CHE327

Petrochemical Technology

Module 13
Catalyst & Catalysis (Catalyst deactivation:
Causes, mechanisms, and treatment)
Course Outcome

Apply and integrate knowledge of

chemical process engineering various
petrochemical processes
Course Learning Outcome
By the end of the module, students should be able to:
• Describe the emergence of catalyst technology & importance of
1 catalyst and catalysis technology

• Identify the catalyst materials, properties, and preparation

2

• Explain the catalyst characterization and selection

3

• Describe the catalyst deactivation: Causes, mechanisms, and

4 treatment

• Explain the specific reactions using catalyst

5
 Emergence of
catalyst
technology &
importance of
catalyst and
catalysis
technology

Catalyst
Specific
materials,
reactions using
properties, and
catalyst
preparation

OUTLINE

Catalyst
deactivation: Catalyst
Causes, characterization
mechanisms, and selection
and treatment
 Poisoning

Attrition
Causes &
Fouling
Mechanism
Of
Deactivation

Thermal Loss Catalytic

Degradation Phase
Poisoning
• Poisoning is the strong chemisorption of reactants,
products or impurities on sites otherwise available for
catalysis.
• Thus poisoning has operational meaning ; that is,
whether a species acts as a poison depends upon its
adsorption strength relative to the other species
competing for catalytic sites.
• For example, oxygen can be a reactant in partial
oxidation of methane to methanol and a poison in
ammonia synthesis.
• In addition to physically blocking adsorption sites,
adsorbed poisons may induce changes in the
electronic or geometric structure of the surface or
cause compound formation.
Poisoning

C
S H H

M M M M M M

M M M M M

Conceptual model of poisoning by sulfur atoms of metal

surface during CO hydrogenation.
Poisoning mechanism

1)strongly
adsorbed
poison

2) Modifies the
abilities to
adsorb

3)restructuring
of the surface
atom
 Poisoning
• The mechanisms by which a poison may affect catalytic
activity are several fold;
• First, the strongly adsorbed poison (in this case an atom of sulfur)
physically blocks a three- or four-fold hollow adsorption / reaction
site (projecting into three dimensions) and three or four topside
sites on the metal surface.
• Second, by virtue of its strong chemical bond, it electronically
modifies its nearest-neighbor metal atoms and perhaps its next-
nearest-neighbor atoms, thereby modifying their abilities to adsorb
and/or dissociate reactant molecules (in this case H2 and CO
molecules).
• A third effect may be the restructuring of the surface by the strongly
adsorbed poison, possibly causing dramatic changes in catalytic
properties, especially for reactions sensitive to surface structure. in
addition, the adsorbed poison blocks access of adsorbed reactants
to each other (a fourth effect) and finally prevents or slows the
surface diffusion of adsorbed reactants (effect number five).
Poisoning
Table 8.2 poisons for selected catalysts in important reactions
Catalyst Reaction Poisons
Aluminosilicates, seolites Cracking Organic bases, hydrocarbons,
heavy metals
Nickel, platinum, copper Hydrogenation, dehydrogenation Compounds of S, P, As, Zn, Hg,
halides, Pb, NH3, C2H2
Nickel Steam reforming of methane, H2S, As
naphtha
Nickel, cobalt and iron CO hydrogenation of biomass-, coal- H2S, COS, As, NH3, HCN, metal
and natural gas-derived syngases carbonyls
Cobalt, noble metals on zeolites Hydrocracking NH3, S, Se, Te, P
Silver Ethylene oxidation to ethylene oxide C2H2
Vanadium oxide Oxidation As
Selective catalytic reduction As, Fe, K, Na from fly ash
Iron Ammonia synthesis, hydrogenation, O2, H2O, CO, S, C2H2, Bi, P, VSO4
oxidation
Platinum, Palladium Oxidation of CO and hydrocarbons Pb, P, Zn, S
Cobalt, and molybdenum Hydrotreating of residue Asphaltenes; N, Ni, and V
sulfides compounds
Coking
Carbon
deposition

Fouling
Fouling

blocks out the

active
compounds

Disintegrate the Block the pore

Catalyst structure

Decease the
active site
Carbon and coke formation
on metals
Block the Plug micro-
Totally
and
access encapsulate
mesopores

strong carbon
disintegration
filaments
of catalyst
build up
Carbon and coke formation on metals
• Carbon may:
1. Chemisorb strongly as a monolayer or physically adsorb in
multilayer and in either case block access of reactants to
metal surface sites
2. Totally encapsulate a metal particle and thereby
completely deactivate that particle
3. Plug micro- and mesopores so that access of reactants to
crystallites inside these pores is denied.
4. Finally, in extreme cases, strong carbon filaments may
build up in pores to the extent that they stress and fracture
the support material, ultimately causing disintegration of
catalyst pellets and plugging of reactor voids.
Thermal degradation and
sintering
crystallite growth  loss
of catalytic surface area

Sintering

Thermally Support pore collapse

induced on metal crystallites 
deactivation Loss of support area
of catalysts
results from:

Transformations of catalytic
Mechanical Failure : Attrition
and crushing of catalysts

Erosion of
catalyst
particles or
Attrition, the monolith
size reduction coatings at
and/ or breakup high fluid
of catalyst velocities.
granules or
Crushing of pellets due to
granular, pellet produce fines,
or monolithic especially in
catalyst forms fluid or slurry
due to a load beds, and
 restore
the
activity

Regeneration Use for

Discard of deactivated another
catayst application

Reclaim
and
recycle
CAUSES & MECHANISMS

Poisoning

• acts as a poison depends upon its adsorption

strength

Fouling

• activity loss due to blockage of sites and/or pores

Thermal Degradation

• Transformations of catalytic phases to non

catalytic phases
Loss of Catalytic Phases

• the temperatures for metal

vaporization exceed 100C

Attrition
Prevention of catalyst decay

Basic mechanism Problem Cause Method of minimization

Poisoning Loss of catalytic Blockage of sites by strong 1. Purification of feed, guard chambers
surface adsorption of impurity 2. Additives, which selectively adsorb
poison
3. Reaction conditions, which lower
adsorption strength
4. Mass transfer regimes, which
minimize loss of activity

Fouling by coke or Loss of catalytic Free radical reactions in 1. Avoid formation of free radicals,
carbon surface sites due to gas phase lower temperature
formation of 2. Minimize free space
carbon or coke 3. Free radical traps, diluents
films 4. Add gasifying agents (e.g. H2, H2O)

Sintering Loss of metal area Metal particle or 1. Lower reaction temperature

subparticle migration at 2. Use support stabilizers
high temperatures 3. Avoid water and other substances
that facilitate metal migration
REGENERATION OF DEACTIVATED
CATALYST

Restore activity

Used for other

application
Alternatives
Reclaim and
recycle

Discard
Summary
References & Acknowledgement
• Jacob A. Moulijn, Michiel Makkee, Annelies Van Diepen
(2007). Chemical Process Technology. John Wiley & Sons.
 Developer

Zarina Omar
zarin363@tganu.uitm.edu.my
Faculty of Chemical Engineering