at 89.4 mole percent ethanol and 78.2 oC. Other
examples are:

Minimum-boiling azeotropes

carbon-disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1 atm)

benzene - water (29.6 mole% H2O, 69.25 oC, 1 atm)

Maximum-boiling azeotropes
hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm)

acetone - chloroform (65.5 mole% chloroform, 64.5 oC, 1 atm)

Minimum-boiling azeotrope
When the positive deviations from ideality are sufficiently large, the mixture is said
to form a minimum-boiling azeotrope. The Figures below show the constant
temperature phase diagram (left) and constant pressure phase diagram plus
equilibrium curve (right) for a minimum-boiling azeotropic mixture of carbon
disulfide (CS2) and acetone. The characteristic of such mixture is that the total
pressure goes through a maximum (constant temperature phase diagram), and
therefore the temperature goes through a minimum (constant pressure phase
diagram), shown as point L.

At point L, the concentration in the vapour phase is the same as the concentration in
the liquid phase ( y = x ), and a = 1.0. This concentration is known as the azeotropic
composition (0.61 mole fraction CS 2). At this point, the mixture boils at a constant
temperature (39.25 oC under 1 atm) and without change in composition. On the
equilibrium diagram, it can be seen that at this point, the equilibrium curve crossed
the 45o diagonal.

Maximum-boiling azeotrope
It occurs when the negative deviations are very large, and the total pressure curve in
this case passes through a minimum, giving rise to a maximum in
the temperature (i.e. boiling point). The Figures below show the constant
temperature phase diagram (left) and constant pressure phase diagram plus
equilibrium curve (right) for a maximum-boiling azeotrope mixture of acetone and
chloroform.
The azeotropic composition is 0.345 mole fraction acetone. Point L in the Figures is
now a minimum on the constant temperature phase diagram, and a maximum
(64.5 oC, under 1 atm) on the constant pressure phase diagram. These azeotropes
are less common than the minimum type.

Types of Distillation

Distillation can be classified by different ways as under.

[a] By method of operation

1 Batch Distillation – operated in a batch manner in unsteady state fashion.

2 Continuous Distillation - operated in a Continuous manner in steady state fashion.

[b] By no of component

1 Binary distillation – having two components to be distilled

2 Multi component distillation – more than two components to be distilled

[c] By operating pressure

1. Atmospheric pressure distillation – operated at normal atmospheric pressure

2 Vacuum distillation - operated at sub or less than normal atmospheric pressure

[d] By number of stages

1 Single stage distillation – operate with one stage for ex. Flash vaporization

2 Multistage distillation - operate with more numbers of trays

Various types of distillation in practice are as under.

 Equilibrium Distillation or Flash Vaporization

 Differential Distillation or simple Distillation

 Continuous Rectification

 Steam distillation

 Azeotropic distillation

 Extractive distillation

 Reactive distillation

Flash Vaporization or Equilibrium Distillation

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

the vapour produced and the residual liquid are in equilibrium, which are then
separated and removed.

See the Figure below :

Consider a binary mixture of A (MVC) and B (LVC). 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 vapour and liquid takes place. How much of A is
produced in the vapour (and remained in the liquid) depends on the condition of the
feed, i.e. how much of the feed is entering as vapour state, which in turn is
controlled by the amount of heating. In other words, the degree of vapourization
affects the concentration (distribution) of A in vapour phase and liquid phase.

There is thus a certain relationship between the degree of heating (vapourization)

and mole fraction of A in vapour and liquid (y and x). This relationship is known as
the Operating Line Equation.

Operating Line Equation for Flash Distillation

We will consider the separation of a binary mixture of A (more volatile) and B (less
volatile).

If no vaporization takes place, then the liquid leaving the separator will have
the same composition as the feed. If total vaporization occurs, the vapor will also
have the same composition as the feed. Clearly, for effective separation, there must
be some vapor-liquid mixture present. This means that there exists a certain
relationship between the extent of heating, and the concentration in the vapor and
liquid streams.

Define

F : Amount of Feed

D : Molal fraction of the feed that is vaporized and withdrawn continuously as

vapour

W : Amount of Residue

Therefore, Let

YD = mole fraction of A in vapour leaving

XB = mole fraction of A in liquid leaving

XF = mole fraction of A in feed entering

As noted earlier, the distribution of A (and B) in the vapor and liquid phases ( YD &

XB) depends on the amount of preheating that takes place. To see YD & XB
how and changes when F change, we will use material balance to obtain a so-called

operating line equation, which relates the variables YD & XB & XF.

