WO2021079660A1 - 炭化水素分解用触媒 - Google Patents

炭化水素分解用触媒 Download PDF

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Publication number
WO2021079660A1
WO2021079660A1 PCT/JP2020/035210 JP2020035210W WO2021079660A1 WO 2021079660 A1 WO2021079660 A1 WO 2021079660A1 JP 2020035210 W JP2020035210 W JP 2020035210W WO 2021079660 A1 WO2021079660 A1 WO 2021079660A1
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Prior art keywords
catalyst
nickel
copper
layer
iron
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PCT/JP2020/035210
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English (en)
French (fr)
Japanese (ja)
Inventor
伊原良碩
天野裕之
小林剛
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Ihara Co Ltd
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Ihara Co Ltd
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Priority to JP2020550889A priority Critical patent/JPWO2021079660A1/ja
Priority to EP20878621.0A priority patent/EP4049751A4/en
Priority to CN202080003307.0A priority patent/CN113039016B/zh
Priority to US17/771,009 priority patent/US12528078B2/en
Publication of WO2021079660A1 publication Critical patent/WO2021079660A1/ja
Anticipated expiration legal-status Critical
Priority to JP2022118022A priority patent/JP7193825B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J23/72—Copper
    • 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
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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
    • 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
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
    • 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
    • C01B2203/1076—Copper or zinc-based 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
    • C01B2203/12—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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 hydrocarbon decomposition catalyst.
  • nickel is known as a catalyst metal used for hydrogen gas production by direct decomposition of methane, but it is supported on silica in order to prevent aggregation of nickel fine particles due to sintering during a high temperature reaction of direct decomposition of methane.
  • Proposed ones Patent Document 1, Non-Patent Document 1
  • those supported on zeolite Patent Document 2, Patent Document 3
  • those supported on titania Patent Document 4
  • Patent Document 5 there is one in which carbon particles are interposed between nickel particles without using a carrier (Patent Document 5), and the conversion rate of methane is maintained at about 50% at a temperature of 500 ° C. and 65% at 600 ° C. Furthermore, at 800 ° C, it is said that a high conversion rate of about 90% was obtained at the initial stage, which reached the thermodynamic equilibrium conversion rate, but the continuous operation time of about several hours was demonstrated, and it deteriorated over time. The resulting catalyst needs to be regenerated by acid treatment and calcination.
  • Patent Document 6 there is a catalyst in which a catalyst material is supported on a similarly expandable porous carrier (Patent Document 6), which enables stable direct decomposition for a long time with a conversion rate of about 60% and hydrogen for 10 hours. It is said that it has become possible to generate a degree, but eventually it will be necessary to replace the cartridge.
  • Japanese Unexamined Patent Publication No. 2001-220103 Japanese Unexamined Patent Publication No. 2003-95605 Japanese Unexamined Patent Publication No. 2003-54904 Japanese Unexamined Patent Publication No. 2004-59340 Japanese Unexamined Patent Publication No. 2004-261771 Japanese Unexamined Patent Publication No. 2005-058908
  • the present invention provides a hydrocarbon decomposition catalyst for producing hydrogen in a high yield for a long time without easily deteriorating the catalyst characteristics.
  • One aspect of the invention made to achieve the above object comprises an exposed nickel-containing layer on a support layer made of iron, cast iron, steel, copper, nickel, copper alloys, or iron-nickel alloys. It is a catalyst for decomposition of hydrocarbons. In such a catalyst, the catalytic ability can be changed by setting the metal or alloy type of the support layer to the above type.
  • an intermediate layer containing copper is formed between the base material and the nickel-containing layer, or a copper base material or a copper alloy base material is used. According to this configuration, there is a tendency that the hydrogen generation efficiency is likely to be improved as compared with the case where the layer containing copper is not formed or the case where the copper base material or the copper alloy base material is not used.
  • the above-mentioned catalyst for decomposition of hydrocarbons is obtained by a step of plating the surface of the support layer with copper and performing a diffusion treatment in vacuum, nitrogen gas or argon gas, and a step of forming the nickel-containing layer.
  • it is preferably obtained by plating the surface of the support layer made of nickel or iron-nickel alloy with copper and subjecting it to diffusion treatment in vacuum, nitrogen gas or argon gas.
