Chemical Reaction Engineering

Lecturer :
Lecture 9
This course focuses on catalysis and catalytic reactors.
Catalysts
Early example of catalysts
wine, cheese and bread production
Berzelius (1835)
initially suggested that small amount of a foreign
source could affect the course of chemical reactions.
This force is called catalytic.
Ostwald (1894)
Catalysts are substances that accelerate the rate of
chemical reactions without being consumed.
Catalyst
A catalyst affects the rate of a reaction but the process
unchanged.
A catalyst usually changes a reaction rate by promoting
a different molecular path/mechanism for the reaction.
A catalyst makes it possible to obtain an end product by
a different pathway, it can affect both the yield and the
selectivity.
A catalyst changes only the rate of a reaction; it does
not affect the equilibrium.
Homogeneous and Heterogeneous
Homogeneous catalysis concerns processes in which a
catalyst is in solution with at least one of the reactants.
A heterogeneous catalytic processes involves more
than one phase; usually the catalyst is a solid and the
reactants and products are in liquid or gaseous form.
Heterogeneous catalysis is the more common type and
has a major advantage:
Simple and complete separation of the fluid product mixture
from the solid catalyst (Many catalysts are quite valuable)
Only heterogeneous catalysts will be studied here.
Catalyst types
Porous
Molecular sieves
Monolithic
Supported
Unsupported
Catalyst
catalyst reaction fluid-solid interface
reaction rate interfical area
Many catalysts are provided by porous structures (called porous catalyst).
A typical silica-alumina cracking catalyst has a pore volume of 0.6 cm
3
/g
and an average pore radius of 4 nm.
The corresponding surface area is 300 m
2
/g.
Sometimes pores are so small that they will
admit small molecules but prevent large ones
from entering. Materials with this type of pore
are called moleular sieves.
Example : zeolite
They are quite selective catalysts.
The pores can control the residence time of various
molecules near the catalytically active surface.
May allow only the desired molecules to react.

Some catalysts are sufficiently active that the
effort to create a porous catalyst would be
wasted. Monolithic catalysts are encountered
in processes where pressure drop and heat
removal are major considerations.
Example : platinum gauze reactor used in the
ammonia oxidation portion of nitric acid
manufacture
Example : catalytic converters used to oxidize
pollutants in automobile exhaust
Supported and unsupported catalysts
A catalyst consist of minute active particles
(frequenly a pure metal or metal alloy) dispersed
over a less active substance (support), such a
catalyst is called a supported catalyst.
Unsupported catalysts have active ingredients as
the major part. Other substances are promoters,
which increase the activity.
The deactivation of catalysts
Deactivation : the decline in a catalysts activity
as time progresses.
By aging phenomenon
gradual change in surface crystal structure
By poisoning phenomenon
deposit of a foreign material on active portions of the
catalyst surface
example : coking in the catalytic cracking of petroleum
naphthas
Micoscopic view of catalytic rxns
Focus on gas-phase reactions catalyzed by solid surfaces :
catalytic surface
Reactant I
Reactant II
adsorption
Adsorption takes place by two different processes: physical adsorption and
chemisortion
Adsorption
Physical adsorption is similar to condensation :
exothermic (low heat of adsorption : 1 ~ 15 kcal/g mol)
weak attraction forces : van der Waals forces
amount of adsorption decreases with increasing temperature
Chemisorption affects the rate of a chemcial reaction :
strong attaching force : valence forces (same type as the
force between bonded atoms in molecules)
exothermic (heat of adsorption is as high as a chemical
reaction : 10 ~ 100 kcal/g mol)
the reaction must be carried out within the temperature range
where chemisorption of the reactants is appreciable.
Active site is a point on the catalyst surface that can form strong
chemical bonds with an adsorbed atom or molecule.
Turnover frequency is used to quantify the activity of a catalyst
and defined as the number of molecules reacting per active site per
second at the conditions of the experiment (i.e. molecules/site s)
Dispersion is fraction of the catalytic atoms deposited that are on
the surface (i.e. active sites)
Fisher - Tropsch Sythesis O H CH H CO
2 4 2
3 + + Catalyst : 0.5 wt% Ru on -Al
2
O
3
.
The catalyst dispersion percentage of atoms exposed, determined from hydrogen chemisorption, was
found to be 49%. At a pressure of 988 kPa and a temperature of 475 K, a turnover frequency of 0.044 s
-1

was reported for methane. What is the rate of formation of methane in mol/s.g of catalyst ?
catalyst g s mol
total g
Ru g
Ru g
Ru mol atom g
Ru mol atom g
Ru atoms
Ru atoms total
atoms surf ace
molecules
CH mol
s Ru atom surf ace
molecules
Ru
MW
D N r
Ru
CH A
=