From material balance for the entire amount

F = D + B…………………………………….(1)

From material balance for the more volatile component (A)

FXF = DYD + BXB ……………………………(2)

Now putting (1) into (2)

(D + B) XF = DYD + BXB

On rearranging

B(XF – XB) = D ( YD-XF)

SO

- B/D = ( YD-XF) / (XF – XB)

It is the operating line equation on xy curve as shown in figure below.

This operating line cuts the equilibrium curve having its coordinate as YD & XB.

Thus equilibrium composition of vapor and liquid leaving the separator can be
estimated and from these data efficiency of the separation can be also computed.
Differential Distillation

Simple distillation, also known as Rayleigh distillation or differential distillation, is the

most elementary example of batch distillation.

If during an infinite number of successive flash vaporizations of a liquid only an

infinitesimal portion of the liquid were flashed each time, the net result would be
equivalent to a differential distillation.

In this distillation system, the vapor is removed from the still during a particular time
interval and is condensed in the condenser. The more volatile component is richer in
the vapor than in the liquid remaining in the still. Over time, the liquid remaining in
the still begins to experience a decline in the concentration of the more volatile

component, while the distillate collected in the condenser becomes progressively

more enriched in the more volatile component.

Schematic representation of differential distillation is as shown in figure.

No reflux is returned to the still, and no stages or packing materials are provided
inside the column; therefore, the various operating approaches are not applicable to
this distillation system. The early analysis of this process for a binary system,
proposed by Rayleigh is given below.

The rate of depletion of liquid is equal to the rate of distillate output. The
instantaneous rate of depletion of a component in the liquid is therefore by following
way.

Considering Material Balance

Total material component A

Moles in 0 0

Moles out dD YdD

Moles accumulated dL d(Lx) = Ldx - xdL

Applying

Input - Output = Accumulation

0 − dD = dL ……………………………….(1)

Taking balance on more volatile component,

0 − y ∗ dD = d(Lx) ………………………(2)

0 − y ∗ dD = xdL + Ldx ……………….(3)

y ∗ dL = xdL + Ldx ……………………..(4)

Therefore rearrangement gives,

In F/W =

This equation can be integrated to get the following form which is called the
Rayleigh’s Equation,

The integral in above equation can be solved analytically (provided the relationship
between y ∗ and x is available) or graphically ( by calculating the area under the
curve for the plot of 1/(y ∗ − x) vs x.

Continuous Rectification – Binary systems

Continuous rectification or fractionation is a multistage countercurrent distillation

operation. It is most widely used in chemical process industries. Here feed is
introduced more or less centrally into a vertical cascade of stages. The section above
the feed point is called Absorption; Enriching or Rectifying section while below the
feed point is called Stripping or Exhausting section.

Vapor rising in the top section is washed with liquid to remove or absorb the less
volatile component. The washing liquid is provided by condensing the vapor issuing
from the top, which is rich in more volatile component.

Distillation can be carried out using tray column or packed column.

Vapor flows upward in the column and becomes richer in more volatile component
[MVC] while liquid flows downdard becomes riher in less volatile component [LVC]

The liquid returned to the column from top of tower is known as Reflux.
The product obtained from top which is rich in MVC is termed as Distillate or top
product while the product obtained from bottom which is rich in LVC is termed as
Residue or waste or bottoms.

Inside the tower, the liquid and vapors are always at their bubble point and dew
points, respectively. Hence, the highest temperature is at bottom and the lowest at
the top. The entire unit is called Fractionators or Distillation column or distillation
tower.

It should be noted that the column can be equipped with different types of trays or
packings or even both at a time.

