EP1758822A1 - Oxyde polymetallique contenant de l'argent, du vanadium et un element du groupe du phosphore, et son utilisation - Google Patents

Oxyde polymetallique contenant de l'argent, du vanadium et un element du groupe du phosphore, et son utilisation

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Publication number
EP1758822A1
EP1758822A1 EP05764306A EP05764306A EP1758822A1 EP 1758822 A1 EP1758822 A1 EP 1758822A1 EP 05764306 A EP05764306 A EP 05764306A EP 05764306 A EP05764306 A EP 05764306A EP 1758822 A1 EP1758822 A1 EP 1758822A1
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EP
European Patent Office
Prior art keywords
multimetal oxide
value
multimetal
vanadium
precatalyst
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.)
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Application number
EP05764306A
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German (de)
English (en)
Inventor
Samuel Neto
Hartmut Hibst
Frank Rosowski
Sebastian Storck
Jürgen ZÜHLKE
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1758822A1 publication Critical patent/EP1758822A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • 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
    • B01J23/38—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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver
    • 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
    • C01P2002/70—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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention relates to a multimetal oxide containing silver, vanadium and an element of the phosphorus group, the use thereof for the production of precatalysts and catalysts for the gas phase partial oxidation of aromatic hydrocarbons, the precatalysts obtained in this way and a process for the preparation of the multimetal oxide or the catalysts.
  • aldehydes, carboxylic acids and / or carboxylic acid anhydrides is produced industrially by the catalytic gas phase oxidation of aromatic hydrocarbons such as benzene, o-, m- or p-xylene, naphthalene, toluene, durol (1, 2,4,5-tetramethylbenzene) or Picolin produced in fixed bed reactors, preferably tube bundle reactors.
  • aromatic hydrocarbons such as benzene, o-, m- or p-xylene, naphthalene, toluene, durol (1, 2,4,5-tetramethylbenzene) or Picolin produced in fixed bed reactors, preferably tube bundle reactors.
  • benzaldehyde, benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic anhydride or nicotinic acid are obtained, for example.
  • WO 00/27753, WO 01/85337 and the earlier application DE-A-10334132 describe multimetal oxides containing silver and vanadium oxide and their use for the preparation of catalysts for the partial oxidation of aromatic hydrocarbons.
  • So-called silver-vanadium oxide bronzes act as the catalytically active constituent of the catalytically active composition of such catalysts.
  • the multimetal oxides illustrated in these documents are produced starting from a suspension of vanadium pentoxide, which is reacted with a solution of a silver compound and optionally other components. In industrial processes, however, the handling of solid suspensions is undesirable since the suspensions tend to inhomogeneity, sedimentation of the solid, clogging of pipes and pumps and the like.
  • the object of the present invention is to provide new, easily accessible multimetal oxides for the production of catalysts for the partial oxidation of aromatic hydrocarbons.
  • the catalysts that can be produced from the multimetal oxides should have similar or better activities and selectivities than the catalysts produced according to the prior art.
  • the object is achieved by multimetal oxides of the general formula (I) Ag a Q b M c V 12 O d * e H 2 O (I), which has a value from 3 to 10,
  • Q represents an element selected from P, As, Sb and / or Bi, has a value from 0.2 to 3,
  • M for one under Li, Na, K, Rb, Cs, Tl, Mg, Ca, Sr, Ba, Cu, Zn, Cd, Pb, Cr, Au, AI, Fe, Co, Ni, Ce, Mn, Nb, W, Ta and / or Mo is selected metal;
  • c has a value from 0 to 3, with the proviso that (a-c)> 0.1,
  • d is a number which is determined by the valency and frequency of the elements other than oxygen in the formula (I), and
  • e has a value from 0 to 20
  • the powder X-ray diffractogram is most preferably characterized by diffraction reflections at all of the specified network plane spacings.
  • the X-ray diffraction reflections are specified in the form of the X-ray radiation independent of the wavelength used
  • Network plane distances d [ ⁇ ] which can be calculated from the measured diffraction angle using Bragg's equation.
