POROZNI MATERIJALI

Teksturalne osobine
Silica Carbon Zeolite
V. Dondur 2011.
Important properties are:

Surface area - determined by BET
Pore structure
Chemical composition of the surface.

Techniques for studying composition of surface include

IR and Raman
X-ray fluorescence (XRF)
Low energy electron diffraction (LEED)
X-ray photoelectron spectroscopy (ESCA)
Auger-electron spectroscopy (AES)


Porosity is usually defined as the ratio of the
volume of pores and voids to the volume occupied
by the solid.

In many cases the internal surface area is
much larger than the external surface area and
the agglomerate then possesses a well-defined
pore structure.


Texture and morphology of porous
systems
pore size
pore shape
pore-size distribution (same size or
various sizes?)
pore volume
specific surface area of adsrbent
0.5nm
Pore diameters
micropores (< 2 nm)
mesopores (2 - 50 nm)
macropores (> 50 nm)
Pore Size and Shape
0.5nm
Table 1. Definitions: porous solids
Term Definition
Porous solid Solid with cavities or channels which are deeper than they are wide
open pore Cavity or channel with access to the surface
Interconnected pore Pore which communicates with other pores
Blind pore' Pore with a single connection to the surface (Deadend pore)
Closed pore Cavity not connected to the surface
Void Space between particles
Miclopore Pore of internal width less than 2 nm
Mesopore Pore of internal width between 2 and 50 nm
Macropore Pore of internal width greater than 50 nm
Pore size Pore width (diameter of cylindrical porc or distance between opposite walls of slit)
Pore volume Volume of pores determined by stated method
Porosity Ratio of total pore volume to apparent volume of particle or powder
Total porosity Ratio of volume of voids and pores (open and closed) to volume occupied by solid
Open porosity Ratio of volume of voids and open pores to volume occupied by solid
Surface area Extent of total surface area as determined by given method under stated
conditions
External surface area Area of surface outside pores
Intemal surface area Area of pore walls
Density Density of solid, excluding pores and voids
Apparent density Density of material including closed and inaccessible pores, as determined by
stated method
ACTIVATED Carbon pores consist of:
1. Micro pores with a radius of less than 1 nm (small pores)
2. Meso pores with a radius of 1-25 nm (medium pores)
3. Macro pores with a radius larger than 25 nm (large
pores)
Large pores are used for the transport of liquid through
the carbon, and absorption occurs in the medium and
small pores. Pores are formed during the
manufacturing process, when the carbon is activated.
The activation basically means that pores are created in
a non-porous material by means of chemical reactions.
AFM image of a typical nanoporous
alumina template (dark areas are
pores and the surrounding light
areas are aluminum oxide around
the pores (pore diameter is ~50nm)
SEM image of a typical nanoporous
alumina (dark areas are pores and
the surrounding light areas are
aluminum oxide around the pores
(pore diameter is ~25nm)
SILICATE / ALUMINOSILICATE POROUS MATERIALS
Macroporous
(>500)
Mesoporous
(20-500)
Microporous
(<20)
Crystalline
Amorphous
Crystalline
Crystalline
Amorphous
Amorphous
ZEOLITES
ZEOTYPES
POROSILS
CLINOPTILOLITE
SILICALITE
MCM-41
ETS-10
Silica Gel
SiO2
?
?
SiO2
SiO2
SiO2
Figure 1 Microporous polymer.
These polymers are formed by
cross-linking linear chains of
monomer. Cross-links (shown as
heavy lines above) create very
small pores within the three
dimensional
matrix.
Figure 2. Macroporous
polymer.
These materials have a high
degree of cross-linking,
preventing
them from swelling in solvents.
Pores are larger than gels,
but are irregular and terminate
inside the matrix. Total pore
volumes are typically 50%.
Figure 3. High internal phase
emulsion. HIPE polymers,
illustrated
above, contain extremely
large cavities that are
interconnected.
Cavities are of micrometer
dimensions, rather than angstrom
dimensions of conventional
polymers. Total pore volume
can exceed 90%.
polymers
Broken sphere of Cavilink polymer.
This is interior
of polymer type shown in Fig. 9
and shows cavities and pores
fully communicating with sphere
surface.
Cavilink polymer with fully open surface.
This SEM
photo shows distinctive regularity
of cavities in Cavilink polymers.
Cavities have diameters greater
than 10,000 . Higher magnifications
reveal characteristic interconnected
structure, (see Fig. 7).
Cavilink polymer with fully open
surface.
Higher magnifications
reveal characteristic interconnected
Structure.
Pore Shapes
Slit
Ink-bottle
Cylindrical
Wedge
a b
d c
Pore Diameters and Measurement
Techniques
Experimental techniques
capillary condensation
Hg intrusion
microscopy
Pore Shape Selectivity
Reactant selectivity
+
Product selectivity
CH
3
OH +
Restricted transition-state selectivity
Why is it important? It dictates the diffusion process through the
material.
Pore Size and Diffusion Regimes
Configurational
diffusion
Surface
migration
1000 100 10 1 0.1
10
-4


