HETEROGENEOUS

CATALYSIS

In

homogeneous reactions conversion

molecular collisions in the bulk phase

occurs

by

When

the energy barrier for reaction is large, kinetic

energy is not sufficient to overcome it, and catalysis is
required
In

heterogeneous solid phase catalysis reaction occurs on

a surface where a different, lower energy complex is
formed. The lower energy barrier permits a higher reaction
rate

HETEROGENEOUS
CATALYSIS
Recall the Arrhenius Law: k Ae E RT

So catalysts produce a faster reaction by reducing the

activation energy. How does it do this?
2

HETEROGENEOUS
CATALYSIS
From
Fogler:
Cumene
Benzene +
Propylene

The top figure is a schematic representation of the adsorption, reaction and

desorption process. On the surface the cumene would look something like the
lower figure, forming a complex of the orbitals which allows the propylene to
break the bond.
3

HETEROGENEOUS
From Nanotechnology in Catalysis vol 1:
CATALYSIS
Often catalysts are precious
metals (e.g. gold or platinum)
so it would be very expensive to
make the catalysts completely
out of this. So the catalyst is
placed on a cheaper and more
robust
support
such
as
aluminium oxide. Also metal
nanopoarticles can be more
catalytically active than metal
sheets or wires. The total
activity of catalyst is related to
how many of these active sites
you can put on the catalyst.

HETEROGENEOUS CATALYSIS
Important Definitions in catalysis. Must remember
Solid density, s
Excludes all voids
Also known as
Skeletal density

Bulk density, b
Includes voids
inside and
between particles
aka Bed density

s p b
p s 1
b p 1 b

Particle density, p
Includes voids inside
particle.
Also known as Pellet
density
Particle porosity
b Bed Voidage (also )
S g Surface area of catalyst (m 2 /g)
d P Pore diameter (m)
rP Pore radius (m)
R0 Particle radius (m) (also rp )
for both sphere and cylinder

N.B in Fogler, Sg = SA
5

HETEROGENEOUS CATALYSIS
Catalyst form:
Surface area (Sg) can be very large depending on whether catalyst is porous or not:

2 mm diameter
nonporous sphere
0
p s 3.0 g/cm3
3
Sg
R0 p
3
cm 2 /g
0.1 3
10 cm 2 /g

103 m 2 /g

Porous sphere with cylindrical

pores of 50 diameter
p s (1 )

= porosity = 0.4

0.6 3
1.8 g/cm 3
2
2 0.4
Sg

rP p 25 108 1.8
1.78 106 cm 2 /g
178 m 2 /g

From the surface area of a

cylinder per unit volume.
Surface of tennis court per
gram! Much greater than
external surface area.
6

Pore Volume and Surface

Pore volume v is defined as the volume of pores per unit mass, cc/g.
Area
p

v p p v p s (1 )

vps
1 vps

Or, v p
s (1 )
2v p
2
and S g

rp p
rp
If rate is taken to be proportional to surface area, for a first order reaction

A B
rA kC Ab S g , mole/g-cat/s
Units of k m/s

RATE PROCESSES
IN
C
C
concentration of A in gas
CATALYSIS CC == Surface
bulk gas concentration of A
Ab

As

As

Ab

CBb
CA(R)

CA(R) = concentration profile of A in pore

space

CBb
Seven Rate Proceses
1.
Transport of reactants from bulk to surface
2.
Transport of reactants into particle through the pores
3.
Adsorption of reactants on pore surface
4.
Chemical reaction of adsorbed reactants to adsorbed
products (surface reaction)
5.
Desorption of adsorbed products
6.
Intrapellet transport of products to external surface
7.
Transport of products to bulk fluid, from surface

At steady state all of the individual steps will have the same rate. This can be used to
develop an overall, or global, rate of reaction.

RATE PROCESSES
IN
C
C
CATALYSIS Definitions
C = Surface concentration of A in the bulk
Ab

As

As

CBb
CA(R)

CAb = bulk gas concentration of A

CA(R) = concentration profile of A in pore space

CBb

These 7 steps always occur in a catalytic system. The only time when
some of these steps do not occur is for a non-porous particle and
steps 2 and 6 do not occur since there are no pores to diffuse into. At
steady state all of the steps will have the same rate. This can be used
to develop an overall, or global, rate of reaction. If one of the steps is
very slow, it will often be called the rate controlling step and some of
the other. steps may be assumed to have a negligible impact on the
overall rate, i.e. negligible resistance.
9

GLOBAL RATE OF REACTION

Global rate of reaction is the overall rate resulting from all the 7 steps in series.
Example
Consider A B via a catalytic reaction on a nonporous particle
Need only steps 1, 3, 4, 5, 7
A, CAb
CAs

rA rate per unit area (mol/m 2 .s)

rA kcC As (assuming first order)
C As Concentration of A at the surface (mol/m3 )
kc Surface rate constant (m/s, for 1st order)

