CHE 319

Separation Processes I

By

DR. F. B. ELEHINAFE
A)Introduction

B)Distillation

C)Liquid-Liquid Extraction
 Reading Materials
• C. J. Geankoplis Transport Processes and Unit
Operations, Prentice Hall, 1993
• 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 Processes in
Process Industries
• 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 science
& engineering.
• 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.
• The two phases in contact may be Gas-solid, Gas-
liquid, liquid-solid, liquid –liquid.
• 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.
.
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
• 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 Example
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, cyclonic separation

• Centrifugation , Chromatography,

• Decantation, Demister (droplets of liquid from

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, dewatering + several stages of
distillation steps to obtain gasoline,
kerosene, diesel etc
 Processing Methods in Terms of
Contact
• 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 phases
• 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.
 Vapour – Liquid Separation Processes

• Distillation
– reliability, simplicity, and low-capital cost
– But energy consuming
• Absorption
• Stripping
• Humidification
• dehumidification
 DISTILLATION
• is a 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.
• it 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 Components
• 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 exacting pressure (vapour

pressure), 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 vapour pressure
(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.
•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
temperatures

same initial compositions but different phase compositions at different

equilibrium temperatures but same pressure
• 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.
 The Phase Diagram
• This is a diagram that shows that components A
and B (a binary mixture) are distributed in
vapour and liquid phases at different
temperatures.

• The data used to obtain such a diagram at

different temperatures but constant pressure
will constitute the T-x-y diagram or constant
pressure phase diagram or Boiling point-
concentration diagram
Changes in distribution of components in
the phases with temperature

saturated vapour
subcooled saturated liquid
liquid
• 0 Super heated vapour

subcooled liquid
• (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 .
• Note:
• The process is unsteady-state in nature for as
heating continues, vaporization occurs over a
range of boiling points.
• 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).
 Types of phase diagrams in distillation:
• Constant-pressure phase diagrams called:
T-x-y diagram/boiling point diagram/boiling point-
concentration diagram.
It is commonly used for distillation calculations
• Constant-temperature phase diagrams called:
P-x-y diagram/Isothermal phase diagram
It is commonly used to depict deviations from
ideal behaviour (Raoult’s law)

•
Constant-Pressure Phase Diagram
 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

• 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
saturated liquid starts to boil.
Constant-Temperature Phase Diagram
/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.
P-x-y Diagram
 Constant Pressure vs. Constant
Temperature Phase Diagrams
• The constant pressure phase diagram is commonly
used in the analysis of VLE
• but the constant temperature phase diagram is
commonly used in the analysis of solution
behaviour that deviates from Raoult's Law
• Note also the regions in the two phase diagram of
– vapour-only,
– liquid-only
– vapour-liquid mixtures.
 Vapour-Liquid Equilibrium[VLE]Curve
• 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
but varying temperatures.
• The curved line is called the equilibrium line and
describes the compositions of the liquid and vapour
in equilibrium at fixed pressure.
• The data used to obtain VLE curve is called VLE data
(generated experimentally)
• 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 in VLE analysis.
• It is useful for graphical design in determining the
number of theoretical stages required for a
distillation column
• Has line y=x for MVC
VLE Cure for Ideal System
 VLE Curves for Non-Ideal Systems
(i.e Azeotropic Systems)

•
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.
• Liquids do not normally exhibit appreciable compressibility until the
pressure gets close to its critical value.
 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 liquid
• For a binary mixture of A and B, therefore:
– Volatility of A = pA / xA
– Volatility of B = pB / xB
Generally,
- volatility of i = pi/xi
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):

Volatility of A P / xA
 AB   A
Volatility of B PB / x B
Effect of Relative Volatility on VLE
• Note, At y = x (straight line through the origin) , α = 1
• A and B have the same volatility and will vapourize
together when heated
• Vapour and liquid will have the same composition.
• No separation is possible
• The larger the value of α 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 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.
• Therefore, separation by distillation is only
feasible within the region bounded by the
equilibrium curve and the 45o diagonal line.
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 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. Can be used to predict 3. Cannot be used to predict

VLE accurately VLE accurately
 T-x-y diagram and VLE Curve 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) according to Antoine eqn:

At constant total pressure , where, A, , C are Antoine constants
• Calculating xAs, then yAs at several boiling point of mixture
between the Boiling Point of A and the Boiling Point of B
yields the data for T-x-y and hence the equilibrium curve

Temp 𝑷𝟎 𝑨 𝑷𝟎 𝑩 𝒙𝑨 𝒚𝑨
T1 (Temp. of A
T2
T3
T4
.

.
.
.
.
Tn (Temp. of B)
 Assignment 1
Assuming Raoult’s law to be valid, prepare a T – x,y diagram and
VLE cure at a pressure of 95 KPa for a Benzene (1)/Ethylbenzene (2)
mixture using the following information:

(Antonie Equation)

𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 (Raoult’s law)

i A B C
1 13.7819 2726.81 217.572
2 13.9726 3259.93 212.300
 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 volume 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:
• In practice, for engineering purposes, many solutions or
organic compounds in a homologous series are considered
approximately ideal.
 General guidelines for vapour–liquid mixtures in
terms of their ideality and non-ideality
• 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
Minimum-Boiling Azeotrope
(E.g carbon-disulfide- acetone of
61.0 mole% CS2, 39.25 oC, 1 atm)
• Note,
• 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
(E.g acetone - chloroform of 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.
 Types of distillation methods
1. Distillation without reflux-
boiling of liquid mixture to be separated and separating the vapour
generated without allowing any liquid to return to the still.
 batch distillation without reflux
- simple/differential distillation
- flash distillation
 continuous distillation without reflux

2. Distillation with reflux returning part of condensate to still in

such a way that it runs counter to the vapour rising to the
condenser
- continuous distillation with reflux
- batch distillation with reflux
 DISTILATION OF
BINARY MIXTURES
 Simple/Differential Distillation
• The system consists of a batch of liquid mixture
• (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 DISTILLATION:
Condensate Composition vs. time
Repeated partial distillation of collected
condensates
Modelling the Process, Material Balance
on A (MVC) is Taken:
• 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.
vapourized within dt
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:
• Integrating from L1 to L2, and from x1 to x2, we obtain the
Rayleigh Equation
 Exercise
• 100 kmol of a 60 mole% benzene–toluene mixture
is subjected to batch distillation without reflux
until a 30 mole% residue is obtained. How many kg
of distillate is obtained, and what is its benzene
content? (Also solve the problem using relative
volatility, average α)
• The Rayleigh-equation can be solved by numerical
integration.
• Use the method of trapezoids.
• Read the corresponding x and y values from the
equilibrium curve, calculate the values of the f(x)
function and perform the numerical integration.