C ATA LY S T S H A P E S A N D

PRODUCTION OF
H E T E R O G E N E O U S C ATA LY S T S
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BULK CATALYST

Precipitation
Bulk catalysts are mainly produced when the active components are cheap. Since
the preferred method of production is precipitation, they are also known as
precipitated catalysts.
Precipitation is mainly used for the production of oxidic catalysts and also for the
manufacture of pure support materials.
Production of a precipitated catalyst
Fusion and Alloy Leaching

Pre-molten catalysts are prepared by fusion of various precursors

Example is an iron oxide catalyst for ammonia synthesis. Iron ore is

melted in an electric furnace at 1600 ∘C, and during this process
promoters such as alumina and silica are introduced into the
furnace, while other promoters (CaO and KNO or K CO ) are added
3 2 3

later in an oxidation step at 1600–2000 ∘C. The melt is cooled, then

crushed, and sieved into several size fractions.
Because of proprietary problems, Raney catalysts are often named differently
(skeletal catalysts, active base metal catalysts). There are many other Raney catalysts
used commercially:

•Raney Cu-Zn catalysts for methanol synthesis and water–gas shift reactions.
•Raney Cu-Zn catalysts modified with Cd for selective hydrogenation of α,β-
•unsaturated aldehydes and ketones.
•Raney Cu for production of methyl formate.
•The Raney catalysts are highly pyrophoric and normally stored and handled as
•wet catalysts.
Sol–Gel Synthesis

The gelation methods are based on the continuous transformation of a solution

into a hydrated solid precursor. Key factors of sol–gel synthesis are hydrolysis
and condensation reactions of alkoxides
 The sol–gel preparation includes four main steps:

•The formation of a hydrogel, a metastable open-structure polymer with the units

bound by chemical, dipole, and van der Waals forces and hydrogen bonds.
•Aging of the gel.
•Drying of the gel for solvent removal (evaporation or supercritical solvent
extraction).
•Heat treatment to obtain different product forms such as powder, monoliths,
thin film, and membranes.
Flame Hydrolysis
Flame hydrolysis is a process for the preparation of catalyst supports in which a
mixture of the catalyst or the support precursor, hydrogen and air are fed into a
flame

The flame methods are rather complex, because they are influenced by a number
of parameters, such as flame temperature, gas and liquid feed rates, type and
concentration of the precursor and solvent, and solvent-to-fuel ratio. Therefore, a
precise control over the size of the particles and the crystallinity is difficult to
achieve.
Hydrothermal Synthesis

Aluminosilicate zeolites are formed by hydrothermal synthesis,

typically under mild conditions (80–250∘C) and autogenous
pressure

Example in hydrothermal synthesis

of zeolite
Heteropolyacids

Heteropolyacids (HPAs) or polyoxometalates are an interesting class of bulk acid

catalysts.

The amphoteric metals of groups V B (V, Nb, Ta) and VI B (Cr, Mo, W) in the +5
or +6 oxidation state form weak acids that can react in condensation reactions
with other acids (e.g., phosphoric or silicic acids) to form HPAs and the
corresponding heteropoly salts
In general, free HPAs and salts, of which the heteropolymolybdates and het-
eropolytungstates are the best known, having very high molecular weights (some
>4000), are very soluble in water and organic solvents and are almost always
highly hydrated. The most common structural feature is the Keggin anion build
up by 12 MO octahedra and one central XO tetrahedron.
6 4
 SUPPORTED CATALYSTS

Impregnation
In the impregnation process, active
components with thermally unstable anions
(e.g., nitrates, acetates, carbonates, and
hydroxides) are used. The support is immersed
in a solution of the active component under
precisely defined conditions (concentration,
mixing, temperature, time). Depending on the
production conditions, selective adsorption of
the active component occurs on the surface or
in the interior of the support. The result is
nonuniform distribution.
If the volume of the solution exceeds the pore volume of the support the
process is called “wet impregnation.” If both volumes correspond to each other
the process is named “dry impregnation” or more often “incipient wetness
impregnation” or “pore volume impregnation” (PVI).

If catalysts with high loadings of the active compounds are to be made, limited
solubility of the precursor compound may cause problems, and multiple
impregnations may have to be applied.
Rate of drying strongly affects the
metal distribution of the catalyst
particles. Catalysts with egg yolk, egg
shell, and homogeneous metal
distributions can be obtained in this
method.
Calcination is heat treatment in an oxidizing atmosphere at a temperature slightly
higher than the intended operating temperature of the catalyst.

In calcination numerous processes can occur that alter the catalyst, such as
formation of new components by solid-state reactions, transformation of
amorphous regions into crystalline regions, and modification of the pore structure
and the mechanical properties.

In the case of supported metal catalysts, calcination leads to metal oxides as

catalyst precursors, and these must subsequently be reduced to the metals. This
reduction can be performed with hydrogen (diluted with nitrogen), CO, or milder
reducing agents such as alcohol vapor.
Coprecipitation

Solutions of salts of the catalytically active material and of the support are
prepared, to which a precipitating agent is added,
The resulting hydroxides or
hydroxyl salts precipitate as a
homogeneous mixture that is
filtered off. Subsequent process
steps such as drying and
calcinations lead to a porous
catalyst. The whole process is
difficult to control, and it is
important that both
components are precipitating
simultaneously.
Adsorption/Ion-Exchange
The adsorption or ion-exchange method of preparation involves soaking
predried catalyst particles in the appropriate metal salt solution

The salt generating the cations or anions of the catalytic element must be
compatible with the surface charge of the carrier.

Adsorption is an efficient and convenient method for obtaining uniformly

and strongly deposited supported catalysts, especially for noble metal
catalysts with low metal loadings. Support surfaces in contact with metal salt
solutions adsorb equilibrium amounts of either cations or anions on active
sites containing either protons or hydroxyl groups
Anchoring/Grafting

anchoring immobilization refers to attachment of a central metal atom of a

mostly transition metal complex to a solid support

Grafting is a procedure of equilibrium adsorption of an active catalytic species

(metal or precursor) by covalent bonding to a solid support from a solution in
which the support is suspended.

anchoring immobilization Grafting catalyst

Monolithic Catalysts

A monolith is a structured support or a structured catalyst characterized by long

parallel channels separated by thin walls

The coated monolith consists of a monolithic backbone and a layer that is coated
onto the so-called washcoat

An integral monolith is made completely of support material providing the

mechanical and the catalytical properties.
S H A P I N G O F C ATA LY S T S A N D C ATA LY S T S U P P O R T S

The shape and size of the catalyst particles should promote catalytic
activity, control the mass transport through a catalyst bed, influence the
bed pressure drop, and strengthen the particle resistance to crushing and
abrasion.

For fixed- bed reactors, relatively large particles of several millimeters are
applied to avoid pressure drop.

Spherical particles are preferred for moving-bed reactors because they allow a
smooth flow. Catalyst powders of various sizes are utilized in slurry three-phase
reactors and in fluidized-bed reactors.