ChE 411: Unit Operations II (3 units)

Prof. Ogbemi O. Omatete/Mrs. M. E.

Ojewumi

Students’ names
Students’ dreams

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 individually.
 Objectives
• Importance of Separation Process (SP)
• 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, 1993
• C. J. King, 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 Process-1
• 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.
• SP 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-solid, Gas-
liquid, liquid-solid, liquid –liquid.
Introduction: Separation Process-2
• 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
.
Feed/mixt
ure to be A product
separated phase
richer in a
Contacting solute
device

Another
product Another
phase poorer phase brought
in a solute in to contact
feed
 Introduction: Separation Process-3
• 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 desired-multiple separation
stages
Two Phases in Contact: Liquid and Gas
Name of separation Phases in Direction of eg
process contact transfer of
solute(e)
Absorption liquid and Gas to liquid SO2 in air to
gas water
NH3 in air to
water

humidification liquid and Liquid(water) to Water into pure

gas gas(air) air

dehumidification liquid and Gas(air) to liquid Drying of moist

gas air

Stripping or liquid and Liquid to gas Steam to

desorption (reverse gas remove volatile
absorption) components
from non-
volatile oils
 L-V, L-L, S-L contacting phases
Distillation Volatile Liquid to Ammonia(aqueous) to vapour
vapour and vapour; richer in ammonia
liquid that vapour to
vapourises liquid

Liquid-liquid Liquid- Liquid- Acetic acid from aqueous

(solvent)extra liquid liquid solution
ction to isopropyl ether

Solid-Liquid Liquid- Solid Solid to Liquid extracting copper from ores using
extraction H2SO4 sol

crystallization Liquid- Solid Liquid to Solid Sugar from conc. sugar solutions
 Other separation processes

• Adsorption, Crystallization, cyclonic separation

• Centrifugation , Chromatography,

• Decantation, Demister (vapor), Drying,

• Electrophoresis, Elutriation, Evaporation,

• Flotation, Flocculation, Filtration,
 TYPICAL CASES
• Gold from ore: mixture of solids
–flotation, roasting (chemical reaction) and
electrolytic refining
• Crude oil :mixture of many components
–Desalting + several stages of distillation
steps to obtain gasoline, kerosene, diesel
etc
 Processing methods: Several
• 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
 Vapour –Liquid Separation Processes

• Distillation
– reliability, simplicity, and low-capital cost
– But energy consuming
• Absorption
• Stripping
• Humidification
• dehumidification
 Vapour-liquid Separation Process:
DISTILLATION
• 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)
 Equilibrium between phases.
• At equilibrium the compositions, temperature
and pressure of the contacting phases remain
constant-no change with time.
• The relationship between the compositions of
a V and a L at equilibrium at some constant
pressure/temperature is the vapour- liquid
equilibrium (VLE)data.
• Data may tabulated or presented graphically
 Equilibrium between phases1
• When two phases(V-L) of different
compositions are brought into contact there is
transfer of solute or redistribution of solutes
between the phases.
• 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 separation that has been
achieved.
 Equilibrium between phases 2
• The important variables affecting the compositions
at equilibrium of a solute in the contacting phases
are:
• Temperature of phase

• pressure of phase

• Composition-in vapour, y and in liquid, x

Experimental VLE Data for Binary Systems
• The VLE data for binary systems obtained
experimentally by mixing:
– two liquid components(A & B) and allowing the
vapour-liquid system to equilibrate
– by changing temperature and/or pressure
• vapour phase and liquid phase temperature and
pressure are measured.
• Samples of the vapour phase and liquid phase are
taken and analyzed.
Distribution of components between vapour
and liquid phases at equilibrium
 Volatility Of Components 1
• The components distribute differently because of
differences in their readiness to vaporize.
• This readiness to vapourise is termed the volatility of the
substance.
• 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
temp.
• a volatile substance will have a low boiling point and vice
versa.
• 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 .
 Vapour pressure 2
• molecules hit the walls of the container-exert a
pressure.
• This pressure is called the saturated vapour
pressure (also known as saturation vapour
pressure) of the liquid
• saturated vapour pressure increases with
temperature
• Increasing temperature, increases the average energy
of the molecules which hit walls with more energy
• -more of them are likely to have enough energy to
escape from the surface of the liquid.
 Vapour pressure 3
• The higher the vapour pressure, the higher the tendency
of the molecules to escape from the liquid and hence the
higher the volatility.
• higher the vapour pressure >> Intermolecular forces
holding liquid molecules together are relatively weak.
• >> Less supply of heat to break them completely and boil
the liquid.
•A liquid boils when its saturated vapour
pressure equals the external pressure on the
liquid.
•On Mount Everest the pressure is so low that water
boils at about 70°C.
•Atop a 10,000’mountain 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.
 volatility of components3
• substance with the higher boiling point is known as the
less volatile component (LVC).
• If we let A = MVC and B = LVC,
• Composition of components in the phases are expressed in
terms of mole fractions:
• yA = mole fraction of component-A in the vapour phase
xA = mole fraction of component-A in the liquid phase
• At a different temperature and/or pressure, the 2
components will distribute differently
• yB =1- yA
• xB =1- xA
 Distribution of components at different
temperatures

same initial compositions but different phase compositions at different

equilibrium temperatures but same pressure
 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 temperature 1

saturated vapour
subcooled saturated liquid
liquid
Distribution of Components in the Phases VS Temp. 3

