Title of Invention

SHELL CATALYST, IN PARTICULAR FOR OXIDATION OF METHANOL TO FORMALDEHYDE, AND ALSO METHOD FOR PRODUCTION THEREOF

Abstract The invention relates to coated catalyst, in particular for oxidation of methanol to formaldehyde, which has at least one coating on an inert, preferably essentially nonporous, support body, which coating, before removal of the organic fractions of the components b) and c) contains: (a) oxides or precursor compounds which can be converted into the corresponding oxides of molybdenum and iron, wherein the molar ratio of Mo:Fe is between 1:1 and 5:1, and also if appropriate further metallic or metal-oxide components or precursor compounds which can be converted into the corresponding oxides, (b) at least one organic binder, preferably an aqueous dispersion of copolymers, in particular selected from vinyl acetate/vinyl laurate, vinyl acetate/ethylene, vinyl acetate/acrylate, vinyl acetate/maleate, styrene/acrylate or mixtures thereof, and (c) at least one further component selected from the group consisting of SiO2 sol or precursors thereof, Al2O3 sol or precursors thereof, ZrO2 sol or precursors thereof, TiO2 sol or precursors thereof, water glass, MgO, cement, monomeric, oligomeric or polymeric silanes, alkoxysilanes, aryloxysilanes, acryloxysilanes, aminosilanes, siloxanes or silanols. A method for producing the catalyst and its preferred use are also described.
Full Text SHELL CATALYST, IN PARTICULAR FOR OXIDATION OF
METHANOL TO FORMALDEHYDE, AND ALSO METHOD FOR
November 23, 2006
4465-X-24.117
PRODUCTION THEREOF
The present invention relates to a shell catalyst, specifically
to a coated catalyst, especially for oxidizing methanol to
formaldehyde, which, on an inert, preferably essentially
nonporous, support body, has a coating composed of a
composition which, as well as an active material, comprises an
adhesion promoter composition which comprises at least one
organic binder and at least one further, at least partly
inorganic, adhesion-promoting component, especially a sol
component.
Molybdenum-iron catalysts for partial oxidation of methanol to
formaldehyde have already been known for some time.
The atomic ratios between molybdenum and iron can vary in these
known catalysts. Moreover, a portion of the active components
can be replaced partly by titanium, antimony, tin, nickel,
chromium, cerium, aluminum, calcium, magnesium, vanadium,
niobium, silver and/or manganese. Such catalysts comprising,
for example, titanium are known for the partial oxidation of
methanol to formaldehyde, for example, from US 3,978,136.
However, in contrast to the inventive catalyst, this is not a
coated catalyst.
Coated catalysts are understood to mean catalysts which arise
through coating of a (nonporous) support body with a porous
layer of the actual active material.

In contrast, in impregnation processes, the catalytically
active sites (frequently noble metals such as Pd, Pt, Au, Ag
etc.) are applied as a solution in disperse form to a porous
support (frequently: SiO2, Al2O3, TiO2, ZrO2, carbon, Nb2O5 etc.) .
In the catalysts prepared by the impregnation process,
chemical-physical interactions usually exist between support
and active sites, which have a crucial influence on the
catalytic events. In contrast, in the case of coated catalysts,
the support body serves merely for structural support. In
contrast to impregnated catalysts, in which the active elements
are present in dispersed form in the porous support - if
appropriate also in an outer shell present in the support
(= shell catalyst) - the (nonporous or essentially nonporous)
support body in the coated catalyst is enveloped by the active
material.
US 3,975,302 describes an Fe/Mo catalyst prepared by the
impregnation process for the oxidation of methanol to
formaldehyde. According to this, iron and molybdenum are
dissolved in water as MoO42- and Fe3+ salts and then impregnated
onto a porous support with a BET surface area of from 1 to
20 m2/g.
US 4,181,629 also describes a catalyst for the oxidation of
methanol to formaldehyde, which is prepared by impregnation in
a fluidized bed process.
EP-A-0 068 192 relates to an abrasion-resistant shell catalyst,
for which the preferred binders in the shell composition are
specified as glucose or urea in aqueous solution.
EP-A-0 294 775 relates to a process for preparing a shell
catalyst by spray application of the catalytically active
material onto moving support particles at temperatures of from
100 to 600°C.
WO 98/23371 describes a coated catalyst for preparing acetic
acid by gas phase oxidation of unsaturated C4 carbons. The

catalyst comprises an inert nonporous support body to whose
surface a catalytically active mixed oxide material has been
applied. This material comprises (a) one or more oxides from
the group of titanium oxide, zirconium dioxide, tin dioxide,
aluminum oxide, and (b) based on the weight of component (a)
and per m2/g of specific surface area of component (a), from 0.1
to 1.5% by weight of vanadium pentoxide. A portion of vanadium
pentoxide, preferably from 10 to 90% by weight, can be replaced
by one or more oxides of molybdenum, chromium and antimony. If
appropriate, as an additional component (b), one or more oxides
of alkali metals, elements of main group 5 and 6 of the
Periodic Table of the elements and the transition metals may
also be present. Among other elements, iron is also mentioned.
The proportion of these dopants is from 0.05 to 15% by weight,
calculated as oxide and based on the total weight of component
(b). The catalytically active mixed oxide material may
optionally also contain 10 to 50% by weight, based on the total
weight of the catalytically active mixed oxide material, of
inert diluents such as silicon dioxide or silicon carbide. The
binders used are organic binders. To prepare the catalysts, the
active components are ground with addition of water.
Subsequently, a copolymer dispersion of vinyl acetate and vinyl
laurate is added. The finished suspension is applied to
steatite spheres with evaporation of the water. The examples do
not describe any catalyst which simultaneously comprises
molybdenum and iron.
WO 99/62637 describes a process for preparing shell catalysts
for the catalytic gas phase oxidation of aromatic hydrocarbons.
The catalyst consists of a support core and catalytically
active metal oxides applied thereto in shell form. The catalyst
is prepared by spraying an aqueous active composition
suspension onto the hot support material. The active
composition suspension comprises an organic binder. This binder
is formed from (A) a polymer which is prepared from (a) from 5
to 100% by weight of monomers in the form of ethylenically
unsaturated acid anhydrides or ethylenically unsaturated

dicarboxylic acids whose carboxyl groups can form an anhydride,
and (b) from 0 to 95% by weight of monoethylenically
unsaturated monomers, with the proviso that the monomers (a)
and (b) have an average of at most 6 carbon atoms which are not
functionalized with oxygen-containing groups, and (B) an
alkanolamine having at least 2 OH groups, at most 2 nitrogen
atoms and at most 8 carbon atoms, where the weight ratio of
(A) : (B) is from 1 : 0.05 to 1 : 1. The catalytically active
constituent used in the catalytically active composition is
generally, as well as titanium dioxide in its anatase
modification, vanadium pentoxide. In addition to these main
constituents, a multitude of other oxidic compounds may be
present, which, as promoters, influence the activity and
selectivity of the catalyst. Examples of promoters include the
alkali metal oxides, thallium(I) oxide, aluminum oxide,
zirconium oxide, iron oxide, nickel oxide, cobalt oxide,
manganese oxide, tin oxide, silver oxide, copper oxide,
chromium oxide, molybdenum oxide, tungsten oxide, iridium
oxide, tantalium oxide, niobium oxide, arsenic oxide, antimony
oxide, cerium oxide and phosphorus pentoxide. Suspension of the
active composition is applied to the support by spraying. This
can be done, for example, in a coating drum or in a fluidized
bed coater. The examples do not describe any catalyst which
simultaneously possesses molybdenum and iron. Apart from the
organic binder, no further binder is used.
US 5,217,936 describes a catalyst for the preparation of
aldehydes from the corresponding alcohols, especially of
formaldehyde from methanol, wherein the catalytically active
composition is applied to a monolithic support. The active
composition may, as well as molybdenum oxide, also comprise
oxides of chromium, vanadium, aluminum, iron, tungsten,
manganese and mixtures thereof. In order to improve the binding
of the active composition to the monolithic support, the active
composition may comprise a binder. Suitable binders specified
are silicon dioxide and titanium dioxide. The use of organic
binders is not described.

