WO2005079983A1 - モリブデンの回収方法及び触媒の製造方法 - Google Patents
モリブデンの回収方法及び触媒の製造方法 Download PDFInfo
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- WO2005079983A1 WO2005079983A1 PCT/JP2005/002593 JP2005002593W WO2005079983A1 WO 2005079983 A1 WO2005079983 A1 WO 2005079983A1 JP 2005002593 W JP2005002593 W JP 2005002593W WO 2005079983 A1 WO2005079983 A1 WO 2005079983A1
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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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
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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
- B01J23/70—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
- B01J23/8876—Arsenic, antimony or bismuth
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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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
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a molybdenum-containing material containing at least molybdenum, element A (phosphorus and Z or arsenic) and element X (at least one element selected from the group consisting of potassium, rubidium, cesium and thallium).
- the present invention relates to a method for recovering a solution containing molybdenum (recovered molybdenum-containing solution) or a precipitate (recovered molybdenum-containing precipitate), and a method for producing a catalyst using the recovered molybdenum-containing solution and z or the recovered molybdenum-containing precipitate.
- Molybdenum-containing substances containing at least molybdenum, element A (phosphorus and Z or arsenic) and element X (at least one element selected from the group consisting of potassium, rubidium, cesium and thallium) are, for example, It is widely known that it is effective as a heteropolyacid catalyst used in the production of methacrylic acid by the dehydrogenation of butyric acid, the production of methacrylic acid by the vapor phase contact of methacrylic acid, and the like. Some are used in the methacrylic acid production process by the dani method.
- a catalyst is used for a certain period of time, and the catalyst after the use period is taken out of the reactor and replaced with a new catalyst.
- the spent catalyst taken out at this time contains many useful elements such as molybdenum, potassium, rubidium, and cesium as raw materials for producing the catalyst.
- useful elements such as molybdenum, potassium, rubidium, and cesium as raw materials for producing the catalyst.
- the heteropolyacid salt catalyst used in the reaction is thermally decomposed with sodium hydroxide and then brought into contact with a sodium-type strongly acidic resin to remove cesium, rubidium, thallium or potassium. Selectively adsorbing and separating, and adsorbed elements are eluted with sulfuric acid to recover them as respective sulfates.
- the sodium salt solution of heteropolyacid separated in the above step is treated with a proton-type strongly acidic ion exchange resin.
- a process power for recovering a heteropolyacid is increased (for example, JP-A-07-213922). See Patent Document 1)).
- Patent Document 4 a regeneration method of treating with an inorganic ion exchanger such as crystalline antimonic acid (for example, see Japanese Patent Application Laid-Open No. 06-285373 (Patent Document 5)) and the like. Te ru.
- Patent Document 1 uses ion-exchange resin in two steps.
- the concentration of the element to be recovered in the solution to be recovered must be reduced.
- the use of ion-exchange resin in the two steps results in a reduction in the equipment area.
- problems such as the following.
- JP-A-54-002293 Patent Document 2
- JP-A-60-232247 Patent Document 3
- JP-A-61-283352 Patent Document 4
- the catalyst is regenerated to a certain level, but is more methacrylic acid than a catalyst produced by a usual method. There is a problem such as a low yield.
- Patent Document 1 Japanese Patent Application Laid-Open No. 07-213922
- Patent Document 2 JP-A-54-002293
- Patent Document 3 JP-A-60-232232
- Patent Document 4 JP-A-61-283352
- Patent Document 5 Japanese Patent Application Laid-Open No. 06-285373
- Patent Document 6 US Pat. No. 6,777,369
- an object of the present invention is to provide a molybdenum-containing material containing at least molybdenum, element A (phosphorus and Z or arsenic) and element X (at least one element selected from the group consisting of potassium, rubidium, cesium and thallium), Particularly, a method of recovering a solution containing at least molybdenum (recovered molybdenum-containing liquid) or a precipitate (recovered molybdenum-containing precipitate) that can be used in the same manner as the novel molybdenum conjugate used in the production of the catalyst, And a method for producing a catalyst using the recovered molybdenum-containing liquid or the recovered molybdenum-containing precipitate as a raw material.
- the present inventors have studied diligently to solve the above-mentioned problems, and have been working to disperse a raw material molybdenum-containing material for recovering molybdenum in an alkaline solution to allow a compound containing magnesium to act in a specific pH range. As a result, the present inventors have found that molybdenum can be recovered in a state where it can be used for the production of various catalysts containing molybdenum.
- the present invention provides:
- a molybdenum-containing material containing at least molybdenum, element A (phosphorus and Z or arsenic) and element X (at least one selected from the group consisting of potassium, rubidium, cesium and thallium) is dispersed in water and alkali is dispersed.
