DE102008040094A1 - Production of an oxidic geometric molded body used as a catalyst in a heterogeneously catalyzed partial gas phase oxidation comprises mechanically compressing a powdered material inserted into a filling chamber of a die - Google Patents

Abstract

Production of an oxidic geometric molded body comprises mechanically compressing a powdered material inserted into a filling chamber of a die and consisting of a metal compound or metal oxide to form a geometric precursor molded body. The die material in contact with the die hole is a hard metal consisting of at least 80 wt.% tungsten carbide and at least 5 wt.% nickel as binder. Independent claims are also included for the following: (1) Oxidic geometric molded body produced by the above process; (2) Method for the heterogeneously catalyzed partial gas phase oxidation of an organic compound on a fixed catalyst bed made from the above oxidic geometric molded body; and (3) Tubular bundle reactor with reaction tubes containing oxidic geometric molded bodies.

Description

• – die Innenwand der Matrizenbohrung,
• – die obere Stirnfläche eines von unten entlang der Bohrachse B in die Matrizenbohrung hub- und senkbeweglich eingeführten unteren Stempels, auf der das in den Füllraum eingebrachte pulverförmige Haufwerk aufliegt, und
• – die längs der Bohrachse B in einem axialen Ausgangsabstand A oberhalb der oberen Stirnfläche des unteren Stempels befindliche untere Stirnfläche eines entlang der Bohrachse B hub- und senkbeweglich angebrachten oberen Stempels, dessen untere Stirnfläche das in den Füllraum eingebrachte pulverförmige Haufwerk von oben berührt, begrenzt wird,

indem man den axialen Ausgangsabstand A der beiden Stirnflächen dadurch auf einen für die Verdichtung vorgegebenen axialen Endabstand E längs der Bohrachse B verringert, dass man den oberen Stempel absenkt und dabei die Position des unteren Stempels beibehält oder den unteren Stempel zusätzlich anhebt und nach beendeter Verdichtung der obere Stempel vom gebildeten geometrischen Vorläuferformkörper abgehoben und der geometrische Vorläuferformkörper durch Anheben des unteren Stempels aus der Matrizenbohrung entfernt wird,
sowie ein sich daran anschließendes Verfahren der thermischen Behandlung des geometrischen Vorläuferformkörpers bei einer Temperatur ≥ 100°C, bei dem sich wenigstens eine Teilmenge seiner Bestandteile unter Ausbildung wenigstens einer gasförmigen Verbindung zersetzt und/oder chemisch umsetzt und der oxidische geometrische Formkörper sich ausbildet.The present invention relates to a process for the production of an oxidic geometric shaped body, comprising the mechanical compacting of a powdery aggregate introduced into the filling space of a matrix, from constituents comprising at least one metal compound which can be converted into a metal oxide by thermal treatment at a temperature ≥ 100 ° C. , or at least one metal oxide, or at least one metal oxide and at least one metal compound, with the proviso that at least one constituent of the powdery aggregate is a nitrate salt, an ammonium salt or ammonium nitrate, to a geometrical precursor shaped body, wherein the filling space in one with a vertical boring axis B is located from top to bottom through the die material passed through the die bore and at least through

• The inner wall of the die bore,
• - The upper end face of a down along the drilling axis B in the die bore hub and lowered vertically introduced lower punch on which the introduced into the filling powdery debris rests, and
• - The along the drilling axis B in an axial output distance A above the upper end face of the lower punch located lower end face of a boring axis B along the drilling axis B and vertically mounted upper punch, the lower end face of the introduced into the filling powdery debris touched from above, is limited .

by the axial initial distance A of the two end faces thereby reduced to an axial final distance E for the compaction along the drilling axis B that lowers the upper punch while maintaining the position of the lower punch or raises the lower punch in addition and after completion of compaction lifted up upper punch from the formed geometric precursor moldings and the geometric precursor moldings is removed by lifting the lower punch from the die bore,
and a subsequent method of thermal treatment of the geometric precursor shaped body at a temperature ≥ 100 ° C, in which decomposes at least a subset of its constituents to form at least one gaseous compound and / or chemically reacts and the oxidic geometric shaped body is formed.

Processes for producing an oxidic geometric shaped body using methods similar to those described in the preamble of this specification are known (cf. EP-A 184 790 . US 2005/0263926 as well as the JP-A 10/29097 ).

she are usually applied to from powdery Mixtures (heaps) of metal oxides and / or of such metal compounds (For example, salts) by heating (thermal treatment) into metal oxides convertible are (at least by thermal treatment in the presence of gaseous molecular oxygen and / or gaseous Oxygen-releasing components) geometric (eg circular cylindrical or circular cylindrical (in short also "annular") To produce precursor shaped body, which after carried out thermal treatment (usually at Temperatures ≥ 100 ° C) as catalysts (in this Case one speaks of solid catalysts) or as a carrier molding (in short, only "carrier body") for catalytic active compounds (eg for (eg annular) Shell catalysts (contain the catalytic active material the outer surface of the carrier molding applied) or for (eg annular) impregnation catalysts (the catalytically active mass becomes (eg by soaking) introduced into the interior of the carrier molding) can be used. The term "oxidic Shaped body "expresses that the molded body at least one metal oxide, often at least one multimetal oxide (In addition to oxygen, it contains at least two of each other different metals; Semi-metals such as phosphorus, antimony, arsenic and silicon should also be attributed to metals in this document).

Instead of the term impregnated catalysts is common also the term used supported catalysts. at the catalytic active compounds are often to multimetal oxides. Use find thus produced geometric shaped catalyst bodies for example for (optionally diluted with inert shaped bodies) the interior of the reaction tubes of a tube bundle reactor with a fixed catalyst bed. As inert shaped body for dilution also come geometrical carrier bodies (eg ring-shaped) into consideration. Such a fixed catalyst bed is suitable inter alia for carrying out heterogeneously catalyzed gas phase reactions (eg, partial oxidations of organic compounds). The corresponding Reaction gas mixture flows through the fixed catalyst bed and during the residence time on the catalyst surface the desired reaction takes place.

adversely by mechanically compacting a powdery heap generated geometric shaped bodies is very general, that the cohesion of the powder grain in the resulting geometric Shaped body essentially not intramolecular chemical bonds, but by lasting interparticular Bindings is accomplished. Although results from particle deformations and fractures during the compression process in the rule an increase in the total interparticle contact area, however, the amount of interparticle generated by compaction is Binding forces a comparatively limited.

As detailed Investigations by the applicant is the aforementioned facts, in particular in Related to according to the preamble method this oxidic geometric shaped bodies produced in this document and their geometric precursor moldings of relevance. As part of the compression of the in the filling space applied to the die introduced powdered aggregate Pressing pressure within the powdery mass essentially spatially acts on all sides, it is unavoidable that at the generation of the geometric precursor shaped body whose lateral surface against the inner wall of the die bore is pressed. The latter requires that the lateral surface of the geometric precursor shaped body in a certain The circumference adheres to the inner wall of the die bore. When removing of the geometric precursor shaped body formed as described from the die hole by lifting the lower punch, must therefore overcome the related friction become. If this is pronounced, it can be overcome in the geometric precursor shaped body for training come from visually barely perceptible cracks. At a subsequent thermal treatment of such geometric precursor shaped bodies, in the context of those in the geometric precursor shaped body in addition gases are released (usually contains the compressed material is subject to thermal treatment Forming gaseous substances decomposing and / or chemically reacting constituents (eg pore formers)), takes an im geometric precursor moldings already existing Cracking usually obviously still develops and develops if necessary until breakage. Partially evolves an existing cracking (which, as already said, often barely visible) even when filling in the z. B. Reaction tubes and / or in the course of performing the catalytic gas phase reaction of unwanted breakage. In many cases, the thermal treatment of the geometric Vorformformkörper also only in the reactor (eg. in the reaction tube) located (for example, by passage correspondingly heated gases through the already charged reaction tubes). However, fragments present in the catalyst bed require a compression of the same and cause when flowing through the same Reaction gas mixture ultimately an increase in the flow suffered pressure loss.

A countermeasure that can be taken to reduce the appearance described above is, for. Example, in it, before the introduction of oxidic geometric moldings in the context of their production incurred break off sieve (see, for. US-B 7,147,011 and the German application with the file reference 102007028332.8 ). In the context of such screening usually also those oxidic geometric shaped bodies, which have previously shown only pronounced cracking, so that the fracture during the filling of the reaction tubes with the screen residue is usually minimal.

adversely However, such a procedure is that the raw material costs for a large-scale catalyst production are not insignificant, which is why the resulting sieving through sieving a not inconsiderable material loss.

A further countermeasure, which is already taken in the relevant prior art to reduce the described appearance, consists in finely divided lubricant (for example boron nitride and / or graphite in the pulverulent aggregate to be compacted for the geometric precursor shaped body; DE-A 102005037678 and the German application with the file reference 102007003778.5 as well as the prior art cited in these documents), in order to reduce in this way the static friction between the lateral surface of the geometrical precursor shaped body and the inner wall of the die bore. A disadvantage of such a procedure, however, is the additional need for an adjuvant, which may also have an adverse effect on the resulting catalytic activity.

Another possible countermeasure will be to use a die whose die bore has the smoothest possible surface. In particular, when at least one constituent of the powdery aggregate to be mechanically compacted is a nitrate salt (eg, at least one metal compound may be a metal nitrate or a metal nitrate hydrate), an ammonium salt (eg, at least one metal compound may be an ammonium salt (e.g. Of course, pore formers added to the pulverulent aggregate may also be ammonium salts such as, for example, NH ₄ HCO ₃ , NH ₄ OH, ammonium haloheptamolybdate tetrahydrate. (NH ₄ ) ₂ CO ₃ , NH ₄ HSO ₄ , (NH ₄ ) ₂ SO ₄ , NH ₄ CHO ₂ , NH ₄ CH ₃ CO ₂ and ammonium oxalate) or ammonium nitrate, however, the abovementioned measures have not been fully understood as proved satisfactory. On the contrary, careful investigations have shown that the matrix material touching the die bore plays a decisive role in the described problem, and that, above all, taking into account the fact that a satisfactory procedure per die, even over prolonged production periods, on oxidic geometric shaped bodies of bis to 20,000 pieces per hour and more.

• – die Innenwand der Matrizenbohrung,
• – die obere Stirnfläche eines von unten entlang der Bohrachse B in die Matrizenbohrung hub- und senkbeweglich eingeführten unteren Stempels, auf der das in den Füllraum eingebrachte pulverförmige Haufwerk aufliegt, und
• – die längs der Bohrachse B in einem axialen Ausgangsabstand A oberhalb der oberen Stirnfläche des unteren Stempels befindliche untere Stirnfläche eines entlang der Bohrachse B hub- und senkbeweglich angebrachten oberen Stempels, dessen unter Stirnfläche das in den Füllraum eingebrachte pulverförmige Haufwerk von oben berührt, begrenzt wird,

indem man den axialen Ausgangsabstand A der beiden Stirnflächen dadurch auf einen für die Verdichtung vorgegebenen axialen Endabstand E längs der Bohrachse B verringert, dass man den oberen Stempel absenkt und dabei die Position des unteren Stempels beibehält oder den unteren Stempel zusätzlich anhebt und nach beendeter Verdichtung der obere Stempel vom gebildeten geometrischen Vorläuferformkörper abgehoben und der geometrische Vorläuferformkörper durch Anheben des unteren Stempels aus der Matrizenbohrung entfernt wird,
sowie ein sich daran anschließendes Verfahren der thermischen Behandlung des geometrischen Vorläuferformkörpers bei einer Temperatur ≥ 100°C, bei dem sich wenigstens eine Teilmenge seiner Bestandteile unter Ausbildung wenigstens einer gasförmigen Verbindung zersetzt und/oder chemisch umsetzt und der oxidische geometrische Formkörper sich ausbildet, zur Verfügung gestellt, das
dadurch gekennzeichnet ist, dass das die Matrizenbohrung berührende Matrizenmaterial ein Hartmetall ist, das zu ≥ 80 Gew.-% aus dem Hartstoff Wolframcarbid und zu wenigstens 5 Gew.-% aus dem metallischen Bindemittel Nickel besteht.Accordingly, with the present patent application, a method for producing an oxidic geometric shaped body, comprising the mechanical compression of a introduced into the filling space of a matrix powdered aggregate, of components, the at least one metal compound by thermal treatment at a temperature ≥ 100 ° C in a Metal oxide, or at least one metal oxide, or at least one metal oxide and at least one metal compound, with the proviso that at least one component of the powdery aggregate is a nitrate salt, an ammonium salt or ammonium nitrate, to a geometric precursor shaped body, in which the filling space in a with a vertical drilling axis B from top to bottom passed through the Matrizenmaterial template bore is located and at least through

• The inner wall of the die bore,
• - The upper end face of a down along the drilling axis B in the die bore hub and lowered vertically introduced lower punch on which the introduced into the filling powdery debris rests, and
• - The along the drilling axis B in an axial output distance A above the upper end face of the lower punch located lower end face of a along the drilling axis B hub- and vertically mounted upper punch whose bottom face of the introduced into the filling powdery debris touches from above, is limited .

by the axial initial distance A of the two end faces thereby reduced to an axial final distance E for the compaction along the drilling axis B that lowers the upper punch while maintaining the position of the lower punch or raises the lower punch in addition and after completion of compaction lifted up upper punch from the formed geometric precursor moldings and the geometric precursor moldings is removed by lifting the lower punch from the die bore,
and a subsequent process of thermal treatment of the geometric precursor shaped body at a temperature ≥ 100 ° C, in which at least a subset of its constituents to form at least a gaseous compound decomposes and / or chemically reacts and forms the oxidic geometric shaped body available asked, that
characterized in that the die material contacting the die bore is a hard metal which is ≥ 80 wt .-% of the hard material tungsten carbide and at least 5 wt .-% of the metallic binder nickel.

Under a cemented carbide in this document is a sintered composite material from ≥ 80 wt .-% tungsten carbide as hard material and ≥ 5 % By weight of nickel as a tough metallic binder become.

When other hard materials can be used according to the invention Carbide additionally other metal carbides, metal nitrides and metal borides, wherein the metal is preferably at least a metal from the group consisting of W, Ti, Zr, Hf, V, Nb, Ta, Mo and Cr is. As a further metallic binder, the carbide nickel and Fe, Co and / or Cr. According to the invention advantageous is attributable to the metallic binder Ni in the hard metal Weight percentage is greater than that on each other metallic binder contained in the carbide Weight.

As further hard materials, hard metals from the group consisting of titanium carbide (TiC), tantalum carbide (TaC), niobium carbide (NbC), vanadium carbide (VC), chromium carbide (Cr ₃ C ₂ ) and mixed metal carbides (eg Tantalum niobium carbide (TaNbC)) containing at least two of the metals contained in the aforementioned metal carbides, which act to inhibit grain growth.

When Tough metallic binders are preferred according to the invention exclusively nickel or nickel and chromium in the invention to be used Hard materials for use.

In general, the amount attributable to the metallic binder weight fraction of the invention according to hard metals used up to 20 wt .-%, often up to 15 wt .-% and often up to 10 wt .-%.

The Production of sintered suitable according to the invention Carbides is preferably carried out so that the desired Amount of refractory hard materials (based on the weight of the resulting carbide ≥ 80 wt .-% WC) and the desired Amount of lower melting metal powder (tough metallic Binder; based on the weight of the resulting cemented carbide ≥ 5 Wt .-% nickel) mixed (preferably homogeneous) and (eg in the electric Oven) to temperatures below the melting point of the refractory Heating hard materials, the temperature and duration of heating be chosen so that the hard material component to a skeleton sintered (the hard phase), in which the metal content as Binding phase (binder) is incorporated. The grain size (in particular of the hard material portion) in the hard metal powder (starting powder) can be z. B. 0.2 microns to 15 microns, advantageous 0.5 to 3 microns, more preferably 1 to 1.5 microns be.

The production of sintered hard metals is z. B. in the writings AT-PS 358833 . EP-A 1364732 . AT-PS 362943 and in the study "Fatigue behavior of carbide G55 Co at room temperature", by Frank Hebner from Erlangen, September 7, 2003, at the Friedrich-Alexander-University Erlangen-Nürnberg, Institute of Materials Science, Chair I - general material properties, Prof. Dr. med. As a rule, hard metals to be used according to the invention have a Rockwell hardness of not less than 80, a Vickers hardness of ≥ 1500 and a flexural strength of N 2000 Nlmm ² .

According to the invention preferred consists of the carbide to be used according to the invention to ≥ 85% by weight, more preferably to ≥ 90% by weight of tungsten carbide (WC) and ≥ 5% by weight of nickel, especially preferably to ≥ 7 wt .-% of nickel.

Even better for the process according to the invention is the use of a hard metal which, based on its weight, consists of 90 to 95% by weight of tungsten carbide (WC), to ≥ 0 to 1% by weight of at least one metal carbide from the group titanium carbide (TiC), tantalum carbide (TaC), niobium carbide (NbC), vanadium carbide (VC), chromium carbide (Cr ₃ C ₂ ) and mixed metal carbides (eg tantalum niobium carbide (TaNbC)) containing at least two of the up to 10% by weight of Ni, Fe, Co and / or Cr (preferably Ni and Cr), with the proviso that the proportion by weight of Ni in the cemented carbide is ≥ 5% by weight, consists.

In the process according to the invention, very particular preference is given to using such a cemented carbide as that consisting of 90 to 95% by weight WC, ≥ 0 to 1% by weight TiC and / or TaNbC; and 5 to 10% by weight Ni or Ni and Cr with the proviso that the weight content of Ni on the hard metal is ≥ 5 wt .-%.

Among the aforementioned carbides are also those favorable, the 89.2 to 94.8% by weight WC, 0.2 to 0.8% by weight TiC and TaNbC, such as 5 to 10% by weight Ni consist.

For the latter group of hard metals include the invention particularly favorable usable carbide G10-Ni hard metal ^® society including in D-70572 Stuttgart.

All The above statements on carbide are in particular for grain sizes (grain diameter) in the hard metal powder (in particular its proportion of hard material) from 0.5 μm to 2 μm, preferably from 1 to 1.5 μm.

in principle can the die in the inventive method exclusively from one of the hard metals described above consist.

Not least for reasons of economy, however, the die is advantageous from a Werkstoffver made of a bunch. This (the die material) consists only on its the die bore-contacting side of the inventively required carbide and on its side facing away from the die bore side advantageously made of a tool steel. Preferably, the tool steel has the following element composition WS: 1.50 to 1.80% by weight C., 0.10 to 0.40 wt% Si, 0.10 to 0.50 wt% Mn, ≥0 to 0.05% by weight P, ≥0 to 0.05% by weight S, 10 to 13% by weight Cr, 0.50 to 0.80 wt% Not a word, 0.10 to 1.10% by weight V, ≥0 to 0.60 wt% W, and ≥ 0 to 0.10% by weight one or more rare earth metals, and in the over ferrous and manufacturing contaminants in which the percentages are in each case based on the Ge total weight are related.

Particularly preferred tool steels WS are the DIN materials 1.2601 and 1.2379 , In other words, according to the invention, the die expediently consists of a core made of cemented carbide having the die bore and a die surround comprising the core of the die made of a tool steel (preferably of one of the elemental composition WS). A wall thickness of the tungsten carbide touching the die bore of a few millimeters (eg 1 to 10 mm, often 2 to 8 mm, or 2 to 6 mm, or 2 to 4 mm) is generally sufficient. The wall thickness of the tool steel die mount will normally be at a few centimeters (eg 0.5 to 3 cm, or 1 to 2 cm).

The mean roughness Ra (after DIN 4768 ) of the inner wall of the die bore should preferably be no more than 0.2 .mu.m and more preferably not more than 0.1 .mu.m and more preferably not more than 0.05 .mu.m in the process according to the invention. The average roughness value is the arithmetic mean of the absolute amounts of the distances of the roughness profile from the middle line within the measurement path.

Corresponding low roughness can be achieved by polishing. The production of a die to be used according to the invention with a core made of hard metal (eg G10-Ni) and a die surround made of tool steel (eg from the DIN material 1.2379 ) is in a simple way z. B. by so-called shrinking possible. It is first made the Matrizeneinfassung from the tool steel. This is then heated, whereby it expands. The tungsten carbide core can be inserted into the expansive die border. Upon cooling, the die border contracts again and forms a quasi-seamless bond with the hard metal core.

As already stated, the invention comprises Process the preparation of geometric precursor moldings from powdered debris that already (under normal conditions (25 ° C, 1 atm.) Usually solid) at least one metal oxide contains, and / or at least one such metal compound (For example, a metal salt) obtained by thermal treatment at a Temperature ≥ 100 ° C in (under normal conditions usually solid) metal oxide is convertible (at least by thermal treatment in the presence of gaseous molecular oxygen and / or gaseous oxygen releasing components; in principle, the oxygen source z. B. in the form of a peroxide also part of the powdery Haufwerks and thus of the invention resulting be geometric precursor molding). The Solid metal oxide can be one that, in addition to oxygen only one or even more than one (eg two or three) metal elements contains. Likewise come as metal compounds in principle those in which only one, or even more than one (z. B. two or three) metal elements.

Furthermore, at least one constituent of the pulverulent aggregate to be compacted according to the invention must be a nitrate salt, an ammonium salt or ammonium nitrate. In principle, such a nitrate salt may be, for example, one of the abovementioned metal compounds. D. h., The powdery debris can be such a nitrate salt (the term should also subsume their hydrates in this document) z. At least one metal nitrate from the group consisting of cobalt nitrate, iron nitrate, bismuth nitrate, nickel nitrate, cesium nitrate, copper nitrate, calcium nitrate, magnesium nitrate and the hydrates of these nitrates. Of course, the term nitrate salt also includes the nitric acid, as the protic salt of the nitrate anion. In principle, the ammonium salt can also be one of the abovementioned metal compounds (to be mentioned by way of example the ammonium metavanadate and the ammonium heptamolybdate tetrahydrate).

Of course, the powdery debris to be compacted according to the invention as ammonium salt may also contain those ammonium salts which contain no metal atom / ion (no metallic constituent) and in the further course of the production according to the invention of an oxidic geometric shaped body essentially function as pore formers. As such pore-forming ammonium salts are exemplified NH ₄ HCO _3, NH ₄ OH, (NH _{4) 2} CO _3, NH ₄ HSO _4, (NH _{4) 2} SO _4, NH ₄ CHO _2, NH ₄ CH ₃ CO ₂ and ammonium oxalate and the hydrates of the aforementioned compounds. Of course, the powdery debris to be compacted according to the invention may also contain ammonium nitrate (or its hydrate) added, which is both a nitrate salt and an ammonium salt.

As a further prerequisite, it is essential for the process according to the invention that the pulverulent aggregate to be compacted according to the invention, and with it the resulting geometric precursor shaped bodies, contain substances (constituents) which differ from those used in the thermal treatment of the geometric precursor shaped bodies (treatment temperature ≥ 100 ° C) decompose at least partially to form gaseous compounds (under the conditions of the thermal treatment of the geometrical precursor shaped bodies) and / or to react them chemically (for example with formation of ammonia, water vapor, CO ₂ , CO and / or nitrogen oxides). As a rule, the weight loss associated with the thermal treatment of the geometric precursor shaped bodies and based on their initial weight (as a result of the aforementioned outgassing) is 0.5 to 40% by weight, frequently 0.8 to 35% by weight or 2 to 30% by weight .-%.

A Formation (release) of gaseous compounds in the Frame of a thermal treatment according to the invention of geometric precursor shaped bodies produced according to the invention is usually z. B. then given when the components of the According to the invention to be compacted powdery debris are at least partially organic in nature or hydroxide ions, Carbonate ions, hydrogen carbonate ions, ammonium ions, hydrogen phosphate ions, Hydrogensulfationen and / or nitrate ions included in the thermal treatment according to the invention in usually at least partially decompose. It can the hydroxide ions, carbonate ions, hydrogen carbonate ions, ammonium ions, Hydrogen phosphate ions and / or nitrate ions in principle already part of the non-oxide metal compounds in The powdery to be compacted according to the invention Be a heap. You can according to the invention to compacting powdery debris but also in addition (or only) as part of at the subsequent thermal Treatment of geometric precursor moldings Pore-forming substances and no metal compounds be added.

Of course can in the method according to the invention The powdery to be compacted according to the invention Heap in inventively advantageous manner As a lubricant additives are added, the static friction between the geometric produced according to the invention Precursor molding and the inner wall of the die bore in addition to the measure according to the invention the use of a specific carbide as the die bore Further reduce touching matrix material. As such Lubricants can z. Graphite, carbon black, Polyethylene glycol, stearic acid, salt of stearic acid, Starch, polyacrylic acid, mineral oil, plant oil, Water, boron nitride, boron trifluoride, glycerol, finely divided Teflon powder and / or cellulose ethers. It is at this point but again stated that the inventive Last but not least, this process impresses with its minimization the need for such aids. The aforementioned Lubricants may be within the scope of the invention thermal treatment of the geometric precursor moldings optionally also with the formation of gaseous substances decompose or chemically react.

When Further shaping aids can according to the invention compacting powdered debris so-called reinforcing agent added, which promote the cohesion in the resulting Comprimat. Such reinforcing agents may be, for example Microfibers made of glass, asbestos, silicon carbide and / or potassium titanate be.

Based on the total amount of the invention to be compacted powdered aggregate becomes the total amount of forming aids usually not more than 30% by weight, usually not more than 20% by weight and often not more than 10 wt .-% amount.

Within the scope of the inventive thermal treatment of the geometric precursor shaped bodies, the formation of the oxidic geometric shaped bodies desired according to the invention occurs. According to the invention, this thermal treatment is carried out at temperatures ≥ 100 ° C. Frequently, the invention takes place appropriate thermal treatment at temperatures ≥ 150 ° C, or ≥ 200 ° C (eg 300 to 800 ° C, or 350 to 750 ° C, or 300 to 700 ° C). In particular, in the case of production of oxidic geometric carrier shaped bodies, the thermal treatment may include such at temperatures ≥ 600 ° C, or ≥ 1000 ° C. 1500 ° C are not exceeded in most cases.

In principle, the thermal treatment according to the invention of geometric precursor shaped bodies produced according to the invention (for example circular-cylindrical, annular, circular-cylinder-like or ring-like) under reduced pressure under an inert atmosphere (eg N ₂ , noble gases, water vapor, CO ₂ etc.) can be reduced Atmosphere (eg, H ₂ or NH ₃ ) or carried out under an oxidizing atmosphere. In general, oxidizing atmospheres will contain molecular oxygen. Typical oxidizing atmospheres are mixtures of inert gas (N ₂ , noble gases, water vapor, CO ₂ etc.) and molecular oxygen. Usually, the content of molecular oxygen while at least 0.1 vol .-%, often at least 0.2 vol .-%, often at least 0.5 vol .-%, often at least 1 vol .-%, or at least 10 vol. -%, or at least 20 vol .-% amount. Of course, the content of molecular oxygen in such mixtures may also be 30% by volume, or 40% by volume, or 50% by volume, or more. Of course, as an oxidizing atmosphere for such a thermal treatment but also pure molecular oxygen into consideration. Frequently, an oxidizing thermal treatment will take place under air. In general, the thermal treatment can take place under a stagnant or under flowing gas atmosphere (eg in the air stream). Advantageously, a flowing gas atmosphere is usually used.

Of the Concept of the atmosphere (or the gas atmosphere) in which the thermal treatment takes place, is in this To understand writing so that it is made from the invention geometric precursor moldings in the context of thermal treatment due to decomposition processes and / or chemical reactions Gases not included. Of course, the gas atmosphere, in which the thermal treatment takes place, but also exclusively or partially composed of these gases. Also, both the treatment temperature as well as the treatment atmosphere over the Duration of the thermal treatment temporally constant or temporally be designed variably. In the event that as a result the subsequent thermal treatment of inventively available geometric precursor shaped bodies oxidic geometric Full catalysts are sought, the active material at least is a multimetal oxide, the thermal treatment is often done at temperatures of 150 to 650 ° C, often 200 to 600 ° C, often 250 to 550 ° C and often 300 to 500 ° C. The term "multimetal oxide" means in this document no simple mixture of various metal oxides, but a complex Polyoxy compound in addition to oxygen at least two from each other contains different metals (metallic constituents).

