WO2023106424A1 - アンモニアの製造方法及び製造装置 - Google Patents

アンモニアの製造方法及び製造装置 Download PDF

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WO2023106424A1
WO2023106424A1 PCT/JP2022/045751 JP2022045751W WO2023106424A1 WO 2023106424 A1 WO2023106424 A1 WO 2023106424A1 JP 2022045751 W JP2022045751 W JP 2022045751W WO 2023106424 A1 WO2023106424 A1 WO 2023106424A1
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cathode
anode
catalyst
ammonia
electrolyte
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French (fr)
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章一 近藤
紀仁 志賀
雅昭 小澤
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Nissan Chemical Corp
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/085—Organic compound
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to a method and apparatus for producing ammonia.
  • Non-Patent Document 1 In a method for producing ammonia from nitrogen molecules by electrolysis in a low-temperature range, there is an example of producing ammonia by electrolysis at 90°C using a platinum electrode as an anode and a cathode in which ruthenium is supported on carbon felt. There is (Non-Patent Document 1). There is a reported example of producing ammonia by electrolysis using Sm 1.5 Sr 0.5 CoO 4 or the like as an electrode that generates ammonia (Non-Patent Document 2).
  • Non-Patent Document 1 operates at around 90 to 100°C, so the problem was that the efficiency of ammonia synthesis decreased at room temperature around 20 to 30°C.
  • Non-Patent Document 2 has a problem of a complicated process of treating the membrane with ammonia before incorporating the membrane to be used as the electrolyte membrane into the electrolytic device.
  • the present invention has been made to solve the above-mentioned problems, and its main purpose is to provide a novel method for electrochemically producing ammonia.
  • the present inventors have investigated the functions of metal complexes represented by complex catalysts, etc., and solid catalysts represented by metal catalysts, transition metal catalysts, noble metal catalysts, alloy catalysts, oxide catalysts, etc. It was found that ammonia can be produced electrochemically in a newly designed ammonia production apparatus using a membrane electrode assembly or a gas diffusion electrode, which is a catalyst layer that combines the functions of , have completed the present invention.
  • the present invention based on these findings is, for example, the following [1] to [10].
  • [1] Providing electrons from a power supply, protons from a proton source, and nitrogen molecules from a means for supplying nitrogen gas in the presence of a metal complex and a solid catalyst at a cathode in a production apparatus that performs an electrolytic reaction; A method for producing ammonia using nitrogen molecules as a raw material by supplying hydrogen molecules from means for supplying hydrogen gas.
  • means for supplying hydrogen gas at the anode comprising means for sending hydrogen gas produced at the cathode to the anode; The method for producing ammonia according to [1].
  • the metal complex is a compound capable of forming a nitrogen complex by coordinating a nitrogen molecule to a metal at the center of the catalyst, and the solid catalyst is a metal catalyst, a transition metal catalyst, a noble metal catalyst, an alloy catalyst, an oxide catalyst, or a combination thereof.
  • the metal complex is bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)zirconium dichloride, rac-dimethylsilylbis(1-indenyl)zirconium dichloride, or rac-ethylenebis(4,5,6,
  • the cathode has a cathode catalyst layer bonded to one side of the electrolyte membrane and a cathode current collector disposed outside thereof, and the anode has an anode catalyst layer bonded to the other side of the electrolyte membrane and has an anode A current collector is disposed, the cathode comprises a cathode catalyst layer and a cathode current collector, the anode comprises an anode catalyst layer and an anode current collector, and the cathode is in solid-liquid-gas contact.
  • a cathode electrolyte bath in which the anode is in solid-liquid-gas contact; means for delivering hydrogen gas to the anode; a power supply for supplying electrons to the cathode;
  • An apparatus for producing ammonia comprising a proton source for supplying protons to a cathode, means for supplying nitrogen gas to the cathode electrolyte tank, the cathode electrolyte, or the cathode, wherein ammonia is produced from nitrogen molecules by an electrolytic reaction.
  • the apparatus for producing ammonia according to [7], wherein the means for sending the hydrogen gas to the anode comprises means for sending the hydrogen gas generated at the cathode to the anode.
  • the cathode has a cathode catalyst layer bonded to one side of the electrolyte membrane and a cathode current collector disposed outside thereof, and the anode has an anode catalyst layer bonded to the other side of the electrolyte membrane and has an anode A current collector is disposed, the cathode comprises a cathode catalyst layer and a cathode current collector, the anode comprises an anode catalyst layer and an anode current collector, and the cathode is in solid-liquid-gas contact.
  • the anode comprises a channel through which solid-liquid-gas contact is provided; means for sending hydrogen gas to the anode; a power supply for supplying electrons to the cathode;
  • An apparatus for producing ammonia comprising a proton source for supply, means for supplying nitrogen gas to the cathode electrolyte tank, the cathode electrolyte, or the cathode, wherein ammonia is produced from nitrogen molecules by an electrolytic reaction.
  • the apparatus for producing ammonia according to [9] wherein the means for feeding the hydrogen gas to the anode comprises means for feeding the hydrogen gas generated at the cathode to the anode.
  • ammonia of the present invention in a production apparatus that performs electrolysis, electrons from a power supply, protons from a proton source, and nitrogen gas from a means for supplying in the presence of a metal complex and a solid catalyst at a cathode
  • nitrogen molecules By providing nitrogen molecules, providing hydrogen molecules from means for supplying hydrogen gas at the anode, and providing hydrogen molecules from means for sending hydrogen gas generated at the cathode to the anode, efficiently , ammonia can be produced from molecular nitrogen.
  • hydrogen gas generated at the cathode can be reused, and an energy-saving apparatus capable of producing ammonia can be provided.
  • FIG. 1 is an explanatory diagram of an ammonia electrolyzer (No. 1);
  • FIG. FIG. 2 is an explanatory diagram of an ammonia electrolyzer (No. 2); It is explanatory drawing of the electrolytic device (3) of ammonia. It is explanatory drawing of the electrolytic device (4) of ammonia. It is explanatory drawing of the electrolytic device (5) of ammonia.
  • FIG. 10 is an explanatory diagram of gas flow during operation of the ammonia electrolyzer (No. 3).
  • FIG. 4 is an explanatory diagram of gas flow during operation of the ammonia electrolyzer (No. 4).
  • n is normal, “s” is secondary, “t” is tertiary, “o” is ortho, “m” is meta, “p” is para, and “rac”. stands for racemic.
  • C a -C b alkyl group is a monovalent group produced by losing one hydrogen atom from a linear or branched aliphatic hydrocarbon having a to b carbon atoms.
  • the method for producing ammonia according to the present embodiment can be carried out in a production apparatus that performs electrolysis.
  • a production apparatus that performs electrolysis may be referred to as an electrolytic apparatus, and is composed of an electrolytic cell, a nitrogen gas supply means, a hydrogen gas supply means, an ammonia recovery means, and an exhaust gas removal means.
  • the electrolytic cell is composed of an electrode, an electrolyte bath, a nitrogen gas supply port, a hydrogen gas supply port, and an exhaust gas outlet.
  • the electrode is an anode where an oxidation reaction occurs, and a reduction reaction occurs.
  • the electrode is the cathode.
  • a catalyst in the form of a combination of this metal complex and a solid catalyst may be referred to as a catalyst body in this specification.
  • the proton source is preferably capable of supplying at least one of protons and hydroxonium ions when the environment in which the catalyst is placed is acidic, and when the environment in which the catalyst is placed is alkaline, A proton source capable of supplying at least one of water and hydroxide ions is preferable, and these proton sources may be used singly or in combination of two or more.
  • the metal complex in the method for producing ammonia of the present embodiment may play a role of capturing nitrogen molecules when the nitrogen molecules react in the vicinity of the electrode, and then a role of reducing by giving protons and electrons. is not particularly limited as long as it forms a compound in which a nitrogen molecule is coordinated at the metal center of . Said compounds are sometimes called nitrogen complexes.
  • the discovery of [Ru(NH 3 ) 5 N 2 ] 2+ described in Non-Patent Literature Science, 1968, vol. 159, pp. 320-322; Am. Chem. Soc. , 1968, Vol. 90, pp. 3263-3264, J. Am.
  • a metallocene compound has two rings of cyclopentadiene, benzene, cyclooctatetraene, the above derivatives, etc., and has a structure in which a metal atom is sandwiched between the rings, and is sometimes called a sandwich compound.
  • a half-metallocene compound has a structure having one ring, and is sometimes called an open sandwich compound.
  • metallocene compound of the present embodiment examples include bis(cyclopentadienyl)titanium dichloride, ⁇ -chloro- ⁇ -methylene[bis(cyclopentadienyl)titanium]dimethylaluminum, and bis(cyclopentadienyl)zirconium dichloride.
  • metallocene compounds include cyclopentadienyl titanium (IV) trichloride, (pentamethylcyclopentadienyl) titanium (IV) trichloride, (indenyl) titanium (IV) trichloride, trichloro (indenyl) titanium (IV), cyclopentadienyl enylzirconium (IV) trichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, rac-dimethylsilylbis(1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride , rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride and the like.
  • bis(cyclopentadienyl)titanium dichloride bis(cyclopentadienyl)zirconium dichloride, rac-dimethylsilylbis(1-indenyl)zirconium dichloride, rac-ethylenebis(4,5,6,7-tetrahydro -1-indenyl)zirconium dichloride is preferred.
  • a metal complex in which a metal complex is supported can also be used.
  • a complex represented by the formula (S1) having a formula (S2) obtained by radical polymerization with styrene The complex represented by is mentioned.
  • a mode in which a metallocene compound is supported on a polymer is described, for example, in Comprehensive Organometallic Chemistry III (2007), pages 728-738 of Non-Patent Literature.