Rate of external mass transfer, per unit area (mol/m 2 .s), to surface km C Ab C As
C Ab Concentration of A in the bulk (mol/m 3 )
km Mass transfer coefficient (m/s)

At steady state, the rate of mass transfer of A to the surface will be equal to the rate at
which A is consumed at the surface. Otherwise it would build up or deplete.
10

GLOBAL RATE OF REACTION

At Steady State:
Rate of reaction at Surface Rate of external mass transfer
kc C As km C Ab C As
kc C As kmC Ab k mC As
C As
rA

kmC Ab
kc km
kc kmC Ab
C Ab
rA
kc k m
1 1

k
c km

if km kc rA kcC Ab
if kc km rA kmC Ab

These simplifications rely on relative values,

not absolute values, of ks.

Rate is in terms of bulk concentration which is what we generally want.

R1

1
g1

R2

1
g2

This has an electrical analogy to resistor in series:

Rate Current I

Potential difference
V
V

total resistance
R1 R2 1
1

g
g
2
1

11

NATURE OF CATALYTIC
Why
did we not consider the adsorption and desorption
REACTIONS
preceding example? Because we did not need to!

process in the

The rate expression rA = -kcCAs has imbedded in it details of the adsorption desorption processes and the reaction at the surface. We need to know what
is going on at the solid surface but it is not completely understood. It is an area
of ongoing research. However, reasonable mechanisms can be developed
based on three general observations.
(i) Catalyst affects the rate of reaction but is not consumed
(ii) The Catalyst does not change the equilibrium
(iii) The total rate increases with increase in surface area, but the rate per unit
area is constant.

12

EXAMPLE OF MECHANISM
e.g.
Mechanism
may be

A+B

A + X1

A X1

B + X2

B X 2

A X1 + B X 2

X is a surface site.
AX is the chemisorbed species.
C + X1 + X 2

X1, X2 are used (occupied) and regenerated. Here C is not in adsorbed state.
e.g. hydrogenation of ethylene

C 2 H 4 + X1

C 2 H 4 X1

H 2 + C2 H 4 X1
C 2 H 4 X1 H 2

C 2 H 4 X1 H2
C 2 H 6 + X1

Activation energy for catalyzed: Ecat = 13000 cal/mol and homogenous:

Ehom = 43000 cal/mol. How does this affect the rate at 600 K?

rcat
e 13000/( R600)
43000/( R600) 1011
rhon e

Catalytic: V 1 Rainwater tank

Non-catalytic: V 20 million ChE buildings

13

RATE EQUATIONS: ADSORPTION

Adsorption:

for any species A

k
A + X ka A
a

A A X

ra ka C A (Cm C A ) kaC A
C m C A Cv

Cm is the total concentration of active sites (mol/m 2 )

Cv is the concentration of vacant active sites (mol/m 2 )

1
ra ka C ACv
C A
K
a

k
where K a a equilibrium constant for adsorption
ka

This is often referred to as Langmuir-Hinshelwood model.

At adsorption equilibrium

C A K a C A Cv

or C A K a C A Cm C A

CA

K a C A Cm
1 K aCA
14

ADSORPTION
Suppose we have a diatomic molecule that requires two active sites:
k
A 2 + 2X ka 2A
a

1 2
ra ka C ACv2
C A
Ka

At equilibrium:
C A K a1 2Cv C 1A 2

C A K a1 2 Cm C A C 1A 2
C A K a1 2C 1A 2C A K a1 2C 1A 2Cm

CA

Cm K a C A
1 KaCA

So again we can get the concentration of

the surface complex in terms of the bulk
concentration and the total number of
active sites (which we can measure, by
various methods, before doing reaction
experiments).
15

SURFACE REACTION
A+B

Two cases or possibilities for surface reaction for this case.

(i) Reaction between adsorbed A and adsorbed B

k
A X + B X ks C X + X
s

k
A + B ks C + X
s

rs ks C ACB k sCC Cv

1
rs ks C ACB
CC Cv
Ks

(ii) Reaction between adsorbed A and gaseous B

k
A X + B ks C X
s

k
A + B ks C
s

rs k s C ACB k sCC

1
rs k s C ACB
CC
K
s

16

SURFACE REACTION
If surface reaction is relatively fast, the reaction on surface is essentially at
equilibrium. This means that another step, e.g. mass transfer and/or
adsorption, is much slower than the surface reaction. The reaction cannot go
faster than the steps that precede or follow it so it has some finite value.
For the first case:

