1

Catalyst:
definition,
effect on activity and selectivity,
classification (homogeneous, heterogeneous, bio-catalysis)
Heterogeneous catalysis:
introduction
steps, macrokinetics
rate determining step (regimes)
mass transport by convection diffusion (Ficks law)
external diffusion
internal diffusion
simultaneous internal and external diffusion
Catalysis and macrokinetics
Catalysis and macrokinetics
2
Catalysis
Catalysis
Importance: approximately 85-90% of the products of
chemical industry are made in catalytic processes.
Definition: catalysis is a process in which the rate of a
reaction is enhanced by a relatively small amount of a
different substance (catalyst) that does not undergo any
permanent change itself.
3
How catalysts act ?
How catalysts act ?
A catalyst accelerates a chemical reaction by forming bonds with the
reactants, allowing them to form the products, which detach from the
catalyst, and leave it unaltered.
catalyst
catalyst
A
catalyst
P
bonding
reaction
separation
A
P
Thus, the catalytic reaction is a cyclic event in which the
catalyst participates and is recovered, in its original form, at the
end of the cycle.
4
1. The catalyst offers an alternative path for the reaction,
which is energetically more favorable
(higher reaction rate implies lower reactor capacity).
A P
(elementary reaction)
E
t
thermal reaction
H
react.
P
A
p
o
t
e
n
t
i
a
l

e
n
e
r
g
y
E
t
thermal reaction
H
react.
catalytic reaction
E
c
reaction
catalyst
A
catalyst
P
P
catalyst
separation
catalyst
A
bonding
reaction coordinate
p
o
t
e
n
t
i
a
l

e
n
e
r
g
y
E
c
< E
t
Catalysis and activity
Catalysis and activity
5
2. The catalysts change the kinetics, not the thermodynamics.
3. The catalysts accelerate both the forward and the reverse
reaction to the same extent.
There are also cases in which the combination of catalyst with
reactant or product is not successful:
Bond with the reactant too weak
Bond with the reactant (or product) too strong (catalyst
poisoning)
6
Catalysis and selectivity
Catalysis and selectivity
In the presence of multiple reactions (consecutive and parallel
reactions), a catalyst can accelerate selectively one reaction, thus
increasing the process selectivity.
Higher selectivity implies reduction of the separation costs and
waste of reactants.
7
Types of catalysis
Types of catalysis
Homogeneous catalysis:
reactants and catalyst are in the same phase (liquid or gas)
Heterogeneous catalysis:
reactants and catalyst are in different phases
Catalyst: solid, liquid
Reactant: liquid, gas
Biocatalysis:
enzymes are natural catalysts composed primarily of proteins
(many aminoacids coupled by peptide bonds).
Enzymes are the most efficient catalysts: highly active
(10
8
10
11
-fold rate increase) and extremely selective.
They work under mild conditions of temperature and pH.
8
Properties of catalysts
Properties of catalysts
easy difficult Catalyst separation
high limited Variety of application
drastic mild Reaction conditions
low high Selectivity
varying varying Activity
Heterogeneous
catalyst
Homogeneous
catalyst
Properties
9
Heterogeneous catalysts
Heterogeneous catalysts
Heterogeneous catalysts are solid materials which can be single or mixture
of substances.
Often, the active component is supported on another, generally inert
substance, called support.
As the reaction occurs on the surface, in general it is important to have
high surface area per unit of weight.
High surface area can be obtained by using porous materials.
The catalytic activity is associated to localized points of the surface, called
active centers. The decrease of the catalyst activity with the time is
referred to as catalyst deactivation and it can be associated to various
phenomena (fouling, sintering, poisoning etc.).
10
Heterogeneous catalyst can have
different shapes (powder,
granules, gauzes, pellets,
extrudate, rings etc.) and different
dimensions depending on the
reactor type.
11
Steps in a heterogeneously
Steps in a heterogeneously
-
-
catalyzed reactions
catalyzed reactions
Heterogeneous catalytic reactions take place on the catalyst surface .
As the reactant have to be transported from the bulk fluid to the
solid/fluid interface, the overall reaction includes also physical
transport processes, beside chemical steps.
Seven different steps :
1. External diffusion: transfer of the reactants from the fluid phase
surrounding the catalyst particle (bulk fluid phase) to the external
surface of the catalyst
2. Internal diffusion: transport of the reactants from the external surface
of the particle through the pores to the active sites on the interior
surface
3. Adsorption of the reactant on the active site
4. Surface reaction
5. Desorption of the product from the active site.
6. Internal counter-diffusion: transport of the product through the pores
to the external surface
7. External counter-diffusion: transport of the product from the external
surface to the bulk fluid phase
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Steps in a heterogeneously
Steps in a heterogeneously
-
-
catalyzed reactions
catalyzed reactions
Steps 3,4,5 are purely
chemical phenomena:
Step 1,2,6,7 are strictly
physical steps
(transport phenomena)
m
a
c
r
o
k
i
n
e
t
i
c
s
microkinetics
The transfer steps 1 and 7 depend upon the flowdynamics of the system.
The transport steps 2 and 5 are present only with porous catalysts and
depend on the geometry of catalyst particles.
13
Rate
Rate
determing
determing
step
step
Steps 1 and 7 (external diff.) are in series with steps 3-5 (chemical steps):
the external transfer occurs separately from the chemical reaction.
Steps 2 and 6 (internal diff.) occur simultaneously with the chemical reaction.
As the heterogeneously catalyzed reaction involves sequential steps, at
steady state the rate of these steps must be the same.
If the rate constant of one of these steps is markedly smaller than the
other, the overall rate is determined by this step, which is called the rate
determining step.
The reaction is said to be under the regime corresponding to the rate
determining step.
14
Regimes
Regimes
Kinetic regime: rds = chemical reaction
(synonym: chemical regime)
External diffusion regime: rds = external diffusion
(synonyms: film diffusion, external mass transfer limitation)
Internal diffusion regime: rds = internal diffusion
(synonyms: pore diffusion, internal mass transfer limitation).
15
Convective and diffusive transport
Convective and diffusive transport
Convection = transport by bulk motion of the fluid
initial condition
As the time passes
mixing occurs
Diffusion = transport due to gradients
(concentration gradients if the transported
property is the mass, temperature gradients if
the transported property is the thermal
energy)
16
Mass transport by diffusion: the Fick
Mass transport by diffusion: the Fick

