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Chemical Reaction Engineering CE103

Section 2: Heterogeneous Reactions


Instructor: Assoc. Prof. Babiker Karama
babiker.k.abdalla@gmail.com[0123890740]
DrBKM 03/10/2010
Postgraduate, Chem.Eng., UofG 1
Chapter Objective:
At the completion of this lecture students should be
able to:
Define a catalyst, a catalytic mechanism and a rate
limiting step
Size isothermal reactors for reactions with
Langmuir-Hinschelwood kinetics.
Discuss catalyst deactivation and reactor types and
describe schemes that can help offset the
deactivation.
Analyze catalyst decay and conversion for CSTRs
and PBRs with temperature-time trajectories,
moving bed reactors, and straight through
transport reactors.
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 2
Definitions
Catalyst: a substance that affects the rate of the
reaction and leaves unchanged
A catalyst changes only the rate of a reaction it does
not affect the equilibrium
Homogeneous Catalyst: catalyst is soluble in at least
one of the reactants
e.g. [CH
3
-CH=CH
2
+CO+H
2
]liquid Cobalt
Heterogeneous Catalyst: reaction involves more
than one phase
e.g. Cyclohexane Benzene + 3H
2

Pt on Al
2
O
3
-H
2
O
DrBKM 03/10/2010
Postgraduate, Chem.Eng., UofG 3
Catalyst Properties
Porous Catalyst has very large interfacial area
E.g Silica-alumina cracking catalyst has pore
volume=0.6 cm
3
/g, pore radius = 4 nm and
surface area = 300 m
2
/g
Molecular Sieves Catalyst has very small pore
size that will admit small molecules and prevent
the large ones
Supported Catalysts are catalysts with small
particles of active materials
Active materials are metals of metal alloys
Unsupported catalysts are catalysts with active
materials of other substances known as
promoters
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 4
Catalyst Properties
Deactivation is the decline of the catalysts
activity with time
The deactivation is due to aging or poisoning
There are two types of adsorption in gas-solid
catalytic reactions
Physical adsorption, similar to
condensation, exothermic with mild heat
generated
Chemisorptions are the ones which affects
the chemical reaction, also exothermic with
higher heat generated
Chemisorptions take place on the active sites
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Catalysts Classification
Halogenation-dehalogenation [CuCl
2
,AgCl, Pd]
Hydration-Dehydration [Al
2
O
3
, MgO]
Alkylation-Dealkylation [AlCl
3
, Pd]
Hydrogenation-Dehydrogenation [Co, Pt, Cr
2
O
3
,
Ni]
Oxidation [Cu, Ag, Ni, V
2
O
3
]
Isomerization [AlCl
3
, Pt/Al
2
O
3
, Zeolite]
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 6
Steps in a Catalytic Reaction
Mass Transfer from Bulk of fluid to catalyst
surface
Diffusion of Reactants through the pores to the
inside the catalyst
Adsorption of Reactants on the Catalyst Surface
Reaction of the Catalyst Surface
Desorption of Products from the Catalyst surface
Diffusion of the products from the pores of the
Catalyst to the surface
Mass Transfer of products from the external
surface to the bulk of the fluid
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 7
Steps in a Catalytic Reaction
Reaction
1- Adsorption on Surface
2- Surface Reaction
Single Site
Dual Site
3- Desorption from Surface
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 8
Steps in a Catalytic Reaction
Reaction
1- Adsorption on Surface
2- Surface Reaction
Dual Site
Eley-Rideal
3- Desorption from Surface
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 9
Adsorption Isotherms
Adsorption of A is given by
Total molar concentration of active site
per unit mass of catalyst = No. of active
sites per unit mass divided by Avogadros
No. [6.02x10
23
]
C
t
(mol/g cat) =C
v
+C
A.S
+C
B.S
[Site Balance]
Adsorption data are explained as
Adsorption Isotherms
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 10
Deriving an Expression for the Concentration of Species A
on the Surface
Beginning with our expression for the rate of
adsorption:
If the surface reaction is limiting, then:
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG
11
Deriving an Expression for the Concentration of
Species A on the Surface
Recall that:
and
Then:
Multiply both sides by C
t
and we're left with:
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 12
Heterogeneous data analysis
After selecting a mechanism
Assuming a rate limiting step
Find expressions for the
concentrations of the adsorbed
species
Make a site balance for the catalyst
surface
Drive the rate expression
Compare with the experimental data
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 13
The Rate Equation
C6H5CH3 + H2 C
6
H6 + CH4
T + H B + M
Rate Law
Rate assuming surface reaction controlled, and
only T and B are adsorbed at the catalyst surface
B B T T
P
M B
H T
T
P K P K
K
P P
P P k
r
+ +

=
1
) (
/
DrBKM 03/10/2010
Postgraduate, Chem.Eng., UofG
14
The Rate Equation Modified
Neglecting the reverse reaction rate will be
Now we are missing
k the rate constant
K
B
adsorption constant of component B
K
T
adsorption constant of component T
B B T T
H T
T
P K P K
P kP
r
+ +
=
1
/
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 15
Preparation for Analysis
Linearization of the rate equation
Using multiple regression techniques of
the Least-Squares Analysis
k
P K
k
P K
k r
P P
T T B B
T
T H
+ + =

