DE102008042060A1 - Preparing catalyst molded body, useful e.g. in ammoxidation of propene to acrylonitrile, comprises mixing starting mass having fine particles of bismuth mixed oxide with another starting mass, and forming geometrical molded bodies - Google Patents

Abstract

Preparing geometrical catalyst molded body (I) containing bismuth-molybdenum-iron oxide (II), comprises preparing fine particles of bismuth mixed oxide (III), as starting mass (A1); producing an aqueous mixture under the use of source of the molybdenum-iron oxide element (IV); passing the sources to a dissipation degree Q; producing a starting mass (A2) by drying and adjusting the dissipation degree of the mixture; mixing the starting masses (A1) and (A2) to obtain a starting mass (A3); forming geometrical molded bodies from the starting mass (A3); and thermally treating the molded bodies. Preparation of geometrical catalyst molded body (I) containing bismuth-molybdenum-iron oxide of formula (((Bi 1Z 1> bO x) aZ 0> cMo 12Fe dZ 2> eZ 3> fZ 4> gZ 5> hZ 6> iO y) 1) (II) as active mass, comprises preparing fine particles of bismuth mixed oxide of formula (Bi 1Z 1> bO x) (III) with an average particle diameter (d 50), as starting mass (A1), under the condition that the particle diameter (d 50) of A1 is 1-100 mu m; producing an aqueous mixture under the use of source of the elements different by oxygen of a part T, which is molybdenum-iron oxide of formula ([Z 0> cMo 12Fe dZ 2> eZ 3> fZ 4> gZ 5> hZ 6> iO y] 1) (IV); passing the sources used in the production of the aqueous mixture to a dissipation degree Q, which has a particle diameter (d 90) of = 5 mu m, where the aqueous mixture contains the elements of Z 0>, molybdenum, iron, Z 2>, Z 3>, Z 4>, Z 5>and Z 6>in stoichiometry of formula (Z 0> cMo 12Fe dZ 2> eZ 3> fZ 4> gZ 5> hZ 6> i) (V); producing a starting mass (A2) with a particle diameter (d 90) of 10-400 mu m, by drying and adjusting the dissipation degree of the aqueous mixture; mixing the starting mass (A1) and starting mass (A2), or starting mass (A1), starting mass (A2) and fine particles of molding auxiliary agent to obtain a starting mass (A3) with stoichiometric bismuth-molybdenum-iron multielement oxide of formula ((Bi 1Z 1> b) aZ 0> cMo 12Fe dZ 2> eZ 3> fZ 4> gZ 5> hZ 6> i) (VI); forming geometrical molded bodies from the fine particles of the starting mass (A3); and thermally treating the molded bodies at high temperature, where (I) has a stoichiometric coefficient, which is greater than 0 and >= 0.8. Z 0>Y or lanthanides excluding La and Ce; Z 1>W or Mo; Z 2>Ni or Co; Z 3>an alkali metal, alkaline earth metal or Tl; Z 4>Ln, Ce, Zn, P, As, B, Sb, Sn, V, Cr or Bi; Z 5>Si, Al, Ti, W or Zr; Z 6>Cu, Ag or Au; a : 0.05-6; b : 0.1-10; c : >= 0.001; d : 0.01-5; e : 1-10; f : 0.01-2; g : 0-5; h : 0-50; i : 0-1; and x, y : numbers, which are determined by the valency and frequency of the elements different from oxygen in (I). An independent claim is included for the geometrical catalyst molded body obtained by the above process.

Description

• – ein feinteiliges Mischoxid Bi₁Z¹ _bO_x mit einem Partikeldurchmesser d A1 / 50 als Ausgangsmasse A1 mit der Maßgabe vorbildet, dass 1 μm ≤ d A1 / 50 ≤ 100 μm erfüllt ist;
• – unter Verwendung von Quellen der von Sauerstoff verschiedenen Elemente des Anteils T^S = [Mo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _iO_y]₁ des Multielementoxids I^S in wässrigem Medium mit der Maßgabe eine innige wässrige Mischung M erzeugt, dass
• – jede der verwendeten Quellen im Verlauf der Herstellung der wässrigen Mischung M einen Zerteilungsgrad Q durchläuft, der dadurch gekennzeichnet ist, dass sein Durchmesser d A2 / 90 ≤ 5 μm beträgt, und
• – die wässrige Mischung M die Elemente Mo, Fe, Z², Z³, Z⁴, Z⁵ und Z⁶ in der Stöchiometrie I^S* Mo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i (I^S*)enthält;
• – aus der wässrigen Mischung M durch Trocknen und Einstellen des Zerteilungsgrades d A2 / 90 eine feinteilige Ausgangsmasse A2 mit einem Partikeldurchmesser d A2 / 90 unter der Maßgabe erzeugt, dass 400 μm ≥ d A2 / 90 ≥ 10 μm erfüllt ist;
• – Ausgangsmasse A1 und Ausgangsmasse A2, oder Ausgangsmasse A1, Ausgangsmasse A2 und feinteilige Formgebungshilfsmittel zu einer feinteiligen Ausgangsmasse A3 mit der Maßgabe miteinander vermischt, dass die Ausgangsmasse A3 die über die Ausgangsmassen A1 und A2 in die Ausgangsmasse A3 eingebrachten, von Sauerstoff verschiedenen Elemente des Multielementoxids I^S in der Stöchiometrie I^S** [Bi₁Z¹ _b]_a[Mo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i]₁ (I^S**),enthält,
• – mit feinteiliger Ausgangsmasse A3 geometrische Formkörper V formt, und
• – die Formkörper V bei erhöhter Temperatur unter Erhalt der geometrischen Katalysatorformkörper K^s thermisch behandelt.

The present invention relates to a process for the preparation of geometric shaped catalyst bodies K ^S , which as an active composition a multielement oxide I ^{S of} the general stoichiometry I ^S , [Bi ₁ Z ¹ _b O _x ] _a [Mo ₁₂ Fe _d Z ² _e Z ³ _l Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] ₁ (I ^S ) With
Z ¹ = one element or more than one element from the group consisting of tungsten and molybdenum,
Z ² = one element or more than one element from the group consisting of nickel and cobalt,
Z ³ = one element or more than one element from the group consisting of the alkali metals, the alkaline earth metals and thallium,
Z ⁴ = one element or more than one element from the group consisting of lanthanum, cerium, zinc, phosphorus, arsenic, boron, antimony, tin, vanadium, chromium and bismuth,
Z ⁵ = one element or more than one element from the group consisting of silicon, aluminum, titanium, tungsten and zirconium,
Z ⁶ = one element or more than one element from the group consisting of copper, silver and gold,
a = 0.05 to 6,
b = 0.1 to 10,
d = 0.01 to 5,
e = 1 to 10,
f = 0.01 to 2
g = 0 to 5,
h = 0 to 50,
i = 0 to 1, and
x, y = numbers determined by the valency and frequency of the elements other than oxygen in I ^S
included, by which one

• A preformed mixed oxide Bi ₁ Z ¹ _b O _x with a particle diameter d A1 / 50 as initial mass A1 is provided with the proviso that 1 μm ≦ d A1 / 50 ≦ 100 μm is fulfilled;
• Using sources of non-oxygen elements of the fraction T ^S = [Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] _{1 of} the multielement oxide I ^S in an aqueous medium with the proviso intimate aqueous mixture M produces that
• - each of the sources used in the course of the preparation of the aqueous mixture M undergoes a degree of division Q characterized in that its diameter d A2 / 90 ≤ 5 microns, and
• The aqueous mixture M contains the elements Mo, Fe, Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in the stoichiometry I ^{S *} Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i (I ^{S *} ) contains;
• From the aqueous mixture M, by drying and adjusting the degree of d 2/90 dewetting, a finely divided starting material A2 with a particle diameter d A2 / 90 is produced, provided that 400 μm ≥ d A2 / 90 ≥ 10 μm is satisfied;
• - Starting mass A1 and A2, or output mass A1, starting mass A2 and finely divided forming aids to a finely divided starting material A3 mixed with the proviso that the starting mass A3 introduced via the starting materials A1 and A2 in the starting mass A3, non-oxygen elements of the multielement I ^S in stoichiometry I ^{S **} [Bi ₁ Z ¹ _b ] _a [Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i ] ₁ (I ^{S **} ) contains
• - formed with finely divided starting mass A3 geometric shapes V, and
• - The moldings V at elevated temperature to obtain the geometric shaped catalyst K ^s thermally treated.

Moreover, the present invention relates to the use of shaped catalyst bodies K ^S.

Geometric shaped catalyst bodies K ^S containing as active material a multi-element oxide I ^S , as well as Processes for the preparation of such shaped catalyst bodies are known (cf., for example, the German application with the file reference 102007003778.5 . EP-A 575 897 . WO 2007/017431 . WO 02/24620 . WO 2005/42459 . WO 2005/47224 . WO 2005/49200 . WO 2005/113127 , the German application with the file reference 102008040093.9 , the German application with the file reference 102008040094.7 and the DE-A 102007005606 ).

It is further known that catalysts K ^S (geometric shaped catalyst bodies K ^S ) are suitable for carrying out heterogeneously catalyzed partial oxidations of alkanes having from 3 to 6 C atoms, alkanols, alkenes and / or alkenals in the gas phase.

Under a complete oxidation of an organic compound With molecular oxygen is understood in this document that the organic compound under the reactive action of molecular Oxygen is converted to that in the organic compound total contained carbon in oxides of carbon and the total hydrogen contained in the organic compound Oxides of hydrogen is converted. All of them different Reactions of an organic compound under reactive action of molecular oxygen are referred to in this document as partial oxidations an organic compound summarized.

in the Special are in this document under partial oxidation such Reactions of organic compounds under reactive action be understood by molecular oxygen, in which the partially too oxidizing organic compound after completion of the reaction at least contains an oxygen atom more chemically bound than before Carrying out the partial oxidation.

Of the Concept of partial oxidation should also be used in this document oxidative dehydrogenation and partial ammoxidation, d. H., a partial oxidation in the presence of ammonia.

Especially suitable are catalysts K ^S (geometric shaped catalyst bodies K ^S ) for carrying out the heterogeneously catalyzed partial gas phase oxidation of propene to acrolein and of isobutene to methacrolein, and for carrying out the heterogeneously catalyzed partial gas phase ammpropriation of propene to acrylonitrile and of isobutene to methacrylonitrile ,

In general, the heterogeneously catalyzed partial gas phase oxidation of propene (isobutene) to acrolein (methacrolein) forms the first stage of a two-stage heterogeneously catalyzed partial gas phase oxidation of propene (isobutene) to acrylic acid (methacrylic acid), as exemplified in US Pat WO 2005/42459 is described.

A with a heterogeneously catalyzed partial gas-phase oxidation from propene (isobutene) to acrolein (methacrolein) By-product formation of acrylic acid (methacrylic acid) is therefore generally not undesirable and subsumed usually below the desired value product formation.

It is furthermore known that the performance of geometric shaped catalyst bodies K ^S in the course of the continuous operation of a heterogeneously catalyzed partial gas phase oxidation of alkanes, alkanols, alkenes and / or alkenals having 3 to 6 C atoms (for example to the corresponding olefinically unsaturated Aldehydes and / or carboxylic acids) decreases with increasing service life (this is especially true in the case of a heterogeneously catalyzed by geometric shaped catalyst body K ^S partial gas phase oxidation of propene to acrolein and / or acrylic acid and of isobutene to methacrolein and / or methacrylic acid; but also applies to the case of a heterogeneously catalyzed partial gas phase oxidation of propene to acrylonitrile and from isobutene to methacrylonitrile). This finding is also true when the geometric shaped catalyst bodies K ^S are subjected to a periodically repeated regeneration process in the course of continuous operation of the heterogeneously catalyzed partial gas phase oxidation, as z. For example, the scriptures WO 2005/42459 such as WO 2005/49200 recommend.

Primarily, it is the activity of the geometric shaped catalyst bodies K ^S , which is reduced in the course of many years of operation of a heterogeneously catalyzed partial gas phase oxidation of an organic compound.

A measure of the activity of the geometric shaped catalyst bodies K ^S or of a catalyst bed containing them is that temperature which is required for passing the reaction gas mixture containing the organic compound to be partially oxidized through the catalyst bed a certain conversion of the organic compound (eg of the organic compound) Propens or iso-butene).

If the activity of the geometric shaped catalyst bodies K ^{S of} a catalyst bed containing them increasingly decreases with increasing partial oxidation operating time, an increasingly elevated temperature is required, under otherwise unchanged reaction conditions, to achieve the same conversion of the organic compound in the single pass of the reaction gas mixture through the catalyst bed If, for example, the catalyst bed in the tubes of a tube bundle reactor flows around a salt bath, the inlet temperature of the salt bath into the tube bundle reactor will be gradually increased with increasing deactivation of the catalyst bed under otherwise unchanged operating conditions, in order to reduce the time required for a single pass of the reaction gas mixture Maintain catalyst-based partial oxidation conversion (cf., for example, US Pat. EP-A 1 734 030 . WO 2007/82827 . WO 2005/47224 and WO 2005/42459 )).

A disadvantage of the procedure described above, however, is that the catalyst deactivation proceeds progressively more rapidly with increasing reaction temperature until the spent catalyst bed has to be replaced at least partially or completely by a catalyst bed with fresh geometric shaped catalyst bodies K ^S (cf. WO 2004/9525 . DE-A 10 2006 00 0996 and WO 2007/77145 ).

One at least partial or complete catalyst bed change but is disadvantageous insofar as with him in a necessary manner an interruption of target product production is associated.

About that addition, with the preparation of fresh catalyst for a large-scale target product production a considerable Investment linked to both the expenses for the investment in this regard required raw materials as well as the production cost are not negligible.

Overall, there is thus a general interest in geometric shaped catalyst bodies K ^S , which have the lowest possible deactivation rate in the continuous operation of the heterogeneously catalyzed partial gas phase oxidation.

The causal relationships, the observance of which in the production of geometric shaped catalyst bodies K ^S necessitates these as long as possible extended stability of the same, are essentially unknown.

Research projects, Those who devote themselves to the problem are enormously time-consuming, since they themselves to deal with an issue that is at first Look only over very long observation periods maps. In addition, errors may also occur Operation of the heterogeneously catalyzed partial gas phase oxidation when using one and the same catalyst bed increased Deactivation rate condition.

basics The basis of the present invention is the observation that the deactivation of a fixed catalyst bed under otherwise predetermined Conditions increase more rapidly, given the load of the fixed catalyst bed increased with reaction gas mixture.

Under the loading of a reaction step catalyzing a catalyst fixed bed with reaction gas mixture is in this document, the amount of reaction gas mixture in standard liters (= Nl; the volume in liters, which is the corresponding Reaction gas mixture amount under normal conditions, d. h., at 0 ° C and 1 atm, which would occupy) the catalyst fixed bed, based on the volume of its bed, d. h., be on Bulk volume (pure inert material sections are thereby not included), is supplied per hour (→ unit = Nl / l · h).

The Strain can only affect one part of the reaction gas mixture (for example, only to the partially oxidized organic Output connection). Then it is the volume amount of this ingredient (eg the organic starting compound of the partial oxidation), the fixed catalyst bed, based on the volume of its bed, is supplied per hour.

An additional essential basis of the present invention is the experimental finding made on corresponding return samples of geometrical shaped catalyst bodies K ^S used for large-scale production, that the order relationship observed in the long-term industrial operation within the different catalyst feeds of the individual reactors under comparable operating conditions with respect to their deactivation rate into a corresponding Ranking could be mapped if the restoring samples were subjected to a relatively much less time-consuming stress test, which is characterized primarily by the fact that the same he terogen catalyzed gas phase partial oxidation is carried out both at a higher temperature and at a higher load of the fixed catalyst bed with the same reaction gas mixture. The difference between the temperature required in advance to carry out the stress test under the operating conditions actually envisaged for setting the desired partial oxidation conversion and the temperature required after the stress test to be below the temperature required for setting the same partial oxidation conversion, with the same operating conditions proved to be an accurate ranking parameter with regard to the long-term stability of the catalyst bed.

From the EP-A 575897 it is known that _x affected during a preparation of geometric shaped catalyst bodies K ^S, the particle size of the preformed finely divided mixed oxides Bi ₁ Z ¹ _b O, the initial activity of such shaped catalyst bodies when they are used for the heterogeneously catalyzed partial gas phase oxidation of propylene to acrolein.

In view of this prior art, the object of the present invention was to provide geometric shaped bodies K ^S and a process for their preparation, which, in particular in the context of a use for a heterogeneously catalyzed partial gas phase oxidation of propene to acrolein in continuous partial oxidation operation a reduced Have deactivation rate, and this if possible without significantly affecting the initial selectivity of the value product formation.

As a solution to the problem, a method is provided, which is characterized in that the proportion T ^{S of} the multielement oxide I ^{S is} additionally there to a limited extent with at least one element Z ⁰ .

• – feinteiliges Mischoxid Bi₁Z¹ _bO_x mit einem Partikeldurchmesser d A1 / 50 als Ausgangsmasse A1 mit der Maßgabe vorbildet, dass 1 μm < d A1 / 50 ≤ 100 μm erfüllt ist;
• – unter Verwendung von Quellen der von Sauerstoff verschiedenen Elemente des Anteils T = [Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _iO_y], des Multielementoxids I in wässrigem Medium mit der Maßgabe eine innige wässrige Mischung M erzeugt, dass – jede der verwendeten Quellen im Verlauf der Herstellung der wässrigen Mischung M einen Zerteilungsgrad Q durchläuft, der dadurch gekennzeichnet ist, dass sein Durchmesser d Q / 90 ≤ 5 μm beträgt, und – die wässrige Mischung M die Elemente Z⁰, Mo, Fe, Z², Z³, Z⁴, Z⁵ und Z⁶ in der Stöchiometrie I*, Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i (I*) enthält;
• – aus der wässrigen Mischung M durch Trocknen und Einstellen des Zerteilungsgrades d A2 / 90 eine feinteilige Ausgangsmasse A2 mit einem Partikeldurchmesser d A2 / 90 unter der Maßgabe erzeugt, dass 400 μm ≥ d A2 / 90 ≥ 10 μm erfüllt ist;
• – Ausgangsmasse A1 und Ausgangsmasse A2, oder Ausgangsmasse A1, Ausgangsmasse A2 und feinteilige Formgebungshilfsmittel zu einer feinteiligen Ausgangsmasse A3 mit der Maßgabe miteinander vermischt, dass die Ausgangsmasse A3 die über die Ausgangsmassen A1 und A2 in die Ausgangsmasse A3 eingebrachten, von Sauerstoff verschiedenen, Elemente des Multielementoxids I in der Stöchiometrie I**, [Bi₁Z¹ _b]_a[Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i]₁ (I**). enthält,
• – mit feinteiliger Ausgangsmasse A3 geometrische Formkörper V formt, und
• – die Formkörper V bei erhöhter Temperatur unter Erhalt der geometrischen Katalysatorformkörper K thermisch behandelt, dadurch gekennzeichnet ist, dass der stöchiometrische Koeffizient c die Bedingung 0 < c ≤ 0,8 erfüllt und Z⁰ ein Element oder mehr als ein Element aus der Gruppe, bestehend aus Yttrium und den Lanthaniden ohne Lanthan und ohne Cer, ist.