  • the plated copper diffuses inside the support layer, resulting in a nickel-containing layer appearing on the exposed surface, or hydrogen by separately forming an exposed nickel-containing layer even if the copper plating remains on the surface. There is a tendency to improve the production efficiency.
  • the thickness of the intermediate layer containing copper is 1 to 1000 ⁇ m.
  • the thickness of the layer containing copper is within the above range, it is difficult to melt even if continuous operation at 800 ° C. is performed, and the catalytic ability can be improved.
  • Another aspect of the present invention made to achieve the above object is to heat a hydrocarbon decomposition catalyst having any one of the above characteristics to 800 ° C. for 4 hours to 72 hours, and an average residence time. It is a hydrocarbon decomposition catalyst obtained by contacting methane gas for more than 14 minutes, more preferably 30 minutes or more and 120 minutes or less. When the treatment is performed under the above conditions, the catalytic performance tends to increase and the hydrogen production efficiency tends to stabilize.
  • a photograph showing one aspect of a catalyst test apparatus containing a hydrocarbon decomposition catalyst according to the present invention The schematic diagram which shows one aspect of the catalyst test apparatus which accommodated the hydrocarbon decomposition catalyst which concerns on this invention.
  • the graph which shows the time-dependent change of the catalyst performance of a pure Ni plate.
  • the graph which shows the result of the data logger of the last day of a pure Ni board.
  • the graph which shows the time-dependent change of the catalyst performance of the SPC / Ni plating plate. Results of the data logger on the last day of the SPC / Ni plating plate.
  • the graph which shows the time-dependent change of the hydrogen production efficiency of the catalyst obtained by performing Ni plating after the Cu plating applied to a Ni plate was diffused in vacuum.
  • the hydrocarbon decomposition catalyst of the present invention includes an exposed nickel-containing layer.
  • the "nickel-containing layer” means a layer containing a nickel-containing component as a catalyst component.
  • the nickel-containing component may be nickel alone or an alloy, and in addition to nickel, Cu, Rh, Ru, Ir, Pd, Pt, Re, Co, Fe, Cr, Al, Mo, Nb, It may contain one or more elements selected from Ti, W, Ta, P and the like.
  • the "exposed nickel-containing layer” means a nickel-containing layer to which the hydrocarbon reaction product can come into contact, and is not limited to the nickel-containing layer that is visually exposed.
  • the nickel-containing layer may be an exposed non-supported nickel-containing layer.
  • “Non-supported” means that nickel-containing components as catalyst components are not dispersed as particles on a porous carrier such as activated carbon or a porous oxide, but are organized together. Means. The "organization” may mean that the particles are welded to each other in a part of the region, or may be welded in the entire region, or the particles are melted and then cooled and solidified. It may be that.
  • the nickel-containing layer is preferably organized at the mm level, more preferably at the ⁇ m level, and even more preferably at the nm level.
  • the "exposed non-supported nickel-containing layer” means a non-supported nickel-containing layer to which the hydrocarbon reaction product can come into contact, and is not limited to the non-supported nickel-containing layer that can be visually confirmed.
  • the nickel-containing layer is preferably a nickel-containing plating layer or a nickel-containing thermal spraying layer.
  • the thickness of the nickel-containing layer is usually formed to be about 5 ⁇ m to 200 ⁇ m. If it is thicker than 200 ⁇ m, it may not be economically viable for the purpose of improving the catalytic capacity.
  • the nickel-containing layer As a method for forming the nickel-containing layer, known forming methods such as electrolytic plating, electroless plating, substitution plating, and vacuum vapor deposition can be adopted. As the electrolytic plating conditions, general conditions used for nickel plating on automobile parts and the like can be adopted.
  • the hydrocarbon decomposition catalyst of the present invention is a catalyst comprising iron, copper, nickel, steel, cast iron, iron-nickel alloy, or copper alloy as a support layer for the nickel-containing layer.
  • support layer means a layer that serves as a base for laminating nickel-containing layers. Therefore, the support layer does not have to be in direct contact with the nickel-containing layer, and the support layer may be formed via one or more intermediate layers.
  • the support layer may be the base material (which may be a structure described later) itself before the nickel-containing layer is laminated, or may be a layer laminated on the base material.
