US20150217278A1 - Catalyst for producing hydrogen and method for producing hydrogen - Google Patents

Catalyst for producing hydrogen and method for producing hydrogen Download PDF

Info

Publication number
US20150217278A1
US20150217278A1 US14/429,274 US201314429274A US2015217278A1 US 20150217278 A1 US20150217278 A1 US 20150217278A1 US 201314429274 A US201314429274 A US 201314429274A US 2015217278 A1 US2015217278 A1 US 2015217278A1
Authority
US
United States
Prior art keywords
catalyst
active metal
catalytically active
compound
hydrogen
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.)
Abandoned
Application number
US14/429,274
Other languages
English (en)
Inventor
Hideo Hosono
Fumitaka Hayashi
Toshiharu Yokoyama
Yoshitake Toda
Michikazu Hara
Masaaki Kitano
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.)
Japan Science and Technology Agency
Tokyo Institute of Technology NUC
Original Assignee
Tokyo Institute of Technology NUC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokyo Institute of Technology NUC filed Critical Tokyo Institute of Technology NUC
Assigned to TOKYO INSTITUTE OF TECHNOLOGY reassignment TOKYO INSTITUTE OF TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HAYASHI, FUMITAKA, TODA, YOSHITAKE, HARA, MICHIKAZU, HOSONO, HIDEO, YOKOYAMA, TOSHIHARU, KITANO, MASAAKI
Publication of US20150217278A1 publication Critical patent/US20150217278A1/en
Assigned to JAPAN SCIENCE AND TECHNOLOGY AGENCY, TOKYO INSTITUTE OF TECHNOLOGY reassignment JAPAN SCIENCE AND TECHNOLOGY AGENCY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TOKYO INSTITUTE OF TECHNOLOGY
Priority to US15/211,599 priority Critical patent/US9981845B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—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 alkali- or alkaline earth 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B01J35/0006—
    • B01J35/0066—
    • B01J35/1009—
    • B01J35/1014—
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/33—Electric or magnetic 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
    • 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
    • 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
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • 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
    • 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
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • 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
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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 present invention relates to a catalyst for producing hydrogen and a method for producing hydrogen from ammonia using the catalyst.
  • ammonia contained in various exhaust gases When ammonia contained in various exhaust gases is discharged in the environment, it is necessary to detoxifying ammonia because ammonia has an odor, and for example, a method of oxidatively decomposing ammonia by contact with oxygen, and a method of directly decomposing ammonia to hydrogen, and the like have been proposed.
  • Ammonia decomposition reaction is industrially used for producing atmospheric gas composed of nitrogen and hydrogen used for bright annealing of stainless steel, nickel steel, and the like.
  • hydrogen is preferred as clean energy, but particularly when hydrogen is used as a raw material of fuel cells for automobile cars, a method of supplying hydrogen to fuel cells has been a problem because of the necessity for a large volume of storage. As a method for resolving the problem, attention has recently been paid to a method of storing hydrogen as liquid ammonia and producing hydrogen by contact decomposition of vaporized ammonia.
  • Decomposition reaction of ammonia is volume expansion-type endothermic reaction represented by 2NH 3 ⁇ 3H 2 +N 2 , and thus the reaction at lower pressure and higher temperature is advantageous for reaction equilibrium.
  • a high temperature of 800° C. or more, preferably 1000° C. or more, is required for ammonia thermal decomposition
  • contact decomposition using a catalyst can be performed at a reaction temperature of 300° C. to 700° C.
  • a catalyst for ammonia synthesis can be considered to be used for ammonia decomposition reaction, but development of a catalyst for ammonia decomposition is required because ammonia decomposition is basically different from ammonia synthesis for two reasons below.
  • the first reasons is that ammonia synthesis reaction is preferably performed under the conditions of a low temperature and high pressure such as 300° C. to 500° C. and 30 MPa due to equilibrium, while ammonia decomposition reaction which is reverse reaction is preferably performed under the conditions of a low pressure and high temperature.
  • the second reason is that a rate-controlling step of ammonia synthesis reaction is activation of nitrogen molecules, while a rate-controlling step of ammonia decomposition reaction is desorption of nitrogen species adsorbed on a catalyst surface and produced by ammonia decomposition.
  • Patent Literature 1 An optimum catalytic metal for ammonia contact decomposition is ruthenium (Ru) and, for example, there have been proposed a method (Patent Literature 1) in which a catalyst including a basic compound which is added to Ru supported on alumina is used as a catalyst suitable for decomposing ammonia recovered from a coke oven into hydrogen and nitrogen at a middle temperature of 400° C. to 500° C. under the atmospheric pressure, a method (Patent Literature 2) in which a catalyst composed of Ru supported on ⁇ -alumina and having a specific surface area of 8.5 to 100 m 2 /g is used at a reaction temperature of 300° C.
  • Patent Literature 2 a method in which a catalyst composed of Ru supported on ⁇ -alumina and having a specific surface area of 8.5 to 100 m 2 /g is used at a reaction temperature of 300° C.
  • Patent Literature 3 a method in which a catalyst prepared by substituting, with a catalytically active metal such as Ru, a portion of A-sites or B-sites of a perovskite-type composite oxide represented by general formula ABO 3 and formed by firing a raw material mixture at a high temperature of 1000° C. or more is used at a reaction temperature of 400° C. to 900° C., and the like.
  • a catalytically active metal such as Ru
  • Patent Literature 4 a method in which a catalyst containing an iron-group metal as an active metal and prepared by supporting an iron-group metal compound on at least one metal oxide selected from the group consisting of ceria, zirconia, yttria, lanthanum oxide, alumina, magnesia, tungsten oxide, and titania and then reducing the compound is used at a reaction temperature of 180° C.
  • Patent Literature 5 a method (Patent Literature 5) in which a catalyst prepared by supporting at least one metal element belonging to the group VIII to group X in the long-period periodic table on a support composed of a composite oxide containing ceria, alumina, and if required, zirconia, is used at a reaction temperature of 150° C. to 650° C.
  • Patent Literature 1 a method (Non-Patent Literature 1) in which a catalyst prepared by compounding a metallic component of Ni, Cu, or Zn with alumina cement composed of calcia and alumina, and the like.
  • Ni easily reacts with alumina to produce a NiO—Al 2 O 3 solid solution, thereby failing to produce a mayenite-type structure.
  • a hydrogen generating apparatus in which hydrogen produced by decomposing liquid ammonia is supplied to a fuel cell preferably uses a hydrogen producing catalyst capable of producing high-purity hydrogen with a high conversion rate at as a low reaction temperature as possible.
  • Patent Literature 6 discloses that a noble metal catalyst such as Pt, Rh, Pd, Ru, or the like is preferred as a hydrogen producing catalyst exhibiting stable performance for ammonia decomposition reaction for fuel cell vehicles in which initiation or termination of reaction is repeated.
  • Patent Literature 7 discloses that a Ni-based hydrogen producing catalyst is a preferred catalyst but requires a longer contact time for achieving the same conversion efficiency as a Ru-based catalyst, and the contact time of the Ru-based catalyst is 1/10 of that of the Ni-based catalyst. It is also disclosed that other preferred ammonia decomposition catalysts include Fe, Rh, Ir, Pd, Pt, and Re catalysts, and compounds containing such an element.
  • Patent Literature 8 discloses that an ammonia decomposition catalyst including a Na metal, K metal, Na compound, or K compound present on the surfaces of composite oxide particles containing La, Ni, Co, and Fe is suitable as a catalyst for efficiently producing hydrogen and nitrogen from ammonia with a high conversion rate.
  • C12A7 12Ca0.7Al 2 O 3
  • C12A7 crystals have a peculiar crystal structure (space group I4-3d) in which among the 66 oxygen ions present in a unit cell containing 2 molecules, 2 oxygen ions are included as “free oxygen” in the space of a cage formed by a crystal skeleton (chemical formula [Ca 24 Al 28 O 64 ] 4+ (O 2 ⁇ ) 2 (referred to as “C12A7:O” hereinafter) (Non-Patent Literature 2).
  • Ca constituting the formula of the typical composition may be partially or entirely substituted by at least one typical metal element or transition metal element selected from the group consisting of Li, Na, K, Mg, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ir, Ru, Rh, and Pt.