EP 1 108 470 A1 describes supported catalysts which are
suitable for the gas phase oxidation of hydrocarbons. The
supported catalysts consist of an active composition which is
applied on an inert support body. The support body has the
shape of a ring in which one or more notches are introduced on
the upper and/or lower flat side of the ring.
WO 99/61433 describes a process for preparing phthalic
anhydride by catalytic gas phase oxidation of xylene or
naphthalene, where a reactor which comprises at least three
layers of a shell catalyst one on top of another, which have
increasing activity from the gas inlet side toward the gas
outlet side of the reactor, is used. The active composition is
formed from oxides of vanadium and of antimony, of phosphorus,
of the alkali metals and of titanium. The activity is adjusted
by the amount of the active composition applied to the support
bodies and by the content of alkaline metal in the active
composition. The catalyst is prepared by spraying an aqueous
suspension of the active composition onto inert support bodies,
for example in a coating drum or in a fluidized bed coater. In
order to reduce losses of active composition in the course of
coating, the suspension may comprise an organic polymer as a
binder. The use of inorganic binders is not described.
DE 10 2004 014 918 describes a catalyst comprising a silver-
vanadium oxide phase and a promoter phase based on titanium
dioxide and vanadium pentoxide, which is suitable for the
preparation of aldehydes, carboxylic acids and carboxylic
anhydrides from aromatic or heteroaromatic hydrocarbons by gas
phase oxidation. The catalyst is preferably configured as a
shell catalyst, the two phases being arranged as concentric
shells on an inert support. To prepare the shell catalyst, an
aqueous slurry of the active materials is sprayed onto the
support bodies with the aid of a coating drum or of a fluidized
bed coater. A binder can be added to the slurry. Suitable
binders specified are higher alcohols, DMF, cyclic ureas, etc.,
and polymeric binders such as vinyl acetate/vinyl laurate

copolymers. The use of inorganic binders is not described.
WO 2005/037427 describes a catalyst bed composed of a physical
mixture of catalytically active and catalytically inactive
shaped bodies, the catalytically inactive shaped bodies having
rounded edges on the outer friction surfaces. When the catalyst
bed is used for the oxidation of methanol to formaldehyde, the
catalytically active material used may, for example, be iron
molybdates.
EP 0 184 790 describes a shaped catalyst for heterogeneously
catalyzed reactions, which consists of an inert support
material shaped to hollow cylinders, on which a catalytically
active material is applied. The external diameter of the hollow
cylinder is from 3 to 20 mm and the internal diameter is from
0.1 to 0.7 times the external diameter. The end surface of the
hollow cylinder is curved such that the radius of curvature is
from 0.4 to 5 times the external diameter. The catalysts are
suitable especially for partial oxidations in the gas phase.
However, there is a demand for improved catalysts for oxidizing
methanol to formaldehyde, which, as well as a very good
abrasion resistance, also have a good activity and selectivity.
It was therefore an object of the present invention to provide
improved catalysts, especially for the oxidation of methanol to
formaldehyde, which have a particularly high abrasion
resistance and avoid the disadvantages of the prior art.
This object is achieved according to claim 1 by a shell
catalyst or coated catalyst, especially for oxidation of
methanol to formaldehyde, which, on an inert, preferably
essentially nonporous, support body, has at least one coating
which comprises, before the removal of the organic fractions of
components b) and c):
a) oxides, or precursor compounds convertible to the
corresponding oxides, of molybdenum and iron, where the
molar ratio of Mo:Fe is between 1:1 and 5:1, and

optionally further metallic components or metal oxide
components or precursor compounds convertible to the
corresponding oxides,
b) at least one organic binder, preferably an aqueous
dispersion of. copolymers, especially selected from vinyl
acetate/vinyl laurate, vinyl acetate/ethylene, vinyl
acetate/acrylate, vinyl acetate/maleate, styrene/acrylate
or mixtures thereof,
c) and at least one further component selected from the
group consisting of SiO2 sol or precursors thereof, Al2O3
sol or precursors thereof, ZrO2 sol or precursors thereof,
TiO2 sol or precursors thereof, waterglass, MgO, cement,
monomeric, oligomeric or polymeric silanes,
alkoxysilanes, aryloxysilanes, acryloyloxysilanes,
aminosilanes, siloxanes or silanols.
It has thus been found that, surprisingly, a coated catalyst or
shell catalyst in which the coating composition of the support
body, as well as the (catalytically) active composition
comprising oxides or precursor compounds of molybdenum and iron
which are convertible to the corresponding oxides (component
a)), comprises a combination of at least one organic binder
which is removed (burnt out) in the course of heat treatment or
calcination, and at least one further component selected from
the group of SiO2 sol and precursors thereof, A12O3 sol and
precursors thereof, ZrO2 sol and precursors thereof, TiO2 sol
and precursors thereof, waterglass, MgO, cement, monomeric,
oligomeric or polymeric silane, alkoxysilane, aryloxysilane,
acryloyloxysilane, aminosilane, siloxane or silanols exhibits a
particularly high abrasion resistance. At the same time, it has
been found that, unexpectedly, not only are the heat-untreated
inventive coated catalysts, i.e. those comprising the organic
parts of the coating composition, particularly abrasion-
resistant, but there is still a particularly high abrasion
resistance after the heat treatment or calcination of the
inventive catalysts, and a porosimetry particularly favorable

for the activity of the catalyst for the oxidation of methanol
to formaldehyde is provided. In this case, the (as yet heat-
untreated and uncalcined) catalyst in which the organic
fractions of components b) and c) are yet to be removed can
also be considered as a catalyst precursor or precursor
catalyst. In the finished catalyst, as used for oxidation of
methanol to formaldehyde, the organic fractions of components
b) and c) are then removed, especially by heat treatment or
calcination.
Stated in simplified terms, the coating in the inventive coated
catalysts, as well as the active composition (component a)),
also comprises at least two components active as adhesion
promoters. Of these, at least one component is an organic
binder (component b)) which can be removed in the course of
heat treatment and calcination of the catalyst. The second
component (component c)) has at least one inorganic fraction or
comprises a purely inorganic compound which, after the heat
treatment or calcination of the coated catalyst, can
advantageously form bridges between the oxidic constituents of
the active composition, i.e. the molybdenum- and/or iron-
containing oxides. The inorganic component or its inorganic
fraction, without the invention being restricted to the
correctness of the theoretical mechanism, apparently forms
bonds between the primary particles of the iron oxides and/or
molybdenum oxides, especially of the iron-molybdenum mixed
oxide or of the other catalytically active components (a)). The
organic compound b) and, where present, the organic fractions
of the component c) (see above), in close association with the
primary particles of the catalytically active component a), but
without impairing the bridging thereof by the adhesion-
promoting inorganic component or the inorganic fractions
thereof, enable the formation of pores and hence, in the
finished catalyst, the optimal access of the reactants to the
active sites. In a particularly preferred embodiment, the
component b) used is an organic binder from the group mentioned
above. The use of this organic binder has the advantage that

