CHAPTER 5 : ADSORPTION

Introduction to adsorption

OBJECTIVES
Students should be able to :
1.

Explain adsorption process and process

application

2.

Identify type and characteristics of adsorbents

Introduction

Definition:

Adsorption process is a process which atoms or

molecules move from a bulk phase (solid, liquid,
gas) onto a solid surface (adsorbent).

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

Regeneration process:
To recover Adsorbate and Adsorbent to be
reused

Adsorbent

Coal-Based Activated Carbon for Gas Purification

Silica Gel

Molecular Sieve Zeolites

Synthetic Polymer

Activated Alumina

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.

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

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

10

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

10

Application of adsorption

Liquid phase :

Removal of organic compounds from water/organic solutions,

Removed colored impurities from organics,

Separations of paraffin from aromatics

Gas phase :

Removal of waste from HC gases

Removal of sulfur compound from NG

Recover solvents from air & other gases

Remove odors from air

11

12

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

13

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

14

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

15

16

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/ intra-phase)
Mass transfer of the solute by pore diffusion
from the outer surface of the adsorbent to the
inner surface of the internal porous structure
Intra-particle (pore and/or surface diffusion)
Physical attachment

Bulk Fluid transport

Film transport
Intra-particle

Physical Attachment

Equilibrium relations for

adsorbents

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

23

Adsorption is usually described through isotherms, that is

functions which connect the amount of adsorbate on the
adsorbent, with its pressure (if gas) or concentration (if
liquid)

Desirable/ favorable isotherm exhibit strong adsorption

Undesirable/ unfavorable isotherm exhibit low/ weak

adsorption
19

Adsoprtion isotherms

Data are plotted as adsorption isotherms as shown in the figure.

The concentration in the solid phase is expressed as q, kg adsorbate (solute)/kg adsorbent (solid)
and in the fluid phase (liquid/gas) as c, kg adsorbate/m3 fluid.

1. Linear Isotherm

Henrys law is obeyed for dilute region solution:

q = Kc

: concentration (fluid is liquid)

: kg adsorbate / m3 fluid

: 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)

21

2. Freundlich isotherm

q=

Kcn

Approximate data for many physical adsorption. Particularly useful

for liquids

K = Freundlich constant

n = constant (n 1)

Both K and n are determined experimentally.

*Plot log q vs log c to get a straight line

*Slope = exp (n)
22

3. Langmuir isotherm

For gases

qo = constant

q = (qo c )/ (K + c)
*Plot 1/q vs 1/c to give a straight line
*Slope = k/qo , intercept = 1/qo

23

Example: Adsorption Isotherms

Example 12.1-1
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 the table below. Determine the isotherm that fits the data.

(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
24

Example: Adsorption Isotherms

Example 12.1-1
Linear Law

Linear: q = Kc

0.16
0.14

q vs c

0.12

straight line with slope K

0.1
0.08
0.06
0.04
0.02
0
0

0.1

0.2
c

0.3

0.4
25

Example: Adsorption Isotherms

Example 12.1-1
Langmuir Isotherm
25

Langmuir:

20

1/q = (K/qo) (1/c) + 1/qo

1/q vs 1/c

15
1/q

slope: K/qo y-axis intercept: 1/qo

10
5
0
0

200

400

600
1/c

800

1000
26

Example: Adsorption Isotherms

Example 12.1-1
q = Kc

Freundlich Isotherm
0
-4

-3

-2

-1

-0.2

-0.4

log q

y = 0.229x - 0.701

-0.6
-0.8

Freundlich:

log q = log K + n log c

log q vs log c
slope: n

y-axis intercept: log K

log K = - 0.701

-1
-1.2
-1.4
-1.6
log c

Gives a straight line, hence follows the Freundlich

isotherm.

K = 0.199
n = 0. 229

q 0.199c

0.229
27

Batch Adsorption
Often used to adsorb solutes from liquid solutions when the quantities
treated are small in 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

28

Batch Adsorption

To get the q and % of adsorbate extracted:

Plot q vs c from material balance
Plot the equilibrium isotherm on the same
graph
The intersection both lines give values of q
and c (final equilibrium values)

29

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?

30

Example: Batch Adsorption

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

qF
q
M
S
cF
c

=
=
=
=
=
=

initial concentration of solute adsorbed on the solid

final concentration at equilibrium
amount of adsorbent, kg
volume of feed solution, m3
initial concentration of solute in the fluid phase
final concentration at equilibrium in the fluid phase

0(1.40) + 0.21(1.0) = q (1.40) + c (1.0)

The given values are:

q = 0.15- 0.714 c

(a)

From the isotherm

q = 0.199 c 0.229

cF = 0.21 kg phenol/m3
S = 1.0 m3
M = 1.40 kg carbon
qF is assumed as zero.