  • Al constituting the formula of the typical composition may be partially or entirely substituted by at least one typical metal element or transition metal element selected from the group consisting of B, Ga, C, Si, Fe, and Ge.
  • O constituting the formula of the typical composition may be partially or entirely substituted by at least one typical element or metal element selected from the group consisting of H, F, Cl, Br, and Au.
  • C12A7 in which free oxygen ions are substituted by electrons can be represented by the chemical formula [Ca 24 Al 28 O 64 ] 4+ (e ⁇ ) 4 (may be referred to as “C12A7:e ⁇ ” hereinafter).
  • Non-Patent Literature 3 and Patent Literature 9 a substance in which anions are substituted by electrons
  • the electride has the characteristic of exhibiting good electron conductive properties
  • electrons in the cage have the property of readily reacting with hydrogen in a gas phase and being taken as hydrogen anions (hydride) in C12A7 (Non-Patent Literature 4).
  • C12A7 is reduced with a reducing agent such as Ca, Ca(OH) 2 , CaH 2 , or the like
  • C12A7 including hydrogen anions can be easily synthesized (Non-Patent Literature 5).
  • the C12A7 including hydrogen anions releases hydrogen and returns to electride by light irradiation, heating, or the like (Non-Patent Literature 4).
  • Patent Literatures 10 to 12 and Non-Patent Literature 5 examples of application of hydrogen anion-including C12A7 are little known.
  • Patent Literature 13 a catalyst for ammonia synthesis reaction, the catalyst containing a conductive mayenite-type compound and a metal, such as Ru, Fe, or the like, supported on the compound, and a method for synthesizing ammonia using the catalyst under the conditions of a reaction temperature of room temperature to 600° C. or less and a reaction pressure of 10 kPa to 20 MPa, and an invention (Patent Literature 14) relating to a method for reducing carbon dioxide to carbon monoxide by using a conductive mayenite-type compound.
  • Patent Literature 14 an invention
  • C12A7 has no conductivity, it has application as a catalyst and a catalyst support and, for example, a catalyst produced by spray-drying a solution of a raw material complex and then calcining at 1300° C. to 1400° C. for 2 hours or more is known to be used as a catalyst for steam decomposition reaction for producing soft olefins (Patent Literature 15).
  • a method for producing a C12A7 powder with a high specific surface area has been proposed, in which a precursor is synthesized by a hydrothermal method or a sol-gel method and is then fired (Non-Patent Literatures 6 and 7).
  • NPL 1 V. I. Yakerso and E. Z. Golosman, “Studies in surface science and catalysis”, 91, 879 (1995)
  • NPL 3 S. Matsuishi, Y. Toda, M. Miyakawa, K. Hayashi, T. Kamiya, M. Hirano, I. Tanaka and H. Hosono, “Science”, 301, 626-629, (2003)
  • NPL 4 K. Hayashi, P. V. Sushko, A. L. Shluger, M. Hirano, and H. Hosono “Journal of Physical Chemistry B”, 109, 23886-23842, (2005)
  • NPL 5 K. Hayashi, “Journal of Solid State Chemistry”, 184, 1428-1432, (2011)
  • NPL 6 L. Gong, Z. Lin, S. Ning, J. Sun, J. Shen, Y. Torimoto and Q. Li, “Material Letters”, 64, 1322-1324, (2010)
  • NPL 7 C. Li, D. Hirabayashi and K. Suzuki, “Materials Research Bulletin”, 46, 1307-1310, (2011)
  • Exhaust gas from a semiconductor manufacturing apparatus, a LCD manufacturing apparatus, and the like contains high concentration of ammonia. Also, air in the vicinities of toilets and the like contains ammonia at a volume fraction of as low as about several to several tens ppm. Therefore, there is demand for an ammonia decomposition catalyst for highly efficient application to ammonia at a high concentration to a low concentration in exhaust gas and environments.
  • Heat-resistant ceramics having a melting point of about 2000° C. or more such as alumina, zirconia, magnesia, titania, and the like, have been used as a support for an ammonia decomposition catalyst.
  • alumina, zirconia, magnesia, titania, and the like have been used as a support for an ammonia decomposition catalyst.
  • decomposition reaction at a relatively low temperature has the problem of a low rate of NH 3 conversion.
  • An object of the present invention is to provide a supported metal catalyst advantageous in view of resources and having high performance and low cost as a hydrogen producing catalyst for decomposing ammonia into hydrogen and nitrogen, and provide a method for producing hydrogen by efficient decomposition of ammonia using the supported metal catalyst.
  • a supported metal catalyst including a base material which is used as a support for an ammonia decomposition catalyst and which is composed of a mayenite-type compound containing oxygen ions or 10 15 cm ⁇ 3 or more of conduction electrons or hydrogen anions has a high efficiency of ammonia decomposition and, for example, a NH 3 conversion ratio of 2 times the case of an alumina support can be achieved.
  • ammonia with a low volume fraction of 0.1% to a high volume fraction of 20% or more and 100% can be decomposed with a high conversion rate by using a hydrogen producing catalyst for producing hydrogen by contact decomposition of ammonia gas even at a relatively low decomposition reaction temperature.
  • the type of balance gas is not particularly limited, and inert gas such as nitrogen, He, or Ar, and oxygen or reducing gas which does not influence on the decomposition reaction may be contained as the balance gas.
  • the present invention relates to a catalyst for producing hydrogen by contact decomposition of ammonia gas, the catalyst including, as a base material, a powder or molded compact of a mayenite-type compound which contains oxygen ions or 10 15 cm ⁇ 3 or more of conduction electrons or hydrogen anions, and catalytic metal particles for ammonia decomposition which adhere to a surface of the base material, and the present invention also relates to a method for producing hydrogen by ammonia decomposition reaction using the catalyst.
  • a mayenite compound represented by C12A7 and containing oxygen ions or less than 10 15 cm ⁇ 3 of conduction electrons or hydrogen anions has high decomposition activity, and a mayenite compound containing a larger amount of conduction electrons or hydrogen anions has a higher efficiency of ammonia decomposition.
  • the mayenite compound in the supported metal catalyst of the present invention contains 10 15 cm ⁇ 3 or more, more preferably 10 17 cm ⁇ 3 or more, of conduction electrons or hydrogen anions, and still more preferably contains 10 18 cm ⁇ 3 or more, of conduction electrons or hydrogen anions.
  • the mayenite-type compound can be produced by the known methods described in “Background Art”, and the compounds produced by the methods can be properly used in the present invention.
  • a catalytically active metal in the hydrogen-producing catalyst of the present invention is at least one selected from the metal elements of Groups VIII, IX, and X in the long-period periodic table.
  • a catalyst used in usual ammonia decomposition reaction and including a catalytically active metal supported on a support such as an oxide or the like is generally once subjected to reduction with hydrogen and then used in ammonia decomposition reaction.
  • the hydrogen-producing catalyst of the present invention is also preferably subjected to reduction before use, but electrons in cages of the mayenite compound may be allowed to react with hydrogen and included as hydrogen anions (hydride) in the reduction process.
  • Transition metal elements are used as homogeneous or heterogeneous catalyst components for various catalytic reactions.
  • the transition metals of Group VI, VIII, or IX such as Fe, Ru, Os, Co, Mo, and the like, are generally known to be suitable as catalysts for synthesizing ammonia by direct reaction of hydrogen with nitrogen.
  • the transition metals of Groups VIII and X such as Ru, Ni, and the like, are reported to exhibit activity for ammonia decomposition.
  • rate-controlling stage of ammonia synthesis is dissociation of nitrogen molecules having a triple bond
  • rate-controlling processes of decomposition are a process of cutting a N—H bond and a process of recombining N atoms.
  • a support powder or compact including catalytically active metal particles adhering to and supported on a surface of a conductive mayenite-type compound as a base material includes the same degree of electrons as the initial degree after a supporting step and has a high electron-donating ability to the catalytically active metal particles because of its small work function as a support. The same can be expected from hydrogen anions.
  • the mechanism by which the hydrogen-producing catalyst of the present invention exhibits a high conversion rate is not clarified, the currently conceivable factor that provides high activity is (1) that electrons or hydrogen anions in cages provide a change in the electron state of the active metal particles such as Ru or the like and promote activation of ammonia or (2) that the cages holding electrons or hydrogen anions function as a storage house for reaction intermediates (for example, NH 2 ⁇ and H ⁇ ) and prevent poisoning of active sites of Ru or the like. It is understood that the ammonia decomposition rate is improved by the two functions of donating ability and storage ability of the electrons or hydrogen anions. The base material having such a peculiar function is considered to be beyond the concept of a usual support.
