Classification of

Catalyst
Catalyst Properties
• Surface area, pore size, Particle distribution,
• Active sites - dispersed throughout the internal surface through which reactants
and products are transported
• Size and number of pores determine the internal surface area.
• Catalyst need to have high surface area (large number of small pores) to maximize
the dispersion of catalytic components.
• Pore size is too small, diffusional resistance becomes a problem.

Nitrogen Porosimetry
• Standardized procedure for determining the internal surface area of a porous material
• Adsorption of N2 at liquid N2 temperature onto the internal surfaces of the carrier
• Each adsorbed molecule occupies an area of the surface comparable to its cross sectional area (16.2 Å2)
• measuring the number of N2 molecules adsorbed at monolayer coverage, internal surface area can be calculated
• Adsorption of N2 first rapidly rises with pressure and then flattens in the
general region where monolayer coverage is occurring
• At high relative N2 partial pressures, coverage beyond a monolayer occurs
• Liquid N2 in the pores, giving rise to the large increase in volume adsorbed
• The Brunauer–Emmett–Teller (BET) equation - the relationship between
volume adsorbed at a given partial pressure and the volume adsorbed at
monolayer coverage

• Mercury intrusion method is preferred (ASTM D4284-83, 1988) method for estimation
of pore size
• Penetration of mercury into the pores of a material is a function of applied pressure
• At low pressures, mercury penetrates the large pores, whereas at higher pressures
the smaller pores are progressively filled
• Due to the non-wetting nature of mercury on oxide carriers, penetration is met with
resistance
• The Washburn equation relates the pore diameter, d p, with the applied pressure, P.
Particle size distribution
• Size of the powdered particles that make up the carrier must be compatible with
the reaction conditions for a slurry phase or fluid bed process
• Carrier powders are ball milled to produce the desired consistent particle size
• Further applications that include separation and recovery of the catalyst from
the product for its reuse
• Sieves of various mesh sizes have been standardized; thus, one can determine
particle size ranges by noting the percentage of material, usually retained on a
specific screen.
• Sieves are stacked with the coarsest on top and the underlying screens
progressively finer.
• Precise weight of catalyst material is added to the top screen.
• The stack of sieves is vibrated, fine particles are passed through coarser
screens Finer ones pass through coarse screen, ultimately retained by screens
finer in opening than the particle size of the material of interest.
• Each fraction is then weighed, and a distribution determined.
• Methods include electronic counting, light scattering,
image analysis, sedimentation, centrifugation &
volume exclusion.
• Laser techniques have been found effective - He–Ne
laser beam is passed through an aqueous
suspension of particles and it is diffracted in
proportion to the radius of the particle.
Characteristics of a Catalyst
• A catalyst remain unchanged in mass and in chemical composition at end of
a reaction. It can undergo a physical change
• A small amount of catalyst is generally needed to initiate a reaction. Infact a
large amount of reactant system can be initiated for reaction using a small
amount of catalyst. Some specific cases demand the use of catalyst in large
amounts to the extent of 30%.
• Finely divided form of catalysts are more effective rather than used in bulk
• A catalyst is specific in its action - While a particular catalyst works for one
reaction, it will not necessarily work for another reaction. Different catalysts,
moreover, can bring about completely different reactions for the same
substance.
• A catalyst cannot, in general, initiate a reaction: In most cases a catalyst
speeds up a reaction already in progress and does not initiate (or start) the
reaction. But there are certain reactions where the reactants do not
combine for very long period
• Catalyst can alter only the speed of the reaction but it
should not affect the equilibrium of the reaction.
• Catalysts are more active at its optimum temperature.
Change of temperature alters the rate of a catalytic
reaction as it would do for the same reaction without a
catalyst.
• The catalytic activity can be altered by adding a small
amount of foreign substance.
• Components which catalyze the catalyst are called as
promoters
• Components which inhibits the reaction are called as
catalytic poisons or anti-catalyst.
Mesoporous & Microporous Catalysts
• IUPAC has classified porous materials into three classes based on their
pore diameter
(a) Microporous, d < 2.0 nm
(b) Mesoporous, 2.0 < d < 50 nm;
(c) Macroporous, d > 50 nm.
• Presence of the mesopores - basically increase the accessibility of large
molecules to the external opening of the pores.
• For large reactant molecules, the presence of mesopores in the crystallites
of the zeolite is equivalent to increasing the external surface of the zeolite
making a larger number of pore openings accessible to the reactant.
• Facilitate low reaction temperatures and only moderate regeneration
temperatures will be necessary.
• Nano porous materials facilitate the production of lighter materials,
contributing to material stability
a. Microporous
material
b. Mesoporous
material
c. Nanoporous
material
Microporous Catalysts
• Common among microporous materials include: Zeolites
• Crystalline hydrated tectoaluminosilicates of alkali and alkaline-earth cations
with fully cross-linked open-framework structures.
• Property of functioning as a sieve on a molecular scale, only adsorbing
molecules with less than certain critical dimensions.
• Term molecular sieve has been coined to describe this selective phenomena

