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WO2024257188A1 - Appareil de production d'hydrogène et procédé de production d'hydrogène - Google Patents

Appareil de production d'hydrogène et procédé de production d'hydrogène Download PDF

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Publication number
WO2024257188A1
WO2024257188A1 PCT/JP2023/021789 JP2023021789W WO2024257188A1 WO 2024257188 A1 WO2024257188 A1 WO 2024257188A1 JP 2023021789 W JP2023021789 W JP 2023021789W WO 2024257188 A1 WO2024257188 A1 WO 2024257188A1
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Prior art keywords
hydrogen production
hydrogen
electrolysis
water
salt water
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English (en)
Japanese (ja)
Inventor
友恵 井藤
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Sumitomo Heavy Industries Ltd
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Sumitomo Heavy Industries Ltd
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Priority to PCT/JP2023/021789 priority Critical patent/WO2024257188A1/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
    • C25B1/02—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
    • 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
    • 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

Definitions

  • the present invention relates to a hydrogen production device and a hydrogen production method.
  • the present invention relates to a hydrogen production device and a hydrogen production method that use water containing chloride ions (chlorine) as a raw material and can suppress the generation of chlorine.
  • Carbon dioxide is believed to have a major impact on environmental issues such as global warming, and reducing its emissions into the environment is an issue that must be addressed immediately.
  • research is being conducted into technologies to reduce carbon dioxide emissions themselves, as well as technologies to capture and immobilize emitted carbon dioxide.
  • Hydrogen has the advantage of not emitting carbon dioxide when used as energy, such as in the generation of electricity by reaction with oxygen or in heat recovery by combustion, and is therefore attracting attention as a next-generation energy source. Hydrogen has the advantage of being able to be produced from a variety of resources, but the currently mainstream steam reforming using fossil fuels poses the problem of emitting carbon monoxide and carbon dioxide when obtaining hydrogen. Therefore, there is a demand for technology that does not emit carbon dioxide even during hydrogen production.
  • Patent Document 1 describes a hydrogen production device that includes a solar power generation unit equipped with a solar power generation module that generates electricity using sunlight, an electrolysis module that uses the electricity obtained by the solar power generation unit to electrolyze water (pure water), and a heating means that heats the water supplied to the electrolysis module.
  • Patent Literature 1 hydrogen production by water electrolysis does not generate carbon dioxide during the process, and hydrogen produced by water electrolysis is also called green hydrogen and has attracted attention.
  • Patent Literature 1 it is known that hydrogen production without carbon dioxide emissions is possible by using renewable energy such as solar power generation as the energy required for water electrolysis and water heating.
  • the subject of electrolysis is pure water.
  • the hydrogen production described in Patent Document 1 will use a large amount of pure water at this time.
  • the objective of the present invention is therefore to provide a hydrogen production device and method that can use salt water as a raw material and suppress the generation of chlorine when producing hydrogen through water electrolysis.
  • the present invention relates to the following hydrogen production device and hydrogen production method.
  • the hydrogen production device of the present invention which is intended to solve the above problems, is a hydrogen production device that produces hydrogen by salt water electrolysis, and is characterized in that it has an electrolysis section in which a cation exchanger is disposed between electrodes, and an electrolyte solution that does not contain chloride ions is introduced to the anode side of the electrolysis section, and salt water is introduced to the cathode side of the electrolysis section.
  • salt water is introduced to the cathode side of the electrolysis section having a cation exchanger disposed between the electrodes, while an electrolyte solution not containing chloride ions is introduced to the anode side.
  • the cation exchanger inhibits the chloride ions from migrating from the cathode side to the anode side, and electrolysis can be performed while maintaining a state in which the chloride ions that cause chlorine gas generation are not present on the anode side.
  • hydrogen is generated on the cathode side, while chlorine gas generation on the anode side can be inhibited.
  • moisture is supplied from salt water via an FO membrane to the electrolytic solution on the anode side of the electrolysis section.
