EP2337630A1 - Procédé de production en continu d'un catalyseur - Google Patents

Procédé de production en continu d'un catalyseur

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Publication number
EP2337630A1
EP2337630A1 EP09781982A EP09781982A EP2337630A1 EP 2337630 A1 EP2337630 A1 EP 2337630A1 EP 09781982 A EP09781982 A EP 09781982A EP 09781982 A EP09781982 A EP 09781982A EP 2337630 A1 EP2337630 A1 EP 2337630A1
Authority
EP
European Patent Office
Prior art keywords
metal
temperature
catalyst
platinum group
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09781982A
Other languages
German (de)
English (en)
Inventor
Ekkehard Schwab
Stefan Kotrel
Alexander Panchenko
Sigmar BRÄUNINGER
Sandra Magnus
Claudia Querner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09781982A priority Critical patent/EP2337630A1/fr
Publication of EP2337630A1 publication Critical patent/EP2337630A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • 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
    • B01J23/42—Platinum
    • 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • B01J6/002—Calcining using rotating drums
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • 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

Definitions

  • the invention relates to a process for the continuous production of a catalyst comprising an alloy of a metal of the platinum group and a second metal selected from the metals of the platinum group or the transition metals.
  • Catalysts containing an alloy of a metal of the platinum group and a second metal are used, for example, in fuel cells.
  • the catalyst is generally applied to an ion-conducting membrane in the form of a catalytically active layer. Usually, such catalyst layers are applied to both sides of the membrane.
  • the membrane provided with the catalyst layers is positioned between two porous gas distribution layers. Through the gas distribution layers, the respective reaction gases are conducted close to the membrane. At the same time, the gas distribution layer also serves to supply and discharge the electrons taken up or released by the reactants.
  • the catalyst layer which is located between the membrane and the gas distribution layer, the actual reduction or oxidation reaction takes place.
  • the membrane in turn ensures ionic current transport in the fuel cell.
  • Another object of the membrane is to form a gas-tight barrier between the two electrodes.
  • the catalysts are suitable, for example, for use as cathode catalysts in fuel cells. Both application in so-called low-temperature fuel cells, for example proton exchange membrane fuel cells (PEMFC), and in high-temperature fuel cells, for example phosphoric acid fuel cells (PAFC), is possible.
  • PEMFC proton exchange membrane fuel cells
  • PAFC phosphoric acid fuel cells
  • cathode catalysts When used in direct methanol fuel cells (DMFC) cathode catalysts must also have a high tolerance to methanol in addition to a high current density for the oxygen reduction.
  • Temperature-treated porphyrin-transition metal complexes e.g. from J. Applied Electrochemistry (1998), pp. 673-682, or transition metal sulfides, for example ReRuS or MoRuS systems, as described e.g. from J. Electrochem. Soc, 145 (10), 1998, pages 3463-3471, see e.g. a high current density for the oxygen reduction and show a good tolerance to methanol.
  • these catalysts do not achieve the activity of Pt-based catalysts and are also not stable enough to ensure a sufficient current density in the acidic environment of a fuel cell for a long time.
  • Suitable methods of preparation include, on the one hand, the impregnation of carbon carriers with metal-containing precursors, the application of colloidal metal alloy particles
  • the application of colloidal metal alloy particles to supports and the synthesis of highly dispersed metal particles in microemulsions require the use of very expensive starting materials, for example surfactants
  • the disadvantage of impregnation is that it is generally difficult to control the size of the nanoparticles and their distribution, and in particular the use of high-boiling solvents, as is often the case during impregnation but problematic in the production of technically relevant amounts of catalyst.
  • a platinum catalyst is first prepared in a first step. This is again after filtration, washing and drying in a liquid reaction medium, generally water, dispersed.
  • the element to be incorporated is added in the form of a suitable soluble salt and precipitated with a suitable precipitant, preferably sodium carbonate.
  • a suitable precipitant preferably sodium carbonate.
  • the resulting dispersion is filtered, the separated solid washed, dried and then subjected to a high temperature treatment under a reducing atmosphere.
  • the disadvantage of this process is that a product which has already been filtered, washed and dried must be subjected a second time to this sequence of processing steps.
  • the object is achieved by a method for producing a catalyst comprising an alloy of a metal of the platinum group and at least one second metal as alloying metal, selected from the metals of the platinum group or the transition metals, comprising the following steps:
