LEARNING OUTCOMES

• To explain the principles of adsorption

• To describe the operations of adsorption units
• To use equilibrium data and differentiate between
Langmuir and BET isotherm
• To compare the structure of adsorbents and select the
suitable adsorption equipment
 Introduction

• Application
• Theory of adsorption
• Mechanism
• Adsorption process
• Types of adsorbents
• Factors affecting
• Characteristics
• Isotherm
 What is adsorption?
Process to remove soluble material from the solution phase (either
gaseous or liquid), onto the surface of a solid substrate.

Adsorbent: The solid itself (e.g. carbon black, silica, etc.); material
doing the adsorbing
Adsorbate: The adsorbed gas (e.g. nitrogen, krypton, argon, etc.); or
other waste (Heavy metals, Dyes, Pharmaceutical waste) material
being adsorbed

Macropore: A pore larger than 50 nm.

Mesopore: A pore having a size from 2 nm to 50 nm;
Micropore: A pore smaller than 2 nm;
There are two types of Adsorption

Physical Adsorption or Physiosorption

Chemical Adsorption or Chemisorption.
 Physical Adsorption
It involves adsorption of gases/waste on solid surface via weak van der Waal’s
forces.

Characteristics of Physical Adsorption

•There is no specificity in case of physical adsorption. Every gas is adsorbed on the

surface of the solid.

•Nature of the adsorbate. Easily liquefiable gases are strongly adsorbed physically.

•Physical adsorption is reversible in nature. If pressure is increased volume of gas

decreases as a result more gas is adsorbed. So, by decreasing the pressure, gas can
be removed from the solid surface. Low temperature promotes physical adsorption
and high temperature decreases the rate of adsorption.

•More surface area more is the rate of adsorption. Porous substances and finely
divided metals are good adsorbents.

•Physical adsorption is an exothermic process.

 Chemical Adsorption
When the gas/solid waste molecules or atoms are held to the solid surface via chemical
bonds

Characteristics of Chemical Adsorption

•This type of adsorption is specific as compared to physical adsorption. Adsorption

occurs only if there is formation of chemical bonds between the adsorbate and
adsorbent.

•Chemical adsorption is irreversible.  It is an exothermic process but the process occurs
slowly at low temperature. Chemisorption is accompanied by increase in temperature.
High pressure promotes chemisorption.

•Chemisorption increases with increase in surface area.

•Due to chemical bond formation enthalpy of chemisorption is high.

•Activation energy is needed.

•It results in unimolecular layer.

 Useful When/Motivation
• The pollutant gas is noncombustible or difficult
to burn
• The pollutant is sufficiently valuable to warrant
recovery
• The pollutant is in very dilute concentration
• It is also used for purification of gases containing
only small amounts of pollutants that are difficult
to clean by other means

9
 Adsorption vs absorption

Adsorption is a surface phenomenon in which

particles or molecules bind to the top layer of
material.
Absorption, on the other hand, goes deeper,
involving the entire volume of the absorbent.
Absorption is the filling of pores or holes in a
substance.
 Adsorption ≠ Absorption

Adsorption is a phenomenon
that occurs on a surface
 Adsorption ≠ Absorption

Adsorption is a phenomenon Absorption is a phenomenon

that occurs on a surface that occurs in a volume
The word sorption encompasses both types of phenomena
Difference between Adsorption and Absorption

Adsorption Absorption
Substance penetrates the surface
Surface phenomenon

Rate increases initially than it It occurs at uniform rate

decreases
It is affected by temperature
It is unaffected by temperature

It is an exothermic process
It is an endothermic process

Concentration on the surface of

It is same throughout the material
adsorbent is different from that in
the bulk
 Applications
Charcoal is used as a decoloriser as it adsorbs the coloring matter from the
coloured solution of sugar.

Silica gel adsorbs moisture from the desiccators.

Silica and alumina gels are used as adsorbents for removing moisture and for
controlling humidity of rooms.

Activated charcoal is used in gas masks as it adsorbs all the toxic gases and
vapours and purifies the air for breathing.

