WO2017132721A1 - Procédé et cellule de conversion de diazote en ammoniac - Google Patents

Procédé et cellule de conversion de diazote en ammoniac Download PDF

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WO2017132721A1
WO2017132721A1 PCT/AU2017/000036 AU2017000036W WO2017132721A1 WO 2017132721 A1 WO2017132721 A1 WO 2017132721A1 AU 2017000036 W AU2017000036 W AU 2017000036W WO 2017132721 A1 WO2017132721 A1 WO 2017132721A1
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electrolyte
dinitrogen
liquid salt
cell
ammonia
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PCT/AU2017/000036
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English (en)
Inventor
Douglas Macfarlane
Xinyi Zhang
Fengling Zhou
Ciaran James McDONNELL- WORTH
Colin Suk Mo KANG
Mega KAR
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Monash University
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Priority claimed from AU2016900354A external-priority patent/AU2016900354A0/en
Application filed by Monash University filed Critical Monash University
Priority to JP2018540776A priority Critical patent/JP2019510874A/ja
Priority to AU2017216250A priority patent/AU2017216250B2/en
Priority to EP17746635.6A priority patent/EP3411514A4/fr
Priority to KR1020187024587A priority patent/KR20180112798A/ko
Priority to US16/075,562 priority patent/US20190040535A1/en
Publication of WO2017132721A1 publication Critical patent/WO2017132721A1/fr

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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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 in the gas phase
    • 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 in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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 an electrochemical apparatus and method for the conversion of dinitrogen (N 2 ) into ammonia.
  • the invention relates to the cathodic reduction of dinitrogen.
  • the present invention is suitable for use in industrial production of ammonia.
  • Ammonia production is a highly energy intensive process, consuming 1 -3% of the world electrical energy and about 5% of the world natural gas production. World production is currently around 200 million tonnes annually, reflecting the vast need for this chemical in agriculture, pharmaceutical production and many other industrial processes.
  • Ammonia is also being considered as a carbon-free solar energy storage material, due to its useful characteristics as a chemical energy carrier. Compared to other chemicals that could be used to store solar energy (such as hydrogen), ammonia is safe, eco-friendly and, most importantly, produces no CO2 emissions. Once stored in this form, the energy is readily recovered via the ammonia fuel cell.
  • the ideal system for the conversion of dinitrogen into ammonia would be economically feasible and easily scalable, would operate at ambient condition and be coupled to renewable energy sources such as wind, hydro or solar.
  • An electrochemical approach is potentially capable of achieving this aim.
  • the electrochemical reduction process involves dinitrogen gas as a starting material and uses various aqueous electrolytes or H 2 gas as the source of the H + .
  • the electrochemical reduction of dinitrogen largely depends on the structure, components, and surface morphology of the electrocatalyst. (van der Ham et al, Chemical Society Reviews 43, 5183-5191 (2014)).
  • Ammonia has also been produced using a mixture of N2 and steam in a molten hydroxide suspension of nano-Fe20 3 at a cell voltage of 1 .2 V and columbic efficiency of 35%.
  • the high temperature used ⁇ 200°C
  • electrochemical conversion has not been sufficiently successful to be considered as a viable replacement for the Haber-Bosch process.
  • electrochemical conversion of the prior art has not reached sufficiently high efficiency levels such as those exhibited by dinitrogen- fixating bacteria. (Rosea et al, Chemical Reviews, 2009, 109, 2209-2244).
  • US patent application 2006/0049063 and US patent 6,712,950 teach the synthesis of ammonia gas by anodic reaction from nitrogen-containing species or dinitrogen gas, and hydrogen-containing species or hydrogen gas in a non-aqueous liquid electrolyte such as a molten salt or an ionic liquid.
  • the method involves the production of the N 3 " ion in the electrolyte and then the reaction of the N 3 " ion at the anode to produce ammonia. This method is limited by the need for the medium to be selected such that it can dissolve useful amounts of the N 3 " to support practical rates of ammonia production.
  • U.S. patent application 2016/0138176 describes a method of synthesizing ammonia using an electrolysis cell containing an aqueous, or liquid electrolyte of an alkali metal (salt) or an ionic liquid.
  • the disclosure includes teaching of the use of electrolytes formed from a wide range of cations and anions (many of which do not form liquid salts) and some of which are of limited stability and utility with regard to efficiency of ammonia synthesis.
  • An object of the present invention is to provide an efficient electrochemical process for production of ammonia.
  • Another object of the present invention is to provide an electrochemical cell suitable for an electrochemical process for cathodic dinitrogen reduction.
  • Another object of the present invention is to provide an improved method for cathodic dinitrogen reduction.
  • a further object of the present invention is to alleviate at least one disadvantage associated with dinitrogen cathodic reduction processes of the prior art.
