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EP2271424A2 - Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène - Google Patents

Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène

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Publication number
EP2271424A2
EP2271424A2 EP09730114A EP09730114A EP2271424A2 EP 2271424 A2 EP2271424 A2 EP 2271424A2 EP 09730114 A EP09730114 A EP 09730114A EP 09730114 A EP09730114 A EP 09730114A EP 2271424 A2 EP2271424 A2 EP 2271424A2
Authority
EP
European Patent Office
Prior art keywords
molybdenum
layer
oxide
carrier body
coated
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Withdrawn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
EP09730114A
Other languages
German (de)
English (en)
Inventor
Alexander Czaja
Martin Kraus
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09730114A priority Critical patent/EP2271424A2/fr
Publication of EP2271424A2 publication Critical patent/EP2271424A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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
    • B01J23/70—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
    • B01J23/8878—Chromium
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/04—Dehydrogenation
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • Shell catalysts containing a molybdenum-containing multimetal Shell catalysts containing a molybdenum-containing multimetal
  • the present invention relates to coated catalysts comprising a catalytically active, molybdenum-containing multimetal.
  • the active Mass is a molybdenum-containing multimetal.
  • the term multimetal oxide expresses the fact that the active mass in addition to molybdenum and oxygen still contains at least one other chemical element.
  • Catalysts of the aforementioned type are suitable, for example, for the catalysis of the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid.
  • EP-A 990636 and EP-A 1106598 suggest that the reduction in the activity of the fixed catalyst bed is largely compensated for by the fact that the temperature of the fixed catalyst bed is gradually increased in the course of the operating time under otherwise largely constant operating conditions in order to reduce the acrolein conversion once Passage of the reaction gas mixture through the fixed catalyst bed substantially maintain.
  • a disadvantage of this procedure is that as the temperature of the fixed catalyst bed increases, the aging process accelerates progressively. Finally, the catalyst bed must be completely replaced.
  • DE-A 102004025445 proposes the long-term operation of the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid, the deactivation of the catalyst. Counteract catalyst fixed bed by the fact that the working pressure in the gas phase is increasingly increased with increasing service life of the fixed catalyst bed. A disadvantage of this procedure is that with increasing working pressure in the heterogeneously catalyzed partial gas phase oxidation increased compression powers are required gene.
  • EP-A 614872 recommends prolonging the service life of the fixed catalyst bed by interrupting the partial oxidation process after several years of operation of the fixed catalyst bed and passing a regeneration gas mixture of oxygen, water vapor and inert gas through the catalyst catalyst bed at elevated temperature, followed by partial oxidation continues.
  • EP-A 0 630 879 describes a process for the catalytic oxidation of propene, isobutene or tert-butanol over a multimetal oxide catalyst comprising molybdenum, bismuth and iron, in the presence of a molybdenum oxide which is essentially catalytically inactive.
  • the presence of the molybdenum oxide inhibits the deactivation of the multimetal oxide catalyst.
  • the molybdenum oxide can be present in the form of separate molybdenum oxide particles, optionally on a support, in admixture with particles of the multimetal oxide catalyst. It is also possible to prepare a mixture of pulverulent molybdenum oxide and pulverulent multimetal oxide catalyst and to extrude the mixture into shaped catalyst bodies or to apply it to a support.
  • German patent application DE 10 2007 010 422 describes a deactivation of shell catalysts for the heterogeneously catalyzed partial gas phase oxidation of acrolein to acrylic acid, the active composition of which is a finely divided multi-element oxide containing Mo and V applied to a support body. that the catalytically active material from the Mo and V-containing multimetal oxide, an oxide of molybdenum or a compound fertilize the molybdenum, from which forms an oxide of molybdenum admixed.
  • the shell catalyst is coated with a mixture of molybdenum oxide or the precursor compound and the multimetal oxide.
  • the object of the invention is to provide catalysts based on molybdenum-containing multi-metal oxides which have improved deactivation behavior.
