1/1/2023 UNIT OPERATION II

CHEMICAL ENGINEERING

CATUC BAMENDA
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GAS ABSORPTION

INTRODUCTION

In gas absorption, a gas phase contacts a liquid phase and mass is transferred from the gas phase to the liquid
phase (liquid solvent). Gas absorption refers to an operation in which a gas mixture is contacted with a liquid
to preferentially dissolve one or more soluble components of the gas mixture in the liquid. This unit
operation is also termed as scrubbing. The differences in solubility of gases in a given solvent are utilised to
effect such a separation. Gas absorption is the second most important mass transfer operation encountered in
the chemical industry and is used for the recovery or removal of the solute gas.

In absorption, the soluble component of a gas mixture is called as the solute gas, the insoluble component is
called as the inert gas or carrier gas and the liquid used for absorption purpose is called as the solvent or
absorbent. Under a given set of operating conditions, the volatility of the solvent used is very low, so it is
essentially immiscible in the gas phase. A typical example of gas absorption is the removal of ammonia from
a mixture of ammonia and air using water as a solvent. Here, since ammonia is soluble in water, air is almost
insoluble and water does not vapourise to an appreciable extent in the gas mixture at ambient temperature, the
only transfer is of ammonia from the gas phase to the liquid phase.

The reverse of absorption is called desorption or stripping. It is an operation in which a dissolved gas from a
solution (a liquid) is removed from the liquid by contacting it with an inert gas (i.e., a stripping medium).
Therefore, the removal of sulfur dioxide from flue gases by alkaline solutions is an example of absorption,
whereas the removal of the volatile components of oil by steam is an example of stripping. The absorption
may be a purely physical phenomenon - physical absorption, e.g., absorption of ammonia from a mixture of
ammonia and air by water or it may be accompanied by a chemical reaction (the transfer of a solute component
to the liquid phase and then reaction of this solute with a constituent of the liquid), e.g., absorption of NO2 in
water to produce nitric acid. Gas absorption is exothermic in nature, so this operation demands a cooling
provision and is normally carried out at low temperatures (since the solubility of a solute gas in a given solvent
is high at low temperatures).Though both the gas absorption and distillation operations can be carried out in
plate or packed columns, packed columns are very common for absorption.
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Condition of Equilibrium : Liquid-Gas :

The degree to which a gas is absorbed from a gaseous mixture by a liquid solvent is determined by its
partial pressure. Each dissolved gas exerts a definite partial pressure at a given temperature and concentration.
The gas is said to be slightly soluble when the partial pressure exerted by the dissolved gas from the solution
is higher, while it is said to be more soluble when the partial pressure exerted by the dissolved gas from the
solution of given concentration is lower. Thus, oxygen is slightly soluble, while ammonia is highly soluble in
water. With water as a solvent, ammonia is very soluble gas, sulphur dioxide is moderately soluble gas and
oxygen is slightly soluble gas.

A given quantity of liquid will dissolve any amount of a slightly or more soluble gas depending upon
the partial pressure of the dissolved gas in the gas phase in contact with the liquid. A slightly soluble (insoluble
gas) gas requires a higher partial pressure of the gas in contact with the liquid to yield the solution of a desired
concentration, while a very soluble gas requires very low partial pressure to give the solution of the same
concentration.

Equilibrium condition will be reached when the partial pressure of solute gas in the gas phase is equal
to its partial pressure from the liquid phase. The equilibrium condition thus fixes the upper limit for operation
of an absorption unit.
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The solubility of a gas (the concentration of a dissolved gas in the liquid at a given temperature and
pressure) is not substantially affected by the total pressure over the system but gets influenced by the
temperature. Generally, the solubility of a gas in a given solvent decreases with increase in temperature.

In a majority of cases, the gas absorption results with the evolution of heat and solubility falls off if
provisions are not made to remove the heat evolved. Usually adequate cooling arrangements are provided to
keep the temperature sufficiently low to achieve a good rate of absorption.

For dilute solutions of most gases, the equilibrium relationship is given by Henry's law:

Selection criteria for solvent in gas absorption :

While selecting a particular solvent for absorption operation, the following properties of the solvent are
considered:

1. Gas solubility:

The solubility of a solute gas in a solvent should be high, i.e., the solvent should have a high capacity for
dissolving the desired solute gas so that the less amount of the solvent will be required for a given absorption
duty. In general, for good solubility, a solvent of chemical nature similar to that of the solute to be absorbed
must be searched out and used. The solvent selected should have a high solubility for the solute to be absorbed.

2. Volatility :

As the gas leaving an absorption unit is generally saturated with the solvent, there will be a loss of the solvent
with the gas leaving the unit operation. Hence, to minimise the solvent loss (in the gas leaving), the solvent
should be less volatile, i.e., it should have a low vapour pressure under given operating conditions.

3. Corrosive nature :

The solvent should not be corrosive (as far as possible) towards common materials of construction so that the
construction material for an absorption equipment will not be too expensive.

4. Viscosity :

The solvent should have a low viscosity for rapid absorption rates, low pumping cost and better heat transfer.
The solvent should be non-viscous.

5. Cost and availability :

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The solvent should be cheap and readily available. Losses are less costly with the cheap solvent.

6. Miscellaneous :

The solvent should be non-toxic, non-flammable, non-foaming, and chemically stable from a handling and
storage point of view.

Material balances – One Component Transferred:

Consider a packed column as shown in Fig. 9.1. Let V1, V2 and V be the molal flow rates of the total gas at
the inlet (rich gas), outlet (lean gas) and at an arbitrary section in the column, respectively. Let y1, y2 and y
be the mole fractions of the solute gas at the respective stations.

Fig. 9.1 : Material balance diagram for Absorption tower

Let L1, L2 and L be the molal flow rates of the liquid (as a whole) at the outlet, inlet and at an arbitrary
sections, respectively and x1, x2 and x be the mole fractions of the solute gas in the liquid at the respective
stations. Also let V' and L' be the molal flow rates of the inert (insoluble) gas and the non-volatile solvent
(solute free solvent), respectively through the

column.

The overall material balance over the control surface 'A' of Fig. 9.1 gives

V1+ L = L1+ V … (9.2)

Material balance of the solute component over the control surface A of Fig. 9.1 :

V1 y1 + L x = L1 x1 + V y … (9.3)

The overall material balance over the entire column is

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V1+ L2 = V2+ L1 … (9.4)

The material balance of the solute over the entire column is

V1 y1 + L2 x2 = L1 x1 + V2 y2 … (9.5)

where y is the mole fraction of the solute in the gas phase

and (1 – y) is the mole fraction of the inert gas in the gas phase

Therefore, … (9.6)

Similarly, (1 – x) be the mole fraction of the solute free solvent in the liquid phase.

(As in 1 mole of a gas mixture, there will be y moles of the solute gas and (1 – y) moles of the inert gas
(insoluble gas).

Equation (9.9) is the equation of the operating line for absorption operation in terms of mole fraction and
is a curve on x - y co-ordinates.

Equation (9.9) in terms of mole ratio is :

V' [Y1– Y] = L' [X1– X] … (9.10)

Equation (9.10) is the equation of the operating line for absorption operation. It is a straight line on x - y
co-ordinates with a slope equal to L'/V' and passes through point (X1, Y1). The line also passes through point
(X2, Y2).

Material balance of the solute gas component over the entire tower/column in terms of
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L', V' and mole ratios is :

V' [Y1 – Y2] = L' [X1 – X2] … (9.11)

Minimum Liquid Gas Ratio

Consider that the values of the terms V', Y1, Y2 and X2 are fixed by a process requirement and the value
of L' is decreased through the absorption tower. The operating line on X, Y coordinates passes through
the point (X2, Y2) and has a slope equal to L'/V'. As the liquid flow rate is decreased, the slope of the
operating line decreases (operating line shifts toward the equilibrium curve) and the exit liquid
composition (with respect to the solute) increases from X'1 to X"1 as indicated by line AC. A reduction
in the liquid flow rate reduces the driving force for mass transfer and absorption becomes more and more
difficult. Further reduction in the liquid flow rate leads to a situation wherein the upper end of the operating
line touches the equilibrium curve as indicated by line AD and the exist liquid composition is then in
equilibrium with the inlet gas. Thus, the driving force for mass transfer becomes zero at the bottom of the
tower, required time of contact for the desired concentration change becomes infinite, and an infinitely
tall tower is required. The value of L'/V' corresponding to this situation (corresponding to the line AD)
represents a minimum liquid-gas ratio. If tower is to operate practically, the liquid flow rate should be
greater than that corresponding to the minimum L'/V' ratio.

Low values of L'/V' ratio result into taller tower and hence there is an increase in the fixed cost but the
recovery cost of the solute will be low (due to small quantities of liquid). High values of L'/V' ratio result
into small tower due to favourable driving force, and hence, there is a decrease in the fixed cost but the
recovery cost of the solute will be higher. Therefore, while selecting L'/V' ratio, a balance must be made
between the fixed and the recovery costs. In general, the operating liquid flow rate for the absorber is
usually 1.1 to 1.5 times the minimum
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Pressure drop in packed columns :

In packed columns operated in a counter current fashion, the liquid fed at the top flows downward under the
influence of gravity/gravitational force and the gas fed at the bottom of the column is moved upward by a fluid
moving machinery such as a blower or fan. So as to maintain the upward flow of gas, pressure at the top must
be less than at the bottom. In packed columns since the same channels are available for liquid downflow and
gas upflow, the gas pressure drop is a function of both the phase flow rates and further its knowledge is must
as it is a important factor in the design of packed towers.

In randomly packed towers, the dependency of a gas pressure drop on the gas and liquid flow rates is
similar to that shown in Fig. 9.3 wherein the pressure drop per unit height of packed bed is plotted against the
superficial gas mass velocity (mass flow rate per unit empty tower cross-section) on logarithmic co-ordinates.

In case of dry packing (L = 0), the relationship between pressure drop and gas mass velocity is represented
by a straight line A indicating that the pressure drop is proportional to (V/A)1.8 – 2 which is consistent with a
usual law of fluid friction in turbulent flow. For wet packing, the relationship is indicated by a straight line B
similar to the line A (for dry packing) but for a given velocity, the pressure drop will be more than that for dry
packing. If in addition to gas flow, liquid flows down the tower at a fixed gas velocity, the pressure drop
increases with increased liquid flow rate (see lines C and D) as most of the free space in the packed bed gets
occupied by the liquid, i.e., the free cross-section available for the gas flow becomes smaller and smaller as
liquid flow increases.
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With liquid flowing down the tower at low and moderate gas velocities, the pressure drop is proportional
to 1.8 th power of the gas velocity but is greater than that for wet packing as liquid flow occupies part of the
free cross-section available for the gas flow. Upto point 'X' the amount of liquid held in packings is constant.
At point 'X', the gas flow begins to impede the downflow of liquid and the local accumulation of liquid appears
here and there in packings.

As the gas velocity increases further (beyond X upto Y), the liquid hold up progressively increases due to
which the free area for the gas flow becomes smaller and the pressure drop rises much more quickly (pressure
drop is proportional to 2.5 th power of the gas mass velocity over the X-Y section). At gas flow rates beyond
Y, the pressure drop rises very steeply for a given liquid flow rate. Point X is called as the loading point and
point Y is called as the flooding point. At a given liquid flow rate at point Y, a layer of liquid may appear at
the top of packings or inversion of phases may occur (the liquid becomes the continuous phase and the gas
becomes the dispersed phase) and the entrainment of liquid by the gas leaving the top of the tower increases
rapidly and tower is then said to be flooded. The gas velocity corresponding to the flooding conditions is called
as the flooding velocity.

The point at which the liquid hold up in the column starts to increase, as indicated by a change in the slope
of the pressure drop line, it is called the loading point.

From this point onward the present drop increases more rapidly with increase in gas velocity.

If tower is to operate practically, the operating gas mass velocity must be lower than the flooding velocity.
For safe operations, the packed towers are designed using gas velocities of about 50 to 70 per cent of the
flooding velocity at the expected liquid rate. This value corresponds to the one somewhere below the loading
point and thus, ensures stable operating conditions.

Gas Absorption Equipments :

Various gas absorption equipments used are :

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1. Mechanically agitated vessels.

2. Packed Columns/towers.
3. Plate Columns.
1. Mechanically agitated vessel :

It is usually used in a small scale industry. This unit gives performance equivalent to one theoretical stage.
It consists of a baffled vessel usually incorporating an open or disc flat blade turbine type agitator as it
maintains very large discharge velocities normal to the gas flow. Solvent liquid with a depth equal to the vessel
diameter is taken in the vessel and gas is introduced below the impeller through a ring shaped sparger under
agitation. Adequate free board is provided over the liquid level for the gas hold up during gas flow and
ultimately the unabsorbed gas leaves the top of the vessel. For a high absorption capacity, the operation is
carried out at low temperature and for maintaining it, a cooling coil is incorporated in the vessel. The diameter
of sparger is equal to or slightly less than that of the impeller and is arranged with holes (3 to 6.5 mm in
diameter) on top.

Deep vessels with usually two impellers are used when the time of contact required is relatively large,
wherein a large interfacial area is maintained by redispersing the gas bubble coalesced.