  • a cell for electrochemical reduction of dinitrogen to ammonia comprising: a cathodic working electrode comprising a nanostructured catalyst for reduction of dinitrogen, a counter electrode, and an electrolyte comprising one or more liquid salts in contact with the working electrode wherein the liquid salt is formed by a combination of :
  • each R group is independently linear, branched or cyclic and preferably comprises from 1 to 18 carbon atoms, optionally partially or completely halogenated, optionally including a heteroatom, optionally including a functional group preferably chosen from ethers, alcohols, carbonyls (acetates), thiols, sulphoxides, sulphonates, amines, azos or nitriles, and wherein two R groups may connect to form a monocyclic or heterocyclic ring; and (ii) an anion selected from the group consisting of (RO) x PF6- x (phosphate), (RO)xBF 4-x (borate), R'S0 2 NS0 2 R' (imide), R'S0 2 C(S0 2 R')(S0 2
  • the liquid salt is formed by a combination of a cation selected from the group consisting of C 4 mpyr (butyl-methyl pyrrolidimium), ⁇ , ⁇ , ⁇ , (trihexyl tetradecyl phosphonium), P(C 2 Rf) 4 (where R f is a perfluoralkyi); and an anion selected from the group consisting of eFAP (C 2 FsPF3), NfO (nonafluorobutane sulphonate), PFO (perfluorooctane sulphonate), FSI (bis(fluorosulphonyl)imide, NTf 2 (bis(trifluoromethylsulphonyl)imide), B(otfe) 4 (tetrakis(2,2,2-trifluoroethane)borate and CF3COO (trifluoroacetate).
  • a cation selected from the group consisting of C 4 mpyr (butyl-methyl
  • the liquid salt includes a cation selected from PRi -4 (phosphonium) cations.
  • the liquid salt includes an anion selected from RSO3 (sulphonate) cations, particularly perfluorobutanesulphonate or perfluoropropanesulphonate, or trifluorophosphates, particularly eFAP (tris(perfluoroethyl)trifluorophosphate).
  • RSO3 sulphonate
  • eFAP tris(perfluoroethyl)trifluorophosphate
  • the cation and/or anion of the liquid salt is fluorinated or perfluorinated.
  • the liquid salt has a relatively high nitrogen solubility (compared, for example, to liquid salts of the prior art such as imidazolium salts and nitrile based anions such as dicyanamide)
  • the reduction of dinitrogen to ammonia occurs principally in a region adjacent a three phase boundary on the working surface of the cathodic working electrode.
  • the nanostructured electrocatalyst is applied to the working surface of the cathodic working electrode to create the gas/electrolyte/metal three phase boundary region where electrolysis principally takes place.
  • the electrolysis cell may include other features well known to those in the art for carrying out electrolytic reactions and controlling the current between the electrodes.
  • the electrolysis cell may be adapted to control the temperature or pressure of operation using well known means such as heaters, cooling units or pressurising means.
  • the cell may include an ultrasonic generator for generating sound waves of energy greater than 20 kHz.
  • the electrolysis cell preferably includes gas flow layers having the function of allowing introduction to the cell of a stream of gas comprising nitrogen and hydrogen or water vapour, and exit of gas containing ammonia.
  • the ammonia is optionally collected external to the cell.
  • an assembly may be formed when two or more cells according to the present invention are stacked in series. One or more of the stacked cells may additionally be folded or rolled. Gas can be introduced at any convenient location including from the "end" of the longest dimension of the assembly or from either side of the assembly.
  • each R group is independently linear, branched or cyclic and preferably comprises from 1 to 18 carbon atoms, optionally partially or completely halogenated, optionally including a heteroatom, optionally including a functional group preferably chosen from ethers, alcohols, carbonyls (acetates), thiols, sulphoxides, sulphonates, amines, azos or nitriles, and wherein two R groups may connect to form a monocyclic or heterocyclic ring; and
  • the method may additionally include a step (3) comprising collecting ammonia generated at the cathodic working electrode, separating the ammonia from other liquids and gases present by using a separate trap or separation unit.
  • the dinitrogen is reduced at the cathodic working electrode to ammonia in the presence of a source of hydrogen, preferably hydrogen gas or water.
  • a source of hydrogen preferably hydrogen gas or water.
  • the dinitrogen gas is humidified with water vapour to a controlled degree and then the humidified gas is passed in a stream over the cathode where the dinitrogen is electrochemically reduced to form ammonia.
  • the anodic counter electrode converts the hydroxyl ions formed at the cathode into water and oxygen.
  • the counter electrode may be placed in the same electrolyte as the working electrode or alternatively, it may be separated by some means such as an electrolyte membrane or separator material. In another embodiment the counter electrode may be located in a compartment which optionally contains a different electrolyte medium, such as an aqueous solution.
  • the counter electrode reaction may be water oxidation or another advantageous oxidation reaction such as sulphite oxidation.
  • the electrolyte in contact with the working electrode may comprise one or more salts, and those salts may be in the solid or liquid states, or combinations thereof.
  • the electrolyte is typically in the form of a layer.
  • the electrolyte includes a spacer or electrolyte membrane (which itself may act as an electrolyte), for example a polymer electrolyte such as NafionTM or a NafionTM-liquid salt blend, or a gelled liquid salt electrolyte, or is an electrolyte soaked into a porous separator such as paper or CeleguardTM.
  • a spacer or electrolyte membrane which itself may act as an electrolyte
  • a polymer electrolyte such as NafionTM or a NafionTM-liquid salt blend
  • a gelled liquid salt electrolyte or is an electrolyte soaked into a porous separator such as paper or CeleguardTM.
  • an electrolyte membrane comprising a thin layer of material combined with one or more liquid salts as herein described for use in the cell of the present invention.
  • the electrolyte of the present invention has high solubility for dinitrogen and low solubility for water.
  • dinitrogen solubility is at least 100 mg/L at the operating temperature and pressure of the cell and more preferably more than 200 mg/L; most preferably the solubility is greater than 400 mg/L.
