CEB2093

REACTION ENGINEERING II

SOLID CATALYZED REACTION

Content prepared by: Dr Mohd Hizami Mohd Yusoff Prof Ir Dr Suzana Yusup
Edited by: AP Dr Suriati Sufian

1
 Topics:
Reaction kinetics (Fogler, pp.666-688)
i. The idea of the rate controlling step
ii. Adsorption controlling
iii. Surface reaction controlling
iv. Desorption controlling
Pore diffusion resistance (Levenspiel, pp.381-387)
i. The Fick’s first law
ii. Effects of porosity and tortuosity
iii. Molecular diffusion and Knudsen diffusion
iv. The transition region
v. Pore diffusion resistance combined with reaction
vi. Pore diffusion/reaction in non-isothermal case
Temperature dependence of rate of reaction
Heterogeneous catalyst reactor
Catalyst deactivation (Fogler, p.650, pp.717)
i. Poisoning
ii. Sintering
iii. Coking
 Learning Outcomes

By the end of this topic, student should be able to:

1. Explain the mechanism involved in catalytic reaction
2. Evaluate the activation energy
3. Evaluate the performance of catalyst in plug flow
reactor
4. Understand the mechanism involved in catalyst
deactivation
Reaction Kinetics
Steps in a Catalytic Reaction

Since steps 1, 2,6 & 7 are fast, only steps 3, 4 and 5

need to be considered
 Steps in a Catalytic Reaction

1. Mass transfer (diffusion) of the reactants (e.g. species A) 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 (e.g. A →B)
5. Desorption of the product from the surface
6. Diffusion of the product 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.
 Steps in a Catalytic Reaction

Let the reaction follows the mechanism below:

Adsorption of reactant A on surface vacant site S

Adsorption of reactant B on surface vacant site S

Surface reaction between adsorbed A and B

Desorption of product C from surface creating a
vacant site
Desorption of product D from surface creating a
vacant site
 Adsorption Step
The adsorption of A (gas phase) on a active site S is represented by:

• Rate is proportional to number of collision with surface, which is

a function of PA
• Rate is proportional to number of vacant (active site), Cv on the
surface
• Active site: site on surface that can form a strong bond with
adsorbed species
 Surface Reaction Step
After the molecule is adsorbed onto the surface, it can react by a few different
mechanism

1. Single site mechanism: Only the site to which the reactant is absorbed
is involved in the reaction

For example, an adsorbed molecule of A may be isomerize (decompose)

directly on the site to which it is attached

N = n-pentene i = i-pentene
 Surface Reaction Step
2. Dual site mechanism: Adsorbed reactant interacts
with another vacant site to form the product

For example, adsorbed A may react with an adjacent vacant site to yield a
vacant site and a site on which the product is adsorbed, such as dehydration
of butanol.
C4H
C4 H2
9 OH
H8 O
 Surface Reaction Step
3. Eley-Rideal mechanism: reaction between adsorbed
reactant and a molecule in the gas phase

For example, reaction of propylene and benzene

C3H6 C3H6
Desorption Step
 Overall Steps
Adsorption of A
Catalytic active site
kA
A+S k-A
AS Product
Reactant
Surface catalytic reaction B
kS A
AS k-S
BS
A B
Desorption of B
kD S S S S S S

BS B+S
k-D CAS CBS
Overall reaction

A → B Cv Vacant or
unoccupied site
CiS: surface concentration of sites occupied by species i
[mol/kg-catalyst]
Ct: total surface concentration of sites [mol/kg-catalyst] Ct = Cv + CAS+CBS
Cv: surface concentration of vacant sites [mol/kg-catalyst]
Pi: partial pressure of species i [Pa]
 Overall Steps
Adsorption of A
kA  C AS  kA
A+S AS rA = k A PACv − k− AC AS = k A  PACv −  KA =
 KA  k− A
k-A
Surface catalytic reaction
 CBS  kS
kS
rS = k S C AS − k− S CBS = k S  C AS −  KS =
AS k-S
BS  KS  k−S

