WO2022034927A1 - 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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WO2022034927A1
WO2022034927A1 PCT/JP2021/029955 JP2021029955W WO2022034927A1 WO 2022034927 A1 WO2022034927 A1 WO 2022034927A1 JP 2021029955 W JP2021029955 W JP 2021029955W WO 2022034927 A1 WO2022034927 A1 WO 2022034927A1
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cathode
catalyst
anode
formula
molybdenum complex
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French (fr)
Japanese (ja)
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仁昭 西林
和也 荒芝
裕也 芦田
章一 近藤
隆正 菊池
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Nissan Chemical Corp
University of Tokyo NUC
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Nissan Chemical Corp
University of Tokyo NUC
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Priority to US18/021,336 priority Critical patent/US20230295818A1/en
Priority to JP2022542886A priority patent/JP7788699B2/ja
Publication of WO2022034927A1 publication Critical patent/WO2022034927A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • C01C1/0494—Preparation of ammonia by synthesis using plasma or electric discharge
    • C—CHEMISTRY; METALLURGY
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
    • C—CHEMISTRY; METALLURGY
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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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    • C25B11/051—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
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing ammonia and a production apparatus.
  • Non-Patent Document 1 In the method of electrolyzing ammonia from nitrogen molecules in the low temperature range, there is a report example in which ammonia was produced by electrolysis at 90 ° C. using a platinum electrode as an anode on a cathode carrying ruthenium on carbon felt. Yes (Non-Patent Document 1). There is a report example in which ammonia is produced by electrolysis using Sm 1.5 Sr 0.5 CoO 4 or the like for an electrode that generates ammonia (Non-Patent Document 2).
  • Non-Patent Documents when a molybdenum complex is used as a catalyst in a reaction for producing ammonia from nitrogen molecules, there is a report example in which samarium (II) iodide is used as a reducing agent and alcohols or water are used as a proton source (Non-Patent Documents). 3). It has been reported that ammonia was produced using a molybdenum complex supported on a polystyrene resin (Non-Patent Document 4).
  • Non-Patent Document 1 operates at a low temperature range of about 90 to 100 ° C. Therefore, it has been a problem to operate at a room temperature of around 20 to 30 ° C.
  • Non-Patent Document 2 has a problem that there is a complicated step of treating the membrane with ammonia before incorporating the Nafion membrane used as the electrolyte membrane into the electrolytic apparatus, and it is not easy from the viewpoint of reuse of the electrolytic apparatus.
  • Non-Patent Document 3 requires the use of samarium (II) iodide as a reducing agent
  • Non-Patent Document 4 requires the use of decamethylcobaltocene as the reducing agent. The problem was that it was not easy to collect and recycle.
  • the present invention has been made to solve the above-mentioned problems, and does not use a reducing agent, avoids pretreatment of the electrolyte membrane, and electrochemically ammonia operates at room temperature of about 20 to 30 ° C.
  • the main purpose is the method of manufacturing.
  • Non-Patent Documents 1 and 2 are examples of electrochemical ammonia production using a solid catalyst, and electrochemically used by producing a membrane electrode assembly or a gas diffusion electrode by combining a complex and a solid catalyst. There are no reports of ammonia production.
  • the present invention based on these findings is, for example, as follows.
  • nitrogen is supplied by supplying electrons from a power source, protons from a proton source, and nitrogen molecules from a means for supplying nitrogen gas in the presence of a complex and a solid catalyst at the cathode.
  • the complex is (A) 2,6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the pyridine ring is an alkyl group or an alkoxy group.
  • a molybdenum complex having may be substituted with an alkoxy group or a halogen atom
  • C A molybdenum complex having a bis (dialkylphosphinoethyl) arylphosphine (where the two alkyl groups may be the same or different) as a PPP ligand, or
  • D trans-Mo (N 2 ) 2 (R 5 R 6 R 7 P) 4 (However, R 5 and R 6 are aryl groups which may be the same or different, and R 7 is an alkyl group. The two R7s may be connected to each other to form an alkylene chain), which is a molybdenum complex.
  • the solid catalyst is a metal catalyst, an oxide catalyst, or a combination thereof.
  • the proton source is an electrolyte membrane, an electrolytic solution, or both an electrolyte membrane and an electrolytic solution. Ammonia production method.
  • the molybdenum complex of the above (A) has the following formula (A1), (A2) or (A3).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl group.
  • the molybdenum complex of the above (B) has the following formula (B1) or (B2).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group.
  • the molybdenum complex of the above (C) has the formula (C1).
  • R 1 and R 2 are alkyl groups which may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom).
  • the molybdenum complex of the above (D) has the formula (D1) or (D2).
  • a membrane electrode assembly in which an electrolyte membrane is sandwiched and bonded between a cathode catalyst layer and an anode catalyst layer.
  • the cathode catalyst layer contains a complex and a cathode solid catalyst.
  • the anode catalyst layer contains an anode solid catalyst and contains.
  • the complex is (A) 2,6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the pyridine ring is an alkyl group or an alkoxy group. Or a molybdenum complex, which may be substituted with a halogen atom), (B) N, N-bis (dialkylphosphinomethyl) dihydrobenzoimidazolidene as a PCP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the benzene ring is an alkyl group.
  • a molybdenum complex having may be substituted with an alkoxy group or a halogen atom
  • C A molybdenum complex having a bis (dialkylphosphinoethyl) arylphosphine (where the two alkyl groups may be the same or different) as a PPP ligand, or
  • D trans-Mo (N 2 ) 2 (R 5 R 6 R 7 P) 4 (However, R 5 and R 6 are aryl groups which may be the same or different, and R 7 is an alkyl group. The two R7s may be connected to each other to form an alkylene chain), which is a molybdenum complex.
  • the cathode solid catalyst and the anode solid catalyst are a metal catalyst, an oxide catalyst, or a membrane electrode assembly which is a combination thereof.
  • the molybdenum complex of the above (A) has the following formula (A1), (A2) or (A3).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl group.
  • the molybdenum complex of the above (B) has the following formula (B1) or (B2).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group. , May be substituted with an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group), which is a molybdenum complex represented by [7]. Joined body.
  • the molybdenum complex of the above (C) has the formula (C1).
  • R 1 and R 2 are alkyl groups which may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom).
  • the molybdenum complex of the above (D) has the formula (D1) or (D2).
  • a molybdenum complex represented by (in the formula, R 5 and R 6 are aryl groups which may be the same or different, R 7 is an alkyl group and n is 2 or 3).
  • a membrane electrode assembly composed of the cathode catalyst layer, the electrolyte membrane and the anode catalyst layer according to any one of [7] to [12] is provided.
  • the cathode has a structure in which a cathode catalyst layer is bonded to one side of the electrolyte membrane and a cathode current collector is arranged on the outside thereof, and the anode has an anode catalyst layer bonded to the other side of the electrolyte membrane and the anode thereof. It is a configuration in which the anode current collector is arranged on the outside.
  • the cathode comprises a cathode catalyst layer and a cathode current collector.
  • the anode comprises an anode catalyst layer and an anode current collector.
  • a cathode electrolyte tank that comes into liquid contact with the cathode is provided. It is provided with an anode electrolyte tank that makes liquid contact with the anode. It is equipped with a power supply that supplies electrons to the cathode. It is equipped with a proton source that supplies protons to the cathode.
  • a means for supplying nitrogen gas to the cathode electrolyte or the cathode is provided.
  • the proton source is an electrolyte membrane, an anode electrolyte, or both an electrolyte membrane and an anode electrolyte.
  • Ammonia production equipment that produces ammonia from nitrogen molecules by electrolysis.
  • a membrane electrode assembly composed of the cathode catalyst layer, the electrolyte membrane and the anode catalyst layer according to any one of [7] to [12] is provided.
  • the cathode has a structure in which a cathode catalyst layer is bonded to one side of the electrolyte membrane and a cathode current collector is arranged on the outside thereof, and the anode has an anode catalyst layer bonded to the other side of the electrolyte membrane and the anode thereof.
  • the cathode comprises a cathode catalyst layer and a cathode current collector.
  • the anode comprises an anode catalyst layer and an anode current collector.
  • An anode electrolytic solution tank for an anode electrolytic solution that comes into liquid contact with the anode of the membrane electrode assembly is provided. It is equipped with a power supply that supplies electrons to the cathode. It is equipped with a proton source that supplies protons to the cathode. A means for supplying nitrogen gas to the cathode is provided.
  • the proton source is an electrolyte membrane, an electrolytic solution, or both an electrolyte membrane and an electrolytic solution.
  • the complex is (A) 2,6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the pyridine ring is an alkyl group or an alkoxy group.
  • a molybdenum complex having may be substituted with an alkoxy group or a halogen atom
  • C A molybdenum complex having a bis (dialkylphosphinoethyl) arylphosphine (where the two alkyl groups may be the same or different) as a PPP ligand, or
  • D trans-Mo (N 2 ) 2 (R 5 R 6 R 7 P) 4 (However, R 5 and R 6 are aryl groups which may be the same or different, and R 7 is an alkyl group.
  • the two R7s may be connected to each other to form an alkylene chain), and the cathode solid catalyst is a metal catalyst, an oxide catalyst, or a gas diffusion electrode which is a combination thereof.
