Unit 11

Diffusion and Reaction in

Porous Catalyst
fluid reactants products
C Ab
external This lecture covers:
C As = f (C Ab ) transport
• Effective diffusivity (De)
• Internal and overall
C As
internal effectiveness factor (η and W)
C A = f (C As ) diffusion
• Thiele modulus (fn)

CA • Design of PBR
adsorption desorption
- rA ' = f (C A )
rxn
solid sites

Porous catalyst pellet

 Objectives – Be able to:
• Derive the Thiele modulus.
• Derive the effectiveness factor for porous catalyst
particles.
• Use the concept of the effectiveness factor and outline
how this factor can be increased by various operation
conditions.
• Use the Thiele modulus for reactions with diffusion.
• Distinguish between internal and overall effectiveness
factor.
• Describe how the reaction rate is influenced by
parameters such as velocity, particle size and
temperature.
P-2
 Porous
catalyst Qualitative Analysis
C Ab C As CA pellet
External Internal Reactant concentration profiles
resistance resistance
around and within a porous pellet.

porous
catalyst
reaction limited
pellet
pore diffusion limited
CA b CAs
C A (x)

CA
external mass
transfer limited

P-3
-R x +R
 Remarks
• When the reactants must diffuse inside the catalyst pellet
in order to react, the concentration at the pore mouth
(CAs) could be higher than that inside the pore (CA(r)).

• Consequently, the entire catalytic surface is not accessible

to the same concentration (i.e., concentration gradient
inside the pellet).

• Therefore the rate of reaction throughout the pellet will

vary.

• To account for these variations, we introduce a parameter

known as effectiveness factor (η) to help determine the
overall reaction rate −rAꞋ in the pellet.
P-4
 Overview of Packed Bed Reactor Design
A® B
C A = f ( r, C As )
R
CA
r

C As
C Ab

PBR A catalyst pellet Porous catalyst pellet

Ac , L R , d p , ac C Ab , C As , C A
C Ab , v0 , U WAr , kc , DAB fn ,h , W
W , S a , rc , rb , f

dC Ab - rA ' = h (-rAs ' ) = h (k n ' C As

n
)
-U + rA ' r b = 0
dz - rA ' = W(-rAb ' ) = W(k n ' C Ab
n
)
P-5
Diffusion in a Porous Spherical Catalyst Pellet

The pores are not straight and cylindrical.

They are a series of tortuous, interconnecting
r paths of pore bodies and pore throats with
varying cross-sectional areas.

Effective diffusivity, De
• Average diffusion taking place at any position r in
the pellet.
• Only consider radial variations in the concentration.
• The radial flux WAr is based on the total area (voids
and solid).

P-6
 Diffusion and Reaction A® B
Porous spherical
catalyst pellet • Mole balance over the shell thickness Dr
(In at r ) - (Out at r + Δr ) + (Generation within Δr ) = 0
R
(WAr ´ 4pr 2 r ) - (WAr ´ 4pr 2 r + Dr ) + ( rA ' r c ´ 4pr 2
Dr ) = 0
Mass catalyst
C As rc = ; density of catalyst particle
Volume catalyst

r d (WAr r 2 )
- rA ' r c r 2 = 0
r + Dr dr

• Constitutive equation
C As CA dC A
EMCD WAr = - De
Internal dr
resistance

CA(r) [
d - De (dC A / dr )r 2 ]
- rA '×r c r 2 = 0
dr
P-7
 S
• Rate law (high T) - rA ' = - rA ' '× = - rA ' '×Sa
W
- rA ' ' = k n ' ' C An

V × rA = W × rA ' = S × rA ' '

Sa : The internal surface area of the catalyst per unit
mass of catalyst.
2
m /g cat

