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WO1999051338A1 - Compositions d'oxydes multimetalliques - Google Patents

Compositions d'oxydes multimetalliques Download PDF

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Publication number
WO1999051338A1
WO1999051338A1 PCT/EP1999/002082 EP9902082W WO9951338A1 WO 1999051338 A1 WO1999051338 A1 WO 1999051338A1 EP 9902082 W EP9902082 W EP 9902082W WO 9951338 A1 WO9951338 A1 WO 9951338A1
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WO
WIPO (PCT)
Prior art keywords
multimetal oxide
oxometalate
antimony
mixture
methacrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/002082
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German (de)
English (en)
Inventor
Hartmut Hibst
Frank Rosowski
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO1999051338A1 publication Critical patent/WO1999051338A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/02—Antimonates; Antimonites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases

Definitions

  • the present invention relates to multimetal oxide compositions of the general formula I.
  • A MO12 Xa b Xc Xd S e xl O x ,
  • X 1 phosphorus, arsenic, boron, germanium, and / or silicon, preferably phosphorus,
  • X 2 vanadium, niobium, tungsten, rhenium and / or rhodium, preferably vanadium and / or tungsten,
  • X 3 lithium, sodium, potassium, rubidium, cesium, silver and / or copper, preferably cesium and / or copper,
  • X 4 antimony and / or bismuth, preferably antimony
  • X 5 hydrogen and / or NH 4 ®
  • X 6 copper, zinc, cobalt, iron, cadmium, manganese, magnesium, calcium, strontium and / or barium, preferably copper,
  • a 1 to 6, preferably 1 to 3,
  • b 0 to 6, preferably 0.2 to 4 and particularly preferably 0.5 to 2.5,
  • c 0 to 5, preferably 1 to 3,
  • d 0 to 6, preferably 0 to 3 and particularly preferably 0 to 1.5,
  • g 0.1 to 50, preferably 0.2 to 20 and particularly preferably 0.2 to 5,
  • h 0 to 50, preferably 0 to 20 and particularly preferably 0 to 12,
  • p, q non-zero numbers whose ratio p / q is 1: 0.01 to 1: 5, preferably 1: 0.02 to 1: 3 and particularly preferably 1: 0.04 to 1: 2,
  • the areas A, B being distributed relative to one another as in a finely divided mixture of A and B, with the proviso that at least one separately formed oxometalate B
  • oxometalate B which contain at least part of the antimony in the oxidation state +5, and this at temperatures of 200 to 1200 ° C., preferably Calcined 200 to 850 ° C and particularly preferably 500 to 850 ° C. 3
  • the present invention relates to processes for the preparation of multimetal oxide materials (I) and their use as catalysts for the gas-phase catalytic oxidation of methacrylic acid to methacrylic acid.
  • EP-A 668103 relates to multi-component multimetal oxide compositions, the gross composition of which and the component composition of the components corresponds to that of the multimetal oxide compositions (I) according to the invention. These multimetal oxide materials are described in EP-A 668103 and others. recommended as catalysts for the gas phase catalytic oxidative production of methacrylic acid from methacrolein.
  • the object of the present invention was therefore to provide multimetal oxide compositions which do not have the disadvantages of the multimetal oxide compositions of the prior art. Accordingly, the multimetal oxide materials (I) defined at the outset were found.
  • EP-A 835, DE-C 3 338 380, DE-A 4 220 859 and DE-A 4 307 381 also relate to multi-component multimetal oxide compositions which are suitable as catalysts for the gas-phase catalytic oxidative production of methacrylic acid from methacrolein, but the element composition of the components of these multimetal oxide compositions of the prior art is different from that of the inventive multimetal oxide compositions (I).
  • the large diameter of which d & or d B (longest connecting section through the center of gravity of the area of two points located on the surface (interface) of the area) is> 0 to 200 ⁇ m, preferably 0.1 to 100 ⁇ m.
  • a particularly favorable large diameter range is the range 0.2 to 50 ⁇ m and the range 0.2 to 30 ⁇ m is particularly advantageous.
  • the large diameters can also be 0.1 to 150 ⁇ m or 75 to 125 ⁇ m (the experimental determination of the large diameters allows, for example, microstructure analysis using a scanning electron microscope (SEM)). 4
  • Both the fraction [A] p and the fraction [B] g can be present in the multimetal oxide compositions according to the invention in crystalline and / or amorphous form. This means that both the areas A and the areas B consist essentially of small 5 crystallites, the size of which is typically 0.1 to 10 ⁇ m.
  • Molybdatophosphoric acid (NH) 3 P0 4 (Mo ⁇ 3 ) ⁇ 2 * 4H 2 0) corresponds.
  • the presence of this type of crystal structure can be demonstrated, for example, by the fact that the X-ray diffraction recordings of the multimetal oxide composition (I) according to the invention reflect the diffraction pattern of the ammonium salt
  • the X-ray diffraction fingerprint of the ammonium salt of molybdatophosphoric acid is e.g. published as index card 9-412 of the
  • 25 salts of crystallites containing molybdate phosphoric acid are installed and are then on the surface of these crystallites or in the interstices.
  • 85 to 95% of its weight is used as antimony to produce the multimetal oxide materials.
  • those multimetal oxide compositions according to the invention are preferred whose regions B essentially consist of crystallites which have the trirutile structure type of the ⁇ - and / or ⁇ -copper antimonate CuSb 2 ⁇ 6 .
  • regions B essentially consist of crystallites which have the trirutile structure type of the ⁇ - and / or ⁇ -copper antimonate CuSb 2 ⁇ 6 .