Heterogeneous Catalysis. The reaction mechanism of how a reactant reacts on a

catalyst surface revolves around adsorption.
 Commercial applications

• Gas cleaning
• Pharmaceutical
• Chemical separation
• Food industries (carbonated drinks, etc)
• Wastewater treatment (heavy metal
removal, dye removal, organic/phenolic
compounds removal etc.)
Adsorption Mechanism
Adsorption Mechanism
 Adsorption Mechanism
– 2) Chemical adsorption
• Results from a chemical interaction between the
adsorbate and adsorbent. Therefore formed bond
is much stronger than that for physical adsorption
• Heat liberated during chemisorption is in the range
of 20-400 kj/g mole
Example – gas –solid adsorption
 Adsorbents & properties

1. Activated carbon
2. Silica gel dehydrating
3. Activated alumina purposes
4. Molecular sieves
zeolites
5. Synthetic polymers or
resins
6. Natural-based
adsorbents

Properties : pore size distribution, surface area

 Adsorbents: Characterization

1) Crystalline/amorphous

2) Hydrophobic/Hydrophilic

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

4) Pore size

r<2nm: microporours
2nm<r<50nm: mesoporous
r>50nm: macroporous

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

 Adsorbents: Examples

Silica gels:

- granular porous form of silica

- amorphous

- hydrophilic

- 700-800m2/g

- water removal
Adsorbents: Examples

Activated Carbon

- partial oxidation of coal

- amorphous

- hydrophobic

- 400-1200m2/g

- organic trace removals

- air filters
 Adsorbents: Examples

Zeolites

- porous crystalline minerals

- hydrophilic

- 600-700m2/g

- highly structured porous Mordenite

space

-N2 removal from air

ZSM-5
-Uniform pores to selectively
separate compounds by size and shape
 Factors to be considered

• Temperature
• Nature of adsorbate and adsorbent.
• Concentration of adsorbent and adsorbate
• pH
• Time
 Factors to be considered
Temperature:

Adsorption is an exothermic process, Hence according to Le Chatelier’s

principle at given pressure low temperature favours adsorption. If the

temperature is increased, adsorbate molecules get removed from the adsorbent

and this process is called as desorption. Hence, as T increases extent of

adsorption decreases
 Factors to be considered
Nature of Adsorbent:
Since adsorption is a surface phenomenon, adsorption increases with the increase
in the surface area of the adsorbent. More finely divided or rougher the surface of
adsorbent, the greater will be the surface area and hence the greater will be the
adsorption. Metal catalysts in the finely divided form, colloidal form, rough
surfaces, activated adsorbent provides more surface area.
A gas will be chemisorbed on a given solid only if it can provide large
surface area. For e.g. Hydrogen gas is adsorbed by nickel but not by iron. The
chemical nature of the adsorbent should be such so that it can cause chemisorption
of adsorbate on the adsorbent.
 Factors to be considered
Nature of Adsorbate:
In case of adsorption of gases by solids, it has been found that more easily liquefiable
and highly water-soluble gases are adsorbed more readily due to greater van der Walls
forces. Hence ammonia, hydrogen chloride, chlorine and sulphur dioxide are more
adsorbed than hydrogen, nitrogen, oxygen.
In physical adsorption, the extent of adsorption depends on the boiling point
of the gases. Gases are adsorbed on solids more readily than liquids.
 Factors to be considered

Concentration of Adsorbate:
When liquid is adsorbed on solid, at higher concentration of adsorbate, the extent of
adsorption is greater, provides that the temperature is kept constant. The concentration of
adsorbate has a similar type of effect as that of pressure.

Concentration of adsorbent:
The removal efficiency of adsorbent increases by raising sorbent dosage due to
the availability of higher numbers of active sites, and it continues until saturation is
reached. The optimum adsorbent dosage varies with its type/category due to
variation in functional groups and the number of active sites.
 Factors to be considered
pH:
pH often affects the surface charge on the adsorbent as well as the
charge on the solute. Generally, for organic material as pH goes
down adsorption goes up.
Time:
Usually, adsorption is reasonably speedy at the start of the process because quite
high numbers of unoccupied active sites are available for the adsorption of
pollutants. However, after a certain time, when the sorbent surface adsorbed a
specific amount of pollutant, the adsorption rate decreases due to a reduction in
the number of active sites and subsequently, the system reached sorption
equilibrium.
 Adsorptive Equilibration in a Porous
Adsorbent
Pore
Early