=
|
|
.
|

\
|
= '

/ 10 07 . 1
005 . 0
1 . 101
) (
) (
10 02 . 6 49 . 0
10 02 . 6
1
) (
044 . 0
100
% 1
6
23
23
4
4
Catalysts used in different classes of
reactions
Alkylation reactions
alkylation is the addition of an alkyl group to an
organic compound, example:

frequently used catalysts
Friedel-Crafts catalyst - AlCl
3
+ trace HCl
Pd


5 2 5 6 4 2 6 6
H C H C H C H C +
Dealkylation reactions
cracking of petroleum products
frequently used catalysts
Silica-alumina, Silica-magnesia
Clay (montmorillonite)
AlCl
3

Pd
Isomerization reactions
conversion of normal hydrocarbon chains to branched
chains, which have higher octane number
frequently used catalysts
Acid-promoted Al
2
O
3
, Pt/Al
2
O
3

AlCl
3

Zeolites

Hydrogenation and Dehydrogen reactions
Low temperatures for hydrogenation and high
temperatures (at least 600 C) for dehydrogenation.
The bonding strength between hydrogen and metal
surface increases with an increase in vacant d-orbitals.
Maximum in catalytic activity occurs when there is
approximately one vacant d-orbital per atom
frequently used metal catalysts
Co, Ni, Rh, Ru, Os, Pd, Ir, and Pt.
MoO
2
and Cr
2
O
3

Too strong bonding (a large number of vacant d-orbitals)
relatively inactive, because of the strong adsorption for the reactants or
the products or both
V, Cr, Mo, Ta, and W
Oxidation reactions
Frequently used catalysts
Transition group element (group VIII) and subgroup I
Ag, Cu, Pt, Fe, Ni, and their oxides
V
2
O
5
and MnO
2

principal types
Oxygen addition


Oxygenolysis of carbon-hydrogen bonds


Oxygenation of nitro-hydrogen bonds

Complete combustion
O H C O H C
Ag
4 2 2 4 2
2 2 +
3 2 2
2 2
5 2
SO O SO
O V
+
2 2
2 2 CO O CO
Cu
+
O H CHO CH O OH H C
Cu
2 3 2 5 2
2 2 2 + +
O H HCHO O OH CH
Ag
2 2 3
2 2 2 + +
O H NO NH O
Pt
2 3 2
6 4 4 5 + +
O H CO O H C
Ni
2 2 2 6 2
6 4 7 2 + +
Hydration and dehydration reactions
Catalysts need to have strong affinity for water
frequently used catalysts
Al
2
O
3
- dehydration of alcohols to form olefins
MgO
Silica-alumina gels
Phosphoric acid
Phosphoric acid salts on inert carriers
Clay (montmorillonite)
Example
OH CH CH O H CH CH
2 3 2 2 2
+ =
Halogenation and dehalogenation reactions
Catalysts may not needed
However, catalysts can increase the product
selectivity and decrease the operating temperature
frequently used catalysts
CuCl
2

AgCl
Pd
Steps in catalytic reaction
Mass transfer (External diffusion)
reactants external surface of the catalyst pellet
Internal diffusion
reactant from the pore mouth through the catalyst pores to
the immediate vicinity of the internal catalytic surface
Adsorption
reactant attaches onto the catalyst surface
Reaction
Desorption
product leaves from the catalyst surface
Page 598
The overall rate of reaction is equal to
the rate of the slowest step in the mechanism.
In this course, we assume that the diffusion steps are very fast, such that
the overall reaction rate is not affected by mass transfer in any fashion.