For the second case:

rs
1
0 C AC B
CC Cv
ks
Ks

rs
1
0 C AC B
CC
ks
Ks

1
0 C AC B
CC
Ks

C AC B

1
CC Cv
Ks

CC Cv

C
C
A B

Ks

CC
Ks

C
C
A B

17

DESORPTION
k
C X ka C + X
a
k
C ka C + X
a

rd kaCC ka CC Cv

1
rd k a CC Cv
CC
Ka

k
where K a a equilibrium constant for adsorption
ka

Surface concentrations are not easy to measure. It is much better to

have rate equations in terms of BULK PHASE CONCENTRATIONS.
To do this, we can combine rates of adsorption, desorption and
reaction to obtain rate in terms of fluid phase concentrations. This in
turn, requires knowledge about the rate controlling step.
18

OVERALL RATE EQUATION

Example

A+X

A X

B + X B X
A X + B X C X
+X
C X

Surface reaction (rate controlling)

C+X

A+B

If the surface reaction is the rate controlling step, the adsorption and desorption
steps can be considered to be at equilibrium:
C A K AC ACv
CB K B CB Cv
CC KC CC Cv
Cm C A CB CC Cv
Cm K AC ACv K B CB Cv K C CC Cv Cv
Cv

Cm
1 K AC A K BCB K C CC

Can now use in rate expression

19

OVERALL RATE EQUATION

Since the surface reaction is the rate controlling step, we can say:
rC rC X

C C
rC k s C ACB C v
Ks

where K s

ks
k s

K C
rC k s K A K B C ACB C C Cv 2
Ks

Subbing in Cv from before:

rC

ks Cm2 K A K B C AC B K C CC / K s

1 K AC A K BCB K C CC

Provides overall rate expression in terms of fluid phase concentrations. This

is typical of what a catalytic rate equation looks like. Even the few simple
steps considered for this reaction can make the rate expression look quite
convoluted. Note the direct analogy between this and the multi-step reactions
from earlier in the course. It is very important that you are able to construct a
rate equation from a multi step process.
20

Example: Ammonia synthesis

The mechanism proposed for catalytic ammonia
synthesis over iron is as follows:
k
N 2 + 2X k1 2N X
1

k
N X + 3 2 H 2 k2 NH 3 + X
2

Rate Determining
Rapid

Determine a rate expression for the reaction assuming that each

of the steps above is elementary.

21

Ammonia synthesis example:

Solution
For reaction 1: N2 + 2X
rate =

2NX (rate determining)

k1CN2 Cv 2 k 1CN2

For reaction 2: NX + 3/2 H2 NH3 + X (rapid)

K2

Site balance:

CNH3 Cv
CN CH32/ 2

Cm CN Cv CN Cm Cv
Cv CNH3 K 2CH32/ 2 [Cm Cv ]
Cv

K 2CH32/ 2Cm
[CNH3 K 2C

3/2
H2

, CN

CNH3 Cm
[CNH3 K 2CH3 2/ 2 ]

Ammonia synthesis example

k1CN2 Cv 2 k 1CN2

rate =
Cv

K 2CH3 2/ 2Cm
[CNH3 K 2C

3/2
H2

, CN

CNH3 Cm
[CNH3 K 2CH32/ 2 ]

Substitution yields
rate = k1CN2
=

K 22CH32 Cm2
[CNH3 K 2C

3/2 2
H2

k 1

2
Cm2 [k1K 22CN2 CH32 k 1CNH
]
3

[CNH3 K 2CH32/ 2 ]2

2
2
CNH
C
m
3

[CNH3 K 2CH32/ 2 ]2

EXTERNAL TRANSPORT
Before a molecule can react on the surface or penetrate the pores it must
PROCESSES
overcome the external mass transfer resistance in the surrounding fluid. The
product must also transfer back to the bulk (Steps 1 and 7, respectively).
Ts
Tb
catalyst
Ts
Cs
Endothermic Reaction

Tb

catalyst
Cb

Cb
Cs
Exothermic Reaction

Additional to the mass transfer that must occur, the heat generated by the
reaction must also be transferred from the surface to the bulk.
The mass transfer rate per unit of external catalyst area is: rm km C Ab C As (mol/m 2 .s)
The heat transfer rate per unit of external catalyst area is: q h Tb Ts

(J/m 2 .s)
24

Heat and mass transfer in packed beds.