  • ⁇ -CuSb 2 0 6 crystallizes in one
  • Areas B are preferred which contain the pyrochloric structure of the mineral Partzite, a copper-antimony oxide hydroxide with the variable composition Cu y Sb 2-2 (0, OH, H 2 0) 6-7 (y ⁇ 2, 0 ⁇ x ⁇ 1) (B. Mason et al., Mineral. Mag. 30 (1953) 100-112 or comparison diagram in index card 7-303 of the JCPDS-ICDD index
  • regions B can consist of crystallites which structure the copper antimonate Cuo, Sb 4 Oi 9 (S. Shimada et al., Chem. Lett. 1983, 1875-1876 or S. Shimada et al., Thermochim. Acta 133 (1988) 73-77 or comparative diagram in index card 45-54 of the JCPDS-ICDD index) and / or the structure of CuSb0 4 , s (S. Shimada et al., Thermochim. Acta 56 (1982) 73-82 or S Shimada et al., Thermochim. Acta 133 (1988) 73-77 or comparison diagram in index card 36-1106 of the JCPDS-ICDD index).
  • the multimetal oxide compositions (I) according to the invention are easily e.g. obtainable by first preparing oxometalates B,
  • the oxometalates B can be prepared by preparing a preferably intimate, expediently finely divided, dry mixture from suitable sources of their elemental constituents, and this at temperatures of 200 to 1200 ° C., preferably 200 to 850 ° C., particularly preferably 500 to 850 ° C calcined (usually a few minutes to several hours).
  • oxometalates B * At least a part of the oxometalates B of the starting mass 1 (hereinafter this part is called oxometalates B *) can be obtained by the fact that suitable sources of the elemental constituents of the oxometalate B, the least a part of the antimony in the Contain oxidation level +5, a preferably intimate, expediently finely divided, dry mixture is prepared and this is calcined at temperatures of 200 to 1200 ° C, preferably 200 to 850 ° C, particularly preferably 500 to 850 ° C (usually a few minutes to several Hours).
  • the calcination of the precursors of oxometalates B can generally be carried out under inert gas, but also under a mixture of inert gas and oxygen, such as air, or even under pure oxygen. Calcination under a reducing atmosphere is also possible. As a rule, the required calcination time decreases with increasing calcination temperature.
  • the proportion of the oxometalates B * in the finely divided starting mass 1 is advantageously at least 10, better at least 20, often at least 30 or at least 40, preferably at least 50, more preferably at least 60, particularly preferably at least 70 or at least 80, often at least 90 or 95 and very particularly preferably 100% by weight, based on the starting mass 1.
  • Oxometalates B * are obtainable, for example, by the preparation methods described in detail in DE-A 2 407 677. Among these, the procedure is preferred in which antimony trioxide and / or Sb0 4 in aqueous 6
  • oxides 25 of oxygen, can be converted into oxides.
  • halides, nitrates, formates, oxalates, acetates, carbonates and / or hydroxides are therefore particularly suitable as starting compounds (compounds such as NH 4 OH, NH 4 CHO 2 , CH 3 COOH, NH 4 CH 3 CO 2 or ammonium oxalate to be gasified at the latest during the later calcination
  • the intimate mixing of the starting compounds can also be carried out in dry or wet form for the preparation of oxometalates B. If it is in dry form, the initial
  • the intimate mixing is preferably carried out in wet form.
  • the starting compounds are mixed together in the form of an aqueous solution and / or suspension. After the mixing process is complete, the fluid mass is dried and
  • drying is preferably carried out by spray drying.
  • the oxometalates B, B * can be comminuted again (for example by wet or dry milling, for example in a ball mill or by jet milling) and from the powder, which often consists of essentially 5 spherical particles, the grain size with a in the large diameter range desired for the multimetal oxide (I) according to the invention (in the 7
  • a preferred method of producing oxometalates B * of the general formula Cu ⁇ Sb g H h O y consists in first dissolving antimony trioxide and / or Sb 2 ⁇ 4 in an aqueous medium using hydrogen peroxide in a, preferably finely divided, Sb (V) compound, eg Sb (V ) Oxide hydroxide hydrate, to transfer the resulting aqueous suspension with Cu carbonate (which may have the composition Cu (OH) 2 CO 3 , for example), the introduced Cu carbonate by adding ammonia (for example as an aqueous solution) to solve, to dry the resulting aqueous mixture, for example spray-drying as described, and to calcine the powder obtained, if appropriate after subsequent kneading with water and subsequent extrusion and drying, as described.
  • the ammonia required to dissolve the Cu carbonate can also be added partially and / or completely before or together with the introduction of the Cu carbonate.
  • oxometalates B different from oxometalates B *, it proves to be particularly advantageous to start from an aqueous antimony trioxide suspension and to dissolve the X 6 elements therein as nitrate and / or acetate, to spray-dry the resulting aqueous mixture as described and then to do so calcine the resulting powder as described.
  • starting mass 2 is usually not precalcined. If the initial mass 2 is pre-calcined, the calcination is expediently carried out at 150 to 450 ° C (under inert gas or inert gas with oxygen, e.g. air).
  • Particularly suitable starting compounds are:
  • Nb ammonium nioboxalate or ammonium niobate
  • Alkali metals alkali metal nitrates
  • Cu copper nitrate
  • the starting mass 1 and the starting mass 2 are then mixed with one another in the desired quantitative ratio, wet or dry (preferably dry), the mixture is shaped and then calcined at temperatures from 150 to 450 ° C. for several hours.