We will focus on the adsorption, surface reaction and desorption steps.
Development of rate laws in
heterogeneous catalysis
Seldom follow power law models
Algorithm for the development
postulate catalytic mechanisms
(typically three steps) adsorption, surface reaction,
desorption
one of which is usually rate-limiting
derive rate laws for the various mechanisms
Adsorption
A
B
S represents an active site
(vacant site , with no atom, molecule, or complex adsorbed on it)
When species A is adsorbed on the site S :
S A S A +
Site balance equation :
S B S A v t
C C C C

+ + =
Total molar concentration of active
sites per unit mass of catalyst
Molar concentration of vacant sites
per unit mass of catalyst
Adsorption isotherms
Adsorption data are frequently reported in the
form of adsorption isotherms.
Isotherms portray the amount of a gas adsorbed
on a solid at different pressures, but at one
temperature.
Postulate model(s)
Fit ?
Experimental data
Postulated model
For carbon monoxide on metal, two models may be proposed
(1) molecular or nondissociated adsorption
S CO S CO +
(2) Dissociated adsorption
S O S C S CO + +2
Which one is the correct model? Ans: depends on the surface
Ni Ni Ni
C
O
Fe Fe Fe
O C
Carbon monoxide molecular adsorption
The carbon monoxide does not react further after being absorded:
S CO S CO +
It is treated as an elementary reaction and :
v CO A
C P k attachment of rate =
Proportional to the number of collisions between
molecules and the surface per unit time
S CO A
C k t detachmen of rate

=
The net rate of adsorption :
S CO A v CO A AD
C k C P k r

=
A
A
A
k
k
K

=
|
|
.
|

\
|
=

A
S CO
v CO A AD
K
C
C P k r
adsorption equilibrium constant
A
A
A
k
k
K

=
Molecular adsorption equilibrium constant
Virtually independent of temperature
Increase exponentially with increasing temperature
When CO is the only material adsorbed on the catalyst :
S CO v t
C C C

+ =
At equilibrium, r
AD
= 0
0 =
|
|
.
|

\
|

A
S CO
v CO A
K
C
C P k
v CO A S CO
C P K C =

) (
S CO t CO A S CO
C C P K C

=
CO A
t CO A
S CO
P K
C P K
C
+
=

1
C
CO S
= f (P
CO
), an equation of adsorption isotherm Langmuir isotherm
Langmuir isotherm
CO A
t CO A
S CO
P K
C P K
C
+
=

1
P
CO

C
CO S

t S CO CO
CO t A S CO CO
C C P
P C K C P
~ |
~ +

Check if Langmuir isotherm ?

CO A
t CO A
S CO
P K
C P K
C
+
=

1
t
CO
t A S CO
CO
C
P
C K C
P
+ =

1
P
CO

P
CO
/C
CO S

linear ?
Carbon monoxide dissociative adsorption
The carbon monoxide does not react further after being absorded:
Adsorption :
(1) Two adjacent vacant active sites are required rather than the single
site needed when a substance adsorbs in its molecular form.
(2) The probability of two vacant sites occuring adjacent to one another is
proportional to the square of the concentration of vacant site.
S O S C S CO + +2
2
v CO A
C P k attachment of rate =
Desorption :
(1) Two occupied sites must be adjacent
S O S C A
C C k t detachmen of rate

=
The net rate of adsorption :
S O S C A v CO A AD
C C k C P k r

=
2
A
A
A
k
k
K

=
|
|
.
|

\
|
=

A
S O S C
v CO A AD
K
C C
C P k r
2
A
A
A
k
k
K

=
Dissociated adsorption equilibrium constant
Increase exponentially with increasing temperature
Increase exponentially with increasing temperature
decrease with increasing temperature
When CO is the only material adsorbed on the catalyst :
S O S C v t
C C C C

+ + =
At equilibrium, r
AD
= 0
S O S C
C C

=
S O S C v t
C C C C

+ + =
0
2
=
|
|
.
|

\
|

A
S O S C
v CO A
K
C C
C P k
for
( )
( )
2
1
2
1
2 1
CO A
t CO A
S O
P K
C P K
C
+
=

( )
( )
( )
t
CO
A t
S O
CO
C
P
K C
C
P
2
1
2
1
2
1
2 1
+ =

P
CO
1/2
/C
O S

linear ?
P
CO
1/2

More than one substance...
Same principle as the single substance
When the adsorption/desorption of both A and
B are first order processes, and both A and B
are adsorbed as molecules :
B B A A
t A A
S A
P K P K
C P K
C
+ +
=