  • the molybdenum complex of the above (A) has the following formula (A1), (A2) or (A3).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl group.
  • the molybdenum complex of the above (B) has the following formula (B1) or (B2).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group.
  • the molybdenum complex of the above (C) has the formula (C1).
  • R 1 and R 2 are alkyl groups which may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom).
  • the molybdenum complex of the above (D) has the formula (D1) or (D2).
  • a molybdenum complex represented by (in the formula, R 5 and R 6 are aryl groups which may be the same or different, R 7 is an alkyl group and n is 2 or 3).
  • the gas diffusion electrode which is the cathode catalyst layer according to any one of [15] to [20] is provided.
  • a cathode current collector is arranged on one side of the cathode catalyst layer, which is the gas diffusion electrode, and a tank of an electrolytic solution that comes into liquid contact with the cathode catalyst layer is provided.
  • the cathode comprises a cathode catalyst layer and a cathode current collector.
  • the anode is a metal plate electrode, It is equipped with a power supply that supplies electrons to the cathode. It is equipped with a proton source that supplies protons to the cathode.
  • a means for supplying nitrogen gas to the electrolytic solution or the cathode is provided.
  • the proton source is an electrolytic solution. Ammonia production equipment that produces ammonia from nitrogen molecules by electrolysis.
  • a cathode membrane electrode assembly in which a cathode catalyst layer is bonded to one side of an electrolyte membrane.
  • the cathode catalyst layer contains a complex and a cathode solid catalyst.
  • the complex is (A) 2,6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the pyridine ring is an alkyl group or an alkoxy group. Or a molybdenum complex, which may be substituted with a halogen atom), (B) N, N-bis (dialkylphosphinomethyl) dihydrobenzoimidazolidene as a PCP ligand (however, the two alkyl groups may be the same or different, and at least one hydrogen atom of the benzene ring is an alkyl group.
  • a molybdenum complex having may be substituted with an alkoxy group or a halogen atom
  • C A molybdenum complex having a bis (dialkylphosphinoethyl) arylphosphine (where the two alkyl groups may be the same or different) as a PPP ligand, or
  • D trans-Mo (N 2 ) 2 (R 5 R 6 R 7 P) 4 (However, R 5 and R 6 are aryl groups which may be the same or different, and R 7 is an alkyl group. The two R7s may be connected to each other to form an alkylene chain), which is a molybdenum complex.
  • the cathode solid catalyst is a metal catalyst, an oxide catalyst, or a cathode membrane electrode assembly that is a combination of two or more of these.
  • the molybdenum complex of the above (A) has the following formula (A1), (A2) or (A3).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl group.
  • the molybdenum complex of the above (B) has the following formula (B1) or (B2).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the benzene ring is an alkyl group. , May be substituted with an alkoxy group or a halogen atom, and at least one of R 3 and R 4 is substituted with a trifluoromethyl group), which is a molybdenum complex represented by [22]. Electrode junction.
  • the molybdenum complex of the above (C) has the formula (C1).
  • R 1 and R 2 are alkyl groups which may be the same or different, R 5 is an aryl group, and X is an iodine atom, a bromine atom or a chlorine atom).
  • the cathode membrane electrode assembly according to [22] which is a molybdenum complex.
  • the molybdenum complex of the above (D) has the formula (D1) or (D2).
  • a molybdenum complex represented by (in the formula, R 5 and R 6 are aryl groups which may be the same or different, R 7 is an alkyl group and n is 2 or 3).
  • the cathode membrane electrode assembly according to any one of [22] to [26], wherein the cathode solid catalyst contains platinum, gold, palladium, or zinc oxide.
  • a cathode membrane electrode assembly in which a cathode catalyst layer is bonded to one side of the electrolyte membrane according to any one of [22] to [27] is provided.
  • a cathode current collector is arranged on the side opposite to the electrolyte membrane of the cathode catalyst layer.
  • the cathode comprises a cathode catalyst layer and a cathode current collector.
  • the anode is a metal plate electrode, It is equipped with a power supply that supplies electrons to the cathode. It is equipped with a proton source that supplies protons to the cathode.
  • a means for supplying nitrogen gas to the electrolytic solution or the cathode is provided.
  • the proton source is an electrolyte membrane, an electrolytic solution, or both an electrolyte membrane and an electrolytic solution. Ammonia production equipment that produces ammonia from nitrogen molecules by electrolysis.
  • ammonia in the production apparatus for electrolysis, in the presence of a complex and a solid catalyst at the cathode, electrons from a power source, protons from a proton source, and nitrogen from a means for supplying nitrogen gas.
  • Ammonia can be produced from nitrogen molecules by donating the molecules.
  • n stands for normal
  • s stands for secondary
  • t stands for tertiary
  • o stands for ortho
  • m stands for meta
  • p stands for para.
  • the notation of the C a to C b alkyl group in the present specification is a monovalent value generated by the loss of one hydrogen atom from a linear, branched or cyclic aliphatic hydrocarbon having a to b carbon atoms.
  • C a to C b alkoxy group represents a monovalent group in which an alkyl group having the above-mentioned meaning of a to b carbon atoms is bonded to oxygen, for example, a methoxy group.
  • halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the notation of the Ar 6 aryl group in the present specification represents a monovalent group generated by the loss of one hydrogen atom from the aromatic ring of an aromatic hydrocarbon having 6 carbon atoms, for example, from the phenyl group and the 2-position.
  • Examples thereof include a phenyl group having a substituent at at least one of the 6-positions.
  • the substituents on the aromatic ring of Ar 6aryl include fluoro groups, chloro groups, bromo groups and iodo groups, which are halogen atoms, as well as methyl groups, trifluoromethyl groups, ethyl groups, n-propyl groups and isopropyl groups.
  • Examples thereof include an n-butyl group, an isobutyl group, an s-butyl group and a t-butyl group.
  • Specific examples of the Ar 6 aryl group include a phenyl group, an o-fluorophenyl group, an m-fluorophenyl group, a p-fluorophenyl group, an o-trifluoromethylphenyl group, an m-trifluoromethylphenyl group, and a p-tri.
  • the method for producing ammonia of the present embodiment can be carried out by a production apparatus that performs electrolysis.
  • the manufacturing apparatus for performing electrolysis may be referred to as an electrolyzer, which is composed of an electrolytic cell, a nitrogen gas supply means, an ammonia recovery means, and an exhaust gas exclusion means, and the details of the electrolysis device will be described later.
  • the electrolytic cell is composed of an electrode, an electrolytic cell, a nitrogen gas supply port, and an exhaust gas outlet.
  • the electrode on which the oxidation reaction occurs is the anode
  • the electrode on which the reduction reaction occurs is the cathode.
  • the method for producing ammonia of the present embodiment is to supply electrons from a power source, protons from a proton source arranged in an electrolytic apparatus, and nitrogen gas in the presence of a complex represented by a molybdenum complex or the like at the cathode and a solid catalyst. It is a method of producing ammonia from a nitrogen molecule by donating the nitrogen molecule of the above.
  • a complex and a solid catalyst are used in combination at the cathode as a catalyst for producing ammonia.
  • a catalyst in the form of a combination of this complex and a solid catalyst may be referred to as a catalyst in the present specification.
  • the complex in the method for producing ammonia of the present embodiment is (A) 2,6-bis (dialkylphosphinomethyl) pyridine as a PNP ligand (however, the two alkyl groups may be the same or different, and the pyridine ring At least one hydrogen atom of the molybdenum complex having an alkyl group, an alkoxy group or a halogen atom), (B) N, N-bis (dialkylphosphinomethyl) dihydrobenzoimidazole as a PCP ligand.
  • a molybdenum complex having lidene (where the two alkyl groups may be the same or different, and at least one hydrogen atom of the benzene ring may be substituted with an alkyl group, an alkoxy group or a halogen atom), (C).
  • R 5 and R 6 are aryl groups that may be the same or different, R 7 is an alkyl group, and two R 7s are connected to each other to form an alkylene chain.
  • a molybdenum complex represented by is used.
  • examples of the alkyl group include C 1 to C 10 alkyl groups, preferably 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and isopropyl. Groups, t-butyl groups and cyclohexyl groups are even more preferred.
  • examples of the alkoxy group include C1 to C8 alkoxy groups, benzyloxy groups and the like, preferably having 1 to 8 carbon atoms, and when the alkoxy group is a benzyloxy group.
  • the benzyloxy group may have at least one hydrogen atom on the benzene ring substituted with a resin.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • Examples of the molybdenum complex (A) include formulas (A1), (A2) or (A3).
  • R 1 and R 2 are alkyl groups which may be the same or different, X is an iodine atom, a bromine atom or a chlorine atom, and at least one hydrogen atom on the pyridine ring is an alkyl group. , May be substituted with an alkoxy group or a halogen atom).
  • Examples of the alkyl group, the alkoxy group and the halogen atom include the same as those already exemplified.
  • R 1 and R 2 bulky alkyl groups such as t-butyl group, isopropyl group or cyclohexyl group are preferable.