- the present invention relates to a process for preparing a molybdenum-containing solution that has a pH of 3 or less by adding an acid to the recovered molybdenum-containing solution. Producing a precipitate containing at least molybdenum, and subjecting the formed precipitate (recovered molybdenum-containing precipitate) to solution force separation.
- the present invention is a method for producing a catalyst using a recovered molybdenum-containing liquid or a recovered molybdenum-containing precipitate recovered by the above-described method for recovering molybdenum.
- a molybdenum-containing material containing at least molybdenum, element A (phosphorus and / or arsenic) and element X (at least one element selected from the group consisting of potassium, rubidium, cesium and thallium)
- useful molybdenum can be recovered from a waste molybdenum-containing catalyst as a reusable solution or precipitate by a simple operation.
- the molybdenum-containing substance used for recovering molybdenum contains at least molybdenum, element A, and element X.
- a reaction for producing methacrylic acid by gas phase contact oxidation of methacrolein is performed.
- a catalyst used in a reaction for producing methacrylic acid by oxidative dehydrogenation of isobutyric acid is performed.
- those having the composition of the following formula (1) are preferred, and those having the composition of the following formula (2) are particularly preferable.
- Mo and O represent molybdenum and oxygen, respectively, A represents phosphorus and Z or arsenic, and Y represents iron, conolute, nickel, copper, zinc, magnesium, calcium, strontium, nickel, titanium, and vanadium.
- Mo, Cu, V, and O represent molybdenum, copper, vanadium, and oxygen, respectively, and A represents phosphorus and Z or arsenic.
- Y ' is iron, cobalt, nickel, zinc, magnesium, calcium, strontium, norium, titanium, chromium, tungsten, manganese, silver, boron, silicon, aluminum, gallium, germanium, tin, lead, antimony,
- X represents at least one element selected from the group consisting of potassium, rubidium, cesium and thallium, preferably potassium, rubidium and cesium.
- a, b, c, f, g, d and e represent the atomic ratio of each element.
- b 12
- a 0.11-3, preferably 0.5-3
- c ' 0- 2.98, preferably 0.1-2.5
- f 0.01-2.99, preferably 0.01-2
- g 0.01-2.99, preferably 0.01-1-2
- d 0.01-3, preferably 0.1-3
- e is the atomic ratio of oxygen necessary to satisfy the atomic ratio of each component.
- (c '+ f + g) 0.02-3.
- a catalyst for recovering molybdenum a catalyst usually used in a reaction for producing methacrylic acid or the like is used, but one which is not used for the reaction due to convenience or is removed from the reactor during use. No particular limitation is imposed on what may be used.
- the molybdenum-containing material containing at least molybdenum, element A and element X is first dispersed in water, and then alkali is added.
- the amount of alkali to be added is more preferably pH 8.5-13 than the amount of pH 8 or more.
- the alkali that can be used here is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, and ammonia water. Is preferred.
- a compound containing magnesium element and aqueous ammonia are added. Thereafter, the pH of the solution is adjusted again to 6-12, if necessary, to produce a precipitate containing at least magnesium and element A. It is preferable that insoluble components contained in the solution before adding the compound containing magnesium element and the aqueous ammonia are removed in advance by filtration or the like. It is preferable that the amounts of the magnesium element and ammonia to be added when the precipitate is formed are at least 1 mol per 1 mol of the A element.
- the compound containing a magnesium element used for forming a precipitate is not particularly limited, and magnesium chloride, magnesium sulfate, magnesium nitrate, and the like can be used.
- the pH of the solution in step 2) is 6-12, preferably 6.5-11, and more preferably 7-10. If the pH is lower than 6, precipitation does not occur, or if it does occur, it is insufficient.Therefore, the trapping of element A in the precipitation becomes insufficient, and the 12-molybdophosphate ammonium salt easily precipitates, It is not preferable because the recovery rate of molybdenum is lowered. On the other hand, if the pH exceeds 12, the magnesium element becomes hydroxide magnesium, and the trapping of the element A becomes insufficient.
- the compound used for adjusting the pH is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonia, sodium hydroxide, potassium hydroxide, and the like, and preferably hydrochloric acid and ammonia.
- the solution After adding the compound containing magnesium element and aqueous ammonia, it is preferable to hold the solution for a certain period of time for precipitation.
- the holding time at this time is preferably about 0.5 to 24 hours, and the temperature of the solution is preferably from room temperature to about 90 ° C. During the holding, it may be allowed to stand still, but it is preferable to stir.
- the precipitate containing at least magnesium and the element A generated in the above-mentioned precipitate generation step is: Separate from a solution containing at least molybdenum (recovered molybdenum-containing solution).
- the method for separating the precipitate and the solution is not particularly limited, and for example, general methods such as gravity filtration, pressure filtration, vacuum filtration, filtration separation such as filter press, and centrifugation can be applied.