s law
s law
The diffusive mass transport transfer can be described by the
Ficks law:
J is the mass flux, i.e. the moles transported per unit of
time and per unit of surface perpendicular to the diffusive
movement
C is the concentration of the diffusing substance,
D is the diffusion coefficient.
The negative sign indicates that the diffusion occurs in the
opposite direction of the concentration gradient.
dx
dC
D J =

s m
mol
2
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External diffusion: film model
External diffusion: film model
Film model:
Existence of a stagnant layer (film), of thickness , surrounding the external
surface of the catalyst, where is located the concentration gradient.
In the bulk fluid phase the concentration is constant.

film bulk
existing conc. profile
conc. profile according the film model
conc
solid
0
distance x
from the interface
C
b
C
s
fluid
If the supply of reactant from the bulk fluid to the external surface of the catalyst is
slower than the rate of the surface chemical reaction, the reactant concentration on
the catalyst surface C
s
will be lower than that in the bulk fluid phase C
b
.
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External diffusion: Fick
External diffusion: Fick

s law
s law

s m
mol
2
The rate of mass transfer is expressed by the Ficks law:
= thickness of the external film

=
b
s
C
C
dC D dx J

0
By integration:
) (
s b
C C
D
J =

As the determination of the thickness of the external film is difficult, normally

s m
mol
2
At steady state, the rate r of mass transfer must be equal to the rate of the surface
reaction, expressed per unit external surface area:
NB. k is the kinetic constant referred to the unit of volume catalyst
( )
n
s s b
kC C C a r = =
volume catalyst of unit per surface external catalyst a =
19
External diffusion: 1
External diffusion: 1
st st
order reaction
order reaction
For 1
st
order reaction (n=1):
( )
s s b
kC C C a r = =
Only the known bulk concentration C
b
appears.
At the denominator there is the sum of resistances for sequential processes:
1/k = chemical resistance
1/ = external mass transfer resistance
By expressing the unknown surface concentration C
s
in function of the known
bulk concentration C
b
:
b
C
a k
r

+
=
1 1
1
20
External diffusion: limit cases
External diffusion: limit cases
for 1
st
order reaction:

film bulk
conc
solid
0
x
C
b
fluid
1
4
2
3
1. No limitation by film diffusion
2.,3 film diffusion and reaction
4. maximum limitation by film diff.
b
C
a k
r

+
=
1 1
1
Strong limitation by film diffusion
(external diffusion regime)
steep gradient concentration
b
C a r = >> a k
b
kC r =
No limitation by film diffusion
(kinetic regime)
No gradient concentration
<< a k
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External diffusion:
External diffusion:
external effectiveness factor
external effectiveness factor

e e
conditions fluid bulk at rate reaction
rate reaction observed
e


=
n
b
obs
kC
r
=
If the supply of reactant from the bulk fluid to the external surface of
the catalyst will be not sufficiently fast to keep place with the potential
intrinsic rate of the chemical reaction, the concentration of the reactant
on the catalyst surface will be lower than that in the bulk fluid phase.
For positive reaction orders, the observed reaction rate is lower than
that corresponding to the bulk concentration (
e
<1)
The degree of the external diffusion limitation is given by the external
effectiveness factor:
22
Internal diffusion
Internal diffusion
For most catalysts the fraction of active sites located at the
external surface can be neglected. The reactant have to be
transported through the pores to reach the active sites.
The driving force for this transport (internal diffusion) is the
concentration gradient inside the catalyst particle due to the
chemical reaction.
The resistance for this transport originates from collisions of the
molecules, either with each other or with the pore walls.
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Internal diffusion
Internal diffusion
dx
dC
D J
e
=
The diffusive mass transport inside the catalyst particle can be formally described
by the Ficks law:
x = perpendicular distance from the center of the particle
D
e
= effective diffusion coefficient (instead of D).