Distillation columns are made up of several components, each of which is used either
to transfer heat energy or enhance material transfer. A typical distillation contains
several major components:

 a vertical shell where the separation of liquid

components is carried out

 column internals such as trays/plates and/or

packings which are used to enhance component
separations

 a reboiler to provide the necessary vaporisation for

the distillation process

 a condenser to cool and condense the vapour

leaving the top of the column

 a reflux drum to hold the condensed vapour from

the top of the column so that liquid (reflux) can be
recycled back to the column

The vertical shell houses the column internals and together with the condenser and
reboiler constitute a distillation column. A schematic of a typical distillation unit with
a single feed and two product streams is shown below:

Design of Distillation Column

There are two primary method of column design:

1. The Ponchon-Savarit Method and
2. The McCabe-Thiele Method.
The main differences between these two methods are presented below:

Ponchon-Savarit Method

 Rigorous and capable of handling all distillations

 It requires detailed enthalpy data for its application
 It requires Simultaneous material and energy balance calculations
  It is to be have detailed calculations of equilibrium conditions
 It is more accurate, but difficult to use
 It is superseded by rigorous computer simulation calculations

McCabe-Thiele Method
 Less rigorous, enthalpy data not required.
 Adequate for many applications,
 More commonly use because of its simplicity
 Uses graphical solution for binary mixture on equilibrium diagram (x-y plot).
 Provides the number of theoretical (ideal) trays required for a given
separation.
 Pressure is assumed constant throughout the entire column.

The development of computers has also made the McCabe-Thiele graphical technique
obsolete for most detailed design calculations. One of the main disadvantages of the
McCabe-Thiele Method is that it is not very useful for analyzing the distillation of
mixtures containing more than two or one can say multi component distillation.

However, the method is still useful as a teaching tool and a conceptual tool. The
graphical procedure is easy to understand and presents a very clear visual picture of
the design problem. The graphs are also very useful in helping to determine what the
effect of changing variables will be. Our focus is restricted to the use of the McCabe-
Thiele Method.

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 is a
simplified method of analysis making use of several assumptions, but nonetheless a
very useful tool for the understanding of distillation operation.
The VLE data must be available at the operating pressure of the column. The other
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.
For example, a column is to be designed for the separation of a binary mixture. The
feed has a concentration of X F (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 (X D, XB and XF)
respectively. These lines represent the relationship between the concentrations in
the vapour 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
used the "Parts-Whole Relationship": analysis is first carried out by partitioning the
column into three sections: rectifying, feed and stripping sections. 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 figure.

In the simplest case, the McCabe-Thiele Method to determine the number of

theoretical stages follows the steps below:

• Analysis of the Rectifying section, and determine the ROL using XD and R
• Analysis of the Feed section, and determine the feed condition (q)
• Determination of the feed line (q-line) using XF and q
• Locate the intersection point between ROL and q-line
• Analysis of the Stripping Section, and determine the SOL using (q) and XB
Assumptions for McCabe-Thiele Method

 Both components have equal and constant molar enthalpies of vaporization

(latent heats).
 Equimolal overflow and vaporization which simlify that liquid and vapor flow
rate as L & G throughout the column but differ in composition from plate to
plate.
 Sensible heat, CpΔT, is negligible compared to latent heat.
 Column is insulated (no heat loss on each stage).
 Column pressure is constant (thermodynamics can be done at a single
pressure).
 Temperature between two adjutant plate is negligible.

It seems the big assumptions, but allow for simple analysis, since L and V are
constant under these assumptions.
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
(Total):
G=L +D
Component
balance (MVC): GYn+1 = L xn + D xD
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
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 (x D , x D) o

on the 45 diagonal line.

The operating line connects the concentrations of the more volatile component in the

vapour 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.

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.

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.

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

When the reflux ratio R changes, the ROL will change.

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 :

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.

Defining 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.

Effect of various feed conditions on vapor and liquid loading in column

The following table summarizes the effect of different feed conditions on the vapour
and liquid flow rates in the rectifying and stripping sections respectively.

As an example, consider the Figure above whereby the feed is a cold liquid. In this
case, all the liquid feed will go to the stripping section. In addition, because the feed
is cold, it will also condense some of the rising vapor. As a result, the amount of
liquid flow in the stripping section L' is much larger than the liquid flow in the
rectifying section L. The vapor flow in the rectifying section V, is lower than the
vapor flow in the stripping section V' because of the condensation into the liquid.
Hence for case (a), we have L' > L and V' > V.
Similar evaluation can be carried out for the other feed conditions. See the
left Figure below for saturated liquid, and the right Figure belowfor vapour-liquid
mixture,

The left Figure below is for saturated vapor and the right Figure below is
for superheated vapour.

