JP4868519B2 - Multi-metal oxide material containing Mo, V and alkali metals present in pure phase I - Google Patents

Description

The present invention is directed to general formula I:
A _a [Mo _5-b-c V _b X _c O _d ] ₁ (I)
[Where,
A is at least one element from the group comprising NH ₄ , Na, K, Rb, Cs and Tl;
X is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, Nb, Ta, W, Mn, Re, Fe , Co, Ni, Cr, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, C, Si, Ge, Sn, Pb, P One or more elements from the group comprising As, Sb, Bi, S, Se and Te,
a is 0.1 to 1,
b is 0.25 to 4.5, and c is 0 to 4.5, provided that
b + c is assumed to be 4.5 or less), and the X-ray diffraction pattern of the multi-metal oxide material uses the following X-ray diffraction pattern RM: Lattice spacing d [Å] independent of line wavelength
d [Å]
3.06 ± 0.2
3.17 ± 0.2
3.28 ± 0.2
3.99 ± 0.2
9.82 ± 0.4
11.24 ± 0.4
13.28 ± 0.5
The multi-metal oxide material of general formula I, which is reproduced in the form of

  A multi-metal oxide material containing Mo and V and a lanthanum series, a transition element of the periodic table, and at least two elements selected from the group including elements of the third to sixth main groups of the periodic table, X X-ray diffractograms of said material having a line diffraction pattern RM are known (eg German Offenlegungsschrift 10248584, German Offenlegungsschrift 10254279, German Offenlegungsschrift Publication No. 10051419, German Patent Application Publication No. 10046672, German Patent Application Publication No. 10261186, European Patent Application Publication No. 1090684, German Patent Application Publication No. 198335247 Description, German Patent Application Publication No. 10254278 (Refer to European Patent Application Publication No. 895809, German Patent Application Publication No. 10122027, Japanese Patent Application Laid-Open Nos. 7-232031, and 11-169716).

  In this case, the X-ray diffractogram RM forms a special crystal structure, i.e. an imprint with a finger of a special crystal phase called the "i phase" in the state of the art adopted above.

  From the above description, it is known that the i phase is simply a crystalline phase, in which case such a multi-metal oxide material can be generated.

The second special crystal structure in which such a multi-metal oxide material can be generated is called k phase in the state of the art. According to the above description, the X-ray diffraction pattern of the crystal structure is, inter alia, the following crystal lattice spacing d [Å]:
4.02 ± 0.2
3.16 ± 0.2
2.48 ± 0.2
2.01 ± 0.2 and
1.82 ± 0.1
It is characterized by showing a diffractive reflection representing.

  The i-phase and the k-phase are similar to each other, but are distinguished, inter alia, by the fact that the k-phase X-ray diffractogram usually shows no diffractive reflection for d ≧ 4.2４. In general, the k-phase does not include diffraction reflection within the range of 3.8Å ≧ d ≧ 3.35Å. Furthermore, the k phase generally does not include diffraction reflection within the range of 2.95２ ≧ d ≧ 2.68Å.

  Also, from the prior art description, such multi-metal oxide materials are non-uniform in lower alkanes, alkenes, alcohols and aldehydes (especially having 2, 3 and / or 4 carbon atoms). Activity for catalyst during partial gas phase oxidation contacted and during partial gas phase ammoxidation contacted heterogeneously (essentially distinct from pure partial gas phase oxidation due to the additional presence of ammonia) It is known that it is suitable as a material. In this case, the partial oxidation products are inter alia α, β-monoethylenically unsaturated aldehydes (eg acrolein and methacrolein) and α, β-monoethylenically unsaturated carboxylic acids (eg acrylic acid and methacrylic acid) and The nitrile (for example, acrylonitrile and methacrylonitrile).

  Furthermore, from the description of the above-mentioned known state of the art, the catalytic action (activity, selectivity of formation of the target product) of the multi-metal oxide material having an i-phase structure is different (for example, k-phase). It is known that it is generally superior in comparison.

  However, at least selected from the group including Mo and V, the lanthanum series, the transition elements of the periodic table, and the elements of the 3rd to 6th main groups of the periodic table from the description of the above-mentioned known state of the art. It is known that it is extremely difficult to produce a multi-metal oxide material containing two elements with an i-phase structure.

  That is, according to the known methods described above, in general, only a certain amount of i-phase content (eg with k-phase) is present, and another phase (eg. , K phase) can be obtained by washing away with an appropriate liquid to obtain a mixed crystal system (for example, WO 0206199, JP-A-7-232071 and DE 10254279). Specification).

  Furthermore, from the description of the cited state of the art, according to the known production method, only when the multi-metal oxide so far still contains at least one of the two elements Nb and Te and Sb together with Mo and V. It is known that the i-phase content deserving can be obtained.

  The object of the present invention is therefore to obtain Mo and V and optionally a lanthanum series, a periodic table, which can be obtained in a relatively simple manner with increased i-phase content or as pure i-phase. And a multi-metal oxide material containing one or more elements selected from the group comprising the elements of the third to sixth main groups of the periodic table.

In order to solve the above problems, Nb, W and O are spatially arranged in the i-phase structure according to the description of Ultramicroscopy 52 (1993), pp. 429 to 435, and Cs tunnel-like voids are formed. It was possible to start with Cs _x (Nb, W) ₅ O ₁₄ having a proportion as ensured in the crystal structure of the i phase known from multi-metal oxides.

  From the description of Journal of Solid State of Chemistry 163, pp. 210-217 (2002), vanadium-molybdenum bronze containing K, Rb or Cs is known, in which case this vanadium-molybdenum bronze is i. Has no phase content.

  From the description of Journal of Solid State of Chemistry 162, pages 341 to 346 (2002), tungsten-molybdenum bronze containing K or Cs is known, in which case the tungsten-molybdenum bronze has an i-phase content. Does not have.

From the description in U.S. Pat. No. 6,428,765 B1, it may actually contain elemental combinations Mo and V and alkali metals and / or MH ₄ , but in the examples this elemental combination Mo / V Multiple metal oxides to which V is not added are known.

  Unlike this, the example of US Pat. No. 6,171,571 B1 actually contains the elemental combination Mo / V, but only in combination with a relatively small atomic alkali metal element Li. Contains the elemental combination.

  The presence of the i-phase content cannot be confirmed in both cases.

  Further, the potassium-containing tungsten-niobium bronze disclosed in Chemica Scripta 1988, 28, pages 77 to 80 does not show any i-phase content.

In light of the known prior art, the solutions to the problems of the present invention include Mo and V, and in some cases, lanthanum series, transition elements of the periodic table, and elements of the third to sixth main groups of the periodic table. When the multimetal oxide containing one or more elements from the group comprising is produced by the presence of NH ₄ or an alkali metal having a radius greater than Li, said multimetal oxide is It has been surprising that it has been found that an i-phase content (or exclusively with an i-phase crystal structure) can be obtained with an increased probability.

  Surprisingly, this is also true when Nb or Te or Sb is contained as an accompanying element in the multimetal oxide.

  Actually, European Patent Application Publication No. 12556381, European Patent Application Publication No. 1254708, European Patent Application Publication No. 1254709, European Patent Application Publication No. 1254707 and European Patent Application Publication No. 1254706. The general formula described in the specification does not exclude the presence of alkali metals, but none of the examples in these patent specifications share alkali metals. In other respects, Li is considered as an equally possible alkali metal companion in the patent specification.