the coating operation can be accomplished in a fluidized bed
apparatus with a particularly low level of spray losses. In
addition, an advantageous pore structure forms at its removal.
According to the invention, the coated catalyst at first
comprises an inert support body. It is possible here in
principle to use all inert support bodies familiar to the
person skilled in the art. The support bodies should, however,
preferably be essentially nonporous and have a BET surface area
(determined to DIN 66131) of less about 1 m2/g. The pore volume
of the inert, essentially nonporous support body should
preferably be less than 0.1 ml/g, determined to DIN 66133. The
material density of the support bodies is preferably in the
range from 2.0 to 4.5 g/cm3, especially preferably from 2.3 to
3.5 g/cm3. Examples of suitable support bodies are those
composed of magnesium silicate (steatite), quartz (SiO2) ,
porcelain, magnesium oxide, tin oxide, silicon carbide, rutile,
alumina (Al2O3) , zirconium silicate, aluminum silicate, cerium
silicate, or of mixtures of these support materials. Particular
preference is given to steatite support bodies. It has been
found that carbide-containing or sintered iron oxide support
bodies provide poorer results.
In a preferred embodiment of the invention, the inert support
bodies used are hollow cylinders. In a further preferred
embodiment, the support body hollow cylinders used have one of
the following sizes (external diameter x height x internal
diameter):
6 x 5 x 3, 6 x 5 x 4 ,6 x 4 x 4, 6 x 4 x 3, 5 x 5 x 3,
4 x 4 x 2, 4 x 4 x 1.5, 5 x 4 x 3, 5 x 5 x 2.5, 5 x 3 x 3,
4 x 3 x 1.5, 4 x 3 x 2, 3 x 3 x 1.5, 3 x 4 x 1.5, in each case
in mm.
It has also been found that, surprisingly, particularly good
results can be obtained with the inventive catalyst in the
oxidation of methanol to formaldehyde when the support body

hollow cylinders have at least one, preferably exactly one,
central passage channel, and the end sides (exit sides of the
passage channel) have (only) edges flattened on the outside,
i.e. end surfaces which run at an acute angle (especially
10-90°C, more preferably 30-85°, even more preferably 40-80°)
relative to the axis of the passage channel; see fig. 1. It is
also possible to use shaped bodies according to EP 1 127 618 Al
or WO 2005/037427 Al.
The above-described preferred support bodies in the shape of a
cylinder with a passage channel and edges flattened on the
outside at the ends offer the following advantages:
1. In the course of loading of the reactor, the shaped bodies
do not as easily form locally ordered tight packings, but
rather are arranged more irregularly, in which case more
turbulences arise in the gas flow through the catalyst bed,
which counter any slight onset of overheating, especially in
the course of oxidation of methanol to formaldehyde. The
reduction of the overheating also leads to an extension of
the lifetime of the catalyst.
2. In the course of preparation of the catalyst in the
preferred fluidized bed coater, there is less fracture at
the edges than in the case of use of cylindrical bodies
without flattened edges.
3. In the course of filling of the catalyst, the support with
flattened edges fit together less than in the case of use of
cylindrical bodies without flattened edges. This is
especially true for the case that the value of reaction
diameter to catalyst diameter is between about 2 and 5. The
fitting together of the particles leads to filling gaps.
At least one layer (shell) of a coating composition which
initially comprises, as an active component a), at least one
molybdenum compound and at least one iron compound or at least
one Fe- and Mo-containing compound, where the molar ratio of
Mo:Fe is preferably between about 1:1 and 5:1, is applied to

the inert support body. Preference is given to using oxides of
molybdenum or iron and/or mixed oxides thereof (such as Fe2
(MoO4)3) or compounds which can be converted to the
corresponding oxides or mixed oxides, for example acetates,
oxalates, acetylacetonates, citrates, nitrates, chlorides,
phosphates, sulfates, or ammonium compounds of iron or of
molybdenum. In a particularly preferred embodiment of the
invention, an iron-molybdenum mixed oxide (Fe2(MoO4)3) is used as
the iron-containing compound, and MoO3 as the molybdenum-
containing compound. In addition, in the above component a) , it
is also optionally possible for further metallic components or
metal oxide components, or compounds which can be converted to
the corresponding oxides or mixed oxides, to be present, which
are familiar to the person skilled in the art with regard to
the use of the catalyst for oxidation of methanol to
formaldehyde. Nonrestrictive examples are the lanthanide metals
and oxides thereof. Preference is given to titanium, antimony,
tin, nickel, cerium, aluminum, calcium, magnesium, chromium,
vanadium, niobium, silver and/or manganese, which may also
partly replace Fe and Mo.
According to the invention, the coating of the inventive
catalyst (before the removal of the organic fractions)
comprises at least one organic binder (component b)). This
binder improves the abrasion resistance of the coating and
contributes to good adhesion of the coating on the inert
support body. In addition, when an organic binder as defined
herein is used, a particularly low spray loss and hence a
particularly high application yield in the course of coating of
the inert support bodies in the fluidized bed process
(fluidized bed coater) are also achieved. In addition, it
contributes to the formation of advantageous pores after the
removal of the organic fractions of the coating composition. It
has now been found that particularly advantageous results are
obtained with aqueous dispersions of copolymers, especially
vinyl acetate/vinyl laurate, vinyl acetate/ethylene, vinyl
acetate/acrylate, vinyl acetate/maleate, or styrene/acrylate as

organic binders. Such copolymers are familiar as such to those
skilled in the art, can be prepared by standard methods and are
commercially available. Suitable dispersions preferably have a
solids content in the range from 20 to 80% by weight,
preferably 40-60% by weight. Suitable binders include, for
example, binder dispersions in which the binder is a copolymer
of an alpha-olefin and of a vinyl C2-C4-carboxylate, whose vinyl
C2-C4-carboxylate content is at least 62 mol%, as specified, for
example, in WO 2005/011862.
In addition, the coating composition of the inventive coated
catalysts comprises at least one further component (c))
selected from the group consisting of SiO2 sol or precursors
thereof, Al2O3 sol or precursors thereof, ZrO2 sol or precursors
thereof, TiO2 sol or precursors thereof, waterglass, MgO,
cement, monomeric, oligomeric or polymeric silane,
alkoxysilane, aryloxysilane, acryloyloxysilane, aminosilane,
siloxane or silanols. These compounds are familiar as such to
those skilled in the art, can be prepared by standard methods
and are commercially available.
Among the particularly preferred components, mention should be
made here of the inorganic sols, especially TiO2 sols, cerium
oxide sols and ZrO2 sols, since particularly good abrasion
resistances and simultaneously high activities of the finished
catalysts have been obtained here in the oxidation of methanol
to formaldehyde.
According to the sol, the solids content is between 10 and 50%
by weight; for example, preference is given to SiO2 sols with
solids content 20 - 40% by weight, ZrO2 sols with solids content
10 - 20% by weight, CeO2 sols with solid content 15 - 25% by
weight and TiO2 sols with solids content 10 - 20% by weight.
TiO2 sols are particularly preferred.
It has been found that, unexpectedly, the above components b)
and c) cooperate in the generation of an optimal abrasion
resistance and porosimetry of the catalyst. As a result of the