1
Surface reaction
Once a reactant has been adsorbed onto the surface,
it is capable of reacting in a number of ways:
Single - site
only the site on which the reactant is adsorbed is involved in the
reaction
for example: isomerize, decompose

rate law
S B S A
|
|
.
|

\
|
=

S
S B
S A s s
K
C
C k r
S
S
S
k
k
K

=
dual - site
the adsorbed reactant interacts with another site
1st mechanism: react with a vacant site

rate law

2nd mechanism: reaction between two absorbed species

rate law

3rd mechanism: reaction of two species adsorbed on different
types of sites S and S

rate law
S S B S S A + +
|
|
.
|

\
|
=

S
v S B
v S A s s
K
C C
C C k r
S
S
S
k
k
K

=
S D S C S B S A + +
|
|
.
|

\
|
=


S
S D S C
S B S A s s
K
C C
C C k r
S
S
S
k
k
K

=
S D S C S B S A +
'

'
+
|
|
.
|

\
|
=
'
'
S
S D S C
S B S A s s
K
C C
C C k r
S
S
S
k
k
K

=
Reactions involving either single - site or dual - site mechanisms are referred to as following
Langmuir - Hinshelwood kinetics
single - site and non-adsorbed molecule
the adsorbed molecule interacts with a molecule in the gas phase


rate law

) ( ) ( g g
D S C B S A + +
|
|
.
|

\
|
=

S
D S C
B S A s s
K
P C
P C k r
S
S
S
k
k
K

=
Reactions involving single - site and non - adsorbed molecule is referred to as following
Eley - Rideal mechanism
Desorption
C
The products of the surface reaction adsorbed on the surface are
subsequently desorbed into the gas phase.
When a species C S is desorbed from a site :
S C S C +
Desorption rate law:
|
|
.
|

\
|
=

DC
v C
S C D D
K
C P
C k r
D
D
DC
k
k
K

=
Desorption step for C is the reverse of the adsorption step for C:
AD D
r r =
C
DC
K
K
1
=
At steady state :
However, one particular step in the series
(adsorption - surface reaction - desorption) is
usually found to be rate-limiting or rate-
controlling
Langmuir - Hinshelwood approach is usually
applied to determine catalytic and
heterogeneous mechanisms.
Rate-limiting step
D S AD A
r r r r = = =
'
Langmuir - Hinshelwood approach example
The synthesis of ammonia from hydrogen and nitrogen,
3 2 2
2 3 NH N H +
mechanisms
S H S H + 2 2
2
S N S N +
2 2
S N S S N + 2
2
S S HN S H S N + +
S S N H S H S NH + +
2
S S NH S H S N H + +
3 2
S NH S NH +
3 3
rapid
rate - limiting
(dissociative adsorption)
rapid
rapid
Two noxious automobile exhaust product react to form environmentally
acceptable products
2 2
2
1
N CO NO CO + +
mechanisms
S CO S CO +
S S N CO S CO S NO + + +
2
S N S N S N +
2
S N S N +
2 2
rapid
rate - limiting
(surface reaction)
rapid
S NO S NO +
Development of rate laws for catalytic reactions that are
not diffusion-limited
Example : the decomposition of cumene
6 3 6 6 2 3 5 6
) ( H C H C CH CH H C +
P B C +
mechanisms
S C S C +
P S B S C +
S B S B +
|
|
.
|

\
|
=
=

C
S C
v C A
S C A v C A AD
K
C
C P k
C k C P k r
|
|
.
|

\
|
=
=

S
S B P
S C S
S B P S S C S S
K
C P
C k
C P k C k r
( )
v B B S B D
DB
v B
S B D
v B D S B D D
C P K C k
K
C P
C k
C P k C k r
=
|
|
.
|

\
|
=
=


Benzene adsorption
equilibrium constant
Whats next?
Assume one of the steps to be rate - limiting
Formulate the reaction rate law in terms of
the partial pressure of the species present
Determine the variation of the initial
reaction rate with the initial total pressure
Compare with the experimental observation
END
No
Yes
The adsorption of cumene rate - limiting
D A
S A
k k
k k
<<
<<
|
|
.
|

