1

Subtopic : Introduction to Adsorption

Definition:
Adsorption is the adhesion of atoms, ions,
or molecules from a gas, liquid, or
dissolved solid to a surface.
It is the separation of components in a fluid
mixtures by the transfer of one or more
components (the adsorbates) to the
internal surface of a porous solid (the
adsorbent) where they are held by
intermolecular forces.
surface-based process
2
2
3
Adsorbed solute: Adsorbate
Solid material: Adsorbent
4
Molecules/atoms/ions in a gas or liquid diffuse to the
surface of a solid, where they bond with the solid surface
or are held there by weak inter-molecular forces
3
5
Adsorption-Saturated-Desorption
Regenerationprocess:
To recover Adsorbate and Adsorbent to be
reused
Use Desorbent or change in temperature or
pressure
Liquid phase :
removal of organic compounds from
water/organic solutions,
colored impurities from organics,
separations of paraffin from aromatics
Gas phase :
Removal of waster from HC gases
Sulfur compound from NG
Solvents from air & other gases
Odors from air
6
4
1. Stirred Tank
2. Cyclic fixed-bed, batch operation
3. Continuous countercurrent operation
7
8
Powdered adsorbent e.g. activated carbon particle diameter
less than 1 mm
Main application wastewater treatment
Spent adsorbent removed by sedimentation or filtration
5
9
Adsorbent particle size 0.05 cm to 1.2 cm
Optimal particle size bed pressure drop & solute transport rate
Main application removal of organic compounds from water
Spent adsorbent regenerated at high temperature
10
Need to circulate solid adsorbent as moving bed to achieve steady
state operation
Difficult in regenerating adsorbent when heavier HC presents
Unfavourableeconomics compared to distillation
6
Shape
i. Small pellets, beads, granules, cylindrical,
powders
ii. Size ranging from 50 m to 1.2 cm
Very porous structure (with many fine pores
and pore volumes up to 50% of total particle
volume)
i. Macropore ( > 500) 50 nm
ii. Mesopore (20 - 500 )
iii. Micropore ( < 20 )
Based on International Union of Pure and Applied
Chemistry (IUPAC)
Specific surface area: 300 to 1,200 m
2
/g
11
Activatedcarbon
- Made by thermal decompositionof wood
- Averagepore diameter 10to 60 A
- Usuallyorganicsadsorbedby activatedcarbon
- surfacearea 300to 1200 m2/g
Silicagel
- Made by acidtreatment of sodiumsilicatesolutionandthendrying
- Surfacearea600 to 800m2/g
- Averagepore diameter 20to 50 A
Activated
alumina
- Hydratedaluminumactivatedbyheatingtodry off thewater
- Usedmainlyto dry gasesandliquids
- Surfacearea200 to 500m2/g
- Averagepore diameter 20to 140 A
Molecular sieve
zeolites
- Porous crystallinealuminosilicates
- Open crystal lattice containing precisely uniformpores; make it
different fromother types of adsorbents
- Different zeoliteshavepore sizesfrom3to 10A
- Usedfor drying, separationof HCs
Synthetic
polymersor resin
-Madeby polymerisingtwomajor typesof monomers
- eg. Styrene and divinylbenzene to adsorb nonpolar organics from
aqueoussolutions
12
7
13
Coal-Based Activated Carbon for
Gas Purification
14
Made by acid treatment of
sodium silicate solution and
then drying
8
15
1. This product is made of the kind of activated alumina.
which is white granule with the big adsorptive capacity
for the polar material. Also, it enable to regeneration by
changing the pressure, temperature.
2. Mainly used in removing water, acetic acid
tetrabromoethane etc.
16
9
17
Unique macro-porous synthetic
polymer absorbent to remove soluble
and insoluble impurities from aquarium
water. For marine and freshwater use.
Resin
DA201-D macro-net non-polar adsorbent resin,
used for discoloration of fruit juice
Movement of an organic and/or inorganic molecule
to a surface site requires four separate phenomena:
Bulk fluid transport (external/ interphase mass transfer)
Mass transfer of the solute from the bulk fluid by convection,
through a thin film or boundary layer , to the outer, solid surface
of the adsorbent
Filmtransport (internal/ intraphase)
Mass transfer of the solute by pore diffusion from the outer
surface of the adsorbent to the inner surface of the internal
porous structure
Intraparticle (pore and/or surface diffusion)
Physical attachment
18
10
19
Bulk Fluid transport
Filmtransport
Intraparticle
Physical Attachment
20
11
For chemisorption, which involves bond formation,
the rate of the fourth kinetic step may be slow and
even controlling
For physical adsorption, however step 4 is almost
instantaneous because it depends only on the
collision frequency and orientation of the molecules
with the porous surface. Thus, only three steps need
to be considered here
During regeneration, the reverse of the four steps
occurs, where the rate of physical desorption is
instantaneous.
Adsorption and desorption are accompanied by heat