  • T he solubility of water in the liquid salt is preferably less than 5 weight% at the operating temperature and pressure of the cell, more preferably less than 2% and most preferably less than 1 %.
  • liquid salt is intended to refer to an electrolyte medium that is liquid at the temperature of use and that contains one or more salts (each of which may be solid or liquid in their pure states).
  • the salts may be chosen from any suitable metal salts, organic salts, protic salts, complex ion salts or the like.
  • the liquid salt medium can also be formed by mixing solid salts to create a liquid salt of the desired characteristics.
  • the liquid salt medium may contain additional components including water or other molecular liquids that are miscible with the liquid salt electrolyte.
  • additional components include dimethylsulfoxide, tetraglyme and other oligio- and poly-ethers, glutaronitrile and other high boiling point nitriles, trifluorotoluene and other wholly or partially fluorinated solvents and propylene carbonate and other carbonate solvents.
  • the N 2 gas stream can be pre-saturated by bubbling through a container of the molecular solvent prior to the gas stream passing into the reduction cell; any molecular liquid passing out of the cell in the product gas stream can be condensed or otherwise captured for re-use.
  • the molecular liquid is fluorinated or perfluorinated.
  • the molecular liquid is present in the liquid salt medium at a level between 90 vol% and 0.1 vol%, more preferably between 20 vol% and 0.2 vol% and most preferably between 50 vol% and 0.5 vol%.
  • the electrolyte comprising liquid salt provides an ion conductive, low water content medium in which the process reactions occur.
  • the electrolyte of the present invention also offers the advantage of low, or zero volatility and some gases are more soluble in these electrolytes comprising liquid salts than in water.
  • some electrolytes comprising liquid salts can provide an elevated solubility for N 2 gas (compared to aqueous and other electrolytes) thereby increasing the concentration of N 2 at the electrolyte/electrode interface.
  • the present invention provides an electrolyte medium for electrochemical reduction of dinitrogen to ammonia according to the method of the present invention, the medium comprising one or more liquid salts having high solubility for dinitrogen and low solubility for water.
  • the electrolyte comprises one or more eFAP liquid salts because they exhibit high N 2 solubility (ref S. Stevanovic et al, Chem. Thermodynamics 59 (2013) 65-71 ).
  • the electrolyte comprising liquid salt can also exhibit a degree of hydrophobicity that offers a controlled water activity to the electrochemical reaction, that is high enough to support the N2 reduction, but not so high as to support rapid reduction of water to H 2 .
  • the electrolyte comprises one or more hydrophobic liquids based on the ⁇ , ⁇ , ⁇ , ⁇ cation.
  • the electrolyte is substantially comprised of the liquid salt, [P6,6,6,i4][ eFAP].
  • the electrolyte is preconditioned prior to use, such as, by contacting it with an aqueous hydroxide solution.
  • the preconditioning may introduce a trace amount of OH " into the liquid salt that provides a defined proton activity in the electrolyte of the present invention.
  • the temperature range applied to the electrolyte materials in a cell according to the present invention may be between -35 and 200°C, preferably 0°C to 150 °C, and most preferably 15°C to 130°C.
  • the pressure range of application is typically between 0.7 bar nitrogen pressure to 100 bar nitrogen pressure, preferably 1 bar to 30 bar and most preferably 1 bar to 12 bar.
  • the pressure may be continuous, that is constant, or constantly increasing over time.
  • the pressure may be discontinuous, that is pulsed over time - alternating between higher and lower pressure values within the aforesaid ranges.
  • a pressure-temperature combination can be chosen to allow elevated N 2 solubility and electrochemical kinetics and also to allow ammonia to be generated at close to, but below, its condensation point (for examplel O bar at 25°C or 40 bar at 79°C).
  • a continuous current will pass between the cathodic working electrode and the counter electrode, however in some applications such as a wind power photovoltaic panel power driven process an intermittent or pulsed current may be suitable.
  • a catalyst for electrochemical reduction of dinitrogen to ammonia comprising nanostructured materials having a high electrochemical working surface area, as indicated by a double layer capacity, measured in an adjacent electrolyte layer of greater than 0.1 mF/cm 2 and preferably greater 1 mF/cm 2
  • the nanostructured catalyst comprises one or more metals in the form of elemental metal or inorganic compounds comprising metals.
  • the nanostructured catalyst may be in the form of discrete particles or sheet or film or three dimensional structure.
  • the nanostructured catalyst embodies morphological features that may be of any shape with at least one dimension in the range of 1 nm to 1000 nm.
  • Suitable metals include any of the transition metals or lanthanide metals including Fe, Ru, Mo, Cu, Pd, Ti, Ce and La as well as their alloys with other metals and semimetals.
  • the aforementioned metals may be surface decorated with an oxide or a sulphide of the metal, or a composite may be formed of the metal with its oxides or sulphides.
  • the catalysts may also comprise a metal complex consisting of two metals bridged by sulphides.
  • the metals are Fe and Mo.
  • the catalyst nanoparticle film may preferably be prepared by a cyclic voltammetry or a pulsed voltammetry electrodeposition method.
  • the catalyst may comprise conductive polymer materials such as PEDOT.
  • the catalyst may comprise doped carbon materials, particularly carbons doped with N and/or S.
  • the catalyst is preferably supported or decorated on an electrically conductive, chemically inert support.