The inventive thermal treatment of the geometric Vorformformkörper can in the inventive Procedure basically both in one for it designed special device (eg in a belt calciner) and only in the reactor in which they are used should (eg in the reaction tubes of a tube bundle reactor) be made. In the latter case, it is more convenient Route hot gases through the reaction tubes.

Usually is the powdery debris in accordance with the invention Method dry used. However, it can save up to 10% of his Total weight substances added in normal conditions (25 ° C, 1 atm) are liquid. The invention However, method is also applicable if the powdered There are no such liquid substances at all contains more. Of course, the powdery Clusters also contain solid solvates (such as hydrates), such liquid substances in chemical and / or physical have bound form. Such solvates decompose in the inventive thermal treatment of the geometric Precursor molded body usually also below gaseous release of the solvate phase. According to the invention advantageous is the residual moisture of the invention to be compacted Heap at <10 % By weight, in the absence of water of crystallization (or crystal solvate phase) usually at <5 Wt .-%.

The Particle diameter of the invention to be compacted finely divided powdery debris (added Molding and porosifying agents excluded) for at least 90% of the weight of the powdered aggregate (added Shaping and porosity agent not included) in terms of application technology suitably in the range of 10 to 2000 μm, often in the range of 20 to 1800 microns, or from 30 to 1700 μm, or from 40 to 1600 μm, or from 50 are up to 1500 microns. Particularly common are the aforementioned Particle diameter in the range of 100 to 1500 microns or 150 to 1500 microns.

Furthermore The following definitions apply to this font.

Of the Term "lower (upper) face" of a stamp means in this document the surface of the forehead of the stamp at its lower (upper) end. If the stamp z. B. a circular ring cylinder, is both its lower face and its upper End face a circular ring. Is the stamp on the other hand? Circular cylinder, is both its under face and as well its upper end face a circle.

Of the Term "circular cylinder" means in this document always a "straight Circular cylinder ", connecting the endpoints of parallel radii of two in parallel planes of equally sized circles by stretching, this creates a circular cylinder. The links hot generatrices of the cylinder. Stand upright on the parallel circle planes, the cylinder is called "straight" or rotary cylinder. The connecting path of the circle centers is the symmetry axis of the right circular cylinder (often also simply "circular cylinder axis" or "axis of the circular cylinder ") The totality of all generatrix lines forms the lateral surface of the cylinder.

In analogously means the term "truncated cone" in this Type another special rotation body. This (The truncated cone) is created by looking from a straight circular cone parallel to the base a smaller straight cone cuts. The larger of the two by the Cutting generated parallel circular faces is in this Font as a base and the smaller as the top surface designated. The distance from the ground and top surface becomes referred to as the height of the truncated cone. The third of the one Truncated cone bounding surfaces is called lateral surface designated the same. The connecting line of the centers of Base and top surface forms the symmetry axis of the truncated cone (often simply "axis of the truncated cone" called). A cone is a body, by a circle (base circle or base circle) and a point is set outside the plane of the circle (top of the cone) and this results in the points on the outline of the Circle with the one point outside the plane of the circle combines. Is the connecting line with the tip of the cone with the center of the base circle of the cone perpendicular to the base plane, so there is a straight circular cone or rotary cone.

Of the Term "circle" in this document means the area between two concentric circles, d. h., between two circles with common center.

connects one of two in parallel planes congruent (congruent) Circular rings (the base circle ring and the cover circle ring) the respective Endpoints of parallel radii on the two outer radii Circles and the respective endpoints of parallel radii on the both inner circles by stretching, so creates a circular ring cylinder. The links of the endpoints on the two inner circles hot inner generatrices of the annular cylinder (their Ensemble forms the inner shell of the circular cylinder) and the links of the endpoints on the two outer ones Circling is called the outer generatrix of the Annular cylinder (their entirety forms the outer Jacket of the annular cylinder). Stand the generators vertically on the two circular rings, this is called the circular ring cylinder straight or not wrong. The term "circular ring cylinder" should in this document always for the straight circular cylinder stand. The connection path of the circular center points is called Axis of the circular ring cylinder.

Of the Concept of "drilling" should not be understood in this document be that the appropriate opening with the help of drills must have been produced by drilling. Rather, the opening can in another way (eg with the help of a laser, a milling cutter) or a cutting torch). The symmetry of the opening However, it should be like drilling with the help of a drill (or more drills) would have been produced (of course it may also have been created this way).

When Lateral surface becomes the surface of a geometric Shaped body without base (base) and lid (Top surface).

The Feature "that the lateral surface of a circular cylinder slides on the inner wall of a bore "(or vice versa) is in to understand this writing so that, unless otherwise stated is, the outer surface corresponding to the outer surface of the circular cylinder over the area of the sliding section (i.e. h., over the sliding area) on the inner wall of the bore even, but permeable to gas as well axially movable rests.

The Compaction process according to the invention is particular in the case of preparing such geometric precursor shaped bodies of interest, in which the final distance E 2 to 10 mm, or 2 to 8 mm, or 3 to 8 mm, or 3 to 7 mm (a possible Curvature of the frontal surface is intended to determine the distances A and E are ignored; d. h., meaning always the distance of the upper / lower outline the lateral surface of the stamp).

In a simple embodiment of the invention Procedure corresponds to the geometric shape of the inner wall of the Matrizenbohrung those of the lateral surface of a circular cylinder KZ * and both the geometric shape of the lower punch and the geometric shape of the upper punch correspond to those a circular cylinder I *.

In the above-described case, both the upper end face of the lower punch and the lower end face of the upper punch are preferably a flat circular surface on which the drilling axis B of the die bore is perpendicular. The drilling axis B and the axes of symmetry of the circular cylinder I * lie on a straight line. The outer diameter of the two punches is suitably marginally smaller in terms of application than the inner diameter of the die bore in the above case, so that both punches with their outer wall on the inner wall of the die bore can be inserted axially slidably into the die bore. In addition, the annular gaps thus formed between the lower (or upper) contour of the upper punch (or lower punch) and the inner wall of the die bore in the state of the exit distance A and in the state of the final distance E for the in the compression process (compression process) Reduction of template filling space Compressed gas phase (usually air or nitrogen). To ensure the most uniform annular gap, z. B. as in the DE-A 197 14 430 be described with respect to the production of circular cylindrical shaped bodies by tableting of powdery debris described. However, the annular gaps described above are also responsible for the fact that a small amount of burr may be produced on the resulting compact both in the area of the base area and in the area of the top area. The compaction of the powdered aggregate within a ridge is less pronounced than in the bulk of the resulting compact.

The removal of the ridge of otherwise circular cylindrical precursor moldings is therefore comparatively easily possible in the further course of the processing thereof. As a rule, the burrs break z. B. in an analogous to the description of German application with the file reference 102007028332.8 to be performed fractional sieving on its own and are separated. Incidentally, the width of the above-described annular gaps must be based inter alia on the grain size of the pulverulent aggregate to be compacted according to the invention. In other words, the width of the annular gaps should as a rule be limited so that they are not greater than twice (better not greater than the simple) of the powdery grain most frequently represented in the pulverulent aggregate to be compacted (the longitudinal expansion of a powder particle) Powder grain is the longest direct straight line joint of two points on the surface of the powder grain, and if the powdery mass consists of secondary grain produced by agglomeration of primary grain, it is normally appropriate to use the longest dimension of the primary grain to measure the still tolerable ring gap width). Frequently, the aforementioned annular gap widths in the method according to the invention amount to a few hundredths of a millimeter. The matrix itself usually has a planar upper end face. In terms of application, the lower end face of the die is designed flat and the drilling axis B is perpendicular to both planes. Preferably, the die (seen from the die bore) from the shape of a circular cylinder with a flat upper and a planar lower end face. In the outer wall of the circular cylinder extends at half height advantageously a horizontally extending ring or a round Ver depression. It serves to fix the die in the die plate by means of one or more fastening screws.

in principle can reduce the process of the invention in the reduction the output distance A to the final distance E done so that both (the lower and upper) stamp are actively moved towards each other. Of course, this can also be done that under the stamp retains its position and only the upper punch is moved (lowered down).

In usually it is as uniform as possible Surface hardness of the method according to the invention resulting compact (geometric precursor body) quite generally advantageous if in reducing the output distance A on the end distance E upper and lower punch together on each other to be moved (the upper punch is lowered, the lower punch is raised). In this case, the required compression pressure on the powdery heap from the top and bottom Punches applied evenly, giving a more uniform lateral compressive strength of the resulting compressed over whose height is conditional. Also results in a geometric Precursor molding having a more homogeneous mass density over his entire dimension. The latter depends on the thermal Treatment a more homogeneous pore structure and on the latter based ultimately on improved catalyst performance. To set the output distance A is the lower punch (linguistically simplified in this writing also "lower stamp") usually in the die hole while the upper punch releases it, so that the powdery debris introduced from above can be.

Subsequently, the upper punch is lowered until its lower end surface touches the lying in the die bore on the upper end face of the lower punch powdery debris. Starting from the output distance A of the two end faces thus set, the axial end distance E of the two end faces is subsequently set, as already described. The pressing pressures exerted in the end distance E in the procedure described above of both punches (or at least of the upper punch) in a typical manner are usually in the range of 50 to 5000 kg / cm ² . If necessary, it is also possible to first compress to a provisional final distance using a form. The forms used in this regard are typically 5-500 kg / cm ³ . The main (compaction) pressures used for subsequent final compaction to the associated final finish are normally larger than the pre-printed forms used.

To completed compression, the upper punch is formed from the circular cylindrical Precursor molded body lifted and the circular cylindrical Precursor molding by lifting the lower Stamp removed from the die bore. To do that between the lateral surface of the circular cylindrical precursor shaped body and the rolling wall friction occurring in the inner wall of the die bore reduce it is appropriate in terms of application technology, the die hole should not be shaped so that the geometric Shape of the inner wall of the die bore that of the lateral surface a circular cylinder KZ * but at least in the upper part of the die bore that of the lateral surface of a from bottom to top corresponds to slightly widening truncated cone whose Cross-sectional area at its lower end of the cross-sectional area of the circular cylinder KZ * corresponds (in contrast to the circular cylinder is the cross-sectional area of a truncated cone over the height of the truncated cone is not constant but decreases from the top to the bottom). The described geometry of upper and lower stamp is doing maintained. The diameter of the upper and lower punches is in the case of a preparation described above of circular cylindrical precursor bodies in many cases also 2 to 10 mm, or 2 to 8 mm, or 4 up to 8 mm, or 5 to 7 mm.

In corresponding manner as circular cylindrical precursor moldings can also circular cylindrical or short "annular" Precursor moldings are produced. For reasons a vanishing as possible rolling friction between the Lateral surface of generated compressed and the inner wall the die hole, is also in this case application technology advantageously used a die hole, the inner wall at least in the upper part of the die bore the geometric shape of the lateral surface one slightly widening from bottom to top Truncated cone has. The following is therefore only this case be executed in detail (the production of annular Precursor molding is analogous, the longitudinal section II of the die hole is then a continuation Longitudinal section I). The resulting geometric precursor shaped bodies are intended in this document as "ring-like" precursor moldings be designated. The production of "ring-shaped" Precursor molding is in completely corresponding Way possible. The only difference is, that the die bore then no Vorweite from top to bottom having.

• – entspricht die geometrische Form der (äußeren) Mantelfläche des unteren Stempels derjenigen der Mantelfläche eines Kreiszylinders I,
• – entspricht die geometrische Form der (äußeren) Mantelfläche des oberen Stempels derjenigen der Mantelfläche eines Kreiszylinders II,
• – ist in der geometrischen Mitte der oberen Stirnfläche des unteren Stempels eine von oben nach unten durch den unteren Stempel hindurchgeführte Mittelbohrung MB^U ausgebildet;
• – ragt im Ausgangsabstand A der beiden Stirnflächen der Mittelstift MF von unten durch die Mittelbohrung MB^U hindurch bis wenigstens zur geometrischen Mitte der unteren Stirnfläche des oberen Stempels hinauf;
• – weist der Mittelstift MF von unten nach oben die geometrische Form eines Kreiszylinders Z mit einer kreiszylindrischen Mantelfläche MZ auf;
• – ist die Länge der Umrisslinie des Kreiszylinders Z kleiner als die Länge der Umrisslinie des Kreiszylinders I sowie kleiner als die Länge der Umrisslinie des Kreiszylinders II;
• – sind die Position des Mittelstiftes MF und die Position der Matrize einschließlich der Matrizenbohrung längs der Bohrachse B während des Verfahrens relativ zueinander fixiert;
• – ist in der geometrischen Mitte der unteren Stirnfläche des oberen Stempels eine in den oberen Stempel hineinführende und mit wenigstens einem Auslass aus dem oberen Stempel (gasdurchlässig) in Verbindung stehende Mittelbohrung MB^O ausgebildet, die den Mittelstift MF bei der Verringerung des Ausgangsabstands A auf den Endabstand E im erforderlichen Umfang aufzunehmen vermag und in die der Mittelstift MF bereits im Ausgangsabstand A hineinragen kann;
• – liegen die Symmetrieachsen der Matrizenbohrung, des Kreiszylinders I, des Kreiszylinders II, der Mittelbohrung MB^O, des Mittelstiftes MF und der Mittelbohrung MB^U auf einer gemeinsamen durch die Matrizenbohrung vertikal verlaufenden geraden Linie L;
• – weist die Matrizenbohrung längs ihrer Bohrachse einen Längsabschnitt I auf, auf dessen Länge I die geometrische Form der Innenwand der Matrizenbohrung derjenigen der Mantelfläche eines Kreiszylinders KZ entspricht, und an dessen oberem Ende sich unmittelbar ein nach oben gerichtete Längsabschnitt II der Matrizenbohrung anschließt, der die Länge II aufweist;
• – sind die Ausmaße des Längsabschnitts I der Matrizenbohrung und des Kreiszylinders I so beschaffen, dass der untere Stempel während des Verfahrens (der Verringerung des Ausgangsabstands A auf den Endabstand E) stets jeweils wenigstens auf einer Teillänge (vorzugsweise auf einer Teillänge von wenigstens 10%, oder von wenigstens 20%, oder von wenigstens 30% (in der Regel jedoch ≤ 90%, oder ≤ 80%) der Länge I) des Längsabschnitts I mit seiner (äußeren) Mantelfläche auf der Innenwand der Matrizenbohrung gleitend in die Matrizenbohrung geführt ist;
• – sind die Ausmaße der Mittelbohrung MB^U und des Kreiszylinders Z so beschaffen, dass der untere Stempel während des Verfahrens (der Verringerung des Ausgangsabstands A auf den Endabstand E) stets wenigstens im Bereich des Eingangs seiner Mittelbohrung MB^U in seine obere Stirnfläche mit der Innenwand der Mittelbohrung MB^U auf der kreiszylindrischen Mantelfläche MZ des Mittelstiftes MF gleitend in die Matrizenbohrung geführt ist;
• – entspricht die geometrische Form der Innenwand der Matrizenbohrung auf der Länge II des Längsabschnitts II von unten nach oben derjenigen der Mantelfläche eines sich von unten nach oben erweiternden Kegelstumpfes KS, dessen Querschnittsfläche an seinem unteren Ende der Querschnittsfläche des Kreiszylinders KZ an dessen oberem Ende entspricht, mit der Maßgabe, dass beim Erreichen des Endabstands E die untere Stirnfläche des oberen Stempels sich im Längsabschnitt II und die obere Stirnfläche des unteren Stempels sich nicht unterhalb des Längsabschnitts I befindet, so dass sich der durch das mechanische Verdichten des pulverförmigen Haufwerks zwischen den beiden Stirnflächen ausgebildete ringähnliche Vorläuferformkörper beim Erreichen des Endabstands E wenigstens teilweise im Längsabschnitt II befindet. D. h., beim Erreichen des Endabstands E zwischen der oberen Stirnfläche des unteren Stempels und der unteren Stirnfläche des oberen Stempels befindet sich wenigstens ein Teil der Abstandsstrecke zwischen den beiden Stirnfläche im Längsabschnitt II.

In the case of production of ring-like precursor shaped bodies, the filling space located in a die bore guided from above downwards through the female material B is suitably applied in addition to the inner wall of the die bore, the upper end face of the lower punch and the lower end face of the upper punch the lateral surface of a from the geometric center of the upper end face of the lower punch out along the drilling axis B in the die bore guided from bottom to top center pin MF, which extends at least up to the geometric center of the lower end face of the upper punch, limited, and, application technology appropriate

• The geometrical shape of the (outer) lateral surface of the lower punch corresponds to that of the lateral surface of a circular cylinder I,
• The geometrical shape of the (outer) lateral surface of the upper punch corresponds to that of the lateral surface of a circular cylinder II,
• - In the geometric center of the upper end face of the lower punch a guided from top to bottom through the lower punch center hole MB ^{U is} formed;
• Protrudes in the initial distance A of the two end faces of the center pin MF from below through the central bore MB ^U up to at least the geometric center of the lower end face of the upper punch up;
• - Has the center pin MF from bottom to top on the geometric shape of a circular cylinder Z with a circular cylindrical surface MZ on;
• - The length of the contour of the circular cylinder Z is smaller than the length of the contour of the circular cylinder I and smaller than the length of the outline of the circular cylinder II;
• - are the position of the center pin MF and the position of the die including the die bore fixed relative to each other along the drilling axis B during the process;
• In the geometric center of the lower end face of the upper punch, a center hole MB ^O leading into the upper punch and communicating with at least one outlet from the upper punch (gas permeable) is formed on the center pin MF in reducing the initial distance A to the Final distance E is able to accommodate the required extent and in the center pin MF can already protrude at the output distance A;
• - Are the axes of symmetry of the die bore, the circular cylinder I, the circular cylinder II, the center hole MB ^O , the center pin MF and the center hole MB ^U on a common through the die bore vertically extending straight line L;
• - The die bore along its bore axis on a longitudinal section I, on the length of which I corresponds to the geometric shape of the inner wall of the die bore that of the lateral surface of a circular cylinder KZ, and at its upper end is immediately followed by an upward longitudinal section II of the die bore, which connects the Has length II;
• The dimensions of the longitudinal section I of the die bore and of the circular cylinder I are such that during the process (the reduction of the exit distance A to the final distance E) the lower die is always in each case at least part of the length (preferably a partial length of at least 10%; or of at least 20%, or of at least 30% (but usually ≤ 90%, or ≤ 80%) of the length I) of the longitudinal section I with its (outer) lateral surface on the inner wall of the die bore slidably guided in the die bore;
• - The dimensions of the center hole MB ^U and the circular cylinder Z are such that the lower punch during the process (the reduction of the output distance A to the final distance E) always at least in the region of the entrance of its central bore MB ^U in its upper end face with the inner wall the central bore MB ^{U is} slidably guided on the circular cylindrical surface MZ of the center pin MF in the die bore;
• - corresponds to the geometric shape of the inner wall of the die bore on the length II of the longitudinal section II from bottom to top of that of the lateral surface of a flared from bottom to top truncated cone KS whose cross-sectional area corresponds at its lower end to the cross-sectional area of the circular cylinder KZ at its upper end, with the proviso that when reaching the final distance E, the lower end face of the upper punch is in the longitudinal section II and the upper end face of the lower punch is not below the longitudinal section I, so that by the mechanical compression of the powdery debris between the two end faces trained ring-like precursor shaped body when reaching the final distance E at least partially located in the longitudinal section II. D. h., When reaching the final distance E between the upper end face of the lower punch and the lower end face of the upper punch is at least a portion of the distance between the two end face in the longitudinal section II.

Advantageous are in the described production of ring-like Precursor moldings when reaching the final distance E between the upper face of the lower punch and the lower end surface of the upper punch at least 20% or at least 30%, preferably at least 40% or at least 50%, more preferably at least 60% or at least 70% and most preferably at least 80% or at least 90% of the Distance distance (or 100% of the distance, that is, the entire Distance between the upper end face of the lower Stamp and the lower face of the upper punch upon reaching the final distance E) between the two end faces in the longitudinal section II of the die bore. Most advantageous is the method described when, when reaching the Final distance E both the under face of the upper punch as well as the upper face of the lower punch in Longitudinal section II of the die bore are located so that the whole by the mechanical compression of the powdery Haufwerks formed between the two end faces ring-like precursor moldings in Reaching the final distance E located in the longitudinal section II. It proves to be favorable in the aforementioned case, if already in the state of the output distance A, both the lower Face of the upper punch as well as the upper end face of the lower punch in the longitudinal section II.

The Outline of the circular cylinder II is the inventive Procedures appropriate in terms of application technology normally longer or equal to the outline of the circular cylinder I. As a rule, the two aforementioned outlines are the same long.

About that In addition, the upper end face of the lower punch lie and the lower end surface of the upper punch advantageous in planes parallel to each other, on which the drilling axis B is vertical stands.

The method described is particularly suitable for the preparation of such ring-like precursors Moldings in which the final distance E (a possible curvature of the end faces should not be taken into account in determining the distances A and E, ie, always means the distance of the upper / lower contour of the cylindrical surface of the stamp) 2 to 10 mm, or 2 to 8 mm, or 3 to 8 mm, or 3 to 7 mm. They are all to be referred to in this document in particular as ring-like precursor shaped bodies F. Frequently, the quotient Q from the length of the outline of the circular cylinder Z (numerator) and the length of the outline of the circular cylinder I (denominator) is 0.3 to 0.7 or 0.4 to 0.6.

D. h., the difference formed by subtracting the radius of the outline of the circular cylinder Z from the radius of the outline of the circular cylinder I, in the case of ring-like moldings F often 1 to 3 mm, or 1 to 2 mm, or 1.5 to 2 mm, or 1 to 1.5 mm. The diameter of the outline of the circular cylinder I is in the case of ring-like moldings F in many cases also 2 to 10 mm, or 2 to 8 mm, or 4 to 8 mm, or 5 to 7 mm.

As already said, is the cross-sectional area of a truncated cone in contrast to the circular cylinder over the height the truncated cone is not constant, but decreases from the top surface towards the base towards.

This Of course, it also applies to the truncated cone KS, which is on the Length of longitudinal section II in the die bore can be inscribed and its cross-sectional area increases from bottom to top ("upside down truncated cone").

If H is the height of the truncated cone KS, it is advantageous if the expansion of the truncated cone KS from below (from the top surface) upwards (to the base surface) is such that between the diameter DD of the top surface, the diameter DG of the base and Height H of truncated cone of KS the following relation is fulfilled: 0.003 × H ≤ DG - DD ≤ 0.050 × H (I).

Preferably, the method of the invention applies 0.005 × H ≤ DG - DD ≤ 0.025 × H (II).

Particularly preferred in the inventive method 0.007 × H ≤ DG - DD ≤ 0.015 × H (III).

The The above applies in particular in the case of an inventive Preparation of ring-like precursor shaped bodies F to.

Normally, in the production of ring-like precursor shaped bodies according to the invention, both the upper end face of the lower punch (accessible to the powdery debris) and the lower end face of the upper punch (accessible to the powdery debris) have the geometrical shape of the face of a circular ring cylinder. That is, both faces are normally circular rings, which are preferably congruent. For various reasons (see eg EP-A 184 790 ), it may be appropriate, one or both of the aforementioned end faces (the two outer and the two inner circles remain preferably congruent) z. B. concave (ie, the annulus is curved inward in the stamp interior). In this case, the corresponding end of the associated punch has the geometric shape of a circular groove ( 36 ) (= a circular depression, in the production of ring-like precursor shaped bodies F, the groove depth is usually ≦ 2 mm). The respectively resulting end face of the ring-shaped precursor shaped body produced according to the invention is then not planed in a corresponding manner but arched outwardly (convexly). Such a configuration proves to be particularly advantageous in the case of carrier moldings produced according to the invention. Due to the curved end faces, the production of undesired twins or triplets of the resulting shaped catalyst bodies occurs to a lesser extent in the production of carrier or shell catalysts resulting therefrom. The radius of such a curvature is usually 0.4 to 5 times the outer diameter of the circular cylinder I. Otherwise, in the EP-A 184 790 The advantages of curved end faces of hollow cylinders are the same in a corresponding manner.

In principle, the profile of the upper end of the lower punch and / or the profile of the lower end of the upper punch of the production of ring-like precursor tablets according to the invention may also be designed in any other manner known for tablets (in particular pharmaceuticals). example wise, one or both of the above-mentioned faces can also be made convex. Also, one of the two end faces can be made concave and the other convex. However, in the case of production of ring-like unsupported catalysts, both end faces are preferably designed flat.

The outer diameter of the lower punch is usually marginally smaller than the inner diameter of the die bore in the longitudinal section I, so that the lower punch with its outer wall on the inner wall of the longitudinal section I of the die bore axially slidably into the die bore can be introduced in the inventive production ring-like precursor. Since not only the lower end face of the upper punch but preferably also the upper end face of the lower punch in the longitudinal section II of the die bore is when reaching the end distance E, the outer diameter of the lower punch is thus regularly smaller than the inner diameter of the die bore at the height Similarly, the outer diameter of the upper punch is suitably in terms of performance usually slightly smaller than the inner diameter of the die bore at the level of the lower end face of the upper punch on reaching the final distance E. In the aforementioned way and It is ensured that both the lower punch and the upper punch can move in the required procedurally required frame relatively freely in the relevant longitudinal sections of the die bore. In addition, the annular gaps thus formed between the lower (or upper) contour of the upper punch (or lower punch) and the inner wall of the die bore in the state of the exit distance A and in the state of the final distance E for the in the compression process (compression process) Reduction of template filling space Compressed gas phase (usually air or nitrogen). To ensure the most uniform annular gap, z. B. as in the DE-A 197 14 430 be described with respect to the production of circular cylindrical shaped bodies by tableting of powdery debris described. The sliding of the lower punch on the inner wall of the die bore of the longitudinal section I proves to be a significant advantage of the described procedure in this context. However, the annular gaps described above are (as already described in the case of circular cylindrical precursor shaped bodies) also the reason for the fact that the burr-like compact produced in accordance with the invention can form a burr to a small extent both in the area of the base area and in the area of the top area. The compaction of the pulverulent aggregate within a ridge is less pronounced than in the bulk of the compact produced according to the invention. The removal of the ridge from the ring-like precursor shaped body is therefore comparatively easily possible in the further course of the processing thereof. As a rule, the burrs break z. B. in the context of a like in the German application with the file reference 102007028332.8 described to be performed fractional sieving by itself and are separated.

Furthermore must (as already said) the width of the above-described annular column among other things on the grain of the invention to orient compacting powdered aggregate. D. h., the width of the annular gap should usually be so limited that it is not larger than twice (better not larger than the simple one) in the to be compacted powdery debris most frequently represented longest extent of the powder grain (the longest dimension of a powder grain is the longest straight-line direct connection between two the surface of the powder grain located points; consists the powdery debris from agglomeration of Primary grain produced secondary grain, it is in the Reason appropriate, for the dimensioning of the still tolerable Ring gap width the longest dimension of the primary grain zoom pull).

in the Frame of the inventive production of ring-like Precursor moldings F are the aforementioned Annular gaps are usually few (usually less than ten, usually less than five) hundredths of a millimeter, and This is also the case when the final distance E reaches both End surfaces are located in the longitudinal section II. Preferably In this case too, the outline of the circular cylinder II is the same long as the outline of the circular cylinder I.

In principle, in the inventive production of ring-like precursor shaped bodies, the die bore can only be formed from the longitudinal sections I (FIG. 31 ) and II ( 32 ) (have only the longitudinal sections I and II).

