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ChE 411: Unit Operations II (3 units)


Text book and notes

Grading: Homework, Test, Midterm
and Final

Teaching Philosophy
What I hear I forget, What I see I remember,
What I do, I understand Confucius (~200 BC)
Lecturing is not teaching, & Listening is not learning You
learn by doing Educational psychologists
Examples: Riding bicycle, driving car, etc.
Our philosophy: teach, tell, show you what to do and make you do
it & test if you know how to do it.
Home works, tutorials, quizzes, tests, EXAMS
You cannot put the same shoe on every foot. We learn
differently: individualistic, group, etc. Work together but answer


Types of SP and underlying principles

Equilibrium in SP, equations, tables, graphs
Types of distillation and equipment used
Number of stages for given separation
Feed plate and Reflux on economics of process

Solvent extraction and other SP

Separation in packed tower/column
NTU & HTU ( number and height of transfer unit)

Reading Materials
C. J. Geankoplis Transport Processes
and Unit Operations, Prentice Hall,
C. J. Separation Processes, McGraw
Hil,l 1980
G. F. Nalven ed. Distillation and other
Industrial Separations, AIChE, 1997.
R. E. Treybal, Mass transfer
Operations, McGraw Hill, 1980

Introduction: Separation
in process industry
removal of contaminants from feed, wastes,
and recycle streams
separation of valuable products from
wastes, impurities and by-products.
separation processes account for 50 to 90%
of the capital costs of most chemical plants
and about 70% of the ultimate product cost.
Separation processes also important in
biological organisms, ecosystems, and
environmental engineering.

Introduction: Separation
a separation process, is any
mass transfer process used to convert a
mixture of substances into two or more
distinct product mixtures, at least one of
which is enriched in one or more of the
mixture's constituents.
done by contacting the mixture with
another phase.
Such two phases are generally only
partially miscible in one another.
The two phases in contact may be Gas-

Introduction: Separation

When such two phases are

brought into contact
there is the transfer of one or
more solutes (components)
from one phase to the other
due to the difference in
concentration, temperature or
pressure of the solutes in the
two phases.

Separation process

ure to be
g device

phase poorer
in a solute

A product
richer in a

phase brought
in to contact

Introduction: Separation
After the contacting, the two phases may
now be separated
The choice of phase and conditions will
ensure that one of the phases in contact
will be depleted or enriched in one or
more components of the original mixture.
Several separations may be required to
achieve the level of purification desiredmultiple separation stages

Two Phases in Contact: Liquid and Gas

Name of separation

Phases in

Direction of
transfer of
Gas to liquid



liquid and


liquid and

Liquid(water) to

Water into pure



liquid and

Gas(air) to liquid

Drying of moist

Stripping or
desorption (reverse

liquid and

Liquid to gas

Steam to
remove volatile
from nonvolatile oils

SO2 in air to
NH3 in air to

L-V, L-L, S-L contacting

Liquid to
Ammonia(aqueous) to vapour


vapour and
liquid that

vapour to

richer in ammonia



Acetic acid from aqueous

to isopropyl ether


Liquid- Solid

Solid to Liquid extracting copper from ores using

H2SO4 sol


Liquid- Solid

Liquid to Solid Sugar from conc. sugar solutions

Other separation
Adsorption, Crystallization,
cyclonic separation
Centrifugation , Chromatography,
Decantation, Demister (vapor), Drying,
Electrophoresis, Elutriation, Evaporation,
Flotation, Flocculation, Filtration,

Gold from ore: mixture of solids
flotation, roasting (chemical
reaction) and electrolytic refining

Crude oil :mixture of many

Desalting + several stages of
distillation steps to obtain
gasoline, kerosene, diesel etc

Processing methods:

single-stage process: mixture to be

separated and contacting phase are mixed
in a vessel and separated
multiple-stage process: after mixing and
separation the phases are contacted again
continuous contacting: contacting of
the phases is continuous throughout
contacting device

Equilibrium between

When two phases(V-L) of different

compositions are brought into
contact there is transfer of solute or
redistribution of solutes between the
The composition of the phases as a
result changes with time until
equilibrium is attained.
The compositions of the phases at
equilibrium is a measure of the