Therefore, as a solution to the problem imposed in the above patent specification, the multimetal oxide of the general formula 1 is
A _a [Mo _5-b-c V _b X _c O _d ] ₁ (I)
[Where,
A is at least one element from the group comprising NH ₄ , Na, K, Rb, Cs and Tl;
X is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, Nb, Ta, W, Mn, Re, Fe , Co, Ni, Cr, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, C, Si, Ge, Sn, Pb, P One or more elements from the group comprising As, Sb, Bi, S, Se and Te,
a is from 0.1 to 1, in particular from 0.2 to 0.8, particularly preferably from 0.3 to 0.7, very particularly preferably from 0.4 to 0.6,
b is 0.25 to 4.5, and c is 0 to 4.5, provided that
b + c is assumed to be 4.5 or less], and the X-ray diffraction pattern of the multi-metal oxide shows the following X-ray diffraction pattern RM of the X-ray used. Wavelength independent lattice spacing d [間隔]
d [Å]
3.06 ± 0.2 (preferably ± 0.1)
3.17 ± 0.2 (preferably ± 0.1)
3.28 ± 0.2 (preferably ± 0.1)
3.99 ± 0.2 (preferably ± 0.1)
9.82 ± 0.4 (preferably ± 0.1)
11.24 ± 0.4 (preferably ± 0.1)
13.28 ± 0.5 (preferably ± 0.1)
A multi-metal oxide of general formula I is provided which is reproduced in the form

  From the described diffractive reflection states, the X-ray diffraction pattern RM of the multi-metal oxide material according to the present invention is often (geometric or small in the geometry of contained elements and crystallites). Depending on the plate shape) it has an additional characteristic diffraction reflection intensity.

In relation to the intensity of diffraction reflections representing the lattice spacing d [Å] = 3.99 ± 0.2, the (relative) diffraction reflection intensity I (%) is as follows:
d [Å] I (%)
3.06 ± 0.2 5-65
3.17 ± 0.2 5-65
3.28 ± 0.2 15-130, often 15-95
3.99 ± 0.2 100
9.82 ± 0.4 1-50, often 1-30
11.24 ± 0.4 1-45, often 1-30
13.28 ± 0.5 1-35, often 1-15.

  According to the invention, preferably A is at least one element from the group comprising K, Rb and Cs. Particularly preferably A is Rb and / or Cs, particularly preferably A is Cs.

  X is particularly Ti, Zr, Ta, Cr, W, Mn, Re, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Al, Ga, In, Ge, Sn, Pb, P, One or more elements from the group comprising Sb, Bi, Se and Te.

  Particularly preferably X is one or more elements from the group comprising Ti, Cr, W, Mn, Re, Fe, Co, Ni, Pd, Pt, Cu, Ag, Ga, Sn, Sb and Te. .

  The stoichiometric coefficient c is in particular greater than 0, particularly preferably 0.05 to 4.5, particularly preferably 0.05 to 4.0. The stoichiometric coefficient b is advantageously between 0.5 and 2.5. Furthermore, what has been described below is generally preferred for the multimetal oxides according to the invention.

a is 0.2 to 0.8, in particular 0.3 to 0.7, particularly preferably 0.4 to 0.6.
The measurement of the oxygen content by an experiment can be performed, for example, using a LECO Corporation (USA) oxygen measuring instrument (for example, using TC-436 manufactured by LECO).

  Furthermore, it is indicated that 25 mol% or more, particularly preferably 50 mol% or more, particularly preferably 75 mol% or more or 100 mol% of V contained in the multimetal oxide is oxidation stage +4. Preferred for multiple metal oxides. The experimental test of the oxidation stage of V can be carried out by titration, as described in EP 774297.

In X-ray diffraction patterns representing i-phases for multi-metal oxides according to the invention, together with diffraction reflections exhibiting the characteristics already described, still often the next diffraction reflection depends on the wavelength of the X-ray used as well. Reproduced with the shape of the lattice spacing d [Å] not recognized:
d [Å]
8.19 ± 0.3 (preferably ± 0.15)
3.51 ± 0.2 (preferably ± 0.1)
3.42 ± 0.2 (preferably ± 0.1)
3.34 ± 0.2 (preferably ± 0.1)
2.94 ± 0.2 (preferably ± 0.1)
2.86 ± 0.2 (preferably ± 0.1).

In relation to the intensity of diffraction reflections representing the lattice spacing d [Å] = 3.99 ± 0.2, the (relative) diffraction reflection intensity I (%) is as follows:
d [Å] I (%)
8.19 ± 0.3 (or ± 0.15) 0-25
3.51 ± 0.2 (or ± 0.1) 2-50
3.42 ± 0.2 (or ± 0.1) 5 to 75
3.34 ± 0.2 (or ± 0.1) 5-80
2.94 ± 0.2 (or ± 0.1) 5-55
2.86 ± 0.2 (or ± 0.1) 5-60.

Often still the following diffraction reflections complement the X-ray diffraction pattern representing the i phase:
d [Å]
2.54 ± 0.2 (preferably ± 0.1)
2.01 ± 0.2 (preferably ± 0.1).

The relevant (relative) diffracted reflection intensities in the same way as described above are often as follows in the case of the diffracted reflection:
d [Å] I (%)
2.54 ± 0.2 (or ± 0.1) 0.5-40
2.01 ± 0.2 (or ± 0.1) 5-60.

  According to the present invention, preferably, in the X-ray diffraction diagram of the multimetal oxide according to the present invention, the lattice spacing d [間隔] = 3.99 ± 0.2 (or ± 0.1) or the lattice spacing. A multi-metal oxide according to the present invention in which the diffraction reflection representing d [Å] = 3.28 ± 0.2 (or 0.1) is the strongest (highest intensity) diffraction reflection.

  Further, a multiple metal oxide having a 2Θ half-value width of diffraction reflection of d [Å] = 3.99 ± 0.2 (or ± 0.1) of 1 ° or less, particularly 0.5 ° or less is preferable. The 2Θ half-width of another described diffraction reflection is usually 3 ° or less, in particular 1.5 ° or less, particularly preferably 1 ° or less.

  All statements relating to X-ray diffractograms herein are attributed to X-ray diffractograms generated as X-rays using Cu-Kα rays (λ = 1.54178Å) (Siemens-Diffraktometer Theta-Theta D-5000, tube voltage: 40 kV, tube current: 40 mA, aperture diaphragm V20 (variable), scattered light diaphragm V20 (variable), secondary monochromator diaphragm (0.1 mm), detector diaphragm (0.6 mm) ), Measurement interval (2Θ): 0.02 °, measurement time per process: 2.4 seconds, detector: scintillation counter tube; definition of intensity of diffraction reflection in X-ray diffractogram is German in this specification Federal Patent Application Publication No. 19835247, German Patent Application Publication No. 10122027 and German Patent Application Publication No. 10051419 and German Federation Connection with the definition set forth in the Republic Patent Application Publication No. during 10046672 Pat; same applies to the definition of 2Θ FWHM.

The X-ray wavelength A and diffraction angle Θ used for diffraction (diffractive reflection position is the reflection vertex in the 2Θ plot used in this specification) is expressed by the following Bragg relation: Are associated with each other:
2sinΘ = λ / d
In this case, d is the lattice spacing of the atomic space arrangement belonging to each diffraction reflection.

  The production of multimetal oxide materials according to the present invention generally produces a dry mixture (desired stoichiometric component) that is as dense as possible, in particular a finely divided dry component (desired stoichiometric component), from a suitable source of elemental components of the multimetal oxide material, This dry mixture is thermally treated at 350-1000 ° C or 400-700 ° C or 400-650 ° C or 400-600 ° C.