• 0 Super heated vapour

subcooled liquid
 changes in distribution of components in
the phases with temperature. 3
• (a): Liquid-phase; no vapour T = 86 oC Conc. of benzene Liquid: x = 0.40;
Vapour: y = 0.00
• (b): Liquid-phase; first bubble of vapour produced. T = 95.2 oC (Bubble
Point - solution about to boil). Conc. of benzene Liquid: x = 0.40; Vapour:
y = 0.61
• (c): Vapour-Liquid Mixture; continued vaporization of liquid as heat is
added T = 98.0 oC Conc. of benzene Liquid: x = 0.31; Vapour: y = 0.52
• (d): Vapour-phase; last droplet of liquid remains T = 101.6 oC (dew point)
Conc. of benzene Liquid: x = 0.21; Vapour: y = 0.40
• (e): Vapour-phase only, no liquid T = 108 oC .The process is unsteady-
state in nature.
• NOTE: from the above Figure.
• As heating continues, vaporization occurs over a range of boiling
points.
• At any time when 2 phases - vapour and liquid - are present, the conc.
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 called
– T-x-y diagram
– Isobaric phase diagram
– boiling point diagram
– boiling point-concentration diagram
– commonly used for distillation calculations
• Constant-temperature- phase diagrams
– P-x-y diagram
– Isothermal phase diagram
– commonly used to depict deviations from ideal
behaviour or Raoult’s law
Constant Pressure Phase Diagram
 PHASE DIAGRAMs 1:T-x-y (Constant Pressure)
• the distribution of components in the liquid and vapour
phases is a function of temperature
• the bubble-point and the dew-point of a binary mixture
at constant pressure.
• Liquids of different composition at the same pressure
will boil at different temperatures- bubble-point curve
• Vapours of different composition at the same pressure
will condense at different temperatures- dew-point
curve
• boiling of a liquid mixture takes place over a range of
boiling points.
• Condensation of a vapour mixture takes place over a
range of condensation points
VLE for Benzene –toluene at 1 atm
 Acetone water system
P=101.3kPa P=344.73 P=344.73
T [K] x1 y1 T [K] x1 y1 T [K] x1 y1
[mol/mol] [mol/mol] [mol/mol] [mol/mol] [mol/mol] [mol/mol]

368.25 0.008 0.138 395.65 0.017 0.349 423.85 0.014 0.249

363.25 0.016 0.277 393.15 0.024 0.398 415.45 0.036 0.395
355.25 0.033 0.479 385.15 0.055 0.518 409.55 0.078 0.507
349.35 0.052 0.604 379.15 0.107 0.608 404.25 0.144 0.582
345.35 0.072 0.675 375.95 0.194 0.67 402.75 0.229 0.618
342.65 0.094 0.719 374.45 0.273 0.695 402.15 0.341 0.65
340.75 0.117 0.738 373.05 0.388 0.718 401.45 0.444 0.665
338.15 0.171 0.776 372.15 0.545 0.747 399.75 0.559 0.7
336.45 0.237 0.8 371.95 0.633 0.768 398.85 0.754 0.781
335.15 0.318 0.822 371.75 0.778 0.83 398.55 0.842 0.845
334.15 0.42 0.839 371.55 0.89 0.903 399.15 0.925 0.912
333.05 0.554 0.863 371.35 0.95 0.951
331.35 0.736 0.909
 PHASE DIAGRAM: features
• 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

 PHASE DIAGRAM 2
• 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.
 PHASE DIAGRAM 3
• a subcooled liquid with mole fraction of A=0.4
(point A) is heated at constant pressure, its
concentration remains constant until it reaches the
bubble-point (point B), when it starts to boil.

• The vapour evolved has the equilibrium

composition given by point C,

• approximately 0.8 mole fraction A. This is

approximately 50% richer in A than the original
liquid
 Constant Temperature (Isothermal) Phase
Diagram:P-x-y Diagram
• 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 Diagrams
• 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-only,
– liquid-only
– 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.
Constant Temperature (Isothermal)/P-x-y Phase
Constant Temperature (Isothermal) Phase Diagram
Diagram
 Equilibrium Curve (at constant pressure)
• 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 included),
• 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: more complicated1
Equilibrium Curve: azeotropic systems

•
Equilibrium Curve from Phase Diagram
Equilibrium Curve from Phase Diagram

•By drawing horizontal lines (constant T) like DF and

HJ on the phase diagram

•obtain the corresponding mole fractions x and y at the

intersections with the horizontal lines.

