Distillation

by Manuel De Guzman

J6 DISTILLATION

J6.1 Introduction

Distillation is defined as an equilibrium-staged separation process in which a liquid or vapor

mixture or both, containing two or more components, is separated into its component fractions
of desired purity by the application and removal of heat. This process is based on the
equilibrium stage concept, which means that vapor and liquid streams, after contacting each
other, leave a stage or unit saturated with the more volatile component (has lower boiling
point) and the less volatile component (has higher boiling point), respectively. The separating
agent for distillation is heat, and the mechanism of distillation is by the addition of heat.

The important variables that affect phase equilibrium (Fig. J6-1) in distillation are
temperature, pressure, and concentration.

A B
vapor
liquid
A B

Fig. J6-1: Phase equilibrium for binary system

Where A = more volatile component

B = less volatile component

Raoult’s law, an ideal law, can be defined for vapor-liquid phases in equilibrium.

PA = PA x A (J6-1)

where PA = partial pressure of component A

PA = vapor pressure of pure component A
xA = mole fraction of component A in liquid phase

Gibbs phase rule restricts equilibrium in vapor-liquid systems, as follows:

F=C–P+2 (J6-2)

where F = number of variants or degrees of freedom

C = number of total components
P = number of phases at equilibrium
2 = refers to temperature and pressure variables

The separation of one or more components from a mixture by distillation, a liquid-vapor

contacting system, involves both mass and heat transfer. As such, the calculation tools for
solving distillation problems are material and energy balances and vapor-liquid equilibrium
relationship. Sources of equilibrium data for distillation include the following:

J6-1
 Distillation
by Manuel De Guzman

1. Vapor pressure data for pure components

2. Vapor pressure-temperature data using Antoine equation
3. Boiling point diagrams
4. Equilibrium curves
5. Relative volatilities
6. Distribution or partition coefficients using dePriestier charts

J6.1.1 Vapor Pressure Data for Pure Components

The compositions of vapor and liquid at equilibrium for a binary system can be expressed as
follows:

PA PB
yA = xA or yB = xB (J6-3)
P P

where y = mole fraction of component A or B in vapor phase

x = mole fraction of component A or B in liquid phase
P = vapor pressure of pure component A or B at a given temperature
P = total pressure

Equation (J6-3) is obtained by combining Raoult’s law (J6-1) and the relation (J6-4) that
states that the partial pressure of a component in an ideal gas or vapor is proportional to its
mole fraction.

PA = y A P or PB = y B P (J6-4)

The relationship between xA and xB and between yA or yB is obtained from the sum of the mole
fractions of components A and B being equal to unity.

xA + xB = 1 and yA + yB = 1 (J6-5)

J6.1.2 Vapor Pressure-Temperature Data using Antoine Equation

Antoine equation (J6-6) is useful in estimating the vapor pressure of a component at a given
temperature.

ln ( P  ) = A +
B
(J6-6)
C +T

where A, B, and C = constants

T = temperature

The vapor pressure ( P  ) calculated from equation (J6-6) can be substituted in equation (J6-3)
to get yA or yB.

J6-2
 Distillation
by Manuel De Guzman

J6.1.3 Boiling-Point Diagrams

The vapor-liquid equilibrium relations for a binary mixture of components A and B are
usually given as boiling-point diagram at a given total pressure (Fig. J6-2). The upper curve is
the saturated vapor curve or the dew-point curve, and the lower curve is the saturated liquid
curve or the bubble-point curve. The area enclosed by these curves is the two-phase region.
The area above the upper curve is the vapor region, whereas the area below the lower curve is
the liquid region.

120
vapor region

110 saturated
vapor curve
Temperature, °C

vapor-liquid
100
T mixture region

90
saturated
liquid curve
80
liquid region
70 xA yA
0 0.2 0.4 0.6 0.8 1
Mole fraction A in liquid or vapor, xA or yA

Fig. J6-2: Boiling-point diagram

From the above boiling-point diagram, the equilibrium values of xA and yA at a given
temperature (T) can be read with the lower and upper curves, respectively, as indicated by
broken lines.