  • an oxygen production reaction by water decomposition proceeds. Therefore, as electrolysis proceeds, the water (moisture) on the anode side decreases, so in order to continuously produce hydrogen, it is necessary to supply water (moisture) to the anode side.
  • the moisture that permeates the FO membrane when saltwater is brought into contact with it can be used as the moisture to be supplied to the anode side, and it becomes possible to further increase the proportion of saltwater used in the hydrogen production device. This makes it possible to further reduce the amount of pure water used in hydrogen production by water electrolysis, making it possible to effectively balance the effective use of water resources and the production of green hydrogen.
  • the hydrogen production method of the present invention for solving the above problems is a hydrogen production method for producing hydrogen by salt water electrolysis, and is characterized in that it uses an electrolysis unit in which a cation exchanger is disposed between electrodes, and includes the steps of introducing an electrolyte solution that does not contain chloride ions to the anode side of the electrolysis unit, introducing salt water to the cathode side of the electrolysis unit, and performing electrolysis in which the generation of chlorine is suppressed.
  • salt water is introduced to the cathode side of an electrolysis unit having a cation exchanger disposed between the electrodes, while an electrolyte solution not containing chloride ions is introduced to the anode side, so that the cation exchanger inhibits the chloride ions from migrating from the cathode side to the anode side during electrolysis, and electrolysis can be performed while maintaining a state in which chloride ions that cause chlorine gas generation are not present on the anode side.
  • electrolysis can be performed in which hydrogen is generated on the cathode side and chlorine gas generation is inhibited on the anode side.
  • the present invention provides a hydrogen production device and method that can use salt water as a raw material and suppress the generation of chlorine when producing hydrogen through water electrolysis.
  • FIG. 1 is a schematic explanatory diagram of a hydrogen production device according to a first embodiment of the present invention.
  • FIG. 1 is a schematic explanatory diagram showing steps related to hydrogen production and recovery in a hydrogen production device according to a first embodiment of the present invention.
  • FIG. 2 is a schematic explanatory diagram of a hydrogen production device according to a second embodiment of the present invention.
  • FIG. 4 is a schematic explanatory diagram showing the steps involved in hydrogen production and recovery in the hydrogen production device according to the second embodiment of the present invention.
  • FIG. 11 is a schematic diagram illustrating a hydrogen production device according to a third embodiment of the present invention.
  • FIG. 11 is a schematic explanatory diagram showing the steps involved in hydrogen production and recovery, and carbon dioxide fixation in a hydrogen production device according to a third embodiment of the present invention.
  • the hydrogen production device and method of the present invention relate to hydrogen production by water electrolysis, and more specifically, to hydrogen production using salt water as a raw material for hydrogen production and involving salt water electrolysis.
  • the salt water in the present invention refers to an aqueous solution containing chloride ions (chlorine).
  • the salt water in the present invention also functions as an electrolyte.
  • Other examples of salt water in the present invention include river water and lake water containing chloride ions, as well as industrial wastewater and factory wastewater containing chloride ions.
  • the salt water is mainly seawater, but is not limited to this.
  • FIG. 1 is a schematic diagram showing the structure of a hydrogen production device according to a first embodiment of the present invention.
  • the hydrogen production device 10A in this embodiment has an electrolysis unit 20 that electrolyzes salt water (hereinafter referred to as "seawater”).
  • the electrolysis unit 20 also includes a seawater inlet (line L1) for introducing seawater, an electrolyte inlet (line L2) for introducing an electrolyte not containing chloride ions (hereinafter simply referred to as "electrolyte E”), a hydrogen recovery unit (line L3) for recovering hydrogen, and an oxygen recovery unit (line L4) for recovering oxygen.
  • the electrolysis unit 20 in this embodiment electrolyzes seawater to generate hydrogen and collects the generated hydrogen.
  • the source of seawater hereinafter referred to as the "seawater source" introduced into the electrolysis unit 20.
