SEPARATION PROCESS II

(CDB 2063)

ADSORPTION

May 2019
Prof Ir Dr Suzana Yusup
 RECALL
 Adsorption
 definition, theory
 adsorbate, adsorbent, desorption
 types
 Mechanism – 4 phenomena
 Bulk fluid transport, Film transport, intraparticle, physical
attachment
 Application
 Liquid vs. gas
 Operation Modes
 Batch vs. Continuous
 Regeneration Methods
 TSA, PSA, Inert-purge gas stripping, displacement-purge
 TODAY’S TOPICS

 Adsorbent
 example, size, application
 Equilibrium relations: Isotherms
 Gas Phase
 Liquid Phase
 Design
 Batch Adsorption
 LESSON OUTCOMES

By the end of lecture, students should be able to

 describe adsorbents
 discuss usage and explain isotherms
 gas phase
 liquid phase
 design and analyze batch adsorption process
 Physical Properties of Adsorbents

 shape
 small pellets, beads, granules, cylindrical, powders
 size: 50 m to 1.2 cm
 porous structure
 Macropore ( > 500 Å or 50 nm )
 Mesopore ( 20 - 500 Å )
 Micropore ( < 20 Å )
 based on International Union of Pure and Applied
Chemistry (IUPAC)
 specific surface area: 300 to 1,200 m2/g

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 Range of Adsorbents available
Activated By thermal decomposition of wood
carbon SA = 300-1200 m2/g, pore = 10-60 Å
Absorb organics
Silica gel By acid treatment of sodium silicate solution
SA = 600-800 m2/g, pore = 20-50 Å
Dehydrate gases & liquids, fractionate HC
Activated By hydrate aluminium oxide (heat & dry water)
alumina SA = 200-500 m2/g, pore = 20-140 Å
Dry gases &liquids
Molecular sieve Porous crystalline aluminosilicates
zeolites SA = 3-10 Å, uniform pores, open crystal lattice
Drying, separation of HC, mixtures
Synthetic By polymerising two major types of monomers
polymers or e.g. aromatics (styrene, divinylbenzene), acrylic esters
resin Adsorbs non-polar, polar organics res., in aq solutions
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Pores in Activated Carbon

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Powdered activated carbon

Granular activated carbon

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 Criteria for Adsorbent Selection

1. High selectivity to enable sharp separations

2. High capacity to minimize amount adsorbent needed
3. Favorable kinetic and transport properties for rapid sorption
4. Chemical and thermal stability to preserve 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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 EQUILIBRIUM RELATIONS FOR ISOTHERMS

Concentration of a solute
in a fluid phase

Data is plotted as
Equilibrium T, P Adsorption Isotherms

Concentration of a solute
in a solid phase

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 Gas Phase Adsorption Isotherms

Type I isotherms
- adsorption is limited to completion of
a single mono-molecular layer or
monolayer of adsorbate at adsorbent
surface
- pore sizes not much larger than
molecular diameter of adsorbate
- example: adsorption of O2 on carbon
black at –183oC.

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 Gas Phase Adsorption Isotherms
Type II isotherms
- indicates an indefinite multi-layer formation after completion of
monolayer
- found in adsorbents with a wide distribution of pore sizes
- example: adsorption of water vapour on carbon black at 30oC.

Type III isotherms

- undesirable, adsorption is low except at high pressure
- example: adsorption of bromine on silica gel at 20oC. 12
 Gas Phase Adsorption Isotherms
Type IV isotherms
- a variation of Type II but with a finite multilayer formation
corresponding to complete filling of capillaries
- example: adsorption of water vapour on activated carbon at 30oC

Property:
Do not return
completely to
original state

Type V isotherms
- a variation of Type III obtained when water vapour is adsorbed on
activated carbon at 100oC
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 Liquid Phase Adsorption Isotherm
 solute is dilute in liquid mixture
Homogenous liquid –  adsorption isotherm is similar to
binary mixture form obtained for Type I for pure
gases
 over wide concentration ranges,
Solute (A) Solvent (B) isotherms of other shapes are
observed
Assumptions:  other possible isotherms:

 changes in concentration of
liquid mixture in contact with solid
adsorbent is due entirely to
adsorption of solute
 solvent is not absorbed

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 Uses of Adsorption Isotherms

 to select suitable adsorbent

 to select separation process:
 Type I, II and IV are desirable isotherms - exhibit strong
adsorption
 Type III and V are undesirable - adsorption is low except
at high pressure

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 Uses of Adsorption Isotherms

Loading, gmol/kg

Pressure, kPa

Adsorption isotherms for pure propane vapour at 25 – 30oC

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 Types of Isotherms: Linear Isotherm
Henry’s law is obeyed:

q=Kc (12.1-1, ref [2])

c : concentration (fluid is liquid)

p : partial pressure (fluid is a gas)
q : mass,moles or volumes of adsorbate per unit mass or per unit
surface area of adsorbent
K : an empirical, temperature-dependent constant (m3/kg
adsorbent)
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 Freundlich Isotherm

q = K cn (12.1-2, ref [2])

 Approximate data for many physical adsorption. Particularly

useful for liquids
 K = Freundlich constant (dimension depends on n)
 n = constant (n > 1)
 K and n are determined experimentally
 e.g. hydrocarbon gases on activated carbon

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 Langmuir Isotherm
q = (qo c )/ (K + c) (12.1-3, ref [2])

 For gases
 qo (kg adsorbate/kg adsorbent, K (kg/m3)
 Assumptions:
 Monolayer coverage on adsorbent
 No interactions between adsorbate molecules
 All adsorbate molecule-adsorbent molecule
interactions are the same
 Only a fixed number of active sites available
 Adsorption is reversible and reached an equilibrium
condition
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 Example: Adsorption Isotherms
Example 12.1-1 (Ref. 2)
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 q
(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

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 Active Learning 3

 Think Pair Share

Individually think how to solve the problem in
3 minutes
Then discuss in pair the answers/ideas for
comparison and better answer/idea
Share the solutions in class

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 Example: Adsorption Isotherms
Example 12.1-1

Linear: q = K c
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
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 Example: Adsorption Isotherms
Example 12.1-1

Linear Law

0.16
0.14
0.12
0.1
q

0.08
0.06
0.04
0.02
0
0 0.1 0.2 0.3 0.4
c
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 Example: Adsorption Isotherms
Example 12.1-1

Langmuir Isotherm

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20

15
1/q

10

0
0 200 400 600 800 1000
1/c
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 Example: Adsorption Isotherms
Example 12.1-1
Freundlich Isotherm

0
-4 -3 -2 -1 0
-0.2

-0.4
log K = - 0.7183
y = 0.229x - 0.701 -0.6 K = 0.199
log q

-0.8

-1
n = 0. 229
-1.2

-1.4

-1.6
q  0.199c 0.229

log c

Plot gives a straight line,

hence follows the Freundelich isotherm.
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References:
1. Seader J. D. and Henley E. J., Separation Process Principles,
John Wiley, 1998
2. Geankoplis C. J., Transport Processes and Unit Operations,
4th Edition, Prentice Hall, 2003.

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THANK YOU

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