Chapter-Two

Distillation
 Introduction
• Distillation is method of separation of components from
a liquid mixture which depends on the differences in
boiling points of the individual components and the
distributions of the components between a liquid and
gas phase in the mixture.
• The liquid mixture may have different boiling point
characteristics depending on the concentrations of the
components present in it.
• Therefore, distillation processes depends on the vapor
pressure characteristics of liquid mixtures.
• The vapor pressure is created by supplying heat as
separating agent.
• Distillation is mostly carried out in multi tray columns.
• Packed column with efficient structured packing has
also led to increased use in distillation.
 Vapor Pressure

• The vaporization process changes liquid to gaseous

state.
• The opposite process of this vaporization is called
condensation.
• At equilibrium, the rates of these two processes are
same.
• The pressure exerted by the vapor at this equilibrium
state is termed as the vapor pressure of the liquid.
• It depends on the temperature and the quantity of the
liquid and vapor.
• From the following Clausius - Clapeyron equation or
by using Antoine equation, the vapor pressure can be
calculated.
 (2.1)

Where,
pv and p1v are the vapor pressures in Pascal at absolute
temperature T and T1 in K. λ is the molar latent heat of
vaporization which is independent of temperature.
Antoine equation:

(2.2)
• Typical representative values of the constants A, B and C are given in the
following Table 2.1 (Ghosal et al., 1993).
Table 2.1. Typical representative values of the constants A, B and C
 Phase Diagram
• For binary mixture phase diagram only two-component
mixture, (e.g. A (more volatile) and B (less volatile)) are
considered.
There are two types of phase diagram:
1. Constant pressure
2. Constant temperature.
 Constant Pressure Phase Diagram
• The figure 2.1 shows a constant pressure phase diagram for an ideal
solution (one that obeys Raoult's Law).
• At constant pressure, depending on relative concentrations of each
component in the liquid, many boiling point temperatures are
possible for mixture of liquids (solutions) as shown in phase
diagram.
• For mixture, the temperature is called bubble point temperature when
the liquid starts to boil and dew point when the vapor starts to
condense.
• Boiling of a liquid mixture takes place over a range of boiling points.
Likewise condensation of a vapor mixture takes place over a range of
condensation points.
• The upper curve in the boiling point diagram is called the dew-point
curve (DPC) while the lower one is called the bubble-point curve
(BPC).
• At each temperature, the vapor and the liquid are in equilibrium.
• The constant pressure phase diagram is more commonly used in the
analysis of vapor-liquid equilibrium.
Figure 2.1: Phase diagram of binary system at constant pressure
 Constant Temperature (isothermal) Phase Diagram

• The constant temperature phase diagram is shown in

Figure 2.2.
• The constant temperature phase diagram is useful in the
analysis of behavior of the solution.
• The more volatile liquid will have a higher vapor
pressure.
Figure 2.2: Binary Phase diagram at constant temperature
 Relative volatility
• Relative volatility is a measure of the differences in volatility between
two components, and hence their boiling points.
• It indicates how easy or difficult a particular separation will be.
• The relative volatility of component ‘A’ with respect to component ‘B’ in
a binary mixture is defined as

(2.3)

• where,
yA = mole fraction of component ‘A’ in the vapor, xA = mole fraction of
component ‘A’ in the liquid.
• In general, relative volatility of a mixture changes with the mixture
composition. For binary mixture, xB = 1-xA. So equation (2.3) can be
rearranged, simplifying and expressed by dropping subscript 'A' for more
volatile component as:
 (2.4)

