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Chemical Reaction Engineering II

This chapter discusses diffusion and reaction processes in porous catalysts. It covers diffusion and reactions in spherical catalyst pellets, including the effective diffusivity and internal effectiveness factor. It also addresses mass transfer and reactions in packed beds. The key concepts covered are Thiele modulus, Weisz-Prater criterion, and how internal diffusion limitations can lead to falsified kinetics if not properly accounted for in kinetic measurements.

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Sasmilah Kandsamy
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79 views

Chemical Reaction Engineering II

This chapter discusses diffusion and reaction processes in porous catalysts. It covers diffusion and reactions in spherical catalyst pellets, including the effective diffusivity and internal effectiveness factor. It also addresses mass transfer and reactions in packed beds. The key concepts covered are Thiele modulus, Weisz-Prater criterion, and how internal diffusion limitations can lead to falsified kinetics if not properly accounted for in kinetic measurements.

Uploaded by

Sasmilah Kandsamy
Copyright
© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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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
(4r2)
– 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
THANK YOU

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