Chemical Reaction
Engineering II
Diffusion and Reaction in
Porous Catalyst
3.0 Diffusion and Reaction in
Porous Catalysts
3.1 Diffusion and reaction in spherical
catalyst pellet
3.2 Internal effectiveness factor
3.3 Falsified kinetics
3.4 Mass transfer and reaction in a
packed bed
3.5 Determination of limiting situation
from reaction data.
Outcome of Chapter 3
The student should be able to:-
Describe diffusion and reactions in
porous catalyst.
Define the Thiele modules and the
effectiveness factor.
Describe the regions of reaction
limitations and internal diffusion
limitations and the conditions that
affect them.
Steps in Catalytic Reaction
Steps in Catalytic Reaction
1. Mass transfer (diffusion) of the reactant(s) from the bulk fluid
to the external surface of the catalyst pellet
2. Diffusion of the reactant from the pore mouth through
the catalyst pores to the immediate vicinity of the
internal catalytic surface
3. Adsorption of reactant A onto the catalytic surface
4. Reaction on the surface of the catalyst
5. Desorption of the products from the surface
6. Diffusion of the products from the interior of the pellet to
the pore mouth at the external surface
7. Mass transfer of the products from the external pellet surface to
the bulk fluid
3.1 Diffusion and reaction in
spherical catalyst pellet
The pores in the pellet are
not straight & cylindrical.
Radial variations in the
concentration generalize
the effective diffusivity.
– WAr based on total area
normal to diffusion transport
(4r2)
– WAr = JAr (no bulk flow!!!)
Effective
= - De x Fn[CA. r] Diffusivity
3.1.1 Effective Diffusivity
Knudsen Diffusivity
DAB p c Dk p c
De ~
~
where
~ Actual distance a molecule travels btw 2 points
tortousity
Shortest distance btw 2 points
Volume of void space
p pellet porosity
Total volume (voids and solids)
c Constriction factor
Modeling Diffusion with
Chemical Reaction
Step 1: Define the problem and state the assumptions
Step 2: Define the system on which the balances are to be made
Step 3: Perform the differential mole balance on a particular
species
Step 4: Obtain a differential equation in WA by rearranging your
balance equation properly and taking the limit as the
volume of the element goes to zero
Step 5: Substitute the appropriate expression involving the
concentration gradient for WA from sec 11.2 to obtain a
second-order differential equation for the concentration of A
Modeling Diffusion with
Chemical Reaction
Step 6: Express the reaction rate rA in terms of concentration and
substitute into a differential equation
Step 7: State the appropriate boundary and initial conditions
Step 8: Put the differential equations and boundary conditions in
dimensionless form
Step 9: Solve the resulting differential equation for the concentration
profile
Step 10: Differentiate the concentration profile to obtain an expression
for the molar flux of A
Step 11: Substitute numerical values for symbols
3.1.2 Derivation of the Differential
Equation ~ Diffusion and Reaction
d (WAr r 2 ) Molar flux reaction
rA c r 2 0 EQUALS TO
dr molar flux diffusion
Fn[CA, r]
dy A dC A
WAr cDe De
dr dr
=r+Δr
Boundary
d [ De (dC A / dr )r 2 ] conditions
rA c r 2 0
dr
Order of -rA=c(-r’A)
reaction?
Let’s simply consider 1 order st
d [ De (dC A / dr )r 2 ]
rA c r 2 0 c(-r’A) =-rA
dr -rA=kCA
d [ De (dC A / dr )r 2 ] Differentiation &
r 2k1C A 0
dr Divide by –r2De
What about n-th order ?
d [ De (dC A / dr )r 2 ] Differentiation &
r 2k nC An 0 Divide by –r2De
dr
Let’s simply consider 1st order
d 2C A 2 dC A k1
2
CA 0
dr r dr De
What about n-th order ?