  • the catalyst prepared according to the invention is stable to acids and has a high current density for the oxygen reduction, as desired by cathode catalysts in fuel cells.
  • the catalyst containing the metal of the platinum group is mixed with the at least one complex compound containing the alloy metal in step (a), preferably to a dry or wet powder. This avoids having to refilter, wash and dry the already washed and dried catalyst containing the metal of the platinum group. All that follows is heating in step (b) to obtain the alloy. - A -
  • a rotary kiln or a belt calciner is preferably used as a continuously operated furnace used to form the alloy.
  • a rotary kiln the amount of gaseous compounds which is formed in the preparation of the alloy by decomposition of the complex compound, remove, so that the production of larger amounts of catalyst is possible.
  • the catalyst containing the platinum group metal is present, for example, as a metallic powder.
  • the catalyst has a large specific surface area. This is preferably achieved in that the catalyst contains a carrier, wherein the alloy of the metal of the platinum group and the second metal is applied to the carrier. To achieve a large surface area, it is preferred if the support is porous.
  • the catalyst When the catalyst is supported on the carrier, individual particles of the catalyst material are generally contained on the carrier surface. Usually, the catalyst is not present as a continuous layer on the support surface.
  • the catalyst containing the metal of the platinum group already includes the carrier.
  • the carrier used here is generally a catalytically non-active material, to which the catalytically active material is applied, or which contains the catalytically active material.
  • Suitable, non-catalytically active materials which can be used as carriers are, for example, carbon or ceramics.
  • Other suitable support materials are, for example, tin oxide, preferably semiconducting tin oxide, ⁇ -alumina, which is optionally carbon-coated, titanium dioxide, zirconium dioxide or silicon dioxide, the latter preferably being highly dispersed, the primary particles having a diameter of 50 to 200 nm.
  • tungsten oxide and molybdenum oxide which are also known as bronzes, d. H. may be present as substoichiometric oxide.
  • a carrier material is carbon.
  • An advantage of carbon as a carrier material is that it is electrically conductive.
  • the carbon used as a carrier may be, for example, as Activated carbon, carbon black, graphite or nanostructured carbon. Suitable carbon blacks are, for example, Vulcan XC72 or Ketjen black EC300. When the carbon is nanostructured carbon, carbon nanotubes are preferred.
  • the metal of the platinum group is combined with the carrier material.
  • the metal of the platinum group is first deposited on the support. This is generally done in solution.
  • Metal compounds be dissolved in a solvent.
  • the metal can be bound covalently, ionically or complexed.
  • the metal is deposited reductively, as a precursor or alkaline by precipitation of the corresponding hydroxide.
  • Further possibilities for the deposition of the metal of the platinum group are also impregnations with a metal-containing solution (Incipient Wetness), Chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD) processes as well as all other processes known to the person skilled in the art where a metal can be deposited.
  • a salt of the metal of the platinum group is first precipitated. After precipitation, drying and temperature treatment are carried out to prepare the catalyst containing the metal of the platinum group.
  • the metal of the platinum group is rhodium, iridium, nickel, palladium, platinum, copper, silver and gold.
  • the platinum group metal is platinum or palladium, most preferably platinum.
  • the metal of the platinum group is preferably present as a powder having a particle size in the range of 1 to 200 microns.
  • the metal of the platinum group has primary particle sizes in the range of 2 to 20 nm.
  • the powder of the metal of the platinum group can also contain further, catalytically inactive constituents. These serve, for example, as release agents.
  • all materials which can also be used as catalyst supports are suitable for this purpose.
  • the at least one alloying metal contained in the thermally decomposable compound preferably a complex compound, especially an organometallic complex compound, and is selected from the metals of the platinum group or the Transition metals, is preferably selected from the group consisting of ruthenium, cobalt, nickel and palladium.
  • the at least one alloying metal is present as an organometallic complex compound.
  • Preferred ligands for forming the organometallic complex compound are olefins, preferably dimethyloctadiene, aromatics, preferably pyridine, 2,4-pentanedione.
  • the at least one alloying metal is in the form of a mixed cyclopentadienyl-carbonyl complex or as a pure or mixed carbonyl, phosphine, cyano or isocyano complex.
  • the at least one alloying metal is present as organometallic complex compound with acetylacetonate or 2,4-pentanedione as ligand.
  • the at least one alloying metal is preferably ionic.