Notation.
There
is a lot of notation that goes with transport processes:

Sc Schmidt number (-)

DAB
Pr Prandtl number (-)

CP
kt

Sh Sherwood number (-)

Nu Nusselt number (-)

km d p
DAB

ud p
Re Reynold's number (-)

St D Mass transfer Stanton Number (-)

Sh
Re Sc

St H Heat transfer Stanton Number (-)

Nu
Re Pr

hd p
kt

d p Particle diameter
(or characteristic length) (m)

G Superficial mass velocity (kg/m 2 .s) u

Viscosity (kg/m.s)

Density of the fluids (kg/m3 )

kt Thermal conductivity (W/m.K)

u Superficial velocity (m/s)

DAB Bulk phase binary diffusity (m 2 /s)

25

FLUID-PARTICLE HEAT AND MASS

TRANSFER COEFFICIENTS IN PACKED
k and h are the mass and heat transfer coefficients, respectively. They are a
BEDS
m

function of the particle size, geometry, flow rate and fluid properties. The
transfer coefficients are often calculated using j-factor equations:
2/3
km
2/3
Mass transfer j -factor: jD

St DSc
G DAB
CPm
Heat transfer j -factor: jH

CPmG kt
h

2/3

St H Pr 2/3

The reason j-factors are convenient, is that, according to the Chilton-Colburn

analogy, the two are equal and can thus be determined from the same
correlation. One such correlation is:
0.407
0.455 d P G
0.455 0.407 This is a useful correlation that applies to a
jD jH

Re

wide range of Re when Sc > 100. Better

b
b
correlations do exist for specific conditions.
See Section 11.3 in Fogler for more.
26

FLUID-PARTICLE HEAT AND MASS

TRANSFER COEFFICIENTS IN PACKED
Remember that a correlation is just the best fit of a lot of data. The fit of the jBEDS
factor correlation from the previous slide to a selection of data is given in Fogler.
Note that the y-axis is in the log scale, so differences between the correlation and
actual results can easily be 50-100%. Should check design to see if it is sensitive
to this uncertainty.

27

EXTERNAL TEMPERATURE RISE

At steady state, the heat produced by the reaction must equal the heat
removed by convection:
Q h Tb Ts rm( H R ) k m C Ab C As ( H R )
k ( H R )
Ts Tb m
C Ab C As
h
km

G D AB

2/3

CPm

CPmG kt
h

e.g. Typical gas phase data:

2 kg/m 3
C p 0.5 kJ/kg.K
H R -20,000 J/mol.K
kt 0.02 W/m.K
DAB 0.2 cm 2 /s
C Ab 1 mol/m 3

2/3

23
km
DAB
1 3 1 3 2/3
h CPm kt
23
DAB
( H )
Ts Tb 1 3 1 3 2/3R (C Ab C As )
CPm kt

e.g. Ts Tb

0.2 104

23

(20000)

2 500 0.02
13

13

23

(1 0) 20 K

Typical temperature rise from ~ 0 to 20 K. Usually negligible for liquid phase.

28

EXTERNAL TEMPERATURE RISE

At steady state, the heat produced by the reaction must equal the heat
removed by convection:
Q h Tb Ts rm( H R ) k m C Ab C As ( H R )
k ( H R )
Ts Tb m
C Ab C As
h
km

G D AB

2/3

CPm

CPmG kt
h

e.g. Typical gas phase data:

2 kg/m 3
C p 0.5 kJ/kg.K
H R -20,000 J/mol.K
kt 0.02 W/m.K
DAB 0.2 cm 2 /s
C Ab 1 mol/m 3

2/3

23
km
DAB
1 3 1 3 2/3
h CPm kt
23
DAB
( H )
Ts Tb 1 3 1 3 2/3R (C Ab C As )
CPm kt

e.g. Ts Tb

0.2 104

23

(20000)

2 500 0.02
13

13

23

(1 0) 20 K

Typical temperature rise from ~ 0 to 20 K. Usually negligible for liquid phase.

29

PACKED BED REACTOR

Assumptions
1. Isothermal
2. No intra-particle gradients
3. Effectively first order reaction

CAb

A
B
rA = -ksCA (per unit pore area)
ksC A S g P (4 Ro3 / 3) km (C Ab C A )4 Ro2
k m '

CA

3k m
R0
km ' C Ab

k ' k S
m

k s k m' C Ab
k m' k s P S g S g P ( 1 B )
k ebC Ab
k s k m' S g P ( 1 B )
where k eb
k m' k s P S g

rAb

CA
CAb

Example
An exhaust stream from a chemical process contains small amounts of
butane that is catalytically oxidized in a fluidized bed reactor. The catalyst
comprises of nonporous particles of density 2.5 g/cm3 and diameter 2 mm.
The reaction is effectively first order in butane concentration, with air being far
in excess. The reactor is maintained isothermal at 450 K, and there are no
heat transfer resistances. At this temperature the effective surface reaction
rate constant has the value k = 0.01 m/s.
1. Determine the design flow rate of the butane air mixture at 450 K if 95%
conversion of butane is required, with 5 kg of catalyst in the reactor.
Assume the fluid phase is completely micro mixed as in a CSTR.
2. Determine the flow rate needed for the same conversion, if instead the
fluid phase is assumed to be in plug flow.
3. For flow past a sphere the mass transfer coefficient follows the relation

km d p
D

2.0 0.6 Re1/2 Sc1/3

The Reynolds number in the reactor is 10, and it is known that the Schmidt
number for the butane air mixture at 450 K is 0.8 while the diffusivity of butane is
1 cm2/s. Determine if the mass transfer resistance is significant.
31

