EP1546080A1 - Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique - Google Patents

Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique

Info

Publication number
EP1546080A1
EP1546080A1 EP03778268A EP03778268A EP1546080A1 EP 1546080 A1 EP1546080 A1 EP 1546080A1 EP 03778268 A EP03778268 A EP 03778268A EP 03778268 A EP03778268 A EP 03778268A EP 1546080 A1 EP1546080 A1 EP 1546080A1
Authority
EP
European Patent Office
Prior art keywords
multimetal oxide
diffraction
ray diffractogram
elements
group
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.)
Withdrawn
Application number
EP03778268A
Other languages
German (de)
English (en)
Inventor
Martin Dieterle
Frieder Borgmeier
Klaus Joachim MÜLLER-ENGEL
Hartmut Hibst
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10245585A external-priority patent/DE10245585A1/de
Priority claimed from DE2002146119 external-priority patent/DE10246119A1/de
Priority claimed from DE10248584A external-priority patent/DE10248584A1/de
Priority claimed from DE2002154278 external-priority patent/DE10254278A1/de
Priority claimed from DE10254279A external-priority patent/DE10254279A1/de
Priority claimed from DE10261186A external-priority patent/DE10261186A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1546080A1 publication Critical patent/EP1546080A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/006—Compounds containing vanadium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing molybdenum, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/80—Compounds containing cobalt, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G51/82—Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/88—Thick layer coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2484—Coating or impregnation is water absorbency-increasing or hydrophilicity-increasing or hydrophilicity-imparting