Vapour Liquid Separation Processes

reliability, simplicity, and low-capital
But energy consuming


Vapour-liquid Separation Process:


Process in which a liquid or vapour or a vapour -liquid

mixture of two or more substances is separated into its
component fractions of desired purity, on the basis of
difference in relative volatility(or boiling point),
by the application and removal of heat
relies on differences in the concentrations of components
in the liquid and vapour phases at equilibrium.
This is related to components differences in the
1. Volatilities 2. vapour pressures 3. boiling points
The components that make up the mixture
distribute themselves unequally in both the vapour and liquid

Applications of distillation
1. separate crude oil into fractions for specific uses
such as transport, power generation and heating.
2. Water is distilled to remove impurities-salt from
sea water.
3. Air is distilled to separate its components - notably
oxygen, nitrogen and argon- for industrial use.
4. Distillation of fermented solutions- used since
ancient times to produce distilled beverages with a
higher alcohol content-whiskey, gin etc
5. Small-scale Purification of liquid mixtures:

i. benzene-toluene; Acetic acid acetone

ii. methanol or ethanol from water
iii. production of deuterium(heavy water)

Distribution of components between vapour

and liquid phases at equilibrium

Volatility Of Components1;

The components distribute differently because of

differences in their readiness to vaporize.
This readiness to vapourise is termed the volatility of the
substances with the lower boiling points will vaporize
more easily than those with a higher boiling point.
Volatile substances have higher vapour pressure at a given
a volatile substance will have a low boiling point and vice
substance with lower boiling point is known as the more
volatile component (MVC)

Vapour Pressure And Volatility

Some molecules with above average energy are able to
break away from the surface of the liquid into space above

gaseous molecules bounce around, some of them will hit the

surface of the liquid again, and be trapped there
Equilibrium set up -when the number of molecules leaving
the surface is exactly balanced by the number rejoining it.
number of the gaseous molecules in the space above the
liquid at equilibrium is fixed .

A liquid boils when its saturated vapour

pressure equals the external pressure on the
On Mount Everest the pressure is so low that water
boils at about 70C.
Atop a 10,000mountain the boiling point of
water would be 90 C.
Liquid with the higher vapour pressure at a
particular temperature is the one with the lower
boiling point.
more volatile substance escapes to form a vapour
more easily than the less volatile ones.

Distribution of components at different


same initial compositions but different phase

compositions at different equilibrium temperatures but

Distribution of components
At higher temperature T2 but at the same pressure P,
equilibrium is attained, with different phase
compositions than at temperature T1.
mole fractions of A in the vapour and liquid are yA2 and
xA2 respectively.
components A and B are distributed in vapour and
liquid phases at different temperatures. Such a
diagram is called the phase diagram.
Such data at different temperatures but constant
pressure will constitute the T-x-y diagram or
constant pressure phase diagram or Boiling
point-concentration diagram
Also called boiling point diagram-gives the boiling
point of liquids of different compositions

Changes in distribution of
components in the phases with

saturated vapour
d liquid

saturated liquid

changes in distribution of components in the

phases with temperature3

Super heated

subcooled liquid

changes in distribution of components in

the phases with temperature.3
(a): Liquid-phase; no vapour Temperature 86 oC Concentration of benzene
Liquid: x = 0.40; Vapour: y = 0.00
(b): Liquid-phase; first bubble of vapour produced. Temperature 95.2 oC
(Bubble Point - solution about to boil). Concentration of benzene Liquid: x
= 0.40; Vapour: y = 0.61
(c): Vapour-Liquid Mixture; continued vaporization of liquid as heat is
added Temperature 98.0 oC Concentration of benzene Liquid: x = 0.31;
Vapour: y = 0.52
(d): Vapour-phase; last droplet of liquid remains Temperature 101.6 oC
(dew point) Concentration of benzene Liquid: x = 0.21; Vapour: y = 0.40
(e): Vapour-phase only, no liquid Temperature 108 oC .The process is
unsteady-state in nature.
NOTE: from the above Fig.
As heating continues, vaporization occurs over a range of boiling
At any time when 2 phases - vapour and liquid - are present, the
concentration of benzene (more volatile component) in the vapour (y) is
always higher than that in the liquid (x). The reverse is true for toluene
(less volatile component).

