[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2018194182A1 - Procédé de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène, et procédé et dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite - Google Patents

Procédé de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène, et procédé et dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite Download PDF

Info

Publication number
WO2018194182A1
WO2018194182A1 PCT/JP2018/016440 JP2018016440W WO2018194182A1 WO 2018194182 A1 WO2018194182 A1 WO 2018194182A1 JP 2018016440 W JP2018016440 W JP 2018016440W WO 2018194182 A1 WO2018194182 A1 WO 2018194182A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
hydrogen gas
fuel cell
hydrogen
gas
Prior art date
Application number
PCT/JP2018/016440
Other languages
English (en)
Japanese (ja)
Inventor
永佳 松島
亮太 小河
Original Assignee
国立大学法人北海道大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人北海道大学 filed Critical 国立大学法人北海道大学
Priority to JP2019513716A priority Critical patent/JP7164882B2/ja
Publication of WO2018194182A1 publication Critical patent/WO2018194182A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D59/00—Separation of different isotopes of the same chemical element
    • B01D59/38—Separation by electrochemical methods
    • B01D59/40—Separation by electrochemical methods by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B5/00—Water
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing water or an aqueous solution enriched with hydrogen isotopes, a method for producing hydrogen gas with reduced hydrogen isotope concentration, and a production apparatus. More specifically, the present invention relates to a method for producing water or an aqueous solution enriched with hydrogen isotopes from water or an aqueous solution containing hydrogen isotope-containing water, a method for producing hydrogen gas with reduced hydrogen isotope concentration, and a production apparatus. In the method and apparatus for producing water or an aqueous solution enriched with hydrogen isotopes, hydrogen gas with a reduced hydrogen isotope concentration can be produced together.
  • Hydrogen isotopes of deuterium and tritium are important as raw materials for fusion reactor fuels and medical materials. Furthermore, as for the contaminated water related to the Fukushima nuclear accident, an effective method for separating tritium has not been found, and it is still the biggest concern for the treatment of contaminated water.
  • Separation and concentration techniques for deuterium and tritium, which are hydrogen isotopes include distillation using differences in boiling point, water-hydrogen sulfide exchange method (GS method) by exchange substitution with light hydrogen atoms, water electrolysis method and platinum catalyst. (CECE method) (see Non-Patent Document 1 (provided by TEPCO)).
  • Non-patent document 1 http://www.tepco.co.jp/nu/fukushima-np/roadmap/images/c130426_06-j
  • the water electrolysis method started in 1933 when G.N. Lewis et al. Continuously electrolyzed the water in the old electrolyzer to obtain a small amount of heavy water, and this method is still used industrially.
  • the Fukushima nuclear power plant needs to process a large amount of contaminated water every day, and its power consumption is enormous, making it unsuitable for large-scale production.
  • An object of this invention is to provide the new concentration technique of the water containing a hydrogen isotope.
  • the present invention is as follows. [1] A fuel cell connected in series to at least one water electrolyzer and at least two hydrogen gas streams (FCn, where n is an integer greater than or equal to 2 and connected to the water electrolyzer in the first stage) Is made into FC1, and power generation is performed independently in each fuel cell, and water electrolysis is performed in a water electrolysis apparatus, so that water or an aqueous solution containing a hydrogen isotope (hereinafter referred to as an aqueous solution AS 0 ).
  • FCn water electrolyzer and at least two hydrogen gas streams
  • a method for producing water or an aqueous solution (AS e ) having a higher hydrogen isotope content than the aqueous solution AS 0 (We1) hydrolyzing the aqueous solution AS 0 in a water electrolyzer to obtain hydrogen gas and oxygen gas; (Fc1) Hydrogen gas obtained by the electrolysis is supplied to the negative electrode side of the fuel cell 1 (FC1), a part of the hydrogen gas (HG 0 ) is reacted at the negative electrode, and the remaining hydrogen gas (HG 1 ) is reacted at the negative electrode side.
  • FC1 to the positive electrode side of the ⁇ FCn is supplied oxygen gas or an oxygen-containing gas, at least partially supplied to the water electrolysis apparatus from said recovered hydrogen isotope-containing water W 1 W n, [1] The method described. [3] Wherein providing at least a portion of the recovered hydrogen isotope-containing water W 1 W n with an aqueous solution AS 0 to the water electrolysis apparatus, the method described in [1] or [2]. [4] Any one of [1] to [3], wherein the hydrogen isotope-containing water W 1 to W n is recovered from the fuel cell by being accompanied by oxygen gas or oxygen-containing gas discharged from the positive electrode side of the fuel cell. The method described in 1.
  • a fuel cell connected in series to at least one water electrolyzer and at least two hydrogen gas streams (FCn, where n is an integer greater than or equal to 2 and connected to the water electrolyzer in the first stage) Is made into FC1, and the method of producing hydrogen gas with reduced hydrogen isotope concentration, including generating electricity independently in each fuel cell and performing water electrolysis in a water electrolyzer Because (We1) water electrolysis of water or an aqueous solution containing a hydrogen isotope in a water electrolyzer to obtain hydrogen gas (HG 0 ) and oxygen gas; (Fc1h) The hydrogen gas HG 0 obtained by the electrolysis is supplied to the negative electrode side of the fuel cell 1 (FC1), a part of the hydrogen gas HG 0 is reacted at the negative electrode, and the remaining hydrogen gas (HG 1 ) (Fc2h) The recovered hydrogen gas HG 1 is supplied to the negative electrode side of the fuel cell 2 (FC2), a part of the hydrogen gas HG 1 is reacted at the negative electrode, and