• Topology of the framework can be described in terms of a finite number

of specific combinations of tetrahedral sites called “secondary building
units (SBU’s)
• Zeolite framework of different topologies are identified through a three
letter code: FAU ( Zeolite – Y)
• Characteristic features of zeolites and analogues are a high surface
area (about 1000 m2/g),
• Highly ordered micropore channel system with uniform pore sizes and
shape,
• Presence of charges and ions at well-defined sites in the framework.
• Well defined pore system results in the molecular sieving property
exclude molecules with a too large kinetic diameter from the pore
system – molecular sieving effect
• Presence and the particular distribution of the charges and ions create
a specific electric field within the framework,
• This controls property of hydrophilicity and the introduction of ion-
exchange properties.
• Widespread applications as dehydrating agents, selective adsorbents,
ion exchangers, and, most importantly, catalysts of both high activity
and selectivity for a huge number of different reaction.
FA ZSM –
U 5
Mesoporous Catalysts
• Mesoporous materials have pore sizes in the range
between 2 nm and 50 nm
• The approximate surface area is in the range of 400 –
500 m2/g
•• Most
Ordered
importantand disordered
materials pore
in category of systems
ordered mesoporous materials
• Pore size ( 5 – 40 nm)
• Variety of surface properties – MCM – 41
• Silica still remains as a prevalent material in this field
• Production of silica by sol gel method (highly irreversible – Si – O bonds)
• Free energy of silica is very close to that of its most stable form, crystalline
quartz.
• Silica units are available to be synthesized in anionic, neutral, or cationic form,
depending on the pH conditions
Applications
• Mesoporous Materials as Catalyst Supports
• Thin Films and Membranes—Separation
• Adsorbents—Gas/Liquid Adsorption
• Stationary phase in normal phase high-performance liquid
chromatography (HPLC).
• Acidic and/or basic properties of mesoporous materials -
chromatographic separation of acidic, neutral, and basic
compounds.
Introduction to Supported Catalysts
• Catalysts in which active phase is dispersed on inert support.
• Silica, activated alumina) or forming a second active phase
(acidic aluminas, silica-aluminas, zeolites, - bifunctional
catalysts (Pt /Alumina, Pd /HY ; Cu/ZSM-5)
• Catalyst support are generally provide high surface area for
catalyst.
• Variation in selectivity.
• Process – Minimises loss of catalyst.
• Carbon (many variations) – high surface area adsorbs
impurities of all kind for VOCs
• Additional porosity, Mechanical Properties, Stability, Dual
functional activity, Modification in function of active
component.
 Preparation of Bulk Catalytic phase
• Dissolution Starting compounds, very soluble in the chosen solvent: Ex. - Nitrate in
aqueous solution

• Precipitation (to obtain a solid phase from a liquid phase - conditions to be satisfied:
thermodynamics (solubility product is reached); kinetics (the supersaturation state is
reached): usually a hydroxide, by varying the pH.

• Precipitates can be crystalline or amorphous, and their formation takes place in two steps:
(i) nucleation (formation of precipitate); (ii) growth of precipitate and / or aggregation of
the particles.

