SHMT (CHE-402)

Adsorption

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If we have to remove soluble material from the solution
phase, but the material is neither volatile nor biodegradable,
we often employ adsorption processes.
adsorbate: material being adsorbed
adsorbent: material doing the adsorbing.
(examples are activated carbon or silica gel).

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 Diffusion
Adsorption Process As
• Classified as Physical and Chemical
1) Physical adsorption
• The gas molecules adhere to the surface of the solid adsorbent
as a result of intermolecular attractive forces (van der Waals
forces) between them
• The process is exothermic: the heat liberated is in the order of
the enthalpy of condensation of vapor (2-20 kJ/gmole)
• The process is reversible (recovery of adsorbent material or
adsorbed gas is possible) by increasing the temperature or
lowering the adsorbate conc.
• Physical adsorption usually directly proportional to the amount
of solid surface area
• Adsorbate can be adsorbed on a monolayer or a number of
layers
• The adsorption rate is generally quite rapid

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2) Chemical adsorption

• Results from a chemical interaction between the adsorbate and

adsorbent. Therefore formed bond is much stronger than that for
physical adsorption
• Heat liberated during chemisorption is in the range of 20-400 kj/g
mole
• It is frequently irreversible, On desorption the chemical nature of
the original adsorbate will undergone a change.
• Only a monomolecular layer of adsorbate appears on the
Diffusion
adsorbing medium
As

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Adsorption Mechanism

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 Adsorbent Material
– Silica gel
– Activated alumina
– Activated carbon
– Synthetic zeolite
• Molecular sieve

Silica gels:

- granular porous form of silica

- amorphous
- hydrophilic
- water removal
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 Adsorbent Material

Activated Carbon

- partial oxidation of coal

- amorphous

- hydrophobic

- organic trace removals

- air filters

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 Adsorbent Material

Zeolites

- porous crystalline minerals

- hydrophilic

- highly structured porous Mordenite

space

- N2 removal from air

ZSM-5
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 ADSORPTION EQUILIBRIA
• If the adsorbent and adsorbate are contacted long enough an
equilibrium will be established between the amount of adsorbate
adsorbed and the amount of adsorbate in solution. The equilibrium
relationship is described by isotherms.

• Define the following:

qe = mass of material adsorbed (at equilibrium) per mass of adsorbent.

Ce = equilibrium concentration in solution when amount adsorbed

equals qe.

• qe/Ce relationships depend on the type of adsorption that occurs, multi-

layer, chemical, physical adsorption, etc. 10
 Isotherm models:
 Five types of physisorption isotherms are found over all solids
I
◦ Type I is found for porous materials with small pores e.g. charcoal.
It is clearly Langmuir monolayer type, but the other 4 are
not
II

◦ Type II for non-porous materials

amount adsorbed

III ◦ Type III porous materials with cohesive force between adsorbate
molecules greater than the adhesive force between adsorbate
molecules and adsorbent
IV
◦ Type IV staged adsorption (first monolayer then build up of
additional layers)

◦ Type V porous materials with cohesive force between adsorbate

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molecules and adsorbent being greater than that between adsorbate
molecules
1.0

relative pres. P/P0

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 Isotherm models:
• Langmuir Isotherm:
• This model assumes monolayer coverage and constant binding energy between
surface and adsorbate.
 At higher gas phase concentrations, the number of molecules absorbed soon
increases to the point at which further adsorption is hindered by lack of space
on the adsorbent surface.
 At a fixed temperature, the rate of desorption will be proportional to the surface
area occupied by adsorbate. When the rates of adsorption and desorption are
equal, a dynamic equilibrium exists.

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 BET (Brunauer, Emmett and Teller) isotherm:
• As in the case in Langmuir’s isotherm, the theory is based on the
concept of an adsorbed molecule which is not free to move over
the surface, and which exerts no lateral forces on adjacent
molecules of adsorbate.
• The BET theory allow different numbers of adsorbed layers to
build up on different parts of the surface, although it assumes that
the net amount of surface which is empty or which is associated
with a monolayer, bilayer and so on is constant for any particular
equilibrium condition.
• Monolayers are created by adsorption on to empty surface and by
desorption from bilayers.
• Monolayers are lost both through desorption and through the
adsorption of additional layers.
• The rate of adsorption is proportional to the frequency with
which molecules strike the surface and the area of that surface.
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 The rate of adsorption on to empty surface =
 The rate of desorption from a monolayer =

Where a is the external area of the absorbent per unit volume of

bed, Ko is the adsorption equilibrium constant at a standard
condition, k1’ is desorption velocity constant for monolayer.