  • the hydrogen atom on the pyridine ring is not substituted, or the hydrogen atom at the 4-position is substituted with a C 1 to C 10 alkyl group, a C 1 to C 8 alkoxy group, or a benzyl oxy group. More preferred alkoxy groups include benzyloxy groups in which at least one hydrogen atom on the benzene ring is substituted with a resin, wherein the resin is a chloromethyl resin (eg, polymer-bound 5- [4-(, for example).
  • the molybdenum complex of (B) has the following formula (B1) or (B2).
  • R 1 and R 2 are C 1 to C 10 alkyl groups which may be the same or different
  • X is an iodine atom, a bromine atom or a chlorine atom
  • a molybdenum complex represented by may be substituted with a C 1 to C 10 alkyl group, a C 1 to C 8 alkoxy group, or a halogen atom) at least one hydrogen atom on the benzene ring can be mentioned.
  • Examples of the C 1 to C 10 alkyl group, C 1 to C 8 alkoxy group and halogen atom include the same as those already exemplified.
  • R 1 and R 2 bulky alkyl groups such as t-butyl group, isopropyl group or cyclohexyl group are preferable.
  • R 3 and R 4 of the molybdenum complex of (B2) independently represent an electron-withdrawing group, and R 3 and R 4 may be electron-withdrawing groups, and when R 3 is an electron-withdrawing group. , R 4 may be a hydrogen atom.
  • An electron attracting group is also called an electron attracting group or an electron accepting group, and is a theory that focuses on changes in the electron density and bond state of a substance and tries to interpret it as uniformly as possible. By the effect, it represents a substituent that attracts an electron from the bonded electron side as compared with a hydrogen atom.
  • Examples of the electron-withdrawing group include a substituent in which the mesomeric effect is electron-donating but a large contribution of the electron-withdrawing property of the inductive effect, and a substituent in which the mesomeric effect and the inductive effect are electron-withdrawing.
  • substituents whose mesomeric and induced effects are electron-attracting are quaternary ammonium groups, trifluoromethyl groups, perfluoroalkyl groups, trichloromethyl groups and cyano groups having an anion as a counter ion.
  • Counterions for the nitrogen atom constituting the quaternary ammonium group include hexafluorophosphate ion, hexachloroantimonate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, phosphate ion, sulfonate ion, chloride, bromide, and the like. Examples thereof include iodide and hydroxyd.
  • R 3 and R 4 are preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a trifluoromethyl group, and more preferably a chlorine atom and a trifluoromethyl group.
  • the molybdenum complex of (C) is, for example, the formula (C1).
  • R 1 and R 2 are C 1 to C 10 alkyl groups which may be the same or different, R 5 is an Ar 6 aryl group, and X is an iodine atom, a bromine atom or a chlorine atom.
  • the molybdenum complex represented by is mentioned.
  • Examples of the C 1 to C 10 alkyl groups include the same as those already exemplified.
  • Examples of the C 1 to C 10 alkyl group and Ar 6 aryl group include the same as those already exemplified.
  • R 1 and R 2 bulky alkyl groups such as t-butyl group, isopropyl group or cyclohexyl group are preferable.
  • R5 a phenyl group is preferable.
  • the molybdenum complex of (D) includes the formula (D1) or (D2).
  • R 5 and R 6 are Ar 6 aryl groups which may be the same or different, R 7 is a C 1 to C 10 alkyl group, and n is 2 or 3). Examples thereof include molybdenum complexes. Examples of the Ar 6 aryl group and the C 1 to C 10 alkyl group include the same as those already exemplified.
  • R 5 and R 6 are phenyl groups and R 7 is a C 1 to C 4 alkyl group.
  • R5 and R6 are phenyl groups and n is 2 .
  • Examples of the solid catalyst in the method for producing ammonia of the present embodiment include a metal catalyst, an oxide catalyst, and the like, and two or more of these solid catalysts can be used in combination.
  • the metal catalyst is used as a transition metal oxide when it is used as a metal catalyst having a single composition or when a plurality of metal components are mixed like an alloy catalyst, and when it is used as a metal oxide of a typical element. Or an oxide catalyst having a case where a plurality of metal oxides are mixed.
  • the metal oxide may be used as a carrier for a solid catalyst.
  • Examples of the solid catalyst in the method for producing ammonia of the present embodiment include a metal catalyst, an oxide catalyst, and the like, and two or more of these solid catalysts can be used in combination.
  • Examples of the metal catalyst include a metal catalyst having a case where it is used in a single composition and a case where a plurality of metal components are mixed like an alloy catalyst, and those in which metal nanoparticles are formed from a surfactant or the like or a thiol compound. It is also possible to utilize metal particles, metal nanoparticles, metal films, metal foils and the like having a portion self-assembled by the bond between the metal and the thiol.
  • R 1 is not particularly limited and may be an appropriate one in consideration of the boiling point of R 1 to SH, the ease of isolation by chromatography, etc., but is an organic group having 1 to 20 carbon atoms. Is preferable, and an organic group having 6 to 16 carbon atoms is more preferable.
  • 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 the like.
  • Examples thereof include those in which a part of the carbon-carbon bond of the group is interrupted by a hetero atom, or those in which a substituent containing a hetero atom is substituted.
  • Specific examples of the thiol compound include, for example, 2-methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, phenylmethanethiol, 1-butanethiol, 1-decanethiol, 1-dodecanethiol, 1.
  • the oxide catalyst examples include an oxide catalyst having a case where it is used as a typical element metal oxide, a case where it is used as a transition metal oxide, or a case where a plurality of metal oxides are mixed. It may be used as a carrier for a solid catalyst.
  • Examples of the solid catalyst in the method for producing ammonia of the present embodiment include iridium oxide (IV) powder catalyst, iridium oxide catalyst, platinum catalyst, gold catalyst, silver catalyst, ruthenium catalyst, iridium catalyst, rhodium catalyst, palladium catalyst, and osmium.
  • iridium oxide (IV) powder catalyst iridium oxide catalyst, platinum catalyst, gold catalyst, silver catalyst, ruthenium catalyst, iridium catalyst, rhodium catalyst, palladium catalyst, and osmium.
  • Metals such as catalysts, tungsten catalysts, lead catalysts, iron catalysts, chromium catalysts, cobalt catalysts, nickel catalysts, manganese catalysts, vanadium catalysts, molybdenum catalysts, gallium catalysts, aluminum catalysts and their alloys, 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, cerium oxide, samarium oxide, ruthenium oxide, rhodium oxide, silver oxide, tantalum oxide, Examples thereof include tungsten oxide, osmium oxide, iridium oxide, indium oxide, platinum oxide, gold oxide, magnesium oxide, silica, silica-alumina, silica-magnesia, or a combination of the above-mentioned solid catalysts.
  • platinum catalyst, gold catalyst and silver catalyst examples include thiol-protected platinum nanoparticles catalyst, thiol-protected platinum catalyst, thiol-protected gold nanoparticles catalyst, thiol-protected gold catalyst, thiol-protected silver nanoparticles catalyst, or thiol-protected silver.
  • examples include catalysts.
  • the solid catalyst used on the cathode side is defined as the cathode solid catalyst, and the preferred cathode solid catalysts are platinum catalyst, thiol-protected platinum nanoparticles catalyst, thiol-protected platinum catalyst, gold catalyst, thiol-protected gold nanoparticles catalyst, and thiol.
  • gold catalysts include gold catalysts, iridium catalysts, palladium catalysts, zinc oxide, molybdenum oxide, cerium oxide, and samarium oxide, more preferably platinum catalysts, thiol-protected platinum nanoparticles catalysts, gold catalysts, thiol-protected gold nanoparticles catalysts, Examples include thiol-protected gold catalysts, palladium catalysts, and zinc oxide.
  • a platinum catalyst and zinc oxide are used in combination
  • a platinum catalyst and a gold catalyst are used in combination
  • a platinum catalyst and a thiol-protected gold catalyst are used in combination
  • a platinum catalyst and a palladium catalyst are used in combination
  • thiol is used.
  • Combination of protected platinum nanoparticles catalyst and zinc oxide, combination of thiol-protected platinum nanoparticles catalyst and gold catalyst, combination of thiol-protected platinum nanoparticles catalyst and thiol-protected gold catalyst, thiol-protected platinum nanoparticles catalyst and palladium catalyst Is preferable in combination with.
  • a catalyst on the cathode side which is a catalyst in which a complex and a cathode solid catalyst are combined in the method for producing ammonia of the present embodiment, is defined as a cathode catalyst, and a preferable combination of the cathode catalyst is molybdenum of the formula (A1).
  • 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 which is a catalyst in which a complex and a cathode solid catalyst are combined.
  • a cathode catalyst which is a catalyst in which a complex and a cathode solid catalyst are combined.
  • the cathode catalyst layer 103 including the cathode catalyst body, the catalyst carrier, the electron conductor, the electrolyte and the gas diffusion layer in which the complex and the cathode solid catalyst are assembled may be referred to as a gas diffusion electrode 133.
  • the catalyst carrier in the cathode catalyst layer 103 of the present embodiment may carry electron conduction, and is not particularly limited as long as it carries the catalyst of the present embodiment.
  • the catalyst carrier include carbon black, carbon material, metal mesh, metal foam, metal oxide, composite oxide, polymer electrolyte, ionic liquid and the like.
