ADSORPTION

The removal of dissolved substances

from solution using adsorbents such
as activated carbon
Absorption, in biology, is the process of taking or assimilating substances
into the cell or across the tissues by the process of diffusion or osmosis.
•Absorption of substances into a cell or tissue usually occurs through the general
surface of the cell.
•The rate and process of absorption depend on a number of factors like the
concentration of the substance, surface area and duration of contact, and
solubility of the material.
•Absorption takes place due to the presence of empty spaces within the
molecules of the absorbent, which are then filled by the molecules of absorbate.
•The process of absorption might occur either without the application of energy
(diffusion) or with the expenditure of energy (active transport).
•In most of the cases of absorption, solid substances dissolve in the liquid phase
and then are absorbed into the cell or tissue.
•Absorption is a bulk phenomenon where the absorbed material is uniformly
distributed throughout the absorbent and thus affects the entire system.
•Absorption occurs in all living and non-living systems either to intake nutrients
or to maintain the homeostasis or concentration of substances across a surface.
•The interactions between the absorbent and absorbate are physical and non-
specific. Also, no chemical forces are involved
Adsorption is the process of adhesion of molecules of liquid or gases onto the surface
of a solid particle.
•This is the ability of solid particles/surfaces to attract the molecules of liquid and gas towards their
surface after they come in contact with the molecules.
•Adsorption is a surface phenomenon where the molecules form a layer of adsorbate around the
adsorbent.
•The process of adsorption occurs due to the surface energy where the attachment is facilitated either
by Van der Wall’s force or by covalent bonds depending on the nature of the substances involved.
•In physical adsorption molecules are attached to each other simply by Van der Wall force of attraction
and no chemical specificity is present between the particles.
•In chemical adsorption, however, bonds are formed between the adsorbate and the adsorbent and the
bonds are specific for each adsorbate-adsorbent combination.
•Adsorption is widely utilized in various separation techniques like adsorption chromatography and
ion-exchange chromatography.
•These processes allow the separation of molecules by selectively transferring the molecules of the
liquid phase onto the surface of solid adsorbent.
•Adsorption is also utilized by viruses where they attach to the surface of either bacteria or other
organisms before penetration.
•Adsorption is affected by a number of factors depending on the nature of the substances involved.
•Some common factors include pressure, temperature, area of contact, and the nature of the interaction
between the adsorbent and the adsorbate.
•The process of adsorption is always exothermic as it leads to a decrease in the residual forces on the
surface of the adsorbate
Basis for
Absorption Adsorption
comparison
Adsorption is a surface
Absorption is a bulk
phenomenon where the
phenomenon where
Phenomenon molecules simply attach to
molecules of solute enter
the surface of the
into the solvent.
adsorbent.

Substances get adsorbed

onto the surface of an
Substances get absorbed adsorbent because the
into an absorbent due to adsorbent has vacant
Principle
the time of contact and the spaces that stimulate the
nature of the solute. adhesion of particles onto
the spaces.
Absorption is an
Adsorption is an
endothermic process as the
exothermic process as the
energy is given from the
energy of the surface
Heat exchange outside of the surface, and
decreases as it leads to a
the overall energy of the
reduction in residual forces
absorbent increases after
of the surface.
absorption.
Basis for comparison Absorption
Rate Absorption takes place at a uniform rate.
The absorbed materials remain in the
Bonding absorbent without having any chemical
interactions with the absorbent.
Absorption depends on the temperature
Temperature
of the system and reduces at higher temp
The concentration of the absorbate in the
Concentration
absorbent is uniform after absorption.
Absorbed materials can be separated into
Separation different phases based on their chemical
interaction with the phases.
Various living and non-living systems utilize utilize adsorption. Living systems like
absorption. Living systems like unicellular viruses use the phenomenon of
organisms use the absorption
Application phenomenon for the intake of nutrients
and water. Non-living systems like
refrigerators utilize absorption for cold
storage.
Adsorption
The rate of adsorption increases steadily
until it reaches equilibrium.
The adsorbed materials remain attached
to the adsorbent with either Van der
Wall’s forces or covalent bonds.
Adsorption is a temperature-dependent
phenomenon. Reduces at higher
temperature
The adsorbate is more concentrated on
the surface than the other parts of the
adsorbent.
Adsorbed materials can be separated by
passing new substance through the
surface of the adsorbent, which replaces
the previously adsorbed material.
Various living and non-living systems also
adsorption for attachment to the
bacteria or other organisms. Separation
processes like adsorption
chromatography use the principle of
adsorption for the separation of
mixtures.
The physical form of the GAC may
depend on source of raw materials
MANUFACTURE OF
ACTIVATED CARBON:
DIFFERENT RAW
MATERIALS
Prior carbonization is for softer raw materials
MANUFACTURE OF ACTIVATED
CARBON FROM COAL
Multiple Hearth ↑
ACTIVATION
FURNACE
TYPES
Rotary kiln 
DIFFERENT PHYSICAL FORMS
OF ACTIVATED CARBON
First magnification of carbon granules
Continued magnification
Continued magnification
Continued conceptual
magnification
Continued conceptual
magnification
Continued conceptual
magnification
Scanning
Electron
Microscope
Photo of
GAC
Area of a few
grams of
activated
carbon
Application
Methodology
Gas Purification
Contacting
Column
Internals
REACTIVATION OF ACTIVATED CARBON
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.
• 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:

• Physical adsorption - results from the

intermolecular forces of attraction between a solid
and the substance adsorbed. Reversible

• Chemi-sorption - result of chemical interaction,

generally stronger than physi-sorption between the
solid and the adsorbed substance. This process is
irreversible. It is of importance in catalysis
Sl. Adsorbent Source Application
No.
1. Fuller’s earth Naturally occurring clay is De-colorizing, drying of
heated and dried to get a lubricating oils, kerosene and
porous structure. engine oils.
2. Activated Bentonite or other activated Used for de-colorizing
Clay clay which activated by petroleum products.
treatment with sulfuric acid
and further washing, drying
and crushing.
3. Bauxite A naturally occurring hydrated Used for de-colorizing
alumina, activated by heating petroleum products and for
to 230 to 815oC. drying gases.
4. Alumina A hard hydrated aluminium Used as desiccant.
oxide, which is activated by
heating to drive off the
moisture and then crushed to
desired size.
5. Bone-char Obtained by destructive Used for refining sugar and
distillation of crushed bones at can be reused after washing
600-900oC. and burning.
6. Activated i) Vegetable matter is mixed with
carbon calcium chloride, carbonized and
finally the inorganic compounds
are leached away.
ii) Organic matter is mixed with
porous pumice stones and then
heated and carbonized to deposit
the carbonaceous matter
throughout the porous particle.
iii) Carbonizing substances like
wood, saw dust, coconut shells,
fruit pits, coal, lignite and
subsequent activation with hot
air steam. It is available in
granular or pellated form.
7. Silica gel A hard granular and porous
product obtained from sodium
silicate solution after treatment
with acid. Normally has 4 to 7%
water in the product.
8. Molecular These are porous synthetic
sieves zeolite crystals, metal alumino -
silicates.
De-colorizing of sugar
solutions, chemicals, drugs,
water purification, refining of
vegetable and animal oils,
recovery of gold and silver
from cyanide ore-leach
solution, recovery of solvent
vapour from gas-mixtures,
collection of gasoline hydro-
carbons from natural gas,
fractionation of hydrocarbon
gases.
Used for de-hydration of air
and other gases, fractionation
of hydro-carbons.
Dehydration of gases and
liquids, and separation of gas-
liquid hydrocarbon mixture.
Adsorption Equilibria, Hysteresis

Equilibriu Adsorption

m partial
pressure,
mm Hg

Desorption

kg adsorbed /kg adsorbent

Heat of adsorption:
The differential heat of adsorption (-H) is defined as the heat
liberated at constant temperature when unit quantity of vapor 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, (ΔH) 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.
Adsorption of solute from dilute solutions
• The solution is of original concentration C0,
Treated 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.
• Assuming 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,
• C* = K [v (C0-C*)]n .
If ‘n’ is high, say 2 to 10, adsorption is good. If it lies between 1 and 2,
moderately difficult and less than 1
 Adsorption of concentrated solutions
• Curve ‘1’ occurs when the solute
is more strongly adsorbed in R
(1)
comparison to solvent at all
solute concentration.
Conce
ntratio Q
n of
• Whenever both solute and solute
in
(2)

solvent are adsorbed to nearly liquid

same extent, the ‘S’ shaped curve

‘2’occurs. In the range PQ solute
is more strongly adsorbed than
solvent. At point Q both are
equally well adsorbed. In the
range QR solvent is more P

strongly adsorbed kg Solute apparently adsorbed /kg adsorbent

Langmuir adsorption Isotherm:
• The theory proposed by Langmuir postulates that gases being
adsorbed by a solid surface cannot form a layer more than a simple
molecule in depth.
• Adsorption as a process consisting two opposing actions, -----
a condensation of molecules from the gas phase on to the surface
and an evaporation of molecules from the surface back into the body
of the gas.
• When adsorption starts, every molecule colliding with the surface
may condense on it. However, as adsorption proceeds, only those
molecules which strike the uncovered area surface can be adsorbed.
• The initial rate of condensation of molecules on the surface is very
high and decreases as time progresses.
• The molecules attached to the surface also get detached by factors
like thermal agitation.
• The rate at which desorption occurs depends on the amount of
surface covered by molecules and will increase as the surface
becomes more fully saturated.
• When the rate of adsorption and desorption become equal,
adsorption equilibrium is said to be reached. If ‘θ’ is the fraction
of surface covered by adsorbed molecules at any instant, the
fractional area available for adsorption is ‘(1- θ)’. The rate at
which the molecules strike the unit area of surface is
proportional to Pressure.
• Therefore the rate of condensation = k1(1- θ)P, Where k1 is a
constant
• Similarly, the rate of evaporation α k2 θ, Where, k2 is a constant
• Under adsorption equilibrium, k1(1- θ)P = k2 θ
• (i.e.) θ = k1P/(k1P+k2)
• = bP/1+bP where, b = k1/k2.
• Now the gas adsorbed per unit area or unit mass of adsorbent, y,
must obviously be proportional to the fraction of surface
covered. Hence,
• y = k θ = k{ bP/1+bP}= aP/1+bP , where, a and b are constants.
vm

BET Adsorption Isotherm:

• This postulates that the adsorption phenomenon involves
the formation of many multilayers on the surface rather than
a single one.
• Brunauer, Emmett and Teller derived the following
adsorption isotherm popularly called BET adsorption
Isotherm.
•

• where, v is the volume, reduced to standard conditions of

gas adsorbed at pressure P and temperature T
• P° the saturated vapor pressure of the adsorbate at
temperature T,
• vm the volume of gas reduced to standard conditions,
adsorbed when the surface is covered with a unimolecular
layer, c is a constant at any given temperature equal to
approximately exp[(E1-E2)/RT]
 Single stage

• Gs [Y0 – Y1] = LS [X1 – X0]

LS, X0


LS

Y0  Y1
GS X0  X1

GS, Y0 GS, Y1

LS, X1
Adsorption Isotherm and its use for batch
process

Y0
X

Y1

0 X0 X1
, ,
Multistage cross-current operation:

LS, X0 LS,X0 LS, X0

GS, Y0 GS,Y1 GS, Y2

GS,Y3
1 2 3
Feed

LS,X1 LS,X2 LS,X3

 Freundlich adsorption Isotherm: Y* = m xn

This operation is represented graphically, as shown in Fig

GS (Y0-Y1) = LS1 (X1 – X0) (12.10)
According to Eq.(12.9),
LS1 Y0  Y1
 (12.11) Y0
GS  Y1 1 / n
  Operating line
m slope = - LS1/GS
A material balance of solute for stage 2 yields,
GS (Y1 – Y2) = LS2 (X2-X0) (12.12)
Y
Use of Freundlich equation for the entry of pure adsorbent gives
LS2 Y1  Y2 
 1/n
(12.13)
GS  Y2 
  Operating line
m Y1
slope = - LS2/GS
A similar material balance for stage ‘p’ yields
GSYp  1  Yp   LSp Xp  X0  (12.14) Y2
Using Freundlich equation as before gives
0
LSp Yp - 1  Yp  X0 X2 X1
X
 1/n , ,
GS  Yp 
 
m
Multistage counter-current adsorption

12.10.3 Multistage Counter current adsorption:

GS,Y0 GS,Y1 GS,Y2 GS,Y3 YNP - 1 GS,YNp Final

Solution to
be treated solution
1 2 3 NP
Spent Fresh
adsorbent LS, X1 X2 X3 X4 XNp LS, XNp+1 adsorbent
GS (Y0 – YNP) = LS (X1 – XNP+1)

(i.e.)
 LS  Y0  YNp 
 
 GS  X1  XNp  1

Y0 B

Operating line
slope = LS/GS
1
Y1

Y
2
Equilibrium curve

Y2
YNp -1

A Np
YNp

XNp+1 XNp X3 X2 X1
X

Fig.12.13: Counter current multistage adsorption

Optimization of 2 stage processes
 LS, X0 LS,X0

GS, Y0 GS, Y1 GS, Y2

Feed 1 2

LS,X1 LS,X2

Fig. 12.10:Two stage cross current operation

LS1 Y0  Y1

 1/n
GS  Y1 
 
m

LS2

Y1  Y2 
1/ n
GS  Y2 
 
 m 

Adding equations (12.11) and (12.12) we get,

 LS1  LS2  Y0  Y1 Y1  Y2 
   (12.16)
   Y1 
1/n 1/n
G S  Y2 
   
m m
 1/n
 Y1   1  Y0  1
       1   
 Y2   n  Y1  n

we can get the intermediate concentration.

 Y0 Y1
Y2
1 2
X1 X2 X3 = 0

Fig. 12.15: Two stage counter current adsorption

Solute balance for the system as a whole with pure adsorbent yields,
LS (X1 – 0) = GS [Y0 – Y2] (12.25)
Applying Eq. (12.8) yields
1/n
 Y1 
LS   GSY0  Y2  (12.26)
m
LS Y0  Y2 
 (12.27)
GS  Y1 1/n
 
m
Applying a similar balance for stage 2 yields,
1/n
 Y2 
GS (Y1-Y2) =LS(X2 – 0) = LS   (12.28)
m
 LS  Y1  Y2 
  (12.29)
 GS   Y2 
1/n

 
m
Equating (12.27) and (12.29) we get
Y0  Y2   Y1  Y2 
1/n 1/n
 Y1   Y2 
   
m m
Y0  Y2   (Y1  Y2)  Y1 1/n   Y2  -1/n 
    
Y2 Y2  m  m 
 Y1   Y1  
1/n
 Y0 
   1       1 (12.27)
 Y2   Y2   Y2  
Continuous adsorption
• Solute balance for the entire tower is
GS (Y1 – Y2) = LS (X1 – X2) … (12.31)
Solute balance for the upper part of the
tower is
X2 Y2
• GS (Y-Y2) = LS (X- X2)…. (12.32)
2
• Using Eq. (12.31), one can draw the
operating line and Eq. (12.32) gives us the
concentration of the two phases at any
Y point in the tower .
• Making a solute balance across the
dz z element of thickness ‘dz’,
LS (dx) = GS dY = Ky a (Y – Y*) dZ .. (12.33)
X
where Ky a is mass transfer coefficient
based on the outside surface area ‘a’ of
particles, kg/m3.s.(∆Y) and Y* is equilibrium
1 concentration of the fluid corresponding to
Y1
its concentration X
X1
Fig.12.17: Continuous differential contact tower
Eq.(12.33) on integration yields,
Y2 Z
dY KYa Z
NtoG =    dz  (12.34 )
Y2 (Y  Y*) GS 0
HtoG

where HtoG = GS/Kya

NtoG can be determined graphically as usual.
Unsteady state adsorbers

B
Concentration

A
0
Volume of effluent
Equipment:

1) Contact filtration : Mixing +Filtration

(Centrifuge/Filter press/Rotary filter0

2) Fluidised beds:
Higgins contactor
 Problems for Practice
1) An aqueous solution containing valuable solute is coloured by the
presence of small amounts of impurity. It is decolourised using
activated carbon adsorbent. The equilibrium relationship is Y =
0.00009X 1.7 where, X = Colour units/Kg carbon and Y = colour
units/kg solution. If the original solution has 9.8 colour units/kg
solution, calculate (i) the amount of colour removed by using 30 kgs of
adsorbent in a single stage operation and (ii) the amount of carbon
needed for a two stage counter current operation if the final colour in
the solution is to be 10% of original value and the solution leaving the
first stage has 4 times the final colour of the solution
2) Experiments on decolourisation of oil yielded the following relation
ship y = 0.5x 0.5, where y is the gram of colour removed per gram of
adsorbent and x is the gram of colour/1000 grams of colour free oil. If
1000 kg of oil containing 1 part of colour per 3 parts of colour free oil
is contacted with 250 kgs of adsorbent calculate the percent of colour
removed by (i) single stage process (ii) Two stage cross current contact
process using 125 kg adsorbent in each stage.