Heterogeneo

us Catalysis
Brief History

Basic variables to control chemical reaction

❑ Temperature
❑ Pressure
❑ Concentration
❑ Contact time
In 19th and early 20th centuries, Sledgehammer approach: High T & P to achieve reasonable rate of
production
❑ Energy intensive
❑ Corrosive OR damage equipments
❑ Nonselective
In last few decades, Feather approach:
❑ Extensive use of catalyst
❑ Improved method of contacting
 Year Event
1836 The word ‘catalysis’ was coined by Berzelius
1875 industrial catalyst technology had its real beginning with large-scale production of sulfuric acid on Pt
catalysts
1903 Ammonia oxidation on Pt gauze developed by Ostwald and leading to the production of nitric acid

1908 to The discovery of promoted iron for ammonia synthesis by Mittasch, and the subsequent development of
1914 the ammonia synthesis process by Bosch and Haber. This important advance was no accident, since
Mittasch, with typical German thoroughness, investigated over 2500 catalyst compositions in his search for
the optimum.
1935 Catalytic cracking was the first, significant use of solid catalysts in the petroleum industry-a very important
and 1940 development, which allowed refiners to increase gasoline yield and thereby use petroleum crude feedstock
more efficiently
1950 development of catalytic naphtha reforming

1955 Ziegler-Natta discovered that AlCl3 catalysts could be used for production of polypropylene at low pressures

1960 beginning of hydrotreating catalyst technology at refineries to remove sulfur, nitrogen, and metals from
petroleum feedstocks
1960 Weisz and Frilette coined the word ‘shape-selective catalysis’ to describe the unique selectivity properties
of crystalline molecular sieves or zeolites in cracking n-alkanes
 COMPANY KEY PRODUCTS
BASF SE - FCC & Hydroprocessing, hydrogenation, and dehydrogenation processes Catalysts. Their
petrochemical catalysts are designed to enhance efficiency and selectivity in producing
olefins and aromatics.

Albemarle - FCC Catalysts, Hydroprocessing Catalysts, Heavy Oil Upgrading Catalysts

Corporation - Conductive Carbon Black Catalysts for Polymerization and Fuel Cell Applications
(KETJENBLACK)

W. R. Grace & Co. - FCC Catalysts enhancing octane levels, Hydrotreating Catalysts for ultra-low-sulfur diesel

Johnson Matthey - Hydrogenation Catalysts, Syngas Catalysts for clean fuel and chemical production

Honeywell UOP - Hydroprocessing Catalysts, Reforming Catalysts, Unicracking® Process Catalysts for high-
quality diesel and jet fuels

Clariant AG - Propane Dehydrogenation (PDH) Catalysts, Oxidation Catalysts for efficient chemical
production

Haldor Topsoe - Hydroprocessing Catalysts, Ammonia and Methanol Synthesis Catalysts for fertilizers and
chemicals

Axens Group - Hydrocracking Catalysts, Hydrotreating Catalysts, Catalytic Reforming Catalysts

Shell Catalysts &

- Hydroprocessing Catalysts, FCC Catalysts optimized for modern refineries
Technologies
Fundamental Catalytic Phenomena and Principles
A catalyst, in simplest terms, is a material that
enhances the rate and selectivity of a chemical
reaction and in the process is cyclically regenerated.

Heterogeneous catalysis is the process whereby

reactants adsorb onto the surface of a solid catalyst,
are activated by chemical interaction with the catalyst
surface, and are rapidly and selectively transformed to
adsorbed products, which desorb from the catalyst
surface.

Once the product is desorbed from its surface the

catalyst momentarily returns to its original state until
additional reactants adsorb, repeating the catalytic
cycle.

A catalyst has been likened (Mills, 1994) to a mountain

guide, who directs a group of people (molecules) over
a highly favorable mountain pass (low activation
energy path) to a selected valley (of products) and
returns unchanged to guide additional groups.
Components of Industrial Catalysts
ACTIVE PHASE
❑ The active phase is the component that provides the active sites for the chemical reaction.
❑ This is usually a metal, metal oxide, or metal sulphide.
❑ The active metal component must be well-dispersed to have a large surface area when
contacted with the support.
SUPPORT
❑ The support provides a large surface area for the dispersion of the active phase and helps
to stabilize it.
❑ Common support materials include alumina, silica, zirconia, active carbons, magnesia, and
zeolites.
❑ The nature of the catalytic reaction determines the activity of the support.
❑ The support is often porous and heat-resistant.
❑ Alumina has good textural, mechanical properties, better catalyst dispersion which
consequently increases the catalytic performance and is relatively cost-effective.
Components of Industrial Catalysts

PROMOTERS
❑ Promoters are substances added to a catalyst to enhance its activity, selectivity, or
stability.
❑ They may modify the structure of the active phase, facilitate reactant adsorption, or
favour specific reaction pathways.
❑ Chemical promoters are typically alkali and alkaline earth metals or oxides.