(b)
31

Example: Batch Adsorption

Example 12.2-1:

At intersection q = 0.106 kg phenol/kg carbon

c = 0.062 kg phenol/m3

% extracted = (cF - c)(100)/cF = (0.21-0.062)(100)/0.21

= 70.5 %

32

Problem 12.1-1

Equilibrium isotherm data for adsorption of glucose from an

aqueous solution to activated alumina are as follows:
c (g/cm3)
q(g solute/g

0.0040 0.0087

0.019 0.027 0.094

0.195

0.026

0.075 0.082 0.123

0.129

0.053

Alumina)
Determine the isotherm that fits the data and give the constants of
the equation using the given units

Problem 12.2-1

A wastewater solution having a volume of 2.5 m3 contains 0.25 kg phenol/m3 of

solution. This solution is mixed thoroughly in a batch process with 3.0 kg of granular
activated carbon until equilibrium is reached. Use the isotherm from example 12.2-1
and calculate the final equilibrium values and the percent phenol extracted.

Design of Adsorption Column

36

Coverage

Fixed bed adsorption design

Students should be able to :

1.

Design a fixed bed adsorption column

37

Fixed Bed Adsorption Design

Introduction and concentration profiles
-

A widely used method for adsorption of solutes from liquid or gases employs a fixed
bed of granular particles

The fluid to be treated is usually passed down through the packed bed at a constant
flow rate

As the fluid passes through the bed, the concentration in this fluid drops very rapidly
with distance in the bed to zero

The fluid concentration co is the feed concentration and c is the fluid concentration at a
point in the bed

Concentration profiles in fixed bed

Figure 12.3-1. Concentration

profiles for adsorption in a fixed
bed:
a) profiles at various positions and
times in the bed;
b) breakthrough concentration
profile in the fluid at outlet of bed.

Concentration profiles

The concentration profile at the start at time t1 is shown in Figure 12.3-1 a, where the concentration
ratio c/co is plotted versus bed length.

The fluid concentration co is the feed concentration and c is the fluid concentration at a point in the
bed.

After a short time, the solid near the entrance to the tower is almost saturated. At a time t2 and later,
the mass transfer zone where most of the concentration change takes place has moved farther
down the bed.

The concentration profiles shown are for the fluid phase.

The dashed line for time t3 shows the concentration in the fluid phase in equilibrium with the solid.

Breakthrough concentration curve

As the solution continues to flow, the mass-transfer zone (S-shaped), moved down the column.

At time t3, most half of the bed is saturated with solute and the outlet concentration is still
approximately zero.

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

At t5, the outlet concentration has risen to cb which is called the break point.

The concentration 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.

Fixed Bed Adsorption Design

c
Time equivalent to the total
tt (1 )dt
or stoichiometric capacity
0
c0

41

Shaded area =The total or stoichiometric capacity of the packed bed tower

tb = break-point time

Fixed Bed Adsorption Design

Time equivalent to the
usable capacity

tu

tb

42

c
(1 ) dt
c0

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

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

43

Fixed Bed Adsorption Design

HB : length of bed used up to the break point
( HT : Total bed length)

tu
H B HT
tt
HUNB : Length of unused bed (mass transfer zone)

H UNB

tu
(1 ) H T
tt

HT = HUNB + HB

44

Fixed Bed Adsorption Design

1.
2.
3.

Assume the breakthrough curve is symmetrical at c/co at ts.

This assumes that the area below the curve between tb and ts is
equal to the area above the curve between ts and td.
Then ts is simply equal to tt (Eqn. 12.3-1)

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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

46

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

47

Example: Fixed Bed Adsorption Design

Example 12.3-1

The plotted data from

Table 12.3-1

Figure 12.3-3. Breakthrough curve for

Example 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
)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
tt (1

0.5

tu / tt = 3.65/5.16 = 0.707

tu
H B H T = 0.707(14) = 9.9 cm
tt
tu
H UNB (1 ) H T = (1 - 0.707)14 = 4.1 cm
tt

0.01
= 3.65

5.16

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Example: Fixed Bed Adsorption Design

Example 12.3-1
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

600g 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

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)

50

Problem 12.3-1

Using the breakpoint time and other results from Example 12.3-1 , do as follows :
a)

The break-point time for a new column is to be 8.5h. Calculate the new total
length of the column required, column diameter and the fraction of
total/capacity used up to the break point. The flow rate is to remain constant at
754 cm3/s

b)

Use the same conditions as part (a), but the flow rate is to be increased to 2000
cm3/s

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THANK YOU.