CATALYST DEACTIVATION

M.Ali Gholamalian
Lead Process Engineer
Darquein Oil Field
 I NTRODUCTION

Over the past

Time scales three decades,
for catalyst the vary
deactivation science of catalyst
considerably; for
• Catalyst Deactivation deactivation
example, in the hascase
beenofsteadily
crackingdeveloping, while literature
catalysts, catalyst mortality
• Definition addressing
may be onthis thetopic
orderhas expanded
of seconds, considerably
while in ammonia to synthesis
include
• Life time books
the iron [1–4], comprehensive
catalyst may last forreviews
5–10 [5–8],
years.proceedings
However, itofis
• Importance international
inevitable that symposia [9–14],
all catalysts topical journal issues (e.g.,
will decay.
[15]), andofmore
This area than provides
research 20,000 U.S. patents
a critical for the period
understanding thatofis
the loss over time of catalytic activity 1976–2013.
the foundation(In a U.S.for
patent search conducted
modeling deactivation in November
processes,
and/or selectivity, is a problem of great and 2013 for thestable
designing keywords catalyst
catalysts, andand deactivation,
optimizing catalyst
processes to
continuing concern in the practice of and life, or
prevent andslowcatalyst and
catalyst regeneration, 14,712, 62,945, and
deactivation.
industrial catalytic processes. Costs to 22,520 patents were found respectively.) This area of
industry for catalyst replacement and research provides a critical understanding that is the
process shutdown total billions of dollars foundation for modeling deactivation processes, designing
per year. stable catalysts, and optimizing processes to prevent or slow
catalyst deactivation.

No. 1 Butt, J.B.; Petersen, E.E. Activation, Deactivation, and Poisoning of Catalysts; Academic Press: San Diego, CA, USA, 1988 M.A. Gholamalian
 MECHANISMS OF DEACTIVATION

1. Poisoning
2. Fouling
3. Thermal degradation
4. Vapor formation
5. Vapor-Solid / Solid-Solid reactions
6. Attrition / Crushing

No. 2 M.A. Gholamalian

 1.POISONING
Reaction Catalyst Poisons
Poisoning is the strong chemisorption of reactants, products, or
Organic bases,
Cracking Silica–alumina, zeolites hydrocarbons,
Typecatalysis.
of heavy
interactionThus,
with
impurities on sites otherwise available for
• Definition Chemical type Examples metals
metals
Hydrogenation
poisoning has operational meaning; Compounds of S, P, As, Zn,
Nickel, platinum, that is, whether
palladium a species
• Mechanism Dehydrogenation Hg, halides, Pb, NH3, C2H2
Through s and p orbitals;
actsGroups
Steam as a VA
reformingand
of VIA
poison N, P, As,
depends uponSb, O,
itsS,adsorption
Se, Te shielded structures are less
strength
• Physically block Nickel toxic H2S, Asrelative to
methane, naphtha
• Change adsorption ability the othersynthesis
Ammonia species competing for catalytic sites.
Iron, ruthenium O2, H2O, CO, S, C2H2, H2O

• Restructuring of the surface Group VIIA synthesis

Fischer–Tropsch F, Cl, Br, I iron
Cobalt,
Through s and
H2S, COS,pAs,
orbitals;
NH3, metal
oxygen can be a reactant in partial oxidation of ethylenehalides
formation of volatile
carbonyls to
• Effect on adsorbed reactants Hydrocracking Noble metals on zeolites NH3, S, Se, Te, P
ethylene oxide on As,aPb,silver
Hg, Bi, Sn,catalyst and
Occupyad orbitals;
poisonmayin
• Effect on diffusion of reactants Toxicoxidation
Ethylene heavy metals
to Cd, Cu,
and oxide
ethylene ions Fe Silver C2H2
form alloys
hydrogenation of ethylene on nickel
• Catalyst poisons classification Oxidation/selective
Vanadium oxide As/Fe, K, Na from fly ash
catalytic reduction
• chemical origin Molecules that CO, NO, HCN, benzene, Chemisorption through
Oxidation of with
CO and multiple
adsorb multiple
acetylene, other
Platinum, palladium Pb,bonds and back
P, Zn, SO2, Fe
• important reactions hydrocarbons
bonds unsaturated hydrocarbons bonding
Cobalt and molybdenum Asphaltenes, N compounds,
Hydrotreating of residuum
sulfides Ni, V

