Chrmicsl E#tgi#vring Sckncr Vol. 36. No. 9. pp. 1431-1445.
1981
Printed in Great Britain.
REVIEW
THEORY AND PRACTICE OF THE FORMULATION
OF HETEROGENEOUS CATALYSTS
Imperial Chemical Industries Limited, Agricultural Division, Billingham, Cleveland, England
Abstract-This review has been written from the viewpoint of the formulator of industrial catalysts with the
objective of explaining the practice but giving only such general theories and speculations as the author has found
to be of real utility. All the important industrial aspects of formulation are covered from the initial choice of
catalytic species, through the processes of fabrication of the catalyst to its final reductioo in the reactor.
INTRODUCTION
Outside of the vast and confusing patent literature there
is little publicly available information on the formulation
of industrial heterogeneous catalysts. The only text book
that the writer has come across being Catalyst Tech-
no&y, editor I. P. Mukhlyonov, Mir, Moscow 1976. The
very considerable scientific literature on catalysts is for
the most part concerned with investigations into and
speculations on the theory of catalysis, when written by
chemists, and algebraic and computational exercises on
diffusional and beat flow effects in catalyst parti-
cles and reactor optimisation, when written by chemical
engineers. This review does not touch on either of these
areas in any depth as an attempt is made to present a
balanced picture of catalyst formulation.
CHOOSING THE ACTIVE SPECIES
The first stage in catalyst formulation is the choice
of the active catalytic species. This choice is
invariably made by experiment guided by knowledge of
the catalytic properties of substances. Experiment is
necessary as the general catalytic properties of metals,
metal oxides etc. are not so well defined that the precise
active species can be selected from the literature alone.
Past knowledge is a guide to the most fruitful areas for
experimental investigations. In order to use this know-
ledge it is necessary to consider the reaction which it is
desired to catalyse in some detail and to decide which of
the bonds in the reagent molecules it is hoped will be
ruptured so as to bring about the reaction. First,
however, it is as well to check that the thermodynamic
maximum possible yield of the reaction is adequate, and
whilst doing this to check what yields of undesired
products would be possible if the catalyst was somewhat
unselective.
With very many reactions it is evident that there are an
embarrassingly great number of thermodynamically
possible products formed either from the reagents taken
singly, or from the reagents together, or from a reagent
and a product or by reaction together of products. In
organic systems, carbon is usually one of these undesired
possible products. It is therefore necessary to list also
ARTICLE NUMBER 2
S. P. S. ANDREW
those bonds which it is not desirable to acitvate. The
choice of active species is then made bearing the nega-
tive criterion as wetl as the positive criterion in mind,
Table 1 shows a typical list of the types of bond activa-
tion usually associated with different species. Depending
on the species and on the composition of the reagents
and their partial pressures and temperatures, the cataly-
tic species can either, in use, be in the elemental (usually
metallic) form, or with more oxidising conditions it could
exist as an oxide or a sulphide or halide etc. The process
of bond activation required in catalysis requires a rever-
sible chemical reaction to take place between the reagent
species and the solid catalytic surface. This is ter-
med”chemisorption”. For this to take place the catalytic
species must be, thermodynamically, operating close to a
readily reversible change between the reacted and un-
reacted state. Thus metallic iron is a good catalytic
species for synthesising NH3 from N2 and Hz because,
under synthesis conditions, it operates close (but not too
close) to the formation of solid iron nitride, thereby
rupturing the N-N bond, and also the formation of iron
hydride, thereby rupturing the H-H bond. Ruthenium,
osmium and molybdenum are also good catalysts. Pal-
ladium, platinum, rhodium and iridium, though also
excellent catalysts for the activation of the H-H bond are
no good for rupturing the N-N bond (see Table I).
Ammonia synthesis catalyst must therefore be chosen
from species that are present in both the first and fourth
lines in Table 1.
With ammonia synthesis, at the temperature at which
these catalysts are reasonably active ( > 350°C). ammonia
is thermodynamically the only likely product. The situa-
tion with methanol synthesis from CO and H2 is more
complex. Not only is C a possible product, but also CH4,
higher alcohols, and higher paraffins. It is therefore
necessary to seek selectivity by first ensuring that CO
and H-H are activated but the bond between C and 0 is
not activated otherwise CH, and paraffins, waxes and
even C could be formed. The choice is therefore between
those species falling in line 1 of Table 1, H-activation,
provided they also fall in the line for CO activation and
do not fall in the line for CEactivation.
1431
1432 S. P. S. ANDREW

Table 1 Selection of catalytic species

TiVATlON
QUIRED STATE OF CATALYST HIGH ACTIVITY MEDlUM ACTtVlTY

H- METAL, CXIDE,SULPHIDE Pd. Pi.Rh,Ru, ,r Mn,Fe,Ni,Cu,W,Ag,Cr, Co,zn,V,Mo

3= METAL OR OXIDE PI, Pd, Mn,Co. C” Ag,NI,Fe,V, MO,Sb,Cr, TI

ce METAL Fe,Ru,Os, Rh Ni,Co

NE METAL Fe,Ru,Os,Mo w, t-m,U

51 SULPHIOE Mo,W Cc,Ni,Cu,Fe,Sn,Zn,V

C CARBONATE K, Na CQ

ct - CHLORIDE Cu.Zn, Hg,Ag

2O,OH_ OXIDE OR HYDROXIDE W,q V,Ca,Th,Mg B,AI,Tl,Hg,Zn, SlAC

n+ OXIDE OR IiALlOE (Si AtaP, Cr,W) OXIDES (~t,Sn,~n,zr,B) HALIDES

HC.! OXIDE OR CHLORIDE SIAP,AI

ZCZC’
METAL OR OXIDE Pd,Pl, Rh,Ru Co,Ni,Fe,Ir,W,Mo,Cr,Cu
-c:c-
>
-CEC- SALT5 H%CU,A9 Ztl

co METAL OR OXIDE Pt ,Cu,Pd, lr Zn,Co,Fe,Mn.Ag

METAL OR OXIDE PI ,v Fe,AC

502

UGNE OXIDE I AP, Mg, MgAI,Mg Si, Co At2

So far it has been assumed that a single species must
be used for carrying out the reaction. This is, indeed,
desirable but not always essential, as certain reaction
intermediates can, after activation on one species, spill
over onto another cataIytic species. The hydrogen atom
H is well known for this ability. In general, however,
larger surface (chemisorbed) species are inadequately
mobile. Two or even more catalytic reactions may be
carried out in a single reactor and indeed in a single
catalyst particle by incorporating more than one catalytic
satisfactory. Even when the two catalytic components
are in no way miscible or apparently capable of mutual
reaction on the bulk scale, as with platinum metal crys-
tals on a ceramic oxide component, it is quite possible
that some interaction occurs which alters the catalytic
properties of the very small platinum crystals (5%1dia.)
due to electron transfer between the metal and the
underlying oxide.
DEVICES TO ENHANCE CATALYTIC SEL.ECTIVlTY