  • Hydrogen gas circulation means is provided in the negative electrode chamber of the fuel cell adjacent to the water electrolyzer of the fuel cell connected in series from the cathode chamber of the water electrolyzer,
  • the fuel cells connected in series have hydrogen gas circulation means between the negative electrode chambers of the fuel cells sequentially connected from the fuel cells adjacent to the water electrolysis device,
  • the fuel cells connected in series have oxygen gas or oxygen-containing gas flow means between the positive electrode chambers of the fuel cells sequentially connected from the fuel cells adjacent to the water electrolysis device, and Having distribution means for recovering water generated from the fuel cell to the water electrolyzer;
  • An apparatus for producing water or aqueous solution enriched with hydrogen isotopes [14] The production apparatus according to [13], for producing hydrogen gas with a reduced isotope concentration.
  • At least one water electrolyzer and at least two fuel cells connected in series with a flow of hydrogen gas the water electrolyzer having a cathode chamber and an anode chamber, wherein the fuel cell comprises a negative electrode chamber and a positive electrode chamber, respectively.
  • Have Hydrogen gas circulation means is provided in the negative electrode chamber of the fuel cell adjacent to the water electrolyzer of the fuel cell connected in series from the cathode chamber of the water electrolyzer,
  • the fuel cells connected in series have hydrogen gas circulation means between the negative electrode chambers of the fuel cells sequentially connected from the fuel cells adjacent to the water electrolyzer.
  • the hydrogen isotope concentration of water containing hydrogen isotopes can be concentrated by combining water electrolysis and power generation by a fuel cell, the concentration efficiency is high, and power is generated by the fuel cell. Since electricity can be used for water electrolysis, power consumption of the entire system can be suppressed.
  • hydrogen gas having a reduced hydrogen isotope concentration can be produced together.
  • a method and apparatus capable of producing hydrogen gas having a reduced hydrogen isotope concentration can be provided.
  • Example 1 It is a schematic explanatory drawing of the one aspect
  • An outline of the experimental apparatus used in Example 1 is shown.
  • the experimental result of Example 1 is shown.
  • the experimental result of Example 2 is shown.
  • An outline of the experimental apparatus used in Example 3 is shown.
  • the experimental result of Example 3 is shown.
  • 6 is a schematic explanatory diagram of an oxygen forward flow type apparatus of the present invention used in Example 5.
  • FIG. FIG. 5 is a schematic explanatory diagram of an oxygen backflow type apparatus of the present invention used in Example 5.
  • the experimental result of Example 5 is shown.
  • the experimental result of Example 5 is shown.
  • the present invention uses a fuel cell connected in series to at least one water electrolyzer and at least two hydrogen gas streams, and generates power independently in each fuel cell, and the water electrolyzer in the water electrolyzer And a method for producing water or an aqueous solution (AS e ) having a hydrogen isotope content higher than that of the aqueous solution AS 0 from water or an aqueous solution containing hydrogen isotopes (hereinafter referred to as an aqueous solution AS 0 ).
  • the present invention further relates to an apparatus for producing hydrogen isotope-enriched water or an aqueous solution (hydrogen isotope-enriched water / aqueous solution), comprising at least one water electrolyzer and at least two fuel cells connected in series.
  • the water electrolysis apparatus has a cathode chamber and an anode chamber, and the fuel cell has a negative electrode chamber and a positive electrode chamber, respectively.
  • FIG. 1 A schematic diagram of one embodiment of the production apparatus of the present invention is shown in FIG.
  • the apparatus shown in FIG. 1 includes one water electrolyzer (water electrolyzer) 10 and fuel cells FC1, FC2,... FCn connected in series.
  • n is an integer of 3 or more. There is no restriction
  • FCn is shown, but there are two fuel cells, FC1 and FC2.
  • the connection mode of the fuel cells in series means that a plurality of fuel cells are connected along the flow of hydrogen gas flowing between the fuel cells. It is not meant to be connected in series by paying attention to the flow of electricity between the plurality of fuel cells. Since the plurality of fuel cells are operated under independent conditions, they are not electrically connected in series.
  • the water electrolyzer 10 has an anode and a negative electrode and a diaphragm (for example, an ion exchange membrane) installed between the anode and the negative electrode in the electrolyzer.
  • a diaphragm for example, an ion exchange membrane
  • an external power source is connected to the anode and the negative electrode.
  • the water electrolyzer there are known a polymer electrolyte water electrolyzer, an alkaline water electrolyzer and the like, but an alkaline water electrolyzer is suitable because it can generate a large amount of hydrogen gas.
