EP3684505A1 - Synthèse d'un catalyseur à coquille movnbte pour la déshydrogénation oxydante d'éthane en éthylène - Google Patents

Synthèse d'un catalyseur à coquille movnbte pour la déshydrogénation oxydante d'éthane en éthylène

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Publication number
EP3684505A1
EP3684505A1 EP18769672.9A EP18769672A EP3684505A1 EP 3684505 A1 EP3684505 A1 EP 3684505A1 EP 18769672 A EP18769672 A EP 18769672A EP 3684505 A1 EP3684505 A1 EP 3684505A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
mixture
tellurium
shell
starting compounds
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.)
Pending
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EP18769672.9A
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German (de)
English (en)
Inventor
Gerhard Mestl
Klaus Wanninger
Silvia Neumann
Peter Schinke
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Clariant International Ltd
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Clariant International Ltd
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Publication of EP3684505A1 publication Critical patent/EP3684505A1/fr
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    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J23/002—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
    • 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
    • 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
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    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • 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
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/0223—Coating of particles by rotation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/16—Clays or other mineral silicates
    • 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
    • C07C2523/20—Vanadium, niobium or tantalum
    • 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
    • C07C2523/20—Vanadium, niobium or tantalum
    • C07C2523/22—Vanadium
    • 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
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/057—Selenium or tellurium; Compounds thereof
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a novel coated catalyst having an outer shell of a high surface area catalyst material containing molybdenum, vanadium, tellurium and niobium and the use of this catalyst for the oxidative dehydrogenation of ethane to ethene or the oxidation of propane to acrylic acid and a method for producing the catalyst.
  • MoVNbTe mixed oxides for the oxidation of propane to acrylic acid or for the oxidative dehydrogenation of ethane to ethene are state of the art. More than 200 patents and numerous scientific publications treat catalysts based on MoVNbTe mixed oxides. The promotion of these mixed oxides with other metals of the periodic table is known. The highest acrylic acid yields described above are 60% and those of ethene are about 80%.
  • JP H07-053414 discloses a catalytic process for the production of ethylene by the oxidative hydrogenation of ethane at low temperature, with a high yield and with a high selectivity.
  • This method of producing ethylene by contacting ethane with a molecular oxygen-containing gas in the presence of a catalyst composition at elevated temperature comprises that the catalyst composition contains a mixed metal oxide comprising as essential components molybdenum, vanadium, tellurium and oxygen and which shows a powder X-ray diffractogram having substantially the following relative peak intensities: 2 ⁇ (+ - 0.4 °), rel. Int: 22.1 ° (100), 28.2 ° (400-3), 36.2 ° (80-3), 45.1 ° (40-3), 50 ° (50-3).
  • MoVNbTe catalysts consist mainly of two orthorhombic phases called "Ml" and "M2" (T. Ushikubo, K. Oshima, A. Kayou, M. Hatano, Studies in Surface Science and Catalysis 112, (1997), 473). The Ml phase seems to play the essential role in the selective oxidation reactions.
  • Ml MoiVo, i5Teo, i2Nbo, 128O3, 7 or M07, sVi, 2 Teo, 937 bi028, 9
  • M2 * MoiV 0 , 32Teo, 42 bo, o804,6 or M04, 31V1, 3 eTei, siNbo, 33O19, si
  • the two main phases can also occur with a slightly different stoichiometry. Both vanadium and molybdenum are at the center of an octahedron of oxygen atoms and therefore partially interchangeable in structure so that the same structure, e.g. the Ml phase, even with a higher vanadium content is possible.
  • the M2 phase is not active for the oxidative dehydrogenation of ethane (see J.S. Valente et al., ACS Catal.4 (2014), 1292-1301, p.1293, in particular).
  • a catalyst which consists of a very pure Ml phase is desired. It is therefore attempted to produce these crystal phases cleanly and separately.