transfer because of the exothermic heat of adsorption and
the endothermic heat of desorption
21
Physical adsorption
Van der Waals adsorption
Low heat of adsorption
Non specific
Monolayer or multilayer
No dissociation of adsorbed
species.
Only significant at
relatively low
temperatures.
Rapid, non-activated,
reversible.
No electron transfer.
Chemisorption
Activated adsorption
High heat of adsorption
Highly specific (to one
adsorbate)
Monolayer only
May involve dissociation
Possible over a wide range
of temperature
Activated, may be slow and
irreversible
Electron transfer leading to
bond formation between
sorbate and surface.
22
12
Physical adsorption from a gas
occurs when the
intermolecular attractive
forces between molecules of a
solid and the gas are greater
than those between molecules
of the gas itself
Adsorption is like
condensation, which is
exothermic and thus is
accompanied by a release of
heat
Magnitude of the HOA can be
less or greater than the heat of
vaporization, and change with
the extent of adsorption
Commercial adsorbents rely on
physical adsorption
Involves the formation of
chemical bonds between the
adsorbent and adsorbate in a
monolayer
Often with a release of heat
much larger than the heat of
vaporization
Chemisorption from a gas
generally takes place only at
T>200
o
C
Catalyst relies on
chemisorption
23
Physical adsorption Chemisorption
1. High selectivity to enable sharp separations.
2. High capacity to minimize the amount
adsorbent needed.
3. Favorable kinetic and transport properties
for rapid sorption.
4. Chemical and thermal stability to preserve
the amount and its properties.
5. Hardness and mechanical strength.
6. High fouling resistance.
7. Capability of being regenerated relatively
low cost.
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13
25
Equilibrium relations for adsorbents
Concentration of a
solute in a fluid phase
Concentration of a
solute in a solid phase
Data is plotted as
adsorptionisotherms
T, P
Equilibrium relations for adsorbents
The equilibrium isotherm places a limit on the extent to
which a solute is adsorbed froma given on an adsorbent of
given chemical composition and geometry for a given set
of conditions
Desirable/ favorable isothermexhibit strong adsorption
Undesirable/ unfavorable isotherm exhibit low/ weak
adsorption
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14
27
Types of Isotherms
Linear Isotherm can be used in dilute region
Henrys law is obeyed:
q = Kc
C : concentration (fluid is liquid)
: kg adsorbate / m
3
fluid
p : partial pressure (fluid is a gas)
q : mass, moles or volumes of adsorbate (solutes) per
unit mass or per unit surface area of adsorbent
: kg adsorbate (solute) / kg adsorbent (solid)
K : an empirical, temperature-dependent constant
(determined experimentally)
28
q = Kc
n
Approximate data for many physical adsorption.
Particularlyuseful for liquids
K =Freundlichconstant
n =constant (n 1)
Bothare determined experimentally.
Freundlich isotherm
15
29
Example: Adsorption Isotherms
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 the
table below. Determine the isothermthat fits the data.
c
(kg phenol/m
3
solution)
q
(kg phenol/kg carbon)
0.322 0.150
0.117 0.122
0.039 0.094
0.0061 0.059
0.0011 0.045
Example 12.1-1
30
Batch Adsorption
When quantities to be treated are of small amount.
Isotherms and material balance are needed.
Material balance on the adsorbate:
q
F
M + c
F
S = q M + cS
where:
q
F
=initial concentrationof solute adsorbed on the solid
q =final concentrationat equilibrium
M =amount of adsorbent, kg
S =volume of feed solution, m
3
c
F
=initial concentrationof solute in the fluid phase
c =final concentrationat equilibriumin the fluid phase
16
Batch Adsorption
31
q
F
M + c
F
S = q M + cS
When variable q is plotted versus c , the result is a straight
line.
If equilibrium isotherm is also plotted on the same graph,
the intersection of both line gives the final equilibrium
values of q and c.
32
Example: Batch Adsorption
Example 12.2-1:
A wastewater solution having a volume of 1.0 m
3
contains
0.21 kg phenol/m
3
of solution . A total of 1.40 kg of fresh
granular activated carbon is added to the solution , which
is then mixed thoroughly to reach equilibrium. Using the
isotherm from Example 12.1-1, what are the final
equilibriumvalues, and what percent of phenol extracted?
17
33
Example: Batch Adsorption
Example 12.2-1:
0(1.40)+0.21(1.0) =q (1.40) +c (1.0)
q =0.15- 4.17 c (a)
From the isotherm
q =0.199 c
0.229
(b)
q
F
M + c
F
S = q M + cS
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Example: Batch Adsorption
Example 12.2-1:
At intersection q = 0.106 kg phenol/kg carbon
c = 0.062 kg phenol/m
3
% extracted = (c
F
- c)(100)/c
F
= (0.21-0.062)(100)/0.21
= 70.5 %
0
0.05
0.1
0.15
0 0.05 0.1 0.15 0.2
c, kg phenol/m3 solution
q
,