\
|
=

C
S C
v C A AD
K
C
C P k r
cannot be measured and must be replaced!
D A
S A
k k
k k
<<
<<
Steady state :
D S AD C
r r r r = = =
'
| + +
A
AD
D
D
S
S
k
r
k
r
k
r
Set as 0
|
|
.
|

\
|
=

S
S B P
S C S S
K
C P
C k r
S
S B P
S C
K
C P
C

=
( )
v B B S B D D
C P K C k r =

v B B S B
C P K C =

|
|
.
|

\
|
=

C
S C
v C A AD
K
C
C P k r
S
S B P
S C
K
C P
C

=
v B B S B
C P K C =

v
C S
P B B
C A AD
C
K K
P P K
P k r
|
|
.
|

\
|
=
B
C S
P
K
K K
K =
v
P
P B
C A AD
C
K
P P
P k r
|
|
.
|

\
|
=

G K RT
P
A = ln
S B S C v t
C C C C

+ + =
S
S B P
S C
K
C P
C

=
v B B S B
C P K C =

B B S B P B
t
v
P K K K P P
C
C
+ +
=
/ 1
v
P
P B
C A AD
C
K
P P
P k r
|
|
.
|

\
|
=
B B S B P B
P
P B
C t A
AD
P K K K P P
K
P P
P C k
r
+ +
|
|
.
|

\
|

=
/ 1
Initial rate : (P
P
= P
B
= 0)
0 0
'
0 C t A AD C
P C k r r = =
-r
C0

linear ?
P
C0

|
|
.
|

\
|
=

S
S B P
S C S S
K
C P
C k r
The surface reacting rate - limiting
D S
A S
k k
k k
<<
<<
|
|
.
|

\
|
=

C
S C
v C A AD
K
C
C P k r
cannot be measured and must be replaced!
D S
A S
k k
k k
<<
<<
Steady state :
D S AD C
r r r r = = =
'
| + +
S
S
D
D
A
AD
k
r
k
r
k
r
Set as 0
v C C S C
C P K C =

( )
v B B S B D D
C P K C k r =

v B B S B
C P K C =

v B B S B
C P K C =

v
S
P B B
C C S S
C
K
P P K
K P k r
|
|
.
|

\
|
=
B
C S
P
K
K K
K =
v
P
P B
C C S S
C
K
P P
P K k r
|
|
.
|

\
|
=

G K RT
P
A = ln
|
|
.
|

\
|
=

S
S B P
S C S S
K
C P
C k r
v C C S C
C P K C =

S B S C v t
C C C C

+ + =
v B B S B
C P K C =

C C B B
t
v
P K K P
C
C
+ +
=
1
C C B B
P
P B
C C t S
S
P K K P
K
P P
P K C k
r
+ +
|
|
.
|

\
|

=
1
Initial rate : (P
P
= P
B
= 0)
0
0
0
0
0
'
0
1 1
C C
C
C C
C C t S
S C
P K
P
P K
P K C k
r r
+
=
+
= =
k
-r
C0

P
C0

v C C S C
C P K C =

v
P
P B
C C S S
C
K
P P
P K k r
|
|
.
|

\
|
=
low initial partial pressure of cemene
high initial partial pressure of cemene
0
'
0 C C
P r k ~
C
C
K
r
k
~
'
0
|
|
.
|

\
|
=

S
S B P
S C S S
K
C P
C k r
The desorption of benzene rate - limiting
S D
AD D
k k
k k
<<
<<
|
|
.
|

\
|
=

C
S C
v C A AD
K
C
C P k r
cannot be measured and must be replaced!
S D
AD D
k k
k k
<<
<<
Steady state :
D S AD C
r r r r = = =
'
| + +
D
D
S
S
A
AD
k
r
k
r
k
r
Set as 0
v C C S C
C P K C =