10
-8


10
-12


10
-16

1000 100 10 1 0.1
100

50

0
E
a
(kJ/mol)
D (m
2
/s)
Pore diameter (nm)
Pore diameter (nm)
Molecular
diffusion
Knudsen
diffusion
Surface
migration
Knudsen number: K
n
= /d
= molecular free path length
d= characteristic pore diameter
K
n
<< 1 bulk diffusion
K
n
>> 1 Knudsen diffusion
Types of diffusion
Molecular
Knudsen
Surface

Cylindrical pore
d
p
d
m

Volumetric Adsorption Measurement
N
2
(77.3 K) or
Ar, He, CH
4
, CO
2
, Kr
adsorbate
adsorbent
pressure
gauge
P
V
1
V
2
high vacuum
PV=nRT
Adsorption Isotherms
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1

Adsorption
Desorption
p is gas pressure
po is vapour pressure
Adsorption Isotherms
III
n
a
d

p / p
0
VI
n
a
d

p / p
0
V
n
a
d

p / p
0
I
n
a
d

p / p
0
p / p
II
n
a
d

0
B
IV
n
a
d

p / p
0
B
Langmuir Adsorption
Isotherm (Type I)
Assumptions:
homogeneous surface
(all adsorption sites energetically identical)
monolayer adsorption (so no multilayer adsorption)
no interaction between adsorbed molecules
p K
p K
n n n
m m ad
+
= u =
1
I
n

a
d

p / p
0
LANGMUIR ISOTHERM

Assumptions

all adsorption sites equivalent
ability of adsorbate to bind is independent of
whether the adjacent sites are occupied or not.
adsorbate behaves as an ideal gas in gas phase
only monomolecular adsorption takes place
adsorbed molecules occupy fixed sites
heat of adsorption is independent of surface
coverage.
Type II and IV Isotherms
Multilayer adsorption (starting at B)
Common for pore-free materials
Similar to II at low p
Pore condensation at high p
p / p
II
n

a
d

0
B
IV
n

a
d

p / p
0
B
Type III and V Isotherms
III
n
a
d

p / p
0
V
n

a
d

p / p
0
Strong cohesion force between
adsorbed molecules, e.g. when
water adsorbs on hydrophobic
activated carbon
Similar to III at low p
Pore condensation at high p
Surface Area & Monolayer Capacity
S = n
m
A
m
N
monolayer
capacity (mol/g)
specific surface
area (m
2
/g)
area occupied by one
molecule (m
2
/molecule)
Avogadros number
(molecules/mol)
BET model: S
BET

