CHAPTER 2 :

SUBTOPIC ADSORPTION

OBJECTIVES
Students should be able to :
1.

Explain adsorption process and process application

2.

Identify type and characteristics of adsorbents

Introduction

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

Adsorbed solute: Adsorbate

Solid material: Adsorbent

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

Desorption

Adsorption-Saturated-Desorption
Regeneration process:
To recover Adsorbate and Adsorbent to be
reused
Use Desorbent or change in temperature or
pressure

Application of adsorption

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

Contacting modes for adsorption

1.

Stirred Tank

2.

Cyclic fixed-bed, batch operation

3.

Continuous countercurrent operation

1. Stirred tank

Powdered adsorbent e.g. activated carbon particle diameter

less than 1 mm
Main application wastewater treatment
Spent adsorbent removed by sedimentation or filtration

2. Fixed bed batch

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

3. Continuous Countercurrent

Need to circulate solid adsorbent as moving bed to achieve steady

state operation
Difficult in regenerating adsorbent when heavier HC presents
Unfavourable economics compared to distillation

11

Physical Properties of Adsorbents

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 m2/g

12

Range of adsorbents available

Activated carbon

Silica gel

- Made by acid treatment of sodium silicate solution and then drying

- Surface area 600 to 800 m2/g
- Average pore diameter 20 to 50 A

Activated
alumina

Molecular
zeolites

Made by thermal decomposition of wood

Average pore diameter 10 to 60 A
Usually organics adsorbed by activated carbon
surface area 300 to 1200 m2/g

Hydrated aluminum activated by heating to dry off the water

Used mainly to dry gases and liquids
Surface area 200 to 500 m2/g
Average pore diameter 20 to 140 A

sieve

- Porous crystalline aluminosilicates

- Open crystal lattice containing precisely uniform pores; make it
different from other types of adsorbents
- Different zeolites have pore sizes from 3 to 10A
- Used for drying, separation of HCs

Synthetic
polymers or resin

-Made by polymerising two major types of monomers

- eg. Styrene and divinylbenzene to adsorb nonpolar organics from
aqueous solutions

13

Activated Carbon

Coal-Based Activated Carbon for

Gas Purification

14

Silica gel

Made by acid treatment of sodium

silicate solution and then drying

15

Activated alumina
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

Molecular Sieve Zeolites

17

Synthetic polymer / RESINS

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

18

19

Adsorption theory
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

Film transport (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

20

Adsorption theory

Bulk Fluid transport

Film transport
Intraparticle

Physical Attachment

Adsorption theory

21

Adsorption theory

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

22

23

Method of adsorption
Physical adsorption

Chemisorption

Van der Waals adsorption

Activated adsorption

Low heat of adsorption

High heat of adsorption

Non specific

Monolayer or multilayer

Highly specific (to one

adsorbate)

No dissociation of adsorbed
species.

Monolayer only

May involve dissociation

Only significant at relatively

low temperatures.

Possible over a wide range

of temperature

Rapid, non-activated,
reversible.

Activated, may be slow and

irreversible

No electron transfer.

Electron transfer leading to

bond formation between
sorbate and surface.

Method of adsorption
Chemisorption

Physical adsorption

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>200oC

Catalyst relies on
chemisorption

24

Criteria for adsorbent

selection

1.
2.
3.
4.
5.
6.
7.

High selectivity to enable sharp separations.

High capacity to minimize the amount adsorbent needed.
Favorable kinetic and transport properties for rapid sorption.
Chemical and thermal stability to preserve the amount and its properties.
Hardness and mechanical strength.
High fouling resistance.
Capability of being regenerated relatively low cost.

25

Equilibrium isotherm

OBJECTIVES
Students should be able to
1.
2.

Identify and explain type of isotherm

Perform calculation for confirmation of adsorption isotherm

Equilibrium relations for

adsorbents
Concentration of a solute
in a fluid phase

T, P

Data is plotted as
adsorption isotherms

Concentration of a
solute in a solid phase

28

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

29

1. Linear Isotherm
Henrys law is obeyed for dilute region
solution:
q = Kc
C

: concentration (fluid is liquid)

: kg adsorbate / m3 fluid

: partial pressure (fluid is a gas)

: mass, moles or volumes of adsorbate (solutes) per unit mass or per unit
surface area of adsorbent
: kg adsorbate (solute) / kg adsorbent (solid)

: an empirical, temperature-dependent constant (determined experimentally)

30

2. Freundlich isotherm
q = Kcn
Approximate data for many
Particularly useful for liquids

physical

adsorption.