The equation (2.4) is a non-linear relationships between x

and y. This equation can be used to determine the
equilibrium relationship (y vs. x).
The average relative volatility, αve is known. If the system
obeys Raoult’s law, i.e pA = PyA, pB = PyB , the relative
volatility can be expressed as:
(2.5)
• where pA is the partial pressure of component A in the vapor,
pB is the partial pressure of component B in the vapor and P
is the total pressure of the system.
• Thus, if the relative volatility between two components is
equal to one, separation is not possible by distillation.
• The larger the value of relative volatility, above 1.0, the
greater the degree of separability, i.e. the easier the
separation.
• Some examples of optimal relative volatility that are used
for distillation process design are given in Table 2.2.
Table 2.2: Some optimal relative volatility that are used for
distillation process design
 Vapor-Liquid Equilibrium (VLE)
• VLE is useful for graphical design in determining the number of
theoretical stages required for a distillation column.
• A typical equilibrium curve for a binary mixture on x-y plot is shown
in Figure 2.3.
• It can be plotted using equations (2.4) or (2.5) as discussed earlier.
• It contains less information than the phase diagram (i.e. temperature
is not included), but it is most commonly used.
• The VLE plot expresses the bubble-point and the dew-point of a
binary mixture at constant pressure.
• The curved line in Figure 2.3 is called the equilibrium line and it
describes the compositions of the liquid and vapor in equilibrium at
some fixed pressure.
• The equilibrium line can be obtained from the equation (2.4) once the
relative volatility is known.
Figure 2.3: Equilibrium diagram for a benzene-toluene mixture at
1 atmosphere
• This particular VLE plot (Figure 2.3) shows a binary ideal
mixture that has a uniform vapor-liquid equilibrium that is
relatively easy to separate.
• On the other hand, the VLE plots shown in Figure 2.4
represented for non-ideal systems.
• These non-ideal VLE systems will present more difficult
separation.

Figure 2.4: Vapor-liquid equilibrium curve for non-ideal systems

• The most challenging VLE curves are generated by azeotropic
systems.
• An azeotrope is a liquid mixture which when vaporized, produces the
same composition as the liquid. Two types of azeotropes are known:
minimum-boiling and maximum-boiling (less common).
• Ethanol-water system (at 1 atm, 89.4 mole % C2H5OH, 78.2 oC;
Carbon-disulfide - acetone (61.0 mole% CS2, 39.25 oC, 1 atm) and
Benzene - water (29.6 mole% H2O, 69.25 oC, 1 atm) are minimum-
boiling azeotropes.
• Hydrochloric acid - water (11.1 mole% HCl, 110 oC, 1 atm); Acetone
- chloroform (65.5 mole% chloroform, 64.5 oC, 1 atm) are the
examples of maximum-boiling azeotropes.
• The Figure 2.5 shows two different azeotropic systems, one with a
minimum boiling point (Figure 2.5a) and one with a maximum
boiling point (Figure 2.5b). The points of intersections of the
equilibrium curves with the diagonal lines are called azeotropic
points.
• An azeotrope cannot be separated by conventional distillation.
However, vacuum distillation may be used as the lower pressures
which can shift the azeotropic point.
Figure 2.5: VLE curves for azeotropic systems: (a) for maximum boiling
point, (b) for minimum boiling point
• Although most distillations are carried out at
atmospheric or near atmospheric pressure, it is not
uncommon to distill at other pressures.
• High pressure distillation (typically 3 - 20 atm) usually
occurs in thermally integrated processes.
• In those cases the equilibrium curve becomes narrower at
higher pressures as shown in Figure 2.6.
• Separability becomes less at higher pressures.
Distillation columns and their process calculations

Figure 2.6: Variation of equilibrium curve with pressure

 Distillation columns and their process
calculations
• There are many types of distillation columns each
of which is designed to perform specific types of
separations.
• One way of classifying distillation column type is to
look at how they are operated.
• Based on operation, they are of two types: batch or
differential and continuous columns.
Batch or differential distillation columns and their
process calculation
• In batch operation, the feed is introduced batch-wise to the
column. That is, the column is charged with a 'batch' and then
the distillation process is carried out.
• When the desired task is achieved, a next batch of feed is
introduced.
• Consider a binary mixture of components A (more volatile)
and B (less volatile). The system consists of a batch of liquid
(fixed quantity) inside a kettle (or still) fitted with heating
element and a condenser to condense the vapor produced as
shown in figure 2.7.
• The condensed vapor is known as the distillate. The distillate
is collected in a condensate receiver. The liquid remaining in
the still is known as the residual.
• The concentration changes can be analyzed using the phase
diagram, and detailed mathematical calculations are carried out
using the Rayleigh Equation.
• As the process is unsteady state, the derivation is based on a
differential approach to changes in concentration with time.
• Let L1 = initial moles of liquid originally in still, L2 = final moles
of liquid remained in still, x1 = initial liquid composition in still
(mole fraction of A), x2 = final liquid composition in still (mole
fraction A).
• At any time t, the amount of liquid in the still is L, with mole
fraction of A in the liquid being x. After a small differential time (t
+ dt), a small amount of vapor dL is produced, and the
composition of A in the vapor is y (mole fraction).
• The vapor is assumed to be in equilibrium with the residue liquid.
• The amount of liquid in the still is thus reduced from L to (L - dL),
while the liquid composition changed from x to (x - dx). Then the
material balance on A can be written as:
Figure 2.7: Simple batch or differential distillation process
• Initial amount in still = Amount left in still + Amount
vaporized
(2.6)

or
(2.7)

