Title of Invention

CATALYST AND METHOD FOR PRODUCING PHTHALIC ANHYDRIDE

Abstract The present invention relates to a catalyst, in particular for the preparation of phthalic anhydride by gas phase oxidation of o-xylene and/or naphthalene, having an inert support and at least one layer which has been applied thereto and has a catalytically active composition comprising TiO2, characterized in that at least a portion of the TiO2 used has the following properties: (a) the BET surface area is more than 15 m2/g, (b) the primary crystal size is more than 210 ångstrøm. Also described is a preferred process for preparing such a catalyst, and the preferred use of the titanium dioxide used in accordance with the invention.
Full Text CATALYST AND METHOD FOR PREPARING PHTHALIC
ANHYDRIDE
DESCRIPTION
The invention relates to a catalyst, in particular for the
preparation of phthalic anhydride (PA) by gas phase oxidation
of o-xylene and/or naphthalene, the catalytically active
composition of the catalyst comprising titanium dioxide
having particular properties.
The industrial-scale preparation of phthalic anhydride is
achieved by the catalytic gas phase oxidation of o-xylene and/or
naphthalene. For this purpose, a catalyst suitable for the
reaction is charged into a reactor, preferably what is known as
a tube bundle reactor in which a multitude of tubes are arranged
in parallel, and flowed through from the top or bottom with a
mixture of the hydrocarbon(s) and an oxygenous gas, for example
air. Owing to the intense heat formation of such oxidation
reactions, it is necessary for a heat carrier medium to flow
around the reaction tubes to prevent what are known as hotspots,
and thus to remove the amount of heat formed. This energy can be

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utilized for the production of steam. The heat carrier medium
used is generally a salt melt and here preferably a eutectic
mixture of NaNO2 and KNO3.
To suppress the unwanted hotspots, it is likewise possible to
charge a structured catalyst into the reaction tube, which
can give rise, for example, to two or three catalyst zones
composed of catalysts of different composition. Such systems
are already known as such from EP 1 082 317 B1 or EP 1 084
115 B1.
The layer-by-layer arrangement of the catalysts also has the
purpose of keeping the content of undesired by-products, i.e.
compounds which are before the actual product of value in a
possible reaction mechanism from o-xylene and/or naphthalene
to phthalic anhydride, in the crude PA as low as possible.
These undesired by-products include mainly the compounds
o-tolylaldehyde and phthalide. The further oxidation of these
compounds to phthalic anhydride additionally increases the
selectivity with regard to the actual product of value.
In addition to the above-addressed under-oxidation products,
over-oxidation products also occur in the reaction. These
include maleic anhydride, citraconic anhydride, benzoic acid
and the carbon oxides. Selective suppression of the formation
of these undesired by-products in favour of the product of
value leads to a further rise in the productivity and
economic viability of the catalyst.
There is constant need for catalysts which enable an increase
in productivity and economic viability.
It is therefore an object of the present invention to develop
a catalyst or a catalyst system which avoids the
disadvantages of known catalysts from the prior art and

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enables an improvement in the activity, selectivity and/or
lifetime of the catalyst.
A first aspect of the invention therefore relates to a
catalyst, in particular for the preparation of phthalic
anhydride by gas phase oxidation of o-xylene and/or naphthalene,
having an inert support and at least one layer which has been
applied thereto and has a catalytically active composition
comprising TiO2, characterized in that at least a portion of the
TiO2 used has the following properties: (a) the BET surface area
is more than 15 m2/g, (b) the primary crystal size is preferably
more than 210 ångstrøm. Preferred embodiments are specified in
the subclaims.
It is assumed, without any restriction of the invention to
the correctness of this theoretical assumption, that the use
of the titanium dioxide having the properties described here
in a catalyst can result in particularly advantageous
reaction spaces being achieved for the desired reactions, in
particular within the pore structure. At the same time, when
the inventive Ti02 matrix is used, advantageous access routes
for the reactants to the reactive sites on the surface of the
Ti02 matrix, and also escape routes for the reaction products,
are provided.
An essential feature of the present invention is the use of a
specific titanium dioxide which is notable for a
comparatively high BET surface area of more than 15 m2/g, in
particular between about 15 and 60 m /g.
In a further preferred aspect of the present invention, Ti02
is used which has a primary crystal size (primary particle
size) of more than about 210 ångstrøm, preferably more than
about 250 ångstrøm, more preferably more than about
300 ångstrøm, further preferred at least 320 ångstrøm, in

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particular at least about 340 ångstrøm, further preferred at
least about 380 ångstrøm. Thus, it has been found that those
TiO2 primary crystals having the aforementioned (minimum) size
enable the preparation of particularly advantageous
catalysts. The primary crystal size is preferably below
900 ångstrøm, in particular below 600 ångstrøm, further
preferred below 500 ångstrøm. The aforementioned crystal size
apparently enables, without a restriction of the invention to
this assumption, the formation of a not excessively compact,
but rather open-pored structure of the titanium dioxide in
the catalyst. One process for determining the primary crystal
size is specified in the method section which follows. In a
further aspect of the invention, it has also been found that
the compliance with the aforementioned primary crystal size
is specified in the method section which follows, in a
further aspect of the invention, it has also been found that
the compliance with the aforementioned primary crystal size
in at least a portion of the titanium dioxide used for the
catalyst preparation in itself (i.e. without compliance with
the aforementioned pore radius distribution) already provides
surprisingly good results, even though the simultaneous
compliance with the above-defined pore radius distribution is
preferred in accordance with the invention.
In a preferred aspect of the present invention, it has been
found that, surprisingly, when titanium dioxide in which at
least 25%, in particular at least about 40%, more preferably
at least about 50%, most preferably at least about 60%, of
the total pore volume is formed by pores having a radius
between 60 and 400 nm is used, particularly advantageous
catalysts can be obtained.
In a further aspect of the present invention, TiO2 is used
which has a bulk density of less than 1.0 g/ml, in particular

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less than 0.8 g/ml, more preferably less than about 0.6 g/ml.
Most preferred are TiO2 materials having a bulk density of not
more than about 0.55 g/ml. One process for determining the
bulk density is specified in the method section which
follows. It has thus been found that the use of titanium
dioxide having a bulk density as defined above enables the
preparation of particularly high-performance catalysts. It is
assumed, without a restriction of the invention thereto, that
the bulk density here is a measure of a particularly
favourable structure of the TiO2 surface made available in the
catalyst, and the loose, not excessively compact structure
provides particularly favourable reaction spaces and access
and escape routes for the reactants and reaction products
respectively. In a particularly preferred inventive
embodiment, the titanium dioxide used will thus, in addition
to the pore radius distribution and primary crystal size
described herein, also have the bulk density defined herein.
In a further aspect of the invention, it has, however, also
been found that a material which, irrespective of the pore
radius distribution described herein and the primary crystal
size, complies with the above-defined bulk density
unexpectedly already has better results than comparative
materials having a higher bulk density.
In yet a further aspect of the present invention, the primary
crystals of the titanium dioxide used are at least partly
combined to form agglomerates which can be recognized
readily, for example, in electron micrographs. When they are
open-pored, in particular "sponge-like", agglomerates, the
preferred, not excessively compact, porous structure of the
titanium dioxide is favoured. In a preferred inventive
embodiment, the primary crystals of the TiO2 are combined to
an extent of more than 30%, in particular more than 50%, to
form agglomerates, in particular open-pored agglomerates.