species. In these cases, however, molecules pass from If adequate selectivity for the desired reaction has not
one catalytic surface to the other through the pores and been attained by adjustment of solid catalytic species
not as chemisorbed species on the surface. The com- there are a number of chemical devices that on some
bination of a hydrogenation activity (line I of Table 1) occasions prove beneficial. These are shown, together
with a hydrocarbon cracking activity (activation of H’) with commercial examples of their use, in Fig. 1. Three
is found in hydrocracking catalysts where naphthenes
are hydrogenated, using a precious metal such as pta-
tinum which is dispersed as small crystals over a crack-
ing catalyst such as a silicalumina compound.
When employing more than one active species in a
formulation the overall result however becomes a little
more unpredictable as even the structure of the catalytic
species itself is open to great uncertainty. If two metals
are employed which are mutually soluble then the for-
mulator is uncertain to what extent he has the two
present unmixed or mixed. Furthermore, when mixed, he
is often uncertain which metal atoms are concentrated on
the surface under reaction conditions and if so to what
extent and where and what effect does this have on
activity and selectivity? Fortunately for industry a
process of trial and error in formulation can arrive at a
satisfactory catalyst even though a further 50 years’
experiments might be required to find out why it is Fig. 1. Typical devices to enhance catalytic selectivity.
 Theory and practice of the formulation of heterogeneous catalysts
of these devices use the addition of a species which is
chemisorbed on the catalytic species, but does not react
with the reagents or products, to modify the catalyst
surface. Volatile species such as HCl or HzS may be
used in very low concentrations so as to chemisorb
preferentially on certain parts of the catalyst surface,
and thereby possibly enhancing selectivity without
excessive loss in activity. Or, like CO, which is employed
during the selective hydrogenation of CH=CH in
CH2=CHz over a palladium catalyst, such species may,
by chemisorption, displace from the catalyst surface a
species which otherwise would have chemisorbed and
then have reacted (ethylene). Inert optically active
molecules may be chemisorbed on a catalytic surface
with the objective of leaving “optically active” (i.e.
handed) holes into which non optically active reagents
could slot, combining on the catalyst to give an optically
active product. More crudely, the catalytic species can
be set in a molecular sized box, such as the cage of a
zeolite, which limits the access to it of molecules and
limits its ability to form large molecules. Zeolitic cages
are used for these purposes in petroleum reforming and
in the synthesis of hydrocarbons from CO and Hz_ Sim-
ple considerations such as the above in a given instance
may lead, when formulating a new catalytic system, to
experiment to show whether a superficially plausible
device may be of benefit.
POISONS
Of the devices listed above several fall into the class
of catalyst poisons used in judicious small amounts.
There is a general rule in heterogeneous catalysis (i.e. a
rule which is usually correct!) that the more active the
catalyst, the less selective, hence the use of small
amounts of poisons. Or some occasions even great
amounts of poisons may be present in the gas stream,
they may even be products of the reaction such as HIS
when hydrodesulphurising oil. In this case a poisoned
catalyst is the active species and the most active
poisoned species must be chosen. Less obvious exam-
ples of poisons are listed in Fig. 2. The surface active,
but non-catalytic, metal or ion is one variety. Thus when
formulating a catalyst for steam reforming methane,
where it is derived to activate Cwso as to form CO from
CH, by reaction with steam, a nickel catalyst is very
effective. Quite low concentrations of copper in the
nickel will, however deactivate it, as copper is surface
active relative to nickel (lower melting point and there-
Fig. 2. Different types of catalyst poisons.
1433
fore lower surface tension) and furthermore copper does
not activate Cm. Similarly low amounts of Ca in Co304
catalyst for ammonia oxidation (which operates at SOOOC)
diffuses to the surface and deactivates the catalyst. Pb in
Fea04 catalyst for the reaction CO + HzO+ COz + H2 is a
similar poison.
Another form of “poison” is a species which ac-
celerates the formation of high molecular weight
“polymer” or “coke” to such an extent that the catalyst
is rapidly deactivated by the formation of a covering of
this by-product. Fe in Cu methanol synthesis catalyst or
Fe in %-AI cracking catalyst are examples.
HCl and l-J20 have a more pernicious effect than
merely acting as temporary poisons, in as much as the
chemisorbed species that they form are mobile and by
diffusing across the surfaces or through the gas phase
from small crystals to large crystals result in a rapid
growth in the average crystal size and hence a loss in
total surface area and in catalytic activity per gram of
catalytic species. This loss is, of course, irreversible even
when the poison has been removed.
ACTIVE SITES
It has often been estimated that only a small fraction
of the surface of catalytic species is active and hence has
arisen the concept of “active sites”. These have been
hypothesised to be caused by dislocations, crystal steps,
corners etc. in metals as well as by impurity atoms in
metals and oxides. With metal catalysts the formulator
normally ignores this aspect as there is no practical way
in which he can affect these sites other than through the
bulk composition of the metal crystal&es, the support on
which these crystallites are dispersed, and the tem-
perature, reagent composition and pressure. Industrial
metal catalysts and some oxide catalysts almost invari-
ably operate at a temperature at which surface restruc-
turing of the metal crystals fairly rapidly takes place,
such that the surface defects and active sites are main-
tained in a dynamic steady state appropriate to their
environment. For this reason the creation of extra
defects in the metal crystals of a catalyst by, for in-
stance, subjecting it to nuclear radiation prior to
employing the catalyst have only a temporary effect.
There is one class of catalysts where the above does
not apply, ceramic acid catalysts such as silica-alumina
gel and its crystalline zeolitic form. Because these cata-
lysts are employed for their H’ exchange ability at a
temperature which is relatively low compared with their
melting points, defects, in the form of Al” ions in place
of Si4’ ions, which are created during the preparation of
the catalyst can last throughout its life and continue to
act as sites of catalytic activity. The activity of the
catalysts can thus be correlated with the density of sites
measured prior to their use by titration methods.
PORES
In order to secure a high activity per unit volume of
solid catalyst it is necessary to produce this catalyst in a
very fine state of subdivision, crystals from 5 to 5008,
diameter are common in industrial catalysts. As these
crystals must be contacted with the the reagent gas or
1434
liquid and then separated from the product, they must be
aggregated into particles of from 50 p to 10 mm in size
and these particles must be porous to allow diffusional
ingress of the reagents and egress of the products. The
size distribution of the voids or pores in a catalyst
particle is dependent on the processes of preparation of
the catalyst. Roughly three sorts of pore may exist-see
Fig. 3. Smallest-falling in the range 2-g A, are pores that
are formed in a crystal lattice by some type of phase
change involving a loss in volume. The dehydration of
chromium hydroxide, for example, produces such
shrinkage holes but these are too small to be of use in
catalysis. The regular passages and cages in zeolites are
sufficiently large to admit usefully sized reagent mole-
cules and to allow the egress of useful product mole-
cules. The next larger range of pores falls between
30 and 200 A and is formed by the spaces between particles
of a very fine precipitate of catalytic species and support
which usually range in the 20-500~ crystal diameters.
The final stage of catalyst forming may involve compaction
of a powder made from aggregates of these precipitates in,
for instance, a tabletting machine. The spaces left between
the crushed together aggregates usually falls in the range
500-2oooA.
These size ranges are compared with the boundary
between bulk gaseous diffusion and Knudsen diffusion in
the pores in Fig. 3. Catalysts operating in gases at
pressures below 5 bar and containing internal porosity
made by precipitation almost invariably fall in the
Knudsen regime in which the gaseous diffusion mean
free paths are restricted by the closeness of the catalyst
particles. When operating above 50 bar, little restriction
of the mean free path occurs.
The extent to which diffusion restricts egress of the
reaction product is particularly important if good selec-
tivity is required of an intermediate product in a series of
consecutive reactions. The gas phase oxidation of an
organic compound is a typical example where over oxi-
dation leads to carbon monoxide. Under these circum-
stances catalysts having little or even no internal
porosity are used. For example-silver needles for the
I I I I
0. I I IO 100 I.000
Pressure, bar
Fig. 3. Mean free paths and pore dimensions in typical hetero-
geneous catalysts.
S. P. S. ANDREW
oxidation of methanol to formaldehyde or platinum wire
for the oxidation of ammonia to NO.
CBOOSINGTHE SUFTORT
The continuous formation and decomposition of sur-
face compounds formed between metal atoms and the
reagents during catalysis on metals results in an effective
mobility of the metal which rapidly results in very small
crystals fusing together with a consequent loss of surface
area and activity per gram. Provided the crystals are in
contact, this sintering process proceeds at a rate which is
determined by the crystal size and the closeness of the
temperature to the melting point, or the decomposition
temperature of the solid if that is lower. Figure 4 gives a
rough indication of the effect and is based on data for
sintering such materials as copper, alumina and carbon.
Thus a compact of copper crystals having a melting point
at lOg2”C, if held at 250°C for 6 months, however small
they were initially, will be at least 1 p in size at the end
of the period. However alumina, melting point 203O’C,
might still be in crystals no bigger than 20 A. If the
substance suffers a decomposition, for instance
2C030d+ 6CoO + 02, then the temperature which should
be taken is the decomposition temperature in using Fig.
4.
The function of a support is, quite simply, to enable a
large particle or tablet of catalyst to be made composed
of very small readily sinterable crystals of catalyst which
are stopped from coalescing by being separated from
each other by the support component. The support
component clearly has to be much more resistant to
sintering than the catalytic species and neither react with
nor be wetted by the catalytic species. Typically refrac-
tory oxides such as alumina, silica and magnesia are used
as supports. Two methods of utilising a support are
common. Firstly, a support may be used as a form of
refractory surface on which the catalyst crystals are
dispersed: rather like putting small drops of mercury on
a table top. Secondly, the support may be used in the
form of a more finely divided refractory crystal than the
catalytic species positioned between particles of this
I
Fig. 4. Minimum crystal sizes for sintered compacts.
 Theory and practice of the formulation of heterogeneous catalysts