  • Suitable supports include fluorine-doped tin oxide, graphene, reduced graphene oxide, porous carbons, carbon cloth, carbon nanotubes, conducting polymers and porous metals.
  • Faradaic efficiency is a particular deficiency of related processes of the prior art. Faradaic efficiency can be used to describe the fraction of electric current that is utilised in the N 2 reduction reaction. The remaining fraction that is, (100 - Faradaic efficiency) 0 /), is consumed in undesirable side reactions including the production of H 2 and hydrazine. These bi-products represent wasted energy and may also require complex separation methods from the desired product. It is one of the purposes of the present invention to provide a method of relatively high Faradaic efficiency preparation of ammonia.
  • embodiments of the present invention stem from the realization that the efficiency of ammonia production can be improved by choice of specific nonaqueous electrolytes that increase the concentration of dissolved N 2 gas and play a certain homogeneous catalysis role to increase the activity of dinitrogen in the reduction reaction while lowering the rate of undesirable competing reactions such as H 2 production.
  • the efficiency is further improved by using specific nanostructured catalysts.
  • Advantages provided by the present invention compared with the processes of the prior art comprise the following: conversion of dinitrogen to ammonia with high Faradaic efficiency; • the reaction can be carried out at ambient temperature and pressure;
  • FIG. 1 is a schematic diagram showing a typical electrochemical cell for N 2 reduction according to the present invention
  • FIG. 2 is a schematic depiction of an N 2 reduction cell according to the present invention and based on hybrid electrodes.
  • FIG.3 is a schematic depiction of a stacked N2 reduction cell arrangement according to the present invention showing cells as described in Figure 2 stacked in series connection.
  • the examples also illustrate the fabrication of electrodes based on various metal nanostructures (nanoparticles or films) using chemical and electrodeposition methods and investigation of their electrocatalytic properties in electrolytes comprising one or more liquid salts.
  • electrolytes comprising liquid salts dinitrogen was successfully converted to ammonia with Faradaic efficiency of >60% at ambient temperature and pressure, which exceeds room temperature efficiencies of processes of the prior art.
  • the method of the present invention utilising a liquid salt based process not only can significantly increase the solubility of dinitrogen but also play a certain homogeneous catalysis role to increase the activity of dinitrogen in the reduction reaction and at the same time lower the rate of undesirable competing reactions such as H 2 production.
  • N 2 electroreduction catalyst films based on Fe were prepared by electrodeposition of the Fe onto a commercially available fluorine-doped tin oxide or porous metal (or carbon) substrates.
  • Fluorine-doped tin oxide coated glass is electrically conductive and ideal for use in a wide range of devices.
  • Fluorine doped tin oxide is relatively stable under atmospheric conditions, chemically inert, mechanically hard, high- temperature resistant, has a high tolerance to physical abrasion.
  • Stainless steel mesh or cloth is useful as a high surface area substrate.
  • the deposition electrolyte comprised 10 mM FeS0 4 , 10 mM NaOH and 10 mM citric acid.
  • the electrodeposition was controlled by a potentiostat using a three-electrode system using fluorine doped tin oxide glass, Ti mesh, and a saturated calomel electrode (SCE) as the working, counter and reference electrode, respectively.
  • SCE saturated calomel electrode
  • a typical electrodeposition of this type is conducted using a cyclic voltammetry method between - 1.8 V and -0.8 V.
  • a black and shining film was formed after several cycles. Changing the number of cycles allows control of the thickness of film, and a typical film was electrodeposited by 10 cycles at a scan rate of 20 mV s "1 .
  • the film was characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and electrochemical surface area (ECSA) measurement.
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • EDX energy-dispersive X-ray spectroscopy
  • ECSA electrochemical surface area
  • the electrochemical N 2 reduction was conducted in a three-electrode system by using the Fe/fluorine doped tin oxide (or porous metla) electrode and platinum wire as the reference and counter electrodes, respectively. Cyclic voltammetry was measured in a one-compartment cell, while the N 2 reduction was conducted in a separated cell by isolating the counter electrode in compartment with a glass frit. Typical reduction was carried out for 3 hrs at -1.2 V vs Pt.
  • the N 2 gas was bubbled through a water trap to saturate it before bubbling into the electrolyte.
  • the synthesized ammonia carried in the exit gas was trapped by passing the gas stream through a weak acid solution (1 mM H 2 S0 4 ).
  • the ammonia produced in the gas phase was bubbled and collected through 1 mM H 2 S0 4 solution.
  • the ammonia remaining in the ionic liquid after completion of the electroreduction was extracted by washing the ionic liquid using 1 mM KOH.
  • the total amount of ammonia is the sum of the ammonia in the acid trap and the basic washing solution and was later quantified using the indophenol blue method.
  • FIG. 1 is a schematic diagram showing a typical electrochemical cell for N 2 reduction according to the present invention comprising a power source (1 ), cathode (2), membrane (3) and anode (4).
  • the counter electrode reaction in the process may be water or hydroxide oxidation as illustrated.
  • the desired product is the fertiliser ammonium sulphate
  • the counter electrode reaction may be S0 3 "2 to S0 4 "2 .
  • An advantage of the latter is that the total energy cost of the process is lower than when oxygen is the cathode reaction product.
  • N 2 reduction cell An N 2 reduction cell according to the present invention and based on hybrid electrodes is described in the following paragraphs.