Desorption of B
kD  PBCv  kD
BS B+S 
rD = k DCBS − k− D PBCv = k D  CBS −  KD =
k-D  KD  k− D
Overall reaction

A → B rA, rS, rD: adsorption, reaction or desorption rate [mol/kg-cat·s]

kA: rate constant of adsorption of A [Pa-1 s-1]
CiS: surface concentration of sites occupied by species i k-A: rate constant of reverse adsorption of A [s-1]
[mol/kg-catalyst] kS: rate constant of surface reaction
Ct: total surface concentration of sites [mol/kg-catalyst] k-S: rate constant of reverse surface reaction
Cv: surface concentration of vacant sites [mol/kg-catalyst] kD: rate constant of desorption of B
Pi: partial pressure of species i [Pa] k-D: rate constant of reverse desorption of B
 Rate Controlling Steps
When catalytic reactions are carried out at steady state:
Or
− rR = rA = rS = rD
 C AS   CBS   PBCv 
k A  PACv −  = k S  C AS −  = k D  CBS −  kA is smaller than
 KA   KS   KD  kS and kD.

Not equal Practically equal (slightly plus)

There three possibilities:
A B A B A B
AS BS AS BS AS BS
Adsorption controlling Surface reaction controlling Desorption controlling

Not at equilibrium
At equilibrium
 Adsorption Controlling

 C AS 
− rR = rA = k A PACv − k− AC AS = k A  PACv − 
 KA 
CBS
C AS − =0
KS

PBCv
CBS − =0
KD
Cv + C AS + CBS = Ct

Ct k A PA − PB /( K A K S K D ) k ' A ( PA − K ' PB )

− rR = =
1 + 1 / K D + 1 /( K S K D )PB 1 + K ' ' PB
 Adsorption Controlling
(Irreversible)
− rR = rA = k A PACv

CBS
C AS − =0
KS

PBCv
CBS − =0
KD
Cv + C AS + CBS = Ct

Ct k A PA k ' A PA
− rR = =
1 + 1 / K D + 1 /( K S K D )PB 1 + K ' ' PB
 Surface Reaction Controlling

 CBS 
− rR = rS = k S C AS − k− S CBS = k S  C AS − 
 KS 

Cv + C AS + CBS = Ct

Ct k S K A PA − PB /( K S K D )
− rR =
1 + K A PA + PB / K D
 Surface Reaction Controlling
(irreversible and low CBS)
− rR = rS = k S C AS

Cv + C AS = Ct

Ct k S K A PA
− rR =
1 + K A PA
 Desorption Controlling

 PBCv 
− rR = rD = k DCBS − k− D PBCv = k D  CBS − 
 KD 

Cv + C AS + CBS = Ct

Ct k D ( K S K A PA − PB / K D )
− rR =
1 + K A PA + K S K A PA
 Desorption Controlling
(Irreversible)

− rR = rD = k DCBS

Ct k D K S K A PA K ' PA
− rR = =
1 + K A PA + K S K A PA 1 + K " PA
 Decomposition of Cumene

C 6 H 5 CH (CH 3 )2 → C 3 H 6 + C 3 H 6
C B P

3 STEPS REPRESENT THE MECHANISME FOR CUMENE DECOMPOSITION

C•S  B•S + P

C
C +S C•S P B•S  B+ S P
C B B

catalyst catalyst catalyst catalyst

Adsorption of Surface reaction to form Desorption of
cumene on the adsorbed benzene & benzene from
surface propylene in the gas surface
phase
Which one is Rate Limiting/Controlling Step???
Adsorption rAD = k A PC CV − k • A CC•S
C +S C•S 
kA C C •S 
Kc = rAD = k A  PC CV − 

k•A  K C 

Surface Reaction rS = k S CC•S − k •S PP C B•S

C•S  B•S + P kS  PP C B•S 
KS = rS = k S  CC•S − 
k •S 
 KS 

Desorption rD = k D PB•S − k •D PB CV
B•S  B+ S KB =
1
K DB rD = k D (C B•S − K B PB CV )
 If Adsorption is Controlling
C +S C•S
The rate of adsorption :