Solution
Assume: - Isothermal - Constant volumetric flow rate - Steady State
1.
Assume:
- Completely micro-mixed
dN A
0 FA0 FA rAV
dt
rAV rA Total catalyst area

Total catalyst area S g mc

0 vC A0 vC A kc C A S g mc
CA

vC A0
v kc S g mc

where Sg is surface area per unit mass, and mc is mass of catalyst. For nonporous
particles of radius rp and density p, the surface area per unit mass is given as:
Sg

4 rp2
(4 r / 3) p

CA

3
p

C A0

3
rp p

1 3kc mc v p rp

For X = 0.95, CA/CA0 = 0.05, and substitution of the

values of k, mc, p and rp yields v = 3.16 lit/s.
32

Solution
2. Assume:

- Perfect plug flow

dFA
rA Catalyst area per kg of catalyst
dW
dC
v A kc C A S g
dW
C A dC
kc S g W
A
CA0 C A v 0 dW
kc S gW 3kcW
CA
ln

C
v
vrp p
A0
For X = 0.95, CA/CA0 = 0.05, and substitution of the values of k, mc, p and rp yields v
= 20 lit/s.

33

Solution (contd.)
3. From the data given, we need to use some sort of correlation to calculate km. A
common correlation is the Frssling correlation (see p776 of Fogler) which we are
given:
km d p
D

2.0 0.6 Re1/ 2 Sc1/ 3

Substitution of the values D = 10-4 m2/s, dp = 0.002 m, Re= 10 and Sc = 0.8 yields km
= 0.25 m/s. From the earlier equation on global rate of reaction, the overall rate of
reaction (when it is a first order reaction on a non-porous particle) is given as:
keff

k m kc
0.25 0.01

0.01 m/s
(km kc ) (0.25 0.01)

Clearly external mass transfer resistance is negligible.

34

Packed Bed Reactor with Axial

Bed Scale Model: As before can use TRAM model
Dispersion
d 2C Ab
dC Ab
DL

u
rAb 0
dz 2
dz

u = superficial velocity based on empty reactor

uC A0 uC Ab DL

dC Ab
dz

at z 0

dC Ab
0
at z L
dz
*
*
dC Ab
Lkeb *
DL L 1 d 2C Ab

C Ab 0
u L2 d 2
d
u
*
*
d 2C Ab
dC Ab
*

Pe
Pe keb C Ab
0
2
d
d

C Ab

*
1 dC Ab

1
Pe d

*
dC Ab
0
d

at 0

As before solution is
C Ab* (1)

C Ab ( L)
1 X exit
C A0

X exit 1

4
(1 ) 2 e Pe (1 )/ 2 (1 ) 2 e Pe (1 )/ 2

4k
where 1 eb
Pe

1/2

The only difference is that k has been

substituted for keb.

at 1

35

INTRAPARTICLE TRANSPORT
In addition to external concentration and temperature gradients, can also have
PROCESSES
intraparticle gradients.

T( r )

Ro
r
C( r )
0

Ro r

Generally internal temperature difference is small and negligible, i.e. the pellet
is essentially at uniform temperature.

INTERNAL MASS
Occurs through diffusion in the pore network. Generally the catalyst particle is
TRANSFER
comprised of compressed microporous micro-particles. Thus, has a
bidisperse structure.

Macropore
(500-10000)

Macropore

Micropore
(20-80)

Reactant diffuses into pellet through the macropores, and into the microparticle
(where most of the active surface lies) through the micropores.

DIFFUSION IN SINGLE PORES

Diffusivity D(rp) varies with pore size. Diffusion occurs through 2 mechanisms.
(i) interparticle collisions
1

1
1
2
2

Interparticle collisions result in a bulk or

molecular diffusivity DM, which depends on
T and P. This dominates when
rP >> (mean free path).