  • the powder X-ray diffractogram of the multimetal oxide according to the invention has the 10 characteristic diffraction reflections listed in Table 1.
  • a multimetal oxide of the formula (I) is adequately characterized by at least 5, preferably at least 7, particularly preferably at least 9 and very particularly preferably all of the diffraction reflections listed in Table 1. The presence of all 10 diffraction reflections in the powder X-ray diffractogram is an indication that the multimetal oxide according to the invention is of particularly high crystallinity.
  • the multimetal oxides according to the invention can have further diffraction reflections in addition to the characteristic diffraction reflections reproduced above. Mixtures of the multimetal oxides according to the invention with other crystalline compounds also have additional diffraction reflections. Such mixtures of the multimetal oxide with other crystalline compounds can be produced in a targeted manner by mixing the multimetal oxide with compounds of this type which arise in the preparation of the multimetal oxides due to incomplete conversion of the starting materials or result from impurities.
  • the variable a preferably has a value from 5 to 9 and particularly preferably from 6.5 to 7.5.
  • the value of the variable b is preferably 0.5 to 1.5 and particularly preferably 0.8 to 1.2.
  • the value of the variable c is preferably less than 1 and is particularly preferably 0. It is particularly preferred that the variable a has a value from 5 to 9 and the variable c has the value 0.
  • Q in particular represents the element P.
  • the metal M in the formula (I) is selected in particular from Na, K, Rb, Tl, Au, Cu, Ce, Mn, specifically M stands for Ce or Mn.
  • the specific surface area according to BET measured in accordance with DIN 66 131, which is based on the "Recommendations 1984" of the IUPAC International Union of Pure and Applied Chemistry (see Pure & Appl. Chem. 57, 603 (1985)) is in generally more than 1 m 2 / g, in particular 3 to 100 m 2 / g, and especially 10 to 80 m 2 / g.
  • the manufacture of the multimetal oxides according to the invention is carried out in particular by a process in which
  • the amounts of vanadium compound, silver salt and source of the element Q and, if appropriate, the source of the metal M which result from a, b and c of the formula (I) are reacted with one another.
  • the multimetal oxide according to the invention is obtained after the reaction has ended.
  • water-soluble vanadium compounds in particular Monovanadate (Me come '2 HVO 4) Divanadate (Me' 3 HV 2 O 7), metavanadates (Me'VO 3) Decavanadate (Me '6V. OO 28, Me' 5 HV 10 O 28 and Me ' 4 H 2 V 0 O 28 ) and the dodecavanadates with the anion [V 12 O 32 ] 4 " into consideration, where Me' each represents a monovalent cation equivalent, for example an alkali metal ion or ammonium ion, in particular the metavanadates and especially NaVO 3 and / or (NH 4 ) VO 3.
  • Such water-soluble vanadium compounds are commercially available or can be obtained by reacting V 2 O 5 with alkali metal hydroxides, and soluble vanadium compounds can also be obtained by reacting V 2 O 5 with reducing agents.
  • the solution of the silver salt can be in water or a water-miscible organic solvent, such as alcohols, e.g. B. methanol, polyols, e.g. B. ethylene glycol, or polyethers, e.g. B. ethylene glycol dimethyl ether. Water is preferably used as the solvent.
  • Silver nitrate is preferably used as the silver salt, the use of other soluble silver salts, e.g. However, silver acetate, silver perchloride or silver fluoride is also possible.
  • the element or elements Q from the group P, As, Sb and / or Bi can be used in elemental form or as oxides or hydroxides.
  • they are used in the form of their soluble compounds, particularly preferably their organic or inorganic water-soluble compounds.
  • the inorganic water-soluble compounds in particular the alkali and ammonium salts and especially the partially neutralized or free acids of these elements, for example phosphoric acid, hydrochloric acid, antimony hydrochloric acid, are very particularly preferred Ammonium hydrogen phosphates, arsenates, antimonates and bismuthates and the alkali hydrogen phosphates, arsenates, antimonates and bismuthates.