  • the catalyst carrier when used as an electrode, it not only plays a role of supporting the catalyst, but can also participate in the reaction occurring at the electrode as a catalyst or a co-catalyst.
  • Examples of the carbon black include channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC and the like
  • examples of the carbon material include carbonizing and activating a material containing various carbon atoms. Examples thereof include treated activated carbon, coke, natural graphite, artificial graphite, graphitized carbon and the like
  • examples of the metal mesh include metal meshes such as nickel, tungsten, titanium, zirconium and hafnium
  • examples of the metal foam include metal foams.
  • metal oxides include 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, Examples thereof include iridium oxide, indium oxide, platinum oxide, gold oxide, magnesium oxide and silica, and examples of the composite oxide include silica-alumina and silica-magnesia.
  • Examples of the polymer electrolyte include a fluorine-based polymer electrolyte, a hydrocarbon-based polymer electrolyte, a carboxyl group-containing acrylic copolymer, a carboxyl group-containing methacrylic copolymer, and the like.
  • Examples of the fluoropolymer electrolyte include fluorine-based polymers such as Nafion (registered trademark) of DuPont, Aquivion (registered trademark) of Solvay, Flemion (registered trademark) of AGC, and Aciplex (registered trademark) of Asahi Kasei.
  • Examples thereof include sulfonic acid polymers, hydrocarbon-based sulfonic acid polymers, and partially fluorine-based introduction-type hydrocarbon-based sulfonic acid polymers.
  • Examples of the hydrocarbon-based polymer electrolyte include sulfonated polyether ketones, sulfonated polyether sulfones, sulfonated polyether ether sulfones, sulfonated polysulfides, and sulfonated polyphenylenes.
  • carboxyl group-containing acrylic copolymer examples include acrylic acid, propiolic acid, crotonic acid, isocrotonic acid, myristoleic acid, palmitoleic acid, and oleic acid, which have a carboxyl group and a copolymerizable double bond.
  • Acrylic acid alkyl esters such as butyl, isobutyl acrylate, tertiary butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, di Acelatin acrylamide, acrylamide, 2-hydroxyethyl acrylamide, N-methyl acrylamide, Nt-butyl acrylamide, N-isopropyl acrylamide, N-phenyl acrylamide, N-methylol acrylamide, dimethyl amino propyl acrylamide, dimethyl amino propyl acrylamide, diacetone Acrylamides such as acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholin, acryloylpiperidin, phosphonic acid such as [3- (acryloyloxy) propyl]
  • Examples thereof include copolymers to which a compound having a possible double bond is added.
  • the above-mentioned homopolymerization or copolymerization can be promoted, for example, by generating a radical with a radical polymerization initiator.
  • a radical polymerization initiator examples include azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2'-azobis-2,4-dimethylvaleronitrile, and 2,2'-azobis [N-].
  • Azo-based compounds such as tetrahydrate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butylper Examples thereof include organic peroxides such as oxides, potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide and the like, and these can be used alone or in combination of two or more.
  • carboxyl group-containing methacrylic copolymer examples include methacrylic acid, ⁇ -carboxy-polycaprolactone monomethacrylate, monohydroxyethyl methacrylate phthalate, and methacrylic acid dimer having a carboxyl group and a copolymerizable double bond.
  • 2-Methacrylic acidpropylhexahydrophthalic acid 2-methacrylic acidethylsuccinic acid and other homopolymers or copolymers, as well as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, Tershally butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate and other alkyl methacrylate esters, methacrylic acid, dimethylaminopropylmethacrylate.
  • tetrahydrofurfuryl methacrylate ester dimethylaminoethyl methacrylate ester
  • methacrylic acid Add compounds with copolymerizable double bonds such as diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropylmethacrylate, styrene, vinyltoluene, etc. Examples
  • the above-mentioned homopolymerization or copolymerization can be promoted, for example, by generating a radical with a radical polymerization initiator.
  • the radical polymerization initiator include azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2-azobis-2,4-dimethylvaleronitrile, and 2,2-azobis [N- (2). -Carboxyethyl) -2-methylpropionamidinemethyl] Azo-based compounds such as tetrahydrate, t-butylhydroperoxide, cumenehydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, etc.
  • Examples thereof include organic peroxides, potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide and the like, and these can be used alone or in combination of two or more.
  • the polymer electrolyte a plurality of these above-mentioned polymer electrolytes can be used in combination, and a mixture of two or more kinds of polymers can be used as a polymer alloy, for example, two or more kinds of polymers. May include a physically mixed polymer blend, an Interpenetrated Polymer Network (IPN) in which the network structure is entangled.
  • IPN Interpenetrated Polymer Network
  • the ionic liquid of this embodiment will be described below.
  • Examples of the ionic liquid include imidazolium salt, pyridinium salt, ammonium salt, phosphonium salt, pyrrolidinium salt, piperidinium salt, sulfonium salt and the like.
  • R 1a to R 5a may be the same or different, and examples thereof include a hydrogen atom, a C 1 to C 10 alkyl group, an allyl group, a vinyl group, and the like.
  • examples of X - in the formula (1) include chlorine ion, bromine ion, iodine ion, tetrafluoroborate, trifluoro (trifluoromethyl) borate, dimethyl phosphate ion, diethyl phosphate ion, and hexafluorophos.
  • Examples thereof include fert, tris (pentafluoroethyl) trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide and the like.
  • formula (1) examples include, for example, 1-allyl-3-methylimidazolium ion, 3-ethyl-1-vinyl imidazolium ion, 1-methylimidazolium ion, 1-ethylimidazolium ion, 1-.
  • R 1b to R 6b may be the same or different, and examples thereof include a hydrogen atom, a hydroxymethyl group, or a C 1 to C 6 alkyl group, respectively.
  • X ⁇ in the formula (2) the same thing as the said formula (1) can be mentioned.
  • formula (2) examples include, for example, 1-butyl-3-methylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-butyl-pyridinium ion, 1-ethyl-3-methylpyridinium ion, 1 Examples thereof include salts of pyridinium ions such as -ethylpyridinium ion and 1-ethyl-3- (hydroxymethyl) pyridinium ion and X - in the above formula (1).
  • ammonium salt As a specific example of the ammonium salt, the formula (3): The one represented by is mentioned.
  • R 1c to R 4c may be the same or different, and are hydrogen atom, methoxyethyl group, phenylethyl group, methoxypropyl group, cyclohexyl group, or C 1 to C 8 alkyl, respectively.
  • the group is mentioned.
  • X ⁇ in the formula (3) the same thing as the said formula (1) can be mentioned.
  • formula (3) examples include, for example, triethylpentylammonium ion, diethyl (methyl) propylammonium ion, methyltri-n-octylammonium ion, trimethylpropylammonium ion, cyclohexyltrimethylammonium ion, diethyl (2-methoxyethyl).
  • -Ammonium ions such as methylammonium ion, ethyl (2-methoxyethyl) -dimethylammonium ion, ethyl (3-methoxypropyl) dimethyl-ammonium ion, ethyl (dimethyl) (2-phenylethyl) -ammonium ion and the above formula ( The salt with X- in 1) can be mentioned.
  • R 1d to R 4d may be the same or different, and examples thereof include a hydrogen atom, a methoxyethyl group, or a C 1 to C 10 alkyl group, respectively.
  • X ⁇ in the formula (3) the same thing as the said formula (1) can be mentioned.
  • the 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.
  • phosphonium ions such as tributylmethylphosphonium ion, tetrabutylphosphonium ion, trihexyl (tetradecyl) phosphonium ion, trihexyl (ethyl) phosphonium ion, and tributyl (2-methoxyethyl) -phosphonium ion.
  • phosphonium ions such as tributylmethylphosphonium ion, tetrabutylphosphonium ion, trihexyl (tetradec
  • R 1e to R 2e may be the same or different, and examples thereof include a hydrogen atom, an allyl group, a methoxyethyl group, or a C 1 to C 8 alkyl group, respectively.
  • X ⁇ in the formula (5) the same thing as the said formula (1) can be mentioned.
  • formula (5) examples include 1-allyl-1-methylpyrrolidinium ion, 1- (2-methoxyethyl) -1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, and the like.
  • a salt of pyrrolidinium ion such as 1-methyl-1-propylpyrrolidinium ion, 1-octyl-1-methylpyrrolidinium ion, 1-hexyl-1-methylpyrrolidinium ion and X - in the above formula (1) Can be mentioned.
  • R 1f to R 2f may be the same or different, and examples thereof include a hydrogen atom or a C 1 to C 6 alkyl group.
  • X ⁇ in the formula (6) the same thing as the said formula (1) can be mentioned.
  • formula (6) examples include a salt of piperidinium ions such as 1-butyl-1-methylpiperidinium ion and 1-methyl-1-propylpiperidinium ion and X - in the formula (1). Can be mentioned.
  • R 1 g to R 3 g may be the same or different, and examples thereof include a hydrogen atom or a C 1 to C 4 alkyl group.
  • X ⁇ in the formula (3) the same thing as the said formula (1) can be mentioned.
  • formula (7) include salts of sulfonium ions such as triethylsulfonium ion and trisulfonium ion and X ⁇ in the formula (1).
