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Catalyst performance
A good catalyst should have high activity. A high activity allows
relatively small reactor volumes, short reaction times, and operation
under mild conditions. High selectivity is often more important than
high activity. Furthermore, a catalyst should maintain its activity and
selectivity over a period of time, i. e. it should have sufficient stability.

Catalysts are developed for specific processes, e. g. for a specific reaction in a

specific reactor under specific reaction conditions. Therefore, there are many
requirements for an industrial catalyst:
– High activity/unit of reaction volume
– High selectivity with reference to the desired product at the required conversion
in the reactor
– Sufficient stability with regard to deactivation
– Possibilities for regeneration, especially for fast deactivation processes
– Reproducible production method
– Sufficient thermal stability against sintering, structural change or loss via gas
phase (e.g if H2O-vapor is produced as side product)
– High compressive strength (with reference to the catalyst bed and shape of the
catalyst!)
– High resistance against mechanical stress

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The catalytic performance can be affected by many influences such as:

– Active phase (metal, metal oxide; type, morphology …)
– Support (type, texture, chirality …)
– Environment of the reaction (solvent etc)
– Promoters (inorganic, organic, chiral)
– Inhibitors

Supported catalysts

Supported catalysts represent the largest group of heterogeneous

catalysts and are of major economic importance, especially in refinery
technology and the chemical industry.
Supported catalysts are heterogeneous catalysts in which small amounts
of catalytically active materials, especially metals, are applied to the
surface of porous, mostly inert solids – the so-called supports. The
supports can have special forms such as pellets, rings, extrudates, and
granules.
Typical catalyst supports are porous solids such as aluminum oxides, silca
gel, MgO, TiO2, ZrO2, aluminosilicates, zeolites, activated carbon, and
ceramics.

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Why supported catalysts

Costs

Activity

Selectivity

Regenerability

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Costs

The catalytically active components of supported catalysts are often

expensive metals.
Since this active component is applied in a highly dispersed form, the
metal represents only a small fraction of the total catalyst mass.
For example, the metals Rh, Re, and Ru are highly effective
hydrogenation catalysts for aromatic hydrocarbons.
They are sometimes used in mass fractions as low as 0.5 % on Al2O3 or
activated carbon.

Activity

The high activity leads to fast reaction rates, short reaction times,
and maximum throughput.

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Selectivity

It facilitates the following: maximum yield, elimination of side

products, and lowering of purification costs; it is the most important
target parameter in catalyst development.

Regenerability

It helps keep process costs low.

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Factors influencing
The main factors are the choice of the most suitable support material
and the arrangement of the metal atoms in the pore structure of the
support. In choosing catalyst supports, numerous physical and chemical
aspects and their effects must be taken into account

The main function of the catalyst support is to increase the

surface area of the active component.
Catalytic activity generally increases with increasing catalyst
surface area, but a linear relationship can not be expected since
the reaction rate is often strongly dependent on the structure of
the catalyst surface. However, in many reactions, the selectivity
decreases when the catalytic surface is enlarged.
As a general rule, catalysts for the activation of hydrogen
(hydrogenation, hydrodesulfurization, hydrodenitrogenation)
require high support surface areas, while selective oxidations
(e. g., olefin epoxidation) need small support surface areas to
suppress problematic side reactions.

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The choice of the appropriate catalyst support for a particular

active component is important because in many reactions the
support can significantly influence the reaction rate and the
course of the reaction.
The nature of the reaction system largely determines the type of
catalyst support. If a support material with a large surface area
such as activated carbon is used as support, then the metal is
present as discrete crystallites, only a few atomic layers thick,
with a very high surface area.
In batch liquid-phase reactions, powder supports are used
exclusively, whereas in gas-phase and continuous liquid-phase
reactions (trickle columns), supports in pellet or granule form
can be employed

The pore structure of the support can also have an influence on

the role of the active component, since the course of the reaction
is often strongly dependent on the rate of diffusion of the
reactants.
Furthermore, the size of the support surface can limit the
exploitable metal concentration.

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Acetone hydrogenation

Kinetic measurements on a Pt catalyst showed no dependence on the

size of the crystallites. On an inert SiO2 support the catalyst turnover
number remained virtually constant over the particle size range 2–1000
nm; that is, the reaction is structure-insensitive.
With a TiO2 support, the TON was increased by a factor of 500
following high-temperature reduction.

Hydrogenation of acetone to isopropanol

on supported platinum catalysts

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Promoters

Promoters are substances that are themselves not catalytically active

but increase the activity of catalysts.
The function of these substances, which are added to catalysts in
amounts of a few per cent, has not been fully elucidated.
There are four types of promoters:
- Structure promoters
- Electronic promoters
- Textural promoters
- Catalyst-poison-resistant promoters

Structure promoters

Structure promoters increase the selectivity by influencing the

catalyst surface such that the number of possible reactions for the
adsorbed molecules decreases and a favored reaction path
dominates.
They are of major importance since they are directly involved in the
solid-state reaction of the catalytically active metal surface.