  • Iron means a simple substance of iron or an iron alloy having a carbon content of less than about 0.02%.
  • the steel means an iron alloy with a carbon content of about 0.02 to 2.14%.
  • the steel is not particularly limited, and examples thereof include mild steel (SPC), carbon tool steel, alloy tool steel, and stainless steel.
  • Cast iron means an iron alloy having a carbon content of more than about 2.14%.
  • the copper alloy means a copper alloy to which one or more metal elements and / or non-metal elements are added.
  • copper-nickel alloys such as constantan and monel metal
  • copper and nickel such as white copper and white copper are used.
  • Examples thereof include alloys containing other components, alloys containing elements other than nickel such as copper and copper, and may contain transition elements such as chromium, molybdenum and cobalt.
  • the iron-nickel alloy means an alloy of iron and nickel, or an iron and nickel to which one or more metal elements and / or non-metal elements are added as required.
  • the iron-nickel alloy include iron and nickel alloys. , Permalloy, amber and the like, and may contain transition elements such as chromium, molybdenum and cobalt.
  • Permalloys include not only permalloys having a higher nickel content than iron (for example, Permalloy A and Permalloy C in the JIS standard), but also some permalloys containing more iron than nickel (for example, Permalloy B in the JIS standard). Permalloy D) is also included.
  • Permalloy Permalloy
  • the composition of a typical permalloy is shown below.
  • the hydrocarbon decomposition catalyst of the present invention is a single Ni or copper nickel in which the nickel-containing layer and the support layer are integrated. It may be an alloy or an iron-nickel alloy itself, or a support layer made of Ni alone, a copper-nickel alloy or an iron-nickel alloy, in which a layer containing a nickel-containing component having a component composition different from that of the support layer is laminated. There may be.
  • the thickness of the support layer is appropriately selected from the viewpoint of heat resistance, processability, etc. of the base material, and is usually 0.5 mm to 10 mm.
  • the hydrocarbon decomposition catalyst of the present invention preferably has an intermediate layer containing copper between the support layer and the nickel-containing layer.
  • the intermediate layer containing copper means a layer made of elemental copper or a copper alloy, which is clearly distinguished from the support layer and the nickel-containing layer in terms of composition.
  • the copper alloy may contain one or more elements selected from Zn, Al, Sn, and Ni.
  • the thickness of the intermediate layer containing copper is preferably 1 to 1000 ⁇ m. If it is thinner than 1 ⁇ m, it is easily melted and may not be able to withstand a reaction temperature of about 800 ° C. On the other hand, even if it is thicker than 1000 ⁇ m, it may not be economically viable for the purpose of improving the catalytic ability.
  • a more preferable lower limit of the thickness of the intermediate layer is 1.5 ⁇ m, a further preferable lower limit is 2 ⁇ m, a more preferable upper limit is 500 ⁇ m, and a further preferable upper limit is 200 ⁇ m.
  • Known methods for forming the intermediate layer containing copper include plating (electrolytic plating, electroless plating), thermal spraying (plasma spraying, cluster ion beam, gas deposition, CS method, WS method, high-speed solid particle deposition method).
  • a forming method can be adopted, and in general, electrolytic plating can be mainly adopted when the layer thickness can be thin, and plasma spraying can be mainly adopted when the layer thickness can be increased.
  • electrolytic plating conditions general conditions used for copper electrolytic plating on automobile parts and the like can be adopted.
  • the plasma spraying conditions the general conditions of the plasma spraying method used for copper spraying on automobile parts and the like can be adopted.
  • the catalyst for hydrocarbon decomposition of the present invention was obtained by plating the surface of the support layer with copper and performing diffusion treatment in vacuum, nitrogen gas or argon gas, and forming a nickel-containing layer. Or, it is preferably obtained by plating the surface of a support layer made of nickel or an iron-nickel alloy with copper and subjecting it to diffusion treatment in vacuum, nitrogen gas or argon gas.
  • the diffusion treatment may be carried out by a conventionally known method, temperature and time, but the plated copper diffuses inside the support layer, and as a result, a nickel-containing layer appears on the exposed surface or the copper plating remains on the surface. Even if it is present, the condition is not particularly limited as long as the exposed nickel-containing layer can be separately formed.