• Hydrothermal Treatments: may occur during various stages of catalyst preparation:

(i) Dissolution of part of the solid by the solvent;
(ii) Precipitation of a solid component different from the initial,
(iii) Washing – removal of nitrates, chlorides
(iv) Drying;
(v) Calcination (determines the proper functioning of the catalyst: pore
diameter, particle size, surface area),
(vii) Activaiton
 Preparation of Supported Catalysts
Preparation of the support ( normally a bulk species), as described for the bulk
catalysts;

Impregnation (introduction of the active phase on the support);

Filtration and drying (normally can determine location of active species in the
support structure);

Calcination & Reduction (High temperature and formation of metal reduced

species)
Case Study - Pt/Alumina catalyst (commercial alumina)
1 - Tetramine platinum nitrate aqueous solution impregnated in
alumina (Stirring for 2 hours)
2- filtration and drying (120 °C)
3 - calcination in air at 450 °C (removal of nitrates ~ 350 oC and
formation of the metal oxide, PtO)
4 – metal oxide reduction under hydrogen at 500 ° C (Pt0 /Alumina)
 Catalytic Deactivation
Loss of activity with time on
stream
Activity

Time
 Catalysts Deactivation
Loss of activity with time on
stream
1. Poisonin
g
2. Coking
3. Sinterin
g
4. Phase Transformation
1.
Poisoning
Loss of activity due to the strong chemisorption on
the active sites of impurities present in the feed
stream

• Geometric effect: blocking an active site

• Electronic effect: alter the adsorptivity of other species

• Chemical effect: alter the chemical nature of the

active site

• Reconstruction: formation of new compounds

1.
Poisoning
• Reversible: not too strongly adsorbed
• Irreversible: irreversible damages

• Selective: contribution of the characteristics of the

active site
• Non-Selective: poison occurs in a uniform manner

Affected

Selectivity

Not Affected (Selective Poisoning)

1b. Preventing
Poisoning
Best method: Decrease to acceptable levels the poison
content in the feed stream
• Carbon monoxide: Can decrease the activity of iron catalysts
used in the production of ammonia
• Hydrogen sulfide: Can decrease the activity of iron catalysts
used in the production of ammonia

Another approch: Choose proper catalyst formulation and

design
2.
Cokin
g Catalytic reactions involving HC or CO

Formation of carbonaceous residues

Coke or Carbon
Coking or condensation CO disproportionation
of HC 2 CO C+
CHx: 0.5 < x < 1 CO2

Physically cover the active sites

Coke or
Carbon
Pore blocking
2.
Cokin
Mechanism of coke formation
g
• Olefin polymerization
• Olefin cyclization to substituted benzenes
• Formation of polynuclear aromatics from benzenes

via carbonium ions intermediates

Analytical techniques
• IR • UV-vis
• TG-DTA • 13C-NMR
• Evolution of combustion products
(CO2 and H2O)
2.
Cokin
Coke deposition
g
Preferencially on the exterior of the particles

Resistance to the transport

of reactants and products in
the pores
Pore blocking
2b. Preventing
Coking
Appropriate combination of process conditions
The gas mixture composition is kept as far as
possible from conditions under which carbon
formation is thermodynamically favored
• High H2 pressure in catalytic reforming
• Low HC / H2O ratios in steam reforming over Ni catalysts

Optimal catalyst composition

Promoters or additives that enhance the rate
of gasification or coke precursors and / or
depress the carbon - forming reactions.
• K in Ni - based steam - reforming catalysts
• Pt - Re / Al2O3
3.
Sintering
Loss of active surface area via structural modificaion
of the catalyst.

• Metal catalysts (supported or unsupported)

Agglomeration and coalescence of small metal crystallites

into larger ones with low surface - to - volume ratio.

Crystalline Atomic Result:

migration migration Particle size growth

Low High
Temperature Temperature
3.
Sintering
• Oxide catalysts
Coalescence and growth of bulk oxide cristallites
1250°C 1400°C

Result:
• Increase in
crystallite dimension
• Increase in grain
1550°C 1600°C dimensions
• Decrease of surface
area and porosity

SEM images of CeO2 sintered at different temperatures

Zhang T. et al. Materials Letters 57 (2002), 507 - 512
3.
Sintering
Key
factors:
Temperature
Sinterisation is a thermic activated process