k
g

p
h
e
n
o
l/
k
g

a
d
s
o
r
b
e
n
t
18
Fixed Bed Adsorption Design
35
Introduction and concentration profiles
- Usually employ fixed bed of granular particles
- The fluid to be treated is usually passes down
through the packed bed at a constant flow rate
- Mass transfer resistances are important in the fixed-
bed process, and the process is unsteady state.
- The overall dynamic of the system determine the
efficiency of the process, rather than just the
equilibrium considerations
Fixed Bed Adsorption Design
36
Introduction and concentration profiles (contd)
- The concentration of the solute in the fluid phase and of the
solid adsorbent phase changewith TIME and POSITIONin the
fixed bed as the adsorption proceeds
- Inlet: solid is assumed to contain no solute at the start of the
process
- As the fluid first come into contact with the inlet, most of the
MASS TRANSFER and ADSORPTIONtakes place here
- As fluid passes thru the bed, the concentration in this fluid
DROPS VERY RAPIDLY with distance in bed and REACHES
ZERO well before the end of the bed reached
19
37
After a short time, solid near entrance almost SATURATEDand most of
the mass transfer and adsorption now takes place at a point slightly
farther from the inlet
The major part of the adsorption at any time takes place in a relatively
narrow adsorption or mass transfer zone
As the solution continues to flow, this mass-transfer zone (S-shaped),
moved down the column.
This outlet concerntration remains near zero until the mass transfer zone
starts to reach the tower outlet at t
4
.
Then the outlet concentration starts to rise.
Fixed Bed Adsorption Design
38
Breakthrough Concentration Curve
- Then, the outlet conc starts to rise, and at t
5
the outlet conc has risen
to c
b
, which is called the break point
- After the break-point time is reached, the concentration c rises very
rapidly up to point c
d
, which is the end of the breakthrough curve,
where the bed is judged ineffective.
- The break-point concentration represents the maximum that can be
discarded and often taken as 0.01 to 0.05 for c
b
/ c
o
.
- For a narrow MTZ, the breakthrough curve is very steep and most of
the bed capacity is used at the break point (this makes efficient use of
the adsorbent and lowers energy costs for regeneration)
breakthrough concentration profile in the fluid at outlet of bed
20
Fixed Bed Adsorption Design
39
Capacityof Column and Scale-Up Design Method
- Mass Transfer Zone (MTZ) width and shape depends on:
- the adsorption isotherm
- flowrate
- mass transfer rate to the particles
- diffusionin the pores.
- For systems with a favorable isotherm, similar to
Freundlich and Langmuir; MTZ acquires the typical S
shape. MTZ is constant in height as it moves thru d
column
- For unfavorable isotherm i.e. Isotherm is linear; MTZ
widthincreases with bed length
- A favorable isotherm for adsorption is unfavorable for
effectiveregeneration
Fixed Bed Adsorption Design
40
Capacityof Column and Scale-Up Design Method
- A number of theoritical methods have been published
which predict the Mass Transfer Zone (MTZ) and
concentrationprofiles in the bed.
- Hence, experiments in laboratory scale are needed in
order to scale up the results.
21
Fixed Bed Adsorption Design
41
Shaded area =Total or stoichiometric capacity of the packed tower
dt
c
c
t
t
) 1 (
0
0
}