  • the temperature at which the water electrolysis apparatus is operated is, for example, preferably in the range of 20 ° C to 70 ° C. However, it is not intended to be limited to this range.
  • the amount of hydrogen generated can be controlled by adjusting the amount of current.
  • a preferred current can be, for example, in the range of 0.1-100A. However, it is not intended to be limited to this range.
  • the anode chamber has a circulation means for supplying water / aqueous solution and an oxygen gas circulation means for discharging oxygen gas generated at the anode by electrolysis.
  • the cathode chamber may have hydrogen gas circulation means for discharging hydrogen gas, and the cathode chamber may have circulation means for supplying water / aqueous solution.
  • the flow means for supplying water / aqueous solution is connected to the anode chamber side.
  • the fuel cells FC1, FC2,... FCn each have a catalyst layer serving as a positive electrode and a catalyst layer serving as a negative electrode on both sides of an electrolyte, and a catalyst layer serving as a positive electrode chamber and a negative electrode outside the catalyst layer serving as a positive electrode.
  • a negative electrode chamber is provided on the outside of the substrate.
  • the type, structure, shape, and dimensions of the electrolyte, positive electrode, and negative electrode are not particularly limited.
  • the catalyst used for the catalyst layer serving as the positive electrode is preferably a material that can preferentially generate a water generation reaction between hydrogen isotope ions and oxygen compared to a water generation reaction between hydrogen ions and oxygen.
  • the catalyst used for the catalyst layer serving as the negative electrode is preferably a material capable of preferentially producing an oxidation reaction of hydrogen gas containing a hydrogen isotope as compared with an oxidation reaction of hydrogen gas.
  • examples of such materials include noble metals such as platinum and ruthenium, transition metals such as nickel and cobalt, alloys and oxides thereof.
  • the electrolyte is preferably a material that easily allows diffusion of not only hydrogen ions but also hydrogen isotope ions in the electrolyte.
  • Examples of such a material include a proton conductive solid polymer membrane and an anion conductive solid polymer membrane.
  • the oxygen gas flow means (supply side and discharge side) are connected to the positive electrode chamber, and the hydrogen gas flow means (supply side and discharge side) are connected to the negative electrode chamber.
  • the oxygen gas circulation means is means for circulating oxygen gas or oxygen-containing gas.
  • the positive electrode chamber can further be provided with circulation means (supply side and discharge side) for supplying water / aqueous solution.
  • the water / water solution can be discharged by accompanying the oxygen-containing gas discharged from the positive electrode chamber.
  • Flow means (supply side and discharge side) for supplying water / aqueous solution provided in the fuel cell, oxygen gas flow means (supply side and discharge side), and hydrogen gas flow means (supply side and discharge side) are adjacent to each other.
  • FC1 is adjacent to the water electrolysis tank
  • the oxygen gas circulation means (supply side) of FC1 adjacent to the water electrolysis tank is connected to the anode chamber of the water electrolysis tank
  • the hydrogen gas circulation means of FC1 ( The supply side) is connected to the cathode chamber of the water electrolyzer.
  • the distribution means (discharge side) for supplying the water / aqueous solution of FC1 may be a water electrolysis tank.
  • distribution means for supplying water / aqueous solution of FCn, oxygen gas distribution means (discharge side), and hydrogen gas distribution means (discharge side) are connected to the outside of the apparatus.
  • the oxygen gas circulation means (supply side) to each fuel cell is not connected to the adjacent water electrolyzer or the oxygen gas circulation means (discharge side) of the adjacent fuel cell, and independently oxygen gas (for example, air It can also be connected to a source.
  • the hydrogen gas circulation means for connecting the fuel cells connected in series communicates between the negative electrode chambers of adjacent fuel cells.
  • the oxygen gas circulation means for connecting the fuel cells connected in series communicates between the positive electrode chambers of the adjacent fuel cells.
  • the water or aqueous solution circulation means can connect between the positive electrode chambers of the adjacent fuel cells of the fuel cells connected in series.
  • the method for producing a hydrogen isotope concentrated water / water solution of the present invention can be carried out, for example, using the apparatus of the present invention.
  • the method of the present invention will be described with reference to FIG.
  • (We1) The aqueous solution AS 0 is hydroelectrolyzed in a water electrolyzer to obtain hydrogen gas and oxygen gas.
  • (Fc1) Hydrogen gas obtained by the electrolysis is supplied to the negative electrode side of the fuel cell 1 (FC1), a part of the hydrogen gas (HG 0 ) is reacted at the negative electrode, and the remaining hydrogen gas (HG 1 ) is reacted at the negative electrode side.
  • Hydrogen gas obtained by the electrolysis is supplied to the negative electrode side of the fuel cell 1 (FC1), a part of the hydrogen gas (HG 0 ) is reacted at the negative electrode, and the remaining hydrogen gas (HG 1 ) is reacted at the negative electrode side.
  • W 1 hydrogen isotope-containing water
  • the aqueous solution AS 0 is hydroelectrolyzed to obtain hydrogen gas and oxygen gas, and the water or the aqueous solution AS e having a higher hydrogen isotope content than the aqueous solution AS 0 after the electrolysis is recovered.