  In principle, the thermal treatment can be carried out in an oxidizing atmosphere, a reducing atmosphere or an inert atmosphere. Examples of the oxidizing atmosphere include air, air with an increased molecular oxygen content, or air with a reduced oxygen content. However, advantageously, the thermal treatment is carried out under an inert atmosphere, ie for example under molecular nitrogen and / or noble gases. Usually, the thermal treatment is performed at normal pressure (1 atm). Of course, the thermal treatment can also be carried out under vacuum or overpressure.

  When the thermal treatment is performed in a gaseous atmosphere, the atmosphere may be stationary or fluidized. Advantageously, this atmosphere is fluid. Overall thermal treatment can be applied up to 24 hours or more.

  Preferably, the thermal treatment is first carried out under an oxidizing (containing oxygen) atmosphere (under oxygen) at a temperature of 150-400 ° C. or 250-350 ° C. (= pre-decomposition step). Following this, the thermal treatment proceeds preferably at a temperature of 350 to 1000 ° C. or 400 to 700 ° C. or 400 to 650 ° C. or 400 to 600 ° C. under inert gas.

  Intimate mixing of the starting compounds can be done in dry or wet form.

  When the mixing is carried out in dry form, the starting compound is preferably used as a finely divided powder and subjected to calcination (thermal treatment) after mixing and optionally pressing.

  However, advantageously, intimate mixing takes place in wet form. In this case, the starting compounds are usually mixed with one another in the form of an aqueous solution (possibly in the presence of a complexing agent; for example, DE 10145958) and / or in the form of a suspension. The The aqueous material is subsequently dried and calcined after drying. Preferably, the aqueous material is an aqueous solution or an aqueous suspension. In particular, the drying process directly involves the preparation of an aqueous mixture (especially in the case of aqueous solutions; see, for example, JP-A-7-315842). In the case of liquids, it is carried out by spray drying (exit temperature is generally between 100 and 150 ° C .; spray drying can be carried out in cocurrent or countercurrent), inducing a particularly tight dry mixture. However, the aqueous material may also be dried by evaporation in a vacuum, freeze spraying, freeze drying or conventional evaporation.

  Preference is also given to the production of multimetal oxides according to the invention by the hydrothermal method, as described, for example, in DE 100 03 338 A1 and JP 12-143244 A.

  Oxides and / or hydroxides during heating (possibly with air) within the scope of the implementation of the above-described method for producing multi-metal oxide materials according to the invention as a source for elemental constituents This is the case for all sources that can form It is self-evident that the oxides and / or hydroxides of the elemental constituents can already be shared or used exclusively as such starting compounds. That is, in particular, all the starting compounds described in the patent specifications of the known state of the art that have been justified.

  Sources for elemental Mo that are more suitable according to the invention are, for example, molybdenum oxides such as molybdenum trioxide, molybdates such as ammonium heptamolybdate tetrahydrate and molybdenum halides such as molybdenum chloride.

Suitable starting compounds for element V that can be shared according to the invention are, for example, vanadium oxysulfate hydrate, vanadyl acetylacetonate, vanadate, such as ammonium metavanadate, vanadium oxide, such as pentoxide Vanadine (V ₂ O ₅ ), vanadium halides such as vanadium tetrachloride (VCl ₄ ) and vanadium oxyhalides such as VOCl ₃ . In this case, a vanadium starting compound containing vanadium in the oxidation step +4 may be used as the vanadium starting compound.

  According to the invention, it is advantageous to use, as a source for element V, a mixture of a compound containing element V in the oxidation stage +5 and elemental vanadine. Furthermore, a preferred average oxidation stage +4 according to the invention of V can be formed from the mixture at the latest during calcination.

When a compound containing exclusively V in the oxidation stage +5 is used as the source of V, according to the invention, starting compounds containing a reducing agent different from elemental vanadium are used together (for example , NH ₄ ⁺ or its decomposition product NH ₃ ), and the ability to reduce the starting compound of V ⁵⁺ to V ⁴⁺ is preferred. Such reducing agents are succinic acid, succinate (eg, as nioboxalate), hydrazine dihydrochloride, hydrazine sulfate, hydrazine (monohydrate), hydroxylamine, hydroxylamine hydrochloride or a salt thereof. Good. In particular, the preparation of an intimate dry mixture takes place under an inert gas atmosphere (eg N ₂ ), and the oxidation process ensures even better control.

Suitable sources of elemental tellurium are tellurium oxides according to the invention, such as tellurium dioxide, metallic tellurium, tellurium halides, such as TeCl _2, but telluric acids, such as orthotelluric acid H ₆ TeO ₆ are also suitable. is there. Also, elemental tellurium or another component may be shared as a reducing agent (eg for V ⁵⁺ ) in the form of an element (eg antimony, iron, samarium, zinc, aluminum, arsenic) It is self-evident.

Further preferred antimony starting compounds are antimony halides such as SbCl ₃ , antimony oxides such as antimony trioxide (Sb ₂ O ₃ ), antimonic acids such as HSb (OH) ₆ , but antimony oxides, For example, antimony oxide sulfate (SbO) ₂ SO ₄ is also preferable.

Suitable niobium sources according to the invention are, for example, niobium oxides such as niobium pentoxide (Nb ₂ O ₅ ), niobium oxide halides such as NbOCl ₃ , niobium halides such as NbCl ₅ , but niobium and organic Preference is also given to complex compounds consisting of carboxylic acids and / or dicarboxylic acids such as oxalates and alcoholates. It is obvious that the solution containing Nb used in EP-A-895809 as a niobium source also falls under this category.

  In connection with all other possible elements (in particular Fe, Pb, Ni, Cu, Co, Bi and Pd and alkali metal elements), suitable starting compounds include, inter alia, halides, nitrates, formic acid of the compounds. This includes salts, oxalates, acetates, bicarbonates, carbonates and / or hydroxides. Suitable starting compounds are often their oxo compounds, such as tungstates or acids derived from these oxo compounds. Often ammonium salts are also used as starting compounds.

  Further, as the starting compound, an Anderson type polyanion described in, for example, Polyhedron Vol. 6, No. 2, pp. 213 to 218, 1987 corresponds to this. Another publication source suitable for Anderson type polyanions is Kinetics and Catalysis, Vol. 40, No. 3, 1999, pages 401-404.

  Another polyanion suitable as starting compound is, for example, a polyanion of the Dawson structure type or the Keggin structure type. Advantageously, starting compounds are used which are converted to oxides at elevated temperatures in the presence of oxygen or in the absence of oxygen, optionally with the release of gaseous compounds.

  It is obvious that the teachings of Japanese Patent Application Laid-Open No. 8-57319 and European Patent Application No. 1254707 can be used for the multi-metal oxide material according to the present invention. For example, the catalytic performance (activity and selectivity of target product formation) of multi-metal oxide materials containing Mo and V can be improved by treatment with a suitable liquid, such as an acid.

  Examples of such liquids include organic acids and inorganic acids and aqueous solutions thereof (for example, oxalic acid, formic acid, acetic acid, citric acid, tartaric acid, nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, telluric acid, boric acid. And mixtures thereof and aqueous solutions), but alcohols, alcoholic solutions of said acids and aqueous hydrogen peroxide solutions also apply to this.

  Notably, such washing increases the i-phase content when the multimetal oxide according to the invention is phase inhomogeneous (another phase, for example the k phase, is advantageously eliminated). ).

  Furthermore, such cleaning generally reduces the content of the multi-metal oxide material according to the invention with respect to the element A relative to the Mo content, in this case formed in the multi-metal oxide material. The i phase is not impaired.

