WO2004091779A1 - 金属酸化物触媒の製造方法 - Google Patents
金属酸化物触媒の製造方法 Download PDFInfo
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- WO2004091779A1 WO2004091779A1 PCT/JP2004/005264 JP2004005264W WO2004091779A1 WO 2004091779 A1 WO2004091779 A1 WO 2004091779A1 JP 2004005264 W JP2004005264 W JP 2004005264W WO 2004091779 A1 WO2004091779 A1 WO 2004091779A1
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- metal
- compound
- tellurium
- metal oxide
- oxide catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- 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
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- 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
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- 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
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- 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
- acrylic acid is produced by contacting propylene with oxygen in the presence of a catalyst to produce acrolein, and then producing the acrolein by a two-step oxidation reaction in which it is contacted with oxygen.
- a niobium compound is further mixed with an aqueous solution obtained by reacting a molybdenum compound, a vanadium compound and an antimony compound in an aqueous medium at 70 ° C. or higher. Thereafter, a method for producing a catalyst in which the obtained mixture is evaporated to dryness and calcined at a high temperature is disclosed.
- Japanese Patent Application Laid-Open No. H10-2301664 discloses that when each metal compound is heated in the aqueous medium described in Japanese Patent Application Laid-Open No. H10-137585, an aqueous medium is used. It describes that a gas containing molecular oxygen is blown into the gas. Further, it is described that the use of the catalyst produced by this method in the gas phase catalytic oxidation reaction of propane improves the yield of acrylic acid.
- Japanese Patent Application Laid-Open No. H11-2856583 describes in the above-mentioned Japanese Patent Application Laid-open No. Hei10-137585 and Japanese Patent Laid-open No. Hei10-230164. It describes that hydrogen peroxide is added to a reaction solution in which each metal compound is heated and reacted in an aqueous medium or to a reaction solution after the reaction.
- JP-A-11-226408 discloses that a metal tellurium powder and an oxo acid salt (oxometalate) containing other elements, such as ammonium metavanadate, molybdic acid, and ammonium paramolybdate, are reacted in an aqueous medium.
- a method is disclosed in which metal powder is dissolved in a reaction solution and the obtained reaction solution is used as a raw material for a metal oxidation catalyst.
- the particle size of tellurium particles used in the invention described in this publication exceeds 100 111, and the reaction in an aqueous medium took a long time.
- the obtained metal oxidation catalyst when used for the ammoxidation of propane, it can produce acrylonitrile with a propane conversion of 25-30% and a selectivity of almost 60%, but it can produce acrylic acid from propane.
- the obtained metal oxidation catalyst when used for the ammoxidation of propane, it can produce acrylonitrile with a propane conversion of 25-30% and a selectivity of almost 60%, but it can produce acrylic acid from propane.
- the present inventors have conducted intensive studies to obtain a catalyst capable of producing acrylic acid and acrylonitrile at a high yield in one step by a catalytic oxidation reaction of propane, and as a result, have found a metal oxide catalyst obtained by the following production method.
- the present invention relates to a method for producing a metal oxide catalyst represented by the following composition formula, wherein a metal obtained by reducing a Te ′′ compound or a Te 6+ compound in the presence of a reducing agent and water or an organic solvent is used.
- This is a method for producing a metal oxide catalyst, comprising reacting fine particles of tellurium in the presence of a compound containing a Mo compound, a V compound, an element A and water, followed by drying and calcining.
- A is at least one element selected from Nb, Ta, W, Ti, Zr, Re, Fe, Ni, Co, Sn, Tl, Cu, a rare earth element and an alkali metal element.
- the present invention provides a method for producing a metal oxide catalyst represented by the following composition formula, comprising the following steps (1), (2), (3), (4) and (5).
- This is a method for producing a metal oxide catalyst, characterized by employing the following.
