WO2015050106A1 - Structure de catalyseur sous forme de papier, et procédé de fabrication de celle-ci - Google Patents

Structure de catalyseur sous forme de papier, et procédé de fabrication de celle-ci Download PDF

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WO2015050106A1
WO2015050106A1 PCT/JP2014/076027 JP2014076027W WO2015050106A1 WO 2015050106 A1 WO2015050106 A1 WO 2015050106A1 JP 2014076027 W JP2014076027 W JP 2014076027W WO 2015050106 A1 WO2015050106 A1 WO 2015050106A1
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paper
catalyst structure
aluminum
catalyst
nickel
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PCT/JP2014/076027
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English (en)
Japanese (ja)
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康男 柿原
真司 高橋
祐介 白鳥
美緒 坂本
卓也 北岡
一成 佐々木
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戸田工業株式会社
国立大学法人九州大学
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Priority to JP2015540499A priority Critical patent/JPWO2015050106A1/ja
Publication of WO2015050106A1 publication Critical patent/WO2015050106A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • 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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
    • C01B2203/1017—Packed bed of catalytic structures, e.g. particles, packing elements characterised by the form of the structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a paper-like catalyst structure for efficiently producing hydrogen from a gas containing hydrocarbon and a method for producing the same.
  • a catalyst used in the reforming reaction a catalyst is used in which ruthenium or cheaper nickel is supported on a carrier mainly composed of alumina and the catalyst is further shaped into a pellet.
  • Patent Documents 1 and 2 Also proposed are powders of complex metal oxides containing magnesium and aluminum carrying inexpensive nickel fine particles, and reforming catalysts in which the powders are formed into pellets.
  • Patent Documents 3 and 4 As a catalyst molded body, a paper-like catalyst structure molded into a sheet shape different from the pellet-shaped structure and the conventional honeycomb structure has been proposed (Patent Documents 3 and 4).
  • the paper-like catalyst structure can be easily obtained by a wet papermaking method. Furthermore, it is considered that the reaction of the reaction gas can proceed efficiently by the unique fiber network structure possessed by the paper-like catalyst structure and the metal catalyst supported on the fiber network. Further, there is an advantage that the reactivity can be controlled by stacking a plurality of types of paper-like catalyst structures together with high shape processability. Furthermore, a configuration in which a paper-like catalyst structure is arranged in front of the fuel electrode of a solid oxide fuel cell has also been proposed (Patent Document 5).
  • Biogas which is a mixed gas of methane gas and carbon dioxide gas, is generated from domestic wastewater and wastewater from the livestock industry by methane fermentation.
  • it is better to convert the biogas directly into hydrogen and carbon monoxide by dry reforming and to generate electricity with a solid oxide fuel cell.
  • no catalyst structure having sufficient reforming performance has been reported so far.
  • the carbon component deposited in the catalyst is always a problem when reforming hydrocarbons containing methane gas.
  • the carbon component When the carbon component is deposited on the metal serving as the reforming catalyst to deteriorate the reforming performance, the carbon component causes problems such as blocking the gas diffusion flow path in the porous catalyst structure. In order to maintain the reforming performance for a long time, it is necessary to suppress carbon precipitation.
  • a noble metal such as ruthenium with relatively little carbon deposition is used as a reforming catalyst, but ruthenium metal is generally an expensive material. Therefore, various inexpensive catalysts using nickel metal have been studied, but dry reforming of biogas is possible, but it is difficult to suppress carbon deposition.
  • Patent Document 4 a paper-like catalyst structure for steam reforming a gas mainly composed of methane such as city gas has been proposed (Patent Document 4).
  • Patent Document 4 requires firing at 1000 ° C. or higher in order to improve the gas reforming ability of a paper catalyst in which a nickel metal catalyst is held by an inorganic binder.
  • the nickel metal particles acting as a catalyst will sinter and become coarser, and the catalytic ability will deteriorate, and the general heat-resistant fiber constituting the paper-like catalyst structure will increase the crystallinity. Therefore, there is a concern about deterioration of mechanical strength.
  • Non-patent Document 1 As a catalyst for carbon dioxide reforming (dry reforming) of methane gas, a composite metal oxide powder of magnesium and aluminum produced from hydrotalcite and containing nickel fine particles has been proposed (Non-patent Document 1).
  • the catalyst is considered to be very effective as a catalyst that has high reforming characteristics and suppresses carbon deposition.
  • it is considered desirable to form a paper-like catalyst structure as shown in the present invention rather than as a catalyst powder. There has been no evaluation of reformability when a method or dry reforming is performed.
  • carbon deposition may be observed after the biogas reforming test, and it is necessary to improve the composition and manufacturing method of the paper-like catalyst structure in order to maintain stable reforming for a longer time. there were.
  • an object of the present invention is to provide a paper-like catalyst structure for efficiently producing hydrogen.
  • the present invention provides a paper-like catalyst structure capable of performing the reforming reaction at a low temperature in order to efficiently produce hydrogen during biogas dry reforming. Further, the present invention provides a paper-like catalyst structure having a high carbon deposition resistance during dry reforming of biogas.