Later

Laminar
Boundary
Layer GAC Particle
Equilibrium
Adsorbed Molecule
Diffusing Molecule
 ADSORPTION EQUILIBRIA

If the adsorbent and adsorbate are contacted long enough

an equilibrium will be established between the amount of
adsorbate adsorbed and the amount of adsorbate in solution.
The equilibrium relationship is described by isotherms.
 What is Adsorption Isotherm?
The process of Adsorption is usually studied through graphs know as adsorption
isotherm. It is the graph between the amounts of adsorbate (x) adsorbed on the surface
of adsorbent (m) and pressure at constant temperature. (pressure (if gas) or
concentration (if liquid) at constant temperature). The adsorption isotherm is the
equilibrium relationship between the concentration in the fluid phase and the
concentration in the adsorbent particles at a given temperature.

In the process of adsorption, adsorbate gets adsorbed on adsorbent.

According to Le-Chatelier principle, the direction of equilibrium would shift in that
direction where the stress can be relieved. In case of application of excess of pressure
to the equilibrium system, the equilibrium will shift in the direction where the number of
molecules decreases. Since number of molecules decreases in forward direction, with
the increases in pressure, forward direction of equilibrium will be favored.
From the graph, we can predict that after saturation pressure Ps, adsorption does
not occur anymore. This can be explained by the fact that there are limited numbers
of vacancies on the surface of the adsorbent. At high pressure a stage is reached
when all the sites are occupied and further increase in pressure does not cause any
difference in adsorption process. At high pressure, Adsorption is independent of
pressure.
 Physical meanings of the isotherm models

 Isotherm refers to the relationship between the equilibrium

adsorbate concentrations in the liquid-phase and the equilibrium
adsorption amount on the solid-phase at a certain temperature.

 We can model the equilibrium adsorption data by the isotherms,

and investigate the adsorption information, such as the adsorption
mechanisms, the maximum adsorption capacity, as well as the
properties of adsorbents by the isotherm.
 a. Linear

 The linear model has the following form

qe= mass of material adsorbed (at equilibrium) per mass of adsorbent.

Ce= equilibrium concentration
a. Linear
b. Langmuir Isotherm
 b. Langmuir Isotherm

This model assumes monolayer coverage and constant binding energy between surface and
adsorbate.

qe= mass of material adsorbed (at equilibrium) per mass of adsorbent.

0
Q a : represents the maximum adsorption capacity (monolayer coverage)
(g solute/g adsorbent).
Ce= equilibrium concentration in solution.
 b. Langmuir Isotherm

 Langmuir model describes equilibrium condition of

monolayer homogeneous adsorption
 d. Freundlich Isotherm

For the special case of heterogeneous surface energies (particularly good for mixed
wastes) in which the energy term, “KF”, varies as a function of surface coverage we
use the Freundlich model.

n and KF are system specific constants.

If a log-log plot of qe vs Ce is made, slope = 1/n
 c. BET (Brunauer, Emmett and Teller) isotherm

 It is a theoretical multi-layer physical adsorption model (Fig.). It has been applied for
calculation the specific areas and the pore size distribution of the porous materials.

 The basic presumptions of BET isotherm are that the adsorption is multi-layer
homogeneous adsorption, the adsorption energy in the first layer is different with
other layers, and for each layer, the adsorption rate equals to the desorption rate.
c. BET (Brunauer, Emmett and Teller) isotherm

This is a more general, multi-layer model. It assumes that a Langmuir isotherm

applies to each layer and that no transmigration occurs between layers. It also
assumes that there is equal energy of adsorption for each layer except for the first
layer.