  • Examples of the solid catalyst in the ammonia production method of the present embodiment include metal catalysts and oxide catalysts, and it is also possible to use a plurality of these solid catalysts in combination.
  • Examples of metal catalysts include metal catalysts that are used in a single composition or mixed with a plurality of metal components such as alloy catalysts, and metal nanoparticles formed using a surfactant, and thiol compounds. It is also possible to use metal particles, metal nanoparticles, metal films, metal foils, etc. that have self-organized portions by binding metals and thiols.
  • R 1 a compound represented by R 1 —SH (R 1 has the same definition as below) can be used.
  • R 1 is not particularly limited and can be an appropriate one in consideration of the boiling point of R 1 —SH, ease of isolation by chromatography, etc., but an organic group having 1 to 20 carbon atoms is preferred, and an organic group having 6 to 16 carbon atoms is more preferred.
  • the organic group include a hydrocarbon group, a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, an aromatic hydrocarbon group, and these groups.
  • thiol compounds include, for example, 2-methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, phenylmethanethiol, 1-butanethiol, 1-decanethiol, 1-dodecanethiol, 1 -heptanethiol, 1-hexadecanethiol, 1-hexanethiol, 1-nonanethiol, 1-octadecanethiol, 1-octanethiol, 1-pentadecanethiol, 1-pentanethiol, 1-propanethiol, 1-tetradecanethiol, 1 -undecanethiol, 11-mercaptoundecyltrifluoroacetate, 1H,1H,2H,
  • oxide catalysts examples include oxide catalysts that are used in the case of metal oxides of typical elements, in the case of transition metal oxides, or in the case of mixing a plurality of metal oxides, and the metal oxides are It may be used as a support for solid catalysts.
  • solid catalysts in the ammonia production method of the present embodiment include iridium (IV) oxide powder catalysts, iridium oxide catalysts, platinum catalysts, gold catalysts, silver catalysts, ruthenium catalysts, iridium catalysts, rhodium catalysts, palladium catalysts, and osmium.
  • platinum catalysts, gold catalysts and silver catalysts include thiol-protected platinum nanoparticle catalysts, thiol-protected platinum catalysts, thiol-protected gold nanoparticle catalysts, thiol-protected gold catalysts, thiol-protected silver nanoparticle catalysts, and thiol-protected silver catalysts. is mentioned.
  • the solid catalyst used on the cathode side is defined as a cathode solid catalyst
  • preferred cathode solid catalysts include platinum catalysts, thiol-protected platinum nanoparticle catalysts, thiol-protected platinum catalysts, gold catalysts, thiol-protected gold nanoparticle catalysts, and thiols.
  • protected gold catalysts iridium catalysts, palladium catalysts, zinc oxide, molybdenum oxide, cerium oxide, and samarium oxide, more preferably platinum catalysts, thiol-protected platinum nanoparticle catalysts, gold catalysts, thiol-protected gold nanoparticle catalysts, Thiol-protected gold catalysts, palladium catalysts, and zinc oxide are included.
  • the cathode-side catalyst which is a catalyst obtained by combining a metal complex and a solid catalyst, is defined as a cathode catalyst.
  • titanium dichloride with a platinum catalyst bis(cyclopentadienyl)titanium dichloride with a thiol-protected platinum nanoparticle catalyst, bis(cyclopentadienyl)titanium dichloride with a palladium catalyst, bis(cyclopenta dienyl)titanium dichloride in combination with a gold catalyst, bis(cyclopentadienyl)titanium dichloride in combination with a thiol-protected gold nanoparticle catalyst, bis(cyclopentadienyl)titanium dichloride in combination with a thiol-protected gold catalyst, Combination of bis(cyclopentadienyl)titanium dichloride and zinc oxide, combination of bis(cyclopentadienyl)titanium dichloride and zinc
  • the cathode catalyst layer 103 for producing ammonia of the present embodiment includes a catalyst carrier, an electron conductor, an electrolyte, and a gas diffusion layer in addition to a cathode catalyst body which is a catalyst in which a metal complex and a solid catalyst are combined.
  • the cathode catalyst layer 103 comprising a cathode catalyst body, a catalyst carrier, an electron conductor, an electrolyte, and a gas diffusion layer, which is a combination of a metal complex and a cathode solid catalyst, may be referred to as a gas diffusion electrode 133. .
  • the catalyst carrier in the cathode catalyst layer 103 of the present embodiment may conduct electrons, and is not particularly limited as long as it supports the catalyst of the present embodiment.
  • Catalyst carriers include carbon black, carbon materials, metal meshes, metal foams, metal oxides, composite oxides, polymer electrolytes, ionic liquids, activated carbon, graphene oxide, reduced graphene oxide, carbon nitride, g-carbon nitride, etc. is mentioned. Further, when the catalyst carrier is used in the electrode, it not only plays the role of supporting the catalyst, but also participates as a catalyst or co-catalyst in the reaction occurring at the electrode.
  • Examples of carbon black include channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC, and the like.
  • Examples of carbon materials include carbonizing and activating materials containing various carbon atoms. Treated activated carbon, coke, natural graphite, artificial graphite, graphitized carbon, etc., and metal meshes include metal meshes of nickel, tungsten, titanium, zirconium, hafnium, and the like.
  • Metal foams include, for example, Metal foams such as aluminum, magnesium, tungsten, titanium, zirconium, hafnium, zinc, iron, tin, lead, or alloys containing these can be mentioned.
  • Metal oxides include, for example, aluminum oxide, zirconium oxide, titanium oxide, Vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, silver oxide, tantalum oxide, tungsten oxide, osmium oxide, oxide
  • Examples include iridium, indium oxide, platinum oxide, gold oxide, magnesium oxide, silica, and the like.
  • composite oxides include silica-alumina, silica-magnesia, and the like.
  • polymer electrolytes examples include fluorine-based polymer electrolytes, hydrocarbon-based polymer electrolytes, carboxyl group-containing acrylic copolymers, and carboxyl group-containing methacrylic copolymers.
  • fluorine-based polymer electrolytes include Nafion (registered trademark) from DuPont, Aquivion (registered trademark) from Solvay, Flemion (registered trademark) from AGC, and Aciplex (registered trademark) from Asahi Kasei.
  • Hydrocarbon polymer electrolytes include, for example, sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • carboxyl group-containing acrylic copolymers include acrylic acid, propiolic acid, crotonic acid, isocrotonic acid, myristoleic acid, palmitoleic acid, oleic acid, which have a carboxyl group and a copolymerizable double bond.
  • radical polymerization initiators include azobisisobutyronitrile, azobis(2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis[N- Azo compounds such as (2-carboxyethyl)-2-methylpropionamidine methyl]tetrahydrate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butylperoxide
  • organic peroxides such as oxides, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, and hydrogen peroxide, and these can be used alone or in combination of two or more.
  • Carboxyl group-containing methacrylic copolymers specifically include methacrylic acid, ⁇ -carboxy-polycaprolactone monomethacrylate, monohydroxyethyl phthalate methacrylate, and methacrylic acid dimer having a carboxyl group and a copolymerizable double bond.
  • the above-mentioned homopolymerization or copolymerization can be advanced, for example, by generating radicals with a radical polymerization initiator.
  • radical polymerization initiators examples include azobisisobutyronitrile, azobis(2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis[N- Azo compounds such as (2-carboxyethyl)-2-methylpropionamidine methyl]tetrahydrate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butylperoxide Examples include organic peroxides such as oxides, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, and hydrogen peroxide, and these can be used alone or in combination of two or more.
  • FUMION registered trademark
  • FAA-3-SOLUT-10 manufactured by FUMATECH BWT GmbH, A3ver. 2, AS-4 (A3ver.2 and AS-4 are described in, for example, the magazine "Hydrogen Energy System", Vo1.35, No.2, 2010, page 9.), and the electrolyte membrane described later
  • a cation exchange membrane hereinafter also referred to as a cation exchange membrane
  • Nafion registered trademark
  • Aquivion registered trademark
  • an anion exchange membrane hereinafter also referred to as an anion exchange membrane
  • it is also possible to use a combination of a plurality of these polymer electrolytes. may include physically mixed polymer blends, interpenetrated polymer networks (IPNs).
  • ionic liquid of this embodiment will be described below.
  • ionic liquids include imidazolium salts, pyridinium salts, ammonium salts, phosphonium salts, pyrrolidinium salts, piperidinium salts, and sulfonium salts.
  • imidazolium salts include formula (1): Those represented by are mentioned.
  • R 1a to R 5a may be the same or different, and may each be a hydrogen atom, a C 1 to C 10 alkyl group, an allyl group, or a vinyl group.
  • X - in formula (1) includes, for example, chloride ion, bromide ion, iodine ion, tetrafluoroborate, trifluoro(trifluoromethyl)borate, dimethyl phosphate ion, diethyl phosphate ion, hexafluorophosphate ion, fart, tris(pentafluoroethyl)trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide and the like.
  • formula (1) include, for example, 1-allyl-3-methylimidazolium ion, 3-ethyl-1-vinylimidazolium ion, 1-methylimidazolium ion, 1-ethylimidazolium ion, 1- n-propylimidazolium ion, 1,3-dimethylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1-ethyl- 3-methylimidazolium ion, 1-ethyl-2,3-dimethylimidazolium ion, 1,2,3,4-tetramethylimidazolium ion, 1,3-diethylimidazolium ion, 1-methyl-3-n -propylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 2-ethyl-1,3-dimethylimidazolium ion, 1-ethyl-2,3-dida
  • pyridinium salts include formula (2): Those represented by are mentioned.
  • R 1b to R 6b may be the same or different, and each includes a hydrogen atom, a hydroxymethyl group, or a C 1 to C 6 alkyl group.
  • X 1 - in formula (2) includes the same ones as in formula (1).