 C C •S 
rAD = k A  PC CV − 

 K C 

Assumption For Adsorption Limited Reaction ;

✓Rate constant for this step (kA) is SMALL with respect to the
specific rates of other steps (kS and kD).
✓Ratio rS/kS and rD/kD very SMALL (approximately 0)
✓Ratio rAD/kA is LARGE
 If Adsorption is Controlling
The rate of adsorption :  CC•S  ….(1)
rAD = k A  PC CV − 

 K C 

For steady state operation :− rC ' = rAD = rS = rD ….(2)

 PP C B•S  ….(3)
The surface reaction rate expression is :rS = k S  CC•S − 
 
 K S 
For adsorption limited reaction, kS is large…..so, we set ; rS
= 0 ….(4)
kS
Thus, rS  PP C B•S 
=  CC•S − =0
kS  K S 
PP C B•S We evaluate CB.S to express CC.S
C C •S = ….(5)
in term of partial pressure
KS
 If Adsorption is Controlling

The desorption rate expression is : rD = k D (C B•S − K B PB CV ) ….(6)

For adsorption limited reaction, kD is large…..so, we set ; rD

= 0 ….(7)
kD
Thus, rD
= (C B•S − K B PB CV ) = 0
kD
C B•S = K B PB CV ….(8)

Combine (5) and (8),

K B PB PP CV
C C •S = ….(9)
KS
 If Adsorption is Controlling
We know that…
 C C •S 
rAD = k A  PC CV − 

 K C 

Substitute (9) in above equation;

 K B PB CV PP  This terms is simply the overall

rAD = k A  PC CV − 
 partial pressure equilibrium
 K S K C  constant for this reaction.
C  B+P
 K B PB PP 
rAD = k A CV  PC − 

 K S K C 
Where…
 PB PP  ….(10) KP =
K S KC
rAD = k A CV  PC − 
KB
….(11)
 K P 
 If Adsorption is Controlling

To eliminate Cv, we use SITE BALANCE, Ct = Cv + CC.S. + CB.S ….(12)

Vacant Occupied Site

Substitute (8) and (9) in (12)…….. Site (cumene &
benzene adsorb
K B PB CV PP
Ct = CV + + K B PB CV on the surface)
KS
Solving for Cv,

Ct = CV (1 + + K B PB )
K B PB PP
KS
Ct
Thus…CV = ….(13)
K B P B PP
1+ + K B PB
KS
 If Adsorption is Controlling

Now, substitute (13) in (10)……..  PB PP 

rAD = k ACV  PC − 
 KP 
 
 
rAD = kA  Ct  P − PB PP 

 K B PB PP  C
 1+ + K B PB   KP 
Thus…  KS 
k ACt ( PC − PS PP / K P )
− rc ' = rAD = ….(14)
1 + K B PB PP / K S + K B PB
 If Adsorption is Controlling
Now, we wish to sketch a plot of the initial rate as a function of partial pressure of
cumene,Pco Initially, no product are present, so… P = P = 0 p B

k ACt ( PC − PS PP / K P )
Thus, the initial rate, − rc ' = rAD =
1 + K B PB PP / K S + K B PB
If the cumene decomposition
−rCO ' = k A Ct PCO = kPCO is ADSORPTION
CONTROLLING, then the initial
initial rate, − rCO ' rate will be linear with the
initial partial pressure of
cumene

initial partial pressure of cumene,Pco

 If Surface Reaction is Controlling

C•S  B•S + P
The rate of SURFACE REACTION :  PP C B•S 
rS = k S  CC•S −  ….(1)

 KS 
Since we cannot readily measure the conc of the adsorbed species, we must utilize the
adsorption & desorption step to eliminate CC.S and CB.S from this equation.