  • phosphorus alone as element Q, in particular in the form of phosphoric acid, phosphorous acid, hypophosphorous acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphoric acid ester, especially as ammonium dihydrogen phosphate or phosphoric acid and very particularly as phosphoric acid.
  • the salts of the metal component M are generally those which are soluble in the solvent used, in particular the water-soluble salts, e.g. Perchlorates, carboxylates, acetates and nitrates, especially acetates and nitrates, of the relevant metal component M.
  • water-soluble salts e.g. Perchlorates, carboxylates, acetates and nitrates, especially acetates and nitrates, of the relevant metal component M.
  • the solution of the vanadium compound can be combined with the solution of the silver salt and the source of the element Q and, if appropriate, the source of the metal M.
  • the solution of the vanadium compound is reacted with a source of element Q and, if appropriate, a source of metal M, and the solution obtained is combined with the solution of the silver salt.
  • the reaction of the vanadium compound with the source of the element Q and optionally the compound of the metal component M in the presence or absence of the silver compound can generally be carried out at room temperature or at an elevated temperature.
  • the reaction is carried out at temperatures from 20 to 375 ° C., preferably at 20 to 100 ° C. and particularly preferably at 60 to 100 ° C. If the temperature of the reaction is above the temperature of the boiling point of the solvent used, the reaction is expediently carried out in a pressure vessel under the autogenous pressure of the reaction system.
  • the reaction conditions are preferably selected so that the reaction can be carried out at atmospheric pressure.
  • the duration of this reaction can be 10 minutes to 3 days, depending on the type of starting materials used and the temperature conditions used.
  • An extension of the reaction time of the reaction for example to 5 days and more, is possible.
  • the implementation is carried out over a period of 6 to 24 hours.
  • the multimetal oxide according to the invention thus formed can be isolated from the reaction mixture and stored until further use.
  • the multimetal oxide can be isolated, for example, by filtering off the suspension and drying the solid obtained, the drying being able to be carried out both in conventional dryers and also, for example, in freeze dryers.
  • the drying of the multimetal oxide suspension obtained by spray drying is particularly advantageous. guided. It may be advantageous to wash the multimetal oxide obtained in the reaction salt-free before it dries.
  • Spray drying is generally carried out under atmospheric pressure or reduced pressure.
  • the inlet temperature of the drying gas is determined depending on the pressure applied and the solvent used; air is generally used as such, but other drying gases such as nitrogen or argon can also be used.
  • the inlet temperature of the drying gas into the spray dryer is advantageously chosen so that the outlet temperature of the drying gas cooled by evaporation of the solvent does not exceed 200 ° C. for a longer period.
  • the initial temperature of the drying gas is set to 50 to 150 ° C, preferably 80 to 140 ° C.
  • the solution of the vanadium compound is reacted with the source of the element Q and, if appropriate, the source of the metal M, a stream of the solution obtained is continuously mixed with a stream of the silver salt solution and the mixed stream is spray-dried.
  • the multimetal oxide suspension obtained can also be used without further isolation and drying of the multimetal oxide, for example for the production of the precatalysts according to the invention by coating.
  • the multimetal oxides according to the invention are used as a precursor compound for producing the catalytically active composition of catalysts, such as are used for the gas phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides with a gas containing molecular oxygen.
  • the multimetal oxides according to the invention are preferably used for the production of so-called coated catalysts, they can also be used as a precursor for the production of conventional supported catalysts or of unsupported catalysts, that is to say catalysts which do not contain any support material.
  • catalysts for the partial oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides from the multimetal oxides according to the invention expediently takes place via the stage of a so-called “precatalyst” according to the invention, which can be stored and handled as such and from which the active catalyst can be prepared either by thermal treatment can be produced or generated in situ in the oxidation reactor under the conditions of the oxidation reaction.