  • the present invention is a paper-like catalyst structure (catalyst sheet) comprising inorganic fibers and a composite metal oxide containing magnesium and aluminum on which nickel metal fine particles having an average particle diameter of 1 to 20 nm are supported (the present invention). 1).
  • the present invention is a paper-like catalyst structure (catalyst sheet) according to the first aspect of the present invention, wherein the inorganic fiber is a fiber containing at least one selected from alumina, silica, zirconia, and ceria (Invention 2).
  • the present invention is the paper-like catalyst structure (catalyst sheet) according to the first or second aspect of the present invention, wherein the inorganic fibers include low crystalline fibers (Invention 3).
  • the present invention provides a sheet-like formed body by a wet papermaking method using a slurry containing inorganic fibers, an inorganic binder, and layered double hydroxide particles containing magnesium and aluminum or composite metal oxide particles containing magnesium and aluminum,
  • the molded body is fired at a temperature of 500 ° C. or more and 950 ° C. or less, immersed in an aqueous solution in which a nickel compound is dissolved, dried, and then heated and reduced at a temperature of 700 ° C. or more and 950 ° C. or less.
  • a method for producing a paper-like catalyst structure (catalyst sheet) according to any one of 3 (present invention 4).
  • the present invention provides a slurry containing inorganic fibers, inorganic binders and layered double hydroxide particles containing magnesium, aluminum and nickel or composite metal oxide particles containing magnesium, aluminum and nickel by a wet papermaking method.
  • Is a method for producing a catalyst structure (catalyst sheet) (Invention 5).
  • the present invention provides the paper-like catalyst according to the present invention 4 or 5 using layered double hydroxide particles or composite metal oxide particles having a BET specific surface area of 100 m 2 / g or less after calcination at 600 ° C. for 5 hours. It is a manufacturing method of a structure (catalyst sheet) (Invention 6).
  • the paper-like catalyst structure of the present invention carries fine particles of nickel metal and can efficiently produce hydrogen from a hydrocarbon-containing gas such as methane.
  • a hydrocarbon-containing gas such as methane.
  • high reforming characteristics are provided, so that hydrogen can be efficiently produced even in dry reforming of biogas which is a mixed gas of methane gas and carbon dioxide gas.
  • the paper-like catalyst structure of the present invention can improve the carbon precipitation resistance by the composite metal oxide particles contained in the catalyst structure, so that there is no blockage of the gas diffusion region in the catalyst structure. A stable reforming reaction for a long time can be maintained.
  • a paper-like catalyst structure that can easily carry fine nickel metal particles on the paper-like catalyst structure and can efficiently produce hydrogen.
  • a catalyst structure can be produced.
  • the paper-like catalyst structure according to the present invention includes inorganic fibers and a composite metal oxide containing magnesium and aluminum on which nickel metal fine particles having an average particle diameter of 20 nm or less are supported.
  • the “paper” is a catalyst sheet or a catalyst inorganic fiber sheet in which the catalyst structure of the present invention contains the above-mentioned components, and is obtained by a method of producing paper using a paper making apparatus or the like using inorganic fibers as constituent components It means having properties as an aggregate of inorganic fibers such as paper. Therefore, it is described as “paper” for convenience.
  • the thickness of the paper-like catalyst structure (catalyst sheet) according to the present invention is usually 0.5 to 3 mm, although it depends on the type of inorganic fiber used and the type and amount of oxide particles to be formed. When the thickness exceeds 3 mm, the shape workability deteriorates, and when the thickness is less than 0.5 mm, the strength as the catalyst structure is insufficient.
  • the inorganic fiber constituting the paper-like catalyst structure a fiber body made of an inorganic substance having high thermal stability and chemical stability under the use conditions of the paper-like catalyst structure of the present invention can be used.
  • inorganic substances include metal oxides, metal carbides, and metal nitrides, and are usually metal oxides.
  • the fiber body made of such an inorganic material include alumina and fiber bodies mainly composed of alumina and silica.
  • the paper-like catalyst structure according to the present invention may use ion conductive oxide fibers in combination as part of the inorganic fibers.
  • an ion conductive oxide in combination, it acts as a promoter for suppressing carbon deposition.
  • ion conductive oxides include zirconia (ZrO 2 ) -based oxides and ceria (CeO 2 ) -based oxides, and the ion-conductive oxide is particularly high because of its high chemical stability in a high-temperature reducing atmosphere. It is preferable that a stabilized zirconia fiber is included as a physical fiber.
  • yttria stabilized zirconia YSZ
  • ScSZ scandia stabilized zirconia
  • CaSZ calcia stabilized zirconia
  • YSZ yttria-stabilized zirconia
  • the inorganic fiber constituting the paper-like catalyst structure includes a low crystalline fiber.
  • the paper-like catalyst structure has high mechanical strength and toughness.