  • catalyst carrier of the present embodiment carbon black, Ketjen black, Ketjen black EC, Nafion (registered trademark), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl -1-Methylpyrrolidinium bis (fluorosulfonyl) imide, 1-butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorotrifluorophosphate are preferred.
  • These catalyst carriers may be used alone or in combination of two or more, in combination with carbon black and zinc oxide, in combination with Ketjen Black EC and zinc oxide, carbon black and molybdenum oxide.
  • Ketjen Black EC and molybdenum oxide carbon black, zinc oxide and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide
  • Chen Black EC zinc oxide and 1-butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorotrifluorophosphate in combination.
  • the electron conductor in the cathode catalyst layer 103 of the present embodiment is not particularly limited as long as it is responsible for electron conduction.
  • 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, etc.
  • Examples thereof include carbon materials such as graphitized carbon, metal meshes such as nickel or titanium, and metal foams.
  • the electron conductor of the present embodiment has a high specific surface area and excellent electron conductivity, and is carbon black, Ketjen black, Ketjen black EC, nickel metal mesh, titanium metal mesh, and metal foam. Is preferable, and a titanium metal mesh and a metal foam are more preferable because they are more durable.
  • the electrolyte in the cathode catalyst layer 103 of the present embodiment is not particularly limited as long as it is responsible for ionic conduction. Fluorine-based polyelectrolytes and hydrocarbon-based polyelectrolytes can be mentioned. Examples of the fluoropolymer electrolyte include fluorine-based polymers such as Nafion (registered trademark) of DuPont, Aquivion (registered trademark) of Solvay, Flemion (registered trademark) of AGC, and Aciplex (registered trademark) of Asahi Kasei.
  • Examples thereof include sulfonic acid polymers, hydrocarbon-based sulfonic acid polymers, and partially fluorine-based introduction-type hydrocarbon-based sulfonic acid polymers.
  • Examples of the hydrocarbon-based polymer electrolyte include sulfonated polyether ketones, sulfonated polyether sulfones, sulfonated polyether ether sulfones, sulfonated polysulfides, and sulfonated polyphenylenes.
  • 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 above-mentioned electrolyte may be mixed and used, and it is preferable to contain a perfluoroic acid-based polymer such as Nafion.
  • the gas diffusion layer in the cathode catalyst layer 103 of the present embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and diffusion of the electrolytic solution.
  • carbon paper, carbon felt, carbon cloth and the like can be mentioned.
  • the cathode catalyst layer 103 including a complex, a cathode solid catalyst, or a catalyst body which is a 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 Industries, Inc.'s TGP-H-060, TGP-H-090, TGP-H-120, TGP-H-060H, TGP-H-090H, TGP-H-120H, and Electrochem's. Examples thereof include EC-TP1-030T, EC-TP1-060T, EC-TP1-090T, EC-TP1-120T, and SIGRACET's 22BB, 28BC, 36BB, 39BB and the like.
  • Examples of the carbon cloth include EC-CC1-060, EC-CC1-060T, EC-CCC-060 of Elecrotochem, and Trading Card (registered trademark) cloth of Toray Industries, Inc., CO6142, CO6151B, CO6343, CO6343B, CO6347B. , CO6644B, CO1302, CO1303, CO5642, CO7354, CO7359B, CK6244C, CK6273C, CK6261C and the like.
  • Examples of the carbon felt include H1410 and H2415 manufactured by Freudenberg.
  • the gas diffusion layer in the cathode catalyst layer 103 of the present embodiment is preferably TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H, and EC-TP1-060T.
  • the proton source arranged in the electrolytic apparatus for example, the electrolyte membrane 102 arranged next to the cathode catalyst layer 103, the electrolytic solution derived from the electrolyte membrane, and the side of the cathode catalyst layer 103.
  • the electrolytic solution in the electrolytic solution tank arranged in the above examples thereof include the electrolytic solution in the electrolytic solution tank arranged in the above, and the electrolytic solution 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 alone or in combination of two or more.
  • Examples of the solution in the electrolytic solution in the method for producing ammonia of the present embodiment include water, ionic liquid, methanol, isopropyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.
  • Examples thereof include diethylamine, hexamethylphosphonic acid triamide, acetic acid, acetonitrile, methylene chloride, trifluoroethanol, nitromethane, sulfolane, pyridine, tetrahydrofuran, dimethoxyethane, propylene carbonate and the like, and water and ionic liquids are preferable.
  • Examples of the ionic liquid include the above-mentioned imidazolium salt, pyridinium salt, ammonium salt, phosphonium salt, pyrrolidinium salt, piperidinium salt, sulfonium salt and the like.
  • an acid such as sulfuric acid or trifluoromethanesulfonic acid
  • the preferred ionic liquid to which the acid is added is 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl). Imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorotrifluorophosphate.
  • 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 ion, etc. alone or in combination, on the other hand, chlorine ion, bromine ion, iodine ion, tetrafluoroborate, trifluoro (trifluoromethyl) borate, dimethyl phosphate ion, diethyl phosphate ion.
  • Hexafluorophosphate Tris (pentafluoroethyl) trifluorophosphate, trifluoroacetate, methylsulfate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, perchlorate ion, sulfate ion, nitrate ion, etc.
  • Examples thereof include anions that are used alone or in combination of two or more.
  • the electrolyte may be used alone or in combination of two or more.
  • Examples of the quaternary ammonium ion in the electrolyte include triethylpentylammonium ion, diethyl (methyl) propylammonium ion, methyltri-n-octylammonium ion, trimethylpropylammonium ion, cyclohexyltrimethylammonium ion, and diethyl (2-methoxyethyl) -methyl.
  • imidazolium ion, pyridinium ion, phosphonium ion, pyrrolidinium ion and phosphonium ion in the electrolyte include the above.
  • the cation which is an electrolyte contained in the electrolytic solution of the present embodiment is preferably a proton, an imidazolium ion, or a pyrrolidinium ion, and the anion which is the electrolyte is preferably a perchlorate ion or a sulfate ion.
  • cathode electrolyte 106 used in the cathode electrolyte tank 105 of the present embodiment are water, an aqueous sulfuric acid solution, and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.
  • the seeds may be used alone or in combination of two or more.
  • the anode electrolytic solution 116 used in the anode electrolytic solution tank 115 of the present embodiment is preferably water or a sulfuric acid aqueous solution.
  • the electrolyte membrane 102 includes a polymer electrolyte membrane, and examples of such a polymer electrolyte membrane include Neosepta (registered trademark) of Astom Co., Ltd. and Celemion (registered trademark) of AGC Co., Ltd.
  • Asahi Kasei's Aciplex (registered trademark), Fumatech's Fumasep (registered trademark), Fumatech's fumapem (registered trademark), DuPont's Nafion (registered trademark), Solvay's Aquivion (registered trademark), AGC Flemion (registered trademark), Gore Select (registered trademark) of Japan Gore GK.
  • Asahi Kasei's Aciplex registered trademark
  • DuPont's Nafion registered trademark
  • Solvay's Aquivion (registered trademark)
  • AGC's Flemion registered trademark
  • As the electrolyte membrane 102 As the electrolyte membrane 102, Asahi Kasei's Aciplex (registered trademark), DuPont's Nafion (registered trademark), Solvay's Aquivion (registered trademark), and AGC's Flemion (registered trademark) are preferable
  • the reaction temperature is preferably ⁇ 40 ° C. to 120 ° C., more preferably 0 ° C. to 50 ° C., which is the normal temperature.
  • the reaction atmosphere may be a pressurized atmosphere, and usually a normal pressure atmosphere.
  • the reaction time is not particularly limited, but usually it may be set in the range of several tens of minutes to several tens of hours, and it is possible to carry out the reaction continuously, but it is also possible to stop it in the middle. For example, it is possible to carry out the reaction for several hours, then stop the reaction once and then carry out the reaction again.
  • FIG. 1 shows the ammonia electrolyzer of Example 1 for the production of ammonia (No. 1) 100
  • FIG. 2 shows the ammonia electrolyzer of Example 2 for the production of ammonia (No. 2) 200
  • the ammonia electrolyzer of Example 3 for the production of ammonia (No. 3) 300 and FIG. 4 show the ammonia electrolyzer of Example 4 for the production of ammonia (No. 4) 400, respectively.
  • the ammonia electrolyzer (No. 1) 100 of the present embodiment includes a cathode 108 and an anode 118, and includes a membrane electrode assembly 131 in which the cathode catalyst layer 103 and the anode catalyst layer 113 are integrated via an electrolyte membrane 102. It is a production device for ammonia.
  • the cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and the cathode current collector 104 is arranged outside the cathode catalyst layer 103, and the 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 at the center.
  • the cathode catalyst layer 103 includes a complex and a cathode solid catalyst, and the anode catalyst layer 113 includes an anode solid catalyst.
  • the manufacturing apparatus includes a cathode electrolytic solution tank 105 of a cathode electrolytic solution 106 that makes liquid contact with the cathode 108 of the membrane electrode junction 131, and an anode electrolytic solution of the anode electrolytic solution 116 that makes liquid contact with the anode 118 of the membrane electrode junction 131.
  • the tank 115 is provided with a power source (power supply device 101) for supplying electrons to the cathode 108, a proton source for supplying protons to the cathode 108, and means for supplying nitrogen gas to the cathode electrolytic solution 106 and the cathode 108. ..
