Adsorption

Introduction  BATCH ADSORPTION IN A

types of adsorption STIRRED VESSEL

adsorbents and their applications  ADSORPTION IN FIXED BED AND

MOVING BED
characteristics and properties of
adsorbents  ADSORPTION IN FLUIDIZED BED
adsorption equilibria  PRESSURE SWING ADSORPTION
adsorption isotherm  TYPES OF OPERATION
heat of adsorption  CONTINUOUS ADSORPTION
specific surface area of an
adsorbent
selection of adsorbents
 Adsorbent Adsorbate
The solid that adsorbs a The component that adsorbed
component
Flow diagram of a dual-bed adsorption-desorption system
 Applications of adsorption
The process of adsorption is very important as it has many applications in domestic as well as
in industrial processes. Some of them are as follows:
1. In heterogeneous catalysis: Surface active materials are widely used as catalysts mostly
due to adsorption processes. If the surface active materials (adsorbents) have a different
phase from that of substrates, then the catalysis is called heterogeneous catalysis. A system
where both the catalyst and the substrate are in same phase is called homogeneous
(catalysis).
2. In removal of colouring material: Many coloured materials or impurities are removed
through adsorption by suitable surface active materials like charcoal. Activated charcoal
has been extensively used for this purpose.
3. In ion exchange resins: Several polymeric materials are used for the separation of ionic
substances in chromatography through ion-exchange.
4. In adsorption indicators: Several dyes like eosin and fluoresein are used as indicators in
the titrations of Cl-, Br- etc., against Ag+(Fajan’s method).
5. In gas masks : Activated charcoal is used to remove toxic gases in gas masks.
6. In dyeing of cloth: Many substances work as mordants for dyeing of cloths. Several metal
cyanogen complexes and alums work as efficient mordants in dyeing cloths.
7. In de humidizers: Many substances, when they adsorb water, change their colour. Silica
and alumina gels are used as adsorbents for removing moisture. silica is colourless but
after adsorbing water becomes blue.
 Types of Adsorption

Adsorption

Physical Adsorption Chemical Adsorption

or Or
Physisorption Chemisorption
 Types of Adsorption
• The selective transfer of some of the molecules of a mixture to the surface or
into the bulk of a solid (or liquid) is called sorption.
• When the sorbed moleculs or atoms remain concentrated or accumulated at or
near the surface, the process is called adsorption.
• If the sorbed molecules are distributed throughout a liquid phase, the process is
called absorption.
• The reverse of adsorption is called desorption.

Physical adsorption If the force of interaction is rather weak, the type of

adsorption is called physical adsorption or physisorption. The forces of physical
adsorption are Van der Waal’s force (or dispersion force) and electrostatic force,
and the heat of heat of adsorption is best a few times (1-4 times) the heat of
vaporization of the component concerned.