Definitions

  • the diffraction reflex h is the most intense within the X-ray diffractogram, just as it has a half-value width of at most 0.5 °,
  • the half-width of the diffraction reflex i and the diffraction reflex k is in each case ⁇ 1 °.
  • Acrylic acid is an important monomer used as such or in the form of an alkyl ester to produce e.g. polymers suitable as adhesives are used.
  • Gas phase partial oxidation of acrolein to acrylic acid is generally known (see, for example, EP-A 714700 or EP-A 700893, and the literature cited in these documents) and in particular as a second oxidation stage in the production of acrylic acid by two-stage heterogeneously catalyzed gas phase partial oxidation starting from propene from Importance.
  • the procedure recognized in the preamble is from the
  • a disadvantage of the methods of the prior art is that the selectivity of the acrylic acid formation is not fully satisfactory.
  • the object of the present invention was therefore to provide an improved process for the production of acrylic acid starting from acrolein, which among other things. has an increased selectivity of acrylic acid formation. It was known from EP-A 1192987 that when using
  • Multimetal oxide compositions according to the preamble of this document as active compositions for the single-stage production of acrylic acid by heterogeneously catalyzed gas phase partial oxidation of propane or of propane and propene, a process improvement can be achieved by the multimetal oxide compositions having at least one element from the group comprising Ni, Pd, Cu, Ag and Au endowed.
  • the diffraction reflex h is the most intense within the X-ray diffractogram and has a half-value width of at most 0.5 ° C
  • M 1 at least one of the elements from the group comprising Te and Sb;
  • M 2 at least one of the elements from the group comprising Nb, Ti, W, Ta and Ce;
  • M 3 at least one of the elements from the group comprising Pb, Ni, Co, Bi, Pd, Ag, Pt, Cu, Au, Ga, Zn, Sn, In, Re, Ir, Sm, Sc, Y, Pr, Nd and Tb;
  • n a number which is determined by the valency and frequency of the elements other than oxygen in (I),
  • the X-ray diffractogram of multimetal oxide materials (I) to be used according to the invention generally also contains further diffraction reflections, the apex of which lies at the following diffraction angles (20):
  • the X-ray diffractogram of multimetal oxide materials (I) to be used according to the invention frequently also contains the reflections 29.2 ⁇ 0.4 ° () and 35.4 ⁇ 0.4 ° (n) (peak positions).
  • the intensity 100 is assigned to the diffraction reflex h, it is advantageous according to the invention if the diffraction reflexes i, 1, m, n, o, p, q have the following intensities in the same intensity scale:
  • the half-width of the latter is generally ⁇ 1 °.
  • the specific surface area of multimetal oxide compositions (I) to be used according to the invention is frequently 1 to 40 m 2 / g, often 11 or 12 to 40 m 2 / g and frequently 15 or 20 to 40 or 30 m 2 / g (determined according to the BET method, nitrogen).
  • the stoichiometric is preferred
  • Coefficient a of the multimetal oxide materials (I) to be used according to the invention regardless of the preferred ranges for the other Ren stoichiometric coefficients of the multimetal oxide materials (I), 0.05 to 0.6, particularly preferably 0.1 to 0.6 or 0.5.
  • the stoichiometric coefficient b is preferably 0.01 to 1, and particularly preferably 0.01 or 0.1 to 0, 5 or 0.4 ,
  • the stoichiometric coefficient c of the multimetal oxide compositions (I) to be used according to the invention is 0.01 to 1 and particularly preferably 0.01 or 0.1 to 0.5 or 0 ; 4.
  • a range which is particularly preferred according to the invention for the stoichiometric coefficient c and which, independently of the preferred ranges for the other stoichiometric coefficients of the multimetal oxide materials (I) to be used according to the invention, can be combined with all other preferred ranges in this document is the range 0.05 up to 0.2.
  • the stoichiometric coefficient d of the multimetal oxide compositions (I) to be used according to the invention is 0.00005 or 0.0005 to 0.5, particularly preferably 0.001 to 0, 5, often 0.002 to 0.3 and often 0.005 or 0.01 to 0.1.
  • Multimetal oxide materials (I) to be used according to the invention are particularly favorable, their stoichiometric coefficients a, b, c and d simultaneously lying in the following grid:
  • Multimetal oxide materials (I) to be used according to the invention whose stoichiometric coefficients a, b, c and d are simultaneously in the following grid, are particularly favorable:
  • M 1 is preferably Te.
  • M 2 is at least 50 mol% of its total amount of Nb and very particularly preferably 5 when M 2 is at least 75 mol% of its total amount or 100 mol% of its total amount of Nb.
  • M 3 contains at least one element from the group comprising Ni, 10 Co, Bi, Pd, Ag, Au, Pb and Ga or at least one element from the group is Ni, Co, Pd and Bi.
  • M 2 contains at least 50 mol% of its total amount, or at least 15 75 mol%, or 100 mol% Nb and M 3 at least one element from the group comprising Ni, Co , Bi, Pd, Ag, Au, Pb and Ga.
  • M 2 is at least 50 mol%, or at least 75 mol%, or 100 mol-S 20 of its total amount of Nb and M 3 is at least one element from the group comprising Ni, Co, Pd and Bi is.
  • M 1 Te
  • M 2 Nb
  • M 3 5 at least one element from the group comprising Ni, Co and Pd.
  • multimetal oxide materials (I) to be used according to the invention is disclosed, for example, by WO 0206199 and the 0 literature citations cited in this document. Thereafter, in a manner known per se, a multimetal oxide mass is first produced which has the stoichiometry (I), but which is generally a mixed crystal system composed of i-phase and other phases (e.g. k-phase).
  • the k phase is described in DE-A 10119933 and DE-A 10118814, 5 e.g.
