Solid Catalysts

Catalyst composition
-Active phase
Where the reaction
occurs (mostly
metal/metal oxide) Catalyst

-Promoter Support

Textual promoter
(e.g. Al - Fe for NH3
production)
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 Mode of Action of Catalysts
The suitability of a catalyst for an industrial
process depends mainly on the following
three properties:
Activity
Selectivity
Stability (deactivation behavior)
The question which of these functions is the
most important is generally difficult to
answer because the demands made on the
catalyst are different for each process.
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Activity: of a catalyst depends on the texture
and electronic structure. Activity of a
catalyst can be explained by:
Active centers on the surface of the
catalyst
Geometry of surface
Electronic structure
Formation of surface intermediates

Efficiency : of a catalyst depends on Activity,

Selectivity and Life.

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Inhibitor: substances added to the catalyst
during its manufacture to reduce its activity.

Coking/Fouling: deposition of carbonaceous

material on the surface of the catalyst -
Common to reactions involving
hydrocarbons

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Selectivity
The selectivity (Sp) of a reaction is the
fraction of the starting material that is
converted to the desired product P.

It is expressed by the ratio of the amount

of desired product to the reacted quantity
of a reaction A . In addition to the desired
reaction, parallel and sequential reactions
can also occur.
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Selectivity
Stability
The chemical, thermal, and mechanical stability
of a catalyst determines its lifetime in industrial
reactors.
Catalyst stability is influenced by decomposition,
coking, and poisoning. Catalyst deactivation can
be followed by measuring activity or selectivity as
a function of time.

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Presently the efficient use of raw materials and
energy is of major importance, and it is prefer-
able to optimize existing processes than to
develop new ones.
For various reasons, the target quantities
should be given the following order of priority:
Selectivity >Stability> Activity

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 Solid Catalysts
Some common solid support / carrier
materials
Alumina
Inexpensive
Surface area: 1 ~ 700 m2/g
Acidic
Silica
Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic

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Catalysis in the Chemical Industry
Hydrogen Industry (coal, NH3, methanol, FT,
hydrogenations / HDT, fuel cell).

Natural gas processing (SR,ATR,WGS,POX)

Petroleum refining (FCC, Hydrotreating,

Hydrocracking, Reforming, Alkylation etc.
etc.)

Petrochemicals(monomers, bulk chemicals).

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Fine Chem.(pharma, agrochem, fragrance,
textile, coating, surfactants,laundry etc)

Environmental Catalysis (auto exhaust,

deNOx, )

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Catalytic cracking is the Largest user of
any solid Catalyst.

Mineral acids such as H2SO4, HF and AlCl3

are widely used in the industry.

The US petroleum refining industry alone

uses ~ 2.5 M tons of H2SO4 and ~ 5000 tons
of an hydrous HF annually

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 Reactions / processes based on
acid catalysis
Name of Description Solid-acid
reaction catalyst used
Cracking / Crack large molecules in Silica-alumina;
hydrocrac petroleum oils ZeoliteY ZSM-5
king FCC additives for more C3 and
octane

Dewaxing Crak n-paraffins (waxes) in ZSM-5

petroleum oils
Isode- Isomerization of waxy SAPO-11
waxing molecules.
Xylene p- and o-xylenes from m- ZSM-5;
isomeri- xylene. Mordenite
sation
Reactions / processes based on
acid catalysis
Name of Description Solid-acid
reaction catalyst used

Naphtha Isomerization reactions for Chlorided

reforming aromatization of paraffins. alumina

Hydrotrea- Remove N and S from Alumina support

ting petroleum oils
Hydration Hydrate olefins to alcohols. Ion-exchange
resin; ZSM-5;
Heteropolyacids
 Types of Catalysts & Catalytic
Reactions
The types of catalysts
Classification based on the its physical
state, a catalyst can be
gas
liquid
solid
Classification based on the substances
from which a catalyst is made

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 Inorganic (gases, metals, metal oxides,
inorganic acids, bases etc.)
Organic (organic acids, enzymes etc.)
Types of catalysts
Classification based on the ways catalysts work
Homogeneous - both catalyst and all
reactants/products are in the same phase (gas
or liq)
Heterogeneous - reaction system involves
multi-phase (catalysts + reactants/products)

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Classification of Catalysts

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Comparison between Homogeneous
and heterogeneous catalysts

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Comparison between Homogeneous
and heterogeneous catalysts

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 Types of Catalysts & Catalytic
Reactions
The types of catalysts
Classification based on the its physical
state, a catalyst can be
gas
liquid
solid
Classification based on the substances
from which a catalyst is made

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Three fundamental stages of catalyst preparation
may be distinguished:

Preparation of the primary solid (or first precursory

solid) associating all the useful components
(e.g.,impregnation or co-precipitation, or in the case of
zeolites, crystallization);

Processing of that primary solid to obtain the catalyst

precursor, for example by heat treatment;
Activation of the precursor to give the active
catalyst: reduction to metal (hydrogenation
catalysts), formation of sulfides
(hydrodesulphurization), de-ammoniation (acidic
zeolites).
Activation may take place spontaneously at the
beginning of the catalytic reaction (selective
oxidation catalysts).

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Main routes (Catalyst Preparation)
deposition,
Impregnation
Precipitation,
co-precipitation,
gel formation.

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 Solid Catalysts
Support

Drying
& firing

precursor add acid/base

solution with pH control precipitate filter & wash
or deposit the resulting
precipitation precipitate

Support
adsorbed
Amount

Drying
& firing
Concentration

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Potential energy diagram of a heterogeneous catalytic
reaction

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 Steps of Catalytic Reactions

Every catalytic reaction is a sequence of

elementary steps, in which reactant molecules
bind to the catalyst, where they react, after which
the product detaches from the catalyst, liberating
the latter for the next cycle.
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 PORE SYSTEM
The pore system of a support is usually irregular
in shape and contains macropores due to the
spaces between individual crystallites, with
diameters of the order of 100 nm, and micropores
with characteristic dimensions of 5 10 nm.
A good support offers
(1) Controlled surface area and porosity,
(2) Thermal stability,
(3) High mechanical strength against crushing
and attrition.
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 Active site

pore
porous
solid

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31
Pore Size and Shape
Pore Diameter
micropores (< 2 nm)
mesopores (2 50 nm)
macropores (> 50 nm)

Pore Shape
cylinder
slit
ink-bottle
wedge