  • formula (2) include, for example, 1-butyl-3-methylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-butyl-pyridinium ion, 1-ethyl-3-methylpyridinium ion, 1 -ethylpyridinium ion, 1-ethyl-3-(hydroxymethyl)pyridinium ion and other pyridinium ions, and salts of X 1 - in the formula (1).
  • ammonium salts include formula (3): Those represented by are mentioned.
  • R 1c to R 4c may be the same or different, and are each a hydrogen atom, a methoxyethyl group, a phenylethyl group, a methoxypropyl group, a cyclohexyl group, or a C 1 to C 8 alkyl group. groups.
  • X 1 - in formula (3) includes the same ones as in formula (1).
  • formula (3) include triethylpentylammonium ion, diethyl(methyl)propylammonium ion, methyltri-n-octylammonium ion, trimethylpropylammonium ion, cyclohexyltrimethylammonium ion, diethyl(2-methoxyethyl) -methylammonium ion, ethyl(2-methoxyethyl)-dimethylammonium ion, ethyl(3-methoxypropyl)dimethyl-ammonium ion, ethyl(dimethyl)(2-phenylethyl)-ammonium ion and the like and the formula ( Examples thereof include salts with X 1 - in 1).
  • phosphonium salts include formula (4): Those represented by are mentioned.
  • R 1d to R 4d may be the same or different, and each includes a hydrogen atom, a methoxyethyl group, or a C 1 to C 10 alkyl group.
  • X 1 - in formula (3) includes the same ones as in formula (1).
  • formula (4) include phosphonium ions such as tributylmethylphosphonium ion, tetrabutylphosphonium ion, trihexyl(tetradecyl)phosphonium ion, trihexyl(ethyl)phosphonium ion, and tributyl(2-methoxyethyl)-phosphonium ion. and salts of X 1 — in formula (1) above.
  • pyrrolidinium salts include formula (5): Those represented by are mentioned.
  • R 1e to R 2e may be the same or different, and each includes a hydrogen atom, an allyl group, a methoxyethyl group, or a C 1 to C 8 alkyl group.
  • X 1 - in formula (5) includes the same ones as in formula (1).
  • formula (5) include, for example, 1-allyl-1-methylpyrrolidinium ion, 1-(2-methoxyethyl)-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, A salt of a pyrrolidinium ion such as 1-methyl-1-propylpyrrolidinium ion, 1-octyl-1-methylpyrrolidinium ion, 1-hexyl-1-methylpyrrolidinium ion and X- in the formula (1) mentioned.
  • piperidinium salts include formula (6): Those represented by are mentioned.
  • R 1f to R 2f may be the same or different, and each includes a hydrogen atom or a C 1 to C 6 alkyl group.
  • X 1 - in formula (6) includes the same ones as in formula (1).
  • formula (6) include, for example, salts of piperidinium ions such as 1-butyl-1-methylpiperidinium ion and 1-methyl-1-propylpiperidinium ion and X - in formula (1) above. is mentioned.
  • sulfonium salts include formula (7): Those represented by are mentioned.
  • R 1g to R 3g may be the same or different, and each includes a hydrogen atom or a C 1 to C 4 alkyl group.
  • X 1 - in formula (3) includes the same ones as in formula (1).
  • formula (4) include salts of sulfonium ions such as triethylsulfonium ion and trisulfonium ion and X 1 ⁇ in formula (1).
  • ionic liquid 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3- Methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium iodide , 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorotrifluorophosphate, 1-butyl-3-methylimidazolium trifluoro(trifluoromethyl)borate, 1-butyl-2,3-dimethylimidazolium lithium trifluoromethanesulfonate, 1-butyl-3-methylimid
  • These catalyst carriers may be used alone or in combination of two or more types, and include a combination of carbon black and zinc oxide, a combination of Ketjenblack EC and zinc oxide, and carbon black and molybdenum oxide.
  • the electron conductor in the cathode catalyst layer 103 of the present embodiment is not particularly limited as long as it conducts electrons.
  • carbon black such as channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC, activated carbon obtained by carbonizing and activating materials containing various carbon atoms, coke, natural graphite, artificial graphite, Examples thereof include carbon materials such as graphitized carbon, metal mesh such as nickel or titanium, and metal foam.
  • carbon black, Ketjenblack, Ketjenblack EC, nickel metal mesh, titanium metal mesh and metal foam are used because of their high specific surface area and excellent electronic conductivity. is preferable, and titanium metal mesh and metal foam are more preferable because of their excellent durability.
  • the electrolyte in the cathode catalyst layer 103 of this embodiment is not particularly limited as long as it is responsible for ion conduction.
  • Fluorine-based polymer electrolytes, hydrocarbon-based polymer electrolytes, anion-conducting electrolytes, and the like are included.
  • fluorine-based polymer electrolytes include Nafion (registered trademark) from DuPont, Aquivion (registered trademark) from Solvay, Flemion (registered trademark) from AGC, and Aciplex (registered trademark) from Asahi Kasei.
  • Examples include sulfonic acid polymers, hydrocarbon sulfonic acid polymers, and partially fluorine-introduced hydrocarbon sulfonic acid polymers.
  • Hydrocarbon polymer electrolytes include, for example, sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.
  • anion-conducting electrolyte FUMION (registered trademark) FAA-3-SOLUT-10 manufactured by FUMATECH BWT GmbH, A3ver.
  • AS-4 (A3ver.2 and AS-4 are described in, for example, the magazine "Hydrogen Energy System", Vo1.35, No.2, 2010, page 9.), and the electrolyte membrane described later
  • a cation exchange membrane hereinafter also referred to as a cation exchange membrane
  • Nafion registered trademark
  • Aquivion registered trademark
  • an anion exchange membrane hereinafter also referred to as an anion exchange membrane
  • the electrolyte in the cathode catalyst layer 103 of the present embodiment those responsible for proton conduction are preferable, and Nafion, Aquivion, Flemion, and Aciplex are preferable.
  • the electrolyte may be mixed and used, and preferably contains a perfluoroacid polymer such as Nafion.
  • the gas diffusion layer in the cathode catalyst layer 103 of this embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and electrolyte diffusion. Examples thereof include carbon paper, carbon felt, carbon cloth, and the like.
  • the cathode catalyst layer 103 including a catalyst body that is a metal complex, a cathode solid catalyst, or a metal complex and a cathode solid catalyst and having a gas diffusion layer may be referred to as a gas diffusion electrode 133 .
  • Examples of carbon paper include Toray's TGP-H-060, TGP-H-090, TGP-H-120, TGP-H-060H, TGP-H-090H, TGP-H-120H, Electrochem's EC-TP1-030T, EC-TP1-060T, EC-TP1-090T, EC-TP1-120T, SIGRACET 22BB, 28BC, 36BB, 39BB and the like.
  • Examples of the carbon cloth include EC-CC1-060, EC-CC1-060T, and EC-CCC-060 manufactured by Electrochem Corporation, Torayca (registered trademark) cloth manufactured by Toray Industries, Inc., and CO6142, CO6151B, CO6343, CO6343B, and CO6347B. , CO6644B, CO1302, CO1303, CO5642, CO7354, CO7359B, CK6244C, CK6273C, CK6261C and the like.
  • Examples of carbon felt include H1410 and H2415 manufactured by Freudenberg.
  • TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H, and EC-TP1-060T are preferable for the gas diffusion layer in the cathode catalyst layer 103 of this embodiment.
  • the proton source arranged in the electrolytic device includes, for example, the electrolyte membrane 102 arranged beside the cathode catalyst layer 103, the electrolytic solution derived from the electrolyte membrane, and the The electrolyte is not particularly limited as long as it is a solution containing an electrolyte and is responsible for proton conduction. These proton sources may be used singly or in combination of two or more.
  • Examples of the solution in the electrolytic solution in the ammonia production method of the present embodiment include water, aqueous sulfuric acid solution, ionic liquid, methanol, isopropyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N- Methylpyrrolidone, diethylamine, hexamethylphosphonic acid triamide, acetic acid, acetonitrile, methylene chloride, trifluoroethanol, nitromethane, sulfolane, pyridine, tetrahydrofuran, dimethoxyethane, propylene carbonate, etc., water, aqueous sulfuric acid solution and ionic liquid are preferred.
  • ionic liquids include those described above, such as imidazolium salts, pyridinium salts, ammonium salts, phosphonium salts, pyrrolidinium salts, piperidinium salts, or sulfonium salts.
  • Acids such as sulfuric acid and trifluoromethanesulfonic acid can be added to the ionic liquid and used, and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) is preferable as the ionic liquid to which the acid is added.
  • Examples of the electrolyte contained in the electrolytic solution in the method for producing ammonia of the present embodiment include protons, lithium ions, sodium ions, potassium ions, imidazolium ions, pyridinium ions, quaternary ammonium ions, phosphonium ions, and pyrrolidinium ions. , phosphonium ions, etc.
  • Examples include anions singly or in combination.
  • One of the electrolytes may be used alone, or two or more of them may be used in combination.
  • Examples of the quaternary ammonium ion in the electrolyte include triethylpentylammonium ion, diethyl(methyl)propylammonium ion, methyltri-n-octylammonium ion, trimethylpropylammonium ion, cyclohexyltrimethylammonium ion, diethyl(2-methoxyethyl)-methyl ammonium ion, ethyl(2-methoxyethyl)-dimethylammonium ion, ethyl(3-methoxypropyl)dimethyl-ammonium ion, ethyl(dimethyl)(2-phenylethyl)-ammonium ion, tetramethylammonium ion, tetraethylammonium ion, Triethylpentylammonium ion, tetra-n-butyl
  • imidazolium ions, pyridinium ions, phosphonium ions, pyrrolidinium ions, and phosphonium ions in the electrolyte include those described above.