t model: S
t

Properties of Adsorbates for Physisorption
Measurements
Adsorbate Boiling Point (K) A
m
(nm
2
/molecule)
N
2
77.3 0.162
Ar 87.4 0.142
CO
2
194.5 0.17
Kr 120.8 0.152
N
2
Adsorption Isotherm in ZSM-5
0
1
2
3
4
5
6
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)
1
Langmuir Adsorption?
strong adsorption at low p due to condensation in
micropores
at higher p saturation due to finite (micro)pore volume
Adsorption and Desorption Isotherms
BET (Brunauer, Emmett, Teller) Method
Modification of Langmuir isotherm
Both monolayer and multilayer adsorption
Layers of adsorbed molecules divided in:
First layer with heat of adsorption AH
ad,1

Second and subsequent layers with H
ad,2
= AH
cond

BET isotherm:




BET equation does not fit entire adsorption isotherm
different mechanisms play a role at low and at high
p

( )
0
m m
0
ad
1 1
p
p
C n
C
C n p p n
p

+ =

|
.
|

\
|
A A
=
RT
H H
C
cond ad
exp
BET ADSORPTION ISOTHERMS

Assumptions:

Multiple layers form and langmuir model applies to
each layer.
Heat of adsorption, AHads for first layer has a value
determined by properties of surface and adsorbate,
but for second and all subsequent layers, it is equal
to heat of vapourization AH vap.
Evaporation (or desorption) only occurs from
exposed surfaces.
Rate of evaporation is equal to rate of condensation
on preceding layer.
reality model
u
5

u
4

u
3

u
2

u
1

u
0

( ) ... 3 2 1
2 1 0 m ad
+ u + u + u = = u

n n
i
1 - n n 1 - n
1
0
n n 1 - n
1
0 1 0
1
0
1 1
1
0
0
u = u = u u = u
u = u = u u = u

p K p
k
k
k p k
p K p
k
k
k p k
d
a
n
d
n
a
d
a
d a
1
st
layer

n
th
layer
For every layer
Langmuir model

Assume
RT
H
RT
H
RT
H
K K K
K K
cond n
ads
e e
e
0 , n 0 , n n
0 , 1 1
A

~ =
=
( )
|
|
.
|

\
|
+
|
|
.
|

\
|

=
0
0
0
m
ad
1 1 1
p
p
C
p
p
p
p
C
n
n
RT
H H
C
cond ads
e
A A
=
BET Model
( ) ( ) | | x 1 c 1 x 1
cx
V
v
m
+
=
BET Equation
p is gas pressure
po is vapour pressure
Vm is monolayer
volume
V is volume measured
of gas adsorbed
Step 1: Plot x / [V(1-x)] vs x

Step 2: Determine from the plot
Intercept 1 / (cV
m
)
Slope (c-1) / (cV
m
)

Step 3: Calculate c, V
m

V
m
= 1/ (slope + intercept)
( )
( )
o
m m
p p x where
cV
x c
cV x V
x
/
,
1 1
1
=

+ =

V
m
can be used to
calculate Specific Surface
Area,
S
BET
= V
m
A
m


where
A
m
is area per adsorption site
number of gas molecules /
cm3
p/p
0
n
a
d
/
n
m
(B) (A)
Low p/p
0
:
filling of micropores
favoured adsorption at
most reactive sites
(heterogeneity)
High p/p
0
:
capillary condensation
Range 0.05 < p/p
0
< 0.3 is used to determine S
BET

BET equation
Porous Silica and Alumina
Adsorption at Pore Wall
Cylindrical pore
Ink-bottle pore
Pore with shape of interstice
between close-packed particles
Adsorbed layer
t
d
p
d
m

t-method
BET
only valid in small pressure interval
interpretation not very easy
thickness (t) of adsorbed layer can be calculated




plot of t versus p for non-porous materials is the
same (has been checked experimentally)
t-plot helps in interpretation
0.354
nm
t-method
nm 354 . 0
m
ad
=
n
n
t
t
n
S
N A
t
n
S
N A n S
ad
6
t
m
9
ad
t
m m t
10 73 . 5
10 354 . 0
=
=
=

n
ad

t
Proportional to S
t

Shape of t-plots

nm 354 . 0
m
ad
=
n
n
t
t
n
ad
t
n
ad
t
n
ad
Non-porous Microporous
Micro- and
mesoporous
S
t
S
mesopores
p
n
ad
Adsorption isotherm
t = f(p)
Kelvin Equation for Nitrogen
m
0
1 2
ln
r RT
V
p
p
L