Reaction
atmosphere
Water vapor accelerates crystallization and
structural change in oxide catalysts.
Catalytic activity
• Activity of catalyst depend on a large extent on
strength of chemisorption sites.
• Adsorption has to be reasonably strong – not strong
to extent that no space for the reactents to get
adsorbed.
• Denoted by katal (SI unit of activity)
• Unit is mol / sec
• 1 katal = 1 mol / sec
• Not exactly specify reaction rate
• Catalytic activity of 1 katal means amount of catalyst
(in mol) lead to net reaction rate of one mole per
second of reactant
• Outcome should result for intended chemcial
reaction
• Different activity can be exhibited by same catalyst
for distincitve reactions.
 Promoters
• Materials that enhance catalytic effect
• Two classifications: Sturcutral and electronic
1. Structural promoter
• Component added to a catalyst that primarily affects its
physical structure, like increasing its surface area, pore size, or
stability
• Catalytic activity is enhanced without necessarily directly
participating in the chemical reaction itself; essentially, it
modifies the catalyst's architecture to optimize its performance.
• Cerium oxide (CeO2): Often used as a structural promoter in
cobalt-based catalysts, preventing cobalt particles from
sintering and maintaining a stable active phase.
• Aluminum oxide (Al2O3): Can act as a structural promoter in
iron catalysts for ammonia synthesis, helping to maintain a
high surface area.
• Barium (Ba): Can be used as a structural promoter, affecting
the adsorption and reaction of pollutants on the catalyst
surface.
2. Electronic promoter
• Electronic promoters: These alter the electronic properties of
the active metal in a catalyst, influencing its ability to interact
with reactants by donating or accepting electrons.
• Catalytic activity is enhanced by modifying surface interms of
polarization effects
• K or Cs atoms when present in zeolite has the capability to
modify surface by creating dipoles.
• Strongly adsorption effects of atoms with adsorbate are created
accordingly increasing activity.

Active Centers
• Correspond to the sites where adosprtion of
substrate is facilitated on catalyst surface.
 Catalyst Regeneration
• Loss of activity of catalyst with time is inevitable

• Once the activity of catalyst declines to a specific level

an alternative has to be chosen
– Restoring activity of catalyst
– Use it for any other specific application
– Recovering utilizable components
– Recycling of active portion of catalyst
– Safe disposal of catalyst

• Options are specified in decreasing order of alternative

methods
• Envrionmental considerations are to be made before
last option of disposing to environment
• The ability of a catlyst to be reactivated highly depend
on deactivation process
• Carbon and coke formation is relatively easily reversed
through gasification with hydrogen, water, or oxygen.
• Sintering on the other hand is generally irreversible,
although metal redispersion is possible under certain
conditions in selected noble metal systems.
• Specific poisons or foulants can be selectively removed
by chemical washing, mechanical treatments, heat
treatments, or oxidation
• Some others need deactivation or safe disposal of
catalyst.
• Decision to regenerate / recycle catalyst depend on rate
of deactivation
• Rapid deactivation through coking – Continuous
regeneration becomes necessity.
• Three important petroleum refining process – FCC,
Catalytic hydrocarbon reforming, alkylation
 Regeneration of Catalyst Deactivated
by Coke or Carbon
• Carbon deposits can be removed by gasification with O 2, H2O,
CO2 & H2
• Temperature required for gasification depend on type of gas,
sturcture, reactivity of carbon or coke, activity of catalyst.
• Gasification rates are greatly accelarated by metal or metal
oxides.
• Industrial process typically regenerate catalyst deactivated by
carbon in presence of air.
• Air regeneration is also required for using it as a meidum.
• Hot spots to be avoided – further deactivation of catalyst
• Combustion process is carried out by feeding low air
concentrations, followed by increasing oxygen conentrations
increasing carbon converison.
• Shrinking core model – reaction occuring on the surface
followed by reactions at inside surfaces
• Coke – burnoff being an exothermic process – reaction is
controlled in a big way by film heat and mass transfer.
 Regeneration of Poisoned Catalysts

• Sulfur-poisoned Ni, Cu, Pt, and Mo with oxygen/air, steam,

hydrogen, and inorganic oxidizing agents.
• 80% removal of surface sulfur from Mg- and Ca-promoted Ni,
steam reforming catalysts occurs at 700 °C in steam.

• Treatment is partially successful in the case of low-surface-

area steam reforming catalysts
• High temperatures required for these reactions would cause
sintering of high-surface-area catalysts. (Change in crystallite
size, grain dimension, surface area and porosity variations
being contributory factors)