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Chapter 3
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].
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
Toward flocculate
Invisible micelles
Clear solution
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
Xerogel
.I
25 50 75 100
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
2.6. Calcination
1-
I
Al,%
300 C to
n=l.8 gelatinous or
pseudo
PROCESS-AIR ,FEED
T
CYCLONE
ALUMINA
SLURRY
PERFORATED
PLATE
OIL
HARDENING
Pore radius r (A)
SPHERES
AMMONIA -
SMALL ALUMINA
MOISTENED
ALUMINA Io/6YDPF%:E,,,SP,ETS
POWDER
0
ROTATING
PRODUCTSPHERES
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
TYPE
1 II III IV
(uniform) (pelliculot) (egg yolk) (egg while)
~subsutlace~
Table 5
Most common used source of cations, aluminum on silicon in zeolite synthesis [ 141
Charge compensating cations Aluminum Silicon
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).
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