  • EP 529853 A2 discloses a catalyst suitable for preparing a nitrile from an alkane, the catalyst having the empirical formula MoVbTe c XxO n , wherein X is at least one of Nb, Ta, W, Ti, Al, Zr, Cr, Mn Fe, Ru, Co, Rh, Ni, Pd, Pt, Sb, Bi, B and Ce, b is 0.01 to 1.0, c is 0.01 to 1.0; x is 0.01 to 1.0 and n is a number that satisfies the total metal elements and that the catalyst has X - ray diffraction peaks at the following 2 ⁇ angles in its X - ray diffraction pattern: diffraction angle at 2 ⁇ (22.1 ° +/- 0 , 3 °, 28.2 ° +/- 0.3 °, 36.2 ° +/- 0.3 °, 45.2 ° +/- 0.3 °, 50.0 ° +/- 0,3 °)
  • JP H07-232071 discloses a catalytic process for producing a nitrile, at a relatively low temperature and in a high yield, by using an alkane as a raw material and a specific catalyst.
  • the major component of the catalyst is a mixed metal oxide of molybdenum, vanadium, tellurium, oxygen, and X (X is one or more elements selected from the group of niobium, tantalum, etc.) wherein the ratio of the major components, i.
  • a nitrile may be prepared by reacting an alkane without the presence of a halogenated substance, e.g. is reacted with water, etc., in the reaction system at a low temperature with a high yield.
  • the Nb component used in the synthesis of MoVNbTe mixed oxides is usually ammonium niobium oxalate.
  • niobium oxide is sparingly soluble and is therefore only suitable to a limited extent as starting compound.
  • Watanabe (Applied Catal. A General, 194-195 (2000) 479-485) describes inter alia the hydrothermal synthesis from the less soluble precursors Mo0 3 , V 2 0 5 and Te0 2 .
  • the hydrothermal synthesis gives a ammoxidation catalyst precursor which has twice the activity after calcination compared with a catalyst prepared by the known dry method.
  • the mixed oxides produced by the solid-state reaction show rather low activity. It has been suggested that the higher activity of the catalyst prepared by the hydrothermal synthesis has to do mainly with the higher surface area.
  • WO 2013021034 A1 relates to a catalyst material for the oxidation and / or oxidative dehydrogenation of hydrocarbons, in particular for the selective oxidation of propane to acrylic acid, comprising a) molybdenum (Mo), b) vanadium (V), c) niobium (Nb), d ) Tellurium (Te), e) manganese (Mn) and cobalt (Co), in which the molar ratio of at least one element selected from manganese and cobalt to molybdenum ranges from 0.01 to 0.2, more preferably 0, 02 to 0.15 and more preferably from 0.03: 1 to 0.1: 1.
  • a catalyst for the oxidation and / or oxidative dehydrogenation of hydrocarbons a use of the catalyst material or the catalyst, a process for the preparation of a catalyst material for the oxidation and / or oxidative dehydrogenation of hydrocarbons and a process for the selective oxidation of propane to acrylic acid is given.
  • WO 2008068332 A1 relates to novel, mesoporous mixed metal oxide catalysts and to a process for their preparation and to their use as catalysts for the oxidation of hydrocarbons or partially oxidized hydrocarbons.
  • the disclosure relates to mesoporous mixed oxide catalysts containing at least two, preferably at least three different metal species, at least one of which belongs to the group of transition metals, to a process for preparing such a catalyst comprising a neutral templating route and a substantially oxygen-free atmosphere calcining step Temperature between 300 to 700 ° C and the use of such catalysts as oxidation catalysts for the production of oxidized hydrocarbons and in particular for the selective oxidation or ammoxidation of propane to acrylic acid and acrylonitrile
  • a preferred catalyst comprises the elements Mo, V, Te and Nb.
  • WO 0232571 A1 describes a shell catalyst whose shell of active material is a multimetal oxide which contains the elements Mo, V and Te and or Sb and which is provided as a catalyst for the heterogeneously catalyzed gas phase oxidation of propane to acrylic acid.