  • the supported metal catalyst can be produced by, for example, a method such as an impregnation method, a physical mixing method, a thermal decomposition method, a liquid phase method, a vapor deposition method, or the like.
  • a compound of the catalytically active metal as a metal component material is supported on or mixed with the mayenite-type compound base material by any one of these methods to prepare a catalyst precursor.
  • the resultant precursor is heated in a reducing atmosphere to reduce the compound of the catalytically active metal to catalytically active metal particles and adhere the metal particles to a surface of the base material.
  • the catalytically active metal particles may be formed directly on a surface of the base material by a sputtering method.
  • the impregnation method includes a step of dispersing or immersing a powder or compact of the mayenite-type compound as the base material in a solvent solution of the compound of the catalytically active metal, a step of evaporating a solvent of the solvent solution to dry the compound of the catalytically active metal and form the catalyst powder composed of the compound on a surface of the base material, and a step of reducing the compound of the catalytically active metal by heating in a reducing atmosphere to allow particles of the catalytically active metal to adhere to the surface of the base material.
  • Hydrogen can be produced with a high NH 3 conversion rate by continuously supplying ammonia gas with a volume fraction of 0.1 to 100% to a catalyst layer, which is formed by filling a reactor with the supported metal catalyst, and performing contact decomposition reaction at a reaction pressure of 0.01 MPa to 1.0 MPa, a reaction temperature of 300° C. to 800° C., and a weight hourly space velocity (WHSV) of 500/m1g ⁇ 1 h ⁇ 1 or more.
  • WHSV weight hourly space velocity
  • a typical composition of the mayenite-type compound containing conduction electrons is represented by the formula [Ca 24 Al 28 O 64 ] 4+ (O 2 ⁇ ) 2-x (e ⁇ ) 2x (0 ⁇ x ⁇ 2).
  • the mayenite-type compound containing conduction electrons contains, as the conduction electrons, electrons which are substituted for oxide ions (O 2 ⁇ and O 2 2 ⁇ ) included in a structure, and C12A7 is represented by the composition formula ([Ca 24 Al 28 O 64 ] 4+ (O 2 ⁇ ) 2-x (e ⁇ ) 2x ) (0 ⁇ x ⁇ 2). Further substitution of the oxide ions with electrons causes a conduction electron concentration of 1 ⁇ 10 15 cm ⁇ 3 or more.
  • the mayenite-type compound containing conduction electrons can be referred to as a “conductive mayenite-type compound”.
  • the theoretical maximum concentration of conduction electrons in C12A7:e ⁇ is 2.3 ⁇ 10 21 cm ⁇ 3 .
  • the composition of C12A7 including hydrogen anions is represented by the formula [ Ca 24 Al 28 O 64 ] 4+ (O 2 ⁇ ) 2-x (H ⁇ ) 2x (0 ⁇ x ⁇ 2).
  • C12A7 produces light absorption at 2.8 eV and 0.4 eV.
  • the electron concentration can be determined by measuring a coefficient of the light absorption. When a sample is a powder, the electron concentration can be simply determined by a diffuse reflection method. Also, electrons in cages have spin activity, and thus the electron concentration in cages can be measured by using electron spin resonance (ESR). Further, C12A7 including conduction electrons is capable of reducing iodine molecules, and thus the electron concentration in cages can be measured by iodometry.
  • the concentration of hydrogen anions can be determined by a solid-state nuclear magnetic resonance spectroscopy of hydrogen nuclei ( 1 H NMR).
  • An ammonia decomposition method using the hydrogen-producing catalyst of the present invention permits ammonia contact decomposition even under mild conditions of 350° C. and 0.1 MPa and at a high weight hourly space velocity (WHSV) using, as a base material, a mayenite-type compound which is composed of only elements with a high Clarke number, such as calcium, aluminum, and oxygen, and which is an easily synthesizable, low-cost, and nontoxic compound.
  • the method can produce high-purity hydrogen by decomposition with a high conversion rate using a transition metal element, for example, Co, Ni, or the like, other than expensive rare metals such as Ru, and is advantageous from the viewpoint of effective utilization of resources.
  • a transition metal element for example, Co, Ni, or the like, other than expensive rare metals such as Ru, and is advantageous from the viewpoint of effective utilization of resources.
  • an alkali metal or alkaline-earth metal compound or the like need not be added as an accelerator for improving the conversion rate, thereby simplifying a process
  • FIG. 1 is a schematic drawing of a reaction line used for NH 3 decomposition shown in Examples 1 to 8 and Comparative Examples 1 and 2.
  • C12A7 which is a typical composition of a mayenite-type compound is described in detail below, but the present invention is not limited to C12A7 and can be applied to all mayenite-type compounds having the same crystal structure as C12A7, such as 12Sr0.7Al 2 O 3 or the like in which Ca is substituted with Sr.
  • a base material composed of C12A7 and used as a starting material of a method of producing a catalyst of the present invention may be a powder or a compact such as a porous body, a solid sintered body, a thin film, a solid single crystal, or the like, and the compact may have any shape.
  • C12A7 supported on a support composed of another material may be used as the base material.
  • the base material functions as a support for catalytically active metal particles.
  • a raw material of C12A7 is synthesized by a solid-phase method, a hydrothermal method, or the like.
  • Hydrothermal reaction is a reaction involving water at a high temperature and high pressure of 100° C. or more and 5 MPa or more, and a ceramic powder can be synthesized by reaction at a low temperature within a short time.
  • a hydrothermal synthesis method a C12A7 powder with a large specific surface area (about 20 to 60 m 2 g ⁇ 1 ) can be produced.
  • Ca 3 Al 2 (OH) 12 which is a hydroxide used as a precursor of C12A7 can be produced by mixing water, calcium hydroxide, and aluminum hydroxide with a stoichiometric composition, and then heating the resultant mixture, for example, at 150° C. for about 6 hours.
  • the adsorbed water, surface hydroxyl groups, OH ⁇ in the cages, etc. can be removed by vacuum evacuation treatment of the powder at 750° C. to 900° C., thereby preventing deactivation of a reducing agent in the step of injecting electrons.
  • a raw material powder of C12A7 with the stoichiometric composition may be heated in a reducing atmosphere.
  • a raw material powder of C12A7 with the stoichiometric composition may be molded and then heated with Ca, CaH 2 , or the like in a reducing atmosphere.
  • the C12A7 base material including conduction electrons other than a thin film and a solid single crystal can be produced directly from a raw material without passing through the production of a C12A7 base material not containing conduction electrons.
  • a powder, a porous body, or a solid sintered body of the the C12A7 base material containing hydrogen anions can also be synthesized by heating in a hydrogen stream or heating with Ca or the like in a reducing atmosphere.
  • a thin film of C12A7 containing conduction electrons can be produced by forming a thin film of C12A7 on a substrate of MgO, Y 3 Al 5 O 12 , or the like by a pulsed laser deposition (PLD) method, a sputtering method, a plasma spraying method, or the like using a C12A7 solid sintered body as a target and again depositing a C12A7 thin film by the PLD method under heating at 500° C. or more to integrate these thin films.
  • PLD pulsed laser deposition
  • a sputtering method a plasma spraying method, or the like
  • plasmanized C12A7 functions as a reducing agent, and thus conduction electrons are included in the thin film.
  • a thin film of C12A7 containing hydrogen anions can also be synthesized by the same method.
  • a solid single crystal of C12A7 containing conduction electrons may be produced by pulling up a melt (CZ method) prepared by melting a C12A7 raw material powder at about 1600° C. to form a C12A7 single crystal, sealing the single crystal in a vacuum glass tube together with a metal Ca powder or Ti powder, or the like, and heating the single crystal in a reducing atmosphere to include conduction electrons into the solid single crystal.
  • a solid single crystal of C12A7 including hydrogen anions can also be synthesized by the same method.
  • the solid sintered body or solid single crystal of C12A7 including conduction electrons or hydrogen anions can be processed into a powder. Processing into a powder can be performed by grinding in a mortar, grinding by a jet mill, or the like.
  • the size of the powder is not particularly limited, but particles having a distribution of particle diameters in a range of about 100 nm to 1 mm can be produced by the this method.
  • C12A7 including 1 ⁇ 10 15 cm ⁇ 3 or more of conduction electrons or hydrogen anions can be produced by the method.
  • conduction electrons may be removed from a surface portion of the base material according to the production method.
  • the ammonia decomposition of the present invention can be performed by using as the catalytically active metal a transition metal element selected from the Group VIII, Group IX, or Group X in the long-period periodic table.