  • Liquids are, for example, organic acids and aqueous solutions of organic acids (e.g. oxalic acid, formic acid, acetic acid, citric acid and tartaric acid), inorganic acids (e.g. nitric acid), aqueous solutions of inorganic acids (e.g. aqueous 5 telluric acid or aqueous nitric acid), alcohols and aqueous hydrogen peroxide solutions , Furthermore, JP-A 7-232071 also discloses a process for the preparation of i-pha- se-multimetal. The washing process of EP-A 1254707 is also suitable.
  • organic acids e.g. oxalic acid, formic acid, acetic acid, citric acid and tartaric acid
  • inorganic acids e.g. nitric acid
  • aqueous solutions of inorganic acids e.g. aqueous 5 telluric acid or aqueous nitric acid
  • a suitable intimate, preferably finely divided, dry mixture is produced from suitable sources of the elementary constituents of the multimetal oxide composition and this is thermally treated at temperatures of 350 to 700 ° C. or 400 to 650 ° C. or 400 to 600 ° C.
  • the thermal treatment can, in principle, take both
  • the oxidizing atmosphere is e.g. Air, air enriched with molecular oxygen or air de-oxygenated.
  • the thermal treatment is carried out under an inert atmosphere, i.e. e.g. under molecular
  • the thermal treatment is usually carried out at normal pressure (1 atm).
  • the thermal treatment can of course also be carried out under vacuum or under positive pressure.
  • the thermal treatment takes place in a gaseous atmosphere, it can both stand and flow. It preferably flows. In total, the thermal treatment can take up to 24 hours or more.
  • the thermal treatment can also be carried out so that the catalyst precursor composition before its thermal treatment initially (optionally after pulverization) tableted (optionally with the addition of 0.5 to 2 wt '-.% Of finely divided graphite to
  • the intimate mixing of the starting compounds can take place in dry or in wet form. 45 If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and, after mixing and optionally compacting, are subjected to the calcination (thermal treatment).
  • the intimate mixing is preferably carried out in wet form.
  • the starting compounds are usually in the form of an aqueous solution (if appropriate with the use of complexing agents; see, for example, DE-A 10145958). and "/ or suspending medium-mixed each other.
  • the aqueous composition is dried and calcined after drying. Conveniently, If it is in the aqueous composition is an aqueous solution or an aqueous suspension.
  • the drying process immediately after the preparation of the aqueous mixture in particular in the case of an aqueous solution; see, for example, JP-A 7-315842
  • spray drying the outlet temperatures are generally 100 to 150 ° C; the spray drying can be carried out in cocurrent or in countercurrent
  • the a particularly intimate dry mixture is required, especially if the aqueous mass to be spray-dried is an aqueous solution or suspension, but it can also be dried by evaporation in vacuo, by freeze-drying or by conventional evaporation.
  • Suitable sources for the elementary constituents in carrying out the above-described preparation of i- / k-phase crystal multi-metal oxide materials are all those which are capable of forming oxides and / or hydroxides when heated (optionally in air). It goes without saying that oxides and / or hydroxides of the elemental constituents can also be used as such starting compounds or used exclusively. That is, in particular all starting compounds mentioned in the documents EP-A 1254707, EP-A 1254709 and EP-A 1192987 are suitable.
  • Suitable sources for the element Mo are e.g. Molybdenum oxides such as molybdenum trioxide, molybdates such as ammonium heptamolybdate tetrahydrate and molybdenum halides such as molybdenum chloride.
  • Molybdenum oxides such as molybdenum trioxide
  • molybdates such as ammonium heptamolybdate tetrahydrate
  • molybdenum halides such as molybdenum chloride.
  • Suitable starting compounds for element V are, for example, vanadium oxysulfate hydrate, vanadylacetylacetonate, vanadates such as ammonium metavanadate, vanadium oxides such as vanadium pentoxide (V 2 Os), vanadium halides such as vanadium tetrachloride (VC1 4 ) and vanadium oxyhalogenides such as V0C1 3 . It is also possible to use those starting vanadium compounds which contain the vanadium in oxidation state +4.
  • Suitable sources for the element tellurium are tellurium oxides such as tellurium dioxide, metallic tellurium, tellurium halides such as TeCl, but also telluric acids such as orthothelluric acid H 6 e ⁇ 6 .
  • antimony starting compounds are antimony halides such as SbCl, antimony oxides such as antimony trioxide (Sb 2 0 3 ), antimonic acids such as HSb (OH) 6 , but also antimony oxide salts such as antimony oxide sulfate (SbO) S0 4 and antimony acetate.
  • antimony halides such as SbCl
  • antimony oxides such as antimony trioxide (Sb 2 0 3 )
  • antimonic acids such as HSb (OH) 6
  • antimony oxide salts such as antimony oxide sulfate (SbO) S0 4 and antimony acetate.
  • Suitable niobium sources are e.g. B. niobium oxides such as niobium pentoxide
  • niobium oxide halides such as NbOCl
  • niobium halides such as NbCls
  • complex compounds of niobium and organic carboxylic acids and / or dicarboxylic acids such as. B. oxalates and alcoholates.
  • the nb-containing solutions used in EP-A 895 809 are also suitable as niobium sources.
  • suitable starting compounds are, above all, their halides, nitrates, formates, oxalates, acetates, carbonates and / or hydroxides. Suitable starting compounds are often their oxo compounds such. B. tungstates or the acids derived from these. Ammonium salts are also frequently used as starting compounds.
  • polyanions of the Anderson type as z. B. in Polyhedron Vol. 6, No. 2, pp. 213-218, 1987.
  • Another suitable literature source for Anderson type polyanions is Kinetics and Catalysis, Vol. 40, No. 3, 1999, pp 401 to 404.
  • polyanions suitable as starting compounds are e.g. B. Dawson or Keggin type. Preference is given to using starting compounds which, at elevated temperatures, convert into their oxides either in the presence or in the absence of oxygen, possibly with the release of gaseous compounds.
