Distillation components of the original
● A separation technique used to mixture. A distillate is more
separate the components of a specific: this is the light product of
liquid solution a distillation operation. A distillate
● Separate components of a normally comes from a
mixture based on their condenser, but the condensate is
differences in boiling points split in a reflux, sent back to the
● All components are present in column, and in a distillate, the
both phases. product.
● The vapor phase is created from 5. Separation: Meanwhile, the
the liquid phase by vaporization original mixture, now depleted of
at the boiling point some of its more volatile
● The separation of a liquid components, remains in the
distillation apparatus. It becomes
mixture of two or more
richer in the less volatile
substances of different boiling
components, which have higher
points by the processes of boiling points.
partial vaporization and
condensation More volatile component = lower boiling
● When a mixture is heated, the point, higher vapor pressure
components with lower boiling Less volatile component = higher
points will vaporize first -> vapor boiling point, lower vapor pressure
that is richer
Boiling point = temperature where vapor
pressure = external pressure
How it Works? Vapor pressure = pressure exerted by a
1. Heating the Mixture: The mixture vapor in equilibrium with its liquid
is heated in a distillation
apparatus. As the temperature
increases, the components with Various Types of Distillation
lower boiling points start to 1. Simple Distillation
vaporize. 2. Molecular Distillation
2. Vaporization: The vapor formed 3. Vacuum Distillation
is richer in the components with 4. Batch Distillation
lower boiling points. These vapors 5. Continuous Distillation
rise up through the distillation 6. Flash Distillation
apparatus. 7. Fractional Distillation
3. Cooling and Condensation: As 8. Aseotropic Distillation
the vapor rises, it reaches a
condenser, where it is cooled. The
cooling causes the vapor to
condense back into a liquid state.
4. Collection of Condensate: The
condensed liquid, known as the
condensate, is collected. This
condensate will contain a higher
concentration of the more volatile
Simple Distillation evaporate and be
● Single vaporization-condensation removed easily.
cycle ■ Light molecules =
● Produces an impure distillate travel farther =
● Cannot completely separate reach condenser
components ■ Heavy molecules =
● Pure substances can be obtained travel shorter =
from a mixture if the boiling points return to liquid
differ by more than 100°C
● Separation of high-boiling ● The separation happens due to:
components from non-volatile ○ Mean free paths
components ○ Molecular weights
● Separation of high volatile ○ Volatilities
components from a higher ○ Vapor pressures
boiling substance ● How it works?
● Desired substance is ○ Liquid mixture flows over a
immiscible with water heated surface
● How it works? ○ Molecules evaporate
○ Heating the liquid mixture ○ Condensation surface is
to its boiling point placed close to the heating
○ Condensing the vapors surface
○ Collecting the condensate ○ Lighter molecules travel
as the product directly to the condenser
(longer λ)
Molecular Distillation ○ Heavy molecules cannot
● Evaporative distillation or reach the condenser and
Short-path distillation fall back (shorter λ)
● Theory of Molecular Distillation ● Used for:
○ The mean free path (λ) is ○ Purifying heat-sensitive
the "travel distance" a materials
molecule has before it hits ■ Oils, fatty acids,
something else. If you high molecular
increase this distance, weight materials
molecules can escape a ○ Separating of vitamins
surface and move away ● “Only the lighter, faster molecules
more easily without being can jump across the small gap
knocked back. and get collected. The heavier
○ λ increases when: ones can’t make it.”
■ Pressure
decreases Vacuum Distillation
■ Molecular size ● Low-temperature distillation
decreases ● Pressure is reduced below
○ By creating a vacuum, you atmospheric pressure
clear the "traffic" (increase ○ Causing evaporation of
the λ), allowing stubborn, the most volatile liquid
non-volatile substances to ● Boiling occurs when:
○ Vapor pressure of the ■ Reduce column
liquid = surrounding diameter
pressure ■ Lower capital
● When pressure is reduced: investment
○ Boiling point decreases
○ Liquid evaporates at low Batch Distillation
temperature ● A fixed amount of mixture (batch)
○ Most volatile components is charged into a distillation unit
evaporate first ● Mixture is separated into fractions
over time
● After completion, the unit is
Why is it important for emptied -> new batch is fed ->
Temperature-Sensitive Materials? repeat
● Some compounds degrade, ● How it works?
