Applied Catalysis A: General 221 (2001) 1521

New catalyst preparation technologiesobserved

from an industrial viewpoint
F. Schmidt

R&D, Catalyst Division, Sd-Chemie AG, Waldheimer Str. 13, 83052 Brckmhl, Germany
Abstract
Catalyst industry used to be primarily technology driven. Surprisingly, although many new catalyst preparation procedures
and technologies have been developed and published during the past decade, only very few methods have found application
in commercial catalyst production as yet. Temporarily, cost reduction has become the major driving force. But also in future,
all new ideas have to compete cost-wise with state of the art technology.
The alkoxyroute toprepare alumina has beenmodiedtoproduce silicaalumina or hydrotalcites. Inthe area of micro-porous
catalysts, new production methods were necessary for the zeolite bound zeolites that have been introduced to the renery
industry, recently. Conventional parafn isomerization catalysts, based on chlorinated alumina or mordenite zeolites, for the
rst time were confronted with commercial competition from the newly introduced sulfated zirconia catalyst system, that
required a new production technology. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Heterogeneous catalysts; Dry synthesis; Zeolite bound zeolites
1. Introduction
In 1998, the global merchant market for catalyst
products was close to about US$ 8.5 billion. In addi-
tion to this, there is a signicant amount of catalysts
produced for the captive use which is estimated to be
of the order of US$ 1 billion. On top of this, about
US$ 3 billion of royalties and license fees are related
to catalytic processes. With this total investment in
catalysis, about US$ 3 trillion of goods and services
are created [1]. Hence, the factor for the value added
is of the order of 200300.
The following study is restricted to the preparation
of heterogeneous catalysts. Recently, the preparation
of solid catalysts has been summarized by Ertl et al.
(Eds.) [2] and Poncelet et al. (Eds.) [3]. The catalyst
industry rst and foremost used to be a technology

Fax: +49-8061-4903-702.
E-mail address: f.schmidt@sued-chemie.de (F. Schmidt).
driven one. This fact and the high value added has sev-
eral consequences on the introduction of new catalyst
manufacturing procedures.
Firstly, the benet to the catalyst user has to be
considered. Two cases may be regarded separately,
new production procedures for existing processes and
new production procedures for new processes. In the
rst case, which is the most frequent one, the high
value added through catalysis is associated with a
high risk of failure if any completely new production
route does not result in exactly the same performance
of the catalyst as compared to conventionally pro-
duced catalysts, since one day of plant shut down
causes the catalyst user a multiple of the cost of the
catalyst itself. In the second case, the hurdle to apply
completely new production procedures may be lower.
Though, the dominant task for all catalyst produc-
ers, remains the continuous improvement of existing
production technologies. But even in the case of an
improvement of conversion or selectivity, the catalyst
0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0926- 860X( 01) 00802- X
16 F. Schmidt / Applied Catalysis A: General 221 (2001) 1521
user may have to modify his plant to cope with the
altered materials streams. Consequently, in particu-
lar, all catalysts produced via any completely new
procedure need to be extended and therefore, expen-
sive catalyst testing for approval. This is the reason
why all changes in the catalyst production procedure
should be notied to the client in advance.
From the catalyst manufacturers perspective, it is
to note that these days economic and ecological envi-
ronment directs their efforts towards cost/performance
improvement rather than to implement more sophis-
ticated manufacturing technologies, except the new
technology results in a remarkable performance ben-
et of the catalyst at lower manufacturing cost and at
higher environmental standard. New production tech-
nologies, usually, are associated with additional cap-
ital investment. The room for such an investment in
catalyst manufacturing plants gets smaller and smaller
primarily due to low catalyst prices caused by the in-
creased buying power of catalyst users as a result of
recent mega-mergers and also because the industry is
faced with stricter safety and environmental regula-
tions that make production equipment more expensive.