• Neglecting the term (dx)(dL) in equation (2.7) may be

written as:

(2.8)
• Re-arranging and Integrating from L1 to L2, and from x1 to x2,
one can obtain the following equation which is called Rayleigh
Equation:

(2.9)

• The integration of equation (2.9) can be obtained graphically

from the equilibrium curve, by plotting 1/(y-x) versus x.
Example problem 2.1
A mixture of 40 mole % isopropanol in water is to be batch-
distilled at 1 atm until 70 mole % of the charge has been
vaporized. Calculate the composition of the liquid residue
remaining in the still pot, and the average composition of the
collected distillate. VLE data for this system, in mole fraction
of isopropanol, at 1 atm are (Seader and Henley, 1998):
 Continuous distillation columns
• The continuous distillation columns require continuous feed
stream. No interruptions occur unless there is a problem with
the column or surrounding process units.
• They are capable of handling high throughputs. Continuous
column is the more common of the two types.
Types of Continuous Columns
• Continuous columns can be further classified according to
the nature of the feed that they are processing:
• Binary distillation column: feed contains only two components
• Multi-component distillation column: feed contains more than two
components the number of product streams they have.
• Multi-product distillation column: column has more than two product
streams where the extra feed exits when it is used to help with the
separation.
• Extractive distillation: where the extra feed appears in the bottom
product
stream.
• Azeotropic distillation: where the extra feed appears at the top product
stream .
• Tray distillation column: where trays of various designs are used to hold
up the liquid to provide better contact between vapor and liquid, hence
better separation.
• Packed distillation column: where instead of trays, 'packings' are used to
enhance contact between vapor and liquid.
Single-stage continuous distillation (Flash
distillation):
• A single-stage continuous operation occurs where a liquid mixture is
partially vaporized.
• The vapor produced and the residual liquids are in equilibrium in the
process are separated and removed as shown in Figure 2.8.
• Consider a binary mixture of A (more volatile component) and B (less
volatile component). The feed is preheated before entering the separator.
• As such, part of the feed may be vaporized. The heated mixture then flows
through a pressure-reducing valve to the separator.
• In the separator, separation between the vapor and liquid takes place. The
amount of vaporization affects the concentration (distribution) of A in
vapor phase and liquid phase.
• The relationship between the scale of vaporization and mole fraction of A
in vapor and liquid (y and x) is known as the Operating Line Equation.
• Define f as molal fraction of the feed that is vaporized
and withdrawn continuously as vapor. Therefore, for 1
mole of binary feed mixture, (1- f) is the molal fraction
of the feed that leaves continuously as liquid.
• Assume, yD = mole fraction of A in vapor leaving, xB =
mole fraction of A in liquid leaving, xF = mole fraction
of A in feed entering.
• Based on the definition for f, the greater the heating is,
the larger the value of f. If the feed is completely
vaporized, then f = 1.0 .
• Thus, the value of f can varies from 0 (no vaporization)
to 1 (total vaporization). From material balance for the
more volatile component (A) one can write
(3.0)
Figure 2.8: Flash distillation process
 The Equation (3.0) on rearranging becomes:

(3.1)