2. Packed Columns/Towers :
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Packed columns are most frequently used for gas absorption (and are used to a limited extent for
distillation) wherein the liquid is dispersed in the form of film and the gas flows as a continuous phase. These
are continuous contact equipments generally operated in a counter current fashion.

A packed column consists of a vertical cylindrical shell constructed out of metal, plastic, ceramic, etc. and
filled with suitable packings which offer a large interfacial area for gas-liquid contact for mass transfer between
the phases. A bed of the packing rests on a support plate which offers very low resistance to gas flow. It is
provided with a gas inlet and distributing space at the bottom, a liquid inlet and a liquid distributor at the top
and gas and liquid outlets at the top and bottom. A liquid solvent is introduced from the top through the liquid
distributor (which distributes the liquid on the packing), which irrigates/wets the surface of packing uniformly,
liquid trickles down the bed, and finally the liquid enriched in the solute to be absorbed called a strong liquor
(solute + solvent) leaves the bottom of the column. The liquid flow rate should be sufficient for good wetting
of packing. A solute-containing gas (rich gas) is introduced from the bottom of the tower and rise upward
through the interstices/open spaces in the packing counter current to the flow of the liquid. The lean gas (dilute
gas) leaves the column from the top of the tower. In case of tall columns/towers, liquid redistributors are used
to redistribute the liquid to avoid channeling of the same (flow the liquid along the wall).

Advantages of packed columns :

(i) Minimum structure (ii) low pressure drop (iii) low liquid hold-up (iv) handle corrosive liquids and
liquids that tends to foam (v) low initial investment and (vi) high liquid to gas ratios.
Disadvantages of packed columns :

(i) Relatively inflexible (ii) can not operate over wide ranges of either vapour or liquid rates per unit cross
section (iii) distribution of liquid is difficult (iv) can not handle dirty fluids that tend to deposit a sediment on
packings (v) can not be used where large temperature changes are occurred.
Packed columns are well suited for :

1. Small diameters
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2. Handling highly corrosive fluids.

3. Handling liquids that tend to foam.
4. Operations where it is important to have a low pressure drop and low liquid hold up.
Tower Packings :

Many types of packings are in use ranging from simple to complex geometric shapes.

Packings are made of ceramics, metals and plastics and vary in size from 6 to 75 mm.

Characteristics of a Tower Packing :

1. It should provide a large interfacial area for phase contacting., i.e., it should have a large wetted
surface area per unit volume of packed space for high efficiencies.
2. It should provide a large void volume or empty space in the packed bed so that reasonable
throughputs of the phases are handled without excessive pressure drop.
3. It should possess good wetting characteristic.
4. It should have a high corrosion resistance.
5. It should be relatively cheap/inexpensive.
6. It should have a low bulk density so that the weight of the entire packed bed is low which thereby
reduces serious support problems.
7. It should possess enough structural strength.
8. It should be chemically inert to the fluids handled in the tower.
Types of packings :

In order to obtain the efficient gas-liquid contact, many different types of packings are available ranging
from simple to complex geometrical shapes but are generally classified as random packings and regular
packings. If the packings are simply dumped into the tower during installation and fall in a random fashion
(the individual pieces are not arranged in any particular pattern), they are called random packings. The
packings arranged in a particular pattern are called stacked packings.

In case of randomly packed installations for obtaining the high and uniform voidage and preventing
breakage, a tower is first filled with liquid (usually water) and packings are then dumped into it. Most common
random packings used in industrial towers are Raschig rings, Pall rings, Hy-pak, Berl saddles, Intalox saddles,
Super intalox saddles, etc. As Pall rings,
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and Intalox saddles permit a more economical tower design they are replacing older Raschig rings and Berl
saddles. Pall rings are made out of metal or plastic (poly propylene) and have the same general form as Raschig
rings with height equal to diameter, however portions of the original cylinder wall are cut with the projections
bent inward leaving holes in the wall. They are generally available in sizes ranging from 16 to 50 mm (5/8 to
2 in).

Berl saddles and Intalox saddles are available in range 6 to 50 mm and are formed out of plastic or ceramics.
They provide more gas-liquid contacting area than the Raschig rings.

Raschig rings are hollow cylinders with their length equal to outside diameter and usually formed out of
ceramic, carbon and metal. They are generally available in a size ranging from 6 to 100 mm 4 to 4 in . They
are simple in construction and relatively cheap as compared to other packings. When a single web is added to
the inside of the Raschig ring, the packing is called Lessing ring and when a cross web is added to the Raschig
ring, then the packing formed is called cross partition ring. Added webs provide additional active surface.
They are normally available in a size ranging from 75 to 150 mm (3 to 6 in) and usually used as stacked
packings. Stacked packings offer lower pressure drops for the gas than random packings for equivalent phase
flow rates.
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Channeling in Packed Columns :

The tendency of the liquid to segregate towards the walls of a packed column and to flow along
the walls (a region of the greatest void space) is termed as channeling, which leads to low mass transfer
efficiencies. Thus, with a good initial liquid distribution in randomly packed columns, channeling can be
minimised by providing a tower diameter to packing size ratio greater than 8, i.e., the diameter of the tower
should be at least eight times the packing size (or the packing size smaller than at least one-eighth of the tower
diameter).

In packed columns, the region of greatest void space is the region near the wall of the column since the
packing material cannot nest tightly with the plane wall as it does with itself. It is a natural tendency for the
fluid to move toward the region of greatest void space during its flow.

Height Equivalent to an Equilibrium stage (Theoretical Plate) :

The height equivalent to a theoretical plate (HETP) is the height of a section of packing that will give
the same separation as that achieved with one theoretical plate. The HETP is determined
experimentally and is characteristic of each packing. It depends upon the type and size of the packing, flow
rates of fluids and concentration. The height of a packed column (i.e., the height of packing) required to effect
a given degree separation is calculated by multiplying the number of theoretical plates required to achieve the
same degree of separation by HETP.

Liquid distribution :

For maximum active surface area, the packing should be wetted completely by the descending liquid and
this can be achieved by its proper distribution. For efficient column operation, uniform distribution of the
liquid at the top of the packed bed is essential. A liquid distributor is a device that spreads the liquid uniformly
across the top of the packing. Several types of liquid distributors used are : (1) Perforated pipe distributor; (2)
Orifice-type distributor; (3) Trough-type distributor; and (4) Weir-riser distributor.

In packed columns, the packing support must be sufficiently strong as it carries the weight of the entire
packed bed and at the same time it must have a large free area for passage of the gas and liquid phases so as
to offer a very low resistance to flow of the phases.
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Relative merits of plate and packed towers/columns :

The selection of a particular kind of contactor-plate or packed tower for a given mass transfer operation,
generally rests on the cost and profit considerations but in many cases the choice can be made on the basis of
quantitative analysis of relative merits and demerits of the plate or packed tower. For selecting the right type
of contactor for a given mass transfer duty, the following merits and demerits should be considered.

1. Plate columns operate over a wide range of liquid flow rates without flooding.

2. Plate columns by repeatedly mixing and separation provide a more positive contact between fluid
phases, whereas packed columns may lead to backmixing or by passing.
3. Because of the difficulties arising in the dispersion of liquid in a packed tower, a plate tower is more
reliable and needs less safety factors at low liquid to gas mass velocity ratios.
4. Side streams are very easily taken out from plate towers.
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5. For plate towers, design information is generally more readily available and it is more reliable than it
for packed towers.
6. Whenever liquid mixtures containing dispersed solids are to be handled, plate towers should be
preferred as cleaning of the plate is very easy.
7. Whenever intermediate cooling arrangement is required to remove the heat of a solution or reaction,
plate towers are preferred. Cooling coils are easily incorporated in plate towers.
8. For a given duty, the total weight of a dry plate tower is normally less than the weight of a packed
tower but weight of both towers is approximately the same if the liquid holdup in the plate tower during
the operation is taken into account.
9. For a column diameter more than 1200 mm, packed towers are seldom designed and for a column
diameter less than 600 mm, packings are cheaper than plates.
10. For liquids having tendency to foam, packed towers are usually preferred.
11. High values of liquid-gas ratio are best handled in packed towers.
12. Liquid hold-up is considerably low in packed towers so they are used in cases where liquid
deterioration might occur with high temperatures (i.e., used for handling heat-sensitive liquids).
13. The pressure drop through a packed tower is usually low which makes the packed tower particularly
desirable for vacuum distillation operations.
14. Packed towers may be more economical than plate towers when highly corrosive fluids are to be
handled because of corrosion resistant ceramic/plastic packings.
15. Plate towers are often preferred when large temperature changes are involved, as in distillation, thermal
expansion or contraction of the equipment component may crush the packing.
Packed columns and plate columns are the commonly used equipments for gas-liquid operations such as
distillation and gas absorption. They are also used for liquid extraction.

Comparison of packed column and plate column :

Packed columns are differential contactors wherein mass transfer occurs throughout the length of the
contactor and equilibrium is not reached at any point between the phases in contact, whereas plate columns
are stagewise contactors wherein mass transfer occurs intermittently/stagewise and equilibrium is established
between the phases at a number of discrete stages. In packed columns, packings are used as gas-liquid
contacting devices, whereas in plate columns, plates are used as gas-liquid containing devices. Design of a
packed column mainly involves the calculation of the height of transfer unit and number of transfer units
required to effect a given separation, whereas the design of a plate column involves the calculation of the
number of theoretical stages required to effect a given separation Constructionwise-packed columns are simple
in construction, whereas plate columns are complex in construction. Raschig rings, pall rings, berl saddles,
intalox saddles are the various types of packings used in packed columns, whereas bubble cap plate, sieve
plate and valve plate are the various types of plates used in plate columns.
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The selection of a particular type of equipment for gas-liquid operation in a particular situation will depend
upon many factors such as : efficiency, capacity, pressure drop, corrosion, hold up, cost, etc.

EXAMPLES
1. Ammonia from a ammonia-air mixture is to be absorbed in an absorption tower using water as a
solvent. Data for the absorption system is as follows :

Air flow rate – 200 kg/h

Liquid phase compositions :

At the top of packing – 0.000013 kg NH3/kg H2O

At the bottom of packing – 0.0006 kg NH3/kg H2O

Gas phase compositions :

At the bottom of packing – 0.0084 kg NH3/kg inert gas

At the top of packing – 0.0044 kg NH3/kg inert gas.

Calculate flow rate of water entering the absorption tower

2. Gas containing 2 % by volume solute A is fed to an absorption tower at a rate of 0.35 m3/s at 299 K
(26o C) and 106.658 kPa pressure, and 95 % of the original solute is removed by absorbing it in a
solvent B. Solvent containing 0.005 mole fraction of solute enters the tower at the top and the exit
liquid streams from the absorption tower contains 0.12 mole A per mole B. Find out the flow rate of
the solvent entering the absorption tower on solute-free basis.

LIQUID-LIQUID EXTRACTION
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The techniques of removing one component from a solid or liquid by means of a liquid solvent fall into
two categories, the first one is called as leaching or solid extraction and the second as liquid extraction.
Leaching is used to dissolve soluble matter from its mixture with an insoluble solid (Leaching is an operation
in which a particular component of the solid is leached out with the help of a solvent), whereas liquid
extraction is used to separate two miscible liquids using a solvent which preferentially dissolves one of them.
In this chapter, our discussion is restricted to liquid extraction – the extraction of the liquid phase with a
solvent.

When a mixture of liquids is not easily separable by distillation, i.e., when the separation by distillation is
ineffective or very difficult, liquid extraction is used. Close boiling mixtures or substances that cannot
withstand the temperature of distillation, even under vacuum [i.e., substances that are thermally unstable (heat
sensitive)] may often be separated by extraction. In this operation, a solvent is added to the liquid-mixture. As
a result, two immiscible layers are formed, both containing varying amounts of different components. The
isolated layers are then separated using density difference as extract phase and raffinate phase. For the recovery
of the solvent for re-use, extraction is followed often by distillation or evaporation.

Liquid-liquid extraction (liquid extraction) refers to an operation in which the constituents of a

liquid mixture are separated by contacting it with a suitable insoluble liquid solvent, which preferentially
dissolves one or more constituents. This operation is sometimes also termed as solvent extraction. Extraction
utilises the differences in solubility of constituents/components to effect a separation. In this operation, a solute
in a liquid solution is removed by contacting the solution with another liquid solvent. The solvent is relatively
immiscible with the solution. In liquid extraction, the feed solution to be handled represents one phase and the
solvent to be used to effect separation represents the second phase. In this operation, the two immiscible phases
in contact are both liquid and so is a liquid-liquid operation. The mass transfer of the solute (liquid) takes place
from the feed solution to the solvent phase.

Distillation and extraction both are used for separation of the constituents of a liquid mixture based on
relative merits/demerits of the individual methods.

Difference between distillation and extraction.

Distillation Extraction

1. Distillation/fractionation is an operation 1. Extraction is an operation in which the

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in which the constituents of a liquid constituents of a liquid mixture are

mixture are separated by using thermal separated by using an insoluble liquid
energy. solvent.

2. Distillation utilises the difference in 2. Extraction utilises the differences in

vapour pressures of different solubility of different components to
components at the same temperature to effect a separation.
effect a separation.

3. In distillation, relative volatility is used 3. In extraction, selectivity is used as a

as a measure of the degree of separation. measure of the degree of separation.

