Catalysis science and technology

Basic concepts (10%)
Fundamentals of catalysis
Main domains in catalysis
Catalyst preparation
Catalyst characterization

Kinetics (25%)
Rate expressions for catalytic reactions
Reaction orders
Apparent activation energy
Dual-site mechanisms
Kinetic fitting

Chemical Reactor Engineering (20%)
Analytical and numerical modelling of non-ideal catalytic systems

Heterogeneous Catalysis (35%)
Clean fuel technology
Oil refining
Hydrogen manufacture
Ammonia synthesis
Fischer-Tropsch synthesis
Sustainable resources
Methanol value chain
Environmental pollution control
Petrochemistry

Homogeneous Catalysis (10%)
Principles and definitions
Main reactions and catalyst qualifications
Hydrogenations and hydroformylations

Introduction & Basic Concepts
Fundamentals of catalysis:
• Understand the catalytic cycle
• Name main paradigms in catalysis and be able to apply Sabatier’s principle
• Conceptually understand transition state theory
• Evaluate trends in atomic adsorption energy of the transition metals
• Explain the reactivity of different surfaces
• Explain the concept of lateral interactions

Main domains in catalysis:
• Explain the basics of the main domains in catalysis (heterogeneous, homogeneous, biocatalysis)

Catalyst preparation:
• Explain the importance of particle size of the catalyst on the catalytic performance
• Explain the importance of size and shape of support materials on the performance
• Name most important catalyst preparation methods and explain how the procedure works
• Be able to select the most appropriate metal loading method for high dispersion (concept point of zero charge), be able to compute monolayer coverage
• Determine the surface area of a solid using a BET isotherm

Catalyst characterization:
• Identify which methods can be used for characterizing the texture, composition, degree of reduction, morphology, dispersion and structure of the active phase in heterogeneous catalysts
• Explain the basic principles of XRD, XPS, XAS and EM
• Explain in which case XRD, XPS, XAS and EM can be used

Kinetics
Basics of kinetics:
• Conceptually understand the principle of elementary reaction steps
• Construct a rate expression for an elementary reaction step
• Derive higher-level rate expressions using systems of elementary reaction steps based on a given reaction mechanism
• Understand the mean-field approximation when applied to catalytic reactions and its consequences
• Construct a Langmuir-Hinshelwood isotherm from the relevant elementary reaction steps
• Apply assumptions such as steady-state approximation, quasi-equilibrium, rate-determining step, irreversible step, and zero-conversion assumptions to derive the rate expression for a catalytic reaction
• Determine the reaction order
• Derive the reaction order from rate equations and express it as a function of surface coverages
• Determine the apparent activation energy
• Derive the apparent activation energy and express its value in terms of adsorption enthalpies and surface coverage.

Advanced kinetics:
• Construct a set of elementary reaction steps for a dual site mechanism
• Derive the rate equation for a catalytic reaction with a dual-site mechanism
• Derive the reaction orders for a catalytic reaction with a dual-site mechanism
• Derive the apparent activation energy for a catalytic reaction with a dual-site mechanism
• Describe the effect of temperature on the reaction rate, reaction orders and apparent activation energy
• Conceptually understand how to obtain kinetic data experimentally
• Perform kinetic fitting on the basis of experimental data

Chemical Reactor Engineering
• Derive design equations for different reactors with and without transport phenomena
• Derive analytical expressions to model the chemical conversion and concentration profiles of chemical reactors and catalytic particles
• Apply finite difference and finite volume discretization to numerically model the chemical conversion and concentration profiles of chemical reactors and catalytic particles
• Apply numerical criteria to detect mass/heat transport limitations

Heterogeneous Catalysis
Refinery catalysis:
• Describe the overall process scheme of an oil refinery and be able to identify the main unit operations
• Describe the fluid catalytic cracking process, including the catalyst, chemical reactions and reactor design
• Describe the hydrocracking process, including the catalyst, chemical reactions and reactor design
• Describe the catalytic reforming process, including the catalyst, chemical reactions and reactor design
• Describe the hydrotreating process, including the catalyst, chemical reactions and reactor design

Hydrogen production:
• Describe the overall process scheme of hydrogen production and why these steps are necessary
• Describe the steam reforming, partial oxidation, and autothermal reforming of methane, including typical catalysts, associated chemical reactions and reactor design
• Describe how to control the composition of synthesis gas, and why this is important in terms of targeted products
• Describe deactivation phenomena during methane steam reforming
• Describe the water-gas shift reaction, including the catalyst, chemical reaction and reactor design
• Describe the methanation reaction, including the catalyst, chemical reaction and reactor design

Fischer-Tropsch synthesis:
• Describe Fischer-Tropsch synthesis, including typical catalysts, associated chemical reactions and reactor design
• Explain the trends of CO dissociation of transition metals in the periodic table
• Describe the structure sensitivity of the Fischer-Tropsch synthesis
• Describe preparation methods of supported metal catalysts for the Fischer-Tropsch synthesis
• Understand the relation between capital investment of a plant and plant size

Ammonia synthesis:
• Describe ammonia synthesis, including typical catalysts, associated chemical reactions and reactor design
• Explain on the basis of Sabatier’s principle the role of metal-adsorbate adsorption strength on the ammonia synthesis rate
• Describe the structure dependence of the ammonia synthesis
• Describe catalyst deactivation for the ammonia synthesis

Methanol synthesis:
• Describe methanol synthesis, including typical catalysts, associated chemical reactions and reactor design

CO2 hydrogenation in the context of renewable energy and chemicals solutions

• Explain the opportunities of CO2 hydrogenation for renewable energy storage and sustainable chemicals production
• Describe sustainable manners to produce green hydrogen
• Describe main reaction products of CO2 hydrogenation
• Compute forward reaction rate for exothermic CO2 methanation, understand approach to equilibrium, know qualitatively to construct multibed configurations for obtaining high conversion

Emission Pollution control:
• Understand the importance of environmental pollution, oxidation of volatile organic compounds, carbon monoxide, soot, reduction of NOx
• Describe selective catalytic reduction reaction under lean conditions, including typical catalysts, associated chemical reactions and reactor design
• Describe the three-way catalytic convertor, including typical catalysts, associated chemical reactions and reactor design

Petrochemistry:
• Describe generally the different product trees of ethylene, propylene and benzene
• Describe the use of renewable alternatives for obtaining these chemical building blocks

Molecular Catalysis (homogeneous catalysis)
• Principles and definitions of homogeneous catalysis
• Describe advantages (chemo-, regio-, stereoselectivity) and disadvantages (separation) from heterogeneous catalysis
• Classification of molecular catalysts (acids, bases, organocatalysis, enzymes, transition metal complexes)
• Main reactions catalyzed by molecular catalysts: C-C bond making, hydroformylation, metathesis, hydrogenation, oxidation, amination, isomaerization
• Describe the homogeneous catalyzed hydrogenation and hydroformylation reactions

Basic understanding of kinetics, chemical reactor engineering and basic organic and inorganic chemistry (reference level BSc CEC TU/e). Basic understanding of programming, specifically the Python programming language including NumPy, Scipy and Matplotlib modules. Self-assessments, self-learning modules and additional study material are available for the students to bring their knowledge up to the required level.

• Catalysis, Science and Technology, exercises and workouts
• Introduction to microkinetic modeling (ISBN 9789038637938)
• The book “Concepts of Modern Catalysis and Kinetics, 2nd edition” by Chorkendorff and Niemantsverdriet will be used as study material. The book can be obtained via TSV Jan Pieter Minckelers. (ISBN 978-3-527-31672-4)
• Numerical modelling of non-ideal catalytic systems