UNIT – 4

DISTILLATION - II

Introduction to Multistage and Advanced Distillation

In the field of chemical engineering, distillation is one of the primary unit operations used for
separating mixtures of liquids based on differences in boiling points. When dealing with
complex mixtures or when higher efficiency is needed, multistage distillation and advanced
distillation techniques are employed. These methods extend the basic principles of distillation
to optimize separation, energy consumption, and product purity.

1. Multistage Distillation
Multistage distillation refers to the use of multiple distillation stages (or columns) to
progressively separate the components of a mixture. The stages are designed to increase the
efficiency of separation, especially when dealing with mixtures that have close boiling points
or when a high level of purity is required.

Types of Multistage Distillation:

Fractional Distillation: Fractional distillation is a type of multistage distillation in which the
mixture is separated into fractions, each containing a different range of boiling points. The
process is performed in a distillation column, which is packed with materials (such as structured
or random packing) or equipped with trays that allow vapor and liquid to interact multiple
times, promoting separation.

Distillation Column: The key component of multistage distillation is the distillation column,
which provides the necessary surface area for vapor and liquid phases to come into contact.
Each contact point between vapor and liquid allows for a partial separation of the mixture.
Tray Columns vs. Packed Columns: A distillation column can either have trays (for liquid-
vapor separation) or packing (for more efficient mass transfer). Tray columns have discrete
stages where the liquid is partially vaporized and condensed, whereas packed columns use
continuous interaction between the liquid and vapor phases in a packed bed, improving
efficiency and reducing capital costs.
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Process Design:
Reboiler: A heat source at the bottom of the column that provides the necessary heat to vaporize
the liquid mixture.
Condenser: A cooling system at the top of the column that condenses the vapor back into liquid
form.
Benefits of Multistage Distillation:
Improved Separation Efficiency: Each additional stage improves the separation of components,
especially when the differences in boiling points are small.
Better Control over Purity: By adding more stages, chemical engineers can more precisely
control the composition of the top and bottom products.
Handling Complex Mixtures: For mixtures with more than two components, multiple
distillation columns can be used in series to achieve the desired purity of each fraction.
2. Advanced Distillation Techniques
As chemical processes become more complex and the need for energy efficiency and high-
purity products increases, more advanced distillation techniques have been developed to
overcome limitations in traditional multistage distillation. These techniques include methods
such as vacuum distillation, azeotropic distillation, pressure-swing distillation, short-path
distillation, and dividing-wall columns.

A. Vacuum Distillation
Principle: Vacuum distillation reduces the pressure inside the distillation column, lowering the
boiling points of the components in the mixture. This technique is particularly useful for heat-
sensitive materials that decompose at high temperatures.
Applications: It is commonly used for the separation of high-boiling point substances, such as
in the refining of crude oil or the production of solvents and fragrances.
B. Azeotropic Distillation
Principle: Azeotropic distillation is used when a mixture forms an azeotrope, a constant-boiling
mixture where the vapor composition is identical to the liquid composition, preventing
separation by simple distillation. To break the azeotrope, an additional substance (often called
an entrainer) is added to the mixture to form a new azeotrope with one of the components,
allowing separation.
Applications: Commonly used in alcohol dehydration, such as in the production of anhydrous
ethanol.
C. Pressure-Swing Distillation
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Principle: This technique involves varying the pressure during the distillation process to
optimize separation. By changing the pressure, the relative volatility of components can be
manipulated, which allows for better separation of close-boiling mixtures.
Applications: Pressure-swing distillation is particularly useful in the separation of gases and is
often used for natural gas processing or in air separation units.
D. Short-Path Distillation
Principle: Short-path distillation involves reducing the distance that vapor travels before
condensing, which can significantly reduce the energy required for the distillation process. It
is often used when separating substances with very close boiling points or when distilling high-
boiling-point compounds at low pressures.
Applications: It is commonly used in the pharmaceutical industry for purifying sensitive
compounds or for distilling high-boiling, heat-sensitive oils.
E. Dividing-Wall Columns (DWC)
Principle: A dividing-wall column is an advanced configuration of distillation columns that
contains a vertical wall that divides the column into multiple sections. This design enables
multiple separations in a single column, effectively combining the functions of several
distillation columns into one unit. The dividing wall reduces the number of required stages and
improves the overall efficiency of the process.
Applications: Widely used in petrochemical refining, particularly in the separation of
hydrocarbons in the production of fuels and chemicals.
F. Reactive Distillation
Principle: Reactive distillation is a combination of distillation and chemical reaction in the
same unit operation. In this process, the reaction occurs while the components are being
separated by distillation, often involving the production of products like ethers, esters, or other
fine chemicals.
Applications: It is often used for esterification, transesterification (such as biodiesel
production), and acid-catalyzed reactions.
3. Advantages and Challenges of Advanced Distillation
Advantages:

Higher Separation Efficiency: Advanced techniques like dividing-wall columns and azeotropic
distillation can achieve greater separation with fewer stages and less energy consumption.