Accordingly, in the present invention is a method for the preparation of geometric shaped catalyst bodies K, which is a multi-element oxide I of the general stoichiometry I as the active material [Bi ₁ Z ¹ _b O _x ] _a [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] ₁ (I) With
Z = one element or more than one element from the group consisting of tungsten and molybdenum,
Z ² = one element or more than one element from the group consisting of nickel and cobalt,
Z ³ = one element or more than one element from the group consisting of the alkali metals, the alkaline earth metals and thallium,
Z ⁴ = one element or more than one element from the group consisting of lanthanum, cerium, zinc, phosphorus, arsenic, boron, antimony, tin, vanadium, chromium and bismuth,
Z ⁵ = one element or more than one element from the group consisting of silicon, aluminum, titanium, tungsten and zirconium,
Z ⁶ = one element or more than one element from the group consisting of copper, silver and gold,
a = 0.05 to 6,
b = 0.1 to 10,
d = 0.01 to 5,
e = 1 to 10,
f = 0.01 to 2,
g = 0 to 5,
h = 0 to 50,
i = 0 to 1, and
x, y = numbers determined by the valency and frequency of the elements other than oxygen in I,
included, by which one

• - finely divided mixed oxide Bi ₁ Z ¹ _b O _x with a particle diameter d A1 / 50 as initial mass A1 with the proviso that 1 μm <d A1 / 50 ≤ 100 μm is fulfilled;
• Using sources of the non-oxygen elements of the proportion T = [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ], of the multielement oxide I in an aqueous medium with the proviso an intimate aqueous mixture M produces - that each of the sources used in the course of the preparation of the aqueous mixture M undergoes a degree of division Q characterized in that its diameter d Q / 90 ≤ 5 μm, and - the aqueous mixture M the Elements Z ⁰ , Mo, Fe, Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in the stoichiometry I *, Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i (I *) contains;
• From the aqueous mixture M, by drying and adjusting the degree of d 2/90 dewetting, a finely divided starting material A2 with a particle diameter d A2 / 90 is produced, provided that 400 μm ≥ d A2 / 90 ≥ 10 μm is satisfied;
• - Starting material A1 and A2, A2 or A2, starting material A2 and finely divided forming aid to a finely divided starting mass A3 with the proviso mixed with each other, that the starting mass A3 introduced via the starting materials A1 and A2 in the starting mass A3, different from oxygen, elements of Multielement oxide I in the stoichiometry I **, [Bi _{1 b} Z ^1] _a [Z ⁰ _c Mo _{d 12} Fe ² Z _e Z _f ³ Z ⁴ Z ⁵ _{g h i} Z ^6] ₁ (I **). contains
• - formed with finely divided starting mass A3 geometric shapes V, and
• - The moldings V thermally treated at elevated temperature to obtain the geometric shaped catalyst body K, characterized in that the stoichiometric coefficient c satisfies the condition 0 <c ≤ 0.8 and Z ^{0 is} an element or more than one element from the group consisting from yttrium and the lanthanides without lanthanum and without cerium, is.

According to the invention preferred is c ≥ 0.001, preferably ≥ 0.002 and especially preferably, c ≥ 0.003 or ≥ 0.005, or ≥ 0.01.

Under Inclusion of the aspect of one with improved long-term stability possibly at the same time increased Initial selectivity of value product formation when used the inventive geometric shaped catalyst body K as catalysts for heterogeneously catalyzed partial oxidation (in particular those of propene to acrolein or of isobutene to methacrolein), c is suitably from the point of view of application ≦ 0.7 or ≤ 0.6 and optionally ≤ 0.5.

Particularly according to the invention favorable values for c thus fulfill, for example the relations 0 <c ≤ 0.5, or 0.0005 ≦ c ≦ 0.5, or 0.001 ≦ c ≦ 0.4, or 0.001 ≦ c ≦ 0.3, or 0.005 ≦ c ≦ 0.3, and most preferably, the relation is 0.01 ≤ c ≤ 0.2 or 0.01 ≤ c ≤ 0.1.

About that In addition, the stoichiometric coefficient a is advantageous according to the invention 0.1 to 4 or 3, or 0.2 to 2, more preferably 0.3 to 1.5 and most preferably 0.4 to 1.25 or 0.5 to 1.

With regard to Z ¹ , it is advantageous for the process according to the invention if at least 10 mol% of the total molar amount of Z ^{1 is} tungsten.

At least 20 mol%, more preferably at least 40 mol% or at least 50 mol%, more preferably at least 60 mol% or at least 80 mol%, and most preferably at least 90 mol% or 100 mol% of the composition are preferred according to the invention molar total amount of Z ¹ tungsten.

Farther it is for the procedure according to the invention favorable if 1 μm ≦ d A1 / 50 ≦ 75 μm, or 1 μm ≤ d A1 / 50 ≤ 50 μm, or 1 μm ≤ d A1 / 50 ≤ 25 μm is. Further preferred value ranges for d A1 / 50 are the ranges 1 μm ≤ d A1 / 50 ≤ 10 μm, 1.2 μm ≤ d A1 / 50 ≤ 8 μm, 1.5 μm ≤ d A1 / 50 ≤ 6 μm, 1.5 μm ≤ d A1 / 50 ≤ 4 μm and 2 μm ≤ d A1 / 50 ≤ 3 μm.

In Accordingly, it is according to the invention of Advantage, if 300 μm ≥ d A2 / 90 ≥ 10 μm, or 200 μm ≥ d A2 / 90 ≥ 20 μm, or 170 μm ≥ d A2 / 90 ≥ 30 μm, or 150 μm ≥ d A2 / 90 ≥ 40 μm, or 130 μm ≥ d A2 / 90 ≥ 40 μm. Cheap is also 100 μm ≥ d A2 / 90 ≥ 50 μm.

When advantageous for the invention It turns out to be method, if for the finely divided Starting mass A2 also 10 μm ≦ d A2 / 50 ≦ 100 μm, preferably 20 μm ≤ d A2 / 50 ≤ 60 μm is satisfied.

After all it is for the inventive method additionally advantageous if the ratio of the particle diameter d A2 / 90 of the finely divided starting material A2 to the particle diameter d A2 / 10 of finely divided starting material A2, that is d A2 / 90: d A2 / 10 (indicated in the same unit length) in the range of 5 to 20, preferably ranging from 10 to 15.

For the determination of particle diameter distributions in dry powders and the particle diameters taken from them such. B. d ₁₀ , d ₅₀ and d ₉₀ , was (unless explicitly stated otherwise), the respective finely divided powder through a dispersion into the dry disperser Sympatec RODOS (Sympatec GmbH, system-particle technology, Am Pulverhaus 1, D- 38678 Clausthal-Zellerfeld), where it is dispersed dry with compressed air and blown into the measuring cell in the free jet. In this will then after ISO 13320 with the laser diffraction spectrometer Malvern Mastersizer S (Malvern Instruments, Worcestershire WR 14 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. That is, (100 - X)% of the total particle volume consists of particles with a diameter> d _x . Unless explicitly stated otherwise in this document, particle diameter determinations and d _x taken from them refer to e.g. B d Q / 90, d A1 / 50 and d A2 / 90 to a dispersion pressure of 2 bar absolute (determining the degree of dispersion of the dry powder during the measurement).

All in this document referred to an X-ray diffractogram Data refer to using Cu-Kα radiation X-ray generated X-ray diffractogram Theta-Theta Bruker D8 Advance Diffractometer, Tube Voltage: 40 kV, tube current: 40 mA, aperture diaphragm V20 (variable), diffuser V20 (variable), detector aperture (0.1 mm), measuring interval (2θ = 2 theta): 0.02 °, measuring time per step: 2.4 s, detector: Si semiconductor detector).

The definition of the intensity of a diffraction reflex in the X-ray diffractogram in this document refers to that in the DE-A 198 35 247 , as well as in the DE-A 100 51 419 and DE-A 100 46 672 defined definition.

That is, A ¹ denotes the vertex of a reflection 1, and B ¹ in the line of the X-ray diffractogram, when viewed along the intensity axis perpendicular to the 2θ axis, indicates the nearest distinct minimum (reflex shoulders indicating minima are not taken into account) to the left of vertex A ¹ and B ² in a corresponding manner the nearest distinct minimum to the right of the vertex A ¹ and C ¹ denotes the point at which a line drawn from the vertex A ¹ perpendicular to the 2θ-axis intersects a straight line connecting the points B ¹ and B ² , then the Intensity of the reflection 1, the length of the straight line section A ¹ C ¹ , which extends from the vertex A ¹ to the point C ¹ . The term minimum means a point at which the slope gradient of a tangent applied to the curve in a base region of the reflex 1 changes from a negative value to a positive value, or a point at which the gradient gradient approaches zero, wherein for the determination of the gradient gradient, the coordinates of the 2θ axis and the intensity axis are used. An exemplary implementation of an intensity determination shows the 6 in the DE-A 100 46 672 , Detailed explanations for determining the intensity of X-ray diffraction reflexes can be found in the DE-A 101 22 027 , Statements on half-widths of diffraction lines in this document refer in a corresponding manner to the length of the straight line section which results between the two intersections H1 and H2, if one draws a parallel to the 2θ-axis in the middle of the straight section A ¹ C ¹ H ¹ , H ² mean the respective first intersection of these parallels with the line of the X-ray diffractogram as defined above to the left and right of A ¹ . As a rule, the half-value widths of X-ray diffraction reflections of the multielement oxide I active compositions are ≦ 1 °, and usually ≦ 0.5 °.

All information in this document about specific surfaces of solids refers to determinations DIN 66131 (Determination of the specific surface area of solids by gas adsorption (N ₂ ) according to Brunauer-Emmet-Teller (BET)), unless expressly stated otherwise.

The requirement according to the invention that any source of the non-oxygen elements of the proportion T = [Z ⁰ Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] _{1 of} the multielement oxide I in the course of the preparation of aqueous mixture M must pass through a degree of division Q, which is characterized in that its diameter d Q / 90 ≤ 5 microns, expressing that from a coarser-grained source (from a coarse-grained starting material) can be assumed. However, on the way of incorporation of such a source into the aqueous mixture M, this source must satisfy the requirement d Q / 90 ≦ 5 μm at least once (of course, d Q / 90 is always> 0 μm).

The Requirement d Q / 90 ≤ 5 μm is basically then fulfilled when dissolving a source in a solvent (eg in aqueous medium; the term "dissolving") is in the sense of a molecular or ionic solution meant) and the resulting solution for the production the aqueous mixture M used.

This is due to the fact that when a source (output connection, Starting substance) in a solvent the source in Solvent molecular or ionic is divided.

The means the largest one in the solution geometric unit of the dissolved starting substance (source) inevitably has "molecular" dimensions that thus necessarily much smaller than 5 microns are. Of course, in one and the same solution but also more than one source (with one source but more as an element of the proportion T and thus at the same time source can be for more than one element) of an element of the Proportion T solved and the resulting solution for the preparation of the aqueous mixture M can be used.

The Requirement d Q / 90 ≤ 5 μm is fulfilled even then when a source of an element of the moiety T is in a solvent in colloidal solution. Colloidal solutions make a connection between real (molecular or ionic) Solutions and suspensions. In these colloidal disperse Systems are smaller clusters of molecules or atoms, which, however, neither with the naked eye, nor can be seen with the microscope.

The Colloidal solution appears optically clear (although often colored), because the particles contained in it only a diameter of 1 to 250 nm (preferably up to 150 nm and particularly preferably up to 100 nm), which is why the associated d Q / 90 is necessarily ≦ 5 μm. Due to the small size is a separation the colloidally dissolved particles by conventional filtration not possible. You can, however, by ultrafiltration with membranes plant, animal or artificial Origin (eg parchment, pork blister or cellophane) of their "solvent" be separated. In contrast to the "visually empty" real (molecular or ionic) solutions, can one Light beam not without distraction by a colloidal solution pass. The light beam is released from the colloid Particles scattered and distracted. To colloidal solutions stable and prevent further particle agglomeration They often contain wetting and dispersing aids as well added other additives.

For example, the element silicon in the method according to the invention can be introduced in the form of a silica sol for the preparation of the aqueous mixture M. Silica sols are colloidal solutions of amorphous silica in water. They are water-soluble and contain no sedimentable constituents. Their SiO ₂ content can be up to 50% by weight and more, often lasting for years (without sedimentation).

The Requirement d Q / 90 ≤ 5 μm is fulfilled even then if a source z. B. dry to this particle size crushed (eg by grinding) is.

in principle For example, such a powder can be used directly as such the intimate aqueous mixture M can be used. Of course But it can also be suspended in a liquid medium and then in the form of this suspension for the preparation of the aqueous Mixture M are used.

According to the invention preferred is d Q / 90 for all to make the aqueous Mixture M used sources (starting compounds, starting materials) ≤ 4 microns or ≦ 3 μm, more preferably ≦ 2 μm or ≦ 1 μm and most preferably ≦ 0.8 μm or ≦ 0.5 μm. Even better is d Q / 90 for all to manufacture the aqueous mixture M used sources (starting compounds, Starting substances) ≤ 0.3 μm or ≤ 0.2 μm.

Particularly preferred are those inventive methods in which in the course of the preparation of the aqueous mixture M all the sources used of the elements of the share T go through the state of a colloidal or a true (molecular or ionic) solution (the resulting aqueous mixtures M are in this Font be designated as aqueous mixtures M ^L ).

Very particular preference is given to those inventive methods in which in the course of the preparation of the aqueous mixture M all shared sources of silicon-different elements of the share T pass through the state of a true (molecular or ionic) solution (the resulting aqueous mixtures M are in this document may be referred to as aqueous mixture M ^{L *} ). If the aqueous mixture M furthermore contains a source of the element silicon, it is advantageously a colloidal solution thereof (particularly preferably a silica sol). Such aqueous mixtures M are to be referred to in this document as aqueous mixtures M ^{L **} .

An intimate aqueous mixture M is understood in this document to mean such mixtures M. be at least 50% of its weight, advantageously at least 60% of its weight, more preferably at least 70% of its weight, most particularly advantageously at least 80% of its at the transition from the aqueous mixture M in the finely divided starting material A2 gasses escaping material content Weight and even better at least 90% of its weight consists of water vapor. In addition to water, the abovementioned gaseous escaping material fraction may also contain compounds such as HCl, HNO ₃ , carbon dioxide, ammonia, alcohols (eg methanol, ethanol, glycol and glycerol), ketones such as. As acetone or other in water at normal conditions (1 atm, 25 ° C) soluble organic compounds.

When Sources for the elements of the share T of the desired Multielement oxide active composition I according to the invention In principle, such compounds come into consideration, in which it are already oxides and / or such compounds, the by heating, at least in the presence of molecular oxygen, are convertible into oxides.

Next the oxides are present as such starting compounds (sources) halides, nitrates, formates, oxalates, citrates, acetates, Carbonates, amine complexes, ammonium salts and / or hydroxides (and hydrates of the aforementioned salts).

A convenient Mo source is ammonium heptamolybdate tetrahydrate. Basically, but also z. B. molybdenum trioxide used. In accordance with the invention, favorable Z ² sources are the nitrates or nitrate hydrates of the Z ² elements. According to the invention advantageous Z ³ sources are the hydroxides and nitrates of the Z ³ elements or their hydrates. For the element iron, an iron nitrate hydrate is advantageously used in the process according to the invention. If bismuth is also used, water-soluble salts of bismuth, such as nitrates, carbonates, hydroxides and / or acetates, or their aqueous solutions, will be used to prepare the aqueous mixture M. This also applies to the elements lanthanum and cerium.

silica sol forms the preferred Si source according to the invention. According to the invention suitable lanthanides (or lanthanides) are the elements praseodymium (Pr), neodymium (Nd), promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysposium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and Luthetium (Lu).

In other words, the elements Z ⁰ which may be considered according to the invention are characterized in that they are metallic elements whose effective ionic radius in the state of their 6-coordinate trivalent cation [r (Z ⁰ ) ³⁺ ₆ ] in a ver the same narrow range of values (99 pm to 86 pm) (cf. RD Shannon, Acta Cryst. (1976) A32, 751-767 such as NN Greenwood, A. Earnshaw, Chemistry of Elements, VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1st edition 1988, Appendix 5, page 1652) , The latter is likely to be the reason why they are comparatively equivalent in accordance with the invention. The latter no longer applies to the elements Ce and La, whose corresponding ionic radii are 102 pm and 103.2 pm, respectively.

That is, according to the invention possible elements Z ⁰ are the elements Y (90 pm), Pr (99 pm), Nd (98 pm), pm (97 pm), Sm (96 pm), Eu (95 pm), Gd (94 pm), Tb (92 pm), Dy (91 pm), Ho (90 pm), Er (89 pm), Tm (88 pm), Yb (87 pm), and Lu (86 pm), whose effective ionic radii are in the state of their 6-coordinate trivalent cations in the interval 99 pm to 86 pm. Z ⁰ is particularly preferably at least one element selected from the group consisting of Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Most preferably Z ^{0 is} at least one element selected from the group consisting of Y, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb. A particularly pronounced improvement of the long-term stability aimed at according to the invention results in an inventive doping with Y, Ho and Er. As the source of the lanthanides suitable according to the invention, it is preferable, as in the case of Y, to use the corresponding nitrate hydrates and / or their aqueous solutions.

According to the invention, it is surprising that the desired improvement in the long-term stability with not too high a degree of doping with at least one element Z ^{0 is} accompanied by an improvement in the initial selectivity of the desired product formation as a rule. This relationship applies in particular to a doping according to the invention with at least one element Z ⁰ from the group consisting of Gd, Tb and Dy, the particularly marked improvement in initial selectivity of the desired product formation in these cases being at the expense of a not so marked improvement in the long-term stability.

The target product selectivity (value product selectivity) is understood to be the ratio of the molar amount of product product formed during the single pass of the reaction gas mixture through the catalyst bed to the converted molar amount of starting organic compound to be partially oxidized (x 100 in mol%). D. h., An increased initial selectivity of value product formation reduces the for the production of a certain value product required raw material requirement. Typically, in partial oxide oxidations catalyzed by geometric shaped catalyst bodies K of the present invention, the activity and selectivity of target product formation initially increase with the service life of the catalyst feed (usually reaching their respective maximum at different operating times) before their age-related reduction occurs.

These Formation can be accelerated by being used in the Substantially constant sales under increased load the catalyst charge is carried out with reaction gas starting mixture and after largely completed formation the burden on their Target value withdrawn.

In addition to the relevant sources of the elements of the proportion T of the multielement oxide I, it is also possible to incorporate into the respective aqueous mixture M substances which decompose to form gaseous compounds at least under the conditions of the thermal treatment of the geometric shaped bodies V, forming the geometric shaped catalyst bodies K. or decomposed (chemically reacted). Such substances may, for example, act as pore formers and be included for the purpose of adjusting the active inner surface. Examples of such (auxiliary) substances are NH ₄ OH, (NH ₄ ) ₂ CO ₃ , NH ₄ HCO ₃ , NH ₄ NO ₃ , urea, NH ₄ CHO ₂ , H ₂ CO ₃ , HNO ₃ , H ₂ SO ₄ , NH ₄ CH ₃ CO ₂ , NH ₄ Cl, HCl, NH ₄ HSO ₄ , (NH ₄ ) ₂ SO ₄ , ammonium oxalate, hydrates of the aforementioned compounds and organic substances such. As stearic acid, malonic acid, ammonium salts of the aforementioned acids, starches (eg., Potato starch and corn starch), cellulose, ground nutshell, finely divided plastic flour (eg., Of polyethylene, polypropylene), etc. into consideration.

