EP2150497A2 - Procédé de récupération de ruthénium à partir d'un matériau de catalyseur supporté contenant du ruthénium - Google Patents
Procédé de récupération de ruthénium à partir d'un matériau de catalyseur supporté contenant du ruthéniumInfo
- Publication number
- EP2150497A2 EP2150497A2 EP08735260A EP08735260A EP2150497A2 EP 2150497 A2 EP2150497 A2 EP 2150497A2 EP 08735260 A EP08735260 A EP 08735260A EP 08735260 A EP08735260 A EP 08735260A EP 2150497 A2 EP2150497 A2 EP 2150497A2
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- EP
- European Patent Office
- Prior art keywords
- ruthenium
- chloride
- catalyst
- catalyst material
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/005—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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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
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/65—Electrodes comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/008—Disposal or recycling of fuel cells
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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
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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
- Y02P20/584—Recycling of 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- Ruthenium and ruthenium compounds are often components of catalysts, but are not limited to this application.
- ruthenium oxide, ruthenium mixed oxide, ruthenium chloride, ruthenium oxide chlorides and metallic ruthenium, supported or unsupported are used in many applications, i.a. a. Catalysis, used.
- Ruthenium compounds are also often used in electrocatalytic processes or in heterogeneous catalysis.
- the ruthenium component may in particular be metallic ruthenium and also ruthenium chloride, ruthenium oxide or a chlorine-containing ruthenium oxide species.
- EP 424 776 B1 describes a method in which the purification of an aqueous ruthenium-containing solution, in the form of alkali ruthenate, is carried out by oxidation with ozone at a pH above 8 to ruthenium tetroxide.
- a particular disadvantage is the associated considerable procedural expense of an at least two-stage process (first transfer of the Ru-containing starting compound in an alkali ruthenate, then conversion of this ruthenate in RuO 4 ).
- EP 1 026 283 A1 describes a method for the purification of metallic ruthenium powder in order to produce highly pure metallic ruthenium sputtering targets.
- the ruthenium is placed in a sodium hydroxide solution and then reacts with addition of ozone or chlorine-containing gas to Rutheniumtetroxid.
- Ruthenium tetroxide is absorbed in the next step in HCl or HCl / ammonium chloride and dried under a hydrogen atmosphere.
- the metallic ruthenium powder thus obtained can then be pressed to a target.
- a particular disadvantage is the high chlorine consumption typical for the implementation of the process.
- EP 1 072 690 describes a method for ruthenium work-up in the gas phase in the HCl stream and JP 01 142040 represents a procedure in which ruthenium is expelled with chlorine in a reducing atmosphere at 600 0 C - 1200 0 C.
- the invention utilizes the effect that ruthenium compounds which are not in solution form volatile ruthenium tetroxide (RUCM) at elevated temperature in an oxygen-containing atmosphere.
- RUCM volatile ruthenium tetroxide
- the known methods have the disadvantage that they are difficult to apply to oxide-based catalysts.
- additional digestion would have to occur. This can be done after partially known often carried out in aggressive media such as nitrate or chlorate melt at high temperatures digestion process, which materially means a major challenge.
- the disadvantages of known digestion methods can be partially avoided in particular by pretreatment by means of reducing agents.
- the invention relates, on the one hand, to a process for the recovery of ruthenium in the form of ruthenium halide, in particular ruthenium chloride, from a ruthenium-containing supported catalyst material having at least the following steps:
- Suitable oxidizing agents are preferably oxygen-containing mineral salts, in particular nitrates, chlorates, perchlorates, peroxodisulfates, permanganates, peroxides, chromates, dichromates of alkali metals or alkaline earth metals, in particular of alkali metals.
- the oxidizing agents may also be present in any mixtures / combinations.
- the substances used for the oxidation of the ruthenium compounds in particular chlorates, nitrates, peroxides, peroxodisulfates or mixtures thereof by appropriate amounts of alkali metal hydroxide or alkali metal carbonate or mixtures thereof
- commercially available materials such as steel or nickel can be used as the construction material for the reactors for the digestion become. Due to the relatively simple construction the reactors ('tanks') is a possible replacement after appropriate operating time associated with acceptable cost.