Dies with such die bores are to be referred to in this document as "dies with a simple truncated cone." A longitudinal section through dies of this type is shown by way of example 2a and 2 B This font (at its upper and at its lower end, the die bore is suitably slightly rounded in terms of application, in order to minimize the risk of injury from sharp edges; 1 to 8th This font in its graphic representation of the specifications in "tables book metal ", publishing house Europe teaching materials, 41st edition, 1999 (D-42781-Haan Gruiten) ; for the sake of clarity were in 6 not all sections are completely displayed; reference is made to the individual presentations in this regard). Of course, the longitudinal sections I and II of the die bore of a die can be followed by further longitudinal sections both upwardly and downwardly. It is only essential that under stamp (the upper punch) by itself to the longitudinal section I (the longitudinal section II) of the die bore optionally downwards (above) subsequent longitudinal sections in the longitudinal section I (in the longitudinal section II) can be introduced.

Particularly advantageous for economical reasons, the use of dies whose die bore is such that not only at its upper end directly an upwardly directed longitudinal section II, but also at the lower end of a particularly advantageous for producing ring-like precursor shaped body downwardly directed longitudinal section (in this document as longitudinal section II * ( 33 ), in which the geometric shape of the inner wall of the die bore on the length II * of the longitudinal section II * also corresponds to the lateral surface of a truncated cone whose cross-sectional area corresponds at its upper end to the cross-sectional area of the circular cylinder KZ at its lower end (in this document as Truncated cone KS *), but with a downwardly widening cross-section (preferably also the diameter of the top surface, the diameter of the base surface and the height of the truncated cone KS * satisfy at least one of the relationships (I), (II) or (III)) , Matrices with die holes, which have only the longitudinal sections II *, I and II are referred to in this document as "matrices with a double truncated cone" (of course, can also connect to the longitudinal sections II and II * basically immediately further longitudinal sections, as long as the respective Stamp can be inserted in selbige).

Advantageous correspond to the geometric dimensions of the longitudinal section II * those of longitudinal section II. Matrices of the abovementioned Art are particularly advantageous insofar as the inventive Compaction so z. B. first in the upper half of the longitudinal section I and / or in the longitudinal section II of the die hole can be performed. Is the Inner wall of the die bore in the aforementioned area due to multiple Worn process execution in selbigem, the Die in a simple manner turned upside down (around a vertical to the die bore axis rotated by 180 °) and the compression according to the invention subsequently in the other half of the longitudinal section I and / or performed in the longitudinal section II * of the die bore become. Very particularly advantageous is the process implementation with matrices whose template bore only from a longitudinal section I and one immediately adjoining its upper end Longitudinal section II and one at the lower end immediately following longitudinal section II * and wherein the geometry of the longitudinal section II the template bore to the geometry of the longitudinal section II * the template bore is congruent (= "template with congruent double Frustum ").

Further Is it technically adept when the length II (Height) of the longitudinal section II (as well as the length II * of longitudinal section II *) of the die bore of the Implementation of the method according to the invention for producing ring-like precursor shaped bodies used die (that is, the height H of the truncated cone KS (and the truncated cone KS *)) up to four times, preferably up to three times or up to two or one and a half times that of axial end distance E is.

That is, advantageous are methods for which: 4 · end distance E ≥ H ≥ 1 · end distance E (IV); or 3 · End distance E ≥ H ≥ 1 · End distance E (V); or 1.5 · end gap E ≥ H ≥ 1 · end gap E (VI); or 3 · final distance E ≥ H ≥ 1.5 · final distance E (VII); or 2 · End distance E ≥ H ≥ 1.5 · End distance E (VIII).

As a rule, in the method according to the invention for producing ring-like precursor shaped bodies, the length I of the longitudinal section I will be greater than the length II of the longitudinal section II (and greater than the length II * of the longitudinal section II *) ^. However, the length I of the longitudinal section I can also be smaller than the length II of the longitudinal section II (as well as smaller than the length II * of the longitudinal section II *).

Usually However, the length I is not more than three times the Length II (as triple the length II *) amount.

Often the length I is not more than twice (or simple) of length II (as a double (or simple) of length II *).

Usually the length I is not less than 0.1 times (or not less than 0.2 times) the length II (as 0.1 times or 0.2 times the length II *).

frequently the length I is 0.1 to 1 times or 0.5 to 1 times the length II (or the length II *).

Everything The above applies, as usual in this document, in particular in the case of an inventive Preparation of ring-like precursor shaped bodies F.

In particular, all that is said in this document applies to an inventive production of ring-like precursor shaped bodies F, in the production of which, when the final distance E is reached, both the upper end face of the lower punch and the lower end face of the upper punch are in the longitudinal section II (or in the longitudinal section II * ) of the die bore. Such production of ring-like precursor shaped bodies F is referred to in this specification in the narrower sense as a production of ring-like precursor shaped bodies F ^LII (regardless of the quantitative dimensions of the ring-like precursor shaped bodies produced according to the invention, those in the manufacture thereof when reaching the final distance E are both the upper end face the lower die as well as the lower face of the upper punch is in the longitudinal section II (or in the longitudinal section II *) of the die bore, to be referred to in this document as "ring-like precursor shaped body LII").

The advantageousness of processes for the preparation of ring-like precursor shaped bodies, to which at least one of the relationships (IV) to (VIII) applies, is due, inter alia, to the fact that, in particular in the context of the production of a larger batch of ring-like precursor shaped bodies LII with the inventive compaction, first in upper part of the longitudinal section II can be started (ie, in the state of the initial distance A are both the upper end face of the lower punch and the lower end face of the upper punch in the upper part of the longitudinal section II; the output distance A position under the surface of the upper punch so that it flush with the upper end of the longitudinal section II). With increasing wear of the inner wall of the upper part of the longitudinal portion II of the die bore will then move in the state of the starting distance A both the lower end face of the upper punch and the upper end face of the lower punch within the die bore down. The ring-like precursor shaped bodies (for example ring-like precursor shaped bodies LII or ring-like precursor shaped bodies F ^LII ) resulting from such a procedure are geometrically similar to one another such that they can be used equivalently to geometrically uniform precursor shaped bodies (for example as catalysts or catalyst supports). In certain cases (see, for example, the German application with the file reference 102007017080.9 ), a defined variance of the shaped body geometry over a production batch may even be advantageous. It should be noted that during the transition from the ring-like precursor shaped body to the oxidic shaped body by thermal treatment of the former is usually accompanied by a change in the molding geometry.

A longitudinal section through inventively suitable matrices with congruent double truncated cone show by way of example the 3a and 3b ,

Essential for the described method for producing ring-like precursor shaped body is that in the geometric center of the lower end face of the upper punch leading into the upper punch and with at least one outlet from the upper punch in connection center hole MB ^{O is} formed, which the center pin MF in reducing the output distance A to the final distance E can absorb to the required extent and in the center pin MF can already protrude at the output distance A. The center pin MF is in the procedural rensübung especially in the state of the initial distance A already protrude into the central bore MB ^O , if, as described above, in the upper part of the longitudinal section II, the inner wall of the die bore is already worn, and the compression of the invention for this reason is moved to the lower part of the longitudinal section II.

If, in the process according to the invention for producing ring-like precursor shaped bodies, the upper punch is lowered during the compression process, the center bore MB ^O (FIG. 35 However, the center pin MF in each case to the extent absorb by the lowering of the upper punch takes place.

Since the center hole MB ^O (unlike the center hole MB ^U ( 37 ), which is passed through the lower punch) is not normally passed through the upper punch, it requires application technology appropriate at least one outlet ( 34 ), with which the center hole MB ^{O is} in communication and over which the gas phase can escape (is omitted), which displaces the center pin MF when it is received in the central bore MB ^O as part of a lowering of the upper punch. In general, the at least one outlet is also designed as a bore which tapers obliquely to the central bore MB ^O.

The 4a . 4b . 4c and 4d show longitudinal sections through corresponding with at least one outlet provided upper punch, the actual upper punch in the sense of this invention means only the downwardly circular cylindrical (or annular) expiring neck in these figures. The overall figure in each case shows the embodiment of the upper punch according to the invention as a so-called upper "insert punch", to which reference will now be made in the further course of this document The connection of the center bore MB ^O to at least one outlet is of particular importance, if at least the Entrance into the central bore MB ^O preferably circular cylindrical is designed so that the lateral surface of the circular cylinder Z (of the circular cylindrical center pin MF) slides at least in the entrance area thereof on its inner wall when it is received in the central bore MB ^O. According to the invention preferably the center hole MB ^O is designed in that the dimensions of the circular cylindrical center pin MF and the center bore MB ^{O are} preferably designed such that the lateral surface of the circular cylindrical center pin MF (of the circular cylinder Z) slides in the entire circumference of its inclusion in the central bore MB ^O on the inner wall of the central bore MB ^O. In contrast, the center hole MB ^{U is} often slightly extended below the range of their entry into the upper end face of the lower punch, as z. B. in longitudinal section through a lower punch in the 5a will be shown. In contrast, the shows 5b a longitudinal section through a lower punch, in which the center hole MB ^U over the entire length of the lower punch is designed with a constant cylindrical cross-section. Also in the 5a and 5b is meant with the lower punch in the sense of this invention, only the upward kreiszy lindrisch (or annular) expiring neck in these figures. The overall figure in each case shows the embodiment of the lower punch according to the invention as a so-called "lower insert punch", to which reference will be made later in this document The opening of the center bore MB ^U in the upper end face of the lower punch and the opening of the center bore MB ^O in the lower face of the upper punch are usually designed congruent.

is the die is one with a congruent double truncated cone the length of a generatrix of the circular cylinder I in the Usually not greater than the sum of the length II and 0.7 times the length I (and 0.5 times the Length I). If the lower punch is a lower one Designed insert die, it is advantageous according to the invention, if the cross-section of the inlay stamp where it is the bottom End of the lower punch stops, compared to the cross section of the circular cylinder I, has a smaller cross section. A Such a configuration allows the discharge of finely divided Grain that extends between the wall of the die bore and the lateral surface of the circular cylinder I has caught in the course of a lowering of the lower Stamp in the longitudinal section II * inside.

According to the invention the center pin MF from bottom to top the geometric shape of a Circular cylinder Z with a circular cylindrical surface MZ on.

Of Further, it is essential according to the invention that the position of the center pin MF and the position of the die including the die bore during the process along the drilling axis B are fixed relative to each other. The fixation of Matrix is usually made in practice so that the Die precisely in a corresponding receiving opening is inserted within a die plate.

additionally It is usually by means of a fastening screw, the z. B. from Matrizenscheibenrand horizontal to the receiving opening fixed for the matrix can fix. Rejects that Matrizenscheibe several, z. B. equidistant on a circumference placed on receiving openings, the additional Fixation of matrices inserted in same also done so that the fastening screw on a pitch circle between two Admission openings is placed, which the two in this inserted matrices fixed against each other.

For fixing the center pin MF center pen holder are used as a rule. To facilitate the fixation, the center pin MF is usually at its lower end with a head ( 27 ) equipped with a precisely made intermediate space ( 28 ) (Slot) of the center pin holder. For the aforementioned head, a widened cross-section can be attached to the actual center pin, which facilitates the fixation of the center pin (cf., for example, in FIG 6 and in 1 ). The center pen holder itself is also useful in terms of application usually also screwed to the die plate.

However, the present invention is also intended to include that embodiment for producing ring-like precursor shaped bodies, in which the center pin MF initially has the geometric shape of a circular cylinder Z with a circular cylindrical surface MZ from bottom to top, but then tapers conically upwards. This applies in particular when the center pin MF, which is initially circular-cylindrical from bottom to top, tapers conically upwardly within the longitudinal section II of the die bore (and does not widen further up to its upper end). In this case, the center pin MF from bottom to top, the geometry of a circular cylinder Z, which then within the longitudinal section II, an upwardly tapering truncated cone KM ( 30 ) is placed (the cross section of the circular cylinder Z corresponds to the cross section of the base of the truncated cone KM). The height of the truncated cone KM can correspond to the length of the longitudinal section II (which is preferred according to the invention), but also be shorter (in the latter case, the portion of the central post having a circular-cylindrical geometry extends from bottom to top into the longitudinal section II Advantageousness of such a run-off of the center pin MF upwards as a truncated cone KM is, in a similar manner as the advantage of the geometry of the longitudinal portion II of the die bore itself, justified in that due to the conical taper of the center pin MF upwards, upon removal of the formed ring-like shaped body the template bore by lifting the lower punch the rolling friction between the outer wall (the lateral surface) of the center pin MF and the lateral surface of the cavity of the formed ring-like shaped body (eg over the length of the longitudinal section II) can be made to disappear substantially n (for example in the case of the preparation of ring-like precursor bodies LII or F ^LII ). However, the benefit resulting from this situation is comparatively limited, since the lateral surface of the truncated cone KM in comparison to the lateral surface of the truncated cone KS at the same height is normally much smaller.

If H * is the height of the truncated cone KM, it is advantageous if the taper of the truncated cone KM from below (from the base) upwards (to the top surface) is such that between the diameter DG * of the base and the height H * and diameter DD * of a top surface of truncated cone KM the following relation: 0.005 * H * ≤ DG * - DD * ≤ 0.015 * H * (IX).

Preferably: 0.007 * H * ≤ DG * - DD * ≤ 0.013 * H * (X).

Particularly preferred is: 0.009 * H * ≤ DG * - DD * ≤ 0.011 * H * (XI).

It should be noted when using a z. B. to its upper end conically tapered center pin MF, that due to the not constant over the height H * of the truncated cone KM cross section in receiving the truncated cone KM in the central bore MB ^O an annular gap remains (the lateral surface of the truncated cone KM not sliding on the inner wall of the center hole MB ^O ). The still tolerable width of the same must be based again on the grain size of the powdery aggregate to be compacted. Normally, the cross-section of the center hole MB ^O in the case of an upwardly tapered center pin MF dimensioned so that it at a recording of its circular cylindrical portion in the center hole MB ^O with its circular cylindrical surface at least in the region of the entrance to the center hole MB ^O would glide on the inner wall. 7 shows an example of a longitudinal cut through a from bottom to top only the geometric shape of a circular cylinder Z having center pin MF, while 8th exemplarily shows a longitudinal section through such a center pin MF, which initially has the geometry of a circular cylinder Z from bottom to top, and then tapers conically up to its upper end.

All Generally, it is the process of the invention for producing ring-like precursor shaped bodies preferred when the upper end of the longitudinal section II of Die hole, the upper (flat) face of the center pin MF and the upper (plane) face of the die with each other flush (ie, not overhanging).

This especially applies in the case of a machine implementation of the method, since the aforementioned constellation, the mechanical introduction the powdery debris in the filling facilitated (Favored).

In As a rule, the die has a plane upper end face on. Application technology is also appropriate lower end face of the die designed plan. Preferably has the die (you can see from the die bore) the shape a circular cylinder with a flat upper and a lower plan Face on. In the outer wall the circular cylinder is advantageous at half height a horizontally extending ring or a round depression. she serves to fix the die in the die plate by means of a or more fastening screws.

in principle can reduce the process of the invention in the reduction the output distance A to the final distance E done so that both (the lower and the upper punch) stamp actively towards each other to be moved. Of course you can do that too be that the lower punch retains its position and only the upper punch is moved (lowered down).

In usually it is as uniform as possible Surface hardness of the method according to the invention resulting compact (ring-like precursor shaped body) advantageous if in reducing the output distance A on the final distance E upper and lower punch together active towards each other are moved (the upper punch is lowered, the lower punch is raised). In this case, the required compression pressure on the powdery heap of the upper and lower punch exercised equally, resulting in a more uniform Side crushing strength of the resulting compressed over whose height is conditional.

Also This results in a precursor shaped body with a more homogeneous mass density over its entire dimension. The latter requires a more homogeneous after the thermal treatment Pore structure and based on the latter an improved Catalyst performance.

In principle, the method according to the invention can be carried out both manually and by machine. For reasons of economy, a machine exercise of the method according to the invention is preferred. In essence, two types of machines can be used, which are distinguished from one another in the specialist literature as "eccentric press" and as "rotary". In the eccentric press, only the upper punch exerts the actual compression pressure by its downward movement with the aid of the eccentric disc, the lower punch resting during compression and moving upwards (being raised) only for the final ejection of the compact (eg the ring-like precursor shaped body). In the eccentric press, the die is stationary. It rests in the die plate on the stationary die table. The die can have one or (side by side) a plurality of die bores (and thus die filling spaces). In each die bore moves in the rhythm of the eccentric disc consisting of an upper punch and lower punch pair of stamps. In the case of production of ring-like precursor moldings, the center pin MF is also guided in a stationary manner by the die bore and the lower punch and fixed to the die plate with a center pen holder. Depending on whether the die has one or more die holes (Matrizenfüllräume), one speaks of a one-piece or mehrstempligen die. In a corresponding manner, a distinction is made between single and multiple tools. The simple tool consists in the case of production of ring-like precursor moldings from a die with a die bore and a center pin MF and a top and a bottom punch. A multiple tool consists in a similar manner of a die with two or more die holes and with a corresponding number of center pins MF and upper and lower punches. Whether single or multiple tools are used, is essentially based on the size of z. B. ring-like precursor shaped body and the pressing pressure, which can afford the machine decided. The upper limit applicable in the process according to the invention is in the case of preparation of ring-like precursor form bodies with about fifty times the tool. Since the die is stationary in the eccentric press, usually a hopper and filling shoe, which contain the powdery debris to be compacted according to the invention, slide forward and backward on the die table in order to achieve a uniform filling of the filling space or the filling spaces of the die. Filling the filling space, compression (compression) and outlet of z. B. ring-like shaped body carried out at the eccentric in this way time periodically recurring successively and together correspond in each case a full eccentric rotation.

in the The simplest case is the operation of an example Preparation of ring-like precursor shaped bodies in the eccentric machine, therefore, as follows. The lower stamp is located within the die bore initially in its filling position. The filling shoe slides over the die, whose upper flat face with the upper flat face the center pin MF flush, where the contents (the powdered debris) in the Die hole and on the upper face of the lower Stamp comes. When sliding back the filling shoe the punch moves down until it stops with its bottom face touches the contents. Thus, the powdery debris is in the filling space introduced and the state of the output distance A reached. By further downward movement of the upper punch (with fixed lower punch) the filling material becomes a ring-like precursor shaped body compacted until the final distance E together with the associated pressing pressure is reached. Subsequently, the upper punch is formed by the lifted ring-like precursor moldings and by (usually slightly delayed) lifting of the bottom punch of the ring-like precursor moldings removed from the die bore. As a rule, lifting takes place of the lower punch so far that the bottom of the formed Precursor molding the level of the template top barely reached. While now the leading edge of the forward pushing Füllschuhes the precursor shaped body of pushes the die, the lower die is lowered again until its filling position, and the die bore becomes refilled.

At the Rotary stands against the hopper velvet Filling shoe tight, and a die plate in which the dies rest, rotate, with the die holes under the filling shoe be passed. With one revolution of the die discs The individual matrices (or their die holes) are successively filled. Then the fillings are compressed and subsequently ejecting the resulting compressed.

It So a die hole is filled while compressed another stencil filling and simultaneously in turn, another matrix z. B. a ring-like Precursor Mold (the Comprimat) ejected becomes. One turn of Matri zenscheibe so many z. B. ring-like precursor moldings produced, as with the use of one-punched tools, tool sets available. For multi-stamp tools is with the number of the holes per die. While the Eccentric press works discontinuously, work concentric presses continuously. Furthermore, in the rotary the compression pressure with the help of pressure rollers from the upper and lower punches evenly exercised.

At Rundläufern are in the market regarding a production of ring-like precursor moldings for carrying out the inventive Process models for 10 to 100 (or 80) tool sets available, with each toolset normally totaling can be up to six stamps. While at a normal Rotators per matrix disc revolution so many compressed be pressed, like dies (sometimes holes with multiple tools) are present, have so-called Doppelrundläufer (they have a particularly high output power) two press stations, and it will be - at einstempeligen Tool sets - during a die table - rotation two matrices filled at the same time, two fillings compressed and z. B. two ring-like moldings pushed out. For example, for the inventive method the eccentric presses KS, KIS and K III of the company Kilian, D-50735 Cologne, used become. Particularly suitable for the inventive Method, however, runner Kilian (eg., The T series, R series, S series and X series).

Especially is suitable for the invention Process of the Kilian double rotary type RX 73 as well the rotary Kilian Synthesis 700-77 A.

Further are suitable for the invention Method the rotary walker of Korsch AG, D-13509 Berlin, such as For example, the Korsch rotary machines PH800 and PH865.

The individual design of the upper punch, the lower punch and the die together with die hole (ie, the tool) and optionally the center pin MF is incumbent on the user. For use in a Kilian rotary the design thereof in a particularly advantageous for the process according to the invention in the case of production of ring-like precursor moldings z. B. be as follows (the numerical addresses refer to (as always in this document) to the figures accompanying this document).

The single die ( 1 ) is manufactured so that it fits exactly into the receiving opening located in a die plate. Looking from the die hole ( 2 ), the die in terms of application suitably in the form of a circular cylinder with a flat upper and a flat lower end face, in the outer wall at half height either a horizontally extending ring or a round depression ( 3 ) is milled out. It serves to fix the matrix in the die plate (eg by means of at least one fastening screw which, for example, can lead horizontally from the die plate edge to the receiving opening for the die or run on a pitch circle from one die to the die adjacent thereto). According to the invention, the upper punch (belonging to this die) is suitable as an upper insert pel (FIG. 4 ), and the lower punch (belonging to this die) as a lower insertion punch ( 5 ). The lower insert punch (the upper insert punch) can by means of a lower screw cap ( 6 ) (by means of an upper screw cap ( 7 )), in which the lower insert punch (the upper insert punch) can be inserted, on a lower shaft ( 8th ) (on an upper shaft ( 9 )) are screwed centered. The lower shaft (the upper shaft) runs into a lower shaft head ( 10 ) (runs into an upper shaft head ( 11 )), which slides in the guide rails of the rotary. The lower insert punch (the upper insert punch) runs into the actual lower punch ( 12 ) (in the actual upper stamp ( 13 )) (ie, the relevant stamp according to the invention is in both cases the neck into which the respective insertion punch runs out).

The floor ( 14 ) of the upper insert punch (also called "insertion punch") lies in the screwed-in state on the circular pressure surface ( 15 ) of the upper shaft. The design as an insertion stamp opens up a high degree of flexibility when using the same shafts.

The circular bottom ( 16 ) of the lower insertion punch lies in the screwed-in state on the annular pressure surface ( 17 ) of the lower shaft. The circular ring opening of the printing surface ( 17 ) is continued as a cylindrical cavity in the lower shaft. He can continue the continuation of the middle pen MF ( 18 ) take up. Via a lateral opening (a groove) of the lower shaft, the center pin MF can be moved by means of a center pin holder (FIG. 19 ) (be fixed along the drilling axis B relative to the die and its die bore).

The center pen holder itself is fastened to the die plate by means of a screw. 1 shows in a kind of exploded view of the individual elements listed above in longitudinal section.

6 shows a section of a guided through the die plate longitudinal section. He shows the in the receiving opening of the die plate ( 20 ) inserted matrix ( 1 ) and the horizontally extending ring ( 3 ) to their fixation by means of a fastening screw. The part of the die plate in whose receiving openings the dies ( 1 ) is inserted in this document as a die plate tongue ( 21 ). Furthermore, the shows 6 in the die plate above and below the female mold receiving aperture ( 1 ) guide bores ( 22 ) for the shafts ( 8th ) and ( 9 ). On the inner wall of the respective guide bore ( 22 ) with its lateral surface sliding vertically, the lower shaft ( 8th ) or the upper shaft ( 9 ) are raised or lowered. The part of the die plates, which contains the guide bores for the upper shafts, should also be referred to in this document as the die face ( 23 ). The part of the die plate, which contains the guide holes for the lower shaft, is also referred to in this document as the die plate ( 24 ). The center pen holder ( 19 ) is in the 6 from below with the die plate ( 20 ) screwed. The center pin MF extending to its head with a wider cross-section 18 ) leads from the center pin holder ( 19 ) held by the lower shaft and the lower insertion punches led to the flat end face of the die ( 1 ), with which the planar front of the center pin MF ( 18 ) flush. In particular, when multiple tools are used, the shifters in the guide bore ( 22 ) do not turn. This is achieved by splines in the shaft and wedges along the inner wall of the guide bore. The upper shaft head ( 11 ) and the lower shaft head ( 10 ) sitting in a fixed "Oberstempelführungsschiene" or "Unterstempelführungsschiene", the 6 not showing. The inserted matrix ( 1 ) is a template with a congruent double truncated cone.

The Operation of the rotary press is now schematically as follows (this Working principle is essential for all rotary walkers equal).

The z. B. driven by a worm or a gear die plate rotates in the horizontal plane about its axis. The with their respective shaft head in fixed guide rails (usually stainless steel or plastic rails) sitting shafts follow when turning the die plate in the respec gene guide rail sliding their height profile. The lower shaft supporting the lower punch slides in the context of the rotation of the die plate on its slide initially to the filling shoe, where he and thus the lower punch is pulled down so that the upper end face of the lower punch in the die bore at its fill level located. In the further course of the rotary movement, the free space of the die bore located above the upper end face of the lower punch is filled with the finely divided aggregate (the contents) to be compacted according to the invention out of the filling shoe. Upon further rotation of the die plate, the lower shaft and with it the lower punch is raised, so that the upper end face of the lower punch in the die bore is at its fill level. Excess filling is pushed up and scraped off in the course of the rotary motion. Then the lower shaft and with it the lower punch is pulled down again, so that the upper end face of the lower punch in the die bore is at the height to which the initial distance A refers (also referred to herein as "pressing height") the upper punch hovers above the filling shoe and now slides downwards in accordance with the course of the upper rail guide rail until it touches the finely divided heap located in the die bore with its lower end face, thus introducing the pulverized aggregate into the filling space and the state of the initial distance A. Both the upper shaft head and the lower shaft head are driven over a pressure roller in each case during the further rotation of the die disc, thereby pressing both the upper punch and the under punch against the filling material introduced into the filling space (the lower punch is raised , the upper stamp continues abg steers) until the end distance E is reached. During the compression between the pressure rollers, a hold-off time can be achieved as needed, while the distance between upper and lower punch is kept constant (in Exzentertablettiermaschinen there is no period in which the distance between upper and lower punch remains constant, the compression is only by the immersion depth of the upper punch in the powdery debris caused conditional).

The Keep away while the compression pressure is approaching is constant, favors time-dependent plastic Deformation processes in the heap to be compacted. Then the upper shaft is due to the course of its guide rail raised again to the upper punch from the generated ring-like Lift off the molded body. The lower shaft and with it the bottom punch is made by sliding the lower shaft head in raised the lifting track of the guide rail and the on its upper end surface located ring-like Precursor molded body led out of the die bore, and stripped by a scraper (the inventive Method advantageously allows particularly low Ejection forces; usually they are in use fresh matrices ranging from 0.15 to 1.5 kN; in the course the further exercise of the procedure increases the required Ejection force usually on; this increase reaches about 700 N, the die is usually rotated or replaced). about a gutter slips the ring-like precursor shaped body then in a storage container. As part of the further rotation of the die plate becomes the upper punch by sliding the upper shaft head in its Obergleitbahn pushed to its highest point, until he over again the filling shoe is located.

Of the Lower stamp is meanwhile by the sliding on of the lower one Shank head pulled down in its lower slide again (lowered), so that he also submerged on the lower slide again the filling shoe and its upper end face itself in the die bore back to its fill level located. Subsequently, the described repeated Process with the periodicity of the rotation of the die plate.

