D. Adsorption

ADSORPTION
EKC 316
Sem II, 2015/2016
DR. AZAM T MOHD DIN
SCHOOL OF CHEMICAL ENGINEERING,
UNIVERSITI SAINS MALAYSIA
Content
Adsorption theory & concept

Adsorbent
Equilibrium curve & Isotherms
Batch adsorption
Column adsorption

Adsorption is the process of capturing

molecules of dissolved solids, liquids or gases
on the surface of certain active solids.
Adsorption is based on a theory that a solid
surface in contact with a solution tends to
accumulate a surface layer of solute molecules
caused by imbalance of surface forces.

In liquid phase adsorption process, molecules,

ions or atoms in a liquid is diffused to the
surface of a solid, where they bond with the
solid surface through physical attractive
forces, ion exchange, and chemical binding
(Rangabhashiyam et al., 2013).
London, van der waals and electrostatic forces
Covalent bonding, ionic bonding
Physisorption
Chemisorption
The solid, which is insoluble in the liquid, is

the adsorbent. The components being
adsorbed are called solutes in the liquid and
form the adsorbate upon adsorption on the
solid.

Micropore < 2 nm
Mesopore 2 < 50 nm
Macropore > 50 nm

Plate 2.1 SEM image of activated carbon produced from banana

frond (Foo et al., 2013)

Commercial adsorber continuous

General process
Fluid passing through the bed
The solid particles adsorb the components
from the fluid
Bed saturated
Regeneration desorption
The adsorbate recovered and the bed is rady
for next cycle
Physical properties of adsorbents

Different forms: Granules, beads, small pellet.
Different sizes: 0.1 12 mm
Porous materials


MCM-n family - Kresge, 1992

Template Carbonization Kyotani, 1984
Activated
Carbon
1880s
Silica
Clay
Bio
1900s
Hydrogel
Aerogel
Xerogel
Cryogel
Ordered
Mesoporous
Carbon
2000s
MOF
Graphene
???
Char
3000BC
Figure
1: Materials evolution map

Table 2.3 Methylene blue adsorption capacity on various sorbent media

Adsorbents
Adsorption capacity
Reference
(mg.g-1)
Diatomite-templated carbon
505.10
(Liu et al., 2013)
373
(Chang et al., 2013)
Graphene
204.08
(Liu et al., 2012b)
Graphene/magnetite composite
43.82
(Ai et al., 2011)
Rejected tea
156.00
(Nasuha et al., 2010)
Activated clay minerals
558.00
(El Mouzdahir et al.,
Carboxylic acid functionalized

mesoporous silica
2010)
Vetiver root activated carbon
526.00
(Altenor et al., 2009)
CMK-3 ordered mesoporous
207.90
(Asouhidou et al., 2009)
H2SO4 modified activated carbon
16.43
(Karagz et al., 2008)
Norit SA3 Activated carbon
91.00
(Yener et al., 2008)
Rattan dust activated carbon
294.12
(Hameed et al., 2007a)
Algae Gelidium
104.00
(Vilar et al., 2007)
carbon
Activated charcoal
SCHOOL OF CHEMICAL519.75
ENGINEERING,
(Iqbal and Ashiq, 2007)
Equilibrium Curve

Linear relationship is described by Henrys

Law. q = Kc
Freundlich isotherm heterolayer adsorption
Langmuir isotherm monolayer adsorption

According to Crini, comprehensive study on adsorption

isotherms is very important for designing and optimizing
batch adsorption process because the isotherms represent
the behaviour of the adsorbates when interacted with the
adsorbents (Crini, 2008).
The adsorption isotherm provides an important correlation
between the mass of adsorbate adsorbed per unit weight of
adsorbent with the liquid-phase equilibrium concentration of
the adsorbate (Lata et al., 2007).