  • a shell catalyst comprising
  • the object is further achieved by a process for the preparation of the coated catalysts according to the invention, in which applying a first layer of a molybdenum oxide or a precursor compound which forms molybdenum oxide on a carrier body by means of a binder, optionally drying the coated with the first layer carrier body and calcined, and applied to the first layer by means of a binder, a second layer of a molybdenum-containing multimetal, and drying and calcining the coated with the first and second layer carrier body.
  • the object is further achieved by the use of the coated catalysts according to the invention in processes for the catalytical gas-phase oxidation of organic compounds.
  • the first layer may comprise a molybdenum oxide or a precursor compound which forms molybdenum oxide.
  • the precursor compound is a compound of molybdenum from which an oxide of molybdenum forms under the action of elevated temperature and in the presence of molecular oxygen.
  • the action of the elevated temperature and of the molecular oxygen can take place following the application of the precursor compound to the surface of the carrier body.
  • a thermal treatment z. B. under an oxygen or air atmosphere.
  • suitable precursor compounds other than an oxide of molybdenum include ammonium molybdate [(NH 4 J 2 MoO 4 ] and ammonium polymolybdate such as ammonium heptamolybdate tetrahydrate [(NH 4 J 6 Mo 7 O 24 • 4 H 2 O].
  • ammonium molybdate [(NH 4 J 2 MoO 4 ]
  • ammonium polymolybdate such as ammonium heptamolybdate tetrahydrate [(NH 4 J 6 Mo 7 O 24 • 4 H 2 O].
  • molybdenum oxide hydrate MoO 3 ⁇ xH 2 O
  • molybdenum hydroxides are also suitable precursor compounds of this type.
  • the conversion of the precursor compound into an oxide of molybdenum by the action of heat and oxygen can also be carried out only during the use of the catalyst in the catalytic gas phase oxidation.
  • the first layer preferably already contains an oxide of molybdenum.
  • an oxide of molybdenum This is understood as meaning a substance which consists of ⁇ 98% by weight, preferably ⁇ 99% by weight and more preferably ⁇ 99.9% by weight and more, only of Mo and O.
  • Particularly preferred molybdenum oxide is molybdenum trioxide (MoO 3 ).
  • molybdenum oxides are, for example Mo 18 O 52, Mo 8 O 23 and Mo 4 O 11 (see, e.g., Surface Sc;.. Ence 292 (1993) 261-6, or J. Solid State Chem 124 (1996) 104th ).
  • the specific surface area 0 M of a suitable molybdenum oxide is ⁇ 10 2 m 2 / g, preferably ⁇ 5 m 2 / g and particularly preferably ⁇ 2 m 2 / g. In general, however, the specific surface area 0 M will be ⁇ 0.01 m 2 / g, frequently ⁇ 0.05 m 2 / g and in many cases 0.1 m 2 / g.
  • the specific surface area is understood to mean the BET surface area (determined by gas adsorption (N 2 ) according to Brunauer-Emmet-Teller (BET)).
  • BET Brunauer-Emmet-Teller
  • the above statements regarding O M apply in particular when the finely divided molybdenum oxide is MoO 3 .
  • the advantageousness of a low value for O M is due to the fact that a molybdenum oxide with a low value for O M is largely inert in the context of an oxidative alkane dehydrogenation.
  • Particle diameter distributions and particle diameters d x taken from them (eg d 10 , or d 50 , or d 90 ) refer to determinations according to ISO 13320 with the Malvern Mastersizer S laser diffraction spectrometer (Malvern Instruments, Worcestshire WR 14 1AT, United Kingdom).
  • the particle diameter d x indicated as the measurement result is defined such that X% of the total particle volume consists of particles with this or a smaller diameter.
  • precursor compounds or molybdenum oxides are generally used for which 0.1 ⁇ m ⁇ d 50 ⁇ 800 ⁇ m, preferably 0.5 ⁇ m ⁇ d 50 ⁇ 600 ⁇ m, particularly preferably 0.75 ⁇ m ⁇ d 50 ⁇ 400 ⁇ m, and most preferably 1 ⁇ m ⁇ d 50 ⁇ 200 ⁇ m.
