Separation Process-II

(ChE-306)

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Distillation

• A method of separating mixtures based on differences in volatility of

components in a boiling liquid mixture.
• A unit operation, or a physical separation process, and not a chemical
reaction.
Applications:
Use to separate liquid mixtures into various components
Widely used in oil refinery
Used to obtain pure products with greater efficiency
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Importance of VLE data
• Distillation columns are designed based on the boiling
point properties of the components in the mixtures
being separated.
• Thus the sizes, particularly the height, of distillation
columns are determined by the (VLE) data for the
mixtures.

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• For vapor-liquid equilibrium, the separation factor is the relative
volatility.
Light key (more volatile)
Heavy key (less volatile)

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• If the ratio of partial pressure to the mole fraction in liquid is defined
as the volatility, then,

• The ratio of these two volatilities is known as the relative volatility

given as,

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• Relative volatility is a measure of the difference between the vapor pressure of the more volatile
components of a liquid mixture and the vapor pressure of the less volatile components of the
mixture.

• This measure is widely used in designing large industrial distillation processes. In effect, it indicates
the ease or difficulty of using distillation to separate the more volatile components from the less
volatile components in a mixture.

• The higher is the relative volatility of a liquid mixture, the easier it is to separate the mixture
components by distillation.

• By convention, relative volatility is typically denoted as the Greek letter alpha, α.

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Self Study

Study industrial example at start of Chapter 7 (Seader).

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Design Factors

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Distillation Vs. Other separation Techniques
• Absorption
• Adsorption
r a n
• Membrane Separation f
d ss o
p l i e e
• Chromatography s a p ro c
i
e ti on p
• Liquid-Liquid Separation i q u a
c h n a r
• Liquid Solid Separation t e S e p
i c h ed
h
W nten d
• Evaporation i
• Centrifuging
• Crystallization
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Distillation Vs. Other separation Techniques
• To understand the difference , we must know
• Definition of separation
• How actually the separation of mixture occurs.
• Importance of separation in industry
• Selection Criteria of Mass Transfer Operations
• Types/Categories of the separation techniques

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 Introduction

Separation
• to isolate from a mixture
• to divide into constituent parts

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Intro…

Chemist Chemical Engineer

• Small Scale • Large Scale
• In Labs • In industrial process
• Concerned with
economics

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 • To determine composition of
• Analytical Separation complex mixture quantitative.
• Chromatography

• Preparative Separation
• To recover and purify chemicals
• Centrifugation
• Industrial Separation
• To manufacture/separate chemicals
using separation methods
• Distillation

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Importance of Separation Process
• To get pure substance from mixture of 2 or multi-component system
• Chemical plants commonly have 50-90% of their capital investment in
separation equipments.

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Intro…
Key Operations

Chemical Process • chemical reactions.

• separation of chemical mixtures

Auxiliary
Operations
• phase separation
• heat addition or removal
• shaft-work addition
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 Mechanism of Separation

Mixing Separation
• Spontaneous • Non-spontaneous
• Natural process • Expenditure of energy.
• Increase in entropy

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Separation Techniques

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 • An ESA involves heat transfer or transfer of shaft
Energy
work to or from the mixture.
separat • An example of shaft work is the creation of vapor
ing from a liquid phase by reducing the pressure
agent
(ESA)

• An MSA may be partially immiscible or

Mass-
miscible with one or more mixture
separat components depending upon the application
ing required.
agent
(MSA)

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Categories of Separation Operations
1. phase addition
2. phase creation
3. barriers
4. solid agents
5. external field or gradient

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 Separation Operations

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 Partial condensation or
Partial vaporization
• Two phases are created
when a
• vapor feed is partially
condensed by removing heat
• liquid feed is partially
vaporized by adding heat
• Recovery of H2 and N2 from
ammonia.

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Distillation
• It involves multiple
contacts between counter
currently flowing liquid and
vapor phases.
• Each contact is called a
stage, consists of mixing
the phases to promote
rapid partitioning of
species by mass transfer,
followed by phase
separation.
• Purification of styrene
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 Rectification???

Stripping ???

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Absorption
• If the feed is vapor and the
stripping section of the column
is not needed, the operation is
referred to as absorption.
• Do not require an ESA and are
frequently conducted at
ambient temperature and
elevated pressure.
• Species in the feed vapor
dissolve in the absorbent to
extents depending on their
solubilities.
• Separation of CO2 from
combustion products
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Liquid–liquid extraction (LLE)
• Liquid–liquid extraction, with one or two solvents, can be used when
distillation is impractical, especially when the mixture to be
separated is temperature sensitive.
• A solvent selectively dissolves only one or a fraction of the
components in the feed.
• Several counter currently arranged stages may be necessary.
• Additional operations are required for solvent recovery.