Two-Parameter Isotherms
Langmuir model applies to homogeneous adsorption,
which each molecule possess constant enthalpies and
sorption activation energy and postulates no
transmigration of the adsorbate in the plane of the
adsorbent surface (Prez-Marn et al., 2007, Kundu and
Gupta, 2006).
The model assumes monolayer adsorption where one
adsorbate can only attached on the specific identical
sites, with no lateral interaction and steric hindrance
between the adsorbed molecules, even on adjacent
sites (Vijayaraghavan et al., 2006).
The non-linear expression of Langmuir model is

presented in Equation 2.1 as follow:
Qm K L Ce
qe
1 K L Ce
(2.1)
where Ce (mg.L1) and qe (mg.g1) are the liquid

phase
concentration
and
solid
phase
concentration of adsorbate at equilibrium,
respectively. KL (L.mg-1) is the Langmuir isotherm
constant. Qm is corresponded to Langmuir
monolayer adsorption capacity (mg.g-1).
Freundlich has a practical application in

describing the non-ideal and reversible
adsorption of heterogoneous sytem.
This empirical model can be applied to
multilayer adsorption, with non-uniform
distribution energy on the adsorbent surface.

The empirical equation of Freundlich is given in Equation 2.3

as:
1/ n
(2.3)
q K C
e
where KF is the Freundlich constant (L.mg-1), and 1/n is the

heterogeneity factor.
1/n is a measure of the deviation from linearity of the
adsorption between 0 and 1. If the value of 1/n is equal to 1,
the adsorption is linear reduce to Henrys Law.
If 1/n < 1, this implies for physisorption; if 1/n > 1, this
indicates for chemisorption.
The more heterogeneous the surface, the closer 1/n value is
to 0.

Tempkin and Pyzhev takes into consideration

that the heat of adsorption of all molecules in
the layer decreases linearly with coverage due
to the effects of indirect adsorbate/adsorbent
interactions (Hosseini-Bandegharaei et al.,
2013). The non-linear form of Tempkin
equation is given as (Equation 2.4):
(2.4)
RT
qe
bT
Ln( K T Ce )

Tempkin constants, KT and bT can be determined by

plotting a non-linear curve; qe versus Ce. R and T are
the universal gas constant (8.314 J.(K.mol)-1). and
temperature (K), respectively. KT is the equilibrium
binding constant (L.mol-1) corresponding to the
maximum binding energy and subsequently,
constant BT related to the heat of adsorption can be
solved through the following Equation 2.5:
(2.5)
RT
BT
bT

Dubinin-Raduskevich (D-R) is one of the isotherms that widely

used to characterize liquid-phase adsorption process. It is
originally developed to emulate the experimental data of
subcriticals vapors adsorption onto micropore solids based on
pore filling mechanism (Dubinin and Radushkevich, 1947).
The model does not assume a heterogeneous surface and
neither constant adsorption potential. The non-linear form of
D-R equation is presented as follow (Equation 2.6):
1 2
qe q D exp( BD [ RT ln( 1 )] )
Ce

(2.6)
The constant, BD is corresponded to the mean free energy, E

of sorption/mole of the adsorbate as it is migrated to the
surface of the solid from innite distance in the solution and it
can be solved using the following relationship (Ho et al.,
2002). E can be calculated according to the Equation 2.7 as
follow:
1
(2.7)
E
2 BD
D-R model is useful to distinguish between physical or
adsorption process based on the amount of calculated E.
Amount of E less than 8 kJ.mol-1 indicates for possible physical
adsorption while 8-16 kJ.mol-1 could be a sign for
chemisorption (Asgari et al., 2013)
Three-parameter Isotherms
Sips
Koble-Corrigan
Toth
Redlich-Peterson
Etc.