species so that they are kept out of contact-rather like

dust which can be used to stop a heap of mercury drops
form coalescing. With the first method, the volume of
support is always considerably greater than the volume
of catalytic species, consequently this method is nor-
mally employed with precious metal catalysts. The
second method, where the volume of catalyst normally
exceeds that of the support, is employed usually with
non-precious metal catalysts. Combinations of the two
methods are also employed, as the use of the first
method has the additional advantage that the catalyst
particle has a continuous support structure which can be
made mechanically very stmng and being made of inert
species remains so during changing chemical conditions
in the reactor (eg changes from oxidising to reducing). A
very large pore continuous support can therefore give
strength to the particle whilst small metal crystals at
Fig. 5. Bad effects of support components in low temperature
relatively high volumetric concentration are stabilised methanol synthesis catalysts.
against sintering by packing them together with a very
fine refractory support component, into the large pore
structure. A typical catalyst using this technique is nickel silica and alumina-for instance a solution of sodium
hydrogenation catalyst powder where the coarse pore silicate mixed with a solution of aluminium sulphate
structure is made from diatomaceous earth and the fine plus sulphuric acid. If a crystalline zeolite is
support is silica gel. required then a additional component, normally an
Before leaving the subject of the support, it must be organic compound which is soluble in water is often also
emphasised that no support material is completely inert added. This compound affects the type of crystal which
and the effect of the support on the course of the subsequently appears if the amorphous precipitate is
reaction chemistry must be considered. It must further allowed to ripen by holding it a temperature (usually near
be remembered that the use of a support may well 100°C or above) for many hours. This additional com-
introduce into the catalytic system more chemical com- pound sometimes has so large a molecule, for example
ponents than at first expected. Thus alumina frequently the tetrapropyl ammonium cation, that it is trapped in the
contains sodium oxide which may be catalytically active. cages of the forming zeolite crystal and in these circum-
An example of the undesirable effects of components stances is supposed to fulfil the role of a template around
that may be present in a support on the course of which the crystal forms, thereby determining which of
methanol synthesis from CO + CO2 + HP over a copper many possible zeolites having the same chemical com-
catalyst is shown in Fig. 5. Quite small amounts of some position crystallises. The choice of this “template”
of these components have suprisingly large effects on compound is entirely empirical and no very obvious
selectivity and life. relation exists between its molecular form and that of the
zeolite cage it promotes.
STAGES IN PREPARATION OF SILICA-ALUMINA CATALYSB
Having above discussed briefly the fundamentals of
choice of the catalytic species and of the support the
remainder of this review will be concerned with the
practice of industrial catalyst preparation. The silica-
alumina catalysts are an unusual class in as much as was
indicated above, no support is needed and active sites
are built into the catalyst during preparation and remain
structurally present (even though deactivated possibly by
coke coverage) for relatively long periods of catalyst use.
Even here, however, restructuring of the catalyst lattice
occurs in time, particularly if accelerated by the com-
bined effects of high temperature and high steam partial
pressure.
The general technique for preparing silica alumina
catalysts is shown in Fig. 6. If an amorphous lattice is
required then the steps enclosed in double lines are
ommitted. If a crystalline product is required (a zeolite)
then they are included.
The first stage of the preparation involves the rapid
H zeolite
precipitation of an amorphous hydrated silica alumina gel
by mixing aqueous alkaline and acid solutions containing Fig. 6. Typical preparationof SiAl catalyst or of zeolite
1436 S. P. S.
After precipitation, if an amorphous product is
required, or precipitation and ageing if a zeolite is
required, the solid is filtered off, dried and, if containing
trapped “template” molecules, is then subjected to gentle
oxidising conditions which burn away the template
molecules. Subsequently a thorough wash, including an
acid wash, removes the bound sodium ions. The product,
when finally dried, is the active catalytic H’ exchanging
amorphous silica-alumina or crystalline zeolitic catalyst
much used in petroleum refining for cracking and also for
isomerisation duties. The presence of aluminium ions
replacing silicon ions in the structure is an essential
feature of the generation of the H’ activity. The ratio of
Al/Si in the catalyst can be varied very greatly-ertain
zeolites can even be made with no aluminium. Experi-
ment determines which is the best ratio for any particular
duty. Other cations, for example Fe+ and etc, can be
incorporated into the lattice.
THEPREPARATION OF PREFORMED SUPPORT
When the catalytic species is dispersed on the surface
of a support (the first method of using a support des-
cribed above), it is usual to prepare the support
separately as a preformed particle or tablet before in-
serting the catalytic species. In industrial practice this
support is normally made from refractory oxides though
occasionally active carbon is used. The preparative
technique for the refractory oxide supports is that of
making a fired ceramic except that an initial stage of
making the “clay” is often required; particularly if a very
high area but low porosity support is required. This first
stage is essentially a precipitation of the hydroxides of
the support material-for example aluminium hydroxide
gel or magnesium hydroxide. This precipitation is
brought about often by mixing an aqueous solution of the
nitrate with sodium carbonate or of the sulphate with
ammonium carbonate. Thorough washing is usually
required to remove residual sodium in the first case or
sulpbate in the second. Precipitation using a mixture of
the nitrate and ammonium carbonate would eliminate
such washing problems but would introduce a different
hazard! The formation of ultra fine precipitates is an
ill-understood phenomenon. Generally however, it ap-
pears that the lower the solubility of the precipitated
material-the finer the precipitate, and the more complex
the mixture being simultaneously precipitated--the finer
the precipitate. Long ageing is, of course, undersirable
when producing very fine precipitates but flocculation is
essential otherwise filtration and washing is virtually
impossible. Experimental investigation of the effects of
pH, temperature, ageing time and precipitation solution
strengths and compositions is always required in order to
optimise the filtration and washing operations.
The wet paste from the filters is dried and, where
necessary, formed into desired shapes by extrusion or
tabletting (see later in this review) and then given
strength by firing. The fusing operation may roughly be
pictured for a single component such as MgO or Al203
by reference to Fig. 4. High area alumina supports
receive only a relatively low temperature firing, 600-
700“C, whereas low area supports are fired at tem-
ANDREW
peratures of up to 1200°C. The latter are no problem as
the product is very strong. The production of high.area
single component supports with reasonable strength is
much more difficult and various devices, such as im-
pregnating a weak support with nitric acid or with nitrate
and subsequent light firing to “glue” together the struc-
ture may be employed. The addition of small amounts of
other oxides which act as a sinter aid increases strength
but at the possible disadvantage of complicating the
catalytic properties of the support adversely. A typical
additive is a small amount of Ti02 in A1203.
THE PREPARATION OF IMF’REGNATFQ CATALYSTS
Performed supports are normally made into industrial
catalysts by impregnating them with a solution of the
catalytic species. A number of, types of such catalysts
may be distinguished-see Fig. 7. Precious metal cata-
lysts, for reasons of cost, always have a low metal
content. This metal is dispersed in very fine crystals
(5-15 A) either uniformly .on the surface of the support
throughout its volume, or it is distributed only over a
small depth into the particle, thereby forming an outer
shell of catalyst. The choice of which type is employed
depends on the nature of the desired and undesired
catalytic reactions. If the desired product can suffer
further degrading reactions over the catalytic species
then it is usual to employ impregnation in the outer shell
only, in order to eliminate the high build up of product
concentration which could occur particularly with fast
reactions as a result of a diffusive resistance inside a
large particle of a catalyst which was active throughout
its volume. A typical shell type catalyst is that used for
the selective hydrogenation of acetylene in an ethylene
stream. Here the catalytic species is metallic palladium
dispersed in a very thin zone close to the outer surface
of an alumina tablet. A typical example of a catalyst
where the precious metal, for instance platinum, is dis-
persed throughout the volume is petroleum hydrocrack-
ing catalyst where the support also has isomerisation or
cracking activity.
Non precious metal catalysts with a high content of
catalytic species on the support are invariably prepared
by impregnation. Typical examples are nickel methane
steam reforming catalysts which contain Z&30% nickel
Fig. 7.Differing types of impregnated catalysts.
 Theory and practice
supported on preformed ceramic rings. A significantly
different type of catalyst which can be prepared by
impregnation is the cobalt molybdenum sulphide catalyst
for hydrodesulphurisation of hydrocarbons. In this type,
the active species, molybdenum sulphide, exists as a coat-
ing on top of the cobalt sulphide, which modifies its
properties, and the cobalt sulphide itself coats the high
area alumina support. The much higher degree of chem-
ical interaction between the catalytic species and the
support compared with the interaction between a the support is determined by the voidage of the support
reduced metal and a ceramic support such as alumina
results in this coating phenomenon. Reduced metal, hav-
ing little interaction with the support, does not “wet” it
and therefore exists in discrete crystals, which, when
small and in appropriate gas compositions and tem-
peratures, hop around on the surface of the support
being so poorly anchored.
Another type of catalyst which can be formed by
impregnation is that where the catalytic species is a
liquid at operating temperature and the support merely
acts like a sponge. Molten salt catalysts, such as Vz05-
of the formulation of heterogeneous catalysts 1437
support also has a marked effect in reducing the
penetration of metal salts so that pre-impregnation of the
support with alkali followed by drying and then impreg-
nation with a metal salt is a method for producing very
shallow depths of penetration. Limited impregnation is
usually effected either by dipping the dry support into a
bath of solution or by spraying solution onto the dry
support whilst it is being tumbled so as to expose its
surface. In the former case the amount of metal left on
multiplied by the strength of the solution and in the latter
by the quantity of liquid sprayed multiplied by the
strength of the solution. When complete penetration is
required, dipping is normally used.
Usually the support is preformed to its final particle
shape before impregnation, however with some for-
mulations the support is impregnated whilst in a fine
powder state and then the catalyst is formed sub-
sequently.
THE PREPARATION OF CO-PRECIPITATED CATALYSTS