The internal surface area is much greater than

the external surface area, for example, for
porous catalyst particle with dp=1 cm, the
internal surface area might be 150 m2.
P-8
 • The units of the rate constants are:

n -1
n æ m ö
3
m
- rA ' ' = kn ' ' C A ® kn ' ' : çç ÷÷ ×
è kmol ø s
n -1
n æ m ö 3
m3
- rA ' = kn ' C A ® kn ' = Sa kn ' ' : çç ÷÷ ×
è kmol ø kg × s
n -1
æ m ö 3
1
® kn = kn ' r c = r c Sa kn ' ' : çç
n
- rA = knC A ÷÷ ×
è kmol ø s

V × rA = W × rA ' = S × rA ' '

rA = r c × rA ' = r c Sa × rA ' ' Spherical porous
catalyst pellet
P-9
 Spherical porous
[
d - De (dC A / dr )r 2 ] S
- rA '×r c r 2 = 0 - rA ' = - rA ' '× = - rA ' '×Sa
catalyst pellet

dr W
R
kn
[
d - De ( dC A / dr ) r 2 ] + r 2kn ' ' Sa r cC An = 0
dr C As

d 2C A 2 æ dC A ö k n n r
2
+ ç ÷- CA = 0
dr r è dr ø De r + Dr
C A = finite @r = 0
B.C.
C A = C As @r = R

r CA
l= ;y = dimensionless
R C As

d 2y 2 æ dy ö kn R 2C As
n -1 y = finite @l = 0
+ ç ÷ - y n
= 0 B.C. y =1 @l = 1
dl 2
l è dl ø De
Dimensionless form of equation describing
diffusion and reaction P-10
 d 2y 2 æ dy 2 n -1
ö n C As n
k R Dimensionless form
+ ç ÷- y = 0 of equation describing
dl 2
l è dl ø De diffusion and reaction

The Thiele modulus, fn

2 n -1
k R C As
fn =
2 n
De
R × k nC As
n
reaction rate
= =
De [( C As - 0) / R ] diffusion rate
• Large fn: internal diffusion limits
• Small fn: reaction limits

Symbol for porosity of packed bed is f without a subscript.

P-11
A® B - rA ' ' = k1 ' ' C A First-order reaction

d 2y 2 dy
+ - f1y = 0
2

dl 2
l dl C A 1 æ sinh f1l ö
y= = çç ÷÷
y = finite @l = 0 C As l è sinh f1 ø
B.C.
y =1 @l = 1
k1 k '' r S
f1 = R = R 1 c a (Dimensionless)
De De

The hyperbolic functions

• Hyperbolic sine: sinh x =

2
(
1 x
e - e- x )

cosh x = (e x + e - x )
1
• Hyperbolic cosine:
2
• Hyperbolic tangent: sinh x e x - e - x
tanh x = = x
cosh x e + e - x
cosh x e x + e - x
• Hyperbolic cotangent: coth x = = x
sinh x e - e - x P-12
 A® B - rA ' ' = k1 ' ' C A First-order reaction

C A 1 æ sinh f1l ö k1 k '' r S

y= = çç ÷÷ f1 = R =R 1 c a
C As l è sinh f1 ø De De

r Spherical porous
C As CA catalyst pellet
Internal
resistance

1.0 Small f1: reaction controls. A significant amount

Small f1 of reactants diffuses well into the pellet interior
without reacting.
CA
y= Medium f1
C As Large f1: internal diffusion controls. The chemical
Large f1 reaction is rapid and the reactants are consumed
very close to the external pellet surface. Very little
can penetrate into the interior of the pellet.
1 l = r/R 0
P-13
 Internal Effectiveness Factor η
1.0 Small f1
Porous
catalyst CA
C As CA pellet C As Medium f1
Internal Large f1
resistance

R r =0
actual overall rate of reaction
h=
reaction that would occur if entire surface exposed to C As

• a measure of how far the reactants diffuse into the pellet before reacting
• the relative importance of diffusion and reaction limitations