  The subsequent reduction in the content of the multimetal oxide material according to the invention relative to the element A with respect to the Mo content is due to the fact that this multimetal oxide material is advantageously extracted with a liquid capable of absorbing the element A. Is also possible. Such a liquid is a liquid containing a complexing agent (for example, crown ether) for the element A, for example. However, of course, as such a liquid, a solution of an inorganic salt, a molten solution of the salt, or an ionic liquid may be used.

Said treatment of the multi-metal oxide according to the invention with a suitable liquid or salt melt can be carried out at a temperature of 20 to 600 ° C., or 400 ° C., or 40 to 380 ° C. or 45 to 100 ° C., among others. A) Nb free, b) Te free, c) Sb free, d) Nb and Te free, or e) Nb free and Sb free Multiple metal oxides are important. Usually, the treatment is performed under normal pressure, and several hours to several days are applied. In the case of treatment with a solution, it is operated in particular under reflux. Finally, it is usually washed with water.

  According to the invention, the ratio [5-bc] / a is preferably increased by at least 5%, in particular at least 25%, particularly preferably at least 50%, very particularly preferably at least 75% (to the starting value). In contrast, as long as the ratio of [5-bc] / a increases below 200% or below 100%), the content of element A is subsequently removed from the multimetal oxide according to the invention. The element A may be removed afterwards from the multi-metal oxide material according to the invention in the same way as described above, in which case it does not cause a measurable structural change. . For economic reasons, complete removal of element A is often not performed.

  The multimetal oxides according to the invention are either as such (material 1) or after partial or complete removal of the element A (material 2) contained in the multimetal oxide, ie of the promoter element compound. Used as active material for the catalyst after impregnation of material 1 or material 2 in solution (eg aqueous), drying and reheat treatment (preferably in an inert gas stream and especially without pre-decomposition with air) It's okay. Advantageously, a solution of the elements Pb, Ni, Co, Bi, Pd, Ag, Pt, Cu, Au, Ga, Zn, Sn, In, Re, Ir, Sm, Sc, Y, Pr, Nd and Tb Impregnation. The last Tb is particularly preferred when the multi-metal oxide to be impregnated still does not contain the element. Preferably, such impregnation uses an aqueous nitrate and / or halide solution of the element or the element is present in a complex with an organic compound (eg acetate or acetylacetonate). Such an aqueous solution is used.

  In this case, the use as an active material for the catalyst may be carried out in the form of a powder or may be carried out after being transformed into a shaped body. In this case, the catalyst bed can be a fixed bed, a moving bed or a vortex bed.

  The deformation to the shaped body can be carried out on the support in the same way as described, for example, in DE 101 18 814 or PCT / EP / 02/04073 or DE 100 51 419 A1. It can be done by bringing.

  Supports which can be used for this are in particular chemically inert. That is, the carrier is essentially unaffected during the course of partial catalytic gas phase oxidation and is essentially essential during the course of partial catalytic gas phase ammoxidation contacted by the active material. It does not affect.

  As materials for the support, according to the invention, in particular aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite (preferably with a slight alkali metal content which is soluble in water), pumice This includes aluminum silicate and magnesium silicate, silicon carbonate, zirconium dioxide and thorium dioxide.

  The surface of the carrier may be smooth or rough. Preferably, the surface of the carrier is a rough surface. This is because the increased surface roughness generally causes an increased adhesion strength of the applied active material shell.

  Often the surface roughness Rz of the support is in the range of 5 to 200, in particular in the range of 20 to 100 μm (using the “Hommel tester for DIN-ISO surface measurements” from Hommelwerke, Germany). DIN 4768 Measured as described on page 1).

  Furthermore, the support material may be porous or non-porous. Preferably, the support material is non-porous (the total volume of pores with respect to the volume of the support was 1% by volume or less).

  The thickness of the active oxide material shell present on the shell catalyst according to the invention is usually 10 to 100 μm. However, the thickness may be 50 to 700 μm, 100 to 600 μm, or 150 to 400 μm. Possible outer shell thicknesses are 10 to 500 μm, 100 to 500 μm, or 150 to 300 μm.

  In principle, any geometric dimension of the carrier corresponds to the method according to the invention. The longitudinal extension of said geometric dimensions is generally 1-10 mm. However, preferably a sphere or cylinder, in particular a hollow cylinder, is used as the carrier. An advantageous diameter for the support sphere is 1.5 to 4 mm. When a cylindrical body is used as a carrier, the length of this carrier is in particular 2 to 10 mm, and its outer diameter is 4 to 10 mm. Further, in the case of an annular body, the wall thickness is usually 1 to 4 mm. An annular carrier suitable according to the invention may have a length of 3-6 mm, an outer diameter of 4-8 mm and a wall thickness of 1-2 mm. However, an annular geometric dimension of the carrier of 7 mm × 3 mm × 4 mm or 5 mm × 3 mm × 2 mm (outer diameter × length × inner diameter) is also possible.

  The production of such a shell catalyst is the simplest method, in which the active material is preformed, the active material is converted into a particulate form, and finally applied on the surface of the support using a liquid bond. It can be done in this way. For this purpose, the surface of the carrier is wetted with a liquid binder in the simplest way, and the layer of active material is kept on the wetted surface by contact with the finely divided active material. Finally, the coated carrier is dried. It is self-evident that the method is repeated periodically to achieve an increased layer thickness. In this case, the coated substrate is transformed into a new “carrier” or the like.

  The fineness of the catalytically active oxide material to be applied on the surface of the support is of course adapted to the desired shell thickness. For example, an active material powder in which at least 50% of the total number of powder particles yields a sieve with an opening of 1-20 μm and the numerical proportion of particles having a longitudinal elongation of more than 50 μm is less than 10% , Suitable for an outer shell thickness range of 100 to 500 μm. In general, the distribution of elongation in the longitudinal direction of the powder particles corresponds to a Gaussian distribution depending on the production. Often the particle size distribution is as follows:

in this case:
D is the diameter of the particle,
x is the percentage of particles with a diameter greater than or equal to D; and y is the percentage of particles with a diameter less than D.

  In order to carry out the described coating method on an industrial scale, for example, the principle of the method disclosed in DE-A-2909671 as well as in DE-A-10051419 is disclosed. The use of the principle of the method is desirable, i.e. the support which can be coated is particularly inclined (inclination angles are generally greater than 0 ° and less than 90 °, in many cases greater than 30 ° and less than 90 °; The tilt angle is charged into a rotating rotating container (for example a rotating drum or a sugar coating drum) which is the angle of the axis of the rotating container means relative to the horizontal direction. A rotating rotating container allows, for example, a spherical or cylindrical carrier to pass under two metering devices arranged successively at a certain distance. The first metering device of the two metering devices advantageously corresponds to a nozzle (for example a spray nozzle operated with compressed air), by which the carrier rolling in the rotating rotating drum is: Sprayed with liquid binder, controlled and wetted. The second metering device is outside the spray cone of the injected liquid binder and is used to supply finely divided oxide active material (for example by means of a shaking groove or a powder screw). ). The controlled and moistened support spheres absorb the supplied active material powder, which is compressed by rolling on the outer surface of a cylindrical or spherical carrier, for example, and turns into an associated outer shell .

  If necessary, if the carrier thus essentially coated passes through the spray nozzle again during the subsequent rotation, another layer of finely divided oxide active material is formed during the course of the retransfer. It is controlled and wetted so that it can be housed, etc. (intermediate drying is generally unnecessary). In this case, the finely divided oxide active material and the liquid binder are generally fed simultaneously and continuously.

