Adsorption

Adsorption
• Physical vs chemical adsorption

• Sorbent materials
• Mechanism
• Isotherm
• Effects of humidity
• Fixed-bed systems
• Regeneration
• Rotary bed and fluidized bed systems
• Pressure drop
1
Rinat Iskakov, Ph.D. riskakov@mail.ru +7(701)735-5520
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
2010/4/28 2
Introduction to Mass Transfer
Diffusion and convection

Mass transfer refers to the transfer of a species in the presence of
a concentration gradient of the species. Under a concentration
gradient mass transfer can occur by either diffusion or convection.
Diffusion refers to the mass transfer that occurs a stationary solid
or fluid in which a concentration gradient exists. In contrast,
convection refers to mass transfer that occurs across a moving fluid
in which a concentration gradient exists.
Consider the dissolution of a sugar cube
In water, the concentration of sugar molecules
Is significant only in the vicinity of the cube.
By stirring the water with a spoon to create
forced convection, sugar molecules are
transferred to the bulk water much faster.
3
Fick’s law of diffusion
One-dimensional
Consider the diffusion of species A through a thin sheet of thickness L,
as shown. Let wA be the mass fraction of species A in the sheet. A steady-state
concentration profile wA(y) is established in the sheet.
A diffusion flux, jAy, is defined as the amount of material diffused per unit
area per unit time and can be expressed by Fick’s law of diffusion
dwA
j Ay   DA
dy
Where  is the mass density of the solution, DA the diffusion coefficient of
species A in the solution, and wA the mass (or weight) fraction of species A.
Minus sign and unit.
4
Three-dimensional
In the case of three-dimensional diffusion, the diffusion equation can be
expressed as follows
dwA dwA dwA
j Ax   DA j Ay   DA j Az   DA
dx dy dz
Note that is has been assumed that the material is isotropic, that is,  and DA
are direction-independent.
Eqs. can be expressed in a vector form as follows:
jA   DAwA
If the mass density  is constant, Eq can be written as follows:
jA   DA A
Where A =wA is the mass of species A per unit volume of the solution, or
the mass concentration of species A.
5
Fick’s law of diffusion can also be written as
j A  cDAx A
Where jA is the molar diffusion flux vector, c the molar density of the
solution, and xA the mole fraction of species A.
If the molar density of the equation is constant, Eq. can be written as:
j   DAcA
A
Where cA =cxA is the moles of species A per unit volume of the solution,
that is, the molar concentration of species A. In a dilute solution the molar
density of the solution c is essentially constant.
Thermal diffusion (thermal diffusion describes the tendency for species to
diffuse under the influence of a temperature gradient; this effect is quite small,
but devices can be arranged to produce very steep temperature gradients so
that separations of mixtures are effected)
In a nonisothermal system, spatial temperature variations can induce the so-
called thermal diffusion, and Fick’s law of diffusion can be modified as follows:
1
j A   DA (c A   T c AcB ln T ) 6
Rinat Iskakov, Ph.D. 
riskakov@mail.ru +7(701)735-5520
and dividing by MA, the molecular weight of species A,
1
j A   DA (c A   T c AcB ln T )

Where T and T are thermal diffusion factors based on mass and molar
concentrations, respectively. The two factors are related to each other
through T = MBT, where MB is the molecular weight of species B.
Diffusion boundary layer

Consider a fluid approaching a flat plate in the direction parallel to the
the plate is coated with a material containing species A, which has a limited
solubility in the fluid. The composition of the Approaching fluid is wA∞ and that
of the fluid at the plate surface is wAS, both of which are constant.
Because of the effect of diffusion, the concentration of the fluid in the

