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ELSEVIER Catalysis Today 34 (1997) 281-305

Chapter 3

Catalyst preparation methods


Carlo Perego a, Pierluigi Villa b
a Eniricerche S.p.A., Via Maritano, 26, 20097 S. Donato Milanese, Italy
b Politecnico di Milano, Deparhnent of Industrial Chemistry and Chemical Engineering, Piazza Leonardo da Vinci, 32, 20133 Milano, Italy

1. Introduction (1) The chemical and physical transforma-


tions which are implied.
Solid catalysts are highly sophisticated prod- (2) The scientific laws which govern such
ucts derived from chemicals by means of sev- transformations based on fundamental inorganic
eral different procedures. chemistry.
The catalytic properties of heterogeneous cat- (3) The operation variables such as tempera-
alysts are strongly affected by every step of the ture, pressure, pH, time, concentration.
preparation together with the quality of the raw (4) The general characteristics of the prod-
materials. The choice of a laboratory method for ucts of the operation.
preparing a given catalyst depends on the physi- (5) The type of the required apparatus.
cal and chemical characteristics desired in the Table 1 reports the main unit operations usu-
final composition. It is easily understood that ally applied in catalyst preparation, according to
the preparation methods are also dependent on La.
the choice of the base materials and experience Most catalyst formulations involve a combi-
shows that several ways of preparation can be nation of some or even all these operations.
considered, even for a given selection of the However, even though the preparation proce-
base material. dures differ considerably from one catalyst to
This variety of possibilities might seem to another, three broad categories can be intro-
confirm that making a catalyst is a black art duced to classify the catalysts with respect to
[l]. In the recent past, however, some generali- the preparation procedure:
ties have become discernible in catalyst prepara- 1. Bulk catalysts and supports;
tion and it may now be claimed that a catalyst 2. Impregnated catalysts;
preparation science is being built. 3. Mixed-agglomerated catalysts.
Despite the variety of possibilities of prepar- Bulk catalysts are mainly comprised of active
ing catalysts we must consider that most of substances. Important examples include silica-
them can be reduced to a series of elementary alumina for hydrocarbon cracking, Zn-Cr oxide
steps, or unit operations, which present quite catalyst for the conversion of CO-H, mixtures
strongly marked analogies from one catalyst to to methanol, iron-molybdate for methanol oxi-
another, and may therefore be described in a dation. The supports are prepared by similar
general way. procedures (e.g. aluminas, silicas, silica alumi-
Such unit operations can be classified by: nas).

0920-5861/97/$32.00 Copyright 0 1997 Elsevier Science B.V. All rights reserved.


PII SO920-5861(96)00055-7
282 C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

Table 1 in the preparation chain can be considered the


Unit operations in catalyst preparation
precursor of the following one, precipitation
1. Precipitation 7. Calcination
8. Forming operation
gives rise to the basic precursor, because it
2. Gelation
3. Hydrothermal transformation 9. Impregnation really creates the imprint or latent image of the
4. Decantation, filtration, 10. Crushing and grinding final solid that subsequent operations will pro-
centrifugation
gressively reveal.
5. Washing 11. Mixing
6. Drying 12. Activation Precipitation occurs in three steps: supersatu-
ration, nucleation and growth. Pertinent parame-
ters producing supersaturation are shown in Fig.
1. Solubility curves are functions of tempera-
Impregnated catalysts are usually obtained tures and pH. In the supersaturation region the
from preformed supports by impregnation with system is unstable and precipitation occurs with
the active phase. Quite a number of hydrogena- any small perturbation. The supersaturation re-
tion catalysts are prepared in this way. gion can be approached either by increasing the
The last category of mixed-agglomerated cat- concentration through solvent evaporation (A to
alysts comprises those catalysts obtained by C), lowering the temperature (A to B) or in-
mixing the active substances with a powdered creasing the pH (which moves the solubility
support or a support precursor and then agglom- curve to D and A into the supersaturation re-
erating the mixture. As far as the techniques are gion). This last approach is quite usual in the
concerned, such catalysts can be considered bulk preparation of hydroxides and sulfides. Particles
catalysts. But as the mixing operation often within the supersaturation region develop in a
consists of impregnating a powder with a solu- two-stage process: nucleation and growth. Nu-
tion of the active substance precursors, the cata- cleation may proceed spontaneously (homoge-
lysts so obtained may be regarded as impreg- neous nucleation) or be initiated with seed ma-
nated catalysts. Quite a number of catalysts for terials (heterogeneous nucleation). These are
hydrotreating refinery processes can be classed solid impurities such as the dust or the rough
in this hybrid category. edges of the vessel surface. The rate of nucle-
Based on the above considerations we will go ation can be accelerated by deliberate addition
on illustrating the main unit operations for bulk of seed nuclei. The growth process depends on
catalysts and supports preparation (Section 2). concentration, temperature, pH and ripening.
Then we will consider the preparation of sup- The size of the precipitated crystal diminishes
ported catalysts by impregnation or by precipita-
tion on a support (Section 3). The preparation of
a zeolite catalyst will be given as an example in
Section 4. Lastly we will carefully examine the
problem of dispersion of the active components
(Section 5).

2. Main unit operations for bulk catalyst and


support preparation 121

2.1. Precipitation [3,41 TEMPERATURE

Fig. 1. Supersaturation dependence on concentration, T and pH


The aim of this step is to precipitate a solid (reprinted with kind permission from [4]. Copyright by Plenum
from a liquid solution. While each intermediate Press).
C. Perego, P. Villa/ Catalysis Today 34 (19971281-305 283

as their equilibrium solubility diminishes (i.e. as can be prepared from many inorganic com-
supersaturation increases), as Ostwald ripening pounds, such as silicic acid and the hydrous
is slowed down by the reduced transfer rate oxides of aluminum and tin. We will consider
between the suspended particles [l]. Most pre- such gels in Section 2.2.
cipitates are crystalline precipitates. Depending Precipitation procedures can be used to pre-
on the precipitation conditions it is possible to pare either single component catalysts and sup-
obtain amorphous solids. If the supersaturation ports or mixed catalysts. The main purpose in
is very high, the aggregation rate can exceed the the latter case is the intimate mixing of the
orientation rate and the solid obtained is amor- catalyst components that can be achieved either
phous. However, by ripening in the presence of by the formation of very small crystallites or by
the mother liquor, the amorphous solid can be- the formation of mixed crystallites containing
come crystalline. Precipitation can be performed the catalyst constituents. Hydroxides and car-
starting from either true solutions or colloidal bonates are the preferred precipitated intermedi-
solutions (~01s). Fig. 2 shows the characteristics ates for the following reasons [6]:
of such solutions [5]. Particles which show little (1) The solubility of these salts of transition
or no attraction for water form hydrophobic metals are very low. Consequently, very high
colloids. These are easily flocculated and the supersaturations can be reached, leading to very
resulting colloidal precipitates are easily filtered small precipitate particle sizes.
(e.g. arsenic trisulfide, silver chloride). Particles (2) Hydroxides and carbonates are easily de-
which show a strong affinity to water form composed by heat to oxides of high area with-
hydrophilic colloids. These are very difficult to out leaving potential catalyst poisons (as, for
flocculate and the resulting jellylike mass is example, the sulfur left by sulfates calcination).
difficult to filter. Hydrophilic colloidal solutions (3) Safety and environmental problems aris-
ing from the calcination of hydroxide and car-
bonates are minimal.
Size, During coprecipitation care must be taken in
micmns
order to avoid independent or consecutive pre-
1000 c cipitations. Besides, the pH should be adjusted
and kept constant during the operation: this can
100 be done by mixing the starting solution continu-
Emulsions Visible with Retained by
and ordinary ously, instead of adding one solution to the
iuspensions filter paper
10 I other [7].