- a solution containing at least molybdenum obtained by separating a precipitate containing magnesium and element A can be used as it is as a molybdenum raw material for the production of a catalyst.
- a precipitate containing molybdenum (a recovered molybdenum-containing precipitate) is generated.
- the pH at which the recovered molybdenum-containing precipitate is formed is preferably 3 or less, particularly preferably 2 or less.
- the compound used for adjusting the pH is not particularly limited, and includes strong acids such as hydrochloric acid, nitric acid, and sulfuric acid, and is preferably nitric acid or hydrochloric acid.
- After the pH of the solution is adjusted it is preferable to hold the solution for a certain period of time to generate a precipitate.
- the holding time at this time is preferably about 0.5 to 24 hours, and the temperature of the solution is preferably from room temperature to about 90 ° C. During the holding, it may be allowed to stand still, but it is preferable to stir.
- the method of separating the recovered molybdenum-containing precipitate and the residual liquid is not particularly limited, and a general method such as gravity filtration, pressure filtration, reduced pressure filtration, filtration separation using a filter press, or centrifugation is used. Can be.
- the recovered molybdenum-containing precipitate may be washed as necessary to remove impurities.
- the washing liquid used at this time is a force selected in consideration of the solubility of the recovered molybdenum-containing precipitate in use. Examples thereof include pure water and a thin aqueous solution of ammonium nitrate-aluminum-aluminum-ammonium.
- the recovered molybdenum-containing precipitate after washing is preferably 0.1 mol or less, preferably 0.05 mol or less, based on 12 mol of sodium element and chlorine molybdenum element contained in the precipitate. Is more preferred.
- vanadium When a recovered molybdenum-containing precipitate is generated from the recovered molybdenum-containing liquid, vanadium may be contained in the solution depending on the molybdenum-containing material of the recovered material. When used as a raw material for producing a catalyst, it is preferable to remove part or all of vanadium depending on the composition of the produced catalyst. Solution power The method for removing vanadium is not particularly limited.For example, after adjusting the pH of the recovered molybdenum-containing solution containing vanadium in addition to molybdenum, a method of absorbing and removing the solution with a weakly basic anion exchange resin, or a method of removing salt is used.
- Ammonium A method of separating by precipitation using ammonium sulfate is exemplified.
- the time for removing vanadium is not particularly limited as long as the precipitate containing magnesium and element A is separated and before the recovered molybdenum-containing precipitate is generated.
- the recovered molybdenum-containing liquid and the Z or the recovered molybdenum-containing precipitate thus obtained can be used as a raw material for producing a catalyst.
- the recovered molybdenum-containing liquid and the recovered molybdenum-containing precipitate are collectively referred to as “recovered molybdenum-containing material”.
- the state of the recovered molybdenum-containing material used in the production of the catalyst is not particularly limited, and the state of the solution may be either a wet state or a dry state.
- the recovered molybdenum-containing material in particular, a product obtained by firing the recovered molybdenum-containing precipitate to form an oxide can be used.
- the firing conditions are preferably set to 300 to 600 ° C. for 0.5 hours or more in an atmosphere containing oxygen such as air.
- the method for producing the catalyst is not particularly limited, and may be appropriately selected according to the state of the recovered molybdenum-containing material used as a raw material, such as a coprecipitation method, an evaporation to dryness method, and an oxidizing compound mixing method. Is done.
- the catalyst may be produced using only the recovered molybdenum-containing material and Z or a calcined product thereof, or may be produced from molybdenum raw material or molybdenum ore recovered by a method other than the above-mentioned recovery method, if necessary. Used in combination with other molybdenum raw materials such as molybdenum raw materials (hereinafter referred to as “other molybdenum raw materials”).
- the method for producing a molybdenum raw material other than the above-mentioned recovered molybdenum-containing material is not particularly limited.
- the molybdic acid obtained by adjusting the pH with nitric acid is dissolved again in aqueous ammonia, and then concentrated and crystallized to obtain the ammonium paramolybdate and the ammonium paramolybdate.
- Molybdenum trioxide obtained by calcining molybdic acid are not particularly limited, and may be used in combination with nitrates, carbonates, acetates, ammonium salts, oxides, halides, oxyacids, etc. of each element. it can.
- molybdenum raw materials include ammonium paramolybdate, molybdenum trioxide, molybdic acid, and molybdenum chloride.
- phosphoric acid, phosphorus pentoxide, ammonium phosphate, and the like can be used as a raw material of phosphorus.
- a specific method for preparing the catalyst for example, a method of calcining a dried molybdenum-containing slurry and a slurry containing at least the A element and the X element together with the above-mentioned other molybdenum raw materials to be used as necessary. And a method of calcining a dry mixture containing at least an A element and an X element together with the recovered molybdenum-containing material and other molybdenum raw materials used as necessary.