- Step (1) a step of reducing a 6- inch compound or a 6+ compound in the presence of a reducing agent and water or an organic solvent to obtain a dispersion containing fine particles of tellurium metal
- Step (2) a step of removing an unreacted reducing agent and an organic solvent contained in the dispersion obtained in the above step (1) to obtain an aqueous dispersion containing fine particles of tellurium metal.
- Step (3) the process and aqueous dispersions containing metal tellurium fine particles obtained in (2), in mixing the Mo 6 + reduction Gobutsu ⁇ V 5 + compounds, 40 ° C or higher, 1 Step of obtaining a reaction solution by reacting for more than an hour
- Step (4) a step of mixing the reaction solution obtained in the above step (3) with a compound containing the following element A to obtain a mixed solution
- Step (5) a step of evaporating the mixture obtained in the above step (4) to dryness, drying the dried product, and further baking the dried product.
- A is at least one element selected from Nb, Ta, W, Ti, Zr, Re, Fe, Ni, Co, Sn, Tl, Cu, a rare earth element and an alkali metal element.
- the above manufacturing method includes an invention in which the primary particles of metallic tellurium have a size of 4.0 ⁇ or less. Furthermore, the present invention is a process for producing acrylic acid or acrylonitrile, wherein propane is oxidized or ammoxidized by a gas phase contact reaction in the presence of the metal oxide catalyst produced by the above method. . BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is an electron micrograph showing the tellurium metal crystals obtained in Example 1.
- FIG. 2 is an electron micrograph showing the tellurium metal crystals obtained in Example 2.
- FIG. 3 is an electron micrograph showing the crystal of tellurium metal obtained in Example 3. BEST MODE FOR CARRYING OUT THE INVENTION
- steps (1) to (5) a preferred embodiment of the present invention will be described in steps (1) to (5).
- technical means such as heat treatment, coprecipitation, drying, baking, and hydrothermal synthesis known in this field can be used without limitation.
- the Te ′′ compound or the Te 6+ compound is reduced in the presence of a reducing agent and water or an organic solvent to obtain a dispersion containing fine particles of metal tellurium.
- Ding 6 4+ compounds or Ding 6 6+ compounds (compounds of the valence of tellurium 4 or 6), in particular limited Mugu specifically, tellurium dioxide, tellurium trioxide, Four tellurium chloride, Orutoteruru acid, Metateruru Examples include acid, polymetatelluric acid, ammonium tellurate, alkali metal tellurate, zinc tellurate, calcium tellurate, silver tellurate, thallium tellurate, copper tellurate, magnesium tellurate, and the like.
- a chlorine compound may be used as the Te 4+ compound or the Te M compound.
- a reducing substance having an oxidation-reduction potential of 0.53 V or less with respect to a standard electrode (the potential of tellurium dioxide is around 0.53 V) (atoms, molecules, or ions having the property of easily giving electrons to other molecules) Any) can be used.
- Hydrazine, a hydrazinium salt, hydroxylamine and the like are preferred because of the reactivity of the reduction reaction and the fact that they do not react with water. Specifically, hydrazine acetate, hydrazine dihydrobromide, hydrazine dihydrochloride, hydrazine monohydrochloride, hydrazine monohydrate, hydrazine sulfate, hydroxylamine, hydroxylamine ammonium sulfate, hydroxylamine sulfate An example is an ammonia.
- the amount of reducing agent used depends on the type of reducing agent and the reaction conditions.
- the molar ratio of hydrazine to tellurium is preferably from 0.5 to 4.0, and more preferably from 1.0 to 3.0.
- the amount of hydrazine added is less than 0.5 mol, a large amount of unreacted tellurium dioxide remains.
- the amount of hydrazine exceeds 4.0 moles there is no advantage even if the amount of hydrazine is further increased, but rather extra labor and a cleaning solution are required to remove unreacted hydrazine.
- the amount of the reducing agent other than hydrazine is substantially the same as hydrazine.
- the reduction reaction is performed in a liquid such as water or an organic solvent.
- a liquid such as water or an organic solvent.
- organic solvent alcohols, hydrocarbons and the like are preferable.