  • the calcination can be carried out under inert gas, but also under a mixture of inert gas and oxygen, e.g. Air.
  • Forming the mixture of starting mass 1 and starting mass 2 can e.g. by compression (e.g. tabletting, extrusion or extrusion), whereby lubricants such as graphite or stearic acid as well as molding aids and reinforcing agents such as microfibers made of glass, asbestos, silicon carbide or potassium titanate can be added.
  • the compression takes place immediately to the desired catalyst geometry, hollow cylinders with an outer diameter and a length of 2 to 10 mm and a wall thickness of 1 to 3 mm being preferred as such.
  • the mixture of the starting mass 1 and the starting mass 2 can be formed both before and after the calcination. This can e.g. also be carried out in such a way that the mixture is comminuted after the calcination and applied to inert supports for the preparation of coated catalysts.
  • the application can also take place before the final calcination. In this case, the application is preferably carried out in accordance with EP-B 293 859.
  • the multimetal oxide compositions (I) according to the invention can also be used in powder form.
  • the multimetal oxide compositions (I) according to the invention are particularly suitable as catalysts with increased selectivity for a given conversion and increased activity for the gas-phase catalytically oxidative production of methacrylic acid from methacrolein.
  • the catalytic gas phase oxidation of methacrolein to methacrylic acid using the catalysts according to the invention can be carried out in a manner known per se, e.g. shown in DE-A 40 22 212, done.
  • the oxidizing agent oxygen can e.g. in the form of air, but also in pure form.
  • the reactants are preferably diluted with inert gas such as N 2 , CO 2 , saturated hydrocarbons and / or with water vapor.
  • inert gas such as N 2 , CO 2 , saturated hydrocarbons and / or with water vapor.
  • methacrolein oxygen: water vapor: inert gas ratio of 1: (1 to 3): (2 to 20): (3 to 30), particularly preferably 1: (1 to 3): (3 to 10 ): (7 to 18) worked.
  • the methacrolein used can have been obtained in various ways, e.g. by gas phase oxidation of isobutene, tert. -Butanol or the methyl ether of tert-butanol. It is advantageous to use methacrolein, which can be obtained by condensation of propanol with formaldehyde in the presence of secondary amines and acids in the liquid phase in accordance with the processes described in DE-PS 875 114 or DE-AS 28 55 514.
  • the gas phase oxidation can be carried out both in fluidized bed reactors and in fixed bed reactors. It is preferably carried out in tube bundle reactors in the tubes of which the catalyst mass, preferably in the form of cylindrically shaped particles, is fixedly arranged.
  • the reaction temperature is usually 250 to 350 ° C
  • the reaction pressure is usually in the range of 1 to 3 bar
  • the total space load is preferably 800 to 1800 Nl / l / h.
  • the methacrolein conversion in a single reactor pass is usually 60 to 90 mol%.
  • the compositions according to the invention retain their properties essentially unchanged over an extended period of operation.
  • compositions I according to the invention are also able to catalyze the gas phase catalytic oxidation and ammoxidation of other saturated, unsaturated and aromatic hydrocarbons, alcohols, aldehydes and amines.
  • turnover, selectivity and retention time are defined in this document as follows:
  • Methacrylic acid formation Total number of moles of methacrolein implemented
  • Air is gradually heated up to 150 ° C within 1 h, then to 200 ° C within 4 h, then to 300 ° C within 2 h and finally to 400 ° C within 2 h.
  • the powder was then heated to 900 ° C. in the course of 48 h while passing 20 l / h of air and finally cooled to room temperature.
  • the resulting comparison starting mass had the stoichiometry CuSb 2 Og.
  • the hollow cylinders were calcined in an air-circulating air oven as follows (500 Nl / h air per kg hollow cylinder): First, starting from 25 ° C, the heating rate was 4 ° C / h to 270 ° C. The temperature was then increased to 400 ° C. at a heating rate of 2 ° C./h and this temperature was maintained for 5 hours.
  • starting mass 1 (b) were used instead of comparative starting mass 1 (a).
  • the catalysts were placed in a tubular reactor (10 mm inside diameter, 75 g catalyst bed, salt bath temperature) and at reaction temperatures in the range from 290 to 310 ° C. using a residence time of 3.6 seconds with a gaseous mixture of the composition 14
  • the salt bath temperature was adjusted in all cases so that a uniform methacrylic acid conversion U of about 63.0% resulted.
  • a lower salt bath temperature shows an increased catalyst activity.
  • the product gas mixture flowing out of the tubular reactor was analyzed by gas chromatography. The results for the selectivity S of methacrylic acid formation using the various catalysts are shown in the table below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des compositions d'oxydes multimétalliques à structure à deux composants, renfermant du molybdène, de l'hydrogène, un ou plusieurs des éléments phosphore, arsenic, bore, germanium et silicium, un ou plusieurs des éléments cuivre, zinc, cobalt et fer, et l'élément antimoine, ainsi que leur utilisation pour la fabrication d'acide méthacrylique par oxydation catalytique en phase gazeuse.
PCT/EP1999/002082 1998-04-06 1999-03-26 Compositions d'oxydes multimetalliques Ceased WO1999051338A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19815279A DE19815279A1 (de) 1998-04-06 1998-04-06 Multimetalloxidmassen
DE19815279.5 1998-04-06

