WO2018092899A1 - Procédé et appareil de génération d'hydrogène en utilisant une électrodialyse inverse - Google Patents

Procédé et appareil de génération d'hydrogène en utilisant une électrodialyse inverse Download PDF

Info

Publication number
WO2018092899A1
WO2018092899A1 PCT/JP2017/041561 JP2017041561W WO2018092899A1 WO 2018092899 A1 WO2018092899 A1 WO 2018092899A1 JP 2017041561 W JP2017041561 W JP 2017041561W WO 2018092899 A1 WO2018092899 A1 WO 2018092899A1
Authority
WO
WIPO (PCT)
Prior art keywords
chamber
exchange membrane
anion exchange
electrode
exchange membranes
Prior art date
Application number
PCT/JP2017/041561
Other languages
English (en)
Japanese (ja)
Inventor
充 比嘉
敏裕 濱田
正一 土井
渡邉　剛
秀信 二村
碓井　次郎
恒 細川
Original Assignee
株式会社アストム
株式会社正興電機製作所
日本下水道事業団
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 株式会社アストム, 株式会社正興電機製作所, 日本下水道事業団 filed Critical 株式会社アストム
Publication of WO2018092899A1 publication Critical patent/WO2018092899A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/50—Stacks of the plate-and-frame type
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • 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 method and apparatus for generating hydrogen using reverse electrodialysis.
  • a plurality of ion exchange membranes (anion exchange membranes and cation exchange membranes) are alternately arranged between two electrodes, and a high-concentration salt solution is allowed to flow on one side with the ion exchange membrane sandwiched therebetween, while the other A low-concentration salt solution is flowed to the side of the ion exchange membrane, and the potential generated when ions move from the high-concentration side to the low-concentration side due to the concentration difference between one side and the other side of the ion exchange membrane
  • RED Reverse Electrodialysis
  • this power generation system can use seawater and fresh water (river water) as an energy source, is excellent in safety, is not affected by natural phenomena, unlike solar power generation and wind power generation, and further is nuclear power generation.
  • seawater and fresh water river water
  • nuclear power generation As described above, there is a great advantage that no harmful substances such as radioactive substances are generated, and various power generation methods and power generation apparatuses using the same have been proposed (see, for example, Patent Documents 1 and 2). Further, platinum or the like is generally used as the two electrodes.
  • An object of the present invention is to provide a method and an apparatus capable of efficiently generating hydrogen using reverse electrodialysis.
  • a plurality of anion exchange membranes and cation exchange membranes are alternately arranged between a pair of conductive electrode plates, and the electrode plates and the anion exchange membranes or cation exchange membranes
  • the chamber formed between the main electrode chambers and the polar liquid is allowed to flow through each of the main electrode chambers, and at the same time, the chamber formed on one side of the anion exchange membrane or the cation exchange membrane is a thick chamber.
  • one or more water electrolysis units having a structure in which a conductive plate is inserted therebetween, Each of the two chambers formed between the two sides of the conductive plate and the ion exchange membrane is a pseudo electrode chamber, a polar liquid is caused to flow through each of the pseudo electrode chambers, and hydrogen is supplied to one pseudo electrode chamber.
  • a reverse electrodialysis method characterized in that it is generated. Note that hydrogen can also be generated in the one main electrode chamber in which the reduction reaction usually occurs.
  • the reverse electrodialysis method of the present invention is particularly used as a method for producing hydrogen, and can take the following modes.
  • the main electrode chamber in which the reduction reaction occurs is the cathode chamber, and the other main electrode chamber is the anode chamber, so that the rich chamber formed on one surface side of one anion exchange membrane faces the cathode chamber side.
  • a lean chamber formed on the other surface side of the one anion exchange membrane is disposed on the anode chamber side.
  • a high concentration electrolyte solution is allowed to flow through each of the pseudo electrode chambers formed on both sides of the conductive plate.
  • a plurality of anion exchange membranes and cation exchange membranes are alternately arranged between a pair of electrode plates that are electrically connected to each other, and the electrode plates and anion exchange membranes or cation exchanges are arranged.
  • a chamber formed between the membrane and the membrane is used as a main electrode chamber, and a polar solution is allowed to flow into each of the main electrode chambers, and at the same time, a chamber formed on one side of the anion exchange membrane or cation exchange membrane is concentrated.