The removal of the liquid binder can be carried out after the coating has ended, for example by the action of a hot gas, for example N ₂ or air. Notably, the described coating method results in a completely satisfactory deposition of successive layers on each other as well as a completely satisfactory deposition of the basic layer on the surface of the support.

  Essential to the above-described coating method is that the wetting of the surface to be coated of the carrier is performed in a controlled manner. In simple terms, the carrier surface preferably has the carrier surface actually absorbing the liquid binder, but on the carrier surface, the liquid phase itself is visible. Not appearing in When the support surface is wetted, the finely divided catalytically active oxide material agglomerates and turns into separate aggregates instead of being wicked onto the surface. Detailed descriptions for this are found in German Offenlegungsschrift 2,909,671 and German Offenlegungsschrift 10051419. Said final removal of the liquid binder used can be carried out in a controlled manner, for example by evaporation and / or sublimation. In the simplest case, this removal can be effected by acting on a hot gas at a corresponding temperature (often 50-300 ° C., in particular 150 ° C.). However, only pre-drying can be caused by the action of hot gas. Furthermore, the final drying can be carried out in any kind of drying oven (for example a belt dryer) or in a reactor. In this case, the working temperature must not exceed the maximum calcination temperature used in the production of the oxide active material. Of course, the drying may be carried out exclusively in a drying oven.

  As binders for the coating process, the following may be used regardless of the type and geometric dimensions of the support: water, monohydric alcohols such as ethanol, methanol, propanol and butanol, polyhydric alcohols, For example, ethylene glycol, 1,4-butanediol, 1,6-hexanediol or glycerin, monovalent or polyvalent organic carboxylic acids such as propionic acid, succinic acid, malonic acid, glutaric acid or maleic acid, amino alcohols such as ethanol Amines or diethanolamines and mono- or polyvalent organic amides such as formamide. An advantageous binder is a solution composed of 20 to 90% by mass of water and 10 to 80% by mass of an organic compound dissolved in water. In this case, the boiling point or sublimation temperature of the organic compound is normal pressure (1 atm). ) Over 100 ° C., in particular over 150 ° C. Advantageously, the organic compound is selected from possible organic binders from the above description. In particular, the organic content of the aqueous binder solution is 10-50% by weight, particularly preferably 20-30% by weight. In this case, examples of the organic component include polysaccharides and oligopolysaccharides such as glucose, fructose, saccharose or lactose, and polyethylene oxide and polyacrylate.

  What is important is that the production of the outer catalyst can not only be carried out by application of the finished finely divided active oxide material onto the wet support surface.

  Rather, instead of the active oxide material, a particulate precursor material of this active oxide material can be applied (using the same coating method and binder) onto the wet support surface, Calcination can be carried out after drying the coated support (and the support can be impregnated with the precursor solution and then dried and subsequently calcined). Finally, if necessary, the phase different from the i phase and / or the element A can be washed away.

  Such a finely divided precursor material can be produced, for example, as closely as possible from the source of the elemental component of the desired active oxide material, in particular a finely divided dry mixture (for example an aqueous suspension of the source). Or by spray-drying the solution) and thermally treating this finely divided dry mixture at a temperature of 150-350 ° C., in particular 250-350 ° C., in an oxidizing (oxygen-containing) atmosphere (eg under air) This is the case for materials that can be finally obtained by pulverizing if necessary.

  Further, after coating the support with the precursor material, preferably 350-1000 ° C., or 400-700 ° C. or 400-650 ° C. or 400-600 ° C. under an inert gas atmosphere (all other atmospheres apply) Calcined at a temperature of.

  Of course, the active material can be shaped by extrusion and / or pelletization of the finely divided active material and the finely divided precursor material of the active material (if necessary, a phase different from the i phase and / or Or the element can be washed away finally.)

  The geometric shapes of the complete catalyst that can be obtained in this case include spheres, solid cylinders and hollow cylinders (annular bodies). In this case, the elongation in the longitudinal direction of the geometrical body is generally 1 to 10 mm. In the case of a cylindrical body, the length of this cylindrical body is in particular 2 to 10 mm and its outer diameter is 4 to 10 mm. Further, in the case of an annular body, the wall thickness is usually 1 to 4 mm. An annular complete catalyst suitable according to the invention may have a length of 3 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm. However, an annular geometric dimension of a complete catalyst of 7 mm x 3 mm x 4 mm or 5 mm x 3 mm x 2 mm (outer diameter x length x inner diameter) is also possible.

  Of course, the geometric dimensions described in German Offenlegungsschrift 10101695 also apply to this.

  Of course, the active material may be used as the catalytically active material in a form that is diluted with a particulate, for example, colloidal material such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, niobium oxide. In this case, the diluent may be incorporated in the active material or in the precursor material of the active material.

  The active materials described herein are saturated and / or unsaturated hydrocarbons and saturated (modified in powder form or modified into geometric shaped, undiluted or diluted). Suitable as active material for partial gas phase oxidation and / or partial gas phase ammoxidation of aldehydes and / or unsaturated aldehydes with heterogeneous catalysts.

  Such saturated and / or unsaturated hydrocarbons are in particular ethane, ethylene, propane, propylene, n-butane, isobutane and isobutene. In this case, the target products are inter alia acetic acid, vinyl acetate, acrolein, acrylic acid, methacrolein, methacrylic acid, acrylonitrile and methacrylonitrile. However, the target products are also suitable for the partial gas phase oxidation and / or partial gas phase ammoxidation of compounds such as acrolein and methacrolein with heterogeneous catalysts.

  However, ethylene, propylene and n-butene and isobutene may also be target products.

In this specification, the complete oxidation of the hydrocarbon means that the carbon contained entirely in the hydrocarbon is converted into an oxide of carbon (CO, CO ₂ ).

  All other reactions of hydrocarbons under the reaction of molecular oxygen which are different from this are subsumed here together with the concept of partial oxidation. The additional reaction of ammonia indicates partial ammoxidation.

  Advantageously, the active materials described herein contain n-butane to maleic anhydride conversion, propane to acrolein and / or acrylic acid, propane to acrylic acid and / or acrylonitrile. , Conversion of propylene to acrolein and / or acrylic acid, conversion of propylene to acrylic acid, conversion of isobutane to methacrolein and / or methacrylic acid, conversion of isobutane to methacrylic acid and / or methacrylonitrile, isobutene to methacrole Conversion of rhein and / or methacrylic acid, conversion of isobutene to methacrylic acid and / or methacrylonitrile, conversion of ethane to ethylene, conversion of ethane to acetic acid and / or vinyl acetate and ethylene to acetic acid and / or Is suitable as catalytically active material for conversion to vinyl acetate.

  Such partial oxidation and / or partial ammoxidation (depending on the choice of the content of ammonia in the reaction gas mixture, which can be controlled in a manner known per se, the reaction is essentially exclusively as partial oxidation or exclusively. The implementation of partial ammoxidation or as an overlap of two reactions; see, for example, WO 98/22421) is known per se by multi-metal oxide materials containing i-phase / k-phase in the state of the art Can be carried out in a completely corresponding manner.

  Moreover, it can carry out similarly to the method as described in the Federal Republic of Germany patent application publication 10254279 specification.

  If crude propane or crude propylene is used as the hydrocarbon, these hydrocarbons can be obtained from German Offenlegungsschrift 10246119 or German Offenlegungsschrift 10118814, or PCT / EP / The configuration is the same as described in 02/04073. Similarly, it is preferably carried out in the same manner as described in the above specification.