It is advantageous if the filling of the die bore with Filling already during the lowering of the lower Stamp at fill level, so when filling the die hole is not trapped too much air. In the course a complete revolution of the die plate never completely unlock the switch holes led out.

According to the invention, it is preferred to use rotary machines in which, as described above, using only a pair of pressure rollers only one compression process per ring-like precursor shaped body, but by using two pairs of pressure rollers arranged closely behind each other, a preliminary (to the final final distance E ^{V of} the two end faces) and a main compression (to the final distance E, where E ^V > E) per ring-like precursor shaped body is performed (the pre-pressure roller is usually dimensioned smaller than the main pressure roller in a simple manner.) Ensures the application of a pre-compression to a provisional final distance EV (> E) of the two end faces a better deaeration during compression as well as a more uniform compaction of the pulverulent material, since the precompressing converts the contents into a comparatively uniform state of order Generally, slow compression is advantageous for good degassing The sides wall compressive strength of the resulting ring-like precursor shaped body can also be improved by first removing a discharge after precompression followed by the main compaction. The sake of completeness are in the 5c . 5d and 5e shown three lower insertion die, in which the upper end face of the lower punch is not flat. The lower insertion stamp in 5c runs out in a lower punch, in which the doctrine of EP-A 184790 implemented. The 4e and 4f show correspondingly designed upper insertion stamp.

When Fillers come for the invention Method in the case of rotors z. B. vibrating filling shoes, Vibrating filling shoes and agitator filling shoes into consideration. However, stirring pad filling shoes are particularly preferred used. The latter were also used in all embodiments used.

It should also be noted at this point that for the inventive method, the use of such simple rotary or Doppelrundläufern is particularly advantageous in which the die plate ( 20 ) is stored interchangeable. Such a double rotary is z. B. the twin-tube Synthesis 700 from Kilian. Another advantage of this double rotary runner is that it works with pre-compression and main compression. Rotary machines are z. B. in the writings DE-A 2624853 . DE-A 19733969 and DE-A 2435777 described. Incidentally, the tools for tableting according to the invention are very precise to manufacture and the relevant standards of the respective country (eg DIN ISO 2768 ). The respective surfaces of the tools should be made as smooth as possible.

In particular, in the case where the pulverulent aggregate to be compacted according to the invention comprises at least one metal oxide (for example from the group comprising aluminum oxide, tungsten oxide, antimony oxide, zirconium oxide, bismuth oxide, molybdenum oxide, silicon oxide, magnesium oxide and mixed oxides containing at least two of the abovementioned metal oxides contained metal elements (eg, mixed oxides of bismuth and tungsten such as Bi ₂ W ₂ O ₉ )), a metal hydroxide, a metal hydrogen phosphate and / or at least one metal nitrate (this term should also subsubstrate Metallnitrathydrate) such , B. cobalt nitrate, iron nitrate, bismuth nitrate, nickel nitrate, cesium nitrate, copper nitrate, calcium nitrate and magnesium nitrate contains (such powdery heaps are hereinafter referred to as powdery heaps HW *), it is inventively advantageous if the upper punch and the lower punch for the invention Method from the tool steel with the DIN material number 1.2601 are made (in the event that the aforementioned stamp are made as Einlegstempel, the entire insertion die is appropriate from an application point of the DIN material 1.2601 manufactured). Alternative to DIN material 1.2601 can the stamp, especially in the aforementioned cases, also from the DIN tool steel 1.2379 be made. Contains the inventively to de compact de powdered debris nitric acid, it should be referred to below as a powdery debris **.

To the in the WO 2005/115733 To account for problems described, the center pins MF are advantageously from a DIN tool steel 1.2343 manufactured. This applies in particular in the case of compaction of pulverulent aggregates HW * and HW ** (in particular in the case of preparation of ring-like precursor shaped bodies F, in particular in the case of ring-like precursor shaped bodies F ^LII ). The die plate tongue consists in the inventive method, in particular in the case of powdered debris HW * or HW **, advantageously from the DIN nodular cast iron GGG 50 with a thin support from the DIN tool steel 1.0425 , while the Matrizenscheibenstirn and the Matrizenscheibenkinn appropriate from the application technology DIN tool steel 1.6850 (nitrided) are made. The lower shaft, the upper shaft and the associated shaft heads can in the method according to the invention as well as the center pen holder in a conventional manner z. B. from the DIN tool steel 1.25550 (hardened and tempered, Rockwell hardness HRC 58 + 2).

The pressing pressures typically exerted in the end distance E of both punches (or at least the upper punch) when carrying out the process according to the invention for producing annular or ring-like precursor moldings are usually in the range from 50 to 5000 kg / cm ² , preferably from 200 to 3500 kg / cm ² , more preferably 500 to 2500 kg / cm ² and particularly preferably 500 to 1500 kg / cm ² .

The forms (they are exercised in the preliminary final distance E ^V ) are typically 5-500 kg / cm ² and the main pressures are usually 1000-2000 kg / cm ² . The higher the applied main pressure, the more advantageous is the method according to the invention for producing annular or ring-like precursor shaped bodies.

As already mentioned several times in this document, the method according to the invention is particularly suitable for the production of circular-cylindrical, circular-cylinder-like, annular or ring-like Precursor moldings from which circular-cylindrical, circular-cylinder-like, ring-shaped or ring-like catalysts are obtainable by thermal treatment (for example, when the catalytically active component of the oxidic geometric catalyst molding is a multimetal oxide). Such geometric (eg ring-like) precursor shaped bodies which can be obtained according to the invention should also be referred to in this document as geometric (eg ring-like) shaped catalyst precursor bodies.

there may be the oxidic geometric (eg ring-like) shaped catalyst body in the simplest case only from the catalytically active component (z. B. the multimetal) exist. He can the catalytically active Component (eg the multimetal) but also with inert material diluted. In both cases one speaks of geometric (eg ring-like) unsupported catalyst bodies. Is the active component a multimetal oxide intended in this document of geometric (eg, ring-like) multimetal oxide full catalysts become.

Geometric (eg ring-like) multimetal oxide full catalysts are particularly suitable for the heterogeneous catalysis of partial gas-phase oxidations (cf. DE-A 102005037678 , the German application with the file reference 102007028332.8 , the German application with the file reference 102007025869.2 , the German application with the file reference 102007017080.9 and the German application with the file reference 102007003778.5 ) organic compounds with molecular oxygen.

Under a complete oxidation of an organic compound with molecular oxygen should be understood in this document, that the organic compound is under reactive action of molecular Oxygen is converted to that in the organic compound Total contained hydrogen converted into oxides of hydrogen becomes. All of them different exothermic reactions of an organic Compound under the reactive action of molecular oxygen are here as partial oxidation of an organic compound summarized (eg including ammoxidations and oxychlorinations in the co-presence of ammonia or hydrogen chloride are carried out). In particular in this document under partial oxidation such exotherms Reactions of organic compounds under reactive action be understood of molecular oxygen in which the partially to be oxidized organic compound after completion of the reaction at least contains an oxygen atom more chemically bound than before performing the partial oxidation.

As examples of heterogeneously catalyzed partial gas phase oxidations may be mentioned at this point, for example those of propylene to acrolein, that of isobutene to methacrolein, that of methacrolein to methacrylic acid and that of C ₄ hydrocarbons to maleic anhydride. Usually, heterogeneously catalyzed partial gas phase oxidations in z. B. cooled with molten salt tube reactors. The catalysts are in this case, optionally diluted with inert shaped bodies, in the reaction tubes through which the reaction gas mixture flows.

to Preparation of Geometric (eg Ring-like) Multimetal Oxide Full Catalysts can now proceed in such a way that one from sources of elementary Constituents of the catalytically active multimetal and after Need for use of shaping aids (eg porosity agents, Lubricant and reinforcing agent) a finely divided pile generated, and from this according to the invention Method first geometric (eg ring-like) Multimetal oxide unsupported catalyst precursor body manufactures. As sources for the elementary constituents of the multimetal oxide can thereby (under normal conditions usually in the solid state state) metal oxides and / or those metal compounds which are used by heating (thermal treatment) in (under normal conditions usually in solid state) oxides can be converted are (at least by thermal treatment in the presence of gaseous molecular oxygen and / or gaseous oxygen releasing components).

By subsequent thermal treatment of geometric (eg ring-like) Multimetal oxide unsupported catalyst precursor body (eg in the temperature range from 200 to 800 ° C, or 300 up to 600 ° C) are then the geometric (eg ring-like) Multimetal oxide full catalysts available.

The pulverulent aggregates to be used for the production according to the invention of geometrical (eg ring-like) multimetal oxide unsupported catalyst precursor bodies will therefore generally be aggregates HW * or aggregates HW **. All statements made with regard to the compaction according to the invention of pulverulent aggregates HW * and HW ** in this document therefore apply correspondingly. In accordance with the invention, preferred ring-like multimetal oxide unsupported catalyst precursor shaped bodies are generally ring-like shaped bodies F, preferably ring-shaped shaped bodies F ^LII .

Under Another is the method of the invention for the preparation of the precursor moldings of such geometric (eg ring-like) multimetal oxide full catalysts, the at least one multimetal oxide as the catalytically active component in which the element Mo, or the element V, or the Element P is that element other than oxygen, the numerically (molar) is most commonly included (Multimetal oxide means that the oxide at least two of Oxygen contains various elements).

In particular, the process according to the invention is suitable for producing the precursor shaped bodies (in particular of ring-like precursor shaped bodies F or F ^LII ) of such geometrical (eg ring-like) multimetal oxide full catalysts which contain as catalytically active component at least one multimetal oxide which comprises the elements Mo and Fe, or the elements Mo, Fe and Bi, or the elements Mo and V, or the elements Mo, V and P, or the elements V and P contains (especially if at the same time the aforementioned frequency condition is fulfilled). The former geometrical (eg ring-like) multimetal oxide full catalysts in the aforementioned series are particularly suitable for heterogeneously catalyzed partial gas phase oxidations of methanol to formaldehyde. The latter are particularly suitable for the heterogeneously catalyzed partial gas phase oxidation of propylene to acrolein. The latter are particularly suitable for heterogeneously catalyzed partial gas phase oxidations of acrolein to acrylic acid, the fourth mentioned are particularly suitable for the heterogeneously catalyzed partial gas phase oxidation of methacrolein to methacrylic acid and the latter in the above series are particularly suitable for heterogeneously catalyzed partial gas phase oxidation of n Butane to maleic anhydride.

to inventive preparation of ring-like Multimetal oxide unsupported catalyst precursor bodies is preferably a lower punch with a flat upper end face and an upper punch with a flat lower end face used (preferably are the two end faces congruent to each other). Of course you can ring-like multimetal oxide unsupported catalyst precursor bodies but also, as described in this document, with curved ones End surfaces are produced.

Catalytically active multimetal oxides of the abovementioned type, including pulverulent aggregates which can be used for the production according to the invention of associated geometric (eg ring-like) multimetal oxide unsupported catalyst precursor bodies, can be found, inter alia, in the publications WO 2005/030393 . EP-A 467 144 . EP-A 1 060 792 . DE-A 198 55 913 . WO 01/68245 . EP-A 1060792 , Research Disclosure RD 2005-497012, DE-A 102005035978 . DE-A 102005037678 . WO 03/78059 . WO 03/078310 . DE-A 199 22 113 . WO 02/24620 . WO 02/062737 , of the German application with the file reference 102007028332.8 , of the German application with the file reference 102007025869.2 , of the German application with the file reference 102007017080.9 and US-A 2005/0131253 ,

The According to the invention to be compressed powdery (Forerunner) heaps are thereby in the simplest way Available from sources of elemental constituents the desired catalytically active multimetal in accordance with the invention required finely divided, as intimate as possible, the stoichiometry of desired multimetal oxide correspondingly composed, formable mixture produced, which still the already mentioned Shaping aids (including reinforcing aids) can be added (and / or incorporated from the beginning can be).

Suitable sources of the elemental constituents of the desired multimetal according to the invention are, in principle, those metal compounds which are already oxides and / or those metal compounds which release by heating, at least in the presence of gaseous molecular oxygen and / or gaseous oxygen Components that are convertible into oxides. In principle, the oxygen source can also z. B. be in the form of a peroxide component of the precursor mixture (the powdery debris) itself. Also, the powdery (precursor) heap compounds such as NH ₄ OH, (NH ₄ ) ₂ CO ₃ , NH ₄ NO ₃ , urea, NH ₄ CHO ₂ , NH ₄ CH ₃ CO ₂ , ammonium oxalate and / or organic components such. B. stearic acid added, which decompose in the thermal treatment as a pore former to completely gaseous escaping compounds and / or can be decomposed.

The, preferably intimate, mixing of the starting compounds (sources) for the preparation of the finely particulate pulverulent (precursor) formation which can be shaped according to the invention can be carried out in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently in the form of finely divided powders (with a particle diameter d ₅₀ (to determine particle diameter distributions and the particle diameters d ₁₀ , d ₅₀ and d ₉₀ taken from these (generally d _x ) the respective finely divided powder was transferred a dispersing channel in the dry disperser Sympatec RODOS (Sympatec GmbH, System Particle Technology, Am Pulverhaus 1, D-38678 Clausthal-Zellerfeld) out and there with compressed air tro dispersed and blown in the free jet into the measuring cell. In this will then after ISO 13320 using the Malvern Mastersizer S laser diffraction spectrometer (Malvern Instruments, Worcestershire WR14 1AT, United Kingdom), determines the volume-based particle diameter distribution. The particle diameter d _x indicated as the measurement result is defined such that X% of the total particle volume consists of particles with this or a smaller diameter.) Conveniently in the range 1 to 200 μm, preferably 2 to 180 μm, particularly preferably 3 to 170 μm and all particularly preferably 4 to 160 μm, or 5 to 150 μm or 10 to 150 μm, or 15 to 150 μm). After addition of the shaping aids, the shaping according to the invention can then be carried out. Such aids may be, for example, graphite as a lubricant and microfibers of glass, asbestos, silicon carbide and / or potassium titanate. In general, a parent compound can be a source of more than one elemental constituent.

As such, rather than forming the mixture produced by mixing powdery sources as such directly into the desired precursor geometry, it is often convenient to first carry out intermediate compaction as a first shaping step to coarsen the powder (typically to particle diameter d ₅₀ from 100 to 2000 μm, preferably 150 to 1500 μm, particularly preferably 400 to 1000 μm).

there can already before the intermediate compaction z. B. graphite as Kompaktierhilfsmittel be added. Subsequently, with the coarsened Powder the inven tion proper shaping, wherein if necessary beforehand again z. B. finely divided graphite (and optionally other forming aids (including reinforcing agents)) can be added.

Preferably, however, the intimate mixing of the sources takes place in wet form. Usually, the starting compounds z. B. in the form of an aqueous (but also liquids such as iso-butanol come as a solution and / or dispersing medium into consideration) solution and / or suspension mixed together. Particularly intimately formable mixtures are obtained when it is assumed that only the sources of elementary constituents present in dissolved form. Water is preferably used as the solvent (but liquids such as isobutanol are also suitable as solvents). Subsequently, the resulting solution or suspension is dried, wherein the drying process is preferably carried out by spray drying with outlet temperatures of 100 to 150 ° C (in some cases, the drying can also be done by filtration and subsequent drying of the filter cake). The particle diameter d _{50 of} the resulting spray powder is typically 10 to 50 μm. If water is the base of the liquid medium, the resulting spray powder will normally contain no more than 20% of its weight, preferably not more than 15% of its weight, and more preferably not more than 10% by weight of its weight of water. These percentages usually apply even when using other liquid solvents or suspending aids. After addition (or even without such an addition) of the desired shaping assistant to the respective powdered dry mass, the powdery mixture can be compacted (shaped) according to the invention as a finely divided precursor mixture (powdery debris) to the desired multimetal oxide Vollkatalysatorvorläuferformkörper. However, the finely divided shaping aids can also be added in advance (partially or completely) to the spray mixture.

A only partial removal of the solvent or suspending agent may also be appropriate if its co-use is intended as a shaping aid.

advance an addition of z. B. finely divided graphite as a lubricant can also already a first thermal treatment of the dry powder respectively. After addition of the z. B. graphite is then the inventive Shaping and the subsequent thermal Further treatment.

Instead of the finely divided precursor mixture based on the spray powder as such, to form immediately the desired geometry, It is often convenient, as a first Forming step, first an intermediate compaction to coarsen the powder (in usually on particle diameter of 100 to 2000 microns, preferably 150 to 1500 .mu.m, more preferably 400 to 1000 μm).

there can already before the intermediate compaction z. B. graphite as Kompaktierhilfsmittel be added. Subsequently, on the basis the coarsened powder the final (actual), the inventive molding, where necessary previously again finely divided graphite (and optionally further Shaping aids such. B. reinforcing agent) was added can be.

Of course, as sources of elemental constituents also starting compounds which in turn are produced by thermal treatment of precursor compounds (element sources) and are of multimetal oxide nature. In particular, the starting compounds of the elemental constituents may be of a multimetallic nature.

X¹

= Nickel und/oder Kobalt,

X²

= Thallium, Samarium, ein Alkalimetall und/oder ein Erdalkalimetall,

X³

= Zink, Phosphor, Arsen, Bor, Antimon, Zinn, Cer, Blei, Vanadium, Chrom, Niob und/oder Wolfram,

X⁴

= Silicium, Aluminium, Titan und/oder Zirkonium,

a

= 0,2 bis 5,

b

= 0,01 bis 5,

c

= 0 bis 10,

d

= 0 bis 2,

e

= 0 bis 8,

f

= 0 bis 10, und

n

= eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschie denen Elemente in XII bestimmt wird,

oder eine Stöchiometrie der allgemeinen Formel XIII, [Y¹ _a'Y² _b'O_x']_p[Y³ _c'Y⁴ _d'Y⁵ _e'Y⁶ _f'Y⁷ _g'Y⁸ _h'O_y']_q (XIII), mit

Y¹

= nur Wismut oder Wismut und wenigstens eines der Elemente Tellur, Antimon, Zinn und Kupfer,

Y²

= Molybdän oder Wolfram, oder Molybdän und Wolfram,

Y³

= ein Alkalimetall, Thallium und/oder Samarium,

Y⁴

= ein Erdalkalimetall, Nickel, Kobalt, Kupfer, Mangan, Zink, Zinn, Cadmium und/oder Quecksilber,

Y⁶

= Eisen oder Eisen und wenigstens eines der Elemente Vanadium, Chrom und Cer,

Y⁶

= Phosphor, Arsen, Bor und/oder Antimon,

Y⁷

= ein seltenes Erdmetall, Titan, Zirkonium, Niob, Tantal, Rhenium, Ruthenium, Rhodium, Silber, Gold, Aluminium, Gallium, Indium, Silicium, Germanium, Blei, Thorium und/oder Uran,

Y⁸

= Molybdän oder Wolfram, oder Molybdän und Wolfram,

a'

= 0,01 bis 8,

b'

= 0,1 bis 30,

c'

= 0 bis 4,

d'

= 0 bis 20,

e'

> 0 bis 20,

f'

= 0 bis 6,

g'

= 0 bis 15,

h'

= 8 bis 16,

x', y'

= Zahlen, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XIII bestimmt werden, und

p, q

= Zahlen, deren Verhältnis p/q 0,1 bis 10 beträgt,

aufweist.All statements made so far in this document are valid especially when the catalytically active (active) multimetal oxide of the geometric (eg ring-like) multimetal oxide unsupported catalyst has a stoichiometry of the general formula XII, Mo ₁₂ Bi _a Fe _b X ¹ _c X ² _d X ³ _e X ⁴ _f O _n (XII) With

X ¹

= Nickel and / or cobalt,

X ²

Thallium, samarium, an alkali metal and / or an alkaline earth metal,

X ³

Zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead, vanadium, chromium, niobium and / or tungsten,

X ⁴

= Silicon, aluminum, titanium and / or zirconium,

a

= 0.2 to 5,

b

= 0.01 to 5,

c

= 0 to 10,

d

= 0 to 2,

e

= 0 to 8,

f

= 0 to 10, and

n

= a number determined by the valency and frequency of the elements other than oxygen in XII,

or a stoichiometry of the general formula XIII, [Y ¹ _{a '} Y ² _b' O _{x '} ] _p [Y ³ _c' Y ⁴ _{d '} Y ⁵ _e' Y ⁶ _{f '} Y ⁷ _g' Y ⁸ _{h '} O _y' ] _q (XIII) With

Y ¹

= only bismuth or bismuth and at least one of the elements tellurium, antimony, tin and copper,

Y ²

= Molybdenum or tungsten, or molybdenum and tungsten,

Y ³

= an alkali metal, thallium and / or samarium,

Y ⁴

an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury,

Y ⁶

= Iron or iron and at least one of the elements vanadium, chromium and cerium,

Y ⁶

= Phosphorus, arsenic, boron and / or antimony,

Y ⁷

= a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium,

Y ⁸

= Molybdenum or tungsten, or molybdenum and tungsten,

a '

= 0.01 to 8,

b '

= 0.1 to 30,

c '

= 0 to 4,

d '

= 0 to 20,

e '

> 0 to 20,

f '

= 0 to 6,

G'

= 0 to 15,

H'

= 8 to 16,

x ', y'

= Numbers determined by the valency and frequency of elements other than oxygen in XIII, and

p, q

= Numbers whose ratio p / q is 0.1 to 10,

having.

Such z. B. ring-like multimetal oxide unsupported catalysts especially as catalysts with increased selectivity and activity for gas-phase catalytic partial oxidation from propene to acrolein and from isobutene or tert-butanol or its methyl ether to methacrolein.

For the inventive production of the associated z. B. ring-like multimetal oxide Vollkatalysatorläufläuferformkörper one will produce from sources of the elemental constituents of the active multimetal a finely divided, formable by compaction inventive precursor mixture (a powdery Aggregate) and this mixture, after the addition of shaping aids (cf. DE-A 10 2005 037 678 . DE-A 10 2007 003 778 . DE-A 10 2007 028 332 and the cited in these publications state of the art), which optionally also comprises reinforcing agents, compress in accordance with the invention (preferably to ring-like Vollkatalysatorvorläuferformkörpern F or F ^LII ).

The Shaping according to the invention takes place advantageously such that the lateral compressive strength of the resulting ring-like Multimetal oxide unsupported catalyst precursor body ≥ 10 and ≤ 40 N, better ≥ 10 and ≤ 35 N, still better ≥ 12 N and ≤ 30 N. Preferably is the lateral compressive strength of the ring-like Multimetal oxide unsupported catalyst precursor body ≥ 13 N and ≤ 27 N, or ≥ 14 N and ≤ 25 N. Ganz the lateral compressive strength is particularly preferably ringlike multimetal oxide unsupported catalyst precursor body ≥ 15 N and ≤ 22 N.

The Grain (the particle diameter) of the invention to compacting powdery aggregate (excluding the Auxiliary agent to be added) is advantageously 200 to 1500 μm, particularly advantageously set to 400 to 1000 microns (z. B. by intermediate compaction). Conveniently at least 80% by weight, more preferably at least 90% by weight, and especially advantageously 95 or 98 or more wt .-% of the powdered Muck in this grit area.

In this document, lateral compressive strength is understood to mean the compressive strength on compression of the ring-like multimetal oxide unsupported catalyst precursor body perpendicular to the axis of symmetry (ie parallel to the surface of the opening). In this case, all lateral compressive strengths of this document refer to a determination by means of a material testing machine of the company Zwick GmbH & Co (D-89079 Ulm) of the type Z 2.5 / TS15. This material testing machine is designed for quasi-static loading with a smooth, resting, swelling or changing course. It is suitable for tensile, compression and bending tests. The installed force transducer type KAF-TC of the company AST (D-01307 Dresden) with the serial number 03-2038 is thereby according to the DIN EN ISO 7500-1 calibrated and can be used for the measuring range 1-500 N (relative measurement uncertainty: + 0.2%).

The measurements are carried out with the following parameters:
Pre-load: 0.5 N.
Pre-load speed: 10 mm / min.
Test speed: 1.6 mm / min.

there The upper punch is initially slow to just before the Lateral surface of the ring-like unsupported catalyst precursor body lowered. Then the upper punch is stopped in order to subsequently with the significantly slower test speed with minimal, to further lowering necessary to be reduced Vorkkraft.

The Vorkraft, wherein the Vollkatalysatorvorläuferformkörper Cracking is the side crushing strength (SDF).

Concerning the active materials of stoichiometry XII are stoichiometric Coefficient b is preferably 2 to 4, the stoichiometric Coefficient c is preferably 3 to 10, the stoichiometric Coefficient d is preferably 0.02 to 2, the stoichiometric Coefficient e is preferably 0 to 5 and the stoichiometric Coefficient a is preferably 0.4 to 2. The stoichiometric Coefficient f is advantageously 0.5 or 1 to 10. Particularly The aforementioned stoichiometric coefficients are preferred at the same time in the said preferential ranges.

Further, X is preferably cobalt, X ² is preferably K, Cs and / or Sr, particularly preferably K, X ³ is preferably tungsten, zinc and / or phosphorus and X ⁴ is preferably Si. Particularly preferred are the variables X ¹ to X ⁴ simultaneously have the meanings given above.

Particularly preferably, all the stoichiometric coefficients a to f and all variables X ¹ to X ⁴ simultaneously have their aforementioned advantageous meanings.

Z²

= Molybdän oder Wolfram, oder Molybdän und Wolfram,

Z³

= Nickel und/oder Kobalt,

Z⁴

= Thallium, ein Alkalimetall und/oder ein Erdalkalimetall, vorzugsweise K, Cs und/oder Sr,

Z⁵

= Phosphor, Arsen, Bor, Antimon, Zinn, Cer, Vanadium, Chrom und/oder Bi,

Z⁶

= Silicium, Aluminium, Titan und/oder Zirkonium, vorzugsweise Si,

Z⁷

= Kupfer, Silber und/oder Gold,

Z⁸

= Molybdän oder Wolfram, oder Wolfram und Molybdän,

a''

= 0,1 bis 1,

b''

= 0,2 bis 2,

c''

= 3 bis 10,

d''

= 0,02 bis 2,

e''

= 0,01 bis 5, vorzugsweise 0,1 bis 3,

f''

= 0 bis 5,

g''

= 0 bis 10, vorzugsweise > 0 bis 10, besonders bevorzugt 0,2 bis 10 und ganz besonders bevorzugt 0,4 bis 3,

h''

= 0 bis 1,

x'', y''

= Zahlen, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XIV bestimmt werden, und

p'', q''

= Zahlen, deren Verhältnis p''/q'' 0,1 bis 5, vorzugsweise 0,5 bis 2 beträgt,

entsprechen.Within the stoichiometries of general formula XIII, preference is given to those corresponding to general formula XIV [Bi _{a ''} Z ² _{b ''} O _{x ''} ] _{p ''} [Z ⁸ ₁₂ Z ³ _{c ''} Z ⁴ _{d ''} F ⁵ _{f ''} Z ⁵ _{f ''} Z ⁶ _{g ''} Z ⁷ _{h ''} O _{y ''} ] _{q ''} (XIV), With

Z ²

= Molybdenum or tungsten, or molybdenum and tungsten,

Z ³

= Nickel and / or cobalt,

Z ⁴

Thallium, an alkali metal and / or an alkaline earth metal, preferably K, Cs and / or Sr,

Z ⁵

= Phosphorus, arsenic, boron, antimony, tin, cerium, vanadium, chromium and / or Bi,

Z ⁶

= Silicon, aluminum, titanium and / or zirconium, preferably Si,

Z ⁷

= Copper, silver and / or gold,

Z ⁸

= Molybdenum or tungsten, or tungsten and molybdenum,

a ''

= 0.1 to 1,

b ''

= 0.2 to 2,

c ''

= 3 to 10,

d '

= 0.02 to 2,

e ''

= 0.01 to 5, preferably 0.1 to 3,

f ''

= 0 to 5,

G''

= 0 to 10, preferably> 0 to 10, particularly preferably 0.2 to 10 and very particularly preferably 0.4 to 3,

H''

= 0 to 1,

x '', y ''

= Numbers determined by the valency and frequency of elements other than oxygen in XIV, and

p '', q ''

= Numbers whose ratio p "/ q" is 0.1 to 5, preferably 0.5 to 2,

correspond.