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Electronic promoters

Electronic promoters become dispersed in the active phase

and influence its electronic character and therefore the
chemical binding of the adsorbate.

Textural promoters

Textural promoters inhibit the growth of catalyst particles to form

larger, less active structures during the reaction.
Thus they prevent loss of active surface by sintering and increase the
thermal stability of the catalyst.

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Catalyst-poison-resistant promoters

Catalyst-poison-resistant promoters protect the active phase

against poisoning by impurities, either present in the starting
materials or formed in side reactions.

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A catalyst may contain one active component and one or more

promoters. The fraction of active components usually exceeds
75 %. Since the above four effects tend to overlap in practice, it is
sometimes difficult to precisely define the function of a promoter.
Promoters are the subject of great interest in catalyst research due
to their remarkable influence on the activity, selectivity, and stability
of industrial catalysts.
Many promoters are discovered serendipitously; few are the result
of systematic research.

Structure promoters

Structure promoters can act in various ways.

In the aromatization of alkanes on Pt catalysts, nonselective
dissociative reaction paths that lead to gas and coke formation can
be suppressed by alloying with tin. This is attributed to the ensemble
effect, which is also responsible for the action of alkali and alkaline
earth metal hydroxides on Rh catalysts in the synthesis of methanol
from CO/H2 and the hydroformylation of ethylene.
It was found that by means of the ensemble effect the promoters
block active sites and thus suppress the dissociation of CO. Both
reactions require small surface ensembles. As a result, methanol
production and insertion of CO into the alkene are both positively
influenced.

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Promoters can also influence catalytically active phases by

stabilizing surface atoms in certain valence states.
An example is the effect of chlorine on silver catalysts in the
oxidation of ethylene to ethylene oxide. Silver oxide chloride phases
were detected on the surface. The selective epoxidation between
the electrophilic oxygen and the electron-rich double bond of
ethylene is optimized.
Cesium promoters stabilize these silver oxide chloride phases of the
type.

Electronic promoters
Potassium is used as a promoter in many catalytic reactions.
The hydrogenation of CO and ammonia synthesis are two well-
known examples. The strongly electropositive potassium (or,
more often, the oxide K2O) provides electrons that flow to the
metal and then into the chemisorbed molecule.
In this way, p backbonding into the p* orbitals of the adsorbate is
considerably strengthened.
The promoter potassium facilitates the dissociation of N2 and
thus increases the rate of formation of NH3. In investigations of
the chemisorption of N2 on the less active (100) and (110) iron
surfaces, it was shown that low concentrations of potassium increase
the heat of chemisorption of molecular nitrogen by 16 kJ/mol and
increase the rate of N2 dissociation 300-fold.

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The action of potassium promoters in the

dissociative chemisorption of N2 on iron catalysts

Commercial iron catalysts contain ca. 1.8 mol% K.

Potassium increases the reaction rate and the selectivity for C2+
hydrocarbons, as would be expected if dissociation of CO is more
facile.
Evidence for this is that in the presence of potassium, the CO
desorption temperature is 100–200 K higher and the heat of
chemisorption increases by 20–50 kJ/mol.
Vibrational spectroscopy showed that with increasing degree of
coverage by potassium, the CO stretching frequency of 1875 and
2120 cm-1 decreases to 1565 cm-1.
Thus the influence of potassium lowers the CO bond order from
2 to 1.5, so that CO dissociation can more readily occur.

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Besides the purely electronic effects discussed above, the promoter

can also form direct chemical bonds with the adsorbate.
An example is the influence of alkali metal cations on the
synthesis of methanol with copper catalysts. Sodium and
potassium hydroxide can react with CO under relatively mild
conditions to form alkali metal formates, which are hydrogenated to
methanol by hydrogen dissociatively adsorbed on copper.

Promoters are often used to suppress undesired activity of support

materials, such as coke formation. Coking is due to cracking reactions
on Brønsted acid centers, followed by an acid-catalyzed polymerization
to give (CHx)n chains, which cover the active centers on the surface and
block the pores.
Removal of the coke by incineration can lead to loss of activity due
to sintering.
Acidic centers are best neutralized by bases, preferably alkali metal
compounds. Potassium, added as K2CO3 during catalyst production is
the most effective at minimizing the coking tendency of Al2O3
supports.