  • each layer when the layers are clearly formed is not particularly limited except when the catalyst for hydrocarbon decomposition of the present invention is Ni alone, a copper nickel alloy or an iron nickel alloy itself, but the support layer / Surface layer, support layer / intermediate layer / surface layer, or support layer / first intermediate layer / second intermediate layer / surface layer in this order, for example, Fe / Cu / Ni, Fe / X / Cu / Ni, cold rolled steel plate.
  • X is selected from Zn, Sn, Rh, Ru, Ir, Pd, Pt, Re, Co, Fe, Cr, Al, Mo, Nb, Ti, W, Ta, P and the like, Cu or Ni. It is a layer composed of one or more elements other than.
  • the hydrocarbon decomposition catalyst of the present invention is preferably a structure catalyst. Since the structure is used, for example, even if the catalytic function of the nickel-based metal is deteriorated due to the adhesion of the solid product in the direct decomposition reaction of the hydrocarbon, the separation is easier than that of the powder catalyst, and the separation is easy. A wide variety of methods can be adopted.
  • a "structure catalyst” is a catalyst selected from particles, plates, porous bodies, felts, meshes, fabrics or expanded metals, or the structure itself functions as a catalyst, or the structure is referred to. It is the base catalyst.
  • the structure-based catalyst generally refers to a catalyst obtained by impregnating a slurry containing a catalyst component with a base material having a shape such as a honeycomb, but for the purpose of the present invention, the above-mentioned catalyst is generally used.
  • a non-supported catalyst layer (plating layer, thermal spraying layer) exposed by thermal spraying, plating, or the like is formed on the structure.
  • the particles are particles having a diameter of 0.1 to 30 mm, preferably 1 to 30 mm, and more preferably 5 to 30 mm.
  • the board may be composed of a single layer or may be two or more layers of plywood made of different materials.
  • the porous body is a porous body having continuous pores.
  • the porous body preferably has a three-dimensional network structure.
  • the pore diameter is usually about 300 to 4000 ⁇ m, preferably 1100 to 4000 ⁇ m, the porosity is 80% or more, preferably 90% or more, more preferably 95% or more, and the specific surface area is 200 m 2 / m 3 to 6000 m 2 /. m 3 , preferably 500 m 2 / m 3 to 8500 m 2 / m 3 .
  • a typical example is Celmet (registered trademark) manufactured by Sumitomo Electric Industries, Ltd.
  • the felt is a material obtained by randomly entwining and laminating fiber-like constituent materials and sintering them as necessary, and includes a needle punch web and a fiber sintered body.
  • the needle punch web and the fiber sintered body have a fiber diameter of 10 to 150 ⁇ m, a porosity of about 50 to 80%, a weight of 50 to ⁇ 50,000 g / m 2 , and a thickness of 0.1 mm to. It can be 5.0 mm.
  • a mesh is a fiber-like constituent material that is woven by any weave or knitting method regardless of whether it is plain weave or twill weave, or weft knitting or warp knitting, and the intersections are fused as appropriate.
  • the wire diameter is 30 to 800 ⁇ m, and the number of meshes is 5 to 300 / inch.
  • the fabric is a knit that connects meshes with each other by an arbitrary knitting method.
  • Expanded metal is a metal plate that is processed into a rhombus or hexagonal mesh by making staggered cuts at predetermined intervals and spreading it out with a special machine.
  • the mesh dimensions are usually 25 mm to 130 mm for SW and 20 mm to 320 mm for LW, and the strand dimensions are 1 mm to 8.5 mm for plate thickness and 1.2 mm to 9.5 mm for W.
  • the structure may be one of the above-listed ones, or may be a composite structure in which two or more kinds are combined.
  • the method for producing a structure catalyst as described above may include a step of blasting the original structure. If the original structure is made of a non-nickel metal, the structure catalyst can be produced by laminating a layer containing nickel on the surface of the original structure, usually by porous plating or nickel plating. If appropriate blasting is performed, a structure catalyst having a porous surface can be produced. On the other hand, if the original structure is made of a nickel-based metal, a structure catalyst having a porous surface can be produced by performing blasting. If the original structure is a nickel-aluminum alloy, a method of alkali dissolution treatment can also be adopted.