2 types of phase diagrams:

Constant-pressure phase diagrams

T-x-y diagram
boiling point diagram
boiling point-concentration diagram

commonly used for distillation

Constant-temperature- phase diagrams
P-x-y diagram
Isothermal phase diagram
commonly used to depict deviations

Constant Pressure Phase



bubble-point curve or saturated liquid line.
dew-point curve or saturated vapour line
Subcooled liquid region
Superheated vapour region
vapour-liquid region
bubble-point and dew-point temperatures


The boiling point of A(MVC) is that at which the

mole fraction of A is 1.0
The boiling point of B(LVC) is that at which the
mole fraction of A is 0.
In this example, A is therefore has a lower boiling
point than B.
The dew-point is the temperature at which the
saturated vapour starts to condense.
The bubble-point is the temperature at which the
liquid starts to boil.

Constant Temperature
(Isothermal) Phase Diagram:P-x-y

Data at constant temperature (isothermal) are plotted as

two curves:
pressure versus x and pressure versus y,
more volatile liquid will have a higher vapour pressure
(i.e. pA at xA = 1.0) at a fixed temperature.

Unlike in the constant pressure phase diagram, the

bubble point curve is above that of the dew point
higher pressure required to maintain in liquid state
At lower pressure more vapour is formed
vapour-liquid mixture region is between the two curves.

Constant P vs. Constant T phase


The constant pressure phase diagram is

more commonly used in the analysis of VLE
but the constant temperature phase
diagram is also useful in the analysis of
solution behaviour that deviates from
Raoult's Law
the more volatile liquid will have a higher
vapour pressure (i.e. pA at xA = 1.0).
Note also the regions in the two phase diagram of
vapour-liquid mixtures.

Vapour-Liquid Equilibrium[VLE] curve

Constant pressure Equilibrium Curve can
be obtained from boiling point diagrams or
phase diagrams.
VLE Curve of binary mixtures are often
presented as shown i.e. y vs. x
The VLE plot expresses the bubble-point
and the dew-point of a binary mixture at
constant pressure.
The curved line is called the equilibrium
line and describes the compositions of the
liquid and vapour in equilibrium at some
fixed pressure.

Equilibrium Curve (at constant


The Figure shows a typical equilibrium

curve for a binary mixture on x-y plot.
contains less information than the phase
diagram (i.e. temperature is not
but it is most commonly used.
It is useful for graphical design in
determining the number of theoretical
stages required for a distillation column
Has line y=x for MVC

Equilibrium Curve: example

Ideal liquid system

Equilibrium Curve: azeotropic


Equilibrium Curve from Phase Diagram

Effects of Increased Pressures

At Higher Pressures

the phase diagram becomes narrower

and the corresponding bubble point and dew point
temperatures also become higher.
Relative volatilities and hence Separability becomes
less at higher pressures.
At elevated pressures, the vapour phase tends to
deviate from ideal gas behaviour, and modifications to
the VLE data is required (e.g. through the use of the
compressibility factor).
Above the critical pressure of the more volatile
component there is no longer a distinction between
vapour and liquid. Distillation is no longer possible
beyond this point.
The vast majority of distillations are carried out at
pressures below 70% of the critical pressure.

Relative Volatility of A with respect to B

a measure of separability of A and B.

volatility of component-A defined as:
partial pressure of component-A in vapour
divided by mole fraction component-A in
For a binary mixture of A and B, therefore:
Volatility of A = pA / xA
Volatility of B = pB / xB
where Pi is the partial pressure of component i
and xi is mole fraction of i in the liquid.
of volatility of A
of isAtheP
A / xA

to volatility
of B B (LVC):
PB / x B

Effect of Relative Volatility on VLE

At y=x (straight line through the origin)
A and B have the same volatility and will vapourise together
when heated
Vapour and liquid will have the same composition.
No separation is possible
The larger the value of above 1.0, the easier the

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
vertical distance between the equilibrium curve and the
diagonal line( y = x ), the greater the difference in liquid and
vapour compositions and therefore the easier the
separation by distillation.