  • the natural environment may be used as the seawater source, and seawater may be directly introduced from the ocean into the electrolysis unit 20, or artificially temporarily stored seawater, such as seawater used for ocean storage of carbon dioxide or as ballast water for ships, may be used as the seawater source.
  • the cost of procuring seawater as a raw material is mainly the cost of transporting the seawater. For example, by installing the hydrogen production device 10A of the present invention on land near the sea or on the sea (including on a ship, etc.), it becomes possible to use seawater with minimal transportation costs.
  • the electrolysis unit 20 in this embodiment is provided with a pair of electrodes (electrodes 22a, 22b) and a cation exchanger 23 in a treatment tank 21. As shown in FIG. 1, two spaces (spaces 24a, 24b) are formed within the treatment tank 21 via the cation exchanger 23.
  • the treatment tank 21 may be made of any material or shape as long as it is capable of stably storing seawater and electrolyte.
  • it may be made of materials and shapes that are used in structures known as electrolytic cells or electrodialysis cells.
  • the electrodes 22a and 22b are provided in the spaces 24a and 24b, respectively, and are connected to each other using conductors.
  • the electrodes 22a and 22b may be provided on the surface of or in the vicinity of the cation exchanger 23, and the electrodes 22a and 22b and the cation exchanger 23 may be treated as an integrated unit.
  • the electrodes 22a and 22b may be any electrodes that function as an anode or a cathode, and there are no particular limitations on the material and shape of the electrodes 22a and 22b. In this embodiment, the following description will be given assuming that the electrode 22a functions as an anode and the electrode 22b functions as a cathode.
  • Examples of the material of the electrodes 22a and 22b include carbon and metals (stainless steel, platinum, copper, etc.) that are widely used as electrode materials in the field of electrochemistry.
  • Examples of the shape of the electrodes 22a and 22b include, for example, a flat plate, a rod, a mesh, etc.
  • the electrodes 22a and 22b when the electrodes 22a and 22b are provided on the surface of the cation exchanger 23 or in the vicinity thereof, it is preferable that the electrodes 22a and 22b have a shape that can suppress the inhibition of mass transfer to the cation exchanger 23. Examples of such shapes include a mesh shape and a thin rod shape such as a wire.
  • the electrodes 22a and 22b includes an electrode pattern formed directly on the surface of the cation exchanger 23 by a method such as plating.
  • the shape of the electrode pattern is not particularly limited, but it is preferable that the electrode pattern has a shape that can suppress the inhibition of mass transfer to the cation exchanger 23.
  • the electrodes 22a and 22b when connecting the electrodes 22a and 22b with a conductor, it is preferable to provide a DC power supply for supplying electrical energy between the electrodes.
  • the power supply means for the DC power supply connected to the pair of electrodes there are no particular limitations on the power supply means for the DC power supply connected to the pair of electrodes, but it is preferable to use surplus electricity from power supply equipment or other facilities that utilizes renewable energy such as solar, wind, or wave power. This makes it possible to reduce the energy used in hydrogen production (generation and recovery of hydrogen).
  • a power supply means that uses renewable energy that does not emit carbon dioxide when generating electricity, it is also effective in promoting the reduction of carbon dioxide emissions.
  • the cation exchanger 23 is a membrane that partitions the treatment tank 21 and selectively allows cations to pass from the space 24a (hereinafter also referred to as the "anode side") in which the anode (electrode 22a) is disposed to the space 24b (hereinafter also referred to as the "cathode side") in which the cathode (electrode 22b) is disposed.
  • the cation exchanger 23 in this embodiment is preferably a membrane that suppresses the migration of chloride ions on the cathode side to the anode side and allows hydrogen ions (H + ) on the anode side to move to the cathode side.
  • the cation exchanger 23 may be any material that has the function of restricting the movement of anions and at least allowing hydrogen ions to pass therethrough, and there is no particular limitation on the specific components or structure.