  • the i- / k-phase mixed-crystal multimetal oxide compositions obtainable as described can then be washed as described by suitable washing (in which the stoichiometry generally changes only insignificantly) ) are converted into multimetal oxides (I) to be used according to the invention. It is preferred to calcine again after washing, as described in EP-A 1254709.
  • the calcination conditions are usually the same ones that were recommended for the production of the multimetal oxide mass to be washed.
  • i-phase an increased proportion of i-phase (and, in favorable cases, essentially pure i-phase) occurs in the production of precursor multimetal oxides (which can be converted into multimetal oxides (I) according to the invention by washing as described) when they are produced. is carried out by a hydro-thermal route, e.g. describe DE-A 10029338, DE-A 10254278 and JP-A 2000-143244.
  • EP-A 1254709 can be recalcined as follows.
  • Precursor multi-metal oxides have already been described, calcined (preferably in an inert gas stream) (preference is given here to not pre-decomposing in air).
  • aqueous nitrate and / or halide solutions of elements M 3 and / or the use of aqueous solutions in which the elements M 3 are complexed with organic compounds (for example acetates or acetyl acetonates) are particularly advantageous for this production variant.
  • the multimetal oxides (I) which can be used according to the invention and are obtainable as described can be used as such [e.g. as powder or after tabletting the powder (often with addition of 0.5 to 2% by weight of finely divided graphite) and subsequent splitting into chips] or else shaped into shaped bodies for the process according to the invention.
  • the catalyst bed can be a fixed bed, a moving bed or a fluidized bed.
  • the shaping into shaped bodies can e.g. by application to a carrier body, as described in DE-A 10118814 or PCT / EP / 02/04073 or DE-A 10051419. It can also be carried out in accordance with DE-A 4442346.
  • the carrier bodies to be used for the multimetal oxide compositions (I) to be used in the process according to the invention are preferably chemically inert. Ie they intervene in the process of inventing Partial catalytic gas phase oxidation according to the invention, which is catalyzed by the multimetal oxide compositions (I) to be used according to the invention, essentially does not.
  • the material for the carrier bodies is, in particular, aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite (preferably with a low water-soluble alkali content and preferably from Ceramtec in DE), pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide into consideration.
  • silicates such as clay, kaolin, steatite (preferably with a low water-soluble alkali content and preferably from Ceramtec in DE), pumice, aluminum silicate and magnesium silicate, silicon carbide, zirconium dioxide and thorium dioxide into consideration.
  • the surface of the carrier body can be both smooth and rough.
  • the surface of the carrier body is advantageously rough, since an increased surface roughness generally results in an increased adhesive strength of the applied active material shell.
  • the surface roughness R z of the carrier body is often in the range from 5 to 200 ⁇ m, often in the range from 20 to 100 ⁇ m (determined in accordance with DIN 4768 Sheet 1 using a "Hom el Tester for DIN-ISO surface measurement values" from the company Hommelwerke, DE).
  • the carrier material can be porous or non-porous.
  • the carrier material is expediently non-porous (total volume of the pores based on the volume of the carrier body ⁇ 1% by volume).
  • the thickness of the active oxide mass shell located on the shell catalysts according to the invention is usually from 10 to 1000 ⁇ m. However, it can also be 50 to 700 ⁇ m, 100 to 600 ⁇ m or 150 to 400 ⁇ m. Possible shell thicknesses are also 10 to 500 ⁇ m, 100 to 500 ⁇ m or 150 to 300 ⁇ m.
  • any geometries of the carrier bodies come into consideration for the method according to the invention.
  • Their longest dimension is usually 1 to 10 mm.
  • balls or cylinders, in particular hollow cylinders are preferably used as carrier bodies.
  • Favorable diameters for carrier balls are 1.5 to 5 mm.
  • cylinders are used as carrier bodies, their length is preferably 2 to 10 mm and their outside diameter is preferably 4 to 10 mm.
  • the wall thickness is also usually 1 to 4 mm.
  • Annular carrier bodies suitable according to the invention can also 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.
  • a carrier ring geometry 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.
  • Shell catalysts to be used according to the invention can be produced in a very simple manner, for example by forming multimetal oxide compositions of the general formula (I) to be used according to the invention, converting them into a finely divided form and finally applying them to the surface of the support body with the aid of a liquid binder.
  • the surface of the support body is moistened in subtractster manner with the liquid binder and adhered by contacting it with finely piece active oxide material of the "formula (I) a layer of active material on the moistened surface. Finally, the coated support dried.
  • the coated base body becomes the new "support body” etc.
  • it can be calcined again under the conditions already mentioned (preferably again under inert gas, for example washed multimetal oxide (I )).
  • the fineness of the catalytically active multimetal oxide composition of the general formula (I) to be applied to the surface of the support body is of course adapted to the desired shell thickness.
  • the shell thickness range from 100 to 500 ⁇ m, z. B. those active mass powders, of which at least 50% of the total number of powder particles pass a sieve with a mesh size of 1 to 20 ⁇ m and whose numerical proportion of particles with a longest dimension above 50 ⁇ m is less than 10%.
  • the distribution of the longest dimensions of the powder particles corresponds to a Gaussian distribution due to the manufacturing process.
  • the grain size distribution is often as follows:
  • the removal of the liquid binder can be done after the coating z. B. by the action of hot gases such as N or air.
  • hot gases such as N or air.
  • the coating method described brings about both a completely satisfactory adhesion of the successive layers to one another and also the base layer on the surface of the carrier body.
  • the moistening of the surface of the carrier body to be coated is carried out in a controlled manner.
  • Detailed information on this can be found in DE-A 2909671 and in DE-A 10051419.
  • binders for the coating process water, monohydric alcohols such as ethanol, methanol, propanol and butanol, polyhydric alcohols such as ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol or glycerol, mono- or polyvalent organic carboxylic acids such as propionic acid, oxalic acid, malonic acid, glutaric acid or maleic acid, amino alcohols such as ethanolamine or diethanol-a in and mono- or polyvalent organic amides such as formamide.
  • monohydric alcohols such as ethanol, methanol, propanol and butanol
  • polyhydric alcohols such as ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol or glycerol
  • mono- or polyvalent organic carboxylic acids such as propionic acid, oxalic acid, malonic acid, glutaric acid or maleic acid
  • amino alcohols such as ethanolamine or diethanol
  • Such a finely divided precursor mass " is, for example, the mass which can be obtained by first obtaining from the sources of the elemental constituents of the desired active oxide mass of the general formula (I) to be used according to the invention the most intimate, preferably finely divided, Generates dry mix (e.g. by spray drying an aqueous suspension or solution of the sources) and this finely divided
  • Dry mixture (optionally after tableting, the addition of 0.5 to 2 wt .-% of finely divided 'graphite) z at a temperature of 150 to 350 ° C, preferably 250 to 350 ° C (containing oxygen) under an oxidizing atmosphere (. B. thermally treated in air) (a few hours) and then subjected to grinding if necessary.
  • multimetal oxide compositions (I) which can be used according to the invention can also be carried out by extrusion and / or tableting both of. finely divided multimetal oxide mass (I), as well as finely divided precursor mass of a multimetal oxide mass (I) (if necessary, the phases different from the i-phase can be finally washed out, possibly including recalcination).
  • the diffraction reflex h is the most intense within the X-ray diffractogram and has a half-value width of at most 0.5 °
  • a 1 denotes the vertex of a reflection 1 and B 1 in the line of the X-ray diffractogram, when viewed along the intensity axis perpendicular to the 2 ⁇ axis, denotes the closest pronounced minimum (minima showing reflex shoulders are not taken into account) to the left of the vertex A 1 and B.
  • Total masses mentioned) preferably contain> 50% by weight, particularly preferably> 75% by weight, and very particularly preferably 90% by weight or> 95% by weight of the multimetal oxide materials (I) to be used according to the invention.
  • the process according to the invention can also be carried out by passing a reaction gas starting mixture which is essentially free of molecular oxygen at elevated temperature over the multimetal oxide mass, then reoxidizing the spent multimetal oxide mass with a gas containing molecular oxygen (for example air), then again of essentially free reaction gas starting mixture is passed over to molecular oxygen etc.
  • a reaction gas starting mixture which is essentially free of molecular oxygen at elevated temperature
  • a gas containing molecular oxygen for example air
  • the finely divided active material powder was introduced into the drum via a powder screw, the point of the powder additions being within the rolling path or below the spray cone. Due to the periodic repetition of wetting and powder metering, the base-coated carrier body itself became the carrier body in the subsequent period.
  • the carrier body was dried in air in a muffle furnace at 150 ° C. for 16 h.
  • the result was a coated catalyst VB1 with 20% by weight of active mass.
  • the resulting active composition had the composition M ⁇ / 0 o, 33 eo, ⁇ 9 Nbo, ⁇ P o, o ⁇ O ⁇ .
  • BET 9.3 m 2 / g. It was applied in the same way to the same support as in Comparative Example 1, so that a coated catalyst VB2 with 20% by weight active mass fraction resulted.
  • Example 2 As in Example 1, but the active composition from Comparative Example 2 was washed with aqueous nitric acid. The resulting active composition had the composition Mo ⁇ oVo ⁇ sTeo ⁇ Nbo ⁇ Pdo ⁇ olOx.
  • the resulting active composition had the composition o ⁇ , oVo, 8Teo 7 ⁇ Nbo, i3Cuo, o ⁇ 3 ⁇ -
  • BET 23.1 m 2 / g. It was applied in the same way to the same support as in Comparative Example 1, so that a coated catalyst B5 with 20% by weight of active composition resulted.
  • the resulting active composition had the composition Mo 1/0 Vo, 3 4T o, i8 bo, ⁇ Pb 0 , oo4.
  • BET 2.2 m 2 / g. It was applied in the same way to the same support as in Comparative Example 1, so that a coated catalyst VB7 with 20% by weight of active composition resulted.
  • Example 7 As in Example 1, but the active composition from Comparative Example 7 was washed with aqueous nitric acid. The resulting active composition had the composition
  • a tube reactor made of steel (inside diameter: 8.5 mm, length: 140 cm, wall thickness: 2.5 cm) was charged with 35.0 g each of the respective cup catalyst from A (catalyst bed length in all cases approx. 53 cm).
  • a pre-fill of 30 cm steatite balls (diameter: 2.2 to 3.2 mm, manufacturer: Ceramtec) and after the catalyst bed, a subsequent bed of the same steatite balls was added to the remaining length of the tubular reactor.
  • the following table shows the outside temperature T (° C) required for this conversion, as well as the resulting selectivity of the acrylic acidification (S AC s (mol%)).
  • the table shows the intensity ratio R of the active composition on the coated catalyst and the composition of this active composition.