  • the cations that are electrolytes contained in the electrolytic solution of the present embodiment are preferably protons, imidazolium ions, and pyrrolidinium ions, and the anions that are the electrolytes are preferably perchlorate ions and sulfate ions.
  • the cathode electrolyte 106 used in the cathode electrolyte tank 105 of the present embodiment includes water, aqueous sulfuric acid solution, ionic liquid, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methanol, and ethanol.
  • Preferred catholyte 106 are water, aqueous sulfuric acid, ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) is an imide.
  • the anode electrolyte 116 used in the anode electrolyte tank 115 of the present embodiment includes water, an aqueous sulfuric acid solution, an ionic liquid, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methanol, and ethanol.
  • the anode electrolyte 116 is preferably water, an aqueous sulfuric acid solution, an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1- Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.
  • Examples of the electrolyte membrane 102 in the method for producing ammonia of the present embodiment include polymer electrolyte membranes and reinforcing membranes.
  • a bipolar membrane and a mosaic charged membrane can be mentioned as composite charged membranes having a structure of a cation exchange membrane and an anion exchange membrane in one membrane.
  • electrolyte membranes include Nafion membrane (registered trademark) from DuPont, Aquivion membrane (registered trademark) from Solvay, Flemion membrane (registered trademark) from AGC, Aciplex (registered trademark) from Asahi Kasei, Dow Dow membrane (registered trademark) of the company, sulfonated polyether ketone polymer membrane, sulfonated polyether sulfone polymer membrane, sulfonated polyether ether sulfone polymer membrane, sulfonated polysulfide polymer membrane, sulfonated polyphenylene polymer membrane, poly Gore select membrane (registered trademark) of Gore Japan LLC impregnated with perfluorosulfonic acid polymer using tetrafluoroethylene (PTFE) porous material, membrane reinforced with PTFE woven fabric, polyethylene (PE) porous material and polypropylene ( PP) Membrane using
  • Nafion membrane registered trademark
  • Aquivion membrane registered trademark
  • Gore Select membrane from Gore Japan LLC.
  • an anion exchange membrane is preferable, and when an anion exchange membrane is used, Fumasep membrane (registered trademark) of FUMATECH BWT GmbH FAP-450 membrane, FAA-3 membrane, Selemion membrane (registered trademark) of AGC ASVN membrane, and AHO films are preferred.
  • the electrolyte membrane 102 in the ammonia production method of the present embodiment is more preferably Nafion membrane (registered trademark) and Aquivion membrane (registered trademark) of cation exchange membranes.
  • the reaction temperature is preferably -40°C to 200°C, more preferably -10°C to 120°C, and even more preferably 0°C to 100°C.
  • Start-up of the electrolyser can also be started from room temperature.
  • the reaction atmosphere may be a pressurized atmosphere by providing a back pressure valve in the nitrogen supply pipe, or may be a normal pressure atmosphere.
  • the reaction time is not particularly limited, but it can usually be set in the range of several tens of minutes to several tens of hours. For example, after reacting for several hours, it is also possible to once stop the reaction and then react again.
  • FIG. 1 shows an ammonia electrolysis apparatus (part 1) 100 for producing ammonia
  • FIG. 2 shows an ammonia electrolysis apparatus (part 2) 200 for producing ammonia
  • FIG. 4 shows an ammonia electrolysis apparatus (part 3) 300 for producing ammonia
  • FIG. 5 shows an ammonia electrolysis apparatus (part 5) 500 for producing ammonia. respectively.
  • An ammonia electrolysis apparatus (part 1) 100 (FIG. 1) of the present embodiment is an ammonia production apparatus capable of producing ammonia from nitrogen molecules through an electrolytic reaction.
  • This apparatus for producing ammonia includes a membrane electrode assembly 131 integrated with a catalyst layer 113 via an electrolyte membrane 102 .
  • a cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and a cathode current collector 104 is arranged on the outside thereof, and an anode catalyst layer 113 is bonded to the other side of the electrolyte membrane 102, and the outside thereof.
  • the anode current collector 114 is arranged in the .
  • the current collector has a flow path through which the gas, the electrolyte and the reaction liquid flow.
  • the reaction liquid refers to a mixture of a gas and an electrolytic solution produced by an electrolytic reaction in the apparatus.
  • the cathode catalyst layer 103 comprises a metal complex and a cathode solid catalyst, and the anode catalyst layer 113 comprises an anode solid catalyst.
  • the manufacturing apparatus (part 1) 100 includes a flow path 136 for gas, electrolyte, and reaction liquid on the cathode side, which contacts the cathode 108 of the membrane electrode assembly 131 in a solid-liquid-gas manner, and a cathode for storing the cathode electrolyte 106.
  • Equipped with an electrolyte bath 105, an anode-side gas, electrolyte, and reaction liquid flow path 135 that contacts the anode 118 of the membrane electrode assembly 131 in a solid-liquid-gas manner, and an anode electrolyte bath for storing the anode electrolyte 116. 115 are provided.
  • hydrogen gas when hydrogen gas is supplied to the anode, it can be supplied from the hydrogen cylinder 127 through the hydrogen cylinder regulator 128 and the hydrogen gas mass flow controller 129 through the pipe 121.
  • Hydrogen gas supplied through a pipe 121 connected to the electrolyte bath 115 is in solid-gas contact with the anode 118, and when an electrolyte is used, it is supplied through a pipe 121 connected to the anode electrolyte bath 115. Hydrogen gas is in solid-liquid-gas contact with the anode 118 .
  • a power supply (power supply device 101 ) that supplies electrons to the cathode 108 , a proton source that supplies protons to the cathode 108 , and means for supplying nitrogen gas to the cathode electrolyte 106 and the cathode 108 are provided.
  • the proton source can be the electrolyte membrane 102 , the cathode electrolyte 106 , the cathode catalyst layer 103 , the anode electrolyte 116 and the anode catalyst layer 113 .
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the nitrogen cylinder regulator 123 and the nitrogen gas mass flow controller 124. When the nitrogen gas is being supplied, the three-way cock 302 is closed. , connection to the recovery tank 201 for the electrolytic solution and the reaction solution is not made.
  • the means for supplying hydrogen gas to the anode 118 is a means for supplying from a hydrogen cylinder 127 via a hydrogen cylinder regulator 128 and a hydrogen gas mass flow controller 129 through a pipe 121, and can be implemented.
  • Ammonia generated at the cathode 108 can be collected in the cathode electrolyte solution tank 105 for storing the cathode electrolyte solution 106 and the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • the cathode electrolyte 106 can be recovered in the electrolyte and reaction liquid recovery tank 201 , and the next cathode electrolyte 106 can be sent from the storage tank 202 to the cathode electrolyte tank 105 by the liquid sending pump 303 .
  • the by-produced hydrogen and unreacted nitrogen pass through a pipe 121, a diluted sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126. Since it is illustrated as an example, the two-way cock 301 is shown at a representative position, but cocks for protecting the regulator, mass flow controller, etc., which are devices in the apparatus, may be attached to the piping. can.
  • the ammonia electrolysis apparatus (part 3) 300 (FIG. 3) of the present embodiment is an ammonia production apparatus capable of producing ammonia from nitrogen molecules by an electrolytic reaction.
  • a cock 307 and a three-way cock 307 are added.
  • a portion different from the ammonia electrolyzer (part 1) 100 will be described.
  • a mixed gas (mixed gas of nitrogen and hydrogen) that has passed through a dilute sulfuric acid aqueous solution tank for collecting ammonia can be supplied to the anode electrolyte tank 115 and the anode 118.
  • the hydrogen gas inside is in solid-gas contact with the anode 118 .
  • the anode electrolyte 116 can be recovered in the electrolyte and reaction liquid recovery tank 205 , and the next anode electrolyte 116 can be sent from the storage tank 206 to the anode electrolyte tank 115 by the liquid sending pump 303 .
  • the by-produced hydrogen and unreacted nitrogen pass through the pipe 121, pass through the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and can be discharged to the outside through the draft device 126 by the three-way cock 302. It is also possible to send it to the anode 118 via the piping 305, which is the present invention. Since it is illustrated as an example, the two-way cock 301 is shown at a representative position, but cocks for protecting the regulator, mass flow controller, etc., which are devices in the apparatus, may be attached to the piping. can.
  • the ammonia electrolysis apparatus (part 2) 200 of the present embodiment is an ammonia production apparatus capable of producing ammonia from nitrogen molecules through an electrolytic reaction, and includes a cathode 108 and an anode 118, a cathode catalyst layer 103 and an anode catalyst layer 113. is integrated through an electrolyte membrane 102.
  • a cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and a cathode side separator 204 and a cathode current collector 104 are arranged on the outside thereof, and an anode catalyst layer 113 is disposed on the other side of the electrolyte membrane 102.
  • the manufacturing apparatus (part 2) 200 includes a flow path 136 for cathode-side gas, electrolytic solution, and reaction solution that is in contact with the cathode 108 of the membrane electrode assembly 131 in a solid-liquid-gas manner.
  • the anode 118 is provided with a channel 135 for the anode-side gas, electrolytic solution, and reaction solution, which are in solid-liquid-gas contact with the anode 118 .
  • hydrogen gas When hydrogen gas is supplied to the anode, which is the present invention, it can be supplied from the hydrogen cylinder 127 through the hydrogen cylinder regulator 128, the hydrogen gas mass flow controller 129, and the gas humidifier 304 through the pipe 121. .
  • the gas humidifier When the gas humidifier is set to non-humidification, the hydrogen gas supplied from the pipe 121 connected to the flow path 135 of the gas on the anode side, the electrolytic solution, and the reaction solution comes into solid-gas contact with the anode 118, and gas
  • the humidifier When the humidifier is set to humidify, the hydrogen gas supplied from the pipe 121 connected to the flow path 135 for the anode-side gas, electrolyte and reaction liquid contacts the anode 118 in a solid-liquid-gas manner. It comprises a power supply (power supply device 101 ) that supplies electrons to the cathode 108 , a proton source that supplies protons to the cathode 108 , and means for supplying nitrogen gas to the cathode 108 .
