Chemical &Pharma 2 Lecture 4

Introduction to Separation
processes Separations
 What are separation processes? • Separations
Separation processes are defined as those operations • Enrichment
which takes a feed stream with a mixture of substances • Concentration
into one or more products which differ from each other • Purification
in composition. • Refining
• Isolation
 The main goal of separation process is to purify solutions • Drying
 This is done by the addition of a separating agent which • Separations are important to chemist and
may be energy (esa) or another stream of material.(msa) chemical engineers
• Chemist : Small scale (Analytical separation methods)
• Chemical Engineers : Economical, large scale methods
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ChE 334: Separation Processes Dr Saad Al-Shahrani

Basic Description of operations General Separation Technique

 Most separations processes work on a single phase of feed.
1. Separation by Phase Creation Energy (heat/work)
 If it exists as two or more immiscible phases, it must be first separate the
phases by some mechanical means based on gravity, centrifugal force, 2. Separation by Phase Addition (MSA : Mass Separating
pressure reduction, or electric or magnetic field. Then appropriate Agent) (Absorption)
separation techniques are applied to each phase.
3. Separation by Barrier Barrier (membrane)
 A schematic diagram of general separation Product 1

process 4. Separation by Solid Agent (Adsorption)

Product 2
Feed mixture to be Separation
separated process
(S, L, V, Ci) Product N-1 5. Separation by Force Field or Gradient (electrophoresis)

Product N

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Chemical &Pharma 2 Lecture 4

Classification of Separation Techniques

Separation Processes.
Phase 1 Phase 1

Feed Feed

Phase 2 MSA Phase 2

Mass Separating
Agent (ii) By Phase Addition
(i) By Phase Creation

Distillation Phase 1 Absorbtion. (iV) By Solid Agent (V) By Force Field or Gradient
MSA can be
Adsorption onto charcoal of VOC’s.
Feed another Electrodeposition/ electrophoresis.
Reverse Osmosis Barrier solvent that Feed
systems, Ion Phase 2 selectively Phase 1
exchange, dissolves some Phase 1 Feed Force field
Chromatography. of the species or gradient
in the feed
(iii ) By Barrier Phase 2 Phase 2
mixture
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Hypothetical vs. Industrial Processes Driving Force of Separation :

• Rate of Separation : how fast ?

• Simple ,hypothetical • Handbooks
– Governed by mass transfer
process is not possible • Journals
• Extent of Separation : how far ? • Electronic Databases
– Impurities in the feed
– Limited by thermodynamics • Commercial Process Simulators
– Side Reactions
• Properties of Importance
• Separation processes are Molecular Properties Thermodynamic and Transport Properties

important in real industrial Molecular Weight Vapor Pressure

Van der Waals Volume Solubility
application Van der Waals Area Adsorptivity
Molecular Shape (Accentric Factor) Diffusivity
Dipole Moment
Polarizability
Dielectric Constant
Electric Charge
Radius of Gyration
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Chemical &Pharma 2 Lecture 4

Choice of method
 Why Separation?
• Can be a variety of methods to choose from
but main criteria is cost. Separation processes
account for 12% of the value of a chemical
and more for a drug.
• 50 to 90 percent of capital investment in
chemical plant is for separation equipment
• Specification required, available methods and
simplicity of operation are the main criteria.
Introduction to Separation
processes
There are many reasons for wanting pure substances. Some of
these reasons include:
 Need for pure material in engineering applications.
 Preparation of raw materials into their component.
 Need for pure material for materials processing.
 Need to remove toxins or inactive components from solution (drugs)
 Need for ultra-pure samples for testing.
 Need for analysis of the components of mixture (DNA testing)

Basic Description of operations 1. Separation By Phase Creation

 Mechanism of separation:
V V
 The mixing of chemicals to form a mixture is a spontaneous,
natural process that is accompanied by an increase in entropy
or randomness (∆S)
V/L
 The inverse process (the separation of the mixture into its V/L

constituent chemical species) is not spontaneous process, it

ESA
requires an expenditure of energy. (Energy-Separating Agent)

 A mixture to be separated usually originates as a single

homogenous phase (solid, liquid, or gas) L L
Partial Condensation or Vaporization Flash Vaporization
(Heat Transfer) (Pressure Reduction) 12

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Chemical &Pharma 2 Lecture 4

2. Separation by phase addition 3. Separation by barrier

L L
• Using a mass separating agent. (msa) to form
another phase. (2nd most major operation in L
Chem Eng.) solvent
smaller
solute

• Absorption of gases by liquids. Removal of a solvent

component by absorption into a suitable liquid. L L

This can be physical process or chemical reaction. Osmosis Reverse Osmosis Dialysis

• Liquid-Liquid extraction. Separating of the Nonporous membrane Nonporous membrane Porous membrane

components of a liquid mixture by treatment Concentration gradient Pressure Gradient Concentration Gradient
Pressure Gradient
with a solvent that the desired component is
Desalination of sea water Recovery of caustic
preferentially soluble from hemicellulose