=
(12.3-1)
Time
equivalent to
the total or
stoichiometric
capacity
Fixed Bed Adsorption Design
42
Crosshatched area = Usable capacity of bed up to the break-point time, t
b
22
Fixed Bed Adsorption Design
43
t
u
: time equivalent to the usable capacity or time
at which the effluent concentration reaches its
maximumpermissible level.
(12.3-2) dt
c
c
t
b
t
u
) 1 (
0
0
}
=
t
u
very close to t
b
t
u
/t
t
is the fraction of the total bed capacity or
length utilized up to the break point
Fixed Bed Adsorption Design
44
H
B
: length of bed used up to the break point
( H
T
: Total bed length)
(12.3-3)
T
t
u
B
H
t
t
H =
23
Fixed Bed Adsorption Design
45
H
UNB
: Length of unused bed (mass transfer zone)
(12.3-4)
H
T
= H
UNB
+ H
B
(12.3-5)
T
t
u
UNB
H
t
t
H ) 1 ( =
Fixed Bed Adsorption Design
46
Design Steps
1. Determine the the length of bed needed to achieve the
required usable capacity, H
B
2. Determine H
UNB
3. Calculate H
T
24
Fixed Bed Adsorption Design
47
Scale-up principle
1. If a system is tested with different bed
length, it gives breakthrough curve of the
same shape.
2. The amount of length of unused bed (H
UNB
)
does not change with the total bed length.
3. Hence, t
b
is proportional to H
B.
Example: Fixed Bed Adsorption Design
48
Example 12.3-1
A waste streamof alcohol vapour in air froma process was
adsorbed by activated carbon particles in a packed bed
having a diameter of 4 cm and length of 14 cmcontaining
79.2 g of carbon. The inlet gas stream having a
concentration c
o
of 600 ppmand a density of 0.00115 g/cm
3
entered the bed at a flow rate of 754 cm
3
/s. Data in Table
12.3-1 give the concentrations of the breakthrough curve.
The breakpoint concentration is set at c/c
o
= 0.01.
Determine :
1. Break point time
2. Fractionof total capacityused up to the break point time
3. Length of the unused bed
4. Total bed length
25
Example: Fixed Bed Adsorption Design
49
Example 12.3-1
Table 12.3-1
Time,h c/c
o
Time, h c/c
o
0 0 5.5 0.658
3 0 6.0 0.903
3.5 0.002 6.2 0.933
4 0.030 6.5 0.975
4.5 0.155 6.8 0.993
5 0.396
Example: Fixed Bed Adsorption Design
50
Example 12.3-1
The plotted data from Table 12.3-1
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Example: Fixed Bed Adsorption Design
51
Example 12.3-1
Based on Figure 12.3-3
At break point conc. 0.01: t
b
= 3.65 h; t
d
= 6.95 h
dt
c
c
t
t
) 1 (
0
0
}

=
= A
1
+ A
2
= 3.65 + 1.51 = 5.16 h
dt
c
c
t
b
t
u
) 1 (
65 . 3
0
0
}
=
=
= A
1
= 3.65 h
t
u
/ t
t
= 3.65/5.16 = 0.707
T
t
u
B
H
t
t
H = = 0.707(14) = 9.9 cm
T
t
u
UNB
H
t
t
H ) 1 ( =
= (1 - 0.707)14 = 4.1 cm
Example: Fixed Bed Adsorption Design
52
Example 12.3-1
b) If the breakpoint time required for a new column is 6.0 h, what is
the new total length
t
u
is proportional to H
B
t
u
= 3.65 H
B
= 9.9 cm
t
b
= 6 h
dt
c
c
t
b
t
u
) 1 ( '
6
0
0
}
=
= = A
1
= 6 h
B
u
u
B
H
t
t
H
'
'= = (6 /3.65 )(9.9) = 16.3 cm
H
T
= H
UNB
+ H
B
=16.3 + 4.1 = 20.4 cm
799 . 0
4 . 20
3 . 16
'
'
'
'
= = =
T
B
t
u
H
H
t
t
(Fraction of the new bed
used up to the break point)
27
Example: Fixed Bed Adsorption Design
53
Example 12.3-1
c) Determine the saturation loading capacity of the carbon.
Air flow rate= (754 cm
3
/s)(3600s)(0.0115g/cm
3
) = 3122 g air/h
600 ppm = 600 g alcohol in 1 million g of air
Total alcohol adsorbed =
= 9.67 g alcohol
Saturation capacity =
) 16 . 5 )( 3122 (
10
600
6
h
h
air g
air g
adsorbed alcohol g
|
|
.
|

\
|
carbon g
alcohol g
carbon g
alcohol g
1220 . 0
2 . 79
67 . 9
=
Processing Variables and Adsorption
Cycles
54
Large scale adsorption:
1) cyclic batch system -alternately saturated & then
regenerated
2) continuous flow system- continuous flow of adsorbent
countercurrent to a flow of feed
Bed regeneration method
Temperature-swing cycle
Pressure-swing cycle
Inert-purge gas stripping cycle
Displacement-purge cycle.