  • the proton source is both the electrolyte membrane 102, the cathode electrolyte 106, the anode electrolyte 116, the electrolyte membrane 102 and the cathode electrolyte 106, or both the electrolyte membrane 102 and the anode electrolyte 116.
  • it is an ammonia production device that produces ammonia from nitrogen molecules by electrolysis.
  • the means for supplying the nitrogen gas is a means for supplying the nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the regulator 123 of the nitrogen cylinder and the mass flow controller 124 of the nitrogen gas.
  • Ammonia generated in the cathode 108 can be collected in the cathode electrolytic solution tank 105 of the cathode electrolytic solution 106 and the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through the pipe 121, the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through the draft device 126.
  • the ammonia electrolyzer (No. 2) 200 of the present embodiment is an ammonia production device including a cathode 108 composed of a cathode catalyst layer 103 and a cathode current collector 104, and a metal plate electrode 117 as an anode.
  • the cathode catalyst layer 103 includes a complex and a cathode solid catalyst, and is a gas diffusion electrode 133.
  • the manufacturing apparatus includes an anode electrolytic solution tank 115 for an anode electrolytic solution 116 that is in liquid contact with the cathode catalyst layer 103, a power supply (power supply device 101) that supplies electrons to the cathode 108, and a proton source that supplies protons to the cathode 108.
  • a means for supplying nitrogen gas to the cathode 108 For the gas diffusion layer of the cathode catalyst layer 103, it is preferable to use carbon paper which has been water-repellent treated with a fluororesin made of polytetrafluoroethylene (sometimes abbreviated as PTFE) for the cathode catalyst layer 103.
  • PTFE polytetrafluoroethylene
  • TGP-H-060H, TGP-H-090H, TGP-H-120H, EC-TP1-030T, EC-TP1-060T, EC-TP1-090T or EC-TP1-120T are preferable.
  • the proton source is the anode electrolyte 116. Furthermore, it is an ammonia production device that produces ammonia from nitrogen molecules by electrolysis.
  • the means for supplying the nitrogen gas is a means for supplying the nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the regulator 123 of the nitrogen cylinder and the mass flow controller 124 of the nitrogen gas.
  • Ammonia generated in the cathode 108 can be collected in the anode electrolytic solution tank 115 of the anode electrolytic solution 116 and the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through the pipe 121, the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through the draft device 126.
  • the ammonia electrolyzer (No. 3) 300 of the present embodiment includes a cathode 108 and an anode 118, and includes a membrane electrode assembly 131 in which the cathode catalyst layer 103 and the anode catalyst layer 113 are integrated via the electrolyte membrane 102. It is a production device for ammonia.
  • the cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and the cathode current collector 104 is arranged outside the cathode catalyst layer 103, and the 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 at the center.
  • the cathode catalyst layer 103 includes a complex and a cathode solid catalyst, and the anode catalyst layer 113 includes an anode solid catalyst.
  • the manufacturing apparatus includes an anode electrolytic solution tank 115 of an anode electrolytic solution 116 that comes into liquid contact with the anode 118 of the membrane electrode assembly 131, and supplies electrons to the cathode 108 (power supply device 101) and protons to the cathode 108. It is provided with a proton source to be supplied and a means for supplying nitrogen gas to the cathode electrolytic solution 106 and the cathode 108.
  • the proton source is both the electrolyte membrane 102 and the anode electrolyte 116, or the electrolyte membrane 102 and the anode electrolyte 116. Furthermore, it is an ammonia production device that produces ammonia from nitrogen molecules by electrolysis.
  • the means for supplying the nitrogen gas is a means for supplying the nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the regulator 123 of the nitrogen cylinder and the mass flow controller 124 of the nitrogen gas.
  • Ammonia generated at the cathode 108 can be collected in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through the pipe 121, the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through the draft device 126.
  • the ammonia electrolyzer (No. 4) 400 of the present embodiment includes the cathode membrane electrode assembly 132 to which the cathode catalyst layer 103 is bonded to one side of the electrolyte membrane 102, and the cathode 108 composed of the cathode current collector 104. It is an ammonia production apparatus provided with a metal plate electrode 117 as an anode.
  • the cathode catalyst layer 103 includes a complex and a cathode solid catalyst.
  • the manufacturing apparatus includes an anode electrolyte tank 115 of an anode electrolyte 116 that comes into liquid contact with the electrolyte membrane 102 of the cathode membrane electrode assembly 132, and supplies electrons to the cathode 108 (power supply device 101) and the cathode 108. It is provided with a proton source for supplying protons and a means for supplying nitrogen gas to the cathode 108.
  • the proton source is both the electrolyte membrane 102 and the anode electrolyte 116, or the electrolyte membrane 102 and the anode electrolyte 116.
  • it is an ammonia production device that produces ammonia from nitrogen molecules by electrolysis.
  • the means for supplying the nitrogen gas is a means for supplying the nitrogen gas from the nitrogen cylinder 122 through the pipe 121 via the regulator 123 of the nitrogen cylinder and the mass flow controller 124 of the nitrogen gas.
  • Ammonia generated at the cathode 108 can be collected in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia.
  • By-produced hydrogen and unreacted nitrogen pass through the pipe 121, the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia, and are discharged to the outside through the draft device 126.
  • the cathode current collector 104 and the anode current collector 114 in the electrolytic apparatus of the present embodiment are, for example, an alloy containing two or more types of carbon, metal, oxide, and metal, and an oxide containing two or more types of metal.
  • Examples thereof include stainless steel, indium tin oxide, and indium zinc oxide.
  • metals include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, gold, etc.
  • the oxide examples 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, gold oxide and the like.
  • the shape of the current collector is not particularly limited as long as it allows gas or an electrolytic solution to pass through, and is, for example, perforated, linear, rod-shaped, plate-shaped, foil-shaped, net-like, woven fabric, non-woven fabric, expanded, or porous. Examples include bodies and foams. In order to prevent corrosion during production by electrolysis, it is also possible to use a current collector plated with gold or the like.
  • the supply of nitrogen gas in the electrolytic apparatus of the present embodiment can be supplied by controlling the flow rate from the nitrogen cylinder 122 by the regulator 123 of the nitrogen cylinder and the mass flow controller 124 of the nitrogen gas.
  • a method of bubbling and supplying nitrogen gas into the cathode electrolytic solution tank 105 of FIG. 1 and the electrolytic solution of the anode electrolytic solution tank 115 of FIG. 2 is also possible, and as shown in FIGS. 3 and 4, the cathode collection is possible. It is also possible to supply nitrogen gas directly to the cathode catalyst layer 103 through the hole of the electric body 104.
  • the electrolytic reaction for producing ammonia in the cathode catalyst layer 103 in the electrolytic apparatus of the present embodiment will be described.
  • the catalyst body which is a combination of the complex and the solid catalyst of the present embodiment, has three components: nitrogen gas supplied to the cathode 108, protons supplied to the cathode 108, and electrons supplied from the power supply device 101. Therefore, a reaction in which ammonia is generated occurs, and the reaction formula can be described by "N 2 + 6e ⁇ + 6H + ⁇ 2NH 3 ".
  • This by-produced hydrogen can also take the form of dissociation on a solid catalyst or a catalyst carrier.
  • the adsorbed hydrogen is evenly dissociated into hydrogen atoms and metal oxides. It is described in Schreiber Atkins Inorganic Chemistry (above), 6th edition, page 358 of the non-patent document that the adsorbed hydrogen dissociates unevenly into protons and hydrides on zinc oxide. It is speculated that activated hydrogen atoms, protons and hydrides on the solid catalyst promote the reaction to produce ammonia.
  • the ammonia generated at the cathode 108 can be sent to the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia together with the by-produced hydrogen and unreacted nitrogen, and can be sent to the cathode electrolytic solution tank 105 or the anode electrolytic solution tank 115. It is also possible to collect in the electrolytic solution used.
  • the electrolytic solution used in the cathode electrolytic solution tank 105 is preferably water or a dilute sulfuric acid aqueous solution from the viewpoint of recovery and reuse, and the efficiency of ammonia collection is improved by pumping the electrolytic solution in the cathode electrolytic solution tank 105. It is also possible to increase it.
  • the mixed gas composed of ammonia produced in the cathode catalyst layer 103 in the electrolytic apparatus of the present embodiment hydrogen produced as a by-product, and unreacted nitrogen, ammonia is selected by using water or a dilute sulfuric acid aqueous solution as described above. Since it can be collected in a targeted manner, it is possible to simultaneously take out a mixed gas of hydrogen and nitrogen produced as a by-product, and hydrogen useful from the viewpoint of energy carriers can also be obtained in the present embodiment. Further, for safety, the by-produced hydrogen can be discharged to the outside through the draft device 126.
  • the electrolytic reaction in the anode catalyst layer 113 or the metal plate electrode 117 in the electrolytic apparatus of this embodiment will be described.
  • a reaction in which oxygen, electrons and protons are generated from water occurs by the catalyst of the anode 118, and the reaction formula can be described as "2H 2 O ⁇ O 2 + 4e ⁇ + 4H + ".