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Preferably, the TiO2 used (anatase modification) (in all
layers of the catalyst) has an alkali content, especially of
Na, of less than 0.3% by weight, in particular less than 0.2%
by weight, preferably less than 0.15% by weight, further
preferred less than 0.02% by weight, further preferred less
than 0.015% by weight. Preferably, the above threshold values
apply for both Na and K. In a further preferred aspect of the
invention, the fraction of alkali impurities (total alkali
content) of the TiO2 used, determined as sum of impurities of
lithium, sodium, potassium, rubidium and cesium, is less than
1.000 ppm, in particular less than 500 ppm, especially
preferred less than 300 ppm. A method for determination of
the fraction of alkali impurities is given below, prior to
the examples (DIN ISO 9964-3). The aforementioned total
alkali content of the TiO2 enables an exact adjustment of the
alkali promoter content of the catalyst.
The fraction of alkali impurities may, as known to the
expert, optionally be lowered by washing, e.g. with diluted
nitric acid at raised temperature, in order to achieve the
preferred range of less than 1.000 ppm. For example, the TiO2
may be suspended in 0.1 M HNO3 and washed over night with
agitation under reflux, subsequently filtered and washed
three times with bidestilled water and dried at 150°C in air.
Subsequently, the content of alkali impurities is again
determined, and, if too high, the aforementioned procedure is
repeated.
In a particularly preferred embodiment of the present
invention, the TiO2-containing catalyst is used for the gas
phase oxidation of hydrocarbons. Especially preferred is use
for preparing phthalic anhydride by gas phase oxidation of
o-xylene, naphthalene or mixtures thereof. However, a
multitude of other catalytic gas phase oxidations of aromatic

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hydrocarbons such as benzene, xylenes, naphthalene, toluene
or durene for the preparation of carboxylic acids and/or
carboxylic anhydrides are also known in the prior art. These
afford, for example, benzoic acid, maleic anhydride, phthalic
anhydride, isophthalic acid, terephthalic acid or
pyromellitic anhydride. It is also possible in such reactions
to use the inventive catalyst.
In general, in the reaction, a mixture of a molecular oxygen-
containing gas, for example air, and the starting material to
be oxidized is passed through a fixed bed reactor, in
particular a tube bundle reactor, which can consist of a
multitude of tubes arranged in parallel. In the reactor tubes
is disposed in each case a bed composed of at least one
catalyst. The preferences for a bed composed of a plurality
of (different) catalyst zones have already been addressed
above.
When the inventive catalysts are used for the preparation of
phthalic anhydride by gas phase oxidation of o-xylene and/or
naphthalene, it has been found that, surprisingly, the
inventive catalysts afford a high activity with
simultaneously low formation of the undesired by-products COX,
i.e. CO2 and CO. In addition, a very good C8 and PA
selectivity is found, as the result of which the productivity
of the catalyst is increased. In many cases, the high C8
selectivity and the low COX selectivity of the inventive
catalysts in particular will also be of interest. The low COX
selectivity also results in an advantageous manner in lower
heat evolution and also lower hotspot temperatures. This
results in there being slower deactivation of the catalyst in
the hotspot region.

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In a preferred inventive embodiment, the TiO2 used has a BET
surface area (DIN 66131) between about 15 and 45 m2/g, in
particular between about 15 and 30 m2/g.
It is further preferred that up to 80%, in particular up to
75%, more preferably up to 70%, of the total pore volume is
formed by pores having a radius between 60 and 400 nm.
The pore volumes and fractions specified herein are
determined, unless stated otherwise, by means of mercury
porosimetry (to DIN 66133). The total pore volume stated
relates in the present description in each case to the total
pore volume, measured by means of mercury porosimetry,
between 7500 and 3.7 nm pore radius size.
Pores having a radius of more than 400 nm constitute
preferably fewer than about 30%, in particular fewer than
about 22%, more preferably fewer than 20%, of the total pore
volume of the Ti02 used.
It is further preferred that about 50 to 75%, in particular
about 50 to 70%, more preferably about 50 to 65%, of the
total pore volume of the T1O2 is formed by pores having a
radius of 60 to 400 nm, and preferably about 15 to 25% of the
total pore volume is formed by pores having a radius of more
than 400 nm.
With regard to the smaller pore radii, it is preferred that
less than 30%, in particular less than 20%, of the total pore
volume of the titanium dioxide is formed by pores having a
radius of 3.7 to 60 nm. For this pore size, a range which is
particularly preferred here is about 10 to 30% of the total
pore volume, in particular 12 to 20%.

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In a further preferred embodiment, the TiO2 used has the
following particle size distribution: the D10 value is
preferably 0.5 urn or lower; the D50 value (i.e. the value at
which in each case half of the particles have a greater and
smaller particle diameter) is preferably 1.5 μm or below; the
D90 value is preferably 4 urn or below. The D90 value of the
TiO2 used is preferably between about 0.5 and 20 μm, in
particular between about 1 and 10 urn, more preferably between
about 2 and 5 μm. The titanium dioxide is preferably in the
anatase form.
TiO2 materials which are useful according to the invention are
commercially available, e.g. under the tradename NT22-B20 and
NT22-B30 by Nano Inc., Ltd., 1108-1 Bongkok Sabong, Jinju,
Kyoungnam 660-882, Korea).
The skilled person also is aware that the primary crystal
size of TiO2 may be enlarged by heating or calcining. For
example, calcination in a rotary furnace at about 600°C for
24 to 48h in a mixture of 50% water vapour and 50% air may be
carried out to enlarge the primary crystal size. If the
primary crystal size according to the invention has not been
reached, the procedure may be repeated. As, in parallel, the
BET surface may drop, a Ti02 material with relatively high BET
surface should be used as starting material, so that finally
a BET surface of more than 15 m2/g is provided.
Depending on the intended use of the inventive catalyst, the
components which are familiar and customary to those skilled
in the art may be present in addition to the Ti02 used in
accordance with the invention in the active composition of
the catalyst. In one possible inventive embodiment, it is
also possible for only a portion of the titanium dioxide used
for the catalyst preparation to have the properties described
herein, although this is generally not preferred. The shape

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of the catalyst and its homogeneous or heterogeneous
structure is also in principle not restricted in the context
of the present invention and may include any embodiment which
is familiar to those skilled in the art and appears to be
suitable for the particular field of application.
When the inventive catalyst is used, in a particularly
preferred embodiment, for the preparation of phthalic
anhydride, useful catalysts have been found to be what are
known as coated catalysts. In these catalysts, a support
which is inert under the reaction conditions, for example
composed of quartz (SiO2) , porcelain, magnesium oxide, tin
dioxide, silicon carbide, rutile, clay earth (Al2O3),
aluminium silicate, magnesium silicate (steatite), zirconium
silicate or cerium silicate, or composed of mixtures of the
aforementioned materials, is used. The support may, for
example, have the shape of rings, spheres, shells or hollow
cylinders. To this is applied, in comparatively thin layers
(shells), the catalytically active composition. It is also
possible to apply two or more layers of the catalytically
active composition having the same or different compositions.
With regard to the further components of the catalytically
active composition of the inventive catalyst (in addition to
Ti02) , it is possible in principle to make reference to the
compositions and components which have been described in the
relevant prior art and are familiar to those skilled in the
art. These are mainly catalyst systems which, in addition to
titanium oxide(s), comprise oxides of vanadium. Such
catalysts are described, for example, in EP 0 964 744 B1,
whose disclosure on this subject is incorporated explicitly
by reference into the description.
In particular, the prior art describes a series of promoters
for increasing the productivity of the catalysts, which may

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likewise be used in the inventive catalyst. These include the
alkali metals and alkaline earth metals, thallium, antimony,
phosphorus, iron, niobium, cobalt, molybdenum, silver,
tungsten, tin, lead and/or bismuth, and mixtures of two or
more of the aforementioned components. For example, DE 21 59
441 A describes a catalyst which, in addition to titanium
dioxide of the anatase modification, consists of 1 to 30% by
weight of vanadium pentoxide and zirconium dioxide. It is
possible via the individual promoters to influence the
activity and selectivity of the catalysts, in particular by
lowering or increasing the activity. The selectivity-
increasing promoters include, for example, the alkali metal
oxides, whereas oxidic phosphorus compounds, in particular
phosphorus pentoxide, increase the activity of the catalyst
at the cost of the selectivity.
For the preparation of the inventive catalysts, the prior art
describes numerous suitable processes, so that a detailed
illustration is in principle not required here. For the
preparation of coated catalysts, reference can be made, for
example, to the process described in DE-A-16 42 938 or DE-A
17 69 998, in which a solution or suspension, comprising an
aqueous and/or an organic solvent, of the components of the
catalytically active composition and/or precursor compounds
thereof (frequently referred to as "slurry") is sprayed onto
the support material in a heated coating drum at elevated
temperature until the desired content of catalytically active
composition, based on the total catalyst weight, has been
attained. It is also possible, according to DE 21 06 796, to
carry out the application (coating) of the catalytically
active composition to the inert support in fluidized bed
coaters.