K$O, salt mix supported on a silica support for SO2 A particularly effective method of securing intimate
oxidation or CuCll supported on alumina for oxych- mixture of support and catalytic species and one which
lorination of ethylene are examples. is often used with high content non precious metal
Control of the depth of impregnation is primarily by catalyst is co-precipitation of both support pre-
chemical means-see Fig. 8. The objective is to control cursor and catalytic species precursor; for instance, the
the intensity of chemisorption of soluble salts of the co-precipitation of nickel carbonate and aluminium
impregnating solution on the support. With a weak SOIU- hydroxide from aqueous mixed nitrates by a solution of
tion of, for instance, a metal chloride, chemisorption of sodium carbonate. It is important during this operation
the metal ions on the ceramic surface is by exchange: that the intimate mixing of the nickel and aluminium
components when in solution is not entirely lost by
M’Cl- + SOH+SOM f H’Cl-. mismanaging the precipitation. In particular the alkaline
solution must never be added to excess of the metal salt
By introducing a competitive ion, for instance NH; or an solution otherwise precipitation will proceed in a
amine ion, the chemisorption of the metal ions is reduced sequential manner as the pH of the mixture increases
and, as the impregnating solution advances into the sup- and the precipitating components will precipitate
port particle, when the dry particle is immersed in the separately. No subsequent agitation, however vigorous,
impregnating bath, the metal ions penetrate further is capable of effecting the desired intimacy of mixing
before being chemisorbed and removed from the solu- once this has been lost. Figure 9 illustrates the sequential
tion. The chemisorption equilibrium can also be pushed precipitation process by taking as an example the pre-
to the left in the above equation by addition of acid (e.g. paration of a copper on alumina catalyst by adding
HCl) to the impregnating solution. Any free alkali in the sodium carbonate solution sIowly to mixed copper alum-
inium nitrate solution. As precipitation proceeds and the
pH rises, aluminium hydroxide precipitates first followed

II Metal penetration 11

Limited Complete
I I
By strong
chemisorption
and short chsmisorption
due to strong