  • the generated protons move to the cathode 108 through the electrolyte membrane 102 or the electrolytic solution, and the electrons move to the power supply device 101 through the anode current collector 114 or the metal plate electrode 117.
  • the generated oxygen can be released to the atmosphere while being partially dissolved in the water of the anode electrolytic solution tank 115, and oxygen can be forcibly expelled by bubbling nitrogen gas in the anode electrolytic solution tank 115.
  • the anode catalyst layer 113 in the electrolytic apparatus of the present 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, the catalyst carrier, the electron conductor, the electrolyte, and the gas diffusion layer may be referred to as the gas diffusion electrode 133.
  • the solid catalyst in the anode catalyst layer 113 of the electrolytic apparatus of the present embodiment is defined as an anode solid catalyst.
  • the anode solid catalyst include the same catalysts described in the solid catalyst and cathode solid catalyst in the method for producing ammonia in the present embodiment, and specific examples thereof include iridium oxide (IV) powder catalyst and 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, metals such as aluminum catalysts, and alloys thereof.
  • an iridium (IV) oxide powder catalyst, an iridium oxide catalyst, and a platinum catalyst are preferable.
  • the catalyst carrier in the anode catalyst layer 113 of the present embodiment may carry electron conduction, and is not particularly limited as long as it carries the catalyst of the present embodiment.
  • Examples of the catalyst carrier include carbon black, carbon material, metal mesh, metal foam, metal oxide, composite oxide and the like.
  • Examples of the carbon black include channel black, furnace black, thermal black, acetylene black, ketjen black, ketjen black EC and the like
  • examples of the carbon material include carbonizing and activating a material containing various carbon atoms. Examples thereof include treated activated carbon, coke, natural graphite, artificial graphite, graphitized carbon and the like
  • examples of the metal mesh include metal meshes such as nickel and titanium
  • examples of the metal foam include aluminum, magnesium and titanium.
  • Examples thereof include metal foams such as zinc, iron, tin, lead and alloys containing these
  • examples of the metal oxide include aluminum oxide, zirconium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide and iron oxide.
  • examples thereof include magnesium and silica
  • examples of the composite oxide include silica-alumina and silica-magnesia.
  • carbon black, Ketjen black, Ketjen black EC, nickel metal mesh, titanium metal mesh, titanium oxide and metal foam are preferable because of their high specific surface area and excellent electron conductivity. Further, titanium metal mesh, titanium oxide and metal foam are more preferable because of their excellent durability.
  • the electrolyte in the anode catalyst layer 113 of the present embodiment is not particularly limited as long as it is responsible for ionic conduction.
  • the same as those described for the electrolyte in the cathode catalyst layer 103 of the present embodiment can be mentioned, and specific examples thereof include Nafion (registered trademark) of DuPont, Aquivion (registered trademark) of Solvay, and AGC.
  • Examples thereof include fluorine-based sulfonic acid polymers such as Flemion (registered trademark) of Asahi Kasei Co., Ltd., Aciplex (registered trademark) of Asahi Kasei Co., Ltd., hydrocarbon-based sulfonic acid polymers, and partially fluorine-based introduction-type hydrocarbon-based sulfonic acid polymers.
  • fluorine-based sulfonic acid polymers such as Flemion (registered trademark) of Asahi Kasei Co., Ltd., Aciplex (registered trademark) of Asahi Kasei Co., Ltd.
  • hydrocarbon-based sulfonic acid polymers such as hydrocarbon-based sulfonic acid polymers
  • partially fluorine-based introduction-type hydrocarbon-based sulfonic acid polymers such as the electrolyte.
  • the electrolyte those responsible for proton conduction are preferable, and Nafion, Aquivion,
  • the gas diffusion layer in the anode catalyst layer 113 of the present embodiment is not particularly limited as long as it is responsible for electron conduction, gas diffusion, and diffusion of the electrolytic solution.
  • the same as those described for the gas diffusion layer in the cathode catalyst layer 103 of the present embodiment can be mentioned, and carbon paper is preferable, and specific examples thereof include TGP-H-060 and TGP-H- of Toray Industries, Inc.
  • gas diffusion layer TGP-H-060, TGP-H-090, TGP-H-060H, TGP-H-090H, and EC-TP1-060T are preferable.
  • the metal of the metal plate electrode 117 of the present embodiment include stainless steel, indium tin oxide, indium zinc oxide, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.
  • examples thereof include niobium, molybdenum, ruthenium, rhodium, silver, tantalum, tungsten, osmium, iridium, indium, platinum, gold metals and alloys thereof. Of these, platinum is preferable.
  • the shape of the metal plate electrode 117 includes, for example, linear, rod-shaped, plate-shaped, foil-shaped, mesh-shaped, woven fabric, non-woven fabric, expand, porous body, foam, and the like, and is preferably mesh-shaped and porous. The body is mentioned.
  • Example 1 1. Preparation of Electrolyzer for Producing Ammonia
  • the cathode catalyst layer 103 which is a catalyst for producing ammonia, was prepared as follows.
  • the catalyst ink A 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 as a solid catalyst manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum content: 46.6% by weight, product name "TEC10E50E”
  • deionized water deionized water
  • ethanol deionized water
  • Nafion dispersion solution as an electrolyte
  • the catalyst ink A was prepared using the product name "5% Nafion dispersion solution DE520 CS type" manufactured by the company.
  • a carbon-supported platinum catalyst, deionized water, ethanol and a Nafion dispersion solution were added to a glass vial in this order, and the obtained dispersion solution was added to the ultrasonic homogenizer Smut NR-50M manufactured by Microtech Nithion.
  • the catalyst ink A was prepared by setting the output of ultrasonic waves to 40% and irradiating the cells for 30 minutes. Next, this catalyst ink A was applied to carbon paper (manufactured by Toray Industries, Inc., product name "TGP-H-060H”) fixed at a hop rate 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 abbreviated as "GDE") containing Nafion as an electrolyte and a carbon-supported platinum catalyst as a solid catalyst was produced.
  • the gas diffusion electrode 133 is a 2.7 ⁇ 2.7 cm 2 square gas diffusion electrode 133 coated with a platinum catalyst (7.3 mg) which is a solid catalyst.
  • GDE-Cathode-0 ".
  • the catalyst ink B for applying the complex of the present embodiment to the cathode catalyst layer 103 was produced.
  • Molybdenum complex represented by the formula (A1-1) A solution prepared by dissolving (5.8 mg) in dichloromethane (1.0 mL) was used as catalyst ink B. This catalyst ink B (50 ⁇ L) was applied to the “GDE-Cathode-0” of the gas diffusion electrode 133, and dichloromethane was dried to prepare a cathode catalyst layer 103.
  • the gas diffusion electrode 133 which is the cathode catalyst layer 103, has a platinum catalyst (7.3 mg), which is a solid catalyst, and a molybdenum complex (0.29 mg, 0.
  • a 2.7 ⁇ 2.7 cm 2 square gas diffusion electrode 133 coated with 33 ⁇ mol) was designated as “GDE-Cathode-1”.
  • ionomer nafion (hereinafter abbreviated as ionomer) in the above-mentioned catalyst ink.
  • the ratio (% by weight) of ionomer calculated from the following formula was set to 28% by weight.
  • Ratio of ionomer (% by weight) [Ionomer solids (weight) / [ ⁇ Carbon-supported platinum catalyst (weight) + Ionomer solids (weight) ⁇ ] x 100
  • the amount of carbon-supported platinum catalyst was set to 100.0 mg
  • the amount of Nafion dispersion solution was set to 837 ⁇ L
  • the amount of deionized water was set to 0.6 mL
  • the amount of ethanol was set to 5 mL.
  • the Nafion solid content in the Nafion dispersion solution (837 ⁇ L) was 38.9 mg.
  • the anode catalyst layer 113 was prepared as follows. By producing the catalyst ink A described in the cathode catalyst layer 103 by the same method and applying it by the same method, the gas diffusion electrode of the anode catalyst layer 113 containing Nafion as an electrolyte and a carbon-supported platinum catalyst as a solid catalyst. 133 was made. Specifically, the gas diffusion electrode 133, which is the anode catalyst layer 113, is a 2.7 ⁇ 2.7 cm 2 square gas diffusion electrode 133 coated with a platinum catalyst (7.3 mg), which is a solid catalyst. This was designated as "GDE-Anode-0".
  • a membrane electrode assembly (Membrane Electrode Assembly, hereinafter abbreviated as "MEA") composed of an electrolyte membrane 102, a cathode catalyst layer 103, and an anode catalyst layer 113 was prepared as follows.
  • MEA Membrane Electrode Assembly
  • As the ion exchange membrane used for the electrolyte membrane 102 a Nafion 212 membrane (registered trademark) (thickness 50 ⁇ m, 5 cm ⁇ 4 cm) manufactured by DuPont was used.
  • the "GDE-Cathode-1" of the gas diffusion electrode 133 which is a cathode catalyst layer, is arranged on one surface of the ion exchange membrane, and the "GDE-Andode-0" of the gas diffusion electrode 133, which is an anode catalyst layer, is arranged on the other surface.
  • thermocompression bonding was performed under the conditions of an upper and lower board temperature of 132 ° C., a load of 5.4 kN, and a pressure bonding time of 240 seconds to prepare a membrane electrode assembly "MEA-1".
