Solid Catalysts

Requirements of a Successful Catalyst

➢High activity per unit of volume.
➢ High selectivity towards the desired product.
➢ Sufficiently long life time with respect to deactivation.
➢Possibility to regenerate, particularly if deactivation is fast.
➢Reproducible preparation.
➢Sufficient thermal stability against sintering, structural change or
volatilization inside the reaction environment.
➢High mechanical strength with respect to crushing.
➢High attrition resistance (resistance to mechanical wear)
➢the catalyst must be processed into shaped particles
 Structure of Metals, Oxides and Sulfides and their Surfaces
Metal Structures
• The most important metals for catalysis are those of the groups VIII
and I-B of the periodic system. Three crystal structures are important,
face-centered cubic (fcc: Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au), hexagonally
close-packed (hcp: Co, Ru, Os) and bodycentered cubic (bcc: Fe).

➢ the fcc and the hcp lattices have the highest density, possessing about 26% empty space. an atom in the interior has a coordination
number of 12.
➢ The bcc lattice is slightly more open and contains about 32% empty space. The coordination number of a bulk atom inside the bcc
lattice is 8.
Surface Crystallography of Metals
1- Crystal Planes
• The structure and geometry of a surface play a dominant role
with respect to its reactivity in adsorption and catalysis.
• The surface is indicated by the set h, k, and l (hkl)
• An important parameter for surface reactivity is the density of
atoms in the surface.
• The general rule of thumb is that the more open the surface, the
more reactive it is.
• (110) is the most open basal plane of an fcc crystal, whereas
(111) exhibits the closest packing.
• For bcc crystals the order is the opposite, i.e. (111) is the most
open and (110) the most packed.
• The reactivity of a surface depends on the number of
unsaturated bonds.
2- Adsorbate Sites

• The number of adsorption sites on a surface per unit or area

follows straightforwardly from the geometry.
• In many cases the number of occupied adsorption sites is not
equivalent to the number of unit cells. Often, repulsive
interactions between adsorbed species prevents filling of all
sites and adsorption may only be possible if all neighboring sites
are unoccupied.
• The saturation coverage depends on the adsorbate. Adsorbates
on surfaces may attract or repel each other to some extent
Oxides
• Bulk structures of oxides are best described by assuming that they are
made up of positive metal ions (cations) and negative O ions (anions).
• The cations in transition metal oxides often occur in more than one
oxidation state. Molybdenum oxide is a good example, as the Mo cation
may be in the 6+, 5+, and 4+ oxidation states. Oxide surfaces with the
cation in the lower oxidation state are usually more reactive than those in
the highest oxidation state. Such ions can engage in reactions that
involve changes in valence state.
• Cations at the surface possess Lewis acidity, i.e. they behave as electron
acceptors.
• The oxygen ions behave as proton acceptors and are thus Brønsted bases
or electron donors thus Lewis base.
• Densely packed oxide surfaces, such as MgO(100),
are largely inactive, but defects, particularly those
associated with oxygen vacancies, provide sites
where adsorbates may bind strongly.
• Many gases adsorb only after heterolytic dissociation
 Sulfides
• Sulfides play an important role in hydrotreating catalysis.
• Sulfides have covalent bonds and hence the crystal structures of sulfides
differ, in general, greatly from those of oxides.
• The most important sulfides are MoS and WS , which possess a layered
2 2

structure.
• The reactivity of the sulfides is
associated with the edges, the basal
plane consisting of sulfur is largely
inactive. Edges can be sulfur
terminated, or metal terminated, and
in addition there may be sulfur
vacancies
Surface Free Energy
• The surface free energy is always positive.
• Metals possess the highest surface free energies while values for ionic solids and oxides are much lower
• Minimization of the surface free energy is the driving force behind a number of surface processes and
phenomena.
➢ Surfaces are always covered by a substance that lowers the surface free energy of the system. Metals are usually
covered by a monolayer of hydrocarbons, oxides and often also by water (OH groups).
➢ Clean, polycrystalline metals expose mostly their most densely packed surface, because, to create this surface,
the minimum number of bonds have to be broken
➢ In alloys, the component with the lower surface free energy segregates to the surface, making the surface
composition different from that of the bulk
➢ Impurities in metals, such as C, O, or S, segregate to the surface because there they lower the total energy due to
their lower surface free energy.
➢ Small metal particles on an oxidic support sinter at elevated temperatures because loss of surface area means a
lower total energy.
Characteristics of Small Particles and Porous
Material
• Catalysis is a surface phenomenon, hence efficient catalysts have a large surface
area, implying that the active particles must be small.
• The properties of interest are the dispersion, i.e. the fraction of atoms located at
the surface of a particle, and the specific area, i.e. the surface area per unit of
weight.
• Small metal particles are often unstable and prone to sintering, particularly at
temperatures where typical catalytic reactions are carried out. Therefore, most
heterogeneous catalysts that are used in industry consist of particles inside the
pores of an inert support.
• This can also be achieved by adding so-called structural promoters
• Silica, alumina, titania, magnesia, zinc oxide, zirconia, as well as carbon can all be
used as support materials.
• The morphology of the particles is again determined by the surface energy, this
time of the particles themselves and the substrate.
Pore System
• Supports such as silica, alumina and carbon usually contain pores that
offer a high internal surface area.
• The pore system of a support is usually rather irregular in shape and
contains macropores.
• A good support offers
➢controlled surface area and porosity,
➢thermal stability,
➢high mechanical strength against crushing and attrition
• pores may have all kinds of shapes (channels and cages, slit-shaped
pores)
• All support materials may contain micro, meso and macropores
Surface Area
• For a supported metal catalyst, the BET method yields the total
surface area of support and metal.
• If we perform our measurements in the chemisorption domain, for
example with H or CO at room temperature, adsorption is limited to
2