1Diwng 1
Fig. 9. Variation in catalyst composition with acidity during
Fig. 8. Control of depth of impregnation. precipitation for a copper alumina catalyst.
1438 S. P. S.
by copper carbonate. Figure 9 also indicates the hazard
of adding excess alkali, as re-sohttion of the precipitate
occurs, again in sequential manner.
The objective is to produce a flocculated multi-com-
ponent precipitate in which the catalytic metal containing
microcrystals are each surrounded by support precursor
crystals and both these sets of crystals are very small,
preferably less than 5OA. Furthermore it is desirable to
effect this with the maximum ratio of metal precursor
crystals to support precursor crystals. If it assumed that
an effective separation of the metal crystals requires a
“monolayer’ coverage of each by the support crystals,
then this requirement defines a geometrical relation be-
tween the ratio of the crystal size of the metal crystals to
that of the support crystals and the ratio of the volume
of metal to that of the support material. As metal crystals
which are in contact in the final catalyst rapidly unite
when the catalyst is operating, by sintering together, the
attainment of the above geometrical relation is one of the
objectives of the precipitation process. In practice, the
structure is not as regular as implied above and the
proportionality constant between ratio of sintering com-
ponent crystal size (the metal) divided by the support
crystal size to the ratio of volume of sintering component
(the metal) divided by the volume of support component
in the catalyst has been obtained empirically by
reference to a number of good industrial formulations.
The relation so obtained is shown in Fig. 10 and is an
attainable objective in many circumstances. It is the
reviewer’s personal belief that the microgeometrical
relations in supported precipitated catalysts are a key to
the attainment and maintenance of a high exposed sur-
face area of the catalytic species. Unfortunately this is a
particular difficult area to observe directly as the parti-
cles of the support component (dSUPPORT) in Fig. 10
have to be very small. With metal crystals (dSINTER) of
100 A in size-which is readily observable by X-ray
diffraction line broadening or by electron microscopy,
and a high metal content catalyst containing, say 4 times
the volume of metal to that of support, the support
particles must only be about 5 A in size which is difficult
CSINTE. Volume of metal
(-1
“SUPPORT Volume of ossocioted support
Fig. 10. Size of metal crystals stabilised by well dispersed
refractory support.
ANDREW
to observe directly and is obtained by deduction from
surface areas measured by physical absorption.
The desired structure described above can be
produced either by precipitating the metal component
precursor and the refractory support component pre-
cursor as separate particles or in the form of a compound
which is subsequently decomposed. In the first case the
pH of the precipitate is important as it influences the
flocculation process and hence the distribution of the two
types of pL:rticle relative to each other and also the
filterability and washability of the precipitate. Ideally,
opposite charges should be formed on the two types of
particles so that the floes consist of a neutral mass
composed of oppositely charged support precursor par-
ticles surrounding catalyst precursor crystals. In the
second case, ageing of the precipitate at an appropriate
pH and, usually, an elevated temperature is necessary in
order to promote the crystallisation of the compound
phase-a typical example is a basic carbonate of the
form MO, A1203b OH,COw where MO is a metal oxide
(e.g. CuO, NiO).
The process by which comparatively large crystals of
compound are broken down into a supported metal will
be described later.
Thorough washing of the precipitate, preferably with
de-ionised water is usually required in order to remove
unwanted components, for example sodium ions, from
the precipitate. Chloride ions are particularly deleterious
to catalyst life and should not be used (e.g. as metal
chlorides) in catalysts which are expected to operate in
chloride free atmospheres at elevated temperatures
otherwise sintering is accellerated.
Following washing, the precipitate is dried and cal-
cined to convert it from hydroxides and carbonates to
oxides. This calcination must be carefully controlled,
both with respect to temperature and with respect to
degree of completion as it affects both the ease of
reduction of the metal oxide to metal and the ease of
forming the material into a tablet. This subject will
therefore be discussed when outlining the theory and
practice of catalyst particle forming and of reduction.
The relation between metal particle size and support
particle size given in Fig. 10 sets a lower Iimit to the
metal particle size that will exist in the catalyst after
reduction. If the metal precursor crystals (e.g. the metal
carbonate or hydroxide) produced during precipitation
contain more metal than corresponds to this lower limit
size then the reduced and stabilised metal crystals will be
appropriately larger than the lower limit. There is thus no
virtue in increasing the support volume/metal volume
ratio excessively in the hope that this must result in small
metal particles.
This point is illustrated in Fig. 11 which shows how the
reduced and stabilised metal crystals decrease in size as
the support fraction of the mixture increase (the concave
part of Fig. 11 marked “sintering limit”) until the metal
size reaches a limiting smallness set by the size of the
metal precursor precipitate.
THE CREATION OF FORM
Unformed catalyst or support mixtures are shaped
 Theory and practice of the formulation of heterogeneous catalysts
% Metal in catalyst
Fig. 1I. Specific metal surface of a metal-metal oxide catalyst
after sintering.
usually by one of five methods: Extrusion, wet pressing,
dry tabletting, granulation, or casting. The first tHio
essentially are similar from the physico-chemical stand-
point. The powder to be formed is mixed with water and
usually, a plasticising and probably also an extrusion aid,
to give a mouldable clay like body. This is then shaped
either by extrusion through a die or pressing between
male and female moulds. Usually catalyst mixes of
powdered oxides made by precipitation do not by them-
selves have the necessary mouldability and plasticity
even when the optimum water content is added. They
behave rather like wet sand. In order to give plasticity
the particles must be given a lubricating layer of a clay,
such as bentonite and the water made more rigid by
dissolving starch in it. Figure 12 shows how an alum-
inium trihydrate powder mixed with 5% bentonite is
plasticised by addition of starch. The much reduced
sensitivity of yield strength to water content as a result
of adding the starch results in good plastic properties
suitable for feeding an extruder.
Uniformity of feed composition, particularly water
Fig. 12. Typical variation of yield strength with water content
and plasticiser content for an alumina trihydrate +5% bentonite
mixture.
1439
content, and absence of pockets of air is essential when
operating an extruder, as the material must be weak
enough to extrude without the generation of excessive
pressures behind the die and strong enough when it
emerges to retain its form even when sliced off with a
knife. Pockets of air are normally removed by passing
the extruder feed through a vacuum chamber situated
half way along the extruder. The product is normally
quite strong after drying (because of the starch) but must
be fired to give it real strength in use when the starch
decomposes at the catalyst operating temperature.
Normally this firing is effected in a carefully controlled
oxidising atmosphere, to remove the starch residues, and
to form a ceramic bond between the components, a task
which is aided by any bentonite in the formulation. The use
of such additives as bentonite which remain in the catalyst
mixture, however, in some circumstances can have
deleterious effects on the catalyst performance by
promoting undesired reactions. Dry tabletting of a catalyst
powder obviates the necessity for such additives and also
the necessity for producing strength by firing.
Tabletting is however, much more expensive, as each
individual tablet is separately formed however large or
small. The production of small catalyst tablets is, there-
fore, particulady expensive per cubic meter of product,
The production of strong particles by tabletting requires
that the particles of tablet feed are subjected to a
reasonably uniform triaxial (e.g. hydraulic) pressure and
that under this pressure they crush together to form a
dense bed which then welds at points of contact.
At the tabletting stresses capable of being generated
by normal machines the requirement of welding requires
that a sufficient fraction of the material has adequate
ductility, a quantity neither tabulated nor easy to
measure in these circumstances. However a very crude
relationship exists between ductility, melting point, elas-
tic modulus and Mob’s scale of hardness. This is shown
in Fig. 13. Bearing in mind that the tabletting machine
has steel punches-even if hard faced-it is clearly neces-
sary that the material to be tabletted should more ductile
and in general “softer” than the dies otherwise they will
Moh’s scale of hardness
4 5 6 7 e 9 IO
105 lo= 107
Elastic modulus kg/cm’
Fig. 13. The relation between pelletability, crystal strength and
melting point.
1440 S. P. S. ANDREW

rapidly be destroyed mechanically if sufficiently high

pressures are generated to produce strong tablets. Nor-
mally with catalysts given form by tabletting, a sufficient
quantity of hydroxide or carbonate precursor is left in
the tabletting feed (e.g. CuC03, Al(OH)s etc.) to act as a
binder in a mixture which can contain untablettable
material such as C&O, AlzOs. Excessive binder is,
however, deleterious to tablet strength in use, as the COZ -0.01 I
and Hz0 is stripped off leaving a much weakened tablet. IO 100 1000