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Multistage distillation tower
A multistage distillation tower (or distillation column) is a key piece of equipment used in
separating mixtures based on differences in boiling points. It is designed to carry out the
fractionation of liquids into various components by utilizing multiple stages (or trays/plates) to
achieve the required separation.

Here are the key characteristics of a multistage distillation tower:

1. Multiple Stages (or Trays/Plates)

Stages: A distillation column has multiple stages where liquid and vapor phases are in contact.
Each stage represents a vaporization-condensation cycle, and the separation of components
becomes progressively more refined as the vapor moves upward through the column.
Trays (or Plates): In tray columns, each stage is represented by a tray that holds liquid. The
liquid partially vaporizes, and the vapor rises to the next tray. The trays can be sieve trays,
valve trays, or bubble-cap trays, depending on the design.
2. Vapor-Liquid Equilibrium
The principle behind a multistage distillation column is the vapor-liquid equilibrium (VLE).
As the vapor rises through the column, it becomes enriched in the more volatile component
(the component with a lower boiling point), while the liquid descending the column becomes
enriched in the less volatile component.
Contact between phases: Vapor rises through the column, and as it meets the cooler liquid
descending the column, part of the vapor condenses into liquid. The interaction between the
rising vapor and descending liquid leads to mass transfer, which results in separation.
3. Column Design:
Height: The number of stages is directly related to the height of the column. A taller column
allows for more stages and better separation of components, especially when the difference in
boiling points between the components is small.
Diameter: The diameter of the column is designed to handle the flow rates of both vapor and
liquid. It is sized to minimize pressure drop while ensuring that there is enough space for the
vapor and liquid to flow without excessive flooding or channeling.

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Internal Structures: The column may be packed (in the case of packed columns) or have trays
(in tray columns) to facilitate the contact between vapor and liquid. These internals are
designed to maximize mass transfer efficiency and minimize pressure drop.

4. Reboiler and Condenser

Reboiler: The bottom of the column is equipped with a reboiler, which provides the necessary
heat to vaporize the liquid feed. The reboiler supplies the latent heat of vaporization to drive
the distillation process, and it helps maintain the necessary temperature gradient within the
column.
Condenser: At the top of the column, a condenser cools the vapor, causing it to condense back
into liquid form. The condensed liquid can then be withdrawn as a distillate product. In some
designs, the condenser also returns a portion of the condensed liquid back to the column as
reflux, which helps improve separation.
5. Reflux
Reflux Ratio: The amount of liquid returned to the column as reflux is a critical factor in the
distillation process. A higher reflux ratio generally leads to better separation, but it also
increases energy consumption. The reflux increases the interaction between the vapor and
liquid phases, thus improving the purity of the products.
The reflux ratio can be adjusted to optimize the distillation process for a particular separation
task. Too little reflux results in poor separation, while too much reflux can lead to unnecessary
energy consumption.
6. Vapor and Liquid Flows
The vapor flow rises through the column, carrying the more volatile components with it.
The liquid flow moves downward, and as it flows down the column, it becomes richer in the
less volatile components. The liquid and vapor streams are in continuous contact, allowing for
the exchange of mass and energy.
7. Pressure Profile
Pressure Gradient: There is a pressure gradient within the column, with higher pressure at the
bottom (near the reboiler) and lower pressure at the top (near the condenser). The pressure
profile is essential for controlling the boiling and condensation of the components.
Pressure Drop: The design of the column must account for pressure drop (due to friction, vapor-
liquid resistance, etc.), which can reduce the efficiency of the column. Minimizing pressure
drop while ensuring adequate separation is a key aspect of column design.
8. Separation Efficiency
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The efficiency of the multistage distillation column is determined by the number of stages and
the quality of internal structures (such as trays or packing). The number of theoretical stages
represents the number of equilibrium stages required to achieve the desired separation.
Murphree Efficiency: This is a measure of the actual efficiency of a stage compared to its ideal
(theoretical) efficiency. It is affected by factors like tray design, vapor flow rates, and column
flooding.
9. Thermal Gradients
Temperature Profile: A distillation column typically has a temperature gradient, with higher
temperatures at the bottom (near the reboiler) and lower temperatures at the top (near the
condenser). This temperature gradient facilitates the separation of components based on their
boiling points.
10. Capacity
The capacity of a distillation column is a function of both the liquid and vapor flow rates. The
column must be designed to handle the throughput of the mixture being distilled. The capacity
is also influenced by factors such as the size of the trays or packing, the vapor-liquid mass
transfer rates, and the column diameter.
11. Feed Stage
The feed stage is the location in the column where the mixture is introduced. The optimal
placement of the feed is crucial to achieving efficient separation. In a multi-component
distillation, the feed may be introduced at a specific location to maximize the separation of
components.
12. Product Withdrawal
The distillation column is designed to allow for the withdrawal of different products at various
points:
Distillate (top product): The more volatile components are collected at the top of the column.
Bottoms (residue): The less volatile components are collected at the bottom of the column.
Side Draws: In some cases, intermediate products may be withdrawn from the middle of the
column at specific stages.
13. Energy Efficiency
Energy consumption is a key concern in the design and operation of distillation columns. The
reboiler and condenser are major consumers of energy, and optimization of the energy balance
between them is essential for improving overall process efficiency.
Energy integration techniques, such as using heat exchangers or thermally coupling columns,
can help reduce energy usage.
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14. Control and Automation
Distillation towers are often equipped with control systems to regulate important parameters
such as pressure, temperature, flow rates, and reflux. Modern distillation columns are
frequently automated to optimize the process and ensure consistent product quality.