the metallic phase, providing a way to determine the dispersion of

the supported phase.
Catalyst Supports
Silica
• Silica is the support of choice for catalysts used in processes operated
at relatively low temperatures (below about 300 C), such as
hydrogenations, polymerizations or some oxidations.
• Its properties, such as pore size, particle size and surface area are
easy to adjust to meet the specific requirements of particular
applications.
• Compared with alumina, silica possesses lower thermal stability, and
its propensity to form volatile hydroxides in steam at elevated
temperatures also limits its applicability as a support.
• silica supports are amorphous.
• Silica surfaces contain only terminal OH groups, i.e. bound to a single
Si atom
Alumina
• Owing to its excellent thermal and mechanical stability and its rich
chemistry, alumina is the most widely used support in catalysis.
• Although aluminium oxide exists in various structures, only three phases
are of interest, namely
• the nonporous, crystallographically ordered α-Al O , and the porous
2 3

amorphous η- and γ-Al O . 2 3

• The latter is also used as a catalyst by itself, for example in the production
of elemental sulfur from H S (the Claus process), the alkylation of phenol or
2

the dehydration of formic acid.

• As a support, γ -Al O offers high surface areas (50–300 m g ), mesopores of
2 3 2 –1

between 5 and 15 nm, pore volumes of about 0.6 cm g , high thermal

3 –1

stability and the ability to be shaped into mechanically stable extrudates

and pellets.
• The highly stable α -Al O is used in high temperature applications, such as in
2 3

steam reforming, or in cases where low surface areas are desired.

Carbon
• Porous carbons are used as a support for noble metal catalysts in
hydrogenation reactions of organic compounds, particularly in liquid
media.
• The advantages of carbon are relative chemical stability and the easy
recoverability of the expensive noble metals from spent catalysts
Shaping of Catalyst Supports
• to apply catalysts in reactors, they need to be shaped into larger bodies of
sufficient mechanical strength
• The shape of the catalyst body influences the mass transport
characteristics as well as the pressure drop in a catalyst bed
• Pellets or tablets (1.5–10 mm in diameter), rings (6–20 mm) and multi-
channeled pellets (20–40 mmin diameter and 10–20 mmhigh) are used
when a high mechanical strength is required. They are produced by
compressing a mixture of the support powder and several binders (kaolin
clay, stearic acid) and lubricants (graphite) in a press.
• In many cases supports are shaped into simple cylinders (1–5 mm in
diameter and 10–20 mm in length) in an extrusion process
Preparation of Supported Catalysts
• There are in principle two ways to make supported catalysts:
(1) By coprecipitating the catalytically active component and the support to
give a mixture that is subsequently dried, calcined (heated in air), and
reduced to yield a porous material with a high surface area. This procedure is
followed when materials are cheap and obtaining the optimum catalytic
activity per unit volume of catalyst is the main consideration.
(2) By loading pre-existing support materials in the form of shaped bodies
with the catalytically active phase by means of impregnation or precipitation
from solution. This is the preferred method when catalyst precursors are
expensive and the aim is to deposit the catalytically active phase in the form
of nanometre-sized particles on the support. All noble metal catalysts are
manufactured in this way.
Coprecipitation
➢Solutions of salts of the catalytically active material and of the support are
prepared, to which a precipitating agent is added, such as NaOH or
NaHCO . 3

➢ As a result hydroxides or hydroxy salts precipitate and form a homogenous

mixture that is filtered off.
➢Removal of CO and water during drying and calcination, and of oxygen
2

during reduction, yields a porous catalyst.

➢ The process is difficult to control; it is essential to keep the solution
homogeneous to allow the two components to precipitate simultaneously,
and variations of pH throughout the solution should be avoided.
➢ Examples of coprecipitated catalysts are Ni/Al O used for steam reforming
2 3

and Cu-ZnO/Al O applied in the synthesis of methanol.