adhesion promoter combination used in accordance with the
invention (combination of the at least one component b) and at
least one component c)), both adhesion and advantageous
application of the coating composition or of the active
material (component a)) on the shaped body, especially in the
preferred fluidized bed process, and an open-pore structure and
good adhesion of the active composition after the heat
treatment or calcination of the catalyst are provided.
In a preferred embodiment of the invention, the integral pore
volume (determined by Hg porosimetry, DIN 66133) is between
about 100 - 800 mmVg, preferably between about 200 and
700 mm3/g, more preferably between about 250 and 600 mm3/Vg. The
mean pore radius determined by this method is preferably
between about 50 and 1000 nm, preferably between about 100 and
700 run, more preferably between about 150 and 500 nm.
It has also been found that, surprisingly, the inventive heat-
untreated catalyst (precursor catalyst), i.e. before the
removal of the organic fractions of the coating composition,
has a greatly improved transport and filling stability. One
aspect of the present invention thus also relates to the use of
an inventive catalyst, before the removal of the organic
fractions of the coating composition (i.e. as a precursor
catalyst), for the transport from the production site of the
catalyst (or precursor catalyst) to the site of use of the
catalyst, especially in the oxidation of methanol to
formaldehyde. A further aspect relates to the use of such an
inventive catalyst before the removal of the organic fractions
of the coating composition (i.e. as a precursor catalyst) to
fill a reactor, especially for oxidation of methanol to
formaldehyde.
In a preferred embodiment of the invention, the component c)
used is at least one sol with a particle size of 1 to 100 nm,
preferably from 2 to 50 nm, more preferably particle sizes were determined to ASTM B822-97. Alternatively,

ISO 13320-1 can also be used.
More preferably, component c) has a smaller mean particle size
than component(s) a).
It is particularly preferred in this case that component c)
comprises a ZrO2 sol, a CeO2 sol, a TiO2 sol or a mixture of two
or all three of the above components. Moreover, it has been
found that, surprisingly, particularly good abrasion
resistances are obtained with a TiO2 sol which has been
stabilized with nitric acid or with citric acid. In addition,
good abrasion resistances have been found with a CeO2 sol
stabilized with acetic acid or a mixture of the TiO2 sol and the
CeO2 sol. It is particularly advantageous in this case when the
TiO2 sol is present in excess over the CeO2 sol. In addition,
good abrasion resistances have been found with a ZrO2 sol which
has been stabilized with acetate.
In addition to the sols provided in a solvent, it is also
possible to use so-called aerosols, i.e. metal oxides which are
provided as a solid with a very high specific surface area.
Such finely divided solids can be prepared, for example, by
flame hydrolysis, for example SiO2 by hydrolysis of SiCl4 in an
H2/O2 flame. By comparable processes, it is also possible to
prepare the other oxides mentioned above in finely divided
form. However, the use of sols provided in a solvent is
preferred, since the use of these sols leads to catalysts which
exhibit a particularly high abrasion resistance. Moreover, in
the case of use of sols in solvents, particularly low spray
losses are achieved in the coating of the support bodies.
In a preferred embodiment of the invention, the solids content
of component c) (i.e., for example, ZrO2 or TiO2) , after the
removal of the organic fractions of components b) and/or c),
especially after the calcination or heat treatment of the
catalyst (i.e. in the finished catalyst), is between about 0.01
and 30% by weight, preferably between 0.05 and 20% by weight,
more preferably between 0.1 and 10% by weight, based on the

catalytically active coating composition, i.e. the material of
the shell. The corresponding use amounts of component c) can
thus be determined easily by the person skilled in the art
according to the component c) and component a) used.
Moreover, it is preferred in accordance with the invention that
the solids content of component b) is between 5 and 30% by
weight, preferably between about 8 and 25% by weight, based on
the catalytically active coating composition, i.e. the material
of the shell. These data are of course based on the state
before the removal of the organic fractions of the coating
composition.
In a further preferred embodiment of the invention, the active
composition content (component (a) / (component (a) + inert
support)) is between about 3 and 60% by weight, preferably
between about 3 and 50% by weight, more preferably between
about 5 and 40% by weight, based on the mass of inert support
and catalytically active material. The geometries of the inert
support bodies typically used give rise to a thickness, which
is preferred in accordance with the invention, of the coating
on the inert support body between about 30 and 1000 μm,
preferably between about 100 and 700 μm.
In a preferred embodiment of the invention, in the inventive
catalyst, after the removal of the organic fractions of the
coating composition, the integral pore volume (to DIN 66133)
based on the active composition is more than about
0.15 ml/gactive composition, preferably more than 0.2 ml/gactive composition.
A further aspect of the present invention relates to a process
for preparing an inventive coated catalyst, especially for
oxidizing methanol to formaldehyde, comprising the following
steps:
a) providing an inert, preferably essentially nonporous,
support body,
b) preparing an aqueous suspension comprising components a),

b), c) as defined above,
c) applying the aqueous suspension of step b) to the inert
support body, preferably in a fluidized bed process.
In a first step, an inert, preferably essentially nonporous,
support body as described above is provided.
In addition, an aqueous suspension comprising components a),
b), c), as described above, is provided. In this context, it
has been found to be particularly advantageous in accordance
with the invention that all components a), b) and c) are
present in particle form, either suspended or dispersed, and
not in dissolved form. The solids content in the
suspension/dispersion is preferably between 5 and 40% by
weight, more preferably between 10 and 30% by weight.
In the process according to the invention, it is preferred that
the aqueous suspension provided is applied to the inert support
body by means of a fluidized bed process. Preference is given
to the use of a fluidized bed coater, as described, for
example, in DE-A-12 80 756, DE-A-197 09 589, DE 40 06 935 Al,
DE 103 44 845 Al or WO 2005/030388. It has been found in
accordance with the invention that the aqueous suspension
comprising the coating composition can be applied to the
nonporous support body by means of a fluidized bed process, as
detailed above, particularly uniformly and with good adhesion
and with unexpectedly low spray losses.
In addition, it has been found to be advantageous that the pH
of the suspension is matched to the stability range of
component b) and component c). It has been found that, for this
purpose, a pH of the suspension to be applied to the support
bodies of between about 1 and 5 is generally advantageous. It
has also been found that a pH of about 3 - 5 is advantageous in
the case of use of an acetate-stabilized ZrO2 sol, or a pH
between 1 and 5, preferably between 1 and 3, in the case of use
of a TiO2 sol stabilized with nitric acid. In the case of the
CeO2 sol stabilized with acetic acid, a pH of 2 - 4 is