  • a power supply power supply device 101
  • Proton sources include electrolyte membrane 102 , catholyte 106 , cathode catalyst layer 103 , anode electrolyte 116 and anode catalyst layer 113 .
  • the means for supplying nitrogen gas is means for supplying nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the nitrogen cylinder regulator 123, the nitrogen gas mass flow controller 124, the gas humidifier 304, the two-way cock 301 and the three-way cock 302. , humidified nitrogen controlled by relative humidity values can also be supplied.
  • the three-way cock 302 is not connected to the recovery tank 201 for the electrolytic solution and the reaction solution.
  • the gas humidification device 304 can switch between non-humidification and humidification.
  • the means for supplying hydrogen gas to the anode 118 is a means for supplying from a hydrogen cylinder 127 through a hydrogen cylinder regulator 128, a hydrogen gas mass flow controller 129, and a gas humidifier 304, through a pipe 121, and controlled by a relative humidity value. It is also possible to supply humidified hydrogen.
  • Ammonia generated at the cathode 108 can be recovered in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia and the recovery tank 201 for the electrolytic solution and the reaction solution.
  • the electrolytic solution and the reaction solution can be sent to the cathode 108 by the liquid sending pump 303 .
  • the by-produced hydrogen and unreacted nitrogen pass through a pipe 121, a diluted sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through a draft device 126. It is possible to attach cocks to the piping to protect the regulators and mass flow controllers, which are the equipment inside the equipment.
  • the ammonia electrolysis apparatus (part 4) 400 (FIG. 4) of the present embodiment is an ammonia production apparatus capable of producing ammonia from nitrogen molecules by an electrolytic reaction.
  • a cock 307 and a three-way cock 307 are added. Parts different from the ammonia electrolyzer (part 2) 200 will be described.
  • the by-produced hydrogen gas is supplied to the anode 118 at the cathode 108, which is the present invention, the diluted sulfuric acid aqueous solution tank 125 for collecting ammonia and the pipe 305 are connected with a three-way cock 306, and the pipe 305 and the mass flow controller are connected.
  • a mixed gas (mixed gas of nitrogen and hydrogen) that has passed through a dilute sulfuric acid aqueous solution tank for collecting ammonia can be supplied to the anode electrolyte tank 115 and the anode 118.
  • the hydrogen gas inside is in solid-gas contact with the anode 118 .
  • the anode electrolyte 116 can be recovered in the electrolyte and reaction liquid recovery tank 205 , and the next anode electrolyte 116 is transferred from the storage tank 206 to the anode side gas, electrolyte, and reaction liquid flow path by the liquid feed pump 303 .
  • the anode electrolyte 116 can be circulated by the liquid transfer pump 303 .
  • Hydrogen gas is supplied directly to the anode 118 from a hydrogen cylinder 127 via a hydrogen cylinder regulator 128, a hydrogen gas mass flow controller 129, a gas humidifier 304, a two-way cock 301 and a three-way cock 302, and through a pipe 121. It is a supply means, and can also supply humidified hydrogen controlled by a relative humidity value.
  • Ammonia generated at the cathode 108 can be recovered in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia and the recovery tank 201 for the electrolytic solution and the reaction solution.
  • the electrolytic solution and the reaction solution can be sent to the cathode 108 by the liquid sending pump 303 .
  • the by-produced hydrogen and unreacted nitrogen pass through the pipe 121, pass through the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and can be discharged to the outside through the draft device 126 by the three-way cock 302. It is also possible to send it to the anode 118 via the piping 305, which is the present invention.
  • the three-way cock 302 of the ammonia electrolysis apparatus (part 4) 400 (FIG. 4) of the present embodiment is closed after introducing the reaction gas and the electrolytic solution into the anode-side and cathode-side flow paths, thereby forming a cathode catalyst layer. and the anode catalyst layer can be pressurized with a reaction gas or an electrolytic solution, and the electrolytic reaction can be promoted.
  • the ammonia electrolysis apparatus (part 5) 500 (FIG. 5) of the present embodiment is an ammonia production apparatus capable of producing ammonia from nitrogen molecules by an electrolytic reaction.
  • two two-way cocks 308 and two two-way cocks 309 are added. After the two-way cocks 308 are closed on the anode side and the cathode side to introduce the reaction gas and the electrolytic solution, the cocks of the two-way cocks 309 are closed.
  • Each of the electrolytic solution tank and the anode catalyst layer can be pressurized with the reaction gas and the electrolytic solution, and the electrolytic reaction can be promoted.
  • the cathode current collector 104 and the anode current collector 114 in the manufacturing apparatus of the present embodiment are, for example, carbon, metal, oxide, one whose surface is plated with metal, an alloy containing two or more kinds of metals, and two kinds of metals.
  • metals include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, and gold.
  • oxides include titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, and silver oxide. , tantalum oxide, tungsten oxide, osmium oxide, iridium oxide, indium oxide, platinum oxide, and gold oxide.
  • the shape of the current collector is not particularly limited as long as it is a shape through which gas or electrolytic solution can pass. bodies, foams, and the like. In order to prevent corrosion during manufacturing by electrolysis, it is possible to use a current collector plated with gold or the like.
  • Nitrogen gas is supplied from the nitrogen cylinder 122 via the nitrogen cylinder regulator 123, the nitrogen gas mass flow controller 124, and the gas humidifier 304, and humidified nitrogen controlled by the relative humidity value is supplied. It is possible to supply by controlling the flow rate. For example, a method of bubbling nitrogen gas into the electrolyte in the cathode electrolyte bath 105 in FIGS. 1, 3 and 5 and in the anode electrolyte bath 115 in FIGS. As shown in FIG. 4, it is also possible to supply nitrogen gas directly to the cathode catalyst layer 103 through the holes in the cathode current collector 104 . In the electrolytic device (part 2) 200 and the electrolytic device (part 4) 400, humidified nitrogen gas with a set relative humidity can be supplied.
  • the electrolytic reaction for producing ammonia in the cathode catalyst layer 103 in the electrolytic device of this embodiment will be described.
  • a reaction occurs in which ammonia is generated from three of the electrons supplied from the power supply device 101, the nitrogen gas supplied to the cathode 108, and the proton source supplied to the cathode 108
  • the reaction formula is "N 2 +6e - +6H + ⁇ 2NH 3 " or "N 2 +6e - + 6H 3 O + ⁇ 2NH 3 +6H 2 O" when the environment in which the catalyst body is placed is acidic, When the environment in which the catalyst is placed is alkaline, it can be formally described as "N 2 +6e ⁇ +6H 2 O ⁇ 2NH 3 +6OH ⁇ ".
  • Ammonia produced at the cathode 108 can be sent to a dilute sulfuric acid aqueous solution tank 125 for collecting ammonia together with by-produced hydrogen and unreacted nitrogen.
  • ) 300 can also be collected in the electrolyte used in the cathode electrolyte bath 105 .
  • the electrolyte used in the cathode electrolyte bath 105 is preferably water or an aqueous solution of dilute sulfuric acid from the viewpoint of recovery and reuse.
  • the catholyte electrolyte 106 and the catholyte reaction liquid can be circulated by the liquid feed pump 303 .
  • the mixed gas composed of ammonia produced in the cathode catalyst layer 103, by-produced hydrogen, and unreacted nitrogen in the electrolysis apparatus of the present embodiment is selected from ammonia by using water or a diluted sulfuric acid aqueous solution. Since the mixed gas of by-produced hydrogen and nitrogen can be taken out at the same time, hydrogen, which is useful as an energy carrier, can also be obtained in this embodiment. For safety, by-produced hydrogen can also be discharged to the outside through the draft device 126 . As in the present invention, ammonia can be efficiently produced from nitrogen molecules by providing hydrogen molecules by means of sending hydrogen gas generated at the cathode to the anode.
  • the electrolytic reaction in the anode catalyst layer 113 in the electrolytic device of this embodiment will be described.
  • a reaction occurs in which electrons and protons are generated from the supplied hydrogen by the catalyst of the anode 118, and the reaction formula can be described as “H 2 ⁇ 2e ⁇ +2H + ”.
  • the generated protons pass through the electrolyte membrane 102 or the electrolyte and move to the cathode 108 , and the electrons pass through the anode current collector 114 and move to the power supply device 101 .
  • this electrolysis device it is possible to supply electrons and protons by stopping the supply of hydrogen and supplying water to the anode catalyst layer 113 while paying attention to the hydrogen concentration and oxygen concentration.
  • a reaction occurs in which oxygen, electrons and protons are generated, and the reaction formula can be described as “2H 2 O ⁇ O 2 +4e ⁇ +4H + ”.
  • the generated protons pass through the electrolyte membrane 102 or the electrolyte and move to the cathode 108 , and the electrons pass through the anode current collector 114 and move to the power supply device 101 .
  • the generated oxygen can be partially dissolved in the water in the anode electrolyte bath 115 and released to the atmosphere.
  • Oxygen generated when water is supplied to the anode catalyst layer 113 can be partially dissolved in the anode electrolyte tank 115 or the water in the anode-side gas, electrolyte, and reaction liquid channels, but can be released to the atmosphere. It is also possible to stop the supply of water to the anode catalyst layer 113 and supply hydrogen again.
  • the electrolytic device (part 3) 300 and the electrolytic device (part 4) 400 the hydrogen gas in the hydrogen cylinder 127 and the hydrogen gas by-produced in the cathode 108 can be selectively used.
  • the anode catalyst layer 113 in the electrolytic device of this embodiment includes a catalyst carrier, an electrolyte and a gas diffusion layer in addition to the solid catalyst.