4. In distillation, a new phase is created by 4. In extraction, a new insoluble liquid

addition of heat. phase is created by addition of solvent to
the original mixture.

5. In distillation, mixing and separation of 5. In extraction, phases are hard to mix and
phases is easy and rapid. harder to separate.

6. Distillation/fractionation gives almost 6. Extraction itself does not give pure

pure products. products and needs further processing.

7. It does not offer more flexibility in the 7. It does offer more flexibility in the
choice of operating conditions. choice of operating conditions.

8. It requires thermal energy. 8. It requires mechanical energy (for

mixing and separation).

9. It needs heating and cooling provisions. 9. It does not need heating and cooling
provisions.

10. It is a primary choice for separation of 10. It is a secondary choice for separation of
the components of a liquid mixture. the components of a liquid mixture.

11. Extractive distillation is the extraction of 11. Liquid extraction is the extraction of the
the vapour phase with solvent. liquid phase with solvent.

Applications of Liquid Extraction :

Whenever separation by both distillation and extraction is possible, the choice is usually distillation
irrespective of heating and cooling requirements. In extraction, the solvent should be recovered for reuse and
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hence extraction is usually followed by distillation for the recovery of the solvent. This combined operation
is more complicated and more expensive than ordinary distillation. But whenever separation of the
components of a liquid mixture is very difficult or ineffective by distillation, extraction can be thought of as
an alternate process (alternative) to it (distillation).

Thus, (i) whenever very large amount of latent heats are required (as in the case with very dilute solutions
where water must be vaporised, the latent heats of organic liquids are substantially lower than that of water),
(ii) whenever we are dealing with a liquid mixture forming an azeotrope / close boiling mixtures and (iii)
whenever we are dealing with substances that are thermally degradable/heat sensitive, separation by
distillation is expensive, ineffective and difficult. In such cases, extraction is attractive and preferred. For
example, (i) Recovery of acetic acid from dilute aqueous solutions is done more economically by extraction
followed by distillation than distillation alone because of high latent heat of vaporisation of water (distillation
would be possible but extraction reduces substantially the amount of water to be vaporised) (ii) Long chain
fatty acids can be removed from vegetable oils economically by extraction with liquid propane than by a high
vacuum distillation technique. (iii) Separation of petroleum products are having approximately the same
boiling range. The separation of aromatics from lube oil fractions using furfural as a solvent and (iv) Recovery
of penicillin from the fermentation broth using butyl acetate.

Steps and terminology in Liquid Extraction :

A typical liquid-liquid extraction utilising the difference in solubilities of the components of a liquid
mixture may be consisting of the following steps :

1 Contacting the feed with a solvent.

2 Separation of the resulting phases, and
3 Removal / Recovery of solvent(s) from each phase.
In liquid-liquid extraction operation, the liquid solution and a insoluble solvent are brought into intimate
contact, the constituents of the liquid mixture are distributed between the phases resulting into some degree of
separation (which can be improved by a multistage contact), and then the phases are separated from one
another based on density difference. For example, acetone may be preferentially extracted from a solution in
water with the help of chloroform and the resulting chloroform phase is found to contain large part of acetone,
but little water.

In extraction operation, the solution which is to be extracted is called the feed and the liquid with which
the feed is contacted for the extraction of solute (i.e., to bring about the extraction) is called as the solvent.
The solvent lean, residual liquid solution from which solute is removed is called as the raffinate (also termed
as the raffinate phase/layer) and the solvent-rich product of the operation, containing the extracted solute, is
 20

called as the extract (also termed as the extract phase/layer). The extract phase contains the desired product
in a larger proportion.

Thus, if we contact a solution of acetic acid in water with a solvent such as ethylacetate, then the two
phases/layers will result. The extract (ester layer/organic layer) will contain most of the acetic acid in
ethylacetate with some water. While the raffinate (aqueous layer) will contain weaker acetic acid solution with
a small amount of ethylacetate. The amount of water in the extract and ethyl acetate in the raffinate depends
upon their solubilities into one another.

Distribution coefficient :

In dilute solutions at equilibrium, the ratio of the concentrations of the solute in the two phases is
called the distribution coefficient or distribution constant K. It is given by

K = CE/ CR

where CE and CR are the concentrations of the solute in the extract and the raffinate phases respectively.

The distribution coefficient can also be given in terms of weight fraction of the solute in the two phases
in contact at equilibrium.

K' = xE/xR

where xE is the weight fraction of the solute in the extract and xR is the weight fraction of the solute in the
raffinate.

Ternary Systems :

The addition of a new solvent to a binary liquid mixture yields different types of mixtures or systems.

i. The solvent may be completely immiscible with the feed solvent. This is the ideal case.
ii. The solvent may be partially miscible with the feed solvent, forming one pair of partially miscible
liquid. If A is the feed solvent, C is the solute and B is the extracting solvent, then C dissolves in A
and B completely while A and B dissolve only to a limited extent in each other. This is the most
common type of system.
iii. A homogeneous solution may be formed, then the solvent selected is not suitable and should be
rejected.
 21

iv. The solvent may lead to the formation of two or three partially miscible liquids. A and C are
completely soluble, while A and B, and B and C dissolve only to a limited extent in each other (two
pairs partially miscible). It is observed occasionally and not desired.

Triangular Diagrams :
In liquid-liquid extraction, when the solvent is partially miscible with the original solvent (diluent), the
solubility and equilibrium relations are often shown on a triangular diagram. The composition of ternary
systems can be shown by a point lying inside an equilateral triangle.
Consider a system consisting of C (acetone), A (water) and B (methyl isobutyl ketone) at 25o C wherein
acetone is the solute, water is the diluent and methyl isobutyl ketone is the solvent for extracting the solute.
This system is shown in Fig. 10.1. In this system, the (acetone) solute 'C' is completely miscible with the two
solvents A(water) and B(MIK) and the two solvents A - B are partially miscible with each other. Apex C
represents 100% acetone and apexes A and B represent 100% water and 100% Methyl Isobutyl Ketone
respectively. Along line BC, concentration of A is zero and the same is true for B and C along AC and AB.
The ternary system represented by point 'P' consists of three components C, A and B in the ratio of
perpendiculars PL, PJ and PK respectively. The distances AD and BE represent the solubility of solvent B in
A and that of A in B, respectively. Every mixture of MIK and water of composition lying between points D
and E forms two liquid layers, and for calculating mass ratio of these two-layers, centre of gravity principle is
applicable. When acetone is added to the two phase/layer mixture of MIK and water, acetone gets distributed
between the phases/layers, and compositions of phases/layers follow the raffinate phase and extract phase
solubility curves. The curved line ERF indicates composition of saturated MIK layer and the curved line DQF
indicates the composition of saturated water layer. The area under the binodal solubility curve represented by
the curved line DQFRE represents a two - phase region that will split up into two layers in equilibrium with
each other. Equilibrium composition of the two phases lie on this curve. These two layers have composition
represented by points Q and R and QR is a tie - line. The line joining equilibrium compositions of the two
phases is called the tie line. The points of tie lines must be found by experiment. The point F on the binodal
solubility curve represents a single phase which does not split into two phases (i.e. at this point, phases become
identical) and corresponds to a tie line of zero length and is known as a plait point. The plait point must be
found by experiment and at a given temperature and pressure it is fixed. It is not necessary that the plait point
be at the peak of the binodal curve and tie lines be parallel. In the system under consideration wherein C is the
solute and B is the extraction solvent, the separation will increase as the plait point approaches A and tie lines
increase in slope. All points outside the binodal curve represent single phase mixtures.
If a solution of composition X is mixed with another solution of composition Y, then the mixture obtained
will have a composition represented by point Z on the line XY, such that
 22

This type of plot is very useful in selecting the solvent and determining the number of stages required.

One of the important factors in selecting a solvent is the selectivity of the solvent and is given by

β = [xC/xA]E / [xC/xA]R

where xA and xB are the weight fractions/mole fractions of C and A in the extract and the
raffinate phase.
The selectivity has the same significance in extraction as the relative volatility has in distillation. So it
is a measure of the degree of separation by extraction. When selectivity is equal to one, separation by
extraction is not possible. For all practical operations, the selectivity should be greater than one.

Selection of Solvent for Extraction :

Any particular liquid to be used as a solvent for extraction will not possess all the properties considered
desirable for extraction and hence compromise is usually necessary of selecting the best solvent out of
various possible liquid solvents available.

While selecting a solvent for extraction, the qualities such as selectivity, recoverability, distribution
coefficient, density, etc. must be considered.

1. Selectivity : The ratio of the concentration ratio of solute to feed solvent in the extract phase
 23

to that in the raffinate phase is called the selectivity or separation factor. It is a measure of the
effectiveness of solvent for separating the constituents of a solution. The selectivity should be
greater than one for all useful extraction operation and if it is equal to one, separation by extraction
is not possible.
If B is the solvent, feed contains A and C, where C is the solute, and E and R are the equilibrium
phases, then the selectivity or separation factor, β is given by

2. Recoverability : As the solvent should be recovered for reuse frequently by distillation, it

should not form an azeotrope with the extracted solute for low cost recovery, the relative volatility
of the mixture formed should be high.
The latent heat of vaporisation of the solvent selected should be small whenever the solvent is to be
vaproised.
3. Distribution coefficient : Higher values (>1) of the distribution coefficient are generally
desirable as less solvent will then be required for a given extraction duty.
4. Density : The difference in densities of the saturated liquid phases should be larger for ease is
physical separation.
5. Insolubility of solvent : The solvent insoluble in the original liquid solvent should be preferred.
It should have a high solubility for the solute to be extracted as then small amounts of the solvent
are required.
6. Interfacial tension : Interfacial tension should be high for coalescence of emulsions to occur more
readily, as the same is of a greater importance than dispersion.
7. The solvent should be stable chemically. It should be inert towards the components of the system.
8. It should not be corrosive towards common materials of construction.
9. The solvent should be cheap.
10. The solvent should be non-toxic and non-flammable.
11. The solvent should have a low viscosity, freezing point, vapour pressure for ease in handling and
storage.

Extraction Equipments :

In liquid-liquid extraction operation, the two phases must be brought into intimate contact for mass
transfer to occur and then the phases are separated. This operation may be carried out batchwise or
continuously. Whenever we are dealing with simple systems and quantities to be handled are small,
batchwise procedure is adopted and when large quantities are to be handled and several contacts are required,
continuous operation becomes economical.
 24

Most of the extraction equipments are operated continuously with either successive stage contacts
(stagewise contactors) or differential contacts (differential contactors).

Industrial extraction equipments are classified as :

1. Stage-type extractors and

2. Differential (continuous contact) extractors.

Mixer-settler (single and multistage), plate column, pulsed sieve plate column, etc. are examples of
stage-type extractor.

Packed column, spray column, pulsed packed column, rotating disc contactors, etc. are examples of
differential extractor.
In stage-type extractors, the two phases are allowed to mix together in order to reach equilibrium and
then the phases are separated before they are passed countercurrent to each other to the next stages.
Advantages of these contactors : simplicity of design, no axial mixing, high stage and efficiency. These
units are large and bulky owing to the requirement of a separator for the phase separation after each stage.
In differential extractors, the two phases are always in continuous contact. These are compact for a
given capacity and require a small floor space.
In plate columns, packed columns or spray columns used for extraction operation, the phase
interdispersion and countercurrent flow are produced by the force of gravity (acting on the density difference
between the phases), whereas mixer settlers, rotating disc contactors, the phase interdispersion is produced
by mechanical agitation and countercurrent flow is produced by gravity.
Mixer-Settlers :
A mixer-settler is a single-stage extraction device comprising of a mixture for contacting the two liquid
phases to effect mass transfer and a settler for mechanical separation of the phases.

For extraction operations carried out in a batchwise fashion/manner, the mixer and settler may be the
same unit (i.e., mixing and settling is carried out in the same piece of equipment). [Fig. 10.3 (a)]. It consists
of a vertical vessel incorporating a turbine or propeller agitator. It is provided with charging nozzles at the
top and a discharge connection provided with a sight glass at the bottom. The feed solution to be
extracted is taken into the agitated vessel, required amount of the solvent is added, and whole mass
is agitated for a predetermined time. At the end of mixing cycle, agitation is stopped and settling is applied
for the phase separation. Afterwards, the raffinate and extract phases are withdrawn from the bottom
discharge connection into separate receivers
 25

For continuous extraction operation, the mixer and settler are separate units. [Fig. 10.3 (b)].
The mixer is a small baffled-agitated tank provided with inlet-outlet connections and the settler is often a
continuous gravity decanter (simple or settler with coalescer for emulsifying liquids).
In this extractor, the two phases are continuously in contact with each other in the mixer under thorough
agitation before flowing to the settler for the phase separation.
One phase is usually dispersed into the other in the form of small droplets in order to produce large
interfacial areas resulting in faster extraction.
When several contacts are required, a battery/train of mixer settlers operated in a current fashion is
used. Generally the liquids are pumped from one stage to the next, but if sufficient headroom is available,
gravity flow is arranged.