J6.1.4 Equilibrium Curves

A common method of plotting vapor-liquid equilibrium data is the so-called xy plot (Fig. J6-
3). The equilibrium values of x and y at different temperatures, read from the boiling-point
diagram (Fig. J6-2), will result in a plot of equilibrium curve, as shown in Fig. J6-3.

J6-3
 Distillation
by Manuel De Guzman

Mole fraction A in vapor, yA

0.8

equilibrium
0.6 curve

diagonal
0.4

0.2

0
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-3: Equilibrium diagram

J6.1.5 Relative Volatilities

By definition, the volatility of a component is the ratio of its partial pressure to its mole
fraction in the liquid.

P
volatility = (J6-7)
x

Relative volatility, as a source of equilibrium data, is particularly useful in distillation

calculations. It is the ratio of the volatility of the more volatile component to that of the less
volatile component. Therefore, the relative volatility of the more volatile component (A) with
respect to the less volatile component (B) is

α AB =
( P x)A
(J6-8)
( P x)B
For ideal systems, pressure fraction equals mole fraction, i.e.,

PA Ptotal y
= A (J6-9)
PB Ptotal yB

The relative volatiliy (α AB ), since x B = 1 − x A and y B = 1 − y A , may then be expressed as

J6-4
 Distillation
by Manuel De Guzman

α AB =
( y x ) A = y A x B = y A (1 − x A )
(J6-10)
( y x ) B x A y B x A (1 − y A )
Dropping the subscripts A and B, we have

y(1 − x )
α= (J6-11)
x (1 − y )

Separation by distillation is much easier if α > 1; the separation becomes difficult if the value
of α is close to 1.

If Raoult’s law (J6-1) is valid, the volatility is numerically equal to the vapor pressure of the
pure component (or volatility = P x = P ) for ideal systems. Thus, the relative volatility
(α AB) takes the form

α AB =
( P x)A =
PA
(J6-12)
( P x)B PB

J6.1.6 Distribution Coefficients

Equilibrium data for distillation can be obtained from the so-called equilibrium distribution
coefficient (K), which is defined as follows:

y
K= (J6-13)
x

In general, K values depend on temperature, pressure, and composition. For many systems,
however, K values are approximately independent of composition.

J6.2 Types of Distillation

There are a number of ways by which distillation can be classified. Depending on the specific
purpose for which the separation technique is designed, the types of distillation basically can
be grouped into four categories.

1. According to the method of separation: simple or fractional distillation

2. According to the nature of the process feed: binary or multicomponent distillation
3. According to the method of operation: batch or continuous distillation
4. According to the type of column internals: plate-type or packed-type distillation

J6.2.1 Distillation Methods of Separation

In practice, there are two main distillation methods of separation:

J6-5
 Distillation
by Manuel De Guzman

1. Distillation without reflux (= simple distillation)distillation in which no condensate is

allowed to return to the single-stage still pot to contact the rising vapors

2. Distillation with reflux (= fractional distillation)distillation in which a portion of the

condensate is allowed to return to the distilling column to contact the rising vapors

J6.2.2 Number of Components in Distillation

The feed introduced to and processed in the distilling column may consist of two or more
components. We have a binary distillation if the number of components present in the feed
mixture is limited to two, and we have a multicomponent distillation if there are more than
two components in the feed mixture.

J6.2.3 Distillation Methods of Operation

Basically, there are two distillation methods of operation:

1. Batch distillation

In batch distillation, the process is carried out in separate runs; the more volatile
component is evaporated from the still pot, and distillation is continued as long as the
change in the concentration of the more volatile component in the distillate is still
significant. Batch distillation is advantageous if small quantities of mixtures or varying
product compositions are required, if smaller number of plates is used, and if high purity
of the product is not desired.

2. Continuous distillation

In continuous distillation, there is a steady input of feed to the distilling column and a
continuous withdrawal of streams of constant composition from the top and bottom of the
column. In terms of lowest operating costs, continuous distillation is advantageous if a
large number of plates are used and the reflux ratio approaches the minimum value.

J6.2.4 Distillation Calculation Methods

There are two types of distillation columnsstaged and packed columns. For staged
distillation columns, calculations are of the equilibrium-based method; for packed distillation
columns, calculations are of the rate-based method.

