Adsorption

Mass Transfer Operations-II

Introduction
• The Adsorption operation exploits the ability of certain solids preferentially
to concentrate specific substances from solution onto their surfaces.
• Gas:
• Dehumify air
• Remove objectionable odour/impurity like CO2 from industrial gases
• Recover valuable solvent vapours from other gases
• Fractionate mixture of HC gases: methane ethane, propane, ethylene, propylene
• Liquid:
• Removal of moisture from gasoline
• Removal of objectionable taste and odour from water
• Decolourisation of petroleum products and sugar solutions
Types of Adsorption
• Adsorbate
• Adsorbent
• Physical Adsorption, or van der Waals Adsorption
• Chemisorption
Nature of Adsorbents
• Usually granular, dia 50 microns to 12 mm
• Mustn’t offer too great a pressure drop
• Adequate strength and hardness
• Free flowing
• Large surface per unit weight, typical gas mask charcoal has an
effective surface of 10,00,000 m2/kg
• Activation: heated, dried, treated with chemicals (acidic/basic)
Common Adsorbents
Adsorbent Form Activation Application Regeneration
Fuller’s earth natural clays, Heating and drying Decolorizing, neutralizing. washing and
magnesium and drying petroleum burning
aluminium silicate products
Activated Clay bentonite or other treatment with sulfuric petroleum products ordinarily discarded
clays or hydrochloric acid, after application.
washed, dried, and
ground
Bauxite certain form of heating 230 to 815'C decolorizing petroleum heating
naturally occurring products and for drying
hydrated alumina gases
Alumina hard, hydrated heating Dessicant for gases and Heating
aluminum oxide liquids.
Bone char destructive distillation of crushed dried refining of sugar washing and burning
bones at 9000 C
Adsorbent Activation Application Regenerati
on
Decolorizing made by (l) mixing vegetable with solutions of sugar, drug and dry-cleaning
carbons substances such as calcium chloride, liquids, water purification. refining of
carbonizing and leaching away the vegetable and animal oils, and in of gold
inorganic matter, (2) mixing organic and silver from cyanide ore-leach
matter such as sawdust, etc., with porous solutions.
substance such as pumice followed by
heating and carbonizing to deposit the
carbonaceous natter throughout the
porous particles, and (3) carbonizing
wood, sawdust, and the like, followed by
activation with hot air or steam.
Gas carbonization of partial oxidation recovery of solvent vapors from gas evaporatio
adsorbent coconut shells, fruit process, by mixtures, gas masks, collection of n
carbon pits, coal, lignite and treatment with hot gasoline hydrocarbons from natural gas,
wood air or steam. and fractionation of hydrocarbon gases
Molecular pore opening paraffin hydrocarbons, for example, but
screening controlled from 5 to reject isoparaffins of large molecular
activated 5.5 Å dimensions. fractionating acetylene
carbon compound&, alcohols, organic acids,
ketones, aldehydes.
Adsorption Equilibrium
• Y axis: Equilibrium partial pressure
• X axis: concentration of adsorbed
gas on the solid
• Increasing pressure increases
adsorption
• Increasing temp reduces adsorption
• Benzene (78) is more readily
adsorbed than acetone (58) at the
same temp.
• At high • Adsorption isotherms • Adsorption Hysteresis: Different
are not always equilibrium observed over a part of
pressure, gas the curve.
condenses concave to the • Shape of capillaries and pores, wetting
point B pressure axis. phenomena
• Y axis: equilibrium • During Hysteresis, desorption
pp/satd. vp equilibrium pressure is always lower
than that obtained by adsorption
Liquid Adsorption: Freundlich Equation
• v volume solution/mass adsorbent is treated
• Because of preferential adsorption of solute, its concentration in the
solution will fall down from initial c0 to final c* mass solute/volume
liquid
• Apparent adsorption = v(c0-c*) mass adsorbed/mass adsorbent
• Freundlich Adsorption Isotherm, c*= k [v(c0-c*)]n, k and n are
constants
• Ln c* = n.Ln [v(c0-c*)] + Ln k
• Dilute solutions
 Adsorption Operations: Single Stage
Operation
• Ls mass solvent
• Solute conc reduction from Y0 to Y1 mass solute/mass
solvent
• Ss mass adsorbate-free solid
• Solute adsorbate conc increases from X0 to X1; if fresh
adsorbent, X0 = 0
• Solute removed from liquid is picked up by the solid,
Ls (Y0-Y1) = Ss (X1-X0)
• On X-Y coordinates, this is equation of a straight line
passing through (X0,Y0) and (X1,Y1) with slope –Ss/Ls
• Insufficient time, equilibrium not reached:: point A
Application of Freundlich Equation
• Y*= mXn
• At final equilibrium condition
• Adsorbate contains no initial solute X0= 0

• 2<n<10: good
• 1<n<2: moderate
• n<1: poor
Multistage crosscurrent
operation
• Stage 1 and 2
Application of Freundlich Equation
• Stage 1