  The partial oxidation of propane to acrylic acid is the same as described in the multiple metal oxide materials EP 608838, WO 0029106, JP 10-36311 and EP 1192987. May be implemented.

  As source for the required molecular oxygen, for example, air, air with an increased oxygen content or air with a reduced oxygen content or pure oxygen may be used.

Such a process is preferred when the reaction gas starting mixture does not contain a noble gas content, in particular no helium content as an inert diluent gas, which exceeds the noble gas content of air. In other respects, the reaction gas starting mixture can of course contain inert diluent gases such as N ₂ , CO and CO ₂ along with propane and molecular oxygen. Steam according to the reaction gas mixture component is preferred according to the invention.

That is, a reactive gas which can be loaded with an active material according to the invention, for example, at a reaction temperature of 200-550 ° C., or 230-480 ° C. or a reaction temperature of 300-440 ° C. and a pressure of 1-10 bar or 2-5 bar. The starting mixture can have, for example, the following composition:
1-15 vol% propane, especially 1-7 vol%,
44-99% by volume of air and 0-55% by volume of water vapor.

  Preference is given to reaction gas starting mixtures containing water vapor.

Another possible composition of the reaction gas starting mixture is the following:
70-95% by volume of propane,
5-30% by volume of molecular air and 0-25% by volume of water vapor.

Of course, in the case of such a method, a product gas mixture that is not exclusively formed from acrylic acid can be obtained. Rather, the product gas mixture contains by-products such as propene, acrolein, CO ₂ , CO, H ₂ O, acetic acid, propionic acid, etc. along with unreacted propane, from among these by-products, Acrylic acid must be separated.

  This separation can be carried out by methods known from gas phase oxidation of propene to acrylic acid with heterogeneous catalysts.

  However, the multimetal oxide material according to the present invention may be incorporated in another multimetal oxide material (for example, this multimetal oxide material is mixed, optionally compressed and calcined) Or mixed as silt (especially aqueous), dried and calcined (eg as described in the multi-metal oxide material described in EP-A-529853). Preferably, it is calcined again under an inert gas.

Examples and Comparative Examples Comparative Example 1 [Mo _3.8 V ⁴⁺ _1.2 O _13.8 ]
In 6000 ml of water, 115.5 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.96 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 671.1 g of ammonium heptamolybdate tetrahydrate from HC Starck (MoO ₃ content = 81.5% by weight; Mo 3.8 mol) under stirring while maintaining 80 ° C. and nitrogen washing in this solution Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Subsequently, it was spray dried in a spray dryer from Nitro (Nitro, DK spray dryer Niro A / S atomizer, transportable Minor device, centrifugal sprayer). The charge temperature was 60 ° C. The gas inlet temperature ^Tein was 370 ° C., and the gas outlet temperature ^Taus was 105 ° C.

  100 g of the spray powder obtained are obtained for 25 minutes under a flow of 50 Nl / h in a rotating ball furnace (1 l internal volume) as described in FIG. Heated to 275 ° C. using a linear ramp at 0 ° C., then maintained at 275 ° C. for 30 minutes while maintaining airflow. Subsequently, the air flow was changed by a nitrogen flow of 50 Nl / h and heated linearly over 16 minutes from 275 ° C. to 575 ° C. and maintained at this temperature for 360 minutes while maintaining the nitrogen flow. Subsequently, it was cooled to 25 ° C. while maintaining a nitrogen flow. FIG. 1 shows the X-ray diffraction diagram to which it belongs. This X-ray diffractogram does not have an i-phase content.

Example 1 Cs _0.5 [Mo _3.8 V ⁴⁺ _1.2 O _14.05 ] ₁
Manufacture was performed in the same manner as in Comparative Example 1. After the end of 12 hours of stirring the dark blue-black aqueous suspension at 60 ° C., while maintaining the 60 ° C. Chem Pur Co., 76204Karlsruhe standing, of _{Cs 2 CO 3 81.5g (100%} ; Cs 0.5 Mol) was added and subsequently stirred at 60 ° C. for 1 hour (all under nitrogen wash). Thereafter, spray drying and heat treatment were carried out in the same manner as described in Comparative Example 1. FIG. 2 shows the X-ray diffraction pattern belonging to Example 1 of the resulting active material. This active material exhibits an almost pure i phase. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.33 8
11.29 18
9.86 19
8.20 6
3.998 100
3.527 22
3.412 45
3.345 56
3.282 104
3.170 43
3.062 38
2.939 24
2.861 35.

Comparative Example 2 [Mo _3.5 V ^{4 +} ₁ W _0.5 O ₁₄ ]
In 6000 ml of water, 115.5 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.96 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 741.8 g of ammonium heptamolybdate tetrahydrate of HC Starck (MoO ₃ content = 81.5% by mass; Mo 4.2 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, 156.5 g (WO ₃ content = 88.90 mass%; W 0.6 mol) of ammonium paratungstate heptahydrate from HC Starck was added while maintaining the temperature at 60 ° C. in the course of nitrogen cleaning. Stir for 1 hour.

  The obtained aqueous suspension was spray-dried in the same manner as in Comparative Example 1. In this case, 100 g of the obtained spray powder was transferred to a rotating ball furnace (1) shown in FIG. 1 of German Patent Application No. 10122027. heated to 275 ° C. using a linear ramp at 25 ° C. for 50 minutes under an air flow of 50 Nl / h in an internal volume of l) and then maintained at 275 ° C. for 30 minutes while maintaining the air flow did. Subsequently, the air flow was changed by a nitrogen flow of 50 Nl / h and was heated linearly from 275 ° C. to 600 ° C. in 15 minutes and maintained at this temperature for 360 minutes while maintaining the nitrogen flow. Subsequently, it was cooled to 25 ° C. while maintaining a nitrogen flow. FIG. 3 shows the X-ray diffraction diagram to which it belongs. This X-ray diffractogram does not have an i-phase content.

Example 2 Cs _0.5 [Mo _3.4 V ⁴⁺ _1.2 W _0.4 O ₁₄ ] ₁
In 6000 ml of water, 115.5 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.96 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 600.5 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by mass; Mo 3.4 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution. Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, 104.3 g of ammonium paratungstate heptahydrate (WO ₃ content = 88.90% by mass; W 0.4 mol) of HC Starck was added while maintaining the temperature at 60 ° C. while the nitrogen cleaning was in progress. Stir for 1 hour. Thereafter, 81.46 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur, 76204 Karlsruhe was added while maintaining nitrogen cleaning and 60 ° C., and further stirred for 1 hour. The resulting aqueous suspension was spray dried as in Comparative Example 1. Subsequently, 100 g of the spray-dried product was heat-treated in the same manner as in Comparative Example 2. FIG. 4 shows an X-ray diffractogram belonging to 2 in an example of the resulting active material. This active material exhibits an almost pure i phase. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.29 11
11.19 24
9.79 24
8.16 8
3.966 100
3.524 20
3.405 39
3.345 48
3.283 90
3.173 39
3.060 38
2.937 28
2.859 35.

Example 3 Cs _0.5 [Mo _3.5 V ^{4 +} ₁ Te _0.5 O ₁₄ ] ₁
In 6000 ml of water, 96.2 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.8 mol) of HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 618.2 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by mass; Mo 3.5 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution Was dissolved. In this clear aqueous solution, 10.19 g (V100%; V ^{± 0} 0.2 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, 114.82 g of Fluka's Te acid (CH-9471 Buchs, 100%; Te 0.5 mol) was first added while maintaining the temperature at 60 ° C. in the course of nitrogen washing, and further stirred for 1 hour. Next, 81.5 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur was added while maintaining the limit conditions, and the mixture was further stirred for 1 hour.