According to the invention, the finely divided starting composition A2 is preferably produced from the aqueous mixture M (in particular in the case of an aqueous mixture M ^L , or M ^{L *} , or M ^{L **} ) by spray-drying thereof. That is, the aqueous mixture M is first divided into finely divided droplets in this case and the same then dried. According to the invention, the drying preferably takes place in the hot air stream. In principle, however, other hot gases can also be used for the abovementioned spray drying (for example nitrogen, or air diluted with nitrogen and other inert gases).

The Spray drying can basically both in cocurrent as well as in countercurrent of droplets to hot gas done. Preferably, it takes place in countercurrent the droplets to the hot gas. Especially preferred in hot air counterflow. Typical gas inlet temperatures lie in the range of 250 to 450, preferably 270 to 370 ° C. Typical gas outlet temperatures are in the range of 100 to 160 ° C.

According to the invention, the spray-drying is carried out in such a way that the particle diameter d A2 / 90 desired for the finely divided starting material A2 (as a result of spray-drying) immediately sets (that is, the corresponding d _{90 of} the resulting spray powder), so that the resulting spray powder directly can be used according to the invention to be used starting material A2.

is the degree of dewing of the resulting spray powder in Compared to the desired d A2 / 90 too small, so can the same z. B. by subsequent compacting on the for the starting mass A2 coarsely desired degree of division become. Conversely, this can be done directly during spray drying resulting spray powder by grinding if necessary also on the desired for the initial mass A2 degree of division be refined.

Of course The intimate aqueous mixture M but also initially by conventional evaporation (preferably at reduced Print; the drying temperature should normally be 150 ° C do not exceed) and the resulting Dry matter by subsequent comminution to the invention required Degree of division d A2 / 90 are set. Basically the drying of the aqueous mixture M in the inventive Procedure but also done by freeze-drying.

In principle, in the process according to the invention, the step of producing the finely divided starting material A2 by drying and dividing the aqueous mixture M and the step of mixing the finely divided starting material A2 with the finely divided starting material A1 can also be carried out so that the finely divided starting material A1 is already in the In the preparation of the aqueous mixture M into it mixed (especially when the aqueous mixture M is an aqueous mixture M ^L , M ^{L *} or M ^{L **} ) and the resulting total mixture of a spray-drying, in the context of which the droplet size so is set so that the value according to the invention for d A2 / 90 is given.

According to the invention preferred however, is prepared in advance for the preparation of the finely divided starting material A3 finely divided starting material A1 with pre-produced finely divided Starting weight A2, optionally with the co-use of finely divided Forming aids, mixed.

Z ² is preferred in the process according to the invention exclusively Co.

Z ³ in the process according to the invention is preferably K, Cs and / or Sr, more preferably K.

Z ⁵ is preferably Si in the process according to the invention.

Of the stoichiometric coefficient b is advantageous 0.5 to 3, particularly advantageously 1 to 2.5 and very particularly advantageous 1.5 to 2.5.

Of the stoichiometric coefficient e is preferably 3 to 8, particularly advantageously 4 to 7 and very particularly advantageous 5 to 6.

Of the stoichiometric coefficient f is advantageous 0.02 to 2 and more preferably 0.03 to 1 or 0.05 to 0.5.

Of the stoichiometric coefficient d is advantageous 0.1 to 4.5, preferably 0.5 to 4 and particularly preferably 1 to 4 or 2 to 4.

Of the stoichiometric coefficient h is preferably> 0 to 50, especially preferably 0.1 to 20 or 0.2 to 10, very particularly preferably 0.3 to 6 or 0.4 to 5, and most preferably 0.5 to 3 or 1 to Third

The stoichiometric coefficients g and i can both are 0 at the same time, but also independent of each other assume 0 different values.

That is, the embodiments B1 to B6 can be carried out under otherwise unchanged conditions (including the subsequent use as catalysts for the propene partial oxidation) using finely divided starting material A2, whose associated stoichiometry I *
Mo ₁₂ Co _5.5 Fe _3.0 Er _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Er _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Er _0.02 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 He _0.05 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Ho _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Ho _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Ho _0.02 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Ho _0.05 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Dy _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Dy _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Dy _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Dy0, ₀₂ Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Tb _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Tb _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Tb _0.0 5 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Tb _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Gd _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Gd _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Gd _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Gd _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Y _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Y _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Y _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Y _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Eu _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Eu _0.1 Si _1.6 K _0.08
Mo ₁₂ Co _5.5 Fe _3.0 Eu _0.0 5Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Eu _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Tm _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Tm _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Tm _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Tm _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Yb _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Yb _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Yb _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Yb _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Sm _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Sm _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Sm _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Sm _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Nd _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Nd _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Nd _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Nd _0.02 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Lu _0.2 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Lu _0.1 Si _1.6 K _0.08 , or
Mo ₁₂ Co _5.5 Fe _3.0 Lu _0.05 Si _1.6 K _0.08 , or Mo ₁₂ Co _5.5 Fe _3.0 Lu _0.02 Si _1.6 K _{0.08 Act} .

there may be the stoichiometric coefficient a in all of the above Cases, but also in the embodiments B1 to B6 itself also be 0.7 or 0.5.

In the finely divided starting material A2 of Example B1 not included, but elements comprised of the above stoichiometries are using their nitrate hydrates as a source in Solution B dissolved. Deviating from this would W as a component of the proportion T as ammonium paratungstate to the solution A added.

simultaneously can in all the above cases and in the embodiments B1 to B6 d A1 / 50 also 2.2 μm, or 2.4 μm, or 2.6 μm, or 3.0 μm, or 3.5 μm, or 4.0 μm, or 4.5 μm, or 5.0 μm, or 5.5 μm, or 6.0 μm, or 6.5 μm, or 7.0 μm be.

Further can in all the above cases, including all embodiments B1 to B6 d A2 / 90 also 50 microns, or 52 μm, or 54 μm, or 56 μm, or 58 μm, or 62 μm, or 64 μm, or 66 μm, or 68 μm, or 70 μm, or 72 μm, or 74 μm, or 76 μm, or 78 μm, or 80 μm, or 82 μm, or 84 μm, or 86 μm, or 88 microns or 90 microns. By way of example, in all the above cases d A1 / 50 = 2.4 microns and d A2 / 90 = 68 microns be. The stoichiometric coefficient a can also be 0.25, or 0.35, or 0.4.

The preforming of the finely divided mixed oxide Bi ₁ Z ¹ _b can be carried out in a manner known per se (cf. EP-A 575 897 . DE-A 3338380 . EP-A 835 . WO 02/24620 . WO 2007/017431 , the German application with the file reference 102007003778.5 . WO 2005/030393 and the German application with the file reference 102008040093.9 ).

In the rule becomes at least one source of the element Bi and at least one source of elements W and Mo (i.e., at least a Bi-containing starting compound and at least one the element W and / or at least the element Mo containing starting compound intimately mix with each other in an aqueous medium, the aqueous Dry mixture and the resulting dry mass at temperatures in the range of 400 to 900 ° C (preferably 600 to 900 ° C and particularly preferably 700 to 900 ° C) calcine (thermal treat) and by dividing the resulting calcine to obtain the finely divided starting material A1 the invention required Set particle diameter d A1 / 50. As sources of Bi, W and Mo come In principle, such compounds into consideration, in which these are already oxides of these elements, or such compounds, by heating, at least in the presence of molecular oxygen, are convertible into oxides.

Preferably, water-soluble salts of bismuth, such as nitrates, carbonates, hydroxides and / or acetates with tungstic acid (the water-insoluble tungstic acid is preferably used as a finely divided powder whose d _{90 in} terms of application suitably ≤ 5 microns or ≤ 2 microns, preferably 0 1 to 1 μm) and / or their ammonium salts are mixed in water, the aqueous mixture is dried (preferably spray-dried) and the thermal mass is subsequently treated thermally as described. If Mo is used, z. For example, molybdenum trioxide or ammonium heptamolybdate tetrahydrate can be used as Mo source.

If drying by spray-drying takes place, the resulting spray powder will advantageously be coarsened beforehand (for example, it will be advantageous to add an aqueous solution with addition of up to 20% by weight of water and, for example, extruded by means of an extruder into strands which are easier to handle for calcination purposes these are subsequently dried and then calcined). Usually, the thermal treatment is carried out in the air stream (for example, in the case of the aforementioned stringers in a rotary kiln, as in the DE-A 103 25 487 is described). The breaking up of the resulting calcined mixed oxide onto the particle diameter d A1 / 50 according to the invention is normally effected by milling in mills. If necessary, the material to be ground is subsequently classified to the desired degree of division.

Preferred mixed oxides Bi ₁ Z ¹ _b formed in advance in the context of the process according to the invention are the mixed oxides Bi ₁ W ₂ O _7.5 (1 / 2Bi ₂ W ₂ O ₉ · 1WO ₃ ), Bi ₁ W ₁ O _4.5 , Bi ₁ W _1.5 O ₆ (1 / 2Bi ₂ W ₂ O ₉ · ½WO ₃ ), Bi ₁ W _2.5 O ₉ (1 / 2Bi ₂ W ₂ O ₉ · 3 / 2WO ₃ ), Bi ₁ W ₃ O _{10 ,} Bi ₁ W ₄ O _4.5 .2WO ₃ ), Bi ₁ W ₄ O _13.5 (1 / 2Bi ₂ W ₂ O 9 .3WO ₃ ) and Bi ₁ W _0.5 O ₃ , among which the Bi ₁ W ₂ O _7.5 according to the invention is very particularly preferred (the embodiments B1 to B6 and the comparative examples V1 to V5 (including their use for the Propenpartialoxidation) can therefore also using Bi ₁ W _1.5 O ₆ , or Bi ₁ W _2.5 O ₉ , or Bi ₁ W ₃ O _10.5 , or Bi ₁ W ₄ O _13.5 , or Bi ₁ W _0.5 O ₃ , or Bi ₁ W ₁ O _4.5 as a finely divided starting material A1 corresponding grain size as the finely divided Bi ₁ W ₂ O _{7.5 used are} carried out).

As well as in the aqueous mixture M, it is also possible for additional substances to be incorporated into the aqueous mixture of the at least one bi- and at least one W source and / or Mo source) within the scope of the preparation of the mixed oxide Bi ₁ Z ¹ _b O _x . which under the conditions of the training of the Mischoxids Bi ₁ Z ¹ _b O _x applied thermal treatment to gaseous escaping compounds disintegrate and / or decomposed (chemically reacted). Such substances may, for example, act as pore formers and for the purpose of influencing the active inner surface of the mixed oxide Bi ₁ Z ¹ _b O _x . be included.

As such (auxiliary) are substances for example NH ₄ OH, (NH _{4) 2} CO _3, NH ₄ HCO _3, NH4NO _3, urea, NH ₄ CHO _2, H ₂ CO _3, HNO _3, H ₂ SO _4, NH ₄ CH ₃ CO ₂ , NH ₄ HSO ₄ , NH ₄ Cl, HCl, (NH ₄ ) ₂ SO ₄ , ammonium oxalate, hydrates of the aforementioned compounds and organic substances such. Stearic acid, malonic acid, ammonium salts of the abovementioned acids, starches (for example potato starch and corn starch), cellulose, ground nutshell, finely divided plastic flour (for example polyethylene, polypropylene), etc. into consideration.

at the preparation of the finely divided starting material A3 from the finely divided Starting materials A1 and A2 are useful in terms of application technology, but not necessary, finely divided shaping aids concomitantly.

These can already pre-mixing of finely divided Starting materials A1 and A2 in both of these finely divided starting materials or mixed in only one of the two finely divided starting materials A1, A2 become.

Of course but also the fine-particle shaping tools can or only (first) in the finely divided mixture of finely divided starting material A1 and finely divided starting material A2 are mixed.

For the group of finely divided shaping aids (especially if these elements contain Z ⁵ , the shaping aids having a d ₉₀ > 5 μm are used, other elements of the multielement oxide I other than oxygen usually do not contain them) initially include the so-called anticaking agents.

in this connection are finely divided materials, the application technology be advantageously used concomitantly, in the context of mixing z. B. Reagglomeration (a "caking") of particles within the starting mass A1 and / or within the starting mass A2 as far as possible to suppress, since such a reglomeration the effective Could affect particle diameter. A preferred according to the invention Group of finely divided anti-caking agents form finely divided hydrophobicized Silicas, especially finely divided hydrophobized synthetic silicas (silicas). synthetic On the one hand, silicic acids can be directly pyrogenic from sand and on the other hand by precipitation reactions Water glass can be produced. In particular, synthetic silicic acids are due to their surface OH groups hydrophilic, d. they are wetted by water. For example by reaction of these surface OH groups with chlorosilanes can be both from the pyrogenic and from the precipitated silicas hydrophobized products produce. For example, the hydrophobization by reaction with dimethyldichlorosilane in the presence of water vapor at about 400 ° C. take place in a fluidized bed reactor (is preferably at fumed silicas applied).

Especially with precipitated silicas, the chlorosilane is added to the precipitation suspension at a temperature of 50 to 90 ° C with thorough stirring. Followed by filtration, washing with water, drying the filter cake and annealing at 300 to 400 ° C. In H. Brunner, D. Schutte, Chem. Ing. Techn. 89, 437 (1965) as in DT 2435860 and DT 1117245 the production of hydrophobized finely divided silicic acids is described in more detail. Commercial products of hydrophobicized precipitated silicas form z. B. the SIPERNAT ^® brands.

From Degussa or the Fa. EVONIK Industries According to the invention preferably co-used as a finely divided anticaking agent Sipernat ^® D17. Sipernat ^® D17 contains on its weight in relation about 2 wt .-% of chemically bound carbon and is not wetted by water. His shaking weight (according to ISO 787-11 ) is 150 g / l. Its d ₅₀ value is 10 μm (laser diffraction after ISO 13320-1 ) and the specific surface area (nitrogen adsorption after ISO 5794-1 , Annex D) is 100 m ² / g.

Advantageously, finely divided anti-caking agent such. B. Sipernat ^® D17 mixed into the finely divided starting material A1 before it is mixed with the finely divided starting material A2 to finely divided starting material A3. In general, the additional amount of finely divided anticaking agent is 0.1 to 3 wt .-%, based on the weight of the finely divided starting material A1.

Of the Addition of anti-caking agent also reduces the for a homogeneous Mixing of the two starting materials A1 and A2 required energy input, which is particularly relevant to the preservation of the particle size the finely divided starting material A2 has an advantageous effect during mixing.

If the inventive molding of the finely divided starting material A3 to the geometric moldings V according to the invention advantageously by compacting (compressing or compacting), it is appropriate from an application point of view, the finely divided starting material A3 as further finely divided shaping aids lubricant such. For example, graphite, carbon black, polyethylene glycol, polyacrylic acid, stearic acid, starch, mineral oil, vegetable oil, water, boron trifluoride and / or boron nitride. A co-use of lubricants in a corresponding shaping can be found z. B. in the writings DE-A 102007004961 . WO 2005/030393 . US-A 2005/0131253 . WO 2007/017431 . DE-A 102007005606 and in the German Application No. 102008040093.9 described. According to the invention, exclusively finely divided graphite is preferably used as the lubricant. 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.

Advantageously, the finely divided graphite (typical d ₉₀ values according to the invention suitable graphite be 30 to 300 microns) is added to the mixture of finely divided starting material A1 and finely divided starting material A2. However, it can also be mixed in advance of the mixing of the two finely divided starting materials A1, A2 in each of them (or in only one of the two). Based on the weight of the finely divided starting mass A3, this z. B. hold up to 15 wt .-% of finely divided lubricant ent. However, the lubricant content in the finely divided starting composition A3 is usually ≦ 9% by weight, in many cases ≦ 5% by weight, often ≦ 4% by weight; this is especially true when the finely divided lubricant is graphite. In general, the aforementioned additional amount is ≥ 0.5 wt .-%, usually ≥ 2.5 wt .-%.

at The finely divided starting mass A3 can be used as a further requirement Forming aids still finely divided reinforcing agents such as glass microfibers, asbestos, silicon carbide or potassium titanate be added, which after completion of the molding by Condensing conducive to the cohesion of the obtained Compressed (of the resulting molded article V) impact.

In the context of the thermal treatment according to the invention of the shaped bodies V, in which the shaped catalyst bodies K accrue, co-used shaping aids can be obtained both in the resulting shaped catalyst body K and by thermal and / or chemical decomposition to give gaseous compounds (eg CO, CO ₂ ). at least partially gaseous escape from these. In the case of a catalytic use of the latter, shaping aids remaining in the shaped catalyst body K have the effect of diluting in the latter essentially exclusively the multi-element oxide I active mass.

in the As a rule, the compression of the finely divided starting material takes place A3 to the desired geometry of the molding V (of the geometric catalyst precursor molding) by external forces (pressure) on the finely divided precursor mixture. The applicable Shaping apparatus or the forming method to be used is subject to no restriction.

For example can the compacting shaping by extrusion, tableting or extruding. This is the finely divided starting material A3 preferably used dry to the touch. It can, however, z. B. containing up to 10% of their total weight of substances added, at normal conditions (25 ° C, 1 atm) liquid are. Also, the finely divided starting mass A3 solid solvates (z. As hydrates) containing such liquid substances in chemically and / or physically bound form. Of course but the finely divided starting mass A3 but also completely be free of such substances.

According to preferred molding method by compacting the finely divided starting material A3 is the tableting. The basic features of tabletting are z. In "The Tablet", Handbook of Development, Production and Quality Assurance, WA Ritschel and A. Bauer-Brandl, 2nd edition, Edition Verlag Aulendorf, 2002 described and in a completely corresponding manner transferable to a tabletting method according to the invention.

Advantageously, a tabletting according to the invention as in the writings WO 2005/030393 . German Application No. 102008040093.9 . German Application No. 102008040094.7 and WO 2007/017431 described carried out.

Instead of compacting the finely divided starting mass A3 as such directly to the desired geometry of the shaped body V (in a single compacting step), it is often useful according to the invention moderately, as a first shaping step, first carry out a Zwischenkompaktierung to coarsen the finely divided starting mass A3 (usually on particle diameter of 100 to 2000 .mu.m, preferably 150 to 1500 .mu.m, more preferably 400 to 1250 .mu.m, or 400 to 1000 .mu.m, or 400 to 800 μm).

there can already before the intermediate compaction z. B. finely divided lubricant (eg graphite). Then done on the basis of coarsened powder the final Shaping, which if necessary again z. B. finely divided lubricant (For example, graphite) and optionally further shaping and / or Reinforcing aid can be added.

As well as to be used for the compression of the finely divided starting material A3 Forming apparatus or the method of forming to be used, is also subject to the desired geometry of the resulting moldings V in the process of the invention no restriction. That is, the catalyst precursor moldings (the Moldings V) can both regularly as well as being irregular in shape, being regular shaped moldings V are generally preferred according to the invention are.

For example, the shaped body V in the process according to the invention have spherical geometry. In this case, the ball diameter z. B. 2 to 10 mm, or 4 to 8 mm. However, the geometry of the catalyst precursor shaped body (of the shaped body V) can also be full-cylindrical or hollow-cylindrical (annular). In both cases, outside diameter (A) and height (H) z. B. 2 to 10 mm, or 2 or 3 to 8 mm. In the case of hollow cylinders (rings) is usually a wall thickness of 1 to 3 mm appropriate. Of course, as catalyst precursor geometry but also all those geometries are considered that in the WO 02/062737 disclosed and recommended. In the case of solid cylinders, the outer diameter may also be 1 to 10 mm.

The forming pressures used in the course of compaction of finely divided starting material A3 will generally be 50 kg / cm ² to 5000 kg / cm ^{2 in the} process according to the invention. Preferably, the forming pressures are from 200 to 3500 kg / cm ² , more preferably from 600 to 25000 kg / cm ² .