1. Staged columns in distillation

Distillation may be carried out in staged or plate columns in which each plate provides
intimate contact between vapor and liquid in continuous countercurrent flow. Each plate
constitutes a single stage where there is simultaneous partial condensation of vapor and
partial vaporization of liquid.

J6-6
 Distillation
by Manuel De Guzman

2. Packed columns in distillation

Distilling columns dumped with packing material is an alternative arrangement to plate

columns. The packing material provides high interfacial area for the exchange of the
components between the vapor and liquid phases. A true countercurrent flow of vapor and
returning liquid (reflux) occurs in packed columns, in contrast to the stage-to-stage flow in
plate columns.

Packed columns are used for smaller diameter columns since it is expensive to build a
staged column that will operate properly in small diameters. Packed towers have the
advantage of a smaller pressure drop and are, therefore, useful in vacuum fractionation.
Another advantage of packed columns is that they can be used to process corrosive
materials.

J6.3 Simple Distillation

There are three important types of distillation that occur in a single-stage still pot and that do
not involve rectificationsimple batch or differential distillation, equilibrium or flash
distillation, and simple steam distillation.

J6.3.1 Differential or Simple Batch Distillation

In simple batch or differential distillation, the compositions of distillate and bottoms change
with time; the total amounts and average compositions of distillate and bottoms are, therefore,
of more importance than the flow rates.

Consider a liquid charge L1 in the still pot, with a composition x1 of the more volatile
component, A, as in the following diagram:

Vapor condenser Distillate

V, y D, xD

L2, x2

still pot

Fig. J6-4: Differential or simple batch distillation

where L2 = liquid remaining in still pot at any time

V = vapors produced at any time
D = distillate collected at any time
x2 = instantaneous concentration of A in liquid remaining in still pot
y = instantaneous concentration of A in vapors produced
xD = average concentration of A in distillate

J6-7
 Distillation
by Manuel De Guzman

If an amount dL, with a composition y of the more volatile component, is vaporized, then a
material balance on the more volatile component gives

ydL = d ( xL ) = Ldx + xdL (J6-14)

L2 x
dL ⌠ dx
2
⌠ =

⌡L1 L ⌡x 1 y −x
(J6-15)
x
L ⌠ dx
2

ln 2 =  (Rayleigh equation) (J6-16)

L1 ⌡x 1 y − x

This resulting Rayleigh equation is integrated graphically using the equilibrium y vs x data.

There are, however, simplified forms of the Rayleigh equation:

1. If over the range concerned, the equilibrium relationship is a straight line ( y = mx + b )

1 ( m −1) m −1
L2  y2 − x 2   L2  y2 − x 2
=  or   = (J6-17)
L1  y1 − x1   L1  y1 − x1

where m = slope

2. If Henry’s law applies (for dilute solutions)

L  1 x 
ln  2  = ln  2  (J6-18)
 L1  H′ − 1  x1 

where H′ = Henry’s law constant = H/P

y(1 − x ) αx
3. If the relative volatility α = , from which y = , may be assumed
x (1 − y ) ( α − 1) x + 1
constant over the range concerned

• In terms of concentration
1α
(1 − x 2 ) L 2 x L 
=  2 2  Note: α = α1α2 (J6-19)
(1 − x1 ) L1  x1L1 
L  1  x (1 − x1 )   1 − x1 
or ln 2  = ln  2  + ln  (J6-20)
L
 1 α − 1 x
 1 ( 1 − x )
2   1 − x 2

• In terms of components

A  B 
ln 1  = α ln 1  Note: α = αAB αAB (J6-21)
 A2   B2 
1 2

J6-8
 Distillation
by Manuel De Guzman

J6.3.2 Equilibrium or Flash distillation

In flash distillation, the feed stream passes through a valve to reduce its pressure before it is
introduced or “flashed” into a drum where part of the feed stream vaporizes, and the resulting
vapor and liquid in equilibrium with each other are separated. The system is called “flash”
distillation because the feed, after entering the drum, vaporizes very rapidly.