BINDERS
❑ Binders are used to provide mechanical strength and integrity to the catalyst.
❑ They help to hold the catalyst particles together and can also influence the catalyst's
physical properties, such as pore size and surface area.
❑ Common binders include silica, alumina, aluminosilicate clay, and aluminum phosphate
solution. The chemical interaction between the binder and the catalyst can affect the
catalytic properties.
Promotors Poison Catalyst Support
Catalyst Activity

BASIC DEFINITION
• The rate at which a catalyst converts reactants to products under specific conditions

• Usually expressed as reaction rate per unit amount of catalyst

• Measured in terms of turnover frequency (TOF) or specific activity

SPECIFIC ACTIVITY
✔ Rate of reaction per unit surface area or mass of catalyst

✔ Useful for practical applications and catalyst comparison

✔ Expressed as mol/(s·m²) or mol/(s·kg)

TURNOVER FREQUENCY (TOF)

✔ Number of molecules converted per active site per unit time

✔ Most fundamental measure of catalytic activity

✔ Allows comparison between different catalysts

✔ Range (10 -2 to 10 2 sec -1) for enzymatic reaction (103 to 10 7 sec -1)

TURNOVER NUMBER (TON)

✔ The turnover number specifies the maximum use that can be made of a catalyst for a special reaction under
defined conditions by a number of molecular reactions or reaction cycles occurring at the reactive center up
to the decay of activity.

✔ Relationship between TOF and TON: 𝑇𝑂𝑁 = 𝑇𝑂𝐹 −1 × lifetime of the catalyst [time]

✔ For industrial applications, the TON is in the range 103 to 10 7.

FACTORS INFLUENCING CATALYST ACTIVITY
Reaction Conditions: Temperature, pressure, and the presence of solvents play a crucial role in catalyst
performance. Optimal reaction conditions are necessary to maximize catalyst efficiency and selectivity for desired
products.
Temperature Effects:
• Generally, increases with temperature (Arrhenius relationship)
• May lead to deactivation at very high temperatures
• Optimal temperature window exists for each catalyst
Pressure Effects:
• Influences adsorption-desorption equilibrium
• Affects reaction kinetics and mechanism
• Important in gas-phase reactions
Concentration Effects:
• Reactant concentration impacts reaction rate
• Product concentration may cause inhibition
• Follows Langmuir-Hinshelwood or similar kinetics
Catalyst Properties: The chemical state of active phases, promoters, size, and shape of catalyst materials
significantly affect catalytic activity. The specific surface area, pore structure, and oxygen-containing functional
groups also play a role in the performance of activated carbon catalysts.
Surface Area:
• Higher surface area generally increases activity
• Pore size distribution affects accessibility
• Surface roughness impacts active site availability

Deactivation Mechanisms: Catalyst deactivation can occur through poisoning, fouling, thermal degradation, and
vapor compound formation. Higher sulfur content in the feed can negatively impact catalyst activity, and nitrogen
compounds can cause temporary deactivation, lowering the conversion rate.
Poisoning: Sintering:
• Chemical binding of impurities to active • Thermal degradation
sites • Loss of surface area
• Usually irreversible • Usually irreversible
• Common poisons: sulfur, heavy metals Phase Transformation:
Fouling: • Changes in crystal structure
• Physical blockage of active sites • Loss of active phase
• Carbon deposition (coking) • Temperature-induced changes
IDENTIFICATION CATALYST ACTIVITY

Experimental Methods Analytical Methods

Inductively Coupled Plasma Mass

Micromeritics Flow Reactor (FR) Series
Spectrometry (ICP-MS),

Temperature-Programmed Desorption Inductively Coupled Plasma Optical

(TPD) Emission Spectrometry (ICP-OES)

Continuous Flow Measurements X-ray diffraction

X-ray absorption spectroscopy

electron microscopy
 Catalyst Selectivity
BASIC DEFINITION
• Ability to direct a chemical reaction toward a particular product while suppressing the
formation of undesired side products.

MECHANISM

• Through chemisorption • One reaction pathway is • The strongest adsorbed • Porous catalysts like
or physisorption favored over others species tend to stay zeolites restrict certain
• In hydrogenation, • Depends on the catalyst longer, which can lead molecules from entering,
alkynes adsorb more structure, electronic to undesired by-products leading to shape
strongly on Lindlar’s properties, and steric • Reduce adsorption selectivity.
catalyst than alkenes. effects strength for the desired
product
Diffusion
Surface Desorption of
Adsorption of Control
Reaction the Desired
Reactants (Shape
Pathway Product
Selectivity)
TYPES
Product Selectivity
• Determines which product is formed when multiple reaction pathways are possible.
• Example: In hydrocarbon cracking, a catalyst like zeolite can direct the reaction toward producing
gasoline fractions rather than undesired heavy residues.

