Unit Operation In Food

Engineering –II (FD-308)

Adsorption
 ADSORPTION
• Adsorption is the process in which matter is
extracted from one phase and concentrated at the
surface of a second phase.(interface accumulation)
• This is surface phenomenon as opposed to
absorption .

Adsorbate.

Adsorbent
⮚ The process of adsorption arises due to presence of unbalanced or
residual forces at the surface of liquid or solid phase.

⮚ These unbalanced residual forces have tendency to attract and

retain the molecular species with which it comes in contact with
the surface.
 Application in food engineering
● Decolorization of edible oils with ‘ bleaching
earths ’ (activated clays)
● Decolorization of sugar syrup with activated
carbon in the manufacture of sugar.
● Removal of bitter substances from fruit juices by
adsorption on polyamides
● Odor abatement by passing gaseous discharges
through activated carbon
● Various applications of ion exchange.
 Adsorption is an exothermic process
• Adsorption process takes place by adsorbate
getting adsorbed on adsorbent .Forces of
attraction exist between adsorbate and
adsorbent and due to these forces of
attraction, heat energy is released. So
adsorption is an exothermic process.
 Adsorption in liquids
• Water molecule on surface experiencing
unbalanced forces as compared to molecule
inside which experiences forces from all
direction.
 Adsorption in solids

• In case of solid state these residual forces arises because a of

unbalanced valence forces of atoms at the surface.
• Due to cleavage of a big crystal into smaller unit, residual
forces or vacancies gets generated on the surface of the solid.
Occupancy of these vacancies by some other molecular
species results into Adsorption.
Liquid phase adsorption :
• Removal of moisture dissolved in gasoline
• Decolorization of petroleum products and aqueous sugar
solutions,
• Removal of objectionable taste and odor from water.

Gas phase adsorption :

• Dehumidify air and other gases
• Remove objectionable odors and impurities from
industrial gases such ascarbon dioxide
• Recover valuable solvent vapors from dilute mixtures
with air and other gases.
Types of adsorbtion
Physical adsorption(physi-sorption)
• If the forces of attraction existing between adsorbate
and adsorbent are Vander Waal’s forces, the
adsorption is called physical adsorption.

• it directly proportional to the amount of solid surface

available

• Multiple layer

• It can be easily reversed

by heating or decreasing
the pressure.
 Chemical adsorption(chemisorption)
• If the forces of attraction existing between adsorbate
particles and adsorbent are almost of the same strength as
chemical bonds, the adsorption is called chemical adsorption.
• This type of adsorption cannot be easily reversed.
• Slow process and limited to single layer.
 Adsorbents

Adsorbent An adsorbent is a substance, usually

porous in nature and with a high surface area
that can adsorb substances onto its surface by
intermolecular forces.
To be suitable for commercial applications, a sorbent should have

✔ high selectivity to enable sharp separations,

✔ high capacity to minimize the amount of sorbent needed,
✔ favorable kinetic and transport properties for rapid sorption,
✔ chemical and thermal stability, including extremely low solubility in
the contacting fluid, to preserve the amount of sorbent and its
properties,
✔ hardness and mechanical strength to prevent crushing and erosion,
✔ a free-flowing tendency for ease of filling or emptying vessels,
✔ high resistance to fouling for long life,
✔ no tendency to promote undesirable chemical reactions,
✔ the capability of being regenerated when used with commercial
feedstocks that contain trace quantities of high-molecular-weight
species that are strongly sorbed and difficult to desorb, and
✔ relatively low cost.
 Activated carbons:
Fuller’s earths:

Bauxite:

Activated clays:

Silica gel:
Bone char:
Dehumidification of Air Through Silica
Gel Bed
 Adsorbents and their uses
Adsorbent type Major uses
Activated carbon Eliminating odors, purifying gases,
recovering solvents
alumina Drying air, gases and liquids
Activated charcoal Adsorbs poisonous gas, used in gas
masks.
Molasses is decolorized
Silica gel to control humidity by the adsorption
of moisture
Molecular sieves Controlling and recovering
Hg,SO2,NOx
Animal charcoal, when added to acetic acid solution
and shaken vigorously, adsorbs acetic
acid.
Factors on which Adsorption Depends