  • MoVNbTe mixed oxide catalysts could be used as particle squeezed in large industrial reactors.
  • special geometries of the particles prove to be particularly advantageous, for example, rings have a lower pressure loss than full, cylindrical tablets.
  • the disadvantage here is that the pressed particles consist entirely of active material (solid catalysts) and correspondingly large amounts of the expensive elements niobium and tellurium must be used.
  • coated catalysts which have active material only on the surface and consist of an inert carrier in the interior.
  • a prerequisite for the preparation of such coated catalysts is a high activity of the active composition, so that with the, in comparison to the full catalyst, a smaller amount of active mass a comparable catalytic conversion is achieved.
  • the object of the present invention was to find a highly active coated catalyst based on this mixed oxide material, comprising the elements molybdenum, vanadium, tellurium and niobium ("MoVTeNb mixed oxide”), which has the Ml phase and the largest possible specific surface area
  • MoVTeNb mixed oxide molybdenum, vanadium, tellurium and niobium
  • the invention was also to provide a shell catalyst for the oxidation of alkanes, which has the highest possible activity using as low a mass of MoVTeNb mixed oxide. The latter is significant, because MoVNbTe mixed oxide is very particularly because of the rare metals Te and niobium very expensive.
  • a shell catalyst comprising an inert support and a catalytically active outer shell comprising a mixed oxide material comprising the elements molybdenum, vanadium, niobium and tellurium (MoVNbTe mixed oxide), characterized in that the catalyst has a BET surface area of more than 30 m 2 / g.
  • the coated catalyst of the invention is prepared by a process comprising the steps of: a) preparing a mixture of starting compounds containing molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is in the +4 oxidation state, and oxalic acid and at least one further oxo ligands,
  • step c) separating and drying the mixed oxide material contained in the product suspension resulting from step b), d) optionally calcining the mixed oxide material obtained in step c) (MoVTeNb mixed oxide) under inert gas at 300 up to 450 ° C,
  • step e) preparing a coating suspension containing the mixed oxide material from step d) with the addition of organic and / or inorganic binders,
  • step f) calcining the catalyst particles from step f) at a temperature of 80 to 400 ° C.
  • Step g) may optionally be carried out in the preparation of the catalyst or first in the reactor in which the catalytic reaction is carried out before use in the catalytic reaction.
  • the starting compounds are the molybdenum, vanadium, tellurium and niobium containing reactants of the hydrothermal synthesis (precursor compounds). These each contain one or more of the elements molybdenum, vanadium, tellurium or niobium.
  • the molybdenum-containing starting compound may be, for example, an ammonium heptamolybdate or molybdenum trioxide
  • the vanadium-containing starting compound may be, for example, an ammonium metavanadate, vanadyl sulfate or vanadium pentoxide
  • the niobium-containing starting compound may be, for example, ammonium niobium oxalate or niobium oxalate or niobium oxide.
  • the inert catalyst support can be made of aluminum oxide, silicon dioxide, zirconium oxide or mixed oxides of the elements, for example ceramics such as steatite, or consist of silicon carbide.
  • the support molding is particularly preferably composed of inert oxides of very small specific BET surface area without internal porosity, such as steatite, alpha-alumina, quartz (silica), mullite or cordierite.
  • One aspect of the production process of the invention is that a synthesis of the Ml phase from the insoluble and inexpensive oxides, e.g. M0O3, V2O5, b2Üs and TeÜ2 and a combination of oxalic acid with at least one other oxo ligand succeeds.
  • Other oxo ligands i.e., besides oxalic acid
  • dicarboxylic acids and diols as well as organic compounds having two adjacent carbon atoms each having a hydroxy group.
  • Particularly preferred as another oxo ligand is the use of a mixture of citric acid and glycol.
  • the oxalic acid should preferably be in a mixture of the starting compounds in a Mo / oxalic acid ratio of 1: 0.01 to 1: 1, preferably 1: 0.08 to 1: 0.4, more preferably 1: 0.15 to 1: 0 , 25 present.