Ease of separation

Effect of Non-constant Relative Volatilities on

Predicted Equilibrium Curve Data
benzene-toluene (ideal solution)

ethanol-water (non-ideal solution

1. Less variation in
relative volatilities
with composition

1. More variation in
relative volatilities
with composition

2. Lower levels of
2. Higher levels of
deviation from actual
deviation from actual
VLE data
VLE data
3. Cannot be used to
predict VLE
3. Can be used to
predict VLE

Equilibrium Curve and T-x-y diagram from

Vapour Pressure data-valid for ideal solutions
Combining Raoult's Law with Dalton's Law:
Raoults law:

Dalton's Law: PT = PA +PB



Vapour Pressure =f(T),

Calculate xA and yA between Boiling Points of A and Boiling
Point of B yields the data for T-x-y and hence the equilibrium

Equilibrium Curve using vapour

pressure data







Note that from Raoults law:

The partial pressure PA varies linearly with xA.
the partial pressure PB varies linearly with xA.
total pressure PT varies linearly with xA.
shown as PT vs. x; PA vs. x and PB vs. x
respectively in the Figure.
Temperatures should be between the boiling
points of the pure components

Constant-temperature(P-x-y) phase diagram

for an ideal solution
From Raoults law the partial pressures PA and PB vary
linearly with xA as shown
The total pressure varies linearly with xA . This is shown
as PT vs. x in the Figure
Substituting for XA

Solving for PT yields


P = P P / [P - y (P P )]



We note that xA is between 0 and 1.0 .

Hence yA can also be calculated and substituted
into equations for PT vs. xA and PT vs. yA
PT varies linearly with xA
variation of PT with yA is given by equation

VLE Data(P-x-y) from vapour

pressure data


Ideal Solution & Raoult's Law

Ideal Solution: obeys Raoult's Law:
Raoult's Law:PA =PA0 XA
PA =equilibrium partial pressure of a component A,
at a fixed temperature T
PA0 =vapour pressure of pure liquid A at temperature
xA = mole fraction of A in the liquid
Note1: The vapour pressure is constant at constant
Note2: PA0 =f(T)

Characteristics of Ideal Solutions

The average intermolecular forces of attraction and

repulsion in the solution are unchanged on mixing the pure
The volume of the solution varies linearly with
There is neither absorption nor evolution of heat in
mixing the liquids
The total vapour pressure of the solution varies linearly
with composition (in mole fraction)
Ideality requires that molecules be similar in size,
structure, and chemical nature:
the nearest approach is the optical isomers. In practice, for
engineering purposes, many solutions or organic
compounds in a homologous series are considered

general guidelines for vapourliquid mixtures in

terms of their nonideality
a. Mixtures of isomers usually form ideal solutions.
b. Mixtures of close-boiling aliphatic hydrocarbons
nearly ideal below 10 bar.
c. Mixtures of compounds close in molar mass and
frequently do not deviate greatly from ideality
(e.g. ring compounds, unsaturated compounds,
naphthenes etc.).
d. Mixtures of simple aliphatics with aromatic
deviate modestly from ideality

Minimum-boiling azeotrope: carbondisulfide- acetone

(61.0 mole% CS2, 39.25 oC, 1 atm)

Minimum-boiling azeotrope
Mixtures less composition than azeotropes
produce vapour richer than liquid.
Remaining liquid becomes poorer in mvc and moves
away from L

Liquid richer than azeotrope produces vapour that

is poorer in mvc on boiling.
Remaining liquid becomes richer in mvc and moves
away from L

Azeotropic composition and boiling pionts depend

on the pressure of the system
azeotrope may be eliminated by simply changing
the pressure of system
Azeotropes can not be easily separated by
ordinary distillation

Maximum-boiling azeotrope: acetone chloroform

(65.5 mole% chloroform, 64.5 oC, 1 atm.)

It occurs when the negative deviations

are very large:
total pressure on constanttemperature phase diagram passes
through a minimum,

giving rise to a maximum in the

temperature (i.e. boiling point)on
constant-pressure phase diagram
On the equilibrium diagram, it can be
seen that at this point, the equilibrium
curve crossed the 45o diagonal.