•With a set of x-y values, a graph of y vs. x can be

plotted i.e. the equilibrium curve
 Effects of Increased Pressure on phase
diagram
• Most distillations are carried out at atmospheric or near
atmospheric pressure.
• Have High pressure distillation (typically 3 - 20 atm)
– occurs in thermally integrated processes or
– when the normal boiling point of the vapour product is
lower than the temperature of the cooling water
required to condense it.
• normally cheaper to pressurize the column in order to raise
the boiling point of the vapour product than to install a
refrigeration system to condense it.
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.
• 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.
• Liquids do not normally exhibit appreciable compressibility until the
pressure gets close to its critical value.
 Relative Volatility of A with respect to B
• (Separability) volatility of component-A defined as:
– partial pressure of component-A in vapour divided by
mole fraction component-A in liquid
• For a binary mixture of A and B, therefore:
– Volatility of A = pA / xA Raoult’s Law
– Volatility of B = pB / xB
• where Pi is the partial pressure of component i and xi is
mole fraction of i in the liquid.
• Relative volatility is the ratio of volatility of A (MVC) to
volatility of B (LVC): Separation Factor

Volatility of A PA / x A
 AB  
Volatility of B PB / x B
 Relative Volatility of A with respect to B
• Since xB = 1 – xA PA / x A PA (1  x A )
 AB  
PB /(1  x A ) PB x A
• Dalton’s Law
• PA = yA PT ; PB = ( 1 - yA ) PT y A (1  x A )
 AB 
x A (1  y A )

• With the understanding that concentrations are in terms of the MVC and
simplifying, y (1  x)
 
x (1  y )
• in general, relative volatility of a mixture changes with the
mixture’s composition.
• Relative volatilities usually decrease somewhat with
increasing temperature in most systems.
Effect of Relative Volatility on VLE
At y=x (straight line through the origin)  1
• 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
separation.
• 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
Ease of separation
 Equilibrium Curve From Constant Relative
Volatility
• If relative volatility is constant it can be used to
obtain the equilibrium curve data
• more usually, the average relative volatility, ( ave) is
known:
• The composition of the vapour y, in equilibrium
with liquid of composition, x is calculated from :
x
y
1  (  1) x

• where is assumed constant

• Substituting values of x between 0 and 1will yield
the equilibrium curve predictions
 Equilibrium Curve From constant Relative
Volatility
• examples of binary mixtures whose VLE can be
accurately represented with a constant relative
volatility values:

x
y
1  (  1) x
 Effect of non-constant relative volatilities on predicted VLE
data
benzene-toluene (ideal solution) ethanol-water (non-ideal solution
 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 1. More variation in relative

volatilities with volatilities with
composition composition

2. Lower levels of deviation 2. Higher levels of deviation

from actual VLE data from actual VLE data
3. Cannot be used to predict
3. Can be used to predict VLE accurately
VLE accurately
 Calculating Constant Relative Volatility And
Equilibrium Temperature, T
• Binary Mixtures :Constant Relative Volatility

• where TA and TB are the boiling points (in K) of pure

components A and B at the system pressure
• R = 8.314 J/g-mole.K, and
• λ is the average heat of vapourization of the 2 pure
components at the system pressure
• equilibrium temperature T at liquid conc. x (for MVC)
Equilibrium Curve and T-x-y diagram from
Vapour Pressure data-valid for ideal solutions
• Combining Raoult's Law with Dalton's Law:
• Raoult’s law:

• Dalton's Law: PT = PA +PB

• xA=1-xB

• Since:

• 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 curve
 Equilibrium Curve using vapour pressure
data
Temperature, PA0 PB0 xA yA
T

T1
T2
T3
• Note that from Raoult’s 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 Raoult’s 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 from

Solving for PT yields PT = PA0PB0 / [PA0- yA (PA0 – PB0 )]

•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
•The temperature must be clearly stated
 Antoine Equation for Vapour Pressure in SI units:

Pi0 in kPa, T in K )
Antoine’s equation is Log(10) Pi0 =A- [B/(T+C)]

Antoine constants A, B and C for some typical liquids are provided in the Table
VLE Data(P-x-y) from vapour pressure data