oxidize, or polymerize at high ○ Mixture is loaded into a
temperatures still (reboiler)
Beta carotene - is heat sensitive. Using ○ Heat is applied
vacuum distillation allows solvent ○ Most volatile components
removal without damaging the product evaporate first
○ Vapor rises through the
● Industrial applications: column
○ Petroleum refining ○ Condensed and collected
○ Pharmaceuticals ○ As time passes,
○ Food processing composition in the still
○ Specialty chemicals changes
Advantages: ○ Different fractions are
❖ Lower operating temperatures collected at different times
➢ Reduced P -> lower BP by switching receivers
➢ Prevents thermal ○ Only one distillate outlet is
degradation required - just change the
➢ Avoids polymer formation receiving container
❖ Incresed Relative Volatility ● Where it’s used?
➢ At low P ○ Pharmaceutical industry
■ Increases volatility (high purity products)
difference ○ Wastewater treatment
■ Separation ○ Specialty chemicals
becomes easier ○ Laboratory-scale
➢ Improves: Purity, Yield, separations
Separation efficiency ○ Seasonal or low-volume
❖ Improved Product Quality production
➢ Less thermal damage ● Ideal when:
➢ Better color, stability, ○ Production volume is small
composition ○ High purity is required
❖ Capital cost advantage ○ Feed composition varies
➢ Low P ○ Flexibility is needed
■ Reduce required
column height
Continuous Distillation ■ Sometimes side
● The feed mixture is added streams (at
continuously different heights)
● Separated fractions are withdrawn ○ Each fractions has its own
continuously exit point
● System operates at steady state
○ Feed rate = total output ● Design features:
rate ○ Feed location: positioned
○ Temperature and pressure at an optimal height for
is constant best separation
○ Compositions at each ○ Reboiler: supplies heat at
fraction remain constant the bottom
○ Reflux ratio remains ○ Condenser: condenses
constant overhead vapor
● Two main fractions: ○ Reflux: part of condensed
○ Distillate (Overhead liquid returned to improve
Product) separation
■ More volatile
components
Feature Continuous Batch
■ Vaporized,
condensed, Feed Continuous Charged
collected once
○ Bottoms (Residue)
Products Continuous Collected
■ Less volatile
withdrawal over time
components
■ Removed from the Operation Steady Unsteady
bottom of the state state
column or reboiler
Scale Large Small-scal
○ These streams are
industrial e, lab,
withdrawn simultaneously pharma
● How it works?
○ Feed enters the column Efficiency High for Flexible but
continuously large lower
○ Heat is supplied at the production throughput
bottom (via reboiler).
○ Vapor rises upward ● Widely used in industry:
through trays or packing. ○ More efficient for
○ Liquid flows downward. large-scale production
○ Mass transfer occurs ○ Higher throughput
between vapor and liquid. ○ Consistent product quality
○ Components separate ○ Better energy integration
based on volatility. ○ Lower cost per unit
○ Products are continuously product
withdrawn: ● Used in:
■ Overhead distillate ○ Petroleum refining
■ Bottoms product ○ Petrochemical plants
○ Chemical manufacturing
○ Large-scale solvent ○ Pre-flash before the
recovery distillation columns
● Key characteristics
Flash Distillation ○ Single equilibrium stage
● Equilibrium distillation ○ Fast
● A single-stage separation process ○ Simple equipment
● A liquid mixture is partially ○ Used as pre-separation
vaporized (usually by pressure ○ Not very high purity
reduction or heating), and vapor
and liquid are allowed to reach Fractional Distillation
equilibrium before separation. ● Has multiple
How it works? vaporization-condensation cycles
● Liquid feed is heated Fractioning column between the
● Passes through a valve distillation flask and the head
● Pressure suddenly decreases ❖ Packed with material that
● Part of the liquid vaporizes increases the surface area for
instantly vapor-liquid contact
● Vapor and liquid separate inside a ❖ Allows multiple separations and
vessel: flash drum the collection of purer fractions
What happens thermodynamically? ❖ A distillation column is a vertical
● The process is adiabatic separation unit used to separate
● No external heat is added during liqui mixtures based on
flashing differences in volatility
● The vapor and liquid reach ❖ Performs rectification
equilibrium (fractionation)
● Final temperature drops to the ➢ repeated vaporization and
new saturation temperature condensation with reflux
● Cooling effect is: ➢ Series of flash
Auto-refrigeration vaporization stages
○ Liquid propane arranged vertically
○ Liquid ammonia How it works?