With tabletting using a die with a cylindrical hole and
one or two cylindrical punches compressing the powder
charge, the desired uniform triaxial pressure is difficult to
obtain. Indeed, if precautions are not taken the non-
uniform stresses left in the tablet during compaction may
be so great that the tablet breaks up spontaneously on
ejection from the die. Part of the cause of this non-
uniformity is the friction between the powder and the
punch surface and die surface. By adding an extreme
pressure lubricant, such as graphite flakes or calcium
stearate, to the powder this effect is reduced. As the
length/diameter ratio for the tablet is increased the
necessity for good lubrication increases, as can be seen
from Fig. 14. This shows the load on a stationary bottom
punch supporting powder being compacted by driving
down the top punch for different Ild ratios with and
without graphite addition. Tablets which are somewhat
weakened by internal stresses left after tabletting, though
not to the extent of fracturing may, if of appropriate
composition, be strengthened by an annealing operation
(like glass bottles).
Sometimes the catalyst formulator wishes to produce a
strong tablet by tabletting and, at the same time, high
porosity is required. In these circumstances it is im-
portant to use a feed having the minimum practical
particle size as this usually gives the maximum tablet
strength for a given talbetting pressure
and hence for a
given desired tablet density and voidage. Other factors
being constant, the tablet strength, measured, for in-
stance as a stress imposed on the two flat faces at
fracture (the axial crushing strength), is normally pro-
portional to the tabletting pressure applied to these two
faces. The,proportional constant typically falls between
Inltlal averago Particle size (p)
Fig. IS. Influence of initial particle size on tablet strength.
0.02 and 0.1, see Fig. 15. With domed cylindrical tablets,
strengths cannot readily be measured as above and they
are laid horizontally on a flat surface and loaded to
fracture using a cylindrical ram face whose axis is at
right angles to that of the tablet. The loading on the top is
thus a point contact whereas the tablet is supported by a
line contact. The fracture load per unit cross section thus
measured (the maximum horizontal crushing stress,
MHCS) is, it can be shown roughly double the tensile
strength of the material. Typical tabletting pressures, raw
tablet tensile strengths of calcined and reduced tablets
are listed in Table 2 along with typical loads to which
tablets may be subjected during converter charging (due
for instance to dropping from a height) and during steady
operation (due to bed weight and gas pressure drop).
These figures indicate that tablets normally charged in
the raw (oxide) state are adequately strong to resist the
charging operation, but that if reduced they are liable to
break up to some extent during discharging unless spe-
cially designed to be of greater strength.
Granulation, the building up of spherical catalyst par-
ticles by layering as the particle rolls in a granulator (for
instance an inclined dish rotating on its axis) usually
requires a fine powder feed together with a spray of
granulating liquid. The product balls have little strength
unless a hydraulic setting cement is included in the
mixture. Otherwise mixtures rather similar to extruder
compositions can be used, starch may be added and salt
solutions which can crystallise out on drying, for exam-

Table 2. Typical loads on and strengths of catalyst tablets

> 1-1 z”,“,‘s’,‘,‘R:“,” {;F;;;rE ;I &;;oo

RAW TABLET TENSILE STRENGTH :- 2-b
(= ‘/2 M.H.C.S.)

CALCINED & REDUCED TABLET

TENSILE STRENGTH :- 0’5 -2
(=“‘z iM.H.C.5.)

I I I LOADS ON TABLETS DURING :- 0.2 - I’0

0 I 2 CHARGiNG (TENSILE)

LOAD ON TABLETS IN BED

DURING STEADY OPERATION :- 0- o-2
Fig. 14. Influence of pellet shape and graphite lubricrication on
(TENSILE)
uniformity of computation of a cylindrical pellet.
 Theory and practice of the formulation of heterogeneous catalysts
ple, aluminium nitrate. The wet granule, after drying may
then be given further strength as for extrudates, by
burning out any starch and then firing to produce some
sintering Spheres have the minimum outside surface
area per unit volume of any shape and therefore are
more subject to internal diffusion limitation than any
other shape. They can, however, be made very strong,
and they are resistant to attrition and flow readily.
Finally, casting is a method of forming catalysts which
has a number of applications. The gelation of silica, silica
alumina or alumina in the form of a spherical particle
whilst, as it were, being held in the “mould” of an
aqueous drop “suspended” in oil is a form of casting
which has considerable use. Molten mixed oxide catalyst
precursors, such as the Fea04, A120s, I&O etc mixture
for ammonia synthesis may be either cast in the form of
spheres, by breaking up a jet of liquid with cooling
stream of water or air or by casting the liquid into a
mould made of metal or even of catalyst powder-
though these are considerable practical difficulties with
an oxide melt at over 16OPC !
CALCINATtON ANDCATALYWREDUCTION
Catalyst and support precursors such as hydroxides,
carbonates and nitrates are converted first to oxides then
subsequently (and usually in the plant reactor) the
catalytic metal oxides are reduced to metals or sulphided
to metal sulphides. These solid state transformations can
create strength or produce weakness in the catalyst
pieces. They can increase or decrease surface area. They
are often essential to the creation of activity but if
performed without due regard to the kinetics and equili-
bria of solid state transformations the final activity may
be very much less than the optimum.
Many solid oxides are to some extent mutually solu-
ble-quite a few even form compounds. The extent to
which very intimately mixed dry particles of hydroxides,
carbonates or nitrates of support processors and metal
precursors react together, if such is thermodynamically
favourable, is a function of their particle size, the tem-
perature and the presence of “minerahsers”, ie ions such
as OH- and Cl-, which by entering into the structure of
the components render their diffusive interaction faster.
It must be remembered that this interaction has, in part,
to be reversed during the process of catalyst reduction as
metal ions of the catalyst metal must be extracted from,
for instance a ceramic compound, (e.g. Ni” from
NiMgOz) and then reduced to give reduced metal cata-
lyst and that this operation must take place in a reason-
ably short time (a few hours or less) in a specified
environment (often the plant reactor) at a temperature
which is not to exceed a certain value (set often by
metallurgical considerations of the plant vessels). The
precise velocity of these solid state reactions is clearly,
in the present state of knowledge, very much a matter
for experiment. A rough guide in deciding the relation
between calcination temperatures and reduction tem-
peratures is that the former should never substantially
exceed the latter when compound formation between
metal oxide and support oxide is likely. and preferably,
be below the latter. The guide is based on the principle
1441
that the velocity of decomposing by reduction the struc-
ture which was built during calcination must be
adequately rapid and that the “solidity” of the structure
built during catcination (i.e. crystal size and perfection of
solid solutions or compounds) is determined by the tem-
peratures of calcination, the higher the temperature the
more “solid” the structure. More “solid” structures
require higher reduction temperatures to break them
down. Examples of the use of this guide are shown in
Fig. 16. The two left hand columns show respectively the
decomposition temperatures at atmosphere pressure of a
number of hydroxides and carbonates as measured, for
instance, by differential thermal analysis or ther-
mogravimetric analysis using relatively large pieces of
filter cake of the pure components.
The right hand column gives typical catalyst reduction
temperatures for different supported metal catalysts.
These reduction temperatures on the whole equate to the
lower timit of temperature obtaining in the plant reactor
during its steady operation. When the pieces of filter
cake contain more than one component (as they invari-
ably do) the decomposition of the more stable com-
ponent is assisted by the decomposition of the less stable
as, for instance, the CO2 of the carbonates is stripped off
by the steam evolved from the decomposing hydroxides.
A substantial fraction of the copper carbonate that might
be used in preparing a low temperature water gas shift
catalyst can thus be lost at a calcination temperature of
300°C due to the decomposition of the zinc hydroxide.
The difficulty which would arise if a low temperature
methanation catalyst (operating at say 320°C) was to be
prepared from a nickel carbonates magnesium hydroxide
co-precipitate can be seen, as the decomposition of the
mixture during calcination would require temperatures
substantially (at least 15O’C) above the reduction tem-
perature, resulting in the formation of nickel magnesia
spine1 which would be very slow to reduce leading to
poor catalyst activity through lack of free nickel metal.
The reduction process is the last stage of catalyst
preparation with many supported non-precious metal and
some metal oxide catalysts. The fact that this stage often
occurs in the plant reactor should not disguise the fact
that this is the stage where the final solid state trans-
Fig. 16. Calcination and reduction temperatures Cu, Zn, Fe, Ni,
Fe, Al, Mg containing catalysts.
1442 S. P. S. ANDREW