- Crucial for the economy of this digestion process is the preferred use of oxidants, which can be disposed of relatively easily after completion of the melt digestion from an ecological point of view. For example, it is preferable to use chlorates, peroxides or peroxodisulfates - these substances are finally converted into chlorides, hydroxides or sulfates as part of the melt digestion process.
- the ruthenium can be dissolved with acid with addition of an oxidizing agent and separated in a further process stage as RuO 4 .
- the invention further provides a process for the recovery of ruthenium in the form of ruthenium halide, in particular ruthenium chloride, from a ruthenium-containing supported catalyst material having at least the following steps:
- the digestion is carried out with a further purification step c) to improve the content of e.g. to reach Fe, Cu or Pt.
- a further purification step c) to improve the content of e.g. to reach Fe, Cu or Pt.
- the proportion of oxygen in the digestion gas during digestion a ') is 1 to 30% by volume, in particular 2 to 20% by volume, and the content of chlorine is up to 95% by volume.
- the content of hydrogen chloride is up to 95% by volume and the content of ozone is up to 20% by volume.
- the catalyst material originates from a used catalyst for the gas phase oxidation of hydrogen chloride with oxygen or a used electrode material for the electrolysis.
- the catalyst material as support material is a material from the series: tin dioxide, silica, graphite, titanium, titanium dioxide with rutile or anatase structure, zirconium dioxide, alumina, silica, carbon nanotubes, nickel , Nickel oxide, silicon carbide and tungsten carbide or mixtures thereof, preferably tin dioxide, titanium dioxide, zirconium dioxide, aluminum oxide.
- the catalyst material contains ruthenium as metal or in the form of a ruthenium compound selected from the series: ruthenium oxide, ruthenium chloride and ruthenium oxychloride.
- the purification c) in both aforementioned methods characterized in that the crude solution of a purification by means of ion exchange, recrystallization and in particular by expelling gaseous Rutheniumtetraoxid.
- ruthenium halide recovered in step d), in particular ruthenium chloride is reused for the preparation of new catalyst or electrode material, in particular as ruthenium, ruthenium oxide, ruthenium chloride or ruthenium oxychloride catalyst on one Carrier or as electrode coating.
- the content of ruthenium in the catalyst material is typically up to 10 wt .-%, in particular 1 to 5 wt .-%, particularly preferably 1.5 to 4 wt .-%.
- the content of ruthenium in the coating of the electrode material is typically up to 50 wt .-%, in particular 30 to 45 wt .-%, particularly preferably 35 to 40 wt .-%.
- the expelled ruthenium can then be absorbed in a solution and processed further.
- a hydrochloric acid solution in which the ruthenium compound can be converted to ruthenium chloride is suitable.
- Ruthenium chloride is a type of compound that is particularly preferred for the preparation of catalysts.
- the ruthenium salt (in particular RuCh) formed by absorption of RuO 4 in mineral acid has a very high purity, which is necessary for the use of RuCb as starting material for catalyst preparation, in particular for the deacon process or electrolysis. having.
- the ruthenium salt, in particular ruthenium chloride, obtainable by the preferred processes has as traces in total a content of Si, Ca, Mg and Al of at most 220 ppm, more preferably of at most 150 ppm, a content of Rh, Ir, Pt and Pd in the Sum of at most 250 ppm, more preferably of at most 150 ppm, a content of Cu of at most 25 ppm, more preferably of at most 15 ppm and a content of K, Na, Fe of in each case at most 125 ppm, more preferably of at most 100 ppm ,
- the supported ruthenium compound can be used here. This pre-cleaning then allows a more efficient expulsion of the ruthenium compound in that the precious metal is made more accessible, and in the subsequent step a simplified purification of the precious metal.
- Such a method provides a significant advantage, since the ejection times of ruthenium are significantly reduced.
- the ruthenium does not need to be solubilized in a previous step, an expense which is not negligible.
- it is a very environmentally friendly and economical method, since no melting salts are used by dispensing with the carrier digestion. The costs of these molten salts are not insignificant because they must then be disposed of costly and expensive.