Particularly in the case of annular shaped bodies V, the shaping compaction in the method according to the invention is the teaching of the documents German Application No. 102008040093.9 . German Application No. 102008040094.7 and WO 2005/030393 be performed so that the lateral compressive strength SD of the resulting annular shaped body V 12 N ≦ SD ≦ 25 N. Preferably, SD ≥ 13 N and ≦ 24 N, or ≥ 14 N and ≦ 22 N, and very particularly preferably ≥ 15 N and ≦ 20 N.

The experimental determination of lateral compressive strength is as in the writings WO 2005/030393 such as WO 2007/017431 described carried out. Of course, ring-like moldings V, as they are German Application No. 102008040093.9 recommends very particularly preferred according to the invention. The end face of annular or ring-like shaped bodies V can be both curved and not curved in the method according to the invention (cf. DE-A 102007004961 . EP-A 184 790 and the German Application No. 102008040093.9 ). When determining the height of such geometric shaped bodies V, such a curvature is not taken into account.

Available according to the invention Catalyst body K obtained by thermal treatment were produced by molded bodies V, which by compression have been obtained from finely divided starting mass A3, as Vollkatalysatoren (Vollkatalysatorformkörper K) called.

Particularly according to the invention advantageous ring geometries of by compacting finely divided Starting mass A3 available moldings V meet the condition H / A = 0.3 to 0.7. Particularly preferred is H / A = 0.4 to 0.6.

Farther it is for the aforementioned annular shaped body V according to the invention favorable when the ratio I / A (where I is the inner diameter of the ring geometry) 0.3 to 0.7, preferably 0.4 to 0.7.

The aforementioned ring geometries are particularly advantageous if they simultaneously have one of the advantageous H / A ratios and one of the advantageous I / A ratios. Such possible combinations are z. H / A = 0.3 to 0.7 and I / A = 0.3 to 0.8 or 0.4 to 0.7. Alternatively, H / A can be 0.4 to 0.6 and I / A can be 0.3 to 0.8 or 0.4 to 0.7 at the same time. Furthermore, it is favorable for the relevant ring geometries if H is 2 to 6 mm and preferably 2 to 4 mm. Furthermore, it is advantageous if A in the rings 4 to 8 mm, preferably 4 to 6 mm. The wall thickness according to the invention preferred ring geometries is 1 to 1.5 mm.

Possible Ring geometries for the aforementioned annular shaped body V are thus (A × H × I) 5 mm × 2 mm × 2 mm, or 5 mm × 3 mm × 2 mm, or 5 mm × 3 mm × 3 mm, or 5.5 mm × 3 mm × 3.5 mm, or 6 mm × 3 mm × 4 mm, or 6.5 mm × 3 mm × 4.5 mm, or 7 mm × 3 mm × 5 mm, or 7 mm × 7 mm × 3 mm, or 7 mm × 7 mm × 4 mm.

The thermal treatment of moldings according to the invention V (in particular annular shaped body V; everything The following applies in particular to their thermal treatment) to obtain the geometric shaped catalyst bodies K takes place in the context of the method according to the invention usually at temperatures (this is the temperature in this document within the calcination) 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 500 ° C was not exceeded.

Further is used in the context of thermal treatment of the molding V 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. The thermal Treatment in its temporal sequence also in several sections To be arranged. For example, initially a thermal Treatment at a temperature (phase 1) of 150 to 350 ° C, preferably 220 to 290 ° C, and thereafter a thermal treatment at a temperature (phase 2) of 400 to 600 ° C, preferably 430 to 550 ° C carried out become.

Usually takes the thermal treatment of the moldings V several Hours (often more than 5 hours). Extends many times the total duration of the thermal treatment is more than 10 H. Most are in the context of thermal treatment of the molding V treatment periods of 45 h and 25 h not exceeded. Often the total treatment time is less than 20 hours. in principle The thermal treatment can be over at higher temperatures a shorter treatment time or not too high temperatures performed during a longer treatment period become. In an advantageous according to the invention Embodiment of the thermal treatment of the moldings V 465 ° C are not exceeded and the duration of treatment in the temperature window ≥ 440 ° C extends for> 10 to 20 h.

In All examples and comparative examples are final calcination at final calcination temperatures ≤ 490 ° C, especially ≤ 475 ° C. This is partly due to that on a commercial scale in the higher lying Endkalzinationstemperaturbereich the energy expenditure, and, at a Final calcination in the presence of air, the risk of graphite firing disproportionately increase. Furthermore, the long-term stability of the resulting geometric shaped catalyst K under a too high End calcination temperature and / or end calcination time. In a further advantageous according to the invention Embodiment of the thermal loading treatment of the moldings V are exceeded 465 ° C (but not 490 ° C) and the treatment duration in the temperature window of ≥ 465 ° C extends to 2 to 10 h.

in principle can all mentioned in this document or executed Examples and comparative examples under otherwise unchanged Conditions but also at a final calcination temperature of 430 ° C, or 432 ° C, or 434 ° C, or 436 ° C, or 438 ° C, or 440 ° C, or 442 ° C, or 444 ° C, or 446 ° C, or 448 ° C, or 450 ° C, or 452 ° C, or 454 ° C, or 456 ° C, or 458 ° C, or 460 ° C, or 462 ° C, or 464 ° C, or 466 ° C, or 468 ° C, or 470 ° C, or 472 ° C, or 474 ° C or 475 ° C.

The Final calcination in all embodiments B1 to B6 as well as in all comparative examples V1 to V5 (including the subsequent use as catalysts for the Propenpartialoxidation) can but also under otherwise unchanged Conditions during one on 9, or 8, or 7, or 6, or 5, or 4, or 3, or 2, or 1 h shortened final calcination time each time by 2, or 4, or 6, or 8, or 10, or 12, or 14, or 16, or 20 ° C increased final calcination temperature be performed.

The thermal treatment (also called the phase 1 (also called decomposition phase)) of the molded body V can be carried out both under inert gas and under an oxidative atmosphere such. As air (or other mixture of inert gas and oxygen) and under a reducing atmosphere (eg., A mixture of inert gas, NH ₃ , CO and / or H ₂ or under methane, acrolein, methacrolein) take place. Of course, the thermal treatment can also be carried out under vacuum. Also, the Kalzinationsatmosphäre on the calcine be made variable. According to the invention, the thermal treatment of the shaped bodies V preferably takes place in an oxidizing atmosphere. In terms of application technology, it consists predominantly of stagnant or agitated air. However, it may also (for example in the case of all examples and comparative examples) consist of a standing or agitated mixture of 25% by volume of N ₂ and 75% by volume of air, or 50% by volume of N ₂ and 50% by volume. % Air, or 75% by volume of N ₂ and 25% by volume of air, or 100% by volume of N ₂ (in particular in the case of the examples and comparative examples addressed or explained in this document).

In principle, the thermal treatment of the moldings V in different types of furnaces such. B. heated convection chambers (convection ovens), Hordenöfen, rotary kilns, Bandkalzinierern or shaft furnaces are performed. Advantageously according to the invention, the thermal treatment of the shaped bodies V takes place in a belt calcination apparatus such as the one disclosed in US Pat DE-A 10046957 and the WO 02/24620 recommend. A hot spot formation within the Kalzinationsgutes is largely avoided by the fact that with the help of fans by carrying the Kalzinationsgut the gas-permeable conveyor belt increased volume flows are promoted to Kalzinationsatmosphäre by the Kalzinationsgut.

The thermal treatment of the moldings V below 350 ° C. usually pursues the goal of thermal decomposition of in The sources of elements contained in the moldings V (the elementary constituent) of the desired multielement oxide I active composition the shaped catalyst body K as well as possibly used Forming aids. Often, this decomposition phase occurs as part of the heating of the calcination to temperatures ≥ 350 ° C.

Basically, the thermal treatment as in the US 2005/0131253 described described.

In typically, the side compressive strengths are as described According to the invention available annular Full catalyst moldings K 5 to 13 N, often 8 to 11 N.

Unsupported solid catalyst bodies K produced in accordance with the invention need not necessarily be used as such as catalysts for heterogeneously catalyzed partial gas phase oxidations of alkanes, alkanols, alkenes and / or alkenals having from 3 to 6 carbon atoms. Rather, they can also be subjected to grinding and the resulting finely divided material (optionally after classifying the resulting finely divided material) with the aid of a suitable liquid binder (eg., Water) to the surface of a suitable, for. B. spherical or annular support body (geometric carrier molding) are applied (eg., Using the in the DE-A 2909671 , such as DE-A 100 51 419 disclosed method principle). After drying or immediately after application of the active material shell on the support body of the resulting coated catalyst can be used as a catalyst for the aforementioned heterogeneously catalyzed gas phase partial oxidation, as described, for. B. the WO 02/49757 and the DE-A 10122027 describe for similar active compounds.

As carrier materials in the above procedure conventional porous or nonporous aluminas, silica, zirconia, silicon carbide or silicates such as magnesium or aluminum silicate can be used. The carrier bodies can be regularly or irregularly shaped, with regularly shaped carrier bodies having a distinct surface roughness (for example the already mentioned balls or rings) being preferred. Of particular advantage is the use of essentially non-porous, surface-rough rings made of steatite whose longitudinal extension (longest direct straight line connecting two points located on the surface of the support body) typically 2 to 12 mm, often 4 to 10 mm (see also DE-A 4442346 ). The aforementioned longitudinal extents also come for other carrier moldings such. B. balls, solid cylinders and other rings into consideration.

The layer thickness of the active material shell (powder mass) applied to the carrier molding is expediently chosen to lie in the range 10 to 1000 μm, preferably in the range 100 to 700 μm and particularly preferably in the range 300 to 500 μm. Possible shell thicknesses are also 10 to 500 μm or 200 to 300 μm. Frequently, the surface roughness R _{z of} the carrier molding is in the range of 40 to 200 .mu.m, often in the range of 40 to 100 .mu.m (determined in accordance with DIN 4768 Sheet 1 with a "Hommel tester for DIN-ISO surface measurements" from the company Hommelwerke, DE). Expediently, the carrier material is non-porous (total volume of the pores based on the volume of the carrier body ≦ 1% by volume).

In principle, the formation (compression) of the finely divided starting composition A3 into a shaped body V can also be effected by applying the finely divided starting composition A3 to the surface of a geometrical carrier shaped body as described above with the aid of a suitable liquid binder. After drying, the resulting precursor moldings V in accordance with the invention to be thermally treated to obtain shell-type molded articles K according to the invention.

Also can be obtained by grinding inventively produced Vollkatalysatorformkörpern K generated active material powder as such in the fluidized bed for the addressed in these writings heterogeneously catalyzed partial Gas phase oxidations are used.

Furthermore, it is advantageous in view of a pronounced long-term stability of geometric shaped catalyst bodies K according to the invention (in particular when used as catalysts for the heterogeneously catalyzed partial gas phase oxidation of propene to acrolein or of isobutene to methacrolein), if, in addition to the doping of the fraction T according to the invention Amount F (the stability value F of the geometric shaped catalyst body K) of the product (d A1 50 ) 0.7 · (D A2 90 ) 1.5 · (A) -1 ≥ 700, whereby the two diameters d A1 / 50, d A2 / 90 are to be used for product formation in the length unit μm.

According to the invention preferred F ≥ 800, advantageously ≥ 820, or ≥ 840 and even better ≥ 850.

Especially Advantageously, F ≥ 870 or ≥ 900, and particularly advantageously F ≥ 950 or ≥ 1000. Most preferably, F ≥ 1050, or ≥ 1100 or ≥ 1500, or ≥ 2000.

Under Inclusion of the target of satisfactory initial selectivity the Zielproduktbildung already at startup of the catalyst bed F is preferably ≤ 5000 or ≤ 4000, partially ≤ 3000, or ≤ 2500 or ≤ 2000.

Cheap Values for F are also those which are ≤ 1800, or ≤ 1600 or ≤ 1500.

D. h., According to the invention advantageous values for F is 5000 ≥ F ≥ 1000, or 4000 ≥ F ≥ 2000, or 2500 ≥ F ≥ 850, or 2450 ≥ F ≥ 900, or 2400 ≥ F ≥ 950.

Particularly according to the invention advantageous values for F are 1900 ≥ F ≥ 1000, or 1800 ≥ F ≥ 1050.

Completely according to the invention particularly advantageous values for F are 1700 ≥ F ≥ 1100, or 1500 ≥ F ≥ 1150.

The long-term stability of geometric shaped catalyst bodies K according to the invention or of a catalyst bed containing them is particularly pronounced when the activity resulting from the formation is reduced as slowly as possible in the continued operation of the partial oxidation. Periodically repeated regeneration process as z. For example, the scriptures WO 2005/42459 and WO 2005/49200 can additionally extend the catalyst life.

Is in the process according to the invention for the amount F * of the product (the particle diameter d A1 / 50 (the finely divided starting material A1), d A2 / 50 (the finely divided starting material A2) are again given in the unit of length microns) (d A1 50 ) 0.7 · (D A2 50 ) 0.7 · (A -1 ) If the condition F * ≥ 15 (preferably ≥ 18), particularly preferably 35 or 25 ≥ F * ≥ 18, is satisfied, this is beyond the remarks already made, an additional advantage for the objective according to the invention.

A additional doping of the proportion T with Bi ensured even at comparatively high values for F or F * (i.e., at comparatively large d A1 / 50, d A2 / 50 and d A2 / 90 and comparatively small stoichiometric coefficients a) both a satisfactory initial activity and a satisfactory initial selectivity of the desired product formation.

Advantageous processes according to the invention are therefore not least those in which the stoichiometric coefficient g is> 0 to 0.8, and at least 10 mol% (preferably at least 50 mol%, particularly preferably at least 90 mol% and very particularly preferably 100 mol %) of the total molar amount of Z ^{4 is} the element Bi.

The shaped catalyst bodies K obtainable according to the invention are suitable as catalysts for all heterogeneously catalyzed partial gas phase oxidations for which the geometric shaped catalyst bodies K have already been mentioned as suitable in this document. However, geometric shaped catalyst bodies K obtainable according to the invention are particularly suitable as catalysts for the partial oxidations of propene to acrolein and of isobutene and / or tert. Butanol to methacrolein. This applies in particular to inventive annular unsupported catalyst body K. The partial oxidation may be, for. B. as in the scriptures DE-A 102007004961 . WO 02/49757 . WO 02/24620 . German Application No. 102008040093.9 . WO 2005/030393 . EP-A 575 897 . WO 2007/082827 . WO 2005/113127 . WO 2005/047224 . WO 2005/042459 and WO 2007/017431 be described described.

there turn out to be the individualized highlighted in this document Ring geometries of the annular available as described Unsupported catalysts especially also advantageous if the Loading the catalyst charge with in the starting reaction gas mixture contained propene, iso-butene and / or tert. Butanol (or its Methyl ether) ≥ 130 Nl / l catalyst charge h (Supply and / or repackages of pure inert material are not considered to be the catalyst charge for load considerations in this document properly considered).

The Advantageous annular available as described Vollkatalysatorformkörpern K but is also present, if the aforementioned load of catalyst feed ≥ 140 Nl / lh, or ≥ 150 Nl / lh, or ≥ 160 Nl / lh. Normally, the aforementioned Loading of the catalyst charge ≤ 600 Nl / l · h, frequently ≦ 500 Nl / l · h, often ≦ 400 Nl / l · h or ≤ 350 Nl / l · h. charges in the range of 160 Nl / l · h to 300 or 250 or 200 Nl / l · h are particularly useful.

Of course can the available as described annular Vollkatalysatorformkörper K as catalysts for the partial oxidation of propene to acrolein or of isobutene and / or tert. Butanol (or its methyl ether) to Methacrolein also at Loads of the catalyst charge with the partially oxidized Starting compound of ≤ 130 Nl / l · h, or ≤ 120 Nl / l · h, or ≤ 110 Nl / l · h, more advantageous in the invention Be operated way. In general, however, this burden is at values ≥ 60 Nl / l · h, or ≥ 70 Nl / l · h, or ≥ 80 Nl / lh.

• a) die Belastung der Katalysatorbeschickung mit Reaktionsgasausgangsgemisch (das Reaktionsgasgemisch, das dem Katalysatorfestbett zugeführt wird), und/oder
• b) den Gehalt des Reaktionsgasausgangsgemischs mit der partiell zu oxidierenden Ausgangsverbindung.

In principle, the loading of the catalyst charge with the starting compound to be partially oxidized (propene, isobutene and / or tert-butanol (or its methyl ether)) can be adjusted by means of two adjusting screws:

• a) the loading of the catalyst charge with reaction gas starting mixture (the reaction gas mixture which is fed to the fixed catalyst bed), and / or
• b) the content of the reaction gas starting mixture with the starting compound to be partially oxidized.

The According to the invention available z. B. annular Unsupported catalyst bodies K are also particularly suitable when at loads above 130 Nl / l · h the catalyst charge with the partially oxidized organic Connection the load setting especially about the The aforementioned screw a) takes place.

Of the Propene fraction (iso-butene portion or tert-butanol portion (or the Methyl ether)) in the reaction gas starting mixture is usually (i.e., essentially independent of the load) 4 up to 20 vol.%, often 5 to 15 vol.%, or 5 to 12 vol.%, or 5 to 8% by volume (in each case based on the total volume the reaction gas starting mixture).

Often one will the gas phase partial oxidation process with the like described available z. B. annular Vollkatalysatorformkörper K (or other geometric shaped catalyst bodies K) catalyzed partial oxidation (essentially independently from the load) in a partially oxidized (organic) Compound (eg propene): Oxygen: indifferent gases (including Water vapor) volume ratio in the reaction gas starting mixture of 1: (1.0 to 3.0) :( 5 to 25), preferably 1: (1.5 to 2.3) :( 10 to 20).

Under Indifferent gases (or inert gases) become such gases understood that in the course of the partial oxidation to at least 95 mol%, preferably at least 98 mol% chemically unchanged remain.

In the reaction gas starting mixtures described above, the indifferent gas may be ≥20 vol.%, Or ≥30 vol.%, Or ≥40 vol.%, Or ≥50 vol.%, Or ≥60 vol. -%, or to ≥ 70 Vol .-%, or to ≥ 80 Vol .-%, or to ≥ 90 Vol .-%, or to ≥ 95 Vol .-% consist of molecular nitrogen.

However, when the catalyst charge with the organic compound to be partially oxidized is ≥ 150 Nl / l · h, the concomitant use of inert diluent gases such as propane, ethane, methane, pentane, butane, CO ₂ , CO, water vapor and / or noble gases for the starting gas of the reaction gas recommended. In general, however, these inert gases and their mixtures can also be used even at lower loads on the catalyst feed with the organic compound to be partially oxidized. Also, cycle gas can be used as diluent gas. Under circulating gas is understood to mean the residual gas which remains when the target compound is essentially selectively separated from the product gas mixture of the partial oxidation. It should be noted that the partial oxidation to acrolein or methacrolein with the present invention available z. B. annular shaped catalyst bodies K can only be the first stage of a two-stage partial oxidation to acrylic acid or methacrylic acid as the actual target compounds, so that the recycle gas then usually takes place only after the second stage. In the context of such a two-stage partial oxidation, the product mixture of the first stage as such, if appropriate after cooling and / or secondary oxygen addition, is generally fed to the second partial oxidation stage.