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In the steam reforming of naphtha, potassium promoters

accelerate the reaction of carbon with steam. However, this leads
to formation of KOH, which sublimes. In this case, potassium
aluminosilicate was successfully used as promoter.
In the presence of steam and CO2 it decomposes into K2CO3 and
KOH to an extent that is just sufficient to remove the coke that is
formed. This prolonged catalyst lifetimes to 4–5 years.

Inhibitors
An inhibitor is a substance that reduces the rate of a catalytic reaction,
often as a result of bonding chemically to the catalyst. Examples are:
– Pt or Pd catalysts on CaCO3, poisoned by Pb (Lindlar’s catalyst). They
enable selective reduction of triple bonds to double bonds.

– Aprotic solutions (which act by forming H bonds with catalyst molecules

in competition with other reactant molecules).
– Structural effectors in enzyme catalysis which bond to the active sites.
A strong inhibitor is a catalyst poison, e. g. sulfur for Ni hydrogenation
catalysts. For example, partially sulfided Ni catalysts are applied for the
selective hydrogenation of alkynes (lower activity than Lindlar’s catalyst,
reaction temperature 200–250 °C, continuous feed of 1 ppm H2S to the
reactant).

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Catalyst Deactivation and Regeneration

Catalysts have only a limited lifetime. Some lose their activity after
a few minutes, others last for more than ten years.
The maintenance of catalyst activity for as long as possible is of
major economic importance in industry. A decline in activity
during the process can be the result of various physical and chemical
factors, for example:
– blocking of the catalytically active sites
– loss of catalytically active sites due to chemical, thermal, or
mechanical processes.

Deactivation causes

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Catalyst deactivation, also known as ageing, is expressed by the

decrease in catalyst activity with time.
Catalyst activity a is the ratio of the reaction rate at a given time t
to the reaction rate at the time that use of the catalyst began:

Not only does the decreasing catalyst

activity lead to a loss of productivity,
it is also often accompanied by a
lowering of the selectivity.

– Poisoning of the catalyst. Typical catalyst poisons are H2S, Pb, Hg, S, P
– Deposits on the catalyst surface block the active centers and change
the pore structure (e. g., coking)
– Thermal processes and sintering of the catalyst lead to a loss of active
surface area
– Catalyst losses by evaporation of components (e. g., formation of
volatile metal carbonyls with CO)

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Catalyst Poisoning

Catalyst poisoning is a chemical effect. Catalyst poisons form

strong adsorptive bonds with the catalyst surface, blocking
active centers. Therefore, even very small quantities of catalyst
poisons can influence the adsorption of reactants on the catalyst.
The term catalyst poison is usually applied to foreign materials in the
reaction system. Reaction products that diffuse only slowly away
from the catalyst surface and thus disturb the course of the reaction
are referred as inhibitors.

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Poisoning of metals
Metal catalysts are highly sensitive to small amounts of certain
impurities in the reaction medium.
Catalytically active metals make their d orbitals available for adsorption,
and this is the key to understanding both their catalytic activity and their
sensitivity to poisons.
Particularly strong catalyst poisons are the ions of elements of groups
15 (N, P, As, Sb, Bi) and 16 (O, S, Se, Te). The poisoning activity
depends on the presence of electron lone pairs, which have been shown
to form dative bonds with transition metals on chemisorption.
If these are involed in bonding to other elements, then the ions are
nonpoisons:
Poisons: H2S, thiophene, NH3, PH3, AsH3
Nonpoisons: SO4-2, NH4+, PO4-3, AsO4-3, sulfones

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The poisoning effect of metal ions depends on the number of d

electrons. Metals with an empty d shell, such as alkali and alkaline
earth metals, and those with less than 3 d electrons are nonpoisons,
as shown in the following for the example of platinum:
Poisons: Zn2+, Cd2+, Hg2+, In3+, Tl+, Sn2+, Pb2+, Cu+, Cu2+, Fe2+,
Mn2+, Ni2+, etc.
Nonpoisons: Na+, Be2+, Mg2+, Al3+, La3+, Ce3+, Zr4+, Cr2+, Cr3+

Catalyst poisoning can be reversible or irreversible, depending on the

reaction conditions.
For example, sulfur poisoning of nickel catalysts is irreversible at
low temperatures, and methanation catalysts can not be regenerated,
even by treatment with hydrogen. At higher temperatures sulfur can be
removed by hydrogenation and steam, so that nickel catalysts for
steam reforming are considerably more resistant to sufur-containing
poisons.
Poisoning of metal catalysts can best be avoided by pretreatment of
the reactants by:
– Chemical treatment (expensive; can lead to other impurities)
– Catalytic treatment (very effective for organic poisons)
– Use of adsorbers (e. g., ZnO to remove sulfur-containing compounds
in natural gas reforming)

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Poisoning of Semiconductor Oxides

Because of the presence of electron-donor or electron-

acceptor centers with special surface geometries and the fact that
redox reactions are favored, general statements about the
poisoning of semiconductor catalysts can hardly be made.
Any molecule that is strongly adsorbed on the surface is a
potential poison.
Up to now there have been no theoretical models of the
poisoning of semiconductor catalysts. They are quite resistant
to poisoning, the addition of several per cent of foreign materials
being required to give a noticeably lower activity.