- Ruthenium-containing electrode material can be used without prior separation of the ruthenium-containing component in the process according to the invention or, after separation, ruthenium-containing component.
- mechanical methods such as sandblasting with aluminates or silicates, etc., as well as chemical methods can be used.
- the separated from the electrode coating remains and it requires further purification because of foreign bodies from the previous sandblasting.
- the ruthenium recovered by the process according to the invention can subsequently be used again in the preparation of catalysts or electrodes.
- the invention therefore furthermore relates to the use of the recovered ruthenium compound obtained as a catalyst or electrode material, in particular as a ruthenium, ruthenium oxide, ruthenium chloride or ruthenium oxide chloride catalyst, on a support or as an electrode coating.
- the ruthenium compound recovered by the process according to the invention is particularly preferably reused in the catalytic process known as the Deacon process.
- hydrogen chloride is oxidized with oxygen in an exothermic equilibrium reaction to chlorine, whereby water vapor is obtained.
- the reaction temperature is usually 150 to 50O 0 C, the usual reaction pressure is 1 to 25 bar. Since it is an equilibrium reaction, it is expedient to work at the lowest possible temperatures at which the catalyst still has sufficient activity.
- oxygen in excess of stoichiometric amounts of hydrogen chloride. For example, a two- to four-fold excess of oxygen is customary. Since no loss of selectivity is to be feared, it may be economically advantageous to work at relatively high pressure and, accordingly, longer residence time than normal pressure.
- Suitable preferred catalysts for the Deacon process usually include ruthenium oxide, ruthenium chloride, ruthenium oxide chloride or other ruthenium compounds supported on silica, alumina, titania or zirconia. Suitable catalysts can be obtained, for example, by applying ruthenium chloride to the support and then drying or drying and calcining. In addition to the ruthenium compound, suitable catalysts may also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium. Suitable catalysts may additionally contain chromium oxide.
- the catalytic hydrogen chloride oxidation may preferably be adiabatic or isothermal or approximately isothermal, batchwise, but preferably continuously or as a fixed bed process, preferably as a fixed bed process, particularly preferably in tube bundle reactors to heterogeneous catalysts at a reactor temperature of 180 to 500 0 C, preferably 200 to 400 0th C, more preferably 220 to 35O 0 C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, more preferably 1.5 to 17 bar and in particular 2.0 to 15 bar are performed ,
- Typical reactors in which the catalytic hydrogen chloride oxidation is carried out are fixed bed or fluidized bed reactors.
- the catalytic hydrogen chloride oxidation can preferably also be carried out in several stages.
- a further preferred embodiment of a device suitable for the method consists in using a structured catalyst bed in which the catalyst activity increases in the flow direction.
- Such structuring of the catalyst bed can by different impregnation of the catalyst support with active material or by different dilution of the catalyst with an inert material.
- an inert material for example, rings, cylinders or balls of titanium dioxide, zirconium dioxide or mixtures thereof, alumina, steatite, ceramic, glass, graphite or stainless steel can be used.
- the inert material should preferably have similar external dimensions.
- Suitable shaped catalyst bodies are shaped bodies with any desired shapes, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, particular preference being given to rings, cylinders or star strands as molds.
- Ruthenium compounds or copper compounds on support materials are particularly suitable as heterogeneous catalysts, preference being given to optionally doped ruthenium catalysts.
- suitable novel carrier materials are tin dioxide, silicon dioxide, graphite, rutile or anatase titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, preferably tin dioxide, titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably ⁇ - or ⁇ -aluminum oxide or their mixtures mixtures.
- the copper or ruthenium catalysts can be preferably obtained in the form of their chlorides for example by impregnating the support material with aqueous solutions of CuCl or RuCl ⁇ 3 and optionally a promoter for doping.
- the shaping of the catalyst can take place after or preferably before the impregnation of the support material.
- the catalysts are suitable as promoters alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, more preferably lanthanum and cerium, or mixtures thereof.
- alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yt
- the moldings can then be dried at a temperature of 100 to 400 0 C, preferably 100 to 300 0 C, for example, under a nitrogen, argon or air atmosphere and optionally calcined.
- the moldings are first dried at 100 to 150 0 C and then calcined at 200 to 400 0 C.
- the conversion of hydrogen chloride in a single pass may preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 70%. Unreacted hydrogen chloride can be partially or completely separated into the catalytic after separation Hydrogen chloride oxidation can be attributed.
- the volume ratio of hydrogen chloride to oxygen at the reactor inlet is preferably 1: 1 to 20: 1, preferably 2: 1 to 8: 1, particularly preferably 2: 1 to 5: 1.
- the separation step usually comprises several stages, namely the separation and optionally recycling of unreacted hydrogen chloride from the product gas stream of the catalytic hydrogen chloride oxidation, the drying of the obtained, substantially chlorine and oxygen-containing stream and the separation of chlorine from the dried stream.
- the catalyst bed was heated constantly at 682 ° C, the silicon dioxide particles subject to a temperature gradient of> 532 0 C between
- Example 1 shows that optionally O 2 should be used together with HCl.
- the chlorine-containing atmosphere (Cl 2 and / or HCl) promotes a significantly stronger downforce of the RuO 4 .
- Example 3 The decomposition method of an oxidic Ru catalyst shown in Example 3 provided a still comparatively small recovery rate. Therefore, an upstream reduction with hydrogen was used, which caused a considerable increase in the recovery rate.
- ruthenium oxide chloride catalyst (SnO 2 or TiO 2 - supported) with a gas mixture of 4% H 2 /96% N 2 at 550 0 C for 2 h and at least partially reduced to metallic Ru.
- the catalyst thus treated was digested with HCl / NaClO 3 analogously to Example 3.
- the yield obtained after analysis of the HCl wash bottle gave 74 and 65%, respectively (SnO 2 and TiO 2 - supported).
- the catalyst support had been dissolved only to a small extent and had an almost white color. In the clear supernatant of the digestion solution in each case 1% of the amount of ruthenium contained on the catalyst were found again (SnO 2 - or TiO 2 carrier).
- the melt cake was placed in a three necked flask with reflux condenser; Dropping funnel, N 2 - feed (0.25 1 / min) transferred.
- the output of the three-necked flask was connected to two wash bottles - the attached N 2 purge was passed through the wash bottles.
- the first was filled with 15 wt .-% hydrochloric acid, the second with 15 wt .-% sodium hydroxide solution.
- the contents of the three-necked flask were refluxed for about 2 hours with N 2 feed, then cooled with N 2 purge, and a sample of the clear supernatant was drawn.
- Example 5 was repeated with a weight of 5 g NaOH / 4 g Na 2 CO 3 instead of 9 g NaOH -
- the procedure and the work-up were carried out analogously to Example 5.
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Abstract