❖ Vapor rises upward
Single vs. Multi-Component ❖ Liquid flows downward
● Single-Component Liquid ❖ They contact each other
○ A portion vaporizes countercurrently
○ Remaining liquid cools to ➢ Hot vapor moves upward
new saturation ➢ Cooler liquid moves
temperature downward
● Multi-Component Liquid ➢ More volatile components
○ Vapor is richer in more move upward
volatile components ➢ Less volatile components
○ Liquid is richer in less move downward
volatile components ❖ Equilibrium is approached at each
● Common in: stage
○ Petroleum refining Major Components
○ Natural gas processing 1. Vertical Shell
● Tall cylindrical tower
● Houses internal separation ○ Laboratory separations
devices ○ Chemical industries
● Provides space for vapor ○ Petroleum refining
rising and liquid flowing ○ Separating close boiling
downward components
● Actual mass transfer
occurs What happens inside the column?
2. Column Internals ❖ Vapor rises upward
● Enhance vapor-liquid ❖ Liquid flows downward.
contact and improve ❖ Heat exchange occurs
separation efficiency continuously.
● Trays/Plates ❖ Repeated vaporization and
● Packings condensation take place.
3. Reboiler (bottom section) ❖ Each cycle enriches the vapor in
● Supplies heat to the the more volatile (Low BP)
bottom of the column component
● Vaporizes part of the
bottom liquid How it works?
● Generates the upward ● First fraction
vapor flow ○ Vapor becomes
4. Condenser (top section) progressively richer in the
● Cool and condense the lower boiling compound
vapor leaving the top of ○ It condenses and is
the column collected in the receiving
5. Reflux Drum flask
● Holds the condensed ○ As long as this component
vapor domniates, the
● Splits liquid into: temperature remains
○ Distillate product nearly constant at it BP
○ Reflux (to be ● Intermediate Fraction
recycled) ○ Once most of the low BP
● Improves separation compound is removed:
efficiency ■ Temperature
Why reflux is important? begins to rise
● Returns part of condensed ■ Mixed fraction
distillate to the column. (both components)
● Increases internal liquid flow. is collected
● Improves purity. ○ Middle cut or mixed
● Reduces number of stages fractions
required. ● Higher Boiling Point
○ As the temperature
● Higher separation efficiency approaches the BP of the
● Used to separate components higher BP compound
with relatively close boiling points ■ The vapor
● Separates components based on becomes richer in
differences in BP that component
● Where it’s used?
■ The distillate ○ Or they form an azeotrope
collected becomes ○ And ordinary fractional
increasingly pure in distillation cannot achieve
the higher BP good separation
compound ● Principle:
Column Efficiency ○ A separation solvent is
★ The efficiency of a fractionating added to the mixture
column using: ○ Solvent interacts
★ Theoretical Plates differently with each
○ One ideal compound
vaporization-condensation ○ This changes their relative
equilibrium stage volatility
○ One theoretical plate = ○ The separation becomes
one simple distillation step easier in the distillation
★ The smaller the boiling point column
difference between components, ○ The solvent modifies
the more theoretical plates are vapor–liquid equilibrium
required to achieve effective (VLE) without forming an
separation. azeotrope.