  The obtained aqueous suspension was spray-dried in the same manner as in Comparative Example 1. In this case, 100 g of the obtained spray powder was transferred to a rotating ball furnace (1) shown in FIG. 1 of German Patent Application No. 10122027. heated to 275 ° C. using a linear ramp at 25 ° C. for 50 minutes under an air flow of 50 Nl / h in an internal volume of l) and then maintained at 275 ° C. for 30 minutes while maintaining the air flow did.

Subsequently, the air flow was changed by a nitrogen flow of 50 Nl / h and heated from 275 ° C. to 600 ° C. in 17 minutes and maintained at this temperature for 360 minutes while maintaining the nitrogen flow. Subsequently, it was cooled to 25 ° C. while maintaining a nitrogen flow. FIG. 5 shows the X-ray diffraction pattern belonging to Example 3 of the active material. This X-ray diffractogram shows an important i-phase content. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.29 7
11.22 17
9.80 20
8.27 4
4.000 100
3.520 20
3.394 38
3.341 38
3.275 62
3.170 29
3.058 30
2.930 20
2.856 24.

Example 4 Cs _0.5 [Mo _3.7 V ⁴⁺ _1.2 Se _0.1 O ₁₄ ] ₁
In 6000 ml of water, 115.5 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.96 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 653.5 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by mass; Mo 3.7 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution. Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, 12.9 g (CH-9471 Buchs, 100%; Se 0.1 mol) of Fluka's selenic acid (H ₂ SeO ₃ ) was first added while maintaining the temperature at 60 ° C. in the course of nitrogen cleaning. Stir further. Next, 81.5 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur was added while maintaining the limit conditions, and the mixture was further stirred for 1 hour. The obtained aqueous suspension was spray-dried in the same manner as in Comparative Example 1. In this case, 100 g of the obtained spray powder was transferred to a rotating ball furnace (1) shown in FIG. 1 of German Patent Application No. 10122027. heated to 275 ° C. using a linear ramp at 25 ° C. for 50 minutes under an air flow of 50 Nl / h in an internal volume of l) and then maintained at 275 ° C. for 30 minutes while maintaining the air flow did. Subsequently, the air flow was changed by a nitrogen flow of 50 Nl / h and heated from 275 ° C. to 650 ° C. in 20 minutes and maintained at this temperature for 360 minutes while maintaining the nitrogen flow. Subsequently, it was cooled to 25 ° C. while maintaining a nitrogen flow. The X-ray diffraction pattern to which the active material belongs shows an important i-phase content. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.23 7
11.24 18
9.82 15
8.16 7
3.998 100
3.528 24
3.401 40
3.347 57
3.281 85
3.170 39
3.060 32
2.938 25
2.860 31.

Example 5 Cs _0.5 [Mo _3.5 V ⁴⁺ ₁ Sb _0.5 O ₁₄ ] ₁
Dissolve 120.3 g of HC Starck ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V 5 ⁺ 1 mol) in 6000 ml of water while stirring under nitrogen washing at 80 ° C. The solution was changed. Subsequently, 618.2 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by mass; Mo 3.5 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue-black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, while maintaining 60 ° C. in the course of nitrogen cleaning, 72.9 g (100% by mass; Sb 0.5 mol) of antimony (III) oxide from Merck, Darmstadt, was first added, and further for 1 hour. Stir. Next, 81.5 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur, 76204 Karlsruhe was added while maintaining the limit conditions, and further stirred for 1 hour. The obtained aqueous suspension was spray-dried as described in Comparative Example 1, and 100 g of the sprayed powder obtained in this case was heat-treated as described in Example 3. The X-ray diffraction pattern to which the active material belongs shows an important i-phase content. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.29 3
11.26 7
9.82 6
8.19 2
4.000 100
3.510 13
3.404 17
3.340 17
3.278 33
3.176 21
3.057 15
2.933 13
2.856 15.

Example 6 Cs _0.5 [Mo _3.7 V ⁴⁺ _1.2 Bi _0.1 O _13.9 ] ₁
In 6000 ml of water, 115.5 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 0.96 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 653.5 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by mass; Mo 3.7 mol) with stirring while maintaining 80 ° C. and nitrogen washing in this solution. Was dissolved. In this clear aqueous solution, 12.23 g (V100%; V ^{± 0} 0.24 mol) of elemental V powder of Chem Pur, 76204 Karlsruhe, with nitrogen washing and stirring while maintaining 80 ° C. ) And was further stirred for 4 hours while maintaining the limit conditions. The dark blue-black aqueous suspension obtained in this case was cooled to 60 ° C. and stirred at this temperature for 12 hours while maintaining nitrogen washing. Thereafter, 81.5 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur, 76204 Karlsruhe was added while maintaining 60 ° C. under the progress of nitrogen washing, and further stirred for 1 hour. Next, 48.5 g (100%; Bi 0.1 mol) of bismuth nitrate pentahydrate, Riedel de Haen, D-30926 Seelze, was added while maintaining the limit conditions, and the mixture was further stirred for 1 hour. The obtained aqueous suspension was spray-dried as described in Comparative Example 1, and 100 g of the sprayed powder obtained in this case was heat-treated as described in Comparative Example 2. The X-ray diffraction pattern to which the active material belongs shows an important i-phase content. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.28 10
11.23 14
9.80 14
8.11 10
3.990 100
3.533 33
3.407 59
3.346 57
3.279 72
3.173 41
3.059 47
2.934 25
2.863 29.

Example 7 Cs _0.5 [Mo _3.2 V ⁴⁺ ₁ Nb _0.4 O _13.45 ] ₁
In 6000 ml of water, 120.3 g of ammonium metavanadate (V ₂ O ₅ content = 75.6% by mass; V ⁵⁺ 1.0 mol) from HC Starck was dissolved while stirring under nitrogen washing at 80 ° C. Into a yellow solution. Subsequently, 565.2 g of HC Starck ammonium heptamolybdate tetrahydrate (MoO ₃ content = 81.5% by weight; Mo 3.2 mol) under stirring while maintaining 80 ° C. and nitrogen washing in this solution Was dissolved. To the clear aqueous solution obtained in this case, 182.1 g of niobium oxalate (Nb 20.41% by mass; Nb 0.4 mol) from HC Starck was added with nitrogen washing and stirring while maintaining 80 ° C. The mixture was further stirred for 1 hour while maintaining the limit conditions. The resulting dark green solution was cooled to 60 ° C. Thereafter, 194.0 g of Bismuth nitrate pentahydrate (Bi (NO ₃ ) ₃ -5H ₂ O) first in Riedel de Haen, D-30926 Seelze, while maintaining 60 ° C. under the progress of nitrogen washing %; Bi 0.4 mol) was added followed by 81.5 g (100%; Cs 0.5 mol) of Cs ₂ CO _{3 from} Chem Pur, 76204 Karlsruhe and the resulting suspension was stirred for 20 minutes. Next, spray drying was performed in the same manner as in Comparative Example 1. 100 g of the spray powder obtained in this case was heat-treated as described in Example 3. The X-ray diffraction pattern to which the active material belongs shows an important i-phase content. The relative intensities and states of the i-phase diffraction reflections contained are as follows:
d [Å] I (%)
13.29 5
11.27 10
9.84 8
8.24 5
4.004 100
3.514 24
3.426 58
3.348 39
3.275 63
3.178 38
3.057 33
2.939 43
2.856 28.