  • a Group VIII element selected from Fe, Ru, and Os, a Group IX element selected from Co, Rh, and Ir, and a Group X element selected from Ni, Pd, and Pt are particularly preferably used alone or in combination.
  • the C12A7 powder or porous body When the C12A7 powder or porous body is used as the base material, the C12A7:e ⁇ 1 powder or porous body containing 1 ⁇ 10 15 cm ⁇ 3 or more of conduction electrons produced in the above-described steps is mixed with a compound of the catalytically active metal by any one of various methods, for example, a CVD method (chemical vapor deposition method) and an impregnation method.
  • a CVD method chemical vapor deposition method
  • impregnation method any one of various methods, for example, a CVD method (chemical vapor deposition method) and an impregnation method.
  • a compound of the catalytically active metal is deposited on the surface of the base material by the impregnation method, the CVD method, or the sputtering method, and the compound of the catalytically active metal is thermally decomposed in a reducing atmosphere, preferably, at a temperature of 150° C. to 800° C. to deposit and adhere the catalytically active metal to the surface of the base material.
  • each of the metal raw materials is deposited on C12A7 by the CVD method or the like, thermally decomposed, and then nitrided with ammonia gas.
  • Examples of the compound of the catalytically active metal include, but are not particularly limited to, easily thermally decomposable inorganic metal compounds or organic metal complexes, such as triruthenium dodecacarbonyl [Ru 3 (CO) 12 ], dichlorotetrakis(triphenylphosphine) ruthenium(II) [RuCl 2 (PPh 3 ) 4 ], dichlorotris(triphenylphosphine) ruthenium(II) [RuCl 2 (PPh 3 ) 3 ], tris(acetylacetonate) ruthenium(III) [Ru(acac) 3 ], ruthenocene [Ru(C 5 H 5 )], ruthenium chloride [RuCl 3 ], pentacarbonyl iron [Fe(CO) 5 ], tetracarbonyl iron iodide [Fe(CO) 4 I 2 ], iron chloride [FeCl 3 ], ferrocene [Fe
  • the impregnation method can use the following steps.
  • a support powder is dispersed in a solution of the compound of the catalytically active metal (for example, a hexane solution of Ru carbonyl complex) and the resultant dispersion is stirred.
  • the amount of the compound of the catalytically active metal is 0.01 to 40 wt %, preferably 0.02 to 30 wt %, and more preferably 0.05 to 20 wt % relative to the support powder.
  • the solvent is evaporated to dryness by heating in an inert gas stream, such as nitrogen, argon, helium, or the like, or under vacuum at 50° C. to 200° C. for 30 minutes to 5 hours.
  • a catalyst precursor composed of the dried compound of the catalytically active metal is reduced.
  • These steps can yield a supported metal catalyst in which the catalytically active metal is highly dispersed as fine particles having a diameter of several nm to several hundred nm and strongly adheres to the surface of the support powder.
  • the catalyst of the present invention may use an accelerator as an additive.
  • the supported metal catalyst including the 12CaO.7Al 2 O 3 powder as a support has a BET specific surface area of about 1 to 100 m 2 g ⁇ 1 , and the amount of the catalytically active metal is 0.01 to 30 wt %, preferably 0.02 to 20 wt %, and more preferably 0.05 to 10 wt % relative to the support powder.
  • the amount of less than 0.01 wt % is ineffective because of an excessively small number of active points, and the amount of over 30 wt % is undesired for cost because of little increase in catalytic activity.
  • a supported metal catalyst having the same form as described above can be produced by mixing, in a solid phase, a C12A7 powder containing 1 ⁇ 10 15 cm ⁇ 3 or more of conduction electrons and a compound powder of the catalytically active metal by a physical mixing method under the same conditions as described above, and then reducing the mixture by heating.
  • the supported metal catalyst can be used as a compact by using a general molding technique.
  • a shape include a granular shape, a spherical shape, a tablet shape, a ring shape, a macaroni-like shape, a four-leaf shape, a dice shape, a honeycomb shape, and the like.
  • the support coated with the supported metal catalyst can also be used.
  • Ammonia decomposition is a reaction represented by formula 1 below, in which a reactor is filled with the supported metal catalyst to form a catalyst layer, and ammonia gas as a raw material is continuously supplied at a reaction temperature of 350° C. to 800° C. and is brought into contact with the catalyst layer, thereby producing hydrogen and nitrogen.
  • the ammonia decomposition reaction is an equilibrium reaction and is also an endothermic reaction and a volume-increasing reaction, and thus high temperature-low pressure conditions are advantageous.
  • the reaction pressure is preferably in a range of 0.01 Mpa to 1.0 MPa, and the temperature is preferably in a range of 300° C. to 800° C.
  • the reaction pressure of less than 0.1 MPa allows the decomposition reaction to efficiency proceeds but is disadvantageous in view of cost because of the need for a pressure deducing equipment.
  • the reaction pressure of 0.10 MPa (atmospheric pressure) is preferred in view of equipment.
  • the reaction pressure over 1.0 MPa causes an equilibrium advantageous to the raw material side and thus cannot exhibit a satisfactory decomposition rate.
  • the reaction temperature of less than 300° C. is unpractical because of a low reaction rate.
  • the temperature over 800° C. causes a high decomposition rate but is undesired because of the need for an expensive heat-resistant apparatus and the influence on the catalyst life.
  • the reaction temperature is more preferably 400° C. to 750° C.
  • the temperature for a Ru catalyst is more preferably 400° C. to 600° C.
  • the temperature for a Ni or Co catalyst is more preferably 500° C. to 750° C.
  • the C12A7 has a melting point of 1250° C. and is not sintered at about 800° C.
  • the method of the present invention can use, as the raw material, either ammonia gas diluted with a balance gas or ammonia alone, that is, ammonia gas with a volume fraction of 0.1% to 100% can be used.
  • ammonia gas diluted with a balance gas or ammonia alone that is, ammonia gas with a volume fraction of 0.1% to 100% can be used.
  • the suitable volume fraction is 5% or more, preferably 20% or more, and more preferably 70% or more.
  • the decomposition reaction at a weight hourly space velocity (WHSV) of 500 m1g ⁇ 1 h ⁇ 1 or more can exhibit a high NH 3 conversion rate.
  • WHSV weight hourly space velocity
  • the gas produced by the ammonia decomposition method of the present invention theoretically contains hydrogen and nitrogen at a molar ratio of 3:1, and can be used as gas, for example, for bright annealing finish of stainless steel, nickel steel, nickel, nickel-copper or nickel-chromium alloy, or the like. Further, hydrogen produced in the present invention do not contain CO and CO 2 which are harmful to fuel cells, and thus the produced hydrogen separated from nitrogen and purified can be used as, for example, hydrogen for fuel cells.
  • the ammonia decomposition reaction can be performed by using a general gas-solid phase contact reaction apparatus using a corrosion-resistant material such as stainless steel or the like.
  • the reaction system may be any one of a batch reaction system, a closed circulating reaction system, and a flow reaction system, but the flow reaction system is most preferred from a practical viewpoint. Since the reaction is an endothermic reaction, it is advantageous to perform the reaction while supplying reaction heat, and various industrial designs for supplying reaction heat are considered for increasing the yield. For example, a method is proposed, in which ammonia decomposition reaction is performed while combustion heat is obtained by oxidizing a portion of an ammonia raw material with air.
  • the ammonia decomposition reaction can be performed by using a single reactor filled with the catalyst or a plurality of reactors. Also, any one of a method of connecting a plurality of reactors and a method of using a reactor including a plurality of reaction layers formed therein can be used.
  • the catalyst used may be any one of the catalyst of the present invention alone, a combination of two or more catalysts selected from the catalysts of the present invention, or a combination of the catalyst of the present invention and a known catalyst.
  • the catalytic metal is preferably activated by exposing the catalyst to a reducing gas atmosphere of hydrogen or the like at 300° C. to 700° C. for about 30 minutes to 2 hours before the ammonia decomposition reaction.
  • FIG. 1 An atmospheric pressure fixed-bed flow reactor ( FIG. 1 ) was used, and an ammonia decomposition rate was determined by gas-chromatographic quantitative determination of an amount of NH 3 produced to evaluate ammonia decomposition activity.
  • the conversion rate a (%) was determined according to a formula below.
  • P NH3 and P′ NH3 represent ammonia partial pressures before and after the reaction, respectively.
  • FIG. 1 shows the outlines of an apparatus used in experiments.
  • a quartz reactor 1 (inner diameter: 6 mm, length: 24 cm, inner volume: 6.8 ml) was filled with a supported metal catalyst prepared in each of examples and comparative examples described below. Then, the supported metal catalyst was previously reduced by flowing H 2 to the reactor 1 from a cylinder 3 . Then, NH 3 was flowed to the reactor 1 from a cylinder 4 .
