L 29-Heterogeneous Catalysis and

Reactor Design

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
 Diffusion and Reaction in a spherical pellet
(Reading assignment: Fogler, Ch 12))
In – out – disappearance =0 (spherical shell balance)

WAr (4 πr2)r - WAr (4 πr2)r+∆ r - rA’ (4 πr2 c ∆r) =0

Dividing by -4 π ∆ r
Moles = WAr (4 πr2)r
d (WAr r 2 )
 rA c r 2  0
dr
dy A dC A
WAr  cDe   De
dr dr Molar flux

=r+Δr
d[ De (dC A / dr )r 2 ]
 rA c r 2  0
dr r=0, CA finite, r=R, CA=CAS

-rA=c(-r’A) Boundary
conditions
 consider 1st order

d[ De (dC A / dr )r ]
2

 rA c r  0
2

dr
c(-r’A) =-rA
-rA=kCA
d [ De (dC A / dr )r 2 ] 2
 r k1C A  0
dr Differentiation &
Divide by –r2De

What about n-th order ? 

d [ De (dC A / dr )r 2 ] 2 Differentiation &
 r knC An  0 Divide by –r2De
dr
 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   d 
2

Thiele
Module k1 R 2
De
About for n-th order ?
d C A 2  dC A  kn n
2
d 2
 2  d  2 n
    CA  0     n  0
dr 2
r  dr  De d   d 
2

n 1
Thiele k n R 2C As
Module De
 d 2 2  d 
    1  0
2

d 2
  d 
Y =  , , =>= y/ 
d/ d = 1/ (dy/d)- y/ 2

d2/ d2 = 1/ (d2y/d2)- 2/ 2 dy/d + 2y/3

d2y/d 2 - ø2y=0
y= A Cosh ø  + B Sinh ø 
A=0 as φ must be finite at the centre,
(B. C. =0, coshø 1; and
Sinh ø 0.
And at =1, =1,=> B= 1/Sinh ø

Thus , = CA/CAs = 1/  [Sinh ø  / Sinh ø]

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 Thiele Modulus, n
2 n-1 n
k R C k RC "a" surface reaction rate
φn =
2 n As
= n As
=
De De [(CAs - 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 1  sinhφ λ 
ψ= A
= 
1

CAs λ  sinhφ1 
 Internal Effectiveness Factor
Actual overall rate of reaction
η=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions C As ,Ts
• Internal
effectiveness -rA -rA' -rA"
η= = ' = "
Factor,  is: -rAs -rAs -rAs
ranged 0 – 1
•  for a first-order 3
η = 2  φ1cothφ1 -1
reaction in a φ1
spherical catalyst
pellet
 Calculation of Catalytic Effectiveness Factor

η = Actual overall rate(RA /Rate in the absence of diffusion resistance (RAs )

Global rate RA = 4 πR2 De (dCA/dr) at r=R

Or RA = 4 πR De (d  /d ) at  =1

((d  /d  )at  =1 = (ø cot h ø-1)

RA = 4 πR De CAS (ø cot h ø-1) Global Rate.

Thus η = [4 πR De CAS (ø cot h ø-1)] / k’ ρc CAS 4/3 πR 3

 η = 3 (ø cot h ø-1)/ k’ ρc R2/De R

 η = 3 (ø cot h ø-1)/ ø2
for ø> 20, η= 3/ ø strong pore diffusion resistance

  3 (Coth  1 )
 
 Calculation of Catalytic Effectiveness Factor
Catalytic Effectiveness Factor:

  1 (Coth3  1 )
where  3
- Thiele Modulus
1st order reaction rate:
  R kSap / De
Spherical Pellet 3
Cylindrical Pellet  R kSap / De
2
Slab Pellet

  L kSap / De
Internal Effectiveness Factor
 Weisz – Prater Criterion for internal diffusion
Uses the measured values of the rate of reaction to
determine if Internal diffusion controls the rate.

Weisz-Prater Parameter CWP

ηø2 = 3(Ø Coth Ø-1)
ηø2 = (observed rate/rate cal. at CAS) x (rate
calculated at CAS) / diffusion Rate)

η = (-r’A(obs)/ -r’As

Ø2= -r”AS Sa ρp R2/De CAs = -r’AS ρp R2/De CAs

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CWP= (-r’A(obs)/ -r’As )(-r’AS ρp R2/De CAS)

 CWP = (-r’A(obs) (ρp R2/De CAS)

 These are measured or known terms.

 if CWP << 1, No diffusion limitations and

no concentration gradient exists in the pellet.

CWP >> 1, Internal diffusion limits the rate.

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 Non isothermal pellet Energy balance

Energy balance

d[ De (dC A / dr )r ]
2
Mass Balance

 rA c r  0
2

dr

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Non isothermal pellet effectiveness factor

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 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!!!!
 Falsified Kinetics
• With the same rate of production, reaction order and
activation energy to be measured (apparent rate)
Overall effectiveness factor (Both internal and external
diffusion are important

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Overall Effectiveness Factor
At Steady state, Moles transported from bulk fluid to the
external surface of the Catalyst (WAr Ap )= Net Rate of
reaction with in and on the pellet,
MA = WAr Ap = -r”A(As+ Ap),=( Molar Flux x Ext. Surface
Area of pellet)
For a single spherical pellet of Radius R,
AP= 4π R2, and As= SA x mass of pellet,(As >>Ap)
AP = (ext. SA/reactor volume) (reactor volume) = ac ∆V
As= (int. SA/.mass of catalyst) (mass cat./vol. cat) (vol
cat/reactor vol.) . Rect vol.) => AS= SA ρ c (1- ø) ∆V
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