  • the thermally decomposable compound containing the at least one alloy metal dry.
  • the thermally decomposable compound is dissolved in a solvent.
  • the solvent is preferably selected from the group consisting of ethanol, hexane, cyclohexane, toluene and ether compounds.
  • Preferred ether compounds are open-chain ethers, for example diethyl ether, di-n-propyl ether or 2-methoxypropane, and also cyclic ethers, such as tetrahydrofuran or 1,4-dioxane.
  • the thermally decomposable compound containing the at least one alloying metal is dissolved in a solvent
  • the drying can take place at ambient temperature or at an elevated temperature. When drying takes place at elevated temperature, the temperature is preferably above the boiling point of the solvent.
  • the drying time is chosen such that, after drying, the proportion of solvents in the mixture of the catalyst containing the metal of the platinum group and the at least one complex compound is less than 5% by weight, preferably less than 2% by weight. % is.
  • Suitable solids mixers usually comprise a container in which the material to be mixed is moved.
  • Suitable solids mixers are, for example, blade mixers, screw mixers, silo mixers or pneumatic mixers.
  • the thermally decomposable compound is dissolved in a solvent
  • the mixture of the catalyst containing the metal of the platinum group and the at least one dissolved complex compound is prepared by a conventional dispersing method known to those skilled in the art.
  • a container used in the fast rotating blades or blades are included.
  • Such a device is e.g. an Ultra-Turrax®.
  • the catalyst containing the metal of the platinum group is still free-flowing. This is generally the case when the catalyst has a residual moisture of up to 50% by weight of water.
  • the residual moisture content of the catalyst containing the metal of the platinum group is preferably in the range of 20 to 30% by weight of water. Due to the low water content, the mixture of the catalyst containing the metal of the platinum group and the at least one complex compound containing the alloying metal remains free-flowing. This is an essential prerequisite for its operation, in particular when using a rotary kiln as a continuously operated furnace.
  • the residual moisture of the catalyst containing the metal of the platinum group is obtained, for example, by air drying in the production. However, it is of course also possible to use a completely dried catalyst.
  • step (a) To produce an alloy of the metal of the platinum group and the at least one alloying metal selected from the metals of the platinum group or the transition metals, this is by mixing the catalyst containing the metal of the platinum group with the at least one thermally decomposable compound containing the alloying metal heats powders prepared in step (a).
  • the mixture produced in step (a) in a continuously operated oven to a temperature in the range of 90 to 900 0 C, preferably in the range of 350 to 900 0 C, more preferably in the range of 400 to 850 0 C and in particular in the range of 400 to 650 0 C.
  • the at least one complex compound Upon heating, the at least one complex compound is decomposed and the metal bound in it is liberated.
  • the metal combines with the metal of the platinum group.
  • the result is an alloy in which each metal crystallites are juxtaposed.
  • the individual metal crystallites generally have a size in the range of 2 to 7 nm.
  • the heating takes place in two temperature stages, wherein the temperature of the first temperature stage is lower than the temperature of the second temperature stage. It is also possible that the heating takes place in more than two temperature stages. fen. In each case, the temperature of the subsequent temperature stage is preferably higher than the temperature of the preceding temperature stage. However, it is preferred that the heating takes place in two temperature stages.
  • the temperature of the first temperature stage in the range of 300 to 500 0 C., preferably in the range 350-480 0 C and in particular in the range of 370 to 460 0 C, and the temperature of the second temperature stage in the range of 500 to 700 0 C, more preferably in the range of 550 to 680 0 C and in particular in the range of 570 to 660 0 C.
  • the temperature of the second temperature stage is preferably at least 100 0 C, preferably at least 150 0 C, higher than the temperature of the first tem- peraturlace.
  • the residence time in the continuously operated furnace in step (b) is preferably in the range of 30 minutes to 10 hours, more preferably in the range of 45 minutes to 5 hours and in particular in the range of 1 to 2 hours.
  • the heating of the alloy precursor in step (b) is preferably carried out under a reducing atmosphere.
  • the reducing atmosphere preferably contains hydrogen.
  • the proportion of hydrogen is dependent on the composition of the catalyst to be prepared.
  • the proportion of hydrogen in the reducing atmosphere can be up to 100% by volume.
  • a Formiergasatmosphotre is used, wherein the concentration of hydrogen is usually less than 30 vol .-%, generally less than 20 vol .-%.
  • the proportion of hydrogen in the reducing atmosphere is less than 10% by volume and in particular about 5% by volume.