Landscapes

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

Abstract

L'invention concerne un procédé d'oxydation partielle en phase gazeuse à catalyse hétérogène, d'acroléine en acide acrylique, sur une masse d'oxyde polymétallique de structure spécifique, contenant les éléments Mo et V, au moins un des éléments Te et Sb, et au moins un des éléments Nb, Ta, W et Ti, ladite masse étant également dopée avec des éléments promoteurs.
EP03778268A 2002-09-27 2003-09-24 Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique Withdrawn EP1546080A1 (fr)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
DE10245585 2002-09-27
DE10245585A DE10245585A1 (de) 2002-09-27 2002-09-27 Verfahren zur Herstellung von wenigstens einem partiellen Oxidations- und/oder Ammoxidationsprodukt des Propylens
DE10246119 2002-10-01
DE2002146119 DE10246119A1 (de) 2002-10-01 2002-10-01 Verfahren zur Herstellung von wenigstens einem partiellen Oxidations- und/oder Ammoxidationsprodukt des Propylens
DE10248584A DE10248584A1 (de) 2002-10-17 2002-10-17 Multimetalloxidmassen
DE10248584 2002-10-17
DE10254279 2002-11-20
DE2002154278 DE10254278A1 (de) 2002-11-20 2002-11-20 Verfahren zur Herstellung einer Multimetalloxidmasse
DE10254278 2002-11-20
DE10254279A DE10254279A1 (de) 2002-11-20 2002-11-20 Multimetalloxidmassen
DE10261186A DE10261186A1 (de) 2002-12-20 2002-12-20 Verfahren der heterogen katalysierten Gasphasenpartialoxidation von Acrolein zu Acrylsäure
DE10261186 2002-12-20
PCT/EP2003/010611 WO2004031114A1 (fr) 2002-09-27 2003-09-24 Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique

Publications (1)

Publication Number Publication Date
EP1546080A1 true EP1546080A1 (fr) 2005-06-29

Family

ID=32034488

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03778268A Withdrawn EP1546080A1 (fr) 2002-09-27 2003-09-24 Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique

Country Status (6)

Country Link
US (1) US7038080B2 (fr)
EP (1) EP1546080A1 (fr)
CN (1) CN100393684C (fr)
AU (1) AU2003285284A1 (fr)
BR (1) BR0314347A (fr)
WO (1) WO2004031114A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108949048A (zh) * 2018-08-01 2018-12-07 深圳日高胶带新材料有限公司 一种有机硅阻燃压敏胶粘带及其制备方法