K  C  Q0
q e  B e a
(C S  C e ){1  (KB  1)(Ce / CS )}

CS =saturation (solubility limit) concentration of the solute. (mg/liter) K B = a parameter

related to the binding intensity for all layers.
Note: when Ce << CS and KB >> 1 and K = KB/Cs BET isotherm approaches Langmuir
isotherm.
Isotherm models: There are four common models for isotherms
 Adsorption Isotherms
• Plot of the amount of adsorbate on the adsorbent
as a function of its pressure (if gas) or
concentration (if liquid) at constant temperature.
• Langmuir isotherm (adsorbed layer one molecule
thick)
• Brunauer, Emmett and Teller (BET) isotherm
(molecules can be adsorbed more than one layer
thick)
• Freundlich isotherm (Heterogeneous adsorbent
surface with different adsorption sites)
47
Batch test were performed in the laboratory using phenol solutions in water
and particles of granular activated carbon (R5). The equilibrium data at room
temperature are shown in table 12.-1-1. determine the isotherms that fits the
data.
 Solution
c q log c log q 1/c 1/q
0.32 0.15 -0.49 -0.82 3.11 6.67
0.12 0.12 -0.93 -0.91 8.55 8.20
0.04 0.09 -1.41 -1.03 25.64 10.64
0.01 0.06 -2.21 -1.23 163.93 16.95
0.00 0.05 -2.96 -1.35 909.09 22.22
 Solution
c q log c log q 1/c 1/q
0.32 0.15 -0.49 -0.82 3.11 6.67
0.12 0.12 -0.93 -0.91 8.55 8.20
0.04 0.09 -1.41 -1.03 25.64 10.64
0.01 0.06 -2.21 -1.23 163.93 16.95
0.00 0.05 -2.96 -1.35 909.09 22.22
 Solution
c q log c log q 1/c 1/q
0.32 0.15 -0.49 -0.82 3.11 6.67
0.12 0.12 -0.93 -0.91 8.55 8.20
0.04 0.09 -1.41 -1.03 25.64 10.64
0.01 0.06 -2.21 -1.23 163.93 16.95
0.00 0.05 -2.96 -1.35 909.09 22.22
 Solution
c q log c log q 1/c 1/q
0.32 0.15 -0.49 -0.82 3.11 6.67
0.12 0.12 -0.93 -0.91 8.55 8.20
0.04 0.09 -1.41 -1.03 25.64 10.64
0.01 0.06 -2.21 -1.23 163.93 16.95
0.00 0.05 -2.96 -1.35 909.09 22.22
 Solution
c q log c log q 1/c 1/q
0.32 0.15 -0.49 -0.82 3.11 6.67
0.12 0.12 -0.93 -0.91 8.55 8.20 Data fit Freundlich
isotherms
0.04 0.09 -1.41 -1.03 25.64 10.64
Slope, n = 0.229
0.01 0.06 -2.21 -1.23 163.93 16.95 K = 0.199
0.00 0.05 -2.96 -1.35 909.09 22.22 Thus: q= 0.199c0.229
 Problem
The following laboratory data were collected in a batch adsorption study. Plot
the data according to Freundlich Isotherm and determine the values for the
constants n and KF

Ce (mg/L) 0.54 0.72 0.90 1.10 1.31 1.52

qe (mg/mg) 0.05 0.064 0.084 0.11 0.15 0.20

Solution
 Solution

Slope = 1/n= 0.62

n = 1.61
 Adsorption of benzene onto activated carbon has been reported to obey the
following Freundlich isotherm equation, where c is in mg/L and q is in mg/g:
0.533
qbenz  50.1 cbenz

A solution at 25oC containing 0.50 mg/L benzene is to be treated in a batch

process to reduce the concentration to less than 0.01 mg/L. The adsorbent is
activated carbon with a specific surface area of 650 m2/g. Compute the required
activated carbon dose.
Solution. The adsorption density of benzene in equilibrium with ceq of 0.01 mg/L
can be determined from the isotherm expression:

0.533
qbenz  50.1 cbenz  4.30 mg/g

A mass balance on the contaminant can then be written and solved for the
activated carbon dose:
ctot ,benz  cbenz  qbenz c AC
0.50  0.010   4.30 mg/g  c AC

cAC  0.114 g/L  114 mg/L

If the same adsorbent dose is used to treat a solution containing 0.500 mg/L
toluene, what will the equilibrium concentration and adsorption density be? The
adsorption isotherm for toluene is:
0.365
qtol  76.6 ctol
 If the same adsorbent dose is used to treat a solution containing 0.500 mg/L
toluene, what will the equilibrium concentration and adsorption density be? The
adsorption isotherm for toluene is:
0.365
qtol  76.6 ctol