  • a reverse electrodialysis apparatus that allows a relatively high concentration electrolyte solution to flow as a chamber and a chamber formed on the other side of the anion exchange membrane or cation exchange membrane to flow a relatively low concentration electrolyte solution.
  • the plurality of anion exchange membranes and cation exchange membranes move from the cathode chamber toward the anode chamber.
  • a rich chamber formed on one side of one anion exchange membrane is arranged to face the cathode chamber side, and a lean chamber formed on the other side of the one anion exchange membrane is It is arranged on the anode chamber side,
  • two ion exchange membranes selected from either anion exchange membranes or cation exchange membranes face each other.
  • one or more water electrolysis units having a structure in which a conductive plate is inserted therebetween,
  • the two chambers formed between the two sides of the conductive plate and the ion exchange membrane are respectively set as pseudo electrode chambers, and an electrolyte solution is flowed into each of the pseudo electrode chambers, and one pseudo electrode chamber is filled with hydrogen.
  • a reverse electrodialysis apparatus is provided.
  • the reverse electrodialysis method of the present invention is in principle the same as a conventionally known reverse electrodialysis power generation, but a particularly important feature is that a plurality of alternating electrodialysis methods are arranged between a pair of electrode plates that are electrically connected to each other.
  • a ion exchange membranes which can be either an anion exchange membrane or a cation exchange membrane
  • a conductive material inserted between the two ion exchange membranes (anion exchange membrane and cation exchange membrane)
  • a water electrolysis unit comprising a conductive plate is provided, and a pseudo electrode chamber is provided on both surfaces of the conductive plate to perform reverse electrodialysis.
  • a chamber between the pair of electrode plates and the ion exchange membrane adjacent to the electrode plates serves as a main electrode chamber, and a plurality of electrodes are alternately arranged while flowing a polar liquid into each of the two electrode chambers.
  • each of the ion exchange membranes is subjected to dialysis by flowing an electrolyte solution (high concentration solution and low concentration solution) having different concentration difference on both sides thereof, and generating an ion flow by the concentration difference.
  • This method is common to the conventionally known reverse electrodialysis method, but in the present invention, the current obtained from the potential difference generated between the pair of electrode plates is not necessarily taken out as a power generator. .
  • the electrolysis of water is carried out by flowing the polar liquid also into the pseudo electrode chamber formed in the water electrolysis unit provided between the plurality of ion exchange membranes (between the ion flows).
  • This is characterized in that hydrogen is generated in the pseudo electrode chamber, which is greatly different from the conventionally known reverse electrodialysis method.
  • the reverse electrodialysis method of the present invention can be effectively used for the production of hydrogen without discarding the concentrated salt water produced as a by-product when producing water from seawater using a reverse osmosis membrane.
  • FIG. 3 is a schematic diagram showing ion flow and hydrogen generation in an ion exchange membrane arrangement and a concentration difference pattern that are most preferably employed in the reverse electrodialysis method of the present invention.
  • FIG. 1 is a schematic diagram showing ion flow and hydrogen generation in a pattern of ion exchange membrane arrangement and concentration difference most preferably employed in the present invention
  • FIG. 2 is a reverse electrodialysis in this pattern. It is a figure which shows the outline of the apparatus which implements.
  • a plurality of anion exchange membranes A and cation exchange membranes C are arranged between a pair of electrode plates 1a and 1b, respectively.
  • the electrode plates 1a and 1b are connected to each other.
  • electrolytic chamber solutions having different concentrations are flowed on both surfaces thereof. That is, in each of the ion exchange membranes A and C, one side thereof is a thick chamber 3 in which a high concentration electrolyte solution H is flowed, and the other side is a lean chamber in which a low concentration electrolyte solution L is flowed.
  • the anion exchange membrane A and the cation exchange membrane C may be known per se. The number of these ion exchange membranes is arbitrarily determined, but is usually in the range of 10 (10 pairs) to 1000, and preferably in the range of 30 to 300.
  • main electrode chambers 7 and 9 in which the polar liquid E flows between the electrode plates 1a and 1b and the ion exchange membrane A or C adjacent thereto, and the main electrode chambers are electrochemical. A reductive reaction or an oxidation reaction is performed.