 Desorption is an activated process. If E1 is the excess energy required

for one mole in the monolayer to overcome the surface forces, the
proportion of molecules possessing such energy is e−E1/RT . Hence
the rate of desorption from a monolayer may be written as:

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Factors which affect adsorption extent (and
therefore affect isotherm) are:
Adsorbate:
Solubility
In general, as solubility of solute increases the extent of adsorption decreases. This
is known as the “Lundelius’ Rule”. Solute-solid surface binding competes with
solute-solvent attraction. Factors which affect solubility include molecular size
(high MW- low solubility), ionization (solubility is minimum when compounds are
uncharged), polarity (as polarity increases get higher solubility because water is a
polar solvent).

pH
pH often affects the surface charge on the adsorbent as well as the charge on the
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solute. Generally, for organic material as pH goes down adsorption goes up.
• Temperature
• Adsorption reactions are typically exothermic. Here heat is given off by the
reaction therefore as T increases extent of adsorption decreases.

• Presence of other solutes

• In general, get competition for a limited number of sites therefore get reduced
extent of adsorption or a specific material.

• Adsorbent:
• Virtually every solid surface has the capacity to adsorb solutes. From the
wastewater/water treatment point of view activated carbon (AC) is the
adsorbent of choice. AC prepared from many sources:
•Wood
•Lignite
•Coal
•Nutshells
•Bone
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 Regeneration of Adsorbent
 It is most important to ensure that the spent adsorbent can
be regenerated in a given time and that the total inventory
of adsorbent is kept to a minimum.

Thermal swing

• The simplest and the most common way of regenerating an

adsorbent in industrial applications is by heating. The
vapour pressure exerted by the adsorbed phase increases
with temperature, so that molecules desorb until a new
equilibrium with the fluid phase is established.

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 Figure depicts adsorption isotherms for a lower temperature
T1 and a higher temperature T2. For a fixed concentration C in
the fluid phase, the adsorbate concentration falls from Cs1 to
Cs2 when the temperature is increased.

Thermal regeneration utilises the change in concentration that

follows from a change in temperature 18
 Typical arrangement of a two bed dryer
• An adsorption unit using thermal swing
regeneration usually consists of two
packed beds, one on-line and one
regenerating. Regenerating consists of
heating, and purging to remove adsorbate.
• The desorption temperature depends on
the properties of the adsorbent and the
adsorbates.
• Exceeding this temperature may
Separate regeneration
accelerate the ageing processes which
cause pores to coalesce and capacity to be
reduced.
• Too low a temperature may result in
incomplete regeneration so that the
effluent concentration in subsequent
adsorption stages will be higher than its
design value.

Integrated regeneration
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Plug-flow of solids

• Adsorbent were removed for regeneration as soon as it became

saturated, and even better if the advancing adsorption wave were
presented with only sufficient fresh adsorbent to contain the
wave.

• A typical application of plug-flow was the recovery of ethylene

from gas composed mainly of hydrogen and methane, and with
some propane and butane.

• Hypersorber is one of the example of such unit.

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Hypersorber
 The recovery of ethylene from gas composed mainly of hydrogen and methane,
and with some propane and butane.

The mixture is fed to the centre of the

column down which activated carbon
moves slowly. Immediately above the feed,
the rising gas is stripped of ethylene and
heavier components leaving hydrogen,
methane and any non-adsorbed gases to
be discharged as a top-product. The
adsorbent with its adsorbate continues
down the column into an enriching section.
The least-strongly adsorbed ethylene is
desorbed and recovered in a side stream.
The heavy components continue
downwards on the carbon until these are
also desorbed by steam, to be recovered as
a bottom product.
The carbon, now stripped of all the adsorbates, is lifted to the top of the column
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where it is cooled before the cycle starts again.
Rotary bed
 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.
Figure shows the solvent
recovery from air on to activated-
carbon. The activated-carbon is
contained in a thick annular
layer. Air can enter through most
of the drum circumference and
passes through the carbon layer
to emerge free of solvent. The
clean air leaves the equipment
through a duct connected along
the axis of rotation.

As the drum rotates, the carbon enters a section in which it is exposed to steam.
Steam flows from the inside to the outside of the annulus so that the inner layer
of carbon, which determines the solvent content of effluent air, is regenerated
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as thoroughly as possible.
APPLICATIONS
• Charcoal is used as a decoloriser
• Treatment of Diahroea
• Silica and alumina gels are used as adsorbents for removing moisture and for
controlling humidity of rooms.
• Activated charcoal is used in gas masks as it adsorbs all the toxic gases and
vapours and purifies the air for breathing.

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 Adsorption processes: Applications
Purifications: Separations:

- Removal of organics from - N2/O2

vent gases
- Acetone from vent stream
gas phase

- SO2 from vent gases

- C2H4 from vent
- H2O from air, methane, N2
- Normal paraffins/ Iso praffins
- Removal of solvent, odours
from air - CO, CH4, CO2, N2, Ar from
hydrogen
- NOx from N2
liquid phase

- Organics from water solution - Normal paraffins from Iso paraffins

- Water from organic solution - Normal paraffins from olefins

- Decolourization
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Typical applications of commercial adsorbents

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Typical applications of commercial adsorbents

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 Assignment
1. What do you understand by Sorbex Process
2. The moving bed equivalent of Sorbex process
3. Pressure swing regeneration of adsorbants
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