  • the low crystalline fiber for example, an amorphous refractory ceramic fiber (for example, IBI WOOL (registered trademark) manufactured by Ibiden Co., Ltd., isowool manufactured by Isolite Industrial Co., Ltd.) is a fiber body mainly composed of alumina and silica. (Registered trademark)) or low crystalline alumina fiber (for example, Denka Arsen (registered trademark) B80L manufactured by Denki Kagaku Kogyo Co., Ltd.) is preferable.
  • the low crystallinity of an inorganic fiber is maintained, without passing through the high temperature exceeding 950 degreeC.
  • the low crystalline fiber is preferably 30% or more of the inorganic fibers constituting the paper-like catalyst structure.
  • the inorganic fibers constituting the paper-like catalyst structure are bound by the inorganic binder component.
  • the ratio of the composition ratio of magnesium and aluminum is preferably 3: 1 to 1.5: 1.
  • the composite metal oxide containing magnesium and aluminum contained in the paper-like catalyst structure according to the present invention carries nickel metal fine particles having an average particle diameter of 1 to 20 nm. It is difficult to make the average particle diameter of metallic nickel supported on the composite metal oxide less than 1 nm. When the average particle diameter of the nickel metal fine particles exceeds 20 nm, the initial activity of the catalyst is lowered and the carbon deposition resistance is deteriorated.
  • the average particle diameter of the nickel metal fine particles is preferably 1 to 18 nm, more preferably 2 to 15 nm.
  • the particle diameter of the nickel metal fine particles is observed with a scanning transmission electron microscope (STEM), and can be measured from the nickel metal fine particles present on the composite metal oxide containing magnesium and aluminum.
  • STEM scanning transmission electron microscope
  • the amount of nickel contained in the paper-like catalyst structure is appropriately selected according to the use of the paper-like catalyst structure, the composition of the raw material gas, etc., but usually when the entire paper-like catalyst structure is 100% by weight And in the range of 1 to 20% by weight in terms of nickel element.
  • the paper-like catalyst structure according to the present invention preferably has a BET specific surface area of 5 m 2 / g or more. If the BET specific surface area is smaller than 5 m 2 / g, the contact area between the hydrocarbon-containing gas and the nickel fine particles becomes small, resulting in a poor conversion rate.
  • the BET specific surface area is more preferably 6 m 2 / g or more, and even more preferably 6 to 20 m 2 / g.
  • the BET specific surface area is adjusted by the type and amount of layered double hydroxide particles containing magnesium, aluminum and nickel or composite metal oxide particles containing magnesium, aluminum and nickel incorporated into the paper-like catalyst structure. .
  • the strength of the paper-like catalyst structure according to the present invention can be measured by, for example, the maximum load until the test piece is torn when the test piece is held and pulled as shown in FIG.
  • the maximum load until the test piece is torn is preferably 1.0 (N) or more. When the maximum load is less than 1.0 (N), handling is not easy because the paper-like catalyst structure is brittle.
  • the paper-like catalyst structure according to the present invention is a sheet formed by wet papermaking using a slurry containing inorganic fibers, an inorganic binder, and layered double hydroxide particles containing magnesium and aluminum or composite metal oxide particles containing magnesium and aluminum. It can be produced by forming a shaped molded body, dipping the molded body in an aqueous solution in which a nickel compound is dissolved, drying, firing, and heat reduction.
  • inorganic fiber, inorganic binder and layered double hydroxide particles containing magnesium and aluminum, or composite metal oxide particles containing magnesium and aluminum, and other components as necessary (porosity adjusting agent, dispersant, etc.) )
  • solvent to prepare a slurry dispersed until uniform.
  • Water, alcohols, and water-soluble ketones can be used as the slurry solvent.
  • the inorganic fiber various fiber bodies made of an inorganic material having high thermal stability and chemical stability under the use conditions of the paper-like catalyst structure of the present invention can be used.
  • the length and thickness of the inorganic fiber may be within a range in which a paper-like catalyst structure can be formed, and is appropriately determined in consideration of the use of the paper-like catalyst structure of the present invention.
  • the average total length is 30 ⁇ m to 6 mm, preferably 50 ⁇ m to 3 mm
  • the average diameter is 1 to 20 ⁇ m, preferably 4 to 10 ⁇ m
  • the minimum fiber diameter is 3.0 ⁇ m or more.
  • the length and thickness of inorganic fiber can be confirmed with a scanning electron microscope (SEM).
  • inorganic binder component conventionally known as long as it has sufficient chemical stability under the conditions of use of the paper-like catalyst structure of the present invention and can bind inorganic fibers to sufficient mechanical strength.
  • Inorganic binders can be used.
  • commercially available alumina sol, zirconia sol, or ceria sol can be used. Considering the effect of suppressing carbon deposition, zirconia sol or ceria sol is more preferable.
  • the amount of the inorganic binder in the slurry is preferably 1 to 70 parts by weight as the solid content of the inorganic binder with respect to 100 parts by weight of the inorganic fibers.
  • the precursor of the composite metal oxide containing magnesium and aluminum contained in the paper-like catalyst structure is preferably a hydrotalcite-like compound.
