Adsorption

Introduction
• Adsorption is a separation process in which certain components of a fluid phase are
transferred to the surface of the solid adsorbent
• The major applications had been in the separation of solutes from liquid streams and
removal of impurities from gas streams.
• In an adsorption process molecules or atoms or ions in a gas or liquid diffuse to the
surface of a solid, where they bond with the solid surface or are held there by weak
inter-molecular forces.The adsorbed solute is called the adsorbate, and the solid
material is the adsorbent.
 Cont….

• In order to achieve better efficiency a very large surface area is required so most of them are porous
and the porous structure can account for up to 50% of the volume of the material.
• During adsorption, the solid adsorbent becomes saturated or nearly saturated with the adsorbate. To
recover the adsorbate and allow the adsorbent to be reused, it is regenerated by desorbing the
adsorbed substances (i.e. the adsorbates).

• Removal of adsorbates can also be achieved by changing the pressure or the temperature. This will be
covered in more details in later sections
• Adsorption processes can be divided into 2 groups: bulk separation, which involves the separation of
up to half of the components from a process stream, and purification, a process in which a small
amount of impurity is removed from the gas stream.
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 paraffins
- 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
Adsorption processes

Adsorption

Physical (physisorption) Chemical (chemisorption)

- van der Waals interactions - Chemical bonds between adsorbate

(result in attractive forces between and adsorbent formed
adsorbent and adsorbate molecules)
- Adsorbed molecules loose their
- Adsorbed molecules maintain their identity
identity
- Monolayers
- Multilayers
- Can be irreversible
- Always reversible
Adsorption processes
Mechanisms of selectivity

*one component exhibits stronger interaction with adsorbent

and therefore is selectively removed from the mixture

* one component is not able to fit in the pores and therefore is

excluded from adsorption

* one component exhibits higher transport diffusion and is

selectively removed from the mixture
Adsorbents

• Major types of adsorbents in use are: activated alumina, silica gel, activated carbon,
molecular sieve carbon, molecular sieve zeolites and polymeric adsorbents

• Most adsorbents are manufactured (such as activated carbons), but a few, such as some
zeolites, occur naturally. Each material has its own characteristics such as porosity, pore
structure and nature of its adsorbing surfaces

• Pore sizes in adsorbents may be distributed throughout the solid. Pore sizes are classified
generally into 3 ranges: macropores have "diameters" in excess of 50 nm, mesopores have
"diameters" in the range 2 -50-nm, and micropores have "diameters" which are smaller than
2-nm.
Adsorbents: Characterization

1) Crystalline/amorphous

2) Hydrophobic/Hydrophilic

3) Surface area (100-1000m2/g)

4) Pore size
r < 2nm: microporous
2nm < r < 50nm: mesoporous
r >50nm: macroporous

5) Pore shape: slits, channels, cavities, cages, shapeless

- Often modelled as cylindrical channels

Adsorbents: Examples

Activated Carbon

- partial oxidation of coal

- amorphous

- hydrophobic

- 400-1200m2/g

- Removal of organic trace removals

from gas or liquid

- air filters
Adsorbents: Examples

Silica gels:

-Acid treatment of sodium silicate solution and drying

- amorphous

- hydrophilic

- 700-800m2/g

- water removal
Adsorbents: Examples

Zeolites
- porous crystalline minerals

- hydrophilic

- 600-700m2/g

- N2 removal from air Mordenite

ZSM-5
Adsorption Isotherm
• In adsorption, a dynamic phase equilibrium is established for the distribution of the solute between
the fluid (gas, vapour or liquid) and the solid surface

• The equilibrium is usually expressed in terms of partial pressure (gas, vapour) or concentration
(liquid) of the adsorbate in the fluid and the solute loading on the adsorbent, expressed as mass, mole
or volume of adsorbate per unit mass, mole or volume of the adsorbent.

• Unlike vapour-liquid and liquid-liquid equilibria, where theory is often applied to estimate phase
distribution, no acceptable theory has been developed to estimate fluid-solid adsorption equilibria

• Thus it is necessary to obtain experimental equilibrium data for a particular solute, or mixtures of
solutes and/or solvent, and a sample of the actual solid adsorbent material of interest.

• If the data are taken over a range of fluid concentrations at a constant temperature, a plot of solute
loading on the adsorbent versus concentration or partial pressure in the fluid can be made. Such a
plot is called the adsorption isotherm
 Gas-Phase Adsorption

For pure gases, experimental physical adsorption isotherms have shapes, that are classified into 5 types as
discussed below. Each of these types is observed in practice but by far the most common are types I, II and
IV.

Type I isotherm
• is limited to the completion of a single monolayer of
adsorbate at the adsorbent surface

• are observed for the adsorption of gases on microporous

solids whose pore sizes are not much larger than the
molecular diameter of the adsorbate

• An example is the adsorption of oxygen on carbon black at

- 183 oC.
 Cont….