particularly advantageous.
In addition, it has been found that particularly favorable
results are obtained when component a) is not heated to more
than 200°C, and is especially not heat treated or calcined,
before being applied to the inert support body.
However, it is possible in one embodiment to calcine the active
material (component a) before it is applied to the inert
support body, in order, for example, to adjust its activity.
However, preference is given to introducing the catalyst into
the reactor in a form in which the shell of the catalyst
comprises the uncalcined or low-calcination material and the
organic binder. The active material can then be calcined
simultaneously with the burning-off of the organic binder.
In a further preferred embodiment of the invention, the aqueous
suspension is applied to the inert support bodies in a
fluidized bed process at a temperature of less than 100°C,
especially at less than 80°C, more preferably less than 70°C.
The particles of components a), b) and c) in the aqueous
suspension preferably have a D90 value of the particle size of
less than 50 urn, preferably less than 30 μm. Adhering to this
particle size contributes to a particularly uniform and
abrasion-resistant coating on the inert support bodies and
leads to low spray losses during the coating operation. If
materials which have the above particle size are not used in
any case for components a), b) and c), this particle size can
be established by conventional grinding or comminition before,
during or after the preparation of the aqueous suspension.
In a further preferred embodiment, after the application of the
coating composition to the inert support body, the coated
support body is treated thermally. In general, any temperature
and duration for calcination or for heat treatment familiar to
the person skilled in the art can be used. In many cases, a
temperature between 200 and 600°C, especially 200 and 550°C,

will be advantageous. The duration of the calcination or of the
heat treatment will preferably be between 0.5 and 20 h,
especially between 1 and 15 h. In a preferred embodiment, the
coated support body will be introduced into a suitable heated
cabinet, for example a tray oven with metal sheets, which
contains the coated support bodies as a particle bed with a
preferred bed height of 1 - 5 cm, more preferably of 1 - 3 cm.
The heated cabinet is then preferably heated with a constant
rate within a period of from 1 h to 20 h, preferably from 5 h
to 15 h, from room temperature to a temperature T1 of
preferably between 130 and 350°C, especially preferably from
200 to 300°C. The heating rate for the above-described process
step is preferably selected within the range from 0.1 to 5°
C/min, more preferably from 0.2 to l°C/min. The temperature Tl
is then preferably kept constant for the duration of from 1 h
to 5 h. Subsequently, the temperature is heated at a preferably
constant rate, within a period of from 1 h to 10 h, preferably
from 1 h to 5 h, proceeding from the temperature Tl to an end
temperature T2 between 300 and 600°C, preferably from 350 to
550°C, more preferably from 400°C to 550°C. The heating rate
for the above-described process step is preferably selected
within the range from 0.1 to 10°C/min, more preferably from 2
to 5°C/min. The temperature T2 is maintained for a duration of
1 - 10 h, preferably of 2 - 5 h, and the heated cabinet is then
cooled. Preference is given to selecting a cooling rate of
1 - 10°C/min, more preferably of 2 - 8°C/min. During the
thermal treatment, it may be advantageous to flow air or a
mixture of air, nitrogen and optionally steam whose composition
varies with time through the gas space of the heated cabinet.
The organic binders preferred as component b) according to the
above description have the advantage that they, even at the
above relatively low coating temperatures in the fluidized bed
coater, contribute very efficiently to the adhesion and
abrasion resistance of the coating composition, and can
simultaneously be removed at the temperatures preferred for the
heating or calcination of the coated catalyst after the

application of the coating to the inert support body without
impairing the adhesion and abrasion resistance of the coating,
in order to contribute to an advantageous pore structure.
In a preferred embodiment of the invention, the above-described
heating after the application of the coating to the inert
support body is effected in an atmosphere of air, inert gas
and/or steam. When the heating is effected in the presence of
steam, preference is given to a steam content of more than
about 10% by volume, preferably between about 20 and 60% by
volume, of the atmosphere used.
If, as stated above, in a preferred aspect of the present
invention, the inventive coated catalyst before the removal of
the organic fractions of the coating composition is itself used
to fill the reactor, it has also been found in the context of
the present invention that the removal of the organic fractions
of the coating composition (by means of heating or heat
treatment or calcination of the catalyst) advantageously also
directly in the reactor itself, especially in an O2- and N2-
containing gas stream to which steam may optionally be added.
The conditions for the calcination or the removal of the
organic binder are preferably selected according to the
conditions already described for the treatment of the catalyst.
In a further preferred embodiment, the calcination can also
take place under the operating conditions envisaged for the
finished catalyst, such as the conditions of the envisaged
methanol oxidation to formaldehyde.
A further aspect of the invention relates to a catalyst
obtainable by the above process. Such catalysts are notable for
an increased abrasion resistance compared to prior art
catalysts. Moreover, by virtue of an advantageous porosimetry
after the removal of the organic fractions of the coating
composition, a high activity and formaldehyde selectivity,
especially in the oxidation of methanol, is ensured for the
catalysts.

A further aspect of the present invention thus relates to the
use of the above-described coated catalyst for oxidizing
methanol to formaldehyde, especially in a fixed bed process. A
suitable process is known, for example, from DE 103 61 517,
EP 0 001 570 and US 3,852,361. It is also possible to use other
processes familiar to those skilled in the art for preparing
formaldehyde. However, other applications of the catalyst,
especially in partial (gas phase) oxidations of hydrocarbons,
are not ruled out in principle.
The gas phase oxidation is itself carried out in the reactors
known for this reaction under customary conditions. Preference
is given to tubular reactors, in which case the tubes are
cooled for heat removal, for example, with a salt bath or a
thermally stable oil. The tubes preferably have a diameter in
the range from 15 to 30 mm, more preferably of 20 - 25 mm, and
a length in the range of preferably from 80 to 140 cm. The
inventive catalyst is filled into the tubes.
A further aspect of the invention relates to the use of a
combination of the above-described components b) and c) to
increase the abrasion resistance of a coated catalyst,
especially of a catalyst for the oxidation of methanol to
formaldehyde.
Figure 1 shows a cross section through a support body used with
preference in accordance with the invention, with edges
flattened on the outside at the ends. The acute angle a between
the axis of the central passage orifice and the end faces is in
each case about 60 degrees.
Definitions of terms:
a) Active composition content = mass of active composition
(component a)) / (mass of active composition (component
a)) + mass of support body)
b) Solids content of component b = mass of solid in the org.
binder (component b)) / (mass of solid in the org. binder

(Component b)) + mass of active composition (component a)))
c) Solids content of component c = mass of solid in component
c) / (mass of solid in component c) + mass of active
composition (component a)))
According to the invention, the following determination methods
were used:
1. Test for determining the adhesion of the active composition
(abrasion test):
The adhesion of the active composition was tested in an
instrument from ERWEKA, model: TAR 10. To this end, an amount
of 50 g of coated catalyst was rotated a total of 10 times at a
rotational speed of 75 revolutions/min ( = 10 rotations of the
drum). Thereafter, the abrasion was determined as the ratio of
the loose coating no longer bonded to the support body relative
to the total amount of coating applied.
2. BET surface area:
The determination was effected by the BET method to
DIN 66131; a publication of the BET method is also found in
J. Am. Chem. Soc. 60, 309 (1938).
3. Pore radius distribution:
The pore radius distribution was determined mercury
porosimetry to DIN 66133; maximum pressure: 2000 bar,
Porosimeter 4000 (from Porotec, Germany), according to the
manufacturer's instructions.
4. Determination of the particle sizes:
The particle sizes were determined by the laser diffraction
method with a Fritsch Particle Sizer Analysette 22 Economy
(from Fritsch, Germany) according to the manufacturer's
instructions, also with regard to the sample pretreatment:
the sample is homogenized in deionized water without addition
of assistants and treated with ultrasound for 5 minutes. The