  • the grain size of the precursor compound or the molybdenum oxide is adapted to the desired thickness D A of the first layer on the surface of the carrier body.
  • d is 50 ⁇ D A, preferably ⁇ 0,75 • D A, particularly preferably ⁇ 0.5 • D A and very particularly preferably ⁇ 0.3 • D A. Normalerwei- However, d 50 will be ⁇ 0.001 • D A , or> 0.01 • D A , often ⁇ 0.05 • D A and often> 0.1 • D A.
  • a suitable molybdenum oxide (eg MoO 3 ) can be produced from a precursor compound containing another Mo.
  • z. B. of ammonium heptamolybdate tetrahydrate [(NH 4 ) B Mo 7 O 24 • 4 H 2 O] are assumed.
  • thermal treatment at 350 0 C in likewise a temperature of 350 0 C having air flow this is converted into MoO 3 .
  • the grain size of the MoO 3 can be adjusted as required by appropriate grinding and sieving.
  • the specific surface area of the MoO 3 can be adjusted as desired. With increasing duration of the thermal treatment and / or increase in the temperature of the thermal treatment (after MoO 3 has been formed under inert gas or under a molecular oxygen-containing gas atmosphere, eg air), the specific surface area decreases.
  • MoO 3 is suitable for the Climax Molybdenum Marketing Corporation (Phoenix, USA), which has a Mo content of 66.60% by weight and a specific surface O M of 3.7 m 2 / g (trade name : "Pure Mooney Oxide Crystalline POC").
  • the aforementioned MoO 3 additionally has the following foreign constituent specification: Na ⁇ 8 ppm by weight, K ⁇ 29 ppm by weight, Fe ⁇ 4 ppm by weight, Pb ⁇ 1 ppm by weight, Al ⁇ 4% by weight ppm, Cr ⁇ 2 ppm by weight, Ca ⁇ 2 ppm by weight, Cu ⁇ 2 ppm by weight, Mg ⁇ 5 ppm by weight, Ni ⁇ 2 ppm by weight, Si ⁇ 5% by weight. ppm, Sn ⁇ 1 ppm by weight, and Ti ⁇ 2 ppm by weight.
  • MoO 3 from Climax Molybdenum Marketing Corporation of the "POS" type of trade can also be used according to the invention
  • MoO 3 from the company HC Starck, D-38615 Goslar can be used for the process according to the invention as commercial MoO 3 (trade name: "Molybdenum Trioxide I"). This has a specific surface O M of 1 m 2 / g. The Mo content of this MoO 3 is 66.6 wt .-%.
  • MoO 3 from the following manufacturers can also be used:
  • the catalytically active, molybdenum-containing multimetal oxide may be, for example, a Mo and V-containing multimetal oxide of the general formula (I),
  • X 2 Cu, Ni, Co, Fe, Mn and / or Zn,
  • X 3 Sb and / or Bi
  • X 4 one or more alkali metals (Li, Na, K, Rb, Cs) and / or H,
  • Such molybdenum and vanadium-containing multimetal oxides are known as catalysts for the selective gas phase oxidation of propene to acrolein.
  • the catalytically active molybdenum-containing multimetal oxide is preferably a multimetal oxide of the general formula II
  • X 2 Si and / or Al
  • X 3 Li, Na, K, Cs and / or Rb, 0.2 ⁇ a ⁇ 1,
  • the stoichiometric coefficient a is preferably 0.4 ⁇ a ⁇ 1, more preferably 0.4 ⁇ a ⁇ 0.95.
  • the stoichiometric coefficient b is preferably in the range 0.1 ⁇ b ⁇ 2, and particularly preferably in the range 0.1 ⁇ b ⁇ 1.