  • H 2 was diluted, a predetermined amount of He was supplied from a cylinder 2 and mixed with H 2 .
  • the ammonia flow rate was controlled by a ball flow meter 5 so as to be a predetermined weight hourly space velocity. Then, the reaction system was heated to a predetermined temperature, and an activity test was conducted.
  • the reaction product flowing out from the reactor 1 was discharged through an exhaust port 6 (vent), and a part of the product was collected in a measuring tube 7 (Sampling loop) and analyzed by a gas chromatograph 9 (On-line TCD-GC) with a thermal conductive detector to which a carrier gas was supplied from a carrier gas inlet 8 (carrier in) of the gas chromatograph.
  • a gas chromatograph 9 On-line TCD-GC
  • Powders of Ca(OH) 2 (Shuzui Hikotaro Shoten, 23.1 g) and Al(OH) 3 (Kojundo Chemical Laboratory Co., Ltd., 28.4 g) were mixed so that a Ca/Al molar ratio was 12:14, and 449 ml of water was added to the resultant mixture, followed by hydrothermal treatment in an autoclave at 150° C. over 5 hours.
  • the resultant powder was filtered, washed with 500 ml of water, dried at 150° C., fired in an oxygen stream at 800° C.
  • C12A7 (referred to as “C12A7:O” hereinafter) powder having a specific surface area of 40 m 2 g ⁇ 1 and a particle diameter of 0.1 mm to 0.5 mm and containing oxygen ions but not containing conduction electrons and hydrogen anions.
  • the C12A7:O powder prepared by the method described above was inserted into a silica glass tube and pre-treated by vacuum-heating at 800° C. for 15 hours in a vacuum of 1 ⁇ 10 ⁇ 4 Pa. Then, 2.5 g of the resultant powder was inserted, together with 0.1 g of a Ca metal powder, in a silica glass tube and heated at 700° C. for 15 hours to prepare a C12A7:e ⁇ (hereinafter referred to as “C12A7:e”) powder having a conduction electron concentration of 1.5 ⁇ 10 21 cm ⁇ 3 .
  • the prepared powder had a smaller specific surface area of 14 m 2 g ⁇ 1 (particle diameter: 0.2 mm to 1 mm).
  • the C12A7:O powder prepared by the method described above was inserted into a silica glass tube and pre-treated by vacuum-heating at 750° C. for 15 hours in a vacuum of 1 ⁇ 10 ⁇ 4 Pa. Then, 1.5 g of the resultant powder was inserted, together with 45 mg of a Ca metal powder, in a silica glass tube and heated at 700° C. for 15 hours to prepare a C12A7:H ⁇ (hereinafter referred to as “C12A7:H”) powder having a hydrogen anion concentration of 2.5 ⁇ 10 20 cm ⁇ 3 . Inclusion of hydrogen anions was confirmed by 1 H NMR and iodometry. The prepared powder had a smaller specific surface area of 16 m 2 g ⁇ 1 (particle diameter: 0.2 mm to 1 mm).
  • a quartz reaction tube was packed with 60 to 100 mg of the Ru-supported catalyst produced by the method described above to form a catalyst layer, and ammonia decomposition reaction was carried out by using an ammonia decomposition apparatus shown in FIG. 1 .
  • Ru was activated by reducing the Ru-supported catalyst in a hydrogen steam for 2 hours in the quartz reaction tube heated to 400° C. to 450° C. Then, the temperature in the quartz reaction tube was adjusted to 350° C. to 700° C., and ammonia gas with an ammonia volume fraction of 100% was flowed through the catalyst layer at 5 to 100 m1 ⁇ min ⁇ 1 .
  • the reaction results are shown in Table 1. The NH 3 conversion rates at 350° C., 440° C., and 700° C.
  • the weight hourly space velocities are 3000, 15000, and 120000 mlg ⁇ 1 h ⁇ 1 , respectively.
  • a 5 wt % Ru/C12A7:e powder was prepared by the same method as in Example 1 except that the amount of Ru supported was 5 wt %, and ammonia decomposition reaction was carried out.
  • the results are shown in Table 1.
  • the NH 3 conversion rate at 440° C. was 67.2%, and the NH 3 decomposition rate at 440° C. was 6.9 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 2 wt % Ru/C12A7:H powder was prepared by the same method as in Example 1 except that C12A7:H was used as a support, and ammonia decomposition reaction was carried out.
  • the results are shown in Table 1.
  • the NH 3 conversion rate at 440° C. was 76.5%, and the NH 3 decomposition rate at 440° C. was 7.9 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • Example 2 The same catalyst as tested in Example 1 was used and tested at an ammonia volume fraction (V NH3 ) of 1.7% (He balance) and a total gas flow rate of 180 ml/min (WHSV: 216000 mlg ⁇ 1 h ⁇ 1 ). The results are shown in Table 1. The NH 3 conversion rate at 440° C. was 100%, and the NH 3 decomposition rate at 440° C. was 2.1 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 2 wt % Ru/C12A7:O powder was prepared by the same method as in Example 1 except that a C12A7:O powder containing oxygen ions but not containing conduction electrons was used instead of the C12A7:e powder, and ammonia decomposition activity was examined.
  • the results are shown in Table 1.
  • the NH 3 conversion rate at 440° C. was 54.3%, and the NH 3 decomposition rate at 440° C. was 5.6 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 2 wt % Ru/CaO powder was prepared by the same method as in Example 1 except that a CaO powder (Kojundo Chemical Laboratory Co., Ltd., particle diameter: 5 mm to 10 mm) was used instead of the C12A7:e powder, and ammonia decomposition activity was examined.
  • the particle diameter of Ru metal after hydrogen reduction was 4 nm, and dispersibility determined by CO adsorption was 40%.
  • the results are shown in Table 1.
  • the NH 3 conversion rate at 440° C. was 42.1%, and the NH 3 decomposition rate at 440° C. was 4.3 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 6 wt % Ru/ ⁇ -Al 2 O 3 powder was prepared by the same method as in Example 1 except that a ⁇ -Al 2 O 3 powder (Kojundo Chemical Laboratory Co., Ltd., particle diameter: 0.1 mm to 0.5 mm) was used instead of the C12A7:e powder, and ammonia decomposition activity was examined.
  • the particle diameter of Ru metal after hydrogen reduction was 11 nm, and dispersibility determined by CO adsorption was 13%.
  • the results are shown in Table 1.
  • the NH 3 conversion rate at 440° C. was 31.9%, and the NH 3 decomposition rate at 440° C. was 3.3 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • Example 1 C12A7: e 14 1.5 ⁇ 10 21 No 2 350 100 5 100 3000 51.9 1.1 14 1.5 ⁇ 10 21 No 2 440 60 15 100 15000 79.8 8.2 14 1.5 ⁇ 10 21 No 2 700 60 100 100 120000 99.8 82.3
  • Example 2 C12A7: e 14 1.5 ⁇ 10 21 No 5 440 60 15 100 15000 67.2 6.9
  • Example 3 C12A7: H 16 No 2.5 ⁇ 10 2 2 440 60 15 100 15000 76.5 7.9
  • Example 4 C12A7: e 14 1.5 ⁇ 10 21 No 2 440 60 3 1.7 216000 100.0 2.1
  • Example 2 Comparative CaO 3 No No 2 440 60 15 100 15000 42.1 4.3
  • Example 1 Comparative
  • a 5 wt % Co/C12A7:e powder was prepared by the same chemical vapor deposition method as for Ru using a C12A7:e powder described in Example 1 and using a Co 4 (CO) 12 raw material instead of Ru 3 (CO) 12 .
  • the results are shown in Table 2.
  • the NH 3 conversion rate at 600° C. was 54.6%, and the NH 3 decomposition rate at 600° C. was 5.6 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 5 wt % Co/C12A7:O powder was prepared by the same method as in Example 6 except that a C12A7:O powder containing oxygen ions but not containing conduction electrons was used instead of the C12A7:e powder, and ammonia decomposition activity was examined.
  • the results are shown in Table 2.
  • the NH 3 conversion rate at 600° C. was 28.0%, and the NH 3 decomposition rate at 600° C. was 2.9 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • a 5 wt % Ni/C12A7:e powder was prepared by the same chemical vapor deposition method as for Ru using a C12A7:e powder described in Example 1 and using acetylacetonate nickel(II) dihydrate [C 10 H 14 NiO 4 .xH 2 O] instead of Ru 3 (CO) 12 , and ammonia decomposition activity was examined.
  • the results are shown in Table 2.
  • the NH 3 conversion rate at 600° C. was 86.4%, and the NH 3 decomposition rate at 600° C. was 8.9 (kg NH3 kg cat ⁇ 1 h ⁇ 1 ).
  • Example 6 C12A7: e 14 1.5 ⁇ 10 21 No Co 5 600 60 15 100 15000 54.6 5.6
  • Example 7 C12A7: O 40 No No Co 5 600 60 15 100 15000 28.0 2.9
  • Example 8 C12A7: e 14 1.5 ⁇ 10 21 No Ni 5 600 60 15 100 15000 86.4 8.9
  • a contact decomposition method using a hydrogen producing catalyst of the present invention can produce, with a high conversion rate, hydrogen by decomposing ammonia with a low volume fraction to a high volume fraction at about the atmospheric pressure within a wide reaction temperature range of 350° C. to 800° C., and thus the method is considered as a preferred method in view of reduction of energy consumption. Also, hydrogen can be produced by decomposing ammonia with a very high efficiency using inexpensive materials as compared with usual Ru supported catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Sustainable Energy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Catalysts (AREA)
  • Crystallography & Structural Chemistry (AREA)
US14/429,274 2012-09-20 2013-08-20 Catalyst for producing hydrogen and method for producing hydrogen Abandoned US20150217278A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/211,599 US9981845B2 (en) 2012-09-20 2016-07-15 Catalyst for producing hydrogen and method for producing hydrogen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-207548 2012-09-20
JP2012207548 2012-09-20
PCT/JP2013/072182 WO2014045780A1 (fr) 2012-09-20 2013-08-20 Catalyseur de génération d'hydrogène et procédé de production d'hydrogène