A feed solution is introduced in the first mixer and a fresh solvent is fed to the last mixer so that the
raffinate from each settler becomes the feed to the next settler, and the extract from the last settler acts as
the solvent to the second last mixer and so on. Final extract leaves
In case of liquids which emulsify easily and having nearly the same density it is necessary to pass a
mixer discharge through a pad of glass fibre to coalesce the droplets of the dispersed phase before gravity
settling is used.
 26

Since pumps and piping systems are involved in the installation of a train of mixer- settlers, initial investment
on equipment is high.
Advantages of mixer-settlers :
(i) High stage efficiency, (ii) good flexibility (iii) capacity to handle liquids of high viscosity and (iv) high
capacity.
These units are used in the petrochemical, fertilisers and metallurgical industries.
Perforated plate/Sieve Tray Tower/Column :
These are multistage, counter current contactors wherein the axial mixing of the continuous phase is
confined to the region between trays, and redispersion occurs at each tray resulting into effective mass
transfer. These are very effective, especially for systems of low interfacial tension both with respect to the
liquid handling capacity and extraction efficiency. The perforations in the plates are about 1.5 to 4.5 mm in
diameter and the plate/tray spacings are usually 150 to 600 mm.
Fig. 10.6 shows a perforated plate tower wherein the light liquid is dispersed. Here the general
arrangement of plates and downcomers is the same as that used for gas-liquid contact except that a weir is
not needed. Light liquid (dispersed phase) is introduced at the bottom, passes through the perforations in
the plate in the form of fine droplets, which rise through the heavy continuous phase, coalesce into a layer
beneath the plate and again redisperses through the plate above. The heavy liquid (continuous phase) is
introduced at the top, passes across each plate and flows downward from a plate above to the plate
below via downcomers. The principal interface is maintained at the top, the light liquid is removed
from the top and the heavy liquid from the bottom. The heavy liquid can be dispersed in which case,
the tower is turned upside down so that the downcomer of each plate becomes the upcomer.
 27

Spray Tower/Column :
Spray towers are the simplest of differential contactors. In its simplest form, it consists of an empty
tower provided with inlet and outlet connections at the top and bottom, for introducing and removing the
heavy and light liquid phases. Due to maximum freedom for liquid movement, as the shell is empty, there
will be severe axial mixing in these extractors and hence it is practically not possible to obtain the equivalent
of more than one or two theoretical stages even with tall towers. In these towers, mixing and settling occurs
simultaneously, and there is a continuous transfer of material between the phases and the composition of
each phase changes as it flows through the tower/column. Either light or heavy phase may be dispersed
(i.e., introduced in the tower in the form of fine drops), but generally the phase with high flow rate and the
phase of which the viscosity is high should be dispersed. Spray towers are operated into two distinct ways
- Either light phase or heavy phase may be dispersed. When the light phase is to be dispersed, it is introduced
through a nozzle from the bottom, droplets rise through the heavy phase and finally coalesce to form a
liquid-liquid interface at the top. When the heavy phase is dispersed, it enters the tower from the top, droplets
fall through the light-phase and finally coalesce to form a liquid-liquid interface at the bottom of the tower
and then leaves the tower in the form of stream through the bottom outlet. In this case, the light phase
introduced at the bottom flows as a continuous phase and ultimately leaves the tower from the top. Fig. 10.7
shows both the methods of operating spray towers.
 28

In spray towers, droplets of the dispersed phase rise or fall through the continuous phase under the
influence of gravity, thus there is a limit for the amount of dispersed phase that can pass through the tower
for a given flow rate of the continuous phase. Additional light phase fed to the bottom of the tower (wherein
the light liquid is dispersed) in excess of that flows upwards under the influence of gravity will be rejected
through the bottom of the tower and the tower is then said to be flooded.
Advantages of a spray column : Simple in construction and does not contain any internal
structures like plate, packings and thus gives high throughputs per unit cross- sectional area.
Disadvantages of a spray column : low efficiency due to axial mixing in the continuous phase and
necessity for a tall tower to effect a given degree of separation.
Packed tower/Column :
Randomly packed towers used for gas-liquid contact are also adopted for liquid-liquid extraction. Since
the packing provides large interfacial area for the phase contacting and causes the drops to coalesce and
reform, the mass transfer rates in packed towers are very high than those obtained with spray towers as
packings cut down the recirculation of the continuous phase. Packed towers are used in the petroleum
industry. Packed towers are unsuitable to handle dirty liquids, suspensions or high viscosity liquids.
 29

Fig. 10.8 shows a packed tower/column, arranged for light phase dispersed. It consists of a cylindrical shell
filled with packings, the packings rest on a support plate, and the shell is provided with inlet-outlet connections
at the top and the bottom for the introduction and withdrawal of liquid phases. The heavy liquid phase is fed
from the top and the light liquid (dispersed through a distributor) is fed from the bottom. A large portion of the
void space in the packing is filled by the continuous phase (heavy liquid) which flows downward and the
remainder of the void space in the packing is filled with droplets of the light liquid which rise through the
continuous phase and finally coalesce to form a liquid-liquid interface at the top. The light liquid leaves the
tower from the top and heavy liquid leaves from the bottom. There is a continuous transfer of material between
phases, and the composition of each phase changes as it flows through the tower/column. Usually, the packing
material should be such that it should preferentially get wetted by the continuous phase.
Carbon and plastic packings get preferentially wetted by organic liquids and ceramic by aqueous solutions.
The packing size should not be greater than one-eighth the tower diameter. A dispersed phase distributor
is always embedded in the packing whenever the dispersed phase droplets do not wet the material of a packing
support to avoid premature flooding (drops will have difficulty in entering).
Packed columns are easy to construct. They can be made to handle corrosive liquids at a reasonable cost.
Their performance is better than spray columns. The main disadvantage of a packed column is that solids present
tend to collect in the packing and cause channeling.
Rotating Disk Contactor (R.D.C.) :
For systems of high interfacial tension, good dispersion is achieved by mechanical agitation of the
liquids which in turn results in good mass transfer rates.
Rotating disk contactor is a mechanically agitated countercurrent extractor wherein agitation is brought
with the help of rotating disks which usually run at much higher speed than the turbine type impellers.
 30

It consists of a cylindrical column which is divided into a number of compartments that are formed by
a series of stator rings. Each compartment contains a rotating, centrally located horizontal rotor disk that
create a high degree of turbulence inside the column. The diameter of the rotor disk is less than the opening
in the stationary stator rings, usually the disk diameter is 33 to 66 % of the column diameter. The
compartment height for a column of diameter 2 m ranges from 200 to 300 mm. The column is provided
with inlet and outlet connections at the top and the bottom for light and heavy phases. Fig. 10.9 shows a
rotating- disk contactor for light phase dispersed. In these units, disks disperse the liquids and impel them
outward toward the column wall, where the stator rings create quiet zones wherein the two phases can
separate.
Advantages : This extractor is having reasonable capacity, low operating cost, high efficiency and low
maintenance cost. With corrosive liquids it is very difficult to maintain the internal moving parts (the
main disadvantage).
It is commonly used in the petroleum industry for furfural extraction (of lubricating oils), separation of
aromatics from aliphatics, desulphurisation of gasoline and recovery of phenol from waste waters.
Pulsed Column :
A pulsed column may contain ordinary packings or sieve plates without downcomers. In this column,
an oscillating/reciprocating pulse of short amplitude is applied to the liquid contents which increases the
efficiency because the pulse increases both turbulence and interfacial areas.
 31

A reciprocating pump is a common mechanically pulsing device which pulses the entire contents of the
column at a frequent intervals, owing to which a rapid reciprocating motion of relatively small amplitude
is superimposed on usual flow of the liquid phases. Bellows or diaphrams of steel, teflon, etc. are also used
as pulsing devices.
A pulsed sieve plate column consists of a vertical column with a large number of sieve plates without
downcomers. The perforations in the plates of such columns are smaller than nonpulsing columns (1.5 to 3
mm diameter). Pulsing amplitudes of 5 to 25 mm are generally recommended with frequencies of 100 to
260 cycles/minute. The pulsation causes the light liquid to be dispersed into the heavy phase on the upward
stroke and the heavy liquid phase to jet into the light phase on the downward stroke. The column has no
moving parts, low axial mixing and high extraction efficiency.
A pulsed packed column consists of a vertical column filled with packings.
In pulse columns (either sieve plate or packed) the height required for a given number of theoretical
contacts is often less than one-third that needed in a nonpulsing column.

Pulse columns are extensively used for processing radioactive solutions in atomic-energy work. They are
also used in petrochemical and metallurgical industries
SOLVED EXAMPLES

1. Picric acid is to be extracted with benzene from its solution. If the aqueous solution contains 0.2 mol of
picric acid 1 per litre, calculate the volume of benzene with which 1 litre of the solution must be extracted
in order to form a benzene solution containing 0.02 mol of picric acid per litre (Neglect the difference
between the volume of the solution and that of pure solvent). Also calculate the percent recovery of picric
acid from the aqueous solution.
K = distribution coefficient = CE/CR = 0.505
where CE = concentration of picric acid in benzene, mol per litre of solution
CR = concentration of picric acid in water, mol per litre of solution
 32

2. Picric acid is to be extracted with benzene as an extraction solvent. Aqueous solution contains 0.2 mol of
picric acid per litre. Calculate the quantity of benzene required to be contacted with 5 litres of the aqueous
solution in order to form a benzene solution containing 0.02 mol of picric acid per litre. Also calculate
the percent extraction of picric acid.
K = CE/CR = 0.505
where, CE = concentration of picric acid in benzene in mol/l
CR = concentration of picric acid in water, in mol/l

3. A solution of picric acid in benzene contains 30 grams of picric acid per litre. 1 litre of this solution is to
be shaken with water at 291 K (18o C) to reduce the picric acid concentration to 4 g/l in the benzene
phases. Calculate the quantity of water needed.
Molecular weight of picric acid is 229, and the distribution coefficient K is given by
K CE/CR = 0.548
where, CR = concentration of picric acid in water, mol/l
CE = concentration of picric acid in benzene, mol/l

EXERCISES
1. Define liquid extraction and state briefly the fields of application of extraction.
2. Define the following terms with reference to extraction
(i) feed, (ii) solvent (iii) raffinate and (iv) extract.
3. Explain in briefly the selection criteria for solvent to be used for liquid-liquid extraction.
4. Define selectivity and state what it indicates ?
5. Explain in brief, triangular diagram for a ternary system with one pair partially miscible.
6. Give the construction and working of a batch operated mixer-settler with a neat sketch.
7. Explain briefly the mixer-settler assembly operated in a counter current fashion with a sketch.
State advantages of mixer-settlers.
8. Explain in brief the construction and operation of a sieve plate column for extraction.
9. Write briefly on classification of extraction equipments.
10. Discuss in brief with a neat sketch the following equipments used for liquid-liquid extraction.
(a) packed column, (b) spray column, (c) pulsed column.
11. Explain the construction of rotating-disk contactor with its neat sketch.
12. Differentiate between distillation and extraction.
 33

CRYSTALLISATION
In this chapter, our discussion is restricted to crystallisation from solution.
Crystallisation is an operation in which solid particles are formed from a liquid solution.

It is a solid-liquid operation used to separate a solute from its solution in the form of crystals. In this
operation, mass is transferred from the liquid phase (solution) to a pure solid crystalline phase.
Crystallisation is an important operation in the chemical industry as the number of salable products
have to be in the form of crystals. This operation gives almost pure product in the form of crystals of a
desired size ranging from relatively impure solutions in a single processing step. From the energy point of
view, crystallisation requires much less energy for separation as compared to other purification methods
(e.g., distillation). It may be carried out at relatively low temperatures and on a scale ranging from a few
grams to thousands of tons per day.
Crystallisation usually involves : (i) concentration of solution (by evaporating a part of the solvent)
and (ii) cooling of solution until the concentration of solute becomes higher than its solubility at the
prevailing temperature. The solute then comes out of the solution (i.e., precipitates) in the form of pure
crystals.
The performance of crystallisation process is evaluated in terms of size, shape, structure, yield and
purity of crystals. So in commercial crystallisation, the size and shape of crystals are as important as the
yield and purity of crystals.
Solubility :
The solubility of a solute in a given solvent is the concentration of the solute in a saturated solution at
a given temperature.
The concentration of a solute in a saturated solution is called the solubility of the solute in the solvent.
The solubility of a solute in a given solvent depends on the nature of the solute, the nature of the
solvent and the prevailing temperature (solubility mainly depends on temperature). Solubility data are
generally given as parts by weight of anhydrous solute material per 100 parts by weight of the solvent,
e.g., the solubility of MgSO4 in water at 293 K (20o C) is 35.5 kg MgSO4 per 100 kg water.
Solubility data are plotted as solubility curves-curves wherein solubilities are plotted against temperature.

The solubility of the solute in a given solvent is different at different temperatures and it forms
the basis of crystallisation by cooling.
Saturation :

Consider a process of dissolving copper sulphate in water (solvent) at a given temperature.

Initially, when some amount of copper sulphate is added, all of it goes in the solution (i.e., it dissolves in
water). Additional amount can be dissolved further till a stage comes when no more copper sulphate can
be dissolved in a given amount (i.e. a fixed amount) of the solvent. At this stage, the solution is called a
 34

saturated solution.
A saturated solution is defined as the one which is in equilibrium with an excess of solid solute at a
given temperature.