- rA - rA ' - rA ' ' - rA ´ (Volume of catalyst particle) M A

h= = = h= =
- rAs - rAs ' - rAs ' ' - rAs ´ (Volume of catalyst particle) M As

Molar reaction rate: moles per unit time

P-14
 η = f(fn)

- rA ´ (Volume of catalyst particle) M A R

h= = C As
- rAs ´ (Volume of catalyst particle) M As CA
Internal
resistance
1st order reaction
• If the entire surface was exposed to the
concentration at the external surface of the pellet

æ4 ö æ4 ö
M As = -rAs ´ ç pR 3 ÷ = k1C As ç pR 3 ÷
è3 ø è3 ø
• At steady state, the actual rate of reaction is the rate at which the
reactants diffuse into the pellet at the outer surface. ALL the
reactants that diffuse into the pellet are consumed (a black hole).
æ dC ö dψ
M A = -4πR 2 × WAr r=R = -4πR 2 ç - De A ÷ r = R = 4πRDeC As λ =1
è dr ø dλ
P-15
 1st order reaction

C A 1 æ sinh f1l ö k1 k '' r S

y= = çç ÷÷ f1 = R =R 1 c a
C As l è sinh f1 ø De De

dψ
M A = 4πRDeC As λ =1 M A = 4πRDeC As (f1 coth f1 - 1)
dλ

æ4 ö æ4 ö
M As = -rAs ´ ç pR 3 ÷ = k1C As ç pR 3 ÷
è3 ø è3 ø

MA 3
h= = 2 (f1 coth f1 - 1)
M As f1

P-16
 1st order reaction 3 k1 ' ' r c S a k
h= (f1 coth f1 - 1); f1 = R =R 1
f12 De De
Reaction
limited
¯ R ¯ f1 h ®1 Reaction-limited
1.0
Internal
3 3 De
h diffusion f1 > 20 then h = =
limited f1 R k1 ' ' r c S a
0.1 Internal-diffusion-
f1 limited

- rA 3
h= - rA = De S a r c k1 ' 'C As
- rAs R
Overall rate of reaction for a first-order,
internal-diffusion-limited reaction.
To increase rA
1.Decrease the radius R
2.Increase the temperature
3.Increase the concentration
4.Increase the surface area
P-17
For Reactions of Order n

k ' ' r S R 2 n -1
C k R 2 n -1
C As
fn =
2 n c a As
= n
De De

• For large values of the Thiele modulus,

the effectiveness factor is

1/ 2 1/ 2
æ 2 ö 3 æ 2 ö 3 De (1- n ) / 2
h =ç ÷ =ç ÷ C As
è n +1ø fn è n + 1 ø R kn

When reaction order n is greater than 1, the effectiveness factor

decreases with increasing concentration at the external pellet surface.

P-18
 Qualitative Analysis
Reactant concentration profiles around and within a porous pellet.

porous
catalyst
reaction limited
pellet
pore diffusion limited
CA b CAs
C A (x)

CA
external mass
transfer limited

P-19
-R x +R
 Overall Effectiveness Factor W
actual overall rate of reaction
W=
reaction that would occur if entire surface exposed to C Ab

Porous
catalyst
C Ab
External
C As CA
Internal
pellet
- rA ' ' = W(-rAb ' ' )
resistance resistance

Both internal and external

diffusion are important

1st order reaction h

W=
1 + hk1 ' ' S a r b / kc ac
Mass catalyst
rb = = r c (1 - f ); bulk density of bed
Reactor volume
P-20
 Overview of Packed Bed Reactor Design
A® B

R
CA

C As
C Ab

PBR A catalyst pellet Porous catalyst pellet

Ac , L R , d p , ac C Ab , C As , C A
C Ab , v0 , U WAr , kc , DAB fn ,h , W
W , S a , rc , rb , f

dC Ab - rA ' = h (-rAs ' ) = h (k n ' C As

n
)
-U + rA ' r b = 0
dz - rA ' = W(-rAb ' ) = W(k n ' C Ab
n
)
P-21
Mass Transfer and Reaction in a Packed-Bed
Ac