Further, catalytically active multimetal oxides of stoichiometry XIII are preferred which contain three-dimensionally extended regions of the chemical composition Y ¹ _{a '} Y ² _b' O _{x '} from their local environment due to their different compositions from their local environment whose largest diameter (longest through the center of gravity of the area going direct link of two located on the surface (interface) of the area points) 1 nm to 100 microns, often 10 nm to 500 nm or 1 micron to 50 or 25 microns, is.

Particularly advantageous catalytically active multimetal oxides of stoichiometry XIII are those in which Y ^{1 is} only bismuth.

Within the catalytically active multimetal oxides of stoichiometry XIV those are preferred according to the invention in which Z ² _{b ''} = (tungsten) _{b ''} and Z ⁸ ₁₂ = (molybdenum) ₁₂ .

Furthermore, catalytically active multimetal oxides of stoichiometry XIV are preferred, which contain three-dimensionally extended regions of the chemical composition Bi _{a "} Z ² _b" O _{x "which are} delimited from their local environment due to their different composition from their local environment; longest passing through the center of gravity of the area direct connection distance of two located on the surface (interface) of the area points) 1 nm to 100 microns, often 10 nm to 500 nm or 1 micron to 50 or 25 microns, is.

Furthermore, it is advantageous if at least 25 mol% (preferably at least 50 mol% and particularly preferably at least 100 mol%) of the total fraction [Y ¹ _{a '} Y ² _b' O _{x '} ] _p ([Bi _a'' Z ² _b'' O _x'' ] _p ) the catalytically active multimetal oxides of stoichiometry XIII (of stoichiometry XIV) obtainable as described in the catalytically active multimetal oxides of stoichiometry XIII (stoichiometry XIV) in the form of three-dimensionally extended, from their local environment Due to their different chemical composition of their local environment different demarcated, areas of the chemical composition Y ¹ _{a '} Y ² _b' O _{x '} ([Bi _a'' Z ² _b'' O _x'' ]) are present whose largest diameter in the range 1 nm is up to 100 microns.

In the case of a catalytically active multimetal of one of the stoichiometries XII to XIV come for the inventive method of producing ring-like precursor moldings as a lubricant in addition to graphite and carbon black, polyethylene glycol, stearic acid, starch, polyacrylic acid, mineral or vegetable oil, water, boron trifluoride and / or boron nitride consideration. Glycerol and cellulose ethers can also be used as further lubricants. According to the invention, graphite is preferably added as the sole shaping assistant. Based on the mass to be formed according to the invention for the geometric (preferably ring-like) unsupported catalyst precursor, generally ≦ 15% by weight, usually ≦ 9% by weight, often ≦ 5% by weight, often ≦ 4% by weight Added graphite. Usually, the aforementioned additional amount is ≥ 0.5 Wt .-%, usually ≥ 2.5 wt .-%. Preferably added graphites are Asbury 3160 and Asbury 4012 the company Asbury Graphite Mills, Inc. New Jersey 08802, USA and Timrex ^® T44 Timcal Ltd., 6743 Bodio, Switzerland.

at Demand may still finely divided reinforcing agents such as glass microfibers, asbestos, silicon carbide or potassium titanate be added.

The thermal treatment of as just described according to the invention available geometric (eg, ring-like) multimetal oxide unsupported catalyst precursor bodies usually occurs at temperatures exceeding 350 ° C. Normally, as part of the thermal treatment, the temperature of 650 ° C, however, not exceeded. According to the invention advantageous is within the scope of the thermal treatment, the temperature of 600 ° C, preferably the temperature of 550 ° C and more preferably the temperature of 510 ° C was not exceeded. Further, in the context of thermal treatment of the geometric (eg, ring-like) unsupported catalyst precursor body preferably the temperature of 380 ° C, with advantage the temperature of 400 ° C, with particular advantage the temperature of 420 ° C and most preferably the temperature of 440 ° C exceeded. In this case, the thermal treatment in its timing also be divided into several sections. For example, can first a thermal treatment at a temperature from 150 to 350 ° C, preferably 220 to 290 ° C, followed by a thermal treatment at a Temperature of 400 to 600 ° C, preferably 430 to 550 ° C. be performed.

Usually takes the thermal treatment of the geometric (eg ring-like) Multimetal oxide (XII to XIV) full catalyst precursor body several hours (usually more than 5 h) to complete. Often the total duration of the thermal treatment extends to more than 10 h. Most are used in the context of thermal treatment of ring-like unsupported catalyst precursor body Treatment periods of 50 h and 30 h not exceeded. Often the total treatment time is less than 25 h. According to the invention advantageous be in the context of thermal treatment of the relevant geometric (eg, ring-like) unsupported catalyst precursor body 510 ° C (470 ° C) not exceeded and the treatment duration in the temperature window of ≥ 400 ° C (≥ 440 ° C) extends for 5 to 20 h.

The thermal treatment (also referred to below the decomposition phase) of the above-mentioned ring-like multimetal oxide (XII to XIV) -Vollkatalysatorschrittläuferformkörper can both under inert gas and under an oxidative atmosphere such as. As air (mixture of inert gas and oxygen) and also under reducing atmosphere (eg., Mixture of inert gas, NH ₃ , CO and / or H ₂ or methane, acrolein, methacrolein) take place. Of course, the thermal treatment can also be carried out under vacuum. Of course, in the course of a thermal treatment, the gas atmosphere can also be changed.

In principle, the thermal treatment of geometric (eg ring-like) multimetal oxide unsupported catalyst precursor bodies can be carried out in a wide variety of furnace types, such as, for example, B. heated circulating air chambers, Hordenöfen, rotary kilns, Bandcalcinierern or shaft furnaces are performed. The thermal treatment of the geometric (eg ring-like) multimetal oxide unsupported catalyst precursor shaped bodies preferably takes place in a belt calcining apparatus such as the one described in US Pat DE-A 100 46 957 and the WO 02/24620 recommend.

The thermal treatment of geometric (eg ring-like) Multimetal unsupported catalyst precursor bodies below 350 ° C usually pursues the goal of thermal decomposition of in the unsupported catalyst precursor bodies contained sources of elementary constituents of the aspired ring-like multimetal oxide full catalyst. Often This decomposition phase is carried out during heating to temperatures ≥ 350 ° C.

In particular for the preparation of catalytically active multimetal oxides of the stoichiometry of the general formula XIII or XIV, it is advantageous to use a mixed oxide Y ¹ _{a '} Y ² _b' O _{x '} or Bi _{a "} Z ² _b" O _{x "} as the source of Elements Y ¹ , Y ² and Bi, Z ² preform in the absence of the other constituents of the multimetal and thus after its formation, as already described, with sources of the remaining constituents of the multimetal oxide to produce a finely divided moldable mixture, from which, after addition of Shaping aid to form the geometrical (eg ring-like) multimetal oxide unsupported catalyst precursor body according to the invention.

In such an approach, it is merely necessary to ensure that, in the event that the preparation of the fine-particle-formable mixture takes place wet (in suspension), the preformed mixed oxides Y ¹ _{a '} Y ² _b' O _{x '} or Bi _{a "} Z ² _{b ''} O _{x ''} do not go to any appreciable extent in solution.

In detail, a manufacturing method as described above in the writings DE-A 44 07 020 . EP-A 835 . EP-A 575 897 and DE-C 33 38 380 as well as in the German application with the file reference 102007003778.5 described.

For example, one may mix water-soluble salts of Y ¹ such as nitrates, carbonates, hydroxides or acetates with Y ² acids or their ammonium salts in water, dry the mixture (preferably spray-drying) and then thermally treat the dried mass. The thermally treated mass is subsequently suitably comminuted (for example in a ball mill or by jet milling) and from the powder which is generally available in the form of essentially spherical particles, the class of grain having a stoichiometry for the active multimetal oxide of general Particle XIII or XIV desired maximum diameter range lying grain size diameter by in a known manner to be performed classification (eg wet or dry screening) separated and preferably with, based on the mass of this separated grain class, 0.1 to 3 wt .-%, SiO ₂ finely divided (the particle diameter d _{50 of} the usually substantially spherical SiO ₂ particles is suitably 100 nm to 15 microns) mixed and thus a starting material 1 prepared. The thermal treatment is advantageously carried out at temperatures of 400 to 900 ° C, preferably at 600 to 900 ° C. The latter applies in particular when the preformed mixed oxide is one of the stoichiometry BiZ ² O ₆ , Bi ₂ Z ² ₂ O ₉ and / or Bi ₂ Z ² ₃ O ₁₂ , among which the Bi ₂ Z ² ₂ O _{9 is} preferred, especially when Z ² = tungsten.

Usually, the thermal treatment takes place in the air stream (eg in a rotary kiln, as used in the DE-A 103 25 487 is described). The duration of the thermal treatment usually extends to a few hours.

Of the other constituents of the desired active multimetal of the general formula XIII or XIV is normally starting from in a conventional manner suitable sources (see. EP-A 835 and DE-C 33 38 380 such as DE-A 44 07 020 and the German application with the file reference 102007003778.5 ) in accordance with the invention suitably z. B. a very intimate, preferably finely divided dry mixture prepared (eg, water-soluble salts such as halides, nitrates, acetates, carbonates or hydroxides in an aqueous solution and then the aqueous solution, for example, spray-dry or non-water-soluble salts, eg Oxides, suspended in an aqueous medium and then, for example, the suspension is spray-dried), which is referred to herein as the starting material 2. It is only important that the constituents of the starting material 2 are either already oxides or such compounds which can be converted into oxides by heating, if appropriate in the presence of oxygen and / or oxygen sources. It should also be ensured that the nitrate and / or ammonium salts required according to the invention are present. Subsequently, the starting material 1 and the starting material 2 are mixed in the desired ratio and with the addition of shaping aid to form the ring-like Vollkatalysatorvorläuferformkörper moldable mixture.

The Forming can, as already described, application technology appropriate over the stage of a Zwischenkompaktierung done.

In a less preferred embodiment, the preformed mixed oxide Y ¹ _{a '} Y ² _b' O _{x '} or Bi _a'' Z ² _b'' O _x'' with sources of the remaining constituents of the desired active composition in liquid, preferably aqueous, Medium intimately mixed. This mixture is then z. B. dried to an intimate dry mix and then, as already described, molded and thermally treated. The sources of the remaining constituents may be dissolved and / or suspended in this liquid medium, whereas the preformed mixed oxide should be substantially insoluble in this liquid medium, ie it must be suspended.

The preformed mixed oxide particles are substantially unchanged in the completed geometric (eg ring-shaped) unsupported catalyst in the longest extent set by the classification. Incidentally, as in the German application with the file reference 102007003778.5 be executed executed. The in the German application with the file reference 102007003778.5 with respect to annular multimetal oxide unsupported catalyst precursor bodies and to the embodiments resulting from these multimetal all-metal annular catalysts, the annular target objects of this application apply correspondingly.

In typically, the side compressive strengths are as described available ring-like multimetal oxide (XII to XIV) full catalysts 5 to 13 N, often 8 to 11 N.

As already mentioned, the geometrical (preferably ring-like) unsupported catalysts obtainable as described are particularly suitable as catalysts for the partial oxidation of propene to acrolein or of isobutene and / or tert. Butanol to methacrolein. The partial oxidation can be z. B. as in the scriptures WO 00/53557 . WO 00/53558 . DE-A 199 10 506 . EP-A 1,106,598 . WO 01/36364 . DE-A 199 27 624 . DE-A 199 48 248 . DE-A 199 48 523 . DE-A 199 48 241 . EP-A 700 714 . DE-A 10313213 . DE-A 103 13 209 . DE-A 102 32 748 . DE-A 103 13 208 . WO 03/039744 , EP-A 279 374 . DE-A 33 38 380 . DE-A 33 00 044 . EP-A 575 897 . DE-A 10 2004 003 212 . DE-A 10 2005 013 039 . DE-A 10 2005 009 891 , of the German application with the file reference 102007003778.5 . DE-A 10 2005 010 111 . DE-A 10 2005 009 885 such as DE-A 44 07 020 be carried out described for annular unsupported catalysts, wherein the catalyst charge z. B. only as described available ring-like solid catalysts or z. B. may include diluted ring-like catalysts with inert shaped bodies. In the latter case, the catalyst charge is advantageously designed so that its volume-specific activity in the flow direction of the reaction gas mixture increases continuously, abruptly and / or stepwise.

• a) [Bi₂W₂O₉ × 2WO₃]_0,4[Mo₁₂Co_5,5Fe_2,94Si_1,59K_0,08O_x]₁;
• b) Mo₁₂Ni_6,5Zn₂Fe₂Bi₁P_0,0065K_0,06O_x·10SiO₂;
• c) Mo₁₂Co₇Fe_2,94Bi_0,6Si_1,59K_0,08O_x;
• d) wie Multimetalloxid II-Vollkatalysator gemäß Beispiel 1 der DE-A 197 46 210 ; und
• e) wie Beispiel 1c aus der EP-A 015 565 .

For the process of propylene partial oxidation to acrolein, particularly advantageous multimetal oxide stoichiometries are:

• a) [Bi ₂ W ₂ O ₉ x 2WO ₃ ] _0.4 [Mo ₁₂ Co _5.5 Fe _2.94 Si _1.59 K _0.08 O _x ] ₁ ;
• b) Mo ₁₂ Ni _6.5 Zn ₂ Fe ₂ Bi ₁ P _0.0065 K _0.06 O _x 10SiO ₂ ;
• c) Mo ₁₂ Co ₇ Fe _2.94 Bi _0.6 Si _1.59 K _0.08 O _x ;
• d) as Multimetalloxid II full catalyst according to Example 1 of DE-A 197 46 210 ; and
• e) as Example 1c from the EP-A 015 565 ,

X¹

= Kalium, Rubidium und/oder Cäsium,

X²

= Kupfer und/oder Silber,

X³

= Cer, Bor, Zirkonium, Mangan und/oder Wismut,

a

= 0,5 bis 3,

b

= 0,01 bis 3,

c

= 0,2 bis 3,

d

= 0,01 bis 2,

e

= 0 bis 2,

f

= 0 bis 2, vorzugsweise 0,01 bis 2,

g

= 0 bis 1,

h

= 0 bis 0,5, vorzugsweise 0,001 bis 0,5, und

n

= eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschie denen Elemente in XV bestimmt wird.

However, what has been said in this document is also valid if the catalytically active (active) multimetal oxide of the ring-like multimetal oxide unsupported catalyst has a stoichiometry of the general formula XV, Mo ₁₂ P _a V _b X _c ¹ X _d ² X _e ³ Sb _f Re _g S _h O _n (XV) in which variables have the following meaning:

X ¹

= Potassium, rubidium and / or cesium,

X ²

= Copper and / or silver,

X ³

= Cerium, boron, zirconium, manganese and / or bismuth,

a

= 0.5 to 3,

b

= 0.01 to 3,

c

= 0.2 to 3,

d

= 0.01 to 2,

e

= 0 to 2,

f

= 0 to 2, preferably 0.01 to 2,

G

= 0 to 1,

H

= 0 to 0.5, preferably 0.001 to 0.5, and

n

= a number determined by the valence and frequency of the elements other than oxygen in XV.

Prefers are multimetal oxides XV in which h is 0.03 to 0.5.

Particularly preferred stoichiometries of the general formula XV are those of the embodiments B1 to B15 from the EP-A 467 144 even if these exemplary multimetal oxides do not contain K and / or Re.

The aforementioned EP-A 467 144 and the German application with the file reference 102007003778.5 also describe the preparation of annular multimetal oxide (XV) full-catalyst moldings and their use as catalysts for the heterogeneously catalyzed gas phase partial oxidation of methacrolein to methacrylic acid.

These Descriptions are also given in the present application Context z. B. with respect to the production of appropriate ring-like multimetal oxide (XV) full catalysts.

That is, ring-shaped multimetal oxide (XV) full catalyst precursor moldings can be prepared according to the invention by using as starting compounds suitable salts of them elemental constituents, optionally at elevated temperature and with the addition of acids or bases, dispersed in aqueous medium by dissolving and / or suspending and, if necessary under inert gas, to avoid undesired oxidation processes, the mixture is dried (eg evaporated or spray-dried ), the resulting, finely divided form or transferred in finely divided form dry matter z. B. graphite as a lubricant and optionally other of the aforementioned forming aids, and the resulting finely divided mass, which according to the invention must contain at least one nitrate salt and / or ammonium salt inventively forms the desired ring-like geometry (compacted). The resulting catalyst precursor moldings are then thermally treated for conversion into the active ring-like shaped catalyst bodies. The thermal treatment is preferably carried out at temperatures of from 180 to 480 ° C., more preferably at temperatures of from 250 to 450 ° C. The thermal treatment can be carried out under the gas atmospheres already described. By way of example, mention may again be made of flowing air, flowing inert gas atmosphere (eg N ₂ , or CO ₂ , or noble gases) or vacuum. The thermal treatment can be carried out in several temperature stages and / or in different atmospheres. So z. B. in a first stage at 200 to 260 ° C in air, in a second stage at 420 to 460 ° C in nitrogen and in a third stage at 350 to 410 ° C are again thermally treated in air. As a rule, flowing air is the preferred atmosphere for the thermal treatment.

Furthermore This applies in this document in the production of ring-like Full catalyst moldings of multimetal oxides XII to XIV said in a similar way, but with the difference that here the increased lateral compressive strengths for the annular full catalyst precursor moldings to be favoured.

Likewise apply in the German application with the file reference 102007003778.5 with respect to the preparation of annular Vollkatalysatorformkörpern made of multimetal oxides XV statements here in a corresponding manner.

That is, z. B. preferred drying method for the aqueous solution or suspension of the sources of the elemental constituents of the desired active multimetal oxide XV is the spray drying. The resulting spray powder with a particle diameter d ₅₀ between 10 to 50 microns is advantageously compacted after addition of finely divided graphite as an aid to coarsen the powder. Preferably, the Zwischenkompaktierung here on particle diameter of 100 to 2000 .mu.m, preferably from 150 to 1500 .mu.m and more preferably from 400 to 1000 microns. Subsequently, the shaping according to the invention is carried out on the basis of the coarsened powder, it being possible once again to add finely divided graphite (and optionally further shaping auxiliaries) if necessary beforehand.

at the described preparation of ring-like or other geometric full-catalyst moldings of active Multimetal oxides of general formula XV is usually antimony as antimony trioxide, rhenium z. B. as rhenium (VII) oxide, molybdenum preferably as the ammonium salt of molybdenum or phosphomolybdic acid, Boron z. As boric acid, vanadium usually as ammonium vanadate or vanadium oxalate, phosphorus with advantage as ortho-phosphoric acid or di-ammonium phosphate, sulfur, e.g. B. as ammonium sulfate and the cationic metals usually as nitrates, oxides, hydroxides, Carbonates, chlorides, formates, oxalates and / or acetates or their Hydrate used.

X¹

= Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn und/oder Nb,

X²

= K, Na, Rb, Cs und/oder Tl,

b

= 0,9 bis 1,5,

c

= 0 bis 0,1,

d

= 0 bis 0,1,

e

= 0 bis 0,1, und

n

= eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XVI bestimmt wird.

The inventive method is also suitable for the production of z. B. ring-like Multimetalloxid-Vollkatalysatorschrittläuferformkörpern with curved and / or non-curved face of ring-like Multimetalloxidvollkatalysatoren whose multimetal active is a vanadium, phosphorus and oxygen-containing multimetal and as catalysts for the heterogeneously catalyzed gas phase oxidation of at least one hydrocarbon having at least four carbon atoms (in particular n-butane, n-butenes and / or benzene) to maleic anhydride. The stoichiometry of the active multimetal oxide can be z. B. be one of the general formula XVI, V ₁ P _b Fe _c X ¹ _d X ² _e O _n (XVI), in which the variables have the following meaning:

X ¹

= Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb

X ²

= K, Na, Rb, Cs and / or Tl,

b

= 0.9 to 1.5,

c

= 0 to 0.1,

d

= 0 to 0.1,

e

= 0 to 0.1, and

n

= a number determined by the valence and abundance of elements other than oxygen in XVI.

For the preparation of suitable in this regard and according to the invention z. B. ring-like precursor moldings (in particular F or F ^LII ) to be compacted powdery heaps at this point on the WO 03/078310 and German application with the file reference 102007003778.5 , the WO 01/68245 and the DE-A 10 2005 035 978 referred, which relate to the production of corresponding annular systems.

• a) Umsetzung einer fünfwertigen Vanadiumverbindung (z. B. V₂O₅) mit einem organischen, reduzierenden Lösungsmittel (z. B. iso-Butanol) in Gegenwart einer fünfwertigen Phosphorverbindung (z. B. Ortho- und/oder Pyrophosphorsäure) unter Erwärmen auf 75 bis 205°C, bevorzugt auf 100 bis 120°C;
• b) Abkühlen des Reaktionsgemisches auf vorteilhaft 40 bis 90°C;
• c) Zugabe von Eisen(III)phosphat;
• d) Erneutes Erwärmen auf 75 bis 205°C, bevorzugt 100 bis 120°C;
• e) Isolierung der gebildeten festen Vanadium-, Phosphor-, Eisen- und Sauerstoff enthaltenden festen Vorläufermasse (z. B. durch Filtrieren);
• f) Trocknung und/oder thermische Vorbehandlung der Vorläufermasse (gegebenenfalls bis zu beginnender Vorformierung durch Wasserabspaltung aus der Vorläufermasse);
• g) Zugabe von feinteiligem Graphit und feinteiligem Ammoniumnitrat und anschließend erfindungsgemäße Formgebung zum ringähnlichen Multimetalloxid-Vollkatalysatorvorläuferformkörper;

daran anschließend thermische Behandlung der gebildeten Katalysatorvorläuferformkörper durch Erhitzen in einer Atmosphäre, welche Sauerstoff, Stickstoff, Edelgase, Kohlendioxid, Kohlenmonoxid und/oder Wasserdampf enthält (z. B. wie in der WO 03078310 auf Seite 20, Zeile 16 bis Seite 21, Zeile 35 beschrieben).For example, you can proceed as follows:

• a) reacting a pentavalent vanadium compound (eg V ₂ O ₅ ) with an organic, reducing solvent (eg isobutanol) in the presence of a pentavalent phosphorus compound (eg ortho and / or pyrophosphoric acid) with heating at 75 to 205 ° C, preferably at 100 to 120 ° C;
• b) cooling the reaction mixture to advantageously 40 to 90 ° C;
• c) addition of iron (III) phosphate;
• d) reheating to 75 to 205 ° C, preferably 100 to 120 ° C;
• e) isolating the formed solid vanadium, phosphorus, iron and oxygen-containing solid precursor composition (eg by filtration);
• f) drying and / or thermal pretreatment of the precursor composition (if appropriate until incipient preformation by dehydration from the precursor composition);
• g) addition of finely divided graphite and finely divided ammonium nitrate and subsequent shaping according to the invention to the ring-like multimetal oxide unsupported catalyst precursor molding;

Thereafter, thermal treatment of the formed catalyst precursor moldings by heating in an atmosphere containing oxygen, nitrogen, noble gases, carbon dioxide, carbon monoxide and / or water vapor (for example, as in WO 03078310 on page 20, line 16 to page 21, line 35 described).

The inventive method further comprises processes for the preparation of z. B. ring-like multimetal oxide Vollkatalysatorvorläuferformkörpern with curved and / or non-curved face of ring-like multimetal oxide catalysts whose active multimetal is a Mo, V and at least one of the elements Te and Sb-containing multimetal, as z. For example, the scriptures EP-A 962 253 . DE-A 101 22 027 . EP-A 608 838 . DE-A 198 35 247 . EP-A 895 809 . EP-A 1 254 709 . EP-A 1 192 987 . EP-A 1 262 235 . EP-A 1 193 240 . JP-A 11-343261 . JP-A 11-343262 . EP-A 1 090 684 . EP-A 1 301 457 . EP-A 1 254 707 . EP-A 1 335 793 . DE-A 100 46 672 . DE-A 100 34 825 . EP-A 1 556 337 . DE-A 100 33 121 . WO 01/98246 and EP-A 1 558 569 with the proviso that the pulverulent aggregate to be compacted according to the invention contains at least one nitrate salt and / or one ammonium salt.

Often contain the aforementioned Mo, V and at least one of the elements Te and Sb containing multimetal oxides nor the element Nb. The the foregoing resulting ring-like multimetal oxide full catalysts are suitable for all listed in the aforementioned fonts heterogeneously catalyzed gas phase reactions (especially partial Oxidations). These are in particular the heterogeneously catalyzed partial gas phase oxidation of propane to acrylic acid as well from acrolein to acrylic acid, from methacrolein to methacrylic acid and from iso-butane to methacrylic acid.

However, the inventive method is also suitable, as already mentioned several times in this document, for the production of z. B. ring-like (or other geometric) precursor moldings (eg., From ring-like precursor moldings F or ring-like precursor moldings F ^LII ) from which ring-like (oxidic) or other geometric support moldings are available by thermal treatment, the z. B. can be used for producing ring-like shell catalysts or for producing ring-like impregnation catalysts. However, such ring-like carrier shaped bodies can of course also be used as inert shaped bodies for diluting a fixed catalyst bed.

For the inventive production of such z. B. ring-like carrier precursor shaped body is used as inventively to be compacted powdery debris usually such from (usually normal solid under normal conditions) metal oxides and / or from such metal compounds (eg. Salts) which are convertible by heating (thermal treatment) to oxides (usually solid under normal conditions) (at least by thermal treatment in the presence of gaseous molecular oxygen and / or gaseous oxygen releasing components). In addition, the powdery debris may already mentioned in this document forming aids such. As lubricants, porosifying agents and reinforcing agents added. According to the invention, it is also essential here for the pulverulent aggregate to be compacted according to the invention to contain at least one nitrate salt and / or at least one ammonium salt.

The for the production of z. B. ring-like carrier precursor moldings to be used powdery heaps will therefore also be heap W * or heaps HW ** usually also. All statements made with regard to the compaction according to the invention of pulverulent aggregates HW * and HW ** in this document therefore apply correspondingly. Inventively preferred ring-like carrier precursor shaped bodies are generally ring-like precursor shaped bodies F, preferably ring-shaped precursor shaped bodies F ^LII .

The thermal treatment of geometric (eg ring-like) Carrier precursor shaped body for transfer the same in the geometric (eg ring-like) carrier usually takes place at temperatures ≥ 500 ° C, frequently ≥ 600 ° C and often ≥ 700 ° C. In general, however, the aforementioned thermal treatment at temperatures ≤ 1500 ° C. carried out. The thermal treatment can be both under inert gas as well as under an oxidative atmosphere such as As air (mixture of inert gas and oxygen) take place. Needless to say, The thermal treatment can also be done under vacuum or reducing Atmosphere done.

Usually the thermal treatment takes place under an oxidizing atmosphere (generally under air).

From the catalytically active multimetal oxides differ Carrier oxides usually by the thermal Treatment for their production at much higher temperatures and / or over a longer period of time (whereby they are often largely non-porous) and / or that in them numerically (molar) most often contained, other than oxygen, element no transition metal the 5th to 11th subgroup (these are the vanadium group, the chromium group, manganese group, iron group, cobalt group and nickel group) and not phosphorus is. In many cases this is numerical (molar most frequently contained, other than oxygen, Metal is an element of the group consisting of alkaline earth (eg. Mg, Ca), Zn, Zr, Al, Si and Ti.