  • the hydrocarbons to be directly decomposed or steam-modified by the hydrocarbon decomposition catalyst of the present invention include aliphatic hydrocarbons such as methane, ethane, ethylene and propane, cyclic aliphatic hydrocarbons such as cyclohexane and diclopentane, and more.
  • aromatic hydrocarbons such as enzyme, toluene and xylene, but preferably linear aliphatic hydrocarbons, more preferably methane, ethane or propane, and even more preferably methane.
  • the above-mentioned hydrocarbon decomposition catalyst uses a hydrocarbon decomposition catalyst having at least one of the above-mentioned characteristics as a raw material, is heated to 800 ° C. for 4 hours to 72 hours, and has an average residence time of more than 14 minutes and 120 minutes. It may be obtained by contacting methane gas below. If the average residence time is 14 minutes or less, it may be difficult to obtain a surface structure having high catalytic activity, but if it exceeds 120 minutes, it is advantageous from the viewpoint of productivity of the hydrocarbon decomposition catalyst. There is no.
  • the preferable lower limit of the contact time with methane gas is 6 hours, the more preferable lower limit is 7 hours, and the preferable upper limit is 42 hours.
  • a more preferable lower limit of the average residence time is 30 minutes, and even more preferably 57 minutes.
  • Example 1-High temperature test using a pure Ni plate The circumference of the cylindrical SUS304 residence type small reactor 1 (reaction compartment volume: about 570 cm 3 ) shown in FIG. 1 is surrounded by the heater 2 (product number: FPS-100, control method: PID method, manufacturer: Fulltech Co., Ltd.) shown in FIG. Cover with (manufactured by), and from the upper end of the furnace, two pure nickel plate-shaped catalysts 3 (part number: K14062, ASTMB162 compliant and JIS SH4551 compliant, 900 ° C. 1 minute water quenching) with a thickness of 0.35 mm * width 30 mm * length 300 mm.
  • a gas heat conduction type gas analyzer 6 (zero gas: city gas 13A, span gas: 100% hydrogen, gas flow rate: 1.0 L / min, manufactured by Chino Corporation) was attached and measured. The results are shown in FIGS. 3a and 3b. As is clear from FIG. 3b, for safety, after continuous operation for 8 hours each day, the core was cooled and heated again from room temperature to 800 ° C. the next day. As a result, it was found that the hydrogen production efficiency of the nickel plate-shaped catalyst decreased to about 11% in terms of hydrogen gas concentration on the 4th day.
  • Hastelloy product number: Alloy C-276, manufactured by ThyssenKrupp
  • the hydrogen production efficiency was 10% with almost no change during the 3-day test period.
  • Example 3-Change test of catalyst performance when SPC is Ni-plated A cold-rolled steel sheet (product number: COLD ROLLED STEEL SHEET IN COIL DULL FINISHED, manufactured by JFE Steel Co., Ltd.) without carbon containing carbon and Ni-plated (thickness 10 ⁇ m) was used as a plate-like catalyst in Example 1 and The results of investigating the hydrogen production efficiency under the same conditions are shown in FIGS. 4a and 4b. Hydrogen production efficiency converged to 32.5% in 4 days.
  • Example 4-Change test of catalyst performance when Ni plating is performed after laminating an intermediate layer of Cu plating on SPC After laminating a Cu-plated intermediate layer (thickness 2 to 3 ⁇ m) on the cold-rolled steel sheet used in Example 3, Ni-plating under the same conditions as in Example 3 was used as a plate-like catalyst.
  • FIGS. 5a and 5b The results of investigating the hydrogen production efficiency under the same conditions as in Example 1 are shown in FIGS. 5a and 5b. Hydrogen production efficiency converged to 40% in 5 days.
  • Example 5-Change test of catalyst performance when Ni plating is applied to permalloy Permalloy (Permalloy B, YFN-45-R, Ni content 45%, manufactured by DOWA Metal Co., Ltd.) subjected to Ni plating under the same conditions as in Example 3 was used as a plate-like catalyst in the same manner as in Example 1.