If the temperature of the solution is increased, more solute [CuSO4] can be dissolved. Therefore, a
saturated solution will contain different amounts of the solute dissolved in it at different temperatures.

When a saturated solution at a higher temperature (say at T1) is cooled to a lower temperature say to T2,
then theoretically the amount of the solute corresponding to the difference in solubilities of the solute at
these two temperatures will come out of the solution in the form of crystals.

Solubility Curves :

A graphical relationship between the solubility of a solute and temperature is termed as the solubility
curve.

The concentration necessary for crystal formation and chemical species that separate can be determined
from solubility curves. Such curves are obtained by plotting the solubility of a solute as a function of
temperature (solubilities against temperature). It shows the effect of temperature on the solubility of the
solute. The solubility of solutes in a given solvent may increase, decrease, or remains more or less constant
with temperature. Solubility curves have no general shape or slope

Solubility curves of potassium chlorate, sodium chloride are continuous solubility curves as they show
no sharp breaks anywhere. Sometime, the solubility curve exhibit sudden changes of direction and these
curves are therefore referred to as discontinuous solubility curves, e.g., that of FeSO4, Na2SO4, etc.
For some substances, their solubility decreases with increase in temperature and in such cases
their solubility curves are called as inverted solubility curves (e.g., that of MnSO4 · H2O in H2O).

Usually, an increase in temperature of the solution increases the solubility of the solute when no true
compounds are formed between the solute and solvent, e.g., KClO3, KNO3 in H2O. In case of a hydrated
salt, the solubility increases with increase in temperature over a certain temperature range and then
decreases. Fig. 11.1 shows solubility curves for a number of salts in water. In case of potassium chlorate,
the solubility increases with temperature so it can be readily crystallised by cooling its saturated solution.
 35

The solubility of NaCl in water is almost independent of temperature (a slight increase in the solubility
results by a large increase in temperature), so for crystallisation to occur, some of the solvent should be
evaporated.
Supersaturation :
Consider an equilibrium solution (solid solute + liquid solvent). If we disturb this equilibrium
either by cooling the solution or evaporating a portion of the solvent, then the quantity of solute will exceed
the equilibrium concentration and the system will try to attain a new state of equilibrium by expelling
(precipitating) an excess solute present in it in the form of crystals. This process of forming crystals is
called crystallisation from solution and the concentration difference driving force is called supersaturation.

Supersaturation : It is the quantity of solute present in a solution (in which crystals are growing)
compared with the quantity of solute that is in equilibrium with the solution (i.e., the equilibrium
solubility at the temperature under consideration). The supersaturation is expressed as a coefficient, given
as

Crystallisation cannot take place/occur (i.e., crystals can neither form nor grow) unless a solution is
supersaturated. The amount of crystals formed however depend upon the difference in saturation
concentration since once the crystallisation begins the extra solute held in the solution due to
supersaturation also comes out of the solution in the form of crystals.
NUCLEATION or Mechanism of crystallisation / crystal formation :
A knowledge of the mechanism by which crystals form and grow is required in the design and
operation of an equipment used for crystallisation. The formation of a crystal from a solution is a two-
step process.
The first step is called nucleation (the birth of new small particles or nuclei) and the second one is called
crystal growth (growth of crystals to macroscopic size).
The generation of a new solid phase (i.e., new small particles) either on an inert material in the solution
or in the solution itself is called nucleation. The increase in size of these nuclei with a layer-by-layer
addition of solute is called crystal growth. Supersaturation is the common driving force for nucleation and
crystal growth. Crystals can neither form nor grow unless a solution is supersaturated.
The number of nuclei formed and the rate of growth of crystals depend upon the temperature
of operation. The number of nuclei and growth rate of crystals increase with increase in temperature upto
a certain point and then decreases. The temperature corresponding to a maximum number of nuclei
formation is different than the temperature at which a growth rate is maximum.

If initially a large number of nuclei is formed, then the yield of the process contains many small or tiny
crystals and if a few nuclei are formed initially (at the start), then the yield of the process contains large
 36

size crystals. Slow cooling results in the formation of a less number of nuclei and hence large size
crystals are formed (as the material deposits on a relatively few nuclei), whereas rapid cooling results in
the/leads to the formation of a large number of nuclei, giving the yield containing a large number of tiny
crystals.

Methods of Supersaturation :

Unless a solution is supersaturated, neither nucleation nor crystal growth occurs (i.e., crystals can
neither form nor grow). Thus, for crystallisation to occur, supersaturation can be generated by any one of
the following methods :

(a) By cooling a concentrated, hot solution through indirect heat exchange. (b) By
evaporating a part of the solvent/By evaporating a solution.
(c) By adiabatic evaporation and cooling (i.e., by vacuum cooling) : by flashing of a feed solution
adiabatically to a lower temperature and inducing/causing crystallisation by simultaneous cooling
and evaporation of the solvent.

(d) By adding a new substance (i.e., a third substance) which reduces the solubility of the original
solute, i.e., by salting.

(e) By chemical reaction with a third substance.

When the solubility of the solute increases with increase in temperature, a saturated solution becomes
supersaturated, i.e., supersaturation is generated by cooling and temperature reduction. This is
the case with many inorganic salts and organic substances (e.g. potassium nitrate, potassium chlorate,
oxalic acid, etc.). When the solubility of the solute is relatively independent of temperature (as is the
case with common salt (NaCl) in H2O), supersaturation is generated by evaporating a part of the solvent.
When the solubility of the solute is very high then neither cooling nor evaporation helps and
supersaturation may be generated by adding a new substance (a third component). The added component
may get mixed physically with the original solvent to form a mixed solvent in which the solubility of the
solute is reduced. This technique is called salting. The third component added may react with the
original solute and form an insoluble substance. This technique is called precipitation and it is
used in wet quantitative analysis. The rapid creation of very large supersaturations is possible by the
addition of a third component but it is not common in industry.

Miers' Supersaturation theory :

According to Miers' theory there is a definite relationship between the concentration and temperature
at which crystals will spontaneously form in a pure solution. This relationship is represented by the
supersolubility curve which is approximately parallel to the solubility curve. Both the curves are shown in
Fig. 11.2. The curve AB is the solubility curve and the curve PQ is the supersolubility curve. The curve
AB represents the maximum concentration of solutions which can be achieved by bringing solid solute into
equilibrium with a liquid solvent. If a solution having the composition and temperature indicated by point
 37

C is cooled in the direction shown by an arrow, it first crosses the solubility curve AB and we would expect
here crystallisation to start. Actually if we start with initially unseeded solutions, crystal formation will not
begin until the solution is supercooled considerably past the curve AB. According to the Miers' theory,
crystallisation will start in the neighbourhood of point D and the concentration of the solution then
follows roughly along the curve DE. For an initially unseeded solution, the curve PQ represents the
limit at which spontaneous nuclei formation begin and consequently, crystallisation can start. According to
Miers' theory, under normal conditions, nuclei cannot form and crystallisation cannot then occur in area
between the solubility curve and the supersolubility curve i.e. at any position short of point D along the
line CD.

Miers' theory is useful for discussing the qualitative aspects of nucleation from seeded and unseeded
solutions.

Yield of crystallisation process :

Usually, crystallisation processes are carried out slowly and the mother liquor is in contact with
sufficiently large crystals so that at the end of the process, the mother liquor is saturated at the final
temperature. In such cases, the yield of crystallization process is calculated from the initial solution
composition and the solubility of the solute material at the final temperature. If appreciable evaporation of
the solvent occurs during the crystallisation process, the solvent evaporated must be taken into account
in determining the yield. Whenever crystals are anhydrous, the yield is obtained by taking the difference
between the initial composition of the solution and the solubility of the solute corresponding the final
temperature of the process. In cases where material precipitates as a hydrated salt, we have to take into
account the water of crystallisation (in crystals), as this water is not available for retaining solute in the
solution. Under these circumstances, the key to the calculations of yields is to express all the compositions
in terms of hydrated salt and excess water (free water), as the excess water remains constant during
crystallisation operation and the compositions or amounts thus expressed on the basis of excess water
can be deducted in order to obtain the correct results.
 38

The percentage yield of a crystallisation process is the amount of the solute crystallised/
expressed as a percentage of the amount of the solute present in the feed solution.

Crystal form :

The constituent particles of a crystal are arranged in an orderly and repetitive manner. The constituent
particles may be atoms, molecules or ions. They are arranged in orderly three dimensional arrays called
space lattices. Crystals are classified according to the angle between the faces and this is the area of
the science of crystallography. Different forms of crystals based upon the angle between faces and lengths
of axes are : cubic, tetragonal, orthorhombic, hexagonal, monoclinic, triclinic and trigonal.
Caking of Crystals :
Caking of crystalline materials is caused by a small amount of dissolution occuring at the surface of
crystals and subsequent re-evaporation of the solvent. Due to caking, the crystals can get very tightly bonded
together.
Since the vapour pressure of a saturated solution of a crystalline solid is less than that of pure water at
a given temperature, condensation can take place on the surface of the crystals even though the atmospheric
relative humidity is less than 100 percent. The solution thus formed enters into/penetrates into the pack of
crystals as a result of capillary action of the small gaps between the crystals and caking can result due to
subsequent evaporation of moisture when the atmospheric humidity falls. Crystalline materials can also
cake at a constant relative humidity, as the vapour pressure of a solution is less in a small capillary as
compared to it in a large capillary as a result of temperature effect. As condensation occurs, the small
particles get first dissolved and therefore average size of capillaries increases and the vapour pressure of
the solution may increase sufficiently for evaporation to take place. When the particle size is non-uniform,
a crystalline material will cake more rapidly as the porosity of a bed of particles of mixed sizes is less
and fine particles are more readily soluble. Thus, the tendency of crystalline materials to cake can
be reduced by forming crystals of relatively large and uniform sizes or by adding a water repellent agent,
such as stearic acid.
Magma : It is a two-phase mixture of mother liquor and crystals that occupies the crystalliser and
withdrawn as a product.
In order to reduce the load on a crystalliser, evaporation may be carried out to remove the excess solvent
from a solution. Crystallisation is generally followed by filtration for the separation of crystals from the
mother liquor.
Effect of impurities on crystal formation :
(i) Soluble impurities may get adsorbed on the surface of the nuclei or crystals nucleation
sites and hinder the rate of nucleation and crystal growth.
 39

(ii) The shape of crystal may get modified as the adsorption of impurities may occur
preferentially on a particular face.
The impurities may decrease the rate of crystal growth. In some cases it is desirable, e.g., addition of a
small quantity of glue or tannin to boiler feed water prevents nucleation and growth of calcium carbonate
crystals and thus reduces scaling.
Classification of Crystallisers :

Crystallisers may be classified on the basis of mode of operation. These may be operated batch wise or
continuously.

1. Batch crystalliser : stir-tank crystalliser

2. Continuous crystalliser : Swenson-Walker crystalliser.

Crystallisers may also be classified according to the method by which supersaturation is achieved.
Thus, agitated tank crystalliser, Swenson Walker crystalliser are examples of crystallisers wherein
supersaturation is achieved by cooling (or temperature distribution) which is a usual practice for materials
of which the solubility decreases with decrease in temperature. Krystal crystalliser is an example of
evaporative crystalliser wherein supersaturation is achieved by evaporating a part of the solvent and is a
usual practice for materials whose solubility remains almost constant with variation in temperature.
Vacuum crystalliser is an example of crystalliser wherein supersaturation is achieved by adiabatic
evaporation and cooling which is most suitable for heat sensitive materials. This is used for large scale
production in which supersaturation is achieved by introducing the hot solution into a vacuum in which
pressure is less than the vapour pressure of the solvent at the temperature at which it is fed, the solvent
thus flashes or evaporates and the solution is cooled adiabatically. Salting out with the help of a third
substance is not in use and at present, deliberate introduction of a foreign substance to decrease the
solubility is rarely found.
Classification based on the method of achieving supersaturation :
1. Supersaturation by cooling alone :
(a) Batch – Agitated tank crystallisers
(b) Continuous – Swenson-Walker crystalliser
2. Supersaturation by adiabatic evaporation and cooling :
(a) Vacuum crystallisers with and without external classifying seed bed
3. Supersaturation by evaporation : (1) Krystal
crystallisers
(2) Draft-tube crystallisers.
Crystallisers are also classified according to the method of suspending the growing crystals : (a)
where the suspension is agitated in a tank, (b) where the suspension is circulated through a heat exchanger,
e.g., vacuum crystalliser and Oslo crystalliser, (c) where the suspension is circulated through a scraped
 40

surface exchanger.
Agitated Tank Crystalliser :
It is also known as a stir-tank crystalliser or agitated batch crystalliser. This is the simplest and
perhaps the most economical unit. In this crystalliser, supersaturation is generated by cooling so it is a
cooling crystalliser.
This type of crystalliser is commonly used in small scale production or batch processing due to several
advantages, such as low initial cost, simple in construction and flexibility. These are having capacities more
than tank crystallisers.

Construction : Agitated tank crystalliser consists of a cylindrical tank provided with a low speed
agitator and a cooling coil. The tank is having a conical bottom through which the product is withdrawn.
The agitator improves the heat transfer rate, keeps the temperature of the solution uniform and keeps the
fine crystals in suspension which is essential for uniform growth of the crystals.