Ideal
behaviour
 Ideal Solution & Raoult's Law
• Ideal Solution: obeys Raoult's Law:
• Raoult's Law: PA =PA0 XA
• Where
• PA =equilibrium partial pressure of a component A,
at a fixed temperature T
• PA0 =vapour pressure of pure liquid A at temperature
T
• xA = mole fraction of A in the liquid
• Note1: The vapour pressure is constant at constant
temperature.
• 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 liquids
• The vol. of the solution varies linearly with composition
• 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,
many solutions or organic compounds in a homologous
series are considered approximately ideal.
 VLE Data : Non-Ideal Solutions
• do not obey Raoult's Law
• Most solutions show, at least to some extent, non-
ideal behaviour-show deviations from ideal
• equation for describing non-ideal solutions: Henry's
Law: PA=HxA
• H=Henry’s constant
• mole fraction of A in liquid
• Henry's Law also used to determine solubility of
gases in liquids
 Deviation from Raoult's Law: activity
coefficients
• Deviation from Raoult's Law can be accounted for
by the use of activity coefficients
• most of the non-ideal behaviour is caused by liquid-
phase effects.
• In the liquid-phase, the molecules are much more
closely spaced together than in the vapour space
• attractive and repulsive forces among the molecules
have larger effects than vapour-phase
 Deviation from Raoult's Law: activity
coefficients
• When chemically dissimilar components are mixed
together, there can be repulsion or attraction between
dissimilar molecules.
• If the molecules repel each other, they exert a higher
• partial pressure than if they were ideal.
– In this case the activity coefficients are greater than unity
(called a “positive deviation” from Raoult‘s law).
• If the molecules attract each other, they exert a lower
partial pressure than if they were ideal.
– Activity coefficients are less than unity (negative deviations).
• Activity coefficients are usually calculated from
experimental data
general guidelines for vapour–liquid mixtures in
terms of their nonideality
• a. Mixtures of isomers usually form ideal solutions.
• b. Mixtures of close-boiling aliphatic hydrocarbons are
nearly ideal below 10 bar.
• c. Mixtures of compounds close in molar mass and
structure:
– frequently do not deviate greatly from ideality
– (e.g. ring compounds, unsaturated compounds,
naphthenes etc.).
• d. Mixtures of simple aliphatics with aromatic compounds:
– deviate modestly from ideality
 Deviation from Raoult's Law: activity
coefficients
• PA= PA xA γA
0

• PB=PB= PB0 xB γ B
• where
• γA is the (liquid-phase) activity coefficient of
component, A
• γB is the (liquid-phase) activity coefficient of
component, B
• Activity coefficient=f(T & composition)
1. determined experimentally
2. predicted using various equations
• PT=PA+PB= PA0 xA γA +PB0 xB γ B
 Deviation from Raoult's Law: activity coefficients
• For ideal solutions: γA=γ B =1

• Deviations can be either positive or negative

• non-ideal solutions display distortions in their phase

diagrams.
• equilibrium curves show marked deviations from the
uniform curves that are typical of constant relative
volatility systems.
• azeotropes typical of deviations:
1. minimum-boiling and
2. maximum-boiling (less common).
 Deviations: Minimum-boiling azeotropes
carbon-disulfide-acetone (61.0 mole% CS2, 39.25 oC, 1 atm)

• When the positive deviations from ideality are

sufficiently large,
– the mixture is said to form a minimum-boiling
azeotrope.
• characteristic of such mixture in constant-
temperature phase diagram:
– total pressure goes through a maximum
• in constant-pressure phase diagram therefore
– temperature goes through a minimum
(39.250C), shown as point L.
Minimum-boiling azeotrope: carbon-disulfide- 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
 Minimum-boiling azeotrope: carbon-disulfide – acetone
(61.0 mole% CS2, 39.25 oC, 1 atm.)

• At point L, the concentration in the vapour phase is

the same as the concentration in the liquid phase (
y = x ), and a = 1.0.
• known as the azeotropic composition (0.61 mole
fraction CS2).
• At this point, the mixture boils at a constant
temperature (39.25 oC under 1 atm.) and without
change in composition.
• On the equilibrium diagram, it can be seen that at
this point, the equilibrium curve crossed the 45o
diagonal.
 Maximum-boiling azeotrope: acetone - chloroform
(65.5 mole% chloroform, 64.5 oC, 1 atm.)

• It occurs when the negative deviations are very

large:
– total pressure on constant-temperature 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.
Maximum-boiling azeotrope: acetone – chloroform
(65.5 mole% chloroform, 64.5 oC, 1 atm)
 Maximum-boiling azeotropes: acetone - chloroform
(65.5 mole% chloroform, 64.5 oC, 1 atm)

• The azeotropic composition is 0.345 mole

fraction acetone.
• Point L in the Fig. is now a minimum on the
constant temperature phase diagram
• a maximum (64.5 oC, under 1 atm) on the
constant-pressure phase diagram.
• These azeotropes are less common than the
minimum type.
• Azeotropic mixtures cannot be easily separated
by ordinary distillation methods
 Azeotrope= azeotropic mixture, or
constant-boiling mixtures
• a special class of liquid mixture that boils at a constant
temperature at a certain composition.
• it behaves as if it was one component with one
constant boiling point.
• A boiling liquid mixture at the azeotropic composition
produces a vapour of exactly the same composition,
– the liquid does not change its composition as it evaporates
– Very large deviations from ideality lead to azeotropes