- the amount of the raw material containing these elements was adjusted in consideration of the content of impurities derived from the catalyst constituent elements contained in the recovered molybdenum-containing material used as the raw material.
- the shortage of the contained counter ion may be added.
- the amount of vanadium element added is adjusted by decreasing the amount of ammonium metavanadate added, the insufficient amount of ammonium ion can be adjusted by adding potassium or cesium element by adding an aqueous solution such as ammonia water. If the amount is adjusted by reducing the amount of potassium nitrate or cesium nitrate added, the lack of nitrate ions can be adjusted by adding nitric acid or the like.
- ammonia is mixed during the production of the catalyst! , Prefer to.
- the ammonium is not particularly limited, and may be ammonia itself or an aqueous solution or an ammonium salt of various acids. Further, it may be mixed as an ammonium salt such as molybdic acid or phosphoric acid.
- the amount of ammonia used here is preferably 11 to 17 moles, particularly preferably 2 to 13 moles, per 12 moles of molybdenum atoms.
- the ammonium salt include ammonium carbonate, ammonium bicarbonate, and ammonium nitrate. These are not particularly limited, and one type or two or more types may be used.
- the method of mixing ammonia is not particularly limited, and a method of suspending the recovered molybdenum-containing material in water and then adding aqueous ammonia, or at least recovering molybdenum-containing material and element A, A method of heating and stirring a liquid containing the Y element or the like under reflux, cooling the liquid to a predetermined temperature, and removing ammonia water or ammonium nitrate can be used.
- the mixed ammonia may be contained in the recovered molybdenum-containing material. Ammonia can also be added by using those containing an ammonia component as various raw materials used for ordinary catalyst production.
- the solution or slurry in producing the catalyst of the present invention, when the solution or slurry is passed, May be the same as in the case of normal catalyst production without using the recovered molybdenum-containing material of the present invention, but it should be lower than in the case of normal catalyst production in some or all of the steps. Can be.
- the liquid temperature at that time is preferably determined appropriately from the particle size distribution of the precipitated particles in the slurry, the moldability of the obtained powder, the pore distribution of the catalyst, the reaction results of the catalyst, and the like.
- the method for drying the slurry is not particularly limited, and a drying method using a box dryer, a spray dryer, a drum dryer, or the like can be used.
- the dried product (catalyst precursor) obtained at that time is preferably in a powder form in consideration of molding.
- the dried product may be formed as it is, or may be formed after firing.
- the molding method is not particularly limited, and examples thereof include tableting, extrusion, granulation, and supporting.
- an inert carrier such as silica, alumina, silica'alumina, and silicon carnoid can be mentioned.
- inorganic salts such as barium sulfate and ammonium nitrate are used for the purpose of controlling the specific surface area, pore volume and pore distribution of the molded product, and increasing mechanical strength.
- Lubricants such as graphite, organic materials such as celluloses, starch, polyvinyl alcohol and stearic acid, hydroxide sols such as silica sol and alumina sol, whiskers, glass fibers and inorganic fibers such as carbon fibers.
- An additive may be appropriately added.
- the firing may be performed before filling the reactor or in the reactor.
- the calcination conditions vary depending on the raw materials of the catalyst to be used, the catalyst composition, the preparation conditions, and the like, and cannot be unconditionally determined. However, 300 to 500 ° C is preferable under the flow of oxygen-containing gas such as air and Z or inert gas. More preferably, the temperature is 300-450 ° C., and 0.5 hours or more is more preferable, and more preferably, it is 140 hours.
- reaction conditions for performing the reaction using the catalyst produced by the method of the present invention are not particularly limited, and known reaction conditions can be applied.
- a source gas containing at least methacrolein and molecular oxygen is contacted.
- Contact with medium usually, a tubular reactor filled with a catalyst is used for the reaction.
- a multi-tube reactor having a large number of reaction tubes is used.
- the concentration of methacrolein in the raw material gas can be varied over a wide range, and a force of 11 to 20% by volume is preferred, and particularly 3 to 10% by volume is preferred.
- the raw material methacrolein may contain a small amount of impurities, such as water and lower saturated aldehydes, which do not substantially affect the reaction, and may contain such methacrolein-derived impurities. You can! /.
- the raw material gas must contain molecular oxygen, but the amount of molecular oxygen in the raw material gas is 0.4 to 4 moles greater than that of methacrolein, especially 0.5 to 4 moles. 3 mole times is preferred. It is industrially advantageous to use air as the source of molecular oxygen for the source gas, but air enriched with pure oxygen can be used if necessary. Also, the raw material gas is preferably diluted with an inert gas such as nitrogen or carbon dioxide gas, water vapor or the like.
- the reaction pressure of the gas-phase catalytic oxidation is at least one atmospheric pressure.
- the reaction temperature is preferably from 200 to 450 ° C, more preferably from 250 to 400 ° C.
