Question: define catalyst on the basis of definition, how does catalyst affect a chemical process?

what kind
of requirements are there for industrial catalyst?

Definition:

A catalyst is a substance that increases the rate of a chemical reaction without being consumed itself. It
essentially acts as a "middleman," lowering the activation energy required for the reaction to occur,
resulting in faster reaction rates and sometimes even influencing the final product distribution.

How does a catalyst affect a chemical process?

Catalysts work by providing an alternative reaction pathway with a lower activation energy. This
alternative pathway typically involves the formation of intermediate complexes between the catalyst and
the reactants, facilitating the breaking and reforming of bonds. By lowering the activation energy, the
catalyst effectively increases the number of reactant molecules possessing the necessary energy to
overcome the energy barrier and proceed with the reaction.

Here's a summary of the key ways catalysts impact a chemical process:

Increased reaction rate: This translates to faster production and higher efficiency.

Improved selectivity: Some catalysts can steer the reaction towards specific desired products, minimizing
unwanted side reactions.

Lower reaction temperature and pressure: Catalysts often enable reactions to occur at milder conditions,
reducing energy consumption and equipment costs.

Environmental benefits: By enabling efficient transformations using less energy and generating fewer
byproducts, catalysts can contribute to greener chemical processes.

Requirements for industrial catalysts:

For industrial applications, catalysts need to fulfill several criteria:

Activity: The catalyst must be highly efficient in accelerating the desired reaction.
Selectivity: It should preferentially promote the formation of the target product with minimal side
reactions.

Stability: It should be resistant to deactivation due to factors like sintering, coking, or poisoning to ensure
prolonged performance.

Durability: The catalyst should withstand the harsh reaction conditions (high temperatures, pressures,
etc.) commonly encountered in industrial processes.

Recoverability: Ideally, the catalyst should be easily separable from the products and regenerated for
reuse, which lowers costs and promotes sustainability.

Cost-effectiveness: The cost of manufacturing and implementing the catalyst should be balanced against
its benefits in terms of efficiency, selectivity, and lifespan.

Distribution:

"distribution" can refer to various aspects related to the spatial arrangement or composition of various
components within the catalyst material.

Distribution of active sites:

how the active sites, which are the atoms or groups of atoms responsible for catalyzing the reaction, are
arranged on the catalyst surface. This distribution can impact the accessibility of reactants to the active
sites and consequently affect the overall reaction rate and selectivity.

Distribution of support material:

The catalyst often consists of an active component (e.g., metal particles) dispersed on a support material
that provides physical stability and structure. The distribution of the support material influences the
accessibility of reactants to the active sites and can also affect mass and heat transfer within the catalyst.
Factors like the pore size and pore size distribution of the support material play a role in this distribution.

Distribution of Pore Sizes:

Catalyst materials often contain pores of different sizes, including micropores, mesopores, and
macropores. The distribution of pore sizes affects the accessibility of reactant molecules to the active
sites and can influence mass transport properties within the catalyst material
Spatial Distribution of Components:

In multi-component catalysts, the spatial distribution of different components (such as active metals,
promoters, and support materials) can impact catalytic performance. For example, the proximity of
certain components may enhance catalytic synergy or facilitate specific reaction pathways.

Poisoning:

Poisoning is the strong chemisorption of reactants, products, or impurities on sites otherwise available for
catalysis.”

 Whether a species acts as a poison depends upon its adsorption strength relative to the other
species competing for catalytic sites.

Example: oxygen can be a reactant in partial oxidation of ethylene to ethylene oxide on a silver catalyst

and a poison in hydrogenation of ethylene on nickel.

•In addition to physically blocking of adsorption sites, adsorbed poisons may induce changes in the
electronic or geometric structure of the surface .

•Poisoning may be reversible or irreversible (typically it is irreversible).

Selective poisoning the most active sites are blocked at low poison concentrations

• Antiselective poisoning sites of lesser activity are blocked first

•Non selective poisoning loss of activity proportional to poison concentration

Effects of poisoning:

 Decreased reaction rate: Due to a reduction in available active sites, the rate of the catalyzed
reaction significantly drops.
 Loss of selectivity: Poisons can sometimes alter the electronic or geometric properties of the
active sites, leading to the formation of undesired side products.
 Catalyst regeneration: In some cases, poisoned catalysts can be regenerated by removing the
poison through treatments like washing or high-temperature oxidation. However, this may not
always be feasible or cost-effective

Fouling

is the physical (mechanical) deposition of species from the fluid phase onto the catalyst surface, which
results in activity loss due to blockage of sites and/or pores. In its advanced stages, it may result in
disintegration of catalyst particles and plugging of the reactor voids .

•Important examples include mechanical deposits of carbon and coke in porous catalysts , although
carbon and coke forming processes also involve chemisorption of different kinds of carbons or condensed
hydrocarbons that may act as catalyst poisons.

