DISTILLATION

Dr. Khalid Mahmood

SHMT
PRE REQUISITES
 Vapor liquid equilibrium
 Azeotropic mixtures
 Binary component system
 Multi component systems
 Partial vaporization and partial condensation
 Laws of partial pressure
 Relative volatility
 Ideal and non ideal systems
 DISTILLATION
Distillation is based on the fact that the
vapour of a boiling mixture will be richer in
the components that have lower boiling
points.
Therefore, when this vapour is cooled and
condensed, the condensate will contain more
volatile components. At the same time, the
original mixture will contain more of the less
volatile material.
Distillation columns are designed to achieve
this separation efficiently.

distillation is the most common separation

technique
it consumes enormous amounts of energy,
both in terms of cooling and heating
requirements
it can contribute to more than 50% of
plant operating costs
DISTILLATION
 Distillation is
 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.
 DIFFERENT PARTS OF
DISTILLATION
Condenser

Overhead
Vapor

Overhead
Reflux Product
Rectifying
Section

Stripping Reboiler
Section

Bottoms
Product
 DISTILLATION PRINCIPLES
 The vapour pressure of a liquid at a particular temperature is
the equilibrium pressure exerted by molecules leaving and entering
the liquid surface.
Here are some important points regarding vapour pressure:
 Energy input raises vapour pressure
 Vapour pressure is related to boiling
 A liquid is said to ‘boil’ when its vapour pressure equals the
surrounding pressure
 The ease with which a liquid boils depends on its volatility
 Liquids with high vapour pressures (volatile liquids) will boil at
lower temperatures
 The vapour pressure and hence the boiling point of a liquid mixture
depends on the relative amounts of the components in the mixture
 Distillation occurs because of the differences in the volatility of the
components in the liquid mixture
BASIC DISTILLATION EQUIPMENT
 Distillation columns are made up of several components, each of which is used
either to transfer heat energy or enhance material transfer. A typical
distillation contains several major components:
BASIC OPERATION AND TERMINOLOGY
 The liquid mixture that is to be processed
is known as the feed and this is introduced
usually somewhere near the middle of the
column to a tray known as the feed tray.
The feed tray divides the column into a top
(enriching or rectification) section and a
bottom (stripping) section. The feed flows
down the column where it is collected at
the bottom in the reboiler.

 Heat is supplied to the reboiler to generate vapour. The source of

heat input can be any suitable fluid, although in most chemical plants
this is normally steam. In refineries, the heating source may be the
output streams of other columns.  The vapour raised in the reboiler is
re-introduced into the unit at the bottom of the column. The liquid
removed from the reboiler is known as the bottoms product or
simply, bottoms.
BASIC OPERATION AND TERMINOLOGY

 The vapour moves up the column, and as it exits the top of the unit, it
is cooled by a condenser. The condensed liquid is stored in a holding
vessel known as the reflux drum. Some of this liquid is recycled back to
the top of the column and this is called the reflux. The condensed
liquid that is removed from the system is known as the distillate or top
product.

 Thus, there are internal flows of vapour and liquid within the column
as well as external flows of feeds and product streams, into and out of
the column.
DISTILLATION TYPES
Binary distillation
 Differential distillation
 Flash or equilibrium distillation
 Rectification
Multicomponent distillation
 Fractional distillation
Classified on type of process
 Batch distillation
 Continues distillation

Classified as
 Extractive distillation
 Steam distillation
 TYPES OF DISTILLATION COLUMNS
 Batch Columns the feed to the column is introduced batch-
wise. That is, the column is charged with a 'batch' and then
the distillation process is carried out. When the desired
task is achieved, a next batch of feed is introduced.