=
micro meso macro
V
L
= 34.6810
-6
m
3
/mol molar volume
= 8.88 mN/m surface tension
r is surface radius
d
m
(nm)
R
e
l
a
t
i
v
e

p
r
e
s
s
u
r
e

p
/
p
0

0
0.2
0.4
0.6
0.8
1
0.1 1 10 100 1000 10000
Pore filling Model
Cylindrical Pore Channel
Pore Size Distribution
Charge in vapor pressure for a curved surface
Hysteresis Loops
HI
n
a
d
p/p
0
H2
n
a
d
p/p
0
H3
n
a
d
p/p
0
Information on pore shape
t-curves
p/p
0

A
d
s
o
r
b
e
d
-
l
a
y
e
r

t
h
i
c
k
n
e
s
s

t

(
n
m
)

0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.2 0.4 0.6 0.8 1
a
b
Halsey
Harkins-Jura-de Boer
( )
333 . 0
0
/ ln
00 . 5
354 . 0
(

=
p p
t
( )
5 . 0
0
/ log 034 . 0
99 . 13
1 . 0
(

=
p p
t
t-plot of -alumina
0
2
4
6
8
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
mesopores
macropores
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
S
t
= 200 m
2
/g
Interpretation of t-Plot

nm 354 . 0
m
ad
=
n
n
t
Dubinin-Radushkevich equation

Where c
x
represents the work done by the adsorption
forces when adsorbate is brought up to a distance l
from surface
p
p
RT
o
x
ln = c
For porous solids Vo is taken to be the pore volume,
and V, the volume adsorbed at given po/p value.
|
|
.
|

\
|
|
.
|

\
|
=
p
p
E
RT
V V
o
o
ln ln ln
2
Volume of micropores
) exp(
2
c b V V
o
=
Pore Size Distribution
alumina

0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
p
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
+ =t r
o
o
p
p
RT
V
t r
ln
2
+ =
nm 354 . 0
m
ad
=
n
n
t
|
|
.
|

\
|
|
.
|

\
|
=
p
p
E
RT
V V
o
o
ln ln ln
2
t-plot of N
2
Physisorption on
ZSM-5
t (nm)
0 0.5 1
n
2

n
1

n
1
= liquid N
2

n
2
= solid N
2

n
a
d

(
m
m
o
l
/
g
)

6


3


0
Mercury Intrusion Curve of -
Alumina
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
Texture Data of Commercial Catalysts
Material Mean d
p
(nm) S
BET
(m
2
/g)
Catalyst supports
Silica gel 10 200
6 400
4 800
-Al
2
O
3
10 150
5 500
Zeolite 0.6-2 400-800
Activated carbon 2 700-1200
TiO
2
400-800 2-50
Aerosil SiO
2
- 50-200
Catalysts
MeOH synthesis (Cu/ZnO/Al
2
O
3
) 20 80
NH
3
synthesis (Fe/Al
2
O
3
/K
2
O) 100 10
Reforming (Pt/Re/Al
2
O
3
) 5 250
Epoxidation (Ag/o-Al
2
O
3
)
200 0.5
Mercury Intrusion Porosimetry
p
d
14860
p
=
Hg does not wet surfaces; pressure is needed to
force intrusion

From a force balance:

(d in nm, p in bar)