region near the plate is affected by the coating, varying from wAS at the
plate surface to wA∞ in the stream. This region is called the diffusion or
concentration boundary layer.
7
The thickness δc of the concentration boundary layer is taken as the
distance from the plate surface at which the dimensionless concentration
(wA-wAS)/(wA∞ -wAS) or (wAS-wA)/(wAS-wA∞) levels off to 0.99. In practice it is
usually specified that wA = wAS and wA / y  0 at y = δc .
With increasing distance from the leading edge of the plate, the effect of
diffusion penetrates farther into the stream and the boundary layer grows
in thickness. The effect of diffusion is significant only in the boundary layer.
Beyond it the concentration is uniform and the effect or diffusion is no longer
significant.
8
Mass transfer flux
Let vA and vB be the velocities of species A and B with respect to stationary
coordinates, respectively. These species velocities result from both the bulk
motion of the fluid at velocity v and the diffusion of the species super imposed
on the bulk motion. The mass flux of species A with respect to stationary
coordinates, specially, nA = AvA, can be considered to result from a mass
flux due to the bulk motion of the fluid, Av, and a mass flux due to the
diffusion superimposed on the bulk motion, jA. In other words,
n A   A v A   A v  jA
For a binary system consisting of species A and B, which is the focus of
the present chapter, the velocity v is a local mass average velocity defined by
 A vA + B v B  A vA + B v B n B +n B
v    wA vA  wB v B
 A + B  
Substituting Eq
n A  wA v  jA  wA (n A  n B )  jA
9
Similarly, the molar flux of species A with respect to stationary coordinates,
specially, n A  cA vA , can be considered to result from a molar flux, ,c Adue
v
to the bulk motion of the fluid at velocity v and a molar flux due to the diffusion
superimposed on the bulk motion, jA. In other words,
n A  cA vA  cv  jA
Where the local molar average velocity
cA v A  cB v B cA v A  cB v B n  nB
v  ( A )  xA v A  x B v B
cA  cB c c
Substituting Eq. we have
n A  xAcv  jA  xA (n A +n B )  jA
10
Mass transfer coefficient
Consider fluid flow over a flat plate. The mass diffusion
flux across the solid/liquid interface is
wA
j Ay    DA
y 0 y y 0
This equation cannot be used to calculate the diffusion flux when the
concentration gradient is an unknown. A convenient way to avoid this problem
is to introduce a mass transfer coefficient.
At the solid/liquid ( or liquid/gas) interface the mass transfer coefficient km is
defined by
nAy  km   A0   A 
y 0
nAy  km   wA0  wA 
y 0
Where A0 and A∞ are the mass concentrations of species A in the fluid at the
interface and in the bulk (or free-stream) fluid, respectively. If  is constant,
Eq. can be rewrite as
nAy  km   wA0  wA 
y 0
11
If the solubility of species A in the fluid is limited so that vy is essentially zero
at the interface, the following approximation can be made in view of Eq.
nAy  j Ay
y 0 y 0
Substituting Eqs, we have
j Ay
y 0
 DA  wA y  y 0
km  
  wAS  wA   wAS  wA 
For fluid flow through a pipe, we can write
j Ar  DA  wA r  r  R
km  r R

  wAS  wA,av  wAS  wA,av
Where the average concentration is defined as follows
k A,av 
A
 w vdA 

A A
 wAvdA

 A
 wAvdA
  vdA m  vav A
A
Notice that the numerator is the species mass flow rate. 12

Similar equations on the molar basis can be written for flow over a flat plate
jAy
y 0
 DA  xA y  y 0
km  
c  xAS  xA  xAS  xA
and for flow through a tube

jAy  DA  xA r  r  R
km  r R

c  xAS  xA,av  xAS  xA,av
Where the average concentration is defined as follows
xA,av 
A
cx vdA 

A A
cxA vdA

 A
cx A vdA
 cvdA
A
m cvav A
13
Diffusion in solids
Diffusion mechanisms
Vacancy diffusion and interstitial diffusion are the two most frequently
encountered diffusion mechanisms in solids, although other mechanisms
have also been proposed.
In vacancy diffusion an atom in a solid

jumps from a lattice position of the
solid into a neighboring unoccupied
lattice site or vacancy, as illustrated in .
At temperature above
absolute zero all solids contain some
vacancies; the higher the temperature,
the more the vacancies. The atom
can continue to diffuse through the
solid by a series of exchanges with
vacancies that appears to be adjacent
to it from time to time.
14
Vacancy diffusion is usually the diffusion
mechanism for substantially solid solutions.
In such materials the solute atoms, which are
comparable to the solvent atoms in size,
substitute the solvent atoms at their lattice
sites. Examples of substitutional solid
solutions are Cu-n alloy and Au—Ni alloy.
In interstitial diffusion an atom in a solid
jumps from an interstitial site of the lattice to
a neighboring one, as illustrated in Fig.
The atom can continue to diffuse through the
solid by a series of jumps to neighboring
interstitial sites that are unoccupied.
Interstitial diffusion is the diffusion mechanism for interstitial solid solutions.