Consider the following flash drum:

Vapor
V, y

Feed
F, xF

Liquid
L, x
Fig. J6-5: Flash distillation

For a binary system subjected to flash distillation, an overall mass balance gives

F =V +L (J6-22)

where F = feed
V = vapor
L = liquid

and on the more volatile component

x F F = yV + xL (J6-23)

where xF = fraction of more volatile component in feed

y = fraction of more volatile component in vapor
x = fraction of more volatile component in liquid

Therefore,

V xF − x
= (J6-24)
F y −x

If we let f be the fraction of feed vaporized (= V F ), the above equation becomes

1−f x
y=− x+ F (equation of a straight line) (J6-25)
f f

J6-9
 Distillation
by Manuel De Guzman

A graphical solution to flash distillation problems constitutes a plot of equation (J6-25) in an

xy equilibrium plot (Fig. J6-6) and its intersection with the equilibrium line, whose
coordinates are x and y (indicated by broken lines). Or we can have an analytical solution by
trial-and-error method, since there are four unknowns (V, L, y, and x), and only three
equations are availabletwo material balances, (J6-22) and (J6-23), and the equilibrium
relationship between y and x.

equilibrium
curve
Mole fraction A in vapor, yA

0.8

y 1 −f
0.6 slope = −
f

0.4

0.2

0 x
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-6: Plot of solution to flash distillation

J6.3.3 Simple Batch Open Steam Distillation

In simple batch open steam distillation, steam is injected directly into the still pot. The reasons
for adding steam directly to the still pot are that it keeps the temperature below the boiling
point of water, which is good for heat-sensitive components, and it does not anymore require
heat transfer surface area.

The general equation for simple batch open steam distillation is as follows:

 nA 
P − εPA  
dnS  n A + n C  dn S  P  n P 1
− = or − =   − 1 + C  (J6-26)
dn A  nA  dn A  εPA  εPA n A
εPA  
 n A + n C 

where S = open steam

J6-10
 Distillation
by Manuel De Guzman

A = volatile component
C = nonvolatile impurity
n = moles
ε = correction factor if vapor deviates from ideal behavior
PA = vapor pressure of volatile component
P = total pressure

Equation (J6-26) takes different forms depending on the following cases:

1. Dissolved nonvolatile impurity is present in large amounts

 P  n P  nA 
( )
n S =   − 1 n A1 − n A 2 + C  ln 1
εPA  n A 2

 (J6-27)
 εPA  

where n A1 = initial moles of volatile component in still pot

nA2 = final moles of volatile component in still pot

2. Dissolved nonvolatile impurity is negligible

nS P − εPA mS P − εPA M S
= or = (J6-28)
n A1 − n A 2 εPA mA εPA M A

where mS = mass of steam

MS = molar mass of steam
mA = mass of volatile component distilled
MA = molar mass of volatile component

J6.4 Fractional Distillation

The industrial distillation column is a series of units in which two processes of partial
vaporization and partial condensation occur simultaneously. The liquid from a stage flows
down to the next stage where it is contacted with the rising vapor. This contact of liquid and
vapor flowing countercurrently with each other is repeated within the entire distilling column.

In analyzing the distilling column for calculation purposes, it may be divided into three
sections, as indicated in Fig. J6-7.
condenser

L0 Distillate
D, xD
n
Ln, xn Vn+1, yn+1
Feed
F, xF
J6-11
 Distillation
by Manuel De Guzman

m
Lm, xm Vm+1, ym+1

Bottoms
B, xB
reboiler

Fig. J6-7: Fractional distillation column

Material balances can be made about each of the above three sections of the distilling column,
resulting in operating-line equations that relate the concentrations of the vapor and liquid
streams passing each other in each stage. An overall material balances at the top section of the
column gives the rectifying operating line; balances at the bottom section gives the stripping
operating line; and balances at the feed stage gives the feed line equation.

With these operating lines, the calculation of the amounts of streams entering and leaving the
column can be made. Calculations can be graphical using the McCabe-Thiele method
(sections J6.5 and J6.6) or the Ponchon-Savarit method (section J6.7), or they can be
analytical using the stage-to-stage method.