D Values reported are based on the sample volume.
The invention is illustrated in detail with reference to the
nonrestrictive examples which follow:
Example 1 (inventive):
To prepare the inventive catalyst with an active composition
content (component a)) of 20% by weight, a solids content of an
organic binder (component b)) of 20% by weight and a solids
content of the inorganic adhesion-promoting component c)) of 1%
by weight, 700 g of steatite bodies (density 2.7 g/cm3) in the
form of hollow cylinders of dimensions 5 x 5 x 2.5 mm were
coated in a fluidized bed coater with a suspension which was
prepared as follows:
A glass vessel was initially charged with 1100 ml of
demineralized water. 184 g of the active composition powder
(mixture of Fe2(MoO4)3 and MoO3, prepared according to example 1
of EP 1 674 156 A1 (molar Mo : Fe ratio = 2.5)) are suspended
with stirring. For better homogenization, the suspension is
treated with an Ultra - Turrax® at level 6 for 3 min. With
stirring, 9.22 g of the ZrO2 sol (solids content 20%, acetate-
stabilized, from Nyacol, trade name: NYACOL® Zirconia (Acetate))
are added thereto. The pH of the suspension is adjusted to 4
with a 25% ammonia solution. To the suspension are added 92 g
of the organic binder (50% dispersion of water and vinyl
acetate/ethylene copolymer, Vinnapas® EP 65 W, from Wacker), and
the suspension is homogenized with stirring for one hour.
The coating composition thus obtained is applied to the
steatite bodies in a fluidized bed in the form of thin layers
at a temperature between 60 - 8 0°C. The layer thickness of the
catalytically active material on the outer wall of the hollow
cylinder was 300 urn.
At a temperature of 400°C or 500°C, a portion of the coated
catalyst was treated thermally under air for a period of

2 hours, in the course of which the organic fractions of the
coating composition (the organic binder) were removed. The
abrasion of the catalyst calcined at 400°C was 1.3% by weight;
the abrasion of the catalyst calcined at 500°C was 3.1% by
weight. The abrasion of the uncalcined catalyst was « 1%.
The integral pore volume measured by means of Hg porosimetry is
0.42 ml/g for the catalyst calcined at 400°C, and 0.37 ml/g for
the catalyst calcined at 500°C.
Example 2 (inventive):
To prepare the inventive catalyst with an active composition
content (component a)) of 20% by weight, a solids content of an
organic binder (component b)) of 20% by weight and a solids
content of the inorganic adhesion-promoting component c)) of
4.7% by weight, 700 g of steatite bodies (density 2.7 g/cm3) in
the form of hollow cylinders of dimensions 5 x 5 x 2.5 mm were
coated in a so-called fluidized bed coater with a suspension
which was prepared as follows:
A glass vessel was initially charged with 1100 ml of
demineralized water. 184 g of the active composition powder
(mixture of Fe2(MoO4)3 and MoO3, prepared according to example 1
of EP 1 674 156 A1 (molar (Mo : Fe ratio = 2.5)) are suspended
with stirring. For better homogenization, the suspension is
treated with an Ultra - Turrax® at level 6 for 3 min. With
stirring, 76 g of the TiO2 sol (solids content 12%, stabilized
with nitric acid, from Sachtleben, trade name: Hombikat™ XXS
100) are added thereto. The pH of the suspension was 2.2. To
the suspension are added 92 g of the organic binder (50%
dispersion of water and vinyl acetate/ethylene copolymer,
Vinnapas® EP 65 W, from Wacker), and the suspension is
homogenized with stirring for one hour.
The coating composition thus obtained is applied to the
steatite bodies in a fluidized bed in the form of thin layers
at a temperature between 60 - 80°C. The layer thickness of the

catalytically active material was 305 μm.
At a temperature of 400°C or 500°C, a portion of the coated
catalyst was treated thermally under air for a period of
2 hours, in the course of which the organic fractions of the
coating composition (the organic binder) were removed. The
abrasion of the catalyst calcined at 400°C was 2.7% by weight;
the abrasion of the catalyst calcined at 500°C was 5.3% by
weight. The abrasion of the uncalcined catalyst was « 1%.
The integral pore volume measured by means of Hg porosimetry is
0.44 ml/g for the catalyst calcined at 400°C, and 0.38 ml/g for
the catalyst calcined at 500°C.
Example 3 (inventive):
To prepare the inventive catalyst with an active composition
content (component a)) of 26% by weight, a solids content of an
organic binder (component b)) of 20% by weight and a solids
content of the inorganic adhesion-promoting component c)) of
4.7% by weight, 700 g of steatite bodies (density 2.7 g/cm3) in
the form of hollow cylinders of dimensions 5 x 5 x 2.5 mm were
coated in a fluidized bed coater with a suspension which was
prepared as follows:
A glass vessel was initially charged with 1100 ml of
demineralized water. 245 g of the active composition powder
(mixture of Fe2(MoO4)3 and MoO3, prepared according to example 1
of EP 1 674 156 A1 (molar (Mo : Fe ratio = 2.5)) are suspended
with stirring. For better homogenization, the suspension is
treated with an Ultra - Turrax® at level 6 for 3 min. With
stirring, 46 g of the cerium oxide sol (solids content 20%, 3%
acetic acid) are added thereto. The pH of the suspension is
adjusted to 4 with a 25% ammonia solution. To the suspension
are added 122 g of the organic binder (50% dispersion of water
and vinyl acetate/ethylene copolymer, Vinnapas® EP 65 W, from
Wacker), and the suspension is homogenized with stirring for
one hour.

The coating composition thus obtained is applied to the
steatite bodies in a fluidized bed in the form of thin layers
at a temperature between 60 - 80°C. The layer thickness of the
catalytically active material was 424 urn.
At a temperature of 400°C or 500°C, a portion of the coated
catalyst was treated thermally under air for a period of
2 hours, in the course of which the organic fractions of the
coating composition (the organic binder) were removed. The
abrasion of the catalyst calcined at 400°C was 0.7% by weight;
the abrasion of the catalyst calcined at 500°C was 1.3% by
weight. The abrasion of the uncalcined catalyst was « 1%.
The integral pore volume measured by means of Hg porosimetry is
0.41 ml/g for the catalyst calcined at 400°C, and 0.37 ml/g for
the catalyst calcined at 500°C.
Example 4 (inventive):
To prepare the inventive catalyst with an active composition
content (component a)) of 20% by weight, a solids content of an
organic binder (component b)) of 20% by weight and a solids
content of the inorganic adhesion-promoting component c)) of
4.7% by weight, 700 g of steatite bodies (density 2.7 g/cm3) in
the form of hollow cylinders of dimensions 5 x 5 x 2.5 mm were
coated in a fluidized bed coater with a suspension which was
prepared as follows:
A glass vessel was initially charged with 1100 ml of
demineralized water. 184 g of the active composition powder
(mixture of Fe2(MoO4)3 and MoO3, prepared according to example 1
of EP 1 674 156 A1 (molar (Mo : Fe ratio = 2.5)) are suspended
with stirring. For better homogenization, the suspension is
treated with an Ultra - Turrax® at level 6 for 3 min. With
stirring, 46 g of the SiO2 sol (GRACE Davidson, solids content
30%, trade name: Ludox® AS-30) are added thereto. The pH of the
suspension is adjusted to 4 with a 25% ammonia solution. To the
suspension are added 92 g of the organic binder (50% dispersion