  • the at least one further oxo ligand, or all other oxo ligands together, should preferably be more preferably in a mixture of the starting compounds in a Mo / oxo ligand ratio of 1: 0.01 to 1: 1, preferably 1: 0.025 to 1: 0.2 1: 0.05 to 1: 0.1.
  • the D50 value of the particular metal oxide used is less than 10 ⁇ m. If the metal oxide powders have too large particles, they must first be ground wet or dry until their Dso values are ⁇ 10 pm.
  • the synthesis according to the invention provides the Ml phase already after the hydrothermal synthesis and drying. Subsequent calcining under nitrogen at 300 to 400 ° C provides a catalyst having a surface area greater than 30 m 2 / g.
  • the mixture of starting compounds for the hydrothermal synthesis is preferably present as an aqueous suspension and is subsequently treated hydrothermally.
  • the term "hydrothermal” refers mainly to the reaction conditions for producing a catalyst ⁇ materials in the presence of water and under elevated temperature and / or elevated pressure, for example in an autoclave.
  • bar of the pressure ranging from 5 to 30, preferably from 10 to 27 bar are exemplary pressure ranges are 11 to 20 bar.
  • the hydrothermal treatment (step b)) gives a product suspension which contains the MoVNbTe mixed oxide as a solid.
  • the separation of the solid from the suspension in step c), which is the MoVNbTe mixed oxide can take place in one or more filtration steps, for example by filtering off the mother liquor.
  • the drying may be carried out in one or more, preferably two, steps in flowing or static air.
  • the first drying step is preferably at 60 ° C to 150 ° C (more preferably at 80 ° C to 120 ° C), a second drying step can be carried out at 200 to 400 ° C.
  • step c) of the process according to the invention may comprise one or more washing, calcining (thermal treatment) and / or grinding steps include.
  • the calcination can be carried out at 200 ° C to 450 ° C, preferably 300 ° C to 400 ° C in inert gas.
  • a coating suspension with the addition of a solvent, preferably water, is first prepared from the MoVNbTe mixed oxide.
  • This coating suspension then contains organic and / or inorganic binders.
  • organic binders are e.g. Plastics or emulsions of plastics polyvinyl acetate, ethylene vinyl acetate, polyacrylates and other acrylate copolymers.
  • Possible inorganic binders are e.g. Brine of silica, zirconia or titania.
  • This coating suspension is applied to the inert support to form the catalytically active outer shell.
  • this application is done by spraying.
  • a coating is carried out by spraying the suspension into a moving bed of inert catalyst carrier body.
  • the coated catalyst support bodies are dried and optionally calcined, with any existing organic binder being burned out.
  • this treatment can also be carried out in the reactor in which the shell catalyst is used, before the actual commissioning.
  • the shell catalyst preferably has a catalytically active outer shell with a layer thickness of between 200 and 400 ⁇ m.
  • the coated catalyst according to the invention can be used as a catalyst for the oxidation and / or oxidative dehydrogenation ("ODH") of
  • Hydrocarbons in particular for the oxidative dehydrogenation of ethane to ethylene are used.
  • the BET surface area of the shaped catalyst bodies was determined by the BET method according to DIN 66131; a publication of the BET method can also be found in J. Am. Chem. Soc. 60,309 (1938). The measurements were carried out on a TriStar from Micromeritics at 77K. Before the measurement, the sample was evacuated for 2 h at 523 K. The linear regression of the isotherms according to the BET method was in a
  • the pore size distribution of a catalyst powder was determined by nitrogen adsorption measurements on a: TriStar of
  • BJH Barrett-Joyner-Halenda
  • Tablets are made entirely of porous material, so that the
  • Pore volume is always related to the entire measured tablet.
  • Coated catalysts have in their interior a carrier material which usually has almost no internal surface (BET). Surface ⁇ 0 m 2 / g) and almost no pore volume (pore volume ⁇ 0 cm 3 / g).
  • the determined pore volume must be divided by the (mass) proportion of the porous layer in the total mass.