J6.4.1 Rectifying Operating Line

An overall material balance at the top section of the distilling column gives

Vn +1 = L n + D (J6-29)

A total material balance on the more volatile component is given by

y n +1Vn +1 = x n L n + x D D (J6-30)

From these two material balances, the following rectifying operating line equation results:

Ln x D
y n +1 = xn + D (J6-31)
Ln + D Ln + D

Equation (J6-31) is commonly expressed in terms of the reflux ratio R ( = L 0 D ), as follows:

R x
y n +1 = xn + D (J6-32)
R +1 R +1

J6.4.2 Stripping Operating Line

J6-12
 Distillation
by Manuel De Guzman

An overall material balance at the bottom section of the distilling column gives

Vm +1 = L m − B (J6-33)

A total material balance on the more volatile component is given by

y m +1Vm +1 = x m L m − x B B (J6-34)

From these two material balances, the following stripping operating line equation results:

Lm x B
y m +1 = xm − B (J6-35)
Lm − B Lm − B

J6.4.3 Feed Line

An overall material balance at the feed section of the distilling column gives

F + Vm +1 + L n = Vn +1 + L m (J6-36)

A total material balance on the more volatile component is given by

x F F + y m +1Vm +1 + x n L n = y n +1Vn +1 + x m L m (J6-37)

From these two material balances, the following feed line equation results:

y m +1Vm +1 − y n +1Vn +1 = x m L m − x n L n − x F ( Vn +1 − Vm +1 + L m − L n ) (J6-38)

Another form of equation (J6-38), in terms of the liquid content of the feed, q, is given as
follows:

q x
y= x− F (feed line or q-line) (J6-39)
q −1 q −1

J6.5 McCabe-Thiele Method

The graphical solution for fractional distillation problems developed by McCabe and Thiele is
based on the following assumptions:

1. There are no heat losses in the distilling column or the column is adiabatic.
2. The specific heat changes are negligible compared to latent heat changes.
3. The heat of vaporization per mole is constant; that is, the effect of concentration on the
molal latent heat of vaporization is insignificant.

The last assumption is the statement of constant molal overflow (CMO) and is the most
important.
J6-13
 Distillation
by Manuel De Guzman

It follows from the assumption of CMO for the McCabe-Thiele method that the V’s above the
feed or in the upper section of the distilling column are equal to each other, which means that
the L’s are also equal to each other; the same is true for the V’s and the L’s below the feed or
in the lower section.

The McCabe-Thiele method makes use of an xy diagram on which the following are plotted:
diagonal, equilibrium data, and operating linesthree straight lines that represent the entire
distilling column.

These three operating lines for the McCabe-Thiele y-x diagram have the following forms:

1. Rectifying operating line  this equation given in (J6-31) is commonly expressed in terms
of the reflux ratio R ( = L 0 D ), as follows:

R x
y n +1 = xn + D (J6-32)
R +1 R +1

2. Stripping operating line  this equation given in (J6-6), with the assumption of CMO,
becomes

L x B
y m +1 = xm − B (J6-40)
L−B L−B

3. Feed  together with equations (J6-41) and (J6-42) from the definition of q (quality of
feed or its liquid content),

L m = L n + qF (J6-41)
Vn = Vm + (1 − q ) F (J6-42)

material balances made at the feed stage (final form is given in equation (J9-38)), noting
that the feed line will intersect the rectifying and stripping operating lines at common
values of y and x, will give the following form of the feed line equation:

q x
y= x− F (feed line or q-line) (J6-39)
q −1 q −1

The feed entering the distilling column may have different conditions, as follows:

Feed Condition q q-line slope

subcooled slant upward to the right,
>1 >1
liquid 1st quadrant
saturated
=1 =∞ vertical
liquid

J6-14
 Distillation
by Manuel De Guzman

wet between 1 slant upward to the left,

= negative
vapor and 0 2nd quadrant
saturated
=0 =0 horizontal
vapor
superheated between 1 slant downward to the left,
<0
vapor and 0 3rd quadrant

The above description of the McCabe-Thiele method can be visualized in Fig. J6-8.