Assumption For SURFACE REACTION Limited Reaction ;

✓Rate constant for kA is LARGE (rAD)
✓Rate constant for kD is LARGE (rD)
✓Rate constant for kS is SMALL (rAD)
✓Ratio rAD/kA and rD/kD very SMALL (approximately 0)
✓Ratio rS/kS is LARGE
 If Surface Reaction is Controlling

 CC•S  ….(2)
The adsorption rate expression is : rAD = k A  PC CV − 

 K C 

For adsorption limited reaction, kA is large…..so,; rAD

=0 ….(3)
Thus, kA
rAD CC . S
= PC CV −
kA KC
CC .S
0 = PC CV −
KC
CC . S = K C PC CV ….(4)
 If Surface Reaction is Controlling

The desorption rate expression is : rD = k D (C B•S − K B PB CV ) ….(5)

For SURFACE REACTION limited reaction, kD is large…..so, we set ;

rD
= 0 ….(6)
kD
= (C B•S − K B PB CV ) = 0
rD
So,
kD
C B•S = K B PB CV ….(7)
 If Surface Reaction is Controlling
Now, substitute (4) and (7) in (1)….
 PP C B•S 
rS = k S  CC•S − 

 K S 
 PP K B PB CV 
rS = k S  K C PC CV − 

 KS 
 PP K B PB 
rS = k S CV  K C PC − 

 K S 
We know that,,
 PP PB 
rS = k S K C CV  PC −  ….(8) K S KC
= K P ….(9)
 KP  KB
 If Surface Reaction is Controlling

Site Balance….

Ct = CV + C B•S + CC•S ….(10)

Ct = CV + K P PB CV + K C PC CV
Ct = CV (1 + K B PB + K C PC )
Ct
CV = ….(11)
1 + K B PB + K C PC
 If Surface Reaction is Controlling

Substitute (11) in (8)….

 Ct  PP PB 
rS = k S K C   PC −
 
 1 + K B PB + K C PC  KP 

k S K C Ct ( PC − PP PB / K P )
− r 'c = rS =
1 + K B PB + K C PC
 If Surface Reaction is Controlling

Now, we wish to sketch a plot of the initial rate as a function of partial

pressure of cumene,Pco
Initially, no product are present, so… Pp = PB = 0
Thus…the initial rate, k S K C Ct ( PC − PP K B / K P )
− r 'c = rS =
1 + K B PB + K C PC
k S K C Ct PCO
− r 'c = rCO =
1 + K C PCO
kPCO where,
− r 'c = rCO =
1 + K C PCO k = k S K C Ct
 If Surface Reaction is Controlling

At low partial pressure of K C PCO  1

cumene, kPCO
− r 'c = rCO =
We observed that the initial rate will increase linearly 1 + K C PCO
with the initial pressure of cumene. − rCO ' = kPCO
At high partial pressure of cumene, K C PCO  1
kPCO
− r 'c = rCO =
We observed that the initial rate 1 + K C PCO
will independent with the initial
kPCO k
pressure of cumene. − r 'c = rCO = =
K C PCO K C
 If Surface Reaction is Controlling

The initial rate of reaction as a

function of initial partial
pressure of cumene for the
case of surface reaction
initial rate, − rCO ' controlling..

initial partial pressure of cumene,Pco

 If Desorption is Controlling
B•S  B+ S
The rate of DESORPTION:

rD = k D (C B•S − K B PB CV ) ….(1)

Assumption For DESORPTION Limited Reaction ;

✓Rate constant for kA is LARGE (rAD)
✓Rate constant for kS is LARGE (rS)
✓Rate constant for kD is SMALL (rD)
✓Ratio rAD/kA and rS/kS very SMALL (approximately 0)
✓Ratio rD/kD is LARGE
 If Desorption is Controlling