Ponchon–Savarit Method
There are two methods by which the design of the continuous fractionator can be established.
Let us first consider Ponchon–Savarit method where it requires both enthalpy and
concentration data.
Envelope I: Condenser section Envelope II: Full distillation unit Envelope III:
Enriching/Rectifying section Envelope IV: Stripping/Exhausting section
The numbering of plates or trays is accounted from the top to bottom. Suffix denotes the
properties of streams leaving a particular plate or tray. Let n and m, denote general plates in
the enriching section and stripping section respectively. Let G be the molar flow rate of vapour
in enriching section, G the molar flow rate of vapour in stripping section, L the molar flow rate
of liquid in enriching.
section, L the molar flow rate of liquid in stripping section, HG the Enthalpy of vapour, HL the
Enthalpy of liquid, y the mole fraction of more volatile component in vapour and x the mole
fraction of more volatile component in liquid. Let R be the external reflux ratio L0/D, QC the
load on condenser, QB the heat supplied in reboiler and QL the total heat loss.

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McCabe–Thiele Method
When systems exhibit ideal behaviour, the time-consuming Ponchon–Savarit method of
determining the number of ideal stages, can be replaced with the following technique. Let us
begin our analysis by considering enriching section for total condensation of distillate as shown
in Fig. 9.18

Assuming the application of equimolar counter diffusion, i.e. the molar flow rates are assumed
to be constant for both the vapour and liquid steams irrespective of the stages, we get

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Steps involved in the determination of number of trays
The equilibrium curve along with the operating lines for both enriching and stripping sections
to determine the number of stages is shown in Fig. 9.22.

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1. Draw the equilibrium curve and diagonal.
2. Locate F, D and W corresponding to feed, distillate and residue compositions based on more
volatile component.
3. Estimate xD/(R + 1) and locate it on y-axis as S.
4. Join SD, this is the operating line for enriching section.
5. From F draw q-line depending on feed condition. Let it cut the operating line for enriching
section at T.
6. Join TW-operating line for stripping section.
7. Construct stepwise from D to W and the steps so constructed will give the number of stages.