In the partial oxidation of propene to acrolein, using the z. B. annular shaped catalyst body K, a typical composition of the reaction gas starting mixture measured at the reactor inlet (regardless of the selected load) z. B. contain the following components: 6 to 6.5% by volume propene, 1 to 3.5 vol.% H ₂ O, 0.2 to 0.5 vol.% CO, 0.6 to 1.2% by volume CO ₂ , 0.015 to 0.04 vol.% acrolein, 10.4 to 11.3% by volume O ₂ , and as residual amount ad 100% by volume of molecular nitrogen; or: 5.6 vol.% propene, 10.2% by volume Oxygen, 1.2% by volume CO _x , 81.3% by volume N ₂ , and 1.4% by volume H ₂ O.

The former Compositions are particularly suitable for propene loads of ≥ 130 Nl / lh and the latter composition especially at propene loads <130 Nl / l · h, in particular ≤ 100 Nl / lh of the fixed catalyst bed.

Suitable alternative compositions of the starting reaction gas mixture (regardless of the selected load) are those which have the following component contents: 4 to 25 vol.% propene, 6 to 70 vol.% Propane, 5 to 60 vol.% H ₂ O, 8 to 65 vol.% O ₂ , and 0.3 to 20 vol.% H ₂ ; or 4 to 25 vol.% propene, 6 to 70 vol.% Propane, 0 to 60 vol.% H ₂ O, 8 to 16 vol.% O ₂ , 0 to 20 vol.% H ₂ , 0 to 0.5 vol.% CO, 0 to 1.2% by volume CO ₂ , 0 to 0.04 vol.% acrolein, and as a residual amount ad 100% by volume of substantially N ₂ ; or 50 to 80 vol.% Propane, 0.1 to 20 vol.% propene, 0 to 10 vol.% H ₂ , 0 to 20 vol.% N ₂ , 5 to 15 vol.% H ₂ O, and so much molecular oxygen that the molar ratio of Oxygen content to propene content 1.5 to 2.5. or 6 to 9 vol.% propene, 8 to 18% by volume molecular oxygen, 6 to 30 vol.% Propane, and 32 to 72 vol.% molecular nitrogen.

The reaction gas starting mixture may also be composed as follows: 4 to 15 vol.% propene, 1.5 to 30 vol.% (often 6 to 15% by volume) of water, ≥ 0 to 10% by volume (preferably ≥ 0 to 5% by volume) of propene, water, oxygen and nitrogen different Be constituents, so much molecular sow that the molar ratio of included molecular Oxygen to be contained molecule larem propene is 1.5 to 2.5, and as a remainder up to the 100th Vol .-% total molecular weight Nitrogen.

Another possible reaction gas starting mixture composition may include: 6.0% by volume propene, 60% by volume Air and 34 vol.% H ₂ O.

Alternatively, reaction gas starting mixtures of the composition according to Example 1 of EP-A 990 636 , or according to Example 2 of EP-A 990 636 , or according to Example 3 of EP-A 1,106,598 , or according to Example 26 of EP-A 1,106,598 , or according to Example 53 of EP-A 1,106,598 be used.

Also suitable are the z. B. annular shaped catalyst body K for the process of DE-A 10246119 respectively. DE-A 10245585 ,

Further reaction gas starting mixtures which are suitable according to the invention can be in the following composition grid: 7 to 11 vol.% propene, 6 to 12 vol.% Water, ≥ 0 to 5 vol.% of propene, water, oxygen and nitrogen of various Be constituents, so much molecular oxygen that the molar ratio of containing molecular oxygen to be contained propene 1,6 to 2.2, and as residual amount up to 100 vol .-% total amount of molecular Nitrogen.

In the case of methacrolein as the target compound, the starting reaction gas mixture may in particular also as in DE-A 44 07 020 be composed described.

The Reaction temperature for the propene partial oxidation is when using the z. B. annular Catalyst body K often at 300 to 380 ° C. The same is true in the case of methacrolein as the target compound.

Of the Reaction pressure is for the aforementioned partial oxidation usually at 0.5 or 1.5 to 3 or 4 bar (meant in this document, unless expressly mentioned otherwise is, always absolute pressures).

The Total load of the catalyst charge with reaction gas starting mixture is typical in the aforementioned partial oxidation to 1000 to 10000 Nl / l · h, usually to 1500 to 5000 Nl / l · h and often at 2000 to 4000 Nl / l · h.

As to be used in the starting reaction gas mixture propene are mainly polymer grade propene and chemical grade propene into consideration, as z. B. the DE-A 102 32 748 describes.

When Oxygen source is normally used air.

The partial oxidation using the z. B. annular shaped catalyst body K can in the simplest case z. B. be carried out in a one-zone Vielkontaktrohr fixed bed reactor, as him DE-A 44 31 957 , the EP-A 700 714 and the EP-A 700 893 describe.

Usually, in the aforementioned tube bundle reactors, the contact tubes are made of ferritic steel and typically have a wall thickness of 1 to 3 mm. Their inner diameter is usually 20 to 30 mm, often 21 to 26 mm. A typical contact tube length amounts to z. B. at 3.20 m. In terms of application, the number of catalyst tubes accommodated in the tube bundle container amounts to at least 1000, preferably to at least 5000. Frequently, the number of catalyst tubes accommodated in the reaction container is 15000 to 35000. Tube bundle reactors having a number of contact tubes above 40000 tend to be the exception. Within the container, the contact tubes are normally distributed homogeneously, the distribution is suitably chosen so that the distance between the central inner axes of closest contact tubes (the so-called contact tube pitch) is 35 to 45 mm (see. EP-B 468 290 ).

The partial oxidation can, however, also be carried out in a multizone (eg "two-zone") multi-contact-tube fixed bed reactor, such as the DE-A 199 10 506 , the DE-A 103 13 213 , the DE-A 103 13 208 and the EP-A 1,106,598 especially at he elevated loads the catalyst charge with the partially oxidized organic compound recommend. A typical contact tube length in the case of a two-zone multi-contact fixed bed reactor is 3.50 m. Everything else is essentially as described in the single-zone multi-contact fixed bed reactor. Around the catalyst tubes, within which the catalyst feed is located, a heat exchange medium is guided in each tempering zone. As such are z. B. Melting of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate, or of lower melting metals such as sodium, mercury and alloys of various metals. The flow rate of the heat exchange medium within the respective tempering zone is usually selected so that the temperature of the heat exchange medium from the point of entry into the temperature zone to the exit point from the temperature zone by 0 to 15 ° C, often 1 to 10 ° C, or 2 to 8 ° C, or 3 to 6 ° C increases.

The inlet temperature of the heat exchange medium, which, viewed over the respective temperature control, can be conducted in cocurrent or in countercurrent to the reaction gas mixture is preferably as in the publications EP-A 1,106,598 . DE-A 199 48 523 . DE-A 199 48 248 . DE-A 103 13 209 . EP-A 700 714 . DE-A 103 13 208 . DE-A 103 13 213 . WO 00/53557 . WO 00/53558 . WO 01/36364 . WO 00/53557 as well as the other writings cited in this document as prior art recommended. Within the tempering zone, the heat exchange medium is preferably guided in meandering fashion. In general, the multi-contact fixed-bed reactor also has thermal tubes for determining the gas temperature in the catalyst bed. Conveniently, the inner diameter of the thermo tubes and the diameter of the inner receiving sleeve for the thermocouple is chosen so that the ratio of heat of reaction evolving volume to heat dissipating surface is the same or only slightly different in thermal tubes and work tubes.

The pressure loss should be the same for work tubes and thermo tubes, based on the same GHSV. A pressure loss compensation in the thermal tube can be done by adding split catalyst to the shaped catalyst bodies. This compensation is expediently homogeneous over the entire thermal tube length.

to Preparation of the catalyst charge in the catalyst tubes can, as already mentioned, only available as described z. B. annular shaped catalyst bodies K or z. B. also largely homogeneous mixtures of as available available z. B. annular shaped catalyst bodies K and have no active material, with respect to the heterogeneous catalyzed partial gas phase oxidation of substantially inert behaving Moldings are used. As materials for such inert shaped bodies come z. B. porous or non-porous aluminum oxides, silicon dioxide, zirconium dioxide, Silicon carbide, silicates such as magnesium or aluminum silicate and / or Steatite (for example of the type C220 from CeramTec, DE).

The Geometry of such inert shaped diluent bodies can be arbitrary in principle. That is, it can, for example Spheres, polygons, solid cylinders or even, such. B. in the case of annular Catalyst bodies K, rings. Frequently becomes it is possible to choose such as inert dilution molded bodies their geometry is that of the one to be thinned with them Catalyst body K corresponds. Along the Catalyst charging can also change the geometry of the Catalyst body K changed or shaped catalyst body K of different geometry in a largely homogeneous mixture be used. In a less preferred approach also the active material of the shaped catalyst body K longitudinally the catalyst charge can be changed.

All Generally, as already mentioned, the catalyst feed designed with advantage such that the volume-specific (i.e., the Normalized to the unit of volume) activity in the flow direction of the reaction gas mixture either remains constant or increases (continuously, erratic or stepped).

A Reduction in volume-specific activity may occur in simple way z. B. be achieved by giving a basic amount of uniformly produced according to the invention z. B. annular shaped catalyst bodies K with inert diluent bodies homogeneously diluted. The higher the proportion of the diluent tablets is chosen, the lower is the one in a given Volume of the feed contained active material or catalyst activity. A reduction can also be achieved by one the geometry of the inventively available Catalyst body K changed so that the in the unit of reaction tube internal volume contained amount of active mass gets smaller.

For the heterogeneously catalyzed gas phase partial oxidations with described available annular Vollkatalysatorformkörpern K is preferably the catalyst feed either on the full length uniform with only one type of full catalyst ring molding K designed or structured as follows. At the reactor entrance is at a length of 10 to 60%, preferably 10 to 50%, especially preferably 20 to 40% and most preferably 25 to 35% (i.e. h., z. B. on a length of 0.70 to 1.50 m, preferably 0.90 to 1.20 m), in each case the total length of the catalyst charge, a substantially homogeneous mixture of obtainable according to the invention annular unsupported catalyst body K and inert Dilution molding (both preferably having substantially the same geometry), wherein the proportion by weight of the diluent tablets (the Bulk densities of shaped catalyst bodies K and diluent bodies usually differ only slightly) normally 5 to 40 wt .-%, or 10 to 40 wt .-%, or 20 to 40 wt .-%, or 25 to 35 wt .-% is. Following this first Loading section is then advantageous to the end the length of the catalyst feed (i.e., e.g. a length of 1.00 to 3.00 m or 1.00 to 2.70 m, preferably 1.40 to 3.00 m, or 2.00 to 3.00 m) either one diluted only to a lesser extent (than in the first section) Batch of the available as described annular Unsupported catalyst body K, or, very particularly preferably, a sole (undiluted) bed of the same annular unsupported catalyst body K, the has also been used in the first section. Naturally can also be a constant dilution over the entire feed to get voted. Also, in the first section only with one According to the invention available annular Vollkatalysatorformkörper K of less, on its space requirements referred, active mass density and in the second section with a According to the invention available annular Full catalyst molding K with high, on its space requirements referred to, be charged active mass density (eg 6.5 mm × 3 mm × 4.5 mm [A × H × I] in the first section, and 5 × 2 × 2 mm in the second section).

Overall, in a z with the available as described. B. annular shaped catalyst bodies K carried out as catalysts partial oxidation for the preparation of acrolein or methacrolein the catalyst charge, the starting reaction gas mixture, the load and the reaction temperature usually chosen so that the single passage of the reaction gas mixture through the catalyst charge a conversion of the partially oxidized organic compound (propene, isobutene, tert-butanol or its methyl ether) of at least 90 mol%, or at least 92 mol%, preferably of at least 94 mol% results. The selectivity of acrolein or methacrolein formation will be regularly ≥ 80 mol%, or ≥ 85 mol%. In the natural way, the lowest possible hotspot temperatures are sought.

Finally It should be noted that as described available annular Vollkatalysatorformkörper K also an advantageous fracture behavior have at the reactor filling.

The commissioning of a (s) fresh, according to the invention available geometric shaped catalyst K containing catalyst feed (fixed catalyst bed) can, for. B. as in the DE-A 103 37 788 described described.

Furthermore are geometrically available according to the invention Catalyst body K in general as catalysts with reduced deactivation rate and at the same time more satisfactory Initial selectivity of value product formation for gas-phase catalytic partial oxidations 3 to 6 (i.e., 3, 4, 5 or 6) C atoms containing alkanes (in particular propane), alkanols, Alkanals, alkenes and alkenals to e.g. B. olefinically unsaturated Aldehydes and / or carboxylic acids, and the corresponding Nitriles (ammoxidation, especially of propene to acrylonitrile and of 2-methylpropene or tert-butanol (or its methyl ether) to methacrylonitrile) as well as for gas-phase catalytic oxidative Dehydrations of the aforementioned 3, 4, 5 or 6 carbon atoms containing suitable organic compounds.

The industrial production of shaped catalyst bodies K according to the invention (as well as all exemplary embodiments B1 to B6 and comparative examples C1 to V5) is carried out appropriately in terms of application technology, as in FIGS German Applications No. 102008040093.9 and 102008040094.7 (particularly advantageous in accordance with Example 1.3 of application no. 102008040094.7 ).