  • a membrane that has been treated to selectively allow monovalent cations to pass therethrough a so-called monovalent ion selective membrane
  • a known cation exchange membrane that allows the movement of divalent or higher cations in addition to monovalent cations can be used.
  • the treatment tank 21 is connected to a line L1, which serves as a seawater inlet for introducing seawater from a seawater source to the cathode side (space 24b) of the electrolysis unit 20, and a line L2, which serves as an electrolyte inlet for introducing electrolyte E to the anode side (space 24a) of the electrolysis unit 20.
  • the line L1 for introducing seawater to the cathode side of the electrolysis unit 20 is not particularly limited as long as it is connected to the space 24b and has a material and structure that allows stable transport of seawater. It is preferable to provide a means on the line L1 for preventing foreign matter and organisms in the seawater from entering the treatment tank 21. For example, a filter or a net for capturing foreign matter and organisms in the seawater may be provided on the line L1.
  • the line L2 for introducing the electrolytic solution E to the anode side of the electrolysis unit 20 is not particularly limited as long as it is connected to the space 24a and has a material and structure that allows stable transfer of the electrolytic solution E.
  • the electrolyte E may be any solution that does not contain chloride ions and has electrical conductivity.
  • As the electrolyte E in this embodiment for example, one prepared by dissolving an electrolyte (excluding substances containing chloride ions) in pure water may be used.
  • Specific examples of the electrolyte E include an aqueous solution of a strong acid (excluding hydrochloric acid) or a strong base, in terms of ease of procurement, cost, and the degree of ionization.
  • an aqueous solution of a hydroxide strong base
  • a hydroxide strong base
  • the reaction efficiency related to water electrolysis is improved in the entire electrolysis unit 20, thereby enabling high efficiency in hydrogen production.
  • the treatment tank 21 is provided with a line L3 as a hydrogen recovery section that recovers the gas (hydrogen) generated on the cathode side, and a line L4 as an oxygen recovery section that recovers the gas (oxygen) generated on the anode side.
  • the hydrogen recovered by the hydrogen recovery section (line L3) in this embodiment is produced without emitting carbon dioxide, as described below, and is known as green hydrogen, a substance that is attracting attention as a next-generation energy source. Therefore, it is preferable to provide a means for removing gases other than hydrogen (such as water vapor) on line L3. This makes it possible to recover high-purity hydrogen and more effectively use the recovered hydrogen as an energy source.
  • Line L3 may also be connected to equipment for storing hydrogen and equipment for controlling the amount of hydrogen supplied. This makes it possible to appropriately use the generated and recovered hydrogen as an energy source.
  • the oxygen recovered by the oxygen recovery section (line L4) in this embodiment can be utilized by connecting line L4 to equipment related to the recovery and utilization of high-purity oxygen, just like hydrogen, or it can be discharged directly to the outside of the system.
  • the treatment tank 21 may also be provided with separate discharge lines for discharging the solutions on the cathode side and the anode side after electrolysis (not shown).
  • the method for producing hydrogen by salt water electrolysis in this embodiment involves electrolyzing salt water (seawater) using a treatment tank 21 partitioned by a cation exchanger 23, and generating and recovering hydrogen.
  • the steps involved in the production and recovery of hydrogen in the electrolysis unit 20 will be described below with reference to FIG.
  • Fig. 2 is a schematic diagram showing the hydrogen production and recovery process in the electrolysis unit 20 of the hydrogen production device 10A of this embodiment.
  • the configuration inside the treatment tank 21 in Fig. 2 is the same as the configuration shown in Fig. 1. Note that Fig. 2 mainly shows the movement of ions and molecules involved in the production and recovery of hydrogen, and some ions and molecules are not shown.