Publications (1)

Publication Number Publication Date
WO1999051338A1 true WO1999051338A1 (fr) 1999-10-14

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10101695A1 (de) 2001-01-15 2002-07-18 Basf Ag Verfahren zur heterogen katalysierten Gasphasenpartialoxidation von Vorläuferverbindungen der (Meth)acrylsäure

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547484A (en) * 1984-04-09 1985-10-15 Monsanto Company Method of preparing a catalyst for the oxidation and ammoxidation of olefins
EP0404529A1 (fr) * 1989-06-23 1990-12-27 Nitto Chemical Industry Co., Ltd. Procédé de préparation de catalyseurs d'oxydation à base d'oxydes métalliques contenant du fer, de l'antimoine et du phosphore.
EP0486291A1 (fr) * 1990-11-14 1992-05-20 MITSUI TOATSU CHEMICALS, Inc. Catalyseur pour l'oxydation de la méthacroléine et méthode de préparation de l'acide métacrylique
EP0668102A1 (fr) * 1994-02-17 1995-08-23 BASF Aktiengesellschaft Masses d'oxydes multimétalliques
EP0668103A1 (fr) * 1994-02-17 1995-08-23 BASF Aktiengesellschaft Masses d'oxydes multimétalliques
US5693587A (en) * 1995-06-06 1997-12-02 The Standard Oil Company Method for preparing vanadium antimony oxide based oxidation and ammoxidation catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547484A (en) * 1984-04-09 1985-10-15 Monsanto Company Method of preparing a catalyst for the oxidation and ammoxidation of olefins
EP0404529A1 (fr) * 1989-06-23 1990-12-27 Nitto Chemical Industry Co., Ltd. Procédé de préparation de catalyseurs d'oxydation à base d'oxydes métalliques contenant du fer, de l'antimoine et du phosphore.
EP0486291A1 (fr) * 1990-11-14 1992-05-20 MITSUI TOATSU CHEMICALS, Inc. Catalyseur pour l'oxydation de la méthacroléine et méthode de préparation de l'acide métacrylique
EP0668102A1 (fr) * 1994-02-17 1995-08-23 BASF Aktiengesellschaft Masses d'oxydes multimétalliques
EP0668103A1 (fr) * 1994-02-17 1995-08-23 BASF Aktiengesellschaft Masses d'oxydes multimétalliques
US5693587A (en) * 1995-06-06 1997-12-02 The Standard Oil Company Method for preparing vanadium antimony oxide based oxidation and ammoxidation catalysts

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