  • the precatalyst is therefore a precursor of the catalyst which can be converted into one, consisting of an inert non-porous support material and at least one layer applied thereon, which is a multimode contains talloxide according to formula (I).
  • This layer is preferably applied in shell form to the carrier material and preferably comprises 30 to 100% by weight, in particular 50 to 100% by weight, based on the total weight of this layer, of a multimetal oxide of the formula (I).
  • the layer particularly preferably consists entirely of a multimetal oxide of the formula (I).
  • the catalytically active layer contains other components besides the multimetal oxide according to formula (I), this can e.g. Inert materials, such as silicon carbide or steatite, or else other known catalysts for the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides on vanadium oxide. Be anatase base.
  • the precatalyst preferably contains 5 to 25% by weight, based on the total weight of the precatalyst, of multimetal oxide.
  • non-porous is to be understood in the sense of "except for technically ineffective amounts of pores non-porous", since technically inevitably a small number of pores can be present in the carrier material, which ideally should not contain any pores.
  • Steatite and silicon carbide are particularly worth mentioning as advantageous carrier materials.
  • the shape of the support material is generally not critical for the precatalysts according to the invention.
  • catalyst supports in the form of spheres, rings, tablets, spirals, tubes, extrudates or grit can be used.
  • the dimensions of these catalyst supports correspond to the catalyst supports usually used for the production of shell catalysts for the gas phase partial oxidation of aromatic hydrocarbons.
  • the abovementioned support materials can also be mixed in powder form with the catalytically active composition of the shell precatalysts according to the invention.
  • the suspension obtained in the reaction of the vanadium compound with the source of the element Q, the silver compound and optionally the compound of the metal component M according to the processes of DE-A 16 92 938 and DE-A 17 69 998 in a heated coating drum at elevated temperature are sprayed onto the catalyst support, which consists of an inert support material, until the desired amount of multimetal oxide, based on the total weight of the precatalyst, is reached.
  • fluid bed coaters as described in DE-A 12 80 756, can be used analogously to DE-A 21 06 796 for the shell-shaped application of the multimetal oxide according to the invention to the catalyst support.
  • a slurry of the powder of the multimetal oxide according to the invention obtained after isolation and drying can be used in these coating processes.
  • the suspension of the multimetal oxide according to the invention as it is produced during its production, or a slurry of a powder of the dried multimetal oxide according to the invention in water, an organic solvent, such as higher alcohols, polyhydric alcohols, for example ethylene glycol, 1, 4-butanediol or glycerin, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone or cyclic ureas, such as N, N'-dimethylethylene urea or N, N'-dimethylpropylene urea, or in mixtures of these organic solvents with water , organic binders, preferably copolymers, dissolved or advantageously added in the form of an aqueous dispersion, generally using binder contents of 10 to 20% by weight, based on the solids content of the suspension or slurry of the multimetal oxide according to the invention.
  • an organic solvent such as higher alcohols, polyhydric alcohols, for example ethylene glycol,
  • Suitable binders are, for example, vinyl acetate / vinyl laurate, vinyl acetate / acrylate, styrene / acrylate, vinyl acetate / maleate or vinyl acetate / ethylene copolymers. If organic copolymer polyesters, for example based on acrylate / dicarboxylic acid anhydride / alkanolamine, are added as a binder in a solution in an organic solvent to the slurry of the multimetal oxide according to the invention, the content of binder can be analogous to the teaching of DE-A 198 23 262.4 1 to 10% by weight, based on the solids content of the suspension or slurry, can be reduced.
  • coating temperatures of 20 to 500 ° C. are generally used, it being possible for the coating in the coating apparatus to be carried out under atmospheric pressure or under reduced pressure.
  • the coating is generally carried out at 0 ° C. to 200 ° C., preferably at 20 to 150 ° C., in particular at room temperature to 100 ° C.
  • higher coating temperatures e.g. Temperatures of 200 to 500 ° C apply.
  • the binder escapes from the applied layer by thermal decomposition and / or combustion.
