2012/4/14 Aerosol & Particulate Research Lab 1

Adsorption
Physical vs chemical adsorption
Sorbent materials
Mechanism
Isotherm
Effects of humidity
Fixed-bed systems
Regeneration
Rotary bed and fluidized bed systems
Pressure drop
Reading: Chap. 12
2012/4/14 Aerosol & Particulate Research Lab 2
Definition
The concentration of gases, liquids or dissolved substances
(adsorbate) on the surface of solids (adsorbent)
Physical Adsorption (van der Waals adsorption):
weak bonding of gas molecules to the solid;
exothermic (~ 0.1 Kcal/mole);
reversible
Chemisorption:
chemical bonding by reaction;
exothermic (10 Kcal/mole);
irreversible
Q: Examples in your daily life?
Physical vs Chemical
2012/4/14 Aerosol & Particulate Research Lab 3
Sorbent Materials
Activated Carbon
Activated Alumina
Air Pollution Engineering Manual., 1992
Silica Gel
Molecular Sieves (zeolite)
Polar and Non-polar adsorbents
Q: If an activated carbon granule is a solid particle with
1 mm diameter, what is the specific surface area ( = 0.7 g/cm
3
)?
Properties of Activated Carbon
Bulk Density 22-34 lb/ft
3

Heat Capacity 0.27-0.36 BTU/lb
o
F
Pore Volume 0.56-1.20 cm
3
/g
Surface Area 600-1600 m
2
/g
Average Pore Diameter 15-25
Regeneration Temperature
(Steaming)
100-140
o
C
Maximum Allowable
Temperature
150
o
C
http://www.activatedcarbonindia.com/activated_carbon.htm
2012/4/14 Aerosol & Particulate Research Lab 4
OH OH
heating
H
2
O
H
2
O
hydrophilic
OH OH
O
hydrophobic
H
2
O
Q: What if it is heated
over 250
o
C?
Properties of Silica Gel
Bulk Density 44-56 lb/ft
3

Heat Capacity 0.22-0.26
BTU/lb
o
F
Pore Volume 0.37 cm
3
/g
Surface Area 750 m
2
/g
Average Pore Diameter 22
Regeneration Temperature 120-250
o
C
Maximum Allowable Temperature 400
o
C
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Crystalline zeolite
Uniform pores to selectively separate compounds by size & shape
Air Pollution Engineering Manual., 1992
Properties of Activated Alumina
Bulk Density
Granules 38-42 lb/ft
3

Pellets 54-58 lb/ft
3

Specific Heat 0.21-0.25 BTU/lb
o
F
Pore Volume 0.29-0.37 cm
3
/g
Surface Area 210-360 m
2
/g
Average Pore Diameter 18-48
Regeneration Temperature (Steaming) 200-250
o
C
Maximum Allowable Temperature 500
o
C
Properties of Molecular Sieves
Anhydrous Sodium
Aluminosilicate
Anhydrous Calcium
Aluminosilicate
Anhydrous
Aluminosilicate
Type 4A 5A 13X
Density in bulk (lb/ft
3
) 44 44 38
Specific Heat (BTU/lb
o
F) 0.19 0.19 -
Effective diameter of pores () 4 5 13
Regeneration Temperature (
o
C) 200-300 200-300 200-300
Maximum Allowable Temperature (
o
C) 600 600 600
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Adsorption Mechanism
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Rate of adsorption
Rate of desorption
) 1 ( f p k r
a a
=
f k r
d d
=
At equilibrium
d a
a
k p k
p k
f
+
=
Mono-layer coverage
f k m
a
' =
( m: mass of adsorbate adsorbed
per unit mass of adsorbent)
Langmuir Isotherm
Adsorption Isotherm: the mass of adsorbate per unit
mass of adsorbent at equilibrium & at a given
temperature
(f: fraction of surface
area covered)
f
1-f
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p
p
k
k
k m
p
p k
p k
m
1
2
1 2
1
1