 CC•S  ….(2)
The adsorption rate expression is : rAD = k A  PC CV − 

 K C 

For adsorption limited reaction, kA is large…..so,; rAD

=0 ….(3)
Thus, kA
rAD CC . S
= PC CV −
kA KC
CC .S
0 = PC CV −
KC
CC . S = K C PC CV ….(4)
 If Desorption is Controlling
The SURFACE REACTION rate expression is :
 PP C B•S 
rS = k S  CC•S − 

….(5)
 KS 
For DESORPTION limited reaction, kS is large…..so, we set ;
rS
= 0 ….(6)
kS
rS  PP C B•S 
Thus, =  CC•S − =0

KS  KS 

K S C C •S
C B• S = ….(7)
PP
 If Desorption is Controlling

Now, substitute (4) and (7) in (1)….

rD = k D (C B•S − K B PB CV )
 K S C C •S 
rD = k D  − K B PB CV 
 PP 
 K S K C Pc CV 
rD = k D  − K B PB CV  We know that,,
 PP  K S KC Gas phase
= KP
 Pc PB  KB equilibrium
rD = k D K S K C  − CV ….(8) constant
 PP K P 
 If Desorption is Controlling
Site Balance….

Ct = CV + C B•S + CC•S ….(9)

K S C C •S
Ct = CV + K c Pc CV +
PP
K S K C PC
Ct = CV (1 + K C PC + )
PP
Ct
CV = ….(10)
K S K C PC
1 + K C PC +
PP
 If Desorption is Controlling
Substitute (10) in (8)….
 
 
 PC PB  Ct 
rD = k D K C K S  − 
 
 PP K P  1 + K C PC + K C K S PC 
 PP 
 PC PB  K C K S PC
rD = k D Ct K C K S  −  / 1 + K C PC +
 PP K P  PP
 PB PP 
k D Ct K C K S  PC − 
− rC ' = rD =  K P  ….(11)
PP + K C PC PP + K C K S PC
 If Desorption is Controlling
To determine the dependence of the initial rate on partial pressure of cumene,
Initially, no product are present, so… Pp = PB = 0
So…the initial rate,  PB PP 
k D Ct K C K S  PC − 
− rCO ' = rD =  KP 
PP + K C PC PP + K C K S PC
initial rate, Initial rate independent of the
− rCO ' = rD = k D C t − rCO ' initial partial pressure of
cumene

initial partial pressure of cumene,Pco

 SURFACE Reaction is controlling
The experimental observation of –rco as a function of Pco are shown in figure..from that,
we clearly can see that either adsorption nor desorption is RATE LIMITING…
C 6 H 5 CH (CH 3 )2 → C 3 H 6 + C 3 H 6
initial rate, − rCO ' C B P

initial partial pressure of cumene,Pco

The rate law derived by assuming that SURFACE REACTION is RATE LIMITING / CONTROLLING
agrees with experimental data.
k S K C Ct ( PC − PP K B / K P ) Eley-Rideal Mechanism-reaction
− r 'c = rS = between adsorbed molecule & a
1 + K P PB + K C PC molecule in the gas phase.
 DETERMINATION OF REACTION MECHANISM
& RATE CONTROLLING STEPS
1) Select a mechanism for adsorption, surface reaction & desorption (treat each reaction step
as an elementary reaction when writing rate law)
2) Assume a rate limiting step. Choose the SURFACE REACTION first since >than 75% of all
heterogeneous reactions that are not diffusion limited are surface reaction limited.
3) Write down the rate law for surface reaction step
4) Solve concentration of adsorbed species using other step that are not limiting reaction.
(expression for adsorption & desorption rate law)
5) Assume, ratio rAD/kA and rD/kD very SMALL (approximately 0)
6) Write a site balance
7) Derive the rate law by combining step (2,3,4,5,6)
8) Compare with data experiment- if they agree, its mean you have found the correct
mechanism & rate limiting step. If not, assume a different rate limiting step and different
mechanism.
Pore Diffusion Resistance
 Pore Diffusion Resistance