1 __-__-_-_ 2.2. Gelation and flocculation [2,41

0.1 -
I- -+-
Visible with Jot retained
Hydrophilic colloidal solutions are formed of
Colloidal ultra- by ordinary micelles that remain separated because of elec-
solutions filter trical charges on their surfaces and in the sur-
paper
0.01 - rounding solution. These charges create re-
__---__-- pelling forces which prohibit coagulation of the
0.001 I--____--_- , micelles. Such micelles are produced via chemi-
True Not visible cal reactions of polymerization and polyconden-
o~ooo, ; solutions sation. For instance, a silica sol can be obtained
starting from sodium silicate and a mineral acid
I by polycondensation of the intermediate silicic
Fig. 2. Properties of colloidal particles [5]. acid.
284 C. Perego, P. Villa/ Catalysis Today 34 (1997) 281-305

I Clear concentrated sol I


Toward-
Hydrogel or gel

Toward flocculate

Invisible micelles
Clear solution

Path II leads from the sol to a hydrogel through the chemical


reticulation of micelles surrounded by their double layers of
electrostatic charges. Flocculate or gelatinous
Path F leads from the sol to a flocculate of micelles through precipitate through
neutralization of their charges. agglomerization of micelles

Fig. 3. Formation of gels and flocculates (reprinted with kind permission from [2]. Copyright by Editions Technip).

The reticulation of these micelles gives rise vantages over precipitation. In general, sol-gel
to a hydrogel, a three-dimensional network that synthesis offers better control over surface area,
imprisons molecules of water. The mechanism pore volume and pore size distribution. Besides,
of a hydrogel formation is reported in Fig. 3.
The point at which this process, also called
gelation, occurs depends on the concentration of
micelles, the temperature, the ionic strength of
the solution and especially on the pH. For silica
sols the gelation time ranges from a few min-
utes to a hundred hours while the pH varies
from 2 to 7 [8] (Fig. 4).
The density of the gel will increase with the
concentration of the original salts in the solution
and with the gelation rate. Cogel can be ob-
tained by gelation of sols containing two or
more species (Si0,/A1,03, SiO,/Cr,O,).
The starting sol can also be obtained by
hydrolysis of alkoxides such as tetraethyl or-
thosilicate. This is the first step in the well
known sol-gel process largely used to produce
homogeneous ceramics, glass and composites
[9,10]. The sol-gel process can also be success-
fully applied for catalysts preparation [ 111. Fig. 4. Gelation of silica: influence of pH on gelation time (upper
Sol-gel methods have several promising ad- curve) and surface area (lower curve) [8].
C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305 285

the number of alkoxides commercially available transformations usually occur within a liquid
allows the formulation of quite a number of phase. However they can also be performed in
cogel with high uniformity and stability. an atmosphere of steam, such as the steam
The flocculation of a sol can be obtained stabilization procedure of Y zeolites [ 131.
through the neutralization of the micelle charges The variables of these types of operations for
(Fig. 3). The micelles thus coagulate into floc- a given solid are: pH, temperature, pressure,
culates that more or less precipitate well. Hy- time and concentration. When a hydrothermal
drophilic sols generally give jellylike flocculates transformation is distinct from other operations,
that contain large amounts of water (e.g. the it is carried out in specific reactors. In other
amorphous flocculate of Al(OH),). Such floccu- instances the hydrothermal transformations are
lates are denser than hydrogels, but in both carried out during other unit operations such as
cases the elementary solid particle has the di- precipitation, washing, drying, extrusion.
mensions of the original micelles. The surface
area of the final solid depends on the original 2.4. Decantation, filtration, centrifugation and
micelle size and also on the ripening and drying washing
conditions.
Decantation, filtration and centrifugation are
2.3. Hydrothermal transformations [21 well known unit operations, the aim of which is
the separation of the solid phase from the mother
For hydrothermal transformations we usually liquor. Washing of the solids is then required to
consider the modification of precipitates, gels or remove the mother liquor completely and to
flocculates, induced by temperature, under ag- eliminate impurities.
ing or ripening in the presence of the mother The separation of the mother liquor is quite
liquor (usually water). These transformations easy for crystalline precipitates, difficult for
are usually carried out at rather low tempera- flocculates and of no use for hydrogels. The
tures (loo-300C). They involve textural or selection of the separation method will also
structural modifications of the solid that can be depend on the particle size of the solids.
summarized as follow: A satisfactory but time-consuming method is
(1) small crystals + large crystals; decantation [4]. Washing is carried out simulta-
(2) small amorphous particles + large amor- neously with it. The slurry is added to a large
phous particles; volume of distilled water and the suspension is
(3) amorphous solid -+ crystalline solid; thoroughly mixed. Upon standing, particles set-
(4) crystal 1 + crystal 2; tle down. When a definite interface is visible,
(5) high porous gel + low porous gel (Aging water is removed by decantation and the process
or syneresis of a gel [lo]). repeated till the desired purity is reached. When
All such transformations obey the laws of washing flocculates, problems may arise as the
thermodynamics and thus proceed in a direction purified flocculate takes longer to settle with
corresponding to a decrease in free energy of each washing, since removal of counter-ions
the system. reverts the flocculate to sol. This is the well
Increasing interest has been devoted in the known phenomenon called peptization. Care
last decades to the hydrothermal synthesis of must be taken not to wash too much or allow
zeolites and molecular sieves, which is a partic- settling times to become too long. When wash-
ular application of the hydrothermal transforma- ing is completed the solid is filtered. If the
tions [ 121. A detailed description of zeolite cata- particles are too small and the settling time too
lyst preparation will be given later (Section 4). high, filtration or centrifugation must be used.
In most ripening treatments hydrothermal Again care must be taken not to wash too much
286 C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305

with water, otherwise the flocculates peptize Pore


and pass through the filter. volume
Washing can also be applied to exchange (cm 3/9)
certain undesirable or useless ions for others / Dehydration
i
that are easily decomposable by calcination. For hydrogel
I
this purpose a proper salt solution in water will
/ I
be used instead of distilled water. High tempera- I

tures (e.g. 100C) can increase the efficiency by


increasing the exchange rate. For example the
exchange of Na+ for NH,f is used to obtain the
ammonium form of a zeolite, which is trans-
formed into the acidic form by calcination [14].
1 -_---_---_f--.

Xerogel

.I

25 50 75 100

2.5. Drying [44] Hz0 content %


Fig. 5. Pore volume reduction on drying a silica hydrogel [4].
Drying is described as the elimination of the
solvent (usually water) from the pores of a
solid. This is a routine procedure for crystalline reported in Fig. 5 [4]. High temperature gradi-
solids but becomes critical for flocculates and ents should be avoided in order to reduce such
even more for hydrogels that can contain up to effects. The effect of temperature is shown in
90% of water. Therefore we will discuss only Fig. 6. Gel breakage is reduced by lowering the
the drying of such gels. drying temperature, increasing the relative hu-
The removal of water can result in a certain midity of the drying medium or reducing air-
collapse of the structure. Care must be taken to flow through the gel bed [15]. Vacuum drying at
properly control the drying operations if high lower temperatures is an advisable laboratory
porosity is desired. procedure.
Initially drying occurs through evaporation of Dried xerogels contain 25-30% of water,
moisture from the outside surface of hydrogel. encapsulated in fine pores or chemically bound
The water loss rate is constant and the mass to the oxide. In this moist state it is sometimes
transfer is controlled by temperature, relative easier to form the material into pellets or extru-
humidity, flow rate of air over the surface and dates. This is sometimes done for convenience,
size of the gel particles. This process continues
until the moisture content is reduced to about Surface
50%. Then the gel mass begins to shrink. The area
(~&I 700-
material so obtained is called xerogel.
50 C
The subsequent moisture loss occurs with a
600-
declining rate, in which evaporation is con-
trolled by capillary forces. The saturation point
500 - 100C
decreases as pores become smaller and evapora- 400 _ 7:
tion slows until water is forced into larger pores
by concentration gradients. If evaporation oc-
curs but removal of moisture is blocked by 300
25 50 75 100
smaller pores, an internal pressure of steam
develops and the structure collapses, with loss l-$0 content %
of pore volume and surface area. The pore Fig. 6. Effect of drying temperature on the surface area of a silica
volume loss on drying of a silica hydrogel is hydrogel [4].
C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305 287

AI,(SO,), + NH,OH
provided subsequent calcination does not
weaken or damage the particles.
Large capillary stresses can be avoided by
I
operating at temperatures higher than the critical AI( gel
pH=Q, 30 C
temperature of water or by vaporizing the water Z-IO days
I
under vacuum at temperatures ranging from bohemite
-50 to - 5C [2]. The solid structure under- AI,O, nH,O

goes only a small modification by retaining the n=l .O crystalline


textural properties of the wet gel and leading to
a highly porous dry solid called aerogel [ 161.