  • the aqueous solution AS 0 can be water (aqueous solution) containing water containing deuterium (D) or tritium (T) which are hydrogen isotopes.
  • Water containing deuterium (D) which is a hydrogen isotope element contains H 2 O, HDO and / or D 2 O.
  • Water containing tritium (T) which is a hydrogen isotope element contains H 2 O, HTO and / or T 2 O.
  • the concentration of water (such as HDO and / or D 2 O, HTO and / or T 2 O) containing a hydrogen isotope element contained in the aqueous solution AS 0 is not particularly limited.
  • the hydrogen isotope element can be in the range of 0.1 to 100 atomic%. However, it is not intended to be limited to this range.
  • the aqueous solution is preferably pure water containing no electrolyte.
  • the aqueous electrolysis solution supplied with the aqueous solution AS 0 or the aqueous solution AS 0 preferably contains an electrolyte.
  • an electrolyte can be added to the aqueous solution AS n .
  • the electrolyte can be, for example, an alkaline substance from the viewpoint of having no adverse reactivity such as corrosiveness, and the alkaline substance is preferably, for example, sodium hydroxide, potassium hydroxide, or the like.
  • the aqueous solution containing the electrolyte can also be seawater. It can also be pond water. The concentration of the electrolyte can be appropriately determined in consideration of electrolysis conditions and the like.
  • the conditions for electrolysis of water in the water electrolysis apparatus are not particularly limited as long as oxygen molecules are generated at the anode and hydrogen molecules at the cathode in the water electrolysis tank.
  • water electrolysis water containing a hydrogen isotope element contained in an aqueous solution is less susceptible to electrolysis than water (H 2 O) not containing a hydrogen isotope element.
  • water containing hydrogen isotopes contained in an aqueous solution is not necessarily electrolyzed at all.
  • the ratio of light hydrogen and hydrogen isotope elements that are decomposed into oxygen molecules and hydrogen molecules in water electrolysis (denoted as H / X (X is D or T)) Although it varies depending on the apparatus and operating conditions, it exceeds 1, and is, for example, in the range of 1.5 to 5.
  • the hydrogen isotope concentration in the hydrogen gas produced by electrolysis is lower than that of the aqueous solution AS 0.
  • the hydrogen gas also contains hydrogen isotopes, and water containing deuterium (D), which is a hydrogen isotope element. in the electrolysis, in addition to H 2, HD and / In the electrolysis of water containing tritium (T) is a. Hydrogen isotopes containing D 2, in addition to H 2, containing HT and / or T 2.
  • step (fc1) a hydrogen gas HG 0 generated by water electrolysis on the negative electrode side of FC1 is supplied.
  • This hydrogen gas contains a hydrogen isotope as described above.
  • Hydrogen gas containing hydrogen isotopes reacts with oxygen on the positive electrode side in the fuel cell to produce water.
  • the reaction formula in the positive electrode and the negative electrode of the fuel cell is illustrated in FIG.
  • the reactivity with oxygen in a fuel cell varies depending on the type of hydrogen isotope, the type of fuel cell (electrode, electrolyte, etc.) and operating conditions, but in general, the hydrogen isotope X is less than light hydrogen (H). Is higher.
  • X / H is greater than 1, for example, in the range of 1.5-5.
  • the concentration of the hydrogen isotope element in the remaining hydrogen gas HG 1 is lower than the concentration of the hydrogen isotope element in HG 0 .
  • the concentration of the hydrogen isotopes contained in the water produced at the positive electrode side of the fuel cell is higher than the concentration of the hydrogen isotopes in HG 0. That is, the hydrogen isotope element is concentrated on the water side and reduced in hydrogen gas.
  • step (fc1) (fc2), except that a hydrogen gas HG 1 to FC2 is supplied, it is similar to the operation in the FC1 in step (fc1). If hydrogen gas to the negative electrode side of FC2 remains, the concentration of the hydrogen isotopes of hydrogen gas HG 2 remaining is lower than the concentration of the hydrogen isotopes in HG 1. Further, while the concentration of the hydrogen isotopes contained in the water produced at the positive electrode side of the FC2 is higher than the concentration of the hydrogen isotopes in HG 1. That is, the hydrogen isotope element is concentrated on the water side and reduced in hydrogen gas. This relationship continues to FCn in step (fc3).
  • Ratio of the amount of hydrogen gas HG 0 supplied to the negative electrode side of FC1 in step (fc1) and the amount of hydrogen gas HG 2 or HG n recovered from FC2 or FCn in (fc2) or (fc3) (HG 0 : HG 2 or HG n ) can be in the range of, for example, 100: 0-50.
  • 100: 0 means that all hydrogen gas is consumed in FCn, and more than 100: 0 means that a part of hydrogen gas is recovered in FCn.
  • the consumption of hydrogen gas in each FC can be adjusted by adjusting the power generation amount in each FC.
  • the amount of power generation is adjusted by controlling the external electric load that is set.
  • the concentration of the hydrogen isotope element contained in HG n varies depending on the concentration of the hydrogen isotope element contained in HG 0 , the number of connected fuel cells, the operating conditions of the fuel cell, and the like. , for example, 50% of the concentration of hydrogen isotopes contained in HG 0 or less, preferably to 10% or less.
  • hydrogen gas HG 2 or HG n having a hydrogen isotope content lower than hydrogen gas HG 0 can be recovered from FC 2 of (fc 2) or FC n of (fc 3), and hydrogen gas can be co-produced.
