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CHAPTER 1

(Lecture Note Part 4)

CATALYTIC REACTION
AND
MASS TRANSFER

Catalyst
Subtopic covered in Chapter
1
Catalytic Reactions and Reactors
Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Catalytic Wall Reaction
Langmuir-Hinshelwood Kinetic Mechanism
Temperature Dependence of Catalytic Reaction
Rates
Application of Reaction Engineering in
Microelectronic Fabrication
Catalyst Deactivation
Catalyst Deactivation
So far, we have assumed that the
activity of the catalyst remains
constant throughout the catalysts
C = total
t
concentration
life. of active
sites
Unfortunately,
this is not the
case in most
industrially dCt / dt =
significant
catalytic 0
reactions!!

Catalyst
Deactivation
Catalyst deactivation
Defined as the loss of catalytic activity that occurs
as the reaction takes place on the catalyst.
Major problem faced by most industries when
conducting catalytic reactions.
Known to strongly affect the conversion, hence as a
result, affect the performance of the reactor itself.
Catalysts have only a limited lifetime. Some lose
their activity after a few minutes, others last for
more than ten years.
The maintenance of catalyst activity for as long as
possible is of major economic importance in
indu$try.
In catalyst deactivation, the most
important quantity that need to be
described is the activity of the catalyst,
a(t):

?
Naturally, the activity of catalyst is going to
change (decrease) with time. , a typical
curve of the activity as a function of time is:

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006


Catalyst deactivation is the result of
number of unwanted chemical and
physical changes.
Decline in activity is due to
- Blocking of the catalytically active
sites
- Loss of catalytically active sites due to
chemical,
thermal or mechanical processes.
Types of catalyst
deactivation
The decaying of catalyst activity can
traditionally happens through 3 ways:
Types of Catalyst Deactivation

/
Sinte
ring / Fouling
Aging Coking

Poisoning
Deactivation by Sintering

(Aging)
Loss of catalytic activity due to a loss of active surface
area (due to prolonged exposure to high gas-phase
temperatures).
The active surface area may be lost by:
Crystal agglomeration and growth of the metals
deposited on the support.

Loss of activity by narrowing or closing of the


pores inside the catalyst pellet.

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 www. Chemical Engineering Guy .com
Deactivation by Coking or
Fouling
This mechanism of decay is common
to reactions involving hydrocarbon.
It results from a carbonaceous (coke)
material from fluid phase being
deposited on the surface of a catalyst,
causing activity loss due to blocking of
sites and/or pores.

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006 www. Chemical Engineering Guy .c
Deactivation by Coking or
Fouling
When the catalyst is already Fouled
or coked, the material is normally
called spent catalyst

Fresh Spent
catalysts Catalysts

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The amount of coke deposited on the surface
after a time t has been found to obey the
following empirical relationship (Voorhies,
1945):

Concentration Fouling parameter,


of carbon on value typically
the surface 0.5
(g/m2)
Fouling parameter, which
is a function of feedstock
and reactor type

Coke deposited can be measured using TGA,


DTA or by monitoring the evolution of CO 2
and H2O.
Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006
Deactivation by Poisoning
Poisoning molecules become irreversibly
chemisorbed to active sites.
This reduce the number of sites available for
the main reaction.

The poisoning molecule, P may be a reactant or


a product in the main reaction, but normally is
the impurities in the feed stream.

www. Chemical Engineering Guy .com, www.n-u.


Deactivation by Poisoning
Petroleum feed stocks contain trace
impurities such as:
sulfur, lead, and other components
which are too costly to remove.

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Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006
Summary: Types of Catalyst
Deactivation
Decline on catalysts
activity with time
Sintering/Aging
phenomena
Loss of catalytic activity due
to loss of active surface
area (due to prolonged
exposure to high T).
Poisoning
irreversible chemisorption
of substances on the active
sites.
Fouling/coking
carbonaceous deposition on
active catalytic sites.

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Rate Law with Catalyst Deactivation
In order to take into consideration catalyst
deactivation in the rate law, some adjustment of the
rate law has to be made so that the decay of the
catalyst can be incorporated in the rate law.
Rate law that incorporates catalyst deactivation can
be categorized as:
a) Separable kinetics:

b) Nonseparable kinetics:

In our syllabus we shall only be looking at separable kinetics!


Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006
General reaction rate accounting for
catalyst activity/deactivation (separable
kinetics)

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006


Read the decay law for sintering
process, pg. 710 Fogler 4th ed.
Reactor design algorithm for the case of
decaying catalyst (fluid-solid system)

Fogler (4th Ed.)-Elements of Chemical Reaction Engineering, Copyright 2006


Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford

The Catalytic Wall Reactor


University Press

PFR
Design
Equatio PF
n R

Since the reaction happens at surface of reactors


wall, the rate of reaction involve is surface rate of
reaction (r).
=-
(area/volume) r
The Catalytic Wall Reactor
(cont.)
=-
(area/volume) r

For cylindrical
tube,

=- = - (4 /d) k CA
(area/volume) r

Integration of the equation above using the boundary conditions that C A


= CAo at z = 0 yields:

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford
The Catalytic Wall Reactor
(cont.)
For reaction limiting process:

For external mass transfer limiting


process:

For pore diffusion limiting process:

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford
Problem 7-12:

Answer: 14.7 cm

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University