2.6. Calcination
1-
I
Al,%
300 C to
n=l.8 gelatinous or
pseudo

usually from higher values


of n
250 m*/g
I
450 C y group
Y - 40, low temperature
Calcination is a further heat-treatment be- AI,O, mH,O
4 900 C : m = 0 to 0.6
yond drying. As with drying, this unit operation
6 - AI,O,
can be located before or after the forming opera- I
+ 1000 C s group
tion, depending on the case. We will refer in the
8 - AI,O, high temperature
following to calcination in air, typically at tem- anhydrous AI,O,
4 1200 C
peratures higher than those used in the catalytic a - AI,O, i
reaction and catalyst regeneration. Other ther-
Fig. 7. Alumina modification upon calcination [4].
mal treatments, such as reductions or sulfida-
tions, are performed in special atmospheres, so
surface area oxides and are not suitable for
they will be designated as activation operations.
porous supports. They are used in applications
The latter are usually performed in the industrial
where mechanical strength is required. Chang-
reactor at the start-up of the unit. Therefore they
ing the calcination temperature, even when phase
are not considered to be preparation procedures.
transitions are avoided, can affect the pore size
Several processes occur during calcination: loss
distribution. In Fig. 8 is reported the effect of
of the chemically bonded water or CO,, modifi-
the calcination temperature on a y-alumina [4]:
cation of the texture through sintering (small
increasing the temperature results in a collapse
crystals or particles which turn into bigger ones),
of micropores and in the increase of the mean
modification of the structure, active phase gen-
pore size.
eration and stabilization of mechanical proper-
ties. Alumina is a good example with which to
demonstrate all these features. Fig. 7 outlines
the principal decomposition sequences that oc-
cur upon heating the aluminum hydroxide [4].
Upon calcination of bohemite above 3OOC, a
series of phase changes occur, simultaneously
with loss of hydroxyl groups and hence of
water. These result in the formation of a series
of oxides (q-, y- and &phases), known as
pseudo y-alumina, good for binder and catalysts
support, and therefore useful ingredients in cata-
CALCINATION TEMPERATURE, C
lyst preparation [17]. Above 1000C monoclinic
Fig. 8. Effect of calcination temperature on the pore size of
@Al 203 forms, transforming into hexagonal y-Al,O, (reprinted with kind permission from [4]. Copyright by
CY-A~~O~at 1200C. These are anhydrous, low Plenum Press).
288 C. Perego, P. Villa/ Catalysis Today 34 (1997) 28X-305

By calcining a xerogel various types of sin- Table 2


Different types of catalyst shapes [19]
tering can result with two extremes: (1) sinter-
Shape Size Type of reactor
ing at constant pore radius and (2) sintering at
Extrudate d=l-50mm Fixed bed reactor
constant pore volume [2].
1=3-3omm
The first is the case of a xerogel with cova- Pellet d= 3-15 mm Fixed bed reactor
lent bonds (silica and silica-alumina), calcined h=3-15mm
in dry air. The textural modification results in a Granule, Bead d=l-20mm Fixed bed reactor
d=l-5mm
contraction of the untouched xerogel around Sphere d= l-10 mm Fixed bed reactor
pinpoints of crystallization. The overall pore Moving bed reactor
volume reduces. Microspheroidal d = 20-100 pm Fluid bed reactor
Slurry reactor
The second case is typified by ferric hydrox-
ide, a xerogel with ionic bonds, which retains its
pore volume, even in dry air, by calcination and
sintering. The particles get bigger and the pore nomic trade-off [ 181. The selection of the shape
size increases. and size is driven by the type of reactor. Table 2
Between the two extremes the intermediate gives a rough survey of the different shapes and
cases are observed. Thus calcining a xerogel the reactors in which they are used [19]. For a
with covalent bonds in the presence of steam given reactor the shape and the size of the
results in a sintering at constant pore volume. catalytic particles will depend on the hydrody-
The addition of a specific agent can affect the namic and on heat and mass transfer limitations.
sintering. For instance the addition of sodium to Here we will describe the different techniques
silica lowers the sintering temperature. A sub- for shaping the catalysts into the shape men-
stance which inhibits the sintering is called tioned in Table 2.
textural promoter [ 171. Two extreme types of shaping can be distin-
In conclusion, the calcination operating vari- guished [2], depending on whether the desired
ables for a given gel are time and temperature products are powder microgranules or grains of
and the presence of steam. the size order of one to several millimeters.

2.7. Forming operations 2.7. I. Forming microgranules (20-l 00 p,m)


Crushing and grinding are of no use to pro-
Forming operations are applied to obtain suit- duce microgranules for such a purpose. Actually
ably sized particles of catalyst to be used in the the powder so obtained has a broad particle size
reactor. Therefore, forming and shaping of sup- distribution, with a lower limit of few microns.
ports and catalysts is an important step in the Such a powder is not usable in fluidized beds
preparation procedure of a catalyst. A catalyst because of its poor mechanical resistance. Spray
particle shape and dimension should promote drying is a suitable technique to produce micro-
catalytic activity, strengthen the particle resis- spherical materials. In a spray dryer a hydrogel
tance to crushing and abrasion, minimize bed or a sol is sprayed through nozzles into a heated
pressure drop, lessen fabrication cost and dis- zone. Depending on the temperature, either dry-
tribute dust build-up uniformly. Unfortunately, ing or both drying and calcination occur as the
these objectives are not easily achieved. Indeed, drops fall. Examples of catalyst produced by
several are mutually exclusive. For instance, a this procedure are: catalytic cracking catalysts
smaller particle size increases activity but also (silica-alumina doped with X or Y type zeolites)
increases bed pressure drop. The best opera- [22]; titanium silicalite catalyst [20]; silica gel
tional catalyst, therefore, has the shape and size Dl.
that, in the end, represent the optimum eco- The process itself is more art than science
C. Perego, P. Villa/ Catalysis Today 34 (1997) 281-305 289

PROCESS-AIR ,FEED
T
CYCLONE

Fig. 9. Spray dryer (reprinted with kind permission from 1191.


C:opyright by Elsevier Science B.V.).

[ 191. There is hardly any information in the


aIpen scientific literature [21]. Important
process
parameters are the viscosity of the liquid, the
solid content of the suspension, the film-for-
ming characteristics, the type of atomizer, the
temperature, the gas velocity. In Fig. 9 is re-
ported the scheme of a spray dryer. Fig. 10
shows two different kinds of particles obtained
by different feeds.

2.7.2. Forming grains ( > 1 mm)


The raw materials comprise a calibrated pow-
der or paste with suitable rheological properties.
Table 3 summarizes the methods used for mak-
ing grains according to the nature of the original
charge.