  • This electrolysis cell is designed to optimally support electrolysis when the reactants which are one or more gases are only of low solubility in the electrolyte and therefore it is desirable to have the reaction occur principally in the region at or near the three phase boundary (that is, the boundary between the electrode material, the gas phase and the electrolyte) within the body of the hybrid electrode.
  • the hybrid electrode of this invention preferably comprises a porous conductive electrode material, optionally decorated with nanostructured catalyst, such that the electrode has a high electrochemically active surface area and has a multiplicity of pores allowing both gas access and electrolyte access within the body of the electrode.
  • the gas remains adjacent one surface and the pores of the hybrid electrode are at least partially filled with the ion conducting material so that transfer of reactants and products occurs in the region where the reduction of N2 to NH3 occurs.
  • the cathodic working electrodes are hybrid ion-conducting electrodes or "electrode membranes" prepared by creating porous metal membranes and impregnating the porous structure with an ion conducting material for example NafionTM or a NafionTM gel or a gelled liquid salt. Decorating the cathode with electrocatalysts creates a gas/electrolyte/metal three phase boundary region where electrolysis can take place.
  • the reactant gas is introduced directly to the electrocatalyst from the flowing gas.
  • the reactant or product ions diffuse through the electrolyte part of the electrode membrane and the gaseous products pass directly into the flowing gas phase.
  • the cell according to this embodiment is comprised of two porous electrodes (1 1 ,12) separated by an electrolyte layer (13). Electrode 1 is the cathodic working electrode at which nitrogen is reduced and electrode (12) is the counter electrode (anode) at which water oxidation or other desirable oxidation takes place. On the rear side of each electrode is a spacer layer (14, 15) which conducts gases in and out of the cell.
  • the electrodes comprise layers of flexible and porous conductive electrode sheet materials that have the electro-catalyst (16) loaded onto the sheet and exposed directly to the gas layer (14,15) respectively.
  • the catalysts (16) can be deposited throughout the structure of the electrode (11 ) to form a multiplicity of regions where gas, electrolyte, catalyst and conductive electrode come into contact.
  • the porosity of the conductor sheet is preferably such that the sheet is porous from one face to the other.
  • the porous conductive electrode material may be a macro- or micro- or nano- porous metal such as stainless steel, iron, nickel, copper, ruthenium or their alloys in the form of a mesh, foam or wool.
  • Porous carbon materials including carbon cloth, carbon particle/binder composites, graphene and reduced graphene oxide and conducting polymers are also suitable as porous conductive electrode materials.
  • the external encasement encloses the cell.
  • the cell In one form of the cell the cell is rolled or z-folded.
  • an assembly is formed by a number of cells stacked in series.
  • the electrolyte in the cell layers (18) must be isolated from one another and the encasement (17) is a conductive material so that a series connection is created between cells.
  • the stacked cells may also be folded or rolled.
  • the electrolyte can comprise a spacer or be in the form of an electrolyte membrane, for example a polymer electrolyte, including NafionTM or gelled NationTM or gelled liquid salt electrolyte, or an electrolyte soaked into a porous separator such as paper or CeleguardTM type materials that are well known in the battery field.
  • an electrolyte membrane for example a polymer electrolyte, including NafionTM or gelled NationTM or gelled liquid salt electrolyte, or an electrolyte soaked into a porous separator such as paper or CeleguardTM type materials that are well known in the battery field.
  • the layers (1 1 , 13 and 12) are pressed together and then the electrolyte is gelled in-situ to produce a self adhering assembly.
  • Gas flow layers (14) have the function of allowing the introduction of a stream of flowing gas that contains nitrogen and water vapour.
  • the exiting gas contains ammonia which is optionally trapped external to the cell.
  • the gas flow layer (15) is designed to allow entry or exit of the gaseous reactions or products produced on that side of the cell, optionally a flow of air or other gas can be introduced to dilute and carry this gas out of the cell.
  • the gas flow layers (14,15) are created either by use of a highly porous separator or mesh, or by printing or otherwise creating a pattern on one or both sides of layer (17).
  • the gas can be introduced at any convenient location including from the "end" of the longest dimension of the assembly or from either side of the assembly. Each of these arrangements requires alternate sealing arrangements of layers (17).
  • the whole assembly may be as little as 1 mm thick, maximizing the surface area and minimising the amount of electrolyte material needed.
  • Example 2 preparation of a nanostructured catalyst suitable for use in the present invention.
  • a fluorine doped tin oxide electrode (5 x 5 mm) was placed in an electrochemical cell and connected as the cathode.
  • a standard calomel electrode (SCE) acted as reference electrode and a Ti mesh served as the counter electrode.
  • the electrolyte solution for production of the catalyst comprised 10 mM FeS0 4 , 10mM NaOH, and 10 mM citric acid in water.
  • Electrodeposition of Fe was carried out by cycling the potential of the fluorine doped tin oxide electrode between - 0.8 and -1.8 V vs SCE at 20 mV/s for 10 cycles.
  • the electrodeposited Fe nanostructured layer appeared as a porous black layer comprising nanoparticles on the fluorine doped tin oxide.
  • the deposited material is composed of mainly metallic Fe with homogenous distribution of partially oxidized iron (with 10% oxides).
  • the iron oxide forms during the anodic part of the deposition cycle.
  • the formation of iron oxide can control the iron nanoparticle size.
