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Adsorption Operation
By: In. Nurul Hasyimah Mohd Amin
Objectives
At the end of this lessons, students should be
able to:
Define adsorption process and its
mechanism.
Explain and differentiate physical and
chemical adsorption.
Discuss the adsorption isotherms.
Perform calculation related to this topic.
Introductions
Adsorption: The accumulation of
molecular species at the surface of a
solid or liquid rather than in the bulk
is called adsorption.
Bul
Surfac
Adsorbedmaterial
Freematerials
How it is happen?
Surface of solids and liquids has the
tendency to attract and retain other
molecules with which it is brought in to
contact.
How it is happen?
This is due to unbalanced residual
inward forces of attraction at the
surface of solids and liquids.
How it is happen?
Due to these residual forces,
surface of solid or liquid has a
higher concentration of other
molecular species than the bulk.
Adsorbate:
The
molecular
species that accumulate at the
surface.
Adsorba
te
Adsorbe
nt
of
Absorption
Adsorption
Absorption
It is a surface
phenomenon
It is a bulk phenomenon
Adsorbed species is
accumulated in the
surface
It is a fast process
It is uniformly distributed
throughout the bulk
Rate of adsorption
decreases gradually
It is a slow process
Types of Adsorption
Adsorption
Physisorption
Chemisorptio
n
Physical
Adsorption
or
Physisorption
Characteristics of Physisorption
1. Non-specific nature: An adsorbent does not show any preference
for a gas as the van der Waals forces are universal.
2. Easily liquefiable gases like CO2, SO2, NH3 etc, are readily
adsorbed.
3. Reversible nature: Physisortion of a gas by a solid is reversible.
4. Increases by increase of pressure.
5. Surface area of adsorbant: When the surface area of the adsorbent
increases, more gas is adsorbed, ie extent of adsorption increases.
6. Enthalpy of adsorption: Enthalpy of adsorption of physisorption
is very low (20-40 KJ mol-1)
Since adsorption is exothermic, physisorption takes place
readily at low temperature and desorption takes place at higher
temperature.
Chemical
Adsorption
or
Chemisorption
Characteristics of Chemisorption
Physisorption
Chemisorption
Chemical Bond
Reversible
Irreversible
Not specific
Specific
More liquefiable gases are adsorbed Gases which form compounds with
readily
adsorbent alone undergo chemisorption
High pressure favors physisorption and High pressure is favorable but decreases of
decrease of pressure causes desorption
pressure does not cause desorption
10
11
It is instantaneous
It is a slow process
Factors Influencing
Adsorption
2. Temperature
Adsorption of a gas generally decreases with
rise in temperature. This is because adsorption
is exothermic and increases of temperature
favors the backward process which is
desorption.
Heat
3. Pressure
Adsorption of a gas by an adsorbent at constant
temperature increases with increase of
pressure.
Applications
Adsorption
1. In Gas Masks
2. Production of High
Vacuum
3. Softening of Hard
water
Ca
2+
Ca
Ca
2+
2+
Ca
2+
Exchange
resin
4. Heterogeneous
Catalysis
5. Refining of Petroleum
6. Chromatographic Separation
Mechanisms of ad
1
2
diffuse
from the
bulk of
phase to
the
exterior
surface
of the
adsorbent
3
diffuse
inside the
pore and
to the
surface
of the
pore.
adsorbed
on the
surface
Adsorbents
Adsorbents
PAC
Molecularsieve
Silicagel
Activated
GAC
zeolites
alumina
EAC
Characteristics of Adsorbents
Adsorbents
Pore
structure
Nature
Porosity
Characteristics of Adsorbents
Porestructure
zeolite
Silicagel
ActivatedCarbon
Characteristics of Adsorbents
Porosity
Micropores
Mesopores
Macropores
D=250nm
D>50nm
D<2nm
Characteristics of Adsorbents
Nature
Hydrophobic
interaction
Hydrophilic
repulsion
Adsorption equilibrium
If the adsorbent an adsorbate are
contacted long enough, an equilibrium
will be established
Eq between amount of the adsorbate
in solution and being adsorbed on the
adsorbent
isotherms
Adsorption equilibrium
qe = mass of material adsorbed per mass of
adsorbent (at eq)
Ce = concentration in solution when amount
adsorbed equal to qe (at eq) (mg/L)
qe/ Ce depend on the types of adsorption
(physical or chemical adsorption)
Adsorption equilibrium
Adsorption equilibrium
Isotherms
Linear
Favorable
Strongly
favorable
HenrysLaw
Langmuir
isotherm
Freundlich
isotherm
Henrys Law
Assume that the concentration in one phase is
proportional to the concentration in the other.
Can be expressed by equation:
Langmuir isotherm
Assume monolayer coverage and constant binding
energy between surface and adsorbate.
Maximum adsorption occurs when the surface is
covered by a monolayer of adsorbate.