Working : A known quantity of hot solution is charged to the crystalliser, cooling is applied by
circulating a coolant through the coil and agitator is started. The mass in the crystalliser cools due to heat
transfer to the circulated coolant and as the temperature decreases, crystals are formed due to decrease in
the solubility of the solute. The mass is cooled to a predecided temperature and finally a product stream
containing crystals plus mother liquor is withdrawn from the bottom of the crystalliser.
The disadvantages of this crystalliser include : the solids deposited on the surface of the coil add
resistance to heat transfer so that it ceases to function efficiently, difficulty in controlling nucleation and
size of crystals, frequent washing and scrapping of the cooling surface and high labour costs.
This type of crystalliser is used to produce fine chemicals, pharmaceutical products and dye
intermediates.
Scrapped surface crystalliser :
 41

(i) Swenson-Walker crystalliser and (ii) Double pipe crystalliser.

Swenson-Walker Crystalliser :
The Swenson-Walker crystalliser is a cooling type, continuous, jacketed trough crystalliser. It is an
example of the scrapped surface crystalliser and is probably the most widely used crystalliser.
Construction :
It consists of a long open rectangular trough with a semi-cylindrical bottom, i.e., U-shaped
trough, of width 0.6 m and length 3 to 6 m. The trough is jacketed externally for circulating the coolant
during operation. A spiral agitator rotating at about 7 rpm is incorporated in the trough in such a way that
it is as close to the bottom of the trough as possible. The capacity of this crystalliser can be increased by
arranging a number of units in series (four troughs of 3 metre length each may be arranged). At one end
of the crystalliser, an inlet for the hot solution is provided and at the other end of the crystalliser, an overflow
gate for the crystals and mother liquor discharge is provided. The functions of the spiral agitator are : (i)
to scrap the crystals from the cooling surface (i.e., to prevent accumulation of the crystals on the heat
transfer surface), (ii) to lift and shower the crystals through the solution so that the crystals will be held
in suspension and thereby the crystals of uniform size can be obtained (as deposition occurs mainly by
build up on previously formed crystals) and (iii) to convey the crystals from one end of equipment to the
other end.

The trough is formed out of metal sheets welded to an angle-iron frame at the top. A jacket is
usually made of mild steel. The spiral agitator is supported at either ends outside the trough. A stuffing
box assembly is attached to the cover on either ends that prevents leakage of the liquor from the opening
provided for a shaft. The shaft is driven by belt, etc.

Working :

A hot concentrated solution is fed at one end of the open trough and flows slowly towards the
other end of the trough. Water is fed to the jacket in such a way that it flows in a counter current fashion
 42

with respect to the solution. The solution while flowing through the trough cools by heat transfer to water.
Once the solution becomes supersaturated, crystals start forming and building. A spiral agitator keeps
the crystals in suspension so that previously formed crystals grow instead of formation of new crystals
and ultimately the two phase mixture of crystals and liquor leaves the crystalliser through an overflow gate.

Advantages of this crystalliser include : saving in floor space, in material in process and saving in
labour.
This crystalliser is suitable only when supersaturation can be achieved by cooling alone.
Double pipe scrapped surface crystalliser :
Less common type of continuous scrapped surface crystalliser that is somewhat similar to the jacketed
trough crystalliser, i.e., Swenson-Walker crystalliser is a double pipe crystalliser. It consists of a
concentric double pipe, the outer pipe acting as a jacket. Cooling water flows through the annular space
between the two pipes and a long pitch spiral agitator rotates in the inner pipe at 5 to 30 rpm. These are
also arranged in series (3 pipes each of 3 m long). The other constructional features and the method of
operation is the same as of the Swenson-Walker crystalliser.
It is used in crystallising ice cream and plasticizing margarine.
Vacuum Crystalliser :
In this crystallizer, supersaturation is achieved by adiabatic evaporative cooling. A hot solution (feed)
is introduced into a vessel wherein a vacuum is maintained that corresponds to the boiling point of the
solution lower than the temperature of the feed solution. Evaporation will result due to flashing. The energy
needed for vaporisation is taken from the feed (sensible heat), so that the temperature of a liquor-
vapour mixture after flashing becomes much lower than the temperature of the liquor before flashing.
Vacuum crystallisers often operated continuously but they can also be operated batch- wise. These
crystallisers are very simple and contain no moving parts and therefore, they can be constructed out of
corrosion resistant materials or lead or rubber lined mild steel.
Construction :
A continuous vacuum crystalliser consists of a tall vertical cylindrical vessel with a conical bottom, a
circulating pump (screw pump) of low head and a vertical tubular heater on the shell side of which, steam
is condensing. A low pressure (i.e., vacuum) in the vertical cylindrical vessel (crystallising body) is
maintained by a condenser, usually with the help of a steam jet ejector. A tangential inlet is provided on the
cylindrical vessel for introducing a hot solution into it and a vapour outlet is provided on the top. A discharge
connection for mother liquor and crystal is provided on a down-pipe just above the feed connection.
 43

The magma from the bottom of a cylindrical vessel goes to a pump via a down-pipe and is pumped
through a vertical tubular heater where it is heated by means of condensing steam and finally a hot stream
enters the cylindrical vessel tangentially just below the level of the magma surface. Flash evaporation of
the solution takes place and produces rapid cooling, resulting into supersaturation, which is the driving
force for nucleation and growth. Fresh solution enters the down pipe just before the suction of the
circulating pump and a suspension of crystals is continuously taken out from a discharge pipe located
above the feed inlet in the down pipe. The suspension of crystals is fed to a centrifuge machine, the crystals
are taken out as a product, and the mother liquor is recycled to the down-pipe with a small part of it
continuously bled.
It is used for the production of large crystals.

Krystal or Oslo Crystalliser :

It is used whenever large quantities of crystals of controlled size are to be produced.

In this crystalliser, a supersaturated solution is passed upward through a bed of crystals which are
maintained in a fluidised state whereby uniform temperature is maintained and the crystals segregate in the
bed with large ones at the bottom and small ones at the top.
Oslo Cooler Crystalliser :

In this crystalliser, supersaturation is generated by indirect cooling. It consists of a crystallising

chamber, a circulating pump, and a external cooler for cooling the solution. It is a circulating liquid cooling
crystalliser.

The solution to be crystallised is fed from the top. Mother liquor from a crystallising chamber is
withdrawn near a feed point 'A' with the help of a circulating pump and it is then admitted to a cooler (E)
wherein supersaturation is achieved by cooling. The supersaturated solution from the cooler is finally fed
back to the bottom of the crystallising chamber through a central pipe (P). Usually, nucleation takes place
 44

in the bed of crystals in the crystallising chamber. The nuclei formed circulate with mother liquor and once
they grow sufficiently large, they will be retained in the fluidised bed. Once the crystals grow to a
required size, they are removed as product from the bottom of the crystallising chamber through a valve 'V'
as these cannot be retained in the fluidised bed by the circulation velocity.

Oslo Evaporative Crystalliser :

In this crystalliser, supersaturation is generated/achieved by evaporation. It is a circulating liquid

evaporative crystalliser.

It consists of a crystallising chamber containing a bed of forming and growing crystals, a circulating
pump, an external heater for heating the solution with the help of condensing steam and a vapour - head
wherein reduced pressure is maintained by a vacuum generating equipment. The heater is maintained under
sufficient hydrostatic head to avoid the boiling on the heating surface.

It is used for the production of small and uniform crystals.

 45

The solution from the crystallising chamber is pumped by a circulating pump on the suction side of
which the feed solution forming a small part of the total circulating liquid is introduced into a heater, where
it is heated by means of condensing steam (on the shell side of the heater) and then fed to a vapour head
wherein some of the solution flashes into vapour resulting into some degree of supersaturation. The
supersaturated solution is then returned to the bottom of the crystallising chamber through a central duct
prolonged from the vapour head into the crystallising chamber. Nucleation takes place in the crystal bed
which is maintained in a fluidised state by means of a upward flowing stream of liquid through the duct.
The nuclei formed circulate with the mother liquor and once they grow sufficiently large they will be
retained in the fluidised bed. When the crystals grow to a required size, they will be withdrawn as a
product from the bottom of the crystallising chamber as they will not be maintained in the fluidised bed
by the circulation velocity.
Material balances of crystalliser
Material balances are used to calculate the yield of crystallisation operation which is the mass of crystals
obtained from a given mass of solution.

Consider the crystallisation process carried out under steady state conditions and shown in Fig. 11.8.
Let

Overall material balance :

F = C+L+V … (11.1)
 46

Energy balances :
Energy balance calculations in a crystallisation process are essential to determine the cooling requirements or to
determine the final conditions. In these calculations, heat of crystallisation is important and it is the latent heat
evolved when crystals are formed from a solution. Generally, the crystallisation process is exothermic and heat of
crystallisation varies with temperature and concentration. Heats of crystallisation are not available, but heat of
solution data are available. The process of crystallisation is the reverse of dissolution. Therefore, the heat of
solution (i.e., the heat of dissolution) with a reverse sign is taken as heat of crystallisation (heat of crystallisation
= – heat of solution). In case of a cooling crystalliser with no evaporation, the heat balance is
 47

SOLVED EXAMPLES

a) A solution of sodium nitrate in water contains 48 % NaNO3 by weight at 313 K (40o C) temperature. Calculate
the percentage yield of NaNO3 crystals that may be obtained when the temperature is reduced to 283 K (10o C).
Also, calculate the quantity of NaNO3 crystals obtained from 100 kg of the solution.
Data : Solubility of NaNO3 in water at 283 K (10o C) is 80.18 kg NaNO3 per 100 kg water.

b) Find the yield of Na2S2O3. 5H2O crystals when 100 kg of 48% Na2S2O3 solution is cooled to 293 K (20o C).
Also calculate the percentage yield of the hydrated crystals. (At. Wt. : Na = 23, S = 32, O = 16, H = 1)
Data : Solubility of Na2S2O3 is 70 parts per 100 parts water at 293 K (20o C).
 48

DRYING

Drying refers to an operation in which the moisture of a substance (usually solid) is removed by thermal
means (i.e., with the help of thermal energy).
Drying usually refers to the removal of relatively small amounts of water from a solid or nearly solid
material. It involves the transfer of liquid from a wet solid into an unsaturated gas phase (drying medium).
During drying operation, mass and heat transfer occur simultaneously. Heat is transferred from the the bulk
of the gas phase (drying medium) to the solid phase and mass is transferred from the solid phase to the gas phase
in the form of liquid and vapour through various resistances. The material (liquid) that is transferred is the
solute and transfer takes place as the gas phase is always unsaturated with respect to the solute material.
In drying, relatively small amounts of water or other liquid is removed from a solid or semi-solid material
(using thermal energy), whereas in evaporation relatively large amount of water is removed from solutions.
Drying involves the removal of water at a temperature below the boiling point, while evaporation involves
the removal of water as vapour at its boiling point. Drying involves circulation of a hot air or other gas over a
solid material for the removal of water, whereas evaporation involves use of steam heat for the removal of water.
To obtain products almost in the dried form is the purpose of drying operation, while to obtain concentrated
solutions is the main purpose of evaporation.
As the removal of moisture by thermal means is more costly than mechanical means
(e.g., filtration), the moisture content of material must be reduced to the minimum possible level by the latter
means before the material is fed to drying equipments.
In most of the drying operations, the heat (required to evaporate water) is provided by hot air or any other
gas-drying medium.
Drying is frequently the last operation in manufacturing processes and is usually carried after evaporation,
filtration, or crystallisation.
This operation is carried out in food, chemical, agricultural, pharmaceutical and textile industries.
Drying operation is carried out for the reasons given below :
(i) For reducing the transport cost.
(ii) For purifying a crystalline product so that the solvent adhering to the crystals is removed.
(iii) For making a material more suitable for handling and storage. Handling and storage of dry
solids is easy.
(iv) To meet the market specifications of solid products set by the customers. (v) For
providing definite properties to materials.
(vi) In some cases for preventing corrosion arising due to the presence of moisture. Dry chlorine gas is
not corrosive but traces of moisture make it very corrosive.
(vii) Sometimes it is an essential part of the process (e.g., drying of paper in paper making).
General Definitions :
The moisture content of a wet material may be expressed on the wet or dry basis.
Moisture content, wet basis :
The moisture content of a wet feed material, on wet basis, is defined as the ratio of the weight of the
moisture to the weight of the wet feed material. If X is the kg moisture associated with one kg of dry
solids, then

The weight percent moisture of a wet feed material, on wet basis, is defined as the weight of the moisture
expressed as a percentage of the weight of the wet feed material (i.e., wet solid).
 49

Moisture content, dry basis:

The moisture of a wet feed material, on dry basis, is defined as the ratio of the weight of the moisture to the
weight of the dry solids present in the wet feed material. If the feed material contains X kg moisture and 1 kg of
dry solids, then

Equilibrium moisture content (X*) :

It is the moisture content of a substance that is in equilibrium with its vapour in the gas phase under the
specified humidity and temperature of the hot gas or air. It represents the limiting moisture content to which a
given material can be dried under constant drying conditions.
It is the moisture content of a substance which is in equilibrium with a given partial pressure of the vapour.
Bound Moisture content :
It is the moisture content in a material which exerts a vapour pressure less than that of the pure liquid at
the same temperature.
Unbound moisture content :
It is the moisture held by a material in excess of the equilibrium moisture content corresponding to
saturation humidity. It is primarily held in the voids of solid.
It is the moisture content in a material which exerts an equilibrium vapour pressure equal to that of the
pure liquid at the same temperature.
Free moisture content :
It is the moisture contained by a material in excess of the equilibrium moisture content (X – X*). At a
given temperature and humidity, it is the moisture content of a material that can be removed by drying. It may
include bound and unbound moisture.
Critical moisture content :
It is the moisture content of a material at which the constant rate period ends and the falling rate period
starts. This moisture content is a function of constant drying rate, material properties and particle size.
Constant rate period :
It is that part of the drying process during which the rate of drying expressed as the moisture evaporated
per unit time per unit area of drying surface remains constant.
Falling rate period :
It is that part of the drying process during which the rate of drying varies with time and the instantaneous
drying rate expressed as the amount of moisture evaporated per unit time per unit area of drying surface
continuously decreases.
Properties of air-water system :
The moisture removed (from a wet solid) during drying operation gets added in the hot gas or air which
in turn depends upon the temperature and humidity of the gas or air. Usually, in drying operation the hot
air is used as a drying medium, so it is essential to know some of the properties of the air-water vapour system.
Relative humidity (R.H.) :
It is a measure of the degree of saturation of air at the dry bulb temperature.
It is defined as the ratio of the partial pressure of water vapour in the air water-vapour mixture to the
vapour pressure of pure water at the temperature of the mixture, expressed on a percentage basis.
 50

The relative humidity is defined as the ratio of the actual water vapour content of air to the water vapour
content of the fully saturated air at the same temperature, expressed on a percentage basis.
Humidity (H)/Absolute humidity :
It is the ratio of the mass of water vapour to the mass of dry air present in the air-water vapour mixture
under any given set of conditions.