Before discussing the new production technologies
in detail, it should be mentioned, that the down stream
unit operations of the catalyst manufacture such as
product separation, mixing, shaping or calcination
have not changed during the past decade since only
minor technical improvements of the equipment but
no step change could be observed. Therefore, in the
following chapters, only the recently developed new
production technologies of the catalyst precursor will
be investigated with respect to their technical and
economical realization. In addition to precursor for-
mation, however, new trends in catalyst forming will
also be discussed. Almost all solid catalysts includ-
ing powders for slurry phase application are shaped
catalysts. Catalyst shape, attrition resistance, crush
strength and porosity have strong inuence on the
performance, i.e. on activity, selectivity and life. Re-
garding formed catalyst, some remarkable progress
has been reported, recently.
2. Bulk catalysts and supports
Table 1 summarizes the major catalyst preparation
technologies for bulk catalysts and supports that are
Table 1
Bulk catalyst and carrier preparation technologies
Basic technology
and processes
Recent
technology
steps
Large industrial
scale catalyst
production
Fused catalysts No Yes
Skeletal metal catalysts No Yes
Metallic glasses No No
Conventional precipitation Yes Yes
Activated preparation Yes Yes
Solgel process Yes Yes
Flame hydrolysis No Yes
Solid state reaction Yes Yes
Carbides and nitrides No No
Carbons Yes Yes
Heteropoly compounds No Yes
Hydrothermal synthesis Yes Yes
Pillard clays No No
discussed in the public and patent literature. Recent
technology steps refer to the step changes in technol-
ogy of catalyst preparation. The following discussion
will be concentrated on those new technologies, that
show both, a real step change and application in an
industrial scale or at least have been proven to be suit-
able for being scaled up. Therefore, not all technolo-
gies indicated in Table 1 will be discussed.
2.1. Conventional precipitation
The properties of the catalyst precursor and, in the
end of the catalyst may be inuenced by either (i)
using an organic solvent (or an organic/water mixture)
or (ii) using organo-metallic precursors in organic or
aqueous solvents (or an organic/water mixture) or (iii)
adding organic salts or other modiers to the aqueous
solution. For the latter two routes, recent progress has
been reported.
2.1.1. Organic solvents
Usually, catalyst producers try to avoid organic sol-
vents since these do not t into the infrastructure of
the catalyst production plants and solvent work up as
well as recycling is expensive. In some cases, how-
ever, the benet achieved by using organic solvents or
water/alcohol mixtures seems to justify research work.
There is some indication that VPO catalyst precur-
sors are prepared preferably by using alcoholic solu-
tions to reduce V
5+
in V
2
O
5
to V
4+
, but in this case,
F. Schmidt / Applied Catalysis A: General 221 (2001) 1521 17
the alcohol is more of a reduction agent than a solvent.
A review regarding the VPO catalyst for conversion
of n-butane to maleic anhydride has been published
by Cavani and Trir [4]. Although a rst commercial
plant started operation already in 1974, recent progress
has been made by using moving bed technology [5].
DuPont for instance reported [6] on the re-circulating
solids reactor technology which later on was scaled
up to their rst plant that recently went on stream
in Spain. The catalyst seems to be porous VPO
micro-spheres formed from micronized VPO crys-
tals. But it is not clear which method of catalyst pre-
cursor preparation was used. However, prior to spray
drying, an organic silicon compound is reported to be
added which migrates to the external surface of the
micro-sphere upon calcination and thus forming very
abrasion resistant particles.
2.1.2. Organo-metallic precursors in aqueous solvent
Since many years, metal organic precursors are used
on industrial scale for some hydrothermally produced
zeolite catalysts such as TS-1 [7].
2.1.3. Organo-metallic precursors in organic solvents
Since the late 1950s, aluminum alkoxides were used
as precursors for the production of active alumina.
The alkoxides were a by-product of the production
of straight chain, even numbered fatty alcohols in
the so-called Ziegler ALFOL process. Later on, an
on-purpose process was developed by Condea Chemie
to produce high purity aluminum oxide monohydrate
of boemite or pseudoboemite structure. In the rst re-
action step, aluminum metal reacts with an alcohol
to form aluminum alkoxide. Subsequent hydrolysis
leads to alumina slurry, hydrogen and alcohol. The al-
cohol then is recycled. Today, more than 60,000 mt
of alumina are produced by the Condea group. In
contrast to conventional plants to produce heteroge-
neous catalysts, these aluminum-to-alumina-plants are
equipped to handle organic solvents on a large scale.
