Distillation

It is the physical process of separating liquid mixture into various components on the basis of
difference in their boiling points.
External pressure affects the boiling point. The boiling point of a liquid will rise as external
pressure rises. The volatile components are those with a high boiling point. Only when the
components in question are volatile can distillation be used. Partial evaporation and partial
condensation are two essential processes in distillation.
The temperature at the bottom of the distillation column is higher than the temperature at the top.
There are more volatile components at the top and less volatile components at the bottom. When
the amount of the more volatile component in the vapour and liquid phases is the same, total
evaporation occurs, which is undesirable. Partial evaporation and partial condensation are
required. Because latent heat is released to condense vapour, the boiling point of the mixture
drops, allowing separation to occur at low temperatures.

Principle of Distillation
The volatility difference is used to separate the components in the distillation column. When a
liquid mixture of two or more volatile liquids is heated, the more volatile components rise to the
top as vapors, resulting in a higher concentration of the more volatile components from which
they evolved. Less volatile components descend the column, and the bottom product can be used.
Relative Volatility
It 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.
Relative volatility should be greater than 1. If relative volatility is l or less than 1 separation
between components is impossible. The higher is the relative volatility of a liquid mixture, the
easier it is to separate the mixture components by distillation.

Basic Distillation Equipment

A typical distillation contains several major components
 A vertical shell where separation of liquid components is carried out
 column internals such as trays/plates and/or packings which are used to enhance
component separations
 In tray columns, trays of various designs are used to hold up the liquid to provide better
contact between vapour and liquid, hence better separation
 In packed column, packings are used to enhance contact between vapour and liquid
 a reboiler to provide the necessary vaporization for the distillation process
 a condenser to cool and condense the vapor leaving the top of the column
 a reflux drum to hold the condensed vapor from top of the column so that liquid(reflux)
can be recycled back to the column

Basic Distillation Operation

The feed is the liquid mixture that will be processed, and it is normally fed to a tray called the
feed tray near the middle of the column. The feed tray separates the column into two sections:
top (enriching or rectification) and bottom (stripping). The feed travels down the column until it
reaches the bottom of the reboiler, where it is collected.

The reboiler receives heat in order to produce vapor. Any suitable fluid can be used as a heat
source, though steam is most commonly used in chemical plants. The heating source in refineries
could be the output streams of other columns. At the bottom of the column, the vapor generated
in the reboiler is reintroduced into the unit. The bottoms product, or simply bottoms, is the liquid
that is taken from the reboiler.
The vapor goes up the column and is cooled by a condenser as it exits the top of the unit. The
condensed liquid is collected in a reflux drum, which serves as a holding vessel. The reflux is the
process of returning some of this liquid to the top of the column. The distillate, or top product, is
the condensed liquid that is taken from the system.
Thus, there are internal flows of vapor and liquid within the column as well as external flows of
feeds and product streams, into and out of the column.

Laws Governing Distillation

For a mixture of liquids, the distillation process is dependent on
 Dalton’s Law
 Raoult’s Law

Dalton’s Law
It states that the total pressure exerted by a mixture of gases is equal to the sum of the partial
pressures of all the constituent gases.
Raoult’s Law
It states that the partial pressure of a single liquid component in an ideal liquid mixture equals
the product of the vapor pressure of the pure component and its mole fraction.

Modes of Distillation
There are two modes of operation of distillation
1. Batch Distillation
2. Continuous Distillation

Batch Distillation
The feed is introduced to the column in batches in batch operation. That is, a 'batch' is loaded
into the column, and then the distillation process begins. A new batch of feed is introduced once
the intended task has been completed. As shown in Figure, a binary mixture of components A
(more volatile) and B (less volatile) is placed in a still with a heating element and a condenser to
condense the vapor produced. Distillate refers to the condensed vapor. In a condensate receiver,
the distillate is collected. The residual is the liquid that remains in the still. The procedure is in an
insecure condition. We heat the mixture here, and as each component reaches its boiling point,
we remove it. To get another component, boil the mixture again. As we remove the components
one by one, the purity of the combination deteriorates. In batch distillation, 100 percent purity is
not possible, therefore relative volatility for 100 percent purity should be infinite. We have total
vapors and total residue at the end of the day, and there is no equilibrium between them. For a
brief amount of time, equilibrium is established between the vapors generated at the start and the
residue at that time.
Continuous Distillation
Continuous column process a continuous feed stream. No interruptions occur unless there is a
problem with a column or surrounding process units. They are capable of handling high
throughputs. Continuous column are of following types.
1. Binary Distillation
In this column feed contains only two components.