( )
v B B S B D D
C P K C k r =

|
|
.
|

\
|
=

P
S C
B S B
P
C
K C
v
P
B
P
C
S C D D
C
K
P
P
P
K K k r
|
|
.
|

\
|
=
B
C S
P
K
K K
K =

G K RT
P
A = ln
( )
v B B S B D D
C P K C k r =

v C C S C
C P K C =

|
|
.
|

\
|
=

P
S C
B S B
P
C
K C
S B S C v t
C C C C

+ + =
C C P S C C
t
v
P K P K K P
C
C
+ +
=
/ 1
C P C S C C P
P
P B
C S C t D
D
P P K K K P P
K
P P
P K K C k
r
+ +
|
|
.
|

\
|

=
Initial rate : (P
P
= P
B
= 0)
t D D C
C k r r = =
0
'
0 -r
C0

P
C0

v C C S C
C P K C =

|
|
.
|

\
|
=

P
S C
B S B
P
C
K C
v
P
B
P
C
S C D D
C
K
P
P
P
K K k r
|
|
.
|

\
|
=
Final decision...
From experimental observation :
-r
C0

P
C0

Therefore, cumene decomposition is surface-reaction-limited.
S C S C +
P S B S C +
S B S B + C C B B
P
P B
C
S C
P K K P
K
P P
P k
r r
+ +
|
|
.
|

\
|

= =
1
'
In fact, more than 75% of all heterogeneous reactions that are not
diffusion-limited are surface-reaction-limited.
Adding of inert?
S C S C +
P S B S C +
S B S B +
S I S I +
What would be affected?
|
|
.
|

\
|
=

S
S B P
S C S S
K
C P
C k r
|
|
.
|

\
|
=

C
S C
v C AC ADC
K
C
C P k r
( )
v B B S B D D
C P K C k r =

|
|
.
|

\
|
=

I
S I
v I AI ADI
K
C
C P k r
D S
AI S
AC S
k k
k k
k k
<<
<<
<<
0 ~ ~ ~
D
D
AI
ADI
AC
ADC
k
r
k
r
k
r
v
S
P B B
C C S S
C
K
P P K
K P k r
|
|
.
|

\
|
=
v
S
P B B
C C S S
C
K
P P K
K P k r
|
|
.
|

\
|
=
S I S B S C v t
C C C C C

+ + + =
v B B S B
C P K C =

v C C S C
C P K C =

|
|
.
|

\
|
=

C
S C
v C AC ADC
K
C
C P k r
( )
v B B S B D D
C P K C k r =

|
|
.
|

\
|
=

I
S I
v I AI ADI
K
C
C P k r
0 ~ ~ ~
D
D
AI
ADI
AC
ADC
k
r
k
r
k
r
v I I S I
C P K C =

S I S B S C t v
C C C C C

=
I I C C B B
P
P B
C
S
P K P K K P
K
P P
P k
r
+ + +
|
|
.
|

\
|

=
1
Another example : isomerize straight-chain hydrocarbon molecules to
increase the octane number (i.e. the reforming process)
e ntan pe i e entan p n
O Al Pt wt

+
3 2
% 75 . 0
e ntan pe i pentene i pentene n e entan p n
Pt O Al P
t

3 2
We will study this part.
Isomerization of n-pentene to i-pentene
I N
Propose mechanisms
S N S N +
S S I S S N + +
S I S I +
Select rate-limiting step
|
|
.
|

\
|
=

S
S I v
S N v S S
K
C C
C C k r
Elimination
0 / ~
AD AD
k r
0 / ~
D D
k r
v N N S N
C K P C =

D
v I
S I
K
C P
C =

( )
2
1
I I N N
P
I
N
S
P K K P
K
P
P k
r
+ +
|
|
.
|

\
|

=
This does not fit the experimental observation.
The results obtained from the selection of the other
steps as the rate-limiting steps are not fit, either.
Propose other reaction mechanisms !!
Isomerization of n-pentene to i-pentene
I N
Propose other mechanisms
S N S N +
S I S N
S I S I +
Select rate-limiting step
|
|
.
|

\
|
=

S
S I
S N S S
K
C
C k r
Elimination
0 / ~
AD AD
k r
0 / ~
D D
k r
v N N S N
C K P C =

D
v I
S I
K
C P
C =

( )
I I N N
P
I
N
S
P K K P
K
P
P k
r
+ +
|
|
.
|

\
|

=
1
Fit the experimental observation !