The in the production of z. B. ring-like carrier precursor moldings co-used organic (including graphite) forming aids decompose in the aforementioned thermal treatment in the Usually gaseous escaping compounds (and / or settle to gaseous escaping chemical compounds around). Often there is the z. B. ring-like carrier moldings made of a ceramic material. Examples include silicate ceramics and other metal oxide ceramics. In the corresponding way contains to prepare a ring-like carrier precursor body According to the invention to be compacted powdery Heap as mineral raw materials often powdered Silicates such. Zirconium silicate, aluminum silicate (eg mullite), Magnesium silicate (eg steatite) and other powdered Metal oxides such. For example, alumina, magnesia and zirconia.

Exemplified in more detail at this point is the production of in the WO 99/48606 carrier moldings in ring form suitable for the preparation of supported catalysts for the conversion of ethylene and hydrogen chloride in the presence of molecular oxygen to 1,2-dichloroethane ("oxychlorination").

As finely divided mineral raw material, a finely divided mixture of pseudoboehmite and γ-Al ₂ O ₃ in a weight ratio of 4: 1 to 1: 4, preferably 1: 1 to 1: 3 is used. To this mixture, whose particle diameter d ₅₀ is useful from an application 10 to 100 microns are, based on its weight, 0.5 to 7 wt .-% (preferably 2 to 5 wt .-%) by weight of magnesium stearate and 0.5 to third -% (preferably 1 to 1.5 wt .-%) of finely divided graphite (d ₅₀ particle diameter 15 to 30 microns) and 1 to 2 wt .-% ammonium nitrate added as a shaping aid.

The resulting powdery debris is then in accordance with the invention to the z. B. ring-like carrier precursor moldings compacted (the doctrine of EP-A 184790 following, the upper end face of the lower punch and the lower end face of the upper punch are advantageously concave (ie, they preferably have a circular groove)). These are then oxidized in Atmosphere (preferably under air) at temperatures of 500 to 800 ° C, preferably 700 to 750 ° C thermally treated (usually 0.5 to 10 h).

The resulting ring-like carrier shaped body is then impregnated with an aqueous CuCl ₂ / KCl solution. After impregnation, the ring-like shaped bodies to the active ring-like catalysts are dried (usually at temperatures of 80 to 300 ° C, preferably 100 to 200 ° C). Drying is usually done in air.

Typical drying times are from 0.2 to 10 h, in the range of elevated temperatures from 0.5 to 2 h. The concentration and the volume of the impregnation solution are suitably selected in terms of application technology so that the resulting supported catalysts have a Cu content of from 1 to 15% by weight, preferably from 2 to 10% by weight, and a K content of 0 , 1 to 8 wt .-%, preferably from 0.3 to 3 wt .-%. Otherwise, as in the WO 99/48606 be described described.

However, what has been said in this document is also valid when the catalytically active (active) multimetal oxide of the ring-like multimetal oxide unsupported catalyst has the stoichiometry (Fe ₂ O ₃ ) _1. (MoO ₃ ) _5.25 . As starting compounds for the preparation of the same are suitable, for. As iron (III) nitrate and molybdenum trioxide. Particularly preferred Fe source is iron (III) nitrate nonahydrate melt according to the teaching of PCT / EP2008 / 050341 , Both are preferably mixed together in aqueous ammoniacal solution. The same is then spray-dried and the resulting spray powder is compacted in accordance with the invention into preferably ring-like precursor shaped bodies. The end distance E is preferably 5 mm, the length of the outline of the circular cylinder Z is preferably 2 · π mm (π is the ratio of circumference to circle diameter) and the diameter DD of the top surface of the truncated cone KS about 5 mm. Finally, the ring-like precursor moldings are thermally treated in the temperature range of 400 to 500 ° C under air. The resulting ring-like multimetal oxide Vollkatalysatorformkörper are suitable for. As catalysts for the partial oxidation of methanol to formaldehyde.

The inventive method is then special advantageous if in accordance with the invention to be compacted The total amount of powdered aggregate contained weight at nitrate ions and at ammonium ions ≥ 0.1 wt .-%, or ≥ 0.2 Wt%, or ≥ 0.5 wt%, or ≥ 0.75 wt%, or ≥ 1.0 wt%, or ≥ 1.5 wt%, or ≥ 2 Wt .-%, or ≥ 3 wt .-%, or ≥ 5 wt .-%, or ≥ 10 Wt .-% is.

• 1. Verfahren zur Herstellung eines oxidischen geometrischen Formkörpers, umfassend das mechanische Verdichten eines in den Füllraum einer Matrize eingebrachten pulverförmigen Haufwerks, aus Bestandteilen, die wenigstens eine Metallverbindung, die durch thermische Behandlung bei einer Temperatur ≥ 100°C in ein Metalloxid überführbar ist, oder wenigstens ein Metalloxid, oder wenigstens ein Metalloxid und wenigstens eine solche Metallverbindung mit der Maßgabe umfassen, dass wenigstens ein Bestandteil des pulverförmigen Haufwerks ein Nitratsalz, ein Ammoniumsalz oder Ammoniumnitrat ist, zu einem geometrischen Vorläuferformkörper, bei dem sich der Füllraum in einer mit einer vertikalen Bohrachse B von oben nach unten durch das Matrizenmaterial hindurchgeführten Martrizenbohrung befindet und wenigstens durch – die Innenwand der Matrizenbohrung, – die obere Stirnfläche eines von unten entlang der Bohrachse B in die Matrizenbohrung hub- und senkbeweglich eingeführten unterem Stempels, auf der das in den Füllraum eingebrachte pulverförmige Haufwerk aufliegt, und – die längs der Bohrachse B in einem axialen Ausgangsabstand A oberhalb der oberen Stirnfläche des unteren Stempels befindliche unter Stirnfläche eines entlang der Bohrachse B hub- und senkbeweglich angebrachten oberen Stempels, dessen untere Stirnfläche das in den Füllraum eingebrachte pulverförmige Haufwerk von oben berührt, begrenzt wird, indem man den axialen Ausgangsabstand A der beiden Stirnflächen dadurch auf einen für die Verdichtung vorgegebenen axialen Endabstand E längs der Bohrachse B verringert, dass man den oberen Stempel absenkt und dabei die Position des unteren Stempels beibehält oder den unteren Stempel zusätzlich anhebt und nach beendeter Verdichtung der obere Stempel vom gebildeten geometrischen Vorläuferformkörper abgehoben und der geometrische Vorläuferformkörper durch Anheben des unteren Stempels aus der Matrizenbohrung entfernt wird, sowie ein sich daran anschließendes Verfahren der thermischen Behandlung des geometrischen Vorläuferformkörpers bei einer Temperatur ≥ 100°C, bei dem sich wenigstens eine Teilmenge seiner Bestandteile unter Ausbildung wenigstens einer gasförmigen Verbindung zersetzt und/oder chemisch umsetzt und der oxidische geometrische Formkörper sich ausbildet, dadurch gekennzeichnet, dass das die Matrizenbohrung berührende Matrizenmaterial ein Hartmetall ist, das zu ≥ 80 Gew.-% aus dem Hartstoff Wolframcarbid und zu wenigstens 5 Gew.-% aus dem metallischen Bindemittel Nickel besteht.
• 2. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass das Hartmetall neben dem Hartstoff Wolframcarbid zusätzlich wenigstens einen weiteren Hartstoff aus der Gruppe bestehend aus Metallnitriden, Metallboriden und von Wolframcarbid verschiedenen Metallcarbiden enthält.
• 3. Verfahren gemäß Ausführungsform 2, dadurch gekennzeichnet, dass der metallische Anteil des wenigstens einen weiteren Hartstoffs wenigstens ein Metall aus der Gruppe bestehend aus Ti, Zr, Hf, V, Nb, Ta, Mo, Cr und W ist.
• 4. Verfahren gemäß einer der Ausführungsformen 1 bis 3, dadurch gekennzeichnet, dass das Hartmetall als metallisches Bindemittel entweder nur Nickel oder neben Nickel noch wenigstens ein metallisches Bindemittel aus der Gruppe bestehend aus Fe, Co und Cr enthält.
• 5. Verfahren gemäß Ausführungsform 4, dadurch gekennzeichnet, dass der auf das metallische Bindemittel Ni im Hartmetall entfallende Gewichtsanteil größer ist, als der auf Jedes andere im Hartmetall enthaltene metallische Bindemittel entfallende Gewichtsanteil.
• 6. Verfahren gemäß einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, dass das Hartmetall neben dem Hartstoff Wolframcarbid zusätzlich wenigstens einen weiteren Hartstoff aus der Gruppe bestehend aus TiC, TaC, NbC, VC, Cr₃C₂ und Mischmetallcarbide, die wenigstens zwei der in den vorgenannten Metallcarbiden enthaltenen Metalle enthalten, enthält.
• 7. Verfahren gemäß einer der Ausführungsformen 1 bis 6, dadurch gekennzeichnet, dass das Hartmetall zu ≥ 7 Gew.-% aus dem metallischen Bindemittel Nickel besteht.
• 8. Verfahren gemäß einer der Ausführungsformen 1 bis 7, dadurch gekennzeichnet, dass das Hartmetall zu ≥ 85 Gew.-% aus Wolframcarbid besteht.
• 9. Verfahren gemäß einer der Ausführungsformen 1 bis 7, dadurch gekennzeichnet, dass das Hartmetall zu ≥ 90 Gew.-% aus Wolframcarbid besteht.
• 10. Verfahren gemäß einer der Ausführungsformen 1 bis 9, dadurch gekennzeichnet, dass das Hartmetall zu 90 bis 95 Gew.-% aus Wolframcarbid, zu ≥ 0 bis 1 Gew.- % aus wenigstens einem Metallcarbid aus der Gruppe bestehend aus TiC, TaC, NbC, VC, Cr₃C₂ und Mischmetallcarbiden, die wenigstens zwei der in den vorgenannten Metallcarbiden enthaltenen Metalle enthalten, sowie bis zu 10 Gew.-% aus den metallischen Bindemitteln Ni, Fe, Co und/oder Cr mit der Maßgabe besteht, dass der Gewichtsanteil des Ni am Hartmetall ≥ 5 Gew.-% beträgt.
• 11. Verfahren gemäß Ausführungsform 10, dadurch gekennzeichnet, dass das Hartmetall als metallisches Bindemittel nur Nickel oder nur Nickel und Chrom enthält.
• 12. Verfahren gemäß einer der Ausführungsformen 1 bis 11, dadurch gekennzeichnet, dass die Korngröße der Hartstoffe im Hartmetall im Bereich 0,5 μm bis 2 μm liegt.
• 13. Verfahren gemäß einer der Ausführungsformen 1 bis 12, dadurch gekennzeichnet, dass die Matrize ausschließlich aus dem Hartmetall besteht.
• 14. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Matrize nur auf ihrer die Matrizenbohrung berührenden Seite aus dem Hartmetall und auf ihrer von der Matrizenbohrung abgewandten Seite aus einem Werkzeugstahl der Elementzusammensetzung

1,50 bis 1,80 Gew.-% C, 0,10 bis 0,40 Gew.-% Si, 0,10 bis 0,50 Gew.-% Mn, ≥ 0 bis 0,05 Gew.-% P, ≥ 0 bis 0,05 Gew.-% S, 10 bis 13 Gew.-% Cr, 0,50 bis 0,80 Gew.-% Mo, 0,10 bis 1,10 Gew.-% V, ≥ 0 bis 0,60 Gew.-% W, und ≥ 0 bis 0,10 Gew.-% eines oder mehrere seltene Erdmetal le, und im übrigen Fe und herstel lungsbedingte Verunreinigungen, besteht.

• 15. Verfahren gemäß einer der Ausführungsformen 1 bis 14, dadurch gekennzeichnet, dass das pulverförmige Haufwerk wenigstens ein Nitratsalz aus der Gruppe bestehend aus Kobaltnitrat, Eisennitrat, Wismutnitrat, Nickelnitrat, Cäsiumnitrat, Kupfernitrat, Calciumnitrat, Magensiumnitrat und den Hydraten der vorgenannten Nitrate, enthält.
• 16. Verfahren gemäß einer der Ausführungsformen 1 bis 15, dadurch gekennzeichnet, dass das pulverförmige Haufwerk wenigstens ein Ammoniumsalz aus der Gruppe bestehend aus NH₄HCO₃, NH₄OH, (NH₄)₂CO₃, NH₄HSO₄, (NH₄)₂SO₄, NH₄CHO₂, NH₄CH₃CO₂, Ammoniumoxalat und die Hydrate der vorgenannten Ammoniumsalze enthält.
• 17. Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass sich bei der thermischen Behandlung der geometrischen Vorläuferformkörper wenigstens eine gasförmige Verbindung aus der Gruppe bestehend aus Ammoniak, Wasserdampf, CO₂, CO und Stickoxiden bildet.
• 18. Verfahren gemäß einer der Ausführungsformen 1 bis 17, dadurch gekennzeichnet, dass mit der thermischen Behandlung der Vorläuferformkörper ein Gewichtsverlust einhergeht, der, auf deren Ausgangsgewicht vor deren thermischen Behandlung bezogen, 0,5 bis 40 Gew.-% beträgt.
• 19. Verfahren gemäß einer der Ausführungsformen 1 bis 18, dadurch gekennzeichnet, dass der Endabstand E 2 bis 10 mm beträgt.
• 20. Verfahren gemäß einer der Ausführungsformen 1 bis 18, dadurch gekennzeichnet, dass der Endabstand E 2 bis 8 mm beträgt.
• 21. Verfahren gemäß einer der Ausführungsformen 1 bis 20, dadurch gekennzeichnet, dass der Mittenrauhwert R_a der Innenwand der Matrizenbohrung ≤ 0,1 μm beträgt.
• 22. Verfahren gemäß einer der Ausführungsformen 1 bis 21, dadurch gekennzeichnet, dass im Endabstand E von beiden Stempeln ein Pressdruck ausgeübt wird, der im Bereich 50 bis 5000 kg/cm² liegt.
• 23. Verfahren gemäß einer der Ausführungsformen 1 bis 22, dadurch gekennzeichnet, dass im Endabstand E von beiden Stempeln ein Pressdruck ausgeübt wird, der im Bereich 500 bis 2500 kg/cm² liegt.
• 24. Verfahren gemäß einer der Ausführungsformen 1 bis 23, dadurch gekennzeichnet, dass das Verfahren der thermischen Behandlung der hergestellten Vorläuferformkörper bei einer Temperatur ≥ 200°C erfolgt.
• 25. Verfahren gemäß einer der Ausführungsformen 1 bis 24, dadurch gekennzeichnet, dass das Verfahren der thermischen Behandlung der hergestellten Vorläuferformkörper bei einer Temperatur ≥ 300°C erfolgt.
• 26. Verfahren gemäß einer der Ausführungsformen 1 bis 25, dadurch gekennzeichnet, dass das pulverförmige Haufwerk Graphit, Stärke, gemahlene Nussschale, feinteiliges Kunststoffgranulat, Cellulose, Stearinsäure, Malonsäure, Salz der Stearinsäure und/oder Salz der Malonsäure zugesetzt enthält.
• 27. Verfahren gemäß einer der Ausführungsformen 1 bis 26, dadurch gekennzeichnet, dass der in dem mechanisch zu verdichtenden pulverförmigen Haufwerk insgesamt enthaltene Gewichtsanteil an Nitrationen und Ammoniumionen ≥ 0,1 Gew.-% beträgt.
• 28. Verfahren gemäß einer der Ausführungsformen 1 bis 26, dadurch gekennzeichnet, dass der in dem mechanisch zu verdichtenden pulverförmigen Haufwerk insgesamt enthaltene Gewichtsanteil an Nitrationen und Ammoniumionen ≥ 0,2 Gew.-% beträgt.
• 29. Verfahren gemäß einer der Ausführungsformen 1 bis 28, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid ausgebildet wird, das die Elemente Mo und Fe, oder die Elemente Mo, Fe und Bi, oder die Elemente Mo und V, oder die Elemente Mo, V und P, oder die Elemente V und P enthält.
• 30. Verfahren gemäß einer der Ausführungsformen 1 bis 29, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid ausgebildet wird, in welchem das Element Mo, oder das Element V, oder das Element P dasjenige von Sauerstoff verschiedene Element ist, das molar gerechnet das numerisch am häufigsten enthaltene ist.
• 31. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid der allgemeinen Formel XII, MO₁₂Bi_aFe_bX¹ _cX² _dX³ _eX⁴ _fO_n (XII),mit

  X¹

  = Nickel und/oder Kobalt,

  X²

  = Thallium, Samarium, ein Alkalimetall und/oder ein Erdalkalimetall,

  X³

  = Zink, Phosphor, Arsen, Bor, Antimon, Zinn, Cer, Blei, Vanadium, Chrom, Niob und/oder Wolfram,

  X⁴

  = Silicium, Aluminium, Titan und/oder Zirkonium,

  a

  = 0,2 bis 5,

  b

  = 0,01 bis 5,

  c

  = 0 bis 10,

  d

  = 0 bis 2,

  e

  = 0 bis 8,

  f

  = 0 bis 10, und

  n

  = eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XII bestimmt wird,

  ausgebildet wird.
• 32. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbiglen ein Multimetalloxid der allgemeinen Formel XIII, [Y¹ _a'Y² _b'O_x']_p[Y³ _c'Y⁴ _d'Y⁵ _e'Y⁶ _f'Y⁷ _g'Y⁸ _h'O_y']_q (XIII),mit

  Y¹

  = nur Wismut oder Wismut und wenigstens eines der Elemente Tellur, Antimon, Zinn und Kupfer,

  Y²

  = Molybdän oder Wolfram, oder Molybdän und Wolfram,

  Y³

  = ein Alkalimetall, Thallium und/oder Samarium,

  Y⁴

  = ein Erdalkalimetall, Nickel, Kobalt, Kupfer, Mangan, Zink, Zinn, Cadmium und/oder Quecksilber,

  Y⁵

  = Eisen oder Eisen und wenigstens eines der Elemente Vanadium, Chrom und Cer,

  Y⁶

  = Phosphor, Arsen, Bor und/oder Antimon,

  Y⁷

  = ein seltenes Erdmetall, Titan, Zirkonium, Niob, Tantal, Rhenium, Ruthenium, Rhodium, Silber, Gold, Aluminium, Gallium, Indium, Silicium, Germanium, Blei, Thorium und/oder Uran,

  Y⁸

  = Molybdän oder Wolfram, oder Molybdän und Wolfram,

  a'

  = 0,01 bis 8,

  b'

  = 0,1 bis 30,

  c'

  = 0 bis 4,

  d'

  = 0 bis 20,

  e'

  > 0 bis 20,

  f'

  = 0 bis 6,

  g'

  = 0 bis 15,

  h'

  = 8 bis 16,

  x', y'

  = Zahlen, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XIII bestimmt werden, und

  p, q

  = Zahlen, deren Verhältnis p/q 0,1 bis 10 beträgt,

  ausgebildet wird.
• 33. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid der allgemeinen Formel XIV, [Bi_a''Z² _b''O_x'']_p''[Z⁸ ₁₂Z³ _c''Z⁴ _d''Fe_e''Z⁵ _f''Z⁶ _g''Z⁷ _h''O_y'']_q'' (XIV),mit

  Z²

  = Molybdän oder Wolfram, oder Molybdän und Wolfram,

  Z³

  = Nickel und/oder Kobalt,

  Z⁴

  = Thallium, ein Alkalimetall und/oder ein Erdalkalimetall,

  Z⁵

  = Phosphor, Arsen, Bor, Antimon, Zinn, Cer, Vanadium, Chrom und/oder Bi,

  Z⁶

  = Silicium, Aluminium, Titan und/oder Zirkonium,

  Z⁷

  = Kupfer, Silber und/oder Gold,

  Z⁸

  = Molybdän oder Wolfram, oder Wolfram und Molybdän

  a''

  = 0,1 bis 1,

  b''

  = 0,2 bis 2,

  c''

  = 3 bis 10,

  d''

  = 0,02 bis 2,

  e''

  = 0,01 bis 5,

  f''

  = 0 bis 5,

  g''

  = 0 bis 10,

  h''

  = 0 bis 1,

  x'', y''

  = Zahlen, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XIV bestimmt werden, und

  p'', q''

  = Zahlen, deren Verhältnis p''/q'' 0,1 bis 5 beträgt, ausgebildet wird.

• 34. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid der allgemeinen Formel XV, Mo₁₂P_aV_bX_c ¹X_d ²X_e ³Sb_fRe_gS_hO_n (XV),mit

  X¹

  = Kalium, Rubidium und/oder Cäsium,

  X²

  = Kupfer und/oder Silber,

  X³

  = Cer, Bor, Zirkonium, Mangan und/oder Wismut,

  a

  = 0,5 bis 3,

  b

  = 0,01 bis 3,

  c

  = 0,2 bis 3,

  d

  = 0,01 bis 2,

  e

  = 0 bis 2,

  f

  = 0 bis 2,

  g

  = 0 bis 1,

  h

  = 0 bis 0,5, und

  n

  = eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XV bestimmt wird,

  ausgebildet wird.
• 35. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein Multimetalloxid der allgemeinen Formel XVI, V₁P_bFe_cX¹ _dX² _eO_n (XVI),mit

  X¹

  = Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn und/oder Nb,

  X²

  = Li, K, Na, Rb, Cs und/oder Tl,

  b

  = 0,9 bis 1,5,

  c

  = 0 bis 0,1,

  d

  = 0 bis 0,1,

  e

  = 0 bis 0,1, und

  n

  = eine Zahl, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in XVI,

  ausgebildet wird.
• 36. Verfahren gemäß einer der Ausführungsformen 1 bis 28, dadurch gekennzeichnet, dass bei dem anschließenden Verfahren der thermischen Behandlung der hergestellten geometrischen Vorläuferformkörper in selbigen ein bei Normalbedingungen festes Oxid ausgebildet wird, in welchem kein Übergangsmetall der 5. bis 11. Nebengruppe und auch nicht Phosphor dasjenige von Sauerstoff verschiedene Element ist, das molar gerechnet das numerisch am häufigsten enthaltene ist.
• 37. Verfahren gemäß einer der Ausführungsformen 1 bis 28, dadurch gekennzeichnet, dass das pulverförmige Haufwerk wenigstens ein Metalloxid aus der Gruppe bestehend aus Aluminiumoxid, Wolframoxid, Antimonoxid, Zirkoniumoxid, Wismutoxid, Molybdänoxid, Siliciumoxid, Magnesiumoxid und Mischoxiden, die wenigstens zwei der in den vorgenannten Metalloxiden enthaltenen Metallelemente enthalten, enthält.
• 38. Oxidischer geometrischer Formkörper, erhältlich nach einem Verfahren gemäß einer der Ausführungsformen 1 bis 37.
• 39. Verfahren der heterogen katalysierten partiellen Gasphasenoxidation wenigstens einer organischen Verbindung an einem Katalysatorfestbett, dadurch gekennzeichnet, dass das Katalysatorfestbett einen geometrischen oxidischen Formkörper gemäß Ausführungsform 38 enthält.
• 40. Verfahren gemäß der Ausführungsform 39, dadurch gekennzeichnet, dass die heterogen katalysierte partielle Gasphasenoxidation diejenige a) von Propylen zu Acrolein und/oder Acrylsäure oder b) von Acrolein zu Acrylsäure, oder c) von Methacrolein zu Methacrylsäure, oder d) von iso-Buten zu Methacrolein und/oder Methacrylsäure, oder e) von Propan zu Acrolein und/oder Acrylsäure, oder f) von iso-Butan zu Methacrolein und/oder Methacrylsäure, oder g) von wenigstens einem C₄-Kohlenwasserstoff und/oder Benzol zu Maleinsäureanhydrid, oder h) von Methanol zu Formaldehyd oder i) die Oxichlorierung von Ethylen zu 1,2-Dichlorethan ist.
• 41. Rohrbündelreaktor, dessen Reaktionsrohre wenigstens einen oxidischen geometrischen Formkörper gemäß Ausführungsform 38 enthalten.

Thus, the present patent application comprises in particular the following embodiments according to the invention:

• Anspruch [en] A process for producing an oxidic geometric shaped body, comprising mechanical compacting of a powdery aggregate introduced into the filling space of a matrix, from constituents comprising at least one metal compound which can be converted into a metal oxide by thermal treatment at a temperature of .gtoreq.100.degree at least one metal oxide, or at least one metal oxide, and at least one such metal compound, provided that at least one constituent of the powdered aggregate is a nitrate salt, ammonium salt or ammonium nitrate, to a geometric precursor shaped body having the filling space in one with a vertical drilling axis B is guided from top to bottom through the Matrizenmaterial Martrizenbohrung and at least by - the inner wall of the die bore, - the upper end face of a down along the drilling axis B in the die bore hub and lowered introduced under em stamp on which the introduced into the filling space powdery debris rests, and - located along the drilling axis B at an axial output distance A above the upper end face of the lower punch located under the end face of a along the drilling axis B liftable and vertically mounted upper punch whose lower end face of the introduced into the filling powdery debris is touched from above, limited by the axial output distance A of the two end faces thereby reduced to a predetermined axial axial distance for the compression E along the drilling axis B that lowers the upper punch and thereby the Maintains position of the lower punch or raises the lower punch in addition and lifted after completion of compression of the upper punch from the formed geometric Vorformformkörper and the geometric precursor shaped body is removed by lifting the lower punch from the die bore, as well as dara n subsequent process of the thermal treatment of the geometric precursor shaped body at a temperature ≥ 100 ° C, in which decomposes at least a subset of its constituents to form at least one gaseous compound and / or chemically reacts and the oxidic geometric shaped body is formed, characterized in that the Matrizenbohrung touching die material is a hard metal, which consists of ≥ 80 wt .-% of the hard tungsten carbide and at least 5 wt .-% of the metallic binder nickel.
• 2. Method according to embodiment 1, characterized in that the hard metal in addition to the hard material tungsten carbide additionally contains at least one further hard material from the group consisting of metal nitrides, borides and metal carbides different from tungsten carbide.
• 3. The method according to embodiment 2, characterized in that the metallic portion of the at least one further hard material is at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, Cr and W.
• 4. The method according to any one of embodiments 1 to 3, characterized in that the hard metal contains as metallic binder either only nickel or nickel in addition to at least one metallic binder selected from the group consisting of Fe, Co and Cr.
• 5. The method according to embodiment 4, characterized in that the weight fraction attributable to the metallic binder Ni in the hard metal is greater than the weight fraction attributable to any other metallic binder contained in the hard metal.
• 6. The method according to any one of embodiments 1 to 5, characterized in that the hard metal in addition to the hard material tungsten carbide additionally at least one further hard material from the group consisting of TiC, TaC, NbC, VC, Cr ₃ C ₂ and Mischmetallcarbide, the at least two of contained in the aforementioned metal carbides contained metals.
• 7. The method according to any one of embodiments 1 to 6, characterized in that the hard metal to ≥ 7 wt .-% consists of the metallic binder nickel.
• 8. The method according to any one of embodiments 1 to 7, characterized in that the hard metal to ≥ 85 wt .-% consists of tungsten carbide.
• 9. The method according to any one of embodiments 1 to 7, characterized in that the hard metal consists of ≥ 90 wt .-% of tungsten carbide.
• 10. The method according to any one of embodiments 1 to 9, characterized in that the hard metal to 90 to 95 wt .-% of tungsten carbide, to ≥ 0 to 1% by weight of at least one metal carbide selected from the group consisting of TiC, TaC, NbC, VC, Cr ₃ C ₂ and Mischmetallcarbiden containing at least two of the metals contained in the aforementioned metal carbides, and up to 10 wt .-% of the metallic binders Ni, Fe, Co and / or Cr with the proviso is that the proportion by weight of Ni in the hard metal is ≥ 5% by weight.
• 11. The method according to embodiment 10, characterized in that the hard metal contains as metallic binder only nickel or only nickel and chromium.
• 12. The method according to any one of embodiments 1 to 11, characterized in that the grain size of the hard materials in the hard metal in the range 0.5 microns to 2 microns.
• 13. The method according to any one of embodiments 1 to 12, characterized in that the die consists exclusively of the hard metal.
• 14. The method according to any one of claims 1 to 12, characterized in that the die only on its the die bore-contacting side of the hard metal and on its side remote from the die bore side of a tool steel of the elemental composition

1.50 to 1.80% by weight C., 0.10 to 0.40 wt% Si, 0.10 to 0.50 wt% Mn, ≥0 to 0.05% by weight P, ≥0 to 0.05% by weight S, 10 to 13% by weight Cr, 0.50 to 0.80 wt% Not a word, 0.10 to 1.10% by weight V, ≥0 to 0.60 wt% W, and ≥ 0 to 0.10% by weight one or more rare earth metals le, and otherwise Fe and herstel pollution-related contaminants, consists.