2. Multicomponent Distillation
In this column feed contains more than two components.

3. Multiproduct Distillation
column has more than two product streams where the extra feed exits when it is used to
help with the separation.

Types of Distillation
Following are the types of Distillation
 Simple Distillation
 Flash/Equilibrium Distillation
 Fractional Distillation
 Steam Distillation
 Vacuum Distillation
 Azeotropic Distillation
 Extractive Distillation
Simple Distillation
When there are large boiling point differences between the components of a liquid combination,
simple distillation is used (boiling point difference of at least 70 oC). A combination is heated to
convert the most volatile component from a liquid to vapor in simple distillation. The vapor rises
to the top and condenses in a condenser. The condenser is usually chilled (e.g., by circulating
cold water around it) to encourage the vapor to condense and be collected.
For example, Separation of alcohol water mixture to obtain high quality alcohol.
Flash/Equilibrium Distillation
A single-stage separation technique known as flash distillation (sometimes known as
"equilibrium distillation"). To raise the temperature and enthalpy of the combination, a liquid
mixture feed is pushed via a heater. It then passes through a valve, where the pressure is
decreased, partially vaporizing the liquid. The liquid and vapor split once the mixture reaches a
large enough volume (the "flash drum"). The product liquid and vapor phases approach
equilibrium since the vapour and liquid are in such close proximity until the "flash" happens.
It is commonly used in petroleum refining industry such as crude oil distillation, hydrotreating,
reforming, isomerization, etc.
Fractional Distillation
Fractional distillation is used to separate mixtures in which the components' volatility is nearly
identical and cannot be separated by simple distillation. A fractioning column is used to perform
numerous vaporization-condensation operations. To boost the purity of the product, we add some
of it to the distillation. This is referred to as correction. The plates in the fractionating column are
positioned so that the compounds with the lowest boiling points are at the top and those with the
highest boiling points are at the bottom. A succession of compounds are separated one by one at
the same time.
The basic principle of this type of distillation is that different liquids boil and evaporate at
different temperatures. So when the mixture is heated, the substance with lower boiling point
starts to boil first and convert into vapors.
A common example of fractional distillation in industries is the separation of various
components of crude oil. Crude oil normally contains substances such as paraffin wax, gasoline,
diesel, naphtha, lubricating oil and kerosene. The distillation process helps in separating these
components effectively.
Steam Distillation
The heat-sensitive components that disintegrate at high temperatures are separated via steam
distillation. Steam is created by boiling water at a lower temperature, allowing the compounds to
boil at a lower temperature. The temperature-sensitive chemicals are isolated in this manner
before breakdown. As with other forms of distillation, the vapours are collected and condensed.
The resultant liquid consists of two phases, water and compound, which is then purified by using
simple distillation.
An example of steam distillation is used to obtain essential oils and herbal distillates from
several aromatic flowers/herbs.
Vacuum Distillation
For separating mixtures of liquids with extremely high boiling points, vacuum distillation is
ideal. By lowering the surrounding pressure, vacuum distillation can be carried out without
heating the mixture. Because the pressure is reduced, the component can boil at lower
temperatures. The component is transformed to a vapor when its vapor pressure equals the
ambient pressure. The distillate is made by condensing the vapors and collecting them. High-
purity samples of chemicals that degrade at high temperatures are also obtained using the
vacuum distillation method. When a compound's typical boiling point is higher than its
breakdown temperature, vacuum distillation comes in handy.
Vacuum distillation is mostly used in pharmaceutical and chemical industry
Azeotropic Distillation
Azeotropic distillation is a type of distillation in which certain components are added to the
mixture to improve separation. Constant boiling distillation is the name given to azeotropic
distillation. Because the components to be separated have nearly identical boiling points,
separation is challenging. To circumvent this, an entertainer is added to the distillation column,
causing one of the components to dissolve in it and the remaining components to be separated.
The principle of azeotropic distillation is to introduce a new material into a mixture in order to
increase the relative volatility of one of the two components, allowing separation.
For example, production of ethanol in ethanol-water mixture by adding benzene as a third
component.
Extractive Distillation
Extractive distillation is a method of separating two substances with comparable boiling points
by adding a third material to change one of the compounds' boiling point, making it easier to
separate them.
The addition of a third, miscible, high-boiling-point solvent to the mixture changes the
volatilities of the components. These components are then heated to vaporisation and cooled in a
condenser by the action of cold water.
One of the major applications of extractive distillation in the petrochemical and refining industry
is the recovery of aromatic hydrocarbons.
Industrial Application of Distillation
Following are the industrial applications of Distillation