of water and vinyl acetate/ethylene copolymer, Vinnapas® EP 65
W, from Wacker), and the suspension is homogenized with
stirring for one hour.
The coating composition thus obtained is applied to the
steatite bodies in a fluidized bed in the form of thin layers
at a temperature between 60 - 80°C. The layer thickness of the
catalytically active material was 300 μm.
At a temperature of 400°C or 500°C, a portion of the coated
catalyst was treated thermally under air for a period of
2 hours, in the course of which the organic fractions of the
coating composition (the organic binder) were removed. The
abrasion of the catalyst calcined at 400°C was 2.7% by weight;
the abrasion of the catalyst calcined at 500°C was 4.2% by
weight. The abrasion of the uncalcined catalyst was « 1%.
The integral pore volume measured by means of Hg porosimetry is
0.39 ml/g for the catalyst calcined at 400°C, and 0.35 ml/g for
the catalyst calcined at 500°C.
Example 5 (comparative):
To prepare the comparative catalyst with an active composition
content (component a)) of 21% by weight and a solids content of
the organic binder (component b)) of 20% by weight, 700 g of
steatite bodies (density 2.7 g/cm3) in the form of hollow
cylinders of dimensions 5 x 5 x 2.5 mm were coated in a
fluidized bed coater with a suspension which was prepared as
follows:
A glass vessel was initially charged with 1100 ml of
demineralized water. 184 g of the active composition powder
(mixture of Fe2(MoO4)3 and MoO3, prepared according to example 1
of EP 1 674 156 A1 (molar (Mo : Fe ratio = 2.5)) are suspended
with stirring. For better homogenization, the suspension is
treated with an Ultra - Turrax® at level 6 for 3 min. The pH of
the suspension is adjusted to 4 with a 25% ammonia solution. To

the suspension are added 92 g of the organic binder (50%
dispersion of water and vinyl acetate/ethylene copolymer,
Vinnapas® EP 65 W, from Wacker), and the suspension is
homogenized with stirring for one hour.
The coating composition thus obtained is applied to the
steatite bodies in a fluidized bed in the form of thin layers
at a temperature between 60 - 80°C. The layer thickness of the
catalytically active material was 312 urn.
At a temperature of 400°C or 500°C, a portion of the coated
catalyst was treated thermally for a period of 2 hours, in the
course of which the organic binder was removed. The abrasion of
the catalyst calcined at 400°C was 37.9% by weight; the
abrasion of the catalyst calcined at 500°C was 38.3% by weight.
The abrasion of the uncalcined catalyst was somewhat below 1%
and significantly higher than in the case of the above
inventive catalyst.
The integral pore volume measured by means of Hg porosimetry is
0.46 ml/g for the catalyst calcined at 400°C, and 0.42 ml/g for
the catalyst calcined at 500°C.

AMENDED CLAIMS
1. A coated catalyst, especially for oxidation of
methanol to formaldehyde, which, on an inert,
preferably essentially nonporous, support body, has at
least one coating which comprises, before the removal
of the organic fractions of components b) and c):
a) oxides, or precursor compounds convertible to the
corresponding oxides, of molybdenum and iron, where
the molar ratio of Mo:Fe is between 1:1 and 5:1, and
optionally further metallic components or metal
oxide components or precursor compounds convertible
to the corresponding oxides,
b) at least one organic binder,
c) and at least one further component selected from the
group consisting of SiO2 sol or precursors thereof,
Al2O3 sol or precursors thereof, ZrO2 sol or
precursors thereof, TiO2 sol or precursors thereof,
waterglass, MgO, cement, monomeric, oligomeric or
polymeric silanes, alkoxysilanes, aryloxysilanes,
acryloyloxysilanes, aminosilanes, siloxanes or
silanols.
2. The coated catalyst as claimed in claim 1, wherein the
organic binder is an aqueous dispersion of copolymers,
especially selected from vinyl acetate/vinyl laurate,
vinyl acetate/ethylene, vinyl acetate/acrylate, vinyl
acetate/maleate, styrene/acrylate or mixtures thereof,

3. The coated catalyst as claimed in either of the
preceding claims, characterized in that molybdenum and
iron are present in the form of oxides, mixed oxides
or a mixture of mixed oxide and the pure oxides.
4. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the component
c) used is at least one sol with a particle size of
from 1 to 100 nm, preferably from 2 to 50 run, more
preferably 3-40 nm.
5. The coated catalyst as claimed in any one of the
preceding claims, characterized in that component c)
comprises TiO2 sol or ZrO2 sol or CeO2 sol or a mixture
of two or all three components mentioned.
6. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the ZrO2 sol
is acetate-stabilized.
7. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the TiO2 sol
is stabilized either with nitric acid or citric acid.
8. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the CeO2 sol
is stabilized with acetic acid.
9. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the solids
content of component c) after removal of the organic
fractions of components b) and c) and based on the
catalytically active coating composition is between
0.01 and 30% by weight, preferably between 0.05 and
20% by weight, more preferably between 0.1 and 10% by

weight.
10. The coated catalyst as claimed in any one of the
preceding claims, characterized that the solids
content of component b) based on the catalytically
active coating compositioin and based on the state
before the removal of the organic fractions of the
coating composition is between 5 and 30% by weight,
preferably between 8 and 25% by weight.
11. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the inert
support bodies used are hollow cylinders.
12. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the hollow
cylinders used have one of the following sizes
(external diameter x height x internal diameter):
6 x 5 x 3, 6 x 5 x 4, 6 x 4 x 4, 6 x 4 x 3 , 5 x 5 x 3,
4 x 4 x 2, 4 x 4 x 1.5, 5 x 4 x 3, 5 x 5 x 2.5, 5 x 3
x 3, 4 x 3 x 1.5, 4 x 3 x 2, 3 x 3 x 1.5, 3 x 4 x 1.5,
in each case in mm.
13. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the inert
support body is a cylinder with a passage channel and
edges flattened on the outside at the ends.
14. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the active
composition content is between about 3 and 60% by
weight, preferably between about 3 and 50% by weight,
more preferably between about 5 and 40% by weight.
15. The coated catalyst as claimed in any one of the

preceding claims, characterized in that the thickness
of the coating on the inert support is between about
30 and 1000 μm, preferably between about 100 and 700
μm.
16. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the inert
support body has a porosity of less than 0.1 ml/g and
preferably has a BET surface area of less than 1 m2/g.
17. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the further
metallic components or metal oxide components of
component a) are selected from the group of the
lanthanides and their oxides.
18. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the further
metallic components or metal oxide components of
component a) are selected from titanium, antimony,
tin, nickel, chromium, aluminum, calcium, magnesium,
vanadium, niobium, silver and/or manganese.
19. The coated catalyst as claimed in any one of the
preceding claims, characterized in that the integral
pore volume of the coating, after removal of the
organic fractions of components b) and c), is greater
than 0.2 ml/g, especially greater than 0.25 ml/g.
20. A process for preparing a coated catalyst as claimed
in any one of the preceding claims, especially for
oxidizing methanol to formaldehyde, comprising the
following steps:
a) providing an inert, preferably essentially
nonporous, support body,