1 1
equilibrium 2
curve
3
Mole fraction A in vapor, yA

0.8
4
q-line
0.6
5
rectifying
6 operating line
0.4
7

0.2
8
stripping
9 operating line
10
0 xB xF xD
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-8: McCabe-Thiele diagram

The above McCabe-Thiele diagram is used in determining graphically the total number of
stages for a given distillation operation. This is done by stepping off alternating horizontal and
vertical lines, with the operating lines and the equilibrium curve as boundaries, from xD to xB.
Each step represents a stage, and as shown in Fig. J6-8, the total theoretical number of steps
or stages is 9.6.

J6.5.1 Total Reflux for McCabe-Thiele Method

At total reflux,

L 0 L0
R= = =∞ (J6-43)
D ≈0

And the y-intercept of the rectifying operating line becomes 0.

J6-15
 Distillation
by Manuel De Guzman

xD x
= D =0 (J6-44)
R +1 ∞ +1

Therefore, the overall operating line is the 45º diagonal line. This results in the number of
stages N being minimum.

at total reflux ( R = ∞ ), → the number of stages N = N min (J6-45)

1 1
2
Mole fraction A in vapor, yA

0.8 3

0.6 4

45° line
0.4
5

0.2 6
7
8
0 xB xF xD
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-9: Minimum number of stages by McCabe-Thiele method

As indicated in Fig. J6-9, the minimum theoretical number of stages is 7.1. This number is
based on stepping off horizontal lines then vertical lines, with the diagonal and the
equilibrium curve as boundaries, from xD to xB.

J6.5.2 Minimum Reflux Ratio for McCabe-Thiele Method

The minimum reflux ratio is one of the limiting operating conditions for distillation. It is a
useful hypothetical concept, which refers to the smallest amount of returning liquid to the top
of the column, at which the desired separation could just be obtained with an infinite number
of stages.

at R = R min , → the number of stages N = ∞ (J6-46)

For an ideal equilibrium curve, the graphical representation on the McCabe-Thiele diagram of
an infinite number of stages, as shown in Fig. J6-10, is the intersection of the rectifying

J6-16
 Distillation
by Manuel De Guzman

operating line and the feed line at the equilibrium curve. This point of intersection is called
the pinch point.

Mole fraction A in vapor, yA

0.8

0.6
pinch
point
0.4
y-intercept for
Rmin

0.2

0 xB xF xD
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-10 Minimum reflux ratio for ideal system by McCabe-Thiele method

To have an infinite number of stages for a nonideal equilibrium curve, the rectifying operating
line must touch the equilibrium curve at the point of tangency, as illustrated in Fig. J6-11.
This point is called the pinch point at which the compositions of vapor and liquid do not vary
from stage to stage.

J6-17
 Distillation
by Manuel De Guzman

0.8 pinch

Mole fraction A in vapor, yA

point

0.6

y-intercept for 0.4

Rmin

0.2

0 xB xF xD
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid, xA

Fig. J6-11 Minimum reflux ratio for nonideal system by McCabe-Thiele method

J6.5.3 Optimum Feed Plate for McCabe-Thiele Method

The optimum feed plate location results in the fewest number of plates in the distilling
column. On the McCabe-Thiele diagram given in Fig. J6-8, this location is the step with one
end at the rectifying operating line and the other end at the stripping operating line. From Fig.
J6-8, the optimum feed plate is the 6th plate from the top of the column.

J6.6 Variation of Conditions for Fractionation using McCabe-Thiele

Method

J6.6.1 Two-Feed Stream Distillation

In distillation with two feeds, the overall operating line includes a third operating line in
addition to top and bottom operating lines. This third line is the middle operating line, which
can be obtained by making material balances around the upper section of the distilling column
that includes the first feed stream (positioned above the second feed stream).

J6.6.2 Distillation with Side Stream

If a product of intermediate composition is required, a side stream may be withdrawn. Three

additional variables are necessary, such as flow rate, type of side draw (vapor or liquid), and
location or composition. The operating line for the middle section can be derived from

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material balances around the upper or lower section of the distilling column that includes the
side stream.