No. 3 Maxted, E.B. The poisoning of metallic catalysts. Adv. Catal. 1951, 3, 129 177 M.A. Gholamalian
 1.POISONING
□ N-butyl amine poison
• Important Poisoning parameters ○ Carbon disulfide Poison
• Reversibility
• Reversible
• Irreversible
• Selectivity
• Selective poisoning
• Anti-selective poisoning
• Non-selective Poisoning
• Activity (α)
• Susceptibility (σ)
• Toxicity
• Resistance
• Tolerance

No. 4 Bartholomew C.H., “Mechanisms of Catalyst Deactivation”, Appl. Catal. A: General, 212, 17-60 (2001). M.A. Gholamalian
 1.POISONING

• Advantages
• Pt-containing naphtha reforming catalysts are often pre-sulfided to minimize
unwanted cracking reactions.
• S and P are added to Ni catalysts to improve isomerization selectivity in the fats
and oils hydrogenation industry.
• V2O5 is added to Pt to suppress SO2 oxidation to SO3 in diesel emissions control
catalysts.
• S and Cu added to Ni catalyst in steam reforming to minimize coking.
• For selective hydrogenation from alkynes to alkenes, Lindlar catalyst (Pt/CaCO3)
is partially poisoned with Pb and quinoline

Bartholomew, C.H.; Farrauto, R.J. Fundamentals of Industrial Catalytic Processes, 2nd ed.; W iley-Interscience: Hoboken, NJ, USA,
No. 5
2006. M.A. Gholamalian
 2.FOULING, COKING, AND CARBON
DEPOSITION
1. Fouling Fouling is the physical (mechanical) deposition of species from the fluid
• Definition phase onto the catalyst surface, which results in activity loss due to blockage
• Carbon and coke deposition of sites and/or pores. Important examples include mechanical deposits of
• Coke-sensitive
carbon and coke in porous catalysts, although carbon- and coke-forming
• Coke-insensitive
processes also involve chemisorption of different kinds of carbons or
2. Carbon and Coke Formation on
condensed hydrocarbons that may act as catalyst poisons. Carbon is typically
Supported Metal Catalysts
a product of CO disproportionation while coke is produced by decomposition
• Surface adsorption
or condensation of hydrocarbons on catalyst surfaces and typically consists of
• Encapsulation of metal particles
• Pores plugging polymerized heavy hydrocarbons. Nevertheless, coke forms may vary from

• Strong carbon filaments in pores high molecular weight hydrocarbons to primarily carbons such as graphite,
depending upon the conditions under which the coke was formed and aged.

No. 6 Trimm, D.L. Catalyst design for reduced coking (review). Appl. Catal. 1983, 5, 263 290 M.A. Gholamalian
 2.FOULING, COKING, AND CARBON
DEPOSITION
3. Coke Formation on Metal Oxide and
Sulfide Catalysts
• Polymerization of Olefins
• Cyclization from Olefins
• Formation of Polynuclear Aromatics
Mode 1 Mode 2
• Zeolite Coking (HZSM-5)
1. Reversible adsorption on acid sites
2. Irreversible adsorption on sites
3. Partial steric blocking of pores
Mode 3 Mode 4
4. Extensive steric blocking of pores

No. 7 Gates, B.C.; Katzer, J.R.; Schuit, G.C.A. Chemistry of Catalytic Processes; McGraw-Hill:New York, NY, USA, 1979 M.A. Gholamalian
 3.THERMAL DEGRADATION AND
SINTERING
• Definition Thermally induced deactivation of catalysts results from (1) loss
• Loss of surface area of catalytic surface area due to crystallite growth of the catalytic
Sintering
phase, (2) loss of support area due to support collapse and of
• Loss of support area catalytic surface area due to pore collapse on crystallites of the
active phase, and/or (3) chemical transformations of catalytic
• Chemical transformation Solid-Solid
phasesreaction
to noncatalytic phases. The first two processes are
typically referred to as “sintering”. The third is discussed in the
next section under solid–solid reactions. Sintering processes
• Metal crystallite growth mechanism generally take place at high reaction temperatures (e.g., > 500 °C)
a) Crystallite migration and are generally accelerated by the presence of water vapor.
b) Atomic migration
c) Vapor transport (Phase change)