  • the results of investigating the hydrogen production efficiency under the above conditions are shown in FIGS. 6a and 6b. Hydrogen production efficiency increased to 68% in 9 days. As described above, it was found that the hydrogen production efficiency increases with the passage of time even when permalloy, which is an iron-nickel alloy, is used as the support layer.
  • Example 6-Test for change in catalyst performance of a plate in which the Cu support layer is Ni-plated The results of investigating the hydrogen production efficiency under the same conditions as in Example 1 using Cu (1100) plated with Ni under the same conditions as in Example 3 are shown in FIGS. 7a and 7b. .. Hydrogen production efficiency converged to 93.8% in 4 days. The result was close to the theoretical value.
  • FIG. 8 shows the results of investigating the hydrogen production efficiency under the same conditions as in Example 1 using Constantin (product number: CN-49, manufactured by Daido Steel Co., Ltd.) as a plate-shaped catalyst. Hydrogen production efficiency increased to 37% in 5 days.
  • Example 8-Test of change in catalyst performance when constantan is Ni-plated The results of investigating the hydrogen production efficiency under the same conditions as in Example 1 using the same constantan plate used in Example 7 plated with Ni under the same conditions as in Example 3 as a plate catalyst. It is shown in FIGS. 9a and 9b. Hydrogen production efficiency has converged to 90%.
  • Example 9 When Cu is diffused in a vacuum on a Ni plate and then Ni-plated, A nickel plate having a thickness of 0.6 mm, a width of 30 mm, and a length of 300 mm was plated with copper having a thickness of 1 to 2 ⁇ m, and diffused in a vacuum furnace at 900 ° C. for 13 hours. When the surface to be treated of the obtained object to be treated was examined by an X-ray diffractometer, copper was not detected on the surface as a result of the copper-plated portion being diffused inside the nickel plate.
  • FIG. 10 shows the results of investigating the hydrogen production efficiency under the same conditions as in Example 1. Hydrogen production efficiency increased sharply in 4-8 hours and converged to 90% on day 3. After that, even if the methane supply pressure was gradually increased to 0.4 MPa on the 4th day and 0.5 MPa on the 5th day, there was almost no change. Furthermore, on the 6th day, a flow rate increase test was conducted.
  • the hydrogen production efficiency of the product obtained by the diffusion treatment was improved as compared with that of the product not subjected to the diffusion treatment (83%), and the start-up of the catalytic action was also improved.
  • FIG. 14 shows the results of investigating the hydrogen production efficiency under the same conditions as in Example 1 using this as a plate-shaped catalyst. Hydrogen production efficiency increased sharply in 4-8 hours and eventually converged to about 85%. It can be seen that this is a significant improvement in characteristics as compared with the result of Example 1 (pure Ni plate) shown in FIG. It is considered that the nickel surface layer portion was changed by the diffusion of Cu on the surface of the nickel plate.
  • the hydrogen generator incorporating the hydrocarbon decomposition catalyst of the present invention can be used as a fuel cell vehicle equipped with a polymer electrolyte fuel cell [PEFC] by attaching a device for increasing the purity of hydrogen contained in the produced gas at the subsequent stage. It is suitably applicable to hydrogen supply through on-site stations and the like.
  • PEFC polymer electrolyte fuel cell
  • Solid Oxide Fuel Cell which can directly use methane by utilizing the city gas infrastructure in addition to hydrogen, have been attracting attention.
  • SOFC Solid Oxide Fuel Cell
  • the problems of carbon precipitation on the surface of metallic nickel due to the thermal decomposition reaction of methane and the deterioration of performance due to the inhibitory action of the electrode reaction due to the adsorption of produced CO on the surface of metallic nickel have been recognized (Sato et al., " From the viewpoint of fuel cell / methane utilization technology ”, J. Plasma Fusion Res. Vol. 87, No. 1 (2011) pp. 36-41), the hydrocarbon decomposition of the present invention as a fuel reformer arranged in the preceding stage. It is expected that the use of a hydrogen generator incorporating a catalyst for SOFC will lead to a reduction in precipitated carbon and a longer life in SOFC.

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CN202080003307.0A CN113039016B (zh) 2019-10-23 2020-09-17 用于烃裂解的催化剂
US17/771,009 US12528078B2 (en) 2019-10-23 2020-09-17 Catalyst for decomposition of hydrocarbons
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