  • the iron oxide is at least partially reduced during the initial stages of use as a cathode in ammonia production.
  • the Fe/FeOxide composite may enhance the catalytic activity through a synergistic effect of the two oxidation states of iron.
  • the electrochemical surface area was determined by measuring the double layer charging current at 0 V vs Pt by cyclic voltammetry at 5mV/s in butyl methylpyrrolidinium eFAP liquid salt at room temperature. A double layer capacity of 2 mF/cm 2 was measured under these conditions.
  • the fluorine doped tin oxide electrode bearing the Fe electrocatalyst layer was placed in an electrochemical cell as the cathode.
  • the electrolyte comprised the liquid salt [P6,6,6,i4 ][eFAP].
  • the electrolyte was preconditioned prior to use by shaking with 1 mM aqueous KOH solution.
  • the aqueous solution was only sparingly soluble in the liquid salt, such that the excess solution can be removed as a separate layer in a separating funnel.
  • the preconditioning may introduce a trace amount of OH " into the salts that provide a defined proton activity in the electrolyte.
  • the counter electrode (Pt) was placed in a fritted compartment, which also contains the saturated liquid salt.
  • the reference electrode is Pt.
  • Dinitrogen gas at 10 ml/min was introduced into the cell using a bubbler directing N 2 bubbles over the cathode.
  • the dinitrogen was pre-saturated with water by bubbling through a solution of low water vapour pressure.
  • Electrolysis was carried out for 2 to 5 hours at voltages between -1.0 to -2.0 V. At the end of the electrolysis the electrolyte was thrice washed with 1 mM KOH solution to extract any retained ammonia. The three washes were also analysed for ammonia. The result was combined with the result form the trap solution analysis. The Faradaic efficiency was 73% (+/-5%).
  • N 2 reduction was carried out as described in Example 2 except that the electrolyte comprised the liquid salt [C 4 mpyr][eFAP].
  • the Faradaic efficiency in this case was 47% (+/-5%).
  • the electrolyte comprised the liquid salt [P6,6,6,i4][FgC 4 S0 3 ].
  • a constant current of 4 uA cm "2 was applied for 2 hrs. Ammonia measurement showed that the Faradaic efficiency for ammonia was 51 %.
  • the electrolyte comprised the liquid salt [ ⁇ ⁇ , ⁇ , ⁇ , ⁇ ] [PFO].
  • a constant current of 4 uA cm “2 was applied for 2hrs. Ammonia measurement shows that the Faradic efficiency% for ammonia was 39%.
  • Example 6 Reduction of N 2 reduction with assistance of sonication.
  • Example 2 Following the same procedure as Example 2, the whole electrochemical cell was immersed into the bath of a sonicator. A constant potential of -1.2V vs NHE was applied on the working electrode for 30min, and sonication was applied to the electrochemical cell to promote the N 2 reduction. The current increased by approximately 125% compared to its previous value in the presence of the sonication.
  • Example 7 Reduction of N 2 in the presence of a molecular liquid component.
  • the electrolyte can by a combination of two or more salts to create a liquid salt of the desired characteristics.
  • the liquid salt may contain additional components including water or other molecular liquids as illustrated by the following Examples.
  • [0121] [C 4 mpyr][perfluorobutanesulfonate] has an elevated melting point (112°C) and could be used for N 2 reduction at temperatures above this point.
  • the melting point can also be lowered by the addition of a molecular liquid component as described in Example 7.
  • [0122] [C 4 mpyr][PFO] has an elevated melting point (87°C) and could be used for N 2 reduction at temperatures above this point.
  • the melting point can also be lowered by the addition of a molecular liquid component as described in Example 7.
  • the electrolyte used in the present invention may comprise a spacer or electrolyte membrane which itself is an electrolyte, for example a polymer electrolyte, such as NafionTM or gelled liquid salt electrolyte, or is an electrolyte soaked into a porous separator such as paper or CeleguardTM.
  • a spacer or electrolyte membrane which itself is an electrolyte, for example a polymer electrolyte, such as NafionTM or gelled liquid salt electrolyte, or is an electrolyte soaked into a porous separator such as paper or CeleguardTM.
  • a PVDF-HFP copolymer gel electrolyte membrane was prepared as follows using a liquid salt such as described in Example 3. A 9 to 1 ratio by weight of the liquid salt to copolymer was dissolved in dimethylformamide and heated slightly. The solution was spread onto a 34 mm diameter circle of SolupourTM membrane and left to dry. After drying, the excess gel on the outside of the membrane was removed.
  • a gas flow cell was constructed with a carbon paper/platinised carbon anode, the membrane and an Fe electrodeposited on stainless steel mesh (400 mesh) cathode. Hydrogen gas was introduced at the anode side of the gas flow cell and nitrogen gas was passed through the cathode side at a rate of 180 mL/min each. The pressure of gas inside the cell was 1 atmosphere. A constant potential of -1.2V relative to the anode was applied to the cathode for 30 mins.
  • Example 11 Preparation and Use of a Gel Membrane with [C 4 mpyr][eFAP] liquid salt suitable for use as a free standing membrane
  • a membrane was prepared as for Example 10 except that the liquid salt to polymer ratio was 7:3 by weight and the solution was cast to form a free-standing membrane. Ammonia produced over 30mins of applied potential was 59.5 nmoles with a Faradaic efficiency of 71.5%.