- the tellurium compound is dispersed by the presence of the solvent, and the reduction reaction proceeds easily. As a result, the obtained particles of metallic tellurium become uniform.
- the conditions for reducing the tellurium compound are appropriately selected in consideration of the solubility of the tellurium compound used in water or an organic solvent and the reactivity of the reducing agent.
- the reduction reaction proceeds only by adding hydrazine to an aqueous solution of telluric acid at room temperature, and fine particles of metallic tellurium are dissolved in water. It is formed.
- the reaction is carried out at a temperature of 40 ° C. to the boiling point of water at a stirring speed of 100 to 500 times / minute for 1 to 20 hours, preferably at a temperature of 60 ° C. to the boiling point of water.
- the reaction is carried out at a temperature of 200 to 300 times / minute with stirring speed for 2 to 10 hours.
- the organic solvent used in the pulverization is not particularly limited, but is preferably an organic solvent which is liquid at ordinary temperature and can be easily removed in a subsequent step.
- alcohols such as methanol, ethanol, and propanol
- hydrocarbons such as hexane, cyclohexane, and toluene are preferable.
- the coexistence of water and organic solvent during milling mitigates the increase in surface energy associated with milling and increases milling efficiency.
- the mixing ratio of the tellurium compound and water or the organic solvent at the time of pulverization is preferably 100 to 100 parts by mass of the tellurium compound per 100 parts by mass of the tellurium compound. 3300 parts by mass is more preferable. If the mixing ratio of water or the organic solvent to the metal A is less than 10 parts by mass, the crushed material adheres to the crushing container and crushing becomes difficult. If the amount exceeds 1000 parts by mass, the solvent absorbs the impact at the time of pulverization and the pulverization efficiency is reduced.
- the milling machine is preferably of the type of milling by driving the container itself containing the material to be milled. Specifically, a pole mill, a vibration mill, a planetary pole mill, or the like can be used. A suitable grinding time is 0.5 to 24 hours.
- the size of the primary particles of metallic tellurium obtained by the above reduction reaction is in a range of not more than 4.0 ⁇ , preferably not more than 2.0 m in at least one direction. Although there is no particular lower limit on the size of the primary particles, it is preferably 0.01 or more from the viewpoint of ease of operation. When the size of the primary particles is 4.0 im or more, the dispersibility of the metal tellurium particles in water or an organic solvent is deteriorated, which easily affects the production of the catalyst.
- the unreacted reducing agent contained in the dispersion containing the fine metal tellurium particles obtained in the step (1) is removed.
- an organic solvent used as a medium for the reduction reaction, the violent agent is removed, and water is added later to obtain an aqueous dispersion.
- a method for removing the unreacted reducing agent and the organic solvent include a method of distilling off under reduced pressure and a method of separating and removing the reducing agent and the organic solvent by centrifugation or filtration. After the removal, the obtained metal tellurium fine particles are redispersed in water, whereby an aqueous dispersion of metal tellurium fine particles can be obtained.
- the reducing agent does not remain in the obtained aqueous dispersion, and it is preferred that the metal tellurium particles obtained by filtration are sufficiently washed with water and then dispersed in water to obtain an aqueous dispersion.
- the solid content concentration in the aqueous dispersion is preferably 10 to 100 liters of water per mole of metallic tellurium fine particles.
- the reconstituted aqueous dispersion containing the metal tellurium fine particles obtained in the step (2) is mixed with the Mo 6+ compound and the V 5+ compound, and the mixture is heated at a temperature of 40 ° C. or more for 1 hour or more. Let react.
- Mo 6+ compound examples include ammonium molybdate, molybdenum oxide, molybdic acid, and the like. Of these compounds, ammonium molybdate is preferred because of its water solubility.
- V 5+ compound ammonium metavanadate, vanadium pentoxide and the like are preferable.
- the addition amount of the Mo 6+ compound and the V 5+ conjugate is such that the atomic ratio (i and j) of V and Te to Mo is 0.01 to 1.5, respectively, and the atom of Te to V
- the ratio (j / i) is set to 0.3 to 1.0. If Mo, V, and Te deviate from the above ranges, a metal oxide catalyst having the expected performance cannot be obtained.
- the aqueous dispersion may be diluted by further adding water as necessary for the purpose of improving operability and the like.
- the reaction temperature is 40 ° C. or higher, preferably 40 to 100 ° C.
- the heating time is preferably 1 to 10 hours, more preferably 2 to 5 hours. It is preferable to stir the aqueous dispersion during the reaction.
- the reaction solution obtained in the above step (3) is mixed with a compound containing a metal element A described below (hereinafter, referred to as an A-containing compound).
- the mixing temperature is not particularly limited, but is usually room temperature.
- the metal element A is preferably mixed in the form of an aqueous solution or an aqueous dispersion. Since a fine precipitate is formed during the mixing, the mixed liquid is usually in the form of a slurry.
- Metal element A is Nb, Ta, W, Ti, Zr, Re, Fe, Ni, Co, Sn, Tl, C u is at least one element selected from the group consisting of rare earth elements and alkali metal elements.
- the A-containing compound used in the present invention includes an oxide, a nitrate, a carboxylate, an oxoacid, and an acid chloride.
- the insoluble A-containing compound may be dispersed in water and mixed, but in this case, it may be possible to dissolve in water by using oxalic acid or the like in combination.
- the mixing amount of the A-containing compound is such that the metal element A is 0.001 to 3.0 in terms of the atomic ratio of the metal in the obtained metal oxide catalyst, where Mo is 1.
- the ratio of the metal element A when Mo is set to 1 is less than 0.001
- the obtained catalyst tends to deteriorate.
- it exceeds 3.0 the activity of the obtained catalyst is low, and the conversion of propane is poor.
- step (4) the metal oxide obtained by adding ammonia water and nitric acid or ammonium nitrate to the mixture obtained by mixing the reaction solution obtained in step (3) and the A-containing compound is further added.
- the performance of the catalyst is further improved.
- the preferred amounts of ammonia water, nitric acid or ammonium nitrate are as follows: an amount of ammonia water containing 0.4 or more ammonia in a molar ratio with respect to metal A; and a nitrate ion in a molar ratio of 2.0 or more with metal A. In an amount of nitric acid or ammonium nitrate. ⁇ Process (5)
- the slurry mixture obtained in the step (4) is evaporated to dryness, and the obtained dried product is dried and fired.
- a method for removing water from the mixed solution there are various conventionally known methods such as evaporation to dryness and spray drying.
- the mixture When evaporating to dryness, the mixture may be simply heated to evaporate water, but it can be efficiently dried by blowing an inert gas such as nitrogen or air into the evaporating to dryness.
- the temperature for evaporation to dryness is preferably 50 to 130 ° C.
- the dried product obtained by the above operation is fired.
- the firing is preferably performed in two stages. First, calcinate at 250 to 380 ° C in the presence of oxygen (preferably at 280 to 330 ° C for 2 to 20 hours, preferably 3 to 10 hours. It is calcined at 660, preferably at 570 to 620 ° C. for 0.5 to 6 hours, preferably for! To 3 hours, whereby the metal oxide catalyst according to the present invention can be produced.
- the content of the metal element in the metal oxide catalyst obtained by the above calcination can be determined by X-ray fluorescence analysis.
- the metal oxide catalyst obtained by the above method can be used as it is, but it is preferable to use the metal oxide catalyst after pulverizing it to an appropriate particle size to increase the surface area of the catalyst.
- a known dry pulverization method or wet pulverization method can be adopted.
- Specific examples of the milling device include a mortar, a pole mill, and the like.
- the solvent used as a grinding aid includes water, alcohols, and the like.
- the particle size of the catalyst after milling is preferably 20 m or less, more preferably 5; tim or less.