Types of distillation
1. Distillation without reflux1. boiling of liquid mixture to be separated
and separating the vapour generated
without allowing any liquid to return to
the still

2. Continuous Distillation with reflux

returning part of condensate to still in
such a way that it runs counter to the
vapour rising to the condenser

binary mixture of A (MVC) and
The system consists
of a batch of liquid
(fixed quantity) inside a kettle (or still)
fitted with heating element or steam jacket
a condenser to condense the vapour
The condensed vapour is known as the
distillate. The distillate is collected in a
condensate receiver.
The liquid remaining in the still is known
as the residual.


Condensate Composition vs. time

Repeated partial distillation of

collected condensates

Rayleigh Equation: material

balance on A

Initial moles in still(at t) = moles left in

still(at t+dt) + moles vaporized(within dt)
i.e. amt. in still at t=amt. in still at t+dt +
amt. vapourised within dt
Moles of A=total moles x mole fraction of A
xL = (x - dx) (L - dL) + y dL
xL = xL - x dL - L dx + dx dL + y dL
Neglecting the term dx dL(product of 2
small quantities), the equation reduces to:

or ideal mixture: constant relative volatili

Suppose there are LA moles of A and LB moles of B of liquid
dL moles of liquid ( containing dLA moles of A and dLB moles of B)
are distilled off: hence

dLA / dL dLA
dLB / dL dLB

LA / L
LB / L

Separating variables and Integrating

AB ln
LB 0


LA 0
LB 0


LB = total mole of B left in still,

LA = total mole A left in still.
LB0 = total initial mole of B in
LA0 = total initial mole A in still

Simple Batch or Differential Distillation

with reflux
The pot is filled with
liquid mixture and
Vapour flows upwards
though the column and is
condensed at the top.
Part of the liquid is
returned to the column
as reflux, and the
remainder withdrawn as
Nothing is added or
withdrawn from the still


A single-stage continuous operation

where a liquid mixture is partially
the vapour produced and the residual
liquid are in equilibrium, which are
then separated and removed.





1. 100 kg mols of a mixture which contains 60 mol% n-pentane (A)
and 40 mol% n-heptane (B) is vaporized at 101.32 kPa pressure
under differential conditions until 40 kg mol are distilled. What is
the average composition of the vapour formed and of liquid
remaining in the still.
2. If 100 kg mols of the same mixture is flash distilled such that 40
kg mol are vapourised, what are the compositions of the vapor
and liquid left?
100 kg mols of a binary mixture (n-pentane and n-heptane ) is
distilled until the % composition of n-heptane in the still increases from
40% to 70% at 101.32 kPa pressure and under differential conditions . What
is the average composition of the vapour formed and of liquid remaining in
the still. How much liquid remains in in the still

Equilibrium data for n-pentane-n-heptane, x and y are mole fraction

of n-pentane
x 0.0 0.059 0.145 0.254 0.398 0.594 0.867 1.000
y 0.0 0.271 0.521 0.701 0.836 0.925 0.984 1.000

Homework No.7
1. A mixture containing 50 g mol of benzene and 50 g
mol of chlorobenzene is distilled by simple distillation
without reflux until 40 percent of the initial charge is
taken off as overhead. The system benzenechlorobenzene may be considered ideal, with an
averge relative volatility of 5.3
(a) What are the compositions of overhead and residue
after distillation is complete?
(b) The overhead from the first distillation is subjected to
a second simple distillation. Again 40 percent of the
charge is taken overhead. What is the composition of
the second over head product? What is its mass in
grams? How many grams of chlorine does it contain?