Procédé de récupération de ruthénium sous forme d'halogénure de ruthénium, en particulier de chlorure de ruthénium, à partir d'un matériau de catalyseur supporté contenant du ruthénium, qui comprend au moins les étapes suivantes : a) décomposition chimique du matériau de catalyseur, b) production d'une solution saline de ruthénium brute, c) purification de la solution saline de ruthénium brute et éventuellement élimination du tétraoxyde de ruthénium gazeux de la solution, d) traitement subséquent du composé de ruthénium purifié obtenu à l'étape c), en particulier du tétraoxyde de ruthénium avec de l'halogénure d'hydrogène ou de l'acide halohydrique pour récupérer de l'halogénure de ruthénium, et en particulier avec du chlorure d'hydrogène ou de l'acide chlorhydrique, pour récupérer du chlorure de ruthénium.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE200710020142 DE102007020142A1 (de) | 2007-04-26 | 2007-04-26 | Verfahren zur Rückgewinnung von Ruthenium aus einem rutheniumhaltigen geträgerten Katalysatormaterial |
PCT/EP2008/003005 WO2008131856A2 (fr) | 2007-04-26 | 2008-04-16 | Procédé de récupération de ruthénium à partir d'un matériau de catalyseur supporté contenant du ruthénium |
Publications (1)
Publication Number | Publication Date |
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EP2150497A2 true EP2150497A2 (fr) | 2010-02-10 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08735260A Withdrawn EP2150497A2 (fr) | 2007-04-26 | 2008-04-16 | Procédé de récupération de ruthénium à partir d'un matériau de catalyseur supporté contenant du ruthénium |
Country Status (8)
Country | Link |
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US (1) | US20080287282A1 (fr) |
EP (1) | EP2150497A2 (fr) |
JP (1) | JP2010524672A (fr) |
KR (1) | KR20100015859A (fr) |
CN (1) | CN101663242A (fr) |
DE (1) | DE102007020142A1 (fr) |
TW (1) | TW200906731A (fr) |
WO (1) | WO2008131856A2 (fr) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008006797B4 (de) * | 2008-01-30 | 2014-05-22 | Heraeus Precious Metals Gmbh & Co. Kg | Verfahren und Vorrichtungen zum Entfernen von Ruthenium durch Destillation als RuO4 aus ruthenathaltigen Lösungen |
DE102008039278A1 (de) * | 2008-08-22 | 2010-02-25 | Bayer Materialscience Ag | Verfahren zur Gewinnung von metallischem Ruthenium oder Rutheniumverbindungen aus Ruthenium-haltigen Feststoffen |
CN102405298B (zh) * | 2008-12-30 | 2014-08-27 | 巴斯夫欧洲公司 | 从用过的含氧化钌催化剂中回收钌的方法 |
JP5642706B2 (ja) * | 2008-12-30 | 2014-12-17 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | 塩化水素の酸化用のルテニウム及びニッケル含有触媒 |
DE102010039735A1 (de) | 2010-08-25 | 2012-03-01 | Bayer Materialscience Aktiengesellschaft | Katalysator und Verfahren zur Herstellung von Chlor durch Gasphasenoxidation |
DE102010039734A1 (de) * | 2010-08-25 | 2012-03-01 | Bayer Materialscience Aktiengesellschaft | Katalysator und Verfahren zur Herstellung von Chlor durch Gasphasenoxidation |
EP2439293A1 (fr) | 2010-10-06 | 2012-04-11 | Ferro Duo GmbH | Procédé de récupération de lanthane à partir de zéolithes contenant du lanthane |
CN102108444B (zh) * | 2011-04-01 | 2013-04-17 | 开滦能源化工股份有限公司 | 从负载型钌金属或氧化钌催化剂中回收钌的方法 |
JP5843065B2 (ja) * | 2012-01-26 | 2016-01-13 | 三菱マテリアル株式会社 | ルテニウムの回収方法 |
CN102560128B (zh) * | 2012-03-05 | 2013-10-09 | 武汉凯迪工程技术研究总院有限公司 | 氧化铝负载钌废催化剂中回收钌的方法 |
CN102616868B (zh) * | 2012-03-05 | 2014-04-30 | 阳光凯迪新能源集团有限公司 | 利用含钌废催化剂制备固体亚硝酰硝酸钌的方法 |
CN103540760B (zh) * | 2013-09-26 | 2014-10-08 | 宁波大地化工环保有限公司 | 一种从废氢氧化钌/硅藻土催化剂中回收钌的方法 |
WO2018065127A1 (fr) * | 2016-10-07 | 2018-04-12 | Heraeus Deutschland GmbH & Co. KG | Procédé de séparation de métal noble à partir d'un matériau réfractaire particulaire renfermant du métal noble |
IL248600A0 (en) | 2016-10-30 | 2017-02-01 | Yeda Res & Dev | A method for obtaining platinum group metals from spent catalysts |