  • the stoichiometric coefficient c is preferably in the range 4 ⁇ c ⁇ 8, and particularly preferably in the range 6 ⁇
  • the value for the variable d is advantageously in the range 1 ⁇ d ⁇ 5 and with particular advantage in the range 2 ⁇ d ⁇ 4.
  • the stoichiometric coefficient f is expediently> 0. Preferably, 0.01 ⁇ f ⁇ 0 , 5 and more preferably 0.05 ⁇ f ⁇ 0.2.
  • Coated catalysts according to the invention with catalytically active oxide whose molar ratio of Co / Ni is at least 2: 1, preferably at least 3: 1 and more preferably at least 4: 1. The best is only Co.
  • Such molybdenum-containing multimetal oxides are not only suitable for the selective gas phase oxidation of propene to acrolein, but also for the partial gas phase oxidation of other alkenes, alkanes, alkanones or alkanols to alpha, beta-unsaturated aldehydes and / or carboxylic acids.
  • Examples include the preparation of methacrolein and methacrylic acid from isobutene, isobutane, tert-butanol or tert-butyl methyl ether.
  • Preferred gas phase oxidations for which the coated catalysts according to the invention are used are oxidative dehydrogenations of alkenes to 1,3-dienes, in particular of 1-butene and / or 2-butene to 1,3-butadiene.
  • one of the starting compounds of the elemental constituents of the catalytically active oxide material produces an intimate dry mixture and treating the intimate dry blend at a temperature of 150 to 350 0 C thermally.
  • suitable finely divided multimetal oxide masses starting from known starting compounds of the elemental constituents of the desired multimetal oxide composition in the respective stoichiometric ratio is started, and from these produces a very intimate, preferably finely divided dry mixture, which then undergoes thermal treatment is subjected.
  • the sources can either already be oxides, or those compounds which can be converted into oxides by heating in the presence of oxygen.
  • suitable starting compounds are, in particular, halides, nitrates, formates, oxalates, acetates, carbonates or hydroxides.
  • Suitable starting compounds of Mo are also its oxo compounds (lybdate) or derived from these acids.
  • Suitable starting compounds of Bi, Fe and Co are in particular their nitrates.
  • the intimate mixing of the starting compounds can in principle be carried out in dry or in the form of aqueous solutions or suspensions.
  • the intimate mixing takes place in the form of aqueous solutions or aqueous suspensions.
  • Particularly intimate dry mixtures are obtained in the described mixing process when starting exclusively from sources and starting compounds present in dissolved form.
  • the solvent used is preferably water.
  • the aqueous mass (solution or suspension) is dried and the resulting intimate dry mixture optionally directly thermally treated.
  • the drying process is carried out by spray drying (the outlet temperatures are generally 100 to 150 0 C) and immediately after the completion of the aqueous solution or suspension.
  • the resulting powder for immediate further processing often proves to be too finely divided, it is expediently kneaded with the addition of water.
  • a lower organic carboxylic acid eg acetic acid
  • Typical additional amounts are from 5 to 10 wt .-%, based on the powder mass.
  • Support materials suitable for shell-type catalysts obtainable according to the invention are e.g. porous or preferably non-porous aluminum oxides, silicon dioxide, zirconium oxide, silicon carbide or silicates such as magnesium or aluminum silicate (for example C 220 steatite from CeramTec).
  • the materials of the carrier bodies are chemically inert.
  • the carrier bodies may be regularly or irregularly shaped, with regularly shaped carrier bodies having a distinct surface roughness, e.g. B. balls, cylinders or hollow cylinder with chippings, are preferred. Their longest extent is usually 1 to 10 mm.
  • the support materials may be porous or non-porous.
  • the carrier material is preferably non-porous (total volume of the pores based on the volume of the carrier body preferably ⁇ 1% by volume).
  • An increased surface roughness of the carrier body usually requires an increased adhesive strength of the applied shell of the first and second layers.
  • the surface roughness R z of the carrier body is in the range of 30 to 100 ⁇ m, preferably 50 to 70 ⁇ m (determined according to DIN 4768 Part 1 with a "Hommel tester for DIN-ISO surface measurement quantities" from Hommelwerke).