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/072182 A-371-Of-International WO2014045780A1 (fr) 2012-09-20 2013-08-20 Catalyseur de génération d'hydrogène et procédé de production d'hydrogène

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/211,599 Division US9981845B2 (en) 2012-09-20 2016-07-15 Catalyst for producing hydrogen and method for producing hydrogen

Publications (1)

Publication Number Publication Date
US20150217278A1 true US20150217278A1 (en) 2015-08-06

Family

ID=50341104

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/429,274 Abandoned US20150217278A1 (en) 2012-09-20 2013-08-20 Catalyst for producing hydrogen and method for producing hydrogen
US15/211,599 Active US9981845B2 (en) 2012-09-20 2016-07-15 Catalyst for producing hydrogen and method for producing hydrogen

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/211,599 Active US9981845B2 (en) 2012-09-20 2016-07-15 Catalyst for producing hydrogen and method for producing hydrogen

Country Status (7)

Country Link
US (2) US20150217278A1 (fr)
EP (1) EP2898946B1 (fr)
JP (1) JP6143761B2 (fr)
KR (1) KR102159678B1 (fr)
CN (1) CN104640628B (fr)
CA (1) CA2883503C (fr)
WO (1) WO2014045780A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018189218A1 (fr) 2017-04-11 2018-10-18 Basf Se Procédé de préparation d'un composé électrure
WO2018189216A1 (fr) 2017-04-11 2018-10-18 Basf Se Matériau composite comprenant un composé électrure
CN111558377A (zh) * 2020-05-12 2020-08-21 中国石油天然气集团有限公司 一种加氢精制催化剂及其制备方法与应用
CN112473680A (zh) * 2020-12-10 2021-03-12 华中科技大学 一种双功能钙基催化剂及其制备方法和应用
US11235310B2 (en) * 2016-08-08 2022-02-01 Tokyo Institute Of Technology Method for manufacturing ammonia synthesis catalyst, and method for manufacturing ammonia
CN114097120A (zh) * 2019-07-12 2022-02-25 学校法人东洋大学 燃料电池催化剂用组合物及包含其的燃料电池
CN114921823A (zh) * 2021-02-01 2022-08-19 芜湖美的厨卫电器制造有限公司 一种镀层的制备方法、应用该制备方法的电极、家电设备
US11772071B2 (en) 2017-05-15 2023-10-03 Starfire Energy Metal-decorated barium calcium aluminum oxide and related materials for NH3 catalysis
US11772979B2 (en) * 2019-01-31 2023-10-03 Starfire Energy Metal-decorated barium calcium aluminum oxide catalyst for NH3 synthesis and cracking and methods of forming the same
US11795062B2 (en) 2018-03-14 2023-10-24 Japan Science And Technology Agency Electron or hydride ion intake/release material, electron or hydride ion intake/release composition, transition metal-supported material and catalyst, and use in relation thereto
US11807541B2 (en) 2016-03-01 2023-11-07 Starfire Energy Electrically enhanced Haber-Bosch (EEHB) anhydrous ammonia synthesis
US11819827B2 (en) 2017-03-17 2023-11-21 Japan Science And Technology Agency Supported metal material, supported metal catalyst, method of producing ammonia, method of producing hydrogen and method of producing cyanamide compound