• 1. Verfahren zur Herstellung von geometrischen Katalysatorformkörpern K, die als Aktivmasse ein Multielementoxid I der allgemeinen Stöchiometrie I [Bi₁Z¹ _bO_x]_a[Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶iO_y]₁ (I),mit Z¹ = ein Element oder mehr als ein Element aus der Gruppe bestehend aus Wolfram und Molybdän, Z² = ein Element oder mehr als ein Element aus der Gruppe bestehend aus Nickel und Kobalt, Z³ = ein Element oder mehr als ein Element aus der Gruppe bestehend aus den Alkalimetallen, den Erdalkalimetallen und Thallium, Z⁴ = ein Element oder mehr als ein Element aus der Gruppe bestehend aus Lanthan, Cer, Zink, Phosphor, Arsen, Bor, Antimon, Zinn, Vanadium, Chrom und Wismut, Z⁵ = ein Element oder mehr als ein Element aus der Gruppe bestehend aus Silizium, Aluminium, Titan, Wolfram und Zirkonium, Z⁶ = ein Element oder mehr als ein Element aus der Gruppe bestehend aus Kupfer, Silber und Gold, a = 0,05 bis 6, b = 0,1 bis 10, d = 0,01 bis 5, e = 1 bis 10, f = 0,01 bis 2, g = 0 bis 5, h = 0 bis 50, i = 0 bis 1, und x, y = Zahlen, die durch die Wertigkeit und Häufigkeit der von Sauerstoff verschiedenen Elemente in I bestimmt werden, enthalten, bei dem man – feinteiliges Mischoxid Bi₁Z¹ _bO_x mit einem Partikeldurchmesser d A1 / 50 als Ausgangsmasse A1 mit der Maßgabe vorbildet, dass 1 μm ≤ d A1 / 50 ≤ 100 μm erfüllt ist; – unter Verwendung von Quellen der von Sauerstoff verschiedenen Elemente des Anteils T = [Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _iO_y]₁ des Multielementoxids I in wässrigem Medium mit der Maßgabe eine innige wässrige Mischung M erzeugt, dass – jede der verwendeten Quellen im Verlauf der Herstellung der wässrigen Mischung M einen Zerteilungsgrad Q durchläuft, der dadurch gekennzeichnet ist, dass sein Durchmesser d Q / 50 ≤ 5 μm beträgt, und – die wässrige Mischung M die Elemente Z⁰, Mo, Fe, Z², Z³, Z⁴, Z⁵ und Z⁶ in der Stöchiometrie I*, Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i (I*),enthält; – aus der wässrigen Mischung M durch Trocknen und Einstellen des Zerteilungsgrades d A2 / 90 eine feinteilige Ausgangsmasse A2 mit einem Partikeldurchmesser d A2 / 90 unter der Maßgabe erzeugt, dass 400 μm ≥ d A2 / 90 ≥ 10 μm erfüllt ist; – Ausgangsmasse A1 und Ausgangsmasse A2, oder Ausgangsmasse A1, Ausgangsmasse A2 und feinteilige Formgebungshilfsmittel zu einer feinteiligen Ausgangsmasse A3 mit der Maßgabe miteinander vermischt, dass die Ausgangsmasse A3 die über die Ausgangsmassen A1 und A2 in die Ausgangsmasse A3 eingebrachten, von Sauerstoff verschiedenen, Elemente des Multielementoxids I in der Stöchiometrie I**, [Bi₁Z¹ _b]_a[Z⁰ _cMo₁₂Fe_dZ² _eZ³ _fZ⁴ _gZ⁵ _hZ⁶ _i]₁ (I**).enthält, – mit feinteiliger Ausgangsmasse A3 geometrische Formkörper V formt, und – die Formkörper V bei erhöhter Temperatur unter Erhalt der geometrischen Katalysatorformkörper K thermisch behandelt, dadurch gekennzeichnet, dass der stöchiometrische Koeffizient c die Bedingung 0 < c ≤ 0,8 erfüllt und Z⁰ ein Element oder mehr als ein Element aus der Gruppe, bestehend aus Yttrium und den Lanthaniden ohne Lanthan und ohne Cer, ist.
• 2. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass c ≥ 0,001 beträgt.
• 3. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass c ≥ 0,003 beträgt.
• 4. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass c ≥ 0,005 beträgt.
• 5. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass c ≥ 0,01 beträgt.
• 6. Verfahren gemäß einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, dass c ≤ 0,7 beträgt.
• 7. Verfahren gemäß einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, dass c ≤ 0,6 beträgt.
• 8. Verfahren gemäß einer der Ausführungsformen 1 bis 5, dadurch gekennzeichnet, dass c ≤ 0,5 beträgt.
• 9. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass 0,0005 ≤ c ≤ 0,5 erfüllt ist.
• 10. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass 0,001 ≤ c ≤ 0,4 erfüllt ist.
• 11. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass 0,005 ≤ c ≤ 0,3 erfüllt ist.
• 12. Verfahren gemäß Ausführungsform 1, dadurch gekennzeichnet, dass 0,01 ≤ c ≤ 0,2 erfüllt ist.
• 13. Verfahren gemäß einer der Ausführungsformen 1 bis 12, dadurch gekennzeichnet, dass a 0,1 bis 4 ist.
• 14. Verfahren gemäß einer der Ausführungsformen 1 bis 12, dadurch gekennzeichnet, dass a 0,1 bis 3 ist.
• 15. Verfahren gemäß einer der Ausführungsformen 1 bis 12, dadurch gekennzeichnet, dass a 0,2 bis 2 ist.
• 16. Verfahren gemäß einer der Ausführungsformen 1 bis 12, dadurch gekennzeichnet, dass a 0,3 bis 1,5 ist.
• 17. Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass wenigstens 10 mol-% der molaren Gesamtmenge an Z¹ Wolfram ist.
• 18. Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass wenigstens 50 mol-% der molaren Gesamtmenge an Z¹ Wolfram ist.
• 19. Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass wenigstens 90 mol-% der molaren Gesamtmenge an Z¹ Wolfram ist.
• 20. Verfahren gemäß einer der Ausführungsformen 1 bis 16, dadurch gekennzeichnet, dass die molare Gesamtmenge an Z¹ Wolfram ist.
• 21. Verfahren gemäß einer der Ausführungsformen 1 bis 20, dadurch gekennzeichnet, dass 1 μm ≤ d A1 / 50 ≤ 50 μm beträgt.
• 22. Verfahren gemäß einer der Ausführungsformen 1 bis 20, dadurch gekennzeichnet, dass 1 μm ≤ d A1 / 50 ≤ 10 μm beträgt.
• 23. Verfahren gemäß einer der Ausführungsformen 1 bis 20, dadurch gekennzeichnet, dass 1,5 μm ≤ d A1 / 50 ≤ 6 μm beträgt.
• 24. Verfahren gemäß einer der Ausführungsformen 1 bis 20, dadurch gekennzeichnet, dass 2 μm ≤ d A1 / 50 ≤ 3 μm beträgt.
• 25. Verfahren gemäß einer der Ausführungsformen 1 bis 24, dadurch gekennzeichnet, dass 200 μm ≥ d A2 / 90 ≥ 20 μm beträgt.
• 26. Verfahren gemäß einer der Ausführungsformen 1 bis 24, dadurch gekennzeichnet, dass 150 μm ≥ d A2 / 90 ≥ 40 μm beträgt.
• 27. Verfahren gemäß einer der Ausführungsformen 1 bis 24, dadurch gekennzeichnet, dass 100 μm ≥ d A2 / 90 ≥ 50 μm beträgt.
• 28. Verfahren gemäß einer der Ausführungsformen 1 bis 27, dadurch gekennzeichnet, dass der Partikeldurchmesser d A2 / 50 der feinteiligen Ausgangsmasse A2 die Bedingung 10 μm ≤ d A2 / 50 ≤ 100 μm erfüllt.
• 29. Verfahren gemäß einer der Ausführungsformen 1 bis 27, dadurch gekennzeichnet, dass der Partikeldurchmesser d A2 / 50 der feinteiligen Ausgangsmasse A2 die Bedingung 20 μm ≤ d A2 / 50 ≤ 60 μm erfüllt.
• 30. Verfahren gemäß einer der Ausführungsformen 1 bis 29, dadurch gekennzeichnet, dass das Verhältnis des Partikeldurchmessers d A2 / 90 der feinteiligen Ausgangsmasse A2 zum Partikeldurchmesser d A2 / 10 der feinteiligen Ausgangsmasse A2 im Bereich von 5 bis 20 liegt.
• 31. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass d Q / 90 für jede der verwendeten Quellen ≤ 3 μm ist.
• 32. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass d Q / 90 für jede der verwendeten Quellen ≤ 1 μm ist.
• 33. Verfahren gemäß einer der Ausführungsformen 1 bis 30, dadurch gekennzeichnet, dass d Q / 90 für jede der verwendeten Quellen ≤ 0,5 μm ist.
• 34. Verfahren gemäß einer der Ausführungsformen 1 bis 33, dadurch gekennzeichnet, dass jede der verwendeten Quellen im Verlauf der Herstellung der wässrigen Mischung M den Zustand einer kolloidalen oder einer echten Lösung durchläuft.
• 35. Verfahren gemäß einer der Ausführungsformen 1 bis 33, dadurch gekennzeichnet, dass der Anteil T das Element Si enthält und jede der verwendeten Quellen der von Silizum verschiedenen Elemente im Verlauf der Herstellung der wässrigen Mischung M den Zustand einer echten Lösung durchläuft und als Quelle des Elements Si ein Kieselsol verwendet wird.
• 36. Verfahren gemäß einer der Ausführungsformen 1 bis 35, dadurch gekennzeichnet, dass die feinteilige Ausgangsmasse A2 durch Sprühtrocknung der wässrigen Mischung M erzeugt wird.
• 37. Verfahren gemäß einer der Ausführungsformen 1 bis 35, dadurch gekennzeichnet, dass die Erzeugung der feinteiligen Ausgangsmasse A2 durch Trocknen und Zerteilen der wässrigen Mischung M und die Vermischung der feinteiligen Ausgangsmasse A2 mit der feinteiligen Ausgangsmasse A1 so durchgeführt wird, dass man die feinteilige Ausgangsmasse A1 bei der Herstellung der wässrigen Mischung M in selbige einmischt und das dabei resultierende Gesamtgemisch einer Sprühtrocknung unterwirft.
• 38. Verfahren gemäß einer der Ausführungsformen 1 bis 37, dadurch gekennzeichnet, dass Z⁰ ein Element oder mehr als ein Element aus der Gruppe, bestehend aus Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb und Lu, ist.
• 39. Verfahren gemäß einer der Ausführungsformen 1 bis 37, dadurch gekennzeichnet, dass Z⁰ ein Element oder mehr als ein Element aus der Gruppe, bestehend aus Y, Eu, Tm, Yb, Gd, Tb, Dy, Ho und Er, ist.
• 40. Verfahren gemäß einer der Ausführungsformen 1 bis 37, dadurch gekennzeichnet, dass Z⁰ ein Element oder mehr als ein Element aus der Gruppe, bestehend aus Y, Ho und Er, ist.
• 41. Verfahren gemäß einer der Ausführungsformen 1 bis 37, dadurch gekennzeichnet, dass Z⁰ ein Element oder mehr als ein Element aus der Gruppe bestehend aus Gd, Tb und Dy ist.
• 42. Verfahren gemäß einer der Ausführungsformen 1 bis 41, dadurch gekennzeichnet, dass Z² = Co ist.
• 43. Verfahren gemäß einer der Ausführungsformen 1 bis 42, dadurch gekennzeichnet, dass Z³ = K, Cs und/oder Sr ist.
• 44. Verfahren gemäß einer der Ausführungsformen 1 bis 43, dadurch gekennzeichnet, dass Z⁵ = Si ist.
• 45. Verfahren gemäß einer der Ausführungsformen 1 bis 44, dadurch gekennzeichnet, dass b 0,5 bis 3 ist.
• 46. Verfahren gemäß einer der Ausführungsformen 1 bis 44, dadurch gekennzeichnet, dass b 1 bis 2,5 beträgt.
• 47. Verfahren gemäß einer der Ausführungsformen 1 bis 44, dadurch gekennzeichnet, dass b 1,5 bis 2,5 beträgt.
• 48. Verfahren gemäß einer der Ausführungsformen 1 bis 47, dadurch gekennzeichnet, dass g > 0 bis 0,8 beträgt, und wenigstens 10 mol-% der molaren Gesamtmenge an Z⁴ das Element Bi ist.
• 49. Verfahren gemäß einer der Ausführungsformen 1 bis 47, dadurch gekennzeichnet, dass e 3 bis 8 oder 4 bis 7 ist.
• 50. Verfahren gemäß einer der Ausführungsformen 1 bis 49, dadurch gekennzeichnet, dass f 0,03 bis 1 ist.
• 51. Verfahren gemäß einer der Ausführungsformen 1 bis 49, dadurch gekennzeichnet, dass f 0,05 bis 0,5 ist.
• 52. Verfahren gemäß einer der Ausführungsformen 1 bis 51, dadurch gekennzeichnet, dass d 1 bis 4 ist.
• 53. Verfahren gemäß einer der Ausführungsformen 1 bis 52, dadurch gekennzeichnet, dass h 0,1 bis 20 ist.
• 54. Verfahren gemäß einer der Ausführungsformen 1 bis 52, dadurch gekennzeichnet, dass h 0,5 bis 10 ist.
• 55. Verfahren gemäß einer der Ausführungsformen 1 bis 54, dadurch gekennzeichnet, dass das feinteilige Mischoxid Bi₁W₂O_7,5 ist.
• 56. Verfahren gemäß einer der Ausführungsformen 1 bis 55, dadurch gekennzeichnet, dass der Betrag F des Produktes (dA150 )0,7·(dA290 )1,5·(a–1)≥ 700 beträgt, wobei die beiden Partikeldurchmesser d A1 / 50 und d A2 / 90 in der Längeneinheit μm anzugeben sind.
• 57. Verfahren gemäß Ausführungsform 56, dadurch gekennzeichnet, dass 820 ≤ F ≤ 5000 ist.
• 58. Verfahren gemäß Ausführungsform 56, dadurch gekennzeichnet, dass 1000 ≤ F ≤ 4000 ist.
• 59. Verfahren gemäß einer der Ausführungsformen 1 bis 58, dadurch gekennzeichnet, dass der Betrag F* des Produktes (dA150 )0,7·(dA250 )0,7·(a–1)≥ 15 beträgt, wobei die beiden Partikeldurchmesser d A1 / 50 und d A2 / 50 in der Längeneinheit μm anzugeben sind.
• 60. Verfahren gemäß Ausführungsform 59, dadurch gekennzeichnet, dass 35 ≥ F* ≥ 18 ist.
• 61. Verfahren gemäß einer der Ausführungsformen 1 bis 60, dadurch gekennzeichnet, dass feinteilige Ausgangsmasse A1, feinteilige Ausgangsmasse A2 und feinteilige hydrophobisierte Kieselsäure umfassende Formgebungshilfsmittel zu der feinteiligen Ausgangsmasse A3 miteinander vermischt werden.
• 62. Verfahren gemäß einer der Ausführungsformen 1 bis 61, dadurch gekennzeichnet, dass feinteilige Ausgangsmasse A1, feinteilige Ausgangsmasse A2 und feinteiligen Graphit umfassende Formgebungshilfsmittel zu der feinteiligen Ausgangsmasse A3 miteinander vermischt werden.
• 63. Verfahren gemäß einer der Ausführungsformen 1 bis 62, dadurch gekennzeichnet, dass die Formung von geometrischen Formkörpern V mit feinteiliger Ausgangsmasse A3 durch Verdichten der feinteiligen Ausgangsmasse A3 erfolgt.
• 64. Verfahren gemäß Ausführungsform 63, dadurch gekennzeichnet, dass das Verdichten durch Strangpressen, Extrudieren oder Tablettieren erfolgt.
• 65. Verfahren gemäß einer der Ausführungsformen 1 bis 64, dadurch gekennzeichnet, dass der geometrische Formkörper V ein Ring ist.
• 66. Verfahren gemäß Ausführungsform 65, dadurch gekennzeichnet, dass die Seitendruckfestigkeit SD des ringförmigen Formkörpers V die Bedingung 12 N ≤ SD ≤ 25 N erfüllt.
• 67. Verfahren gemäß einer der Ausführungsformen 1 bis 64, dadurch gekennzeichnet, dass der geometrische Formkörper V eine Kugel ist.
• 68. Verfahren gemäß einer der Ausführungsformen 1 bis 64, dadurch gekennzeichnet, dass der geometrische Formkörper V ein Vollzylinder ist.
• 69. Verfahren gemäß Ausführungsform 65 oder 66, dadurch gekennzeichnet, dass der Außendurchmesser = 2 bis 10 mm, die Höhe = 2 bis 10 mm und die Wandstärke des Rings 1 bis 3 mm betragen.
• 70. Verfahren gemäß Ausführungsform 67, dadurch gekennzeichnet, dass der Kugeldurchmesser 2 bis 10 mm beträgt.
• 71. Verfahren gemäß Ausführungsform 68, dadurch gekennzeichnet, dass der Außendurchmesser = 1 bis 10 mm und die Höhe des Vollzylinders 2 bis 10 mm betragen.
• 72. Verfahren gemäß einer der Ausführungsformen 1 bis 62, dadurch gekennzeichnet, dass die Formung von geometrischen Formkörpern V mit feinteiliger Ausgangsmasse A3 dadurch erfolgt, dass man die feinteilige Ausgangsmasse A3 mit Hilfe eines flüssigen Bindemittels auf die Oberfläche eines geometrischen Trägerformkörpers aufbringt.
• 73. Verfahren gemäß einer der Ausführungsformen 1 bis 72, dadurch gekennzeichnet, dass im Rahmen der thermischen Behandlung der Formkörper V die Temperatur 350°C überschritten und die Temperatur 600°C nicht überschritten wird.
• 74. Verfahren gemäß einer der Ausführungsformen 1 bis 72, dadurch gekennzeichnet, dass im Rahmen der thermischen Behandlung der Formkörper V die Temperatur 420°C überschritten und die Temperatur 500°C nicht überschritten wird.
• 75. Verfahren gemäß einer der Ausführungsformen 1 bis 74, dadurch gekennzeichnet, dass die thermische Behandlung im Beisein von Luft erfolgt.
• 76. Verfahren gemäß einer der Ausführungsformen 1 bis 71 oder gemäß einer der Ausführungsformen 73 bis 75, dadurch gekennzeichnet, dass der Katalysatorformkörper K ein Vollkatalysatorformkörper K ist und sich an das Verfahren seiner Herstellung ein Verfahren der Mahlung zu feinteiligem Material anschließt und von dem feinteiligen Material mit Hilfe eines flüssigen Bindemittels auf die Oberfläche eines geometrischen Trägerformkörpers aufgebracht wird.
• 77. Katalysatorformkörper erhältlich nach einem Verfahren gemäß einer der Ausführungsformen 1 bis 76.
• 78. Katalysator erhältlich durch Mahlen eines Katalysatorformkörpers der ein Vollkatalysatorformkörper und nach einem Verfahren gemäß einer der Ausführungsformen 1 bis 71 erhältlich ist.
• 79. Verfahren der heterogen katalysierten partiellen Gasphasenoxidation eines 3 bis 6 C-Atome enthaltenden Alkans, Alkanols, Alkanals, Alkens und/oder Alkenals an einem Katalysatorbett, dadurch gekennzeichnet, dass das Katalysatorbett einen Katalysatorformkörper gemäß Ausführungsform 77 oder einen Katalysator gemäß Ausführungsform 78 umfasst.
• 80. Verfahren gemäß Ausführungsform 79, dadurch gekennzeichnet, dass es ein Verfahren der heterogen katalysierten partiellen Gasphasenoxidation von Propen zu Acrolein ist.
• 81. Verfahren gemäß Ausführungsform 79 dadurch gekennzeichnet, dass es ein Verfahren der heterogen katalysierten partiellen Gasphasenoxidation von iso-Buten zu Methacrolein ist.
• 82. Verfahren gemäß Ausführungsform 79, dadurch gekennzeichnet, dass es ein Verfahren der Ammoxidation von Propen zu Acrylnitril oder ein Verfahren der Ammoxidation von iso-Buten zu Methacrylnitril ist.
• 83. Verwendung eines Katalysatorformkörpers gemäß Ausführungsform 77 oder eines Katalysators gemäß Ausführungsform 78 als Katalysator in einem Verfahren der heterogen katalysierten partiellen Gasphasenoxidation eines 3 bis 6 C-Atome enthaltenden Alkans, Alkanols, Alkanals, Alkens und/oder Alkenals.
• 84. Verwendung gemäß Ausführungsform 83, dadurch gekennzeichnet, dass sie in einem Verfahren der heterogen katalysierten partiellen Gasphasenoxidation von Propen zu Acrolein, von iso-Buten zu Methacrolein, oder in einem Verfahren der Ammoxidation von Propen zu Acrylnitril oder von iso-Buten zu Methacrylnitril erfolgt.