  • Surface-roughened carrier bodies from CeramTec made of steatite C 220 are particularly preferred.
  • Particularly suitable according to the invention is the use of substantially nonporous, surface-rough, spherical supports made of steatite (eg steatite of the C 220 type from CeramTec) whose diameter is 1 to 8 mm, preferably 2 to 6 mm, particularly preferably 2 to 3 or 4 to 5 mm.
  • steatite eg steatite of the C 220 type from CeramTec
  • cylinders as support bodies whose length is 2 to 10 mm and whose outer diameter is 4 to 10 mm.
  • the wall thickness is usually 1 to 4 mm.
  • annular support body Preferably to be used annular support body have a length of 2 to 6 mm, an outer diameter of 4 to 8 mm and a wall thickness of 1 to 2 mm.
  • rings of geometry 7 mm x 3 mm x 4 mm outer diameter x length x inner diameter
  • the shell thickness D A of the applied on the support body first layer of molybdenum oxide or the precursor compound is usually at 5 to 1000 microns. Preferred are 10 to 500 microns, more preferably 20 to 250 microns and most preferably 30 to 150 microns.
  • the shell thickness D 8 of the second layer of a molybdenum-containing multimetal oxide material applied to the first layer is generally from 5 to 1000 ⁇ m. Preferred are 10 to 500 microns, more preferably 20 to 250 microns and most preferably 30 to 150 microns.
  • the grain size (fineness) of the Mo-containing finely divided multimetal oxide is adjusted in the same way as the grain size of the molybdenum oxide or the precursor compound to the desired shell thickness D B. All statements made with regard to the longitudinal expansion d L of the molybdenum oxide or of the precursor compound therefore apply correspondingly to the longitudinal expansion d L of the finely divided Mo-containing multimetal oxide.
  • the mass ratio of the second layer of multimetal oxide to the first layer of molybdenum oxide in the final calcined catalyst is generally from 100: 1 to 1: 1, preferably from 50: 1 to 5: 1.
  • the application of the finely divided masses (molybdenum oxide or precursor compound or molybdenum-containing multimetal oxide) to the surface of the carrier body can in accordance with the methods described in the prior art, for example as described in US-A 2006/0205978 and EP-A 0 714 700.
  • the finely divided masses are applied to the surface of the carrier body or to the surface of the first layer by means of a liquid binder.
  • a liquid binder z.
  • water an organic solvent or a solution of an organic substance (eg., An organic solvent) in water or in an organic solvent into consideration.
  • organic binders mono- or polyhydric organic 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 diethanolamine and mono- or polyhydric organic amides such formamide.
  • organic soluble organic binder promoters are, for.
  • monosaccharides and oligosaccharides such as glucose, fructose, sucrose and lactose suitable.
  • the liquid binder used is particularly advantageously a solution consisting of 20 to 98% by weight of water and 2 to 80% by weight of an organic compound.
  • the organic content of the aforementioned liquid binders is 2 to 50 and more preferably 5 to 20 wt .-%.
  • the boiling point or sublimation point of such organic binders or binder constituents is at the same time below the highest calcination temperature used in the preparation of the finely divided multimetal oxide containing the Mo moieties.
  • Ub SHORT- is this highest calcination temperature at ⁇ 600 0 C, often at ⁇ 500 0 C or at ⁇ 400 0 C, sometimes even at ⁇ 300 0 C.
  • Particularly preferred liquid binders are solutions which consist of 20 to 98% by weight of water and 2 to 80% by weight of glycerol.
  • the proportion of glycerol in these aqueous solutions is preferably 2 to 50% by weight and more preferably 5 to 20% by weight.
  • the application of the molybdenum oxide or the precursor compound and the Mo-containing finely divided multimetal oxide can be carried out in such a way that the finely divided ge substance disperses dispersed in the liquid binder and sprayed the resulting suspension to moving and optionally hot carrier body, as described in DE-A 1642921, DE-A 2106796 and DE-A 2626887.