 Continuous Columns process a continuous feed stream. No

interruptions occur unless there is a problem with the
column or surrounding process units. They are capable of
handling high throughputs and are the most common of
the two types.
TYPES OF CONTINUOUS COLUMNS
 VAPOUR LIQUID EQUILIBRIUM
 Vapor–liquid equilibrium (VLE) is a condition where
a liquid and its vapor are in equilibrium with each other
 A condition or state where the rate of evaporation equals the
rate of condensation on a molecular level such that there is no
net vapor–liquid interconversion
 A substance at vapor–liquid equilibrium is generally referred
to as a saturated fluid
 For a pure chemical substance this implies that it is at
its boiling point.
 The notion of "saturated fluid" includes saturated liquid
(about to vaporize), saturated liquid–vapor mixture, and
saturated vapor (about to condense).
SEPARATION OF BINARY
MIXTURES
MULTICOMPONENT SEPARATION
 VAPOUR LIQUID EQUILIBRIUM
 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 vapour liquid
equilibrium (VLE) data for the mixtures.
 Constant pressure VLE data is obtained from boiling point
diagrams.
 The composition of vapour in equilibrium with a liquid of
given composition is determined experimentally by using
a equilibrium still.
 The results are conveniently shown on temperature
composition diagrams
 VAPOUR-LIQUID-EQUILIBRIUM
(VLE) CURVES
Ideal Binary system
VLE data of binary mixtures is often
presented as a plot, as shown in the
figure on the right. 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. This particular VLE plot shows
a binary mixture that has a uniform
vapour-liquid equilibrium that is
relatively easy to separate
BENZENE-TOLUENE SYSTEM
MINIMUM BOILING POINT
AZEOTROPS
MAXIMUM BOILING POINT
AZEOTROPS
 EQUILIBRIUM CURVES
•In figure a, curve ABC shows the composition of liquid that
boils at any temperature, and curve ADC shows composition of
vapours at that temperature
•In figure b and c, there is a critical composition Xg where the
vapour has the same composition as the liquid, so that no
separation occurs at boiling. Such critical mixtures are called
azeotropes. Special techniques are required to separate them.
•The most important VLE curves are generated by azeotropic
systems. An azeotrope is a liquid mixture which when
vaporized, produces the same composition as the liquid.
The two VLE plots below, show two different azeotropic
systems, one with a minimum boiling point and one with a
maximum boiling point
EQUILIBRIUM CURVES
• In both plots, the equilibrium curves cross the diagonal
lines, and this are azeotropic points where the
azeotropes occur. In other words azeotropic systems
give rise to VLE plots where the equilibrium curves
crosses the diagonals.
• For composition other than Xg, the vapour formed has a
different composition from that of liquid.
• These curves are drawn on constant pressure and
composition, and by changing the pressure of liquid
composition of vapour liquid equilibrium will also changes
• For distillation purpose it is more convenient to plot a y
against x at constant pressure. In this case temperature
varies along each curve
AZEOTROPIC MIXTURES
 Note the shapes of the respective equilibrium lines in relation to
the diagonal lines that bisect the VLE plots.
 Both plots are however, obtained from homogenous azeotropic
systems. An azeotrope that contains one liquid phase in contact
with vapour is called a homogenous azeotrope. A homogenous
azeotrope cannot be separated by conventional distillation.
However, vacuum distillation may be used as the lower pressures
can shift the azeotropic point. Alternatively, an additional
substance may added to shift the azeotropic point to a more
‘favorable’ position.
 When this additional component appears in appreciable amounts
at the top of the column, the operation is called azeotropic
distillation.
 When the additional component appears mostly at the bottom of
the column, the operation is called extractive distillation
CRITICAL FACTORS TO VAPOR-LIQUID
EQUILIBRIUM DURING DISTILLATION
 Relative Volatility
 Activity Coefficient (Surface Tension)
 Solubility
 Maximum achievable concentration
 Surface area
PARTIAL VAPORIZATION AND
PARTIAL CONDENSATION
 Partial condensation or partial vaporization is a separation operation
used when the feed mixture consists of different chemical species that
have different tendencies to condensate/evaporate (different boiling
point).
 By adding heat to the liquid feed mixture, a part of the components will
evaporate, thus the partial vaporization. The vapors, with the lower
density, will go up the fraction column and the liquid remained will go on
the bottom of the column (higher density).
 By removing heat from a gas feed mixture, part of components will
condensate, thus the partial condensation. The liquid has the tendency
to go on the bottom of the fraction column and the vapors will have the
tendency to separate from the liquid and move to the top of the column.
 The property that makes this separation possible is the volatility of the
components. A component with a higher volatility will evaporate faster,
and thus has the tendency to move up to the top of the column. The
components with a lower volatility will remain on the bottom of the
column, as a liquid phase.
PARTIAL VAPORIZATION AND
PARTIAL CONDENSATION
The main problem with this kind of separation is that usually, the components have a low
volatility range which means it is quite difficult to perform the operation of separation
through only one partial condensation/vaporization process.
PARTIAL VAPORIZATION AND
PARTIAL CONDENSATION
PARTIAL VAPORIZATION AND
PARTIAL CONDENSATION
RELATIVE VOLATILITY
 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.
RELATIVE VOLATILITY
 Relative volatilities are used in the design of all types of
distillation processes as well as other separation or absorption
processes that involve the contacting of vapor and liquid
phases in a series of equilibrium stages.
 Relative volatilities are not used in separation or absorption
processes that involve components that chemically react with
each other (for example, the absorption of gaseous carbon
dioxide in aqueous solutions of sodium hydroxide which yields
sodium carbonate).

 where      pa is the partial pressure

  xa is the mole fraction in the liquid phase