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Preference is given to preparing coated catalysts by the
application of a thin layer of 50 to 500 urn of the active
components to an inert support (for example US 2,035,606).
Useful supports have been found to be in particular spheres or
hollow cylinders. These shaped bodies give, rise to a high
packing density at low pressure drop and reduce the risk of
formation of packing faults when the catalyst is charged into
the reaction tubes.
The melted and sintered shaped bodies have to be heat-resistant
within the temperature range of the reaction as it proceeds. As
detailed above, useful substances are, for example, silicon
carbide, steatite, quartz, porcelain, SiO2, Al2O3 or clay earth.
The advantage of the coating of support bodies in a fluidized
bed is the high uniformity of the layer thickness, which plays a
crucial role for the catalytic performance of the catalyst. A
particularly uniform coating is obtained by spraying a
suspension or solution of the active components onto the heated
support at from 80 to 200°C in a fluidized bed, for example
according to DE 12 80 756, DE 198 28 583 or DE 197 09 589. In
contrast to the coating in coating drums, it is also possible,
when hollow cylinders are used as a support in the fluidized bed
processes mentioned, to uniformly coat the interior of the
hollow cylinders. Among the abovementioned fluidized bed
processes, the process according to DE 197 09 589 in particular
is advantageous, since the predominantly horizontal, circular
motion of the supports, in addition to uniform coating, also
achieves low abrasion of apparatus parts.
For the coating operation, the aqueous solution or suspension of
the active components and of an organic binder, preferably a
copolymer of vinyl acetate/vinyl laurate, vinyl acetate/ethylene
or styrene/acrylate, is sprayed via one or more nozzles onto the

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heated, fluidized support. It is particularly favourable to
introduce the spray liquid at the point of highest product
speed, as the result of which the sprayed substance can be
distributed uniformly in the bed. The spray operation is
continued until either the suspension has been consumed or the
required amount of active components has been applied to the
support.
In a particularly preferred inventive embodiment, the
catalytically active composition of the inventive catalyst,
comprising the TiO2 as defined herein, is applied in a
fluidized bed with the aid of suitable binders, so that a
coated catalyst is obtained. Suitable binders include organic
binders familiar to those skilled in the art, preferably
copolymers, advantageously in the form of an aqueous
dispersion, of vinyl acetate/vinyl laurate, vinyl
acetate/acrylate, styrene/acrylate, vinyl acetate/maleate and
vinyl acetate/ethylene. Particular preference is given to
using an organic polymeric or copolymeric adhesive, in
particular a vinyl acetate copolymer adhesive, as the binder.
The binder used is added in customary amounts to the
catalytically active composition, for example at about 10 to
20% by weight based on the solids content of the
catalytically active composition. For example, reference can
be made to EP 744 214. When the catalytically active
composition is applied at elevated temperatures of about
150°C, an application to the support without organic binders,
as is known from the prior art, is also possible. Coating
temperatures which can be used when the above-specified
binders are used are, according to DE 21 06 796, for example,
between about 50 and 450°C. The binders used burn off within
a short time in the course of baking-out of the catalyst when
the charged reactor is put into operation. The binders serve
primarily to reinforce the adhesion of the catalytically

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active composition on the support and to reduce attrition in
the course of transport and charging of the catalyst.
Further possible processes for preparing coated catalysts for
the catalytic gas phase oxidation of aromatic hydrocarbons to
carboxylic acids and/or carboxylic anhydrides have been
described, for example, in WO 98/00778 and EP-A 714 700.
According to these, from a solution and/or a suspension of
the catalytically active metal oxides and/or their precursor
compounds, optionally in the presence of assistants for the
catalyst preparation, a powder is prepared initially and is
subsequently, for the catalyst preparation on the support,
optionally after conditioning and also optionally after heat
treatment to generate the catalytically active metal oxides,
applied in coating form, and the support coated in this way
is subjected to a heat treatment to generate the
catalytically active metal oxides or to a treatment to remove
volatile constituents.
Suitable conditions for carrying out a process for the gas
phase oxidation of hydrocarbons, in particular for the
preparation of phthalic anhydride from o-xylene and/or
naphthalene, are likewise known to those skilled in the art
from the prior art. In particular, reference is made to the
comprehensive description in K. Towae, W. Enke, R. Jackh,
N. Bhargana "Phthalic Acid and Derivatives" in Ullmann' s
Encyclopedia of Industrial Chemistry Vol. A. 20, 1992, 181
and this is incorporated by reference. For example, the
boundary conditions known from the aforementioned reference,
WO-A 98/37967 or WO 99/61433 may be selected for the steady
operating state of the oxidation.
To this end, the catalysts are initially charged into the
reaction tubes of the reactor which are thermostatted
externally to the reaction temperature, for example by means

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of salt melts. The reaction gas is passed through the thus
prepared catalyst bed at temperatures of generally from 300
to 450°C, preferably from 320 to 420°C, and more preferably
from 340 to 400°C, and at an elevated pressure of generally
from 0.1 to 2.5 bar, preferably from 0.3 to 1.5 bar, at a
space velocity of generally from 750 to 5000 h"1.
The reaction gas fed to the catalyst is generally obtained by
mixing a molecular oxygen-containing gas which, apart from
oxygen, may also comprise suitable reaction moderators and/or
diluents, such as steam, carbon dioxide and/or nitrogen, with
the aromatic hydrocarbon to be oxidized, and the molecular
oxygen-containing gas may generally contain 1 to 100 mol%,
preferably 2 to 50 mol% and more preferably 10 to 30 mol%, of
oxygen, 0 to 30 mol%, preferably 0 to 10 mol%, of steam, and
0 to 50 mol%, preferably 0 to 1 mol%, of carbon dioxide,
remainder nitrogen. To obtain the reaction gas, the molecular
oxygen-containing gas is generally charged with 30 to 150 g
per m3 (STP) of gas of the aromatic hydrocarbon to be
oxidized.
In a particularly preferred inventive embodiment, the
inventive catalyst has an active composition content between
about 7 and 12% by weight, in particular between 8 and 10% by
weight, the active composition (catalytically active
composition) containing between 5 and 15% by weight of V205, 0
and 4% by weight of Sb203, 0.2 and 0.75% by weight of Cs, 0
and 3% by weight of Nb2Os. Apart from the components
aforementioned, the remainder of the active composition
comprises at least 90% by weight, preferably at least 95% by
weight, further preferred at least 98% by weight, in
particular at least 99% by weight, further preferred at least
99.5% by weight, especially 100% by weight Ti02. Such an
inventive catalyst may be used as such, or, for example, in