  • the coated carrier body After application of the first layer of molybdenum oxide or the precursor compound, the coated carrier body can be dried and calcined. Subsequently, in the same manner, the second layer of Mo-containing multimetal oxide is applied to the first layer, dried and calcined. However, it is also possible to apply the second layer directly to the first layer in the manner described above without drying and calcining beforehand, and drying and calcining first the carrier body coated with first and second layers. Preferably, after application of the first layer, the coated carrier body is dried.
  • the carrier body is first moistened with the liquid binder, and subsequently the finely divided mass (molybdenum oxide or precursor compound) is applied to the surface of the carrier body moistened with the binder by rolling the moistened carrier body in the finely divided mass.
  • the method described above is preferably repeated several times, i. H. the base-coated carrier body is moistened again and then coated by contact with dry finely divided mass.
  • the coated carrier body After application of the first layer of molybdenum oxide or the precursor compound, the coated carrier body can be dried and calcined. Subsequently, the second layer of multimetal oxide is applied in the same manner, and dried the first and second layer coated carrier body and calcined.
  • the coated carrier body is calcined at a temperature of 150 to 600 0 C, preferably from 270 to 500 0 C.
  • the calcination time is generally 2 to 24 hours, preferably 5 to 20 hours.
  • the calcination is carried out in an oxygen-containing atmosphere, preferably air and / or lean air.
  • the calcination is carried out according to a temperature program in which a total of 2 to 10 h at temperatures between 150 and 350 0 C, preferably calcined 200 to 300 0 C and then calcined at temperatures between 350 and 550 0 C, preferably 400 to 500 0 C calcined.
  • a calcining temperature of about 300 0 C is sufficient, wherein after application of the second layer is preferably calcined at at least 400 0 C.
  • the molybdenum oxide, the molybdenum oxide-forming precursor compound and the catalytically active molybdenum-containing multimetal oxide composition may each contain a pore-forming agent. This may be contained in the finely divided masses or added to the liquid binder.
  • Suitable pore formers are, for example, malonic acid, melamine, nonylphenol ethoxylate, stearic acid, glucose, starch, fumaric acid and succinic acid. Preference is given to stearic acid, nonylphenol ethoxylate and melamine.
  • Pore formers are generally present in amounts of from 1 to 40% by weight, preferably from 1 to 20% by weight, in the masses applied to the carrier body, these details being based on the sum of all components of the respective layer (molybdenum oxide or precursor compound, Pore-forming agent, binder or multimetal oxide, pore-forming agent, binder).
  • the carrier bodies to be coated are filled into a preferably inclined (the angle of inclination is generally 30 to 90 °) rotating rotary container (eg turntable or coating pan).
  • the rotating rotary container guides the in particular spherical, cylindrical or hollow-cylindrical carrier bodies under two metering devices arranged at a certain distance one after the other.
  • the first of the two metering devices is expediently a nozzle, through which the carrier bodies rolling in the rotating turntable are sprayed with the liquid binder to be used and moistened in a controlled manner.
  • the second metering device is located outside of the atomizing cone of the sprayed liquid binder and serves to supply the finely divided mass, for example via a vibrating trough.
  • the controlled moistened carrier balls take up the supplied active mass powder, which compacts by the rolling movement on the outer surface of the cylindrical or spherical carrier body to form a coherent shell.
  • the support body coated in this way in the course of the subsequent revolution, in turn, passes through the spray nozzle, is moisturized in a controlled manner in order to receive a further layer of finely divided mass in the course of the further movement can, etc.
  • An intermediate drying is usually not required.
  • the removal of the liquid binder used in the invention may, partially or completely, by final heat, for. B. by the action of hot gases such as N 2 or air done.
  • a particular advantage of the above-described embodiment of the method according to the invention is that shell catalysts with shells consisting of two or more different masses can be produced in one operation.
  • the method according to the invention in this case brings about both a fully satisfactory adhesion of the successive layers to one another, as well as the base layer on the surface of the carrier body. This also applies in the case of annular carrier bodies.
  • the present invention also provides for the use of the shell catalysts according to the invention in processes for the catalytic gas-phase oxidation of organic compounds, for example from propene to acrolein, from acrolein to acrylic acid, from isobutene or tert-butanol to methacrolein or methacrylic acid, or in processes for oxidative Dehydrogenation of olefins to serve.
  • organic compounds for example from propene to acrolein, from acrolein to acrylic acid, from isobutene or tert-butanol to methacrolein or methacrylic acid, or in processes for oxidative Dehydrogenation of olefins to serve.
  • the use of the coated catalysts in processes for the oxidative dehydrogenation of olefins to dienes, especially 1-butene and / or 2-butene to butadiene is particularly preferred.
  • the solution B was pumped to solution A by means of a hose pump within 15 min. During the addition and then by means of an intensive mixer (Ultra-Turrax) was stirred. After completion of the addition, stirring was continued for a further 5 minutes.
  • an intensive mixer Ultra-Turrax
  • the suspension obtained was spray-dried in a spray tower from NIRO (spray head No. FO A1, rotational speed 25,000 rpm) over a period of 1.5 h.
  • the original temperature was kept at 60 0 C.
  • the gas inlet temperature of the spray tower was 300 0 C, the gas outlet temperature 110 0 C.
  • the obtained powder had a particle size (d90) of less than 40 microns.
  • the resulting powder was calcined batchwise (500 g) in a covered porcelain dish in a convection oven (500 Nl / h) at 460 ° C.
  • the finely powdered precursor composition A was introduced into the drum via a powder screw, with the point of powder addition being within the unrolling section but below the spray cone. The powder addition was metered so that a uniform distribution of the powder on the surface was formed. After completion of the coating, the resulting coated catalyst from precursor material A and the support body was dried in a drying oven at 120 ° C. for 2 hours.
  • the shell catalyst was then calcined at 455 ° C. in a convection oven from Heraeus, DE (type K, 750/2 S, internal volume 55 l).
  • Pore former, 2nd layer precursor material A with melamine as pore former
  • the coated catalyst S2 was prepared:
  • the shell catalyst S3 was prepared:
  • the coated catalyst S4 was prepared as follows: 49.5 g precursor A was applied to 425 g S4a according to the procedure at VS1. The consumption of binder was 31 ml, the application time was 36 min. The resulting double-shelled catalyst was S4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne un catalyseur en coquille contenant (a) un corps support; (b) une première couche renfermant un oxyde de molybdène ou un composé précurseur formant de l'oxyde de molybdène; et (c) une deuxième couche renfermant un oxyde multimétallique contenant du molybdène et au moins un autre métal. L'oxyde de molybdène de la première couche est de préférence MoO3, et l'oxyde multimétallique de la deuxième couche est de préférence un oxyde multimétallique représenté par la formule générale (Il): Mo12BiaCrbX1 cFedX2 eX3 fOy.
EP09730114A 2008-04-09 2009-04-08 Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène Withdrawn EP2271424A2 (fr)

Priority Applications (1)

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EP09730114A EP2271424A2 (fr) 2008-04-09 2009-04-08 Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène

Applications Claiming Priority (3)

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EP08154240 2008-04-09
PCT/EP2009/054238 WO2009124974A2 (fr) 2008-04-09 2009-04-08 Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène
EP09730114A EP2271424A2 (fr) 2008-04-09 2009-04-08 Catalyseur en coquille contenant un oxyde multimétallique renfermant du molybdène

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WO2009124974A3 (fr) 2010-01-21
CN101990459A (zh) 2011-03-23
JP2011516256A (ja) 2011-05-26
TW200948474A (en) 2009-12-01
CA2719532A1 (fr) 2009-10-15
US20110034326A1 (en) 2011-02-10
US8461074B2 (en) 2013-06-11

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