  • the conversion of the precatalyst into a coated catalyst can also be carried out by thermal treatment at temperatures above 500 ° C., for example at temperatures up to 650 ° C., preferably the thermal treatment at temperatures from 200 to 500 ° C., in particular at 300 to 450 ° C. carried out.
  • the multimetal oxides according to the invention decompose with the formation of catalytically active silver vanadium oxide bronzes.
  • Silver-vanadium oxide bronzes are understood to mean silver-vanadium oxide compounds with an atomic Ag: V ratio of less than 1. They are generally semiconducting or metallically conductive, oxidic solids, which preferably crystallize in layer or tunnel structures, the vanadium in the [V 2 O 5 ] host lattice being partially reduced to V (IV).
  • some of the multimetal oxides applied to the catalyst support can already be converted to catalytically active silver-vanadium oxide bronzes and / or silver-vanadium oxide compounds which are not elucidated crystallographically with regard to their structure and which can be converted into the silver-vanadium oxide bronzes mentioned. be decomposed. This decomposition takes place practically completely at coating temperatures of 300 to 500 ° C., so that with a coating at 300 to 500 ° C. the finished coated catalyst can be obtained without going through the precursor of the precatalyst.
  • the multimetal oxides contained in the precatalyst decompose to form silver vanadium oxide bronzes.
  • This conversion of the multimetal oxides according to the invention contained in the precatalyst to silver-vanadium oxide bronzes takes place in particular in situ in the reactor for the gas phase partial oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides, for example in the reactor for producing phthalic anhydride from o-xylene and / or naphthalene , at the generally applied temperatures of 300 to 450 ° C instead of using a precatalyst according to the invention in this reaction instead of a finished shell catalyst.
  • a constant increase in the selectivity of the coated catalyst can generally be observed.
  • the resulting silver vanadium oxide bronzes are thus a catalytically active component of the catalytically active layer of the finished coated catalyst.
  • coated catalyst consists in the thermal treatment of the multimetal oxide powder according to the invention at temperatures of above 200 to 650 ° C. and the coating of the inert non-porous catalyst support, optionally with the addition of a binder, with the silver-vanadium oxide bronze obtained in this way.
  • the coated catalysts from the precatalysts according to the invention can be particularly advantageously in one stage or, if appropriate, after a thermal treatment in the course of or after the coating of the catalyst support, in multiple stages, in particular in one stage, in each case in situ in the oxidation reactor under the conditions of the oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides.
  • Another object of the invention is thus a process for the preparation of catalysts for the gas phase partial oxidation of aromatic hydrocarbons, consisting of an inert non-porous support and at least one layer applied thereon, which comprises a silver-vanadium oxide-bronze as catalytically active composition, by heat treatment of a precatalyst according to the invention.
  • the catalysts obtained in this way are used for the partial oxidation of aromatic or heteroaromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic acid anhydrides, in particular for the gas phase partial oxidation of o-xylene and / or naphthalene to phthalic anhydride, from toluene to benzoic acid and / or benzaldehyde, or from methylpyridines, such as / ff-picoline to pyridinecarboxylic acids, such as nicotinic acid, used with a molecular oxygen-containing gas.
  • the catalysts can be used alone or in combination with other, differently active catalysts, for example catalysts based on vanadium oxide / anatase, the different catalysts generally in separate catalyst beds arranged in one or more fixed catalyst beds can be arranged in the reactor.
  • the BET surfaces, crystallographic structures and vanadium oxidation levels of the silver vanadium oxide bronzes which can be produced from the multimetal oxides according to the invention are essentially comparable to those of the known silver vanadium oxide bronzes.
  • a powder X-ray diffractogram was obtained from the powder obtained using a D 5000 diffractometer from Siemens using Cu-K ⁇ radiation (40 kV, 30 mA) added.
  • the diffractometer was equipped with an automatic primary and secondary diaphragm system as well as a secondary monochromator and scintillation detector.