The feed section operating line (or simply the q-line) can be obtained by performing
a material balance around the feed tray. Click here for more information.

Plotting of the q-line requires the q-value and the feed MVC mole fraction, X F. 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. The feed tray location can be identified once the
number of theoretical trays is determined.

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

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 x D + B x B

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.
Stripping Section Operating Line (SOL)

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.
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
o
45 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.

On the completed design (equilibrium diagram): The number of triangles drawn =

Number of theoretical trays + 1 Reboiler (last triangle).

Reminder: The last "stage" on the graphical construction represents the reboiler.

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 X B 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.

It should be noted that 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.

Analysis of Reflux Ratio Changes

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 a (higher R, lower N), figure b (high R, low
N) and Figure c (low R, high N) below:
 Figure a figure b

Figure c

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.

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

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.

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).

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.
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. We then look at the

methodology of finding Rmin. This requires the analysis of ROL when R decreases.

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.

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 this point.

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 theminimum 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 or 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
o
approaches 0. The ROL (thus the SOL as well) coincides with the 45 diagonal line.
This is shown in the Figure below.

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.

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.

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.

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.

Column Internals

Trays and Plates

The terms "trays" and "plates" are used
interchangeably. There are many types of tray designs,
but the most common ones are :

Bubble cap trays

A bubble cap tray has riser or chimney fitted over each hole, and a cap that covers
the riser. The cap is mounted so that there is a space between riser and cap to allow
the passage of vapour. Vapour rises through the chimney and is directed downward
by the cap, finally discharging through slots in the cap, and finally bubbling through
the liquid on the tray.
Valve trays

In valve trays, perforations are covered by liftable caps.

Vapour flows lifts the caps, thus self creating a flow
area for the passage of vapour. The lifting cap directs
the vapour to flow horizontally into the liquid, thus
providing better mixing than is possible in sieve trays.

Valve trays (photos courtesy of Paul Phillips)

 Sieve trays

Sieve trays are simply metal plates with holes in them.

Vapour passes straight upward through the liquid on the
plate. The arrangement, number and size of the holes
are design parameters.

Because of their efficiency, wide operating range, ease of maintenance and cost
factors, sieve and valve trays have replaced the once highly thought of bubble cap
trays in many applications.

Liquid and Vapour Flows in a Tray Column

The next few figures show the direction of vapour and liquid flow across a tray, and
across a column.
 Each tray has 2 conduits, one on each side, called
‘downcomers’. Liquid falls through the downcomers by gravity
from one tray to the one below it. The flow across each plate is
shown in the above diagram on the right.

A weir on the tray ensures that there is always some liquid

(holdup) on the tray and is designed such that the the holdup is
at a suitable height, e.g. such that the bubble caps are covered
by liquid.

Being lighter, vapour flows up the column and is forced to pass

through the liquid, via the openings on each tray. The area allowed for the passage
of vapour on each tray is called the active tray area.

The picture on the left is a photograph of a section of

a pilot scale column equiped with bubble capped trays.
The tops of the 4 bubble caps on the tray can just be
seen. The down- comer in this case is a pipe, and is
shown on the right. The frothing of the liquid on the
active tray area is due to both passage of vapour from
the tray below as well as boiling.

As the hotter vapour passes through the liquid on the

tray above, it transfers heat to the liquid. In doing so,
some of the vapour condenses adding to the liquid on
the tray. The condensate, however, is richer in the less volatile components than is
in the vapour. Additionally, because of the heat input from the vapour, the liquid on
the tray boils, generating more vapour. This vapour, which moves up to the next
tray in the column, is richer in the more volatile components. This continuous
contacting between vapour and liquid occurs on each tray in the column and brings
about the separation between low boiling point components and those with higher
boiling points.
Tray Designs

A tray essentially acts as a mini-column, each accomplishing a fraction of the

separation task. From this we can deduce that the more trays there are, the better
the degree of separation and that overall separation efficiency will depend
significantly on the design of the tray. Trays are designed to maximise vapour-liquid
contact by considering the

liquid distribution and

vapour distribution
on the tray. This is because better vapour-liquid contact means better separation at
each tray, translating to better column performance. Less trays will be required to
achieve the same degree of separation. Attendant benefits include less energy usage
and lower construction costs.