By using this alkoxide technology, further progress
has been made in the early 1990s to produce also
alumosilicates allowing to adjust a broad range of
acidities or to make pure silica. Very recently also, hy-
drotalcites are produced via this route [8]. Aluminum
and magnesium react with a hexanol/octanol/butanol
mixture. The product is ltered and thereafter hy-
drolyzed by transferring it carefully into water. Most
of the alcohol is decanted and the remaining alcohol is
steam distilled. The slurry obtained thereafter is spray
dried.
2.1.4. Organic salts or modiers
Since many years, organic modiers are well known
templates in zeolite synthesis. Further use is (i) in an-
choring and grafting of metal complexes to the surface
of the support, (ii) as precursor for solgel technology
and/or to control the kinetics of the solgel transition,
or (iii) as burn-out material to achieve a desired poros-
ity. In some cases, however, organic salts or modiers
are used as an additive in the catalyst precursor pre-
cipitation to control the morphology and thereby the
number of active sites as well as the size or size dis-
tribution of the precipitate. This technology usually is
not published.
2.2. Activated preparation
During the last decade, several academic papers
have been published devoted to microwave, ultrasonic
or mechanical activation. Only mechanical activation
(mostly using ball mills) is used in large scale pro-
duction but this technology is known since several
decades. Catalysts for dehydrogenation, e.g. ethylben-
zene to styrene are manufactured by this route since
more than 40 years [9].
In case of precipitation from solution, one starts
with atomically totally dispersed species; whereas in
case of milling, one starts from the opposite side,
namely from macroscopic particles. The mechanical
energy, locally, is transformed to heat and if heat con-
ductivity is poor, high temperature spots are created
which lead only locally to solid state reaction. The
particles are just crushed into smaller size thereby
creating additional external surface and physical con-
tact. Therefore, usually homogeneous dispersion of
multi-component catalyst precursors is poor as com-
pared to the case of precipitation. Only if the bulk pre-
cursor thereafter is treated at high temperatures, the
distribution may be improved via solid state reaction.
The dispersion, at very high temperatures, nally de-
creases due to sintering. Under optimum conditions,
dry mix milling or dry intensive mixing of catalyst
precursors nally may result in well performing cata-
lysts [10,11]. This process has the advantage of being
a waste water-free production and from this point of
18 F. Schmidt / Applied Catalysis A: General 221 (2001) 1521
view, it is an environmentally friendly route. But this
technology has the drawback, that todays environ-
mental restrictions regarding metal and metal-oxide
dust are very stringent and all tools to guarantee the
health of the production staff are very expensive. All
these reasons may explain, why dry milling today is of
less importance for catalyst production. Milling is also
reported in conjunction with spreading active compo-
nents on a support.
In general, wet milling may be advantageous. In this
case, shear force is the major energy for achieving the
high distribution of the active component. However,
the method itself is also not new. Since wet milling is
essentially dust-free, this method in future may nd
some niches in industry where conventional impreg-
nation methods fail to obtain a high distribution of the
active components.
2.3. Solgel process
The precursor in a solgel preparation can either
be a metal salt or metal alkoxide or a stable col-
loidal suspension of preformed sols. The important
variables are the relative rates of hydrolysis and con-
densation. The high purity obtained by solgel tech-
nology starting from alkoxides can also be obtained
in case of conventional precipitation if high purity
raw materials are used. Conventional precipitation
usually results in an homogeneous distribution on an
atomic level but is mostly restricted to stoichiometric
compositions, whereas in case of solgel technology,
molecular distribution can only be obtained under
ideal hydrolysiscondensation conditions. However,
solgel methods are superior to precipitation in the
ability to vary compositional homogenity on a molec-
ular level.
Another advantage of the solgel preparation lies
in the possibility to better control grain size or poros-
ity of the formed catalyst precursor as compared to
conventional precipitation where these parameters are
very difcult to control.