- the contact time between the raw material gas and the catalyst is preferably 1.5 to 15 seconds, more preferably 2 to 7 seconds.
- part is parts by mass.
- the quantitative analysis of the contained elements (or molecules) was performed by ICP emission spectrometry and atomic absorption spectrometry.
- the analysis of raw material gas and products in the production of methacrylic acid was performed by gas chromatography.
- W is the mass of the element contained in the obtained composition, and W is the rs used for recovery.
- A is the number of moles of supplied methacrolein
- B is the number of moles of reacted methacrolein and the number of moles of methacrylic acid generated.
- the obtained solid was dried at 130 ° C for 16 hours, subjected to pressure molding, further crushed, and passed through a sieve having an opening of 1.70 mm to fractionate particles passing through a sieve having an opening of 0.85 mm. And heat-treated at 380 ° C for 5 hours under air flow to obtain catalyst A (P Mo Sb Cu V Cs)
- This catalyst A was charged into a reaction tube, and a mixed gas of methacrolein 5% by volume, oxygen 10% by volume, steam 30% by volume and nitrogen 55% by volume was passed at a reaction temperature of 290 ° C and a contact time of 3.6 seconds.
- the conversion of methacrolein was 82.9 mol%
- the selectivity of methacrylic acid was 83.7 mol%
- the single flow yield of methacrylic acid was 69.3 mol%.
- a methacrylic acid production test A was performed for 2,000 hours using a catalyst (composition excluding oxygen atoms: P Mo Cs) produced in the same manner as the methacrylic acid production catalyst A of Reference Example 1, and then the catalyst was recovered.
- a catalyst composition excluding oxygen atoms: P Mo Cs
- 100 parts of the recovered catalyst contained 56.3 parts of molybdenum, 2.4 parts of phosphorus and 6.5 parts of cesium. 100 parts of this used catalyst was dispersed in 400 parts of pure water. To this, 130 parts of a 45% by mass aqueous sodium hydroxide solution was added, followed by stirring at 60 ° C for 3 hours. pH was 12.3. After neutralizing this solution to pH 7 with 36% by mass hydrochloric acid, a solution prepared by dissolving 20.5 parts of Shiridani magnesium hexahydrate in 50 parts of pure water and 4.5 parts of 29% by mass aqueous ammonia were added. After adjusting the pH to 9 by adding 29% by mass aqueous ammonia, the mixture was kept at 30 ° C.
- the recovered molybdenum-containing solution obtained in this manner was adjusted to pH 1.0 by adding 36% by mass hydrochloric acid and then kept at 30 ° C for 3 hours with stirring.
- the precipitate thus obtained was filtered and washed with a 2% by weight ammonium nitrate solution to obtain “recovered molybdenum-containing substance 1”.
- Recovered molybdenum content 1 contained 55.5 parts molybdenum and 2.9 parts cesium.
- the recovery of molybdenum at this time was 98.6% by mass. Note that phosphorus in the recovered molybdenum-containing material 1 was not detected.
- the total amount of the recovered molybdenum-containing material 1 obtained above (55.5 parts as molybdenum) was dispersed in 280 parts of pure water, and 29.1 parts of 29% by mass aqueous ammonia was added and dissolved at 60 ° C. 4.5 parts of ammonium metavanadate and 5.2 parts of cesium nitrate were dissolved therein. Then, a solution prepared by dissolving 8.9 parts of 85% by mass phosphoric acid in 10 parts of pure water was added, and 5.6 parts of antimony trioxide was added. The mixture was heated to 95 ° C with stirring, and then copper nitrate was added. 1. A solution prepared by dissolving 2 parts in 10 parts of pure water was prepared.
- the amount of ammonia was 11.1 mol per 12 mol of molybdenum.
- the mixture was further stirred at 95 ° C. for 15 minutes, and then evaporated to dryness while heating and stirring.
- the solid thus obtained was dried, molded, crushed, sieved, and calcined in the same manner as in the production of the methacrylic acid production catalyst A of Reference Example 1 to obtain Catalyst 1.
- the composition of this catalyst 1 excluding the oxygen atom was the same as that of the catalyst A produced in Reference Example 1 with P Mo Sb Cu V
- the total amount of the recovered molybdenum-containing substance 2 obtained above (53.5 parts as molybdenum) was dispersed in 270 parts of pure water, and 28.1 parts of 29% by mass ammonia water was added and dissolved at 60 ° C. 0.2 parts of ammonium metavanadate and 5.2 parts of cesium nitrate were dissolved therein. Next, a solution prepared by dissolving 8.6 parts of 85% by mass phosphoric acid in 10 parts of pure water was added, and 5.4 parts of antimony trioxide was added. The mixture was heated to 95 ° C with stirring, and then copper nitrate was added. 1. A solution prepared by dissolving 1 part in 10 parts of pure water was prepared.
