Exercise 1
Heterogeneous catalysis and catalysis in environmental technology
WS 2022/23
Dr. Anna Katharina Beine
Exercise 1
1) What is a catalyst?
“Catalyst is a substance which speeds up and
speeds down a chemical reaction without itself
being used up.”
-Berzelius (1836)-
“A substance which changes the reaction rate
without affecting the overall energetics of the
reaction is termed as a catalyst and the
phenomenon is known as catalysis.”
A catalyst… -Ostwald (1895)-
Increases the reaction speed, is not used up, does not change the
thermodynamic equilibrium.
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2) Name the main differences between homogeneous catalysis,
heterogeneous catalysis and biocatalysis.
Heterogeneous Homogeneous
Biocatalysis
catalysis catalysis
• The catalyst is present • Catalyst and • Enzymes serve as
in a different substrate/product catalysts of chemical
aggregate state than are present "in reactions.
substrate and product. solution", i.e. in the • Either isolated or in the
• usually solids. same state of form of whole cells.
aggregation.
• primarily in the liquid
phase; individual
examples exist for
the gas phase.
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3) There are full and supported/carrier catalysts.
a) How do they differ?
In a full catalyst, all solid In the supported catalyst,
matter consists of active catalytically active components are
components. e.g. present in the form of
nanoparticles dispersed on an inert
carrier material.
γ-Al2O3
Pt-Re nanoparticles
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3) There are full and supported/carrier catalysts.
b) Give two industrially relevant examples (material + process) and
formulate the reaction scheme.
γ-Al2O3
Pt-Re nanoparticles
Claus Process Catalytic reforming of Naphtha
Dehydrogenation, isomerisation,
aromatisation, hydrocracking
Pt-Rh Gauzes: HNO3 production V2O5/SiO2: Oxidation of SO2 in
in the Ostwald-Process the contact process
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3) There are full and supported/carrier catalysts.
c) How to define the dispersion of an active component?
Dispersion is the number of
surface atoms relative to the total
number of atoms of the active
component.
d) Why is the specific surface of catalysts important?
Because the reaction always takes place at
the surface and only active components at
the surface can act in the reaction.
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3) There are full and supported/carrier catalysts.
e) What is structural sensitivity? Discuss this effect for both full catalysts and
supported catalysts.
The geometric nature and/or environment of the active center influences the
reaction.
Full catalyst with narrow pore size Supported nanoparticles have a different
distribution of very small pores (micropores) activity/selectivity of the corner, edge or
influence the selectivity of a reaction, e.g. surface atoms. Therefore, size and shape of
are only accessible for a substrate. the particles play an important role.
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4) Raney catalysts are important examples of melt catalysts. Explain
how to make a Raney-nickel catalyst. For which reaction is this
catalyst technically used?
Production by melting metallic nickel with aluminum to form the corresponding alloy.
Aluminium is then dissolved out of the alloy with concentrated aqueous NaOH.
Raney nickel and copper are widely used catalysts for selective hydrogenation in
the fine chemicals industry. Raney nickel is also used for the hardening of fats.
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5) Name the 7 steps of heterogeneous catalysis and assign them to
micro- and macrokinetics. Also add a sketch with the 7 steps.
1. film-diffusion of the
substrate macrokinetics
2. Pore-diffusion of the
substrate
3. Adsorption to the active
site
4. Reaction microkinetics
5. Desorption of the product
6. Pore-diffusion of the
product
7. Film-diffusion of the macrokinetics
product
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6) Identify the 4 main causes of deactivation of solid catalysts.
Accumulation
in case of carbon deposition: Coking
Sintering of metal or support particles
Poisoning of the active component
Leaching of the active component
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7) In many cases, it is not the chemical reaction on the catalyst that
determines the overall reaction rate, but the transport of the
substance to or from the active site.
a) Sketch the concentration course of the substrate from the bulk phase, over the
film and along a catalytically active ideal cylindric pore.
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7) In many cases, it is not the chemical reaction on the catalyst that
determines the overall reaction rate, but the transport of the
substance to or from the active site.
b) Sketch a diagram that plots ln reff (effective reaction rate) against 1/T,
corresponding to an arrhenius diagram. Now draw the concentration profile for a
reaction in the kinetic regime, a reaction limited by pore diffusion and a reaction
limited by film diffusion. Explain the concentration profile.
The film diffusion is almost temperature
independent, therefore the reaction rate
with T hardly changes for a film diffusion
film- pore-
diffusion diffusion limitation;
In pore diffusion limitation, the reaction rate
kinetic
regime is determined by the diffusion process,
according to Fick's law of diffusion; where
𝐷 ≈ 𝑇
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8) You have succeeded in producing five supported platinum catalysts. All 5
catalysts contain 5 wt .% Pt supported on Al2O3 in form of Pt
nanoparticles. However, the catalysts have very different mean Pt
particles sizes of 2, 5, 12, 16 and 30 nm diameter. In a hydrogenation
reaction, you examine the activity of the catalysts and normalize the
activity for a more direct comparison of the intrinsic activity of the
catalytically active Pt sites.
How would you normalize and why?
𝑛(𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒)
𝑇𝑂𝑁 = n(catalyst) = number of surface metal atoms
𝑛(𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡)
At constant activity the reaction is not
𝑇𝑂𝑁 structure sensitive. Therefore, it makes
𝑇𝑂𝐹 =
𝑡 sense to optimize the catalyst towards
maximum dispersion.
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Thank you for your attention