  • the powder obtained had a BET specific surface area of 14 m 2 / g and a vanadium oxidation state of 5.
  • a powder X-ray diffractogram was recorded from the powder obtained.
  • the following network plane distances d [ ⁇ + 0.04] with the associated relative intensities l r ⁇ ⁇ [%] were determined from the powder X-ray diffractogram: 7.13 (18.6), 5.52 (19.3), 5.14 ( 43.7), 3.57 (33.0), 3.25 (73.4), 2.83 (64.1), 2.79 (100), 2.73 (85.1), 2, 23 (31, 4), 1.71 (46.4).
  • the powder obtained had a BET specific surface area of 24 m 2 / g and a vanadium oxidation state of 5.
  • a powder X-ray diffractogram was recorded from the powder obtained. From the powder X-ray diffractogram, the following network plane distances d [ ⁇ ⁇ 0.04] with the corresponding relative intensities l re , [%] determined: 7.13 (17.9), 5.53 (15.0), 5.15 (48.4), 3.57 (34.7), 3.25 (80.2), 2.83 (64.2), 2.79 (100), 2.73 (88.8), 2.23 (30.1 ), 1.72 (53.2).
  • the powders A1, A2 and A3 prepared were applied to magnesium silicate spheres as follows: 300 g steatite spheres with a diameter of 3.5 to 4 mm were placed in a coating drum at 20 ° C. for 20 min with 40 g of the respective powder and 4.4 g of oxalic acid with the addition of 35.3 g of a mixture containing 60% by weight of water and 40% by weight of glycerol and then dried.
  • the weight of the catalytically active composition thus applied determined on a sample of the precatalyst obtained, was 10% by weight, based on the total weight of the finished catalyst, after heat treatment at 400 ° C. for one hour.
  • the precatalysts A.1, A.2 and A.3 (coated steatite balls) produced according to B were filled into an 80 cm long iron tube with a clear width of 16 mm up to a bed length of 66 cm.
  • the iron pipes were surrounded by an electric heating jacket for temperature control.
  • 360 Nl / h of air were passed through the tubes from top to bottom at 350 ° C. with a load of 98.5% by weight o-xylene of 60 g o-xylene / Nm 3 air.
  • Table 2 The results obtained are summarized in Table 2 below.
  • CO x selectivity corresponds to the proportion of o-xylene converted to combustion products (CO, CO 2 ); the residual selectivity to 100% corresponds to the proportion of the o-xylene converted to the valuable product phthalic anhydride and the intermediates o-tolylaldehyde, o-tolylic acid and phthalide and by-products such as maleic anhydride, citraconic anhydride and benzoic acid.
  • a BET surface area of the active composition of 6.7 m 2 / g and a vanadium oxidation state of 4.63 were determined on an expansion sample of the catalyst A.1.
  • the following network plane distances d [A] with the associated relative intensities l re ⁇ [%] were determined from the powder X-ray diffractogram: 4.85 (9.8), 3.50 (14.8), 3.25 (39.9) , 2.93 (100), 2.78 (36.2), 2.55 (35.3), 2.43 (18.6), 1.97 (15.2), 1.95 (28, 1), 1, 86 (16.5), 1, 83 (37.5), 1, 52 (23.5).
  • the expansion samples of catalysts A.2 and A.3 show similar powder X-ray diffractograms, the BET surface area is in each case approx. 6 m 2 / g and the vanadium oxidation state is 4.69.