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

• 1. A process for the preparation of geometric shaped catalyst bodies K, the active material as a Multielementoxid I of the general stoichiometry I [Bi ₁ Z ¹ _b O _x ] _a [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ iO _y ] ₁ (I) where Z ¹ = one element or more than one element from the group consisting of tungsten and molybdenum, Z ² = one element or more than one element from the group consisting of nickel and cobalt, Z ³ = one element or more than one element the group consisting of the alkali metals, the alkaline earth metals and thallium, Z ⁴ = one element or more than one element selected from the group consisting of lanthanum, cerium, zinc, phosphorus, arsenic, boron, antimony, tin, vanadium, chromium and bismuth, Z ⁵ = one element or more than one element from the group consisting of silicon, aluminum, titanium, tungsten and zirconium, Z ⁶ = one element or more than one element from the group consisting of copper, silver and gold, a = 0.05 to 6, b = 0.1 to 10, d = 0.01 to 5, e = 1 to 10, f = 0.01 to 2, g = 0 to 5, h = 0 to 50, i = 0 to 1 , and x, y = numbers determined by the valence and abundance of the non-oxygen elements in I, comprising: - finely divided mixed oxide Bi ₁ Z. ¹ _b O _x with a particle diameter d A1 / 50 as initial mass A1 with the proviso that 1 μm ≤ d A1 / 50 ≤ 100 μm is fulfilled; Using sources of non-oxygen elements of the proportion T = [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] _{1 of} the multielement oxide I in an aqueous medium with the proviso an intimate aqueous mixture M produces that Each of the sources used in the course of the preparation of the aqueous mixture M undergoes a degree of division Q characterized in that its diameter d Q / 50 ≤ 5 μm, and the aqueous mixture M contains the elements Z ⁰ , Mo, Fe, Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in the stoichiometry I *, Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i (I *), contains; From the aqueous mixture M, by drying and adjusting the degree of d 2/90 dewetting, a finely divided starting material A2 with a particle diameter d A2 / 90 is produced, provided that 400 μm ≥ d A2 / 90 ≥ 10 μm is satisfied; - Starting material A1 and A2, A2 or A2, starting material A2 and finely divided forming aid to a finely divided starting mass A3 with the proviso mixed with each other, that the starting mass A3 introduced via the starting materials A1 and A2 in the starting mass A3, different from oxygen, elements of Multielement oxide I in the stoichiometry I **, [Bi _{1 b} Z ^1] _a [Z ⁰ _c Mo _{d 12} Fe ² Z _e Z _f ³ Z ⁴ Z ⁵ _{g h i} Z ^6] ₁ (I **). contains, - formed with finely divided starting mass A3 geometric moldings V, and - the moldings V thermally treated at elevated temperature to obtain the geometric shaped catalyst bodies K, characterized in that the stoichiometric coefficient c satisfies the condition 0 <c ≤ 0.8 and Z ⁰ is an element or more than one of the group consisting of yttrium and the lanthanides without lanthanum and without cerium.
• 2. Method according to embodiment 1, characterized in that c ≥ 0.001.
• 3. Method according to embodiment 1, characterized in that c ≥ 0.003.
• 4. Method according to embodiment 1, characterized in that c ≥ 0.005.
• 5. Method according to embodiment 1, characterized in that c ≥ 0.01.
• 6. The method according to any one of embodiments 1 to 5, characterized in that c ≤ 0.7.
• 7. The method according to any one of embodiments 1 to 5, characterized in that c ≤ 0.6.
• 8. The method according to any one of embodiments 1 to 5, characterized in that c ≤ 0.5.
• 9. A method according to embodiment 1, characterized in that 0.0005 ≤ c ≤ 0.5 is satisfied.
• 10. The method according to embodiment 1, characterized in that 0.001 ≤ c ≤ 0.4 is satisfied.
• 11. The method according to embodiment 1, characterized in that 0.005 ≤ c ≤ 0.3 is satisfied.
• 12. The method according to embodiment 1, characterized in that 0.01 ≤ c ≤ 0.2 is satisfied.
• 13. The method according to any one of embodiments 1 to 12, characterized in that a is 0.1 to 4.
• 14. The method according to any one of embodiments 1 to 12, characterized in that a is 0.1 to 3.
• 15. The method according to any one of embodiments 1 to 12, characterized in that a is 0.2 to 2.
• 16. The method according to any one of embodiments 1 to 12, characterized in that a is 0.3 to 1.5.
• 17. The method according to any one of embodiments 1 to 16, characterized in that at least 10 mol% of the total molar amount of Z ^{1 is} tungsten.
• 18. The method according to any one of embodiments 1 to 16, characterized in that at least 50 mol% of the total molar amount of Z ^{1 is} tungsten.
• 19. The method according to any one of embodiments 1 to 16, characterized in that at least 90 mol% of the total molar amount of Z ^{1 is} tungsten.
• 20. The method according to any one of embodiments 1 to 16, characterized in that the total molar amount of Z ^{1 is} tungsten.
• 21. Method according to one of embodiments 1 to 20, characterized in that 1 μm ≦ d A1 / 50 ≦ 50 μm.
• 22. Method according to one of embodiments 1 to 20, characterized in that 1 μm ≦ d A1 / 50 ≦ 10 μm.
• 23. The method according to any one of embodiments 1 to 20, characterized in that 1.5 microns ≤ d A1 / 50 ≤ 6 microns.
• 24. The method according to any one of embodiments 1 to 20, characterized in that 2 microns ≤ d A1 / 50 ≤ 3 microns.
• 25. The method according to any one of embodiments 1 to 24, characterized in that 200 microns ≥ d A2 / 90 ≥ 20 microns.
• 26. The method according to any one of embodiments 1 to 24, characterized in that 150 microns ≥ d A2 / 90 ≥ 40 microns.
• 27. The method according to any one of embodiments 1 to 24, characterized in that 100 microns ≥ d A2 / 90 ≥ 50 microns.
• 28. The method according to any one of embodiments 1 to 27, characterized in that the particle diameter d A2 / 50 of the finely divided starting material A2 satisfies the condition 10 microns ≤ d A2 / 50 ≤ 100 microns.
• 29. The method according to any one of embodiments 1 to 27, characterized in that the particle diameter d A2 / 50 of the finely divided starting material A2 satisfies the condition 20 microns ≤ d A2 / 50 ≤ 60 microns.
• 30. The method according to any one of embodiments 1 to 29, characterized in that the ratio of the particle diameter d A2 / 90 of the finely divided starting material A2 to the particle diameter d A2 / 10 of the finely divided starting material A2 in the range of 5 to 20.
• 31. Method according to one of the embodiments 1 to 30, characterized in that d Q / 90 is ≤ 3 μm for each of the sources used.
• 32. Method according to one of the embodiments 1 to 30, characterized in that d Q / 90 is ≤ 1 μm for each of the sources used.
• 33. Method according to one of the embodiments 1 to 30, characterized in that d Q / 90 is ≤ 0.5 μm for each of the sources used.
• 34. The method according to any of embodiments 1 to 33, characterized in that each of the sources used in the course of the preparation of the aqueous mixture M undergoes the state of a colloidal or a true solution.
• 35. Method according to one of the embodiments 1 to 33, characterized in that the portion T contains the element Si and each of the sources used of the elements different from silicon passes through the state of a true solution in the course of the preparation of the aqueous mixture M and as the source of the Elements Si a silica sol is used.
• 36. The method according to any one of embodiments 1 to 35, characterized in that the finely divided starting material A2 is produced by spray-drying the aqueous mixture M.
• 37. The method according to any one of embodiments 1 to 35, characterized in that the production of the finely divided starting material A2 by drying and dividing the aqueous mixture M and the mixing of the finely divided starting material A2 with the finely divided starting material A1 is carried out so that the finely divided starting material Al in the preparation of the aqueous mixture M in selbige mixed and subjects the resulting total mixture to a spray drying.
• 38. The method according to one of embodiments 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, is.
• 39. The method according to one of embodiments 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Eu, Tm, Yb, Gd, Tb, Dy, Ho and Er.
• 40. The method according to any one of embodiments 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Ho and Er.
• 41. The method according to one of embodiments 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Gd, Tb and Dy.
• 42. The method according to any one of embodiments 1 to 41, characterized in that Z ² = Co.
• 43. The method according to any one of embodiments 1 to 42, characterized in that Z ³ = K, Cs and / or Sr.
• 44. The method according to any one of embodiments 1 to 43, characterized in that Z ⁵ = Si.
• 45. The method according to any one of embodiments 1 to 44, characterized in that b is 0.5 to 3.
• 46. The method according to any one of embodiments 1 to 44, characterized in that b is 1 to 2.5.
• 47. The method according to any one of embodiments 1 to 44, characterized in that b is 1.5 to 2.5.
• 48. The method according to any one of embodiments 1 to 47, characterized in that g> 0 to 0.8, and at least 10 mol% of the total molar amount of Z ^{4 is} the element Bi.
• 49. Method according to one of embodiments 1 to 47, characterized in that e is 3 to 8 or 4 to 7.
• 50. The method according to any one of embodiments 1 to 49, characterized in that f is 0.03 to 1.
• 51. The method according to any one of embodiments 1 to 49, characterized in that f is 0.05 to 0.5.
• 52. The method according to any one of embodiments 1 to 51, characterized in that d is 1 to 4.
• 53. The method according to any one of embodiments 1 to 52, characterized in that h is 0.1 to 20.
• 54. The method according to any one of embodiments 1 to 52, characterized in that h is 0.5 to 10.
• 55. The method according to any one of embodiments 1 to 54, characterized in that the finely divided mixed oxide Bi ₁ W ₂ O is _7.5 .
• 56. Method according to one of the embodiments 1 to 55, characterized in that the amount F of the product (d A1 50 ) 0.7 · (D A2 90 ) 1.5 · (A -1 ) ≥ 700, whereby the two particle diameters d A1 / 50 and d A2 / 90 are to be specified in the unit of length μm.
• 57. Method according to embodiment 56, characterized in that 820 ≤ F ≤ 5000.
• 58. Method according to embodiment 56, characterized in that 1000 ≤ F ≤ 4000.
• 59. The method according to any one of embodiments 1 to 58, characterized in that the amount F * of the product (d A1 50 ) 0.7 · (D A2 50 ) 0.7 · (A -1 ) ≥ 15, whereby the two particle diameters d A1 / 50 and d A2 / 50 are to be specified in the unit of length μm.
• 60. Method according to embodiment 59, characterized in that 35 ≥ F * ≥ 18.
• 61. The method according to any one of embodiments 1 to 60, characterized in that finely divided starting material A1, finely divided starting material A2 and finely divided hydrophobized silica comprehensive forming aids to the finely divided starting material A3 are mixed together.
• 62. The method according to any one of embodiments 1 to 61, characterized in that finely divided starting material A1, finely divided starting material A2 and finely divided graphite comprising forming aids are mixed together to form the finely divided starting material A3.
• 63. Method according to one of embodiments 1 to 62, characterized in that the formation of geometric shaped bodies V with finely divided starting mass A3 is effected by compacting the finely divided starting mass A3.
• 64. The method according to embodiment 63, characterized in that the compression is carried out by extrusion, extrusion or tableting.
• 65. The method according to any one of embodiments 1 to 64, characterized in that the geometric shaped body V is a ring.
• 66. Method according to embodiment 65, characterized in that the lateral compressive strength SD of the annular shaped body V satisfies the condition 12 N ≤ SD ≤ 25 N.
• 67. The method according to any one of embodiments 1 to 64, characterized in that the geometric shaped body V is a ball.
• 68. The method according to any one of embodiments 1 to 64, characterized in that the geometric shaped body V is a solid cylinder.
• 69. The method according to embodiment 65 or 66, characterized in that the outer diameter = 2 to 10 mm, the height = 2 to 10 mm and the wall thickness of the ring 1 to 3 mm.
• 70. The method according to embodiment 67, characterized in that the ball diameter is 2 to 10 mm.
• 71. The method according to embodiment 68, characterized in that the outer diameter = 1 to 10 mm and the height of the solid cylinder 2 to 10 mm.
• 72. The method according to any one of embodiments 1 to 62, characterized in that the formation of geometric shapes V with finely divided starting material A3 is effected by applying the finely divided starting material A3 with the aid of a liquid binder on the surface of a geometric support molding.
• 73. The method according to any one of embodiments 1 to 72, characterized in that in the context of the thermal treatment of the molded body V, the temperature exceeded 350 ° C and the temperature is not exceeded 600 ° C.
• 74. The method according to any one of embodiments 1 to 72, characterized in that in the context of the thermal treatment of the molded body V, the temperature exceeded 420 ° C and the temperature is not exceeded 500 ° C.
• 75. The method according to any one of embodiments 1 to 74, characterized in that the thermal treatment takes place in the presence of air.
• 76. The method according to any one of embodiments 1 to 71 or according to any one of embodiments 73 to 75, characterized in that the shaped catalyst body K is a Vollkatalysatorformkörper K and is followed by the process of its preparation a method of grinding into finely divided material and of the finely divided material is applied to the surface of a geometric carrier molding with the aid of a liquid binder.
• 77. A shaped catalyst body obtainable by a process according to one of embodiments 1 to 76.
• 78. A catalyst obtainable by grinding a shaped catalyst body which is obtainable as a solid catalyst molding and by a process according to any one of embodiments 1 to 71.
• 79. Method of heterogeneously catalyzed partial gas phase oxidation of a 3 to 6 carbon atoms the alkanes, alkanols, alkanals, alkenes and / or alkenals on a catalyst bed, characterized in that the catalyst bed comprises a shaped catalyst body according to embodiment 77 or a catalyst according to embodiment 78.
• 80. The method according to embodiment 79, characterized in that it is a method of heterogeneously catalyzed partial gas phase oxidation of propene to acrolein.
• 81. Method according to embodiment 79, characterized in that it is a method of heterogeneously catalyzed partial gas phase oxidation of isobutene to methacrolein.
• 82. Method according to embodiment 79, characterized in that it is a process of ammoxidation of propene to acrylonitrile or a process of ammoxidation of isobutene to methacrylonitrile.
• 83. Use of a shaped catalyst body according to embodiment 77 or a catalyst according to embodiment 78 as a catalyst in a process of heterogeneously catalyzed partial gas phase oxidation of a 3 to 6 carbon atoms-containing alkane, alkanols, alkanals, alkenes and / or alkenals.
• 84. Use according to embodiment 83, characterized in that it takes place in a process of heterogeneously catalyzed partial gas phase oxidation of propene to acrolein, of isobutene to methacrolein, or in a process of ammoxidation of propene to acrylonitrile or of isobutene to methacrylonitrile ,

EXAMPLES AND COMPARATIVE EXAMPLES (for reasons of expediency, Z ⁰ subsites used here for comparison ("not according to the invention") are also subsumed below "Z ⁰ ")

I) Preparation of annular unsupported catalyst bodies B1 to B6 and annular comparative volumizer shaped bodies V1 to V5 with the following stoichiometry of the active composition: [Bi ₁ W ₂ O _7.5 ] ₁ [Z ⁰ _c Mo ₁₂ Fe _3.0 Co _5.5 K _{0, 08} Si _1.6 O _x ] ₁ .

a) Preparation of the starting material 1 (Bi ₁ W ₂ O _7.5 = ½Bi ₂ W ₂ O ₉ · 1WO ₃ )

In a 1.75 m ³ Doppelmantelbehälter (the space was traversed by tempering water) made of stainless steel with bar stirrer were in 780 kg of 25 ° C having aqueous Nitrate bismuth nitrate solution (11.2 wt .-% Bi, free nitric acid 3 to 5 wt bismuth metal produced by Sidech SA, 1495 Tilly, Belgium, purity:> 99.997% by weight of Bi, <7 mg / kg of Pb, each <5 mg / kg of Ni, Ag, Fe, je < 3 mg / kg of Cu, Sb and <1 mg / kg Cd, Zn) at 25 ° C within 20 min portionwise 214.7 kg 25 ° C having tungstic acid (74.1 wt .-% W, average particle size (according to Manufacturer determined according to ASTM B 330) 0.4 to 0.8 microns, loss on ignition (2 h at 750 ° C in air) 6-8 wt .-%, bulk density 5-8 g / in ³ , HC Starck, D-38615 Goslar) stirred (70 U / min). The resulting aqueous mixture was then stirred for 3 h at 25 ° C and then spray-dried. The spray drying was carried out in a rotary screen spray tower of the type FS 15 from Niro 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, a throughput of 200 l / h and an air volume of 1800 Nm ³ / 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). Table 1 below gives an overview of representative d _x values of the spray powder as a function of the applied absolute dispersing pressure. Table 1 2 bar 1.5 bar 1.2 bar 1.1 bar d ₁₀ (μm) d ₅₀ (μm) d ₉₀ (μm) 0.91 5.8 27.5 1.17 8.5 34.3 3.4 19.7 47.2 9,1 28,0 55,2

The spray powder obtained was then pasted with 16.7 wt .-% (based on the powder) of water having 25 ° C in a Auspresskneter for 30 min and extruded by means of an extruder into 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 around 830 ° C. (calcined, in the rotary kiln with air flow (0.3 mbar vacuum, 200 Nm ³ / h air, 50 kg / h extrudate, speed: 1 rpm) ). It is essential in the exact setting of the calcination temperature that it must be oriented toward the desired phase composition of the calcination product, but that the calcined material, on the other hand, has a BET surface area ≥ 0.2 m ² / g.

Wanted are the phases WO ₃ (monoclinic) and Bi ₂ W ₂ O ₉ (orthorhombic), undesirable here is the presence of γ-Bi ₂ WO ₆ (Russellite). Therefore, after calcination, the content of the compound γ-Bi ₂ WO _{6 should be} more than 5 intensity% (calculated as the ratio (Int.-V) of the intensity of the diffraction reflection of γ-Bi ₂ WO ₆ in the X-ray powder diffractogram at 2θ = 28, 4 ° (CuKα radiation) to the intensity of the reflectance of Bi ₂ W ₂ O ₉ at 2θ = 30.0 °), repeat the preparation and increase the calcination temperature or the residence time at the same calcination temperature until the limit is reached or is fallen short of. The preformed calcined mixed oxide thus obtained was ground with a Biplex Querstromsichtmühle type 500 BQ Hosokawa Alpine AG, Augsburg with 2500 rev / min, so that the d A1 / 50 value of the finely divided starting material 1 2.8 microns (at a dispersing pressure measured from 2.0 bar absolute), the BET surface area is 0.6 m ² / g (measured by nitrogen adsorption after activation in vacuo for 4 h at 200 ° C.) and the γ-Bi ₂ WO ₆ content is 2 intensity % (= 100% · int.-V). Before the further processing described under c), the finely divided starting material 1 in portions of 20 kg in a tilt mixer with mixing and cutting blade (speed mixing blade: 60 rev / min, blade speed: 3000 rev / min) within 5 min with homogeneous . 0.5 wt .-% (relative to the finely divided starting material 1) finely divided hydrophobized SiO ₂ from Degussa (Sipernat ^® type D17 bulk density was 150 g / l; d ₅₀ value of the SiO ₂ particles (laser diffraction after ISO 13320-1 ) = 10 μm, the specific surface area (nitrogen adsorption after ISO 5794-1 , Annex D) = 100 m ² / g).

b) Preparation of the starting materials 2 (Z ⁰ _c Mo ₁₂ Fe _3.0 Co _5.5 K _0.08 Si _1.6 )

A solution A was prepared in each case by mixing in an open, water-tempered 10-dm ³ stainless steel pot with an anchor stirrer at 60 ° C with stirring (150 U / min) to 4.8 l a temperature of 60 ° C containing water 7.83 g of an aqueous potassium hydroxide solution having a temperature of 60 ° C. (47% by weight of KOH) and, after stirring for 1 minute, 1.766 kg of ammonium heptamolybdate tetrahydrate in portions (white 25 ° C. crystals with a particle size d <1 mm, 81.5%) Wt .-% MoO ₃ , 7.0-8.5 wt .-% NH ₃ , max 150 mg / kg alkali metals, HC Starck, D-38642 Goslar) metered and the resulting slightly cloudy solution at 60 ° C for 20 min stirred (150 rpm).

A solution B was prepared in each case by dissolving 2.091 kg of an aqueous cobalt (II) nitrate solution (12.4% by weight of Co, pH = 1) in an open, water-tempered 5 dm ³ stainless steel pot with an anchor stirrer. made with cobalt metal nitric acid from MFT Metals & Ferro-Allogs Trading GmbH, D-41747 Viersen, purity,> 99.6% by weight, <0.3% by weight Ni, <100 mg / kg Fe, < 50 mg / kg of Cu) with stirring (150 U / min) heated to 60 ° C and to this solution with continued stirring and maintaining the 60 ° C (150 rev / min) first in Table 2 for the respective example or comparative example specified amount of Z ⁰ source mentioned there and after 5 minutes further stirring at 60 ° C 986 g of crystalline iron (III) nitrate nonahydrate (13.6 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 20 minutes. Then, the respective solution B within 30 minutes in the now both with the anchor stirrer (150 U / min) and with an Ultra-Turrax (Janke & Kunkel GmbH & Co. KG - IKA Laboratory, Janke - & - Kunkel -Str. 10, 79219 Staufen, Germany, shank type: S50KR-G45 F fine, shank tube diameter: 25 mm, stator diameter: 45 mm, rotor diameter: 40 mm, setting: level 5) intensively stirred, 60 ° C having solution A with Help of a peristaltic pump (type: BVP, company: Ismatec SA., Laboratory technology analysis, Feldeggstr 6, 8152 Glattbrugg, Switzerland, setting: about 300 scale parts) recirculated. The resulting yellow-apricot-colored suspension whose viscosity went through a maximum in the course of dosing, was stirred for 15 minutes at 60 ° C. Subsequently, the resulting aqueous mixture 157 g of a silica gel from Grace Ludox TM 50 type (50.1 wt .-% SiO ₂ , density: 1.29 g / ml, pH 8.5 to 9.5, alkali content max 0.5% by weight) and then stirred at 60 ° C. for a further 15 minutes.

Subsequently, the still stirred at 60 ° C by means of anchor agitator (150 rev / min) suspension in a spray tower Mobile Minor ^™ 2000 type (MM-I) Niro A / S, Gladsaxevej 305, 2860 Søborg, Denmark with a centrifugal atomizer type Spray-dried F01A and an atomizer wheel type SL24-50 in hot-air direct current within 105 minutes (gas inlet temperature: 350 ± 10 ° C, gas outlet temperature: 140 ± 5 ° C). By setting a speed of the atomizer of about 25,000 U / min so each about 2.6 kg of orange-brown spray powder as starting material A2 with the particle diameters d A2 / 50 = 26 ± 2 microns and d A2 / 90 = 60 ± 3 μm (measured at a dispersion pressure of 2.0 bar absolute), a BET surface area of 19 ± 3 m ² / g (measured by nitrogen adsorption after activation in vacuum for 12 h at 200 ° C) and an ignition loss of 31 ± 1 Wt .-% (3 hours at 600 ° C under air glow).

c) Preparation of the annular Unsupported catalyst bodies B1 to B6 and V1 to V5

The respective starting material 2 was added with the Sipernat ^® D17 containing starting material 1 in a multimetal oxide of the stoichiometry [Bi ₁ W ₂ O _7.5 · WO _{3] 1} [Z ⁰ _c Mo ₁₂ Fe _3.0 Co _5.5 K _0.08 Si _1.6 O _x ] ₁ required quantities (total amount: 3 kg) in an Eirich intensive mixer (type R02, filling volume: 3-5 l, power: 1.9 kW, Maschinenfabrik Gustav Eirich GmbH & Co KG, D-74736 Hardheim) with counter-rotating to the plate cutter heads (speed plate: 44 rpm, speed cutterheads: 2500 rev / min) homogeneously mixed within 5 min. Based on the aforesaid total mass was added to this in an adequate mixer (wheel diameter: 5 l: 650 mm, drum volume) in addition 1 wt .-% of graphite TIMREX ^® T44 (d ₅₀ = 20.8 microns) Timcal AG within 30 min homogeneously mixed at a speed of about 30 rpm. The resulting mixture (whose stoichiometry I ** Table 2 also shows as r (Z ⁰⁾ ₆ ³⁺⁾ was then compacted in a laboratory calender with counter-rotating steel rolls 2 at a pressure of 9 bar and through a sieve having a mesh width of 0.8 mm. The Kompaktat was then mixed in the above Rhönradmischer at a speed of about 30 U / min within 30 minutes with respect to its weight, a further 2.5 wt .-% of said graphite and then as in German application with the file number 10 2008 040 093.9 described with a Kilian S100 (Kilian, D-50735 Köln) 9-fold tableting machine under nitrogen atmosphere to form annular unsupported catalyst precursor moldings (5 × 3 × 2 mm, A (outer diameter) × H (height) × I (inner diameter)) with a lateral compressive strength of 20 ± 1 N and a mass of 125 ± 5 mg compacted (filling height: 7.5-9 mm, pressing force: 3.0-3.5 kN).