• Stage 2

• Total amount of Adsorbent

Multistage countercurrent operation

• Solute balance
Minimum adsorbent/solvent ratio
• Minimum adsorbent/solvent ratio
will be the largest which results in
an infinite number of stages for
the desired change in
concentration.
• This corresponds to the operating
line of largest slope that touches
the equilibrium curve within
specified range of concentration.
Application of Freundlich Equation
• Fresh Adsorbent XNp+1 = 0
• 2 stage cascade
• Solute balance for entire plant
• Freundlich Equation
• Applying to stage 1
• Combining
• Second equilibrium stage

• Eliminating Ss/Ls

• Find intermediate
concentration Y1
• An aqueous solution containing a valuable solute is coloured by small
amount of an impurity. Before crystallisation, the impurity is to be removed
by adsorption on a decolourising carbon which adsorbs only insignificant
amounts of the principle solute. A series of laboratory tests was made by
stirring various amounts of the adsorbent into batches of the original
solution until equilibrium was established, yielding the following data at
constant temperature.
kg carbon/kg solution 0 0.001 0.004 0.008 0.02 0.04

Equilibrium colour, units/kg soln 9.6 8.6 6.3 4.3 1.7 0.7

• The colour intensity was measured on an arbitrary scale, proportional to

the concentration of the coloured substance. It is desired to reduce the
colour to 10% of its original value, 9.6. Determine the quantity of fresh
carbon required per 1000 kg of solution for a single stage operation, two-
stage cross current process using the minimum total amount of carbon
,and for a two-stage countercurrent operation.
Solution
• Step 1: Convert experimental data to a suitable form for plotting the
equilibrium curve
• Defining Y: units of color per kg of solution
• X: units of color adsorbed per kg of carbon
• Step 2: Plot Y* and X on logarithmic coordinates
• Slope n=1.66, m= 8.91 x 10-5
• Freundlich equation is
• Step 3: Plot Y* and X on arithmetic coordinates
• Single-stage operation:
• Y0= 9.6 units of color/kg soln
• Y1= 0.10 x 9.6 = 0.96
• Ls= 1000 kg soln
• Fresh solvent, X0= 0
• Mark A: Initial solution, fresh
adsorbent
• Find B: Final solution equilibrium
concentration
• At B, X1= 270

• Alternatively, since Freundlich

Isotherm is applicable
• Two-stage crosscurrent
• Minimum total amount of carbon is
found by trial and error method.
• Assume C, draw operating lines AC and
DB, find slopes find Ss1 and Ss2, change
position of C until Ss1+Ss2 is minimum.
• Finally, C at (X1= 565, Y1= 3.30) gives
X2= 270 at B.
• Alternately,
• Since Freundlich equation
is applicable,

• n= 1.66,
• Two-stage countercurrent operation

• Operating line is drawn by trial and

error method till two stages can be
drawn between operating line and
equilibrium curve.
• Alternatively,
Unsteady-state: Fixed bed Adsorbers
• Fluid mixture to be treated is passed through a stationary bed of
adsorbent.
• Unsteady state operation
• Applications:
• Recovery of valuable solvent vapours from gases
• Purifying air as with gas masks
• Dehydration of gases and liquids
• Decolorizing mineral and vegetable oil
• Concentration of valuable solutes from liquid solutions
The Adsorption Wave
• Fixed bed Absorber
• Binary solution, solute conc. Co
• Adsorbent initially free of adsorbate
• Ca, practically solute-free
• Uppermost layer of the bed starts
becoming saturated.
• This adsorption zone moves
downwards
• c: lower portion of the adsorption
zone reached the bottom of the bed
The Adsorption Wave
• Cc: conc of the solute in the effluent
suddenly rises to an appreciable
value.
• System has reached breakpoint
• Solute conc. In the effluent rises
rapidly; at d, it is Co.
• Conc. Curve between c and d is called
breakthrough curve (S shaped)
• Heat of Adsorption follows an
opposite curve and used to find the
breakpoint
Ion-exchange
• Metathetical chemical reaction between an electrolyte in solution and an
insoluble electrolyte with which the solution is contacted.
• Principle: cations of a solution which are capable of diffusing through the
pores will exchange with Na+ ions of a zeolite material known as a cation
exchanger. Example,

• Where R represents residual material of the zeolite

• In this way, “hard” water containing Ca2+ can be softened by contact with
the zeolite, the less objectionable Na+ replacing the Ca2+ in the solution
and the latter becoming immobilised in the solid.
• Zeolite regenerated after saturation:
Ion-exchange
• Zeolites:
• Carbonaceous cation exchangers: coal + fuming H2SO4
• Synthetic resinous ion exchangers, insoluble polymeric resins
• Anionic exchange: not so simple

• Where RNH3 is the immobile cationic portion of the resin.

• Regeneration: contact with solutions of sodium carbonate or
hydroxide
• Techniques: • Rate of ion exchange:
• batch • diffusion of ions from the bulk of the
• stagewise liquid to the external surface of an
• fluidised exchanger particle
• fixed • inward diffusion of ions through the
solid to the site of exchange
• continuous
• exchange of the ions
• Application: • outward diffusion of the released ions
• water softening to the surface of the solid
• complete deionisation of water by • diffusion of the released ions from the
percolation first through a cation surface of the solid to the bulk of the
exchanger and them through an liquid
anion exchanger
• treatment of dilute waste solution