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004099081A1 (fr) * 2003-05-12 2004-11-18 Basf Aktiengesellschaft Matieres a base d'oxydes polymetalliques, contenant mo, v et un metal alcalin et presentes en phase i pure
RU2361853C2 (ru) 2003-08-14 2009-07-20 Басф Акциенгезельшафт Способ получения (мет)акролеина и/или (мет)акриловой кислоты
US7019169B2 (en) * 2003-09-23 2006-03-28 Basf Aktiengesellschaft Preparation of (meth)acrylic acid
DE102004027999A1 (de) * 2004-06-09 2005-01-27 Basf Ag Verfahren zur Herstellung einer Multimetalloxidmasse
DE102005010586A1 (de) * 2005-03-08 2006-09-14 Basf Ag Verfahren zur Herstellung von Propen aus Propan
WO2008116081A2 (fr) * 2007-03-21 2008-09-25 Albemarle Netherlands B.V. Hétéropolyanions de type anderson
DE102008044946B4 (de) * 2008-08-29 2022-06-15 Evonik Superabsorber Gmbh Einsatz von Schaumkörpern in Oxidations-Reaktoren zur Herstellung ungesättigter Carbonsäuren
DE102012207811A1 (de) 2012-05-10 2012-07-12 Basf Se Verfahren der heterogen katalysierten Gasphasenpartialoxidation von (Meth)acrolein zu (Meth)acrylsäure
CN104923245B (zh) * 2014-03-17 2018-01-09 中国石油化工股份有限公司 丙烯酸催化剂及丙烯酸合成方法
KR20180100178A (ko) 2016-01-09 2018-09-07 어센드 퍼포먼스 머티리얼즈 오퍼레이션즈 엘엘씨 아크릴로나이트릴 반응기 공급 스트림에서 사이안화 수소의 직접 제조를 위한 촉매 조성물 및 공정
DE102017121709A1 (de) 2017-09-19 2019-03-21 Clariant International Ltd Synthese eines MoVNbTe-Schalenkatalysators für die oxidative Dehydrierung von Ethan zu Ehtylen
CN110590539A (zh) * 2018-06-12 2019-12-20 中国石油化工股份有限公司 丙烯酸生产方法
CN110590536A (zh) * 2018-06-12 2019-12-20 中国石油化工股份有限公司 丙烯酸的合成方法
CN110639505A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 丙烯酸的生产方法
CN110639537A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 丙烯醛氧化合成丙烯酸的方法
CN110642709A (zh) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 丙烯醛氧化制备丙烯酸的方法
WO2024006155A1 (fr) * 2022-06-29 2024-01-04 Rohm And Haas Company Conversion directe de glycérol en acide acrylique sur wox/zrox et oxyde métallique mixte

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4431949A1 (de) * 1994-09-08 1995-03-16 Basf Ag Verfahren zur katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure
DE4442346A1 (de) 1994-11-29 1996-05-30 Basf Ag Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
DE69713515T2 (de) 1996-04-01 2003-01-09 Union Carbide Chemicals & Plastics Technology Corp., Danbury Verfahren zur oxidation von alkanen
DE19835247B4 (de) * 1997-08-05 2022-04-28 Asahi Kasei Kabushiki Kaisha Ammonoxidationskatalysator und Verfahren zur Herstellung von Acrylnitril oder Methacrylnitril aus Propan oder Isobutan durch Ammonoxidation
ID20720A (id) * 1997-08-05 1999-02-18 Asahi Chemical Ind Larutan berair yang mengandung niobium untuk digunakan dalam pembuatan katalis oksida yang mengandung niobium
JP4174852B2 (ja) 1998-05-28 2008-11-05 東亞合成株式会社 アクリル酸の製造方法
JPH11343262A (ja) 1998-05-28 1999-12-14 Toagosei Co Ltd アクリル酸の製造方法
DE19910508A1 (de) * 1999-03-10 2000-09-21 Basf Ag Verfahren der katalytischen Gasphasenoxidation von Acrolein zu Acrylsäure
EP1090684A1 (fr) 1999-10-01 2001-04-11 Rohm And Haas Company Catalyseur pour l'oxydation en phase gazeuse d'alcanes, d'alcènes ou d'alcools en aldehydes ou acides carboxyliques unsaturés
DE10118814A1 (de) 2001-04-17 2002-10-24 Basf Ag Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Gasphasenoxidation von Propen mit molekularem Sauerstoff in einer Reaktionszone
DE10046672A1 (de) 2000-09-20 2002-03-28 Basf Ag Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Gasphasenoxidation von Propan
DE50111556D1 (de) * 2000-06-14 2007-01-11 Basf Ag Verfahren zur herstellung von acrolein und/oder acrylsäure
DE10119933A1 (de) 2001-04-23 2002-10-24 Basf Ag Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Gasphasenoxidation von Propan
DE10051419A1 (de) 2000-10-17 2002-04-18 Basf Ag Katalysator bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
DE10122027A1 (de) 2001-05-07 2002-05-23 Basf Ag Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Partialoxidation von Propan
DE10028582A1 (de) * 2000-06-14 2001-12-20 Basf Ag Verfahren zur Herstellung von Acrolein oder Acrylsäure oder deren Gemischen aus Propan
AU2001287622A1 (en) 2000-07-18 2002-01-30 Basf Aktiengesellschaft Method for producing acrylic acid by the heterogeneously catalysed gas-phase oxidation of propane
US6407280B1 (en) 2000-09-28 2002-06-18 Rohm And Haas Company Promoted multi-metal oxide catalyst
US6642173B2 (en) * 2001-04-25 2003-11-04 Rohm And Haas Company Catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004031114A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108949048A (zh) * 2018-08-01 2018-12-07 深圳日高胶带新材料有限公司 一种有机硅阻燃压敏胶粘带及其制备方法
CN108949048B (zh) * 2018-08-01 2021-03-30 深圳日高胶带新材料有限公司 一种有机硅阻燃压敏胶粘带及其制备方法