• Previously, we assumed each point on the interior of catalyst surface was

accessible to the same concentration.
• However, we know there are many, many situations where this equal
accessibility will not be true.
• For example, when the reactants must diffuse inside the catalyst pellet in
order to react, we know the concentration at the pore mouth must be higher
than that inside the pore.
• Consequently, the entire catalytic surface is not accessible to the same
concentration; therefore, the rate of reaction throughout the pellet will vary.
 Thiele Modulus

Consider a single cylindrical

pore of length L, with reactant
A diffusing into the pore and
reacting on the surface by a
first-order reaction taking
place at the walls of the pore
and the product diffusing out
of the pore.
Thiele Modulus – describe the
relationship between diffusion
and reaction rate in porous
catalyst pellet.

Representation of a cylindrical catalyst

 Pore Diffusion

• For example, for a reaction;

• Occurring in inert carrier U, the rate expression when adsorption of A
control is;

• When chemical reaction between adjacent site attached molecules of

A and B control it is
 Pore Diffusion

• Each detailed mechanism of reaction with its controlling factor has its
corresponding rate equation involving anywhere from three to seven
arbitrary constants, the K values. These complicated equations shall not
be used but we shall use the contact time or space time instead.
• Pore diffusion resistance combined with surface kinetics
• First consider a single cylindrical pore of length L, with reactant A
diffusing into the pore, and reacting on the surface by a first-order
reaction taking place
 Pore Diffusion
• At the walls of the pore and the product diffusing out of the pore
• The rate is given by;

The flow of materials into and out of any section of pore (Fig. 3). At
steady state a material balance for reactant A for this elementary
• section gives output - input + disappearance by reaction = 0
 Pore Diffusion
• Or in equationn form;

• Rearranging it gives;

• Taking the limit as Δx approaches zero,

• In general, the interrelation between rate constants on different bases

is
 Pore Diffusion
• Thus for the cylindrical catalyst pore;

• In terms of volumetric units, we have

• Which is the frequently met linear differential equation whose general solution is;

• Where aand M1 and M2 are constants

 Pore Diffusion

• Here the boundary conditions have to be specified. For this system they
are two; at the entrance of the pore,
• And at the end of pore;
• With the appropriate mathematical manipulation, Figure (18.4) is
obtained;

where
• Hence the concentration of reactants within the pore is
Concentration vs Pore distance
This figure shows the
progressive drop in
concentration on
moving into the pore

For small mL, mL < 0.4, ,

the concentration of
reactant does not drop
appreciably within the
pore, thus diffusion offers
negligible resistance.

For large mL, or mL >4,

the reactant
concentration drops
rapidly to zero on moving
into the pore, hence
diffusion strongly
influences the rate of
reaction (strong pore
resistance regime)
https://www.youtube.com/watch?v=GOb1dl9hliY
Effectiveness Factor

60
 Effectiveness Factor

Fig 4: The effectiveness factor as a function of the parameter mL called the Thiele modulus
61
 Porous Catalyst Particles
1. Use of the proper diffusion coefficient.
Replace the molecular diffusion coefficient by the effective diffusion coefficient of fluid in the
porous structure.

2. Proper measure of particle size. To find the effective distance penetrated by gas to get to all the
interior surfaces we define a characteristic size of particle

3. Measures of reactions rates. In catalytic systems the rate of reaction can be expressed in
one of many equivalent ways. For example, for first-order kinetics 62
 Porous Catalyst Particles

These relationships are shown in Fig. 18.6. If you know D, k"', and L you can find the reaction rate from
MT and Fig. 18.6. However, what if you want to evaluate k from an experiment in which you measure
a rate which could have been slowed by diffusional resistance, but which you are unsure of? 63
Porous Catalyst Particles