K = Freundlich constant
n = constant (n 1)
Both are determined experimentally.

31

3. Langmuir isotherm
q = (qo c )/ (K + c)

(12.1-3)

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
32

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.

Example 12.1-1
c

(kg phenol/m3 solution)

(kg phenol/kg carbon)

0.322

0.150

0.117

0.122

0.039

0.094

0.0061

0.059

0.0011

0.045
33

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/qo) (1/c) + 1/qo

1/q vs 1/c
slope: K/qo y-axis intercept: 1/qo
34

Example: Adsorption Isotherms

Example 12.1-1
Linear Law
0.16
0.14
0.12

0.1
0.08
0.06
0.04
0.02
0
0

0.1

0.2
c

0.3

0.4
35

Example: Adsorption Isotherms

Example 12.1-1
Langmuir Isotherm
25
20

1/q

15
10
5
0
0

200

400

600
1/c

800

1000
36

Example: Adsorption Isotherms

Example 12.1-1
Freundlich Isotherm

log K = - 0.7183

0
-4

-3

-2

-1

-0.2

K = 0.199

-0.4

log q

y = 0.229x - 0.701

-0.6

n = 0. 229

-0.8
-1
-1.2

q 0.199 c

0.229

-1.4
-1.6
log c

Gives a straight line, hence follows the

Freundelich isotherm.
37

Batch Adsorption
When quantities to be treated are of small amount.
Isotherms and material balance are needed.
Material balance on the adsorbate:
qF M + cF S = q M + cS
where:
qF = initial concentration of solute adsorbed on the solid
q = final concentration at equilibrium
M = amount of adsorbent, kg
S = volume of feed solution, m3
cF = initial concentration of solute in the fluid phase
c = final concentration at equilibrium in the fluid phase
38

Batch Adsorption

qF M + cF 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.
39

Example: Batch Adsorption

Example 12.2-1:
A wastewater solution having a volume of 1.0 m3 contains
0.21 kg phenol/m3 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?

40

Example: Batch Adsorption

Example 12.2-1:
qF M + cF S = q M + cS

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)
41

Example: Batch Adsorption

q, kg phenol/kg adsorbent

0.15

Example 12.2-1:

0.1

0.05

0
0

At intersection q = 0.106 kg phenol/kg carbon

0.05

0.1

0.15

0.2

c, kg phenol/m3 solution

c = 0.062 kg phenol/m3
% extracted = (cF - c)(100)/cF = (0.21-0.062)(100)/0.21
= 70.5 %

42

Design of Adsorption
Column

44

Coverage

Fixed bed adsorption design

Regeneration of adsorbents

Students should be able to :

1.

Design a fixed bed adsorption column

2.

Explain regeneration process of adsorbents

Fixed Bed Adsorption Design

45

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

46

Introduction and concentration profiles (contd)

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
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 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

47

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 concerntration remains near zero until the mass transfer zone starts to
reach the tower outlet at t4.
Then the outlet concentration starts to rise.

Fixed Bed Adsorption Design

Breakthrough Concentration Curve
-

Then, the outlet conc starts to rise, and at t5 the outlet conc has risen to cb,
which is called the break point
After the break-point time is reached, the concentration c rises very rapidly up
to point cd, 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 cb/co.
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

48

49

Fixed Bed Adsorption Design

Capacity of 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
- 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 favorable isotherm for adsorption is unfavorable for effective regeneration

50

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.

Fixed Bed Adsorption Design

c
Time equivalent to the total
tt (1 )dt (12.3-1)
or stoichiometric capacity
0
c0
Shaded area =Total or stoichiometric capacity of the packed tower

51

52

Fixed Bed Adsorption Design

Crosshatched area = Usable capacity of bed up to the break-point time, tb

53

Fixed Bed Adsorption Design

tu : time equivalent to the usable capacity or time
at which the effluent concentration reaches its
maximum permissible level.

tu

tb

c
(1 ) dt
c0

(12.3-2)

tu very close to tb
tu/tt is the fraction of the total bed capacity or
length utilized up to the break point

54

Fixed Bed Adsorption Design

HB : length of bed used up to the break point

( HT : Total bed length)

tu
H B HT
tt

(12.3-3)

55

Fixed Bed Adsorption Design

HUNB : Length of unused bed (mass transfer zone)

HUNB

tu
(1 ) H T
tt

HT = HUNB + HB

(12.3-4)

(12.3-5)

56

Fixed Bed Adsorption Design

Design Steps
1. Determine the the length of bed needed to achieve the
required usable capacity, HB
2. Determine HUNB
3. Calculate HT

58

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 (HUNB)
does not change with the total bed length.
3. Hence, tb is proportional to HB.