b)preparing an aqueous suspension comprising
components a), b), c) as defined in the preceding
claims,
c)applying the aqueous suspension of step b) to the
inert support body in a fluidized bed process.
21. The process as claimed in claim 19, characterized in
that the application of the coating in a fluidized bed
process is carried out at less than 100°C, preferably
at less than 80°C, especially at less than 70°C.
22. The process as claimed in any one of the preceding
claims, characterized in that components a) and b),
preferably components a), b) and c), are present in
the aqueous suspension according to step b) of claim
15 in the form of a suspension or dispersion and not
in dissolved form.
23. The process as claimed in any one of the preceding
claims, characterized in that the pH of the aqueous
suspension according to step b) of claim 20, when an
acetate-stabilized ZrO2 sol is used, is between about
3 and 5.
24. The process as claimed in any one of the preceding
claims, characterized in that the pH of the aqueous
suspension according to step b) of claim 20, when a
nitric acid-stabilized TiO2 sol is used, is between
about 1 and 3.
25. The process as claimed in any one of the preceding
claims, characterized in that the pH of the aqueous
suspension according to step b) of claim 20, when an
acetic acid-stabilized CeO2 sol is used, is between
about 2 and 4.

26. The process as claimed in any one of the preceding
claims, characterized in that component a) is not
heated to more than 200°C, and is especially not heat
treated or calcined, before being applied to the inert
support body.
27. The process as claimed in any one of the preceding
claims, characterized in that the aqueous suspension
has a particle size (d90) of less than 50 urn,
preferably less than 30 urn.
28. The process as claimed in any one of the preceding
claims, characterized in that the particle sizes of
components a), b) and c) are established by a grinding
operation before, during or after preparation of the
aqueous suspension.
29. The process as claimed in any one of the preceding
claims, characterized in that the coated catalyst is
heated to a temperature between about 150 and 600°C,
preferably between 200 and 550°C, more preferably
between 250 and 500°C, after being applied to the
inert support body.
30. The process as claimed in any one of the preceding
claims, characterized in that the heating is effected
in an atmosphere of air, inert gas and/or steam.
31. The process as claimed in any one of the preceding
claims, characterized in that the heating is effected
as a calcination at a temperature between about 350
and 450°C, preferably at about 400°C.
32. The process as claimed in any one of the preceding
claims, characterized in that the heating rate in the
course of heating or calcination is between 0.1 and

10°C/min.
33. The process as claimed in any one of the preceding
claims, characterized in that the steam content in the
course of heating or calcination is more than 10% by
volume, preferably between 20 and 60% by volume of the
atmosphere used.
34. The process as claimed in any one of the preceding
claims, characterized in that the heating or
calcination takes place directly within the reactor in
an O2/N2 gas stream or under the operating conditions
envisaged for the coated catalyst.
35. The use of a catalyst as claimed in any one of claims
1 to 18 for oxidizing methanol to formaldehyde,
especially in a fixed bed.

The invention
relates to coated catalyst, in
particular for oxidation of methanol
to formaldehyde, which has at
least one coating on an inert,
preferably essentially nonporous,
support body, which coating, before
removal of the organic fractions
of the components b) and c)
contains: (a) oxides or precursor
compounds which can be converted
into the corresponding oxides of
molybdenum and iron, wherein the
molar ratio of Mo:Fe is between
1:1 and 5:1, and also if appropriate
further metallic or metal-oxide
components or precursor
compounds which can be converted
into the corresponding oxides,
(b) at least one organic binder,
preferably an aqueous dispersion
of copolymers, in particular
selected from vinyl acetate/vinyl
laurate, vinyl acetate/ethylene,
vinyl acetate/acrylate, vinyl
acetate/maleate, styrene/acrylate
or mixtures thereof, and (c) at least
one further component selected
from the group consisting of SiO2 sol or precursors thereof, Al2O3 sol or precursors thereof, ZrO2 sol or precursors thereof, TiO2
sol or precursors thereof, water glass, MgO, cement, monomeric, oligomeric or polymeric silanes, alkoxysilanes, aryloxysilanes,
acryloxysilanes, aminosilanes, siloxanes or silanols. A method for producing the catalyst and its preferred use are also described.

Documents:

01421-kolnp-2008-abstract.pdf

01421-kolnp-2008-claims.pdf

01421-kolnp-2008-correspondence others.pdf

01421-kolnp-2008-description complete.pdf

01421-kolnp-2008-drawings.pdf

01421-kolnp-2008-form 1.pdf

01421-kolnp-2008-form 3.pdf

01421-kolnp-2008-form 5.pdf

01421-kolnp-2008-gpa.pdf

01421-kolnp-2008-international exm report.pdf

01421-kolnp-2008-international publication.pdf

01421-kolnp-2008-international search report.pdf

01421-kolnp-2008-pct priority document notification.pdf

01421-kolnp-2008-pct request form.pdf

1421-KOLNP-2008-(14-02-2012)-CORRESPONDENCE.pdf

1421-KOLNP-2008-(23-11-2011)-CORRESPONDENCE.pdf

1421-kolnp-2008-abstract.pdf

1421-kolnp-2008-amanded claims.pdf

1421-KOLNP-2008-ASSIGNMENT.pdf

1421-KOLNP-2008-CORRESPONDENCE 1.1.pdf

1421-KOLNP-2008-CORRESPONDENCE-1.2.PDF

1421-kolnp-2008-description (complete).pdf

1421-kolnp-2008-drawings.pdf

1421-kolnp-2008-english translation.pdf

1421-KOLNP-2008-EXAMINATION REPORT REPLY RECIEVED.pdf

1421-kolnp-2008-form 1.pdf

1421-kolnp-2008-form 18.pdf

1421-kolnp-2008-form 2.pdf

1421-KOLNP-2008-FORM 3 1.1.pdf

1421-KOLNP-2008-FORM 3-1.2.pdf

1421-kolnp-2008-form 3.pdf

1421-KOLNP-2008-OTHERS.pdf

1421-KOLNP-2008-PETITION UNDER RULE 137.pdf

1421-kolnp-2008-reply to examination report.pdf

abstract-1421-kolnp-2008.jpg


Patent Number 255184
Indian Patent Application Number 1421/KOLNP/2008
PG Journal Number 05/2013
Publication Date 01-Feb-2013
Grant Date 31-Jan-2013
Date of Filing 08-Apr-2008
Name of Patentee SUD-CHEMIE AG
Applicant Address LENBACHPLATZ 6, D-80333 MUNCHEN
Inventors:
# Inventor's Name Inventor's Address
1 GUCKEL, CHRISTIAN 10B FORSYTHIA LANE, 07652 PARAMUS, NEW JERSEY
2 ESTENFELDER, MARVIN C/O FAM. MEIβNER, ELFENWEG 24, D-76199 KARLSRUHE
3 FISCHER, CLAUDIA OLYMPIASTR. 16, D-85622 FELDKIRCHEN
4 DURR, UWE OSTLICHE WALDRINGSTR. 3C, D-90765 FURTH
5 WANNINGER, KLAUS AM EGLSEE 2, D-83059 KOLBERMOOR
PCT International Classification Number B01J 23/881
PCT International Application Number PCT/EP2006/011256
PCT International Filing date 2006-11-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05025497.8 2005-11-23 Germany
2 102005055827.5 2005-11-23 Germany