CN108504867B (zh) * | 2018-04-28 | 2019-08-27 | 长江师范学院 | 从钌废料中回收钌的碱性熔剂和钌的回收方法 |
CN109266853B (zh) * | 2018-09-13 | 2020-05-08 | 陈永福 | 一种联合提取铂钌的工艺 |
DE102020209881A1 (de) * | 2020-08-05 | 2022-02-10 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren zur Gewinnung von Platin und/oder Ruthenium |
DE102022111440B3 (de) | 2022-05-09 | 2022-08-25 | Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts | Verfahren zur Rückgewinnung von Ruthenium aus einem Ruthenium-haltigem Material |
WO2024101331A1 (fr) * | 2022-11-08 | 2024-05-16 | 株式会社レゾナック | Procédé de décomposition de chlore gazeux et procédé d'élimination de chlore gazeux |
CN115872466B (zh) * | 2022-12-15 | 2023-09-08 | 苏州擎动动力科技有限公司 | 一种铱的氧化物及其制备方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6404460A (fr) * | 1964-04-23 | 1965-10-25 | ||
GB1527758A (en) | 1974-12-10 | 1978-10-11 | Japan Carlit Co Ltd | Process for recovering ruthenium |
US4132569A (en) | 1977-10-25 | 1979-01-02 | Diamond Shamrock Corporation | Ruthenium recovery process |
JPS5997536A (ja) * | 1982-11-26 | 1984-06-05 | Permelec Electrode Ltd | 金属電極からルテニウムを回収する方法 |
JPH01142040A (ja) | 1987-11-30 | 1989-06-02 | Tanaka Kikinzoku Kogyo Kk | Ruを回収する方法 |
DE3935798A1 (de) * | 1989-10-27 | 1991-05-02 | Basf Ag | Verfahren zur gewinnung von rutheniumtetroxid durch oxidation von waessrigen loesungen von alkaliruthenaten |
JP2000034563A (ja) | 1998-07-14 | 2000-02-02 | Japan Energy Corp | 高純度ルテニウムスパッタリングターゲットの製造方法及び高純度ルテニウムスパッタリングターゲット |
GB9917564D0 (en) | 1999-07-27 | 1999-09-29 | Anglo American Platinum Corp | Improvements in refining |
US6458183B1 (en) * | 1999-09-07 | 2002-10-01 | Colonial Metals, Inc. | Method for purifying ruthenium and related processes |
DE10000275C1 (de) * | 2000-01-05 | 2001-05-03 | Heraeus Gmbh W C | Verfahren zur Abtrennung von Ruthenium aus Edelmetall-Lösungen |
WO2002053788A1 (fr) * | 2000-12-29 | 2002-07-11 | Nichromet Extraction Inc. | Procede de recuperation de metaux de base et de metaux precieux par chloruration extractive |
CA2435779A1 (fr) * | 2003-07-22 | 2005-01-22 | Institut National De La Recherche Scientifique | Un procede de recuperation de metaux du groupe du platine dans des minerais et des concentres |
DE102005061954A1 (de) * | 2005-12-23 | 2007-07-05 | Basf Ag | Verfahren zur Wiedergewinnung von Ruthenium aus gebrauchten Rutheniumoxid-haltigen Katalysatoren |
-
2007
- 2007-04-26 DE DE200710020142 patent/DE102007020142A1/de not_active Withdrawn
-
2008
- 2008-04-16 JP JP2010504499A patent/JP2010524672A/ja active Pending
- 2008-04-16 EP EP08735260A patent/EP2150497A2/fr not_active Withdrawn
- 2008-04-16 WO PCT/EP2008/003005 patent/WO2008131856A2/fr active Application Filing
- 2008-04-16 KR KR1020097022230A patent/KR20100015859A/ko not_active Application Discontinuation
- 2008-04-16 CN CN200880012993A patent/CN101663242A/zh active Pending
- 2008-04-23 US US12/108,085 patent/US20080287282A1/en not_active Abandoned
- 2008-04-25 TW TW97115160A patent/TW200906731A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
DE102007020142A1 (de) | 2008-10-30 |
CN101663242A (zh) | 2010-03-03 |
US20080287282A1 (en) | 2008-11-20 |
WO2008131856A3 (fr) | 2009-06-25 |
WO2008131856A2 (fr) | 2008-11-06 |
TW200906731A (en) | 2009-02-16 |
KR20100015859A (ko) | 2010-02-12 |
JP2010524672A (ja) | 2010-07-22 |
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