Convenient method for determining pore volume
versus pore size
Discrepancy S
Hg
and S
BET

for Microporous Materials
Hg cannot penetrate small (micro)pores,
N
2
can
Uncertainty of contact angle and
surface tension values
Cracking or deforming of samples
Surface Areas - S
Hg
and S
BET

Adsorbent S
Hg
S
BET
u
m
2
/g m
2
/g deg
Iron Oxide 14.3 13.3 130
Tungsten Oxide 0.11 0.10 130
Anatase 15.1 10.3 130
Hydroxy Apatite 55.2 55.0 130
Carbon Black (Spheron-6) 107.8 110.0 130
0.5 % Ru/-Al
2
O
3
237.0 229.0 140
0.5 % Pd/-Al
2
O
3
115.0 112.0 140
TiO
2
Powder 31.0 25.0 140
Sintered Silica Pellets 20.5 5.0 140
Zeolite H-ZSM-5 39.0 375.0 140
Norit Active Carbon R1 Extra 112.0 915.0 140
Texture Properties
N
2
-physisorption Hg-porosimetry
S
BET
S
t
V
p
d
p
S
Hg
V
p
d
p
m
2
/g m
2
/g ml/g nm m
2
/g ml/g nm
Wide Pore Silica 78 52 0.91 47 80 0.92 54
-Alumina
196 202 0.49 10 163 0.49 10
o-Alumina
9 8 0.12 112 12 0.48 150
Active Carbon 1057
a
28 0.51 2 0.6 0.46 106
Raney Ni 76 - 0.14 5.80 - - -
ZSM-5 345 344 0.19 0.58 11 1.1 820
b
a
p/p
0
range of 0.01-0.1 was used in the calculation.
b
intraparticle voids.
N
2
Adsorption Isotherms & Pore Volume
Distributions
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1



wide-pore silica -alumina
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
N
2
Adsorption Isotherms & Pore Volume
Distributions
o-alumina activated carbon
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)


1
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
0.000
0.002
0.004
0.006
0.008
0.010
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
}
Tensile strength effect
N
2
Adsorption Isotherms & Pore Volume
Distributions
Raney Ni ZSM-5
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
0
5
10
15
20
25
0 0.2 0.4 0.6 0.8 1
p/p
0
n
a
d

(
m
m
o
l
/
g
)

1
0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0
2
4
6
8
10
0.0 0.5 1.0 1.5 2.0
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
Hg Intrusion Curves & Pore Volume
Distributions
wide-pore silica -alumina
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0
0.02
0.04
0.06
0.08
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
Hg Intrusion Curves & Pore Volume
Distributions
o-alumina activated carbon
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0.000
0.001
0.002
0.003
0.004
0.005
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0.000
0.002
0.004
0.006
0.008
0.010
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
Hg Intrusion Curves & Pore Volume
Distributions
Raney Ni ZSM-5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0.1 1 10 100 1000
p (MPa)
V

(
m
l
/
g
)
0.00
0.02
0.04
0.06
0.08
0.10
1 10 100 1000 10000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
0
0.001
0.002
0.003
0.004
0.005
1 10 100 1000 10000 100000
d
pore
(nm)
d
V
/
d
d

(
m
l
/
g
/
n
m
)
BET- & t-plots
wide-pore silica -alumina
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 78 m
2
/g
C = 146
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 196 m
2
/g
C = 97
0.0
0.5
1.0
1.5
2.0
2.5
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
=28 m
2
/g
V
t,micro
= 0.013 ml/g
0
2
4
6
8
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
o-alumina activated carbon
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 9.3 m
2
/g
C = 142
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 1057 m
2
/g
C = 1057
p/p
0
= 0.01 - 0.1
0.00
0.05
0.10
0.15
0.20
0.25
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t, micro
= 1.4 m
2
/g
V
t,mcro
= 0.001 ml/g
0
5
10
15
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 856 m
2
/g
V
t,micro
= 0.42 ml/g
BET- & t-plots
Raney Ni ZSM-5
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 76 m
2
/g
C = 46
0.0
0.1
0.2
0.3
0.4
0.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30
p/p
0
p
/
[
n
a
d
(
p
0
-
p
)
]