- the metal oxide catalyst can be used without a carrier, but can also be used by being supported on a known carrier such as silica, alumina, silica alumina, or silicon carbide having an appropriate particle size. There is no particular limitation on the amount supported, and the amount is based on the conventional amount supported.
- a method for producing acrylic acid from propane using the metal oxide catalyst produced by the above production method will be described.
- propane and oxygen gas as raw materials for producing acrylic acid into a reactor filled with a metal oxide catalyst
- propane is catalytically oxidized by the metal oxide catalyst to produce acrylic acid.
- Preferred reaction temperatures are 300-600. C, more preferably 350-500 ° C.
- Propane and oxygen gas may be separately introduced into the reactor, and both may be mixed in the reactor, or may be introduced into the reactor in a state where both are mixed in advance.
- oxygen gas examples include pure oxygen gas, air, and a gas obtained by diluting them with nitrogen, steam, carbon dioxide, or the like.
- the ratio of air to propane is preferably 30 times or less by volume, more preferably 0.2 to 20 times.
- An appropriate space velocity (hereinafter referred to as SV) for the raw material gas is 1000 to 8000 hr- 1 . If the space velocity is less than 1000 hr- 1, the yield of acrylic acid per unit mass of the catalyst will be low, and if it exceeds 8000 hr- 1 , the reaction rate will decrease.
- Unreacted raw material propane and intermediate propylene present in the reaction gas discharged from the reactor outlet can be used directly as fuel, but after being separated from other components in the reaction gas, the reactor It can be returned to and reused.
- the metal oxide catalyst produced according to the present invention can also be applied to ammoxidation of propane, and can synthesize acrylonitrile in high yield.
- the ammoxidation conditions substantially conform to the above-described conditions for the vapor-phase catalytic oxidation of propane.
- Example 4 the respective raw materials were blended so that the molar ratio of each metal constituting the obtained metal oxide catalyst was as follows.
- the molar ratio of each metal in the metal oxide catalyst obtained in Example 4 is as described below.
- the metal oxide catalyst obtained in each case was used for tableting once and then crushing the molded product to a size of 16-30 mesh.
- 1.1 ml (about 1.0 g) of the catalyst obtained in each case was filled in a quartz reaction tube having an inner diameter of 10 mm.
- the reaction tube was heated to 400 ° C, and a mixed gas of 6.4% by volume of propane, 9.6% by volume of oxygen, 36.1% by volume of nitrogen, and 47.7% by volume of steam was introduced into the reaction tube at 3924Zhr- 1 .
- Acrylic acid was produced by feeding at space velocity.
- the resulting dispersion was filtered through filter paper to obtain a black solid and a transparent colorless filtrate.
- the solid on the filter paper was washed with 200 ml of distilled water. After washing, the solid matter remaining on the filter paper was collected in a sample bottle while diluting with distilled water to obtain 80 ml of an aqueous dispersion (containing 0.28 mol as metallic tellurium).
- This aqueous dispersion was divided into two equal parts with stirring. Half of it was dried at 50 ° C for 2 hours and used for X-ray diffraction analysis and electron microscopy samples.
- the obtained black powder was 2 mm, 22.98, 27.52, 38.24, 40.42, 43.32, 45.88, 49.62.
- a diffraction line was shown at an angle of, and no crystalline phase of tellurium dioxide was observed, indicating that the crystalline phase was pure metallic tellurium.
- the particle shape of the black powder was a needle-like crystal having a diameter of 0.1 m and a length of a number of am; the variation in the size of each crystal was small.
- the obtained dried product was fired in air at 300 ° C. for 5 hours. Thereafter, the mixture was calcined at 600 ° C. for 2 hours in a nitrogen gas atmosphere to obtain a metal oxide catalyst. As described above, the obtained catalyst was processed into 16 to 30 mesh and used for the production reaction of acrylic acid.
- the obtained black slurry was filtered with filter paper to obtain a solid and a transparent colorless filtrate.