  • Example 12 Preparation and Use of a NationalTM Gel Membrane with a [C 4 mpyr][eFAP] liquid salt
  • a cell was constructed as described in Example 10, except that the electrolyte comprised a NafionTM-gel membrane and was prepared as described in the following example.
  • a solution containing 1 to 9 ratio by weight of NafionTM and [C 4 mpyr][eFAP] was prepared by mixing 9 parts of [C 4 mpyr][eFAP] and 20 parts of a 5 w/w% solution of Nafion in lower aliphatic alcohols and water, as supplied by Aldrich. This was dropped on to a 34mm diameter SolupourTM membrane to achieve complete coverage of the solution over the membrane. It was then dried overnight in an oven at 60°C. The gas flow cell was constructed with this NafionTM-gel membrane between the cathode and the anode. Ammonia produced was found to be 93.1 nmoles with a Faradaic efficiency of 30.6%.
  • Example 13 Preparation and Use of a free-standing electrolyte membrane comprising a NafionTM Membrane with a liquid salt
  • a cell was constructed as described in Example 11 except that the membrane was a NafionTM-gel membrane.
  • the membrane was prepared as follows. A 3 to 7 weight ratio mixture of NafionTM and liquid salt was prepared as described in example 12 and drop cast. It was then dried overnight in an oven at 60°C.
  • Example 15 N 2 reduction on Ru catalyst.
  • Example 3 Following the same procedure as Example 3, a ruthenium film was deposited onto the working electrode. A constant potential of -0.8 V vs NHE was applied on the working electrode for 30 min. The current density was approximately twice that of Example 3. Ammonia measurement shows that the Faradaic efficiency for ammonia production in this system was 28%. Use of other Electrode substrates
  • Comparative Examples 16 and 17 relate to salts disclosed in US 2016/0138176 however in the method of the present invention, the salt of Comparative Example 16 results in an untenably low Faradaic efficiency while the salt of Comparative Example 17 becomes unstable.
  • Comparative Example 18 illustrates more generally that certain ionic salts become unstable when used in the method of the present invention and for that reason are unsuitable.
  • N 2 reduction was carried out as described in Example 2 except that the liquid salt comprised the electrolyte [HMIM][NTf 2 ] and the working electrode employed the catalyst of Example 1. Since ionic liquids are generally regarded as salts having a melting point ⁇ 100°C [HMIM][NTf 2 ] may be regarded as an ionic liquid. As the melting point of this salt is around 70°C the reduction was carried out at 70°C in the liquid state.
  • N 2 reduction was carried out as described in Example 2 except that the electrolyte comprised the liquid salt [EMIM][B(CN) 4 ] and the working electrode employed the catalyst of Example 1 .
  • N 2 reduction was carried out as described in Example 2 except that the electrolyte comprised the liquid salt [EMIM][eFAP] and the working electrode employed the catalyst of Example 1 .

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Abstract

La présente invention concerne un procédé et une cellule électrochimique comprenant une électrode de travail cathodique comprenant un catalyseur nanostructuré, une contre-électrode et un électrolyte pour la réduction de diazote en ammoniac. L'invention comprend l'introduction de diazote et d'une source d'hydrogène dans l'électrolyte, le diazote étant réduit en ammoniac au niveau de l'électrode de travail cathodique. L'électrolyte comprend un ou plusieurs sels liquides formés de la combinaison d'un ensemble spécifié de cations et d'un ensemble spécifié d'anions.
PCT/AU2017/000036 2016-02-03 2017-02-03 Procédé et cellule de conversion de diazote en ammoniac WO2017132721A1 (fr)

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JP2018540776A JP2019510874A (ja) 2016-02-03 2017-02-03 二窒素をアンモニアへ転換する方法および電池
AU2017216250A AU2017216250B2 (en) 2016-02-03 2017-02-03 Method and cell for conversion of dinitrogen into ammonia
EP17746635.6A EP3411514A4 (fr) 2016-02-03 2017-02-03 Procédé et cellule de conversion de diazote en ammoniac
KR1020187024587A KR20180112798A (ko) 2016-02-03 2017-02-03 이질소를 암모니아로 전환하기 위한 방법 및 셀
US16/075,562 US20190040535A1 (en) 2016-02-03 2017-02-03 Method and cell for conversion of dinitrogen into ammonia

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020000044A1 (fr) * 2018-06-28 2020-01-02 Monash University Composition électrocatalytique et cathode pour réaction de réduction d'azote
CN111094629A (zh) * 2017-09-08 2020-05-01 冰岛大学 使用过渡金属氧化物催化剂电解生产氨
WO2020110155A1 (fr) * 2018-11-29 2020-06-04 Atmonia Ehf. Procédé de production électrolytique d'ammoniac à partir d'azote à l'aide d'une surface catalytique à base de sulfure métallique
EP3658505A4 (fr) * 2017-07-27 2021-04-14 Monash University Procédé, cellule et électrolyte pour la conversion de diazote