In such materials the solute atoms, which are significantly smaller than the
solvent atoms, occupy the interstitial sites of the lattice. The most well know
example of interstitial solid solution is the iron-carbon alloy, specially, carbon
steel, in which the small carbon atoms occupy the interstitial sites of the iron
15
lattice.
Diffusion coefficients
In the so-called self-diffusion experiment, a solute A in the form of a radio-
active isotope, such as Ni, is allowed to diffuse through the lattice of a non-
radioactive solid of the same material, Ni. The diffusion coefficient DA is known
as the self-diffusion coefficient, in view of the absence of a chemical
composition gradient as the driving force for diffusion.
In practical situations, however, diffusion usually occurs under the influence
of a chemical composition gradient, such as the diffusion of carbon in steel
from a higher-carbon-concentration region to the lower one. This diffusion
coefficient DA is known as the intrinsic diffusion coefficient. The so-called
interdiffusion coefficient D is often used to describe situations involving the
interdiffusion of two different chemical species, such as Au into Ni and Ni into
Au as in an Au-Ni diffusion couple.
Effect of temperature
The diffusion coefficient has been observed to increase with increasing
temperature according to the following Arrhenius equation:
D  D0eQ / RT
Where D: diffusion coefficient; D0: a proportional constant; Q: the active energy
R: the gas constant; T: absolute temperature 16
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 ( = 0.7 g/cm3)?
Air Pollution Engineering Manual., 1992
17
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
2010/4/28 18
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
2010/4/28 19
Adsorption Mechanism
2010/4/28 20
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  kd 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)
2010/4/28 21
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
2010/4/28 22
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.
2010/4/28 23
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?

2010/4/28 24
Fixed-Bed Adsorption System
Q: How will the OUTLET concentration

as a function of TIME look like?
2010/4/28 25
2010/4/28 26
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?
2010/4/28 27
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?
2010/4/28 28
Rotary Bed
System
Mycock et al., 1995
2010/4/28 29
Fluidized-Bed
System
Q: Benefits?
2010/4/28 Aerosol & Particulate Research Lab 30

Pressure Drop
Pg 3d p  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
2010/4/28 31
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
2010/4/28 32
Other Systems: Nongenerable
Canister adsorber
Thin-bed adsorber
Q: What need to be known to start the design of an adsorption

bed system?
2010/4/28 Mycock et al., 1995 33
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?
2010/4/28 34
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.
2010/4/28 35
2010/4/28 36
I II III IV V
Ve locity 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  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
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
2010/4/28 37

Adsorption

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Adsorption

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Adsorption

• Physical vs chemical adsorption

Diffusion and convection

Eqs. can be expressed in a vector form as follows:

Diffusion boundary layer

Because of the effect of diffusion, the concentration of the fluid in the

Where the local molar average velocity

Substituting Eq. we have

Substituting Eqs, we have

Notice that the numerator is the species mass flow rate. 12

and for flow through a tube

Where the average concentration is defined as follows

In vacancy diffusion an atom in a solid

Interstitial diffusion is the diffusion mechanism for interstitial solid solutions.

H2O H2O H2O

Properties of Molecular Sieves

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

Q: Calculate the equilibrium adsorptivity of 1000 ppm toluene in

Q: How can we adjust the system to reduce the impact of humidity?

Q: How will the OUTLET concentration

Q: In addition to steam, what else can we use?

Mycock et al., 1995

2010/4/28 Aerosol & Particulate Research Lab 30

Typical operating range:

Minimum Adsorbent Bed Depth

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

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