Bartholomew, C.H. Sintering and redispersion of supported metals: Perspectives from the literature of the past decade. In Catalyst
No. 8 Deactivation 1997 (Studies in Surface Science and Catalysis); Bartholomew, C.H., Fuentes, G.A., Eds.; Elsevier: Amsterdam, The M.A. Gholamalian
Nethelands, 1997; Volume 111, pp. 585 592
 3.THERMAL DEGRADATION AND
• Complexity of sintering mechanisms
1. Dissociation/emission of metal
atoms or metal-containing
molecules from metal crystallites
2. adsorption and trapping of metal
atoms or metal-containing
molecules on the support surface
3. diffusion of metal atoms, metal-
containing molecules and/or metal
crystallites across support surfaces
4. metal or metal oxide particle
spreading
5. support surface wetting by metal
particles
No. 9
SINTERING
6. metal particle nucleation
7. coalescence of, or bridging
between, two metal particles
8. capture of atoms or molecules by
metal particles
9. liquid formation
10. metal volatilization through volatile
compound formation
11. splitting of crystallites in O2
atmosphere owing to formation of
oxides of a different specific
volume
12. metal atom vaporization
M.A. Gholamalian
 3.THERMAL DEGRADATION AND
SINTERING
• Factors Affecting Metal Particle Growth and Redispersion in Supported Metals
• Temperature
• Exponentially
• Atmosphere
• Sintering Decreases for supported Pt as: NO>O2>H2>N2
• Metal
• Thermal stability in O2 atmosphere:
• Volatility of metal oxide
• Strength of metal oxide–support interaction
• Support
• Thermal stability for a given metal: Al2O3>SiO2>Carbon
• Promoters
• Decrease atom mobility: C, O, CaO, BaO, CeO2, GeO2
• Increase atom mobility: Pb, Bi, Cl, F, or S
• Trapping agents (Decrease sintering): Oxides of Ba, Ca, or Sr
• Pore size
• Lower sintering for porous vs. nonporous support

Bartholomew, C.H.; Farrauto, R.J. Fundamentals of Industrial Catalytic Processes, 2nd ed.; W iley-Interscience: Hoboken, NJ, USA,
No. 10
2006 M.A. Gholamalian
 3.THERMAL DEGRADATION AND
SINTERING
• Sintering of Catalyst Carriers
• Surface diffusion
• Solid-state diffusion
• Evaporation/Condensation of volatile atoms or molecules
• Grain boundary diffusion
• Phase transformations
• Effects of Sintering on Catalyst Activity
• Structure-sensitive
• Structure-insensitive

Baker, R.T.; Bartholomew, C.H.; Dadyburjor, D.B. Sintering and Redispersion: Mechanisms and Kinetics. In Stability of Supported
No. 11
Catalysts: Sintering and Redispersion; Horsley, J.A., Ed.; Catalytica: Mountain View, CA, USA, 1991; pp. 169-225 M.A. Gholamalian
 4. GAS/VAPOR–SOLID AND SOLID-STATE
REACTIONS
1. Vapor phase with the catalyst surface
a) Inactive bulk and surface phases
b) Volatile compounds
2. Solid state Reactions
a) Catalytic solid-support or catalytic
solid-promoter reactions
b) Solid-state transformations of the
catalytic phase
3. Chemical assisted sintering

Bartholomew, C.H.; Farrauto, R.J. Fundamentals of Industrial Catalytic Processes, 2nd ed.; W iley-Interscience: Hoboken, NJ, USA,
No. 12
2006 M.A. Gholamalian
 5.MECHANICAL FAILURE OF CATALYSTS

• Forms and Mechanisms of Failure

• crushing of granular, Pellet and

Monolithic catalyst forms Loading of Fixed bed reactors

• Attrition
• Size reduction Fluid or slurry bed reactors
• breakup of granules/pellets

• Erosion of catalyst particles

• Monolith coatings at high fluid Any type of reactor
velocities

Argyle, Morris D., and Calvin H. Bartholomew. "Heterogeneous catalyst deactivation and regeneration: A review." Catalysts 5.1
No. 13
(2015): 145-269. M.A. Gholamalian
 SUMMARY OF DEACTIVATION
MECHANISMS FOR SOLID CATALYSTS
Causes of solid (heterogeneous) catalyst deactivation
1. Chemical
2. Mechanical
3. Thermal
Mechanisms of heterogeneous catalyst deactivation
1. Chemical degradation including volatilization and leaching
2. Fouling
3. Mechanical degradation
4. Poisoning
5. Thermal degradation
❖Poisoning and thermal degradation are generally slow processes, while fouling and some
forms of chemical and mechanical degradation can lead to rapid, catastrophic
catalyst failure. Some forms of poisoning and many forms of fouling are reversible;
hence, reversibly poisoned or fouled catalysts are relatively easily regenerated. On the
other hand, chemical, mechanical, and thermal forms of catalyst degradation are rarely
reversible.

No. 14 Bartholomew, Calvin H. "Mechanisms of catalyst deactivation." Applied Catalysis A: General 212.1 (2001): 17 -60. M.A. Gholamalian
 THANKS FOR YOUR ATTENTION

No. 15 M.A. Gholamalian