  • layered double hydroxide particles containing magnesium and aluminum which are hydrotalcite-like compounds, or a composite containing magnesium and aluminum from which interlayer water of hydrotalcite-like compounds has been released. It is preferred to add a metal oxide to the solvent.
  • the hydrotalcite-like compound is dehydrated and decarboxylated from the structure by heating to become a composite metal oxide, but afterwards it is known that the layered structure of the hydrotalcite-like compound is regenerated by immersion in an aqueous solution. It has been. At this time, by immersing in an aqueous solution in which nickel ions are dissolved, a part of magnesium ions is replaced with nickel ions while the layered structure is regenerated. Thereafter, it is known that nickel ions become fine metal particles when heated and reduced. Alternatively, it is known that nickel metal fine particles are precipitated by mixing a nickel ion in place of a part of magnesium ion to prepare a hydrotalcite-like compound, followed by heat reduction (Non-patent Document 2). ).
  • the layered double hydroxide particles containing magnesium and aluminum added to the slurry or the composite metal oxide particles containing magnesium and aluminum preferably have an average particle size of preferably 50 to 500 nm, more preferably 70. ⁇ 150 nm.
  • the ratio of the composition ratio of magnesium to aluminum in the layered double hydroxide containing magnesium and aluminum added to the slurry or the composite metal oxide containing magnesium and aluminum should be 3: 1 to 1.5: 1. preferable.
  • the layered double hydroxide particles containing magnesium and aluminum used in the present invention or the composite metal oxide particles containing magnesium and aluminum have a BET specific surface area of 100 m 2 / g after being heated and fired at a temperature of 600 ° C. It is preferable not to exceed the carbon deposition resistance.
  • the BET specific surface area can be adjusted to the above range by adjusting the particle size and composition ratio of the layered double hydroxide particles containing magnesium and aluminum, or the composite metal oxide particles containing magnesium and aluminum. . Note that the layered double hydroxide containing magnesium and aluminum added to the slurry, or the composite metal oxide containing magnesium and aluminum does not have to be heated and fired at 600 ° C.
  • a layered double hydroxide containing magnesium and aluminum or a composite metal oxide containing magnesium and aluminum having a BET specific surface area of greater than 100 m 2 / g under heating conditions of 600 ° C. is heated and fired to produce a paper-like catalyst structure During the process, it strongly interacts with the inorganic binder present at around 500 to 600 ° C., thereby inhibiting the melting and particle growth of the inorganic binder. Therefore, a fine inorganic binder exists in the paper-like catalyst structure. This fine inorganic binder remains in the paper-like catalyst structure. It is believed that thermal decomposition of the methane component in the biogas occurs remarkably on this fine inorganic binder, and as a result, carbon is deposited.
  • a layered double hydroxide containing magnesium and aluminum having a BET specific surface area of less than 100 m 2 / g under a heating condition of 600 ° C. or a composite metal oxide containing magnesium and aluminum has a small interaction with an inorganic binder. Or almost no melting and particle growth between the inorganic binders during the heating and baking process for producing the paper-like catalyst structure, and the thermal decomposition reaction of methane hardly occurs, and as a result, it does not cause carbon precipitation. Yes.
  • the amount of the layered double hydroxide particles containing magnesium and aluminum or the composite metal oxide particles containing magnesium and aluminum in the slurry is preferably 1 part by weight to 70 parts by weight with respect to 100 parts by weight of the inorganic fibers. .
  • the layered double hydroxide particles containing magnesium and aluminum, or the composite metal oxide particles containing magnesium and aluminum contain a metal or metal oxide such as nickel or ruthenium in advance when the slurry is prepared. May be.
  • the layered double hydroxide particles containing magnesium and aluminum or the composite metal oxide particles containing magnesium and aluminum are dispersed as necessary in order to disperse them uniformly in the paper-like catalyst structure. It may be dispersed in advance. Further, a dispersant or the like may be added.
  • the pulp ensures the strength in the wet state after paper making, and facilitates the collection of the sheet-like molded body before firing from the mesh for filtration. Further, since the pulp is burned off during the firing of the sheet-like molded body and voids (diffusion paths) are generated, the pores inside the paper-like catalyst structure can be adjusted.
  • the amount of the pulp is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the inorganic fibers. It is preferable to use a pulp that has been beaten in advance.
  • a floc is formed by adding a flocculant such as an ionic polymer to the slurry, and the floc is collapsed by applying a hydraulic shear force.
  • a sheet-like composite is obtained.
  • the obtained sheet-like composite is dried and subjected to heat treatment and pressure treatment to obtain a sheet-like molded article having a uniform thickness.
  • the sheet-like molded body is fired in a temperature range of 500 ° C. or more and 950 ° C. or less (first firing).
  • Air, inert gas (nitrogen gas, argon gas, etc.), etc. are used for the baking atmosphere at the time of baking, but air is usually used.
  • the composite metal oxide containing magnesium and aluminum is bound to the inorganic fiber and the inorganic fibers are bonded together. Do the binding.