• The fraction f depends on the enthalpy of the liquid feed, the enthalpies of
the vapor and liquid leaving the separator.
• For a given feed condition, and hence the known value of f and x F, the
Equation (3.0) is a straight line Equation with slope - (1-f)/f and intercept x F/f
as shown in Figure 2.9.
• It will intersect the equilibrium line at the point (xB, yD). From this value, the
composition of the vapor and liquid leaving the separator can be obtained.
Figure 2.9: Graphical presentation of flash vaporization
 Multi-stage Continuous distillation-Binary system
• A general schematic diagram of a multistage counter-current
binary distillation operation is shown in Figure 3.0.
• The operation consists of a column containing the equivalent N
number of theoretical stages arranged in a two-section cascade
containing;
• Condenser in which the overhead vapor leaving the top stage is
condensed to give a liquid distillate product and liquid reflux
that is returned to the top stage.
• Reboiler in which liquid from the bottom stage is vaporized to
give a liquid bottom products and the vapor boil off returned to
the bottom stage.
• Accumulator is a horizontal (usually) pressure vessel whereby
the condensed vapor is collected.
• Heat exchanger where the hot bottoms stream is used to heat
up the feed stream before it enters the column.
• The feed enters the column at feed stage contains more
volatile components (called light key, LK) and less volatile
components (called heavy key, HK).
• At feed stage the feed may be liquid, vapor or mixture of
liquid and vapor.
• The section above the feed where vapor is washed with the
reflux to remove or absorb the heavy key is called enriching
or rectifying section.
• The section below the feed stage where liquid is stripped of
the light key by the rising vapor is called stripping section.
Figure 2.10: Multi-stage binary distillation column
Analysis of binary distillation in tray towers:
McCabe Thiele Method
• McCabe and Thiele (1925) developed a graphical
method to determine the theoretical number of
stages required to effect the separation of a binary
mixture (McCabe and Smith, 1976).
• This method uses the equilibrium curve diagram to
determine the number of theoretical stages (trays)
required to achieve a desired degree of separation.
The following assumptions are implied when using
this method (McCabe, 1993):
a) Constant Molal Overflow. The molar flow rates of
the vapor and liquid are nearly constant in each
section of the column. This also ensures the
operating lines are straight lines.
b) Heat Effects are negligible. For example, heat
losses to and from the column are small and
neglected.
c) For every mole of vapor condensed, another mole
of liquid is vaporized.
d) The liquid and vapor leaving the tray is in
equilibrium with the vapor and liquid entering the
tray.
The information required for the systematic
calculation are:
• VLE data
• Feed condition (temperature, composition)
• Distillate and bottom compositions
• The reflux ratio, which is defined as the ratio of
reflux liquid over the distillate product.
For example, a column is to be designed for the
separation of a binary mixture as shown in Figure 3.1.
Figure 2.11: Schematic of column for separation of binary mixture
• The feed has a concentration of xF (mole fraction) of
the more volatile component and a distillate having
a concentration of xD of the more volatile
component and a bottoms having a concentration of
xB is desired.
• In its essence, the method involves the plotting on
the equilibrium diagram three straight lines: the
rectifying section operating line (ROL), the feed
line (also known as the qline) and the stripping
section operating line (SOL).
• An important parameter in the analysis of
continuous distillation is the Reflux Ratio, defined
as the quantity of liquid returned to the distillation
column over the quantity of liquid withdrawn as
product from the column, i.e. R = L / D.
• The reflux ratio R is important because the
concentration of the more volatile component in the
distillate (in mole fraction xD) can be changed by
changing the value of R.
• The steps to be followed to determine the number of
theoretical stages by McCabe-Thiele Method are:
• Determination of the Rectifying section operating
line (ROL).
• Determination the feed condition (q).
• Determination of the feed section operating line (q-
line).
• Determination of required reflux ratio (R).
• Determination of the stripping section operating line
(SOL).
• Determination of number of theoretical stage
Determination of the Rectifying section
operating line (ROL)
• Consider the rectifying section as shown in the Figure 3.2.
• Material balance can be written around the envelope
shown in Figure 3.2.
• Overall or total balance:
(3.2)

• Component balance for more volatile component:

(3.3)

• From the above Equations (3.2) and (3.3), it can be written

as
 (3.4)

Consider the constant molal flow in the column, and

then one can write:
L1 = L2 = .......... Ln-1 = Ln = Ln+1 = L = constant and
V1 = V2 = .......... Vn-1 = Vn = Vn+1 = V = constant.
Thus, the Equation (3.4) becomes:
(3.5)
Figure 2.12: Outline graph of rectifying section
• After rearranging, one gets from Equation (3.5) as:
(3.6)

• Introducing reflux ratio defined as: R = L/D, the

Equation (3.6) can be expressed as:
(3.7)