2.7.2.1. Extrusion and wet pressing. Extrusion


is the most commonly applied shaping tech-
nique for catalysts and catalyst supports. A wet
paste is forced through a die. As the ribbon of
the extrudate paste emerges from the die it is
cut to the desired length by a proper device.
Usually catalyst mixes of powdered oxides made
by precipitation do not by themselves have the
necessary mouldability and plasticity even when
the optimum water content is added. They be-
have rather like sand. Fig. 10. Microgranules obtained by spray drying: (a) titania; (b)
Besides, quite a number of such materials silica-alumina.
290 C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

Table 3 pressure and that under this pressure they are


Influence of the starting material on the choice of grain-forming
process [2]
crushed together to form a dense bed which
Starting material Process
then welds at points of contact. At the tabletting
stresses capable of being generated by normal
Monolithic blocks Crushing and grinding
Powders Dry tabletting machines, the requirement of welding implies
Granulation that a sufficient fraction of the material has
Extrusion adequate ductility. A very crude relationship
Pastes, hydrogels Extrusion, wet pressing
Sols Drop coagulation exists between ductility, melting point, elastic
modulus and Mohs scale of hardness, This is
shown in Fig. 11 [7]. Additives such as lubri-
cants (mineral oil, talc, graphite, various
need a binder to produce extrudates with good stearates) and binders (bohemite, clays) are
mechanical behavior. added to give the powders proper qualities. For
So in the formulation of the paste different example, when tabletting untablettable material
additives can be used: such as Cu,O, Al,O, (see Fig. 111, a sufficient
compounds for improving the rheological be- quantity of hydroxide or carbonate precursor is
havior of the paste (clays or starch); left in the tabletting feed (e.g. CuCO,, Al(OH),)
binders (aluminas, clays); to act as binder [7]. The tabletting pressure
peptizing agents to deagglomerate the parti- heavily affects the porosity of the tablet. This is
cles (acetic acid, nitric acid); shown in Fig. 12 for the tabletting of bohemite
combustible materials to increase the macro- [23].
porosity (the so called pore formers like carbon Compared to other shaping methods tablet-
black, starch). ting is quite an expensive method.
Extruding equipment can be classed in one of Tabletting is widely used as preliminary
two categories: press extruders (for wet press- forming method in order to prepare samples for
ing) and screw extruders. The operating vari- catalyst testing in fixed bed microreactors, start-
ables include: mixing time, additives content, ing from powders. Depending on the reactor
water content, paste aging, extrusion tempera- diameter the pellets are then crushed and sieved
ture. The quality of the extrudates will also
depend on the drying and calcining procedure.
Special shapes such as trilobates, rings, hol- Mohs scale of hardness
low cylinders can be obtained by using proper 1 2 3 4 5678910
dies. Monolith or honeycomb supports are also
manufactured by extrusion of a thick inorganic
dough through a special die. Such unusual sup-
port form is used in automobile catalytic con-
verters, where a very low pressure drop is re-
quired to minimize power loss from the engine
1171.

2.7.2.2. Dry tabletting. In this shaping process a


dry powder is pressed between two punches in a
tabletting press. IO6 IO'
The production of strong particles by tablet- Elastic modulus (kg/cm)
ting requires that the particles of the tablet feed Fig. 11. The relation among pelletability, crystal strength and
be subjected to a reasonably uniform triaxial melting point [71.
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305 291

d(log r), cm3/Q


4

ALUMINA
SLURRY

PERFORATED
PLATE

OIL

HARDENING
Pore radius r (A)
SPHERES

Fig. 12. Influence of pelleting pressure on bohemite pore size


distribution [23].

AMMONIA -

to a suitable particle size (reactor to particle


diameter ratios of 5- 10) [4].
Fig. 14. Production of spheres by drop coagulation (reprinted with
2.7.2.3. Granulation. Granules are particles with kind permission from [4]. Copyright by Plenum Press).

more or less spherical shape. The diameter of


these particles ranges between 2 to 30 mm. The or less spherical particles. After drying, the
principle of the shaping method is best de- green spheres are calcined to obtain higher me-
scribed by the snowball effect [19]. A round chanical strength. Sometimes some binder and
dish (see Fig. 13) rotating on an inclined axis is
used. Small particles are fed into the dish. At
the same time a cohesive slurry is sprayed onto
the particles. The particle surface becomes wet
and granules begin to grow. The small particles
rotating develop layer by layer into larger, more

SMALL ALUMINA
MOISTENED
ALUMINA Io/6YDPF%:E,,,SP,ETS
POWDER
0

ROTATING

PRODUCTSPHERES

Fig. 13. Production of spheres by rotating dish granulator (re-


printed with kind permission from 141. Copyright by Plenum
Press). Fig. 15. Alumina spheres obtained by drop-coagulation,
292 C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305

cement are used to make the layers adhere tant to sintering than the catalytic species. Two
better. methods of utilizing support are common [7].
Firstly, a support may be used as a form of
2.7.2.4. Drop coagulation (sol-gel method). refractory surface on which the catalyst crystals
Drop coagulation results from sols suspended in are dispersed; rather like putting small drops of
an immiscible liquid, by simultaneous gelation, mercury on a table top. Secondly, the support
ripening and forming. Fig. 14 illustrates the may be used in the form of more finely divided
principle of the method. In the form of droplets refractory crystals than the catalytic species,
the aqueous sol is forced, through a sparger in a positioned between particles of such species so
water-immiscible solvent, the temperature of that they are kept out of contact - rather like
which is raised to around 100C. The surface dust which can be used to stop a heap of
tension created on the droplets permits the for- mercury drops from coalescing. With the first
mation of gel spheres that are than ripened and method, the volume of support is considerably
dried. The gelation can also be induced by greater than the volume of catalytic species,
increasing the pH [4]. During drying a contrac- consequently this method is normally employed
tion of the bead without deterioration is ob- with precious metal. The preferred preparation
served as long as the diameter is not too large. procedure for such catalysts is impregnation on
Accordingly, this method is suitable for produc- a preformed support.
ing beads such as alumina beads used as support Preparation procedures for the second type of
(Fig. 15). catalysts usually start from powders of support
or support precursors (e.g. precipitation of ac-
tive species on powder support). Then a form-
3. Supported catalysts ing operation will follow.
A thorough description of the techniques for
Supported catalysts are often applied because the dispersion of the active components will be
they combine a relatively high dispersion given in Section 5. In this section we will
(amount of active surface) with a high degree of consider the support selection (Section 3.2) and
thermostability of the catalytic component. the most common preparation methods: precipi-
The preparation of supported catalysts aligns tation (Section 3.2) and impregnation (Section
all the unit operations toward dispersing an 3.3).
active agent on a support, that may be inert or
catalytically active. The wetting of the support 3. I. Support selection
with a solution or a slurry of the active phase
precursors is the operation that characterizes The selection of a support is based on its
such a preparation. The other operations (dry- having certain desirable characteristics. Princi-
ing, washing, calcination, forming) are ruled by pally they are [17]:
the same laws, depend on the same parameters 1. Inertness.
and use the same equipment described in Sec- 2. Desirable mechanical properties, including
tion 2. attrition resistance, hardness and compressive
The function of a support is, quite simply, to strength.
enable the formation of a large particle or tablet 3. Stability under reaction and regeneration
of catalyst composed of very small readily sin- conditions.
terable crystals of catalyst which are prevented 4. Surface area. High surface area is usually,
from coalescing by being separated from each but not always, desirable.
other by the support component. The support 5. Porosity, including average pore size and
component clearly has to be much more resis- pore size distribution. High area implies tine
C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305 293