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the case of a two-zone or multizone catalyst, as a first
catalyst zone disposed toward the gas inlet side.
In a particularly preferred inventive embodiment, the BET
surface area of the catalyst is between 15 and about 25 m2/g.
It is further preferred that such a first catalyst zone has a
length fraction of about 40 to 60% of the total length of all
catalyst zones present (total length of the catalyst bed
present).
In a further preferred inventive embodiment, the inventive
catalyst has an active composition content of about 6 to 11% by
weight, in particular 7 to 9% by weight, the active composition
containing 5 to 15% by weight of V205, 0 to 4% by weight of
Sb203, 0.05 to 0.3% by weight of Cs, 0 to 2% by weight of Nb205.
Apart from the components aforementioned, the remainder of
the active composition comprises at least 90% by weight,
preferably at least 95% by weight, further preferred at least
98% by weight, in particular at least 99% by weight, further
preferred at least 99.5% by weight, especially 100% by weight
Ti02. Such an inventive catalyst may, for example, be used as
the second catalyst zone, i.e. downstream of the first catalyst
zone disposed toward the gas inlet side (cf. above). It is
preferred that the catalyst has a BET surface area between about
15 and 25 m2/g. It is further preferred that this second zone
has a length fraction of about 10 to 30% of the total length of
all catalyst zones present.
In a further inventive embodiment, the inventive catalyst has an
active composition content between about 5 and 10% by weight, in
particular between 6 and 8% by weight, the active composition
(catalytically active composition) containing 5 to 15% by weight
of V205, 0 to 4% by weight of Sb203, 0 to 0.1% by weight of Cs, 0
to 1% by weight of Nb205. Apart from the components
aforementioned, the remainder of the active composition

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comprises at least 90% by weight, preferably at least 95% by
weight, further preferred at least 98% by weight, in
particular at least 99% by weight, further preferred at least
99.5% by weight, especially 100% by weight Ti02. Such an
inventive catalyst may be used, for example, as the third
catalyst zone disposed downstream of the above-described second
catalyst zone. Preference is given to a BET surface area of the
catalyst which is somewhat higher than that of the layers
disposed closer to the gas inlet side, in particular in the
range between about 25 to about 45 m2/g. It is further preferred
that such a third catalyst zone has a length fraction of about
10 to 50% of the total length of all catalyst zones present.
It has also been found that, surprisingly, the inventive
multizone or multilayer catalysts, in particular having three
or more layers, can be used particularly advantageously when
the individual catalyst zones are present in a certain length
ratio relative to one another.
Thus, in a particularly preferred inventive embodiment, the
first catalyst zone disposed toward the gas inlet side has a
length fraction, based on the total length of the catalyst
bed, of at least 40%, in particular at least 45%, more
preferably at least 50%. It is especially preferred that the
proportion of the first catalyst zone in the total length of
the catalyst bed is between 40 and 70%, in particular between
40 and 55%, more preferably between 40 and 52%.
The second zone takes up preferably about 10 to 40%, in
particular about 10 to 30%, of the total length of the
catalyst bed. It has also been found that, surprisingly, a
ratio of the length of the third catalyst zone to the length
of the second catalyst zone of between about 1 and 2, in
particular between 1.2 and 1.7, more preferably between 1.3
and 1.6, provides particularly good results with regard to

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the economic viability such as the efficiency of raw material
utilization and productivity of the catalyst.
It has been found that the aforementioned selection of the
length fractions of the individual catalyst zones enables
particularly advantageous positioning of the hotspot, in
particular in the first zone, and good temperature control
for the prevention of excessively high hotspot temperatures
even in the case of prolonged operating time of the catalyst.
This improves the yield, in particular based on the lifetime
of the catalyst. It is assumed, without the invention being
restricted to this assumption, that the aforementioned zone
length ratio of the individual catalyst zones relative to one
another results in virtually full conversion of the o-xylene
used actually within the second catalyst zone and thus, in
the third catalyst zone with the advantages described above,
in what is known as "product polishing", i.e. the cleaning of
the reaction gas to free it of undesired by-products by
oxidation to the actual product of value. In addition, it is
known to those skilled in the art that, after a certain
running time, such catalysts deactivate in the region of the
hotspot (generally in the first zone). This deactivation
results in a shifting of the reaction into the second, more
active zone, which leads to very high hotspot temperatures
and the associated problems in relation to selectivity and
plant safety. The zone ratios selected in the inventive
catalyst, in particular of the first zone, ensure a maximum
residence time of the hotspot in the first zone with the
known advantages, and the inventive length of the second and
third zone at the same time ensures a minimum proportion of
undesired by-products with simultaneously maximum yield of
actual product of value.

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The temperature management in the gas phase oxidation of
o-xylene to phthalic anhydride is sufficiently well known to
those skilled in the art from the prior art, and reference can
be made, for example, to DE 100 40 827 A1.
It is further preferred in accordance with the invention that,
when the inventive catalyst is used in a multizone catalyst bed,
the content of alkali metals in the catalyst zones falls from
the gas inlet side toward the gas outlet side.
It has also been found that, surprisingly, particularly
favourable three-zone or multizone catalysts can be obtained in
many cases when the active composition content decreases from
the first catalyst zone disposed toward the gas inlet side to
the catalyst zone disposed toward the gas outlet side. It has
been found to be advantageous that the first catalyst zone has
an active composition content between about 7 and 12% by
weight, in particular between about 8 and 11% by weight, the
second catalyst zone has an active composition content
between about 6 and 11% by weight, in particular between
about 7 and 10% by weight, and the third catalyst zone has an
active composition content between about 5 and 10% by weight,
in particular between about 6 and 9% by weight.
The terms first, second and third catalyst zone are used in
conjunction with the present invention as follows: the first
catalyst zone refers to the catalyst zone disposed toward the
gas inlet side. Toward the gas outlet side, another two
further catalyst zones are present in the inventive catalyst,
which are referred to as the second and third catalyst zone.
The third catalyst zone is closer to the gas outlet side than
the second catalyst zone.
In a particularly preferred inventive embodiment, the
inventive catalyst has three catalyst zones. In that case,

- 20 -
the third catalyst zone is at the gas outlet side. The
presence of additional catalyst zones upstream of the first
catalyst zone in the gas flow is, however, not ruled out. For
example, in one inventive embodiment, the third catalyst zone
as defined herein may be followed by another fourth catalyst
zone (having an active composition content equal to or even
lower than the third catalyst zone).
According to the invention, the active composition content
between the first and the second catalyst zone and/or between
the second and the third catalyst zone may decrease.
In a particularly preferred inventive embodiment, the active
composition content decreases between the second and the
third catalyst zone. It goes without saying that the active
composition content never increases in the sequence of the
catalyst zones from the gas inlet side to the gas outlet
side, but at worst remains the same.
It is assumed, without the invention being restricted to the
correctness of this assumption, that, as a result of the
different layer thicknesses, associated with the different
active composition contents, of the catalytically active
composition in the individual zones, more preferably the
decreasing layer thicknesses of the catalytically active
composition from the first to the third zone, firstly the
reaction of o-xylene up to PA in the first and, if
appropriate, second zone is influenced, and additionally, in
the third zone with the even thinner layer of active
composition, the remaining under-oxidation products are
oxidized, for example phthalide to PA, but not PA to the
over-oxidation products, for example COX. As a result, over
the entire structured packing, the maximum productivity for
the oxidation of o-xylene to PA is achieved at a minimum
proportion of the undesired by-products.

