EKB3143: SEPARATION

PROCESSES
ADSORPTION
Muhammad Syafiq
e-mail: muhammad.syafiq@miu.edu.my

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 ADSORPTION Part 1

Introduction to Adsorption & Applications

Contacting Modes of Adsorption
Types of Adsorbents
Theory of Adsorption, Chemisorption
Adsorption Isotherms
 Introduction
• Definition: Adsorption 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.

 Adsorbed solute: Adsorbate

 Solid material: Adsorbent 3
 Introduction (Cont)
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

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

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 Application
• Purification:
– small impurity is removed
from gas stream

• Bulk separation:
– separation of up to half of
the components from a
process stream

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 Applications of Adsorption
Liquid phase; Removal of
 organic components from drinking water or
aqueous wastes
 coloured impurities from sugar solutions and
vegetable oils
 separation of paraffins from aromatics, fructose
from glucose
Gas-phase; Removal of
 water from hydrocarbon gases
 sulfur from natural gas
 odorous compounds from air
 separation of oxygen and nitrogen
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 More Specific Applications
• Gas separation using molecular sieves by pressure swing
adsorption
• Removal of toxic gases from air (e.g. gas masks)
• Fractionation of industrial chemicals using gas or liquid
chromatography
• Removal of trace amounts of CS2 and H2S
• Removal of phenolic and other toxic chemical from waste
water
• Removal of chlorinated hydrocarbons from waste gas
streams
• De-hydration or de-humidification of gases
• Water purification by deionization and ion-exchange
• Fractionation and recovery of protein bio-products
• Affinity separations of bio-products
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 Contacting modes for adsorption
• Stirred Tank

• Cyclic fixed-bed, batch operation

• Continous countercurrent operation

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 Stirred tank
 Powdered adsorbent e.g. activated carbon – particle
diameter < 1 mm
 Main application – wastewater treatment
 Spent adsorbent – removed by sedimentation or filtration

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 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

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Continuous Countercurrent
• Need to circulate
solid adsorbent as
moving bed to
achieve steady state
operation
• Difficult in
regenerating
adsorbent when
heavier HC present
• Unfavourable
economics compared
to distillation
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 Physical Properties of Adsorbents
Shape
 Small pellets, beads, granules, cylindrical, powders
 Size ranging from 50 m to 1.2 cm
Porous structure
 Macropore ( > 500Å) 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 carbon Made by thermal decomposition of

wood
Silica gel Acid treatment of sodium silicate
solution
Activated alumina Hydrated aluminium activated by
heating to dry off the water
Molecular sieve Porous crystalline aluminosilicates
zeolites
Synthetic polymers Polymerising two major types of
or resin monomers eg. Styrene and
divinylbenzene 14
Adsorbents

Coal-Based Activated Carbon for

Gas Purification:

Used for gas purification

Silica gel

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Adsorbents

Molecular Sieve Zeolites

DA2 Resin:
DA201-D macro-net non-polar
adsorbent resin, used for
decoloration of fruit juice

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Adsorbents

Unique macro-porous synthetic

polymer absorbent to remove
soluble and insoluble impurities
from aquarium water. For
marine and freshwater use.

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 Adsorbents

This product is made of the kind of γ 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. mainly used in removing water, acetic acid
tetrabromoethane and etc

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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
• 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.
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Questions
1. What are contacting modes for adsorption?
2. Give two example of adsorption application?
3. What is purpose using the adsorbent in
adsorption?

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 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
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Adsorption theory