• Temperature
Adsorption increases at low temperature conditions.
Adsorption process is exothermic in nature. So low temperature favour
forward direction.
• Pressure
By Adsorption Isotherm, with the increases in pressure, adsorption increases up
to a certain extent till saturation level is achieved.
After saturation level is achieved no more adsorption takes place no matter how
high the pressure is applied.
• Activation of Adsorbent
Activation of adsorbent surface is done so as to provide more number of vacant
sites on surface of adsorbent. This can be done by breaking solid crystal in small
pieces, heating charcoal at high temperature, breaking lump of solid into powder
or other methods suitable for particular adsorbent.
• Surface Area of Adsorbent
As adsorption is a surface phenomenon, surface area offered by Adsorbent
becomes important factor for consideration.
 Adsorption isotherm

Adsorption is recorded by using equilibrium data and is plotted

by using partial pressure (or concentration) as a function of
grams absorbed. These plots are referred to as isotherms.
 The simplest isotherm is Type I, which corresponds to
unimolecular adsorption, as characterized by a maximum
limit in the amount adsorbed. This type applies often to
gases at temperatures above their critical temperature.

The more complex Type II isotherm is associated with

multimolecular adsorption of the BET type and is observed
for gases at temperatures below their critical temperature
and for pressures below, but approaching, the saturation
pressure (vapor pressure).
 The Type III isotherm with its convex nature, is undesirable
because the extent of adsorption is low except at high
pressures.

Adsorption isotherms of Types IV and V in Figure ,where we

see that the maximum extent of adsorption occurs before
the saturation pressure is reached.
Type IV is the capillary-condensation version of Type II
Type V is the capillary-condensation version of TypeIII
The equilibrium between the water content and the water activity of a material is described
by the sorption isotherm .
In most cases the sorption isotherm of a foodstuff is an S-shaped curve.
• The first part of the curve (a) is convex toward the water content axis, and this part is
normally said to correspond to the monomolecular layer of adsorbed water.
• The middle part (b) is an almost straight line and corresponds to the multimolecular layer.
• In the third part (c) capillary condensation takes place.
✔ Sugars or salt, the isotherm appears as concave shape type III.
✔ Most other foods result sigmoid isotherm type II. The inflection point of the
isotherm indicates the change of water-binding capacity or of the relative
amounts of free and bound water.
✔ Type I is indicative of a non-swelling porous solid, such as slicate anticaking
agents.
Hysteresis
• The difference in the equilibrium moisture content between the adsorption and
desorption curves is called hysteresis and is shown in figure below.
• In region II of this figure, the water is held less tightly and is usually present in small
capillaries, whereas in region III, the water is held loosely in large capillaries or is free.
Hysteresis in sorption has important theoretical and practical implications in foods.
• The practical implications deal with the effects of hysteresis on chemical and
microbiological deterioration and its importance on low- and intermediate-moisture
foods.

Factors Affecting Hysteresis

• Types of Foods Affecting Hysteresis
• Temperature Effects on Hysteresis
• Effects of Physicochemical Nature
 Types of adsorption isotherms

• Freundlich adsorption isotherms

• Langmuir adsorption isotherms
• BET adsorption isotherms
 Langmuir Adsorption Isotherm
assumptions
• Fixed number of vacant or adsorption sites are available on the surface of solid.
• All the vacant sites are of equal size and shape on the surface of adsorbent.
• Each site can hold maximum of one gaseous molecule and a constant amount of
heat energy is released during this process.
• Dynamic equilibrium exists between adsorbed gaseous molecules and the free
gaseous molecules.

Where A (g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB
is Adsorbed gaseous molecule.
• Adsorption is monolayer or unilayer.
• Langmuir Equation

• Where
• θ the number of sites of the surface which are covered with gaseous molecule,
• P represents pressure
• K is the equilibrium constant
 Limitations of Langmuir Adsorption Equation

• The adsorbed gas has to behave ideally in the vapor phase. This condition can be
fulfilled at low pressure conditions only. Thus Langmuir Equation is valid under low
pressure only.

• Langmuir Equation assumes that adsorption is monolayer. But, monolayer

formation is possible only under low pressure condition. Under high pressure
condition the assumption breaks down as gas molecules attract more and more
molecules towards each other.