• 15. The method according to any one of embodiments 1 to 14, characterized in that the powdery debris at least one nitrate salt selected from the group consisting of cobalt nitrate, iron nitrate, bismuth nitrate, nickel nitrate, cesium nitrate, copper nitrate, calcium nitrate, magnesium nitrate and the hydrates of the aforementioned nitrates.
• 16. The method according to any one of embodiments 1 to 15, characterized in that the powdery debris at least one ammonium salt from the group consisting of NH ₄ HCO ₃ , NH ₄ OH, (NH ₄ ) ₂ CO ₃ , NH ₄ HSO ₄ , (NH ₄ ) ₂ SO ₄ , NH ₄ CHO ₂ , NH ₄ CH ₃ CO ₂ , ammonium oxalate and the hydrates of the aforementioned ammonium salts.
• 17. The method according to any one of embodiments 1 to 16, characterized in that forms at least one gaseous compound from the group consisting of ammonia, water vapor, CO ₂ , CO and nitrogen oxides in the thermal treatment of the geometric precursor shaped body.
• 18. The method according to any one of embodiments 1 to 17, characterized in that associated with the thermal treatment of the precursor molded body, a weight loss, based on their initial weight before their thermal treatment, 0.5 to 40 wt .-% is.
• 19. The method according to any one of embodiments 1 to 18, characterized in that the final distance E is 2 to 10 mm.
• 20. The method according to any one of embodiments 1 to 18, characterized in that the final distance E is 2 to 8 mm.
• 21. The method according to any one of embodiments 1 to 20, characterized in that the average roughness R _{a of} the inner wall of the die bore is ≤ 0.1 microns.
• 22. The method according to any one of embodiments 1 to 21, characterized in that in the end distance E of both punches a pressing pressure is exerted, which is in the range 50 to 5000 kg / cm ² .
• 23. The method according to any one of embodiments 1 to 22, characterized in that in the end distance E of both punches a pressing pressure is exerted, which is in the range of 500 to 2500 kg / cm ² .
• 24. The method according to any one of embodiments 1 to 23, characterized in that the method of thermal treatment of the prepared precursor molded body takes place at a temperature ≥ 200 ° C.
• 25. The method according to any one of embodiments 1 to 24, characterized in that the method of thermal treatment of the prepared precursor molded body is carried out at a temperature ≥ 300 ° C.
• 26. The method according to any one of embodiments 1 to 25, characterized in that the powdery debris contains graphite, starch, ground nutshell, finely divided plastic granules, cellulose, stearic acid, malonic acid, salt of stearic acid and / or salt of malonic acid added.
• 27. Method according to one of the embodiments 1 to 26, characterized in that the total weight fraction of nitrate ions and ammonium ions contained in the pulverulent aggregate to be mechanically compacted is ≥ 0.1% by weight.
• 28. The method according to any one of embodiments 1 to 26, characterized in that the weight fraction of nitrate ions and ammonium ions contained in total in the pulverulent aggregate to be mechanically compacted is ≥ 0.2% by weight.
• 29. The method according to any one of embodiments 1 to 28, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal oxide is formed, the elements Mo and Fe, or the elements Mo, Fe and Bi, or the elements Mo and V, or the elements Mo, V and P, or the elements V and P contains.
• 30. The method according to any one of embodiments 1 to 29, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal oxide is formed, in which the element Mo, or the element V, or the element P that of Oxygen is a different element, which is the numerically most frequently included molar.
• 31. The method according to any one of embodiments 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XII, MO ₁₂ Bi _a Fe _b X ¹ _c X ² _d X ³ _e X ⁴ _f O _n (XII), With

  X ¹

  = Nickel and / or cobalt,

  X ²

  Thallium, samarium, an alkali metal and / or an alkaline earth metal,

  X ³

  Zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead, vanadium, chromium, niobium and / or tungsten,

  X ⁴

  = Silicon, aluminum, titanium and / or zirconium,

  a

  = 0.2 to 5,

  b

  = 0.01 to 5,

  c

  = 0 to 10,

  d

  = 0 to 2,

  e

  = 0 to 8,

  f

  = 0 to 10, and

  n

  = a number determined by the valency and abundance of elements other than oxygen in XII,

  is trained.
• 32. The method according to any one of embodiments 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbiglen a multimetal of the general formula XIII, [Y ¹ _{a '} Y ² _b' O _{x '} ] _p [Y ³ _c' Y ⁴ _{d '} Y ⁵ _e' Y ⁶ _{f '} Y ⁷ _g' Y ⁸ _{h '} O _y' ] _q (XIII) With

  Y ¹

  = only bismuth or bismuth and at least one of the elements tellurium, antimony, tin and copper,

  Y ²

  = Molybdenum or tungsten, or molybdenum and tungsten,

  Y ³

  = an alkali metal, thallium and / or samarium,

  Y ⁴

  an alkaline earth metal, nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury,

  Y ⁵

  = Iron or iron and at least one of the elements vanadium, chromium and cerium,

  Y ⁶

  = Phosphorus, arsenic, boron and / or antimony,

  Y ⁷

  = a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium,

  Y ⁸

  = Molybdenum or tungsten, or molybdenum and tungsten,

  a '

  = 0.01 to 8,

  b '

  = 0.1 to 30,

  c '

  = 0 to 4,

  d '

  = 0 to 20,

  e '

  > 0 to 20,

  f '

  = 0 to 6,

  G'

  = 0 to 15,

  H'

  = 8 to 16,

  x ', y'

  = Numbers determined by the valency and frequency of elements other than oxygen in XIII, and

  p, q

  = Numbers whose ratio p / q is 0.1 to 10,

  is trained.
• 33. The method according to any one of embodiments 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XIV, [Bi _{a ''} Z ² _{b ''} O _{x ''} ] _{p ''} [Z ⁸ ₁₂ Z ³ _{c ''} Z ⁴ _{d ''} Fe _{e ''} Z ⁵ _{f ''} Z ⁶ _{g ''} Z ⁷ _{h ''} O _y'' ] _q'' (XIV), With

  Z ²

  = Molybdenum or tungsten, or molybdenum and tungsten,

  Z ³

  = Nickel and / or cobalt,

  Z ⁴

  = Thallium, an alkali metal and / or an alkaline earth metal,

  Z ⁵

  = Phosphorus, arsenic, boron, antimony, tin, cerium, vanadium, chromium and / or Bi,

  Z ⁶

  = Silicon, aluminum, titanium and / or zirconium,

  Z ⁷

  = Copper, silver and / or gold,

  Z ⁸

  = Molybdenum or tungsten, or tungsten and molybdenum

  a ''

  = 0.1 to 1,

  b ''

  = 0.2 to 2,

  c ''

  = 3 to 10,

  d '

  = 0.02 to 2,

  e ''

  = 0.01 to 5,

  f ''

  = 0 to 5,

  G''

  = 0 to 10,

  H''

  = 0 to 1,

  x '', y ''

  = Numbers determined by the valency and frequency of elements other than oxygen in XIV, and

  p '', q ''

  = Numbers whose ratio p "/ q" is 0.1 to 5 are formed.

• 34. The method according to any one of embodiments 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XV, Mo ₁₂ P _a V _b X _c ¹ X _d ² X _e ³ Sb _f Re _g S _h O _n (XV) With

  X ¹

  = Potassium, rubidium and / or cesium,

  X ²

  = Copper and / or silver,

  X ³

  = Cerium, boron, zirconium, manganese and / or bismuth,

  a

  = 0.5 to 3,

  b

  = 0.01 to 3,

  c

  = 0.2 to 3,

  d

  = 0.01 to 2,

  e

  = 0 to 2,

  f

  = 0 to 2,

  G

  = 0 to 1,

  H

  = 0 to 0.5, and

  n

  = a number determined by the valence and frequency of elements other than oxygen in XV,

  is trained.
• 35. The method according to any one of embodiments 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XVI, V ₁ P _b Fe _c X ¹ _d X ² _e O _n (XVI), With

  X ¹

  = Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb

  X ²

  = Li, K, Na, Rb, Cs and / or Tl,

  b

  = 0.9 to 1.5,

  c

  = 0 to 0.1,

  d

  = 0 to 0.1,

  e

  = 0 to 0.1, and

  n

  = a number determined by the valence and frequency of elements other than oxygen in XVI,

  is trained.
• 36. The method according to any one of embodiments 1 to 28, characterized in that in the subsequent process of thermal treatment of the prepared geometric precursor moldings in selbigen a solid oxide is formed under normal conditions, in which no transition metal of the 5th to 11th subgroup and also not Phosphorus is that element other than oxygen, which in molar terms is numerically most abundant.
• 37. The method according to any one of embodiments 1 to 28, characterized in that the powdery debris at least one metal oxide selected from the group consisting of alumina, tungsten oxide, antimony oxide, zirconium oxide, bismuth oxide, molybdenum oxide, silica, magnesium oxide and mixed oxides containing at least two of the in the contain metal elements contained above metal oxides contains.
• 38. Oxidic geometric shaped body obtainable by a process according to one of embodiments 1 to 37.
• 39. A process of heterogeneously catalyzed partial gas phase oxidation of at least one organic compound on a fixed catalyst bed, characterized in that the fixed catalyst bed contains a geometric oxidic shaped body according to embodiment 38.
• 40. The process according to the embodiment 39, characterized in that the heterogeneously catalyzed partial gas phase oxidation that a) of propylene to acrolein and / or acrylic acid or b) of acrolein to acrylic acid, or c) of methacrolein to methacrylic acid, or d) of iso- Butene to methacrolein and / or methacrylic acid, or e) from propane to acrolein and / or acrylic acid, or f) from isobutane to methacrolein and / or methacrylic acid, or g) from at least one C ₄ hydrocarbon and / or benzene to maleic anhydride or h) from methanol to formaldehyde or i) the oxychlorination of ethylene to 1,2-dichloroethane.
• 41. tube bundle reactor whose reaction tubes contain at least one oxidic geometric shaped body according to embodiment 38.

Examples and Comparative Examples

I. Preparation of ring-like Mulitmetalloxid unsupported catalyst precursor bodies, wherein the active multimetal oxide is stoichiometry

• [Bi ₂ W ₂ O ₉ • 2WO ₃ ] _0.40 [Mo ₁₂ Co _5.4 Fe _3.1 Si _1.5 K _0.08 O _x ] ₁

1. Preparation of a starting material 1

In 780 kg of an aqueous nitric acid bismuth nitrate solution (11.2% by weight of Bi; free nitric acid 3 to 5% by weight, mass density: 1.22 to 1.27 g / ml, prepared with bismuth metal nitric acid of Firma Siech SA, 1495 Tilly, Belgium, purity:> 99.997% by weight Bi, <7 mg / kg Pb, each <5 mg / kg Ni, Ag, Fe, <3 mg / kg Cu, Sb and <1 mg / kg Cd, Zn) were portionwise at 25 ° C within 20 min 214.7 kg of a 25 ° C having tungstic acid (74.1 wt .-% W, HC Starck, D-38615 Goslar, purity> 99.9 wt .-% WO ₃ after annealing at 750 ° C, 0.4 microns <d ₅₀ <0.8 μm) (70 rpm or "70 rpm") The resulting aqueous mixture was then stirred for a further 3 hours at 25 ° C. and then spray-dried.

The spray drying was carried out in a rotary disk spray tower in hot air direct current at a gas inlet temperature of 300 ± 10 ° C, a gas outlet temperature of 100 ± 10 ° C, a disk speed of 18000 U / min and a throughput of 200 l / h. The resulting spray powder had an ignition loss of 12.8 wt .-% (3 hours at 600 ° C in a porcelain crucible (which had been annealed at 900 ° C to constant weight) under air) and (at a dispersion pressure of 1.1 bar absolute) a d ₅₀ of 28.0 μm (d ₁₀ = 9.1 μm, d ₉₀ = 55.2 μm). 9 shows the particle diameter distribution of the resulting spray powder as a function of the applied dispersion pressure.

The The abscissa shows the particle diameter in logarithmic plot in μm.

• 
  : Dispergierdruck = 2 bar abs..
• 
  : Dispergierdruck = 1,5 bar abs..
• 
  : Dispergierdruck = 1,2 bar abs..
• ♦: Dispergierdruck = 1,1 bar abs..

The ordinate shows the volume fraction in% of the total particle volume, which has the corresponding particle diameter as a function of the applied dispersion pressure:

• 
  : Dispersing pressure = 2 bar abs ..
• 
  : Dispersion pressure = 1.5 bar abs ..
• 
  : Dispersion pressure = 1.2 bar abs.
• ♦: dispersion pressure = 1.1 bar abs.

The following table gives an overview of representative d _x values depending on the applied absolute dispersion pressure: 2 bar 1.5 bar 1.2 bar 1.1 bar d ₁₀ (μm) 0.91 1.17 3.4 9.1 d ₅₀ (μm) 5.8 8.5 19.7 28.0 d ₉₀ (μm) 27.5 34.3 47.2 55.2

The resulting spray powder was then pasted with 16.7 wt .-% (based on the powder) of 25 ° C water in a kneader (20 rev / min) for 30 min and by means of an extruder (torque: ≤ 50 Nm) Extruded strands of diameter 6 mm. These were cut into 6 cm sections on a 3-zone belt dryer with a residence time of 120 minutes per zone at temperatures of 90-95 ° C (zone 1), 115 ° C (zone 2) and 125 ° C (zone 3) dried in air and then thermally treated at a temperature in the range of 830 ° C. (calcined, in the rotary kiln with air flow (0.3 mbar vacuum, 1.54 m ³ internal volume, 200 Nm ³ / h air, 50 kg / h extrudate, Speed: 1 rpm, at 4 m length of the rotary tube 7 cm inclination)). Essential in the exact setting of the calcination temperature is that it has to be oriented on the desired phase composition of the calcination product. The phases WO ₃ (monoclinic) and Bi ₂ W ₂ O ₉ (orthorhombic) are desired, the presence of γ-Bi ₂ WO ₆ (Russellite) is undesirable. If, therefore, after the calcination, the compound γ-Bi ₂ WO ₆ can still be detected by means of a reflection in the X-ray powder diffractogram at a reflection angle of 2 Θ = 28.4 ° (CuKa radiation), the preparation must be repeated and the calcination temperature within the specified range Increase the temperature range or the residence time at the same calcination temperature until the disappearance of the reflex is achieved. The preformed calcined mixed oxide thus obtained was milled with a BQ500 Bip500 at 2500 rpm, so that the d ₅₀ value was 2.45 μm (d ₁₀ = 1.05 μm, d ₉₀ = 5.9 μm, measured at a dispersion pressure of 2 bar absolute) and the BET surface area was 0.8 m ² / g.

The millbase was then in portions of 20 kg in a tilting mixer (type VIS, filling volume: 60 l, Aachener mixing and kneading machine factory) with mixing and cutting blades (speed mixing blade: 60 U / min, speed cutting blade: 3000 U / min ) within 5 (min homogeneous particulate with 0.5 wt .-% (based on the material to be ground) SiO ₂ from Degussa type Sipernat ^® D17 bulk density was 150 g / l;. d ₅₀ value of the SiO ₂ particles (laser diffraction to ISO 13320-1 ) was 10 μm, the specific surface area (nitrogen adsorption after ISO 5794-1 , Annex D) was 100 m ² / g) mixed.

2. Preparation of a starting material 2

A solution A was prepared by stirring at 60 ° C with stirring (70 rpm) to 660 l of water at 60 ° C for one minute, 1.075 kg of an aqueous potassium hydroxide solution (47.5%) having a temperature of 60 ° C Wt .-% KOH) and then with a Dosiergeschwin of 600 kg / h 237.1 kg of ammonium heptamolybdate tetrahydrate (white crystals with a particle size d <1 mm, 81.5% by weight MoO ₃ , 7.0-8.5% by weight NH ₃ , max. 150 mg / kg alkali metals, HC Starck, D-38642 Goslar) and the resulting slightly turbid solution was stirred at 60 ° C. for 60 minutes.

A solution B was prepared by mixing at 60 ° C in 282.0 kg of a 60 ° C aqueous cobalt (II) nitrate solution (12.5 wt .-% Co, prepared with cobalt metal nitric acid from the company MFT Metals & Ferro-Allogs Trading GmbH, 0-41747 Viersen, purity,> 99.6 wt.%, <0.3 wt.% Ni, <100 mg / kg Fe, <50 mg / kg Cu) and to this under stirring (70 rev / min) 142.0 kg of a 60 ° C warm iron (III) nitrate nonahydrat melt (13.8 wt .-% Fe, <0.4 wt .-% alkali metals , <0.01% by weight of chloride, <0.02% by weight of sulfate, Dr. Paul Lohmann GmbH, D-81857 Emmerthal). The mixture was then stirred while maintaining the 60 ° C for 30 minutes. Then, while maintaining the 60 ° C, the solution B was drained into the initially charged solution A and stirred at 60 ° C for a further 15 minutes. Na ^+; particle charge: negative; stabilizing counterion, then 19.9 kg of a silica gel of the company Grace GmbH were added to the resulting aqueous mixture in D-67547 Worms ^® type Ludox TM-50 (50 wt .-% SiO _2. Si: Na ratio by weight SiO ₂ / Na ₂ O: 225, SiO ₂ content: 50% by weight, pH value: 9.0, mass density (25 ° C., 1 atm.): 1.40 g / cm ³ Sulfates (as Na ₂ SO ₄ ): 0.08% by weight; titratable alkali (as Na ₂ O): 0.21% by weight; viscosity (25 ° C., 1 atm): 40 cP; specific surface area the SiO ₂ particle: 140 m ² / g) was added and then stirred at 60 ° C for a further 15 minutes.

Subsequently, it was spray-dried in a hot-air countercurrent in a rotary disk spray tower of the FS-15 type from Niro (gas inlet temperature: 350 ± 10 ° C., gas outlet temperature: 140 ± 5 ° C., disk speed: 18000 rpm, throughput: 270 kg / h). The resulting spray powder had a loss on ignition of 30.5 wt .-% (3 hours at 600 ° C in the porcelain crucible (which had been annealed at 900 ° C to constant weight) under air) and (at a dispersing pressure of 2.0 bar absolute) a d ₅₀ of 23.6 μm (d ₁₀ = 5.2 μm, d ₉₀ = 49.5 μm). 10 shows the particle diameter distribution of the resulting spray powder as a function of the applied dispersion pressure.

• 
  : Dispergierdruck = 2 bar abs..
• ♦: Dispergierdruck = 1,1 bar abs..

The abscissa shows the particle diameter in logarithmic plots in μm. The ordinate shows the volume fraction in% of the total particle volume, which has the corresponding particle diameter as a function of the applied dispersion pressure:

• 
  : Dispersing pressure = 2 bar abs ..
• ♦: dispersion pressure = 1.1 bar abs.

The following table gives an overview of representative d _x values depending on the applied absolute dispersion pressure: 2 bar 1.1 bar d ₁₀ (μm) 5.2 9.9 d ₅₀ (μm) 23.6 28.5 d ₉₀ (μm) 49.5 56.3

3. Preparation of the Multimetalloxidkatalysatorformkörper and their forerunners

110 kg of the starting material 2 were then placed in a tilting mixer (type VIL, filling volume: 200 l, Aachener mixing and kneading machine factory) with mixing and cutting blades (speed mixing blade: 39 U / min, speed blade: 3000 U / min) submitted and 1 mm premixed. Within 10 mm for this purpose, with continued mixing via a rotary feeder, the initial mass 1 in the case of a multimetal oxide active mass of stoichiometry was: [Bi ₂ W ₂ O ₉ .2WO ₃ ] _0.40 [Mo ₁₂ Co _5.4 Fe _3.1 Si _1.5 K _0.08 O _x ] ₁ required amount added within 10 mm. Then the mixing was continued for a further 15 mm to achieve an intense and complete homogenization (including the breaking up of any agglomerates present) of the two starting materials (required to achieve high activity and acrolein selectivity). Based on the aforementioned total mass, within a further 2 mm 1% by weight of graphite TIMREX T44 from Timcal AG was mixed in.

The resulting mixture was then mixed in a compactor type K200 / 100 from Hosokawa Bepex GmbH) with concave, corrugated smooth rolls (gap width: 2.8 mm, roller speed: 9 rpm, press force target value: approx. 75 kN). Using integrated vibrating sieves from Allgaier (mesh oversize: 1.5 mm, mesh undersize: 400 μm) with ball screen aids (diameter 22 mm), a compactate with a particle size largely between 400 μm and 1.5 mm was isolated.

For the tableting was added to the compactate in a turbulent mixer the company Drais within 2 min further 2.5 wt .-% of graphite TIMREX T44 from Timcal AG.

Subsequently, the pulverulent debris produced as described was compacted according to the invention with the aid of a Korsch PH 865 rotary under air _[g1] (simple tool, 65 matrices). The basic device layout was like in 6 , The diameter of the pre-pressure roller was 100 mm and the diameter of the main pressure roller was 300 mm. The distance between two matrices lying opposite one another on the matrix disk was 780 mm.

The matrices used were matrices with a congruent double truncated cone as in Figs 3a . 3b shown schematically.

The Length I of the longitudinal section I was 6.22 mm.

The Length II (the length II *) of the longitudinal section II (of the longitudinal section II *) was 8 mm.

The Outline of the circular cylinder I and the circular cylinder II amounted 15.7 mm.

Of the Diameter DD of the top surface of the truncated cone KS was 5.1 mm.

Of the Diameter DG of the base of the truncated cone KS was 5.0 mm.

The Length of the outline of the circular cylinder Z (of the continuous circular cylindrical center pin) was 2.5 · π mm. The plane upper end face of the center pin MF closed flush with the flat upper die face from.

Only ring-like precursor shaped bodies F ^LII were produced, the final distance E always being 3 mm. The upper end face of the lower punch and the lower end face of the upper punch were both planed. The drilling axis B was perpendicular on both faces.

Both center holes, MB ^U and MB ^O (the latter was associated with two gas-permeable outlets (cf. 4d )), had in the entrance area in the associated end face on a circular cylindrical geometry with identical radius. The contact of their inner walls to the outer surface of the center pin MF was slidable in the possible contact area.

The single die was made of a composite material. This consisted on its the die bore touching side of the cemented carbide G10-Ni (6.9 to 7 mm wall thickness), which at a particle size of 1.2 microns to 92.8 wt .-% of WC, to 0.2 wt % of TiC and TaNbC and 7% by weight of Ni, with R _a = 0.1 μm and on its side facing away from the die bore DIN tool steel 1.2379 (9 mm wall thickness) with R _a = 0.8 μm. The upper punch and the lower punch were out DIN material 1.2601 manufactured. The center-circular center pin MF was off on its entire length DIN tool steel 1.2343 manufactured (R _a = 0.4 microns). R _{a of} the two end faces was also 0.4 microns.

The in the filling space introduced amount of powdery Heap was 129 mg.

While the entire procedure closed the lower face of the upper punch in the state of the output distance A with the upper one End of the longitudinal section II flush.

The applied pre-pressure force (press force) was at each of the two Stamp 0.3 kN, the applied main compressive force (pressing force) was 4.2 kN for each of the two punches.

The Side compressive strengths of the resulting ring-like Multimetal oxide unsupported catalyst precursor body ranged from 21 to 23 N.

The Turning rate of the rotary was 35 to 45 rpm.

Regarding of the material of die plate tongue, die plate face and Die top chin applies the same in the description.

In order to avoid the release of dust, the tabletting machine was sucked off (300 to 400 Nm ³ / h). The exhaust air was passed through a filter, which was cleaned periodically.

The Procedure was over a period of 5 days (120 h), apart from two short (about 30 minutes each) interruptions for the purpose of sucking accumulated particulate matter, without interruption carried out.

Subsequently, the ring-like multimetal oxide unsupported catalyst precursor bodies prepared in this period were prepared as in Example 1 of U.S. Pat DE-A 100 46 957 (but the height of the decomposition (chambers 1 to 4) was 53 mm with a residence time of 1.23 h per chamber and in the calcination (chambers 5 to 8) it was 153 mm with a residence time of 3 , 89 h) described by means of a ribbon calciner thermally treated; the chambers had a base area (with a uniform chamber length of 1.40 m) of 1.29 m ² (decomposition) and 1.40 m ² (calcination) and were from below through the coarse-mesh band of 50-210 Nm ³ / h to 100 ° C (decomposition) or 450 ° C (calcination) preheated incoming air flows through; in addition, the air was circulated by rotating fans (900 to 1450 rpm). Within the chambers was the temporal and local deviation of the temperature from the set point (typical values for zones 1-8 are: 140 ° C, 190 ° C, 220 ° C, 265 ° C, 380 ° C, 425 ° C, 460 ° C, 460 ° C) always ≤ 2 ° C. Behind chamber 8 was followed by a tempered to 70 ° C 2 m long cooling zone. Incidentally, as in Example 1, the DE-A 100 46 957 described procedure.

Subsequently became the formed ring-like multimetal oxide full catalyst moldings subject to underscoring. The seven used acted they are long-hole sieves. Your straight edge length was 20 mm and the distance between the two edges was 1.8 mm. Based on the weight of the total screened material to be screened the resulting undersize fraction was 0.52% by weight.

Was in the same manner as described above, the compression of the powdery aggregate but by means of a die of appropriate geometry and material quality, but with the carbide G10-Co (wall thickness 6.9 to 7 mm, R _a = 0.1 microns) on the Matrizenbohrung touching side (grain size = 2.5 microns, 93.5 wt .-% WC, 6.5 wt .-% Co, 0.5 wt .-% TiC and TaNbC) carried out, was the resulting in the screening Unterkornanteil included 0.78 wt .-%.

The ring-shaped multimetal oxide full catalysts prepared as described are suitable for. B. for the heterogeneously catalyzed partial Gas phase oxidation of propylene to acrolein.

alternative for compression according to the invention by means of a Korsch PH 865 Rundläufers can the inventive Compaction also with a Kilian Synthesis 700-77A rotary be executed. As pre-pressure force (pre-compression force) can with each of the two punches 0.6 kN and as Main pressure force (main pressure force) at each of the two punches 5.0 kN can be applied. Furthermore, the inventive Compression also carried out in a nitrogen atmosphere become.

II. Preparation of ring-like multimetal oxide unsupported catalyst precursor bodies, wherein the active multimetal the stoichiometry Mo ₁₂ Co ₇ Fe _2.94 Bi had _0.6 Si _1.59 K _0.08 O _x

At 60 ° C 213 kg of ammonium heptamolybdate tetrahydrate (81.5 wt .-% MoO ₃ ) were dissolved in 600 l of water. 0.97 kg of a 46.8% strength by weight aqueous potassium hydroxide solution at 20.degree. C. were stirred into this solution whilst maintaining the 60.degree. C. (thereby obtaining solution A).