pores, but relatively small pores (for example support interact with the metal. For example,
< 5 nm) could become plugged during impreg- silanols group of silica interact with Ni(NO,),,
nation, especially if high loading is sought. resulting in a surface hydrosilicate formation,
6. Low cost. rather than hydroxide deposition [25].
Of a wide variety of possible materials, only Rapid nucleation and growth in the bulk solu-
three of them possess a good combination of the tion must be avoided, since it produces a depo-
characteristics mentioned: alumina, silica and sition only outside the support porosity. An
activated carbon. Alumina is the most widely effective method to obtain a uniform precipita-
used industrially. tion is to use urea rather than conventional
Table 4 reports the main characteristics of alkalis. Urea dissolves in water but decomposes
some typical supports [24]. Materials with low very slowly at 90C giving a uniform concen-
surface area are generally useful in supporting tration of OH- in the bulk and in the pores. So
very active catalytic components in reaction precipitation takes place homogeneously over
where further side reactions may affect activity the support surface [25].
and selectivity. Examples of catalysts prepared The precipitation is the preferred deposition
with low surface area supports are: Fischer- route for loading higher than lo-20%. Below
Tropsch cobalt catalyst on diatomaceous earth this value, impregnation is usually practiced.
and ethylene oxide silver catalyst on pumice
[24]. Supports with high surface area are widely 3.3. Impregnation
used in precious metal catalyst preparation.
The impregnation method involves three
3.2. Precipitation (41 steps: (1) contacting the support with the im-
pregnating solution for a certain period of time,
In precipitation, the objective is to achieve a (2) drying the support to remove the imbibed
reaction of the type: liquid and (3) activating the catalyst by calcina-
tion, reduction or other appropriate treatment.
Metal Salt Solution + Support Two methods of contacting may be distin-
oxalate powder NaOH
nitrate KOH
guished, depending on the total amount of solu-
particle
sulfate NH,OH tion.
NaHCO, (1) With excess of solution. The support is
placed on a screen and dipped into an excess
Metal hydroxide or carbonate on support
quantity of solution for the time necessary for
The choice of the salt or alkali depends on total impregnation. The solid is then drained
factors similar to those considered in Section and dried. This operation can be done continu-
2.1. Powders or particles are slurred with an ously as shown in Fig. 16a. In such an operation
amount of salt sufficient to give the required the composition of the batch solution will change
loading. and the release of debris can form a mud which
Enough alkali solution is added to cause pre- makes it difficult to completely utilize the solu-
cipitation, the powder is then treated with the tion [17].
same operations already discussed for bulk cata- (2) With repeated application of solution. A
lyst preparation. When preformed support is more precise control is achieved by this tech-
used forming operations are avoided. nique, termed dry impregnation or impregnation
Two process are involved in the deposition: to incipient wetness. The support is contacted
(1) precipitation of solution in bulk and pore with a solution of appropriate concentration,
fluid; (2) interaction with the support surface. corresponding in quantity to the total known
Best results occur when the OH groups of the pore volume or slightly less [17]. This operation
294 C. Perego, P. Villa/ Catalysis Today 34 (1997) 281-305

Table 4
Typical catalyst support 1241
support Specific surface area (m/g) Pore volume (ml/g)
Low area:
Alundum, Norton o-1 0.33-0.45
Corundum, Alcoa T-61 0.07-0.34 0.08
Silicon carbide, Carborundum <l 0.40
Pumice, Italian 0.04
Diatomaceous earth 2-30 0.5-6.1
Asbestos 1-16
Fiiebrick <l
High area:
Alumina:
Alcoa F-10 100 0.3
Alcoa XF-2 1 200 0.2
Silica-alumina:
Alcoa H-41 350 0.5
Cracking catalysts 400-600 0.6-0.9
Bauxite 150 0.25
Clays, bentonite 150-280 0.3-0.5
Magnesia 30-140 0.3
Silica gel 400-800 0.4-4.0
Activated carbon 90-l 100 0.3-2.0

can be performed continuously as shown in Fig. crystallization and (X + y) gives the number of
16b. The catalyst is kept in motion in a rotating AlO, and SiO, tetrahedra in the unit cell. In the
cylinder or drum, and is sprinkled as required zeolites that are catalytically active for hydro-
with a solution of salt by sprayers. The disad- carbon transformation, M+ is typically H+; the
vantage is the poorer distribution of the precur- catalytic activity is associated with the Bronsted
sors [2]. and Lewis acid sites within the crystalline struc-
For both techniques the main operating vari- ture [27].
able is the temperature which affects both the Zeolites are usually crystallized from alkaline
precursor solubility and the solution viscosity aqueous gels at temperatures roughly between
and, as a consequence, the wetting time. 70 and 300C. The composition of the reaction
In Fig. 17 are shown four limiting types of mixture is suitably defined by a set of molar
impregnation profiles. A proper control of the ratios SiO,/Al,O, H,O/SiO, OH-/SiO,
operating conditions during impregnation and M+/SiO, where M+ represents an alkali, alka-
drying determines the impregnation profile of line earth or ammonium ions. Most of the early
the final catalyst [26]. work in the synthesis of zeolites involves crys-
tallization of the alumosilicate gel from a solu-
tion containing alkali hydroxide as the base. In
4. Zeolite catalyst preparation: an example Table 5 the most commonly used source of
cations, aluminum and silicon are reported. Bar-
Zeolite are crystalline aluminosilicates with a rer [ 121 discovered that the presence of organic
framework structure enclosing channels in which cations along with the alkali led to more open
cations and water molecules are located. The crystal structures. The results of research efforts
general empirical formula of zeolites is: in the use of organic cations during zeolite
(M),,,(AlO,),(SiO,),mH,0, where M is a synthesis have led to the discovery of many new
cation, m is the number of moles of water of zeolite materials [28]. Among them, ZSM-5 is
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305 295

the most interesting for catalytic application second steps for ZSM-5 preparation is reported
[29]. So the preparation of a ZSM-5 zeolite in Fig. 18, according to Jacobs [30].
catalyst will be discussed as an example. (1) Hydrothermal synthesis. For the synthesis
of ZSM-5 Aerosil (Grace Davison) as silica
4.1. Preparation of a ZSM-5 zeolite catalyst source is added to an aqueous solutions of
tetrapropyl ammonium hydroxide (TPAOH).
The preparation of a zeolite catalyst consists Sodium aluminate is dissolved in a concentrated
of the following main steps: NaOH solution and added to the first solution
1. Hydrothermal synthesis of zeolite; under vigorous stirring. The gel formed has the
2. Ionic exchange to obtain the acidic form; following m olar corn position:
3. Binding and shaping. (TPA,O),,(Na,O),,,(Al,O,)(SiO,),,(H,O),,,,.
A schematic diagram of the first and the The gel is transferred to an autoclave and

Bucket conveyor

Tipper

To drymg
Bucket filler

lmpregnatmg ban

Impregnating solutmn

b.

Fig. 16. Support impregnation processes: (a) with excess of solution; (b) impregnation to incipient wetness (reprinted with kind permission
from [2]. Copyright by Editions Technip).
296 C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

Aerosil (Silica Source)

TYPE
1 II III IV
(uniform) (pelliculot) (egg yolk) (egg while)

~subsutlace~

Fig. 17. Four limiting types of impregnation or activity profiles.


Hatched areas in the cross sections of slabs and pellets (top and ZSM-5 SiO, 97.10 %
AJO, 2.08 %
middle rows) indicate the regions where active components are Na,O 0.78 %
deposited. The bottom row shows schematic examples of impreg-
nation or activity profiles (reprinted with kind permission from
[26]. Copyright by Marcel Dekker, Inc.). (Under reflux
conditions)

stirred at 150C for 3 days. Under ripening


crystallization occurs. The solid so obtained is
filtered, washed five times with distilled water
and dried. H-ZSM-5
(2) Ionic exchange. The solid obtained con- Fig. 18. Schematic diagram of ZSM-5 preparation [30].
tains both Na+ and TPAOH. The latter must be
removed from the zeolite framework to allow composition and burning. So the solid is cal-
access to the intercrystalline pore channel sys- cined under a flow of dry nitrogen at 300C, the
tem. This is usually performed by thermal de- heating rate being lC/min. Calcination up to

Table 5
Most common used source of cations, aluminum on silicon in zeolite synthesis [ 141
Charge compensating cations Aluminum Silicon

Alkali metal hydroxides Metal aluminates Silicates and silicate hydrates


Alkaline earth hydroxides Al(O Also,, Water glass
and oxides AlO-OH Al alkoxides
Other oxides and hydroxides Al salts Silica sols
Glasses Silica gels
Salts (fluorides, halides, Sediments Silica and other synthetic glasses
carbonates, phosphates,
sulfates, etc.)
Minerals, especially Silicon esters
clay minerals, fel-sphathoids
and other zeolites
Tuffs and volcanic glass minerals, including clay minerals, felspathoids,
feldspars, and other zeolites
Silicates and aluminates Basalts and mineral mixtures
Mixtures of two or more Sediments
of the above
Combinations of two or more of the above
C. Per-ego, P. Villa / Catalysis Today 34 (1997) 281-305 291