Coke is produced by decomposition or condensation of hydrocarbons on catalyst surfaces and typically

consists of polymerized heavy hydrocarbons.

How does coke form?

Coke formation typically occurs through several steps:

 Decomposition of hydrocarbons: Reactant hydrocarbons partially decompose on the catalyst

surface, leaving behind carbon fragments.
 Polymerization: These carbon fragments can react with each other and grow into larger carbon
structures.
 Condensation: Further reactions lead to condensation and dehydrogenation, forming more stable
coke deposits.

Impact of coke formation:

Coke deposits have several detrimental effects on catalysts:

 Active site blockage: They block access of reactants to the active sites, reducing the reaction rate
and catalyst efficiency.
 Mass and heat transfer limitations: They hinder the diffusion of reactants and products within the
catalyst, further affecting performance.
  Catalyst structure damage: In severe cases, coke buildup can cause mechanical stress and damage
the catalyst support material.

Sintering:

sintering refers to the gradual growth and agglomeration of active metal particles supported on a larger
surface material. This phenomenon can significantly impact the performance of a catalyst by decreasing
its efficiency. Here's a deeper dive into what sintering is and its consequences:

Sintering is driven by the minimization of surface energy. Under the influence of thermal vibrations and
surface diffusion, smaller metal particles tend to move and merge with each other, forming larger
particles. This process results in:

 Reduced surface area: Smaller particles have a larger overall surface area compared to their
volume, meaning more active sites are available for reactant adsorption and reaction. Sintering
leads to a decline in surface area, consequently reducing the number of active sites and the
potential for the catalyst to participate in the reaction.
 Loss of active sites: Some active sites may be buried within the bulk of the sintered particles,
rendering them inaccessible to reactants. This further contributes to the deactivation of the
catalyst.
 Changes in pore structure: Depending on the catalyst material and reaction conditions, sintering
can also affect the pore size and pore size distribution within the catalyst. This can hinder the
diffusion of reactants and products, further decreasing efficiency.

Factors influencing sintering:

Several factors can influence the rate and extent of sintering in catalysts:

 Temperature: Higher temperatures generally accelerate the sintering process due to increased
mobility of atoms.
 Support material: The interaction between the metal and the support material can influence
sintering. Some supports can help stabilize the metal particles and resist sintering.
 Presence of additives: Promoters or stabilizers can be added to the catalyst formulation to
mitigate sintering and improve catalyst stability.
 Reaction atmosphere: The gas phase composition surrounding the catalyst can sometimes affect
the surface tension and sintering behavior.

Langmuir adsorption isotherm:

The Langmuir adsorption isotherm is a model used to describe the adsorption of gas molecules onto a
solid surface, which is commonly applied in the context of catalysts. The model was developed by Irving
Langmuir in 1916 and is based on several assumptions:
 1. Adsorption occurs on a homogeneous surface with a finite number of identical adsorption sites.

2. Adsorption and desorption processes are reversible and reach dynamic equilibrium.

3. Each adsorption site can only accommodate one adsorbate molecule.

4. There is no lateral interaction between adsorbed molecules.

The Langmuir adsorption isotherm equation is given by:

The Langmuir adsorption isotherm describes how the adsorption of gas molecules onto a solid surface
varies with pressure. At low pressures, the adsorption is linearly proportional to pressure, indicating a
monolayer coverage of adsorbate molecules on the surface. As the pressure increases, the adsorption
eventually reaches a maximum value corresponding to saturation, where all available adsorption sites are
occupied.

Tammann temperature :

Approximately half of the temperature of the melting point (in K).

For instance, in catalysts used in high-temperature processes, such as steam reforming or catalytic
cracking, the Tamman temperature provides insight into the temperature range at which catalyst
deactivation, sintering, or structural changes might occur.

Limitations:

Approximation: Not a definitive threshold, as specific material properties, presence of additives, and
reaction conditions can influence actual behavior.

T_T provides a starting point for understanding catalyst behavior at high temperatures, but context and
specific factors are crucial for accurate assessment.
Point of zero charge:

The point of zero charge (PZC) in a catalyst, also known as the isoelectric point, is the pH value at which
the catalyst surface carries no net electrical charge. At the PZC, the number of positively charged sites
(protons) on the catalyst surface equals the number of negatively charged sites (hydroxyl ions), resulting
in a neutral surface charge overall.

 Catalyst surfaces can interact with water molecules, acquiring positive or negative charges
depending on the surrounding pH.
 At acidic pH, the surface tends to attract and hold positive charges (protons).
 At basic pH, the surface tends to attract and hold negative charges (hydroxide ions).
 At the PZC, there is no net charge because the number of positive and negative charges balance
out.