1. Distillation of Crude Oil

Crude oil is made up of hundreds of different liquid hydrocarbons. Many other
hydrocarbons are dissolved in it, some of which are solids and some of which are gases.
The oil is distilled into liquid fractions with distinct boiling point ranges at refineries,
where it is then further processed.
The crude oil is heated in a furnace (about 650 K) and the vaporised mixture is fed into a
fractionating tower with a height of 25-100 m and a daily capacity of around 40 000 m3.
The column may have 40-50 steel'sieve trays,' which fit horizontally across the column
and are designed to ensure that the falling liquid created by condensation and the
ascending vapour are intimately mixed. The trays contain holes in them ('the sieve')
through which the vapour rushes up into the liquid collected on the trays to achieve this
intimate contact.

The tower has a temperature gradient, with the top being cooler than the bottom. The
ascending vapour partially condenses when it reaches a tray containing liquid at a
temperature below the vapor's boiling point (bp). The dissipated latent heat from some of
the vapour condensing to a liquid heat more liquid, and the more volatile components of
the liquid evaporate, joining the remaining vapour and passing up the tower. The less
volatile liquid runs across the tray and into the tray below via a pipe.

In each tray, this process continues, with the least volatile vapour components condensing
and the most volatile vapour components evaporating. As a result, each tray contains
items with a very narrow range of boiling points (referred to as a 'close cut' of products).
Low relative molecular mass constituents (high bp) accumulate near the top of the tower,
while low relative molecular mass products (low bp) accumulate near the bottom.
 The crude oil residue with a high boiling point is then transported to another column and
distilled under vacuum; the lower the pressure, the lower the boiling point, and the
constituents condense at temperatures below their decomposition temperature.
Lubricating oils and waxes are produced as a result of this procedure. Bitumen is the
ultimate product of the process.

2. Steam Distillation for production of Essential Oil

The most common method for extracting and isolating essential oils from plants for use
in natural products is steam distillation. This occurs when steam vaporises the volatile
compounds in the plant material, which then condense and accumulate.

Steam is added to a huge container called a still, which is usually made of stainless
steel and holds the plant material.

Steam is pumped through an input into the plant material containing the desired oils,
releasing the aromatic molecules of the plant and turning them into vapour.
 The vaporised plant chemicals make their way to the Condenser or the condensation
flask. Two different pipes allow hot water to escape and cold water to enter the
Condenser in this location. As a result, the vapour cools and returns to a liquid state.

The fragrant liquid by-product drips from the Condenser and accumulates in a
separator beneath it. The essential oil floats on top of the water since water and oil do
not mix. It is syphoned off from here.

Complex Engineering Problem in Distillation

Distillation columns are the most common piece of equipment used in the chemical processing
sector to separate organic compounds. Typically, the distillation tower does not operate
independently; it is linked to upstream and downstream equipment to form a complete process
system. As a result, the better the distillation column works, the better the entire system
performs.
Major problems bottlenecking the distillation process include
1. Fouling
2. Weeping
3. Flooding
 4. Foaming

1. Fouling:
Fouling is described as an accumulation of undesirable particles on a solid's surface that reduces
the rate of heat transfer. Depending on the type of the fouling agent, it can be caused by
microorganisms known as biofouling, inorganic or organic fouling. Fouling reduces the flow
through pipes and channels, resulting in increased energy consumption. Depending on the size of
the pollutants, fouling is characterized as macrofouling or microfouling.

Methods to control fouling

a) Keeping fouling materials out of column

Fouling is defined as an accumulation of unwanted particles on the surface of a
substance that slows heat transfer. Microorganisms classified as biofouling, inorganic
fouling, or organic fouling can induce fouling depending on the type of fouling agent.
Fouling lowers the flow of water through pipes and channels, increasing energy
consumption. Fouling is classified as macrofouling or microfouling depending on the size
of the pollutants.
b) Process control to avoid fouling
Fouling can be avoided with good process control. In order to avoid fouling,
process control is required if the feed has degraded or is of poor quality. This can be both
inefficient and costly. For product optimization, the highest quality product with the least
amount of energy usage is required.
c) Use of anti-fouling agents
Anti-fouling compounds may be utilised in various cases. These are widely used
in the manufacturing of olefins. They function by preventing the fouling-causing
polymerization process.

2. Weeping
A reduction in vapour flow will result in a reduction in separation efficiency. As a result,
the overall pressure inside the column drops, making it difficult to keep the liquid in place. As a
result, liquid will begin to seep through the perforations. Weeping is the word for this
phenomenon. Excessive weeping would result in liquid pouring at the bottom of the column,
requiring the column to be restarted.