J6.6.3 Partial Condensers

A partial condenser converts only part of the overhead vapor stream to liquid and returns this
liquid as reflux. The remaining vapor is withdrawn as the distillate product. The partial
condenser acts as one equilibrium stage.

J6.6.4 Total Reboilers

A total reboiler converts all the liquid from the bottom of the distilling column to vapor,
which, in turn, is returned to the bottom of the column. The material balances and the bottom
operating line with a total reboiler are exactly the same as with a partial reboiler. The only
difference is that a total reboiler is not an equilibrium stage.

J6.7 Ponchon-Savarit Method

If the assumption of constant molal flow of McCabe-Thiele method is no longer valid, the
solution to distillation problems is to solve material and energy balances simultaneously on
each stage in the distilling column. This solution can be done graphically by Ponchon-Savarit
method (Fig. J6-12), in which enthalpy-compositions are used, enthalpy being the vertical
axis and composition the horizontal axis.
40000
H vs yA (saturated vapor)
Enthalpy of mixture, H or h (kJ/kmol)

30000

20000 tie line

10000

h vs yA (saturated liquid)

0
0 0.2 0.4 0.6 0.8 1

Mole fraction A in liquid or vapor, xA or yA

Fig. J6-12 Ponchon-Savarit enthalpy-concentration diagram

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Fig. J6-12 shows the enthalpy-concentration plot for a binary vapor-liquid mixture of A and B
at a given constant pressure. The plot is based on arbitrary reference states of liquid and
temperature, and it considers latent heats, heats of solution or mixing, and sensible heat of the
components of the mixture.

J6.8 Analytical Calculation Methods for Distillation

J6.8.1 Total Reflux Ratio

If the relative volatility, α , of a binary mixture is approximately constant, the following

Fenske equation can be used to calculate the minimum number of stages when a total
condenser is used:

 x 1 − xB 
log  D 
 1 − x D x B  Note: α = αtop αbottom (J6-47)
Nm =
log α

where Nm = minimum number of stages

α top = relative volatility at top temperature
α botto = relative volatility at bottoms temperature
m

J6.8.2 Minimum Reflux Ratio

For ideal mixtures, or if the relative volatility, α , of a binary mixture could be taken as
constant, Rm may be obtained analytically using the Underwood equation as follows:

1  x D α (1 − x D ) 
Rm = − (J6-48)
α − 1  x F 1 − x F 

where Rm = minimum reflux ratio

J6.9 Complex Distillation Methods

Complex mixtures constitute less ideal mixtures, and their equilibrium data deviate from ideal
behavior. The methods for separating complex mixtures are azeotropic and extractive
distillation.

J6.9.1 Azeotropic Distillation

Azeotropic distillation is based on the addition of a new substance to the mixture to increase
the relative volatility of the two key components, and thus make the separation relatively
easy.

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J6.9.2 Extractive Distillation

With extractive distillation, the substance added is relatively nonvolatile compared with the
components to be separated.

J6.10 Multicomponent Distillation

The process of multicomponent distillation involves the separation of more than two
components from a mixture. The general principles of design of multicomponent distillation
columns are similar in many respects as to those described for binary systems. There is one
material balance for each component in the multicomponent mixture. Enthalpy or energy
balances are made, which are similar to those for binary case. Equilibrium data are used to
determine boiling points and dew points.

J6.11 Packed Columns for Distillation

The process of distillation in packed columns is one of continuous countercurrent mass

transfer. As mentioned in section J6.2.4, the method of calculations for packed distillation
columns is rate-based, i.e., calculations are based on mass transfer rate equations.

Although packed towers have continuous contact of vapor and liquid, they can be analyzed
like staged towers in which contact between vapor and liquid is discontinuous. The
assumption is that the packed column could be divided into segments of equal height. Each
segment is taken as an equilibrium stage where leaving streams of vapor and liquid are in
equilibrium with each other. This staged model is only fictitious, but the model can be useful
for the purpose of designing packed columns.

The height of each imaginary stage is referred to as the height equivalent to a theoretical plate
(HETP).

height of packing
HETP = (J6-49)
number of theoretic al stages

The number of theoretical stages is calculated using the McCabe-Thiele or Ponchon-Savarit

graphical method.

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