Chemical adsorption If the interaction between a solute and the adsorbent is very
strong, a chemical bond may be formed between them. This is called chemical
adsorption or chemisorption. The heat of chemisorption is considerably larger
than that of physical adsorption. Chemisorption occurs as an essential step of a
heterogeneous catalytic reaction.
 Physical Adsorption or physisorption
Some features which are useful in recognizing physisorption include:
a. the phenomenon is a general one and occurs in any solid/fluid system, although certain
specific molecular interactions may occur, arising from particular geometrical or electronic
properties of the adsorbent and/or adsorptive;
b. evidence for the perturbation of the electronic states of adsorbent and adsorbate is minimal;
c. the adsorbed species are chemically identical with those in the fluid phase, so that the
chemical nature of the fluid is not altered by adsorption and subsequent desorption;
d. the energy of interaction between the molecules of adsorbate and the adsorbent is of the
same order of magnitude as, but is usually greater than, the energy of condensation of the
adsorptive;
e. the elementary step in physical adsorption from a gas phase does not involve an activation
energy. Slow, temperature dependent, equilibration may however result from rate-
determining transport processes;
f. in physical adsorption, equilibrium is established between the adsorbate and the fluid
phase. In solid/gas systems at not too high pressures the extent of physical adsorption
increases with increase in gas pressure and usually decreases with increasing temperature.
In the case of systems showing hysteresis the equilibrium may be metastable;
g. under appropriate conditions of pressure and temperature, molecules from the gas phase
can be adsorbed in excess of those in direct contact with the surface (multilayer adsorption
or filling of micropores,
 Chemical Adsorption or chemisorption
Some features which are useful in recognizing chemisorption include:
a. the phenomenon is characterized by chemical specificity;
b. changes in the electronic state may be detectable by suitable physical means (e.g. UV,
infrared or microwave spectroscopy, electrical conductivity, magnetic susceptibility);
c. the chemical nature of the adsorptive(s) may be altered by surface dissociation or reaction in
such a way that on desorption the original species cannot be recovered; in this sense
chemisorption may not be reversible;
d. the energy of chemisorption is of the same order of magnitude as the energy change in a
chemical reaction between a solid and a fluid: thus chemisorption, like chemical reactions in
general, may be exothermic or endothermic and the magnitudes of the energy changes may
range from very small to very large;
e. the elementary step in chemisorption often involves an activation energy;
f. where the activation energy for adsorption is large (activated adsorption), true equilibrium
may be achieved slowly or in practice not at all. For example in the adsorption of gases by
solids the observed extent of adsorption, at a constant gas pressure after a fixed time, may in
certain ranges of temperature increase with rise in temperature. In addition, where the
activation energy for desorption is large, removal of the chemisorbed species from the
surface may be possible only under extreme conditions of temperature or high vacuum, or by
some suitable chemical treatment of the surface;
g. since the adsorbed molecules are linked to the surface by valence bonds, they will usually
occupy certain adsorption sites on the surface and only one layer of chemisorbed molecules
is formed
 Difference Between Physisorption and Chemisorption
Physical Adsorption (Physisorption) Chemical Adsorption (Chemisorption)
1. Physisorption is non- specific in nature. 1. Chemisorption is highly specific in
It involvesVan der Waal’s interaction nature as it involves chemical bond
between adsorbate and adsorbent. formation between adsorbate and
adsorbent.
2. On increasing the temperature 2. On increasing the temperature
physisorption decreases. chemisorption increases.
3. Physisorption is reversible in nature. 3. Chemisorption is irreversible in nature.
4. In case of physisorption, enthalpy 4. In case of chemisorption, enthalpy
change is small (20 to 40 kJ/mol). change is high (80 to 240 kJ/mol).
5. No significant activation energy is 5. Usually, high activation energy is
required. required.
6. It forms multimolecular layers. 6. It forms unimolecular layers.
 Commercially Important Adsorbents and Their Characteristics
Adsorbent Characteristics Commercial Uses
Activated carbon Hydrophobic surface, favours Removal of organic pollutants
organics over air or water from aqueous or gaseous
effluents
Carbon molecular sieve Separates on the basis of Production of N2 from air
(CMS) difference in intraparticle
diffusivity
Silica gel High capacity, hydrophilic Drying of air and other gases
adsorbent
Activated alumina High capacity, hydrophilic Drying of gas streams
adsorbent
Zeolite molecular sieve Hydrophilic surface, polar Dehydration, air separation,
(ZMS) regular channels separation of molecules based
on size and shape
Silicalite Hydrophobic surface Removal of organics from gas
streams
Polymer adsorbents Styrene/divinyl benzene Removal of organics from gas
copolymer is most common streams
Applications of Adsorbents
Applications of Adsorbents
Characteristics and Properties of Adsorbents

 Selectivity
 Adsorption capacity
 Reversibility of adsorption

 Particle size and its distribution

 Porosity and pore size distribution
 Specific surface area
 Structural strength and stability
 Adsorption Equilibria