  • the anode catalyst layer 113 including the anode solid catalyst, catalyst carrier, electron conductor, electrolyte, and gas diffusion layer may be referred to as the gas diffusion electrode 133 .
  • anode solid catalyst which is the solid catalyst in the anode catalyst layer 113 of the electrolytic device of this embodiment.
  • the anode solid catalyst include those described in the solid catalyst and the cathode solid catalyst in the method for producing ammonia of the present embodiment. Specific examples include iridium (IV) oxide powder catalyst, oxidation Iridium catalyst, platinum catalyst, gold catalyst, silver catalyst, ruthenium catalyst, iridium catalyst, rhodium catalyst, palladium catalyst, osmium catalyst, tungsten catalyst, lead catalyst, iron catalyst, chromium catalyst, cobalt catalyst, nickel catalyst, manganese catalyst, vanadium catalyst , molybdenum catalysts, gallium catalysts, aluminum catalysts, and alloys thereof.
  • iridium (IV) oxide powder catalyst oxidation Iridium catalyst, platinum catalyst, gold catalyst, silver catalyst, ruthenium catalyst, iridium catalyst, rhodium catalyst, palladium catalyst, osmium catalyst, tungsten catalyst, lead catalyst, iron catalyst
  • the iridium (IV) oxide powder catalyst, the iridium oxide catalyst, and the platinum catalyst are preferable as the anode solid catalyst. Furthermore, from the viewpoint of being able to efficiently carry out an electrolytic reaction both when water is supplied to the anode catalyst layer 113 and when hydrogen gas is supplied, an iridium oxide catalyst and a platinum catalyst are combined to produce iridium (IV) oxide. It is also possible to use powder catalysts and platinum catalysts in combination.
  • the catalyst carrier in the anode catalyst layer 113 of the present embodiment may conduct electrons, and is not particularly limited as long as it supports the catalyst of the present embodiment.
  • catalyst carriers include carbon black, carbon materials, metal meshes, metal foams, metal oxides, composite oxides, and the like.
  • Examples of carbon black include channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC, and the like.
  • Examples of carbon materials include carbonizing and activating materials containing various carbon atoms. Treated activated carbon, coke, natural graphite, artificial graphite, graphitized carbon, and the like can be mentioned.
  • Metal meshes include metal meshes such as nickel or titanium.
  • Metal foams include, for example, aluminum, magnesium, titanium, Metal foams such as zinc, iron, tin, lead, or alloys containing these metal oxides include, for example, aluminum oxide, zirconium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, Cobalt oxide, nickel oxide, copper oxide, zinc oxide, niobium pentoxide, molybdenum oxide, ruthenium oxide, rhodium oxide, silver oxide, tantalum oxide, tungsten oxide, osmium oxide, iridium oxide, indium oxide, platinum oxide, gold oxide, oxide Magnesium, silica and the like can be mentioned, and examples of composite oxides include silica-alumina, silica-magnesia and the like.
  • carbon black, Ketjenblack, Ketjenblack EC, nickel metal mesh, titanium metal mesh, titanium oxide and metal foam are preferable as the catalyst carrier because of their high specific surface area and excellent electronic conductivity.
  • Metal mesh of titanium, titanium oxide and metal foam are more preferable because they are more durable.
  • the electrolyte in the anode catalyst layer 113 of this embodiment is not particularly limited as long as it is responsible for ion conduction. Examples thereof include the same as those described for the electrolyte in the cathode catalyst layer 103 of the present embodiment. Specific examples include Nafion (registered trademark) manufactured by DuPont, when a cation exchange membrane is used as the electrolyte membrane, Aquivion (registered trademark) from Solvay, Flemion (registered trademark) from AGC, Aciplex (registered trademark) from Asahi Kasei, and other fluorine-based sulfonic acid polymers, hydrocarbon-based sulfonic acid polymers, partially fluorine-introduced hydrocarbon-based sulfonic acid polymers and the like.
  • Nafion registered trademark
  • Aquivion registered trademark
  • Flemion registered trademark
  • Aciplex registered trademark
  • electrolyte may be mixed and used, and preferably contains a perfluoroacid polymer such as Nafion.
  • a perfluoroacid polymer such as Nafion.
  • an anion-exchange membrane is used as the electrolyte membrane, it preferably conducts hydroxide ions, and FAA-3-SOLUT-10 and AS-4 are preferred.
  • the gas diffusion layer in the anode catalyst layer 113 of this embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and electrolyte diffusion.
  • the same materials as those described in the gas diffusion layer in the cathode catalyst layer 103 of the present embodiment can be mentioned, and carbon paper is preferable.
  • Specific examples include TGP-H-060 and TGP-H- 090, TGP-H-120, TGP-H-060H, TGP-H-090H, TGP-H-120H, Electrochem EC-TP1-030T, EC-TP1-060T, EC-TP1-090T, EC- TP1-120T, SIGRACET 22BB, 28BC, 36BB, 39BB and the like.
  • TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H and EC-TP1-060T are preferable for the gas diffusion layer.
  • the cathode catalyst layer 103 which is a catalyst layer for producing ammonia, was prepared as follows.
  • the catalyst ink 1A used for the cathode 108 is an ink for applying the cathode solid catalyst of the present embodiment to the cathode catalyst layer 103 .
  • Carbon black-supported platinum catalyst manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 46.6% by weight, product name "TEC10E50E" as a solid catalyst, deionized water, ethanol and Nafion dispersion solution as an electrolyte (Fujifilm Wako Pure Chemical Industries, Ltd.
  • Catalyst Ink 1A was prepared using the product name "5% Nafion Dispersion Solution DE520 CS Type" manufactured by Nafion Corporation.
  • the platinum catalyst supported on carbon black may be abbreviated as the platinum catalyst supported on carbon.
  • Carbon-supported platinum catalyst, deionized water, ethanol and Nafion dispersion solution are added in this order to a glass vial bottle, and the resulting dispersion solution is treated with an ultrasonic homogenizer Smurt NR-50M manufactured by Microtech Nithion.
  • Catalyst Ink 1A was prepared by irradiating for 30 minutes with ultrasonic waves set at an output of 40%.
  • this catalyst ink 1A was applied to carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) fixed on a hop plate set at 80° C., and ethanol and water were dried. The coating amount was adjusted so that the amount of platinum per 1 cm 2 was 1.0 mg.
  • a gas diffusion electrode 133 Gas Diffusion Electrode, hereinafter sometimes abbreviated as "GDE" containing Nafion as an electrolyte and carbon-supported platinum catalyst as a solid catalyst was produced.
  • the gas diffusion electrode 133 is a square gas diffusion electrode 133 of 2.8 ⁇ 2.8 cm 2 coated with a platinum catalyst (7.8 mg), which is a solid catalyst.
  • GDE-Cathode-1A is a square gas diffusion electrode 133 of 2.8 ⁇ 2.8 cm 2 coated with a platinum catalyst (7.8 mg), which is a solid catalyst.
  • a catalyst ink 1B was prepared by applying the metal complex of the present embodiment to the cathode catalyst layer 103 .
  • a solution of rac-dimethylsilylbis(1-indenyl)zirconium dichloride (7.1 mg, 16 ⁇ mol) as a metal complex dissolved in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (2.4 mL) was used as a catalyst.
  • Ink 1B was used.
  • This catalyst ink 1B (20 ⁇ L) was applied to the “GDE-Cathode-1A” of the gas diffusion electrode 133 to prepare the cathode catalyst layer 103 .
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, is coated with platinum catalyst (7.8 mg), which is a solid catalyst, and rac-dimethylsilylbis(1-indenyl)zirconium dichloride (0.13 ⁇ mol).
  • the gas diffusion electrode 133 which is a square of 2.8 ⁇ 2.8 cm 2 , was designated as “GDE-Cathode-1”.
  • ionomer The proportion of Nafion (hereinafter abbreviated as ionomer) in the above catalyst ink 1A will be described.
  • Catalyst ink 1A was prepared so that the proportion (% by weight) of ionomer calculated from the following formula was 28% by weight.
  • Proportion of ionomer (% by weight) [Ionomer solid content (weight) / [ ⁇ carbon-supported platinum catalyst (weight) + ionomer solid content (weight) ⁇ ] ⁇ 100
  • the amount of carbon-supported platinum catalyst was set at 100.0 mg
  • the amount of Nafion dispersed solution was set at 837 ⁇ L
  • the amount of deionized water was set at 0.6 mL
  • the amount of ethanol was set at 5 mL.
  • the Nafion solid content in the Nafion dispersion solution (837 ⁇ L) was 38.9 mg.
  • the anode catalyst layer 113 was produced as follows. By preparing the catalyst ink 1A described in the cathode catalyst layer 103 by the same method and applying it by the same method, the anode catalyst layer 113 containing Nafion as an electrolyte and a carbon-supported platinum catalyst as a solid catalyst, gas diffusion An electrode 133 was produced. Specifically, the gas diffusion electrode 133, which is the anode catalyst layer 113, is a 2.8 ⁇ 2.8 cm 2 square gas diffusion electrode 133 coated with a platinum catalyst (7.8 mg), which is a solid catalyst. , which was named "GDE-Anode-1".
  • a membrane electrode assembly (hereinafter sometimes abbreviated as “MEA”) consisting of the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-1" of the gas diffusion electrode 133 which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane, and the "GDE-Anode-1" of the gas diffusion electrode 133, which is the anode catalyst layer, is arranged on the other side of the ion exchange membrane. ' was arranged, and thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 240 seconds to fabricate a membrane electrode assembly "MEA-1".
  • Ammonia was manufactured by electrolysis under the following conditions using the electrolytic apparatus (No. 1) assembled as described above for producing ammonia.