Control of weeping in distillation column

Weeping is caused by a shortage of heat in the column, which can be controlled by using the
reboiler to provide extra heat to the column. The difficulty can be mitigated by maintaining a
steady vapor flow rate.
3. Flooding
Flooding happens when a large amount of liquid accumulates inside the distillation column.
Excessive vaporization of the bottom liquid in a distillation column causes liquid entrainment in
the downcomer. As a result, the liquid holdup on the plates increases, resulting in a downcomer
flooding problem. If the flooding persists, the liquid may be driven out of the column's top.
Puking is the medical term for this ailment. The separation effectiveness of the column is
significantly lowered depending on the degree of flooding. Flooding in a distillation column is
indicated by an increase in differential pressure and a decrease in separation efficiency.

Methods to eliminate flooding

Flooding can be controlled by
 Lowering of feed rate
 Decreasing liquid concentration in the liquid
 Lowering of reflux ratio
 Reducing reboiler steam to decrease to decrease vapor concentration

4. Foaming
Foaming in distillation columns occurs when a liquid expands due to the passage of air or gas,
resulting in a high interfacial liquid vapor contact. Foaming can cause a build-up of liquid on the
trays. Foam formation is primarily influenced by the physical qualities of the liquid, but it can
also be influenced by tray design and circumstances. Corrosion inhibitors can also cause
foaming. Foams are also stabilized by suspended particles and polymers.
Control:
Foaming can be controlled by using foam inhibitors which are mainly liquid but some solids like
wax and soaps can be used.

Numerical Problem
A distillation column receives a feed that is 40 mole % n-pentane and 60 mole % n-hexane. Feed
is saturated liquid at 2,500 lbmol/hr. The column is at 1 atm. A distillate that is 97 mole % n-
pentane is desired. A total condenser is used. Reflux is a saturated liquid. The external reflux
ratio is L0/D = 3. Bottoms from the partial reboiler is 98 mole % n-hexane. Determine the
number of equilibrium trays and their compositions for the stripping section.
Data: Vapor pressure, Psat, data: ln Psat = A − B/(T + C), where Psat is in kPa and T is in K.
Compound A B C
n-pentane 13.9778 2554.6 -36.2529
n-hexane 14.0568 2825.42 -42.7089
Solution:
Overall material balance over the entire tower gives
D + B = 2,500
Material balance for n-pentane over the entire tower gives
0.97D + 0.02B = (0.4)(2,500) = 1,000 ⇒ 0.97(2,500 − B) + 0.02B = 1,000
Solving for B and D from the above equations we have B = 1,500 lbmoles/hr and D = 1000
lbmoles/hr.

Since the column has a partial reboiler, the vapor composition yB is determine from the
equilibrium curve at xB = 0.02. The equilibrium curve y versus x for n-pentane and n-hexane
system is plotted in Figure E-2 where x and y are the mole fraction of n-pentane in the liquid and
vapor phase, respectively. At x = xB = 0.02, y = yB = 0.053. We can also perform a bubble point
temperature calculation with x = xB = 0.02.

We start with the equation y1 + y2 = 1 (E-1)

Substituting yi = xiPi sat/P into equation (E-1) yields
x1P1 sat + x2P2 sat = P (E-2)
With the numerical values for mole fractions and pressure, equation (E-2) becomes
.02exp(13.9778− 2554.6/(T − 36.2529)) + 0.98exp(14.0568 − 2825.42/(T − 42.7089)) = 101.325 (E-3)

The bubble point temperature should be between the boiling points of n-pentane and n-hexane
given by
Solution of Eq. E-3 is given by

T = 340.9753
The bubble point temperature of the n-pentane and n-hexane mixture is 340.9753 K. At this
temperature, the vapor pressure of n-pentane is
P1 sat = exp(13.9778 - 2554.6/( 340.9753 - 36.2529)) = 268.9249 kPa
The mole fraction of n-pentane in the vapor stream leaving the reboiler is then

The liquid composition leaving tray N, xN, is then solved from the operating line,

We need to determine the liquid and vapor flow rates L and V , respectively, for the operating
line. Since the external reflux ratio R is 3,
we have L = 3D = (3)(1000) = 3000 lbmoles/hr
The vapor flow rate in the rectifying section is then V = L + D = 3000 + 1000 = 4000 lbmoles/hr

Making materials balance over the feed plate gives

V/ = V = 4000 lbmoles/hr
L/ = L + F = 3000 + 2500 = 5500 lbmoles/hr
The mole fraction of n-pentane in the liquid stream leaving plate N is then
Next yN is determined from the equilibrium curve and xN-1 is determine from the operating line

This process continues until xm > xF