  • the ratio of the amount of hydrogen gas supplied to the negative electrode side of any fuel cell FCn-1 and the amount of hydrogen gas recovered from the negative electrode side of FCn-1 ie, hydrogen gas Is not particularly limited, but is, for example, in the range of 100: 10 to 90 (provided that when n is 3 or more and n is 2, the ratio is in the range of 100: 0 to 50). is there).
  • the consumption ratio of hydrogen gas in each FC can be set independently between FCs.
  • Oxygen gas or oxygen-containing gas is supplied to the positive electrodes of FC1 to FCn.
  • oxygen gas is also generated as described above. At least a part of the oxygen gas can be supplied to the positive electrode side of at least a part of the fuel cells.
  • the oxygen gas supplied to the positive electrode side of the fuel cell can be not only oxygen gas obtained by water electrolysis, but also oxygen gas in the air or a mixture of both.
  • a plurality of options are described as a method for supplying oxygen gas in each fuel cell, and at least one of them can be adopted.
  • oxygen gas generated by water electrolysis can be sequentially circulated from FC1 to FCn, and air can be further added to the oxygen gas.
  • the oxygen gas generated by the water electrolysis can be temporarily stored in a pool (not shown) of oxygen gas and then supplied independently to each of the fuel cells FC1 to FCn.
  • FCn fuel cell n-1
  • water containing a hydrogen isotope is generated as described above.
  • This water is recovered.
  • the recovery method is not particularly limited. For example, when unconsumed oxygen gas is supplied to the positive electrode chamber and discharged from the positive electrode chamber, it can be discharged and recovered along with the gas. At least part of the recovered hydrogen isotope-containing waters W 1 to W n depends on the concentration of the hydrogen isotopes contained therein, but when the hydrogen isotope concentration is relatively high (for example, recovered water from FC1 and FC2), hydrogen It can be joined to AS e as an isotope-enriched aqueous solution. Alternatively, if a relatively hydrogen isotope concentration is low (e.g., recovered water from FCn), it may be subjected to water electrolysis with AS 0.
  • At least part of the power for water electrolysis in the water electrolyzer can be covered by the power generated in the fuel cell.
  • the power for water electrolysis can be power other than the power generated by the fuel cell.
  • the at least two fuel cells connected in series can be, for example, three to ten fuel cells connected in series, and the number of fuel cells connected in series is 2, 3, 4, 5, Any of 6, 7, 8, 9, 10 may be used.
  • Each fuel cell may be one or more fuel cells connected in parallel.
  • Each fuel cell may be the same type of fuel cell or a different type of fuel cell.
  • the fuel cell can generate power independently.
  • hydrogen gas generated from the water electrolysis apparatus is consumed under independent operating conditions to generate power, and the hydrogen isotope element is concentrated in the water generated at the same time.
  • the enrichment effect of the hydrogen isotope element is expressed synergistically by making the fuel cell multistage.
  • the hydrogen gas generation amount (corresponding to energy consumption) in the water electrolysis apparatus and the hydrogen gas consumption amount (corresponding to energy generation amount) in each fuel cell are It is an important factor for designing the overall energy balance.
  • the amount of energy generated in each fuel cell can be controlled independently, and the maximum hydrogen isotope enrichment effect, which is the object of the present invention, and the maximum energy efficiency can be achieved. It will be possible. Note that the amount of energy generated in each fuel cell can be adjusted by, for example, the degree of load of electrical resistance.
  • the fuel cell examples include a phosphoric acid fuel cell, a solid oxide fuel cell, a solid polymer fuel cell, an alkaline membrane fuel cell, and an alkaline fuel cell.
  • a polymer electrolyte fuel cell it is preferable because power can be generated at a temperature in the range of 20 to 90 ° C.
  • the temperature is particularly preferably in the range of 60 to 80 ° C.
  • the production apparatus of the present invention can also be used to produce hydrogen gas with a reduced isotope concentration.
  • the isotope concentration is reduced to, for example, about 1/100 times, and the hydrogen gas with the reduced isotope concentration should be used for other purposes as high-purity hydrogen. Can do.
  • the present invention is a fuel cell (FCn, where n is an integer greater than or equal to 2) connected in series to at least one water electrolyzer and at least two hydrogen gas streams.
  • Hydrogen gas having a reduced hydrogen isotope concentration including using FC1 as a connected fuel cell), generating power independently in each fuel cell, and performing water electrolysis in a water electrolyzer
  • FCn fuel cell
  • This manufacturing method is (We1) water electrolysis of water or an aqueous solution containing a hydrogen isotope in a water electrolyzer to obtain hydrogen gas (HG 0 ) and oxygen gas; (Fc1h)
  • the hydrogen gas HG 0 obtained by the electrolysis is supplied to the negative electrode side of the fuel cell 1 (FC1), a part of the hydrogen gas HG 0 is reacted at the negative electrode, and the remaining hydrogen gas (HG 1 )
  • the recovered hydrogen gas HG 1 is supplied to the negative electrode side of the fuel cell 2 (FC2), a part of the hydrogen gas HG 1 is reacted at the negative electrode, and the remaining hydrogen gas (HG 2 ) is recovered at the negative electrode side.
  • the step (we1) is synonymous with the step (we1) in the method for producing hydrogen isotope concentrated water / aqueous solution.