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REFLUX RATIO
It is one of the important operating parameters in distillation, by which the quality of the
products can be changed. Let us deal with the relationship between reflux ratio and the
number of trays in the tower.
Determination of Minimum Reflux Ratio

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Total Reflux

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Optimum Reflux Ratio

At minimum reflux ratio the column requires infinite number of stages or trays. However, as
reflux ratio increases from minimum, for a given feed and specified

AZEOTROPIC DISTILLATION
This is a technique which is used for the separation of binary mixtures which are either difficult
or impossible to separate by ordinary fractionation. This happens when either the mixture to be
separated has a very low relative volatility, in which case one may require high reflux ratio and
more number of trays, or when the
mixture forms an azeotrope. Under such circumstances, a third component called an ‘entrainer’
is added to the binary mixture to form a new low boiling heteroazeotrope with one of the
components in the original mixture whose volatility is such that it can be separated from the
other original constituent. A typical example for this operation is presented in the flow diagram
of Fig. 9.31 where the separation of acetic acid (BP: 118.1°C) and water (BP: 100°C) mixture
is demonstrated. This mixture has a low relative volatility and hence separation by conventional

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methods is not economical. Here Butyl acetate, which is slightly soluble in water, is added to
the mixture from the top of the column as an entrainer. It forms a ‘hetero-azeotrope’ with all
the water in the feed and readily distills out from the high boiling acetic acid and the acetic acid
leaves as a residue product. The hetero-azeotrope on condensation forms two insoluble layers
which can easily be separated. The water layer obtained is saturated with ester and vice versa.
The ester layer saturated with water is returned back to the column as a source of entrainer for
further separation. The aqueous layer is also sent to another column to separate water and ester.
The separated ester is also sent back as entrainer. Sometimes the new azeotrope formed
contains all the three constituents. In the dehydration of ethanol water mixture, benzene is
added as an entrainer which gives a ternary azeotrope containing benzene (53.9 mole %), water
(3.3 mole %) and ethanol (22.8 mole %) boiling at 64.9°C as distillate and ethanol (BP: 78.4°C)
as residue. Benzene is separated and sent back to the top of the column as entrainer. Since water
– ethanol are equally present in distillate, the mixture should be given a preliminary
rectification to produce an alcohol rich binary azeotrope. Azeotropic distillation is shown in
Fig. 9.31.

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Desired Properties of an Entrainer for Azeotropic Distillation
(i) Should be cheap and easily available.
(ii) Chemically stable and inactive towards the solution to be separated.
(iii) Non-corrosive.
(iv) Non-toxic.
(v) Low latent heat of vaporization.
(vi) Low freezing point to facilitate storage and easy handling.
(vii) Low viscosity to provide high tray efficiency and minimum pumping cost.

EXTRACTIVE DISTILLATION
This method is also used under similar circumstances as in the case of azeotropic distillation.
Here a third component called solvent is added, instead of entrainer, which alters the relative
volatility of the original constituents, thus permitting the separation. The added solvent should
have low volatility and not vaporized in the fractionator. One such example is the separation

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of toluene (BP: 110.8°C) from isooctane (BP: 99.3°C). Their separation is relatively difficult.
In the presence of Phenol (BP: 181.4°C), the relative volatility of isooctane increases, so that
with an increase in phenol content, the separation becomes more and more easy. A typical flow
diagram of the process is shown in Fig. 9.32.

Here, the toluene–isooctane binary mixture is introduced in the middle of the column and
phenol near the top of the column. Isooctane is readily distilled as an overhead product, while
toluene and phenol are collected as residue. The residue from the tower is rectified in the
auxiliary tower to separate toluene and phenol as distillate and residue respectively. Phenol is
returned to the main column as solvent. Similarly a mixture of acetone (BP: 56.4°C) and
methanol (BP: 64.7°C) can be separated by using Butanol (BP: 117.8°C) solvent.

Desired Properties of Solvent for Extractive Distillation

(i) High selectivity and capability to alter VLE for easy separation. (ii) Ability to dissolve the
components in the mixture. (iii) Low volatility in order to prevent vaporization of solvent. (iv)
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Easy separability, for easier removal of solvent. (v) Non-corrosive. (vi) Non-toxic. (vii) Cheap
and easily available. (viii) Low freezing point. (ix) Low viscosity. (x) Chemical stability and
inertness towards the components to be separated.

COMPARISON OF AZEOTROPIC AND EXTRACTIVE DISTILLATION

In both the processes an additional external agent is added, which is undesirable. Solvent to
feed ratio in extractive distillation greater than 3 or 4 is found to be effective. Proper choice of
material of construction and recovery technique are to be examined. However, of the two,
extractive distillation is said to be more favoured than azeotropic distillation since (i) there is a
greater choice of solvent, (ii) the smaller quantity of solvent to be volatilized. In spite of the
above advantages, the azeotropic distillation is said to be more effective in the dehydration of
ethanol from an 85.6 mole % Ethanol–water solution. In this case water is azeotroped with n–
pentane and then separated rather than using extractive distillation with ethylene glycol as
solvent.

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