Mono and multi layer adsorption and capillary

condensation
 Adsorption Equilibria

The equilibrium relation between the amount adsorbed q (mass adsorbed per unit mass of the
adsorbent) and the concentration C (or partial pressure p) of the adsorbate or solute at a
constant temperature T, is called an adsorption isotherm.

q = q(C) (at a constant temperature T)

Five basic types of isotherms

 Adsorption Equilibria

Type I: Favourable. Type III: Rare type of isotherm and

• mono-molecular layer formation
• Concave downwards
• Used to remove solutes in low
concentrations
• Ensures a relatively high solute
loading in the solid
• Example- oxygen adsorption on
carbon black at -183℃
Type II:
• Multilayer forms after completion of
the monolayer
• Physical adsorption
• Example- adsorption of water
vapour on carbon black at 30℃
Unfavourable.
• Relative saturation approaches unity
• Heat of adsorption is equal to or less
than heat of liquefaction
• Convex downwards
• Solute loading is low at a small
concentration in the fluid
• Example- adsorption of N2 on ice
Type IV and V:
• Alternating convex and concave regions
• Reflect the phenomenon of capillary
condensation within the pores
 Adsorption Isotherm

 Langmuir Isotherm
 Freundlich Isotherm
 Toth Isotherm
 Sips Isotherm
 BET Equation (Stephen Brunauer, Paul Emmet and Edward Teller)
 Langmuir Isotherm
The Langmuir isotherm (1918) is based on the simplest model of physical adsorption
which assumes that –
i. The molecules are adsorbed at discrete active sites on the surface
ii. Each active site adsorbs one molecule only
iii. The adsorbing surface is energetically uniform
iv. There is no interaction among the adsorbed molecules
As a result, the rate of capture of adsorbate molecules by the surface is proportional to
the fraction of uncovered area, (1-θ), and the partial pressure p or concentration of the
adsorbate.

or,
The rate of desorption is proportional to the fraction of surface covered only, i.e. θ.

or,
 Langmuir Isotherm
At equilibrium, R1 = R2.

If we write,

Here, q = amount of gas adsorbed at equilibrium per gram of adsorbent at a partial pressure p

and, qm = maximum quantity of gas adsorbed per gram of adsorbent (at a large pressure)

This equation can be rearranged as-

The above equation represents the Langmuir isotherm which has two “adjustable parameters” qm
and K.

If the Langmuir model applies to a particular system, a lot of the experimental data in the form of
p/q versus p should yield a straight line of slope 1/qm and intercept 1/qmK. From the values of the
slope and the intercept, the parameters qm and K can be calculated.
 Langmuir Isotherm

 The Langmuir adsorption isotherm is used to describe the equilibrium between adsorbate and

adsorbent system, where the adsorbate adsorption is limited to one molecular layer at or before
a relative pressure of unity is reached.
 At a low partial pressure of the adsorbate (Kp << 1),

q = qmKp = KH p

The above equation is of the form of Henry’s law; KH is the “Henry’s law constant’ for
adsorption. This particular form represents a ‘linear isotherm’.

 At a large pressure (Kp >> 1), q = qm and the fractional coverage of the adsorption sites is θ =
1.

Problem :- The volume of CH4 (corrected to STP) adsorbed per gram of charcoal at 240K
various pressures of CH
p (mmHg) 384 is: 55 78 104 133 173 218
q (cm3.g-1) 14.14 17.52 21.38 24.72 28.00 31.35 34.50

Determine Langmuir constant K and the volume corresponding to complete surface coverage.
Calculate the fraction of charcoal surface which is covered by CH4 molecules at p = 150 mmHg.
 Heat of Adsorption
 The temperature dependence of K can be used to determine the isosteric enthalpy of
adsorption ( ΔH, the enthalpy of adsorption at a fixed surface coverage)
From Langmuir adsorption isotherm, fraction of covered surface,

From Gibb’s free energy equation we know,

 Heat of Adsorption
 From equation (1) and (2)