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LLE

Recovery of penicillin from Use of propane and cresylic acid as

aqueous fermentation medium by solvents to separate paraffin from
methyl isobutyl ketone. aromatics and naphthenes.
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SEPARATIONS BY BARRIER

• Known as Membrane based separations.

• Microporous/Non-porous membranes.
• Membrane act as a barrier and allow only selective material to pass
through it.
• Transfer takes place due to concentration/Pressure gradient.

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Leaching (liquid–solid extraction)
• Leaching is used in the
metallurgical, natural
product, and food
industries.
• To promote rapid solute
diffusion out of the solid
and into the liquid solvent.
• Particle size of the solid is
usually reduced.
Extraction of sucrose from sugar beets with hot
water.

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SEPARATIONS BY BARRIER
Micro Ultra
(Suspended
solids) (Proteins)

Nano RO
(Multivalent (Monovalent
ions) ions)
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Reverse osmosis
• Transport of solvent in the opposite direction is effected by imposing
a pressure, higher than the osmotic pressure, on the feed side.
•Desalination

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SEPARATIONS BY SOLID AGENTS
• Adsorption
• Chromatography
• Ion exchange

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 • Separation of gas or liquid
mixtures by passing them
Chromatography through a packed bed.
• The bed may be solid
particles (gas–solid
chromatography) or a solid–
inert support coated with a
viscous liquid (gas–liquid
chromatography).
• Separation of ethylbenzene

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 • To remove species in low
concentrations.
Adsorption • Needs desorption to
regenerate the adsorbents.
• Adsorbents include
activated carbon, aluminum
oxide, silica gel, and
synthetic sodium or calcium
aluminosilicate zeolites.
• Purification of p-xylene

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 • Resembles adsorption in
that solid particles are used
Ion Exchange and regenerated. However,
a chemical reaction is
involved.
• Water softening
/Demineralization of water

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 SEPARATIONS BY EXTERNAL FIELD
OR GRADIENT

• Centrifugation
• Thermal diffusion
• Electrolysis
• Electrodialysis
• Electrophoresis
• Field-flow fractionation

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Centrifugation • Establishes a pressure field that
separates fluid mixtures according
to molecular weight.
• Separation of uranium isotopes
(235UF6 from 238UF6)
• Separation of polymers according
to molecular weight.

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 Thermal
diffusion • If a temperature gradient is
applied to a homogeneous
solution, concentration gradients
are established, and thermal
diffusion is induced
• Enhance separation of Uranium
isotopes in gas permeation
processes.
• Separation of Chlorine isotopes

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Extent of separation
The extent of separation possible depends on the exploitation of
differences in;
• Molecular
• Thermodynamic/Transport properties

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 Molecular
Vapor
Properties pressure

Thermodynamic/
Molecular Molecular Electric Transport Properties
weight shape charge Diffusivity Solubility

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Separation Power
Described by ;
• Split Ratio
• Separation Factor

Separation Power referred to the “purity that can be achieved for key
component”.

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SELECTION OF FEASIBLE
SEPARATIONS
Feed Conditions
Product conditions
Property differences
Maturity of separation operation
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Distillation
• It is a method used to separate the components
of solution based on the boiling points.
• Distillation is concerned that all components are
volatile.
• Both, Liquid and vapor phase are present.

How the vapor phase is generated???

• Vapor phase is generated from the liquid

phase by vaporization at the boiling point.
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Boiling Point Diagram

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Equilibrium Diagram
• Greater is the distance between
equilibrium line and 45O line, Equilibrium Line
greater is the difference between
liquid & vapor composition.

What about ease of separation???

Ease of separation is defined

by relative volatility

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Relative Volatility

y= concentration of vapor
x= concentration of liquid
𝑥 𝐴 + 𝑥 𝐵 =1 𝑦 𝐴 + 𝑦 𝐵 =1

𝑦 𝐴
𝑥𝐴 α 𝑥𝐴
α 𝐴𝐵 =
1− 𝑦 𝐴 y 𝐴=
1−𝑥𝐴
1+(α − 1) 𝑥 𝐴

𝜶>𝟏 ≫ 𝑺𝒆𝒑𝒂𝒓𝒂𝒕𝒊𝒐𝒏 𝒊𝒔𝒑𝒐𝒔𝒔𝒊𝒃𝒍𝒆

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Distillation Column

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Methods of Distillation (Binary Mixtures)
• Differential distillation
• Flash or equilibrium distillation
• Rectification
• Batch distillation

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Differential Distillation
• Was first proposed by Rayleigh
• Single stage
• Production of vapors by boiling the liquid mixture in a pot
• Heated at constant rate
• Vapors are condensed and removed from system
• Vapors are richer in more volatile component than liquid
• Composition of the product changes
• No liquid is recycled to column/still
• Total vapors formed are not in equilibrium with the liquid left (bottom
product)

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• No of moles of material in still = S
• Mole fraction of component A = x
• Amount vaporized = dS
• Mole fraction of A in vapor phase = y
• Material balance on component A will give:

Rayleigh equation

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Flash or Equilibrium Distillation
• Continuous process
• Vaporizing a fraction of liquid into vapor
• Vapor evolved is in equilibrium with the
residual liquid
• Vapors removed from top and condensed
• Liquid collected from bottom

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• For a binary mixture of A and B, the overall balance applied will be:

• If,
• F = moles per unit time of feed of mole fraction xf of A
• V= moles per unit time of vapor formed with y mole fraction of A
• S= moles per unit time of liquid with x mole fraction of A
• For more volatile component

• Equation of a straight line.