Dry bulb temperature :

The temperature of the air-water vapour mixture recorded by a thermometer whose bulb is kept dry is called
dry bulb temperature.
Wet bulb temperature :
The temperature of the air-water vapour recorded by a thermometer whose bulb is kept wet by wrapping a
wet cloth in the open air is called wet bulb temperature.
Since the latent heat of vaporisation required for natural evaporation of water from the cloth will be supplied
from the bulb, the temperature of the bulb decreases. The evaporation is continued until the air surrounding the
bulb becomes saturated. Some of the heat will flow from the surrounding air to the bulb by temperature
difference, even then the temperature of bulb will not rise as that heat gets consumed in evaporation of water.
At one particular point, the temperature becomes constant and is recorded as wet bulb temperature.
When the air is more unsaturated, then the difference between dry bulb temperature and wet bulb
temperature is more and is less for a more humid air. The relative humidity of the air is found out from a
psychrometric chart knowing wet bulb and dry bulb temperatures.
Saturation humidity :
It is the humidity of air when it is fully saturated with water vapour. It is denoted by the symbol Hs.

Percentage humidity/Percentage saturation :

It is the ratio of the actual humidity (H) to the saturation humidity (Hs).

Equilibrium :
The moisture of wet solids exerts a definite vapour pressure depending upon the temperature and the
nature of solid and the moisture. Consider that the wet solids containing
o
liquid which exerts a vapour pressure of pm are exposed to a continuous supply of fresh gas
o
(usually air) with a fixed partial pressure of the vapour (pA). If pm is greater than pA, then the
o
solids will lose moisture (reverse is true for pm < pA) by evaporation till the vapour pressure
of the moisture of the solids equals the partial pressure of the vapour in the gas. The solid
and the gas are then said to be in equilibrium with each other and the corresponding moisture content is referred
 51

to as equilibrium moisture content. The equilibrium data in case of drying operations are given as the relationship
between the moisture content of a solid (expressed on a dry basis) and the relative humidity of a gas in contact
with the solid.

When the humidity of air is less as compared with the moisture content of the solids, then the solids will lose
moisture by evaporation and dry to equilibrium and if the air is more humid than the solids, then they will gain
moisture until the equilibrium is attained. A typical equilibrium curve for drying of a certain wet solid is shown
in Fig. 12.1 where the ordinate is the relative humidity of the gas and the abscissa is the moisture content on
dry basis. When solids having very high initial moisture content (X) are exposed to a continuous supply of air
with relative humidity of (RH1), the solids will lose moisture by evaporation and thus go on drying until the
moisture content corresponding to the point A is reached (equilibrium moisture content X*).
Beyond this, no drying takes place even if the solids are exposed to this air for infinitely long periods. The
moisture content of solids can be reduced below X* (below that corresponding to point A) only by exposing
the solids to air of a lower humidity and to obtain bone-dry solids, we have to expose it to perfect dry air which
corresponds to the origin of curve.
Constant drying conditions :
These conditions mean the conditions under which the temperature, humidity, velocity and direction of
flow of the hot air or gas across the drying surface are constant during drying operation.
Rate-of-drying curve :
The drying characteristics of wet solids are generally described by the drying rate curves obtained under
constant drying conditions. These curves : moisture content v/s time and drying rate v/s moisture content
are shown in Figs. 12.2 and 12.3. Generally, the experimental evaluation of these curves is done before
design calculations.
Consider that the wet solids with an initial moisture content (X1) are exposed to air of constant temperature
and humidity. If we then measure the moisture content as a function of time (i.e., moisture content of the
material is measured at various values of time), then a curve as shown in Fig. 12.2 (a) is obtained from the
collected data. The curve relates the moisture content on dry basis with time. It is clear from the curve that the
moisture content of solids decreases with time and after sometime it remains constant at X*, which is
the equilibrium moisture content.

From this curve, we can draw another type of curve which is known as the rate of drying curve. This curve
gives much more information regarding the drying process. The rate of drying curve gives a relationship between
the rate of drying, expressed as, the moisture evaporated per unit time per unit area of the drying surface and the
 52

moisture content on a dry basis. This curve can be constructed by measuring the slopes of tangents drawn
to the curve of Fig. 12.2 (a) at various values of the moisture content and then calculating rate as

Fig. 12.3 shows the rate of drying curve. The section AB of the curve represents the warming up period
during which the temperature of the solid is becoming equal to the temperature of drying air. From B to C,
the curve is a straight line parallel to X-axis representing the constant rate of drying, thus the section BC
is called the constant rate period during which the layer of water on the surface of solid is being evaporated.
The rate of drying is constant from B to C as the drying takes place from a saturated surface. The section (CE)
of the curve represents the falling rate period composed of the first falling rate period (CD) and the second
falling rate period (DE). From point 'C' onwards some dry patches starts forming on the surface of the solid.
The rate of drying decreases for the unsaturated portion and hence the rate for total surface decreases. The
section CD of the curve represents the period corresponding to the zone of unsaturated surface drying. The
moisture content at which the constant rate period ends and the drying rate starts to fall (i.e. at which
unsaturated surface drying starts) is known as the critical moisture content.
After point D, the surface of the solid is completely dry and now the internal moment of moisture starts coming
to the surface and this is continued upto the point E, where the equilibrium is attained. The rate of drying over
section DE is governed by the rate of internal moisture movement. The second falling rate period (DE) represents
zone where the internal moisture movement controls.

The rate of drying curve consists of two parts : (i) a period of constant rate/a constant rate period, wherein
the rate of drying is constant and (ii) a period of falling rate/a falling rate period, wherein the rate of drying is
falling.
The rate of drying as a function of time is given in Fig. 12.4, which indicates how long each drying period
lasts.

Factors on which the rate of drying depends :

(a) Gas velocity : When the velocity of the gas or air is high, the rate of drying will also be high.
(b) Humidity of gas : Lesser the relative humidity, the more will be the rate of drying.
 53

(c) Area of drying surface : If the area of the wet surface exposed to the gas or air is more, the rate of
drying will also be more.
(d) Temperature : If the temperature of the gas is increased, its relative humidity decreases (i.e., gas
becomes more unsaturated) and thus increases a driving force (i.e., the concentration difference of
moisture between the solid and gas) and so the rate of drying increases.
Time of drying under constant drying conditions :
Consider that the wet solids are to be dried by passing the hot air over them under constant drying
conditions. The time of drying required to dry the material from the initial moisture to the final moisture content
of solids, is the sum of the time required during the constant rate period and time required during the falling
rate period (when the final moisture is less than the critical).
(a) Constant rate period :
Let X1 be the initial moisture content of the wet solids and X2 be the final moisture content of the wet
solids during the constant rate period. Let Xc be the critical moisture content of the wet solids. [X1, X2 > Xc]
The rate of drying is given by

Equation (12.5) gives the time required for drying the material from X1 to X2 in the constant rate
period.
If the material is to be dried to the moisture content of Xc, then the time required during the entire
constant rate period is given by
 54

(b) Falling rate period :

During this period, the rate of drying is proportional to the free moisture content.

where X* is the equilibrium moisture content and X is the moisture content of wet solids less than critical
moisture content.
Let X1 be the initial moisture content and X2 be the final moisture content such that
X1, X2 < Xc.

Equation (12.12) gives the time of drying during the falling rate period to dry the material from X1
to X2.
If the material is to be dried from the critical moisture content Xc to the final moisture content X2 (X2 < Xc),
then the time required for drying during the entire falling rate period is given by tf as :
 55

Appropriate equations and values of X1, X2 and Xc are to be used for the calculation of the time required
during a particular period or for calculating the total time required for drying.

DRYING EQUIPMENTS :
Dryers used in industry may be classified on the basis of (a) mode of operation (b) physical
properties and handling characteristics of the material and (c) the method of supplying heat to the material to be
dried, i.e., method of heat transfer.
(i) Mode of operation :
On the basis of mode of operation that is based on the production schedule there are two types of drying
equipments – (i) batch dryers and (ii) continuous dryers.
In case of batch dryer, a definite size of batch of the wet feed is charged to the dryer and drying is carried
out over a given time period. These dryers operate under unsteady state conditions.
Drying in batches is relatively expensive operation and consequently batch dryers are preferred for small-
scale production, pilot plant and for drying valuable materials.
In case of continuous dryer, the material flows in and out continuously and drying is carried out under steady
state conditions continuously. These are generally used for large scale production.
Advantages of continuous drying include :
Equipment necessary is small relative to the quantity of product. Product has
more uniform moisture content.
Cost of drying per unit of product is relatively small.
(ii) Physical properties and handling characteristics of material :
The wet feed material may be a liquid solution, a slurry, a paste, a sludge, free flowing powder, granular,
crystalline or fibrous solid. The design of a dryer depends upon the physical properties of the wet feed
material and therefore dryers handling similar feed materials may have many common design features.
(iii) Method of heat transfer :
On the basis of method of heat transfer, dryers are classified as (a) direct dryers, and
(b) indirect dryers.
Direct dryers :
In such dryers, heat transfer is accomplished by direct contact between the wet feed material and hot gases.
The heat of evaporation is supplied by the sensible heat of the gas in contact with the material to be dried
(adiabatic dryer). The moisture evaporated from the wet feed is carried by the hot gases.
Indirect dryers :
In such dryer, heat necessary for drying is transferred to the wet feed by conduction through a metal surface/wall
in contact with the feed material to be dried (non-adiabatic dryer). The moisture evaporated from the wet feed is
carried by the air or other gas independently of a heating medium.
SOLVED EXAMPLES
 56

1. A 50 kg batch of granular solids containing 25 % moisture is to be dried in a tray dryer to 12 % moisture

by passing a stream of air at 360 K (87 oC) tangentially across its surface at a velocity of 2 m/s. The
constant rate of drying under these conditions is
0.0008 kg moisture/(m2·s) and the critical moisture content is 10 %. Estimate the drying time. The surface area
available for drying is 1.0 m2.
2. A 100 kg bath of granular solids containing 30 % moisture is to be dried
in a tray dryer to 16 % moisture by passing a current of air at 350 K tangentially across its
surface at a velocity of 1.8 m/s. If the constant rate of drying under these conditions is
0.7 × 10–3 kg/(m2·s) and the critical moisture content is 15 %, calculate the time required for drying the solids.
Drying surface = 0.03 m2/kg dry weight.

HUMIDIFICATION

INTRODUCTION
Humidification operation is a classical example for an interphase transfer of mass and energy, when a gas
and a pure liquid are brought into intimate contact. The term humidification is used to designate a
process where the liquid is transferred to gas phase and dehumidification indicates a process where the
transfer is from gas phase to liquid phase. The matter transferred between phases in both the cases is the
substance which constitutes liquid phase and it either vapourises or condenses indicating either
humidification or dehumidification process.
DEFINITIONS
The substance that is transferred (vapour) is designated by A and the main gas phase is designated by B.
Molal Absolute Humidity
It is defined as the moles of vapour carried by a unit mole of vapour free gas.

where yA, yB are moles of A and B respectively, PA is the partial pressure of A and Pt is total pressure.
When the quantities yA and yB are expressed in mass, then it is called mass absolute humidity (Y’) or
Grosvenor humidity.