Solution. The mass balance on toluene is:

ctot ,tol  ctol  qtol c AC

0.50  ctol   76.6 ctol 0.365   0.114 g/L 

ctol  3.93x104 mg/L

 General Process Design Features

• Contactors provide large surface area

• Types of contactors
– Continuous flow, slurry reactors
– Batch slurry reactors (infrequently)
– Continuous flow, packed bed reactors
• Product water concentration may be
– Steady state or
– Unsteady state
 CARBON CONTACTORS

Activated carbon reactors are usually called carbon contactors because the
waste stream is “contacted” with the carbon. Many times the contactor is
of the columnar fluidized or fixed-bed type. Sometimes (less often) the
contactor is in a slurry form.

Fixed or fluidized beds have the advantage of not having to separate the
carbon from the liquid stream after the contact period.

Slurry systems need some sort of activated carbon removal process to

separate the AC from the liquid stream.
 Packed bed (fixed carbon bed)

contactors provide filtration as well as adsorption so they have to be

periodically backwashed or cleaned.
This is one reason why we only want to run soluble material through a
contactor.
Fluidized Bed Contactors:

In a fluidized bed mode (upflow) carbon can be continuously

removed from the bottom of the contactor as it ’s exhausted.

Fresh make-up carbon can than be added to the top of

contactor at the same rate.

Upflow fluidized beds also minimize clogging and unintentional

filtration.
 Treated
Fresh Carbon Effluent

Effluent zone C approx.

0

“S” zone: C goes from C0 to

approx.
0

0 Saturated zone: C = C0
C/C0 1

Waste
Exhausted Carbon Influent
Carbon Regeneration

Since activated carbon is relatively expensive, adsorption would not be

feasible unless the carbon can be regenerated after exhaustion.

Spent carbon is usually regenerated at 500 oC under low oxygen

conditions in the presence of steam.

Activated carbon loss is about 5-15% for each regeneration. Adsorbed

organics are volatilized and oxidized during the regeneration process.
Activated carbon is mostly applied in water treatment for:
-The removal of taste and odor producing compounds
-the elimination of inconvenient or toxic often-non polar compounds.
-additional efforts are the removal of heavy metals, if present.
The application of AC in powder form is specially suitable in cases low
dosage are needed or intermittent use (removal of taste originated from an
algae-bloom)
Common apparent contact times are in dependence of the goal between 5
and 30 minutes; bed thickness up to 2-3 m are applied in water treatment.

Proper application of activated carbon needs experiments to decide

for the proper type (adsorption isotherm) and the proper dose.
 Powdered Activated Carbon (PAC)
PAC +
Coagulants Settled
Water

Sludge Withdrawal
PAC particles may or
may not be equilibrated

PAC + Flocculated
Coagulants Water

Process Operates at Steady-State, cout = constant in time

 Packed Bed Adsorption
v, c0
Natural Packed Bed – subsurface
with groundwater flow
Engineered Packed Bed- granular
activated carbon

EBCT = empty-bed contact time (Vbed/Q)

Adsorptive capacity is finite (fixed amount

of adsorbent in bed)

Process operates at unsteady state, cOUT

v, c must increase over time
 Fixed-bed adsorption
• Widely used for adsorption of solutes from liquid or gases employs a
fixed bed of granular particles.
• The fluid is treated is usually passed down through packed bed at
constant flow rate. Mass transfer are resistances is important and
the process is unsteady state.
Process configurations
Fixed-bed system: Breakthrough development
C0 C0 C0 C0 C0

Saturated zone The time to

Adsorption zone breakthrough is
decreased by:
Clean zone Increased particle
size of carbon
C C Cb Ce C0 Higher
C0 concentration in the
Exhaustion influent
Cout

Breakthrough curve Increased pH of the

water
Breakthrough point (switch
Ce to clean bed occurs before) Increased flow rate
Amount of water treated
Lower bed depth
Water Supply: Adsorption 72