  • Device temperature 25-28°C (room temperature)
  • Power supply 101 Versa STAT4 manufactured by Princeton Applied Research was used to measure voltage and current.
  • Cathode electrolyte bath 105 10 mL/min of nitrogen was passed through an aqueous sulfuric acid solution (0.02 mol/L, 6 mL) by bubbling.
  • Anode electrolyte bath 115 Hydrogen gas flowed at 5 mL/min.
  • Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia sulfuric acid aqueous solution (0.02 mol/L, 10 mL)
  • Electrolysis conditions constant potential electrolysis was performed at -2.3 V for 1 hour.
  • Ammonia was quantified using Thermo Scientific Dionex ion chromatography (IC) system, Dionex Integrion manufactured by Thermo.
  • IC Dionex ion chromatography
  • the sulfuric acid aqueous solution in the dilute sulfuric acid aqueous solution tank 125 for ammonia collection and the sulfuric acid aqueous solution in the cathode electrolyte tank 105 were recovered, and the amount of ammonia was quantified to obtain the amount of ammonia production.
  • the amount of ammonia produced in this example was 1.21 ( ⁇ mol).
  • Example 2 Preparation of Electrolytic Device for Producing Ammonia
  • the cathode catalyst layer 103 was prepared as follows.
  • the catalyst ink 2A used for the cathode 108 is an ink for applying the cathode solid catalyst of this embodiment to the cathode catalyst layer 103 .
  • Carbon black-supported platinum catalyst manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 46.5% by weight, product name "TEC10E50E" as a solid catalyst
  • 2-propanol manufactured by Junsei Chemical Co., Ltd.
  • Nafion dispersion solution Nafion dispersion solution
  • Catalyst ink 2A was prepared by setting and irradiating ultrasonic waves for 30 minutes. The proportion of Nafion (hereinafter abbreviated as ionomer) in the above catalyst ink 2A will be described. Catalyst ink 2A was prepared so that the proportion (% by weight) of ionomer calculated from the above formula was 28% by weight.
  • the amount of carbon-supported platinum catalyst was 100 mg
  • the amount of Nafion dispersion was 837 ⁇ L (the amount of Nafion solids in the dispersion was 38.9 mg)
  • the amount of 2-propanol was 2.5 mL.
  • Application of the catalyst ink 2A was performed by the following operation. Carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) was attached to a fixture so that the surface to be coated could be set to a square of 6.8 cm ⁇ 6.8 cm, and an applicator was used.
  • the entire amount of prepared catalyst ink 2A is used for coating, and the solvent and 2-propanol in the Nafion dispersion solution are dried to obtain a gas diffusion electrode 133 with a platinum amount of 1 mg per 1 cm 2 of the coated surface. made.
  • the gas diffusion electrode 133 is a square gas diffusion electrode 133 of 2.8 ⁇ 2.8 cm 2 coated with a platinum catalyst (7.8 mg), which is a solid catalyst.
  • GDE-Cathode-2A ”.
  • a catalyst ink 2B for applying the metal complex of this embodiment to the cathode catalyst layer 103 was prepared.
  • rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (6.8 mg, 16 ⁇ mol) was converted to 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (2 .4 mL) was used as catalyst ink 2B.
  • This catalyst ink 2B (20 ⁇ L) was applied to the “GDE-Cathode-2A” of the gas diffusion electrode 133 to prepare the cathode catalyst layer 103 .
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, is composed of a platinum catalyst (7.8 mg), which is a solid catalyst, and rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)
  • a 2.8 ⁇ 2.8 cm 2 square gas diffusion electrode 133 coated with zirconium dichloride (0.13 ⁇ mol) was designated as “GDE-Cathode-2”.
  • the anode catalyst layer 113 was produced as follows. By preparing the catalyst ink 2A described in the cathode catalyst layer 103 by the same method and applying it by the same method, the anode catalyst layer 113 containing Nafion as an electrolyte and a carbon-supported platinum catalyst as a solid catalyst, gas diffusion An electrode 133 was produced. Specifically, the gas diffusion electrode 133, which is the anode catalyst layer 113, is a 2.8 ⁇ 2.8 cm 2 square gas diffusion electrode 133 coated with a platinum catalyst (7.8 mg), which is a solid catalyst. , which was named "GDE-Anode-2".
  • a membrane electrode assembly comprising the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-2" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-2" of the gas diffusion electrode 133, which is the anode catalyst layer is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 240 seconds to fabricate a membrane electrode assembly "MEA-2".
  • a platinum-plated titanium separator 214 was attached to the anode-side surface of the obtained "MEA-2", and a carbon separator 204 was attached to the cathode-side surface together with a Teflon (registered trademark) sheet as a gasket 134, followed by gold-plating.
  • the current collectors 104 and 114 were attached while sandwiched from both sides, and the electrolytic device (part 2) 200 shown in FIG. 2 was assembled.
  • the separator has channels 135 and 136 through which gas, electrolyte, reaction solution, etc. flow.
  • An aqueous sulfuric acid solution (0.02 mol/L, 6 mL) is added through a liquid feed pump 303 to the aqueous sulfuric acid solution of the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and to the flow path 136 for the cathode-side gas, electrolytic solution, and reaction solution, An aqueous solution of sulfuric acid was recovered from the cathode through the pipe 121 into the electrolytic solution and reaction solution recovery tank 201 on the cathode side.
  • the amount of ammonia produced in this example was 2.02 ( ⁇ mol).
  • Example 1 The same electrolytic device (part 1) as in Example 1 was produced, and the same as in Example 1 described above except that hydrogen was not supplied to the anode electrolyte tank and the anode catalyst layer, and water (6 mL) was added. Experimental operation was performed. As a result of this example, the amount of ammonia produced was 0.32 ( ⁇ mol).
  • Example 3 Preparation of Electrolyzer for Producing Ammonia
  • GDE-Cathode-1 and “GDE-Anode-1” were prepared.
  • Electrode (Part 3) An "MEA" consisting of the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-1" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-1" of the gas diffusion electrode 133, which is the anode catalyst layer is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 240 seconds to fabricate a membrane electrode assembly "MEA-1".
  • Anode electrolyte bath 115 Hydrogen gas generated at the cathode was connected by a pipe 305 and sent to the anode. No anolyte 116 was used.
  • Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia sulfuric acid aqueous solution (0.02 mol/L, 10 mL)
  • Electrolysis conditions constant potential electrolysis was performed at -2.0 V for 1 hour.
  • the amount of ammonia was quantified by the method described in Example 1.
  • the amount of ammonia produced in this example was 0.94 ( ⁇ mol).
  • Example 4 Preparation of Electrolyzer for Producing Ammonia “GDE-Cathode-2” and “GDE-Anode-2”, which are the same gas diffusion electrodes as in Example 2, were prepared.
  • a membrane electrode assembly comprising the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-2" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-2" of the gas diffusion electrode 133, which is the anode catalyst layer is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 240 seconds to fabricate a membrane electrode assembly "MEA-2".
  • a platinum-plated titanium separator 214 was attached to the anode-side surface of the obtained "MEA-2", and a carbon separator 204 was attached to the cathode-side surface together with a Teflon (registered trademark) sheet as a gasket 134, followed by gold-plating.
  • the current collectors 104 and 114 were attached while being sandwiched from both sides, and the electrolytic device (part 4) 400 shown in FIG. 4 was assembled.
  • the separator has channels 135 and 136 through which gas, electrolyte, reaction solution, etc. flow.
  • the amount of ammonia was quantified by the method described in Example 2.
  • the amount of ammonia produced in this example was 1.31 ( ⁇ mol).
  • Example 2 The same electrolytic device (3) as in Example 3 was produced, and the same as in Example 3 described above except that hydrogen was not supplied to the anode electrolyte tank and the anode catalyst layer, and water (6 mL) was added. Experimental operation was performed. As a result of this example, the amount of ammonia produced was 0.27 ( ⁇ mol).
  • Example 5 Preparation of Electrolyzer for Producing Ammonia “GDE-Cathode-2A” and “GDE-Anode-2”, which are the same gas diffusion electrodes as in Example 2, were prepared.
  • a catalyst ink 5B for applying the metal complex of this embodiment to the cathode catalyst layer 103 was prepared.
  • a solution of bis(cyclopentadienyl)titanium (IV) dichloride (4.0 mg, 16 ⁇ mol) as a metal complex dissolved in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (2.4 mL) was used as a catalyst.
  • Ink 5B was used.
  • This catalyst ink 5B (20 ⁇ L) was applied to the “GDE-Cathode-2A” of the gas diffusion electrode 133 to prepare the cathode catalyst layer 103 .
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, is coated with platinum catalyst (7.8 mg), which is a solid catalyst, and bis(cyclopentadienyl)titanium (IV) dichloride (0.13 ⁇ mol).
  • the gas diffusion electrode 133 which is a square of 2.8 ⁇ 2.8 cm 2 , was designated as “GDE-Cathode-5”.
  • Electrode (Part 3) An "MEA" consisting of the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-5" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-2" of the gas diffusion electrode 133 which is the anode catalyst layer, is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 360 seconds to fabricate a membrane electrode assembly "MEA-5".
  • Anode electrolyte bath 115 Hydrogen gas generated at the cathode was connected by a pipe 305 and sent to the anode. A sulfuric acid aqueous solution (0.02 mol/L, 6 mL) was used as the anode electrolyte 116, and hydrogen gas generated at the cathode was bubbled together with nitrogen. Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia: sulfuric acid aqueous solution (0.02 mol/L, 10 mL) Electrolysis conditions: constant potential electrolysis was performed at -2.3 V for 1 hour.
  • the amount of ammonia was quantified by the method described in Example 1.
  • the amount of ammonia produced in this example was 1.43 ( ⁇ mol).