Homework No.7 (continue)

2. A mixture of 50 g mol of liquid benzene and 50 g mole
water. Determine the boiling at 101.32 kPa pressure.
Liquid benzene is immiscible in water. Determine the
boiling point of the mixture and the composition of the
vapor. Which component will first be removed
completely from the still? Vapor pressure data of the
pure components are as follows:

(mm Hg)

(mm Hg)

















Separation in Flash Distillation1

If no vapourization takes place, then the liquid
leaving the separator will have the same
composition as the feed.
If total vapourization occurs, the vapour will also
have the same composition as the feed.
Clearly, for effective separation, there must be some
vapour-liquid mixture present.
This means that there exists a certain relationship
between the extent of heating, and the concentration
in the vapour and liquid streams.
f =molal fraction of the feed that is vaporized
and withdrawn continuously as vapour
Therefore, for 1 mole of binary feed mixture, (1- f) is
the molal fraction of the feed that leaves continuously
as liquid

Flash Distillation: material balance for

the MVC (A)[1mole of feed]
For a given feed condition, and hence the
known value of f and xF, equation is a straight
line with slope [-(1-f)/f and intercept xF / f.
The operating line crosses the point (xF, xF) for
all values of f
Since the liquid and vapour are assumed to be
in equilibrium, the intersection of this line with
the equilibrium curve is the solution of the
material balance
the intersection of straight line with slope [-(1f)/f, through (xF, xF)and intercept xF / f is
drawn to obtain the solution

Solution to flash distillation

Case of constant relative volatility

the intersection point can be
determined mathematically by
simultaneously solving the operating
line equation and equilibrium curve
equation as given below:

The quadratic equation is solved for x

y is solved from equilibrium curve

Binary Distillation: A (more

volatile) and B (less
1 feed stream F:mixture
of 2 components
separated into 2 product streams:
D:distillate (top product or overhead product)
The more volatile component will vaporize more and is
removed mainly in the distillate stream
the less volatile component will remain mainly in the
bottoms stream.
bottoms stream is in liquid phase
distillate stream is produced by condensing the vapour

Equipment for Continuous Distillation

Tray Column or Packed Column

Overhead condenser
a heat exchange equipment for condensing the hot
vapour leaving the top of the distillation column.
Either cooling water (e.g. using shell-and-tube heat
exchanger) or air (using fin-fan condensers) can be
used as the cooling medium.
In either case, partial or total condensation may be
In the case of total condensation (as in the analysis
above), all the vapour is converted into liquid.
For partial condensation, there remain in the
vapour state the most volatile components.
The condensed liquid is partially returned to the
distillation column as reflux and partially withdrawn
as distillate product.

Accumulator/ Pump
Overhead accumulator
This is a horizontal (usually) pressure
vessel whereby the condensed vapour is
Pumps :
for returning the reflux liquid back to
the distillation column,
for pumping out the bottoms product for
for pumping the feed into the
distillation column.

Reboiler :
to produce the vapour stream in the distillation
column, called the reboiled vapour or the boil-up
Reboilers can be both external or internal (stab-in).
Steam reboilers or fired reboilers can be used. Fired
reboilers typically uses fuel gas or fuel oil or
combination of both

Feed/Bottom Exchanger
used for heat conservation: the hot bottoms
stream is used to heat up the feed stream before
it enters the distillation column.
As a result the bottoms product is cooled and
then rundown to storage.
For better temperature control of the feed stream,
a separate preheater or charge heater (both not
shown in the above diagram) may be used.
This is usually located downstream of the
feed/bottom exchanger for final temperature
Steam may be used for the preheater, and fuel
gas-fuel oil is used for the charge heater.

Charge Heater / Steam Preheater

This can be a fuel gas/fuel oil-fired

heater or steam-heated exchanger for
final temperature control before the
feed enters the column.
Other distillation columns: different
depends on the types of mixtures to be
separated and the complexity of the

- more than 1 feed inlet, as well as one

or more sidedraws.

Tray/plate columns

Binary Distillation- A (MVC) and B (LVC):

Feed stream F
with mole fraction xF

Distillate D
with mole fraction xD

Bottoms B
with mole fraction xB

The Reflux Liquid is L.

For a total condenser, it has the same
concentration as the distillate.

Tray/plate columns
The feed usually enters somewhere near
the middle of the column.
Distillate D is richer in the more volatile
Bottoms B is richer in the less volatile
want the distillate to be as pure in MVC
as possible (maximum xD = 1.00), and
the bottoms to be as pure in LVC as
possible (minimum xB = 0.00).