s m
mol
2
D
e
takes into account that:
1.
p
= porosity of the catalyst particle (characteristic values: 0,2<
p
<0,7)
(the diffusion does not occur in all the particle volume but only through the pores)
2. =tortuosity of the pores (characteristic values: 3<<7)
(the pores neither are straight nor have the same cross-section: they have
irregular structure)
3. the resistance towards transport originates from collision of the molecules
either which each other (D
m
= molecular diffusivity) or with the pore walls
(D
k
= Knudsen diffusivity)

p
k m
e
D D
D
1 1
1
+
=
24
Internal diffusion:
Internal diffusion:
internal effectiveness factor
internal effectiveness factor

i i
conditions surface external at rate reaction
rate reaction observed
i


=
A degree of the internal diffusion limitation is given by
If the diffusion of the reactant from the external surface inside the
particle is not fast enough to compensate for its disappearance by
reaction, a decreasing concentration profile is established in the
particle.
For positive reaction orders, this leads to lower reaction rates at
positions away from the external surface and, hence, to a lower
reaction rate when averaged over the complete particle volume (
i
<1).
n
s
obs
kC
r
=
25
Thiele modulus
Thiele modulus

It is possible to demonstrate that the internal effectiveness

1 =
( ) 3 . 0 < small
s e
n
s
p
p
C D
kC
A
V

maximum rate
of pore diff.
rate of chem. reac.
without pore diff.
kinetic
regime
Int. diff.
regime
transition
/ 3 =
( ) 3 > large
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Simultaneous external and internal diffusion
At steady state, the rate of external mass transfer must be equal to the rate of the
surface reaction with internal diffusion.
( )
s b ex diff
C C a r =

s m
mol
3
volume catalyst of unit per surface external catalyst a =

s m
mol
3
(for 1
st
order reaction)
. . diff int. react ex diff obs
r r r
+
= =
At steady state:
By substitution:
general formula (for 1
st
order reaction
from this formula all the limited cases
can be obtained)
s i diff int. react
C k r =
+

. .
a
k
C k
r
i
b i
obs

+

=

1
27
rds: surface reaction
general formula (for 1
st
order reaction)
1. At low reaction temperatures, the rate constant is small relative to the
mass transfer coeffient Additionally, the Thiele modulus is small (since k is
small relative to D
e
) and thus is unity. In this case the surface reaction is
controlling and the concentration profile across the film and inside the
pore is flat. The activation energy derived from the reaction rate
correspond to the true activation energy of the chemical reaction
without mass transport limitations
a
k
C k
r
i
b i
obs

+

=

1
b
kC r =
att app
E E =
) / exp( ln
0
RT E k k
att
=
28
general formula (for 1
st
order reaction)
1. At intermediate reaction temperatures, the combination of pore diffusion
and surface reaction is slowest: pore diffusion is controlling and there is a
concentration gradient inside the pore. The activation energy derived
from the observed reaction rate constant corresponds to approximately
the half of the true activation energy
a
k
C k
r
i
b i
obs

+

=

1
b app b e
p
p
b
s
s e
p
p
b
C k C k D
V
A
kC
kC
C D
V
A
kC = =

1
b i
kC r =
rds: internal pore diffusion
att app
E E 5 . 0 =
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general formula (for 1
st
order reaction)
1. At high reaction temperatures, external diffusion is controlling and
there is a concentration gradient across the film. The activation energy
derived from the observed reaction rate constant is generally below
5kJ/mol
a
k
C k
r
i
b i
obs

+

=

1
b
aC r =
rds: external pore diffusion
mol kJ E
app
/ 10 5
30
Arrhenius diagram
ln k
1 / T
E
eff
= 5 kJ/mol
E
eff
= 0,5*E
a
E
eff
=E
a
ln k
1 / T
ln k
1 / T
E
eff
= 5 kJ/mol
E
eff
= 0,5*E
a
E
eff
=E
a
Film Diffusion
Pore
Surface Reaction
31
Van Santen, van Leeuwen, Moulijn, Averill
Catalysis: An Integrated Approach
Octave Levenspiel
Chemical Reaction Engineering, third edition, Wiley (1999).
32
Vocabulary
Active centre
Active component
Activit
Adsorption
Biocatalysis
Chemical regime
Convection
Deactivation
Desorption
Diffusion
Effective diffusion coefficient
Effectiveness
External mass transport regime
Gradient
Heat and mass transport processes
Homogeneous catalysi
Internal diffusion
Knudsen diffusion
Macrokinetics
Mass transfer
Mass transfer coefficient
Microkinetic
Molecular diffusion
Porosity
Porosity factor
Rate determining step
Regime
Selectivity
Stagnant layer
Support
Surface area
Surface reaction
Thiele Modulus
Tortuosity
Heterogeneous catalysis
Porous material