Also Published As

Publication number Publication date
AU2003285284A1 (en) 2004-04-23
US7038080B2 (en) 2006-05-02
US20040062870A1 (en) 2004-04-01
BR0314347A (pt) 2005-07-26
CN1684936A (zh) 2005-10-19
CN100393684C (zh) 2008-06-11
WO2004031114A1 (fr) 2004-04-15

Similar Documents

Publication Publication Date Title
EP1558569B1 (fr) Masses d'oxyde multimetallique
EP1387823B1 (fr) Procede de production d'acide acrylique par oxydation partielle de propane catalysee de facon heterogene
EP1301457B1 (fr) Procede de production d'acide acrylique par oxydation en phase gazeuse de propane, catalysee de maniere heterogene
EP1335793B1 (fr) Catalyseur constitue d'un support et d'une masse d'oxyde catalytiquement active appliquee sur la surface du support
WO2004031114A1 (fr) Procede d'oxydation partielle en phase gazeuse a catalyse heterogene d'acroleine en acide acrylique
EP2846908A1 (fr) Procédé d'oxydation partielle en phase gazeuse à catalyse hétérogène de (méth)acroléine pour obtenir de l'acide (méth)acrylique
WO2002083615A1 (fr) Procede de production d'acide acrylique par oxydation en phase gazeuse a catalyse heterogene de propene avec de l'oxygene moleculaire dans une zone de reaction
EP1755779A1 (fr) Procédé pour produire une masse d'oxyde multimétallique
DE4442346A1 (de) Verfahren zur Herstellung eines Katalysators, bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Oxidmasse
EP3684505A1 (fr) Synthèse d'un catalyseur à coquille movnbte pour la déshydrogénation oxydante d'éthane en éthylène
DE10248584A1 (de) Multimetalloxidmassen
DE10119933A1 (de) Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Gasphasenoxidation von Propan
WO2004099081A1 (fr) Matieres a base d'oxydes polymetalliques, contenant mo, v et un metal alcalin et presentes en phase i pure
EP4139047A1 (fr) Procédé de production d'un oxyde multi-élément catalytiquement actif contenant les éléments mo, w, v et cu
DE102004027999A1 (de) Verfahren zur Herstellung einer Multimetalloxidmasse
DE10254279A1 (de) Multimetalloxidmassen
DE10261186A1 (de) Verfahren der heterogen katalysierten Gasphasenpartialoxidation von Acrolein zu Acrylsäure
DE10254278A1 (de) Verfahren zur Herstellung einer Multimetalloxidmasse
DE112004000501B3 (de) Mo und V enthaltende Multimetalloxidmassen
US7019169B2 (en) Preparation of (meth)acrylic acid
DE19736105A1 (de) Verfahren zur Herstellung von Multimetalloxidmassen
DE10359027A1 (de) Verfahren zur Herstellung einer Multimetalloxidmasse
DE10344265A1 (de) Verfahren zur Herstellung von (Meth)acrylsäure
DE10338529A1 (de) Verfahren zur Herstellung von (Meth)acrylsäure
DE19740493A1 (de) Verfahren zur Herstellung von Multimetalloxidmassen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050427

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

17Q First examination report despatched

Effective date: 20081105

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100317