However, since many catalystsregardless of the
technology used for the precursor preparationneed
further thermal treatment, some of the advantages of
the solgel technology will disappear. The removal
of the solvent must be done very carefully in order
to preserve the desired physical properties of the
grains, which is either time consuming and there-
fore, expensive or needs expensive special production
equipment. Furthermore, since solgel precursors of-
ten need additional calcination, phase segregation and
porosity changes may occur. These weaknesses of
the solgel method are the reason why this method
has not found wide application in commercial cata-
lyst production, except in case of some carriers such
as alumina, silicaalumina and hydrotalcites from
alkoxides (see above) and hydrothermal synthesis of
zeolites.
2.4. Hydrothermal synthesis
2.4.1. Dry synthesis
Several new developments were reported. Firstly,
due to the environmental legislation, many efforts
have been devoted to low efuent zeolite synthesis.
Great progress has been made in the area of dry
synthesis [1214]. As a result, dry synthesis of, e.g.
high silica BEA zeolite could be achieved [15]. This
dry gel conversion method has the benet, that no
mother liquor with high content of organic mate-
rial is created. On the other hand, in this case, no
excess template can be recovered from a mother
liquor for recycling, except a washing step is fol-
lowed subsequently. In essence, if washing water is
needed, the benet of the dry gel conversion method
does not show up in being a more environmentally
friendly production route. The economic advantage
of the dry gel conversion method may be the low
template content. But this benet may be balanced
by the problems to regain template from the diluted
washing water for the purpose of reuse. Another
possible economic benet, the short synthesis time,
may be compensated by the time to prepare the dry
gel.
Several other dry methods are also reported show-
ing the same problem of template recovery. Miller,
for example, reported that the more or less dry paste
is directly formed into the nal shape of the cata-
lyst [16]. This seems to be an advantage since no l-
tration is necessary, but recovery of the paste from
the synthesis vessel and the transport of the mass to
the extruder would need additional plant investment.
However, more importantly, all dry methods require
an homogeneous temperature prole, in particular dur-
ing the heat-up phase. This is extremely difcult to
achieve in existing large scale commercial production
F. Schmidt / Applied Catalysis A: General 221 (2001) 1521 19
vesselseven if heating coils are installed inside the
existing vessel. Apart fromthe fact, that the production
capacity is decreased by the presence of heating coils,
discharging of a paste will become even more difcult.
There are two clear advantages of the dry syn-
thesis, namely that this method allows to synthe-
size zeolites in the form of self-bonded pellets
and that the gel conversion allows to produce uni-
form and large particles. However, these advantages
are only required for niche applications and there-
fore, the dry gel conversion is not known to be
already applied in large scale commercial zeolite
production.
2.4.2. Zeolite bound zeolites
Apart from the dry gel conversion process, another
interesting method of producing self-bonded zeolite
catalysts and the use of this zeolite bound zeolites for
hydrocarbon conversion has been reported recently in
several patents, e.g. [17,18]. In these cases, an appro-
priate binder is transformed into a zeolite via a sec-
ondary synthesis. Excess of template can be recovered
from both synthesis steps.
So far, no process is known that causes conversion
of conventional molecular sieve nutrients that retains
macro and meso porosity characteristics of a geomet-
ric framework cation oxide containing nutrient, except
a process recently published by Lummus [19]. In this
case, a conventional porous carrier like silica spheres is
impregnated with, e.g. an aluminumsalt, dried and cal-
cined and thereafter mixed with an aqueous template
containing solution to form an impregnated paste-free
composition, which is then converted by hydrothermal
synthesis. The water content should be low so as to
avoid surface gelation of the particles, that could result
in inter-particle bridging. The drawback of this method
again is that any excess of template, if used, cannot be
recovered.
2.5. Supported catalysts
Table 2 summarizes the major preparation technolo-
gies for supported catalysts that are discussed in the
public and patent literature. Since only superacids
show both, a real step change and application in an in-
dustrial scale, only this catalyst type will be discussed
in the following section.