Homogenous catalyst:

A homogeneous catalyst is a type of catalyst that exists in the same phase as the reactants in a chemical
reaction. In other words, both the catalyst and the reactants are uniformly dispersed in the same solvent
or phase.

In a homogeneous catalytic reaction, the catalyst molecules directly interact with the reactant molecules
to facilitate the formation of products. The catalyst undergoes reversible chemical transformations during
the reaction but remains uniformly distributed within the reaction mixture.

Q: What are the three fundamental stages of catalyst preparation [according to the lnternational Union of
Pure and Applied Chemistry (IUPAC)I? Describe the principle of the pore volume impregnation method (also
known as "dry impregnation") and how can one control the obtained metal loading with it. What are the
expected benefits and limitations of this method for catalyst preparation?

Three Fundamental Stages of Catalyst Preparation (IUPAC)

According to the International Union of Pure and Applied Chemistry (IUPAC), the three fundamental
stages of catalyst preparation are:

1. Support Formation:

This involves selecting and processing a suitable material to act as the catalyst support. The support
provides mechanical stability and high surface area for the active phase.
Examples of support materials include metal oxides (e.g., alumina, silica), zeolites, activated carbon, and
polymers.

2. Active Phase Introduction:

This is the stage where the desired catalytic material (metal, metal oxide, etc.) is deposited onto the
support. Various methods exist, including impregnation, deposition-precipitation, ion exchange, and
physical vapor deposition.

3. Activation/Pre-Treatment:

This final stage involves converting the deposited precursor into its catalytically active form. This often
involves thermal treatment, reduction, or oxidation depending on the catalyst system.

Pore Volume Impregnation (Dry Impregnation)

In pore volume impregnation, also known as dry impregnation, the active phase precursor is dissolved in
a suitable solvent to create a solution. This solution is then brought into contact with the support
material, allowing it to fill the pores of the support through capillary action. After drying and activation,
the metal ions are anchored onto the support, forming the active phase.

Controlling Metal Loading:

Several factors influence the metal loading achieved with this method:

Concentration of precursor solution: Higher concentrations generally lead to higher metal loading, but can
also cause pore blockage.

Pore volume of the support: Supports with larger pore volumes can accommodate more solution,
potentially leading to higher metal loading.

Impregnation pH: Optimizing pH can influence the adsorption of the precursor onto the support.

Drying conditions: Slow drying minimizes precursor crystallization within the pores, allowing for better
dispersion and potentially higher metal loading.

Benefits and Limitations of Pore Volume Impregnation:

Benefits:

1. Simple and cost-effective technique.

2. Suitable for loading a wide range of metals onto various supports.
3. Offers good control over metal loading through solution concentration and pore volume.
Limitations:

 Difficult to achieve very high metal loadings due to potential pore blockage.
 Non-uniform distribution of metal particles can occur, impacting activity and selectivity.
 Solvent selection can be challenging depending on the precursor and support material.

Question: catalyst deactivation. Describe the phenomenon of catalyst deactivation by coking. Give
example(s) of when it takes place and how it may affect the activity/selectivity/lifetime of the
catalyst. Which measures can be taken to avoid catalyst deactivation by coking?

Catalyst Deactivation by Coking: A Sticky Problem

Coking is a major form of catalyst deactivation, significantly impacting activity, selectivity, and lifetime
across various industrial processes. Let's dive into the details:

Phenomenon:
Coking refers to the deposition of carbonaceous residues (coke) on the catalyst surface during reactions
involving hydrocarbons. These residues can be various forms of carbon, including:

Graphite-like structures: Densely packed, ordered arrangement of carbon atoms.

Amorphous carbon: Disordered arrangement of carbon atoms.

Polymers: Chain-like molecules containing carbon and hydrogen atoms.

Mechanisms:

Coking typically occurs through these steps:

Decomposition of hydrocarbons: Reactant hydrocarbons partially decompose on the catalyst surface,

leaving behind carbon fragments.

Polymerization: These carbon fragments can react with each other and grow into larger carbon
structures.
Condensation: Further reactions lead to condensation and dehydrogenation, forming more stable coke
deposits.
Examples and Impacts:

Coking is prevalent in:

Steam reforming (e.g., for hydrogen production): Coke reduces the active surface area for reforming
reactions, decreasing hydrogen yield and increasing energy consumption.

Fluidized catalytic cracking (FCC) in petroleum refining: Coke buildup blocks catalyst pores, hindering
reactant diffusion and reducing product yield and quality.

Polymerization reactions: Trace impurities in monomers can cause coking, leading to catalyst deactivation
and polymer chain termination.

Effects:

Decreased activity: Reduced surface area and blocked pores limit reactant access to active sites,
decreasing reaction rate and overall productivity.