Liquid distributors - Gravity (left), Spray (right)

Packings
There is a clear trend to improve separations by supplementing the use of trays by
additions of packings. Packings are passive devices that are designed to increase the
interfacial area for vapour-liquid contact. The following pictures show 3 different
types of packings.

By way of dumping they are of two types

1 Regular packing or structured packings

2 Random packing
These strangely shaped pieces are supposed to impart good vapour-liquid contact
when a particular type is placed together in numbers, without causing excessive
pressure-drop across a packed section. This is important because a high pressure
drop would mean that more energy is required to drive the vapour up the distillation
column.

Structured packing

Packings versus Trays

A tray column that is facing throughput problems may be de-bottlenecked by

replacing a section of trays with packings. This is because:
packings provide extra inter-facial area for liquid-vapour
contact
efficiency of separation is increased for the same column
height
packed columns are shorter than trayed columns

Packed columns are called continuous-contact columns while trayed columns are
called staged-contact columns because of the manner in which vapour and liquid are
contacted.
COLUMN REBOILERS

There are a number of designs of reboilers. It is beyond the scope of this set of
introductory notes to delve into their design principles. However, they can be regarded as
heat-exchangers that are required to transfer enough energy to bring the liquid at the
bottom of the column to boiling boint. The following are examples of typical reboiler
types.
A novel development in reboiler design is the
self-cleaning shell-and-tube heat exchangers by
Klarex Technology for applications where heat
exchange surfaces are prone to fouling by the
process fluid. Particles are introduced into the
process stream and these produce a scouring
action on the heat exchange surfaces.
Factors Affecting Distillation Column Operation
*****************

The performance of a distillation column is determined by many factors, for

example:
feed conditions
 state of feed
 composition of feed

 trace elements that can severely affect the VLE of liquid mixtures

internal liquid and fluid flow conditions

state of trays (packings)

weather conditions

Some of these will be discussed below to give an idea of the complexity of the
distillation process.
Feed Conditions
The state of the feed mixture and feed composition affects the operating
lines and hence the number of stages required for separation. It also
affects the location of feed tray. During operation, if the deviations from
design specifications are excessive, then the column may no longer be
able handle the separation task. To overcome the problems associated
with the feed, some column are designed to have multiple feed points
when the feed is expected to containing varying amounts of
components.
Reflux Conditions

As the reflux ratio is increased, the gradient of operating line for the
rectification section moves towards a maximum value of 1. Physically,
what this means is that more and more liquid that is rich in the more
volatile components are being recycled back into the column. Separation
then becomes better and thus less trays are needed to achieve the
same degree of separation. Minimum trays are required under total
reflux conditions, i.e. there is no withdrawal of distillate.
On the other hand, as reflux is decreased, the operating line for the
rectification section moves towards the equilibrium line. The ‘pinch’
between operating and equilibrium lines becomes more pronounced and
more and more trays are required. This is easy to verify using the
McCabe-Thiele method.
The limiting condition occurs at minimum reflux ration, when an infinite

number of trays will be required to effect separation. Most columns are

designed to operate between 1.2 to 1.5 times the minimum reflux ratio
because this is approximately the region of minimum operating costs (more
reflux means higher reboiler duty).
Vapour Flow Conditions
Adverse vapour flow conditions can cause
 foaming
 entrainment
 weeping/dumping
 flooding

Foaming
Foaming refers to the expansion of liquid due to passage of
vapour or gas. Although it provides high interfacial liquid-vapour
contact, excessive foaming often leads to liquid buildup on trays.
In some cases, foaming may be so bad that the foam mixes with
liquid on the tray above. Whether foaming will occur depends
primarily on physical properties of the liquid mixtures, but is
sometimes due to tray designs and condition. Whatever the
cause, separation efficiency is always reduced.
Entrainment
Entrainment refers to the liquid carried by vapour up to the tray
above and is again caused by high vapour flow rates. It is
detrimental because tray efficiency is reduced: lower volatile
material is carried to a plate holding liquid of higher volatility. It
could also contaminate high purity distillate. Excessive
entrainment can lead to flooding.
Weeping/Dumping
This phenomenon is caused by low vapour flow. The pressure
exerted by the vapour is insufficient to hold up the liquid on the
tray. Therefore, liquid starts to leak through perforations.
Excessive weeping will lead to dumping. That is the liquid on all
trays will crash (dump) through to the base of the column (via a