  • the invention is not limited by the following
  • Comparative Example 1 describes a MoVTeNb catalyst which was activated according to the prior art at 600 ° C and was pressed into tablets by conventional methods with the addition of conventional Tablettier additives such as graphite and stearic acid.
  • the amount of water in the autoclave was 8.25 l (stirrer speed 90 rpm). After the autoclave was capped, it was allowed to stir for 5 min
  • Precursor material P2 produced. P2 was subsequently in a
  • the catalyst Kl has a BET surface area of 9 m 2 / g and an N 2 pore volume of 0.04 cm 3 / g.
  • This powder Kl was now used to prepare catalyst tablets K2.
  • 473 g of the powder Kl was intimately mixed with 9.65 g of graphite, 54.96 g of stearic acid and 54.96 g of fine silica (Syloid C809).
  • the catalyst powder K3 was granulated twice (ie pressed and re-comminuted into a granulate with particles in the range of about 30-400 pm through a sieve, with a Powtec roller compactor). It was thus produced the catalyst granules K4.
  • the catalyst powder K3 was granulated twice (ie pressed and re-comminuted into a granulate with particles in the range of about 30-400 pm through a sieve, with a Powtec roller compactor). It was thus produced the catalyst granules K4.
  • Catalyst granulate K4 was tabletted into rings (diameter 5.4 mm, height 5 mm, inside diameter 2.5 mm) in a tablet press (Rotab company) with a contact pressure of about 1 1 kN. It became so
  • the shaped catalyst body K5 was heated at 350 ° C. in air in a Nabertherm circulating air oven at a slow heating rate
  • Comparative Example 2 describes a comparative catalyst wherein the catalyst powder was prepared by the process of the invention, but which was prepared in the same manner as Comparative Example 1
  • TeO 2 Alfa Aesar
  • Citric acid 33.85 g of ethylene glycol, 211.61 g of V2O5, the ground Te2 and the ground Nb2's in oxalic acid were added. The complete
  • the activated solid has a BET surface area of 27 m 2 / g and an N 2 pore volume of 0.116 cm 3 / g.
  • Example 3 describes the catalyst according to the invention, wherein only 20 wt. -% - catalyst mass were coated on an inert carrier.
  • Example 1 First, 116.06 g of Te02 (Alfa Aesar) in 250 g of dist. H2O
  • Retort in the oven was calcined at 400 ° C / 2h, (heating rate 10 ° C / min) under N 2 (0.5 1 / min).
  • the activated solid has a BET surface area of 50 m 2 / g and an N 2 pore volume of 0.27 cm 3 / g.
  • This powder was now used to prepare a coating suspension. To this was added 181 g of the powder in 1047 g of water
  • Bindzil 2034DI silica sol 4.52 g of Syloid C809 and 13.57 g of coconite were added.
  • This suspension was Turrax stirrer homogenized (5 min / 6000 rpm).
  • 54.30 g EP16 vinyl acetate adhesive from Wacker was added and the whole was then stirred for 1 h with a magnetic stirrer.
  • 600 g steatite rings (4 mm diameter, 2 mm inner diameter, 4 mm height) were in a coating system of the company.
  • Coating suspension coated In this case, the bed of the rings with an air flow of 198 m 3 / h to 260 m 3 / h (70 ° C) was offset from below through oblique slots in a plate in a rotating motion. The coating suspension was sprayed into this rotating bed via nozzles (0.3 bar).
  • Example 2 describes a catalytic activity assay in the oxidative dehydrogenation of ethane to ethylene at various
  • the catalysts were tested in a test for the activity in the oxidative dehydrogenation of ethane.
  • This partial analysis stream was first drawn through a sample valve of a GC, through a gas cooler and then dried, through an NDIR analyzer (Rosemount).
  • an NDIR analyzer Rosemount
  • an Rt U-BOND column having a temperature profile of 45 ° C to 190 ° C was analyzed in 8.4 minutes with a gas flow of 10 ml / min of ethane, ethene, acetic acid and water.
  • the NDIR analyzer (Rosemount) contains NDIR cells for CO, CO2, ethane, ethene, and one
  • Comparative catalyst 1 according to the prior art at 330 ° C, because it reaches the same ethane conversion of 67% already at 302 ° C.
  • the salt bath temperature for the catalyst according to Comparative Example 2 can not be adjusted to 330 ° C., because under these conditions an uncontrolled rise in the temperature of the exothermic reaction is observed ("runaway").
  • the catalyst according to Example 3 according to the invention has only 20% of the active material in the same reactor volume and reaches an ethane conversion of 50% at 330 ° C.
  • Table 1 :
  • Table 1 compares the BET surface areas and pore volumes of the inventive catalyst of Example 3 with the other comparative examples.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un catalyseur à coquille, qui comprend dans la coquille externe un matériau d'oxyde mixte comprenant les éléments molybdène, vanadium, niobium et tellure, caractérisé en ce que le catalyseur à coquille présente une surface BET de > 30 m2/g. Le catalyseurselon l'invention est fabriqué par un procédé comportant les étapes : a) de production d'un mélange de composés de départ, qui contient du molybdène, du vanadium, du niobium et un composé de départ contenant du tellure, dans lequel le tellure est présent à l'état d'oxydation +4, ainsi que de l'acide oxalique et au moins un autre ligand oxo , b) de traitement hydrothermique du mélange de composés de départ à une température allant de 100 à 300 °C, pour obtenir un produit en suspension, c) de séparation et de séchage du matériau d'oxyde mixte, qui est contenu dans la suspension résultant de l'étape b). d) optionnellement, de calcination du matériau d'oxydes mixtes obtenu dans l'étape c) avec un gaz inerte à 300 à 450°C, e) de production d'une suspension de revêtement qui contient les matériaux d'oxydes mixtes de l'étape d), avec adjonction de liants organiques et/ou inorganiques, f) de revêtement d'un support de catalyseur inerte avec la suspension de revêtement de l'étape e) par pulvérisation de la suspension de revêtement dans un lit fluidisé du support de catalyseur inerte, ainsi qu'optionnellement g) la calcination des particules de catalyseur de l'étape f) à une température allant de 80 à 400°C.
EP18769672.9A 2017-09-19 2018-09-13 Synthèse d'un catalyseur à coquille movnbte pour la déshydrogénation oxydante d'éthane en éthylène Pending EP3684505A1 (fr)

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DE102017121709.6A DE102017121709A1 (de) 2017-09-19 2017-09-19 Synthese eines MoVNbTe-Schalenkatalysators für die oxidative Dehydrierung von Ethan zu Ehtylen
PCT/EP2018/074756 WO2019057602A1 (fr) 2017-09-19 2018-09-13 Synthèse d'un catalyseur à coquille movnbte pour la déshydrogénation oxydante d'éthane en éthylène

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DE102017000862A1 (de) * 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVNbTe-Katalysators mit reduziertem Gehalt an Niob und Tellur und höherer Aktivität für die oxidative Dehydrierung von Ethan
DE102017000861A1 (de) * 2017-01-31 2018-08-02 Clariant Produkte (Deutschland) Gmbh Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden
DE102021005596A1 (de) 2021-11-11 2023-05-11 Alexander Damps Verfahren zur oxidativen Aromatisierung von kurzkettigen Alkanen
US11890594B2 (en) 2021-12-30 2024-02-06 Uop Llc Chemical homogeneity and catalytic performance of mixed-metal oxide catalysts
CN114272949B (zh) * 2021-12-31 2023-11-21 上海复翼环保科技有限公司 一种低温抗abs中毒的m1型钼分子筛脱硝催化剂及制备方法

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DE102017121709A1 (de) 2019-03-21
US11059032B2 (en) 2021-07-13
US20200215516A1 (en) 2020-07-09
CN111132764A (zh) 2020-05-08

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