Type II isotherm

• This type of isotherm indicates an indefinite multi-layer

formation after completion of the monolayer and is
found in adsorbents with a wide distribution of pore
sizes

• Near to the first point of inflexion (point A) a

monolayer is completed, following which adsorption
occurs in successive layers

• An example is the adsorption of water vapour on carbon

black at 30 oC.
Type III isotherm

• is obtained when the amount of gas adsorbed increases

without limit as its relative saturation approaches unity

• Unfavorable interaction with the adsorbent (porous

materials with cohesive force b/n adsorbate molecules
greater than force b/n adsorbates molecules &
adsorbents )

• This type of isotherm is obtained when bromine is

adsorbed on silica gel at 20 oC.
Type IV isotherm

• is a variation of Type II, but with a finite multi-layer

formation corresponding to complete filling of the
capillaries.

• The adsorption terminates near to a relative pressure of

unity.

• This type of isotherm is obtained by the adsorption of

water vapor on activated carbon at 30 oC.
Type V isotherm
• is similar variation of Type III

• Porous materials with cohesive force b/n adsorbate

molecules & adsorbent being greater than that b/n
adsorbate molecules.

• obtained when water vapour is adsorbed on activated

carbon at 100 oC
Uses of Adsorption Isotherms

• Adsorption isotherms are most commonly used to select the adsorbent or even the
adsorption process as a unit operation for the adsorptive separation of gases.

• If the adsorption isotherm shape is Type I, II or IV, adsorption can be used to separate the
adsorbate from the carrier gas. If it is Type III or V, adsorption will probably not be
economical for the separation

• Although isotherms are indicative of the efficiency of an adsorbent for a particular

adsorbate removal, they do not supply data to permit the calculation of contact time

• or the amount of adsorbent required to reduce the solute concentration below prescribed
limits
Adsorption Equilibria
• A variety of different isotherm equations have been proposed, some of which have a
theoretical foundation and some being of a more empirical nature.

• Many of these equations are valid over small relative pressure ranges but do not fit
experimental data when tested over the full range of relative pressures.

• The same pure gas may also illustrate different isotherms on different adsorbents

Generally there are three most known types of isotherms.

 Langmuir

 Freundlich

 Brunauer-Emmett-Teller (BET)
Langmuir Isotherm
• This isotherm described adsorbate-adsorbent systems in which the extent of adsorbate coverage
is limited to one molecular layer at or before a relative pressure of unity is reached (i.e. Type I).
• The isotherm was formulated on the basis of a dynamic equilibrium between adsorbed phase
and the gaseous or vapour phase.
• The implicit assumptions are

• No lateral interaction between adsorbed molecules

• The heat of adsorption is constant
• The adsorbed molecule remained at the site of adsorption until it is desorbed
Let say
• If theta (Ɵ) is the fraction of adsorbent surface covered by adsorbate,
so , let q is the amount of solute adsorbed and qm is the maximum amount of solute to complete
coverage of the surface adsorbent
Ɵ=
• then (1- Ɵ) is the fraction of surface remaining uncovered and therefore available as adsorption
sites.
• So the rate of adsorption and desorption is proportional to (1- Ɵ) and (Ɵ) respectively
rate adsorption α (1- Ɵ) rate of ads= ka p (1- Ɵ)
rate desorption α ( Ɵ) rate of des= kd (Ɵ)
where ka and kd are the rate constants for adsorption and desorption respectively, p is the partial
pressure of the gas
At equilibrium, these two rates are equal. Thus,
rate adsorption = rate desorption
1

• By rearranging the above equation

where
On linearization, the equation 2 becomes:

• The quantities b and q m are treated as empirical constants.

• Thus the plot of p / q vs. p is linear and the slope (gradient) gives ( 1/qm ) and the y-intercept
gives (1/bqm ).
• At low pressures where bp tends to zero, the equation reduces to the linear form:

At high pressures, bp tends to infinity, and q = qm, i.e. theta = 1.

The Freundlich Isotherm
• This isotherm does not indicate an adsorption limit when coverage is sufficient to fill a
monolayer ( theta = 1). The equation that describes such isotherm is the Freundlich Isotherm,
given as:

5
where n > 1
k is a temperature-dependent constant.

With n = 1, the equation reduces to the linear form: q = k p

On linearization, the equation becomes:

• The plot of log (q) vs. log (p) gives a straight line with slope of (1/n) and y intercept of log (k).
The BET Isotherm

In its most useful form, the BET equation is written as:

where ps is the saturated vapour pressure and C is constant.

• At fixed temperature, a plot of the LHS against p/ps would yield a slope of (C-
1)/qm C and a y-intercept of 1/qm C thus enabling both qm and C to be determined.

• By appropriate choice of C and qm the equation can be made to fit any of the isotherm types
II to V inclusive.
 Adsorption equipment

1. Stirred-Tank Slurry Adsorption

• 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.