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3. Separation by barrier 3. Separation by barrier

L L
L L
solvent solvent
L L
Microfiltration Ultrafilration
Microporous membrane Microporous membrane
Pressure gradient Pressure Gradient
Removal of bacterial Separation of whey from
From drinking water cheese
L
• Barrier can be micro-porous or non porous.
L
• In Reverse Osmosis the liquid feed is
gas (evaporation)
separated by a non porous membrane with
V pressure gradient. Used in the desalination of
Pervaporation seawater. High pressures needed.
Nonporous membrane • Microfiltration and Ultrafiltration for removal
Pressure Gradient
of bacteria or for separating whey from
Separation of azeotropic cheese.
mixtures

0.02-10 mm 1 – 20 nm 15 16

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Chemical &Pharma 2 Lecture 4

4. Separation by solid agent 4. Separation by solid agent

• Uses processes of adsorption , chromatography or Ion
exchange. • Adsorption
– Adsorbent
• Removal of a containment or low level material.
• Activated carbon
• Adsorption of organics on to activated charcoal for aqueous • Aluminum oxide
clean-up. • Silica gel
• Chromatography separates the feed by selective • Zeolite adsorbents
adsorption. Can be selective for different ranges. Highly (Molecular sieve)
valuable drugs. – Adsorption / Regeneration
• Ion exchange for removal of precious metals from waste – Regeneration methods
waters for concentration and then electro winning. Also for • Thermal Swing (TSA)
purifying water, removes hardness. • Pressure Swing (PSA)
• Inert purge stripping
• All of the above the solid agent becomes saturated with the • Displacement desorption
adsorbent and must be regenerated in some way.
Hydrogen PSA Units
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5. Separation by external field or gradient 5. Separation by force Field or gradient

Separation operation Initial or Feed Phase Force field or Industrial Example • Electrophoresis for used protein separation
gradient
Centrifugation Vapor Centrifugal force Separation of • Electrodialysis used in API manufacture
Uranium isotope
Thermal diffusion Vapor or liquid Thermal gradient Separation of • Electrolysis used in heavy metal removal.
chlorine isotope
Electrolysis Liquid Electrical force field Concentration of
heavy water
Electrodialysis Liquid Electrical force field Desalinization of sea
and membrane water
Electrophoresis Liquid Electrical force field Recovery of
hemicelluose

Field-flow Liquid Laminar flow in

fractionaltion force field
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Industrial Separation Processes Distillation

Process Feed Separating
agent
Product Basis of
separation
• Most common separation process
Distillation Liquid Heat Liquid & Diff in • Single distillation involves boiling a liquid,
Vapour volatilities
Evaporation Liquid Heat Solid or Liquid Diff in
condensing the vapours and directing the
& Vapour volatilities liquid into another vessel.
Solvent Liquid Immiscible Two liquids Solubility diff. • How concentrated the condensate is depends
Extraction Liquid
Drying Liquid & Solid Heat Dry solid & Evaporation of
on the difference in vapour pressure between
vapour water/solvent the two liquids and the mole fractions present
Sedimentation Liquid & Solid Gravity Liquid & solid Density
difference
in the original solution.
Filtration Liquid & Solid Filter medium Liquid & solid Difference in
size of liquid &
solid
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Distillation and vapour pressure Vapour Pressure

• A liquid’s boiling point is a temperature at which • The vapour pressure of a liquid at a particular
its vapour pressure is equal to the gas above it. temperature is the equilibrium pressure exerted
(Atm pressure = 1 atm). by molecules leaving and entering the liquid
• Distillation is based on the fact that the vapour of surface.
a boiling mixture will be richer in the components – Energy input raises the VP
that have lower boiling points. – Liquid boils when its VP = surrounding pressure
• Therefore, when this vapour is cooled and – Liquids with high VP (volatile liquids boil at lower
condensed, the condensate will contain more Temps.
volatile components. At the same time, the – VP & B.Pt depend on the relative amounts of the
original mixture will contain more of the less components in the mixture
volatile material. – distillation occurs because of the differences in the
volatility of the components in the liquid mixture
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Example Lab Fractional Distillation

• Assumptions for ideal gases. Temp of a boiling liquid Phase diagram for two components
remains constant even when more heat is applied.
• Raoults law VP of a mixture Pt = P1 + P2.
• Daltons laws partial pressure of a gas is equal to its
mole fraction in the mixture.
• We have a mixture containing 0.33mole fraction
benzene and 0.67 mole fraction toluene. If we distil it
in a simple lab distillation apparatus theoretically what
will the benzene: toluene mole fraction be?
• VP of benzene at 20C = 75 mm
• VP of toluene at 20C = 22mm.
Column filled with glass beads to give the
maximum possible surface area for vapour to
25 condense on. 26