d 2C A 2 dC A k n n
2
CA 0
dr r dr De
3.1.3 Dimensionless Form of the
Equation
Dimensionless symbol was normally
introduced to
– Reduce complexity in equation
– Simplify operation of calculation
– Scale-up the reactor
= CA/CAs and =r/R
When
CA=CAs at r=R, =1 and =1
CA=finite at r=0, =finite and =0
Dimensionless eq – 1st order
d 2C A 2 dC A k1 d 2 2 d 2
CA 0 1 0
dr 2
r dr De d 2
r dr
Thiele
Module
k1 R 2
De
About for n-th order ?
d 2C A 2 dC A k n n d 2 2 d 2 n
CA 0 n 0
d
2 2
dr r dr De r dr
n 1
Thiele k n R 2C As
Module
De
Thiele Modulus, n
2 n 1 n
k R C k RC " a" surface reaction rate
n
2 n As
n As
De De [(C As 0) / R] " a" diffusion rate
•If n is large – internal diffusion limits the overall rate
•If n is small – the surface reaction limits the overall rate
C A 1 sinh 1
CA/CAs
C As sinh 1 Small n
Medium n
Large n
R r=0
3.2 Internal Effectiveness Factor
Internal
effectiveness
Actual overall rate of reaction
Factor, is:- Rate of reaction that would result if entire interior surface were
exposed to the external pellet surface conditions C As , Ts
Ranged 0 – 1 rA rA' rA"
"
rAs rAs rAs
'
for a first-order
reaction in a 3
spherical catalyst 2 1 coth 1 1
1
pellet
3.2 Internal Effectiveness Factor
Sphere pellet
Zero order
second order First order
Weisz Prater Criterion
Tocheck the internal diffusion
resistance
Cwp= 2 <1
Internal diffusion resistance is
negligible.
3.3 Falsified Kinetics
= Measurement of the apparent reaction
order and activation energy results primarily
when internal diffusion limitations are
present.
This becomes serious if the catalyst pellet
shape and size between lab (apparent) and
real reactor (true) regime were TOO
different.
Smaller catalyst pellet reduces the
diffusion limitation?
Higher activation energy more
temperature sensitive RUNAWAY
REACTION CONDITIONS!!!!
3.3 Falsified Kinetics
• Apostrophe/ prime sign denotes the apparent parameter vice
versa
• With the same rate of production, reaction order and activation
energy to be measured
3 2 De 1/ 2 ( n 1) / 2 1 n
rA' k n C As k n' C As
n'
R n 1 n'
2
E
E '
2
Rate of reaction, -rA’
= (Actual overall rate of reaction)/(rate that
would result if the entire surface were exposed
to the bulk conditions, CAb, Ts)
1 k1 S a b / kc ac
"
rA" (rAb
"
) k1"C Ab
rA rA' b rA" S a b k1"C Ab S a b
3.4 Mass transfer and reaction in
a packed bed
V
Ac FA
z=0 z=L
z z+ z
Mole balance in flux form, where Ac is constant and FA = AcWAz
dWAz
rA' b 0
dz
where
dC Ab
WAz DAB C AbU and U superficial velocity
dz
hence
d 2C Ab dC Ab
A b 0
'
DAB 2
U r
dz dz
3.4 Mass transfer and reaction in a
packed bed – cont.
d 2C Ab
Axial diffusion, Da can be neglected
dz 2
when U d r' d
0 p A b p
Da U 0C Ab FA is very large
dC Ab b k " S a Remember the
so C Ab forced convection
dz U in binary external
diffusion, JA is also
neglected
Finally, the conversion for
1st order reaction pf PBR is
C Ab
X 1 1 e ( b k " S a L ) / U
C Ab 0
Example 12-4
3.5 Determination of limiting
situation from reaction data
Variation of Reaction Rate with:
Type of
Limitation Particle
Velocity Size Temperature
External
U½ (dp)-3/2 Linear
diffusion
Internal
Independent (dp)-1 Exponential
Diffusion
Surface
Independent Independent Exponential
Reaction
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