Topics Covered
Adsorbents
Equilibrium isotherms
Adsorption Processes Kinetic and transport considerations
Sorption systems
Process Integration and Unit Temperature and pressure swing processes
Operations
Prof. Joe Wood
1
1/31/2013
2
1/31/2013
Commercial Adsorbents
Types of Adsorption Adsorbent Nature Pore
diameter
Particle
porosity
Particle
Density
Surface
Area
Capacity
for H2O
p p kg m-3 m2g-1 Vap. wt %*
Activated Hydrophilic 10-75 0.5 1.25 320 7
Physisorption Chemisorption alumina amorphous
Van der Waals forces Chemical bond between Silica gel Hydrophilic/
May be more than one layer Small pore Hydrophobic 22-26 0.47 1.09 750 850 11
adsorbate and surface Large pore amorphous 100-150 0.71 0.62 300 350
thick
Monolayer thickness Activated Hydrophobic
Similar to condensation
Heat release can be much carbon amorphous
Heat is released upon Small pore 10-25 0.4-0.6 0.5 0.9 400 1200 1
condensation larger than heat of Large pore >30 0.6 0.8 200 600
Heat of adsorption can be vapourisation Molecular Hydrophobic 2 10 0.98 400
greater or less than heat of Chemisorption from a gas sieve
vapourisation carbon
occurs above 200 C
Important for commercial Zeolites Polar- 3 10 0.2 0.5 600-700 20 - 25
adsorbents Important in catalysis hydrophilic
crystalline
Polymeric 40 - 25 0.4 0.55 80-700
adsorbent
3
1/31/2013
4
1/31/2013
5
1/31/2013
q = kp q = kp1/ n
Where k and n are empirical constants
Converting to linear form
q = equilibrium loading of amount
adsorbed/unit mass of adsorbent log q = log k + (1 / n ) log p
intercept slope
k = empirical experimentally determined
constant (varies with T) Derivation assumes a heterogeneous surface with a non-uniform
distribution of heat of adsorption over the surface
P = partial pressure of gas
6
1/31/2013
dQ Heat transfer
q= = hA(Ts Tb ) coefficient
dt
hD p
Nu =
k
Thermal
conductivity
7
1/31/2013
j D = St M Sc 2 / 3 = f (Re )
C p uD p GD p
Pr = Sc = Re = = j H = St Pr 2 / 3 = f (Re )
k Di
Different functions of Reynolds number apply for different regions
Heat transfer coefficient Mass transfer coefficient
Stanton number
St =
h Stanton number kc
for heat transfer for mass transfer St M =
C pG G
Specific heat capacity Fluid mass velocity Fluid density
0 .6 1/ 3
hd p d G C p
Nu = = 2 + 1.1 p
k k
8
1/31/2013
c q c
4 (r + r ) De
2
= 4r 2 r + 4r 2
r r + r t r r
Effective Amount adsorbed
diffusivity per unit vol of pellet
Dividing by 4rr, taking the limit as r0, and collecting terms gives:
2 c 2 c q
De 2 + +
r r r t
9
1/31/2013
10
1/31/2013
11
1/31/2013
cF Q = cQ + qS
q = Instantaneous adsorbent loading
Equilibrium conc.
c* = q / k
Continuous Adsorption in a CSTR
Analytical integration gives
When both liquid and solids flow through a vessel, the
cF residence time is found from:
c= [exp( k L at ) + ] c + k L at res c*
cout = F
1 + k L at res
Where
Q Q Or rearranging
= = 1+ cF cout
(
= k L a cout c* )
Sk Sk t res
12
1/31/2013
tideal, the time for an ideal front to reach Lideal. LES is Length of
equilibrium section Real Fixed Bed Breakthrough Curve
Q c t
QF cF tideal = qF SLideal / LB Lideal = LES = F F ideal LB
qF S In the real fixed bed the above assumptions
Length of unused bed
are not valid
LUB = LB LES Internal and external transport, and axial
Weight of equilibrium section dispersion influence the process
LES
WES = S These factors contribute to the development
LB of a broader concentration front moving
Weight of unused bed
QF = volumetric flowrate of feed
through the bed
WUB = S WES cF = conc. Solute in feed
qF = loading per unit mass of This is called a breakthrough curve
adsorbent in equilibrium with
feed concentration
S = total mass of adsorbent
13
1/31/2013
Breakthrough
point
Summary
In this lecture we have covered
Adsorption isotherms
External mass transfer
Transport in porous pellets
Liquid and gas phase adsorption
Batch adsorption
Fixed bed adsorption
Temperature and pressure swing processes
14