• Another assumption was that all the sites on the solid surface are equal in size and
shape and have equal affinity for adsorbate molecules i.e. the surface of solid if
homogeneous. But we all know that in real solid surfaces are heterogeneous.

• Langmuir Equation assumed that molecules do not interact with each other. This is
impossible as weak force of attraction exists even between molecules of same
type.

• From above facts we can conclude that, Langmuir equation is valid under low
pressure conditions.
 Freundlich Adsorption Isotherm

• Where q is the mass of the gas adsorbed on mass

of the adsorbent at pressure p and k, n are
constants.
• whose values depend upon adsorbent and gas at
particular temperature.
• It works at low pressure and failed to explain
adsorption value at high pressure.
• Freundlich Adsorption Equation: A Special Case
of Langmuir Equation
 BET(Brunauer, Emmett and Teller) adsorption
isotherm
• Often molecules do form multilayers
• Langmuir isotherm is not valid
The key assumptions
• Solute adsorbs on a flat, uniform surface of the solid
• Uniform heat of adsorption due to van der Waals forces between the solute and the
solid.
• There is no lateral interaction between the adsorbed molecules
• The adsorption of the second and subsequent layers occurs with a heat of adsorption
equal to the heat of liquefaction of the solute
 Why BET isotherms forms
multi layer?

At High pressure &low temperature

thermal energy of gaseous molecules

decreases

more gaseous molecules would be

available per unit surface area.

Due to this multilayer adsorption would

occur
• The following experimental data for the equilibrium
adsorption of pure methane gas on activated carbon
(PCB from Calgon Corp.) at 296 K were obtained by
Ritter and Yang

Fit the data to: (a) the Freundlich isotherm, and (b) the
Langmuir isotherm. Which isotherm provides a better fit
to the data?
 Basic adsorption cycles
• Temperature-swing adsorption (TSA)
• Pressure-swing Adsorption (PSA)

PSA has some advantages over TSA

limitation of TSA
• Energy consumption for heating
of the bed for regeneration
• The solute is released as a dilute
stream and may not be easy to
recover
• Cooling of the bed should follow
regeneration
 Adsorber
Adsorbers, the device that contain the
adsorbent solid through which the effluent
gas must pass.

• fixed bed adsorber

• Moving bed adsorber
• Fluidized bed adsorber
 Fixed bed adsorber
• Container can be vertical or horizontal
cylindrical shell
• More than one bed can also be used.
• Adsorptiononly occurs in a particular
region of the bed, known as the mass
transfer zone (MTZ),
• The factors which determine
the number and arrangement of fixed
beds include
1. total feed flow rate,
2. allowable pressure drop,
3. energy demands, length of the MTZ,
4. method of adsorbent regeneration,
5. and the capital investment
Bed profiles and breakthrough curves
• length equilibrium section (LES),
• The length or weight of unused bed (LUB)
• The mass transfer zone length (MTZ)
Advantages:
• The main advantages of fixed bed system are
• the simplicity of equipment needed
• they are relatively inexpensive to fabricate.

Disadvantages
⮚ they are difficult to design accurately because the progress of the MTZ
introduces time into the design equations.

⮚ In thermal regeneration processes, it is difficult to heat and cool large beds of

highly porous adsorbents quickly because of poor heat transfer
characteristics. Poor heat transfer leads to long heating and cooling times
which creates the need for large beds
 Moving bed adsorber
• Adsorbtion bed is in the form of rotating drum.

• 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.

• Heat transfer in moving and fluidized bed systems

is better than in fixed bed.

• Expensive to fabricate

.
Fluidized bed adsorber

• Contain a shallow,floating bed of

adsorbent
• Air flows upward,expanding the bed and
suspending or fluidizing the adsorbent
Adsorbers can also be classified as

• Regenerative adsorber
• Non-regenerative adsorber (costly process)
• In certain applications it may be more economical to
discard the adsorbent after use. Disposal would be
favoured 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 in external to the adsorption
vessel to an extent that the adsorbents can be reused.
• The final choice of regeneration method(s) depends on
technical and economic considerations.

presented by: Alia Ahrar