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Abstract

L'invention concerne un nouvel oxyde polymétallique de formule générale Aga-cQbMcV12Od * e H2O (I), dans laquelle a désigne une valeur de 3 à 10, Q désigne un élément choisi parmi P, As, Sb et/ou Bi, b désigne une valeur de 0,2 à 3, M désigne un métal, c désigne une valeur de 0 à 3, sous réserve que (a-c)= 0,1, d désigne un nombre qui est déterminé en fonction de la valence et de l'abondance des éléments différents de l'oxygène dans la formule (I), et e désigne une valeur de 0 à 20, ledit oxyde se présentant en une structure cristalline, dont le diffractogramme aux rayons X de la poudre est caractérisé par une réflexion par diffraction, d'au moins 5 pour d = 7,13; 5,52; 5,14; 3,57; 3,25; 2,83; 2,79; 2,73; 2,23 et 1,71Å (± 0,04Å) intervalles de plans de réseau sélectionnés. Les oxydes polymétalliques sont utilisés pour la fabrication de pré-catalyseurs et de catalyseurs pour l'oxydation partielle en phase gazeuse des hydrocarbures aromatiques. Les oxydes polymétalliques sont transformés, par traitement thermique, en bronzes à l'argent-oxyde de vanadium, lesquels sont des composants à activité catalytique des catalyseurs.
EP05764306A 2004-06-15 2005-06-14 Oxyde polymetallique contenant de l'argent, du vanadium et un element du groupe du phosphore, et son utilisation Withdrawn EP1758822A1 (fr)

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DE102004028930A DE102004028930A1 (de) 2004-06-15 2004-06-15 Silber, Vanadium und ein Element der Phosphorgruppe enthaltendes Multimetalloxid und dessen Verwendung
PCT/EP2005/006366 WO2005123596A1 (fr) 2004-06-15 2005-06-14 Oxyde polymetallique contenant de l'argent, du vanadium et un element du groupe du phosphore, et son utilisation

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US (1) US20080019892A1 (fr)
EP (1) EP1758822A1 (fr)
JP (1) JP2008502567A (fr)
KR (1) KR20070028413A (fr)
CN (1) CN1968895A (fr)
BR (1) BRPI0511970A (fr)
DE (1) DE102004028930A1 (fr)
MX (1) MXPA06013510A (fr)
RU (1) RU2007100582A (fr)
TW (1) TW200603884A (fr)
WO (1) WO2005123596A1 (fr)

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DE10334132A1 (de) 2003-07-25 2005-04-07 Basf Ag Silber, Vanadium und ein Promotormetall enthaltendes Multimetalloxid und dessen Verwendung
DE102005061383A1 (de) * 2005-12-21 2007-06-28 Basf Ag Verfahren zur Herstellung einer Silber und Vanadium enthaltenden Multimetalloxidmasse und Katalysator zur Gasphasenpartialoxidation
DE112010001858B4 (de) 2009-05-29 2013-12-24 Hach Company Chrom-freie Anzeigevorrichtung zur Chloriderfassung
BR112013033277B1 (pt) 2011-06-28 2020-03-10 Asahi Kasei Chemical Corporation Catalisador de óxido, e, método para produzir o mesmo
WO2013068898A1 (fr) * 2011-11-11 2013-05-16 Basf Se Phosphate de vanadium-argent
CN109718768B (zh) * 2017-10-31 2024-07-09 中国石油化工股份有限公司 一种钒银钼金属氧化物催化剂、制备方法及其应用
CN110961104A (zh) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 一种钒银钨金属氧化物催化剂、其制备方法及其应用
CN111135829B (zh) * 2020-01-02 2022-09-20 万华化学集团股份有限公司 一种氨氧化催化剂及其制备方法和应用
CN113926452A (zh) * 2020-06-29 2022-01-14 中国石油化工股份有限公司 一种钒银铋金属氧化物催化剂、制备方法及其应用
CN114160133A (zh) * 2020-09-11 2022-03-11 中国石化扬子石油化工有限公司 一种Ag掺杂V2O5纳米带催化剂及其应用

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BRPI0511970A (pt) 2008-01-22
TW200603884A (en) 2006-02-01
CN1968895A (zh) 2007-05-23
JP2008502567A (ja) 2008-01-31
WO2005123596A1 (fr) 2005-12-29
RU2007100582A (ru) 2008-07-20
US20080019892A1 (en) 2008-01-24
MXPA06013510A (es) 2007-03-01
DE102004028930A1 (de) 2006-01-05

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