Example 8
The multi-metal oxide material Cs _0.5 [Mo _3.5 V ⁺⁴ ₁ Te _0.5 O _x ] ₁ 100 g from Example 3 was heated to 85 ° C. in 1 l of a 20 wt% aqueous HNO ₃ solution. The mixture was heated at reflux under normal pressure for 5 hours.

  After cooling the aqueous suspension, the solid content was filtered off, washed 5 times with water and dried in a vacuum drying box at 110 ° C. for 24 hours.

Analysis of the solid revealed that the following composition Cs _0.3 [Mo _3.6 V ₁ Te _0.4 O _y ] ₁
Produced. This X-ray diffractogram was identical to the X-ray diffractogram of the starting powder even though the Cs content was reduced by 40% (relative) by treatment with aqueous nitric acid.

The X-ray diffraction diagram which belongs to the comparative example 1 which does not have i phase content. The X-ray diffraction diagram belonging to Example 1 of the resulting active material. The X-ray diffraction pattern which does not have i phase content and belongs to the comparative example 2. X-ray diffractogram belonging to 2 in an example of the resulting active material. The X-ray diffraction pattern which belongs to Example 3 of an active material.

Claims (25)

Formula I
A _a [Mo _5-b-c V _b X _c O _d ] ₁ (I)
[Where,
A is at least one element from the group comprising NH ₄ , Na, K, Rb, Cs and Tl;
X is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, Nb, Ta, W, Mn, Re, Fe , Co, Ni, Cr, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, C, Si, Ge, Sn, Pb, P One or more elements from the group comprising As, Sb, Bi, S, Se and Te,
a is 0.1 to 1,
b is 0.25 to 4.5;
c is 0 to 4.5, provided that
b + c is assumed to be 4.5 or less), and the X-ray diffraction pattern of the multi-metal oxide material uses the following X-ray diffraction pattern RM: Lattice spacing d [Å] independent of line wavelength
d [Å]
3.06 ± 0.2
3.17 ± 0.2
3.28 ± 0.2
3.99 ± 0.2
9.82 ± 0.4
11.24 ± 0.4
13.28 ± 0.5
A multi-metal oxide material of the general formula I, characterized in that it is reproduced in the form of The following relative diffraction reflection intensity I (%), in which the X-ray diffraction pattern RM is additionally related to the intensity of the diffraction reflection representing the lattice spacing d [Å] = 3.99 ± 0.2:
d [Å] I (%)
3.06 ± 0.2 5-65
3.17 ± 0.2 5-65
3.28 ± 0.2 15-130
3.99 ± 0.2 100
9.82 ± 0.4 1-50
11.24 ± 0.4 1-45
13.28 ± 0.5 1-35
The multi-metal oxide material of claim 1, comprising:   The multi-metal oxide material according to claim 1 or 2, wherein A is at least one of the two elements Rb and Cs.   X is one or more elements from the group comprising Ti, Cr, W, Mn, Re, Fe, Co, Ni, Pd, Pt, Cu, Ag, Ga, Sn, Sb and Te 4. The multi-metal oxide material according to any one of 3 to 3.   The multi-metal oxide material according to any one of claims 1 to 4, wherein c is 0.05 to 4.0.   The multi-metal oxide material according to any one of claims 1 to 5, wherein b is 0.5 to 2.5.   The multimetal oxide material according to any one of claims 1 to 6, wherein a is 0.2 to 0.8.   The multi-metal oxide material according to claim 1, wherein a is 0.3 to 0.7.   The multi-metal oxide material according to claim 1, wherein more than 25 mol% of V contained in the multi-metal oxide material is present in the oxidation stage +4.   The multi-metal oxide material according to claim 1, wherein more than 50 mol% of V contained in the multi-metal oxide material is present in the oxidation stage +4. The X-ray diffractogram of the multimetal oxide material additionally has the following diffraction reflection:
d [Å]
8.19 ± 0.3
3.51 ± 0.2
3.42 ± 0.2
3.34 ± 0.2
2.94 ± 0.2
2.86 ± 0.2
The multi-metal oxide material according to claim 1, comprising: The following relative diffractive reflection intensity I (%), in which the additional diffractive reflection is related to the intensity of the diffractive reflection, which represents the lattice spacing d [Å] = 3.99 ± 0.2:
d [Å] I (%)
8.19 ± 0.3 0-25
3.51 ± 0.2 2-50
3.42 ± 0.2 5-75
3.34 ± 0.2 5-80
2.94 ± 0.2 5-55
2.86 ± 0.2 5-60
The multi-metal oxide material according to claim 11, comprising: X-ray diffractogram of multi-metal oxide material additionally has the following diffraction reflection
d [Å]
2.54 ± 0.2
2.01 ± 0.2
The multi-metal oxide material according to claim 1, comprising: The following relative diffracted reflection intensity I (%) in relation to the intensity of the diffractive reflection where the additional diffractive reflection represents a lattice spacing d [Å] = 3.99 ± 0.2
d [Å] I (%)
2.54 ± 0.2 0.5-40
2.01 ± 0.2 5-60
The multi-metal oxide material of claim 13, comprising:   In the X-ray diffraction pattern of the multi-metal oxide material, the diffraction with the strongest diffraction reflection representing the lattice spacing d [Å] = 3.99 ± 0.2 or the lattice spacing d [Å] = 3.28 ± 0.2 15. A multimetal oxide material according to any one of claims 1 to 14, which is reflective.   16. The diffraction reflection representing a lattice spacing d [Å] = 3.99 ± 0.2 in an X-ray diffraction diagram of a multimetal oxide material has a 2Θ half-width of 1 ° or less. 2. The multi-metal oxide material according to item 1.   17. A process for producing a multi-metal oxide material according to any one of claims 1 to 16, wherein a dry mixture is produced from a suitable source of elemental components of the multi-metal oxide material, the dry mixture being 350 to The method for producing a multimetal oxide material according to any one of claims 1 to 16, wherein the heat treatment is performed at a temperature of 1000 ° C.   The method according to claim 17, wherein the heat treatment is performed under an inert gas. 17. A process for producing a multi-metal oxide material according to any one of claims 1 to 16 , wherein a dry mixture is produced from a suitable source of elemental components of the multi-metal oxide material, in an oxidizing atmosphere to heat treatment at a temperature of 150 to 400 ° C., wherein the heat treatment at a temperature of 350 to 1000 ° C. followed by the inert gas thereto, according to any one of claims 1 to 16 Process for producing multiple metal oxide materials.   20. The production of a dry mixture, as a source for element V, a mixture of at least one compound containing element V in the oxidation stage +5 and elemental vanadium is used. 2. The method according to item 1.   In the method for producing a multimetal oxide, first, the multimetal oxide according to any one of claims 1 to 16 is produced, and then the content of element A in the multimetal oxide is changed to the content of Mo. A process for producing a multi-metal oxide, characterized in that it is reduced in relation. In the method for producing a multimetal oxide, first, the multimetal oxide according to any one of claims 1 to 16 is produced, and subsequently the multimetal oxide is converted into an alcohol, an acid, and an alcoholic solution of the acid. Alternatively, a method for producing a multimetal oxide, characterized by treating with a hydrogen peroxide solution . 23. A method according to claim 22, wherein the acid is an organic acid, an inorganic acid or an aqueous solution of such an acid.   A multi-metal oxide obtainable by the method according to any one of claims 21 to 23. 22. a) no Nb, b) no Te, c) no Sb, or d) no Nb and Te, or e) no Nb and Sb 24. A multimetal oxide obtainable by the method according to any one of items 1 to 23.

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