64
Porous Catalyst Particles

65
Porous Catalyst Particles

66
Porous Catalyst at Different Shapes

67
Porous Resistance Limits

68
Porous Resistance Limits

69
Porous Resistance Limits

70
 Fick’s 1st Law

dC
J = −D
dx
J = flux [mol/(m2∙s)]
D = diffusion coefficient [m2/s]
C = concentration of diffusing species [mol/m3]
x = distance (diffusion direction) [m]
https://youtu.be/ZHhb9JFo01k
 Effects of porosity & tortuosity

n re2 L J = flux [mol/m2•s]

J porous medium = 2 J D = diffusivity [m2/s]
DK = Knudsen diffusivity [m2/s]
1 Lcurved re = pore radius [m]
T = temperature [K]
n re2 Lcurved
2
L  Lcurved  M = molecular weight
e= = n re
2
  e = porosity
12 L Lcurved  L  t = tortuosity
1m
L e Lcurved
n re2 = 2
Lcurved  Lcurved 
 
 L 

1m
e
J porous medium = 2
J
 Lcurved 
 
 L  t n pores of radius re
L [m]
 Effects of porosity & tortuosity
e

Satterfield, C. N., Mass transfer in heterogeneous catalysis, MIT Press (1970).

Effects of porosity & tortuosity
e
J porous medium = J D = diffusivity [m2/s]
t De = effective diffusivity [m2/s]
e = porosity
t = tortuosity (3 to 6, in general)
dC
J = −D
dx
dC
J porous medium = − De
dx

e
De = D Effective diffusivity
t
 Molecular diffusion & Knudsen diffusion

Molecular diffusion
2  How to calculate:
D = v  Chapman-Enskog’s equation
t 3 (Gas phase)

Knudsen diffusion
1/ 2
2re  8RT  T re
DK =   = 3.067re
3  M  M
(
  0.1)

 = (ns ) −1  0.1m for 1atm gas

D = molecular diffusivity [m2/s]  = mean free path [m] <v>=average velocity [m/s]
t = mean free time [s] DK = Knudsen diffusivity [m2/s]
re = pore radius [m] T = temperature [K] M = molecular weight
n = number of molecules per unit vol s= effective cross-sectional area of molecule
Transition region between Molecular
& Knudsen

Effectiveness diffusivity for molecular diffusion

e
D12e = D12
t
Effectiveness diffusivity for Knudsen diffusion

e
DKe = DK
t

Effectiveness diffusivity for the transition region

−1 −1
 1 1  e 1 1 
DTe =  +  =  + 
 D12e DKe  t  D12 DK 
 Transition region between Molecular
& Knudsen
Why do we need to consider the transition region?

Ethylene in hydrogen, pore=570Å, 298K

Satterfield, C. N., Mass transfer in heterogeneous catalysis, MIT Press (1970).
Transition region between Molecular & Knudsen
Why do we need to consider the transition region?

Hydrogen in nitrogen, 1atm, 298K

Satterfield, C. N., Mass transfer in heterogeneous catalysis, MIT Press (1970).

Pore diffusion resistance combined with reaction
Concentration profile within the catalyst particle

C sinh(3S r ) S =
R kv
= R
3 De
CS (r / R) sinh(3S )

Overall reaction rate in the catalyst particle

dC
R = 4R De 2

dr r =R

If the concentration within the whole particle is CS, the overall reaction rate is:
4
R0 = R 3kv CS
3
The effectiveness factor

R 1  1 1  e x − e− x
= =  −  tanh x = x − x
R0 S  tanh(3S ) 3S  e +e
Pore diffusion resistance combined with reaction
s

C sinh(3S r )
= R
CS (r / R) sinh(3S )
C/Cs

r/R Hashimoto, K., Reaction Engineering, Baifu-kan (1979).

Pore diffusion resistance combined with reaction

The internal effective factor, 𝜂 is the ratio of actual overall rate of reaction/rate
of reaction that would result if entire interior surface were exposed to the external
pellet surface conditions,

R 1  1 1 
= =  − 
R0 S  tanh(3S ) 3S  Note: Thiele modulus also known as ϕ
in some books.