2 3
Impregnation, Adsorption and Ion-exchange
• Filling the pores of the support with a solution of the catalytically
active element, after which the solvent is removed by drying, is a
straightforward way to load a support with active material.
• However, in this process various interactions are possible between
the dissolved catalyst precursor and the surface of the support, which
can be used to obtain a good dispersion of the active component over
the support.
Deposition Precipitation
• The essence of this method is that small crystallites of metal hydroxide or
carbonate precipitate from solution, preferably by heterogeneous
nucleation at the interface between liquid and support. To this end the
support powder is suspended in the metal solution, and a base is added to
raise the pH.
• As the pH must be homogeneous throughout the solution, efficient stirring
is required
• This method has been used to prepare supported vanadium, molybdenum,
manganese, iron, nickel, and copper catalysts with a homogenous
distribution throughout the entire support. After precipitation, the solid is
filtered off, washed, dried, and shaped. Finally, the catalyst is calcined and
further activated by reduction or sulfidation
Unsupported Catalysts
• Multicomponent catalysts, particularly those based on mixtures of oxides, can be
prepared by fusion in an electric arc furnace.
• This is only possible for oxides that conduct electric current at high temperatures.
• Various oxides, e.g. iron oxide (magnetite, Fe O ), alumina and potassium oxide for an
3 4

ammonia synthesis catalyst, mix well in their molten state. After cooling, the catalyst is
crushed into fragments, and the particles of desired size are sieved out. Larger particles
are recycled to the crusher, smaller particles go back in the furnace.
• Fused catalysts leave the furnace as nonporous solids, but develop porosity during
reduction. For the ammonia synthesis catalyst, the solid mainly consists of Fe O with
3 4

roughly 1% K O and 2.5% Al O . This is an example of a doubly promoted catalyst since it is

2 2 3

electronically promoted by potassium and structurally promoted by alumina. If CaO is

also added it is triply promoted. During reduction in the synthesis gas, the oxygen in Fe O
3 4

will be removed as water while the other oxides are not so easily reduced. The result is a
porous structure of metallic iron, which is the active part of the ammonia catalyst.
 Zeolites (boiling stone)
• Zeolites form a unique class of oxides, consisting of microporous, crystalline aluminosilicates
• can either be found in nature or synthesized artificially
• The zeolite framework is very open and contains channels and cages where cations, water and
adsorbed molecules may reside and react.
• For fundamental catalysis they offer the advantage that the crystal structure is known, and that
the catalytically active sites (solid acid catalysts) are thus well defined. The fact that zeolites
posses well-defined pore systems in which the catalytically active sites are embedded in a defined
way gives them some similarity to enzymes.
• Natural zeolites may bear the name of the mineral (mordenite, faujasite, ferrierite, silicalite), or
sometimes that of the discoverer, e.g. Barrerite after Professor Barrer, or the place where they
were found, e.g. Bikitaite from Bikita, Zimbabwe.
• Synthetic zeolites are usually named after the industry or university where they were developed,
e.g. VPI comes from Virginia Polytechnic Institute, and ZSM stands for Zeolite Socony Mobil.
 Structure of a Zeolite
• Basically, zeolites consist of SiO4 and AlO4 tetrahedra,
which can be arranged by sharing O-corner atoms in many
different ways to build a crystalline lattice .
• The SiO4 tetrahedra can be arranged into several silicate
units, e.g. squares, sixor eight-membered rings, called
secondary building blocks.
• Zeolite structures are then built up by joining a selection of
building blocks into periodic structures. The same periodic
structures can also be formed from alternating AlO4 and
PO4 tetrahedra; the resulting aluminophosphates are not
called zeolites but AlPOs.
• Zeolites are made by hydrothermal synthesis under
pressure in autoclaves, in the presence of template
molecules such as tetramethylammonium, which act as
structure directing agents.
• Zeolites exhibit various pore systems.
pore system Properties of some common
zeolites
Unique properties of zeolites
• crystallinity
• microporosity
• uniform pore systems
• pore channels or cages
• high internal surface area
• high thermal stability
• ion exchange capabilities
• acidity
• nontoxic
• environmentally safe
 Applications of Zeolites
• Zeolites have reactive surfaces, owing to the incorporation of Al3+ on sites
where normally a Si4+ ion resides. This property, in addition to the
crystalline system of micropores, enables several applications of zeolites.
• Adsorption: in drying, purification and separation. Zeolites can absorb up to
25% of their weight in water.
• Ion exchange: zeolites are builders in washing powder, where they have
gradually replaced phosphates to bind calcium. Calcium and, to a lesser
extent, magnesium in water are exchanged for sodium in zeolite A. This is
the largest application of zeolites today.
• Zeolites are essentially nontoxic, and pose no environmental risk. Zeolite is
also applied in toothpaste, again to bind calcium and prevent plaque.
• Catalysis: zeolites possess acid sites that are catalytically active in many
hydrocarbon reactions. Examples of how zeolites
can be used to increase selectivity for
a reaction.
• Shape selective catalysis: The pore system only allows molecules that are
small enough to enter, hence it affects the selectivity of reactions by
excluding both the participation and formation of molecules that are too
large for the pores.
Types of catalytic Reactors

Fixed bed reactor Fluidized bed reactors

Continuous Stirred-Tank Reactor CSTR Plug Flow Reactor (PFR)