• The Equation (3.7) is the rectifying section operating

line (ROL) Equation having slope R/(R+1) and
intercept, xD/(R+1) as shown in Figure 3.3.
• If xn = xD, then yn+1 = xD, the operating line passed
through the point (xD, xD) on the 45° diagonal line.
• When the reflux ratio R changed, the ROL will
change.
• Generally, the rectifying operating line is expressed
without subscript of n or n+1. Without subscript the
ROL is expresses as:
(3.8)
Figure 2.13: Representation of the rectifying operating line
 Determination the feed condition (q):
• The feed enters the distillation column may consists
of liquid, vapor or a mixture of both.
• Some portions of the feed go as the liquid and vapor
stream to the rectifying and stripping sections.
• The moles of liquid flow in the stripping section
that result from the introduction of each mole of
feed, denoted as ‘q’.
• The limitations of the q-value as per feed conditions
are shown in Table 2.2.
Table 2.2: Limitations of q-value as per feed conditions
 Calculation of q-value
• When feed is partially vaporized: Other than
saturated liquid (q = 1) and saturated vapor (q = 0),
the feed condition is uncertain.
• In that case one must calculate the value of q. The
q-value can be obtained from enthalpy balance
around the feed plate.
• By enthalpy balance one can obtain the q-value
from the following form of equation:
(3.9)
• where HF, HV and HL are enthalpies of feed, vapor and
liquid respectively which can be obtained from
enthalpy-concentration diagram for the mixture.
• When feed is cold liquid or superheated vapor: q can
be alternatively defined as the heat required to
convert 1 mole of feed from its entering condition to
a saturated vapor; divided by the molar latent heat of
vaporization.
• Based on this definition, one can calculate the q-value
from the following Equations for the case whereby q
> 1 (cold liquid feed) and q < 0 (superheated vapor
feed) as:
• For cold liquid feed:

(4.0)

For superheated vapor feed:

(4.1)

where Tbp is the bubble point,  is the latent heat of

vaporization and Tdp is the dew point of the feed
respectively.
Determination of the feed section operating
line (q-line)
• Consider the section of the distillation column (as shown in
Figure 2.14) at the tray (called feed tray) where the feed is
introduced.
• In the feed tray, the feed is introduced at F moles/hr with
liquid of q fraction of feed and vapor of (1-q) fraction of
feed as shown in Figure 2.14.
• Overall material balance around the feed tray:
(4.2)

Component balances for the more volatile component in the

rectifying and stripping sections are: For rectifying section:
(4.3)
• For stripping section

(4.4)

• At the feed point where the two operating lines

(Equations (4.3) and (4.4) intersect can be written
as:
(4.5)
Figure 2.14: Feed tray with fraction of liquid and vapor of feed
• From component balance around the entire column, it can be
written as
(4.6)

(4.7)

For a given feed condition, xF and q are fixed, therefore the

q-line is a straight line with slope - q / (1-q) and intercept xF/
(1-q).
• If x = xF , then from Equation(4.7) y = xF. At this
condition the q-line passes through the point (xF, xF)
on the 45° diagonal.
• Different values of q will result in different slope of
the q-line.
• Different q-lines for different feed conditions are
shown in Figure 2.15.
Figure 2.15: Different q-lines for different feed conditions
 Determination of the stripping section
operating line (SOL):
• The stripping section operating line (SOL) can be
obtained from the ROL and q-line without doing
any material balance.
• The SOL can be drawn by connecting point xB on
the diagonal to the point of intersection between the
ROL and q-line.
• The SOL will change if q-line is changed at fixed
ROL.
• The change of SOL with different q-lines for a
given ROL at constant R and xD is shown in Figure
2.16.
Figure 2.16: Stripping section operating line with different q-lines
• The stripping section operating line can be derived
from the material balance around the stripping
section of the distillation column.
• The stripping section of a distillation column is
shown in Figure 2.17.
• The reboiled vapor is in equilibrium with bottoms
liquid which is leaving the column.
Figure 2.17: Schematic of the stripping section
• Consider the constant molal overflow in the column. Thus
L'm = L'm+1 = .... = L' = constant and V'm = V'm+1 = ..... = V' =
constant.