formation occurs and where the catalyst comes into Nuclei of support phase
being.
With precious metal catalysts and also certain non-
precious metal catalysts this stage is performed before
the catalyst is charged to the plant which therefore
receives active catalyst. Some reduction reactions are
Partlolly
exothermic, in which case careful control of the reduc- reduced catdlyat
tion gas mix compositions is essential if unacceptably
high catalyst temperatures are to be eliminated. These
temperatures would result in catalyst sintering. Nor-
mally, as reduction usually takes place at around the final
catalyst operating temperature and temperature rises of
more than say 50°C are to be avoided, the reduction
All metal crystals
process takes place in an inert gas containing a low separated by support
percentage of reductant-for example 1% HZ, the pos-
Stabilised
sible temperature rise is then limited by the heat capacity reduced catalyst
of the inert gas. With endothermic reductions, the above Fig. 17. Three stages in reduction of a metal-supporl compound.
precautions are unnecessary. Other factors may be im-
portant, particularly the water vapour content of the the refractory alumina crystallite size is given by the
reducing gas. equation at the bottom right of Fig. 17. Combining that
The ratio of the water vapour partial pressure to the equation with one at the top of Fig. 17 gives:
hydrogen partial pressure (pHZ0/pH3 during the reduction
process is very important when reducing compounds or
a “1 metal ] (reduction velocity)-1’2.
solids solutions of metal oxide and support oxide, as this [ volsupport
quantity has a marked effect on the fineness of subdivision
of the resultant metal plus refractory oxide structure. The Experiment shows that the rate of reduction of several
ammonia synthesis catalyst which, before reduction, may metal oxides is roughly proportional to pHZ/pHlo at a
be considered as a solid solution of alumina in Fes04 is the given temperature:
most studied example of this phenomenon. The effect of Hence Da(vol metal/v01 support) (pH20/pHz)“2 which
p~&p~~ may possibly be understood by envisaging the explains the dependence of metal crystallite size and
solid state transformation which gives rise to the free hence catalyst surface area on the ratio pH20/pH2 during
support oxide during the reduction process. The following reduction. By fitting data from a number of catalysts and
analysis is basically a hypothesis as the necessary in- in particular ammonia synthesis a value has been given
vestigation of the reduction process as it proceeds under a to the proportionality constant and the resultant relation
very high resolution electron microscope has not yet been is shown in Fig. 18. Clearly this figure should be looked
done. on merely as a guide or an informed guess in the absence
The un-reduced crystals may be considered as a solid of experimental data on any particular system rather
which is reduced by means of a reduction front moving than as a firm prediction. The quantitative science of
into the crystal leaving a porous mixture of metal crys- these complex phase transformations does not permit
tallites and support oxide behind as the oxygen is anything more substantial at present. Adequately low
removed as water. The support ions (for instance A13’ in partial pressures of water vapour are normally main-
the ammonia synthesis catalyst) presumably migrate in tained during reduction by operating with a high velocity
the reducing oxide being driven by supersaturation of reducing gas and maintaining the rate of reduction low
gradients to nucleation sites where they deposit to form
AIz03. The distance over which this migration can take
place is a function of the time available which is deter-
mined by the velocity and thickness of the reduction
front. This distance determines the number of nucleation
sites triggered and hence the density and size of the
alumina crystallites produced. A simple algebraic analy-
sis generally similar to that which has been applied to the
solid state precipitation of iron carbide from a solid
solution in carbon due to the movement of a cold front
into a hot crystal suggests the relation shown against the
top diagram in Fig. 17. Iron crystallites then form be-
tween the alumina crystallites and, over two or three
days, those in contact sinter together until all that remain
are isolated from each other by alumina crystallites
(bottom diagram in Fig. 17). When this has occurred the Pn, / PHZO

geometric relation indicated earlier in Fig. 10 applies so Fig. 18. Size of metal crystals produced by reducing metal-
that the ratio of the metallic iron crystallite size to that of support compound.
 Theory and practice of the formulation of heterogeneous catalysts 1443

by keeping the catalyst bed temperature low. Reduction again only about 0.5 mm thick and then rolling them up
of metallic catalysts is an autocatalytic phenomenon as together rather like a Swissroll. In both cases the damp
hydrogen atoms formed by chemisorption on the reduced ceramic paste matrix is then dried and fired to give it
metal spill over into the unreduced zone producing fur- strength. Both these operations need to be accomplished
ther reduction. This phenomenon can be utilised to for- with great care otherwise differential shrinkage will
muiate catalysts capable of being reduced at lower tem- occur between diierent parts of the structure leading to
peratures than otherwise by incorporating very small cracking and mechanical failure.
amounts of easily reducible metal into the mixture, for Large ceramic structures such as these, which may be
example, platinum or palladium into a non-precious several tens of centimeters in size, are subject to thermal
metal formulation. These small additions after they have shock failure if suddenly heated or cooled unless they
accelerated the reduction process then dissolve in the are made of a ceramic having a very low volumetric
main catalytic metal species, and, not being surface coefficient of expansion. This additional requirement
active, are effectively lost from the catalytic system. effectively limits the ceramic to a single species, cor-
dierite, a magnesium alumina silicate. When thermal
shock is absent other ceramics such as alumina are used.
TEE FABRICATION OF MATRIX CATALYSTS Metal structures may be made by assembling pre-
Most industrial heterogeneous catalysts are used in the formed metal sheets into a matrix, for instance by wind-
form of powder or of tablets, rings, spheres, extrudates ing corrugated and flat sheets together, Swissroll fashion.
or lumps. With fast reactions and the desire for low This method of construction is used in a current type of
reagent pressure drops through the catalyst bed there has automobile exhaust oxidation catalyst. Both ceramic and
long been a call for more complex structures such as are metal structures, though they have a high external sur-
employed in compact heat exchangers etc. As most face area are unsuitable as anti-sintering supports for
catalyst structures are either ceramic or metal-ceramic metal catalysts. Both catalytic species and supporting
the fabrication of such structures can be expensive and species must, therefore, be coated onto the structure.
they are only used in special circumstances. Matrix This is usually effected by dipping the structure into a
catalysts almost invariably use a pre-shaped macro- suspension of a high area ceramic plus some binding
structure to form the matrix to which the catalyst mix- salts and, drying and firing the coating at sufficient tem-
ture is attached. There are two types-those in which the perature to cause it to adhere to the underlying structure.
pre-shaped structure is ceramic and those where it is a When employing a metal structure the surface pre-
metal-see Fig. 19. paration of the metal before coating is most important
The ceramic structures may be fabricated by extruding (as with all ceramic enamelling processes) if good ad-
a ceramic paste through a complex die which produces a hesion of the coating is to be secured. In general the
large “sausage”-perhaps about 15 cm dia. having a very metal surface must be non greasy and have a thin but
large number of parallel holes throughout its length, the strongly adherent oxide layer. The above automobile
holes being separated by thin ceramic walls perhaps only exhaust catalyst employs Fecralloy, a steel containing
0.5 mm thick. Alternatively they can be fabricated by chromium, aluminium and yttrium which forms a stron-
forming flat and corrugated sheets of ceramic paste, gly adherent oxide layer which resists further oxidation
of the metal and forms a strong base onto which an
aluminia support can be fixed.
Following coating with the high surface area ceramic,
the catalytic species, usually a metal is impregnated from
solution into the coat. Frequently the ceramic coats have
to be rather thin otherwise they detach from the metal
readily when subjected to thermal shock. Thus it may
not be practical to make a supported catalyst having a
high weight of catalytic metal deposited in the ceramic.
In order to obtain good activity, the catalytic metal
should therefore have a high intrinsic activity and this
type of support is often used with precious metal cata-
lysts. The chief use that has been found for matrix
catalysts is in the treatment of automobile exhaust gases
Dip in high orea ceramic suspension where low pressure drop, low thermal inerta and the
ability firmly to grip a matrix block when it is subject to
I the vibration of the exhaust system give them an ad-
Dry ond tire
vantage over more conventional shapes. They are also of
I use in various gaseous effluent treatment systems where
low pressure drop is valuable. A non-matrix use of
similar technology for coating a catalyst mixture on a
metal structure is the catalytic oven liner which main-
tains domestic ovens clean by absorbing and then
Fig. 19. Fabrication of matrix catalysts. catalytically oxidising fat splashes on the walls.
1444 S. P. S. ANDREW