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6280443B2 (ja) * 2014-05-21 2018-02-14 株式会社Ihi 触媒、触媒の製造方法、アンモニア合成方法、アンモニア分解方法
JP2016165664A (ja) * 2015-03-09 2016-09-15 学校法人 工学院大学 Ｍａｙｅｎｉｔｅ構造を有する１２ＳｒＯ・７Ａｌ２Ｏ３化合物を含む担体上、好ましくは当該化合物を主成分とする担体上にＲｕが担持されたことを特徴とする炭化水素の水蒸気改質触媒
JP2016198720A (ja) * 2015-04-09 2016-12-01 国立大学法人宇都宮大学 アンモニア分解触媒、アンモニア分解触媒の製造方法、水素の製造方法及び水素の製造装置
WO2017154732A1 (fr) * 2016-03-07 2017-09-14 昭和電工株式会社 Dispositif de décomposition de l'ammoniac et dispositif de production d'hydrogène gazeux
CN105688876A (zh) * 2016-03-24 2016-06-22 天津大学 应用于CO2光还原的催化剂[Ca24Al28O64]4+(e-)4及其制备方法
CN106178948A (zh) * 2016-08-25 2016-12-07 国网河南省电力公司电力科学研究院 一种基于氨逃逸催化脱除的新型scr脱硝***
JP6941454B2 (ja) * 2017-03-03 2021-09-29 太平洋マテリアル株式会社 触媒担体の製造方法
JP6851860B2 (ja) * 2017-03-03 2021-03-31 太平洋マテリアル株式会社 水素製造用触媒及び水素の製造方法
WO2018185661A1 (fr) 2017-04-04 2018-10-11 Basf Corporation Réducteur à hydrogène pour réduction catalytique de la pollution
KR102471292B1 (ko) 2017-04-04 2022-11-29 바스프 코포레이션 통합된 배출물 제어 시스템
JP2020515768A (ja) 2017-04-04 2020-05-28 ビーエーエスエフ コーポレーション 車載型水素発生および排気流中で使用する方法
KR102470847B1 (ko) * 2017-04-04 2022-11-25 바스프 코포레이션 차량 내장식 암모니아 및 수소 생성
US11181028B2 (en) 2017-04-04 2021-11-23 Basf Corporation Ammonia generation system for NOx emission control
CN110709590B (zh) 2017-04-04 2022-07-05 巴斯夫公司 氢气辅助的集成排放控制***
CN110691649A (zh) 2017-05-31 2020-01-14 古河电气工业株式会社 氨分解催化剂结构体以及燃料电池
EP3805159A4 (fr) * 2018-05-07 2021-07-07 Japan Science and Technology Agency Oxyde composite, matériau à support métallique et catalyseur de synthèse d'ammoniac
BR112021016647A2 (pt) * 2019-02-26 2021-11-03 Tokyo Inst Tech Corpo sinterizado moldado, e método para a produção de corpo sinterizado moldado
CN110327957A (zh) * 2019-06-20 2019-10-15 福州大学化肥催化剂国家工程研究中心 一种氨分解催化剂的制备方法
CN111013584B (zh) * 2019-12-02 2022-07-08 浙江工业大学 一种高温质子膜催化剂及其制备方法和应用
US20230041936A1 (en) * 2019-12-30 2023-02-09 Wonik Materials Co., Ltd. Ruthenium precursor, ammonia reaction catalyst using same, and preparation method thereof
CN111389404A (zh) * 2020-01-21 2020-07-10 天津大学 一种氧化铈负载镍催化剂的制备方法及其用途
CN111558376B (zh) * 2020-05-12 2023-02-07 中国石油天然气集团有限公司 一种铁基加氢催化剂及其制备方法与应用
JP7389065B2 (ja) 2021-01-14 2023-11-29 三菱重工業株式会社 アンモニア分解装置
JP7389066B2 (ja) 2021-01-14 2023-11-29 三菱重工業株式会社 アンモニア分解装置
KR20230154201A (ko) 2021-03-11 2023-11-07 토프쉐 에이/에스 암모니아 분해로부터 수소를 생성하기 위한 방법 및 시스템
EP4326981A1 (fr) * 2021-04-19 2024-02-28 Innio Jenbacher GmbH & Co OG Moteur à combustion interne
KR20230071317A (ko) * 2021-11-16 2023-05-23 아주대학교산학협력단 암모니아 분해 반응용 루테늄 촉매, 이의 제조 방법 및 이를 이용하여 수소를 생산하는 방법
KR102581476B1 (ko) 2023-02-06 2023-09-20 순천대학교 산학협력단 액상 플라즈마 반응에 의한 수소 생성용 촉매 및 이의 제조방법