550C is continued for 3 h in air flow. Decom-


position of the organic cation leads to the for-
mation of protonic sites, but the complete trans-
formation into the acidic form requires the elim-
ination of Na+.
This is obtained by exchange under reflux
condition with 0.5 M solution of NH,NO, at a
liquid to solid ratio of 50. This is repeated
several times, depending on the desired effi-
ciency. The solid is then dried and calcined at
550C under air flow.
(3) Binding and forming. Extrusion is a
widely applied method of shaping a zeolite into
a pellet. For this a purpose a binder must be
used. In fact by extruding the zeolite alone poor 20
mechanical strengths are obtained. The binder sp.gr.: p (g crc3)
can be selected among aluminas and silica- Fig. 19. Relation between density and grain-to-crushing strength
aluminas. In this case a pseudo-bohemite of a iron-molybdate methanol-oxidation catalyst pellet. Point A
corresponds to a powder of different texture before compacting.
(Laroche V-450) is added with the zeolite pow-
By increasing the pore volume the pellet density decreases accord-
der in a weight ratio of 1. A paste is obtained by ing to l/p = (l/p,) + VP where pS is the structural (real) density
mixing the powder with an aqueous solution (reprinted with kind permission from 121. Copyright by Editions
containing a plasticizer (1% Methocel, Fluka) Technip).

and a peptizer (acetic acid, 2% of pseudo-


bohemite). The mixing is performed in a Z-blade the active species , since the catalytic phenom-
mixer till a homogeneous paste is obtained ena occur at the surface of the solid. Thus
(about 2 h). The paste is then aged at room porous solids with a high internal surface area
temperature for 2 h and extruded. The extrudate are often necessary in order to reach reasonable
is then aged (overnight, at room temperature), values of activity. The porous texture is the
dried (at 100C under vacuum) and calcined (at result of the preparation unit operations for the
550C in air flow for 10 h). The extrudate unsupported catalysts or it will be supplied by
(cylinders of 2 X 3 mm) so obtained contains the support itself in the case of supported cata-
ZSM-5 (60.5%) and Al,O, (39.5%). lysts.
Higher surface areas may be obtained to some
extent, ceteris paribus, by increasing the pore
volume. However, the mechanical properties of
5. Techniques used to disperse the active the catalyst pellet are, in general, negatively
species affected by an increase of the pore volume as
shown by Fig. 19 [2].
To a greater extent the surface area may be
5.1. Introduction increased by decreasing the mean pore width
value of the catalyst. Indeed it may easily be
One of the most peculiar and relevant re- shown that the surface area S is related to the
quirements for a solid catalyst to be of practical pore volume VP and pore radius rP in a model
use is an appropriate dispersion of the active
species. A high dispersion is usually desired Dispersion is, by definition, the ratio of the active species
because it corresponds to a greater utilization of present at the surface and those present in the bulk of the solid.
298 C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

is more suitable. In an extreme case the oxida-


tion of NH, to NO is performed on a Pt/Rh
10-Z gauze (which has no porosity) and not on pre-
cious metals supported on a porous carrier: the
reaction is carried out at ca. 850C and is
10-4
controlled by the external diffusion of NH, onto
J2 the surface of the gauze. If the same reaction
%
5 10-e were performed on a porous catalyst, the inter-
>;
.Z nal diffusion would increase the selectivity to
.z
the unwanted product N,, instead of NO.
$ 10-B
Restricted Therefore, the preparation of a suitable cata-
or lyst will take into consideration the different
configurational
lo-0 diffusion aspects involved and often the most satisfactory
catalyst will be a compromise between different
10-12
requirements.
In any case, the preparation and production
of a catalyst must be split into several well
lo-i4 I I I i
10 100 103 10
defined unit operations, which must be repro-
Pore size, nm ducible and uniform also during the scaling-up.
Fig. 20. Effect of pore size on diffusivity (reprinted with kind
permission from P.B. Weisz, Chemtech, 3 (1973) 498. Copyright 5.2. Preparation of single phases containing all
by the American Chemical Society). the active elements

with cylindrical monomodal pores by the ex- Solid catalysts are often multicomponent, i.e.
pression: their formulation contains different elements, all
of which have some specific role. The associa-
s = 2vr/r*
tion of these elements develops the greatest
Therefore the smaller the pore width the synergism if they are all present at the scale
greater the surface area. where the catalytic phenomenon takes place, i.e.
However if the pore dimension becomes too the atomic scale.
small, the internal diffusion of the reagents and Thus a catalyst must have an appropriate
products from and to the external surface is surface area (dispersion) but also a good inter-
hampered as shown by Fig. 20 [31]. spersion of the various constituent elements.
This is one of the reasons for which zeolites The preparation of a catalyst must reach these
are used in association with binders which are two general goals.
provided with relatively wider pore structures. As already reported in Section 2 the most
In the presence of diffusion limitations due to used and preferred sequence for a catalyst
small pore values, the kinetic regime followed preparation starts with a precipitation. If the
by the catalytic reaction will pass from the nature of the active phase, including its chemi-
chemical region to the internal-diffusion-limited cal composition, has already been established, it
region. In this case the activity of the catalyst is necessary to find out, by theoretical consider-
will be affected [32] and where more than a ations and experimental tests, the values of the
single reaction takes place a change of the most convenient preparation parameters such as
selectivity to the various products may also be pH, temperature, reagents concentration, order
affected [33]. This is the reason why in many of mixing, aging of the slurry, etc. For example
selective oxidations a moderate internal surface Trifiro et al. [34] make the point of the influ-
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305 299

ence of such parameters in the preparation of coprecipitation, other routes may be tested. In
molybdates and tungstates. Highly concentrated particular increasing attention has recently been
solutions are generally utilized to favor nucle- given to the sol gel process, which also offers
ation vs. crystal growth rate so as to obtain a some advantage (see Section 2.2) and is also
precipitate made of many small crystallites now better understood in its theoretical bases
which lead, after calcination, to a high surface [351.
area. These conditions, although essential, make Another general method was proposed in the
it necessary to manipulate slurries containing a seventies by Delmon and coworkers [36,37]
solid of small particle size and may create some which makes use of an cx-hydroxyacid such as
complications in the unit operations that follow citric acid as complexing agent. Using about
particularly where decantation and filtration are one equivalent of citric acid per equivalent of
concerned. metal ion, and eventually ammonia, it is possi-
Furthermore, to obtain a good interspersion ble to dissolve almost every ion of the periodic
of the different elements inside the precipitate, table. Therefore, it is possible to mix the citrate
independent or consecutive precipitation must solutions of different metal ions in the desired
be avoided. For example, in coprecipitation of ratio, and then to concentrate the resulting solu-
Cu-Zn-Al hydroxycarbonates, which are the tion by distilling off the water. The viscous
precursors of the low-temperature methanol syn- product so obtained is homogeneous and trans-
thesis catalysts, if the sodium carbonate solution forms into a glassy and brittle substance which
is added to the nitrate solution, Al precipitates may easily be ground into a powder. The or-
first at a pH of about 2.5, then Cu at about 3.0, ganic part may be decomposed by calcination,
then Zn at 4.5, as shown in Fig. 21. leaving a fine powder of oxides of the metal
To avoid this happening it is necessary to ions used with a high surface area.
operate at constant pH during precipitation or to This method has the advantage of starting
reverse the mixing order, i.e. to add the nitrate from readily available salts of the desired metal
solution containing Cu Zn Al ions into the ions, although the calcination of the organic part
sodium carbonate solution. is best performed if nitrates are not used, be-
If the desired phase cannot be formed by cause the decomposition in the presence of oxi-
dizing ions such as Mn, Fe, Co, Ni or Cu may
turn into a sudden, non uniform combustion or,
,PH
in the case of Ag, explode.
8- Both the sol gel and the citrate methods are
7-
excellent for their ability to keep different ele-
ments inside the same structure; furthermore,
6-
since they do not involve any unit operation (for
5- example a filtration) in which part of the metal
4- ions may be lost, they lead to oxides of known
composition (that of the starting solution).