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 Adsorption vs Chemisorption
Physical adsorption Chemisorption
 Van der Waals adsorption  Activated adsorption
 Low heat of adsorption  High heat of adsorption
 Non specific  Highly specific
 Monolayer or multilayer  Monolayer only
 No dissociation of  May involve dissociation
adsorbed species.  Possible over a wide range
 Only significant at of temperature
relatively low  Activated, may be slow and
temperatures. irreversible
 Rapid, non-activated,  Electron transfer leading to
reversible. bond formation between
 No electron transfer. adsorbate and surface. 25
 Analysis of Adsorption
• The analysis of adsorption is based on equilibrium and
material balance. The equilibrium is represented as
adsorption isotherms.
• In adsorption terminology, an isotherm is the equilibrium
relationship between the solute concentration in the liquid
phase and the solute concentration on the adsorbent’s
surface.
• The solute concentration in the solution is usually
represented in terms of mass or moles of solute per unit
mass or volume of solvent.
• The solute concentration on the adsorbent’s surface is
usually expressed in terms of mass/moles of solute per
unit mass of adsorbent.
• In certain special cases it may be expressed in terms of
mass/moles of solute per unit surface area of adsorbent.
 Adsorption Isotherms
• Any adsorption isotherm, which is concave towards the
abscissa, is called "Favorable" since they permit higher solid
loadings at lower solution concentrations. These tend to start
out steep and level out.
• An isotherm concave towards the ordinate is called
"unfavorable“.These isotherms start out flat and they only
work well at high concentrations of solute.
• Linear isotherms are rarely encountered but most isotherms
have a “linear” region when solute concentration is very
dilute.
• Irreversible adsorption is usually independent of the solute
concentration.
• From the point of view of solute adsorption from a liquid
phase, three types of isotherms (i.e. linear, Freundlich and
Langmuir) are commonly encountered.
 Adsorption Isotherms
• Isotherm refers to data being obtained at constant
temperature
 Adsorption isotherms

Freundlich Linear
Langmuir

q Freundlich
Linear

Langmuir

• If T is increased, the amount adsorbed

decreases strongly. This feature is useful during
desorption.
 Determination of isotherm constants
Linear: Determine K from plot of q versus y
Freundlich: Determine K and n from plot of lnq vs lny
Langmuir: Determine q0 and K from plot of (1/q) vs (1/y)
Gas phase adsorption isotherms
Type I isotherms
- adsorption is limited to the
completion of a single
mono-molecular layer or
monolayer of adsorbate at
the adsorbent surface
- pore sizes not much larger
than the molecular
diameter of adsorbate
- example: adsorption of O2
on carbon black at –183oC.
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Type II Isotherms
• Indicates an indefinite
multi-layer formation after Type III isotherms
completion of the • Undesirable, adsorption is
monolayer and is found in low except at high pressure
adsorbents with a wide
distribution of pore sizes. • Example: adsorption of
• Example: adsorption of bromine on silica gel at
20oC.
water vapour on carbon
black at 30oC.
Type IV isotherms
• A variation of Type II but with a
finite multilayer formation
corresponding to complete filling
of the capillaries.
• Example: adsorption of water
vapour on activated carbon at
30oC.
Type V isotherms
• A variation of Type III
obtained when water
vapour is adsorbed on
activated carbon at
100oC.
 Liquid phase adsorption isotherms

Homogenous liquid –
binary mixture

Solute (A) Solvent (B)

Assumption:
• Changes in concentration of liquid mixture that is
in contact with solid adsorbent is due entirely to
the adsorption of the solute.
• Solvent is not adsorbed.

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Liquid phase adsorption isotherms
• If the Solute is dilute in liquid mixture, the adsorption
isotherm is similar to the form of Type I for pure gases.
• Over wide concentration ranges, isotherms of other shapes
are observed. Possible isotherms are shown below.
 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

Act iv at ed Carbon
G
Loading, gmol/kg Columbia

a rb on
ed C
vat
Acti
k Pearls
Bla c
MSC-5A

Davison Silica Gel

Norton Z-900H Zeolite

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

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 Freundlich isotherm
q = Kcn (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.

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 Langmuir isotherm
q = (qo c )/ (K + c) (12.1-3, ref 2)
• Assumptions For gases :
• Monolayer coverage on adsorbent
• No interactions between adsorbate
molecules
• All adsorbate molecule/adsorbent
interactions are the same
• Only a fixed number of active sites
available
• Adsorption is reversible and reaches an
equilibrium condition 40
 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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 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

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 Example:
Example 12.1-1
Adsorption Isotherms

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 Example:
Example 12.1-1
Adsorption Isotherms

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 Example: Adsorption Isotherms
Example 12.1-1

log K = - 0.7183
K = 0.199
n = 0. 229

Gives a straight line, hence follows

the Freundelich isotherm.
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