  • seawater is first introduced into the cathode side (space 24b) of the treatment tank 21 via line L1, and the electrolyte E is introduced into the anode side (space 24a) of the treatment tank 21 via line L2. Then, a voltage is applied between the electrodes 22a and 22b by a DC power source. At this time, the reaction at the electrode 22a in the space 24a (the reaction on the anode side) is represented by the following formula 1.
  • the hydrogen ions generated by formula 1 move to the cathode side (space 24b) via the cation exchanger 23 as shown in FIG. 2.
  • the oxygen generated by formula 1 may be recovered and utilized via line L4 as described above, or may be discharged directly to the outside of the system.
  • an electrolyte that does not contain chloride ions (electrolyte E) is used on the anode side, and the cation exchanger 23 prevents chloride ions from migrating from the cathode side to the anode side. Therefore, unlike normal saltwater (seawater) electrolysis, the reaction in which chloride ions turn into chlorine gas does not proceed.
  • reaction at the electrode 22b in the space 24b (the reaction on the cathode side) is represented by the following formula 2.
  • hydrogen can be generated from salt water (seawater) by the electrolysis unit 20.
  • the generated hydrogen is recovered via line L3 and utilized as an energy source.
  • carbon dioxide is not produced in the processes related to hydrogen generation and recovery, making it possible to suppress carbon dioxide emissions in addition to hydrogen production.
  • the electrolysis unit 20 in the hydrogen production device 10A is not limited to the structure shown in Figs. 1 and 2, and various means for efficiently generating and recovering hydrogen may be added. Examples of such means include means for suppressing the formation of precipitates on the surfaces of the electrodes 22a and 22b, and means for suppressing a decrease in the ion permeation efficiency of the cation exchanger 23.
  • salt water is introduced to the cathode side of the electrolysis section having a cation exchanger disposed between the electrodes, while an electrolyte solution not containing chloride ions is introduced to the anode side.
  • the cation exchanger inhibits the chloride ions from migrating from the cathode side to the anode side, and electrolysis can be performed while maintaining a state in which the chloride ions that cause chlorine gas generation are not present on the anode side.
  • hydrogen is generated on the cathode side, while chlorine gas generation on the anode side can be inhibited.
  • the hydrogen production device 10B according to the second embodiment is provided with a means for supplying moisture to the electrolytic solution E introduced into the anode side (space 24a) of the electrolytic unit 20 according to the first embodiment. More specifically, moisture from salt water is supplied to the electrolytic solution E on the anode side through the FO membrane 25.
  • FIG. 3 is a schematic diagram showing a hydrogen production device 10B according to a second embodiment of the present invention.
  • the hydrogen production device 10B of this embodiment further includes an FO membrane 25 in the treatment tank 21 shown in the first embodiment, and forms a space 24c outside the space 24a. It also includes a salt water supply section (line L5) that supplies salt water (seawater) to the space 24c, a circulation discharge section (line L6) that discharges and circulates the seawater introduced into the space 24b, and a circulation discharge section (line L7) that discharges and circulates the seawater supplied to the space 24c.
  • a salt water supply section line L5
  • a circulation discharge section line L6
  • a circulation discharge section line L7
  • the water decomposition reaction based on formula 1 proceeds on the anode side of the electrolysis unit 20, and the amount of water (moisture) on the anode side decreases as electrolysis proceeds. Therefore, in order to continuously produce hydrogen, it is necessary to supply water (moisture) to the anode side.
  • a water resource other than pure water it is preferable to use a water resource other than pure water as the water supplied to the anode side.
  • salt water as the water resource used in this case, and the same salt water (seawater, etc.) as the salt water introduced to the cathode side can be used. Additionally, it is preferable to enable water supply according to the amount of water consumed on the anode side.
  • the FO membrane 25 used in the hydrogen production device 10B of this embodiment is also called a forward osmosis membrane, and is a type of semipermeable membrane that allows water molecules to pass through but does not allow molecules or ions of a certain size or larger to pass through. Therefore, by using this FO membrane 25, it is possible to allow only water to pass through salt water (seawater). In addition, the FO membrane 25 allows only water (moisture) to pass from a solution with a low osmotic pressure to a solution with a high osmotic pressure.