• Azeotropic mixtures cannot be easily separated by

ordinary distillation
 Types of distillation methods
1. Distillation without reflux-
1. 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
 Distillation without reflux
Two types :
a. Simple (differential )distillation: vapour generated
by boiling of liquid mixture to be separated is
condensed without allowing any liquid to return to
the still
b. Flash or equilibrium distillation: vapourizing a
fraction of the liquid in such a way that the vapour
produced is in equilibrium with the residual liquid
and then separating the two phases
 SIMPLE (DIFFERENTIAL) DISTILLATION:
binary mixture of A (MVC) and B (LVC)
• 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 produced.
• 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.
SIMPLE (DIFFERENTIAL) DISTILLATION
 SIMPLE DISTILLATION:
Condensate Composition vs. time
Repeated partial distillation of collected
condensates
 Repeated partial distillation of collected
condensates2
• The distillate product from the second stage
will be purer in A compared to the first stage
• but the quantity of distillate collected in the
second stage is lower than that of the first
stage.
• As more stages are added, purer distillate
product can be obtained, but the quantity
collected will be lower than the previous stage
 Rayleigh Equation: concentration vs.
quantity in simple distillation
• useful in the analysis of simple distillation
• total moles remaining vs. the mole fraction MVC in the
still.
• 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.
 Rayleigh Equation: concentration vs.
quantity in simple distillation
• After time (t + dt) , vapour dL is produced, composition of A
in the vapour is y
• The vapour is assumed to be in equilibrium with the
residue liquid.
• The liquid in the still is thus reduced from L to (L - dL),
liquid composition changed from x to (x - dx).
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
• Since
• 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:
Rayleigh Equation: material balance on A
• Simplifying

• Integrating from L1 to L2, and from x1 to x2, we obtain the

Rayleigh Equation
 For ideal mixture: constant relative volatility
yA xA
  AB
yB xB
•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   LA / L 

dLB / dL  dLB AB
LB / L 
Separating variables and Integrating
LA LB
ln   AB ln LB = total mole of B left in still,
LA 0 LB 0 LA = total mole A left in still.
LB0 = total initial mole of B in still,

 AB LA0 = total initial mole A in still

LA  LB 

L 

LA0  B0 
 EXAMPLE
• A batch of crude pentane contains 15 mole percent n-
butane and 85 percent n-pentane. If a simple batch
distillation at atmospheric pressure is used to remove 90
percent of butane, how much pentane will be removed?
What will be the composition of the remaining liquid?
• average value of 3.5
Simple Batch or Differential Distillation with reflux
•The pot is filled with liquid
mixture and heated.
•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
distillate.
•Nothing is added or withdrawn
from the still until the run is
completed. 103
 FLASH (EQUILIBRIUM) DISTILLATION
• A single-stage continuous operation where a liquid mixture
is partially vaporized:
• the vapour produced and the residual liquid are in
equilibrium, which are separated and removed.
FLASH (EQUILIBRIUM) DISTILLATION

yA

Separator

heater

xA
 Equilibrium or Flush Distillation

Total mass balance: F  V L

Separator
yA
Component A balance: FxF  V y A  LxA
heater

where
F, V and L are flow rate of feed, vapor and liquid phases.
xA
xF, yA and xA are mole fraction of component A in feed, vapor and
liquid.

Material balance for more volatile component :

( f  1) xF
yA  xA 
Where
f f
f = V/F = molal fraction of the feed that is vaporized and withdrawn continuously as
vapor.
1-f = molal fraction of the feed that remains as liquid 106
 FLASH (EQUILIBRIUM) DISTILLATION: mixture of A
(MVC) and B (LVC)
• The feed is preheated before entering the separator
• As such, part of the feed may be vaporized.
• The heated mixture then flows through a pressure-
reducing valve to the separator.
• In the separator, separation between the vapour and
liquid takes place.
• A produced in the vapour depends on the condition of
the feed
• i.e. how much of the feed is entering as vapour state,
which in turn is controlled by the amount of heating.
• In other words, the degree of vapourization of the feed
affects the concentration (distribution) of A in vapour
phase and liquid phase.
 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
 Separation In Flash Distillation2
• yD = mole fraction of A in vapour leaving
• xB = mole fraction of A in liquid leaving
• xF = mole fraction of A in feed entering
• the greater the heating, the larger the value of f.
• If the feed is completely vapourised, then f = 1.0
• Thus, the value of f can vary from
• 0 (no vapourization) to
• 1 (total vapourization).
Flash Distillation: material balance for the MVC
(A)[1mole of feed]
• 1. xF = f yD + (1 - f) xB

• f yD = xF - (1 - f) xB

• Re-arrange to yield:

• fraction f depends on the enthalpy of the liquid feed,

the enthalpies of the vapour and liquid leaving the
separator

• for a given value of f, we will obtain certain values for yD

and xB.
 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 [-(1-f)/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 equation:
 Homework
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?

3. 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

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
benzene-chlorobenzene 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 (continued)

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:

Temperature Pwater Pbenzene

(mm Hg) (mm Hg)
K ºC
308.5 35.3 43 150
325.9 52.7 106 300
345.8 72.6 261 600
353.3 80.1 356 760
 CONTINUOUS DISTILLATION
• Distillation process, in its simplest form, can be
represented in a block diagram as shown
Distillate:D:

Feed:F

• Bottoms:B
 Binary Distillation: A (more volatile)
and B (less volatile)
• 1 feed stream F:mixture of 2 components
• separated into 2 product streams:
– D:distillate (top product or overhead product)
– B:bottoms.
• 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
phase.
Separation by distillation
 Some industrial-scale binary distillation
processes.
• Note the general inverse relationship between the
relative volatility and the number of trays
Equipment for Continuous Distillation
Tray Column or Packed Column
 A:column
• This is the main equipment where the separation
process described above is carried out.
• In general, column has 3 sections:
1. rectifying (or enriching) section: the more volatile
component is removed through contacting the rising
vapour with the down-flowing liquid. located above
feed entry;
2. stripping section: the down-flowing liquid is stripped
of the more volatile component by the rising vapour.
located below feed entry.
3. feed (or flashing) section.
• column may be equipped with trays or packings or
both.
 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
achieved.
• 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 collected.
• Pumps :
– for returning the reflux liquid back to the
distillation column,
– for pumping out the bottoms product for storage,
– for pumping the feed into the distillation
column.
 Reboiler
• Reboiler :
• to produce the vapour stream in the distillation
column, called the reboiled vapour or the boil-up
vapour.
• 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 adjustment.
• 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 set-ups
– depends on the types of mixtures to be
separated and the complexity of the operation.
• - more than 1 feed inlet, as well as one or
more sidedraws.
Tray/plate columns
 Binary Distillation- A (MVC) and B (LVC):
nomenclature
• 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
component
• Bottoms B is richer in the less volatile component,
• 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: types
• 3 major types:

1. sieve Trays

2. valve Trays

3. bubble cap Trays

 TRAYS/PERFORATIONS/VALVES

(a) perforation (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
 RANDOM PACKING DESIGNS

• SHAPES
– RINGS
– SADDLES
– OTHERS
• MATERIALS
– METAL
– CERAMIC
– PLASTIC

http://www.koch-glitsch.com/koch/products/plastic_random_packing.asp
 •More surface area for mass transfer
•Higher flow capacity
Packing Materails •Lower pressure drop

(a)
(b) Random
Structured
Packing
Packing
Materials
Materials
•Expensive

•Far less pressure drop

•Higher efficiency and capacity

Figure 6.7 Typical materials used in a packed column

 STRUCTURED PACKING
• PACKING IS MADE IN SECTIONS AND FILLS
ENTIRE COLUMN DIAMETER

http://www.sulzerchemtech.com/DesktopDefault.aspx/tabid-232/
 The McCabe-Thiele Method
• uses the equilibrium curve diagram to determine
the number of theoretical stages (trays) required
to achieve a desired degree of separation.
• It is a simplified method of analysis making use of
several assumptions,
• 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 tray.
• 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 stages
• method involves the plotting of 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 adjacent stages (Material Balance Equations)
• 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 (relates y and x on same stage).
The McCabe-Thiele Method 3
Tray/plate columns
 McCabe-Thiele Method-number of
theoretical stages: the steps
1. Analyze the Rectifying section, and determine the ROL
using xD and R
2. Analyze the Feed section, and determine the feed
condition (q)
3. Determination of the feed line (q-line) using xF and q
4. Locate the intersection point between ROL and q-line
5. Analyze 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 point)
 balance around the envelope at steady state:
Rate of flow IN = Rate of flow OUT:ROL

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

• Component (MVC):Vn+1 yn+1 = Ln xn + D xD
• Combining: (Ln + D) yn+1 = Ln xn + D xD
• Under constant molal overflow assumption:
• L1 = L2 = .......... Ln-1 = Ln = Ln+1 = L = constant
• V1 = V2 = .......... Vn-1 = Vn = Vn+1 = V = constant
• The subscripts can be dropped.
 Operating Line Eqn. for the rectifying
section: ROL
• *

Reflux Ratio R = L / D

• ROL Characteristics:
i. Straight Line Equation
ii. Slope= R/(R+1),
Intercept =(xD /R+1),
iii. In addition, if xn = xD, then yn+1 = xD .
iv. Thus, the operating line passes through the point (xD
, xD) on the 45o diagonal line.
R changes, the slope and intercept of the ROL
Rectifying Section: ROL
 Introduction of Feed : the q-line
• Consider the tray where the feed is introduced
(known as the feed tray location), say tray f :

• The feed may consists of:

• liquid, vapour or a mixture of both.
• The quantities of the liquid stream and vapour
stream in the rectifying and stripping sections may
change abruptly because of the addition of the feed
stream.
q = moles of liquid flow in the stripping section that
results from the introduction of each mole of feed.
• q = related to fraction of feed which is liquid
• The value of q can be controlled by adjusting the
amount of preheat the feed stream is subjected to
before entering the column.
• For different feed conditions, numerical limits :
• · cold feed (below bubble point): q > 1
· feed at bubble point (saturated liquid): q = 1
· feed partially vapour: 0 < q < 1
· feed at dew point (saturated vapour): q = 0
· feed superheated vapour: q < 0
• If the feed is a mixture of liquid and vapour, then q
is the fraction of the feed that is liquid
Effect of various feed conditions on
vapour and liquid loading in column
• As an example, consider the Figure below whereby
the feed is a cold liquid.
• In this case, all the liquid feed will go to the stripping
section.
q vs. feed condition
q=0