(
g
/
m
m
o
l
)
S
BET
= 345 m
2
/g
C = -245
p/p
0
: 0.01 -0.1
0
1
2
3
4
5
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t,micro
= 0 m
2
/g
V
t,micro
= 0 ml/g
0
2
4
6
0.0 0.2 0.4 0.6 0.8 1.0 1.2
t ( nm)
n
a
d

(
m
m
o
l
/
g
)
S
t ,micro
= 344 m
2
/g
V
t ,micro
= 0.18 ml/g
BET- & t-plots
Sintering of Alumina upon
Heating
T
calc
(K)
S
B
E
T

(
m
2
/
g
)

Sintering
Reduction of surface area
COMMERCIAL SORBENTS AND APPLICATIONS
Only four types of generic sorbents have
dominated the commercial use of adsorption:
activated carbon, zeolites, silica gel, and activated
alumina. Estimates of
worldwide sales of these sorbents are (Humphrey
and Keller, 1997)
Activated carbon $1 billion
Zeolites $100 million
Silica gel $27 million
Activated alumina $26 million
Table 2. Examples of commercial adsorption processes and sorbents
used
Separation Adsorbent
Gas Bulk Separations
Normal paraffins/isoparaffins, aromatics Zeolite
N2/O2 Zeolite
O2/N2 Carbon molecular sieve
CO, CH4, CO2, N2, Ar, NH3/H2 Activated carbon
followed by zeolite (in
layered beds)
Hydrocarbons/vent streams Activated carbon
H2O/ethanol Zeolite (3A)
Chromatographic analytical separations Wide range of inorganic
and polymer resin agents
Gas Purification
H2O/olefin-containing cracked gas,
natural gas, air, synthesis gas, etc. Silica, alumina, zeolite (3A)
CO2/C2H4, natural gas, etc. Zeolite, carbon molecular
sieve
Hydrocarbons, halogenated organics,
solvents/vent streams Activated carbon, silicalite,
others
Sulfur compounds/natural gas, hydrogen,
liquefied petroleum gas (LPG), etc. Zeolite, activated alumina
SO2/vent streams Zeolite, activated carbon
Odors/air Silicalite, others
Indoor air pollutantsVOCs Activated carbon, silicalite,
resins
Tank-vent emissions/air or nitrogen Activated carbon, silicalite
Hg/chlor-alkali cell gas effluent Zeolite
Liquid Purifications
H2/organics, oxygenated organics,
halogenated organics, etc., dehydration Silica, alumina, zeolite, corn grits
Organics, halogenated organics,
oxygenated organics,etc./H2Owater purification Activated carbon, silicalite, resins
Inorganics (As, Cd, Cr, Cu,
Se, Pb, F,Cl, radionuclides, etc.)/H2Owaterpurification Activated carbon
Odor and taste bodies/H2O Activated carbon
Sulfur compounds/organics Zeolite, alumina, others
Decolorizing petroleum fractions, syrups,vegetable oils, etc. Activated carbon
Various fermentation products/fermentor effluent Activated carbon, affinity agents
Drug detoxification in the body Activated carbon
Liquid Bulk Separations
Normal paraffins/isoparaffins, aromatics Zeolite
p-xylene/o-xylene, m-xylene Zeolite
Detergent-range olefins/paraffins Zeolite
p-Diethyl benzene/isomer mixture Zeolite
Fructose/glucose Zeolite
Chromatographic analytical separations Wide range of
inorganic, polymer,
and
affinity agents
Pore Structures of Zeolites
a b
ZSM-5 Mordenite
Figure 3: Nano-porous materials are generated after etching mesomorphic block
copolymers selectively.