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01119341A (ja) 1987-10-30 1989-05-11 Nkk Corp アンモニア分解用触媒
JP3688314B2 (ja) 1994-07-21 2005-08-24 日本パイオニクス株式会社 アンモニアの分解方法
IT1313698B1 (it) 1999-12-17 2002-09-09 Enichem Spa Catalizzatore per reazioni di steam cracking e relativo procedimentodi preparazione.
US7867300B2 (en) 2001-03-02 2011-01-11 Intelligent Energy, Inc. Ammonia-based hydrogen generation apparatus and method for using same
JP2003040602A (ja) 2001-07-30 2003-02-13 Toyota Central Res & Dev Lab Inc 燃料電池用水素製造装置
EP1500631B1 (fr) * 2002-04-19 2017-08-02 Japan Science and Technology Agency Compose inorganique conducteur electrique comprenant de l'hydrogene
US7507289B2 (en) 2003-06-26 2009-03-24 Japan Science And Technology Agency Electroconductive 12CaO—7Al2O3 and compound of same type, and method for preparation thereof
US20060039847A1 (en) * 2004-08-23 2006-02-23 Eaton Corporation Low pressure ammonia synthesis utilizing adsorptive enhancement
JP4495757B2 (ja) * 2005-05-30 2010-07-07 国立大学法人東京工業大学 導電性マイエナイト型化合物の製造方法
JP5213122B2 (ja) 2007-01-18 2013-06-19 株式会社ファンケル 抗酸化剤
JP5547936B2 (ja) 2008-09-17 2014-07-16 株式会社日本触媒 アンモニア分解触媒およびその製造方法、ならびに、アンモニア処理方法
JP5127672B2 (ja) 2008-11-06 2013-01-23 日立造船株式会社 アンモニア分解触媒
JP2012101945A (ja) 2009-02-17 2012-05-31 Asahi Glass Co Ltd マイエナイト含有酸化物の製造方法
JP5263677B2 (ja) 2009-03-12 2013-08-14 株式会社豊田中央研究所 アンモニア分解触媒、それを用いたアンモニア分解方法、およびアンモニア分解反応装置
PL388518A1 (pl) * 2009-07-10 2011-01-17 Instytut Nawozów Sztucznych Katalizator do wysokotemperaturowego rozkładu podtlenku azotu
JP5530288B2 (ja) 2010-07-26 2014-06-25 国立大学法人東京工業大学 二酸化炭素の吸着還元剤及び還元方法
WO2012077658A1 (fr) * 2010-12-07 2012-06-14 国立大学法人東京工業大学 Catalyseur de synthèse d'ammoniac et procédé de synthèse d'ammoniac
JP5690158B2 (ja) 2011-02-03 2015-03-25 Ａｇｃセイミケミカル株式会社 アンモニア分解触媒およびアンモニアの分解方法
CN106277000B (zh) * 2012-08-30 2019-01-22 国立大学法人东京工业大学 导电性钙铝石型化合物粉末的制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chunshan Li, Daisuke Hirabayashi, Kenzi Suzuki "Development of new nickel based catalyst for biomass tar steam reforming producing H2-rich syngas" Fuel Processing Technology Volume 90, Issue 6, June 2009, Pages 790-796, 14 March 2009 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11807541B2 (en) 2016-03-01 2023-11-07 Starfire Energy Electrically enhanced Haber-Bosch (EEHB) anhydrous ammonia synthesis
US11964260B2 (en) 2016-08-08 2024-04-23 Tokyo Institute Of Technology Method for manufacturing ammonia synthesis catalyst, and method for manufacturing ammonia
US11235310B2 (en) * 2016-08-08 2022-02-01 Tokyo Institute Of Technology Method for manufacturing ammonia synthesis catalyst, and method for manufacturing ammonia
US11819827B2 (en) 2017-03-17 2023-11-21 Japan Science And Technology Agency Supported metal material, supported metal catalyst, method of producing ammonia, method of producing hydrogen and method of producing cyanamide compound
WO2018189216A1 (fr) 2017-04-11 2018-10-18 Basf Se Matériau composite comprenant un composé électrure
WO2018189218A1 (fr) 2017-04-11 2018-10-18 Basf Se Procédé de préparation d'un composé électrure
US11772071B2 (en) 2017-05-15 2023-10-03 Starfire Energy Metal-decorated barium calcium aluminum oxide and related materials for NH3 catalysis
US11795062B2 (en) 2018-03-14 2023-10-24 Japan Science And Technology Agency Electron or hydride ion intake/release material, electron or hydride ion intake/release composition, transition metal-supported material and catalyst, and use in relation thereto
US11772979B2 (en) * 2019-01-31 2023-10-03 Starfire Energy Metal-decorated barium calcium aluminum oxide catalyst for NH3 synthesis and cracking and methods of forming the same
EP3951961A4 (fr) * 2019-07-12 2022-06-22 Toyo University Composition catalytique de pile à combustible et pile à combustible la contenant
CN114097120A (zh) * 2019-07-12 2022-02-25 学校法人东洋大学 燃料电池催化剂用组合物及包含其的燃料电池
CN111558377A (zh) * 2020-05-12 2020-08-21 中国石油天然气集团有限公司 一种加氢精制催化剂及其制备方法与应用
CN112473680A (zh) * 2020-12-10 2021-03-12 华中科技大学 一种双功能钙基催化剂及其制备方法和应用
CN114921823A (zh) * 2021-02-01 2022-08-19 芜湖美的厨卫电器制造有限公司 一种镀层的制备方法、应用该制备方法的电极、家电设备

Also Published As

Publication number Publication date
EP2898946A1 (fr) 2015-07-29
US20160340182A1 (en) 2016-11-24
EP2898946A4 (fr) 2016-04-27
EP2898946B1 (fr) 2020-07-22
CN104640628A (zh) 2015-05-20
CA2883503C (fr) 2020-08-11
JPWO2014045780A1 (ja) 2016-08-18
JP6143761B2 (ja) 2017-06-07
KR102159678B1 (ko) 2020-09-24
WO2014045780A1 (fr) 2014-03-27
CN104640628B (zh) 2016-11-16
KR20150058219A (ko) 2015-05-28
CA2883503A1 (fr) 2014-03-27
US9981845B2 (en) 2018-05-29

Similar Documents

Publication Publication Date Title
US9981845B2 (en) Catalyst for producing hydrogen and method for producing hydrogen
Zhang et al. NixAl1O2-δ mesoporous catalysts for dry reforming of methane: The special role of NiAl2O4 spinel phase and its reaction mechanism
JP5820817B2 (ja) アンモニア合成触媒及びアンモニア合成方法
El Kasmi et al. Innovative CVD synthesis of Cu2O catalysts for CO oxidation
EP3395441B1 (fr) Composé intermétallique de support de métal de transition, catalyseur métallique supporté et procédé de production d'ammoniac
JP4142733B2 (ja) 均一型高分散金属触媒及びその製造方法
Chin et al. Preferential oxidation of CO under excess H2 conditions over Ru catalysts
EP0406896B1 (fr) Catalyseur de reformage à la vapeur d'hydrocarbure
EP3498372A1 (fr) Procédé de fabrication d'un catalyseur de synthèse d'ammoniac, et procédé de fabrication d'ammoniac
Kimura et al. Selective methanation of CO in hydrogen-rich gases involving large amounts of CO2 over Ru-modified Ni-Al mixed oxide catalysts
KR101319137B1 (ko) 탄화수소를 분해하는 촉매, 상기 촉매를 이용한 탄화수소의분해 방법 및 수소의 제조 방법, 및 발전 시스템
TWI600468B (zh) 奈米金承載於氧化銅－二氧化鈰觸媒之製法及其在氫氣流中氧化一氧化碳之應用
CN107308951A (zh) 用于富氢气氛中优先氧化co的宽温催化剂的制备方法及其产品和应用
JP2011078947A (ja) アンモニア分解触媒、及びアンモニアの分解方法
JP2012055826A (ja) 低温酸化触媒とその製造方法およびその触媒を用いた酸化方法
Zhang et al. Selective oxidation of CO in hydrogen rich gas over platinum–gold catalyst supported on zinc oxide for potential application in fuel cell
CN110732335B (zh) 一种用于甲烷干气重整反应的过渡金属@BOx核-壳结构纳米催化剂及其制备方法
JP2002224570A (ja) Ｃｏシフト反応用触媒
Wang et al. H2SO4 poisoning of Ru-based and Ni-based catalysts for HI decomposition in SulfurIodine cycle for hydrogen production
JP2019193913A (ja) 水素製造触媒
EP3932546A1 (fr) Hydrure d'oxynitrure, support métallique contenant de l'hydrure d'oxynitrure, et catalyseur pour la synthèse d'ammoniac
EP3750625A1 (fr) Conjugué, catalyseur et procédé de production d'ammoniac
Wang et al. The study of strong metal-support interaction enhanced PdZn alloy nanocatalysts for methanol steam reforming
KR20140002141A (ko) 탄화수소 개질촉매 및 이의 제조방법
JP2015218091A (ja) アンモニア合成触媒およびアンモニア合成方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: TOKYO INSTITUTE OF TECHNOLOGY, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HOSONO, HIDEO;HAYASHI, FUMITAKA;YOKOYAMA, TOSHIHARU;AND OTHERS;SIGNING DATES FROM 20150203 TO 20150206;REEL/FRAME:035195/0436

AS Assignment

Owner name: TOKYO INSTITUTE OF TECHNOLOGY, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TOKYO INSTITUTE OF TECHNOLOGY;REEL/FRAME:036298/0033

Effective date: 20150602

Owner name: JAPAN SCIENCE AND TECHNOLOGY AGENCY, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TOKYO INSTITUTE OF TECHNOLOGY;REEL/FRAME:036298/0033

Effective date: 20150602

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION