ADSORPTION

Part-I
Adsorption
❑ Unit operation in which one or more components are separated from a mixture of gases using a liquid solvent.
❑ Selective gaseous components exchange their hands with the liquids and dissolve to form a solution.
❑ Very important for different industrial applications, such as separation of ammonia from air-ammonia mixture
using water in ammonia plant, objectionable H2S & CO2 separation from flue gas using amine as absorbent, etc.
❑ Suitable absorption equipment, namely, tray tower, packed column, spray tower, venture scrubber, etc. are
generally used to achieve a desired separation.
❑ When dissolved gaseous components transfer back to the gaseous phase, is known as stripping which is reverse
of absorption operation.

➢ Adsorbent: Solid that adsorbs a component is called adsorbent.

➢ Adsorbate: Component adsorbed is called adsorbate.
➢ Sorption: Selective transfer of molecules of a mixture to the surface or into the bulk of a solid (or liquid) is
called sorption.
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.

The 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 or van der Waals adsorption

✓ Reversible phenomenon which is a result of intermolecular force of

attraction between molecules of the adsorbent & the adsorbate. ∆H
varies between 20-40 KJ/mol.

Chemical adsorption:
✓ Irreversible phenomenon which is a result of bond formation between
atoms of the adsorbent & the adsorbate. ∆H varies between 80-240
KJ/mol.
✓ Requires activation energy. Once it is achieved, it releases a higher
amount of energy than physisorption because of co-valent bond
formation in terms of isosteric heat of adsorption.
Comparison between physisorption & chemisorption:
Characteristics and Properties of Adsorbents:

❖ Selectivity – selectively binding of target components.

❖ Adsorption capacity – should be high so that adsorbent requirement will be low.
❖ Reversibility of adsorption – for recovery of adsorbate and reuse of adsorbent.
❖ Particle size & its distribution.
❖ Porosity & pore size distribution – high porosity and narrow pore size distribution.
❖ Specific surface area.
❖ Structural strength & stability
 Adsorption Equilibria:
➢ Adsorption & desorption of molecules occur simultaneously.
➢ With fresh adsorbent, rate of adsorption is more than rate of desorption.
➢ These rates will be equal and adsorption equilibria is established.
➢ At a constant temperature, amount adsorbed per unit mass of adsorbent
depends on partial pressure of adsorbent in gas phase (or concentration in
case of adsorption from a solution.)
➢ Equilibrium relation between the amount adsorbed q and the concentration
C of the adsorbate or solute at a constant temperature T, is called adsorption

Adsorption isotherms are generally isotherm.

concave to pressure axis.

▪ Repeated adsorption & desorption studies on a particular adsorbent will change the shape of isotherms due to
gradual change in pore structure.
▪ Adsorption is an exothermic process
▪ Hence the concentration of adsorbed gas decreases with an increase in temperature at a constant pressure.
▪ Similarly, an increase in pressure increases the concentration of adsorbed gas in the adsorbent at a constant temp.
ADSORPTION HYSTERESIS

❑ Adsorption & Desorption operations exhibit different

equilibrium phenomena
❑ May be due to the shape of the openings to the capillaries
& pores of the solid or due to the complex phenomena of
wetting of the solid by the adsorbate.
❑ Whenever hysteresis is observed, the desorption curve is
below the adsorption curve
HEAT OF ADSORPTION

▪ 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.
▪ 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 & sufficient pure adsorbed
substance (before adsorption) to provide the required concentration X, at the same temperature.
▪ Differential heat of adsorption & integral heat of adsorption are functions of temperature & adsorbate
concentration.

EFFECT OF TEMPERATURE
▪ Increase of temperature at constant pressure decreases the amount of solute adsorbed from a mixture.
▪ However, a generalization of the result is not easy.
EFFECT OF PRESSURE

▪ Generally lowering of pressure reduces the amount of adsorbate adsorbed upon the adsorbent.

▪ However, the relative adsorption of paraffin hydrocarbon on carbon decreases at increased pressures.

LIQUIDS

▪ Impurities are present both at low and high concentrations in liquids.

▪ These are normally removed by adsorption technique.
▪ Characteristics of adsorption of low & high concentration impurities are different.
Adsorption Isotherms HA= Heat of adsorption in the 1st layer
HL= Heat of liquification for remaining layer

Mono+Multilayer Multilayer Mono+Multilayer Multilayer

Monolayer adsorption adsorption adsorption adsorption
adsorption HL > HA

HL= 0 HL < HA HL > HA

HL < HA

Type I – favorable : O2 adsorption on carbon black at -183 oC on

concave downward.
Type II – BET type : multilayer adsorption of water vapor
on carbon black at 30 oC.
Type III – unfavorable : adsorption of N2 on ice.
Type IV & V – alternating convex and concave (capillary
condensation within pores)
ADSORPTION

Part-II
Langmuir isotherm:
Assumptions: ➢ Molecules are adsorbed at the discrete active sites on the surface.
➢ Each active site adsorbs one molecule only
➢ Adsorbing surface is energetically uniform
➢ There is no interaction among adsorbed molecules

❑ Adsorption as a process consisting two opposite actions,

a condensation of molecules from the gas phase on to the surface
& 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.
❑ Adsorption proceeds, only those molecules which strike the uncovered area surface can be adsorbed.
❑ Due to this, the initial rate of condensation of molecules on the surface is very high & decreases as the time
progresses.
❑ Molecules attached to the surface also get detached by factors like thermal agitation.
❑ Rate at which desorption occurs depends on the amount of surface covered by molecules & will increase as the
surface becomes more fully saturated.
❑ When the rate of adsorption & desorption become equal, adsorption equilibrium is said to be reached.

If “Ɵ” is the fraction of surface covered by adsorbed molecules at any instant,

fractional area available for adsorption is (1 — Ɵ).
Rate at which the molecules strike the unit area of surface is proportional to pressure.
Therefore, the rate of condensation kl is a constant

Rate of evaporation k2 is a constant

Under adsorption equilibrium,

amount of gas adsorbed at equilibrium per gm of adsorbent at a partial pressure p.

maximum quantity of gas adsorbed per gm adsorbent at a large pressure.
 2 adjustable parameters qm & K

Langmuir adsorption Isotherm

At a low partial pressure of the adsorbate (KP << 1), Form of Henry’s law

Henry’s law constant

for adsorption
At a large pressure (KP >> 1), q = qm & fractional coverage of the adsorption sites is Ɵ = 1,
 Adsorption of Solute from Dilute Solutions

▪ If v is the volume of solution per unit mass of adsorbent (cc/g)

▪ Co & C* are the initial & equilibrium concentrations (g/cc) of the solute,
▪ Apparent adsorption of solute per unit mass of adsorbent, neglecting any change in volume is
(g/g). mainly applicable to dilute solutions.
▪ When the fraction of the original solvent which can be adsorbed is small, the C* value depends on the
temperature, nature & properties of adsorbent.
▪ In the case of dilute solutions & over a small concentration range,

Freundlich adsorption Isotherm describes the adsorption phenomena,

▪ Freundlich adsorption equation is also quite useful in cases where the actual identity of the solute is not known,
e.g., removal of coloring substance from sugar solutions, oils etc.
▪ The color content in the solution can easily be measured using spectrophotometer or colorimeter.
 Freundlich Isotherm

Empirical isotherm which assumes that the amount adsorbed at equilibrium has power law dependence on
partial pressure (concentration) of the solute,

Freundlich Isotherm represents,

Two parameter isotherm, k/ & n are “adjustable parameters”

▪ Adsorption on surface that is energetically non uniform.

▪ As a result, heat of adsorption at different sites is not same.
Only isotherm is practically useful & can
▪ n values varies between 1 & 5.
fit many experimental adsorption data.
▪ For n = 1 Freundlich equation transforms into Henrys equation.

▪ It is thermodynamically inconsistent in the sense that it cannot give a finite value of Henrys law
coefficient as the concentration or partial pressure tents to 0.
 Toth Isotherm
▪ Empirical isotherm useful for the correlation of equilibrium adsorption data on heterogenous
adsorbents like activated carbon.

It is three parameter isotherm, qm, b & n

▪ Valenzuela & myers (1989) used this isotherm to correlate adsorption data for a large number of
systems.
BET equation (Braunauer-Emmet-Teller equation)
▪ BET equation represents multilayer adsorption equilibria for many systems.
▪ The equation is given as

qm = quantity of gas to be adsorbed to

form monolayer/gm adsorbent

c/ → temperature dependent constant for a particular gas-solid system

 BET equation (Braunauer-Emmet-Teller equation)
Assumptions:
▪ Heat of adsorption remains constant till the formation of monolayer is complete.
▪ For secondary layer, heat of adsorption is assumed to be equal to heat of liquefaction of adsorbate.

Determination of specific surface area of solid:

The projected area, α of an adsorbed molecule can be calculated from following equation.
Where, M is molecular weight of adsorbate,
N is Avogadro's number
ρ is density of the adsorbate in adsorbed phase
Specific surface area , Sg is given by,

To calculate qm, putting in BET equation.

 Heat of Adsorption:

Differential heat of adsorption

Integral heat of adsorption

Isosteric heat of adsorption

Adsorption operations:

a) Stage-wise operation
✓ Single stage operation.
✓ Multistage cross current operation.
✓ Multistage countercurrent operation
b) Continuous-contacting method

Single stage operation:

▪ Amount of adsorbed is very small compared to amount of solution

▪ Solute to be removed is adsorbed more strongly than other constituents present
▪ Adsorption of other constituents can be ignored
▪ Adsorbent is insoluble in solution

Ls is mass unadsorbed substance, Yo is initial solute conc.

Ss is mass of adsorbent in adsorbate free basis &
Xo is initial solute conc, Xo = 0 if fresh adsorbent is used
Single stage operation:

If insufficient contact time is allowed, equilibrium is not

reached, final liquid & solid concentration corresponds to point A.

Applying Freundlich equation:

one more solute will be separated

small amount of solute will be separated

moderate amount of the solute will be separated

How much amount of solute will be

separated using the different adsorbents
 Multistage cross current operation

Making a material balance of solute for stage 1 & use

of Freundlich equation for the entry of pure adsorbent stage 2
gives

stage p
Steps involved in the determination of number of stages needed for a cross-current adsorption process

1. Draw the equilibrium curve (X vs Y).

2. Locate the point (Xo, Yo) & draw the operating line with a
slope (- Ls1/Gs).
3. Intersection of operating line & equilibrium curve yields
(Xl, Y1) — the conditions of leaving from stage I.
4. Locate (Xo, Y1) & draw the operating line with a slope of
(-Ls2/Gs) (since Xo remains constant for adsorbent for II stage).
5. Intersection of operating line & equilibrium curve yields
(X2, Y2) — the conditions of leaving stream from stage II.
6. Proceed in the same way till the XNp point is crossed & count
the number of stages for the use of specified amount of
adsorbent in each stage.
A solid adsorbent is used to remove colour impurity from an aqueous solution. The original value of colour on
an arbitrary scale is 48. It is required to reduce this to 10% of its original value. Using the following data, find
the quantity of fresh adsorbent used for 1000 kg of solution for (a) a single stage and (b) a two-stage cross-
current operation when the intermediate colour value is 24.
Equilibrium data:
kg adsorbent/kg of solution o 0.001 0.004 0.008 0.02 0.04
Equilibrium colour (Y) 48 43 31.5 21.5 8.5 3.5
Solution.
Xo = units of colour/kg adsorbent = 0
Yo = units of colour/kg solution = 48
The equilibrium decolourisation data for a certain system using activated carbon is given by the equation,
Y = 0.004X2
where Y is g colouring impurity/kg impurity free solution and X is g colouring impurity/kg pure activated carbon.
Calculate the amount of activated carbon required per 1000 kg of impurity free solution to reduce the impurity
concentration from 1.2 to 0.2 g/kg of impurity free solution using (i) a single stage operation and (ii) a two-stage cross-
current operation with intermediate composition of 0.5 g. of colouring impurity per kg of impurity free solution.
Y = 0.004X2
Solution.
Multistage counter-current operation

Solute balance for the system as a whole gives,

➢ gives the slope of the operating line passing through the terminal
conditions (Xl, Yo) and (XNP+1, YNp).
▪ By conventional stepwise construction starting from the point
(Xl, Yo), the number of theoretical stages are estimated.
▪ This operation is represented graphically as shown in Fig.
 In order to determine the minimum amount of adsorbent for the process,
▪ draw a line from the point P (XNP+1, YNp) which could be a tangent to the
equilibrium curve.
▪ In such cases, the slope of the line gives the ratio of (Ls/Gs)min.

▪ However, in the case of

equilibrium curve being a straight
line or concave upwards, draw a
horizontal line from Yo to intersect
the equilibrium curve, (or line) at a
point by Q

▪ then join PQ which gives the slope of the operating line (Ls/Gs)min.
▪ The above two cases have been shown graphically in Figs. (a) and
(b) respectively.
Steps involved in determining the number of stages in a multistage countercurrent operation
1. Draw the equilibrium curve.
2. Locate the point P (XNP+1, YNp).
3. Draw a line with a slope of (Ls/Gs),
where LS is the mass flow rate of solute free adsorbent
GS is the mass flow rate of solution on solute free
basis.
4. Starting from (Xl, Yo) by stepwise construction, estimate the
number of stages till the point (XNP+1, YNp) is crossed.
5. The operation is graphically shown in Fig.

6. If it is desired to determine the amount of adsorbent needed for a specified level of solute removal from a solution
stream with a specified number of stages, draw the operating line of different slopes by trial and error and choose the
one which gives exactly the same number of specified stages and the specified concentration in the liquid stream.
From the slope of the operating line, thus chosen, determine the amount of adsorbent to be used and the solute
concentration in the adsorbent.
A solution of washed raw cane sugar of 48% sucrose by weight is coloured by the presence of small quantities of
impurities. It is to be decolourised at 80 oC by treatment with an adsorptive carbon in a contact filtration plant.
The data for an equilibrium adsorption isotherm were obtained by adding various amounts of the carbon to
separate batches of the original solution and observing the equilibrium colour reached in each case. The data
with the quantity of carbon expressed on the basis of the sugar content of the solution are as follows:
kg carbon / kg dry sugar 0 0.005 0.01 0.015 0.02 0.03
% colour removed 0 47 70 83 90 95
The original solution has a colour concentration of 20 measured on an arbitrary scale and it is desired to reduce
the colour to 2.5% of its original value.
(i) Convert the equilibrium data to Y and X.
(ii) Calculate the amount of carbon required for a single stage process for a feed of 1000 kg solution.
(iii) Estimate the amount of carbon needed for a feed of 1000 kg solution in a two-stage counter-current
process.
Solution.
N02 produced by a thermal process for fixation of nitrogen is to be removed from a dilute mixture with air by
adsorption on silica gel in a continuous counter-current adsorber. The gas entering at the rate of 0.126 kg/s
contains 1.5% of N02 by volume and 90% of N02 is to be removed. Operation is isothermal at 25 oC and 1 atm
pressure. The entering gel will be free of N02.
Partial pressure of N02, mm Hg 0 2 4 6 8 10 12
kg N02 /100 kg gel 0 0.4 0.9 1.65 2.6 3.65 4.85
(a) Calculate the minimum weight of gel required/h.
(b) For twice the minimum gel rate, calculate the number of stages required.

Solution.
 500 kg/min of dry air at 20 oC and carrying 5 kg of water vapour/min. is to be dehumidified with silica gel to
0.001 kg of water vapour/kg of dry air. The operation has to be carried out isothermally and counter-currently
with 25 kg/min. of dry silica gel. How many theoretical stages are required and what will be the water content
in the silica gel leaving the last stage?
kg. of water vapour/ kg of dry silica gel, X 0 0.05 0.10 0.15 0.20
kg of water vapour/ kg of dry air, Y 0 0.0018 0.0036 0.0050 0.0062

Solution.
CONTINUOUS ADSORPTION

▪ In these adsorbers, the fluid and adsorbent are in continuous contact without any separation of the
phases.
▪ This is quite analogous to gas absorption with the solid adsorbent replacing the liquid solvent.
▪ The operation can be carried out in continuous, steady state fashion with both fluid and solid
moving at constant rate and the composition remains constant at a particular point.
▪ It can also be operated on semi-continuous basis with solid particles remaining stationary and
fluid in moving condition.
▪ Such operations constitute unsteady adsorption process.
 Steady State Adsorption

▪ Solute balance for the entire tower is …….(1)

▪ Solute balance for the upper part of the tower is …….(2)

▪ Using Eq.1, one can draw the operating line and Eq. 2 gives us the of the two phases at any
point in the tower.
▪ Making a solute balance across the element of thickness dZ,
…….(3)
where,
Ky a is mass transfer coefficient based on the outside surface area a of particles, kg/m3.s.(ΔY)
Y* is the equilibrium concentration of the fluid corresponding to its concentration X.

Continuous differential Equation (12.33) on integration yields

contact tower …….(4)

where HtoG= Gs / Kya

NtoG can be determined graphically as usual.
 Physical description of adsorption by mass transfer zone (MTZ) and breakthrough

Let, Concentration of solute in feed stream is C0.

Concentration of solute in bulk gas at axial position Z of bed is C.
Concentration of solute in adsorbent in equilibrium with feed
(saturated bed) is q0.
Concentration of solute in adsorbent at axial position Z is q.

x/ = 1 at equilibrium (saturation)

Bed gets saturated near inlet (z = 0, x/ = 1 ).

Thus, Mass
transfer zone
moves along the
bed with time like
a wave.

Flow of feed & adsorption continues → a section of bed near inlet gets saturated.
The S-shaped curves shown are called
“mass transfer wave front”.

Breakthrough:
 ▪ The upper most layer of bed is
saturated.
▪ As solution continues to flow,
mass transfer zone (MTZ) moves
downward as a wave.
▪ At d, lower portion of the
adsorption zone has reached
bottom of the be, & solute
concentration in the effluent has
suddenly risen to an appreciable
value Cd .
▪ The system is said to have
reached the breakpoint.

▪ Then solute concentration in the effluent risen rapidly as MTZ passes through the bottom of
the bed and at e,
▪ it has reached the initial feed concentration (C0).
▪ The portion of the effluent concentration curve between position d & e is termed as
breakthrough curve.
(solute in the feed has been able to breakthrough the barrier of the bed of the adsorbent).
▪ Equilibrium time teq
(time required to get saturated).
(solute in the feed has been able to breakthrough the barrier of the bed of the adsorbent).
 ▪ When flow of feed starts,
initial rate of adsorption is
pretty fast.
▪ As gas flows through bed,
concentration of solute
decreases due to adsorption.
▪ Bed gets saturated near inlet
(Z=0, x/ = 1).

1. Flow of feed and adsorption continues a section of bed near inlet gets saturated.
2. Thus, Mass transfer zone moves along the bed with time like a wave.
3. The S-shaped curves shown are called mass transfer wave front.
4. Effluent concentration, Ca, Cb, Cc, Cd, Ce.
Length of unused bed (LUB)