Again,

Now from (3) and (4)

 Specific Surface Area of An Adsorbent

Problem :- The following data have been collected on equilibrium adsorption of nitrogen on
an oxidation catalyst at 77.4 k, the normal boiling point of nitrogen. Determine the specific
surface area of the catalyst by the BET technique.

p (pressure of 10 20 40 100 150 200 250 300 350 400 500

N2, mmHg)
v (volume of N2 71.3 142.2 287.7 679.4 1025 1429 1751 2174 2914 3451 5283
adsorbed, cm3
at NTP per 100
g solid)
 Selection of Adsorbents

 Ease of separation
 Solute concentration
 Process conditions
 Adsorbent criteria

• A high adsorption capacity

• Reversibility of adsorption
• Selectivity
• Easy regenerability
• Low cost
• Insolubility
• Good mechanical strength when used in bead or pellet form
 Pressure Swing Adsorption

 Pressure swing adsorption (PSA) has evolved as an alternative to the TSA process
because of a few disadvantages of the latter like-
i. Energy consumption for heating of the bed for regeneration
ii. The solute is released as a dilute stream and may not be easy to recover
iii. Cooling of the bed should follow regeneration
 The PSA technique was developed in 1960 by Skarstrom of Exxon Research for
drying of gases by silica gel or alumina.
 It was called heat-less drying at that time because of the particular application.
 Basic Principles of Pressure Swing Adsorption
 In a PSA system adsorption occurs at a higher pressure of the feed gas when it is stripped of the
solute.
 The flow of the feed stops at breakthrough and the bed is regenerated by reducing the pressure.
 The adsorbate is recovered in a relatively concentrated form.
 A packed bed of adsorbent responds more rapidly to changes in pressure than to changes in
temperature.
 The process requires less energy and is operationally simpler than TSA.
 The four basic steps of the process according to the Skarstrom cycle are-

Adsorption – The feed gas flows at a higher pressure through the bed, the more absorbable
component gets trapped; the purified gas is simultaneously drawn as the product.
Depressurization – The pressure in the vessel is reduced; the adsorbed component and the residual
gas in the bed voids are drawn out as another product or may be discarded. It is also called blowdown.
Purging – A small fraction of the product gas from the other bed is passed through the vessel as the
purge gas to remove most of the residual solute from the bed.
Repressurization – Feed is supplied into the adsorption vessel to raise its pressure to that of the feed
(no product is drawn during this step).
 Basic Principles of Pressure Swing Adsorption

 The process generally becomes more efficient if the flow of the gases during
depressurization and purging occurs in the direction countercurrent to the
direction of feed flow.
 Upflow of the feed gas during adsorption and downflow of the adsorbate-rich gas
during depressurization and purging are the convenient flow configurations.
 The beds operate under nearly isothermal condition. The heat liberated during
adsorption remains in the bed and compensates for the heat of desorption during
the regeneration step.
 A variation of PSA uses a vacuum pump to create a low pressure for regeneration
of the bed. This is called vacuum swing adsorption (VSA).
 Applications of Pressure Swing Adsorption
 The most important application of PSA has been for air separation to produce
either oxygen or nitrogen
 Hydrogen purification from steam reformer gases, refinery gases etc. using
activated carbon or zeolite adsorbent
 Separation of CO2 from methane

 Recovery of CO from waste gases of steel plants

 Separation of ammonia synthesis gases
 Helium purification
 Separation of n- and iso-paraffins using zeolite

