ADSORPTION

Main reference :
1. Seader J. D. and Henley E. J., Separation Process Principles, John
Wiley, 1998
2. Geankoplis C. J., Transport Processes and Unit Operations, 4
th

Edition, Prentice Hall, 2003.
2
Equilibrium relations for adsorbents
Concentration of a
solute in a fluid phase
Concentration of a
solute in a solid phase
Data is plotted as
adsorption isotherms
T, P
Equilibrium relations for adsorbents
The equilibrium isotherm places a limit on the extent to
which a solute is adsorbed from a given on an adsorbent of
given chemical composition and geometry for a given set
of conditions
Desirable/ favorable isotherm exhibit strong adsorption
Undesirable/ unfavorable isotherm exhibit low/ weak
adsorption
3
4
Types of Isotherms


Linear Isotherm can be used in dilute region
Henrys law is obeyed:
q = Kc (12.1-1, ref 2)

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)
5

q = Kc
n
(12.1-2, ref 2)

Approximate data for many physical adsorption.
Particularly useful for liquids
K = Freundlich constant
n = constant (n 1)
Both are determined experimentally.
Freundlich isotherm
6
Langmuir isotherm


q = (q
o
c )/ (K + c) (12.1-3, ref 2)
For gases
Assumptions:
Monolayer coverage on adsorbent
No interactions between adsorbent molecules
All adsorbate molecule/adsorbent interactions
are the same
Only a fixed number of active sites available
Adsorption is reversible and reached an
equilibrium condition
7
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 isotherm that 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 (Ref. 2)
8
Example: Adsorption Isotherms


Example 12.1-1
Linear: q = Kc
q vs c
straight line with slope K
Freundlich: log q = log K + n log c
log q vs log c
slope: n y-axis intercept: log K
Langmuir: 1/q = (K/q
o
) (1/c) + 1/q
o

1/q vs 1/c
slope: K/q
o
y-axis intercept: 1/q
o

9
Example: Adsorption Isotherms


Example 12.1-1
Linear Law
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0 0.1 0.2 0.3 0.4
c
q
10
Example: Adsorption Isotherms


Example 12.1-1
Langmuir Isotherm
0
5
10
15
20
25
0 200 400 600 800 1000
1/c
1
/
q
11
Example: Adsorption Isotherms


Example 12.1-1
log K = - 0.7183
K = 0.199
n = 0. 229
Freundlich Isotherm
y = 0.229x - 0.701
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
-4 -3 -2 -1 0
log c
l
o
g

q
229 . 0
199 . 0 c q =
A straight line produced, hence follows the
Freundelich isotherm.
12
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 (12.2-1)

where:
q
F
= initial concentration of solute adsorbed on the solid
q = final concentration at equilibrium
M = amount of adsorbent, kg
S = volume of feed solution, m
3
c
F
= initial concentration of solute in the fluid phase
c = final concentration at equilibrium in the fluid phase

Batch Adsorption
13
q
F
M + c
F
S = q M + cS (12.2-1)

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.
14
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 equilibrium values, and what
percent of phenol extracted?
15
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
16
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
- Fixed bed adsorption design
- Regeneration of adsorbents

Students should be able to :
1. Design a fixed bed adsorption column
2. Understand the regeneration of
adsorbents
17
Fixed Bed Adsorption Design
18
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


19
Fixed Bed Adsorption Design
20
Introduction and concentration profiles (contd)

- Inlet: solid is assumed to contain no solute at the
start of the process
- The concentration of the solute in the fluid phase and
of the solid adsorbent phase change with TIME and
POSITION in the fixed bed as the adsorption
proceeds
- As the fluid first come into contact with the inlet,
most of the MASS TRANSFER and ADSORPTION
takes 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


21
22
After a short time, solid near entrance almost
SATURATED and 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 concentration 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
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.


breakthrough concentration profile in the fluid at outlet of bed
Fixed Bed Adsorption Design
24
Breakthrough Concentration Curve
- 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
25
Fixed Bed Adsorption Design


Capacity of Column and Scale-Up Design Method

- Mass Transfer Zone (MTZ) width and shape depends on:
1. the adsorption isotherm
2. flowrate
3. mass transfer rate to the particles
4. diffusion in 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
width increases with bed length
- A favourable isotherm for adsorption is unfavourable for
effective regeneration


26
Fixed Bed Adsorption Design


Capacity of Column and Scale-Up Design Method

- A number of theoritical methods have been
published which predict the Mass Transfer Zone
(MTZ) and concentration profiles in the bed.
- Hence, experiments in laboratory scale are needed in
order to scale up the results.

27
Fixed Bed Adsorption Design
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
28
Fixed Bed Adsorption Design
Crosshatched area = Usable capacity of bed up to the break-point time, t
b
29
Fixed Bed Adsorption Design
t
u
: time equivalent to the usable capacity or time
at which the effluent concentration reaches its
maximum permissible 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
30
Fixed Bed Adsorption Design


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 =
31
Fixed Bed Adsorption Design


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 ( =
32
Fixed Bed Adsorption Design


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



33
Alternative method:
1. Assume the breakthrough curve is symmetrical at c/c
o
at
t
s
.
2. This assumes that the area below the curve between t
b

and t
s
is equal to the area above the curve between t
s
and
t
d
.
3. Then t
s
is simply equal to t
t
(Eqn. 12.3-1)

34
Fixed Bed Adsorption Design


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.