5.3. Preparation of solid solutions and defect


l- co32-x n/2 M n+ structures
0.2 0.4 0.6 0.6 1.0

Fig. 21, Neutralization of Cu2+ Zn2+A13+ nitrate solution (0.35 The formation of solid solutions, although
M) with a Na,CO, solution (0.4 M) pH vs. Na,CO, equivalents not characterized by specific preparation meth-
(reprinted with kind permission from Ph. Courty and C. Marcilly,
Rev. 1st. Franc. P&role, 39 (1984) 445. Copyright by Editions
ods, significantly widens the possibility of com-
Technip). prising all the desired metal ions inside a single
300 C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

structure. Indeed it is known that many struc- the type of structure and site in which they are
tures may host in a certain position more than hosted [41]. It is beyond the scope of the present
one element [38]. Two solids having, in that work to analyze all the different sorts of devia-
position, two different elements are called iso- tion from the regular structure and of the possi-
morphous, and will display slightly different ble structural and electronic defects [42]: two
X-ray patterns. In particular, where the position examples only will be given.
of the diffraction peaks is concerned, due to the Spine1 related structures have several applica-
different steric requirements of the two ele- tions in catalysis, such as alcohol synthesis, are
ments, the two structures will have slightly dif- cubic and have as general formula A,BO, with
ferent cell parameters. A solid containing both both octahedral and tetrahedral holes partially
elements occupying in a more or less statisti- occupied. The effective site occupancy however
cally random way the above mentioned posi- may widely vary according to the nature of A
tion, is called a solid solution of the two iso- and B, giving rise to a family of structures
morphous structures. It will be characterized by having at one extreme ZnCr,O,, in which all Cr
cell parameters which are intermediate between ions are in octahedral holes and Zn ions in
the values of the two isomorphs, according to tetrahedral ones (normal spinel), and at the other
the degree of the substitution of one element extreme Fe,O,, which may be also written Fe3+
with the other, and therefore will display an [Fe2+Fe3+] Of- in which all divalent Fe ion is
X-ray pattern with position of the lines interme- in octahedral sites (inverse spinel).
diate of those of the two isomorphs, and not the The important role played by Bi and Te ions
superposition of the spectra of the two iso- in promoting the selective ammoxidation of
morphs. The most stringent structural require- propylene to acrylonitrile in multicomponent
ment for a solid solution to occur is the ionic oxide catalysts may not be explained by the
radii compatibility. formation of new phases, but by the presence of
An example of how isomorphous substitution these ions in an interstitial irregular position,
may lead to phases comprising new elements inside the voids of the host structure in a high
and therefore to an unprecedented catalytic reac- oxidation state and high coordination to lattice
tivity occurs in zeolites [39]. oxygen [43].
Another example of solid solution is the
MOO,-V,O, system, which may be used for the 5.4. Use of alloys and bimetallic catalysts
selective oxidation of 1-butene to maleic anhy-
dride and has a maximum of selectivity at about Catalysis by metals has many important ap-
25% MOO, which corresponds to the solubility plications. One of the reasons for their success
limit of the oxides [40]. is based on the possibilities of the associations
The situation is even more complex, but nev- they offer, particularly when highly dispersed
ertheless open, for finding new possibilities of with particle size not greater than a few
associating different elements inside a single nanometers. Unfortunately all metallic catalysts
type of structure, if one consider that the ions tend to sinter. This phenomenon already starts
may significantly deviate from occupying only during their formation by reduction and contin-
regular sites, enlarging the original definition of ues during the thermal treatments and use in the
the structure and introducing different sorts of catalytic reaction, and generates a rapid decay
defects into it. It must also be considered that unless the phenomenon is seriously contrasted,
the possibility of building up a structure with a e.g. by an effective supporting. Some efforts to
hard spheres model is a first approximation get to the root of the problem have been made,
approach. Indeed ionic radii of the elements are by avoiding the necessity of introducing a re-
not absolute values, but may vary according to duction step to obtain the dispersed metal. Small
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305 301

amounts of solvated metal atoms, which may be primarily determines the catalytic properties of
used in organic synthesis can be prepared by an alloy. The surface atoms do not lose their
metal evaporation and low temperature trap- individuality and the reactivity may be under-
ping. When these weakly ligand stabilized metal stood in terms of groups of surface atoms,
atoms are gently warmed in presence of a cata- although some long range effect may also be
lyst support, an exceptional dispersion is ob- present. For example in some reactions per-
tained with unusual reactivity. These dispersed formed on a Ni-Cu catalyst Cu may act as a
heterogeneous catalysts are termed solvated diluent, since it may be considered rather inac-
metal atom dispersed or SMAD [44]. Unfortu- tive when compared to nickel. Ensemble effects
nately this technique has not been developed to may be observed, which will depend on the
such a stage to obtain large amounts of catalysts surface concentration and arrangement of Ni
to be used for high tonnage applications. and Cu. Fig. 22 shows the activity of Ni-Cu
Alloys are solid solutions of different metals. alloys for the hydrogenolysis of ethane to
Their association may offer a different reactivity methane and the dehydrogenation of cyclohex-
in respect to the pure metals: nickel-copper, ane to benzene. The activities refer to reaction
palladium-silver, palladium-gold are examples rates at 3 16C. Ethane hydrogenolysis activities
of alloy systems. A distinct difference between were obtained at cyclohexane and hydrogen
bulk and surface composition, which may also pressures of 0.030 and 0.20 atm, respectively.
be a function of the particle size, is typical of Cyclohexane dehydrogenation activities were
alloys. The nature of the surface composition obtained at cyclohexane and hydrogen pressures
of 0.17 and 0.83 respectively.
The different trend of the two reactions may
be explained by supposing that the carbon-
carbon bond rupture involved in hydrogenolysis
is sensitive to electronic and geometric surface
factors, while cyclohexane dehydrogenation is
Dehydrogenation of cyclohexane comparatively insensitive to such factors [45].
- - r.- - 7 Bimetallic catalysts are an aggregation of two
different metals which may also be immiscible
at the bulk scale. Pt-Re catalysts which were
successfully introduced in reforming catalysts in
the seventies are an example.
Platinum and rhenium have different crystal
structures (fee vs. hcp) and do not exhibit com-
plete miscibility in the bulk [46]. However,
these factors may have limited significance for
Hydrogenolyeis of ethane highly dispersed metals. Moreover, during the
reforming reaction the actual form may change,
\ because Re may be present at the surface not in
a zerovalent state, but in a sulfided state. The
surface structure may be written ReS.,, which
0 20 40 60 80 looJ
acts to divide platinum surface into very many
Copper content, atom %) small clusters of the size of 1 to 3 platinum
atoms [47]. The platinum is partly in zerovalent
Fig. 22. Activities of Ni-Cu catalysts for the hydrogenolysis of
ethane to methane and the dehydrogenation of cyclohexane to
form and partly as PtS, and is adjacent to
benzene [45]. rhenium.
302 C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305