Table 2
Supported catalyst preparation technologies
Basic technology
and processes
Recent
technology
steps
Large industrial
scale catalyst
production
Deposition of
active compound
No Yes
Metal cluster No Yes
Metal complexes No Yes
CVD and CLD Yes No
Depositionpreparation No Yes
Spreading and wetting No Yes
Solid superacids Yes Yes
2.6. Solid superacids
Recently, catalysts comprising solid strong acids
based on zirconia gained interest in industrial cataly-
sis. The synthesis of zirconia based solid acids is well
known since many years. Several different methods are
described. The basic patent was assigned to Phillips
Petroleum [20] in 1962. This publication is related to
sulfated zirconia doped with platinum for isomeriza-
tion processes. The carrier is prepared by precipitat-
ing zirconium hydroxide from a solution of ZrOCl
2
by adding aqueous ammonia. Thereafter, the Zr(OH)
4
is sulfated by stirring the carrier in 1 N H
2
SO
4
. Af-
ter drying, the material is impregnated with a solution
of H
2
PtCl
4
in water and calcined at temperatures be-
tween 500600

C.
Several other methods were published like using a
solution of ammonium m-tungstate instead of sulfuric
acid [21] or using other promoter metals like iron or
manganese [22] as was published by Sun Rening and
Marketing Company.
However, all the methods described the preparation
of powders, whereas formed catalysts are needed for
most of the applications in industry, e.g. for the iso-
merization of C5/C6 mixtures in reneries to enhance
the octane number. In 1996, UOP commercialised the
rst solid acid catalyst based on zirconia (shaped as
extrusions) [23] but the preparation method of this cat-
alyst was never published. Probably, the preparation
procedure is based on the patent of the Research As-
sociation for Utilization of Light Oil [24].
Most recently, Japan Energy Corporation [25] led
a patent where the preparation of a commercial solid
acid catalyst based on sulfated zirconia promoted
20 F. Schmidt / Applied Catalysis A: General 221 (2001) 1521
with platinum is described. According to this publica-
tion, zirconium hydroxide is mixed in a kneader with
a sulfur compound like (NH
4
)
2
SO
4
or H
2
SO
4
and
an alumina binder (e.g. boemite), shaped by using
an extruder and calcined to obtain tetragonal zirco-
nia. After this, the extrusions are impregnated with
a solution containing a platinum compound and cal-
cined again. Although the active zirconia compound
is diluted by the alumina binder, the activity is en-
hanced; so the alumina is not only a binder, but also a
promoter.
This straight forward two-step synthesis is the rst
published example for a procedure to obtain a com-
mercial available shaped solid acid catalyst based on
sulfated zirconia.
3. Outlook
Many innovations that have been published during
the last decade or which are presently in the devel-
opment stage will become commercial in mid-term
future, provided cost benet ratio is acceptable. New
process technologies, that are under discussion, will
require adequate catalysts and corresponding catalyst
manufacturing technologies. This may be the case
in the area of hydrogen management for the energy
and transportation sector. In particular, the produc-
tion of hydrogen for decentralized or mobile (e.g.
fuel cell) applications will require down-scaling of
existing hydrogen plants. However, the correspond-
ing catalyst production technology, basically, will
be available from the experience in the manufacture
of existing automotive or VOV catalysts. Also, in
the case that new processes should require catalytic
membranes, the basic catalyst production technol-
ogy is available. Only few work has been done in
the area of catalyst preparation in supercritical CO
2
.
Since supercritical uids were expected to become
popular solvents for large-scale extraction, the basic
technology has been developed and is available, al-
though the actual use of supercritical CO
2
is much
less than originally expected. With respect to cat-
alyst manufacture, however, this technique would
require new manufacturing technologies and infras-
tructure. Although supercritical CO
2
seems to be an
eco-friendly production, there is not enough infor-
mation available to decide for selected cases whether
CO
2
compression versus waste water treatment is an
economically and ecologically feasible alternative.
In any case, up to today, no catalyst prepared in
supercritical CO
2
has shown equivalent or superior
performance as compared to conventional produc-
tion.
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