(ii) molecule-wall collisions

Knudsen mechanism dominant when
rP << (mean free path).
Both mechanisms occur in parallel for the Knudsen mechanism we have an
associated Knudsen diffusivity DK(rP) given by
T
DK (rP ) 9700rP
cm2 / s
MA
rP in cm , T in K. Overall D(rP) given by
[DA(rP)]-1 = DM-1 + DK(rP)-1

DIFFUSION IN PORE
In pore networks need an effective diffusivity for the entire network. In catalyst
NETWORKS
pellets have two independent networks, that of the macropores and that of the
micropores.
Z
R

Micropores
Macropores

In any network the actual path of a diffusing molecule is larger than the effective
length because of random pore orientations.
R

dZ2 = dR2 + dT2 + dS2

T

dS

Z
dR
dT

DIFFUSION IN PORE NETWORKS

Since the z direction (the pore axis) is random, on the average
|dz cos()| = |dS| = |dT| = |dR|
and
dz 2 3dR 2 dz 2 3cos 2 dZ 2
1
cos2
3
dC A
dCA

D
(
r
)

D
(
r
)
cos

Pore flux in z direction

P
P
dz
dR
dC A

cos

D
(
r
)
cos

Pore flux in R direction

P

dR
dC
cos2 D(rP ) A
dR
D(rP ) dC A

3 dR

DIFFUSION IN PORE NETWORKS

Evaluating D(rP ) at the average pore radius yields
JR

D rP dCA
3 dR

This is per unit pore area. The flux based on the pellet cross-section is then
D rP dC A
J eR
3
dR
2
In general due to nonideal pore shape, and connectivity effects 1 cos 3
, and we write

J eR

D rP dC A

dR

where is called a tortuosity factor.

DIFFUSION IN PORE NETWORKS

It is common to write J D dC A
eR
e
dR
with
D rP
De

In this expression De is the effective diffusivity for any network, and can be
applied individually to the macropores and micropores. Thus, the effective
macropore diffusivity is
De m

with

m D rPm , where = macropore void fraction

m
m

D rPm DM DK rPm
1

1 1

in which the average macropore size rPm is given by

rPm

2 m
2 m

P S mg s (1 m ) S mg

DIFFUSION IN PORE NETWORKS

Here

DK (rPm ) 9700rPm

T
MA

Similarly in the microparticles

D(rP )
De

2 (1 )
with rP
P Sg
and

D(rP ) DM DK (rP )

DK (rP ) 9700rP

De

T
M

For the pellet as a whole

If = M =

De=Dem+ ( 1 m )De

m D(rPm ) (1 m ) D(rP )

DIFFUSION IN PORE NETWORKS

Example:
Consider a bidisperse catalyst pellet with

M = 0.4
rPm = 500

= 0.45
Sg = 150 m2 /gm
DM = 0.1 cm2 /sec for benzene in nitrogen

P =1.5 gm/cm3
Estimate effective diffusivity for C6H6 assuming
= M = = 3 , T = 600K

DIFFUSION IN PORE NETWORKS

Solution
rp

First need to estimate Sg and

S mg

2m
2 * 0.4 *10 4
2

8 10.67 m / gm
p rPm 15
. * 500 *10

1
D(rPm ) DM 1 DK (rPm )

1
1
1
0.1 0.135

2
0.057cm / sec

DK (rP ) 9700 * 2584

. * 108

S g 150 10.67 139.33 m 2 / gm

rP

2 (1 m )

600
78

0.00695 cm2 / sec

D(rp ) (0.006951 0.11 ) 1 0.00695 cm 2 /sec

P S g

2 * 0.45 * 0.6 *108

1.5 *139.33 *104

De

m D ( rPm ) (1 m ) D ( rP )

0.057 * 0.40 0.0065 * 0.45 * 0.60

3
0.0082 cm 2 / sec

25.84 A
DK (rpm ) 9700 * 500 * 10 8

600
0.135cm 2 / sec
78

Dominated by macropore diffusion.

DIFFUSION AND REACTION

IN CATALYST PELLETS
Given the effective diffusivity and a rate expression need to find the
concentration profile and overall reaction rate in a pellet. Consider a spherical
pellet of radius R0.
CA

R0

CAS
R

R+dR

CAS
R0

DIFFUSION AND REACTION IN CATALYST

PELLETS
Balance over spherical shell of thickness dR gives

dCA
2

R
e

dR

dCA

De
4R 2
dR

R dR

4R 2 dRrA ( CA , CB , )
R

Dividing by 4R2dR and taking the limit dR0,

De d 2 dC A
R
rA (C A , CB , )
R 2 dR
dR
Boundary conditions are
(i) C A C As
at R = R 0
dC A
(ii)
0
at R = 0
dR
Apply to first order case

rA k sC A P S g
D d 2 dC A
2e
R
ks P S g C A
R dR
dR

DIFFUSION AND REACTION IN CATALYST

PELLETS
Let

R
R0

, CA *

CA
CAs

, R0

ks P Sg
De

1 d 2 dC A*

= 2C A*
2
d
d
C A* (1) 1 ,

Define y C A

d2y
2
2 y 0
d
Solution is

dC A*
0 at 0
d

CA y /

1 d2y
2 y

d 2

dCA*
y 1 dy
2
d
d

1 d 2 dC A*
1 d
dy
2

= 2
y
d
d
d
d
1 dy 1 d 2 y 1 dy
2

d d 2 2 d

y A sinh( ) B cosh()
at 0, y (C *A ) 0 0

0 B
y Asinh()

and CA * () sinh()