  • Example 6 Preparation of Electrolyzer for Producing Ammonia “GDE-Cathode-5”, which is the same gas diffusion electrode as in Example 5, and “GDE-Anode-2”, which is the same gas diffusion electrode as in Example 2, were prepared.
  • a membrane electrode assembly comprising the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-5" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-2" of the gas diffusion electrode 133 which is the anode catalyst layer, is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 360 seconds to fabricate a membrane electrode assembly "MEA-6".
  • Cathode electrolyte bath 105 An operation of bubbling 10 mL/min of nitrogen into an aqueous sulfuric acid solution (0.02 mol/L, 6 mL) was performed for 8 minutes, and after 30 seconds had elapsed after closing the two-way cock 308, the two-way After 1 minute and 30 seconds had passed since the cock 309 was closed, the operation of bubbling nitrogen again was repeated 6 times during 1 hour.
  • Anode electrolyte tank 115 The operation of flowing hydrogen gas at 3 mL/min was performed for 8 minutes, the two-way cock 308 was closed, and after 30 seconds had passed, the two-way cock 309 was closed and after 1 minute and 30 seconds, again. of hydrogen was repeated six times during one hour.
  • Electrolysis conditions constant potential electrolysis was performed at -2.3 V for 1 hour.
  • the amount of ammonia was quantified by the method described in Example 1.
  • the amount of ammonia produced in this example was 1.95 ( ⁇ mol).
  • Example 7 Preparation of Electrolyzer for Producing Ammonia “GDE-Cathode-5”, which is the same gas diffusion electrode as in Example 5, and “GDE-Anode-2”, which is the same gas diffusion electrode as in Example 2, were prepared.
  • a membrane electrode assembly comprising the electrolyte membrane 102, the cathode catalyst layer 103 and the anode catalyst layer 113 was produced as follows.
  • the ion-exchange membrane used for the electrolyte membrane 102 was Nafion 212 membrane (registered trademark) manufactured by DuPont (film thickness: 50 ⁇ m, 5 cm ⁇ 5 cm).
  • the "GDE-Cathode-5" of the gas diffusion electrode 133, which is the cathode catalyst layer, is arranged on one side of the ion exchange membrane
  • the "GDE-Anode-2" of the gas diffusion electrode 133 which is the anode catalyst layer, is arranged on the other side of the ion exchange membrane.
  • thermocompression bonding was performed under the conditions of a top and bottom plate temperature of 132° C., a load of 5.4 kN, and a compression bonding time of 240 seconds to fabricate a membrane electrode assembly "MEA-7".
  • a platinum-plated titanium separator 214 was attached to the anode-side surface of the obtained "MEA-7", and a carbon separator 204 was attached to the cathode-side surface together with a Teflon (registered trademark) sheet as a gasket 134, followed by gold-plating.
  • the current collectors 104 and 114 were attached while being sandwiched from both sides, and the electrolytic device (part 4) 400 shown in FIG. 4 was assembled.
  • the separator has channels 135 and 136 through which gas, electrolyte, reaction solution, etc. flow.
  • Device body temperature 80°C Power supply 101: Versa STAT4 manufactured by Princeton Applied Research was used to measure voltage and current.
  • Cathode catalyst layer 103 An operation of flowing humidified nitrogen (relative humidity 95%) at 10 mL/min was performed for 8 minutes, and the two three-way cocks 302 of the cathode catalyst layer were closed to pressurize. of humidified nitrogen was repeated six times during one hour.
  • Anode catalyst layer 113 The hydrogen gas generated at the cathode is sent to the anode via the pipe 305 for 8 minutes, and the two three-way cocks 302 of the anode catalyst layer are closed to pressurize, and then 2 minutes have passed.
  • Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia sulfuric acid aqueous solution (0.02 mol/L, 10 mL)
  • Electrolysis conditions constant potential electrolysis was performed at -2.3 V for 1 hour.
  • the amount of ammonia was quantified by the method described in Example 2.
  • the amount of ammonia produced in this example was 1.57 ( ⁇ mol).
  • Example 8 Fabrication of Electrolyzer for Producing Ammonia The same electrolyzer for producing ammonia as in Example 7 was fabricated.
  • ammonia was produced by electrolysis under the following conditions.
  • the cocks are closed to separate the cathode catalyst layer and the anode catalyst layer from each other.
  • the operation of pressurizing with the reaction gas and the electrolytic solution was repeated.
  • Device body temperature 80°C Power supply 101: Versa STAT4 manufactured by Princeton Applied Research was used to measure voltage and current.
  • Cathode catalyst layer 103 An operation of flowing humidified nitrogen (95% relative humidity) at 50 mL/min was performed for 9 minutes and 30 seconds. After that, the operation of flowing humidified nitrogen again was repeated 6 times during 1 hour.
  • Anode catalyst layer 113 The hydrogen gas generated at the cathode is sent to the anode via the pipe 305 for 9 minutes and 30 seconds. After a second had passed, the operation of supplying hydrogen gas generated at the cathode was repeated six times during one hour.
  • Dilute sulfuric acid aqueous solution tank 125 for collecting ammonia sulfuric acid aqueous solution (0.02 mol/L, 10 mL)
  • Electrolysis conditions constant potential electrolysis was performed at -2.3 V for 1 hour.
  • the amount of ammonia was quantified by the method described in Example 2.
  • the amount of ammonia produced in this example was 1.88 ( ⁇ mol).
  • the present invention can be used for a method for producing ammonia.
  • Ammonia Electrolyzer (Part 1) 200 Ammonia Electrolyzer (Part 2) 300 Ammonia Electrolyzer (Part 3) 400 Ammonia Electrolyzer (Part 4) 500 Ammonia Electrolyzer (Part 5) 101 power supply device 102 electrolyte membrane 103 cathode catalyst layer (catalyst layer for producing ammonia) 104 cathode current collector 105 cathode electrolyte bath 106 cathode electrolyte 108 cathode (cathode catalyst layer and cathode current collector) 113 anode catalyst layer 114 anode current collector 115 anode electrolyte bath 116 anode electrolyte 118 anode (anode catalyst layer or anode current collector) 121 Piping 122 Nitrogen cylinder 123 Nitrogen cylinder regulator 124 Nitrogen gas mass flow controller 125 Dilute sulfuric acid aqueous solution tank for collecting ammonia 126 Draft device 127 Hydrogen cylinder 128 Hydrogen cylinder regulator 129 Hydrogen gas mass flow controller 130

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024185808A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造装置
WO2024185807A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造方法
JP2025043917A (ja) * 2023-09-19 2025-04-01 株式会社東芝 電解装置
WO2025084328A1 (ja) * 2023-10-16 2025-04-24 出光興産株式会社 アンモニア製造装置
WO2025084329A1 (ja) * 2023-10-16 2025-04-24 出光興産株式会社 アンモニア製造装置
EP4617403A1 (en) * 2024-03-11 2025-09-17 Kabushiki Kaisha Toshiba Electrolysis device and electrolysis method
WO2025225524A1 (ja) * 2024-04-26 2025-10-30 Ｅｎｅｏｓ株式会社 有機ハイドライド製造装置、有機ハイドライド製造システム及び移行水の再利用方法
EP4733441A1 (en) * 2024-10-28 2026-04-29 National Taiwan University of Science and Technology Ammonia production method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2023264575A1 (en) * 2022-05-06 2024-12-05 Ohmium International, Inc. Systems and methods for hydrogen and ammonia production

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014040336A (ja) * 2012-08-21 2014-03-06 Nagoya Institute Of Technology アンモニア製造方法およびアンモニア製造装置
CN203741430U (zh) * 2014-03-25 2014-07-30 内蒙古科技大学 低温常压电催化还原氮气合成氨的装置
JP2020528109A (ja) * 2017-07-27 2020-09-17 モナシュ ユニバーシティ 二窒素の変換のための方法、セルおよび電解質

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014040336A (ja) * 2012-08-21 2014-03-06 Nagoya Institute Of Technology アンモニア製造方法およびアンモニア製造装置
CN203741430U (zh) * 2014-03-25 2014-07-30 内蒙古科技大学 低温常压电催化还原氮气合成氨的装置
JP2020528109A (ja) * 2017-07-27 2020-09-17 モナシュ ユニバーシティ 二窒素の変換のための方法、セルおよび電解質

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JEONG EUN-YOUNG, YOO CHUNG-YUL, JUNG CHAN HEE, PARK JONG HYUN, PARK YOUNG CHOON, KIM JONG-NAM, OH SEONG-GEUN, WOO YOUNGMIN, YOON H: "Electrochemical Ammonia Synthesis Mediated by Titanocene Dichloride in Aqueous Electrolytes under Ambient Conditions", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, AMERICAN CHEMICAL SOCIETY, US, vol. 5, no. 11, 6 November 2017 (2017-11-06), US , pages 9662 - 9666, XP093071266, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.7b02908 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024185808A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造装置
WO2024185807A1 (ja) * 2023-03-07 2024-09-12 国立研究開発法人産業技術総合研究所 アンモニア製造方法
JP2025043917A (ja) * 2023-09-19 2025-04-01 株式会社東芝 電解装置
WO2025084328A1 (ja) * 2023-10-16 2025-04-24 出光興産株式会社 アンモニア製造装置
WO2025084329A1 (ja) * 2023-10-16 2025-04-24 出光興産株式会社 アンモニア製造装置
EP4617403A1 (en) * 2024-03-11 2025-09-17 Kabushiki Kaisha Toshiba Electrolysis device and electrolysis method
WO2025225524A1 (ja) * 2024-04-26 2025-10-30 Ｅｎｅｏｓ株式会社 有機ハイドライド製造装置、有機ハイドライド製造システム及び移行水の再利用方法
EP4733441A1 (en) * 2024-10-28 2026-04-29 National Taiwan University of Science and Technology Ammonia production method

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