1>q>0 0>
Relating q with L and L‘; V‘and V
• In addition, because the feed is cold, it will also
condense some of the rising vapour.
• As a result, the amount of liquid flow in the
stripping section L' is much larger than the liquid
flow in the rectifying section L.
• The vapour flow in the rectifying section V, is lower
than the vapour flow in the stripping section V'
because of the condensation into the liquid.
• Hence for case (a), we have L' > L and V' > V.
 Feed Section Operating Line (q-line)
• F moles/hr of feed, with fraction q of liquid
• 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
number of theoretical stages
 Operating Line Equation :
Stripping Section , SOL
• Analysis not really required, as SOL can be
automatically fixed once ROL and q-line are drawn.
• 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 q-
lines, for a given ROL (i.e. fixed R and xD)is shown .
• Thus, the operating line passes through the point
(xB , xB) on the 45o diagonal line.
 Equation for stripping section

Material balance over dashed-line section: Vm1  Lm  B

A component A balance:
Vm1 ym1  Lm xm  Bx B 160
Solving for ym+1, the enriching-section operating line is

Lm Bx B
ym 1  xm 
Vm 1 Vm 1

Again, since equimolal flow flow is assumed,

Lm  LN= constant and
Lm  Vm1
Vm 1  VN= constant,

•SOL eqn. is a straight line when plotted as y versus x:

•slope of Lm/Vm+1 Lm

•It intersects the y = x line at x = xB.

The intercept at x = 0 is at y   Bx B / V. m1 161
 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 manner
• The last "stage" on the graphical construction represents the reboiler
Intersection of operating lines
• Rectifying section : V y = L x + D xD
• Stripping section : V' y = L' x - B xB
• At the feed point where the two lines
operating lines intersect:
• ( V - V' ) y = ( L - L' ) x + D xD + B xB
• we have also:
• V - V' = ( 1 - q ) F
• L - L' = - q F
• In addition, from component balance around the entire
column:
• F xF = D xD + B xB
• Thus, y = - q/ ( 1 - q ) x + xF /( 1 - q )
• This gives the loci of points of intersection as a function
of q
•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 vapor)
q = 1 (saturated liquid)
q > 1(subcooled liquid)
q < 0 (superheated
vapor)
0 < q < 1 (mix of liquid
and vapor)
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
where
HF = enthalpy of feed, evaluated at TF
HV = enthalpy of vapour, and
HL = enthalpy of liquid
 Tbp= bubble point 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 point.
• 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 opti
 Steps/Procedure:
• 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 95ºC 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 20ºC
(specific heat 0.44 cal/g.ºC); (iii) if the feed is a mixture of two-thirds vapor and
one-third liquid.
 Example of use of McCabe Thiele Method
Problem: Continuous distillation of Benzene and Toluene.
Feed is at 30,000 kg/h and 40 wt.% Benzene
Overhead product = 97 wt.% Benzene. Bottom product =
98 wt.% Toluene
Reflux mole ratio = 3.5, Ideal System, alpha, a = 2.5

(a) Calculate: Distillate, D, and Bottoms, B produced per

hour
(b) Determine, N, number of ideal plates to effect this
separation, if (i) Feed is liquid at its bp
(ii) Feed is liquid at 20oC (specific heat = 0.44 cal/g)
(iii) Feed is 2/3 vapour and 1/3 liquid
SOLUTION CONTINUED
THE GRAPHICAL SOLLUTION FOR FEEDAT BUBBLE POINT
Homework

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, the
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 xH and yH.

Temperature Temperature
K ºC xH yH K ºC xH yH
409.3 136.1 0 0 383.8 110.6 0.485 0.730
402.6 129.4 0.08 0.23 376.0 102.8 0.790 0.904
392.6 119.4 0.25 0.514 371.5 98.3 1.000 1.000
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.
 Importance of Reflux Ratio, R
• it can affect the separation efficiency
• 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
trays, N
• a trade-off between R and N, as shown
 ANALYSIS OF REFLUX RATIO CHANGES
• inverse relationship between the reflux ratio
and the number of theoretical stages.
• 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.
• At a specified distillate concentration (i.e. constant
xD), when R changes, the slope and intercept of the
ROL changes. The ROL therefore rotates around the
point (xD, xD).
• with a given feed condition (i.e. xF and q fixed), and
a specified product compositions (i.e. xD and xB
fixed) - increasing R will result in lesser number of
theoretical stages required.
• From the ROL equation, we can see that when R
increases (with xD constant), the slope of ROL
becomes steeper, i.e. (R/R+1) and the intercept
(xD/R+1) decreases.
Effect of R changes on the 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 lines.
• 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 and minimum reflux ratio
• at two extremes of the reflux ratios,
• how to find the most suitable reflux
ratio
• minimum reflux ratio:
• - results in infinite stages
• total reflux or infinite reflux ratio:
• results in minimum stages)
 Fenske equation at total reflux: Nmin
• if the relative volatility of the two components is
approximately constant,
• The minimum number of theoretical steps when
a total condenser and a reboiler are used.