- 21 -
In a preferred inventive embodiment, the BET surface area
increases from the first catalyst zone disposed toward the
gas inlet side to the third catalyst zone disposed toward the
gas outlet side. Preferred ranges for the BET surface area
are 15 to 25 m2/g for the first catalyst zone, 15 to 25 m2/g
for the second catalyst zone and 25 to 45 m2/g for the third
catalyst zone.
In general, it is preferred in accordance with the invention
that the BET surface area of the first catalyst zone is lower
than the BET surface area of the third catalyst zone.
Particularly advantageous catalysts are also obtained when
the BET surface areas of the first and of the second catalyst
zone are the same, while the BET surface area of the third
catalyst zone is greater in comparison. The catalyst activity
toward the gas inlet side, in a preferred inventive
embodiment, is lower than the catalyst activity toward the
gas outlet side.
In principle, in addition to the Ti02 defined in detail herein,
there may also be a blend with another titanium dioxide of
another specification, i.e. another BET surface area,
porosimetry and/or particle size distribution. However, it is
preferred in accordance with the invention that at least 50%, in
particular at least 75%, more preferably all, of the TiO2 used
has a BET surface area and porosimetry as defined herein, and
preferably also has the particle size distribution described. It
is also possible to use blends of different TiO2 materials.
It has also been found that, in a preferred embodiment, in
accordance with the invention, catalysts which do not have any
phosphorus in the catalytically active composition, in
combination with the TiO2 used in accordance with the invention,
enable particularly good activities with simultaneously very
high selectivity. It is further preferred that at least 0.05% by

- 22 -
weight of the catalytically active composition is formed by at
least one alkali metal calculated as alkali metal(s). The alkali
metal used is more preferably caesium.
In addition, according to the inventor' s results, in one
embodiment, it is preferred that the inventive catalyst contains
niobium' in an amount of from 0.01 to 2% by weight, in particular
from 0.5 to 1% by weight, of the catalytically active
composition.
The inventive catalysts are typically thermally treated or
calcined (conditioned) before use. It has been found to be
advantageous when the catalyst is calcined in an O2-containing
gas, in particular in air, at at least 390°C for at least 24
hours, in particular at at least 400°C for between 24 and 72
hours. The temperatures should preferably not exceed about
500°C, in particular about 470°C. However, other calcination
conditions which appear suitable to those skilled in the art are
not fundamentally ruled out.
In a further aspect, the present invention relates to a process
for preparing a catalyst according to one of the preceding
claims, comprising the following steps:
a. providing a catalytically active composition as
defined herein, comprising the TiO2 characterized in
detail above;
b. providing an inert support, in particular an inert
shaped support body;
c. applying the catalytically active composition to the
inert support, in particular in a fluidized bed.

- 23 -
In a further aspect, the present invention also relates to the
use of titanium dioxide as defined above for preparing a
catalyst, in particular for the gas phase oxidation of
hydrocarbons, preferably for the gas phase oxidation of o-xylene
and/or naphthalene to phthalic anhydride.
METHODS
To determine the parameters of the inventive catalysts, the
methods which follow are used:
1. BET surface area:
The determination is effected by the BET method according to
DIN 66131; a publication of the BET method can also be found
in J. Am. Chem. Soc. 60, 309 (1938) .
2. Pore radius distribution:
The pore radius distribution and the pore volume of the TiO2
used were determined by means of mercury porosimetry to
DIN 66133; maximum pressure: 2000 bar, Porosimeter 4000 (from
Porotec, Germany), according to the manufacturer' s
instructions.
3. Primary crystal sizes:
The primary crystal sizes (primary particle sizes) were
determined by powder X-ray diffractometry. The analysis was
carried out with an instrument from Bruker, Germany: BRUKER
AXS - D4 Endeavor. The resulting X-ray diffractograms were
recorded with the "DiffracPlus D4 Measurement" software
package according to the manufacturer' s instructions, and the
half-height width of the 100% reflection was evaluated with
the "DiffracPlus Evaluation" software by the Debye-Scherrer
formula according to the manufacturer' s instructions in order
to determine the primary crystal size.

- 24 -
4. 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.
5. Alkali content of TiO2:
The alkali content of TiO2 is determined according to DIN ISO
9964-3. Thus, alkali may be determined by ICP-AES
(Inductively Coupled Plasma Atomic Emission Spectroscopy) and
optionally added to the total alkali content of Ti02.
6. Bulk density:
The bulk density was determined with the aid of the Ti02 used to
prepare the catalyst (dried at 150°C under reduced pressure,
uncalcined). The resulting values from three determinations were
averaged.
The bulk density was determined by introducing 100 g of the
TiO2 material into a 1000 mi container and shaken for approx.
30 seconds.
A measuring cylinder (capacity precisely 100 ml) is weighed
empty to 10 mg. Above it, the powder funnel is secured over
the opening of the cylinder using a clamp stand and clamp.
After the stopwatch has been started, the measuring cylinder
is charged with the TiO2 material within 15 seconds. The
spatula is used to constantly supply more filling material,
so that the measuring cylinder is always slightly overfilled.
After 2 minutes, the spatula is used to level off the excess,
care being taken that no pressing forces compress the
material in the cylinder. The filled measuring- cylinder is
brushed off and weighed.

- 25 -
The bulk density is reported in g/ml.
The BET surface area, the pore radius distribution and the
pore volume, and also the primary crystal sizes and the
particle size distribution were determined for the titanium
dioxide in each case on the uncalcined material dried at
150°C under reduced pressure.
The data in the present description with regard to the BET
surface areas of the catalysts or catalyst zones also relate
to the BET surface areas of the Ti02 material used in each
case (dried at 150CC under reduced pressure, uncalcined, see
above).
In general, the BET surface area of the catalyst is
determined by virtue of the BET surface area of the Ti02 used,
although the addition of further catalytically active
components does change the BET surface area to a certain
extent. This is familiar to those skilled in the art.
The active composition content (content of the catalytically
active composition, without binder) relates in each case to
the content (in % by weight) of the catalytically active
composition in the total weight of the catalyst including
support in the particular catalyst zone, measured after
conditioning at 400°C over 4 h.
The invention will now be illustrated in detail with
reference to the nonrestrictive examples which follow:
EXAMPLES
Example 1: Preparation of catalyst A (comparison 1)
To prepare catalyst A having an active composition content of
8% by weight and the composition of 7.5% by weight of

- 26 -
vanadium pentoxide, 3.2% by weight of antimony trioxide,
0.40% by weight of caesium (calculated as caesium), 0.2% by
weight of phosphorus (calculated as phosphorus) and remainder
titanium dioxide (Sachtleben Chemie GmbH, Duisburg, Germany,
tradename: Hombikat T; batch no. E3-588-352-001), 2600 g of
steatite bodies in the form of hollow cylinders of size 8x6
x 5 mm were coated at a temperature of 70°C in a fluidized
bed coater with a suspension of 17.9 g of vanadium pentoxide,
7.6 g of antimony trioxide, 1.28 g of caesium sulphate, 1.9 g
of ammonium dihydrogenphosphate, 364.4 g of titanium dioxide,
130.5 g of binder composed of a 50% dispersion of water and
vinyl acetate/ethylene copolymer (Vinnapas® EP 65 W, from
Wacker) and 1000 g of water. The active composition was applied
in the form of thin layers.
The titanium dioxide had a BET surface area of 26 m2/g, a bulk
density of 1.23 g/ml, a primary crystal size of 200 ångstrøm,
a pore radius distribution of
50% of the total pore volume by pores having a radius of
7500 to 400 nm
1.7% of the total pore volume by pores having a radius of
400 to 60 nm
48% of the total pore volume by pores having a radius of 60
to 3.7 nm,
and a particle size distribution of
d10 = 12.4 μm
d50 = 31.6 μm
d90 = 64.7 μm
as well as a total alkali content (Li + Na + K + Rb + Cs) of
more than 2.000 ppm.