Tray/plate columns:
3 major types:
1. sieve Trays
2. valve Trays
3. bubble cap Trays

(b) valve cap(c) bubble cap

(d) Tray with valve caps

Figure 6.4 Three types of tray openings for

passage of vapor up into liquid

Analysis of Continuous Tray Columns

With a tray column, the vapours
leaving the tray will be richer in the
MVC than the vapour entering the tray
by one "step" change

Enrichment of Vapour Occurs

Continuously Over Entire Height of
Packing Used




More surface area for mass transfe

Higher flow capacity
Lower pressure drop

Packing Materails

(a) Structured
Random Packing
Far less pressure drop
Higher efficiency and capacity

Figure 6.7 Typical materials used in a packed column



The McCabe-Thiele
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,
very useful tool for the understanding of
distillation operation.
The VLE data must be available at the
operating pressure of the column.

The McCabe-Thiele Method.2

Information required :
feed condition (temperature, composition)
distillate compositions
bottom compositions
the reflux ratio - the ratio of reflux liquid over the
distillate product.
to determine number of theoretical stages required
for a given separation
Main assumption
1) Equimolar overflow through the tower between the
feed inlet and the top tray and the feed inlet and bottom
2) Liquid and vapor streams enter a tray, are
equilibrated, and leave.

McCabe-Thiele Method:
assumptions of the method
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.

number of theoretical

method involves the plotting on the equilibrium

diagram and 3 straight lines:
rectifying section operating line (ROL)
feed line (or q-line)
stripping section operating line (SOL) .
These operating lines represent the relationship
between the concentrations in the vapour
phase (y) and the liquid phase (x) flowing
counter currently between the stages
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 McCabe-Thiele Method 3

number of theoretical

McCabe-Thiele Method-number of theoretical

stages: the steps

1. Analysis of the Rectifying section, and determine

the ROL using xD and R
2. Analysis of the Feed section, and determine the
feed condition (q)
3. Determination of the feed line (q-line) using xF
and q
4. Locate the intersection point between ROL and qline
5. Analysis of the Stripping Section, and determine
the SOL using (4) and xB
6. Usually the SOL is the last line to draw, after both
ROL and q-line are drawn

Rectifying Section Operating Line (ROL):

(total condenser and the reflux is at bubble

Rectifying Section: ROL

Effect of various feed conditions on

vapour and liquid loading in column
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.

Feed Section Operating Line (q-line

F moles/hr of feed, with fraction q of

By definition:
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

Operating Line Equation :

Stripping Section , SOL
Analysis not really required, as SOL can be
automatically fixed once ROL and q-line are
The SOL is the last line drawn:
by connecting xB on the diagonal to the point of
intersection between the ROL and q-line
With ROL fixed, when the q-line changes the SOL
changes as well.

3 different SOL that correspond to 3 different qlines, for a given ROL (i.e. fixed R and x D)is shown
Thus, the operating line passes through the
point (xB , xB) on the 45o diagonal line.

SOL: equation
Substituting, and re-arrange

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

straight line: slope= L' / (L' - B) ;

intercept= B xB /( L' - B )
passed through ( xB, xB ) on the 45o diagonal line.
the stripping section operating line can be drawn on
equilibrium diagram and the number of theoretical
stages in the stripping section can be done in the same
The last "stage" on the graphical construction
represents the reboiler

For a given feed condition, xF and q

are fixed, therefore the q-line is a
straight line
slope =-q/(1-q) and
Intercept = xF / (1-q).
q-line passes
the point (xF, xF)

Effect of q on the intersection of

operating lines
this also marks the end of each of the
operating lines
q = 0 (saturated
q = 1 (saturated
q > 1(subcooled
q < 0 (superheated

The q-values: not certain of the feed condition

If the condition of the feed is known to be either
saturated liquid or saturated vapour, then the value
of q is either 1 or 0 value of q.
Using enthalpy balance around the feed plate f. :
F HF + L HL,f-1 + V' HV,f+1 = L' HL,f + V HV,f
HF = enthalpy of feed, evaluated at TF
HV = enthalpy of vapour, and
HL = enthalpy of liquid