○ Due to the closer BP
means low relative Separation Solvent Characteristics
volatility ❖ Must alter the relative volatility by
a wide enough margin
★ Each plate = equilibrium stage ❖ Have a high boiling point (so it
★ More plate = higher purity stays in the liquid phase)
★ Column performance depends on: ❖ Be non-volatile
○ Number of plate ❖ Be miscible with the feed mixture
○ Reflux ratio ❖ Not form an azeotrope
○ Feed location ❖ Not react chemically with
○ Relative volatility components
❖ Not cause corrosion
● The more mini-distillations ❖ Be economical and readily
(theoretical plates) you have, the available
better the separation — especially ❖ Be easily separable from the
when boiling points are close. bottom product
❖ Example: Aniline
○ Has been used to help
Extractive Distillation separate hydrocarbons by
● Carried out in the presence of a selectively interacting with
high-boiling, non-volatile miscible certain components and
separation solvent that alters the changing their volatility
relative volatility of the behavior
components in a mixture
● No azeotrope froms ● How it works inside the Column
● Used when: ○ The solvent is fed near the
○ Components have very top of the column.
close boiling point ○ It flows downward.
○ It preferentially interacts 2. Negative Azeotrope
with one component. ● Maximum-boiling
○ This suppresses the ● Boils at a temperature higher than
volatility of that either pure component
component. ● Caused by strong intermolecular
○ The other component interactions
becomes relatively more ● Example: Hydrochloric acid
volatile and leaves as a ○ Hydrogen chloride BP =
distillate. −84 °C
○ The solvent and less ○ Water BP = 100 °C
volatile component leave ○ Azeotrope (~20.2% HCl)
at the bottom. BP = 110 °C
○ A second column is
usually used to recover Azeotropic Distillation
and recycle the solvent. ● Used to break azeotropes
● How it works?
What is an Azeotrope? ○ Adding a third component:
● Mixture of two or more liquids entrainer
that: ○ Forming a new, lower
○ Boils at constant boiling azeotrope that is
temperature often creating a
○ Has vapor composition heterogeneous mixture (2
equal to liquid composition liquid phases)
○ Cannot be separated by ○ Allowing separation that
simple distillation was not possible before
● When boiled:
○ X1 = Y1 Classic Industrial Example: Separating
○ Liquid composition = vapor ethanol beyond 96% purity
composition ● Benzen was added
○ Constant-boiling ● New low-boiling azeotrope formed
mixtures ● Water was removed
Types of Azeotropes ● Toxic and is less common
1. Positive Azeotrope nowadays
● Minimum-boiling
● Boils at a temperature lower than Modern Industrial Method: Ethanol-Water
either pure component Azeotrope
● Caused by weaker intermolecular ● Molecular Sieves
interactions ○ Pressure swing adsorption
● Example: Ethanol-Water using molecular sieves
○ Ethanol BP = 78.4 °C removes water selectively
○ Water BP = 100 °C ● -> Production of: Anhydrous
○ Azeotrope (≈95.6% ethanol (>99%)
ethanol) BP = 78.2 °C ○ Widely used when ethanol
○ Ethanol cannot be purified is blended with gasoline
beyond ~96% by simple
distillation
Binary Distillation Characteristics:
Binary system: 50% Water - 50% ● Single equilibrium stage
Methanol ● No liquid return (no reflux)
Components: ● Simple equipment
● Water ● Suitable when boiling points differ
● Methanol greatly
BP of Components (1atm)
● Water = 100 °C (less volatile Relative Volatility (α)
component) ● The ease or difficulty of the
● Methanol = 65 °C (more volatile separation of two components by
component) distillation
● Mixture BP = 84 °C ● A measure of how easily one
component in a mixture vaporizes
Vapor pressure (84 °C) compared to another
● Water = 60 kPa (less volatile)
● Methanol = 200 kPa (more
volatile)
K = vapor-liquid equilibrium ratio
More volatile component - Represents the ratio of the mole
- Higher vapor pressure at a fraction in the vapor, y1 to the
given temperature mole fraction in the liquid, x1
- Lower boiling point - More volatile components = K
Less volatile component value > 1.0
- Lower vapor pressure at a - Less volatile components = K
given temperature value < 1.0
- Higher boiling point
Raoult’s Law is based on the
assumption that the vapor phase
Methods of Distillation behaves as an ideal phase is an ideal
1. Single Stage solution
● A liquid mixture is boiled, vapor is Antoine equation is for calculating vapor
generated, condensed, and pressure.
collected - all in one stage
● No reflux
● No multiple vapor-liquid contacts
● Vapor does not re-contact liquid
after leaving the surface
How it works?