- the amount of ammonia was 11.1 mol per 12 mol of molybdenum.
- the mixture was further stirred at 95 ° C. for 15 minutes, and then evaporated to dryness while heating and stirring.
- the solid thus obtained was dried, molded, crushed, sieved, and calcined in the same manner as in the production of the methacrylic acid production catalyst A of Reference Example 1 to obtain Catalyst 2.
- the composition of this catalyst 2 excluding oxygen atoms was PMoSbCuVCs.
- the total amount of the recovered molybdenum-containing material 3 obtained above (53.1 parts as molybdenum) was dispersed in 180 parts of pure water, and 27.8 parts of 29% by mass aqueous ammonia was added and dissolved at 60 ° C.
- There Hemetabanajin acid Anmoniumu 0.2 parts of 85 mass 0/0 solution of phosphoric acid 8.0 parts in 30 parts of pure water, solutions and iron nitrate copper nitrate was dissolved 1.1 parts in 30 parts of pure water 3. 7 parts of pure water 10 parts
- the solution dissolved in the solution was heated to 90 ° C with stirring, stirred for 5 hours while maintaining the solution temperature at 90 ° C, and then 5.1 parts of cesium nitrate was added to 57 parts of pure water.
- the dissolved solution was added.
- the amount of ammonia was 10.8 mol per 12 mol of molybdenum.
- the mixture was evaporated to dryness while being stirred with heat.
- the solid thus obtained was dried, formed, crushed, sieved, and calcined in the same manner as in the production of Catalyst B of Reference Example 2 to obtain Catalyst 3.
- the composition of the catalyst 3 excluding oxygen atoms was PMoFeCuVCs.
- the recovered molybdenum content 4 contained 53.9 parts of molybdenum, 2.0 parts of vanadium and 2.5 parts of cesium. At this time, the recovery rate of molybdenum was 97.7% by mass. Note that phosphorus, iron and copper in the recovered molybdenum-containing material 4 were not detected.
- the total amount of the recovered molybdenum-containing material 4 obtained above in 5 parts of pure water (53.9 parts as molybdenum), 5.9 parts of 85% by weight phosphoric acid, 0.3 part of vanadium pentoxide, 0.3 part of copper oxide. 7 parts and 0.2 parts of Soni-Danitsu were kneaded and stirred under reflux for 5 hours. After cooling the obtained mixture to 50 ° C., 30.2 parts of 29% by mass aqueous ammonia was added dropwise and stirred for 15 minutes. Next, a solution obtained by dissolving 3.7 parts of cesium nitrate in 13 parts of pure water was added dropwise. The amount of ammonia was 11.1 moles per 12 moles of molybdenum.
- the total amount of the recovered molybdenum-containing material 5 (55.9 parts as molybdenum), 0.2 parts of vanadium pentoxide and 5.6 parts of 85% by mass phosphoric acid are added to 660 parts of pure water, and the mixture is refluxed for 3 hours. The mixture was heated and stirred. To this was added 1.2 parts of copper oxide, and the mixture was further heated and stirred under reflux for 2 hours. After the reflux, the mixture was cooled to 50 ° C, and a solution prepared by dissolving 4.4 parts of potassium nitrate in 26 parts of pure water was added. Then, a solution prepared by dissolving 8.1 parts of ammonium nitrate in 35 parts of pure water was prepared.
- the amount of ammonia was 2.1 mol per 12 mol of molybdenum.
- the mixture was further evaporated to dryness while heating and stirring.
- the solid thus obtained was dried, formed, crushed, sieved, and calcined in the same manner as in the production of Catalyst D of Reference Example 4 to obtain Catalyst 5.
- the composition of this catalyst excluding oxygen atoms was P Mo Cu VK.
- the catalyst 5 using the results of the reaction was three rows in the same reaction conditions as methacrylic acid production test D of Reference Example 4, the methacrolein conversion rate 85.3 mol 0/0, methacrylic acid selectivity of 84.1 mol% and main methacrylic
- the single acid yield of the acid was 71.7 mol%, and the performance of catalyst 5 was equivalent to that of catalyst D.
- the solution after the ion-exchange resin treatment was used to obtain a recovered molybdenum-containing precipitate (recovered molybdenum-containing material 6) in the same procedure as in the recovery of molybdenum 1 of Example 1.
- the recovered molybdenum content 6 contained 53.6 parts of molybdenum and 0.5 part of potassium. At this time, the recovery rate of molybdenum was 96.2 mass 0 /. Met. Note that phosphorus, arsenic, antimony, bismuth, cerium, copper, and vanadium in the recovered molybdenum-containing material 6 were not detected.