Langmuir isotherm
Can be expressed by:
QoCe
qe
K L Ce
The linear form of equation:
L/mg
1
KL
1
qe QoCe Qo
Maxadsorption
capacity(monolayer)
(gsolute/gadsorbent)
Mg/L
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Freundlich isotherm
For special case: heterogeneous surface energy.
Particularly for mixed wastes.
Can be expressed by:
qe K F C
The linearization will give
1/ n
e
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Freundlich isotherm
For freundlich isotherm, we use log-log version
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Freundlich isotherm
Where
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Freundlich isotherm
Adsorption capacity at equilibrium, qe
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Example 1
Batch tests were performed in the laboratory
using solutions of phenol in water and particles
of granular activated carbon. The equilibrium
data at room temperature are shown in Table 4.1.
Determine the isotherm that fits the data.
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Example 1
Table 4.1: Equilibrium data for example 1
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Answer
Langmuir Isotherm
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Answer
Freundlich Isotherm
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Batch adsoprtion
Batch adsorption is often used to adsorb solutes from liquid
solutions when the quantities treated are small in amount.
Solid will not remove the entire contaminant unless it is
infinitely good mixing.
Total solute removed is the function of amount of contaminant
to mass of solid.
The material balance on the adsorbate is:
qF M C F S qM CS
Where M
S
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Batch adsoprtion
Batch adsorption is often used to adsorb solutes from liquid
solutions when the quantities treated are small in amount.
Solid will not remove the entire contaminant unless it is
infinitely good mixing.
Total solute removed is the function of amount of contaminant
to mass of solid.
The material balance on the adsorbate is:
qF M C F S qM CS
Where M
S
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Batch adsoprtion
An equilibrium relation and material balance are
needed.
CF : initial feed concentration
C : final equilibrium concentration
qF : initial feed adsorbate loading
q : final equilibrium adsorbate loading
qF M C F S qM CS
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Example 2
A waste water (volume 1 m3) contains 0.21
kg phenol/m3. A total of 1.40 kg of fresh granular
activated carbon is added to the solution, mixed
thoroughly to reach equilibrium. Using isotherm in
Example 1, calculate the final equilibrium
values and percentage of phenol adsorbed by the
activated carbon.
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Answer
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Answer
Attheintersection;
q=0.106andc=0.062
%extracted =[(0.2100.062)/(0.21)]x100%
=70.5%
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Breakthrough curve
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Breakthrough curve
The break point occurs when the concentration of the fluid
leaving the bed as unadsorbed solute begins to emerge. The
bed has become ineffective (very small but detectable).
a breakpoint composition is set to be the maximum amount of
solute that can be acceptably lost
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Breakthrough curve
Afterthetbisreached,thec
risesveryrapidlyuptocd,
(endofthebreakthrough
curvewherethebedis
judgedineffective)
cd
cb
t1
t2
t3
t4
t5
Theoutletconcentration(break
At time t1, t2 and t3, the exit
Thebreakpointoccurs
point)startstorisetoc
batt5
concentrationremainsnearzero
whentheconcentration
until ofthefluidleavingthe
the mass transfer zone
startstoreachthet
4
bedstartsrisetoc
b
Breakthrough curve
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Breakthrough curve
The time required for a bed to become totally saturated is
obtained by integrating as time goes to infinity:
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Breakthrough curve
The length of bed used up to break point is:
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Example 3
A waste stream of alcohol vapor in air from a process was
adsorbed by activated carbon particles in a packed bed having a
diameter of 4 cm and length of bed of 14 cm containing 79.2 g of
carbon. The inlet stream having a concentration, Co of 600 ppm
and a density of 0.00115 g/cm3 entered the bed at a flow rate
of 754 cm3/s. Data in the table give the concentrations of the
breakthrough curve. The break point concentration is set at C/C o
= 0.01. Do as follows.
Ce
C
1
eoC
C
o1
e
qe K
.Qa o Q
a eo
q e K .Qa Qa
Example 3
Time, h
C/Co
Time, h
C/Co
5.5
0.658
0.903
3.5
0.002
6.2
0.933
0.03
6.5
0.975
4.5
0.155
6.8
0.993
0.396
Example 3
a) Determine the breakpoint time, the fraction of
total capacity used up to the break point, and the
length of the unused bed. Also determine the
saturation loading capacity of the carbon.
b) If the break point time required for a new column
is 6.0 h, what is the new total length of the column
required?
Example 3
Example 3
a) The break point as c/co = 0.01, t = 3.65hr
td = 6.95
Area A1 = 3.65
Area A2 = 1.51
tT
Graphicallynumericalmethods
Simpsonrule
c
1 dt 3.65 1.51 5.16hr
co
Example 3
tu
tb
c
1 dt 3.65hr
co
Thefractioncapacityusedtobreakuptobreakpoint;
t u 3.65
0.707
tT 5.16
Theunusedbed=(1.00.707)x14cm=4.1m