Selectivity loss: Coke deposits can alter the active site geometry, potentially favoring side reactions and
diminishing desired product selectivity.
Shortened lifespan: Repeated coking and regeneration cycles can damage the catalyst structure,
necessitating more frequent replacements and increasing operational costs.

Countermeasures:

Strategies to mitigate coking include:

Optimizing reaction conditions: Selecting appropriate temperatures, pressures, and feedstock

compositions can minimize coke formation.

Catalyst design: Using coke-resistant supports and promoters can enhance stability and reduce coking
tendency.

Regeneration: Implementing periodic in-situ or ex-situ regeneration steps (e.g., steam purging, oxidation)
to remove coke precursors or burn off existing deposits.

Pre-treatment of feedstock: Removing coke precursors from the feedstock before it enters the reactor
can significantly reduce coking potential.

Seven steps of a heterogeneously catalyzed reaction

1. Diffusion of the reactants through a boundary layer surrounding the catalyst particle.
2. Intraparticle diffusion of the reactants into the catalyst pores to the active sites.
 3. Adsorption of the reactants onto active sites.
4. Surface reactions involving formation or conversion of various adsorbed intermediates, possibly
including surface diffusion steps.
5. Desorption of products from catalyst sites.
6. Intra particle diffusion of the products through the catalyst pores.
7. Diffusion of the products across the boundary layer surrounding the catalyst particle.

Q: Poisoning of catalysts. Describe the phenomenon, provide example(s), how does it affect
activity/selectivity/lifetime of catalyst. How can poisoning be avoided?

Phenomenon:

Poisoning refers to the deactivation of a catalyst due to the adsorption of foreign molecules (poisons)
onto its active sites. These poisons occupy the sites where desired reactants should bind, hindering the
reaction and leading to performance decline.

Examples:

Sulfur: In hydrodesulfurization catalysts, sulfur molecules can strongly bind to active metal sites,
preventing the desired removal of sulfur from hydrocarbon feedstocks.

Halogens: In metallocene-based polymerization catalysts, chlorine or bromine traces can deactivate the
metal center, impacting polymer production and quality.

Heavy metals: Lead in automotive catalytic converters can poison the active sites responsible for pollutant
reduction, hindering emission control.

Impacts:

Poisoning adversely affects a catalyst's performance in several ways:

Decreased activity: With fewer available active sites, the reaction rate slows down, reducing overall
productivity.

Selectivity loss: Poisoning can alter the reactivity of the remaining active sites, potentially promoting
undesired side reactions and diminishing the desired product yield.

Shortened lifetime: Repeated poisoning and regeneration cycles can damage the catalyst structure,
necessitating more frequent replacements and increasing costs.
Prevention Strategies:

Mitigating poisoning involves various approaches:

Feedstock purification: Removing poison precursors from the reactant mixture before it enters the reactor
significantly reduces their chance of encountering and deactivating the catalyst.

Catalyst design: Selecting poison-resistant materials or incorporating poison traps within the catalyst
structure can enhance its tolerance to specific contaminants.

Reaction conditions optimization: Adjusting temperature, pressure, and other reaction parameters can
sometimes influence the adsorption of poisons, making them less likely to bind to active sites.

Sacrificial promoters: Adding specific additives that preferentially bind to poisons before they reach the
active sites can offer temporary protection but often need regeneration themselves.

Describe the principle of at least two characterization methods that could solve the problem and
what information they would provide.
X-ray Diffraction (XRD):

Principle: XRD is based on the interaction of X-rays with crystalline materials. When X-rays strike a
crystalline sample, they undergo constructive interference due to the regular arrangement of atoms in
the crystal lattice.
Information Provided:

Crystal Structure: XRD reveals the crystal structure of the catalyst material. It identifies the lattice
parameters (unit cell dimensions) and the arrangement of atoms.

Phase Identification: By analyzing diffraction patterns, XRD identifies the different phases (e.g., metal
oxides, sulfides, or carbides) present in the catalyst.

Crystallite Size: The broadening of diffraction peaks provides information about the average crystallite
size.

Amorphous Content: Lack of distinct peaks indicates the presence of amorphous (non-crystalline) phases.

Temperature-Programmed Desorption (TPD):

Principle: TPD measures the desorption of adsorbed species (e.g., gases or molecules) from the catalyst
surface as a function of temperature.

Information Provided:

Surface Acidity/Basicity: TPD can assess the strength and quantity of acidic or basic sites on the catalyst
surface by studying the desorption of probe molecules (e.g., ammonia or carbon dioxide).

Active Sites: TPD identifies active sites where reactants adsorb and desorb during catalysis.

Coke Formation: By introducing a hydrocarbon probe (e.g., ethylene), TPD detects coke precursors and
quantifies their desorption temperatures.

Stability: TPD helps evaluate the stability of active sites under varying conditions.