Overall material balance gives

(4.8)

More volatile component balance gives:

(4.9)

Substituting and re-arranging the Equation (4.9) yields

(4.10)
• Dropping the subscripts "m+1" and "m" it becomes:

(4.11)

Substituting V' = L' – B from Equation (4.8), the Equation

(4.11) can be written as:

(4.12)

• The Equation (4.12) is called the stripping operating line

(SOL) which is a straight line with slope ( L' / L' - B) and
intercept ( B xB / L' - B ).
• When x = xB , y = xB, the SOL passes through (xB, xB ) on
the 45° diagonal line.
 Determination of number of theoretical stage
• Suppose a column is to be designed for the separation of
a binary mixture where the feed has a concentration of
xF (mole fraction) of the more volatile component and a
distillate having a concentration of xD of the more
volatile component whereas the bottoms having a
desired concentration of xB.
• Once the three lines (ROL, SOL and q-line) are drawn,
the number of theoretical stages required for a given
separation is then the number of triangles that can be
drawn between these operating lines and the equilibrium
curve.
• The last triangle on the diagram represents the reboiler.
A typical representation is given in Figure 2.18.
Figure 2.18: A typical representation of identifying number of theoretical stages
 Reflux Ratio, R
• The separation efficiency by distillation depends on the reflux
ratio.
• For a given separation (i.e. constant xD and xB) from a given
feed condition (xF and q), higher reflux ratio (R) results in
lesser number of required theoretical trays (N) and vice versa.
• So there is an inverse relationship between the reflux ratio
and the number of theoretical stages.
• At a specified distillate concentration, xD, when R changes,
the slope and intercept of the ROL changes (Equation 3.8).
• From the Equation (3.8), when R increases (with xD
constant), the slope of ROL becomes steeper, i.e. (R/R+1) and
the intercept (xD/R+1) decreases.
• The ROL therefore rotates around the point (xD, xD).
• The reflux ratio may be any value between a minimum
value and an infinite value.
• The limit is the minimum reflux ratio (result in infinite
stages) and the total reflux or infinite reflux ratio
(result in minimum stages).
• With xD constant, as R decreases, the slope (R/R+1) of
ROL (Equation (3.8)) decreases, while its intercept
(xD/R+1) increases and rotates upwards around (xD,
xD) as shown in Figure .
• The ROL moves closer to the equilibrium curve as R
decreases until point Q is reached.
• Point Q is the point of intersection between the q-line
and the equilibrium curve.
Figure 2.19: Representation of minimum reflux ratio
• At this point of intersection the driving force for mass transfer is zero. This is
also called as Pinch Point. At this point separation is not possible.
• The R cannot be reduced beyond this point. The value of R at this point is
known as the minimum reflux ratio and is denoted by Rmin.
• For non-ideal mixture it is quite common to exhibit inflections in their
equilibrium curves as shown in Figure 2.20 (a, b).
• In those cases, the operating lines where it becomes tangent to the equilibrium
curve (called tangent pinch) is the condition for minimum reflux.
• The ROL cannot move beyond point P, e.g. to point K. The condition for zero
driving force first occurs at point P, before point K which is the intersection
point between the q-line and equilibrium curve.
• Similarly, it is the condition SOL also. At the total reflux ratio, the ROL and
SOL coincide with the 45° degree diagonal line.
• At this condition, total number of triangles formed with the equilibrium curve is
equal minimum number of theoretical stages. The reflux ratio will be infinite.
Figure 2.20 (a): Representation of minimum reflux ratio for non-ideal mixture
Figure 5.20 (b): Representation of minimum reflux ratio for non-ideal mixture
 Tray Efficiency
• For the analysis of theoretical stage required for the
distillation, it is assumed that the the vapor leaving
each tray is in equilibrium with the liquid leaving
the same tray and the trays are operating at 100%
efficiency.
• In practice, the trays are not perfect. There are
deviations from ideal conditions.
• The equilibrium with temperature is sometimes
reasonable for exothermic chemical reaction but the
equilibrium with respect to mass transfer is not
often valid.
 The deviation from the ideal condition is due to:
(1) Insufficient time of contact.
(2) Insufficient degree of mixing.
To achieve the same degree of desired separation,
more trays will have to be added to compensate for
the lack of perfect separability.
The concept of tray efficiency may be used to adjust
the actual number of trays required.
metry and design of the contacting trays
wrates and flow paths of vapor and liquid streams
ompositions and properties of vapor and liquid streams (Treybal, 1981; Seader
Overall Efficiency
nley, 1998).