- the total amount of the recovered molybdenum-containing material 6 obtained above (53.6 parts as molybdenum), 2.1 parts of vanadium pentoxide and 5.5 parts of 85% by mass phosphoric acid were added to 650 parts of pure water and refluxed. The mixture was heated and stirred for 3 hours. To this was added 1.1 parts of copper oxide, and the mixture was further heated and stirred under reflux for 2 hours. The refluxed mixture was cooled to 50 ° C, a solution of 4.6 parts of potassium nitrate dissolved in 26 parts of pure water was added, and a solution of 8.0 parts of ammonium nitrate dissolved in 35 parts of pure water was added. I got it.
- the amount of ammonia was 2.1 mol with respect to 12 mol of molybdenum.
- the mixture was further evaporated to dryness while heating and stirring.
- the solid thus obtained was dried, molded, pulverized, sieved, and calcined in the same manner as in the production of Catalyst D of Reference Example 4 to obtain Catalyst 6.
- the composition of this catalyst excluding oxygen atoms was P Mo Cu V K.
- Recovered molybdenum content 7 contained 54.1 parts of molybdenum, 1.2 parts of vanadium and 2.9 parts of cesium. At this time, the recovery rate of molybdenum was 96.8 mass 0 /. Met. The collection model Phosphorus and copper in the molybdenum-containing material 7 were not detected.
- the total amount of the recovered molybdenum-containing material 7 (54.1 parts as molybdenum), 0.9 parts of vanadium pentoxide, and 7.0 parts of 85% by mass phosphoric acid are added to 650 parts of pure water, and the mixture is refluxed for 3 hours.
- the mixture was heated and stirred.
- 0.9 parts of copper nitrate was added thereto, and the mixture was further heated and stirred under reflux for 2 hours.
- the mixed solution after the reflux was cooled to 60 ° C., and a solution of 5.7 parts of cesium bicarbonate dissolved in 14 parts of pure water was stirred for 15 minutes.
- a solution prepared by dissolving 8.1 parts of ammonium nitrate in 24.4 parts of pure water was added.
- the amount of ammonia was 2.2 mol per 12 mol of molybdenum.
- the mixture was further stirred for 15 minutes and then evaporated to dryness while heating and stirring.
- the solid thus obtained was dried, molded, pulverized, sieved, and calcined in the same manner as in the production of Catalyst F of Reference Example 6, to obtain Catalyst 7.
- the composition of this catalyst excluding oxygen atoms is P Mo Cu V Cs.
- the catalyst 7 using the results of the reaction was three rows in the same reaction conditions as methacrylic acid production test F of Reference Example 6, the methacrolein conversion rate 83.6 mol 0/0, methacrylic acid selectivity of 84.5 mol% and main methacrylic
- the single acid flow yield was 70.6 mol%, and catalyst 7 had performance equivalent to that of catalyst F.
- the methacrylic acid production test of Reference Example 1 was repeated except that the reaction temperature was 280 ° C using this catalyst G.
- the reaction was carried out under the same reaction conditions as in Example A.
- the conversion of methacrolein was 80.2 mol%
- the selectivity of methacrylic acid was 82.3 mol%
- the yield of single flow of methacrylic acid was 66.0 mol%. .
- the total amount of the recovered molybdenum-containing material 8 obtained above (54.5 parts as molybdenum) was dispersed in 270 parts of pure water, and 28.6 parts of 29% by mass aqueous ammonia was added and dissolved at 60 ° C. Then, 0.3 parts of ammonium hemetavanadate and 3.6 parts of potassium nitrate were dissolved.
- a solution prepared by dissolving 8.2 parts of 85% by mass phosphoric acid in 10 parts of pure water was added, and then 4.1 parts of antimony trioxide was added. The mixture was heated to 95 ° C while stirring, and nitric acid was added.
- a solution prepared by dissolving 1.1 parts of copper in 30 parts of pure water was added.
- Catalyst H composition excluding oxygen atoms: PA s Mo Fe Cu V Cs.
- Recovered molybdenum content 9 contained 54.3 parts of molybdenum, 1.0 part of vanadium and 2.9 parts of cesium. At this time, the recovery rate of molybdenum was 97.4% by mass. Note that phosphorus, arsenic, iron and copper in the recovered molybdenum-containing material 9 were not detected.o
- the total amount of the recovered molybdenum-containing material 9 (54.3 parts as molybdenum), 0.4 parts of vanadium pentoxide, 5.4 parts of 85% by mass phosphoric acid and 2.2 parts of 60% by mass arsenic acid were purified water In addition to 160 parts, the mixture was heated and stirred under reflux for 5 hours. After cooling to 50 ° C, a solution of 6.7 parts of cesium nitrate dissolved in 15 parts of pure water was added, and the temperature of the mixture was raised to 70 ° C with stirring. Next, 27.4 parts of 29 mass% ammonia water was added, and the resulting mixture was stirred at 70 ° C for 90 minutes.