1
/
j j o j
X a X a a Y
2 2 1 1
+ + =
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 16
Parameter Estimation
Parameters for analysis
Y
j
=P
H
*P
T
/(-r
T
)
X
1j
=P
B
X
2j
=P
T
Parameters to be estimated
a
o
=1/k
a
1
=K
B
/k
a
2
=K
T
/k
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 17
Data for Regression Analysis
Run # Rate P
T
X
1
P
H
X
2
P
T
P
H
/Rate
Y
7 71.8 1 1 0.0129
8 142 1 2 0.0141
9 284 1 4 0.0141
10 47 0.5 1 0.0110
12 117 5 1 0.0427
13 127 10 1 0.0787
14 131 15 1 0.1150
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 18
Least-Squares Analysis
Multiple Linear Regression
Analysis
N= number of runs
Three equations are formed for
obtaining the values of a
o
, a
1
and
a
2
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Equation 1

= = =
+ + =
N
j
j
N
j
N
j
j o j
X a X a Na Y
1
2 2
1 1
1 1
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Equation2

= = = =
+ + =
N
j
j j
N
j
N
j
j
N
j
j o j j
X X a X a X a Y X
1
2 1 2
1 1
2
1 1
1
1 1
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 21
Equation3

= = = =
+ + =
N
j
j
N
j
j j
N
j
N
j
j o j j
X a X X a X a Y X
1
2
2 2
1
2 1 1
1 1
2 2
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 22
Input Data for the Regression
Y
j
X
1
X
2
X
2
1
X
2
2
X
1
Y
j
X
2
Y
j
X
1
X
2
0.0129 1 1 1 1 0.0129 0.0129 1
0.0141 1 2 1 4 0.0141
0.0282
2
0.0141 1 4 1 16 0.0141
0.0516
4
0.0110 0.5 1 0.25 1 0.005
0.0110
0.5
0.0427 5 1 25 1 0.214
0.0427
5
0.0787 10 1 100 1 0.787
0.0787
10
0.1150
15
1 225 1 1.725
0.1150
15
0.289 33.5 11 353.25 25 2.758 0.3401 37.5
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 23
Equations Formed
0.289=7a
o
+33.5a
1
+11a
2
2.758=33.5a
o
+353.25a
1
+37.5a
2
0.3401=11a
o
+37.5a
1
+25a
2
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 24
Solution of the equations
Using Gauss Elimination Method
Program MATLAB can be used for this
solution
The set of equations is a 3X3 Matrix
Solution will be:
Axa=c
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 25
Values of Estimated Parameters
k= 154.46 (mol/kgCat.s.atm)
K
B
=1.39 (1/atm)
K
T
=1.038 (1/atm)
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 26
Design of Packed Bed Catalytic Reactor
Design Equation:
Rate Law:
Stoichiometry:
To
T
F
r
dW
dX
/

=
B T
H T
T
P P
P P
r
39 . 1 038 . 1 1
46 . 154
/
+ +
=
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 27
|
.
|

\
|
+

=
X
X
P P
To T
c 1
1
|
.
|

\
|
+
=
X
X
P P
To B
c 1
|
.
|

\
|
+
+ O
=
X
X
P P
H
To H
c 1
2
2
Solution of Design Equations
Combining the Design Equation,
Rate Law and Stoichiometry and
solve the equation using any
Numerical Techniques
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DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 29
On of the big problem facing catalytic
reactor designers is the decay of catalyst
with time.
Types of Catalyst Deactivation
There are three types of catalyst
Deactivation
Deactivation by Sintering or
Aging
Deactivation by Coking or
Fouling
Deactivation by Poisoning
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Deactivation by Sintering or Aging
Commonly aging is considered as 2
nd
order
r
d
=k
d
a
2
=-da/dt
Integrating with a=1 at t=0
a(t)=1/(1+k
d
t)
Amount of sintering is given by measure of
active surface area
S
a
=S
ao
/(1+k
d
t)
The decay constant can be given by the
Arrhenius equation
( )
(

|
|
.
|

\
|
=
T T
T k k
o
R
E
o do d
d
1 1
exp
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 31
Deactivation by Coking or Fouling
o The decay is caused by coke materials
deposited on the catalyst surface
o The amount of coke on the surface is given
by
o C
C
=At
n
where A and n are fouling
coefficients
o % coke =0.47t
0.5
o There are some commonly used relation for
the decay by fouling
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 32
Common forms
or
Light oil cracking
C
C
e a
2
o
=
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1
1
+
=
np p
t n
a
1
1
+
=
P
C
C
a
2 / 1
6 . 7 1
1
t
a
+
=
C
C
a
2
1
1
o +
=
Deactivation by Poisoning
Poisoning molecules are
irreversibly chemisorbed on an
active site
The number of active site is then
reduces
Poisoning molecules can become a
Reactant or a Product
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 34
Poisoning in the feed stream
A + S A.S
A.S B.S +C(g)
B.S B + S
P + S P.S
The rate of reaction:
B B A A
A
A
C K C K
kC
t a r
+ +
=
1
) (
\
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 35
Poisoning in the feed stream
Rate of decay:
The rate of poisoning is proportional to the
no. of unpoisoned sites
q m
P d D
a C k
dt
da
r
\
= =
P S P to S P
C C C k r ) (
. .
=
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 36
P S P to d S P
S P
C C C k r
dt
dC
) (
. .
.
= =
Poisoning by Reactants or Products
Main
A + S B + S -r
A
=k
A
C
n
A
Poison
A + S A.S r
d
=k
\
d
C
m
A
a
q
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 37
Modified Algorithm of reactor design
Mole Balance
Rate law
Decay Law
Stoichiometry
Combining and Solve
Numerical Technique
DrBKM 03/10/2010 Postgraduate, Chem.Eng., UofG 38