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Batch Distillation
• More volatile component is evaporated from still
• Still becomes richer in less volatile component
• Distillation is continued until:
• The residue of the still has low content of volatile mixture
Or
• Distillate is no longer sufficiently pure

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Rectification
• Vapor obtained is richer in more volatile component than is the liquid
left in the still.
• This happens because of successive vaporization and condensation in
one unit called fractionating column.

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Fractionating Column
• The Fractionating process
• Cylindrical column with two sections
• Series of perforated trays for upward flow of vapor
• Liquid reflux flows through weir and downcomer
• Condenser
• Reflux drum or reflux divider (overhead product D and reflux R)
• Liquid in the bottom is heated (reboiler)
• Vapors rise through perforations
• Bottom cooler (heat exchanged between bottom product and feed)
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Features to remember
• Feed Tray
• Rectifying section
• Stripping section
• Vaporization and condensation on each tray
• Equilibrium between phases
• Sieve trays
• To promote good mixing on trays with a low drop in pressure

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• How is the equilibrium attained on each plate?

• Constant molar overflow

• Continuous process

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69
Distillation with Reflux

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Important Features
• Series of stages/trays arranged in a way that vapor and liquid flow
counter current to each other.
• Liquid flows downwards
• Vapor flows upwards.
• Vapor and liquid are in equilibrium with each other.
• Stages are known as trays or plates.
• Moving upward will increase the concentration of more volatile
component.
• Over head vapors are condensed and its portion is taken as distillate
while a part of it is returned to top plate as Reflux.
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Number of plates required in a distillation
column
• Lewis-Sorel Method
• The method of McCabe and Thiele
• Fenske’s Method
• Ponchon and Savarit Method

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Important Aspects
• Heat and material balance over the trays, the condenser and the
reboiler
• Thermodynamic data are required to establish equilibrium between
the streams leaving each tray
• The diameter of the column will depend upon:
• The desired flow rates
• To operate within the available pressure drop
• Desired degree of mixing of streams on each plate

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Material balance over a plate
• Four streams are involved:
• Ln+1
• Vn-1
• Ln
• Vn
• Objective of the plate is to provide mixing to achieve
equilibrium between liquid, Ln (xn) and vapor Vn (yn)
• The streams Ln+1 and Vn-1 cannot be in equilibrium,
during exchange process some of the more volatile
component is vaporized from Ln+1 decreasing its conc. to
xn and some of the less volatile component is
condensed fromVn-1 increasing the vapor conc. to yn .
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Heat balance over a plate
= Enthalpy per mole of the liquid on plate n
= Enthalpy per mole of vapor rising from plate n
Assumptions to make equation simpler:
• Heat losses will be small and may be neglected.
• For an ideal system heat of mixing is zero.
• Molar heat of vaporization will be constant and independent of
composition, (condensation of one mole of liberates heat which
vaporizes one mole of ), hence .
• Temperature change from one plate to other will be small so,
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• Hence equation will be simplified to
• For rectifying section and are constant
• For stripping section and are constant.

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 Lewis-Sorel Method
• Overall Material balance across section I

• Material balance with respect to MVC

Thus

Also according to constant liquid molar

overflow

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• Overall Material balance across section II

• Material balance with respect to MVC

Thus

• Equations of operating lines in the rectifying and stripping section.

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Separation of Benzene-Toluene Mixture
• Feed = 40% benzene
• Product purity = 90% benzene at top
10% benzene at bottom
• Feed enters at boiling point
• Reflux Ratio = 3 kmol / kmol product
• Find:
• Number of plates
• Position of feed entry

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 𝐿𝑛
𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜=
𝐷

Top operating line equation 80

Bottom operating line equation

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• Starting from top
• Xd = 0.9
• Since all the vapors from the column are condensed, hence the
composition of the vapor yt from the top plate must be equal to that
of product xd and liquid returned as reflux xr.
• Composition of liquid xt at the top plate, from equilibrium curve will
be:

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• Calculate composition of vapor on next plate using equation (i)
• Liquid composition from equilibrium data.
• Continue till feed composition.

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• Below the feed point switch to equation (i), rest of the procedure will
remain same.

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• Continue till the composition of bottom product is obtained.
• There will be seven stages in total.

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