C Ab 0 C AbL Porous catalyst

pellet

z=0 z z + Dz z=L

A steady-state mole balance on reactant A

In – Out + Generation = Accumulation

FAz z - FAz z + Dz + rA ' '×Sa × r b ( Ac Dz ) = 0

1 æ dFAz ö
- ç ÷ + rA ' '×Sa r b = 0 (1)
Ac è dz ø
Molar flow rate of A in the axial direction FAz = AcU × C Ab
(ideal plug flow):
substitute in (1)

dC Ab
-U + rA ' '×Sa r b = 0
P-22 dz
 dC Ab
-U + rA ' '×Sa r b = 0
dz
Overall rate of reaction per
unit surface of catalyst
Recall - rA ' ' = -rAb ' '´W
For first-order reaction

- rA ' ' = Wk1 ' ' C Ab

Therefore dC Ab
-U - Wr b k1 ' ' S a C Ab = 0
dz
C Ab = C Ab 0 @z = 0

C Ab = C Ab 0 e - ( rb k1 ''S a W× z ) / U
h 3 k1 ' ' r c S a
W= h = 2 (f1 coth f1 - 1); f1 = R
1 + hk1 ' ' S a r b / kc ac f1 De
P-23
 For first-order reaction

Ac

C Ab 0 C AbL
C Ab = C Ab 0 e - ( rb k1 ''S a W× z ) / U
z=0 z z + Dz z=L

Porous

X = 1 - e - ( rb k1 ''S a W×L ) / U
catalyst
C Ab C As CA pellet
External Internal
resistance resistance h
W=
1 + hk1 ' ' S a r b / kc ac

3 k1 ' ' r c S a k
h= (f1 coth f1 - 1); f1 = R =R 1
f12 De De

P-24
 Dependence of Reaction Rate on dP
(1st order reaction)
External mass transfer-limited

- rA = -rA ' '×ac = kc ac C Ab 1

- rA ' ' ac µ
2/3
DAB U 1/ 2 1 d P3 / 2
k c µ 1/ 6 ´ 1/ 2 ac µ
n dp dp

Internal mass transfer-limited

3
- rA = h × (-rAb ) = (-rAb ) 1
f1 - rA µ
k1 dP
f1 = R
De
Reaction-limited
- rA = k1C Ab - rA ¹ f (d P )
P-25
Dependence of Reaction Rate on dP, U, and T
(1st order reaction)

External diffusion Internal diffusion Reaction-limited

2/3
DAB U 1/ 2 3
k c µ 1/ 6 ´ 1/ 2 - rA = De k1 C As - rA = k1C Ab
n dp R
® kc µ U 1/ 2T 11/12
P-26
 For 1st order surface reaction in spherical porous catalysts

rate without any

diffusion effects

- rA ' ' = k1 ' ' C As ×h 3

…with… h= (f1 coth f1 - 1) • Effectiveness factor, a fudge
f
1
2
factor which varies between 0
and 1, and which accounts for
the resistance to pore diffusion.

k1 ' ' r c S a • Thiele modulus, useful for

…where… f1 = R
De predicting reactor behavior
from known kinetic information,
thus known k.
• Effective diffusion coefficient
in porous solids.

P-27
Summary
• Scheme of surface reaction kinetics
• The Thiele modulus for porous spheres
A® B f =2
n -1
k n R 2C As
=
R × k n C As
n
=
reaction rate
n
De De [( C As - 0) / R ] diffusion rate

fluid reactants products

• The effectiveness factors
external
transport actual overall rate of reaction
h=
reaction that would occur if entire surface exposed to C As

actual overall rate of reaction

W=
reaction that would occur if entire surface exposed to C Ab
Internal
diffusion
• For large values of Thiele modulus
1/ 2
æ 2 ö 3
h =ç ÷
è n +1ø fn
adsorption desorption

rxn
solid sites

P-28