PHYSICAL SEPARATION PROCESSES

ECH3118

ADSORPTION
 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. The reverse
process is called desorption.

Adsorbent: The solid itself (e.g. carbon black, silica, etc.); material
doing the adsorbing
Adsorbate: The adsorbed gas (e.g. nitrogen, krypton, argon, etc.);
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 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.

•The more the surface area the more is the rate of adsorption. Hence, porous
substances and finely divided metals are good adsorbents.

•Physical adsorption is an exothermic process.

•No activation energy is needed.

 Chemical Adsorption
When the gas 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.

PROPERTIES PHYSISORPTION CHEMISORPTION
Weak - Van der Strong - Chemical
Waals interactions bonding involving
(e.g. London orbital overlap and
dispersion, dipole- charge transfer.
dipole).
5-50 kJ mol-1, no 40-800 kJ mol-1
activation energy activation energy req’d
Multi-layer Mono-layer
No - Adsorbed Yes - Adsorbed
molecules maintain molecules loose their
their identity identity
Reversible Mostly Irreversible
 Advantages of Adsorption

• 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

10
 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
Adsorption vs. Absorption

Surface
Phenomenon 15
Adsorption vs. Absorption

Surface Bulk (Volume)

Phenomenon Phenomenon 16
Difference between Adsorption and Absorption

Adsorption Absorption
Surface phenomenon Substance penetrates the surface

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

adsorbent is different from that in the It is same throughout the material
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)
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
purposes
3. Activated alumina
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: microporous
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
Mordenite
• highly structured porous space

• N2 removal from air

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

• Nature of adsorbate and adsorbent.

• The surface area of adsorbent.
• Activation of adsorbent.
• Experimental conditions. (temperature,
pressure, etc.)
 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 known 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.
Isotherm models: There are four common models for isotherms
 a. Linear

q = Kc

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

Ce= equilibrium concentration in solution when amount adsorbed equals qe
 b. Langmuir Isotherm

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

Linear plot is 1/q vs 1/c.

Slope = K/qo and the intercept is 1/qo

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

Q 0a : represents the maximum adsorption capacity (monolayer coverage)
(g solute/g adsorbent).
Ce= equilibrium concentration in solution when amount adsorbed equals qe.
Ce :has units of mg/l. K : has units of l/mg
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.

 KB  Ce  Qa0
qe
(C S C){1
e  (KB  1)(Ce / C)S}
CS =saturation (solubility limit) concentration of the solute. (mg/liter)
KB = 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.
 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 q vs c is made, slope = n
 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)
39
 Example 12.1-1
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
Plot of the amount of adsorbate on the adsorbent as a function of its concentration
at constant temperature.

Try plot
a) linear q = Kc, or b) Langmuir 1/q vs 1/c or c) Freundlich

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
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

Data fit Freundlich isotherms

Slope, n = 0.229
K = 0.199
Thus: q= 0.199c0.229
Example. 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:
qbenz  50.1 cbenz
0.533

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:
qbenz  50.1 cbenz
0.533
 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  cAC

c AC  0.114 g/L  114 mg/L

Example 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:

qtol  76.6 ctol

0.365
Example 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:

qtol  76.6 ctol

0.365

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

 Test yourself
• A wastewater solution having a volume of 1.0m3
contains 0.21 kg phenol/m3 of solution (0.21 g/L). A
total of 1.40 kg of fresh granular activated carbon
(GAC) is added to the solution, which is then mixed
to reach equilibrium. Using the isotherms, what are
the final equilibrium values, and what are percent of
phenol is extracted?
 Test yourself
• A wastewater solution having a volume of 1.0m3
contains 0.21 kg phenol/m3 of solution (0.21 g/L). A
total of 1.40 kg of fresh granular activated carbon is
added to the solution, which is then mixed to reach
equilibrium. Using the isotherms, what are the final
equilibrium values, and what are percent of phenol is
extracted?

(Ans: at equlibrium q=0.106kg phenol/kg carbon, c=0.062kg

phenol/m3,
% phenol extracted=70.5%)
 Factors which affect adsorption extent
Adsorbate:

Solubility

In general, as solubility of solute increases the extent of

adsorption decreases.

Factors which affect solubility include:

molecular size (high MW- low solubility),
Ionization (solubility is minimum when compounds are
uncharged), polarity (as polarity increases, higher solubility
because water is a polar solvent).
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.
Temperature
Adsorption reactions are typically exothermic. Here heat is given off
by the reaction therefore as T increases extent of adsorption
decreases.
Presence of other solutes
In general, get competition for a limited number of sites therefore get
reduced extent of adsorption or a specific material.
Adsorbent:
Virtually every solid surface has the capacity to adsorb solutes. From the
wastewater/water treatment point of view, activated carbon (AC) is the
adsorbent of choice. AC prepared from many sources: Wood- Lignite,
Coal- Nutshells- Bone
These raw materials are prepared at high temperature under low oxygen
conditions (so we don’t get complete combustion). This forms a “char”.
The char is then activated by heating to 300 – 1000 oC in the presence of
steam, oxygen or CO2.
This process result in “Activated carbon” which is highly porous, micro-
crystalline material which resembles graphite plates with some specific
functional groups (e.g. COOH, OH)
Most of the surface area is in pores of molecular sized dimensions.

This results in slower mass transfer during the adsorption process

but also results in greater binding capacity of the adsorbate.

Adsorption behavior is related in part to the nature of the functional

groups on the carbon surface. In general, carbon manufactured at:
<500 oC is weakly acidic
> 500 oC is weakly basic
Spent AC can be regenerated at high temperatures (roughly a
maximum of fifteen times).
 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 Effluent
Fresh Carbon

Effluent zone C approx. 0

“S” zone: C goes from C0 to

approx. 0

0 Saturated zone: C = C0
C/C0 1

Waste Influent
Exhausted Carbon
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.
 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
 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.
END TOPIC