  • the proportion of hydrogen in the reducing atmosphere preferably in the range of 4 to 10 vol .-%, in particular about 5 vol .-%.
  • the reducing atmosphere preferably contains at least one inert gas.
  • the reducing atmosphere contains nitrogen.
  • nitrogen is used instead of the nitrogen, for example. It is also possible to use a mixture of nitrogen and argon. However, nitrogen is preferred.
  • the reducing atmosphere contains no further constituents in addition to the hydrogen and the inert gas.
  • passivation is preferably carried out.
  • the produced alloy is cooled, for example, to ambient temperature under an inert atmosphere.
  • the inert atmosphere is preferably a nitrogen atmosphere or an argon atmosphere. It is also possible to use a mixture of nitrogen and argon.
  • the alloy produced in step (b) may be introduced, for example, into a water blanket after leaving the continuously operated furnace for passivation.
  • the catalyst prepared by the process according to the invention is suitable, for example, for use as electrode material in a fuel cell.
  • Typical fuel cells in which the catalyst can be used are, for example, proton exchange membrane fuel cells (PEMFC), direct methanol fuel cells (DMFC), direct ethanol fuel cells (DEFC), and phosphoric acid fuel cells (PAFC).
  • PEMFC proton exchange membrane fuel cells
  • DMFC direct methanol fuel cells
  • DEFC direct ethanol fuel cells
  • PAFC phosphoric acid fuel cells
  • the catalyst prepared by the process according to the invention is suitable as a cathode catalyst, i. as a catalyst for oxygen reduction.
  • Other suitable applications are the electro-oxidation of methanol or hydrogen outside of fuel cells, the electroreduction of oxygen, chlor-alkali electrolysis and water electrolysis.
  • the catalyst prepared by the process of the present invention can be e.g.
  • the carbon-supported platinum catalyst thus prepared is then reslurried as a wet washed filter cake in 3 IH 2 O. With about 20 drops of 65% HNO 3 , the pH of the suspension is adjusted to 2.1. To the suspension is 48.86 g Ni (NO 3) ⁇ 6H 2 O dissolved in 400 ml H 2 O was added. The mixture is then thoroughly mixed for 10 minutes, and the pH is increased to 8.5 with about 290 ml of 10% strength Na 2 CO 3 solution. The suspension is stirred for 1 h at 75 0 C and the pH of 8.5. Subsequently, a 6.3% formaldehyde solution, which is prepared by dilution of 18 ml of 35% formaldehyde solution to 100 ml, was added and stirred at 75 0 C again for 1 h.
  • the suspension is cooled to about 60 0 C and the catalyst filtered off by suction through a Buchner funnel with paper filter and washed with 15 liters of cold H 2 O NO 3 -free.
  • the catalyst is then dried for about 48 h at 80 0 C oven temperature under a nitrogen atmosphere.
  • the product obtained is heated in a hydrogen / argon atmosphere with 15 vol .-% hydrogen at a rate of 5 ° C / min to 500 0 C, held for 30 min at this temperature and then also with a Rate of 5 ° C / min heated to 850 0 C, held again for 30 min at this temperature, then cooled to room temperature and in nitrogen, dam stepwise air is added until air atmosphere is present, passivated.
  • the platinum content of the catalyst thus prepared is 23.2 wt .-%, the nickel content at 6.8 wt .-% and the water content at less than 0.5 wt .-%.
  • the PtNi crystallite size is 9.0 nm and the lattice constant is 3.810 ⁇ .
  • Nickel acetylacetonate blended and filled in a batch operated rotary kiln First, the mixture for 2 h at 100 0 C while passing nitrogen dried. Connecting is converted to a stream of 0.8 l / h of hydrogen and 15 l / h of nitrogen and gradually heated up to 600 0 C. Subsequently, the catalyst thus prepared is cooled and passivated at room temperature with air / nitrogen.
  • the prepared catalyst has a platinum content of 21, 6 wt .-%, a nickel content of 8.7 wt .-% and a water content of 0.5 wt .-%.
  • the crystallite size of the PtNi crystallites is 2.4 nm and the lattice constant of the PtNi alloy is 3.742 ⁇ .
  • a carbon supported platinum catalyst is prepared as described in Comparative Example 2.
  • 28.8 g of the carbon-supported platinum catalyst thus prepared are mixed with 1 1, 2 g of nickel acetylacetonate and filled into the reservoir of a continuously operable rotary kiln.
  • the rotary kiln has three heating zones, the first heating zone at 400 0 C and the second and third heating zones are adjusted respectively to 600 0 C.
  • the gas atmosphere in the rotary kiln consists of a mixture of 5 vol .-% hydrogen in 95 vol .-% nitrogen.
  • the capacity of the rotary kiln is adjusted so that per hour 50 g of catalyst are conveyed through the rotary kiln.
  • the residence time of the product in the heated zone of the rotary kiln is 1 h.
  • the product obtained is collected after leaving the rotary kiln in a receiver and finally passivated out of the rotary kiln in an air / nitrogen stream.
  • the catalyst thus prepared has a platinum content of 17.8% by weight, a nickel content of 7.9% by weight and a water content of 0.6% by weight.
  • the crystallite size of the PtNi crystallites is 2.4 nm and the lattice constant of the PtNi alloy is 3.762 ⁇ .

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  • Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un procédé de production en continu d'un catalyseur, comprenant un alliage formé d'un métal du groupe du platine, et d'au moins un second métal, en tant que métal d'alliage, sélectionné à partir des métaux du groupe du platine ou des métaux de transition, procédé caractérisé en ce qu'un catalyseur qui renferme le métal du groupe du platine, ayant au moins un composé complexe, chacun renfermant un métal d'alliage, est mélangé, de manière à former un précurseur d'alliage, et en ce que le précurseur d'alliage est chauffé dans un four entraîné en continu, en vue de produire l'alliage.
EP09781982A 2008-08-26 2009-08-19 Procédé de production en continu d'un catalyseur Withdrawn EP2337630A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09781982A EP2337630A1 (fr) 2008-08-26 2009-08-19 Procédé de production en continu d'un catalyseur

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08163000 2008-08-26
PCT/EP2009/060710 WO2010026046A1 (fr) 2008-08-26 2009-08-19 Procédé de production en continu d'un catalyseur
EP09781982A EP2337630A1 (fr) 2008-08-26 2009-08-19 Procédé de production en continu d'un catalyseur

Publications (1)

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EP2337630A1 true EP2337630A1 (fr) 2011-06-29

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US (1) US8569196B2 (fr)
EP (1) EP2337630A1 (fr)
JP (1) JP5665743B2 (fr)
KR (1) KR101649384B1 (fr)
CN (1) CN102164668B (fr)
WO (1) WO2010026046A1 (fr)

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WO2010139596A2 (fr) * 2009-06-02 2010-12-09 Basf Se Catalyseur pour applications électrochimiques
KR101231006B1 (ko) * 2010-11-26 2013-02-07 현대자동차주식회사 전도성 고분자 보호코팅을 이용한 합금 촉매의 제조방법
JP5829418B2 (ja) * 2011-03-31 2015-12-09 大阪瓦斯株式会社 金属触媒の製造装置
US9272334B2 (en) * 2011-04-12 2016-03-01 GM Global Technology Operations LLC Synthesis of platinum-alloy nanoparticles and supported catalysts including the same
EP2687483A1 (fr) 2012-07-16 2014-01-22 Basf Se Graphène contenant de l'azote et éventuellement du fer et/ou du cobalt
US9543569B2 (en) 2012-12-21 2017-01-10 Lawrence Livermore National Security, Llc Graphene-supported metal oxide monolith
KR101492102B1 (ko) 2013-05-02 2015-02-10 한국에너지기술연구원 연료전지용 합금 촉매 제조방법 및 이에 따라 제조된 연료전지용 합금 촉매
KR101912251B1 (ko) * 2016-09-19 2018-10-29 한국과학기술연구원 개미산의 탈수소화 반응용 촉매 및 이의 제조방법
CN113166944A (zh) * 2018-09-28 2021-07-23 丹麦技术大学 生产合金纳米颗粒的方法

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Publication number Publication date
JP5665743B2 (ja) 2015-02-04
WO2010026046A1 (fr) 2010-03-11
US8569196B2 (en) 2013-10-29
US20110177938A1 (en) 2011-07-21
KR101649384B1 (ko) 2016-08-19
KR20110045087A (ko) 2011-05-03
CN102164668A (zh) 2011-08-24
CN102164668B (zh) 2015-01-21
JP2012500720A (ja) 2012-01-12

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