SOME LESS USUAL METHODS OF CATALYST PREPARATION This method therefore is more of a laboratory curiosity
A number of less commonly used methods of catalyst than industrial process at present.
preparation are shown in Fig. 20. The use of sputtering or ion impregnation techniques
The list is not exclusive. In particular the use of to coat the outer regions of a ceramic powder or coating
homogeneus organo-metallic catalysts made hetero- with very fairly divided metal particles also receives
geneous by chemically anchoring them on a high area episodic attention. The technique employs a high vacuum
support and the vaguely related technique of anchoring and the individual atoms of the metal can be deposited
enzymes on supports are ignored as these methods are of on the surface of the powder, which is tumbled to expose
a different class to the subject of this review. Of the it to the metal beam, with a wide range of energies. High
methods listed in Fig. 20, the Raney method is frequently energy beams result in penetration of the metal atoms
used for preparing a nickel hydrogenation catalyst for below the surface of the ceramic crystallites where they
laboratory organic preparations. The porous nickel are buried and catalyticaNy ineffective. Low energies are
produced has a high surface area and is hence very therefore usually employed. Confinement of the metal-
active at low temperatures, it is not, however, parti- lisation to the outside visible surface of the catalyst
cularly stable and would be unsuitable for commercial particles results in metal contents of the catalyst being
use at higher temperatures as there is little provision in very low and activity per unit volume of reactor cor-
the formulation for stopping nickel crystal coalescence respondingly low. Coupled with the high cost of catalyst
and hence loss of area and activity. fabrications this fact renders this method generally un-
The hydrolysis of urea in a heated aqueous solution attractive.
can be used as a method of generating in situ alkalinity in Condensation of metal oxides and refractory oxides
an otherwise inaccessible place. This phenomenon may from the vapour phase due to sudden quenching of a
be employed, for instance, to cause the precipitation of very high temperature gas stream can produce very
hydroxides uniformly throughout the pores of a support finely divided powders which could be used as a catalyst
which has been impregnated with a solution of metal precursor. The gas stream can be prepared for instance
salts plus urea. For instance, a high strength low surface by passing a cold stream plus a feed of catalyst pre-
area alpha alumina ring could be impregnated with a cusors in solution through a plasma arc which vaporises
solution containing a mixture of aluminium and nickel all the catalyst components. Quenching can be effected
nitrates plus urea, the hydrolysis of the urea would then by adding cold gas. Flocculation of the product in a
precipitate in the pores an intimate mixture of nickel residence chamber is desirable before collection by elec-
hydroxide and aluminium hydroxide which, by cal- trostatic precipitation. No industrial catalysts are so far
cination and reduction could be converted into a high made by this method which is clearly expensive, it is
strength high area nickel catalyst. furthermore not easy to produce crystals of the desired
The use of organo-metallic compounds which are smallness in size (i.e. less than SOA) and to retain them.
decomposed in a reducing atmosphere to form a carbon
supported metallic catalyst has the virtue that the route THE STATE OF THESCIENCE
can be perfectly free from water (an accelerator of The aim of this review is to indicate, in a brief space,
particle sintering with oxides). The disadvantage is that the main factors which a practical formulator of in-
the method is somewhat costly, requiring, for instance, dustrial heterogeneous catalysts must bear in mind.
the synthesis of metal ketenides or at the least oxalates, Success is achieved by optimising what are often a series
citrates etc, and, perhaps more seriously, the car- of conflicting requirements. This optimisation, though
bonaceous support is often unstable and disappears due aided by a knowledge of the relevant theories of the
to oxidation or hydrogenation when the catalyst is in use. catalytic process and theories of the solid state trans-

I Tablet

Fig. 20. Some less usual methods of catalyst preparation.

 Theory and practice of the formulation of heterogeneous catalysts 1445

formation occasioned during catalyst preparation, is not tested under as realistic conditions as can conviently
crucially dependent on such theories which primarily be set up. From the results so obtained the formulations
only shorten the experimental programme and suggest are modified in an attempt to correct observed imper-
further lines of investigation. The complexity of the fections, using general observations of the type
phenomena taking place, together with the fact that they listed in this review. This process of
frequently have opposing influences, means that their formulation + testing+ modification to theory of for-
prediction by numerical means is neither a commercially mulation is repeated again and again until either the
realistic approach nor even scientifically possible in our desired commercial target is reached or it is judged that
present state of knowledge. the laws of nature do not permit it to be reached with the
This is not to argue that pure empiricism is the best facilities that can be pressed into service.
course, for no pocket is sufficiently deep to be able to The subject of laboratory reactors and the testing of
fund the preparation of the infinite variety of for- heterogeneous catalysts has not been touched on in this
mulations that are possible. Rather, what is required, is review, neither has the subject of the measurement of
an intelligent assessment of the relative importance of kinetics or the design of full scale reactors. Nevertheless
the factors which are likely to be of greatest importance the reviewer believes that engineers concerned with such
in the preparation of an heterogeneous catalyst and a measurements and their interpretation for full scale
willingness to discard from experimental consideration design would benefit from an understanding of the com-
those factors judged to be of secondary importance. plexities of catalysts otherwise they are liable to build
Experimental formulations are prepared on this basis and numerical castles on the most unsound of foundations.

CES Vol. M. No. 9-B