  • the firing temperature is preferably 700 ° C. to 950 ° C., more preferably 800 ° C. to 900 ° C.
  • a spinel structure starts to grow by heating at about 1000 ° C.
  • a compound having a spinel structure is difficult to regenerate into a hydrotalcite-like compound even when immersed in an aqueous solution, and at the same time, it is difficult for substitution of magnesium ions and nickel ions to occur. It becomes difficult to obtain. Therefore, it is preferable to perform firing in a temperature range in which a spinel structure compound is not generated or is slightly generated.
  • the firing temperature is higher than 950 ° C.
  • the crystallization of inorganic fibers proceeds excessively, and the mechanical strength of the paper-like catalyst body is lowered, which is not preferable.
  • the fired sheet-like molded body is dipped in an aqueous solution in which a nickel compound is dissolved and dried to incorporate a composite metal oxide containing nickel, whereby a fired sheet-like molded body can be obtained.
  • a nickel compound nitrates, sulfates, carbonates, acetates, halides, ammonium salts, oxalates and the like may be selected as appropriate.
  • the concentration of nickel in the aqueous nickel compound solution is preferably 0.1 mol / L to 1 mol / L.
  • the sheet-shaped molded body may be washed with water after the sheet-shaped molded body is immersed in an aqueous solution in which a nickel compound is dissolved.
  • a nickel compound By washing with water, the nickel compound adhering to the surface of the sheet-like molded body can be washed away, and nickel can be supported only on the precursor of the composite metal oxide containing magnesium and aluminum.
  • Excess nickel component deposited on the inorganic fiber or inorganic binder can cause carbon deposition depending on the conditions during the reforming reaction. Therefore, excess nickel components can be removed by washing or the like according to the reforming conditions.
  • the sheet-like molded body dipped in an aqueous solution in which a nickel compound is dissolved and dried may be further fired at 600 ° C. or more and 950 ° C. or less (second firing).
  • Air, inert gas (nitrogen gas, argon gas, etc.), etc. are used for the baking atmosphere at the time of baking, but air is usually used.
  • the anion components (nitrate ions, carbonate ions, halogen ions, etc.) of the nickel compounds adhering to the surface of the sheet-like molded body can be decomposed and removed, and during the subsequent reduction, nickel fine particles are formed Can be prevented.
  • the layered double hydroxide particles containing magnesium and aluminum or the composite metal oxide particles containing magnesium and aluminum incorporated into the sheet-shaped molded body contain nickel metal or metal oxide in advance
  • the sheet-shaped molded body may be fired only once to obtain a fired sheet-shaped molded body.
  • the sheet-shaped molded body is in an aqueous solution in which the nickel compound is dissolved after the first firing. It is possible to obtain a sheet-like molded body that is immersed in the substrate, contains a large amount of nickel in the precursor of the composite metal oxide containing magnesium and aluminum, and further baked by second baking.
  • the fired sheet-like molded body is heated and reduced at 700 ° C. or more and 950 ° C. or less.
  • the atmosphere during the reduction is not particularly limited as long as it is a reducing atmosphere such as a gas containing hydrogen.
  • a paper-like catalyst structure including a composite metal oxide containing magnesium and aluminum on which nickel fine particles having a particle diameter of 20 nm or less are supported can be obtained.
  • Heat reduction at a temperature higher than 950 ° C. is not preferable because the particle size of the nickel particles increases, the BET specific surface area decreases, and the gas reforming efficiency decreases.
  • the heating reduction temperature is preferably 800 ° C. to 950 ° C.
  • the heating reduction temperature is higher than 950 ° C.
  • the crystallization of inorganic fibers proceeds excessively and the mechanical strength of the paper-like catalyst body is lowered, which is not preferable.
  • the present inventors have found that hydrotalcite-like It has been found that when the compound is a nickel carrier, high catalytic properties are exhibited by heat treatment at 950 ° C. or lower.
  • the methane conversion rate in the reforming tests described in the examples is usually 50% or more, preferably 60% or more.
  • the paper-like catalyst structure is obtained by immersing the hydrotalcite-like compound present in the paper-like catalyst structure bound by an inorganic binder in an aqueous solution containing nickel ions and then heating and reducing it at 950 ° C. or lower.
  • Nickel contained in the body is preferentially produced as ultrafine particles of nickel metal having an average particle diameter of 1 to 20 nm on a composite metal oxide containing magnesium and aluminum, and reforming reaction at a low temperature of 800 ° C. or lower.
  • the present inventors have found that a high conversion rate can be obtained during dry reforming of biogas.
  • the inventors of the present invention have a layered double hydroxide or magnesium and aluminum containing magnesium and aluminum as precursors of a composite metal oxide containing magnesium and aluminum on which nickel as a catalyst is supported.
  • the composite metal oxide containing methane the methane conversion rate of biogas and the carbon deposition resistance
  • it contains magnesium and aluminum having a BET specific surface area of not more than 100 m 2 / g after firing at 600 ° C.
  • an aqueous solution containing nickel ions for layered double hydroxide particles containing magnesium and aluminum or composite metal oxide particles containing magnesium and aluminum present in a paper-like catalyst structure bound by an inorganic binder
  • the nickel contained in the paper-like catalyst structure is preferentially nickel having an average particle diameter of 1 to 20 nm on the composite metal oxide containing magnesium and aluminum by being heated and reduced at 950 ° C. or lower after being immersed therein. It has been found that a high methane conversion rate can be obtained at the time of biogas reforming even in a reforming reaction produced as ultrafine metal particles at a low temperature of 800 ° C. or lower.
  • the length and thickness of the inorganic fibers were confirmed with a scanning electron microscope (SEM) (HITACHI S-4800 type).
  • the average particle diameter of the layered double hydroxide particles containing magnesium and aluminum added to the slurry, or the composite metal oxide particles containing magnesium and aluminum confirmed.
  • the BET specific surface area of the layered double hydroxide containing magnesium and aluminum or the composite metal oxide containing magnesium and aluminum was indicated by a value measured using (BELSOPE-mini II manufactured by Nippon Bell). The BET specific surface area was measured for those dried in air at 105 ° C. for 3 hours and cooled to room temperature, and those fired in air at 600 ° C. for 5 hours and cooled to room temperature.
  • the ratio of magnesium to aluminum contained in the layered double hydroxide containing magnesium and aluminum or the composite metal oxide containing magnesium and aluminum was measured using an ICP plasma emission spectrometer (iCAP-6500DUO manufactured by Thermo Fisher). It was shown by the value.
  • the average particle diameter of the nickel metal fine particles was observed by a scanning transmission electron microscope (STEM) (HD-2300A manufactured by HITACHI) after roughly pulverizing the paper-like catalyst structure, and a composite metal oxide containing magnesium and aluminum It calculated as an average value of 50 nickel metal fine particles existing above.
  • STEM scanning transmission electron microscope
  • the amount of nickel contained in the paper-like catalyst structure is measured by preparing a measurement sample by pulverizing the pulverized paper-like catalyst structure using lithium tetraborate, an ICP plasma emission spectrometer (iCAP-6500DUO manufactured by Thermo Fisher). It showed by the value measured using.
  • the BET specific surface area of the paper-like catalyst structure was indicated by a value measured using (BELSOPE-mini II, manufactured by Nippon Bell).
  • the strength of the paper-like catalyst structure is obtained by chucking a test piece obtained by cutting the paper-like catalyst structure into a strip of 50 mm ⁇ 15 mm with a gripping portion having a width of 5 mm at intervals of 30 mm. The maximum load until the specimen was torn and was pulled with an IMADA tensile tester at a pulling rate of 100 mm / min.
  • Used raw materials Inorganic fiber / Amorphous silica-alumina fiber IBI WOOL (registered trademark) J-15, manufactured by Ibiden Co., Ltd.) Average fiber diameter: 2.3 ⁇ m Average fiber length: 38 ⁇ m 2.
  • Oxide sol (inorganic binder) ⁇ Zirconia sol (manufactured by Daiichi rare element chemical industry) ⁇ Ceria sol (Daiichi Rare Element Chemical Industries) ⁇ Yttria stabilized zirconia sol (manufactured by Nissan Chemical Industries, Ltd.) 3. All of the ionic polymers were prepared in 0.2 wt% aqueous solutions.
  • PDADMAC manufactured by polydyldimethylammonium chloride, Sigma-Aldrich, Ltd.
  • Cationic molecular weight about 3 ⁇ 10 5 Charge density: 5.5 meq / g ⁇ Polyacrylamide (Fujikamizu Co., Ltd.)
  • Anionic molecular weight about 1.2 ⁇ 10 7 Charge density: 0.83-1.36 meq / g
  • Example 1 As inorganic fibers, IBI WOOL J-15 (5 g) and 600 mL of distilled water were mixed with a mixer for about 3 minutes. Next, a magnetic stirrer chip, 1 g of hydrotalcite (average particle size: 150 nm, Mg / Al ratio: 3) and the previously mixed IBI WOOL slurry were put into a 3 L plastic cup, and 1.5 L of the total was added. Distilled water was added to make the volume, and the mixture was stirred for about 30 seconds. While stirring with a stirrer, 15.0 g of an aqueous solution (0.2 wt%) of PDADMAC, which is a cationic polymer, was added and stirred for about 3 minutes.
  • the obtained slurry was poured into a commercially available papermaking apparatus (manufactured by Kumagai Riki Kogyo Co., Ltd.), and the suspension mixture was deposited on a circular metal mesh (200 mesh) having a diameter of 160 mm by dehydration.
  • the formed deposit was peeled off from the mesh, pressed at 350 kPa for 3 minutes, and dried at 105 ° C. for 2 hours to obtain a sheet-like molded body.
  • the obtained sheet-like molded body was first baked at 800 ° C. for 5 hours in an air atmosphere.
  • SEM scanning electron microscope
  • the sheet-like molded body after the first firing was immersed in a 0.1 mol / L nickel nitrate aqueous solution for 1 hour, dried at 105 ° C. for 3 hours, and then subjected to second firing at 800 ° C. for 5 hours.
  • the sheet-like molded body after the second baking was subjected to a reduction treatment in 5% H 2 / N 2 at 800 ° C. for 15 hours to obtain a paper-like catalyst structure having a thickness of about 1 mm.
  • SEM scanning electron microscope
  • Example 2 A paper-like catalyst structure was obtained in the same manner as in Example 1 except that the hydrotalcite was changed to that shown in Table 1.
  • Example 3 A paper-like catalyst structure was obtained in the same manner as in Example 1 except that the hydrotalcite was changed to that shown in Table 1.
  • Example 4 As inorganic fibers, IBI WOOL J-15 (5 g) and 600 mL of distilled water were mixed with a mixer for about 3 minutes. Next, the magnetic stirrer chip, 1 g of hydrotalcite (average particle size: 150 nm, Mg / Al ratio: 3) and the previously mixed IBI WOOL slurry were put into a 3 L plastic cup, and 1.5 L in total. Distilled water was added so that the volume of the mixture became about 30 seconds, followed by stirring for about 30 seconds. While stirring with a stirrer, 15.0 g of an aqueous solution (0.2 wt%) of PDADMAC, which is a cationic polymer, was added and stirred for about 3 minutes.
  • PDADMAC a aqueous solution
  • the obtained slurry was poured into a commercially available paper making apparatus (manufactured by Kumagai Riki Kogyo Co., Ltd.), and the suspension mixture was deposited on a 160 mm circular metal mesh for filtration (200 mesh) by dehydration.
  • the formed deposit was peeled off from the mesh, pressed at 350 kPa for 3 minutes, and dried at 105 ° C. for 2 hours to obtain a sheet-like molded body.
  • the obtained sheet-like molded body was first baked at 800 ° C. for 5 hours in an air atmosphere. Subsequently, the sheet-like molded body was immersed in a 0.1 mol / L nickel nitrate aqueous solution for 1 hour, dried at 105 ° C. for 3 hours, and then subjected to second baking at 800 ° C. for 5 hours. A reduction treatment was performed for 15 hours at 800 ° C. in 5% H 2 / N 2 to obtain a paper-like catalyst structure having a thickness of about 1 mm.
  • Comparative Example 1 A paper-like catalyst structure having a thickness of about 1 mm was obtained by carrying out the same treatment as in Example 1 except that the reduction treatment was carried out in 5% H 2 / N 2 at 1000 ° C. for 1 hour.
  • Table 2 shows the analysis results of the paper-like catalyst structures obtained in Examples 1 to 4 and Comparative Example 1.
  • the paper-like catalyst structures of the examples had mechanical strength, and the nickel metal fine particles had a fine average particle size of 20 nm or less.
  • the paper-like catalyst structure of Comparative Example 1 was brittle because of the reduction at high temperature, and the size of the nickel metal fine particles was large.
  • Example 5 A paper-like catalyst structure was obtained in the same manner as in Example 1 except that the inorganic binder was changed to 1.67 g of yttria-stabilized zirconia sol (solid content concentration 30 wt%).
  • Example 6 A paper-like catalyst structure was obtained in the same manner as in Example 2 except that the inorganic binder was changed to 1.67 g of yttria-stabilized zirconia sol (solid content concentration 30 wt%).
  • Example 7 A paper-like catalyst structure was obtained in the same manner as in Example 2 except that the inorganic binder was changed to 1.67 g of ceria sol (solid content concentration 30 wt%).
  • Example 8 A paper-like catalyst structure was obtained in the same manner as in Example 3 except that the inorganic binder was changed to 1.67 g of yttria-stabilized zirconia sol (solid content concentration 30 wt%).
  • Example 9 A paper-like catalyst structure was obtained in the same manner as in Example 3 except that the inorganic binder was changed to 1.67 g of ceria sol (solid content concentration 30 wt%).
  • Table 4 shows the analysis results of the paper-like catalyst structures obtained in Examples 5 to 9.
  • Table 5 shows the characteristics of the layered double hydroxide or composite metal oxide used in Examples 1 to 9 and the analysis results of carbon deposition of the obtained paper-like catalyst structure.
  • the carbon precipitation was evaluated by observing the paper-like catalyst structure after the reforming test.
  • Table 5 classifies the carbon deposition properties according to the following criteria. Trace amount: Almost no change in the color of the surface of the catalyst structure was observed before and after the reforming test, and carbon deposition was observed on less than 10% of the surface of the catalyst structure. Less: Less than 50% of the surface of the catalyst structure is blackened due to carbon deposition. Many: 50% or more of the surface of the catalyst structure is blackened by carbon deposition.
  • the paper-like catalyst structure according to the present invention is easy to handle because it can efficiently produce hydrogen and has mechanical strength. Further, hydrogen can be efficiently produced even in a reforming reaction at a low temperature, which is suitable for dry reforming of biogas.
  • Test piece 2 Chucking 11: Paper-like catalyst structure 12: Reaction tube 13: Heating device 14: Support GC: Gas chromatograph

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Abstract

L'invention a pour objectif de fournir une structure de catalyseur sous forme de papier et un procédé de fabrication de cette structure qui permet de fabriquer efficacement un hydrogène lors d'une réaction de reformage d'un gaz contenant du méthane, et dont la manipulation est simple en raison de sa résistance mécanique. Plus précisément, l'invention concerne une structure de catalyseur sous forme de papier (feuille de catalyseur) qui est obtenue en cuisant et en réduisant par chauffage à une température supérieure ou égale à 950°C un corps moulé en forme de feuille formé au moyen d'une technique de production de papier humide, et qui contient des fibres inorganiques, et un oxyde métallique composite comprenant un aluminium et un magnésium supportant des microparticules métalliques de nickel de diamètre particulaire moyen compris entre 1 et 20nm.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016185529A (ja) * 2015-03-27 2016-10-27 戸田工業株式会社 水素製造用ペーパー状触媒前駆体及びその製造方法、並びに水素製造用ペーパー状触媒構造体
JP2016185528A (ja) * 2015-03-27 2016-10-27 戸田工業株式会社 水素製造用ペーパー状触媒構造体の製造方法
CN107442119A (zh) * 2017-08-10 2017-12-08 石家庄铁道大学 一种氧化铈/氧化锆纸型催化剂及其制备方法
JP2018034081A (ja) * 2016-08-29 2018-03-08 国立大学法人九州大学 ペーパー状触媒およびその製造方法、ペーパー状触媒配列体並びに炭化水素の改質方法
CN111682228A (zh) * 2020-07-06 2020-09-18 山东交通学院 一种具有促进催化作用的扩散层的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62114650A (ja) * 1985-11-12 1987-05-26 Nippon Shokubai Kagaku Kogyo Co Ltd 燃焼用触媒体
JPH06134307A (ja) * 1992-10-27 1994-05-17 Matsushita Electric Ind Co Ltd 触媒付きセラミックスシートとその製造方法
JP2003225566A (ja) * 2002-02-01 2003-08-12 Hiroshima Industrial Promotion Organization 炭化水素分解用触媒及びその製造法
JP2006061760A (ja) * 2004-08-24 2006-03-09 Toda Kogyo Corp 炭化水素分解用触媒及び該炭化水素分解用触媒を用いた水素の製造方法
JP2006110399A (ja) * 2004-10-12 2006-04-27 Hitachi Zosen Corp 水蒸気改質触媒
JP2011092825A (ja) * 2009-10-28 2011-05-12 F C C:Kk ペーパー触媒及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62114650A (ja) * 1985-11-12 1987-05-26 Nippon Shokubai Kagaku Kogyo Co Ltd 燃焼用触媒体
JPH06134307A (ja) * 1992-10-27 1994-05-17 Matsushita Electric Ind Co Ltd 触媒付きセラミックスシートとその製造方法
JP2003225566A (ja) * 2002-02-01 2003-08-12 Hiroshima Industrial Promotion Organization 炭化水素分解用触媒及びその製造法
JP2006061760A (ja) * 2004-08-24 2006-03-09 Toda Kogyo Corp 炭化水素分解用触媒及び該炭化水素分解用触媒を用いた水素の製造方法
JP2006110399A (ja) * 2004-10-12 2006-04-27 Hitachi Zosen Corp 水蒸気改質触媒
JP2011092825A (ja) * 2009-10-28 2011-05-12 F C C:Kk ペーパー触媒及びその製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUSUKE SHIRATORI ET AL.: "Paper-structured catalyst for the steam reforming of biodiesel fuel", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 38, 17 July 2013 (2013-07-17), pages 11278 - 11287 *
YUSUKE SHIRATORI ET AL.: "Study on paper- structured catalyst for direct internal reforming SOFC fueled by the mixture of CH 4 and CO2", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 38, pages 10542 - 10551 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016185529A (ja) * 2015-03-27 2016-10-27 戸田工業株式会社 水素製造用ペーパー状触媒前駆体及びその製造方法、並びに水素製造用ペーパー状触媒構造体
JP2016185528A (ja) * 2015-03-27 2016-10-27 戸田工業株式会社 水素製造用ペーパー状触媒構造体の製造方法
JP2018034081A (ja) * 2016-08-29 2018-03-08 国立大学法人九州大学 ペーパー状触媒およびその製造方法、ペーパー状触媒配列体並びに炭化水素の改質方法
CN107442119A (zh) * 2017-08-10 2017-12-08 石家庄铁道大学 一种氧化铈/氧化锆纸型催化剂及其制备方法
CN107442119B (zh) * 2017-08-10 2019-10-29 石家庄铁道大学 一种氧化铈/氧化锆纸型催化剂及其制备方法
CN111682228A (zh) * 2020-07-06 2020-09-18 山东交通学院 一种具有促进催化作用的扩散层的制备方法

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