In class example


Langmuir Plot
25
20
y = 0.0148x + 9.6511
R = 0.7841
1/q
15
10
5
0
200
400
600
1/c

800
1000
Freundlich Plot
Log C
0
-3
-2.5
-2
-1.5
-1
-0.5
-0.2
-0.4
y = 0.2184x - 0.7183
R = 0.9941
-0.6
-0.8
-1
-1.2
-1.4
-1.6

Log q
-3.5
Batch Adsorption

In class example



Column Adsorption
Fixed bed column is one of the most widely
employed method in the field of liquid and gas
adsorption.
The technique is desirable due to:
continuous nature of the process,
high efficiency adsorbent utilization,
less number of equipment,
smaller operation area and
cost savings.
The performance and characteristics of

column operation can be determined by
analyzing the breakthrough curve.
The typical breakthrough curve as the ratio of
the effluent concentration (Ce) to the influent
concentration (Ci) versus time or throughput
volume is shown in Figure 2.7.

Figure 2.7: Typical breakthrough profiles in column operation

(Barros et al., 2013)

After a lapse of time, a breakthrough will occur at time, tb

with determined breakthrough concentration, Cb and the
effluent concentration continue to increase till reaching
saturation at time, ts.
Saturation point is a condition where the effluent
concentration becomes equal to the feed concentration
increases with time.
The breakthrough time is normally assumed when
Cb/C0 reached 0.1; while the saturation point is defined ideally
when Cb/C0 reach 1.0 (generally at 0.90-0.95) (Asberry et al.,
2014, Unuabonah et al., 2010, Singh et al., 2009).
However, under certain condition, some researchers would
also consider breakthrough point of Cb/C0 = 0.5(Wu et al.,
2012)


Scale Up Adsorption Column






In Class Example 3

cd
1
0.9
0.8
0.7
c/c 0
0.6
A1
A2
0.5
0.4
0.3
0.2
0.1
cb
0
0
tb
t, hour

td



Commercial operation


D. Adsorption

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ADSORPTION

Adsorption theory & concept

SCHOOL OF CHEMICAL ENGINEERING,

Adsorption is the process of capturing

SCHOOL OF CHEMICAL ENGINEERING,

In liquid phase adsorption process, molecules,

The solid, which is insoluble in the liquid, is

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,

Plate 2.1 SEM image of activated carbon produced from banana

SCHOOL OF CHEMICAL ENGINEERING,

Commercial adsorber continuous

SCHOOL OF CHEMICAL ENGINEERING,

Physical properties of adsorbents

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,

MCM-n family - Kresge, 1992

1: Materials evolution map

SCHOOL OF CHEMICAL ENGINEERING,

Table 2.3 Methylene blue adsorption capacity on various sorbent media

(Liu et al., 2013)

(Chang et al., 2013)

(Liu et al., 2012b)

(Ai et al., 2011)

(Nasuha et al., 2010)

Activated clay minerals

(El Mouzdahir et al.,

Carboxylic acid functionalized

(Altenor et al., 2009)

CMK-3 ordered mesoporous

(Asouhidou et al., 2009)

H2SO4 modified activated carbon

(Karagz et al., 2008)

Norit SA3 Activated carbon

(Yener et al., 2008)

Rattan dust activated carbon

(Hameed et al., 2007a)

(Vilar et al., 2007)

(Iqbal and Ashiq, 2007)

SCHOOL OF CHEMICAL ENGINEERING,

Linear relationship is described by Henrys

SCHOOL OF CHEMICAL ENGINEERING,

According to Crini, comprehensive study on adsorption

SCHOOL OF CHEMICAL ENGINEERING,

The non-linear expression of Langmuir model is

where Ce (mg.L1) and qe (mg.g1) are the liquid

Freundlich has a practical application in

SCHOOL OF CHEMICAL ENGINEERING,

The empirical equation of Freundlich is given in Equation 2.3

where KF is the Freundlich constant (L.mg-1), and 1/n is the

SCHOOL OF CHEMICAL ENGINEERING,

Tempkin and Pyzhev takes into consideration

SCHOOL OF CHEMICAL ENGINEERING,

Tempkin constants, KT and bT can be determined by

SCHOOL OF CHEMICAL ENGINEERING,

Dubinin-Raduskevich (D-R) is one of the isotherms that widely

SCHOOL OF CHEMICAL ENGINEERING,

The constant, BD is corresponded to the mean free energy, E

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,

SCHOOL OF CHEMICAL ENGINEERING,