35
Example: Fixed Bed Adsorption Design


Example 12.3-1
A waste stream of alcohol vapour in air from a process was
adsorbed by activated carbon particles in a packed bed
having a diameter of 4 cm and length of 14 cm containing
79.2 g of carbon. The inlet gas stream having a
concentration c
o
of 600 ppm and 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. Do as
follows.
a) Determine the breakpoint time t
b
, the fraction of total
capacity used up to the breakpoint t
u
/t
t
, and the length of
the unused bed H
UNB
.
36
Example: Fixed Bed Adsorption Design


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
37
Example: Fixed Bed Adsorption Design


Example 12.3-1
The plotted data from Table 12.3-1
38
Example: Fixed Bed Adsorption
Design


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
39
Example: Fixed Bed Adsorption Design


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)
40
Example: Fixed Bed Adsorption Design


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
=
41
Processing Variables and
Adsorption Cycles


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.

Types of adsorption
42
Commercial Methods for Adsorption
43
Agitated vessel
44
A batch of liquid to which is added a powdered
adsorbent such as activated carbon
particle diameter typically less than 1mm, to form a
slurry.
With good agitation and small particles, the external
resistance to mass transfer from the bulk liquid to
the external surface of the adsorbent particles is
small
For small adsorbent particles, the internal resistance
to mass transfer within the pores of the particles is
also small. Hence, the adsorption rate is rapid
Main application: removal of very small amounts
dissolved, and relatively large molecules , such as
coloring agents, from water
Slurry adsorption system (also called contact
filtration) is also operated continuously.



Cyclic fixed-bed, batch operation
45
A cyclic-batch operating mode using fixed-bed
Widely used with both liquid and gas feeds.
Adsorbent particles size ranges from 0.05 to 1.2 cm
Bed pressure drop decreases with increasing particle
size, but the solute transport rate increases with
decreasing particle size. The optimal particle size is
determined mainly from these two factors
To avoid jiggling or fluidizing the bed during
adsorption, the flow of the liquid or gas feed is often
downward
For removal of small amounts of dissolved
hydrocarbons from water, the spent adsorbent is
removed from the vessel and reactivated thermally at
high temperature or it is discarded
Application of fixed-bed adsorption (also called
percolation), include the removal of dissolved organic
compounds from water



46
Temperature Swing Adsorption
(Thermal means)


Regeneration process increase in temperature
Increase in temperature leads to a decrease in the
quantity adsorbed
Important note - regeneration temperature does not
cause degradation of the adsorbents
Mechanism passage of a hot purge gas or steam
Important characteristic to treat feeds with low
concentrations of adsorbates

Temperature Swing Adsorption (Purasiv process)
-Fluidized bed for adsorption
-Moving bed for desorption
47
Purasiv process
Adsorbent particles are attrition-resistance
In the adsorption section, sieve trays are used with
the raw gas passing up through the perforations and
fluidizing the adsorbent particles
The fluidized solids flow like a liquid across the tray,
into the downcomer, and onto the tray below
From the adsorption section, the solids pass to the
desorption section, where, as moving beds, they first
flow down through preheating tubes and then
through desorption tubes.
Steam is used for indirect heating in both sets of
tubes and for stripping in the desorption tubes
At the bottom of the unit, the regenerated solids are
picked up by a carrier gas, which flows up through a
gas-lift line to the top, where the solids settle out
onto the top tray to repeat the adsorption part of the
cycle.



48
Temperature Swing Adsorption


Effect of temperature
on the adsorption
equilibrium of a single
adsorbate
If the partial pressure
remains constant at
p
1
, increasing the
temperature from T
1

to T
2
will decrease the
equilibrium loading
from q
1
to q
2
.
49
Bed TSA System


Cycle Steps
1- adsorption at T
1
to breakthrough
2- heating of the bed to T
2
(T
2
> T
1
)

3- desorption at T
2

4- cooling of the bed to T
1

50
Pressure Swing Adsorption
(Mechanical work)


Regeneration process reducing the partial pressure of the
adsorbate
2 ways:
Introduction of an inert gas while maintaining the total system
pressure
Cycle time very quick (minutes or second)
Operate PSA close to ambient temperature at a given partial pressure,
the loading is increased as temperature decreased
Popular for performing bulk separation of gases controlled by
adsorption isotherm or adsorption kinetics
Use only with gases (liquid has little or no effect with change in pressure)
51
Pressure Swing Adsorption


Effect of partial
pressure on
equilibrium loading at
temperature T
1

Reducing the partial
pressure from p
1
to p
2

causes the equilibrium
loading to be reduced
from q
1
to q
2

52
Bed PSA System
Each bed operates alternately :
Pressurisation followed by
adsorption
Desorption by depressurisation
(blowdown) followed by a purge
Adsorption pressure greater than
atmospheric
Desorption pressure being
atmospheric
Pressurisation feed gas
Purging effluent (non-adsorbed)
product gas
Inert-purge gas stripping cycle
53
Adsorbate is removed by passing a non-adsorbing or inert
gas through the bed.
Mechanism for desorption:
Partial pressure (or concentration) of original adsorbate
in the gas phase surrounding the adsorbent is reduced
54
Displacement-Purge cycle


Removal of adsorbates by replacing them with a more
preferentially adsorbed species
Mechanism for desorption:
Partial pressure (or concentration) of original adsorbate
in the gas phase surrounding the adsorbent is reduced
There is competitive adsorption for the displacement
fluid
One advantage net heat generated or consumed will be
close to zero because heat of adsorption of the
displacement fluid is close to the original adsorbate
adsorbent temperature constant throughout the cycle
55
Displacement Purge Adsorption
56
THANK YOU