  • the step (fc1h) may not include recovering the hydrogen isotope-containing water (W 1 ) generated on the positive electrode side and the step (fc1) in the method for producing the hydrogen isotope concentrated water / aqueous solution. Is synonymous.
  • the step (fc2h) may not include recovering the hydrogen isotope-containing water (W 2 ) generated on the positive electrode side and the step (fc2) in the method for producing the hydrogen isotope concentrated water / aqueous solution. Is synonymous.
  • the step (fc3h) may not include the step (fc3) in the method for producing the hydrogen isotope concentrated water / aqueous solution and the recovery of the hydrogen isotope-containing water (W n ) generated on the positive electrode side. Is synonymous.
  • step hydrogen gas The hydrogen gas HG n recovered in step hydrogen gas is recovered in (fc2h) HG 2 and step (fc3h) is low hydrogen isotope concentration than the hydrogen gas HG 0. This also applies to hydrogen gas HG n recovered hydrogen gas HG 2 and steps to be recovered in step (fc2) in the production method of the hydrogen isotope enriched water / aqueous (fc3).
  • the degree of reduction of the hydrogen isotope concentration in the hydrogen gases HG 2 and HG n varies depending on the hydrogen isotope concentration of the hydrogen gas HG 0 , the configuration and operating conditions of the fuel cell FCn, and can be appropriately controlled.
  • the present invention includes an apparatus for producing hydrogen gas with reduced hydrogen isotope concentration, comprising at least one water electrolyzer and at least two fuel cells connected in series.
  • the water electrolysis apparatus in this production apparatus, the hydrogen gas circulation means between the water electrolysis apparatus and the fuel cell, and the hydrogen gas circulation means between the fuel cells are the water electrolysis apparatus in the hydrogen isotope concentrated water / aqueous solution production apparatus.
  • the hydrogen gas circulation means between the water electrolyzer and the fuel cell and the hydrogen gas circulation means between the fuel cells are synonymous with each other.
  • hydrogen gas with reduced hydrogen isotopes is produced from the hydrogen gas obtained by the water electrolysis apparatus.
  • the method for producing hydrogen gas with reduced hydrogen isotope concentration can be implemented.
  • Example 1 Experimental method: 1-stage fuel cell In this experiment, alkaline water electrolysis (AWE) and polymer electrolyte fuel cell (PEFC) were used. An outline of the experimental apparatus is shown in FIG.
  • PEFC Electrode bonding film (50 ⁇ 50 mm) using a platinum catalyst (Pt supported amount: 0.52 mg / cm 2 ) was used for both positive and negative electrodes, and Nafion (NRE211) was used for the electrolyte film.
  • Hydrogen gas generated from AWE was supplied directly to the negative electrode of PEFC, and pure oxygen gas was supplied to the positive electrode from an oxygen cylinder. Power generation was performed at room temperature.
  • PEFC was connected to a variable resistor (manufactured by Kikusui Electronics Co., Ltd., PLZ164W) and adjusted so that the generated current was constant.
  • a quadrupole mass spectrometer manufactured by ULVAC, Qulee HGM202, Q-Mass
  • the sample gas was supplied to the detector at a constant pressure (10 -5 Pa) with a needle valve.
  • the detector is designed to keep the temperature at 60 ° C and the detection sensitivity does not depend on the external environment.
  • the hydrogen isotope separation coefficient ⁇ was obtained by analyzing the hydrogen gas discharged by PEFC before and after power generation with Q-Mass, and the ratio of both was obtained by equation (1). The results are shown in the figure.
  • Example 2 Concentration dependence The relationship between the separation factor of PEFC alone and the hydrogen isotope concentration (deuterium) was investigated.
  • An electrode bonding film 50 ⁇ 50 mm) using a platinum catalyst (Pt supported amount: 0.52 mg / cm 2 ) was used for both the positive electrode and the negative electrode, and Nafion (NRE211) was used for the electrolyte film.
  • a mixed gas of light hydrogen gas and deuterium gas was supplied to the negative electrode, and pure oxygen gas (80 ml min ⁇ 1 ) was supplied to the positive electrode.
  • the flow rate of light hydrogen gas (H 2 ) is fixed at 20 ml min ⁇ 1
  • the flow rate of deuterium gas (D 2 ) is adjusted with a mass flow controller
  • the D / H ratio is 10 ⁇ 5 to 10 ⁇ 3 .
  • PEFC was connected to a variable resistor (PLZ164W, manufactured by Kikusui Electronics Co., Ltd.), and was generated at room temperature so that the generated current was constant.
  • the hydrogen isotope separation factor ⁇ was obtained by analyzing the hydrogen gas discharged from the PEFC before and after power generation using Q-Mass, and the ratio between the two was obtained by equation (2). The results are shown in FIG.
  • Example 3 Experimental method: Multi-stage fuel cell
  • AWE circular nickel mesh electrodes (actual area 35 cm 2 ) were used for the anode and cathode, and ultrasonic cleaning was performed with acetone and ethanol before electrolysis.
  • a diaphragm was used between the anode and the cathode so that the gas generated at each electrode was not mixed.
  • a potassium hydroxide aqueous solution (pH 15) was used as the electrolytic solution, and deuterated water was added so that the deuterium / light hydrogen (D / H) ratio was 1: 9, and 0.6 L was filled in an acrylic electrolytic cell.
  • the water electrolyzer was circulated by a pump. Water electrolysis was operated at room temperature under a constant current of 5 A using a DC power supply.