WO2022020904A1 (fr) * 2020-07-31 2022-02-03 Monash University Procédé de réduction électrochimique de diazote en continu
RU2803599C2 (ru) * 2017-09-08 2023-09-18 Хаускоули Исландс Электролитическое получение аммиака с использованием катализаторов на основе оксидов переходных металлов
WO2024052575A3 (fr) * 2022-09-09 2024-04-18 Danmarks Tekniske Universitet Cuve à circulation pour synthèse électrochimique d'ammoniac

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102244158B1 (ko) * 2019-02-01 2021-04-23 한국화학연구원 질소산화물로부터 질산암모늄 제조를 위한 전기화학 반응기 및 제조방법
WO2020169848A1 (fr) * 2019-02-22 2020-08-27 Katholieke Universiteit Leuven Réduction électrocatalytique de l'azote en ammoniac
US20220081786A1 (en) * 2020-09-16 2022-03-17 Battelle Energy Alliance, Llc Methods for producing ammonia and related systems
CN114540847B (zh) * 2022-02-15 2024-06-04 中国科学院过程工程研究所 一种含腈基和酚羟基离子液体强化co2电还原制草酸盐的方法
FR3135733A1 (fr) * 2022-05-19 2023-11-24 Centre National De La Recherche Scientifique Procédé de production d’azote ammoniacal

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050103706A1 (en) * 2003-08-21 2005-05-19 Matthew Bennett Ionic solvents used in ionic polymer transducers, sensors and actuators
US20060049063A1 (en) * 2004-09-07 2006-03-09 Murphy Oliver J Electrochemical synthesis of ammonia
WO2009029839A2 (fr) * 2007-08-31 2009-03-05 Energy & Environmental Research Center Foundation Procédé électrochimique de préparation d'engrais azotés
JP2012184132A (ja) * 2011-03-04 2012-09-27 Nagoya Institute Of Technology アンモニア製造方法
WO2016080645A2 (fr) * 2014-11-17 2016-05-26 한국에너지기술연구원 Appareil de synthèse d'ammoniac

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5966762B2 (ja) * 2012-08-21 2016-08-10 国立大学法人 名古屋工業大学 アンモニア製造方法およびアンモニア製造装置
NL2011188C2 (en) * 2013-07-18 2015-01-21 Univ Delft Tech Electrolytic cell for the production of ammonia.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050103706A1 (en) * 2003-08-21 2005-05-19 Matthew Bennett Ionic solvents used in ionic polymer transducers, sensors and actuators
US20060049063A1 (en) * 2004-09-07 2006-03-09 Murphy Oliver J Electrochemical synthesis of ammonia
WO2009029839A2 (fr) * 2007-08-31 2009-03-05 Energy & Environmental Research Center Foundation Procédé électrochimique de préparation d'engrais azotés
JP2012184132A (ja) * 2011-03-04 2012-09-27 Nagoya Institute Of Technology アンモニア製造方法
WO2016080645A2 (fr) * 2014-11-17 2016-05-26 한국에너지기술연구원 Appareil de synthèse d'ammoniac

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AMAR, I. ET AL.: "Electrochemical synthesis of ammonia based on a carbonate-oxide composite electrolyte", SOLID STATE TONICS, vol. 182, 2011, pages 133 - 138, XP028129506 *
See also references of EP3411514A4 *
STEVANOVIC, S. ET AL.: "Solubility of carbon dioxide, nitrous oxide, ethane, and nitrogen in 1-butyl-1-methylpyrrolidinium and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate (eFAP) ionic liquids", THE JOURNAL OF CHEMICAL THERMODYNAMICS, vol. 59, 2013, pages 65 - 71, XP028984474 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3658505A4 (fr) * 2017-07-27 2021-04-14 Monash University Procédé, cellule et électrolyte pour la conversion de diazote
CN111094629A (zh) * 2017-09-08 2020-05-01 冰岛大学 使用过渡金属氧化物催化剂电解生产氨
IL273018B1 (en) * 2017-09-08 2023-07-01 Haskoli Islands Electrolytic ammonia production using transition metal oxide catalysts
RU2803599C2 (ru) * 2017-09-08 2023-09-18 Хаускоули Исландс Электролитическое получение аммиака с использованием катализаторов на основе оксидов переходных металлов
AU2018332238B2 (en) * 2017-09-08 2023-11-16 Haskoli Islands Electrolytic ammonia production using transition metal oxide catalysts
WO2020000044A1 (fr) * 2018-06-28 2020-01-02 Monash University Composition électrocatalytique et cathode pour réaction de réduction d'azote
US12031220B2 (en) 2018-06-28 2024-07-09 Monash University Electrolytic composition and cathode for the nitrogen reduction reaction
WO2020110155A1 (fr) * 2018-11-29 2020-06-04 Atmonia Ehf. Procédé de production électrolytique d'ammoniac à partir d'azote à l'aide d'une surface catalytique à base de sulfure métallique
CN113366151A (zh) * 2018-11-29 2021-09-07 埃特莫尼亚有限公司 使用金属硫化物催化表面由氮气电解生产氨的方法
RU2821712C2 (ru) * 2018-11-29 2024-06-26 Атмония Ехф. Способ электролитического производства аммиака из азота с использованием каталитической поверхности на основе сульфида металла
WO2022020904A1 (fr) * 2020-07-31 2022-02-03 Monash University Procédé de réduction électrochimique de diazote en continu
WO2024052575A3 (fr) * 2022-09-09 2024-04-18 Danmarks Tekniske Universitet Cuve à circulation pour synthèse électrochimique d'ammoniac

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EP3411514A4 (fr) 2019-11-06
AU2017216250B2 (en) 2022-08-04
JP2019510874A (ja) 2019-04-18

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