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Catalyst Deactivation

Catalyst deactivation occurs through several mechanisms: 1. Sintering or phase transformation can occur due to local high temperatures, reducing the catalyst's surface area and changing its chemical properties. 2. Fouling involves physical deposition of substances on the catalyst's active sites, such as carbon deposition blocking sites. 3. Poisoning involves chemisorption of reactants, products, or impurities to catalyst sites, decreasing available sites over time. Poisoning can be reversible or irreversible. 4. Proper design of reactors and process controls can help minimize thermal deactivation, while removing poison materials from feeds can reduce poisoning effects.

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376 views16 pages

Catalyst Deactivation

Catalyst deactivation occurs through several mechanisms: 1. Sintering or phase transformation can occur due to local high temperatures, reducing the catalyst's surface area and changing its chemical properties. 2. Fouling involves physical deposition of substances on the catalyst's active sites, such as carbon deposition blocking sites. 3. Poisoning involves chemisorption of reactants, products, or impurities to catalyst sites, decreasing available sites over time. Poisoning can be reversible or irreversible. 4. Proper design of reactors and process controls can help minimize thermal deactivation, while removing poison materials from feeds can reduce poisoning effects.

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Fachri Arief
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Catalyst Deactivation

• Activity of catalysts normally decreases with time. The life of any


catalyst generally depends on type of reactions as well as reaction
conditions. For example, catalysts for catalytic cracking lose much of
their activity within seconds due to carbon deposition on the surface
while promoted iron catalysts used in ammonia synthesis have a
lifetime of years. For any catalytic process, the life of catalyst is a
major economic factor. To regenerate or replace deactivated catalysts,
the process needs to be shutdown and consequently production is
disrupted. Subsequent separation and regeneration of catalysts also
involve time and cost. Therefore, deactivation of catalysts increases
the cost of production signicantly.
Sintering or phase transformation

• Because of local high temperature, support of catalysts or catalyst


itself may undergo structural modication or sintering causing a
reduction in specic surface area or change in chemical nature of
catalytic agent so that it becomes catalytically inactive. Hence,
poisoning and fouling are dependent on concentration of reactant or
product or impurities. On the other hand, sintering and phase
transformation may be assumed to be independent of uid phase
composition. This is also therefore known as independent
deactivation.
Fouling

• Rapid deactivation can be caused by physical deposition of substance


on the active sites of catalysts. Carbon deposition on catalysts used in
petroleum industry falls in this category. Carbon covers the active site
of the catalysts and may also partially plug the pore entrance. This
type of deactivation is partially reversible and regeneration can be
done by burning in air.
Poisoning

•  Poisoning basically involve chemisorption of reactants or products or


feed impurities on the active sites of the catalyst surface, thereby
decreasing the number of active sites available for catalytic reactions.
Since poisoning involves chemisorptions, it is known as chemical
deactivation. This process can be reversible or irreversible. Compound
of sulphur and other materials are frequently chemisorbed on nickel,
copper and Pt catalysts. In reversible poisoning, the strength of
adsorption bond is not great and activity is regained when the poison
is removed from the feed. When the adsorbed material is tightly held
on the active sites, poisoning is irreversible and permanent.
Steps to reduce deactivation
Following steps can be taken to reduce the possibility of deactivation of
catalysts:
a. Removal of poison material form feed
b. Use of hydrogen which reduces coking
c. Removal of hot spot by proper design of reactor /process control to
prevent any thermal deactivation.  
Mechanism of catalysts deactivation
The deactivation of catalysts can occur by different mechanism as
explained below:
1.  Parallel deactivation
2. Series deactivation
3. Side-by-side deactivations
Parallel deactivation
• Reactant (A) produces a side product (P) which can deposit on the
surface thereby deactivating it. Deposition depends on reactant
concentration
Series deactivation
• Reaction product (R) can decompose or reacts further to produce
material (P) that deposit and deactivate the surface. In this case
deposition depends on product concentration
Side-by-side deactivations

• In this mechanism, impurity in feed (P) deposits on the surface


deactivating it. Deposition depends on concentration of impurities in
the feed
Independent deactivations

• This catalyst decay involves structural modications or sintering of


catalysts surface caused by exposure of catalysts to extreme
conditions such as high temperature. This decay is dependent on time
that the catalyst spends in high temperature conditions and is
independent of the materials in the uid
Activity as function of time (t)

The catalyst activity is defined as

The rate of catalyst decay, rd ,


Types of Catalyst Deactivation
Deactivation by Sintering (Aging)
Deactivation by Coking or Fouling
Deactivation by Poisoning

Deactivation by Sintering (Aging) (Example 10–4, Fogler)


Deactivation by Coking or Fouling

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