Chapter Seven- Adsorption

Chapter Objectives:-
• To give short introduction on
adsorption process, adsorbent
nature and regeneration

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7.1 Introduction
• Although adsorption has been used as a physical-
chemical process for many years, it is recently has
developed to a stage where it is now a major
industrial separation technique
• Here , molecules diffuse from the bulk of the fluid to
the surface of the solid adsorbent forming a distinct
adsorbed phase
• In adsorption, molecules distribute themselves
between two phases, one of which is a solid whilst
the other may be a liquid or a gas
• Typically, gas adsorbers are used for removing trace
components from gas mixtures
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• Separation by adsorption depends on one component
being more readily adsorbed than another
For example:
Separating n- and iso-paraffins by distillation requires a
large number of stages because of the low relative
volatility of the components. It may be economic,
however, to use a selective adsorbent which separates
on the basis of slight differences in mean molecular
diameters, where for example, n- and iso-pentane have
diameters of 0.489 and 0.558 nm respectively. When an
adsorbent with pore size of 0.5 nm is exposed to a
mixture of the gases, the smaller molecules diffuse to
the adsorbent surface and are retained whilst the
larger molecules are excluded
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• In another stage of the process, the retained
molecules are desorbed by reducing the total
pressure or increasing the temperature
• The only reason why certain solids are designated
“adsorbents” is that they can be manufactured in a
highly porous form, giving rise to a large internal
surface
• The adsorption which results from the influence of
van der Waals forces is essentially physical in nature.
Because the forces are not strong, the adsorption
may be easily reversed
• In some systems, additional forces bind absorbed
molecules to the solid surface. These are chemical in
nature involving the exchange or sharing of
electrons, or possibly molecules forming atoms or
radicals 4

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• In such cases the term chemisorption is used to
describe the phenomenon
• This is less easily reversed than physical adsorption,
and regeneration may be a problem
• For physical adsorption, the amount of heat is similar
in magnitude to the heat of condensation
• For chemisorption it is greater and of an order of
magnitude normally associated with a chemical
reaction

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7.2 The Nature of Adsorbents
• Adsorbents are available as irregular granules,
extruded pellets and formed spheres
• To be attractive commercially, an adsorbent should
embody a number of features:
(a) it should have a large internal surface area
(b) the area should be accessible through pores big enough
to admit the molecules to be adsorbed. It is a bonus if
the pores are also small enough to exclude molecules
which it is desired not to adsorb
(c) the adsorbent should be capable of being easily
regenerated

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 (d) the adsorbent should not age rapidly, that is lose its
adsorptive capacity through continual recycling
(e) the adbsorbent should be mechanically strong enough to
withstand the bulk handling and vibration that are a
feature of any industrial unit
• Some common type of adsorbent:
• Molecular sieves
• Activated carbon
• Silica gel
• Activated alumina

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7.3 Adsorption Equilibria
• Adsorption equilibrium is a dynamic concept
achieved when the rate at which molecules adsorb
on to a surface is equal to the rate at which they
desorb
• The physical chemistry involved may be complex and
no single theory of adsorption has been put forward
which satisfactorily explains all systems
• The capacity of an adsorbent for a particular
adsorbate involves the interaction of three
properties—the concentration C of the adsorbate in
the fluid phase, the concentration Cs of the
adsorbate in the solid phase and the temperature T
of the system
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• Most early theories were concerned with adsorption
from the gas phase
• For these limiting conditions it is reasonable to
assume that the concentration in one phase is
proportional to the concentration in the other, that
is:

• This expression is analogous to Henry’s Law for gas–

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 – The BET theory
– The Gibbs isotherm
– The potential theory
• Adsorption from liquids is less well understood than
adsorption from gases
• In principle the equations derived for gases ought to
be applicable to liquid systems, except when capillary
condensation is occurring

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7.4 Structure of Adsorbents
• The equilibrium capacity of an adsorbent for
different molecules is one factor affecting its
selectivity
• Another is the structure of the system of pores which
permeates the adsorbent
• The important parameters are:
»Surface area
»Pore sizes

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• The scale and complexity of an adsorption unit varies
from a laboratory chromatographic column a few
millimeters in diameter, as used for analysis, to a
fluidised bed several metres in diameter
• All such units have one feature in common in that in
all cases the adsorbent becomes saturated as the
operation proceeds
• For continuous operation, the spent adsorbent must
be removed and replaced periodically and, since it is
usually an expensive commodity, it must be
regenerated

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• In most systems, regeneration is carried out by
heating the spent adsorbent in a suitable
atmosphere
• For some applications, regeneration at a reduced
pressure without increasing the temperature is
becoming increasingly common
Fixed or packed beds
• Usually the beds are stationary and the feed is
switched to a second bed when the first becomes
saturated
• We have different correlation for the following cases:
– Equilibrium, isothermal adsorption in a fixed bed
– Non-equilibrium adsorption—isothermal operation
– Non-equilibrium adsorption—non-isothermal operation 13
7.5 Regeneration of Spent Adsorbent
• Most theory concerning the dynamics of an
industrial adsorption unit is directed at sizing a bed
for a given adsorption duty
• In the design of a complete adsorption unit,
however, it is most important to ensure that the
spent adsorbent can be regenerated in a given time
• The equilibrium condition has then to be changed for
regeneration to occur. This is usually brought about
by changing the temperature or the pressure so that
the driving force, which had previously resulted in
the movement of adsorbate from fluid to solid, is
now reversed
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Thermal swing
• The simplest and the most common way of
regenerating an adsorbent in industrial applications
is by heating
• Regenerating consists of heating, and purging to
remove adsorbate
Plug-flow of solids
• Better utilisation of adsorbent would be achieved if a
unit could be designed in which adsorbent were
removed for regeneration as soon as it became
saturated

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Rotary bed
• Because of the difficulty of ensuring that the solid
moves steadily and at a controlled rate with respect
to the containing vessel, other equipment has been
developed in which solid and vessel move together,
relative to a fixed inlet for the feed and a fixed outlet
for the product
Moving access
• In an interesting alternative to a moving-bed or a
moving-container adsorber, a multiway valve
effectively changes the position of the inlet and
outlet valves relative to a fixed bed

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Others:
• Fluidised beds
• Compound beds
• Pressure-swing regeneration and etc

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