- 27 -
Example 2: Preparation of catalyst B (comparison 2)
To prepare catalyst B having an active composition content of
8% by weight and the composition of 7.5% by weight of
vanadium pentoxide, 3.2% by weight of antimony trioxide,
0.40% by weight of caesium (calculated as caesium), 0.2% by
weight of phosphorus (calculated as phosphorus) and remainder
titanium dioxide, 2200 g of steatite bodies in the form of
hollow cylinders of size 8x6x5 mm were coated at a
temperature of 70CC in a fluidized bed coater with a
suspension of 15.1 g of vanadium pentoxide, 6.4 g of antimony
trioxide, 1.08 g of caesium carbonate, 1.5 g of ammonium
dihydrogenphosphate, 178.62 g of titanium dioxide, 130.5 g of
binder (see Example 1) and 2000 g of water. The active
composition was applied in the form of thin layers.
For this purpose, the titanium dioxide of example 1 was
suspended in 1 M agueous HNO3 and washed over night at 90 °C
with agitation under reflux, subsequently filtered and washed
three times with bidestilled water and dried at 150°C in air.
The resulting titanium dioxide had a BET surface of
24.3 m2/g, a bulk density of 1.09 g/ml, a primary crystal
size of 200 ångstrøm, a pore radius distribution of
52% of the total pore volume by pores having a radius of
7500 to 400 nm
4.7% of the total pore volume by pores having a radius of
400 to 60 nm
43% of the total pore volume by pores having a radius of 60
to 3.7 nm,
and a particle size distribution of
d10 = 9.8 μm
d50 = 32.5 μm
d90 = 65.1 μm

- 28 -
as well as a total alkali content (Li + Na + K + Rb + Cs) of
less than 1.000 ppm.
Example 3: Preparation of catalyst C (inventive)
To prepare catalyst C having an active composition content of
8% by weight and the composition of 7.5% by weight of
vanadium pentoxide, 3.2% by weight of antimony trioxide,
0.40% by weight of caesium (calculated as caesium), 0.2% by
weight of phosphorus (calculated as phosphorus) and remainder
titanium dioxide, 2000 g of steatite bodies in the form of
hollow cylinders of size 8x6x5 mm were coated at a
temperature of 70°C in a fluidized bed coater with a
suspension of 17 g of vanadium pentoxide, 7.03 g of antimony
trioxide, 1.14 g of caesium sulphate, 1.7 g of ammonium
dihydrogenphosphate, 195.0 g of titanium dioxide, 130.5 g of
binder (see Example 1) and 2000 g of water. The active
composition was applied in the form of thin layers.
The titanium dioxide (Nano Inc., Ltd., 1108-1 Bongkok Sabong,
Jinju, Kyoungnam 660-882 Korea, tradename NT22-B20) had a BET
surface area of 18 m2/g, a bulk density of 0.52 g/ml, a
primary crystal size of 390 ångstrøm, a pore radius
distribution of
43% of the total pore volume by pores having a radius of
7500 to 400 nm
47% of the total pore volume by pores having a radius of
400 to 60 nm
10% of the total pore volume by pores having a radius of 60
to 3.7 nm,
and a particle size distribution of

- 29 -
d10 = 0.4 μm
d50 = 1.2 μm
d90 = 2.8 μm
and a total alkali content of less than 1.000 ppm.
Example 4: Preparation of catalyst D (inventive)
To prepare catalyst D having an active composition content of
8% by weight and the composition of 7.5% by weight of
vanadium pentoxide, 3.2% by weight of antimony trioxide,
0.40% by weight of caesium (calculated as caesium), 0.2% by
weight of phosphorus (calculated as phosphorus) and remainder
titanium dioxide, 2000 g of steatite bodies in the form of
hollow cylinders of size 8x6x5 mm were coated at a
temperature of 70°C in a fluidized bed coater with a
suspension of 17 g of vanadium pentoxide, 7.03 g of antimony
trioxide, 1.14 g of caesium sulphate, 1.7 g of ammonium
dihydrogenphosphate, 195.0 g of titanium dioxide, 130.5 g of
binder (see Example 1) and 2000 g of water. The active
composition was applied in the form of thin layers.
The titanium dioxide (Nano Inc., Ltd., see above, tradename
NT22-B30) with a BET surface area of 34 m2/g was treated in a
rotary furnace at 600°C for 48h with a mixture of 50% water
vapour and 50% air. After this temperature treatment, the
titanium oxide had a BET surface of 24 m2/g, a bulk density
of 0.47 g/ml, a primary crystal size of 349 ångstrøm and a
pore radius distribution of
19% of the total pore volume by pores having a radius of
7500 to 400 nm
66% of the total pore volume by pores having a radius of
400 to 60 nm

- 30 -
16% of the total pore volume by pores having a radius of 60
to 3.7 nm,
and a particle size distribution of
d10 = 0.4 μm
d50 = 1.4 μm
d90 = 16.9 μm
as well as a total alkali content of less than 1.000 ppm.
Example 5: Determination of the catalytic performance data of
catalyst A (comparison 1)
A 120 cm-long reaction tube having an internal diameter of
24.8 mm is charged to a length of 80 cm with 40 g of catalyst A,
diluted with 200 g of steatite rings of dimensions 8x6x5 mm
to prevent hotspots. The reaction tube is disposed in a liquid
salt melt which can be heated to temperatures up to 450°C. In
the catalyst bed is disposed a 3 mm protective tube with
incorporated thermoelement which can be used to indicate the
catalyst temperature over the complete catalyst combination. To
determine the catalytic performance data, 60 g/m3 (STP) of
o-xylene (purity 99.9%) are passed over the catalyst A at a
maximum of 400 1 (STP) of air/h, so that a catalyst composition-
based space velocity of 5.12 1/h x mcat is established at an
average catalyst temperature of 420°C, and the reaction gas is
analysed for its constituents downstream of the reaction tube
exit. The results of the test run are listed in Table 1.
Example 6: Determination of the catalytic performance data of
catalyst B (comparison 2)
A 120 cm-long reaction tube having an internal diameter of
24.8 mm is charged to a length of 80 cm with 40 g of catalyst B,

- 31 -
diluted with 200 g of steatite rings of dimensions 8x6x5 mm
to prevent hotspots. Otherwise, the procedure is as described
under Example 3. The results of the test run are listed in
Table 1.
Example 7: Determination of the catalytic performance data of
catalyst C (inventive)
A 120 cm-long reaction tube having an internal diameter of
24.8 mm is charged to a length of 80 cm with 40 g of catalyst C,
diluted with 200 g of steatite rings of dimensions 8x6x5 mm
to prevent hotspots. Otherwise, the procedure is as described
under Example 3. The results of the test run are listed in
Table 1.
Example 8: Determination of the catalytic performance data of
catalyst D (inventive)
A 120 cm-long reaction tube having an internal diameter of
24.8 mm is charged to a length of 80 cm with 40 g of catalyst D,
diluted with 200 g of steatite rings of dimensions 8x6x5 mm
to prevent hotspots. Otherwise, the procedure is as described
under Example 3. The results of the test run are listed in
Table 1.
Table 1: List of the experimental results

Example Conversion
[%] C8 selectivity
[mol%] PA selectivity
[mol%] COx selectivity
[mol%]
Catalyst A (Ex. 5) 26 55.7 32.2 39.1
Catalyst B (Ex. 6) 55.3 73.7 52.2 21.3
Catalyst C (Ex. 7) 72.4 86.3 71.2 10.1
Catalyst D (Ex. 8) 95.3 85.6 81.9 11.5
C8 selectivity: selectivity for all products of value having 8 carbon
atoms (phthalic anhydride, phthalide, o-tolylaldehyde, o-toluic acid)

- 32 -
C0X: sum of carbon monoxide and dioxide in the offgas stream
Example 9: Preparation of an inventive three-layer catalyst
An inventive three-layer catalyst can be obtained, for example,
as follows:
To prepare a catalyst E having an active composition content of
9% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.40% by weight
of caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide,
2000 g of steatite bodies in the form of hollow cylinders of
size 8x6x5 mm were coated at a temperature of 70°C in a
fluidized bed coater with a suspension of 17.0 g of vanadium
pentoxide, 7.0 g of antimony trioxide, 1.1 g of caesium
sulphate, 1.65 g of ammonium dihydrogenphosphate, 194.9 g of
titanium dioxide having a BET surface area of 18 m2/g (as in
example 3), 102.1 g of binder composed of a 50% dispersion of
water and vinyl acetate/ethylene copolymer (Vinnapas® EP 65 W,
from Wacker) and 2000 g of water. The active composition was
applied in the form of thin layers.
To prepare a catalyst F having an active composition content of
8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.20% by weight
of caesium (calculated as caesium), 0.2% by weight of phosphorus
(calculated as phosphorus) and remainder titanium dioxide,
2000 g of steatite bodies in the form of hollow cylinders of
size 8x6x5 mm were coated at a temperature of 70°C in a
fluidized bed coater with a suspension of 15.1 g of vanadium
pentoxide, 6.3 g of antimony trioxide, 0.53 g of caesium
sulphate, 1.47 g of ammonium dihydrogenphosphate, 173.7 g of
titanium dioxide having a BET surface area of 18 m2/g (as in