Fractional Distillation
Type of columns
•As the material rises through the
Condenser
column it goes through many
Batch Columns
V
evaporation/condensation stages. • In batch operation, the feed to the column is
The material at the top of the introduced batch-wise. When the desired task is
L
Reflux
column is richest in the most achieved, a next batch of feed is introduced.
Rectifying section volatile component. Continuous Columns
V/L The fractional column must be
• process a continuous feed stream. They are capable of
1.vertical,
handling high throughputs (most common)
2.be at equilibrium all the way up,
Reboil
Stripping section
3. have good mixing of the rising
Second distinction based on feed
vapour and descending liquid all • binary column - feed contains only two components
Reboiler the way. • multi-component column - feed contains more than
L two components

(Heat transfer (ESA) 27 28

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Chemical &Pharma 2 Lecture 4

Introduction to Separation
processes

Condensate

Crude oil

30
ChE 334: Separation Processes Dr Saad Al-Shahrani

Components
1. a vertical shell where the separation of liquid
components is carried out
2. column contains a series of trays/plates and/or
packings which are used to enhance component Vapour passes up the column
separations Vapour passing up the column
countercurrent to the liquid becomes enriched in the most
3. a reboiler to provide the necessary heat for the which flows across each tray
distillation process. The “bottoms” are recirculated volatile component (MVC) and
and down the “downcomers”. the liquid falling down the
through the boiler back into the column.
As vapour bubbles through column is enriched with the
4. a condenser (cooling water) to cool and condense the the liquid on the tray there is
vapour leaving the top of the column least volatile component (LVC).
a mass transfer between
5. a reflux drum to hold the condensate from the top of phases and their
the column so that some liquid (reflux) can be recycled
back to the column and the distillate is the desired compositions approach
product equilibrium.

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Separation of components
• At the top of the column the vapour is
condensed and part of it is returned to depends on :
provide liquid reflux. • the differences in boiling points of the individual
• On the bottom, part of the liquid is components.
evaporated in the reboiler to provide a vapour
• the concentrations of the components present,
phase.
• The reflux: distillate ratio is critical to the • Leads to the liquid mixture will have different
operation and the bottoms recirulation ratio is boiling point characteristics.
also important. • depends on the vapour pressure characteristics of
liquid mixtures.
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Vapour-Liquid-Equilibrium
(VLE) Curves
• 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.
The vapour-liquid
equilibrium
characteristics
(indicated by the shape
of the equilibrium
curve) of the mixture
will determine the
number of stages, and
hence the number of
trays, required for the
see Flash tutorial on Distillation Basics written by Jon Lee
separation. 35
Column design
1.The number of stages can be
visualised graphically by the
McCABE-THIELE DESIGN METHOD
which uses the VLE plot to determine
the theoretical number of plates.
(Computer design systems are far more
accurate).
2. The condition of the feed line (temp,
saturation etc.).
3. The tray number for feed input
All effect the composition profile.
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• Each tray has 2 conduits, one on each side, called

Internal Components
• Trays
Bubble cap trays, valves or sieve
trays. Trays are designed to
maximise the vapour: liquid contract
by working on liquid distribution and
vapour distribution.
‘downcomers’. Liquid falls through the
downcomers by gravity from one tray to the one
below it. The flow across each plate is shown in
the above diagram on the right.
• A weir on the tray ensures that there is always
some liquid (holdup) on the tray and is designed
such that the holdup is at a suitable height, e.g.
such that the bubble caps are covered by liquid.
• Being lighter, vapour flows up the column and is
forced to pass through the liquid, via the
openings on each tray. The area allowed for the
passage of vapour on each tray is called the
active tray area.

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Adverse vapour flow conditions can

FACTORS AFFECTING DISTILLATION
cause
COLUMN OPERATION
• Feed Conditions • Foaming – expansion of liquid due to passage of
vapour/gas
• Internal liquid and fluid flow conditions
• Entrainment - liquid carried by vapour up to the tray
• State of trays above
• The weather. • Weeping/dumping - caused by low vapour flow . liquid
starts to leak through perforations
• Flooding - excessive vapour flow, causing liquid to be
entrained in the vapour up the column
• Column Diameter and design critical.

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An azeotrope or constant boiling

Summary
mixture – non ideal
• Separation processes are major parts of
You hit a barrier at 96.5%
ethanol. It is impossible to chemical technology
get pure ethanol by distiling
any mixture of ethanol and • There are 5 main types of separation process.
water containing less than
95.6% of ethanol. • For Energy separating agent the key process is
This particular mixture of
ethanol and water boils as if it distillation.
were a pure liquid. It has a
constant boiling point, and the
vapour composition is exactly
the same as the liquid.

Ref: Distillation by Ming T. Tham Uni of Newcastle

Ref: Introduction to Industrial Chemistry
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http://www.chemguide.co.uk/physical/phaseeqi 42

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