  • the specific material of the FO membrane 25 in this embodiment is not particularly limited, and a material made of a known material can be used.
  • the hydrogen production device 10B in this embodiment may be any device capable of supplying moisture from saltwater to the electrolytic solution E via the FO membrane 25.
  • the FO membrane 25 is used to partition the treatment tank 21 into a space 24a and a space 24c, and saltwater (seawater) is supplied to the space 24c via a line L5.
  • the saltwater (seawater) in the space 24c and the electrolytic solution E in the space 24a face each other via the FO membrane 25.
  • a means may be provided for lowering the electrolyte concentration of the saltwater supplied to space 24c below the electrolyte concentration of the electrolytic solution E in space 24a.
  • a means for adding an electrolyte (excluding substances containing chloride ions) to the electrolytic solution E or a means for diluting the saltwater supplied to space 24c may be provided.
  • the hydrogen production device 10B in this embodiment be provided with a circulating supply unit (lines L1 and L6) for circulating and supplying salt water (seawater) to be introduced to the cathode side of the treatment tank 21, as shown in FIG. 3. This makes it possible to continue electrolysis (hydrogen production) without causing a decrease in moisture on the cathode side.
  • the hydrogen production device 10B in this embodiment is provided with a circulating supply section (lines L5 and L7) for circulating the saltwater (seawater) supplied to space 24c. This makes it possible to provide a stable supply of moisture to the electrolyte E on the anode side.
  • the hydrogen production method by saltwater electrolysis in the hydrogen production device 10B of this embodiment is similar to the hydrogen production in the first embodiment described above, in that saltwater (seawater) is electrolyzed to generate and recover hydrogen, and in addition, includes a step of supplying moisture from the saltwater to the electrolyte E on the anode side via the FO membrane 25.
  • FIG. Fig. 4 is a schematic diagram showing the hydrogen production and recovery process in the electrolysis section 20 of the hydrogen production device 10B of this embodiment.
  • the configuration inside the treatment tank 21 in Fig. 4 is the same as that shown in Fig. 3.
  • Fig. 4 mainly illustrates the configuration involved in the hydrogen production and recovery (during electrolysis), and some of the configuration is omitted.
  • Fig. 4 also mainly illustrates the movement of ions and molecules involved in the hydrogen production and recovery, and some of the ions and molecules are omitted.
  • seawater is introduced into the cathode side (space 24b) of the treatment tank 21 via line L1, and the electrolyte E is introduced into the anode side (space 24a) of the treatment tank 21 via line L2. Then, a voltage is applied between the electrodes 22a and 22b by a DC power source. At this time, the seawater introduced into the cathode side is discharged through line L6, and then circulated and supplied to space 24b again through line L1.
  • salt water (seawater) is supplied to space 24c of treatment tank 21 via line L5.
  • the timing of supplying salt water to space 24c is not particularly limited, and it may be before, during, or after voltage application. At this time, the salt water supplied to space 24c is discharged via line L7, and then circulated and supplied to space 24c again via line L5.
  • a reaction (anode side reaction) at the electrode 22a in the space 24a proceeds based on Equation 1.
  • the hydrogen ions generated by formula 1 move to the cathode side (space 24b) through the cation exchanger 23 as shown in Fig. 4.
  • water ( H2O ) is consumed from the electrolyte E on the anode side (space 24a).
  • the reaction in which chloride ions become chlorine gas on the anode side does not proceed.
  • the oxygen generated by the reaction of formula 1 may be recovered and utilized via line L4, or may be discharged directly to the outside of the system.
  • Equations 2 and 3 a reaction (cathode side reaction) occurs at electrode 22b in space 24b, generating hydrogen. As described above, the generated hydrogen is recovered via line L3 and utilized as an energy source.