Note: since the Thiele modulus ϕ <0.4, the effectiveness factor is approaching 1.0.

This indicates that the catalyst has short pore, has wide pores, and the reaction rate
constant is small cf diffusion coefficient thus fast diffusion,
the reactant concentration does not drop largely within the pore.

Thus, Pore diffusions offer negligible resistance (reaction is not limited by diffusion)
Pore diffusion resistance combined with reaction
  1 (S  0.1)
1 Pore diffusion effect is significant.
Pore diffusion effect is insignificant
Effectiveness factor, 
(dimensionless)

R 1  1 1  1
= =  −  
S
(S  5)
0.1
R0 S  tanh(3S ) 3S 

If Thiele modulus>, the reactant concentrations drop to zero,

rapidly on moving into the pores, pore diffusion strongly influences
the rate of reaction (reaction is diffusion limited)
” strong pore resistance regime”
0.01
0.01 0.1 1 10 100
Thiele modulus, s (dimensionless)
Pore diffusion resistance combined with reaction

How does the pore diffusion influence the overall reaction rate?

− robserved =  (−rno diffusion lim itation ) =  k v C n

(for all s)

No pore diffusion effect Strong pore diffusion effect

  1 (S  0.1) 1 R kv
 (S  5) S =
S 3 De

− robserved = kv C n 1/ 2
1 3  De 
− robserved = kv C = kv   C n
n

s R  kv 

- Temperature dependency
- Size dependency
Pore diffusion resistance combined with reaction

Determination of effectiveness factor

1) Common method
Crushing the catalyst till the observed reaction rate becomes constant.
2) Only two data set available
-r1 for R1, -r2 for R2
S 2 R2
Assume (1)I
= ---(5.2.1)
Calculate 2 by using EQ 5.2.2
S1 R1

Calculate S2 by using EQ 5.2.3  2 − r2

= ---(5.2.2)
1 − r1
Calculate S1 by using EQ 5.2.1

1  1 1 
Calculate (1)II by using EQ 5.2.3 =  −  ---(5.2.3)
S  tanh(3S ) 3S 
(1)I =(1)II ?
No
Yes
Finish
Pore diffusion resistance combined with reaction

Satterfield, C. N., Mass transfer in heterogeneous catalysis, MIT Press (1970).

 Pore diffusion/reaction in Non-Isothermal case
The effectiveness factor at lower Thiele
modulus is approaching =1,
the catalyst is short,wide pores,
reaction rate constant
is small cf diffusion coeff
E
=
RTS
− H De
=


CS
TS
Exothermic reaction

Isothermal reaction
Endothermic reaction

Ts= temperature at r=R [K]

= effective thermal conductivity [W/(m∙K)]

R kv / De Froment, G.F., and K. B. Bishoff, Chemical Reactor Analysis and Design, John Wiley & Sons (1990).
 Pore diffusion/reaction in Non-Isothermal case

Heat effects (exothermicity/endothermicity ) during reaction

The non-isothermal condition is due to very fast reaction, thus the heat released or adsorbed in the
pellet cannot be removed rapidly.

The temperature of the pellet differs from the surrounding fluids and results in non-isothermal
conditions.

2 types of temperature effects may occur:

-Particle temperature difference within it: A temperature gradient may exist within the particle
-Film temperature difference across the fluid film (between the outer surface of the pellet and
main gas stream):
 Pore diffusion/reaction in Non-Isothermal case

Heat balance at any point of the catalyst at steady state

dT dC
− = De (−H )
dx dx
Integrated form

− H De
T = T − TS = (CS − C )

T − H De C
−1 = CS (1 − )
TS TS Cs
Temperature profile Concentration profile
: Heat generation function
1. Factor between T profile and C profile
2. Max (T/Ts-1)
Summary

90
Summary

91
 Summary

or MW = 0.15.
92
Summary

93