  • PEFC uses an electrode bonding membrane (50 x 50 mm) that uses platinum catalyst (Pt loading: 0.52 mg / cm 2 ) for both positive and negative electrodes in both batteries, and Nafion (NRE211) for the electrolyte membrane. It was used. Hydrogen gas generated from AWE was supplied to the negative electrode of the first stage PEFC, and the hydrogen gas discharged from the first stage was sequentially supplied to the negative electrode of the next stage PEFC. Pure oxygen gas was supplied from the oxygen cylinder to the positive electrode of the first stage, and the oxygen gas discharged from the first stage was sequentially supplied to the positive electrode of the PEFC of the next stage. Each stage PEFC was connected to three independent variable resistors, and the generated current was adjusted to a constant value. The PEFC was set to FC1, FC2, and FC3 from the side closest to AWE, and the following three conditions were examined so that the total generated current would be 4.5A. The operating temperature was room temperature.
  • a quadrupole mass spectrometer manufactured by ULVAC, Qulee HGM202, Q-Mass
  • the sample gas was supplied to the detector at a constant pressure (10 -5 Pa) with a needle valve.
  • the detector is designed to keep the temperature at 60 ° C and the detection sensitivity does not depend on the external environment.
  • the hydrogen isotope separation factor ⁇ was obtained by analyzing the hydrogen gas discharged from the third-stage PEFC with Q-Mass, and the ratio between the two was obtained by equation (3). The results are shown in Table 1 and FIG.
  • the theoretical separation factor ⁇ of the multi-stage fuel cell was defined as follows, assuming that the separation factor for water electrolysis was ⁇ AWE , FC1, FC2, and FC3 were ⁇ FC1 , ⁇ FC2 , and ⁇ FC3 .
  • ⁇ ⁇ AWE ⁇ ⁇ FC1 ⁇ ⁇ FC2 ⁇ ⁇ FC3
  • - ⁇ AFE was set to 6.0 from the results of another experiment.
  • -Fuel cell separation factor ⁇ FC1 , ⁇ FC2 , ⁇ FC3
  • Example 4 When the same amount of hydrogen was used for power generation, the following experiment was conducted to demonstrate that the greater the number of FCs, the better the separation factor and generated power.
  • KOH electrolyte (5 M, 10 at% D 2 O) was electrolyzed at 3.0 A, and the following three experiments were performed using the generated hydrogen gas.
  • the fuel cell FC is the same as that used in Example 1.
  • the results are shown in Table 2. From the results shown in Table 2, it can be seen that when the same amount of hydrogen is used for power generation, the greater the number of FCs, the greater the separation factor and power generation.
  • Example 5 Examination of the direction of oxygen gas introduction into the fuel cell Using two fuel cells FC, the difference in the separation factor due to the difference in the direction of oxygen gas introduction was measured.
  • the oxygen gas introduction direction is the oxygen forward flow type shown in FIG. 8, and hydrogen gas and oxygen gas are sequentially supplied to the fuel cell in the same direction.
  • the oxygen gas reacts in the fuel cell in order from the hydrogen gas having the high D concentration.
  • the direction shown in FIG. 9 is an oxygen reverse flow type, and hydrogen gas and oxygen gas are sequentially supplied to the fuel cell in reverse directions.
  • the oxygen reverse flow type shown in FIG. 9 the oxygen gas reacts in order from the hydrogen gas having a low D concentration. It is expected that the oxygen reverse flow type separation coefficient that can be expected to be separated to the oxygen electrode side will be improved. The following experiment was conducted to confirm this point.
  • Example 4 KOH electrolyte (5 M, 10 at% D 2 O) was electrolyzed at 3.0 A, and the generated hydrogen gas was used.
  • the fuel cell FC is the same as that used in Example 1.
  • the results are shown in FIGS. 10-1 and 10-2.
  • the measurement of Ion Current in Fig. 10-1 was performed by examining the exhaust gas discharged from the fuel cell. For this reason, a decrease in Ion Current means a decrease in the amount of hydrogen isotope D in the exhaust gas (an increase in D consumption in the fuel cell). From the results shown in FIG. 10-1, the D consumption in the fuel cell reaction increased from the oxygen forward flow to the oxygen reverse flow.
  • the present invention is useful in the field of treatment of water containing hydrogen isotopes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Fuel Cell (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un procédé de production, à partir d'eau ou d'une solution aqueuse contenant de l'eau contenant des isotopes d'hydrogène, d'eau ou d'une solution aqueuse ayant une teneur en isotopes d'hydrogène plus élevée que la solution aqueuse AS0, et un procédé de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite, en utilisant au moins un dispositif d'électrolyse de l'eau et au moins deux piles à combustible branchées en série, en produisant de l'électricité dans les piles à combustible et en réalisant une électrolyse de l'eau dans le dispositif d'électrolyse de l'eau. La présente invention concerne également un dispositif de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène et un dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite, comprenant au moins un dispositif d'électrolyse de l'eau et au moins deux piles à combustible branchées en série. La présente invention réalise une technique nouvelle de concentration d'eau contenant un isotope d'hydrogène.
PCT/JP2018/016440 2017-04-21 2018-04-23 Procédé de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène, et procédé et dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite WO2018194182A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019513716A JP7164882B2 (ja) 2017-04-21 2018-04-23 水素同位体が濃縮された水または水溶液の製造方法、水素同位体濃度が低減された水素ガスの製造方法及び製造装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017084386 2017-04-21
JP2017-084386 2017-04-21