- the solid on the filter paper was washed with 20 Oml of distilled water. Thereafter, 8 Oml of an aqueous dispersion (containing 0.28 mol as metallic tellurium) in which the solid matter was dispersed in distilled water was obtained. This aqueous dispersion was divided into two equal parts with stirring.
- the powder was dried at 50 ° C for 2 hours, and the obtained black powder was subjected to X-ray diffraction analysis and measurement by electron microscopic observation.
- the result of the X-ray diffraction analysis was the same as that in Example 1, and it was found that the obtained black powder was a pure metal tellurium crystal.
- the particle shape of the black powder was an aggregate having a size of several m composed of primary particles having a diameter of about 0.1 m.
- a catalyst was prepared in the same manner as in Example 1, except that the above half aqueous dispersion containing metal tellurium was used. Acrylic acid was produced under the same conditions as in Example 1 using the obtained catalyst.
- Example 1 The resulting black slurry was filtered with filter paper. Thereafter, the same operation as in Example 1 was performed to obtain an aggregate of fine particles having a particle diameter of about 0.05 m as shown in FIG.
- the catalyst was produced by calcining the aggregate under the same conditions as in Example 1. Using the obtained catalyst, acrylic acid was produced under the same conditions as in Example 1.
- Example 2 To a 50 Om 1 glass flask, add 3.64 g of tellurium dioxide and 6 Om 1 of distilled water, and stir at 80 ° C at a rate of 300 rpm to obtain hydrazine monohydrate (80 hydrazine). 2. Add 8 g and maintain under these conditions for 12 hours. Over time, the first white powder turned gray and eventually became a black suspension dispersion. Thereafter, the same operation as in Example 1 was performed to obtain an aqueous dispersion of tellurium metal.
- the obtained dried product was fired in air at 320 ° for 1.5 hours. Thereafter, the mixture was calcined at 590 ° for 1.5 hours to obtain a metal oxide catalyst.
- the molar ratio of each metal in the obtained metal oxide catalyst is as follows.
- a catalyst was produced in the same manner as in Comparative Example 1, except that the metal tellurium powder was added to the above solution in Comparative Example 1, and the mixture was heated for 5 hours. Using this catalyst, acrylic acid was produced under the same conditions as in Example 1.
- the obtained dried product was fired in air at 300 ° C. for 5 hours. Thereafter, the mixture was calcined at 600 ° C. for 2 hours in a nitrogen gas atmosphere to obtain a metal oxide catalyst.
- the results of using this in the acrylic acid production reaction are shown in Table 1.
- the obtained dried product was calcined in air at 300 at 5 hours. Thereafter, the mixture was calcined at 600 ° C. for 2 hours in a nitrogen gas atmosphere to obtain a metal oxide catalyst.
- the results of using this in the production reaction of acrylic acid are shown in Table 1.
- fine particles of highly reactive metal tellurium can be reacted with another metal compound in an aqueous medium, thereby obtaining a high-performance metal oxide catalyst.
- this catalyst is used in the production reaction of acrylic acid by the gas phase catalytic oxidation reaction of propane, acrylic acid can be obtained at a high yield.
- the present catalyst can be used in the ammoxidation of propane, and acrylonitrile can be obtained in high yield.