  • the hydrogen production device 10B and hydrogen production method of this embodiment allow the moisture that permeates when saltwater is brought into contact with the FO membrane to be used as moisture to be supplied to the electrolyte on the anode side, which decreases with electrolysis, making it possible to further increase the proportion of saltwater used in hydrogen production.
  • This makes it possible to further reduce the amount of pure water used in hydrogen production by water electrolysis, making it possible to effectively balance the effective use of water resources with the production of green hydrogen.
  • the hydrogen production device 10C according to the third embodiment is provided with a configuration that enables fixation of carbon dioxide in addition to hydrogen production with suppressed carbon dioxide emission. More specifically, the solution (seawater) on the cathode side after electrolysis in the electrolysis unit 20 is used to fix carbon dioxide.
  • the electrolysis unit 20 in this embodiment any of the electrolysis units 20 in the first and second embodiments described above may be used. Note that the electrolysis unit 20 in this embodiment will be described as having the same configuration as the electrolysis unit 20 in the second embodiment, and the description of the same configuration as the second embodiment will be omitted.
  • FIG. 5 is a schematic diagram showing a hydrogen production device 10C according to a third embodiment of the present invention.
  • the hydrogen production device 10C of this embodiment is equipped with a carbon dioxide supply section (line L8) that supplies carbon dioxide to the electrolysis section 20 in order to perform a carbon dioxide fixation process using the solution subjected to electrolysis in the electrolysis section 20.
  • the source (or generation source) of the carbon dioxide supplied via the carbon dioxide supply unit (line L8) is not particularly limited.
  • Specific examples of carbon dioxide sources include gases containing carbon dioxide emitted from various facilities (power generation facilities, factories, ordinary households, etc.) and transportation methods associated with daily life and industrial activities, as well as naturally occurring gases containing carbon dioxide, such as the atmosphere and volcanic gases.
  • the carbon dioxide supply unit (line L8) may be provided with a means for adjusting the amount of carbon dioxide supplied, or a means for more effectively dissolving carbon dioxide in the saltwater on the cathode side. Specific examples include providing a flow control valve or a pressurizing mechanism on line L8, or providing a structure at the end of line L8 for blowing carbon dioxide into the saltwater on the cathode side.
  • the hydrogen production method by salt water electrolysis in the hydrogen production device 10C of this embodiment is similar to the hydrogen production in the first and second embodiments described above, in that salt water (seawater) is electrolyzed to generate and recover hydrogen, and in addition, includes a step of using the solution after electrolysis to fix carbon dioxide.
  • FIG. Fig. 6 is a schematic diagram showing the hydrogen generation and recovery process and the process related to carbon dioxide fixation in the electrolysis unit 20 of the hydrogen production device 10C of this embodiment.
  • the configuration inside the treatment tank 21 in Fig. 6 is the same as the configuration shown in Fig. 5.
  • Fig. 6 mainly illustrates the configuration involved in the hydrogen generation and recovery (during electrolysis) and the fixation of carbon dioxide, and some of the configuration is omitted.
  • Fig. 6 also mainly illustrates the movement of ions and molecules involved in the hydrogen generation and recovery and the fixation of carbon dioxide, and some of the ions and molecules are omitted.
  • Equation 4 the reaction involved in the fixation of carbon dioxide.
  • the carbonate ions (CO 3 2 ⁇ ) generated in formula 4 react with divalent metal ions (calcium ions) to form carbonate as shown in formula 5. This allows the fixation process of carbon dioxide to proceed.
  • formula 5 shows calcium ions as divalent metal ions
  • the present embodiment of the carbon dioxide fixation treatment is not limited to this.
  • divalent ions of Group 2 elements other than Ca (Mg 2+, etc.) and divalent ions of transition metals (Fe 2+ , Co 2+ , Ni 2+, etc.) can be used.
  • the salt water introduced to the cathode side is seawater, a certain amount of Ca and Mg is contained in the ion state, so that it can be used as a divalent metal ion source that can supply a stable amount of divalent metal ions.