Publications (1)

Publication Number Publication Date
WO2018194182A1 true WO2018194182A1 (fr) 2018-10-25

Family

ID=63855824

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/016440 WO2018194182A1 (fr) 2017-04-21 2018-04-23 Procédé de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène, et procédé et dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite

Country Status (2)

Country Link
JP (1) JP7164882B2 (fr)
WO (1) WO2018194182A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5449498A (en) * 1977-09-27 1979-04-18 Mitsubishi Heavy Ind Ltd Separation device of hydrogen isotope
JPH117974A (ja) * 1997-06-18 1999-01-12 Mitsubishi Electric Corp 中、大容量燃料電池発電装置
JP2004337843A (ja) * 2003-04-25 2004-12-02 Showa Denko Kk 水素同位体水の濃縮方法及び装置
JP2007193951A (ja) * 2006-01-17 2007-08-02 Mitsubishi Heavy Ind Ltd 燃料電池及びその運転方法
JP2015187552A (ja) * 2014-03-26 2015-10-29 三菱重工環境・化学エンジニアリング株式会社 放射性物質処理装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012158499A (ja) 2011-02-01 2012-08-23 Fc Kaihatsu Kk 重水素低減水製造方法および装置
JP6745092B2 (ja) 2015-06-17 2020-08-26 デノラ・ペルメレック株式会社 アルカリ水電解装置とアルカリ燃料電池を利用した水処理システム及び該水処理システムを用いた水処理方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5449498A (en) * 1977-09-27 1979-04-18 Mitsubishi Heavy Ind Ltd Separation device of hydrogen isotope
JPH117974A (ja) * 1997-06-18 1999-01-12 Mitsubishi Electric Corp 中、大容量燃料電池発電装置
JP2004337843A (ja) * 2003-04-25 2004-12-02 Showa Denko Kk 水素同位体水の濃縮方法及び装置
JP2007193951A (ja) * 2006-01-17 2007-08-02 Mitsubishi Heavy Ind Ltd 燃料電池及びその運転方法
JP2015187552A (ja) * 2014-03-26 2015-10-29 三菱重工環境・化学エンジニアリング株式会社 放射性物質処理装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MATSUSHIMA, H. ET AL.: "A novel deuterium separation system by the combination of water electrolysis and fuel cell", ENERGY, vol. 30, 2005, pages 2413 - 2423, XP025263267, DOI: doi:10.1016/j.energy.2004.11.013 *

Also Published As

Publication number Publication date
JP7164882B2 (ja) 2022-11-02
JPWO2018194182A1 (ja) 2020-05-28

Similar Documents

Publication Publication Date Title
US6994929B2 (en) Electrochemical hydrogen compressor for electrochemical cell system and method for controlling
JP5422083B2 (ja) ノンフローレドックス電池
EP3017089B1 (fr) Système à hydrogène et procédé de fonctionnement
JP2015029921A (ja) 重水の電解濃縮方法
KR101451630B1 (ko) 이산화탄소 환원방법 및 이를 이용한 이산화탄소 환원장치
WO2016204233A1 (fr) Système de traitement de l'eau à l'aide d'un dispositif d'électrolyse de l'eau alcaline et d'une pile à combustible alcaline
KR101468782B1 (ko) 이산화탄소 환원방법 및 이를 이용한 무격막형 이산화탄소 환원장치
WO2020038383A1 (fr) Procédé et dispositif de purification d'une solution électrolytique d'une batterie à flux
CN114402095B (zh) 错流式水电解
WO2018194182A1 (fr) Procédé de production d'eau ou d'une solution aqueuse enrichie en isotopes d'hydrogène, et procédé et dispositif de production d'hydrogène gazeux ayant une concentration en isotopes d'hydrogène réduite
US20220288532A1 (en) Hydrogen isotope concentrating apparatus
TW201321310A (zh) 產生殺生物劑之方法
JP2015223574A (ja) トリチウム回収用三室型電解槽及びトリチウム回収システム
JPS62182292A (ja) Ｈｃｉの隔膜電解法
US9537167B2 (en) Methods and apparatus of an anode/cathode (A/C) junction fuel cell with solid electrolyte
Matsushima et al. Deuterium isotope separation by polymer electrolyte fuel cells connected in series
RU2548442C1 (ru) Способ получения обедненной дейтерием воды
JPS6038174B2 (ja) 水素同位体の分離装置
CN212077164U (zh) 一种电能补给型电化学反应器
US20170073826A1 (en) Solar-powered single-compartment multi-purpose electrochemical reactor
KR101320328B1 (ko) 독립운전 수소펌프 시스템
TWI652229B (zh) 富氫水生成裝置及其方法
JP2007059196A (ja) 発電システム
CN104862732A (zh) 由含氧气体电化学生成臭氧的方法及设备
KR20220121658A (ko) 물 전기분해를 이용한 수소 생산 시스템에서의 물 관리 장치

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18787151

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019513716

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18787151

Country of ref document: EP

Kind code of ref document: A1