Poisoning of Solid Acids

The poisoning of acid centers can easily be explained. Acid

centers can be neutralized and thus poisoned by basic
compounds such as alkali and alkaline earth compounds
and especially organic bases. Alkali and alkaline earth
compounds are normally used as promoters and are generally
not present in process streams.

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– Poisoning of the catalyst. Typical catalyst poisons are H2S, Pb, Hg, S, P
– Deposits on the catalyst surface block the active centers and change
the pore structure (e. g., coking)
– Thermal processes and sintering of the catalyst lead to a loss of active
surface area
– Catalyst losses by evaporation of components (e. g., formation of
volatile metal carbonyls with CO)

Deposits on the Catalyst Surface

The blocking of catalyst pores by polymeric components,
especially coke, is another widely encountered cause of catalyst
deactivation. In many reactions of hydrocarbons, side reactions lead
to formation of polymers.
If these are deposited near the pore openings, catalyst activity and
selectivity can be influenced due to impaired mass transport into and
out of the pores.
At high temperatures (above 200°C) these polymers are
dehydrogenated to carbon, a process known as coking. Especially
catalysts with acidic or hydrogenating/dehydrogenating properties
cause coking. Coking on acid centers is observed with zeolite and
aluminosilicate catalysts and with acidic supports. The extent of coke
formation depends directly on the acidity.

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Thermal Processes and Sintering

Thermal influences can often affect the catalyst composition.

In many cases one or more metastable phases are formed from the
active components or the support materials. Phase changes can
limit the catalyst activity or lead to catalyst–substrate interactions. An
example is the transformation of g-Al2O3 into a-Al2O3 with its lower
surface area.
Another example is the phase transformation of TiO2 from anatase to
rutile in V2O5 / TiO2 /corundum catalysts for the oxidation of o-xylene
to phthalic anhydride.

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Sintering

Sintering (a process of compacting and forming a solid mass of material

by heat and/or pressure without melting it to the point of liquefaction) is
a well-known phenomenon in metallurgy and ceramics technology.
Sintering processes are also of importance in catalysis, even at low
temperatures. Reasons for this are the extremely small crystallites,
porous supports, and reactive gases. Catalyst atoms already become
mobile at temperatures between one-third and one-half of the melting
point.
The rate of sintering increases with increasing temperature, decreasing
crystallite size, and increasing contact between the crystallite particles.
Other factors are the amount and type of impurities on the crystallite
surface and the support composition in supported catalysts.

Naphta reforming

An informative example is naphtha reforming, in which the influence

of regeneration also becomes apparent. Data suggest that regeneration
of the catalyst by combustion of the coke leads to an increase in
crystallite size, since the catalyst activity, measured by H2 adsorption,
decreases steadily with time, in spite of regeneration.

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In general, the effects of sintering can be counteracted by the

following measures:
– Addition of stabilizing additives (promoters) to the active
components or their dispersion on the surface of the support (e. g.,
nickel can be stabilized by Cr2O3)
– Redispersion of the metals (e. g., chlorine treatment of Pt /Al2O3
reforming catalysts: volatile PtCl2 is re-adsorbed on Al2O3 and finely
distributed)

Catalyst Losses via the Gas Phase

High reaction temperatures in catalytic processes can lead to loss

of active components by evaporation. This does not only occur
with compounds that are known to be volatile (e. g., P2O5 in
H3PO4, silica gel, HgCl2/activated carbon), but also by reaction
of metals to give volatile oxides, chlorides, or carbonyls.
In the oxidation of ammonia on Pt/Rh net catalysts (Ostwald
nitric acid process), the catalyst reacts with the gas phase to form
volatile PtO2.
Furthermore, porous platinum growths are observed on the
surface. This can be prevented by addition of rare earth oxides.

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In hydrogenation processes with molybdenum-containing

catalysts, too high temperature during regeneration due to the
occurrence of hot spots can lead to the formation of MoO3, which
evaporates at temperatures above 800°C with irreversible loss of
activity.
Another example is the use of nickel catalysts in the methanation of
synthesis gas. If the temperature of the catalyst bed drops below
150°C, catalyst is lost by formation of highly toxic nickel
tetracarbonyl.

Catalyst regeneration and loss of

activity during a process

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