 Refineries often use PSA technology in the removal of H 2S from hydrotreating

and hydrocracking units
 Hypoxic air fire prevention systems to produce air with a low oxygen content
 Thermal Swing Adsorption
 Regeneration of adsorbent in a thermal
swing adsorption (TSA) process is
achieved by an increase in temperature.
 The figure showed schematically the
effect of temperature on the adsorption
equilibrium of a single adsorbate.
 For any given partial pressure of the
adsorbate in the gas phase (or
concentration in the liquid phase), an
increase in temperature leads to a
decrease in the quantity adsorbed.
 If the partial pressure remains constant
at p1, increasing the temperature from
T1 to T2 will decrease the equilibrium
loading from q1 to q2.
 Thermal Swing Adsorption
 A relatively modest increase in temperature can effect a relatively large decrease in loading.
It is therefore generally possible to desorb any components provide that the temperature is
high enough.
 However, it is important to ensure that the regeneration temperature does not cause
degradation of the adsorbents.
 A change in temperature alone is not used in commercial processes because there is no
mechanism for removing the adsorbate from the adsorption unit once desorption from the
adsorbents has occurred.
 Passage of a hot purge gas or steam, through the bed to sweep out the desorbed components
is almost always used in conjunction with the increase in temperature.
 A very important characteristics of TSA processes is that they are used virtually exclusively
for treating feeds with low concentrations of adsorbates.
 Countercurrent heating and cooling ensure a low residual solute retention in the bed.
 Heat requirement for regeneration is about 2.5 times the enthalpy of adsorption.
 A hot regenerated bed needs to be cooled down before it goes for the next adsorption half
cycle.
 Applications of Thermal Swing Adsorption

 TSA is required for the removal of the contaminants CO2 and H2O.

 TSA is found in cryogenic oxygen plants and natural gas dehydration units.
 TSA with the use of granular activated carbon (GAC) have been widely applied
to remove the residual amounts of pesticides in water treatment.
 Batch Adsorption in a Stirred Vessel
 Removal of a solute or an impurity from a solution can
be carried out in a batch stirred vessel.
 For fine particles the resistance due to pore diffusion
may be fairly small and the adsorption process may be
controlled by the external transport resistance.
 If the relevant properties of the solid and of the liquid
(particle size, density and porosity, liquid properties), the
adsorption equilibrium (in terms of an adsorption
isotherm), and a suitable mass transfer correlation are
known, it is not difficult to design a stirred vessel.
 In the stirred tank, slurry operation, a batch of liquid is
added to a powdered adsorbent (such as activated
carbon) in an agitated vessel to form a slurry.
 This is shown in the figure.
 The main application of this mode of operation is the
removal of very small amounts of dissolved, and
relatively large molecules, such as colouring agents, from
water.
 Batch Adsorption in a Stirred Vessel
 The required residence time of the operation is
mainly determined by how fast equilibrium is
approached.
 Generally the spent adsorbent is removed from the
slurry by filtration or sedimentation and is
discarded.
 When large quantities of adsorbent is required
consideration should be given to using multiple
batch or cross flow system.
 One way of reducing the total amount of adsorbent
required is to carry out the batch processing in 2
steps as shown in the figure.
 The feed is first contacted with a fresh batch of
adsorbent.
 After separation of the fluid from the adsorbent,
the fluid is contacted with a further fresh batch of
adsorbent.
 Batch Adsorption in a Stirred Vessel

Problem :- Adsorption equilibrium data for the decolourization of a sample of waste oil
using a special type of clay collected from a set of laboratory experiments could be fitted
by a Henry’s law type relation – Y = 4.2×10-4 X*, where Y = number of ‘colour units’ per
kg oil, and X* = number of ‘colour units’ per kg clay in equilibrium. One thousand
kilograms of a waste oil having an initial colour concentration of 50 units has to be
treated to reduce the concentration to 1 colour unit. The adsorbent has an effective
specific surface area of 25 m2/kg, and the surface mass transfer coefficient is kL = 5.2 ×
10-6 m/s (on the solid-phase concentration basis). The density of the oil is 950 kg/m3.
a) Calculate the minimum quantity of adsorbent required.
b) What is the required contact time if 1.2 times the minimum amount of adsorbent is
used?

Solution :- Principles of mass transfer and separation processes – Binay K. Dutta,

Page- 629-630.
THE END