- 33 -
example 3), 101 g of binder composed of a 50% dispersion of
water and vinyl acetate/ethylene copolymer (Vinnapas® EP 65 W,
from Wacker) and 2000 g of water. The active composition was
applied in the form of thin layers.
To prepare a catalyst G having an active composition content of
8% by weight and the composition of 7.5% by weight of vanadium
pentoxide, 3.2% by weight of antimony trioxide, 0.2% by weight
of phosphorus (calculated as phosphorus) and remainder titanium
dioxide, 2000 g of steatite bodies in the form of hollow
cylinders of size 8 x 6 x 5 mm were coated at a temperature of
70°C in a fluidized bed coater with a suspension of 15.1 g of
vanadium pentoxide, 6.25 g of antimony trioxide, 1.47 g of
ammonium dihydrogenphosphate, 174.11 g of titanium dioxide
having a BET surface area of 27 m2/g (mixture of NT22-B20 (see
example 3) and NT22-B30 (see example 4, without calcination)),
101 g of binder composed of a 50% dispersion of water and vinyl
acetate/ethylene copolymer (Vinnapas® EP 65 W, from Wacker) and
2000 g of water. The active composition was applied in the form
of thin layers. The bulk densities of Ti02 for catalysts E, F
and G were each below 0.5 g/ml, the primary crystal size above
340 ångstrøm; at least 25% of the total pore volume is formed by
pores having a radius between 60 and 400 nm.
The sequence of the catalyst zones: 60 cm of catalyst E, 60 cm
of catalyst F, 70 cm of catalyst G.
Example 10: Catalytic performance data of the inventive three-
layer catalyst
A 450 cm-long reaction tube is charged successively with 70 cm
of catalyst G, 60 cm of catalyst F and 160 cm of catalyst E. The
reaction tube is disposed in a liquid salt melt which can be
heated to temperatures up to 450°C. In the catalyst bed is

- 34 -
disposed a 3 mm protective tube with incorporated thermoelement,
which can be used to indicate the catalyst temperature over the
complete catalyst combination. To determine the catalytic
performance data, from 0 to a maximum of 70 g/m3 (STP) of
o-xylene (purity 99.9%) are passed over this catalyst
combination in the sequence DEF at 3.6 m3 (STP) of air/h, and
the reaction gas, downstream of the reaction tube exit, is
passed through a condenser in which all organic constituents of
the reaction gas apart from carbon monoxide and carbon dioxide
are deposited. The deposited crude product is melted off by
means of superheated steam, collected and subsequently weighed.
The crude yield is determined as follows.
Max. crude PA yield [% by weight]
Weighed amount of crude PA [g] x 100/feed of o-xylene [g] x
purity of o-xylene [%/100]
The results of the test run are listed in Table 2.
Table 2

Example Maximum Crude PA yield PA quality Hotspot temperature and
loading (phthalide value in
the reaction gas) position
Example 10: 60 g/Nnf 114.1% by wt. Catalyst combination 55 cm (1st zone)
E (160 cm) F (60 cm) G
(70 cm)
As can be seen from Table 2, the inventive catalyst according to
Example 9 exhibits a very good PA yield and PA quality. The
hotspot is advantageously positioned in the first catalyst zone.

-35-
1. Catalyst, in particular for the preparation of phthalic an-
hydride by gas phase oxidation of o-xylene and/or naph-
thalene, having an inert support and at least one layer
which has been applied thereto and has a catalytically act-
ive composition comprising Ti02, characterized in that at
least a portion of the Ti02 used has the following proper-
ties: (a) the BET surface area is more than 15 m2/g, (b)
the primary crystal size is more than 210 angstram and less
than 900 angstram.
2. Catalyst according to Claim 1, characterized in that the
bulk density is less than 1.0 g/ml, preferably less than
0.8 g/ml, in particular less than 0.6 g/ml.
3. Catalyst according to one of the preceding claims, charac-
terized in that at least a part of the TiQ used has the
following property: at least 25% of the total pore volume
is formed by pores with a radius between 60 and 400 nm.
4. Catalysts according to one of the preceding claims, charac-
terized in that at least a part of the TiCfe used has the
following property: a total alkali content of less than
1.000 ppm.
5. Catalyst according to one of the preceding claims, charac-
terized in that the primary particle size is more than
220 ångstrøm, preferably more than 250 ångstrøm, in par-
ticular more than 300 ångstrøm, further preferred more than
320 ångstrøm, further preferred more than 340 ångstrøm,
further preferred more than 380 ångstrøm

-36-
6. Catalyst according to one of the preceding claims, charac-
terized in that the BET surface area of the TiQ, is between
about 15 and 60 m2/g, in particular about 15 and 45 m2/g,
more preferably 15 and 30 m2/g.
7. Catalyst according to one of the preceding claims, charac-
terized in that at least about 40%, in particular at least
about 50%, of the total pore volume is formed by pores hav-
ing a radius between 60 and 400 run.
8. Catalyst according to one of the preceding claims, charac-
terized in that up to 70%, in particular up to 75%, of the
total pore volume is formed by pores having a radius
between 60 and 400 ran.
9. Catalyst according to one of the preceding claims, charac-
terized in that the catalytically active composition is ap-
plied in the fluidized bed.
10. Catalyst according to one of the preceding claims, charac-
terized in that less than about 30%, in particular less
than 22%, of the total pore volume is formed by pores hav-
ing a radius of more than 400 nm.
11. Catalyst according to one of the preceding claims, charac-
terized in that about 17 to 27% of the total pore volume is
formed by pores having a radius of more than 400 nm.
12. Catalyst according to one of the preceding claims, charac-
terized in that about 50 to 70%, in particular about 50 to
65%, of the total pore volume is formed by pores having a
radius of 60 to 400 nm.
13. Catalyst according to one of the preceding claims, charac-
terized in that less than 30%, in particular less than 20%,
of the total pore volume is formed by pores having a radius
of 3.7 to 60 nm.

37
14. Catalyst according to one of the preceding claims, charac-
terized in that about 10 to 30% of the total pore volume is
formed by pores having a radius of 3.7 to 60 nra.
15. Catalyst according to one of the preceding claims, charac-
terized in that the D90 value of the Ti02 used is between
about 0.5 and 20 urn, in particular between about 1 and
10 μm, more preferably between about 2 and 5 urn.
16. Catalyst according to one of the preceding claims, charac-
terized in that less than 10%, in particular less than 5%,
of the total pore volume is formed by micropores having a
pore radius of less than 3.7 nm.
17. Catalyst according to one of the preceding claims, charac-
terized in that 8% by weight or more of the catalytically
active composition, in particular between about 8 and 15%
by weight, of vanadium, calculated as vanadium pentoxide,
is present.
18. Catalyst according to one of the preceding claims, charac-
terized in that at least 0.05% by weight of the catalytic-
ally active composition of at least one alkali metal, cal-
culated as alkali metal, is present.
19. Catalyst according to one of the preceding claims, charac-
terized in that the adhesive used for the catalytically
active composition is an organic polymer or copolymer, in
particular a vinyl acetate copolymer.
20. Catalyst according to one of the preceding claims, charac-
terized in that the catalyst is calcined or conditioned in
an 02-containing gas, in particular in air, at > 390°C for
at least 24 hours, preferably at > 400°C for between 24 and
72 hours.