• The main application of this mode of operation is the

removal of very small amounts of dissolved, and
relatively large molecules, such as coloring agents, from
water.

• 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
 Cont….

• When large quantities of adsorbent is required consideration

should be given to using multiple batch 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.
 Cont….

• A more efficient way is to use a counter-current

configuration of fluid and adsorbent flows as shown in
the figure

• Here the feed enters Stage 1 and is initially contacted

with a quantity of adsorbent which has passed through
two other stages (2 and 3)

• The quantity of adsorbent required for a given separation

can be reduced by increasing the number of stages
2. Fixed Bed Adsorption (Percolation)
• The cyclic-batch operating mode using fixed bed, is widely used with both gas
and liquid feeds.

• Separation in a fixed bed is, in virtually all practical cases, an unsteady state
rate-controlled process .

• This means that conditions at any particular point within the fixed bed vary with
time.

• Adsorption only occurs in a particular region of the bed, known as the mass
transfer zone (MTZ), which moves through the bed

• Applications of fixed bed adsorption, also called percolation, include the

removal of dissolved organic compounds from water

• In order to achieve a steady flow of product, most applications include at least 2

beds such that one is in the adsorption mode while the other is in the
regeneration mode
3. Moving Bed Adsorption

• The main advantage of moving bed processes is that the

adsorbent can be regenerated as soon as its role in the
adsorption step has been completed.

• Additionally, heat transfer in moving and fluidized bed

systems is better than in fixed beds.

• In contrast, the equipment required for a moving bed

process will inevitably be more complex and hence more
expensive than fixed beds.

• In addition, the equipment will need to be provided to

cope with attrition of the adsorbent which will inevitably
occur.
Desorption and Regeneration of Adsorbents
• During adsorption, the solid adsorbent becomes saturated or nearly saturated with the adsorbate.
• To recover the adsorbate and allow the adsorbent to be reused, it is regenerated by desorbing the
adsorbed substances (i.e. the adsorbates).
• In certain applications it may be more economical to discard the adsorbent after use.
• Disposal would be favored when the adsorbent is of low cost, is very difficult to regenerate, and the
non-adsorbed component is the desired product of very high value.
• In the majority of applications, the disposal of adsorbents as waste is not an economic option and
therefore regeneration is carried out either in situ or external to the adsorption vessel to an extent
that the adsorbents can be reused.
• Practical methods of desorption and regeneration include one, or more usually a combination, of the
following:
Increase in temperature ,
Reduction in partial pressure,
Reduction in concentration,
Purging with an inert fluid,
Displacement with a more strongly adsorbing species,
Change of chemical conditions, e.g. pH
Temperature swing adsorption (TSA)
 Regeneration of adsorbent in a TSA process is achieved by an
increase in temperature.

 The figure showed the effect of temperature on the adsorption

equilibrium (Type I isotherm) of a single adsorbate.

1 Step 1: The feed fluid at p1 and T1 is passed through

2
adsorbent. Equilibrium loading n1 or q1 is reached.

Step 2: The temperature is raised to T2 and the equilibrium

3
partial pressure raises to p2, causing desorption of the component from
the adsorbent
4
Step 3: Purge stream is passed of the sample removing the
component from the gas phase

Step 4: Cooling returns us back to T1 line with some

remaining loading n2 or q2

 In this process it s important to ensure that the regeneration

temperature does not leads to degradation of adsorbent.
Pressure swing adsorption (PSA)

 The bed is desorbed by reducing the pressure at essentially

constant temperature.

 Reduction in pressure shifts the adsorption equilibrium and

1 2 affects the regeneration of the adsorbent

Step 1: The feed fluid at y1=p1/P1 and T1 is passed through

3 adsorbent. Equilibrium loading n 1or q1 is reached.

4 Step 2:Total pressure reduced (blow down step). y 2 = p1/P2>y1

Step 3: Purge stream is passed of the sample removing the

component from the gas phase

Step 4: Repressurization to P1

 Changes in pressure can be effected very much more quickly

than changes in temperature
 PSA process is a popular process for performing bulk
separation of gases
Displacement Purge Adsorption (DPA)

• Adsorbates can be removed from the adsorbent surface by replacing them with a more
preferentially adsorbed species. This displacement fluid, which can be a gas, a vapour or a
liquid, should adsorb about as strongly as the components which are to be desorbed

• The mechanism for desorption of the original adsorbate involves two aspects:
(1) partial pressure (or concentration) of original adsorbate in the gas phase surrounding
the adsorbent is reduced
(2) there is competitive adsorption for the displacement fluid. The displacement fluid is
present on the adsorbent and thus will contaminate the product

• regeneration by displacement purge depend solely on the ability of the displacement fluid to
cleanse the bed in readiness for the next adsorption step
Inert-purge gas stripping cycle
• In this cycle the adsorbate is removed by passing a non adsorbing or inert gas through the
bed. This lowers the partial pressure or concentration around the particles and desorption
occurs.
Thank you