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Adsorption

Reading: Chap. 12

• Physical vs chemical adsorption


• Sorbent materials
• Mechanism
• Isotherm
• Effects of humidity
• Fixed-bed systems
• Regeneration
• Rotary bed and fluidized bed systems
• Pressure drop
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Definition
The concentration of gases, liquids or dissolved substances
(adsorbate) on the surface of solids (adsorbent)
Q: Examples in your daily life?

Physical vs Chemical
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
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Sorbent Materials
• Activated Carbon • Silica Gel
• Activated Alumina • Molecular Sieves (zeolite)
Polar and Non-polar adsorbents
http://www.activatedcarbonindia.com/activated_carbon.htm
Properties of Activated Carbon
Bulk Density 22-34 lb/ft3
Heat Capacity 0.27-0.36 BTU/lboF
Pore Volume 0.56-1.20 cm3/g
Surface Area 600-1600 m2/g
Average Pore Diameter 15-25 Å
Regeneration Temperature 100-140 oC
(Steaming)
Maximum Allowable 150 oC
Temperature
Q: If an activated carbon granule is a solid particle with
1 mm diameter, what is the specific surface area (r = 0.7 g/cm3)?
Air Pollution Engineering Manual., 1992
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Properties of Silica Gel
Bulk Density 44-56 lb/ft3
Heat Capacity 0.22-0.26
BTU/lboF
Pore Volume 0.37 cm3/g
Surface Area 750 m2/g
Average Pore Diameter 22 Å
Regeneration Temperature 120-250 oC Q: What if it is heated
Maximum Allowable Temperature 400 oC over 250 oC?

H2O H2O H2O


OH OH OH OH O

heating

hydrophilic hydrophobic

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Properties of Activated Alumina
Bulk Density
Granules 38-42 lb/ft3
Pellets 54-58 lb/ft3
Specific Heat 0.21-0.25 BTU/lboF
Pore Volume 0.29-0.37 cm3/g
Surface Area 210-360 m2/g
Average Pore Diameter 18-48 Å
Regeneration Temperature (Steaming) 200-250 oC
Maximum Allowable Temperature 500 oC

Properties of Molecular Sieves


Anhydrous Sodium Anhydrous Calcium Anhydrous
Aluminosilicate Aluminosilicate Aluminosilicate
Type 4A 5A 13X
Density in bulk (lb/ft3) 44 44 38
Specific Heat (BTU/lboF) 0.19 0.19 -
Effective diameter of pores (Å) 4 5 13
Regeneration Temperature (oC) 200-300 200-300 200-300
Maximum Allowable Temperature (oC) 600 600 600
Air Pollution Engineering Manual., 1992
• Crystalline zeolite
• Uniform pores to selectively separate compounds by size & shape
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Adsorption Mechanism

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Langmuir Isotherm
Adsorption Isotherm: the mass of adsorbate per unit
mass of adsorbent at equilibrium & at a given
temperature
Rate of adsorption ra  ka p(1  f ) (f: fraction of surface
area covered)
Rate of desorption rd  k d f
ka p
At equilibrium f  f
ka p  kd 1-f

Mono-layer coverage m  ka ' f ( m: mass of adsorbate adsorbed


per unit mass of adsorbent)

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Langmuir Isotherm

k1 p p 1 k2
m    p
k2 p  1 m k1 k1
( p: partial pressure of the adsorbate)

Q: Low P? High P?
p
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Freundlich Isotherm
m  k  pn

Q: Calculate the equilibrium adsorptivity of 1000 ppm toluene in


air on 4X10 mesh activated carbon at 298 K and 1 atm.
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Effects of Humidity
Isotherm for toluene & trichloroethylene Amount of trichloroethylene adsorbed
and water vapor (individual) 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

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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Q: How will you select the regeneration time?
• 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?
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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

Pg 3d p r g 150(1   )  g
  1.75
D(1   )G' 2
d pG'
P: pressure drop (lb/ft2)
D: bed depth (ft)
 : void fraction
G’: gas mass flux (lb/ft2-hr)
g: gas viscosity (lb/ft-hr)
dp: carbon particle diameter (ft)

Typical operating range:


< 20 in H2O; 20 < V < 100 ft/min Q: Why?
==> determine the
Maximum Adsorbent Bed Depth
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Union Carbide Empirical Equation

 V 
1.56 P: bed pressure drop, in H2O
P  0.37 D  V: gas velocity, ~60-140 ft/min
 100  D: bed depth, ~5-50 inches
dp: 4X6 mesh sized carbon

Minimum Adsorbent Bed Depth


Need to be at least longer than the MTZ
1  CB 
MTZ  D1  
1  X s  CS 
CB: breakthrough capacity %
CS: saturation capacity %
XS: degree of saturation in the MTZ (usually 50%)
D: bed depth
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Other Systems: Nongenerable

Canister adsorber

Thin-bed adsorber

Q: What need to be known to start the design of an adsorption


bed system?
2019/6/17 Aerosol & Particulate Research Lab Mycock et al., 1995 19
Exercise I
• An exhaust stream contains 1880 ppm of n-
pentane at 95 oF. 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/ft3. 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 oF 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/ft3)
• Q: how many lb/hr of toluene to be
removed?
• Q: If regeneration at 212 oF, what’s the
working capacity?
• Q: Design an adsorption system with max
P of 8 inH2O, 4 hr cycle, two beds.
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I II III IV V
Velocity P Cross-Sectional Area Allowable bed depth Required bed depth
fpm in H2O / Q (10,000 acfm) / 8 inH2O / Carbon volume (143 ft3) /
ft of bed depth Vel in Column I  P in Column II area 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

4.50
4.00 IV Allowable bed depth 8
inH2O / DP in Column II
3.50
3.00 V Required bed depth
Carbon volume (143 ft3) /
2.50 area in Column III
2.00
1.50
1.00

0.50
0.00
40 50 60 70 80 90 100 110

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Quick Reflection

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