59

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 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 Table 12.3-1 give the concentrations of the
breakthrough curve. The breakpoint concentration is set at c/co = 0.01.
Determine :
1.

Break point time

2.

Fraction of total capacity used up to the break point time

3.

Length of the unused bed

4.

Total bed length

60

Example: Fixed Bed Adsorption Design

Example 12.3-1
Table 12.3-1

Time,h

c/co

Time, h

c/co

5.5

0.658

6.0

0.903

3.5

0.002

6.2

0.933

0.030

6.5

0.975

4.5

0.155

6.8

0.993

0.396

61

Example: Fixed Bed Adsorption Design

Example 12.3-1

The plotted data from

Table 12.3-1

Example: Fixed Bed Adsorption Design

Example 12.3-1

Based on Figure 12.3-3

At break point conc. 0.01: tb = 3.65 h; td = 6.95 h

c
tt (1 )dt = A1 + A2 = 3.65 + 1.51 = 5.16 h
0
c0
tb 3.65
c
tu
(1 )dt = A1 = 3.65 h
0
c0
tu / tt = 3.65/5.16 = 0.707

tu
H B H T = 0.707(14) = 9.9 cm
tt
t
HUNB (1 u ) H T = (1 - 0.707)14 = 4.1 cm
tt

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
tu is proportional to HB
tu = 3.65 HB = 9.9 cm

tb = 6 h t

b 6

c
tu ' (1 ) dt = A1 = 6 h
0
c0
tu '
H B ' H B = (6 /3.65 )(9.9) = 16.3 cm
tu

HT= HUNB + HB = 16.3 + 4.1 = 20.4 cm

tu ' H B ' 16.3

0.799
tt ' H T ' 20.4

(Fraction of the new bed

used up to the break point)

63

64

Example: Fixed Bed Adsorption Design

Example 12.3-1
c) Determine the saturation loading capacity of the carbon.
Air flow rate= (754 cm3/s)(3600s)(0.0115g/cm3) = 3122 g air/h
600 ppm = 600 g alcohol in 1 million g of air

600 g alcohol adsorbed

g air
(3122
)(5.16 h)
Total alcohol adsorbed =
6
10 g air
h

= 9.67 g alcohol
Saturation capacity =

9.67 g alcohol
g alcohol
0.1220
79.2 g carbon
g carbon

65

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.

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

70

Temperature Swing Adsorption (Purasiv process)

-Fluidized bed for adsorption
Purasiv process
-Moving bed for desorption

71

1. Adsorbent particles are attrition-resistance

2. In the adsorption section, sieve trays are used with
the raw gas passing up through the perforations and
fluidizing the adsorbent particles
3. The fluidized solids flow like a liquid across the tray,
into the downcomer, and onto the tray below
4. 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.
5. Steam is used for indirect heating in both sets of
tubes and for stripping in the desorption tubes
6. 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.

72

Temperature Swing Adsorption

Effect of temperature on the
adsorption equilibrium of a
single adsorbate
If the partial pressure
remains constant at p1,
increasing the temperature
from T1 to T2 will decrease
the equilibrium loading from
q1 to q2.

73

Bed TSA System

Cycle Steps
1- adsorption at T1 to breakthrough
2- heating of the bed to T2 (T2 > T1)
3- desorption at T2
4- cooling of the bed to T1

74

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)

75

Pressure Swing Adsorption

Effect of partial pressure on
equilibrium loading at
temperature T1
Reducing the partial pressure
from p1 to p2 causes the
equilibrium loading to be
reduced from q1 to q2

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

76

77

Inert-purge gas stripping cycle

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

78

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

79

Displacement Purge Adsorption

80

THANK YOU.