• Nm= the minimum number of equilibrium

• excluding the reboiler, at total reflux.
 Nm at total reflux: graphical method
-
Operating line and q-line intersect on the equilibrium curve
Operating line at minimum reflux ratio:

Slope=Rm/(Rm+1)

XD/(Rm+1)
 total reflux and minimum reflux ratio
• The minimum reflux ratio and the infinite
reflux ratio place a constraints on the range of
separation operation.
• Any reflux ratio between Rmin and Total R will
produce the desired separation, with the
corresponding number of theoretical stages
varying from infinity at Rmin to the minimum
number (Nmin at Total R).
• The choice of reflux ratio to use is governed
by cost considerations
Number theoretical Stages (N)
Vs. Reflux Ratio(R)
Costs versus Reflux Ratio
 Steps/Procedure:
1. If the external reflux, Lo, is at its bubble point:
2. LR = Lo = (R) D
3. VR = LR + D
4. vs = VR - (1 - q ) F
5. Ls = LR + qF
• 7. Calculate slope of rectifying operating line:=[ R/(R+1)
• 8. Draw rectifying operating line from (xD , xD ) with slope= =[ R/(R+1) -
• 9. Draw stripping operating line from (xB , xB ) to the intersection
• of the q line with the rectifying operating line.
• 10. Check your calculations by seeing whether the slope of stripping operating
• line is Ls/Vs.
• 11. Start from the xB point on the 45” line and step up from the stripping
operating line to the VLE curve.
• The first step corresponds to the partial reboiler. The next step is tray above, the
next is tray 2, and so on.
• 12. When this stepping procedure crosses the intersection of operating lines, this
is the “optimum” feed tray (i.e.? any other feed tray would require a greater total
number of trays). Thus the feed tray NF has been determined.
 Steps/Procedure:
• 13. Switch to the rectifying operating line and continue stepping.
• 14. When the xD point is crossed, this is the total number of trays NT.
• This last step may not go through the xD point exactly, implying a
noninteger
• number of trays.
• Don’t let this worry you. In this procedure we have assumed “perfect” or
• “theoretical” or “100 percent efficient” trays;
• that is, trays on which the vapour and liquid streams leaving the trays are
in perfect phase equilibrium.
• Actual industrial columns seldom achieve this ideal situation, so an
efficiency factor must be used to determine the number of actual trays
installed in the column
• this must be an integer number in an actual column.
• Typical efficiencies run from 40 to 90percent, depending on the system.
 Efficiencies
• Overall efficiency for a column
• Eo = N of Equil stages/N of Actual Stages
• In petroleum industry Eo = 0.6, is used

• Muphree stage Efficiency

• EM = (Yout – Yin)/(Y*-Yin), Y* = Y in eq. with Xout.
• Show this graphical as lower eq. line, or
smaller separation factor, a
Sketch of Murphree Efficiency
Efficiency lowers Eq. Line or Smaller a
 Ponchon-Savarit Method
• No constant molar overflow between trays
• Heat of mixing is not negligible
• Use both mass and heat (energy) balances
• Need Lever - Rule (reverse lever-arm)
• Property is conserved,
• Mixing A & B to C or C separates to A & B
• mA/mB = CB/CA = ratio of the lines (reverse)
Enthalpy–composition diagram - enthalpies of liquid and vapor
Continuous distillation column
 Mass and Enthalpy Balances
Vn − Ln+1 = D overall MB 1
Vn yn − Ln+1 xn+1 = Dxd comp. MB 2
Vn HVn − Ln+1HLn+1= DHLd + Qc CHB 3
Putting H’d = HLd + Qc/D , then
Vn HVn − Ln+1 HLn+1 = DH’d 4
1&2 Ln+1/D = (xd − yn)/(yn − xn+1) 5
1&4 Ln+1/D = (H’d− HVn)/(HVn − HLn+1)
= (xd − yn)/(yn − xn+1) 6
 Mass and Enthalpy Balances - Top
yn = [(H’d-HVn)/(H’d-HLn+1)]xn+1 +
[(HVn-HLn+1)/(H’d-HLn+1)]xd 7
• Eqn 7: the relation between the composition of the
vapor and liquid streams between any two plates
• All such operating lines pass through a common
pole N of coordinates xd and H’d (Delta point)
• N is mixture of mass of vapor & liquid between
plates, & has comp. xd and enthalpy H’d
• Vn ,Ln+1, and N are on a straight line through N
Enthalpy–composition diagram
 Mass and Enthalpy Balances - Bottom
• Material and enthalpy balance from the bottoms
gives same results
• − Vm + Lm+1 = B
• − Vmym + Lm+1 xm+1 = Bxb
• H’ b = HLb − Qb/B
• Define pole (delta point) M such that Vm, Lm+1,
lines pass thru it at H’b and xb
• F= M+N
• M, N & F, must lie on a straight line
• Fxf = Mxw + Nxd
 Get N, no of plates & feed plate
• See the diagram in next slide
• Here W = B
• Given the Enthalpy Versus y and x
• F, xf given, get H’d = HLd + Qc/D
• From xd & H’d, get pole point N
Determination of the number of plates using the enthalpy–composition diagram
Ponchon-Savarit Method
 Number of Equilibrium Stages
• N, M & F on St. line