For the final thermal treatment, in each case 1000 g of the prepared Vollkatalysatorvorläuferformkörper V evenly divided on juxtaposed 4 grids with a square base of 150 mm × 150 mm (height: about 15 mm) in one with 650 Nl / h initially 140 ° C tempered air (instead of air can also be a mixture of 25 vol .-% N ₂ and 75 vol .-% air, or 50 vol .-% N ₂ and 50 vol .-% air, or 75 vol .-% N ₂ and 25 vol .-% air, or 100 vol .-% N ₂ are used) circulating air oven (Heraeus Instruments GmbH, D-63450 Hanau, type: K 750/2) first within 120 min of room temperature (25 ° C) heated to 185 ° C. This temperature was maintained for 1 h and then increased to 225 ° C over 50 min. The 225 ° C was held for 2 h before the temperature was further increased to 270 ° C within 23 min. This temperature was also maintained for one hour before being ramped up to the final calcination temperature (T _{final calc.} ) _Indicated in Table 3 with a heating ramp of 1 ° C / min. This final calcination temperature was held for 10 hours. It was then cooled to 25 ° C within about 12 h.

II. Determination of long-term stability the annular unsupported catalyst body B1 to B6 and V1 to V5 in a catalyzed gas phase partial oxidation from propene to acrolein

to Determination of the long-term stability of the annular Vollkatalysatorformkörper B1 to B6 and V1 to V5 in one by catalyzing gas phase partial oxidation of propene Acrolein, were the annular unsupported catalyst bodies B1 to B6 and V1 to V5 the stress test described below subjected.

A reaction tube (V2A steel, 21 mm outer diameter, 3 mm wall thickness, 15 mm inner diameter, 120 cm length) was charged from top to bottom in the flow direction of the reaction gas mixture in each case as follows: Part 1: about 30 cm in length 40 g steatite balls (C220 steatite from CeramTec) with a Diameter of 1.5 to 2.0 mm as pre-filling (heating zone). Section 2: about 70 cm in length A homogeneous mixture of 90 g of the respective annular full Catalyst body and 10 g steatitrings (C220 steatite from. CeramTec) the same ring geometry as the respective Vollkatalysa torformkörper as fixed catalyst bed.

The temperature control of the reaction tube was carried out in each case by means of a bubbled with molecular nitrogen, the respective required salt bath temperature T ^S (° C) having salt bath (53 wt .-% potassium nitrate, 40 wt .-% sodium nitrite and 7 wt .-% sodium nitrate).

During the performance of the stress test, the reaction tube was continuously charged with a reaction gas starting mixture (feed gas mixture of air, polymer grade propene and molecular nitrogen) of the following composition: 5 vol.% Propene (polymer grade), 9.5 vol.% molecular oxygen, and 85.5% by volume N ₂ .

For the purpose of forming the catalyst fixed bed freshly introduced into the reaction tube, T ^{S was} adjusted to 90 Nl / h during the first 210 h service life with a volume flow of the reaction gas starting mixture (whose inlet temperature into the reaction tube was about 30 ° C.) into the reaction tube, that the propene conversion U ^P in the case of a single pass of the feed gas mixture through the reaction tube was continuously about 95 mol% (which, after a starting time of 90 h, initial selectivities of target product total formation S AC + AA / 90h (acrolein + acrylic acid) are shown in Table 3 in mol % of the molar amount of propene reacted in the single pass through the reaction tube). The pressure at the entrance to the reaction tube was 1.2 bar absolute. The salt bath temperature TS / 210 h (° C.) required at the end of the formation phase for the target conversion (95 mol%) is a measure of the respective initial activity of the respective fixed catalyst bed. Table 3 indicates that the annular unsupported catalyst bodies B1 to B6 and V1 to V5 had a substantially identical initial activity. Table 3 also shows the stoichiometry of the respective I-multielement oxide active material and r (Z ^{0) 3+} ₆ of the respective doping element Z ^0th

Subsequent to the formation, the volume flow of reaction gas starting mixture fed into the reaction tube was increased to 200 Nl / h and maintained for a period of 216 h. The salt bath temperature T ^S was set to the constant value of 380 ° C. in the abovementioned period, irrespective of the propene conversion taking place in each case (the pressure at the inlet to the reaction tube was 1.6 bar absolute).

After completion of the aforementioned stress phase, the volume flow of starting reaction gas mixture conducted into the reaction tube was reduced again to the 90 Nl / h intended for the actual normal operation of the propene partial oxidation. While maintaining this volumetric flow over 94 additional operating hours, the salt bath temperature T ^S was adjusted again so that the targeted target conversion of propene (U ^P ), which was envisaged for a single pass of the reaction gas starting mixture through the reaction tube, continuously adjusted to about 95 mol% ,

The At the end of the total then 520 operating hours to obtain the Target conversion (95 mol%) required salt bath temperature T S / 520h (° C) reflects the final activity at the end of the stress test of the respective fixed catalyst bed.

The difference TS / 520h (° C) - TS / 210h (° C) = ΔT ^S determines the order relation within the annular unsupported catalyst bodies B1 to B6 and V1 to V5 with respect to their long-term stability in the catalyzed propene partial oxidation to acrolein (main product) and acrylic acid (by-product). The smaller the ΔT ^S , the lower the deactivation rate of the fixed catalyst bed or the annular unsupported catalyst body contained therein in the partial oxidation operation.

Table 3 shows the determined ΔT ^S values.

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 (84)

Process for the preparation of geometric shaped catalyst bodies K, which contains as active material a multielement oxide I of general stoichiometry I. [Bi ₁ Z ¹ _b O _x ] _a [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ hZ ⁶ _i O _y ] ₁ (I) where Z ¹ = one element or more than one element from the group consisting of tungsten and molybdenum, Z ² = one element or more than one element from the group consisting of nickel and cobalt, Z ³ = one element or more than one element the group consisting of the alkali metals, the alkaline earth metals and thallium, Z ⁴ = one element or more than one element selected from the group consisting of lanthanum, cerium, zinc, phosphorus, arsenic, boron, antimony, tin, vanadium, chromium and bismuth, Z ⁵ = one element or more than one element from the group consisting of silicon, aluminum, titanium, tungsten and zirconium, Z ⁶ = one element or more than one element from the group consisting of copper, silver and gold, a = 0.05 to 6, b = 0.1 to 10, d = 0.01 to 5, e = 1 to 10, f = 0.01 to 2, g = 0 to 5, h = 0 to 50, i = 0 to 1 , and x, y = numbers determined by the valence and abundance of the non-oxygen elements in I, comprising: - finely divided mixed oxide Bi ₁ Z. ¹ _b O _x with a particle diameter d A1 / 50 as initial mass A1 with the proviso that 1 μm ≤ d A1 / 50 ≤ 100 μm is fulfilled; - Using sources of non-oxygen elements of the proportion T = [Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i O _y ] _{1 of} the multielement oxide I in aqueous medium with the Assuming an intimate aqueous mixture M produces that each of the sources used in the course of the preparation of the aqueous mixture M undergoes a degree of division Q characterized in that its diameter d Q / 90 ≤ 5 μm, and the aqueous mixture M the elements Z ⁰ , Mo, Fe, Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ in the stoichiometry I *, Z ⁰ _c Mo ₁₂ Fe _d Z ² _e Z ³ _f Z ⁴ _g Z ⁵ _h Z ⁶ _i (I *), contains; From the aqueous mixture M, by drying and adjusting the degree of d 2/90 dewetting, a finely divided starting material A2 with a particle diameter d A2 / 90 is produced, provided that 400 μm ≥ d A2 / 90 ≥ 10 μm is satisfied; - Starting material A1 and A2, A2 or A2, starting material A2 and finely divided forming aid to a finely divided starting mass A3 with the proviso mixed with each other, that the starting mass A3 introduced via the starting materials A1 and A2 in the starting mass A3, different from oxygen, elements of Multielement oxide I in the stoichiometry I **, [Bi _{1 b} Z ^1] _a [Z ⁰ _c Mo _{d 12} Fe ² Z _e Z _f ³ Z ⁴ Z ⁵ _{g h i} Z ^6] ₁ (I **). contains, - formed with finely divided starting mass A3 geometric moldings V, and - the moldings V thermally treated at elevated temperature to obtain the geometric shaped catalyst bodies K, characterized in that the stoichiometric coefficient c satisfies the condition 0 <c ≤ 0.8 and Z ⁰ is an element or more than one of the group consisting of yttrium and the lanthanides without lanthanum and without cerium. Method according to claim 1, characterized in that that c ≥ 0.001. Method according to claim 1, characterized in that that c ≥ 0.003. Method according to claim 1, characterized in that that c ≥ 0.005. Method according to claim 1, characterized in that that c ≥ 0.01. Method according to one of claims 1 to 5, characterized in that c ≤ 0.7. Method according to one of claims 1 to 5, characterized in that c ≤ 0.6. Method according to one of claims 1 to 5, characterized in that c ≤ 0.5. Method according to claim 1, characterized in that that 0.0005 ≤ c ≤ 0.5 is satisfied. Method according to claim 1, characterized in that that 0.001 ≤ c ≤ 0.4 is satisfied. Method according to claim 1, characterized in that that 0.005 ≤ c ≤ 0.3 is satisfied. Method according to claim 1, characterized in that that 0.01 ≤ c ≤ 0.2 is satisfied. Method according to one of claims 1 to 12, characterized in that a is 0.1 to 4. Method according to one of claims 1 to 12, characterized in that a is 0.1 to 3. Method according to one of claims 1 to 12, characterized in that a is 0.2 to 2. Method according to one of claims 1 to 12, characterized in that a is 0.3 to 1.5. Method according to one of claims 1 to 16, characterized in that at least 10 mol% of the total molar amount of Z ^{1 is} tungsten. Method according to one of claims 1 to 16, characterized in that at least 50 mol% of the total molar amount of Z ^{1 is} tungsten. Method according to one of claims 1 to 16, characterized in that at least 90 mol% of the total molar amount of Z ^{1 is} tungsten. Method according to one of claims 1 to 16, characterized in that the total molar amount of Z ^{1 is} tungsten. Method according to one of claims 1 to 20, characterized in that 1 micron ≤ d A1 / 50 ≤ 50 microns is. Method according to one of claims 1 to 20, characterized in that 1 micron ≤ d A1 / 50 ≤ 10 microns is. Method according to one of claims 1 to 20, characterized in that 1.5 microns ≤ d A1 / 50 ≤ 6 microns is. Method according to one of claims 1 to 20, characterized in that 2 microns ≤ d A1 / 50 ≤ 3 microns is. Method according to one of claims 1 to 24, characterized in that 200 microns ≥ d A2 / 90 ≥ 20 microns. Method according to one of claims 1 to 24, characterized in that 150 microns ≥ d A2 / 90 ≥ 40 microns. Method according to one of claims 1 to 24, characterized in that 100 microns ≥ d A2 / 90 ≥ 50 microns. Method according to one of claims 1 to 27, characterized in that the particle diameter d A2 / 50 of the finely divided Starting mass A2 the condition 10 microns ≤ d A2 / 50 ≤ 100 microns Fulfills. Method according to one of claims 1 to 27, characterized in that the particle diameter d A2 / 50 of the finely divided Starting mass A2 the condition 20 microns ≤ d A2 / 50 ≤ 60 microns Fulfills. Method according to one of claims 1 to 29, characterized in that the ratio of the particle diameter d A2 / 90 of the finely divided starting material A2 to the particle diameter d A2 / 10 of finely divided starting material A2 in the range of 5 to 20. Method according to one of claims 1 to 30, characterized in that d Q / 90 for each of the used Sources ≤ 3 microns. Method according to one of claims 1 to 30, characterized in that d Q / 90 for each of the used Sources ≤ 1 micron. Method according to one of claims 1 to 30, characterized in that d Q / 90 for each of the used Sources ≤ 0.5 microns. Method according to one of claims 1 to 33, characterized in that each of the sources used in Course of preparation of the aqueous mixture M the state undergoes a colloidal or a true solution. Method according to one of claims 1 to 33, characterized in that the proportion T contains the element Si and each of the sources used by the elements other than Silizum in the course of the preparation of the aqueous mixture M den State of a real solution goes through and as Source of the element Si a silica sol is used. Method according to one of claims 1 to 35, characterized in that the finely divided starting material A2 by spray-drying the aqueous mixture M is produced. Method according to one of claims 1 to 35, characterized in that the generation of the finely divided Starting material A2 by drying and dividing the aqueous Mixture M and the mixing of the finely divided starting material A2 with the finely divided starting mass A1 is carried out so that the finely divided starting material A1 in the production of aqueous mixture M in selbige and mixes it resulting total mixture subjected to spray drying. Method according to one of claims 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, is. Method according to one of claims 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Eu, Tm, Yb, Gd, Tb, Dy, Ho and Er. Method according to one of claims 1 to 37, characterized in that Z ^{0 is} an element or more than one element from the group consisting of Y, Ho and Er. Method according to one of claims 1 to 37, characterized in that Z is an element or more than one Element from the group consisting of Gd, Tb and Dy is. Method according to one of claims 1 to 41, characterized in that Z ² = Co. Method according to one of claims 1 to 42, characterized in that Z ³ = K, Cs and / or Sr. Method according to one of claims 1 to 43, characterized in that Z ⁵ = Si. Method according to one of claims 1 to 44, characterized in that b is 0.5 to 3. Method according to one of claims 1 to 44, characterized in that b is 1 to 2.5. Method according to one of claims 1 to 44, characterized in that b is 1.5 to 2.5. Method according to one of claims 1 to 47, characterized in that g> 0 to 0.8, and at least 10 mol% of the total molar amount of Z ^{4 is} the element Bi. Method according to one of claims 1 to 47, characterized in that e is 4 to 7. Method according to one of claims 1 to 49, characterized in that f is 0.03 to 1. Method according to one of claims 1 to 49, characterized in that f is 0.05 to 0.5. Method according to one of claims 1 to 51, characterized in that d is 1 to 4. Method according to one of claims 1 to 52, characterized in that h is 0.1 to 20. Method according to one of claims 1 to 52, characterized in that h is 0.5 to 10. Method according to one of claims 1 to 54, characterized in that the finely divided mixed oxide Bi ₁ W ₂ O is _7.5 . Method according to one of claims 1 to 55, characterized in that the amount F of the product (d A1 50 ) 0.7 · (D A2 90 ) 1.5 · (A -1 ) ≥ 700, whereby the two particle diameters d A1 / 50 and d A2 / 90 are to be specified in the unit of length μm. Method according to claim 56, characterized in that that 820 ≤ F ≤ 5000. Method according to claim 56, characterized in that that 1000 ≤ F ≤ 4000. Method according to one of claims 1 to 58, characterized in that the amount F * of the product (d A1 50 ) 0.7 · (D A2 50 ) 0.7 · (A -1 ) ≥ 15, whereby the two particle diameters d A1 / 50 and d A2 / 50 are to be specified in the unit of length μm. Method according to claim 59, characterized that 35 ≥ F * ≥ 18. Method according to one of claims 1 to 60, characterized in that finely divided starting material A1, finely divided Starting material A2 and finely divided hydrophobized silica comprehensive shaping aids to the finely divided starting material A3 are mixed together. Method according to one of claims 1 to 61, characterized in that finely divided starting material A1, finely divided Starting material A2 and finely divided graphite comprehensive shaping aids to the finely divided starting material A3 are mixed together. Method according to one of claims 1 to 62, characterized in that the shaping of geometric shaped bodies V with finely divided starting mass A3 by compacting the finely divided Starting mass A3 is done. Method according to claim 63, characterized that compacting by extrusion, extrusion or tabletting he follows. Method according to one of claims 1 to 64, characterized in that the geometric shaped body V is a ring. Method according to claim 65, characterized that the side crushing strength SD of the annular shaped body V satisfies the condition 12 N ≦ SD ≦ 25 N. Method according to one of claims 1 to 64, characterized in that the geometric shaped body V is a ball. Method according to one of claims 1 to 64, characterized in that the geometric shaped body V is a solid cylinder. Method according to claim 65 or 66, characterized that the outer diameter = 2 to 10 mm, the height = 2 to 10 mm and the wall thickness of the ring is 1 to 3 mm. Process according to claim 67, characterized in that that the ball diameter is 2 to 10 mm. A method according to claim 68, characterized that the outer diameter = 1 to 10 mm and the height of the solid cylinder 2 to 10 mm. Method according to one of claims 1 to 62, characterized in that the shaping of geometric shaped bodies V with finely divided starting mass A3 is carried out by the finely divided starting mass A3 with the aid of a liquid Binder on the surface of a geometric carrier molding applies. Method according to one of claims 1 to 72, characterized in that in the context of the thermal treatment the molded body V, the temperature exceeded 350 ° C. and the temperature does not exceed 600 ° C. Method according to one of claims 1 to 72, characterized in that in the context of the thermal treatment the molding V the temperature 420 ° C exceeded and the temperature does not exceed 500 ° C. Method according to one of claims 1 to 74, characterized in that the thermal treatment in the presence done by air. Method according to one of claims 1 to 71 or according to one of claims 73 to 75, characterized that the shaped catalyst body K is a Vollkatalysatorformkörper K is and to the process of its preparation a process the grinding to finely divided material connects and from the finely divided material with the aid of a liquid binder on the surface of a geometric carrier molding is applied. Catalyst moldings available according to a method according to one of the claims 1 to 76. Catalyst obtainable by grinding a Catalyst molding of a full catalyst moldings and according to a method according to one of the claims 1 to 71 is available. Process of heterogeneously catalyzed partial Gas phase oxidation of a 3 to 6 carbon atoms-containing alkane, alkanols, Alkanals, alkenes and / or alkenals on a catalyst bed, thereby characterized in that the catalyst bed is a shaped catalyst body according to claim 77 or a catalyst according to claim 78 includes. Method according to claim 79, characterized that it is a method of heterogeneously catalyzed partial gas phase oxidation from propene to acrolein. Method according to claim 79, characterized that it is a method of heterogeneously catalyzed partial gas phase oxidation from isobutene to methacrolein. Method according to claim 79, characterized that it is a process of ammoxidation of propene to acrylonitrile or a process of ammoxidation of isobutene to methacrylonitrile is. Use of a catalyst molding according to claim 77 or a catalyst according to claim 78 as a catalyst in a process of heterogeneously catalyzed partial gas phase oxidation of a 3 to 6 C atoms containing Alkanes, alkanols, alkanals, alkenes and / or alkenals. Use according to claim 83, characterized that they are in a process of heterogeneously catalyzed partial Gas-phase oxidation of propene to acrolein, of isobutene to methacrolein, or in a process of ammoxidation of propene to acrylonitrile or from iso-butene to methacrylonitrile.