CA * (1) A sinh( ) 1
1
A
sinh( )
and C A* ()

sinh()
sinh( )

DIFFUSION AND REACTION IN CATALYST

ks S g P
PELLETS
Need
overall reaction rate in pellet.
R
Thiele Module
0

This is given by
Rate De

dC A
dR

=measure of relative reaction rate

4R0 2

in comparison to diffusion rate

R0

dC *A
De 4R0C As (
)
d 1

4R0C As De coth( ) 1

Can define internal effectiveness factor

Ei

De

actual rate
rate at surface condition

At low , i.e. 0
diffusion is relatively rapid and Ei 1
At high , i.e.
diffusion is relatively slow, coth() 1
and Ei 3/
Ei

Ei =3/

1.0

4 R0C As De coth( ) 1

k sC As S g P 4 R03 / 3
3
E
coth( ) 1

i
2

Rate per unit volume = k CAs P Sg Ei

EFFECT OF TEMPERATURE
At low temperature k is relatively small and << 1, Ei 1
rate / volume ksPSgCA0
= k0 e-E/RTPSgCA0
Thus, measured activation energy is falsified to half its true value at high T.
Large Diffusional Resistance
Slope = -E/2R
Ln[Rate]

Negligible diffusional
resistance
Slope = -E/R

1/T

Thus we can get intrinsic kinetics, with diffusional effects at low temperature
(or low particle sizes) for which << 1 and Ei 1.

EFFECT OF TEMPERATURE
DM T ( 3/2 )2 , DK T 1/2

Generally

De T 12

k s e E / RT

with E 10 30 kcal/mole

k increases much more strongly with temperature than De, and therefore
increases with T. At high T, becomes large, and Ei 3/

rate per unit volume

3
k s S g PC A0 Ei ( ) ks S g PC AO

3C
A0 k s S g P De
R0

3C A0
R0

k0 e E / RT S g P De

EXAMPLE OF DIFFUSION AND

REACTION
Measurements for a catalytic first order reaction yield
(AB)
effective diffusivity of A,

DeA = 4x10-4 cm2/s

reaction rate = 4x10-5 gmole B/s.cm3

CAs = 0.6x10-5 gmol/cm3
pellet radius,

R0 = 0.088 cm

Estimate the effectiveness factor, and find the rate of reaction at this temperature.

Solution
rate k sC As P S g Ei
k sC As P S g
rB ( rA )

3
( coth( ) 1)
2

3DeA C As
coth( ) 1
R02

R0 2 ( rA )
coth( ) 1
3DeAC As
0.0882 * 4x10 5

3* 4x104 * 0.6x105
43

coth( ) 44

Solution yields (coth()1 for large )

= 44

3
coth( ) 1 0.067 ( 3 / )
2
( rA )
4 x105
ks P S g

99.5 sec-1
5
Ei C As 0.067 *0.6 x10
Ei

Strongly diffusion controlled.

How can we predict conversion in a
packed bed ?
In packed bed can define effective rate
constant
ke k s p S g E (1 b )
If plug flow is assumed
X 1 exp( ke )
is residence time based on empty
reactor volume.

Effect of External Mass Transfer

Resistance
A
A

rate per unit volume

CAb

CAs

Balance at external surface yields

4 R03
Ei k sC As P S g
km (C Ab C As )4 R0 2
3
kmC Ab
C As
km ks S g P R0 Ei / 3

k s S g P Ei kmC Ab

km k s S g P R0 Ei / 3
ks S g PC Ab Ei
1 k s S g P R0 Ei / 3km

Effect of External Mass Transfer Resistance

Define a modified Sherwood number Sh =
while Ei

k mR0
De

3( coth( ) 1)

rate per unit volume

ks S g PC Ab Ei

1 coth( ) 1 / Sh

Overall effectiveness factor

actual rate
E0
rate at bulk condition (=k s S g PC Ab )

Ei
1 coth( ) 1 / Sh

As Sh , no external gradient and E0 Ei

As Sh 0

Ei Sh
3Sh
3km R0
3k m
E0

coth( ) 1 2 R0 2 ks P S g R0k s P S g

Back to the Seven Steps

Seven Rate Processes
1. Transport of reactants from bulk to surface km
2.