Tbp= bubble point of the feed of the feed

Tdp is the dew point of the feed

Feed Plate Location

Optimum location would be the one represented by the

triangle that has one corner on the rectifying line
and the other corner on the stripping line.
In transferring from the rectifying section to the
stripping section, the steps on the diagram should be
kept as large as possible, and the transition is made at
the first opportunity after passing the intersection
the optimum feed location is stage no.5 that results in
the least number of stages.
Any other location would
result in more than 5 trays

If "staircase" construction is continued beyond

tray 5 along the ROL to tray 6 and tray 7 instead
of down to SOL, note that the triangles become
smaller, which means that the driving force for
mass transfer is smaller.
As a result, more trays will be required to
achieve the desired separation.
tray 6 for the first case is more effective than
that for the second case - the triangle is larger.

If the change to SOL is made too soon, at tray 4. Again the result is less than opt

1. Draw VLE curve.
2. Draw 45" line.
3. Locate xB, xD, and ZF on y=x line.
4. Calculate slope of q line [ -q/( 1 - q)]
and draw q line from (zF, zF)
5. Calculate B and D from overall balances
6. Calculate liquid and vapour flow rates in
rectifying and stripping sections.

stepping off stages

Using Operating Lines and the Feed Line in

McCabe-Thiele Design

Slope = R/(R+1)
Slope = q/(1-q)
Slope = L/ V

Ex 4.7 A continuous fractioning column is to be designed to

separate 30,000 kg/h of a mixture of 40 percent benzene and
60 percent toluene into an overhead product containing 97
percent benzene and a bottom product containing 98 percent
toluene. These percentages are by weight. A reflux ratio of 3.5
mol to 1 mol of product is to be used. The molal latent heats of
benzene and toluene are 7,360 and 7,960 cal/g mol,
respectively. Benzene and toluene from a nearly ideal system
with a relative volatility of about 2.5. The feed has a boiling
point of 95C at a pressure of 1 atm.
a) Calculate the moles of overhead product and bottom product
per hour.
b) Determine the number of ideal plates and the position of the
feed plate (i) if the feed is liquid and at its boiling point; (ii) if
the feed is liquid and at 20C (specific heat 0.44 cal/g.C); (iii) if
the feed is a mixture of two-thirds vapor and one-third liquid.

Homework No.8
1. A saturated liquid feed of 200 mol/h at the boiling
point containing 42mol% heptane and 58% ethyl
benzene is to be fractionated at 101.32 kPa abs to give
a distillate containing 97 mol% heptane and a bottoms
containing 1.1 mol% heptane. The reflux ratio used is
2.5:1. Calculate the molar flow rate of the distillate and
the bottoms, theoretical number of trays required to
achieve the separation, and the optimum feed tray
location. Equilibrium data are given below at 101.32
kPa abs pressure for the mole fraction n-heptane x H
and yH.





























2. Determine the minimum reflux ration Rm

and the minimum number of theoretical
plates at total reflux for the rectification of
a mixture of heptane and ethyl benzene as
given in problem 1. Do this by the graphical
methods of McCabe-Thiele.

it can affect the separation

for given feed condition (xF and q):
higher reflux ratio (R) will results in
lesser number of theoretical trays
(N) required, and vice versa.
In other words:
there are many possible
combinations of reflux ratio R
and number of theoretical


inverse relationship between the reflux

ratio and the number of theoretical
new design, of course the reflux ratio
and number of theoretical stages can both
be varied to achieve an optimum balance.
For an existing column, the number of
trays used is fixed, hence:
higher distillate concentration (mole
fraction xD) can only be obtained by
increasing the reflux ratio.

Effect of R changes onthe slope and

intercept of the RO

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,
draw larger triangles between the operating
This means that there are now greater driving
force for separation,
this in turn means that lesser number of
theoretical stages are required.
The reverse is true when R decreases.

total reflux andminimum reflux ratio

at two extremes of the reflux

how to find the most suitable
reflux ratio
minimum reflux ratio:
- results in infinite stages
total reflux or infinite reflux rati

Nm at total reflux: graphical method


Operating line at minimum

reflux ratio:

Operating line and q-line intersect on the

equilibrium curve