Catalyst Deactivation

朱信
Hsin Chu
Professor
Dept. of Environmental Eng.
National Cheng Kung University
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1. Introduction
 Deactivation
a. high temperature exposure: automobile catalytic
converter, close to 1000℃
b. poisoning: exhaust or process contaminants
adsorbing onto or blocking active sites
c. attrition and erosion of the washcoat from the
support
 Model Reaction
A convenient tool for studying deactivation and
regeneration
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2. Thermally Induced Deactivation

A perfectly dispersed (100% dispersion)

catalyst is one in which every atom (or
molecule) of active component is available to
the reactants. This is shown is Fig. 5.1 (next
slide).

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 Some catalysts are made in this highly active state but
are highly unstable, and thermal effects cause crystal
growth, resulting in a loss of catalytic surface area.
 Additionally, the carrier with a large internal surface
network of pores tends to undergo sintering with a
consequent loss in internal surface area.
 Besides, reactions of the catalytically active species
with the carrier, resulting in the formation of a less
catalytically active species.

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2.1 Sintering of the Catalytic Component

 Next slide (Fig. 5.2)

Sintering by growth of catalyst crystals
This condition can be measured by selective chemisorptions
techniques in which a thermally aged catalyst adsorbs much
less adsorbate than when it was fresh.
 Stabilizer
Certain rare-earth oxides such as CeO2 and La2O3 have been
effective in reducing sintering rates of Pt in the automobile
exhaust catalytic converter.
It may fix the catalytic components to the surface minimizing
mobility and crystal growth.

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2.2 Carrier Sintering
 Within a given crystal structure, such as γ-Al2O3, the
loss of surface area is associated with loss of H2O and
a gradual loss of the internal pore structure network,
as shown in the next slide (Fig. 5.3)
 The presence of these phenomena is determined by a
progressive decrease in the activation energy of the
reaction.
 Second slide (Fig. 5.4)
Conversion profiles for various deactivation modes

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 Second mechanism for carrier change in crystal structure
γ-Al2O3 → α-Al2O3
150 m2/g < 5 m2/g
Anatase TiO2  o
550 C
 Rutile TiO2
60 m2/g < 10 m2/g
 Stabilizer
BaO, La2O3, SiO2, or ZrO2 can retard the rate of sintering in
certain carriers.
They are believed to form solid solutions with the carrier
surface, decreasing their surface reactivity, which leads to
sintering.

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2.3 Catalytic Species-Carrier Interactions

 Rh2O3 reacts with a high-surface-area γ-Al2O3,

forming an inactive compound during high-
temperature lean conditions in the automobile
exhaust. (for NOx removal)
Rh2O3  Al2O3 
 Rh2 Al2O4
800o C
air

 Therefore, it is better to use carriers such as SiO2,

ZrO2, TiO2, and their combinations that are less
reactive with Rh2O3 than Al2O3.
However, these alternative carriers are not as stable
against sintering.
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3. Poisoning

Selective poisoning
A chemical directly reacts with the active site
or the carrier, rendering it less or completely
inactive.
Nonselective poisoning
Deposition of fouling agents onto or into the
catalyst carrier, masking sites and pores,
resulting in a loss in performance.

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3.1 Selective Poisoning
 Next slide (Fig. 5.5)
A poison directly reacts with an active site
 Permanent deactivation
Pb, Hg, and Cd react directly with Pt, forming a
catalytically inactive alloy.
 Reversible deactivation
SO2 merely adsorbs onto a metal site (i.e., Pd). Heat
treatment, washing, or simply removing the poison
from the process stream, often desorbs the poison
from the catalytic site and restoring its catalytic
activity.
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 When active sites are directly poisoned, there is a
shift to high temperature but with no change in the
slope of conversion profile since the remaining sites
can function as before with no change in activation
energy.
 When the carrier reacts with a constituent in the gas
stream to form a new compounds, as in the case of
Al2(SO4)3, pores are generally partially blocked,
resulting in increased diffusion resistance. This will
cause a decrease in the activation energy.
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 SO2 chemisorbs onto Pd/γ-Al2O3, causing deactivation for
methane oxidation. Some of the adsorbed SO2 is converted to
SO3, which spills over, forming Al2(SO4)3.
Using nonsulfating carriers such as ZrO2 or SiO2 leads to a
faster rate of deactivation since no reservoir is available for
spillover.
 With the Pt/γ-Al2O3 catalyst the SO2 is readily converted to
SO3, which rapidly desorbs and reacts with the Al2O3, forming
Al2(SO4)3, which slowly causes pore plugging.
By using nonsulfating carriers, the Pt catalyst can be made
resistant to deactivation.

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3.2 Nonselective Poisoning
 Aerosol or high-molecular-weight material from upstream
equipment physically deposit onto the surface of the washcoat
to cause deactivation is referred to as “fouling” or “masking”.
 Reactor-scale metals (Fe, Ni, Cr, etc.) resulting from corrosion,
silica/alumina-containing dusts, phosphorous from lubricating
oils, and similar compounds are good examples.
 Next slide (Fig. 5.6)
Masking or fouling of a catalyst washcoat
 Second slide (Fig. 5.7)
SEM of fresh and aged Pt/Al2O3 surfaces

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4. Washcoat Loss

Attrition or Erosion
Irreversible deactivation
a. high linear velocities of gas flow
b. thermal expansion differences between the
washcoat and the monolith, especially metal
substrates

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