● Mixture is heated
● Vapor forms at the liquid surface
● Vapor travels directly to
condenser
● Condensed liquid is collected as
distillate
● Remaining liquid stays in the still Vapor Liquid Equilibrium (VLE)
● Only one ● Distillation columns are designed
vaporization-condensation cycle based on the boiling point
properties of the components in ● Trays:
the mixtures being separated ○ Usually perforated (sieve
● Sizes, and height are determined trays)
by VLE data ○ Allow vapor to rise from
● Constant pressure VLE data is the bottom to the top
from BP diagram ○ Equilibrium of mass
transffer and heat transfer
is established between the
rising vapor and
descending liquid
● Liquid flow downward from top to
bottom and guided by
downcomers across trays
3. Mass and Heat Transfer
● Rising vapour contacts
descending liquid at each tray.
● Mass transfer: Components in
Equilibrium Line vapour and liquid phases adjust to
● The curved line approach equilibrium.
● Describes the composition of the ● Heat transfer: Temperature
liquid and vapor in equilibrium gradients are established to
maintain phase change.
● At the bottom of the column:
○ Part of the liquid is
withdrawn as bottoms
product.
○ The rest is sent to the
reboiler and returned as
vapour to the column.
Operation of a Typical Distillation ● Recirculation: Liquid molecules
Column continually contact vapour across
1. General Overview trays, ensuring the desired
● The distillate is drawn as vapor at product composition.
the top of the column and 4. Feed Introduction
condensed fully/partially ● The feed stream is introduced
● Reflux: a portion of the continuously at an intermediate
condensed liquid is returned to tray.
the top of the column by: gravity ● Chosen tray: Where the liquid
or pumped from reflux drum composition approximately
○ To ensure continuous matches the feed.
vapor-liquid contact above ● Column sections:
the feed tray for efficient ○ Above feed tray:
separation Rectifying or enrichment
2. Column Structure section – increases
● The fractionating column is concentration of more
cylindrical and divided into volatile component.
sections by trays
○ Below feed tray: Stripping Key Assumptions:
section – removes the Constant Molar Overflow (CMO)
more volatile component ❖ .Molar heat of vaporization of
from the bottom product. components are roughly the same
5. Component Definitions ❖ Heat effects are negligible
● More volatile component: ❖ For every mole of vapor
Component with lowest boiling condensed, 1 mole of liquid is
point. evaporated
● Mass balance: ❖ Operating lines are straight
○ Typically focuses on more Methodology
volatile component, 1. VLE Diagram: Start with the VLE
ignoring the less volatile Plot of the binary mixture
component. 2. Operating Lines: Draw two lines
● Notation: representing mass balance
○ xf,xd,xw → mol fraction of relationships
more volatile component a. Rectifying (top): enriches
in feed, distillate, and the more volatile
bottoms, respectively component
○ If two components A and b. Stripping (bottom):
B: removes the more volatile
■ A = more volatile: components from the
xf,xd,xw refer to A bottoms product
■ B = less volatile: 3. Graphical steps:
xfB,xdB,xwB refer to B a. Start at the desired
distillate compositions on
McCabe Thiele Method the y-axis
Developed by: McCabe & Thiele b. Step off stages between
Type: Graphical method for binary operating lines and
mixtures equilibrium curve
Purpose c. Number of steps =
❖ Determine the theoretical number theoretical stages required
of stages required for a given
separation
❖ Distillation columns are designed
using Vapor-Liquid Equilibrium
(VLE) data of the mixture
❖ The VLE characteristics (shape
of the equilibrium curve)
determine:
➢ The number of
theoretical stages
required.
➢ The number of trays
needed for separation
The Effect of Feed Conditions