1
+ =
+
=
Langmuir Isotherm
( p: partial pressure of the adsorbate)
Q: Low P? High P?
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Freundlich Isotherm
n
p k m =
Q: Calculate the equilibrium adsorptivity of 1000 ppm toluene in
air on 4X10 mesh activated carbon at 298 K and 1 atm.
2012/4/14 Aerosol & Particulate Research Lab 10
Effects of Humidity
Isotherm for toluene & trichloroethylene
and water vapor (individual)
Amount of trichloroethylene adsorbed
as a function of relative humidity
Q: How can we adjust the system to reduce the impact of humidity?
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Fixed-Bed Adsorption System
Q: How will the OUTLET concentration
as a function of TIME look like?
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Regeneration
Theodore & Buonicore, 1988
Q: In addition to steam, what else can we use?
Q: Typically only 30 ~ 40% of the equilibrium isotherm is used. Why is that?
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A well-designed system has steam consumption in the range of 1 to 4 lb
of steam/lb of recovered solvent or 0.2 to 0.4 lb of steam/lb of carbon
In a continuous operation, a minimum of 2 adsorption units is required.
Q: Three-units? Any advantage?
Q: How will you select the regeneration time?
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Rotary Bed
System
Mycock et al., 1995
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Fluidized-Bed
System
Q: Benefits?
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Pressure Drop
75 . 1
'
) 1 ( 150
' ) 1 (
2
3
+

A
G d G D
d Pg
p
g g p
c
c
c
Typical operating range:
< 20 in H
2
O; 20 < V < 100 ft/min
==> determine the
Maximum Adsorbent Bed Depth
AP: pressure drop (lb/ft
2
)
D: bed depth (ft)
c : void fraction
G: gas mass flux (lb/ft
2
-hr)

g
: gas viscosity (lb/ft-hr)
d
p
: carbon particle diameter (ft)
Q: Why?
2012/4/14 Aerosol & Particulate Research Lab 18
Union Carbide Empirical Equation
56 . 1
100
37 . 0
|
.
|

\
|
= A
V
D P
AP: bed pressure drop, in H
2
O
V: gas velocity, ~60-140 ft/min
D: bed depth, ~5-50 inches
d
p
: 4X6 mesh sized carbon
Minimum Adsorbent Bed Depth
Need to be at least longer than the MTZ
|
|
.
|

\
|

=
S
B
s
C
C
D
X
MTZ 1
1
1
C
B
: breakthrough capacity %
C
S
: saturation capacity %
X
S
: degree of saturation in the MTZ (usually 50%)
D: bed depth
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Other Systems: Nongenerable
Thin-bed adsorber
Canister adsorber
Mycock et al., 1995
Q: What need to be known to start the design of an adsorption
bed system?
2012/4/14 Aerosol & Particulate Research Lab 20
Exercise I
An exhaust stream contains 1880 ppm of n-
pentane at 95
o
F. The flow rate to be treated
is 5500 acfm. Carbon capacity is 3.5 lb n-
pentane/100 lb AC. Carbon density is 30
lb/ft
3
. 2-bed system: 1 hr for adsorption and
the other hr for regeneration.
Q: Mass flow rate of n-pentane? Volume
of carbon bed? Flow velocity? Steam
requirement? Pressure drop?
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Exercise II
Conditions: 10,000 acfm of air @ 77
o
F at 1
atm containing 2000 ppm toluene (MW =
92) to be treated. 95% removal efficiency by
4X10 mesh carbon expected (density of
carbon = 30 lb/ft
3
)
Q: how many lb/hr of toluene to be
removed?
Q: If regeneration at 212
o
F, whats the
working capacity?
Q: Design an adsorption system with max
AP of 8 inH
2
O, 4 hr cycle, two beds.
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0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
40 50 60 70 80 90 100 110
IV Allowable bed depth 8
inH2O / DP in Column II
V Required bed depth
Carbon volume (143 ft3) /
area in Column III
I II III IV V
Ve locity
A
P Cros s -S e ctiona l Are a Allowa ble be d de pth Re quire d be d de pth
fpm in H2O / Q (10,000 a cfm) / 8 inH2O / Ca rbon volume (143 ft3) /
ft of be d de pth Ve l in Column I
A
P in Column II a re a in Column III
40 2 250.00 4.00 0.62
50 2.7 200.00 2.96 0.775
60 3.7 166.67 2.16 0.93
70 4.6 142.86 1.74 1.09
80 5.4 125.00 1.48 1.24
90 6.5 111.11 1.23 1.4
100 7.6 100.00 1.05 1.55
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Quick Reflection