3S
21. Catalyst according to one of the preceding claims, charac-
terized in that niobium is present in an amount of 0.1 to
2% by weight, in particular 0.5 to 1% by weight, of the
catalytically active composition.
22. Catalyst according to one of the preceding claims, charac-
terized in that only one Ti02 source is used, all of the
TiCb used having the BET surface area or pore radius dis-
tribution defined in one or more of the preceding claims.
23. Catalyst according to one of the preceding claims, charac-
terized in that no phosphorus is present in the active com-
position.
24. Catalyst according to one of the preceding claims, compris-
ing a first catalyst zone disposed toward the gas inlet
side, a second catalyst zone disposed toward the gas outlet
side and a third catalyst zone disposed even closer to or
at the gas outlet side, the catalyst zones having different
composition and each having an active composition compris-
ing Ti02, and the active composition content decreasing
from the first to the third catalyst zone, with the proviso
that

a) the first catalyst zone has an active composition con-
tent between about 7 and 12% by weight,
b) the second catalyst zone has an active composition con-
tent in the range between 6 and 11% by weight, the active
composition content of the second catalyst zone being less
than or equal to the active composition content of the
first catalyst zone, and
c) the third catalyst zone has an active composition con-
tent in the range between 5 and 10% by weight, the active
composition content of the third catalyst zone being less

39
than or equal to the active composition content of the
second catalyst zone.
25. Catalyst according to one of the preceding claims, charac-
terized in that the first catalyst zone has an active com-
position content between about 8 and 11% by weight.
26. Catalyst according to one of the preceding claims, charac-
terized in that the second catalyst zone has an active com-
position content between about 7 and 10% by weight.
27. Catalyst according to one of the preceding claims, charac-
terized in that the third catalyst zone has an active com-
position content between about 6 and 9% by weight.
28. Catalyst according to one of the preceding claims, charac-
terized in that the catalyst activity of the catalyst zone
toward the gas inlet side is lower than the catalyst activ-
ity of the catalyst zone toward the gas outlet side.
29. Catalyst according to one of the preceding claims, charac-
terized in that the BET surface area of the first catalyst
zone is lower than the BET surface area of the third cata-
lyst zone.
30. Catalyst according to one of the preceding claims, charac-
terized in that the BET surface area of the first and of
the second catalyst zone are the same, while the BET sur-
face area of the third catalyst zone is greater in compar-
ison.
31. Catalyst according to one of the preceding claims, charac-
terized in that the BET surface area of the first and the
second catalyst zone is in each case between about 15 and
25 m2/g, and the BET surface area of the third catalyst
zone is between about 25 and 45 m2/g.

40
32. Catalyst according to one of the preceding claims, charac-
terized in that the first catalyst zone disposed toward the
gas inlet side has a length fraction, based on the total
length of the catalyst bed, of at least 40%, in particular
at least 45%, more preferably at least 50%.
33. Catalyst according to one of the preceding claims, charac-
terized in that the proportion of the first catalyst zone
in the total length of the catalyst bed is between 40 and
70%, in particular between 40 and 55%, more preferably
between 40 and 52%.
34. Catalyst according to one of the preceding claims, charac-
terized in that the proportion of the second catalyst zone
in the total length of the catalyst bed is between about 10
and 40%, in particular between about 10 and 30%.
35. Catalyst according to one of the preceding claims, charac-
terized in that the ratio of the length of the third cata-
lyst zone to the length of the second catalyst zone is
between about 1 and 2, in particular between 1.2 and 1.7,
more preferably between 1.3 and 1.6.
36. Process for preparing a catalyst according to one of the
preceding claims, comprising the following steps:
a. providing an active composition comprising at least
Ti02, as defined in one of the preceding claims 1 to
15,
b. providing an inert support, in particular an inert
shaped support body,
c. applying the catalytically active composition to the
inert support, in particular in a fluidized bed.

41
37. Use of titanium dioxide having a BET surface area of more
than 15 m2/g and a primary crystal size of more than 210
angstrszim and less than 900 ångstrøm, for preparing a cata-
lyst, in particular for the gas phase oxidation of hydro-
carbons, preferably for the gas phase oxidation of o-xylene
and/or naphthalene to phthalic anhydride.
38. Use according to Claim 37, characterized in that the ti-
tanium dioxide has a bulk density of less than 1.0 g/ml,
preferably less than 0.8 g/ml, in particular less than
0.6 g/ml.
39. Use according to Claim 37 or 38, characterized in that the
titanium dioxide has a primary crystal size of more than
250 ångstrøm, in particular more than 300 ångstrøm, further
preferred more than about 320 ångstrøm, preferably more
than about 340 ångstrøm, further preferred more than
380 ångstrøm.


The present invention relates to a catalyst, in particular for the preparation of phthalic anhydride by gas phase oxidation of
o-xylene and/or naphthalene, having an inert support and at least one layer which has been applied thereto and has a catalytically active composition comprising TiO2, characterized
in that at least a portion of the TiO2 used has the following properties: (a) the BET surface area is more than 15 m2/g, (b)
the primary crystal size is more than 210 ångstrøm. Also described is a preferred process for preparing such a catalyst, and the preferred use of the titanium dioxide used in accordance
with the invention.

Documents:

04791-kolnp-2007-abstract.pdf

04791-kolnp-2007-claims 1.0.pdf

04791-kolnp-2007-claims 1.1.pdf

04791-kolnp-2007-correspondence others.pdf

04791-kolnp-2007-description complete.pdf

04791-kolnp-2007-form 1.pdf

04791-kolnp-2007-form 3.pdf

04791-kolnp-2007-form 5.pdf

04791-kolnp-2007-gpa.pdf

04791-kolnp-2007-international exm report.pdf

04791-kolnp-2007-international publication.pdf

04791-kolnp-2007-pct priority document notification.pdf

04791-kolnp-2007-pct request form.pdf

4791-KOLNP-2007-ABSTRACT.pdf

4791-KOLNP-2007-AMANDED CLAIMS.pdf

4791-KOLNP-2007-AMANDED PAGES OF SPECIFICATION.pdf

4791-KOLNP-2007-ASSIGNMENT.pdf

4791-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

4791-KOLNP-2007-DESCRIPTION (COMPLETE).pdf

4791-KOLNP-2007-ENGLISH TRANSLATION.pdf

4791-KOLNP-2007-EXAMINATION REPORT REPLY RECIEVED.pdf

4791-KOLNP-2007-FORM 1.pdf

4791-kolnp-2007-form 18.pdf

4791-KOLNP-2007-FORM 2.pdf

4791-KOLNP-2007-FORM 3 1.1.pdf

4791-KOLNP-2007-FORM 3-1.2.pdf

4791-KOLNP-2007-OTHERS.pdf

4791-KOLNP-2007-PETITION UNDER RULR 137-1.1.pdf

4791-KOLNP-2007-PETITION UNDER RULR 137.pdf


Patent Number 254736
Indian Patent Application Number 4791/KOLNP/2007
PG Journal Number 50/2012
Publication Date 14-Dec-2012
Grant Date 13-Dec-2012
Date of Filing 10-Dec-2007
Name of Patentee SUD-CHEMIE AG
Applicant Address LENBACHPLATZ 6, D-80333 MUNCHEN
Inventors:
# Inventor's Name Inventor's Address
1 HARTSBERGER HELMUT PLUMSERJOCHSTR. 6A, D-81825 MUNCHEN
2 ESTENFELDER MARVIN C/O FAM. MEISSNER, ELFENWEG 24, D-76199 KARLSRUHE
3 GUCKEL CHRISTIAN HESSELFURTHER STR. 1, D-85567 GRAFING
PCT International Classification Number B01J 35/10
PCT International Application Number PCT/EP2005/012701
PCT International Filing date 2005-11-28
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 PCT/EP05/05546 2005-05-22 EUROPEAN UNION