5.5. Preparation of supported catalysts slows down the process of crystal growth (not
the transformation into the final active species).
As already pointed out in Section 3 a way of The final dispersion depends on many parame-
improving the dispersion of the active species is ters, such as support texture, precursor solubility
to spread them on a support. The preferred and drying velocity and on the nature of the
preparation procedure starts from a preformed starting salts.
support because in this case it will impart its The interaction of the support with the active
porous textures and mechanical toughness, and species is not only physical in nature, but there
no further forming operation will be required. is always a more or less pronounced influence
The active species are introduced into a porous of its chemical nature. For example alumina,
support not in their final form but by impregna- one of the most used supports, may often influ-
tion with a solution containing a precursor, the ence the chemical evolution of the supported
choice of which is crucial for the final disper- active species or may even give rise to some
sion. sort of aluminates.
The impregnation will be called with no in- The impregnation with interaction tries to
teraction when no specific interaction between take advantage of a chemical interaction of the
the impregnating solution and the support is support with the impregnating solution so as to
foreseen or no particular attention is given to obtain a better dispersion of the active species:
following this aspect. In this case the greater dispersion reaching almost the value of 1 (atomic
dispersion of the active species observed for a dispersion) may be reached during this stage.
supported catalyst must be ascribed to differ- The problem is to keep high values also in the
ences in the precipitation of the precursor occur- following operations of drying, calcination, or
ring during drying. In fact, although the forma- reduction (in the case of metal supported cata-
tion of the precipitate particles is ruled by the lyst). Often the particle size of a metal sug-
same laws for supported and unsupported cata- ported by this procedure is of the order of 10 A,
lysts, the heterogeneous nucleation is enor- while by impregnation with no, interaction it is
mously enhanced inside the pores by the high rare to reach values below 50 A [31].
surface area available of the support in contact In order to perform an impregnation with an
with the solution. In the thermal treatments effective interaction it is necessary to consider
which follows the support acts as a spacer, i.e. that true ion exchange reactions between ions of
keeps separated the small crystals formed and the precursor in solution and the surface of the

zero point of charge


acid pH or basic pH
isoelectric point
Fig. 23. Schematic representation of a surface polarization of an oxide particle as a function of the solution pH [48].
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305 303

support occur during impregnation. These reac- Oxide I.E.P.S.

tions are characterized by a kinetics and by S%O, co.4


wo, Hydrous so.5 CATIONS
equilibrium constants. The kinetics of exchange SiO, ~ydm~s 1.0-2.0
will in general be very fast for reactions highly
favored from the thermodynamic point of view, -4.0
3.94.5
and will lead to non-uniform distribution of the -5.5 CATIONS
-6.0
precursor inside the particle, because diffusion or
5.7-6.7
of the precursor inside the pores during impreg- 6.5-6.9 ANIONS
nation will be a slow process compared to the -6.7
-6.75
ion exchange with the surface. In order to re- 6.6-7.5
7.0-9.0
duce the exchange rate and extension of ex-
change other ions may be introduced which may Y,O, Hydrour -8.9
a Fe,O, 8.4-9.0
compete for the same site: e.g. Cl- may be used ZnO 6.7-9.7 ANIONS
La,O, HUMUS -10.4
as a competitor with PtCli- in the exchange WO 12.1-12.7
process.
Fig. 24. Isoelectric points of various oxides [48].
Furthermore it must be considered that the
surface of the support changes its polarization of some oxides which may be used as supports
according to the value of the pH of the solution are reported. Much of the irreproducibility which
and to the isoelectric point of the solid [48]. is frequently reported in the literature for sup-
Schematically the equation involved in the sur- ported catalysts must also be ascribed to the fact
face polarization may be written, in acidic that these simple principles are not taken into
medium (pH below the isoelectric point) consideration.
S-OH + H+A-@ S-OH;A- A uniform distribution of small particles over
a support may be obtained also with the deposi-
while in a basic medium (pH above the isoelec- tion-precipitation proposed by Geus [49,50]. In
tric point) the equilibrium involved is this method a metal solution containing urea is
S-OH + B+OH-ti S-O-B++ H,O well mixed with the support powder at room
temperature. Then the temperature is raised to
The situation is depicted in Fig. 23 at pH 70-90C, where the hydrolyses reaction takes
below the isoelectric point the surface will be place:
positively charged and will be surrounded by
CO(NH,), + 3H,O P 2NH,+ + CO, + 20H-
anions for simple electrostatic reasons and
therefore the surface will attract and absorb The hydroxyls are produced homogeneously
anions, while at pH above the isoelectric point throughout the solution, preventing the forma-
the surface will be negatively charged, will be tion of regions of high local pH. Since in the
surrounded by cations which, therefore, will be presence of an active precursor-support interac-
absorbed from the solution. To get information tion, nucleation of the catalyst precursor at the
on the capacity of ion absorption, additional surface of the support proceeds at lower concen-
information on the evolution of the polarization tration than those needed for precipitation in the
as a function of pH is necessary. This can be bulk of the solution, precipitation exclusively on
done, for example, either by measuring elec- the support surface may be achieved.
trophoretic velocity, or by neutralization experi-
5.6. Other methods for dispersing metals
ments at constant pH. Since the isoelectric point
of the support plays an important role together Dispersed metals may be obtained by numer-
with the pH of the solution and the ionic species ous other techniques of which we shall give
of the precursor, in Fig. 24 the isoelectric point only a few examples in this brief introduction.
C. Perego, P. Villa/Catalysis Today 34 (1997) 281-305

PtO, is slightly volatile and moves downstream


where it may eventually be recovered in part.
Using a Pt/Rh alloy instead of pure Pt has as
a consequence a surface enrichment of Rh [51].
Rhodium itself is slightly less active than Pt but
much less volatile. Alloying Pt with 5-10% Rh
therefore significantly reduces metal losses and
increases the gauze life.
Finally we shall give two examples in which
the catalyst particle becomes porous by the
selective removal of some component.
The preparation of the ammonia synthesis
catalyst starts from a melt obtained at about
1500C and in an inert atmosphere of Fe,O,
Al,O, and K,O (2-5% each) plus small quanti-
ties of other promoters, which however are not
Fig. 25. Scanning electron micrographs of 10% Rh-90% Pt wire.
(a) Original gauze as drawn, showing uniform grain structure and essential. The melt is cast, allowed to cool and
absence of nodules on the wires. (b) The gauze in part (a) after ground. At this stage Fe and Al are well inter-
one-half the normal gauze life installed in a nitric acid plant, spersed in an oxide matrix, because they form a
showing the nodular pattern typical of an active gauze. (c) An
enlarged view of the crossover point of the two gauze wires in
solid solution with spine1 structure. The catalyst
part (b) showing the characteristic octagonal crystal structure and precursor is then slowly reduced, most fre-
nodules, which are concentrates on the wire surface between quently inside the reactor, in a gas circulating at
crossover points [Platinum Met. Rev., 15 (1971) 521.
the maximum possible rate, the temperature in-
crease is controlled so that the water vapor
concentration never exceeds 3000 ppm [52].
As already mentioned the oxidation of NH, Although a substantial amount of oxygen is lost
to NO is performed on Pt/Rh gauzes, i.e. on a during this reduction process, the catalyst main-
catalyst which has no porosity to avoid internal tains its external geometrical dimensions, the
diffusion limitations. The gauzes are laid one on oxygen loss generates a high surface area with
the top of the other to form a pad about 5 mm small pores [53]. Collapse of the structure dur-
thick containing as many as 40 gauzes. The ing reduction and reaction temperatures is pre-
standard is 80 mesh (31.5 wires per cm) woven vented by alumina acting as a spacer.
from wire 0.003 in (0.075 mm) in diameter. The K,O mainly acts as an electronic pro-
This represents a reasonable optimum between moter, facilitating the dissociative chemisorp-
the desire for fine wire and high area on the one tion of N,.
hand and mechanical requirements on the other. Nickel, copper and cobalt can be prepared in
The substantial increase in activity which is a form of pyrophoric highly reactive powders
initially observed is due to the increase of which can be used as catalysts in hydrogenation
roughness of the woven wire which signifi- reactions to be carried out in slurry reactors,
cantly increases the external surface, as shown using the preparation proposed and patented by
in Fig. 25. Raney in 1925.
This increase of roughness of the wires, when This technique starts from an alloy - in the
powders are carefully eliminated from the gas case of Raney nickel typically a 1: 1 nickel
flow, are ascribed to the reaction [51]: aluminum alloy which is reacted with a 20%
solution of sodium hydroxide, which leaches
Pt,,, + 0, + PQ,,, out much of the aluminum leaving Ni un-
C. Perego, P. Villa / Catalysis Today 34 (1997) 281-305 305

[26] M. Komiyama, Catal. Rev., 27 (1985) 341.


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