Transport of reactants into particle through the pores De

Eo

5.

Adsorption of reactants on pore surface

Chemical reaction of adsorbed reactants to Choose one as rate
controlling ks
adsorbed products (surface reaction)
Desorption of adsorbed products

6.

Transport of products out of particle through the pores We have ignored these

3.
4.

7.

Transport of products to bulk fluid, from surface

Ei

as we can define a rate

with the preceding
steps as long as one of
6 or 7 is NOT rate
limiting
56

Effect of External Mass Transfer

Resistance
An irreversible first-order reaction occurs on the interior pore surface of
catalyst particles in a fixed-bed tubular reactor. Assume isothermal operation
and the dispersion model for the reaction mixture flowing through the bed.
The reactant concentration in the feed is CA0. Derive an equation for the
conversion in the reactor effluent. How is the equation simplified if:
a)
b)
c)
d)
e)

intraparticle diffusion resistance is unimportant ?

Fluid-to-particle (or external) mass transfer resistance is unimportant?
The global rate is controlled by the intrinsic reaction at an interior site?
Axial dispersion is unimportant (plug flow conditions)?
Both conditions (c) and (d) apply?

57

Effect of External Mass Transfer

ForResistance
axial dispersion and a 1 order reaction in a packed bed:
st

X 1

4
(1 ) 2 e Pe (1 )/2 (1 ) 2 e Pe (1 )/ 2

4k
where 1 e
Pe

1/ 2

and Pe

Lu
DL

The key to the question, is what do we use as ke in each case. To start with,
we will write a general equation for ke and then tailor to each situation:
r keC Ab

ke ks S g Eo p (1 b )
a)

intraparticle diffusion resistance is unimportant. In this case Ei 1, Sh

0 and we can use the simplification:

E0

Ei
Sh
Sh

1 coth( ) 1 / Sh
Sh coth( ) 1 Sh 2 3

ke

3k s S g p (1 b )Sh
3Sh

3k s S g p (1 b ) km
3km R0 k p S g

as Sh =

km R0
, R0
De

ks S g p
De
58

Effect of External Mass Transfer

Resistance
b)
Fluid-to-particle (or external) mass transfer resistance is unimportant, so E

Ei. Substitute the expression for Ei:

3( coth( ) 1)
2
3ks S g p (1 b )( coth( ) 1)
ke
2
Ei

c) The global rate is controlled by the intrinsic reaction at an interior site, so Eo

and Ei 1. Substitute the expression for Ei:
ke ks S g Eo p (1 b ) ks S g p (1 b )

Alternately, since both internal and external mass transfer are rapid
compared to chemical reaction, use result of (a) with km .

59

Effect of External Mass Transfer

Resistance
b)
Fluid-to-particle (or external) mass transfer resistance is unimportant, so E

Ei. Substitute the expression for Ei:

3( coth( ) 1)
2
3ks S g p (1 b )( coth( ) 1)
ke
2
Ei

c) The global rate is controlled by the intrinsic reaction at an interior site, so Eo

and Ei 1. Substitute the expression for Ei:
ke ks S g Eo p (1 b ) ks S g p (1 b )

Alternately, since both internal and external mass transfer are rapid
compared to chemical reaction, use result of (a) with km .

60

Effect of External Mass Transfer

Resistance
d) Axial
dispersion is unimportant (plug flow conditions)?
dFA
rA keC Ab
dV
dX A
FA0
ke C A 0 1 X A
dV
XA
ke C A 0 V
dX A

0 1 X A FA0 0 dV
ln 1 X A

keV
v0

X A 1 e ke

where ke k s S g Eo p (1 b )

3k s S g p (1 b )( coth( ) 1)

2 1 coth( ) 1 / Sh

e) Both conditions (c) and (d) apply gives as per above with the same ke as (c):
X A 1 e ke
where ke kS g p (1 b )
61

Exam tips
1.
2.
3.

4.

5.

6.

7.

8.

Do as many problems as you have time to do.

Understand all reaction equations on the exam resources sheet.
Be familiar with the mathematical functions on the exam resources sheet.
These may save you time and/or enable you to answer a question.
The past few years final exams are a good guide of the length, difficulty
and content.
Fogler questions of type A and B, near questions you did in the
assignments, are good for pratice. These will generally be longer than
exam questions but test the concepts well.
If you are given an equation, use it. Deriving an equation you already have
(regardless of how difficult or lengthy it is to derive) is worth zero marks.
Read available if you do the question very carefully, and make sure you
understand it..
Include units with answer where appropriate (e.g. CA = 1.2 mol/m3)

62