- Example 9 Total amount of recovered molybdenum-containing material obtained in the same manner as in Example 9 (54.3 parts as molybdenum), and obtained by calcining ammonium paramolybdate at 550 ° C for 3 hours. 50 parts of molybdenum trioxide, 1.7 parts of vanadium pentoxide, 8.8 parts of 85% by weight phosphoric acid and 3.6 parts of 60% by weight arsenic acid were added to 260 parts of pure water, and the mixture was refluxed. The mixture was heated and stirred for 5 hours.
- the solid thus obtained was dried, molded, crushed, sieved, and calcined in the same manner as in the production of Catalyst H of Reference Example 8, to obtain Catalyst 10.
- the composition of this catalyst excluding oxygen atoms was P As Mo Fe Cu V Cs.
- molybdenum is contained at a higher rate than a molybdenum-containing material containing at least molybdenum, element A (phosphorus and Z or arsenic) and element X (at least one element selected from the group consisting of potassium, rubidium, cesium and thallium). Since it can be recovered, the molybdenum-containing material after use, particularly the catalyst after use can be effectively used.
- a catalyst can be produced using a recovered molybdenum-containing material recovered from a molybdenum-containing material containing at least molybdenum, an element A, and an element X, and a molybdenum containing at least molybdenum, an element A, and an element X. It can be effectively used even after using the content, especially the catalyst for producing methacrylic acid.
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JP2006519351A JP4764338B2 (ja) | 2004-02-24 | 2005-02-18 | モリブデンの回収方法及び触媒の製造方法 |
CN2005800056684A CN1921941B (zh) | 2004-02-24 | 2005-02-18 | 钼的回收方法和催化剂的制造方法 |
US10/590,291 US20070167321A1 (en) | 2004-02-24 | 2005-02-18 | Method for recovering molybdenum and method for preparing catalyst |
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Cited By (6)
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JP2011031169A (ja) * | 2009-07-31 | 2011-02-17 | Sumitomo Chemical Co Ltd | モリブデン及びコバルトの回収方法 |
JP2011072909A (ja) * | 2009-09-30 | 2011-04-14 | Sumitomo Chemical Co Ltd | 複合酸化物触媒の製造方法 |
KR101048293B1 (ko) | 2010-03-02 | 2011-07-13 | 전남대학교산학협력단 | 비소제거를 통한 고순도 몰리브덴 산물 제조방법 |
JP2012206867A (ja) * | 2011-03-29 | 2012-10-25 | Sumitomo Metal Mining Co Ltd | 三酸化モリブデンの製造方法 |
JP2013023414A (ja) * | 2011-07-21 | 2013-02-04 | Sumitomo Metal Mining Co Ltd | 易溶解性三酸化モリブデン |
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BRPI0703015A2 (pt) * | 2007-07-25 | 2008-11-25 | Diaz Samuel Aguirre | processo para produÇço de derivados de molibdÊnio, a partir de catalisadores exauridos de molibdÊnio |
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US20130108526A1 (en) * | 2011-10-31 | 2013-05-02 | Basf Se | Method for materials recovery from catalysts comprising iron, cerium, molybdenum, and potassium |
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FR3117381B1 (fr) | 2020-12-15 | 2023-03-03 | Ifp Energies Now | Procédé de production d’un catalyseur comprenant au moins un métal du groupe VIB, au moins un métal du groupe VIIIB et un support à base d’oxyde(s) |
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- 2005-02-18 WO PCT/JP2005/002593 patent/WO2005079983A1/ja active Application Filing
- 2005-02-18 US US10/590,291 patent/US20070167321A1/en not_active Abandoned
- 2005-02-18 JP JP2006519351A patent/JP4764338B2/ja active Active
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011031169A (ja) * | 2009-07-31 | 2011-02-17 | Sumitomo Chemical Co Ltd | モリブデン及びコバルトの回収方法 |
JP2011072909A (ja) * | 2009-09-30 | 2011-04-14 | Sumitomo Chemical Co Ltd | 複合酸化物触媒の製造方法 |
KR101048293B1 (ko) | 2010-03-02 | 2011-07-13 | 전남대학교산학협력단 | 비소제거를 통한 고순도 몰리브덴 산물 제조방법 |
JP2012206867A (ja) * | 2011-03-29 | 2012-10-25 | Sumitomo Metal Mining Co Ltd | 三酸化モリブデンの製造方法 |
JP2013023414A (ja) * | 2011-07-21 | 2013-02-04 | Sumitomo Metal Mining Co Ltd | 易溶解性三酸化モリブデン |
CN112867560A (zh) * | 2018-10-18 | 2021-05-28 | 国际壳牌研究有限公司 | 用于烷烃氧化脱氢和/或烯烃氧化的催化剂 |
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CN1921941A (zh) | 2007-02-28 |
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