  • a cathode membrane electrode assembly 132 composed of an electrolyte membrane 102 and a cathode catalyst layer 103 was produced as follows.
  • a Nafion 212 membrane registered trademark
  • Thickness 50 ⁇ m, 5 cm ⁇ 4 cm was used.
  • the "GDE-Cathode-1" of the gas diffusion electrode 133 is placed on one surface of the ion exchange membrane, and thermocompression bonding is performed under the conditions of an upper and lower plate temperature of 132 ° C., a load of 5.4 kN, and a pressure bonding time of 240 seconds to obtain a cathode film.
  • a stainless steel current collector with 25 circular holes having a diameter of 2.5 mm was attached to a surface of "MEA-2" that was not on the electrolyte membrane side.
  • As the anode a platinum mesh electrode was used as the metal plate electrode 117.
  • the ammonia electrolyzer (No. 4) 400 shown in FIG. 4 equipped with both of the above electrodes was assembled.
  • Cathode electrolyte tank 105 0.02 mol / L sulfuric acid aqueous solution (6 mL)
  • Anode electrolyte tank 115 0.02 mol / L sulfuric acid aqueous solution (6 mL)
  • Dilute sulfuric acid aqueous solution tank for collecting ammonia 125 0.02 mol / L sulfuric acid aqueous solution (10 mL)
  • Measurement conditions Constant potential measurement was performed at -2.3V.
  • Ammonia was quantified using the Thermo Scientific Dionex Ion Chromatography (IC) system, Dionex Integrion, manufactured by Thermo.
  • the amount of ammonia in the sulfuric acid aqueous solution in the dilute sulfuric acid aqueous solution tank 125 for collecting ammonia and the sulfuric acid aqueous solution in the cathode electrolytic solution tank 105 was quantified to determine the amount of ammonia produced.
  • the amount of ammonia produced per complex in the catalyst body was defined as the catalyst rotation speed and calculated by the following formula.
  • the amount of electricity used was obtained from the data of Versa STAT4 of the power supply device 101, and the conversion efficiency was calculated.
  • Catalyst rotation speed (mol / mol) [ammonia production amount ( ⁇ mol) / complex ( ⁇ mol)] (mol / mol)
  • Example 2 In the preparation of the cathode catalyst layer 103, the solvent of the catalyst ink B was changed from dichloromethane to 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide which is an ionic liquid, and the catalyst ink was applied and then dried.
  • An ammonia electrolyzer No. 1 was produced in the same manner as in Example 1 described above, except that the above-mentioned was not performed. Specifically, the molybdenum complex (5.8 mg, 6.6 ⁇ mol) represented by the formula (A1-1) is converted into an ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (1).
  • the solution dissolved in (0.0 mL) was used as catalyst ink C.
  • the catalyst ink C (50 ⁇ L) is applied to the “GDE-Cathode-0” of the gas diffusion electrode 133, and a platinum catalyst (7.3 mg) as a solid catalyst, molybdenum represented by the formula (A1-1).
  • a gas diffusion electrode 133 coated with the complex (0.33 ⁇ mol) and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (50 ⁇ L) was prepared and used as “GDE-Cathode-2”.
  • a membrane electrode assembly was manufactured by the same method as the above-mentioned electrolytic device (No.
  • Example 3 An ammonia electrolyzer (No. 1) was produced in the same manner as in Example 2 described above, except that the coating amount of the catalyst ink A was changed in the production of the cathode catalyst layer 103.
  • 133 was produced as "GDE-Cathode-3A”.
  • the catalyst ink C (50 ⁇ L) is applied to the “GDE-Cathode-3A” of the gas diffusion electrode 133, and a platinum catalyst (1.4 mg) as a solid catalyst, molybdenum represented by the formula (A1-1).
  • a gas diffusion electrode 133 coated with the complex (0.33 ⁇ mol) and 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (50 ⁇ L) was prepared and used as “GDE-Cathode-3”.
  • a membrane electrode assembly was manufactured by the same method as the above-mentioned electrolytic device (No. 1) except that the gas diffusion electrode of the cathode catalyst layer was changed to "GDE-Cathode-3". ..
  • the gas diffusion electrode 133 of the cathode catalyst layer is arranged with the gas diffusion electrode 133 "GDE-Cathode-3", and the gas diffusion electrode 133 of the anode catalyst layer is an electrolyzer using a membrane electrode assembly in which the gas diffusion electrode 133 is arranged.
  • the 1) was produced, and the production of anode by electrolysis was carried out in the same manner as in Example 1. The results of this example are shown in Table 3 below.
  • An ammonia electrolyzer (No. 1) was produced in the same manner as in Example 1 described above, except that a carbon black-supported platinum catalyst as a solid catalyst was not used for the cathode catalyst layer 103.
  • a cathode catalyst layer 103 was prepared by applying the catalyst ink B (50 ⁇ L) to a carbon paper (manufactured by Toray Industries, Inc., product name “TGP-H-060H”) having a size of 2.7 ⁇ 2.7 cm 2 . Specifically, it is a gas diffusion electrode 133 coated with only a molybdenum complex (0.33 ⁇ mol) represented by the formula (A1-1) without using a platinum catalyst which is a solid catalyst, and the electrode is used.
  • An electrolyzer (No. 1) was produced, and ammonia was produced by electrolysis in the same manner as in Example 1. The results of this example are shown in Table 4 below.
  • Example 3 An ammonia electrolyzer (No. 1) was produced in the same manner as in Example 1 described above, except that a carbon black-supported platinum catalyst as a solid catalyst and a molybdenum complex were not used in the cathode catalyst layer 103. Specifically, the carbon paper (manufactured by Toray Industries, Inc., product name "TGP-H-060H”) is used as it is as a cathode catalyst layer to prepare an electrolytic apparatus (No. 1), and the same as in Example 1 is performed. Ammonia was produced by electrolysis. The results of this example are shown in Table 6 below.
  • Table 7 shows the results of Examples from Example 1 to Example 3 and the results of the blank test from Comparative Example 1 to Comparative Example 3.
  • Example 1 In the comparison between Example 1 and Comparative Example 1 (using only the complex as a catalyst), the amount of ammonia produced was the same when the reaction time was 1 hour, but when the reaction time was 3 hours, Example 1 was compared with Comparative Example 1. A 2.8-fold increase in the amount of production was observed, and the amount of increase in ammonia production when the reaction time was 2 to 3 hours was 800% when Comparative Example 1 was taken as 100%. This result indicates that the amount of ammonia produced was improved by the system of the catalyst body in which the complex and the solid catalyst were combined.
  • Example 2 In the comparison between Example 2 and Comparative Example 1 (using only the complex as a catalyst), the production amount increased by 6.8 times that of Comparative Example 1 when the reaction time was 1 hour, and Example 1 when the reaction time was 3 hours. An increase of 6.7 times the production amount of Comparative Example 1 was observed, and the increase in the reaction time from 2 hours to 3 hours was 400% when Comparative Example 1 was taken as 100%.
  • Example 3 In the comparison between Example 3 and Comparative Example 1 (using only the complex as a catalyst), the production amount increased 4.2 times as much as that of Comparative Example 1 when the reaction time was 1 hour, and Example 1 when the reaction time was 3 hours. An increase of 4.6 times the production amount of Comparative Example 1 was observed, and the increase in the reaction time from 2 hours to 3 hours was 400% when Comparative Example 1 was taken as 100%.
  • Example 4 In the preparation of the cathode catalyst layer, the same experimental operation as in Example 2 described above was performed except that a gold catalyst as a solid catalyst was added. Specifically, 3-mercaptopropylmethyldimethoxysilane (2.5 mg, 0. The catalyst ink E was prepared by irradiating the mixture to which 014 ⁇ mol) was added with ultrasonic waves for 5 minutes with the oscillation power set to High using an ultrasonic cleaner ASU-6. This catalyst ink contains a gold catalyst in which gold is reacted with 3-mercaptopropylmethyldimethoxysilane.
  • the whole amount of the catalyst ink E was applied to the above-mentioned "GDE-Cathode-0", and the step of drying the solvent tetrahydrofuran was performed in four steps to prepare "GDE-Cathode-4A”.
  • the molybdenum complex (5.8 mg, 6.6 ⁇ mol) represented by the formula (A1-1) is added to the ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (1.0 mL). ) was dissolved in the catalyst ink C.
  • a membrane electrode assembly was manufactured by the same method as the above-mentioned electrolytic device (No. 1) except that the gas diffusion electrode of the cathode catalyst layer was changed to "GDE-Cathode-4". ..
  • the gas diffusion electrode 133 of the cathode catalyst layer is arranged with the gas diffusion electrode 133 "GDE-Cathode-4", and the gas diffusion electrode 133 of the anode catalyst layer is an electrolyzer using a membrane electrode assembly in which the gas diffusion electrode 133 is arranged.
  • the 1) was produced, and the production of anode by electrolysis was carried out in the same manner as in Example 1. The results of this example are shown in Table 8 below.
  • the present invention can be used as a method for producing ammonia.

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WO2024207073A1 (en) * 2023-04-05 2024-10-10 Newsouth Innovations Pty Limited Renewable power to x module based on ozonation assisted electrochemical energy conversion reaction
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
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