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Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US10/553,397 US7375052B2 (en) | 2003-04-16 | 2004-04-13 | Process for producing metal oxide catalyst |
EP04727101A EP1618952A4 (en) | 2003-04-16 | 2004-04-13 | PROCESS FOR PRODUCING A METAL OXIDE CATALYST |
Applications Claiming Priority (2)
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JP2003112137A JP4155087B2 (ja) | 2003-04-16 | 2003-04-16 | 金属酸化物触媒の製造方法 |
JP2003-112137 | 2003-04-16 |
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WO2004091779A1 true WO2004091779A1 (ja) | 2004-10-28 |
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US (1) | US7375052B2 (ja) |
EP (1) | EP1618952A4 (ja) |
JP (1) | JP4155087B2 (ja) |
CN (1) | CN100534614C (ja) |
WO (1) | WO2004091779A1 (ja) |
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EP1755779A1 (de) * | 2004-06-09 | 2007-02-28 | Basf Aktiengesellschaft | Verfahren zur herstellung einer multimetalloxidmasse |
NZ591207A (en) * | 2008-07-18 | 2013-03-28 | Grt Inc | Continuous process for converting natural gas to liquid hydrocarbons |
US8835666B2 (en) * | 2012-11-26 | 2014-09-16 | Ineos Usa Llc | Pre calcination additives for mixed metal oxide ammoxidation catalysts |
CN110180538A (zh) | 2013-04-08 | 2019-08-30 | 沙特基础工业公司 | 用于将丙烯转化为包含羧酸部分的产物的催化剂 |
US9856200B2 (en) | 2013-04-24 | 2018-01-02 | Saudi Basic Industries Corporation | Supported catalyst for production of unsaturated carboxylic acids from alkanes |
WO2014174375A2 (en) | 2013-04-24 | 2014-10-30 | Saudi Basic Industries Corporation | High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes |
JPWO2018016155A1 (ja) * | 2016-07-20 | 2019-05-09 | 東亞合成株式会社 | 金属酸化物触媒の製造方法 |
DE102017000848A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung molybdänhaltiger Mischoxidmaterialien |
DE102017000861A1 (de) | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden |
CN109569667A (zh) * | 2019-01-15 | 2019-04-05 | 山东玉皇化工有限公司 | 复合金属氧化物催化剂的制备方法、复合金属氧化物催化剂及应用 |
CN109569668A (zh) * | 2019-01-15 | 2019-04-05 | 山东玉皇化工有限公司 | Mo-V-Te-Nb-O催化剂的制备方法及应用 |
CN113492017A (zh) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | 一种负载型丙烷催化氧化制丙烯酸催化剂及其制备方法与应用 |
CN113070079B (zh) * | 2021-04-13 | 2022-01-11 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Sb-Nb-O催化剂的制备方法及系统 |
CN113083283B (zh) * | 2021-04-13 | 2022-03-08 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Nb-O催化剂及其制备方法与应用 |
CN116273035B (zh) * | 2023-03-10 | 2023-09-22 | 绍兴绿奕化工有限公司 | 一种固体酸成型催化剂及其制备方法和应用 |
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JPH11226408A (ja) * | 1998-02-18 | 1999-08-24 | Mitsubishi Chemical Corp | 金属酸化物触媒の製造方法 |
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US3716496A (en) * | 1969-09-06 | 1973-02-13 | Nitto Chemical Industry Co Ltd | Catalyst composition for the oxidation and the oxidative dehydrogenation of olefins |
JPS5318014B2 (ja) * | 1974-02-09 | 1978-06-13 | ||
JPS59227703A (ja) * | 1983-06-07 | 1984-12-21 | Nitto Chem Ind Co Ltd | 金属テルルの溶解法 |
RU2285690C2 (ru) * | 2000-06-20 | 2006-10-20 | Басф Акциенгезельшафт | Способ получения акролеина и/или акриловой кислоты |
KR100407528B1 (ko) * | 2000-09-18 | 2003-11-28 | 아사히 가세이 가부시키가이샤 | 산화 또는 가암모니아산화용 산화물 촉매의 제조 방법 |
ES2192983B1 (es) * | 2002-01-31 | 2004-09-16 | Universidad Politecnica De Valencia. | Un catalizador para la deshidrogenacion oxidativa de etano a eteno. |
JP4155034B2 (ja) * | 2003-01-21 | 2008-09-24 | 東亞合成株式会社 | 金属酸化物触媒の製造方法 |
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US7375052B2 (en) | 2008-05-20 |
CN100534614C (zh) | 2009-09-02 |
EP1618952A4 (en) | 2010-10-06 |
JP4155087B2 (ja) | 2008-09-24 |
JP2004313956A (ja) | 2004-11-11 |
EP1618952A1 (en) | 2006-01-25 |
CN1774295A (zh) | 2006-05-17 |
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