A second solution B was prepared by stirring to 333.7 kg of an aqueous cobalt (II) nitrate solution (12.4 wt.% Co) at 30 ° C, 116.25 kg of an aqueous iron containing 20 ° C - (III) nitrate solution (14.2 wt% Fe). After the addition was still 30 min. stirred at 30 ° C. Thereafter, at 60 ° C., 112.3 kg of an aqueous bismuth nitrate solution (11.2% by weight of Bi) containing 20 ° C. was stirred to obtain the solution B. Within 30 min. at 60 ° C, the solution B was stirred into the solution A. 15 minutes. After stirring was completed at 60 ° C 19.16 kg of silica sol (Ludox TM-50 from Grace GmbH in D-67547 Worms) in the resulting mash. While maintaining the 60 ° C was still 15 min. stirred. Then, the obtained mash was spray-dried in a hot air countercurrent process (gas inlet temperature: 400 ± 10 ° C, gas outlet temperature: 140 ± 5 ° C) to obtain a spray powder whose ignition loss (3 hours at 600 ° C under air) was 30% of its weight. The spray powder had egg d ₅₀ of 20.3 microns and a d ₁₀ of 3.24 microns and a d ₉₀ of 53.6 microns (measured at a dispersing pressure of 2 bar absolute) on.

An additional 1.0% by weight (based on the amount of spray powder) of graphite Asbury 3160 _[g2] from Asbury Graphite Mills, Inc. New Jersey 08802, USA, was mixed into the spray powder.

The The resulting dry mixture was determined by means of a compactor the company Hosokawa Bepex GmbH (D-74211 Leingarten) of the Kompaktor type K 200/100 under the conditions of 2.8 mm gap width, 1.0 mm mesh, 200 μm mesh size undersize, 35 kN pressing force and 65 to 70 rpm screw speed by precompacting to a substantially uniform grain size from 200 μm to 1 mm coarsened.

The Kompaktat was then mixed with, based on its weight, a further 2 wt .-% of the same graphite and then using a Kilian rounder type RX 73, the company Kilian, D-50735 Cologne, under air atmosphere to ring-like Multimetalloxid-Vollkatalysatorvorläuferformkörpern F ^LII compressed with non-curved (ie, with a flat) end face. The basic device layout was like in 6 , The tool used for this purpose (die, stamp, etc.) as well as the materials for die plate tongue, die face and die disc chin corresponded to those of example I. This also applies to the other compression conditions including the final distance E of 3 mm. The lateral compressive strength of the resulting ring-like multimetal oxide precursor shaped bodies was 19 to 21 N.

• – mit 1°C/min. von 25°C auf 160°C erhöht;
• – dann 100 min. bei 160°C gehalten;
• – danach mit 3°C/min. von 160°C auf 200°C erhöht;
• – dann 100 min. bei 200°C gehalten;
• – danach mit 2°C/min. von 200°C auf 230°C erhöht;
• – dann 100 min. bei 230°C gehalten;
• – danach mit 3°C/min. von 230°C auf 270°C erhöht;
• – dann 100 min. bei 270°C gehalten;
• – danach mit 1°C/min. auf 380°C erhöht;
• – dann 4,5 h bei 380°C gehalten;
• – danach mit 1°C/min. auf 430°C erhöht;
• – dann 4,5 h bei 430°C gehalten;
• – danach mit 1°C/min. auf 500°C erhöht;
• – dann 9 h bei 500°C gehalten;
• – danach innerhalb von 4 h auf 25°C abgekühlt.

For their subsequent thermal treatment, in each case 1900 g of the ring-like multimetal oxide Vollkatalysatorvorläuferformkörper in a heated circulating air chamber (0.12 m ³ internal volume) was added (2 Nm ³ air / min.). Subsequently, the temperature in the bed was changed as follows:

• - at 1 ° C / min. increased from 25 ° C to 160 ° C;
• - then 100 min. kept at 160 ° C;
• - afterwards with 3 ° C / min. increased from 160 ° C to 200 ° C;
• - then 100 min. kept at 200 ° C;
• - afterwards with 2 ° C / min. increased from 200 ° C to 230 ° C;
• - then 100 min. kept at 230 ° C;
• - afterwards with 3 ° C / min. increased from 230 ° C to 270 ° C;
• - then 100 min. maintained at 270 ° C;
• - afterwards with 1 ° C / min. increased to 380 ° C;
• - Then held at 380 ° C for 4.5 h;
• - afterwards with 1 ° C / min. increased to 430 ° C;
• - Then held at 430 ° C for 4.5 h;
• - afterwards with 1 ° C / min. increased to 500 ° C;
• - then held at 500 ° C for 9 h;
• - Then cooled within 4 h at 25 ° C.

there were made from the ring-like multimetal oxide unsupported catalyst precursor bodies Ring-like multimetal oxide Vollkatalysatorformkörper receive. These are suitable for. As catalysts for the heterogeneously catalyzed partial gas phase oxidation of propylene to acrolein.

These were subjected to undersize screening according to Example I. Based on the weight of the total screened material to be screened the resulting undersize fraction was 0.68% by weight.

Has been in the same way as described above and the compression performed with appropriate matrices whose carbide component however, was G10-Co, was the amount of undersize that accumulated during the screening at 0.99 wt .-%.

III. Preparation of ring-like multimetal oxide unsupported catalyst precursor bodies wherein the active multimetal oxide had the stoichiometry Mo ₁₂ P _1.5 V _0.6 Cs _1.0 Cu _0.5 Sb ₁ S _0.04 O _x

In 619 l at 45 ° C tempered water in a water-tempered jacketed vessel with stirring (70 revolutions per minute (RPM)) 537.5 kg of ammonium heptamolybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ · 4 H ₂ O (81 wt. % MoO ₃ , 8% by weight of NH ₃ , ≦ 50 ppm by weight of Na and ≦ 100 ppm by weight of K) The temperature of the solution dropped to 37 ° C. in this case to ensure reliable dissolution of the ammonium heptamolybdate , stirring was continued for 15 minutes at the end of the metered addition, maintaining the temperature at 37 ° C. With further stirring, 17.82 kg of ammonium metavanadate (NH ₄ VO ₃ , 77% by weight of V ₂ O ₅ , 14.5 wt.% NH ₃ , ≤ 150 wt. Ppm Na and ≤ 500 ppm by weight K). It was stirred for 2 minutes. Then, a produced within one minute in a separate dissolving tank, colorless, clear, 60 ° C warm solution of 49.6 kg of cesium nitrate (CsNO ₃ with 72 wt .-% Cs ₂ O and ≤ 50 ppm by weight Na, ≤ 100 Ppm by weight K, ≦ 10 ppm by weight Al and ≦ 20 ppm by weight Fe) are stirred into 106 l of water. In this case, the temperature of the resulting suspension rose to 39 ° C. After stirring for one minute, 31.66% by weight of 175% strength by weight phosphoric acid (density at 25 ° C. and 1 atm: 1.57 g / ml, viscosity at 25 ° C. and 1 atm: 0.147 cm ² / S) added. Due to the exothermic reaction, the temperature rose to 42 ° C. Again, stirring was continued for 1 minute. Then 1.34 kg of ammonium sulfate ((NH ₄ ) ₂ SO ₄ (> 99 wt .-%)) were stirred in within one minute and stirred for a further 1 minute. 37.04 kg antimony tri oxide (Sb ₂ O ₃ , particle diameter d ₅₀ = about 2 microns, crystal structure according to XRD:> 75% Senarmontit, <25% Valentinit, purity:> 99 , 3% by weight, ≦ 0.3% by weight of As ₂ O ₃ , ≦ 0.3% by weight of PbO and ≦ 300 ppm by weight of FeO) (commercially available as Triox White, Code No. 639000) Fa. Antraco, D-10407 Berlin). Now the stirrer speed was reduced from 70 to 50 rpm. Subsequently, the stirred suspension was heated by steam in a double jacket within 30 minutes linearly to 95 ° C. At this temperature and 50 rpm, 51.64 kg of copper nitrate solution (aqueous Cu (NO ₃ ) ₂ solution containing 15.6% by weight of Cu) were added over the course of 4 minutes. After 56 minutes of stirring at 95 ° C, the stirring speed was further reduced from 50 to 35 rpm. Subsequently, the entire suspension was drained within 4 minutes in a nitrogen-overlaid, tempered at 85 ° C and stirred at 35 rpm stirring tower reservoir tank and it was rinsed with 20 liters of water (25 ° C). For this purpose, the suspension was spray-dried in a rotary disk spray tower type FS-15 from Niro in hot air direct current (gas inlet temperature: 285 ± 10 ° C, gas outlet temperature: 110 ± 5 ° C, disk speed: 18000 U / min, throughput: 270 kg / h ), the resulting spray powder having a loss on ignition (1 h at 500 ° C. in air) of 17.2% by weight and a d ₅₀ of 35.9 μm (d ₁₀ = 14.3 μm, d ₉₀ = 65, 6 μm, measured at a dispersion pressure of 2 bar absolute).

The Spray powder was mixed with 1.5% by weight of Graphite Timrex 44 homogeneously mixed and compacted by Timcal (Kompaktor der Hosokawa Bepex GmbH, D-74211 Leingarten, type K200 / 100 with concave, fluted plain rollers, gap width: 2.8 mm, mesh width: 1.25 mm, Screen size undersize: 400 μm, screw speed: 65 to 70 rpm). For the tableting Kompaktat were more 1 wt .-% of the same graphite mixed.

Subsequently, the pulverulent debris produced as described was compacted according to the invention with the aid of a Korsch PH 865 rotary traveler under an air atmosphere (simple tool, 65 matrices). The basic device layout was like in 6 , The diameter of the pre-pressure roller was 100 mm and the diameter of the main pressure roller was 300 mm. The distance between two matrices lying opposite each other on the die plate was 780 mm.

The matrices used were matrices with a congruent double truncated cone as in Figs 3a . 3b shown schematically. The length I of the longitudinal section I was 2.2 mm. The length II (the length II *) of the longitudinal section II (the longitudinal section II *) was 10 mm.

The Outline of the circular cylinder I and the circular cylinder II amounted 22 mm. The diameter DD of the top surface of the truncated cone KS was 7.1 mm. The diameter DG of the base of the Truncated cone KS was 7.0 mm. The length of the outline of the circular cylinder Z (of the continuous circular cylindrical center pin) was 3.0 · π mm. The plane upper end face of the center pin MF closed with the plane upper die face flush off.

Only ring-like precursor shaped bodies F ^LII were produced, the final distance E always being 7 mm. The upper end face of the lower punch and the lower end face of the upper punch were both planed. The drilling axis B was perpendicular on both faces.

Both center holes, MB ^U and MB ^O (the latter was associated with two gas-permeable outlets (cf. 4d )), had in the entrance area in the associated end face on a circular cylindrical geometry with identical radius. The contact of their inner walls to the outer surface of the center pin MF was slidable in the possible contact area.

The single die was made of a composite material. On its side touching the die bore, this consisted of carbide G10-Ni (2.5 to 2.6 mm wall thickness) with R _a = 0.1 μm and on its side facing away from the die bore DIN tool steel 1.2379 (9 mm wall thickness) with R _a = 0.8 μm. The upper punch and the lower punch were out DIN material 1.2601 manufactured. The on his overall circular cylindrical center pin MF was off DIN tool steel 1.2343 manufactured (R _a = 0.4 microns). R _{a of} the two end faces was also 0.4 microns.

The in the filling space introduced amount of powdery Heap was 576 mg.

While the entire procedure closed the lower face of the upper punch in the state of the output distance A with the upper one End of the longitudinal section II flush. The at each of the two stamp applied pre-compression force (press force) was 0.3 kN, the main compressive force applied to each of the two punches (Press force) was 3.5 kN.

The Side compressive strengths of the resulting ring-like Multimetal oxide unsupported catalyst precursor body ranged from 33 to 37 N. The number of revolutions of the rotary was 20 to 25 rpm. With regard to the material of the die plate tongue, Die plate face and die plate chin is the same in the description Said.

The Procedure was over a period of 5 days (120 h), apart from two short-term (about 30 minutes each) interruptions for the purpose of sucking accumulated particulate matter, without interruption carried out.

Subsequently, in each case 8 kg of the ring-like multimetal oxide Vollkatalysatoraktläufer moldings were evenly distributed in a wire container of the base 33.0 cm × 49.5 cm, resulting in a bed height of 4 cm. The wire container was placed in a chamber furnace (Elino Industrie-Ofenbau, Carl Hanf GmbH & Co., D-52355 Düren, type KA-040 / 006-08 EW.OH, dimensions: length = 57 cm, width = 57 cm, height = 80 cm) arranged so that the bed of tablets was flowed through evenly. 2 Nm ³ / h of fresh air were supplied and the air circulation in the oven adjusted so that the bed at a rate of 0.9 m / s (determined by aerometer, Messrs. Testo, type 445) was flowed through. The oven was then heated to 380 ° C. with the following temperature ramp: heating to 180 ° C. within 40 minutes, holding for 30 minutes, heating to 220 ° C. within 10 minutes, holding for 30 minutes, to 270 ° C. within 13 minutes Heat up, hold for 30 min, heat to 340 ° C within 25 min and then to 380 ° C within 40 min. This temperature was then held for 390 minutes. Meanwhile, the NH ₃ content in the extracted atmosphere of the thermal treatment was continuously monitored by FTIR spectroscopy (Nicolet spectrometer, "Impact" type, IR stainless steel cell with CaF ₂ window, 10 cm layer thickness, temperature control to 120 ° C. , Determination of the concentration on the basis of the intensity of the band at 3333 cm ^-1 ) The NH ₃ content remained during the entire thermal treatment ≤ 2.4 vol .-% This maximum value was reached at 220 ° C.

The obtained ring-like multimetal oxide Vollkatalysatorformkörper are suitable for. B. as catalysts for the heterogeneously catalyzed partial gas phase oxidation of methacrolein to methacrylic acid.

After that became the formed ring-like multimetal oxide full catalyst moldings subject to underscoring. The seven used acted they are long-hole sieves. Your straight edge length was 20 mm and the distance between the two edges was 6 mm. Based on the weight of the total screened material to be screened the resulting undersize fraction was 15.6 wt .-%.

Has been in the same way as described above and the compression of the powdered aggregate with corresponding matrices performed their carbide component but G10-Co the sub-grain fraction of the screening was 18.1 Wt .-%.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (41)

A process for the production of an oxidic geometric shaped body, comprising the mechanical compacting of a pulverulent aggregate introduced into the filling space of a matrix, from constituents which contain at least one metal compound which can be converted into a metal oxide by thermal treatment at a temperature ≥ 100 ° C, or at least one Metal oxide, or at least one metal oxide and at least one such metal compound, with the proviso that at least one constituent of the powdered aggregate is a nitrate salt, an ammonium salt or ammonium nitrate, to a geometrical precursor shaped body, wherein the filling space in one with a vertical drilling axis B of is located at the top down through Martrizenbohrung passed through the Matrizenmaterial and at least by - the inner wall of the die bore, - the upper end face of a bottom along the bore axis B in the die bore hub and lowered introduced lower Stamp, on which the introduced into the filling space powdery debris rests, and - along the drilling axis B at an axial exit distance A above the upper end face of the lower punch located under the end face of a along the drilling axis B liftable and vertically mounted upper punch, the lower End face of the introduced into the filling powdery debris touched from above, is limited by the axial output distance A of the two end faces thereby reduced to a predetermined axial axial distance for compression E along the drilling axis B that lowers the upper punch and thereby the position maintains the lower punch or raises the lower punch in addition and lifted after completion of compression of the upper punch from the formed geometrical precursor shaped body and the geometric precursor shaped body is removed by lifting the lower punch from the die bore, and a thereon a nschließendes method of thermal treatment of the geometric precursor shaped body at a temperature ≥ 100 ° C, in which decomposes at least a subset of its constituents to form at least one gaseous compound and / or chemically reacts and the oxidic geometric shaped body is formed, characterized in that the Matrizenma touching a Matrizenma material is a hard metal, which consists of ≥ 80 wt .-% of the hard material tungsten carbide and at least 5 wt .-% of the metallic binder nickel. Method according to claim 1, characterized in that that the carbide in addition to the hard tungsten carbide in addition at least one further hard material from the group consisting of Metal nitrides, metal borides and other than tungsten carbide Contains metal carbides. Method according to claim 2, characterized in that that the metallic portion of the at least one further hard material at least one metal from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, Cr and W. Method according to one of claims 1 to 3, characterized in that the hard metal as metallic Binders either only nickel or next to nickel at least a metallic binder selected from the group consisting of Fe, Co and Cr contains. Method according to claim 4, characterized in that that attributable to the metallic binder Ni in the hard metal Weight percentage is greater than that on each other in the carbide contained metallic binder weight fraction. Method according to one of claims 1 to 5, characterized in that the hard metal in addition to the hard material tungsten carbide additionally at least one further hard material from the group consisting of TiC, TaC, NbC, VC, Cr ₃ C ₂ and Mischmetallcarbide, at least two of the in the containing metals mentioned above metal carbides contains. Method according to one of claims 1 to, characterized in that the hard metal to ≥ 7 wt .-% consists of the metallic binder nickel. Method according to one of claims 1 to 7, characterized in that the hard metal to ≥ 85 wt .-% made of tungsten carbide. Method according to one of claims 1 to 7, characterized in that the hard metal to ≥ 90 wt .-% made of tungsten carbide. Method according to one of claims 1 to 9, characterized in that the hard metal to 90 to 95 wt .-% of tungsten carbide, to ≥ 0 to 1 wt .-% of at least one metal carbide selected from the group consisting of TiC, TaC, NbC, VC, Cr ₃ C ₂ and Mischmetallcarbiden containing at least two of the metals contained in the aforementioned metal carbides, and up to 10 wt .-% of the metallic binders Ni, Fe, Co and / or Cr with the proviso that the weight fraction of the Ni on the hard metal is ≥5% by weight. Method according to claim 10, characterized in that that the carbide as a metallic binder only nickel or contains only nickel and chromium. Method according to one of claims 1 to 11, characterized in that the grain size Hard materials in carbide in the range 0.5 μm to 2 μm lies. Method according to one of claims 1 to 12, characterized in that the die exclusively consists of the carbide. Method according to one of claims 1 to 12, characterized in that the die on its side touching the die bore made of the hard metal and on its side facing away from the die bore side of a tool steel of the elemental composition 1.50 to 1.80% by weight C., 0.10 to 0.40 wt% Si, 0.10 to 0.50 wt% Mn, ≥0 to 0.05% by weight P, ≥0 to 0.05% by weight S, 10 to 13% by weight Cr, 0.50 to 0.80 wt% Not a word, 0.10 to 1.10% by weight V, ≥0 to 0.60 wt% W, and ≥ 0 to 0.10% by weight one or more rare earth metals le, and otherwise Fe and herstel pollution-related contaminants, consists. Method according to one of claims 1 to 14, characterized in that the powdery debris at least one nitrate salt selected from the group consisting of cobalt nitrate, Iron nitrate, bismuth nitrate, nickel nitrate, cesium nitrate, Copper nitrate, calcium nitrate, magnesium nitrate and the hydrates of Nitrates mentioned above contains. Method according to one of the claims 1 to 15, characterized in that the powdery debris at least one ammonium salt from the group consisting of NH ₄ HCO ₃ , NH ₄ OH, (NH ₄ ) ₂ CO ₃ , NH ₄ HSO ₄ , (NH ₄ ) ₂ SO ₄ , NH ₄ CHO ₂ , ammonium metavanadate, ammonium heptamolybdate, NH ₄ CH ₃ CO ₂ , ammonium oxalate and the hydrates of the aforementioned ammonium compounds. Method according to one of claims 1 to 16, characterized in that forms at least one gaseous compound from the group consisting of ammonia, water vapor, CO ₂ , CO and nitrogen oxides in the thermal treatment of the geometric precursor shaped body. Method according to one of claims 1 to 17, characterized in that with the thermal treatment the precursor shaped body is associated with a loss of weight, the, on their initial weight before their thermal treatment based, 0.5 to 40 wt .-% is. Method according to one of claims 1 to 18, characterized in that the end distance E is 2 to 10 mm. Method according to one of claims 1 to 18, characterized in that the end distance E is 2 to 8 mm. Method according to one of claims 1 to 20, characterized in that the average roughness R _a the inner wall of the die bore is ≤ 0.1 μm. Method according to one of claims 1 to 21, characterized in that in the final distance E of both punches a pressing pressure is exerted, which is in the range 50 to 5000 kg / cm ² . Method according to one of claims 1 to 22, characterized in that in the final distance E of both punches a pressing pressure is exerted, which is in the range 500 to 2500 kg / cm ² . Method according to one of claims 1 to 23, characterized in that the method of thermal treatment the prepared precursor molded body in a Temperature ≥ 200 ° C takes place. Method according to one of claims 1 to 24, characterized in that the method of thermal treatment the prepared precursor molded body in a Temperature ≥ 300 ° C takes place. Method according to one of claims 1 to 25, characterized in that the powdery debris Graphite, starch, ground nutshell, finely divided plastic granules, Cellulose, stearic acid, malonic acid, salt of Stearic acid and / or salt of malonic acid added contains. Method according to one of claims 1 to 26, characterized in that in the mechanically to be compacted total amount of powder contained in aggregate at nitrate ions and ammonium ions ≥ 0.1 wt .-% is. Method according to one of claims 1 to 26, characterized in that in the mechanically to be compacted total amount of powder contained in aggregate at nitrate ions and ammonium ions ≥ 0.2 wt .-% is. Method according to one of claims 1 to 28, characterized in that in the subsequent process the thermal treatment of the prepared geometric precursor moldings in which a multimetal oxide is formed, which is the elements Mo and Fe, or the elements Mo, Fe and Bi, or the elements Mo and V, or the elements Mo, V and P, or the elements V and P contains. Method according to one of claims 1 to 29, characterized in that in the subsequent process the thermal treatment of the prepared geometric precursor moldings in which a multimetal oxide is formed, in which the Element Mo, or element V, or element P that of Oxygen is a different element, which is numerically the molar most common is. Method according to one of claims 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XII, Mo ₁₂ Bi _a Fe _b X ¹ _c X ² _d X ³ _e X ⁴ _f O _n (XII) with X ¹ = nickel and / or cobalt, X ² = thallium, samarium, an alkali metal and / or an alkaline earth metal, X ³ = zinc, phosphorus, arsenic, boron, antimony, tin, cerium, lead, vanadium, chromium, niobium and or tungsten, X ⁴ = silicon, aluminum, titanium and / or zirconium, a = 0.2 to 5, b = 0.01 to 5, c = 0 to 10, d = 0 to 2, e = 0 to 8 , f = 0 to 10, and n = a number determined by the valence and frequency of the non-oxygen elements in XII is formed. Method according to one of claims 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbiglen a Multimetal oxide of general formula XIII, [Y ¹ _{a '} Y ² _b' O _{x '} ] _p [Y ³ _c' Y ⁴ _{d '} Y ⁵ _e' Y ⁶ _{f '} Y ⁷ _g' Y ⁸ _{h '} O _y' ] _q (XIII) with Y ¹ = only bismuth or bismuth and at least one of the elements tellurium, antimony, tin and copper, Y ² = molybdenum or tungsten, or molybdenum and tungsten, Y ³ = an alkali metal, thallium and / or samarium, Y ⁴ = an alkaline earth metal , Nickel, cobalt, copper, manganese, zinc, tin, cadmium and / or mercury, Y ⁵ = iron or iron and at least one of the elements vanadium, chromium and cerium, Y ⁶ = phosphorus, arsenic, boron and / or antimony, Y ⁷ = a rare earth metal, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and / or uranium, Y ⁸ = molybdenum or tungsten, or Molybdenum and tungsten, a '= 0.01 to 8, b' = 0.1 to 30, c '= 0 to 4, d' = 0 to 20, e '> 0 to 20, f' = 0 to 6, g '= 0 to 15, h' = 8 to 16, x ', y' = numbers determined by the valency and frequency of the elements other than oxygen in XIII, and p, q = numbers whose ratio p / q 0.1 to 10, formed becomes. Method according to one of claims 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XIV, [Bi _{a ''} Z ² _{b ''} O _{x ''} ] _{p ''} [Z ⁸ ₁₂ Z ³ _{c ''} Z ⁴ _{d ''} F ⁵ _{f ''} Z ⁵ _{f ''} Z ⁶ _{g ''} Z ⁷ _{h ''} O _{y ''} ] _{q ''} (XIV), Z ² = molybdenum or tungsten, or molybdenum and tungsten, Z ³ = nickel and / or cobalt, Z ⁴ = thallium, an alkali metal and / or an alkaline earth metal, Z ⁵ = phosphorus, arsenic, boron, antimony, tin, cerium, Vanadium, chromium and / or Bi, Z ⁶ = silicon, aluminum, titanium and / or zirconium, Z ⁷ = copper, silver and / or gold, Z ⁸ = molybdenum or tungsten, or tungsten and molybdenum a "= 0.1 to 1, b "= 0.2 to 2, c" = 3 to 10, d "= 0.02 to 2, e" = 0.01 to 5, f "= 0 to 5, g '' = 0 to 10, h '' = 0 to 1, x '', y '' = numbers determined by the valency and frequency of elements other than oxygen in XIV, and p '', q '' = Numbers whose ratio p '' / q '' is 0.1 to 5 is formed. Method according to one of claims 1 to 30, characterized in that in the subsequent process of thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XV, Mo ₁₂ P _a V _b X _c ¹ X _d ² X _e ³ Sb _f Re _g S _h O _n (XV) With X ¹ = potassium, rubidium and / or cesium, X ² = copper and / or silver, X ³ = cerium, boron, zirconium, manganese and / or bismuth, a = 0.5 to 3, b = 0.01 to 3 , c = 0.2 to 3, d = 0.01 to 2, e = 0 to 2, f = 0 to 2, g = 0 to 1, h = 0 to 0.5, and n = a number that is determined by the valency and frequency of elements other than oxygen in XV. Method according to one of claims 1 to 30, characterized in that in the subsequent process of the thermal treatment of the prepared geometric precursor moldings in selbigen a multimetal of the general formula XVI, V ₁ P _b Fe _c X ¹ _d X ² _e O _n (XVI), with X ¹ = Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb, X ² = Li, K, Na, Rb, Cs and / or Tl, b = 0.9 to 1.5, c = 0 to 0.1, d = 0 to 0.1, e = 0 to 0.1, and n = a number determined by the valency and frequency of the is formed of elements other than oxygen in XVI. Method according to one of claims 1 to 28, characterized in that in the subsequent process the thermal treatment of the prepared geometric precursor moldings in which a solid oxide is formed under normal conditions, in which no transition metal of the 5th to 11th subgroup and also not phosphorus that element other than oxygen is, in molar terms, the numerically most frequently included is. Method according to one of claims 1 to 28, characterized in that the powdery debris at least one metal oxide selected from the group consisting of aluminum oxide, Tungsten oxide, antimony oxide, zirconium oxide, bismuth oxide, molybdenum oxide, Silica, magnesia and mixed oxides containing at least two of the contain metal elements contained in the aforementioned metal oxides, contains. Oxidic geometric shaped body, available according to a method according to one of claims 1 to 37. Process of heterogeneously catalyzed partial Gas phase oxidation of at least one organic compound on a Fixed catalyst bed, characterized in that the fixed catalyst bed a geometric oxidic shaped body according to claim 38 contains. A method according to claim 39, characterized in that the heterogeneously catalyzed partial gas phase oxidation that a) of propylene to acrolein and / or acrylic acid or b) of acrolein to acrylic acid, or c) of methacrolein to methacrylic acid, or d) of isobutene to methacrolein and / or methacrylic acid, or e) from propane to acrolein and / or acrylic acid, or f) from isobutane to methacrolein and / or methacrylic acid, or g) from at least one C ₄ -hydrocarbon and / or benzene to maleic anhydride, or h) from methanol to formaldehyde or i) the oxychlorination of ethylene to 1,2- Dichloroethane is. Tube bundle reactor whose reaction tubes at least one oxidic geometric shaped body according to claim 38 included.