Chemoselectivity
• The catalyst promotes one chemical transformation over another.
• Example: In hydrogenation, Lindlar’s catalyst (Pd poisoned with lead) selectively hydrogenates alkynes to
alkenes without further reduction to alkanes.

Regioselectivity
• The catalyst favors the formation of one structural isomer over another.
• Example: In hydroformylation, rhodium-based catalysts direct aldehyde formation at a specific carbon in
the chain.

Stereoselectivity
• The catalyst controls the formation of a specific stereoisomer (cis/trans, enantiomer, or diastereomer).
• Example: Ziegler-Natta catalysts selectively produce isotactic or syndiotactic polypropylene.

Shape Selectivity
• The catalyst allows only specific molecules to enter its pores and undergo reaction, based on molecular size
and shape.
• Example: Zeolites in isomerization reactions selectively allow certain hydrocarbons to diffuse into their pores
while excluding others.
FACTORS AFFECTING CATALYST SELECTIVITY

Catalyst Composition

Catalyst Structure and Active Sites

Pore Size and Shape (Zeolites and MOFs)

Reaction Conditions (Temperature, Pressure, pH, Solvent Effects)

Catalyst Promoters and Inhibitors

Catalyst Deactivation
CATALYST PREPARATION
YOUYUBE VIDEO link

Channel: Polimi OpenKnowledge

https://www.youtube.com/
watch?v=Z51Lk3TD8PU&list=PLmKUwJ0KJ
QnW_OxxkfEBFO2f6tKKDb2fj
Routine Testing During the Production of an Industrial Catalyst

Test Properties
Routine chemical analysis
Major metal components, metal impurities, well-mixed phases.
(products and raw materials)
Compression strength between faces (vertical) or across diameter
Crushing strength
(horizontal).

Attrition/tumbling loss Dust formed during rotation in a tube under standard conditions.

Micromeritics Surface area, helium and mercury density, pore volume, mean pore radius.

Average length of pellets, average diameter of spheres, average length of

Particle size
extrusions.

Particle size distribution Proportion of required, undersize, and oversize particles.

Particle porosity Internal volume available during impregnation and operation.

Bulk density Indication of pelletting or granulation efficiency.

Catalyst activity and stability Determines preliminary reduction and operating efficiency.
 Physical Testing of Industrial Catalysts.

Test Procedure
X-ray fluorescence (XRF) - Samples emit secondary X-rays following
Chemical analysis
bombardment with hard X-rays, allowing complete elemental analysis.
Particle size Simple measurement of solid particles or size grading of powders.
Determined by compressing catalyst particles between anvils or by bulk
Crushing strength
crushing the catalyst in a standard container.
Packing weight per unit volume of loose or densely packed catalyst
Bulk density
particles.
Dust formation after rotating the catalyst for a fixed period in a standard
Attrition loss
cylinder.
X-ray diffraction (XRD) - Identifies crystalline compounds by referencing
Crystalline phases standard tables. The proportion of each phase in the sample can also
be calculated.
Estimated using X-ray diffraction line broadening, which increases as
Crystallite size
crystallite size decreases.
Calculated using the volume of a gas monolayer adsorbed on the
Surface area/pore size catalyst and the known area covered by a gas molecule. Pore volume is
calculated from helium and mercury density differences.
Measures the weight loss as the catalyst composition changes with
Thermogravimetric analysis (TGA)
increasing temperature in oxidizing or inert atmospheres.
Tracks exothermic or endothermic temperature changes as catalysts
Chemical and Structural Analyses of Industrial
Catalysts.
Test Result/Purpose
Extends the use of optical microscopy for
Electron Microscopy surface structure and composition analysis of
catalyst particles.
Provides magnification of 20,000–50,000;
Scanning Electron Microscopy (SEM) focuses on sizes down to 5 nm; reveals
crystallite shape, size, and size distribution.
Offers higher magnification and resolution;
provides three-dimensional images of
Transmission Electron Microscopy (TEM)
crystallites down to 0.5 nm; tracks changes
during operation.
Analyzes elements and atomic electron binding
X-Ray Photoelectron Spectroscopy (XPS/
energies; gives structural data and compound
ESCA)
types in surface layers.
Auger Electron Spectroscopy (AES) Enables elemental analysis of surface layers.
Secondary Ion Mass Spectroscopy (SIMS) Conducts elemental analysis of surface layers.
High-Resolution Electron Energy-Loss
Identifies types of chemical bonds present.
Spectroscopy (HREELS)
 ASSIGNMENT
Some of the most used characterization techniques for industrial catalyst. (min
25.)
Acronyms Full name Application Working Principle Remarks
XRF X-ray allowing complete Samples emit secondary X-
fluorescence elemental analysis. rays following bombardment
with hard X-rays