  • carbonates of Group 2 elements have low solubility in water and are harmless, there is no need to further treat the generated carbonates.
  • the generated carbonates have the advantage that they are easy to recover and can be used as resources for various purposes.
  • Equations 4 and 5 show that the efficiency of the carbon dioxide fixation process can be improved by progressing the chemical equilibrium reaction in the direction of producing carbonate ions. In other words, by progressing the chemical equilibrium in equation 4 toward the right and increasing the amount of carbonate ions in equation 5, the efficiency of the carbon dioxide fixation process can be improved.
  • salt water electrolysis is performed using the electrolysis unit 20 of this embodiment, similarly to the second embodiment.
  • hydroxide ions are generated based on formula 2, and hydrogen is released as a gas from the cathode side through line L3, thereby alkalizing the salt water (seawater) on the cathode side.
  • the hydrogen production device 10C of this embodiment can effectively promote the fixation process of carbon dioxide in addition to hydrogen production.
  • the above-described embodiment shows an example of a hydrogen production device and a hydrogen production method.
  • the hydrogen production device and the hydrogen production method according to the present invention are not limited to the above-described embodiment, and the hydrogen production device and the hydrogen production method according to the above-described embodiment may be modified within the scope of the gist of the claims.
  • the hydrogen production device and method of the present invention can be suitably used as a technology for producing hydrogen using salt water.
  • the hydrogen production device and method of the present invention can be suitably used as a technology for producing green hydrogen.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un appareil de production d'hydrogène et d'un procédé de production d'hydrogène qui, dans la production d'hydrogène par électrolyse de l'eau, permettent l'utilisation d'eau salée en tant que charge d'alimentation tout en supprimant la génération de chlore.　Afin de résoudre le problème décrit ci-dessus, la présente invention concerne : un appareil de production d'hydrogène pour produire de l'hydrogène par électrolyse d'eau salée, l'appareil de production d'hydrogène comportant une unité d'électrolyse dans laquelle un échangeur de cations est disposé entre des électrodes, une solution électrolytique qui ne contient pas d'ions chlorure étant introduite dans le côté anode de l'unité d'électrolyse, et de l'eau salée étant introduite dans le côté cathode de l'unité d'électrolyse; et un procédé de production d'hydrogène.　Selon la présente invention, l'électrolyse peut être effectuée tout en maintenant un état dans lequel des ions chlorure qui provoquent la génération de chlore gazeux n'existent pas sur le côté anode. Par conséquent, dans la production d'hydrogène par électrolyse de l'eau, de l'eau salée peut être utilisée en tant que charge d'alimentation pour la production d'hydrogène tout en supprimant la génération de chlore, et, lorsque l'appareil de production d'hydrogène est amené à plus grande échelle, le coût et la charge environnementale peuvent être réduits.
PCT/JP2023/021789 2023-06-12 2023-06-12 Appareil de production d'hydrogène et procédé de production d'hydrogène Pending WO2024257188A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107331A (ja) * 2010-10-26 2012-06-07 Frd:Kk 水電解システム
KR20220078185A (ko) * 2020-12-03 2022-06-10 한국에너지기술연구원 해수전해장치 및 이를 포함하는 해수전해 연료전지 연계시스템
US20230032928A1 (en) * 2019-12-26 2023-02-02 Vito Nv Method for generating hydrogen and oxygen from a liquid feed stream comprising water, and device therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107331A (ja) * 2010-10-26 2012-06-07 Frd:Kk 水電解システム
US20230032928A1 (en) * 2019-12-26 2023-02-02 Vito Nv Method for generating hydrogen and oxygen from a liquid feed stream comprising water, and device therefor
KR20220078185A (ko) * 2020-12-03 2022-06-10 한국에너지기술연구원 해수전해장치 및 이를 포함하는 해수전해 연료전지 연계시스템

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