Saturated Absolute Humidity

When the vapour-gas mixture is saturated, then the partial pressure becomes equal to the vapour pressure of
that substance
 57

When the quantities are expressed in mass,

Dry Bulb Temperature (DBT)

The temperature indicated by the thermometer by ordinary immersion in the vapour–gas mixture is called dry
bulb temperature.
Relative Humidity or Relative Saturation (% RH)
It is normally expressed as a percentage. If pA is the partial pressure under a given condition and PA is the
vapour pressure at any dry bulb temperature (DBT) of the mixture then,

Percentage Saturation or Percentage Humidity Hp

It is defined as the percentage of humidity under given condition to the humidity under the saturated condition.

Dew Point
This is the temperature tDP at which a vapour–gas mixture becomes saturated when cooled at constant total
pressure out of contact with a liquid. Moment the temperature is reduced below dew point, vapour will
condense as a liquid dew.
Humid Heat
The humid heat CS is the heat required to raise the temperature of unit mass of gas and its accompanying
vapour by one degree at constant pressure.

where CA and CB are specific heats of vapour and gas respectively.

LEACHING
INTRODUCTION
Leaching is one of the oldest operations in chemical industries which involves the use of a solvent to remove
a solute from a solid mixture. Though originally it was referred to the percolation of liquid through a bed of
solids, it is now used to refer the operations by other contacting means also. Lixiviation is used for the leaching
 58

of alkali from wood ashes. Decoction refers to the operation where the solvent at its boiling is used. Whenever
the solute material is present largely on the surface of an insoluble solid and is merely washed off by the
solvent, the operation is called elutriation or elution. It is one of the most important operations in metallurgical
industries for the extraction of metals from ores of Al, Ni, Co, Mn and Zn. It is also used for the extraction of
sugar from sugar beets with hot water, extraction of oil from oil seeds using organic solvents, removal of
tannin from various tree barks by leaching with water, preparation of tea and coffee and extraction of many
pharmaceutical products from plant roots and leaves.
The success of this operation depends on the proper preparation of the given solid. Depending on the nature
of solid, the solid is crushed and ground to desired size to accelerate the leaching action. For example, a certain
copper takes about 6 hours if crushed to – 60 mesh size and about 5 days for a size of 6 mm. Gold is sparsely
distributed in its ore. Hence it is crushed to – 100 mesh size to have an effective leaching. Sugar beets are cut
into thin wedge shaped slices called cassettes before leaching to enable the solvent water to reach the individual
plant cells. In the manufacture of pharmaceutical products from plants they are dried in order to rupture the
cell walls so that solvent can reach the solute easily. Vegetable seeds when used for the extraction of oil are
crushed to a size of 0.15 to 0.5 mm to enable easier extraction. However, when the solid is present on the
surface, no grinding or crushing is necessary and the particles can be washed directly.
To summarize, the leaching action depends on:
The nature of solid/cell structure.
Diffusion of solute from the material to surface and then to the bulk of the solution.
Particle size and its distribution.
Solubility of solute in solvent and the temperature of operation.

UNSTEADY STATE OPERATION

These operations are carried out batchwise or semibatchwise.
In Place (in-situ) Leaching
This operation is also called solution mining which refers to the percolation leaching of minerals in place at a
mine, by circulation of the solvent over and through the ore bed. This technique is adopted for the leaching of
low-grade copper. In these operations, the solvent/reagent is injected continuously through one set of pipes
drilled down to the ore and the resulting solution is pumped out through another set of pipes. Alternatively,
the solvent/reagent can be pumped into the ore bed intermittently and withdrawn through the same well. In
this technique crushing and grinding of ore are avoided. In place leaching also called in-situ leaching is shown
in Fig. 11.1.
Heap Leaching
Low-grade ores can be easily leached by this technique where the ore is gathered as a heap upon impervious
ground. The leach liquor is pumped over the ore, which percolates through the heap and collected as it drains
from the heap. This technique is used for the extraction of copper and uranium from their low grade ores. Heap
leaching is shown in Fig. 11.2.
 59

Percolation Tank
Whenever small tanks are to be used, they can be made of metal or wood. The solid particles to be leached,
rest on a false bottom which could be made of wood strips and may be covered by a coconut matting and a
tightly stretched canvas filter cloth. The leach liquor flows to a collection pipe leading from the bottom of the
tank. A very large percolation tanks are made of reinforced concrete and lined with lead or bituminous mastic.
Small tanks may be provided with side doors near the bottom for removing the leached solid while the large
tanks are emptied by excavating from the top. It is always preferable to fill the tanks with particles of uniform
size so that voids will be more and the pressure drop required for flow of leaching liquid is least. This also
leads to uniform leaching of individual particles. For these operations the crushed solids may be filled in the
tank initially and then the solvent is allowed to enter in. The solid and solvent may remain in contact with each
other for a specified amount of time and then drained. During the process, if necessary, the liquid can also be
circulated through the bed. The liquid can also be allowed to enter in continuously and also drained
continuously. The liquid from the exit can also be recirculated, if necessary. The flow of liquid could either
be downwards or upwards with proper distribution of liquid. Percolation tank is shown in Fig. 11.3.
 60

Countercurrent Contact
At times, one is interested in getting a strong solution, which can be obtained by a countercurrent operation.
This arrangement, also called Shanks system, contains number of tanks as shown in Fig. 11.4. The number of
tanks generally vary from 6 to 16. In a typical system with 8 tanks at a particular time, tank 8 is empty and
tanks 1 to 7 contain solids. Fresh solvent enters tank 1, where the solid has spent maximum amount of time
and the material in tank 2, 3, 4, 5, 6 and 7 have progressively spent lesser time. The material in 7th tank has
spent the least amount of time. The solution withdrawn from the 7th tank has the maximum solute
concentration because the solution comes after contact with fresh solids. The solution withdrawn from tank 1
goes to tank 2, from tank 2 to tank 3, …, tank 6

to tank 7. The leached solid is discarded from tank 1 and fresh solid is now added in tank 8. The solution is
transferred from tank 7 to 8, 6 to 7, 5 to 6, …, 2 to 3. Here the fresh solvent is added in tank 2, and the solid
from tank 2 is finally discarded. The solution now obtained from tank ‘8’ will have maximum solute
concentration. Tank 1 which is now empty will be loaded with a fresh batch of solids. This is nothing but
 61

advancing the tanks by one. The operation is continued in this manner by keeping successive tanks as the first
tank in which the fresh solvent enters. The solids move counter currently to liquid flow.
Percolations in Closed Vessels
At times the pressure drop for flow of liquids by gravity is high or the solvent is highly volatile. Under such
circumstances the liquid is pumped through the bed of solids in vessels called diffusers. The main advantage
of these units is the prevention of evaporation losses of solvent, when they are operated above the boiling point
of solvent (e.g. leaching of tannins using water at 120°C, 345 kN/m2).
Filter–Press Leaching
When the solids are in finely divided form, percolation tanks are not suitable. Under such circumstances, solids
can be filtered and leached in the filter press by pumping the solvent through the press cake. This is also a
common feature while washing the filtered cakes.
Leaching of Vegetable Seeds
Soya beans, cotton seeds, rice bran and castor seeds are some of the products regularly leached with an organic
solvent for removing the oil present in them. The process involves dehulling, precooking, adjustment of water
content and flaking. In some cases solvent extraction of oil is preceded by mechanical expression of oil from
oil seeds. Leaching solvents are generally petroleum fractions. Chlorinated hydrocarbons leave the residue
meal a toxic one. The oil-solvent solution containing a small amount of finely divided suspended solids is
called miscella and the leached solid is called marc.
DEFINITIONS
Let, B = insoluble solid or inert solid (kg),
C = soluble solute (kg),
A = pure solvent (kg),

ADSORPTION
INTRODUCTION
 62

Adsorption operation involves contact of solids with either liquids or gases in which the mass transfer is
towards solids. The reverse of this operation is called
Desorption. Adsorption operations exploit the ability of certain solids to concentrate specific substances from
fluid on to their surfaces. The adsorbed substance is called adsorbate and the solid substance is called
adsorbent.
Typical applications of this solid–liquid operation are as follows:

• removal of moisture dissolved in gasoline

• de-colorization of petroleum products and sugar solutions
• removal of objectionable taste and odour from water.
The solid–gas operations include:
• dehumidification of air and gases
• removal of objectionable odours and impurities from gases
• recovery of valuable solvent vapours from dilute gas mixtures
• to fractionate mixtures of hydrocarbon gases such as methane, ethane and
propane.

TYPES OF ADSORPTION
The two types of adsorption are physical adsorption or physi-sorption (van der Waals adsorption) and chemi
sorption (activated adsorption).
 Physical adsorption is a readily reversible phenomenon, which results from the intermolecular forces
of attraction between a solid and the substance adsorbed.
 Chemi-sorption is the result of chemical interaction, generally stronger than physi-sorption between the
solid and the adsorbed substance. This process is irreversible. It has importance in catalysis.
NATURE OF ADSORBENTS
Adsorbents are usually in granular form with their size ranging from 0.5 mm to 12 mm. They must neither
offer high pressure drop nor get carried away by flowing stream. They must not loose their shape and size
while handling. They must have larger surface area per unit mass and also lot of pores.
Some of the commonly used adsorbents, their sources and applications are given below:
 63

ADSORPTION EQUILIBRIA
Different gases and vapours are adsorbed to different extent under comparable conditions as shown in Fig.
12.1.
 64

As a general rule, vapours and gases with higher molecular weight and lower critical temperature are more
readily adsorbed. To some extent, level of saturation also influences the degree of adsorption. The adsorption
isotherms are generally concave to pressure axis. However, other shapes are also exhibited as shown in Fig.
12.2.
Repeated adsorption and desorption studies on a particular adsorbent will change the shape of isotherms due
to gradual change in pore-structure. Further, adsorption is an exothermic process and hence the concentration
of adsorbed gas decreases with an increase in temperature at a constant pressure. Similarly an increase in
pressure increases the concentration of adsorbed gas in the adsorbent at a constant temperature. There are three
commonly used mathematical expressions to describe vapour adsorption equilibria, viz. Langmuir, Brunauer-
Emmett-Teller (BET) and Freundlich isotherms. The first two are derived from theory whereas the last one is
derived by a fit technique from the experimental data.
 65

ADSORPTION HYSTERESIS
The adsorption and desorption operations exhibit different equilibrium phenomena as shown in Fig. 12.3 and
is called adsorption hysteresis.

This may be due to the shape of the openings to the capillaries and pores of the solid or due to the complex
phenomena of wetting of the solid by the adsorbate. Whenever hysteresis is observed, the desorption curve is
below the adsorption curve.
HEAT OF ADSORPTION
The differential heat of adsorption (–H) is defined as the heat liberated at constant temperature when unit
quantity of vapour is adsorbed on a large quantity of solid already containing adsorbate. Solid so used is in
such a large quantity that the adsorbate concentration remains unchanged. The integral heat of adsorption,
(∆H) at any concentration X is defined as the enthalpy of the adsorbate–adsorbent combination minus the sum
of the enthalpies of unit weight of pure solid adsorbent and sufficient pure adsorbed substance (before
adsorption) to provide the required concentration X, at the same temperature. The differential heat of
adsorption and integral heat of adsorption are functions of temperature and adsorbate concentration.
EFFECT OF TEMPERATURE
Increase of temperature at constant pressure decreases the amount of solute adsorbed from a mixture. However,
a generalization of the result is not easy. Figure 12.1 also indicates the effect of temperature.
EFFECT OF PRESSURE
Generally lowering of pressure reduces the amount of adsorbate adsorbed upon the adsorbent. However, the
relative adsorption of paraffin hydrocarbon on carbon decreases at increased pressures.
LIQUIDS
The impurities are present both at low and high concentrations in liquids. These are normally removed by
adsorption technique. The characteristics of adsorption of low and high concentration impurities are different.
They are discussed below.
Adsorption of Solute from Dilute Solutions
Whenever a mixture of solute and solvent is adsorbed using an adsorbent, both the solvent and solute are
adsorbed. Due to this, only relative or apparent adsorption of solute can alone be determined.
 66

Hence, it is a normal practice to treat a known volume of solution of original concentration C0, with a known
weight of adsorbent. Let C* be the final equilibrium concentration of solute in the solution. If v is the volume
of solution per unit mass of adsorbent (cc/g) and C0 and C* are the initial and equilibrium concentrations
(g/cc) of the solute, then the apparent adsorption of solute per unit mass of adsorbent, neglecting any change
in volume is v(C0 – C*), (g/g). This expression is mainly applicable to dilute solutions. When the fraction of
the original solvent which can be adsorbed is small, the C* value depends on the temperature, nature and
properties of adsorbent. In the case of dilute solutions and over a small concentration range, Freundich
adsorption Isotherm describes the adsorption phenomena,

Freundlich adsorption equation is also quite useful in cases where the actual identity of the solute is not known,
e.g. removal of colouring substance from sugar solutions, oils etc. The colour content in the solution can easily
be measured using spectrophotometer or colorimeter. The interpretation of this data is illustrated in worked
example 2. If the value of n is high, say 2 to 10, adsorption is good. If it lies between 1 and 2, moderately
difficult and less than 1 indicates poor adsorption characteristics. A typical adsorption isothermal for the
adsorption of various adsorbates A, B and C in dilute solution at the same temperature for the same adsorbent
is shown in Fig. 12.4.