  • the electrode plate 1a is a cathode
  • the main electrode chamber 7 including the electrode plate 1a (cathode) is a cathode chamber in which an electrochemical reduction reaction is performed
  • the electrode plate 1b is an anode.
  • the main electrode chamber 9 including the electrode plate 1b (anode) is an anode chamber in which an electrochemical oxidation reaction is performed.
  • a conventionally known material can be used without limitation as an electrode for electrodialysis or electrolysis.
  • the electrode plate 1a functioning as a cathode in general, Ni, Au, Ag (AgCl partially) (Including coated silver / silver chloride electrodes) Further, Pt, Pd, and other metals such as platinum, Ni—Sn, Ni—Fe—C alloys, stainless steel, etc. are used.
  • the electrode plate 1b functioning as the anode generally, Ni, Au, Ag (including a silver / silver chloride electrode partially coated with AgCl), a single metal such as platinum group such as Pt, Pd, etc.
  • a metal oxide composite electrode in which RuO 2 , IrO 2 , or TiO 2 is formed on a Ti base material, graphite, or the like is used.
  • the anion exchange membrane A and the cation exchange membrane C are alternately arranged in this order, and the cathode 1a and the anion exchange membrane A form the cathode.
  • a chamber 7 is formed, and an anode chamber 9 is formed by the anode 1b and the cation exchange membrane C.
  • a water electrolysis unit generally indicated by 11 is provided between a plurality of alternately arranged ion exchange membranes A and C. It is formed as described above.
  • the water electrolysis unit 11 is formed by inserting a conductive plate 13 between the anion exchange membrane A and the cation exchange membrane C.
  • a case where one water electrolysis unit is inserted will be described.
  • the conductive plate 13 has a function as a so-called bipolar electrode. Between the conductive plate 13 and the anion exchange membranes A and C adjacent to the conductive plate 13. Is a pseudo electrode chamber through which the polar liquid E flows.
  • a pseudo electrode chamber located on the anode 1b (anode chamber 9) side is indicated by 15a
  • a pseudo electrode chamber located on the cathode 1a (cathode chamber 7) side is indicated by 15b.
  • the surface of the conductive plate 13 facing the cathode chamber 7 side functions as the anode surface 13b
  • the surface facing the anode chamber 9 side functions as the cathode surface 13a. That is, as can be understood from FIG. 1, the water is electrolyzed on both surfaces of the conductive plate 13.
  • the polar liquid E is circulated and supplied from a predetermined polar liquid tank to the cathode chamber 7, the anode chamber 9, and the pseudo electrode chambers 15a and 15b.
  • aqueous solutions of various salts are used, and the type of salt is not particularly limited, but in general, aqueous solutions of alkali metal chlorides such as Na and K, sulfates, phosphates, nitrates, etc. Is used.
  • the concentration is preferably as high as possible. Therefore, the concentration should be equal to or lower than the saturated concentration, and is generally 0.1 M to saturated concentration. For example, in the case of sodium sulfate, 0.1 to 2.5 M is preferable.
  • FIG. 1 an example in which a NaCl aqueous solution is used as the polar liquid E is shown.
  • each concentrated chamber 3 is supplied with a high concentration electrolyte solution H from a predetermined concentrated liquid tank (not shown), and each diluted chamber 5 is supplied with a low concentration electrolyte solution L in a predetermined diluted liquid tank (Not shown).
  • the electrolyte solution is not particularly limited, and in principle, an aqueous solution of various salts, an organic solvent solution, or the like can be used. However, from the viewpoint of implementation on an industrial scale, an aqueous NaCl solution is preferably used in all cases.
  • the high-concentration electrolyte solution H about 0.1 to 5M, specifically, seawater or concentrated water of seawater is preferably used.
  • seawater concentrate produced as a by-product of seawater desalination using a reverse osmosis membrane as seawater concentrate is not only high in concentration, but also warmed in the treatment process, so that improvement in power generation efficiency can be expected.
  • the low-concentration electrolyte solution L specifically, a solution obtained by adding a slight amount of electrolyte (about 0.001 to 0.1 M) to fresh water, particularly river water, sewage treated water, or the like is used.
  • sewerage treated water can stably supply clear fresh water regardless of the weather, and is heated in the treatment process, so that improvement in power generation efficiency can be expected.
  • Electrode reaction at the cathode (reduction reaction) 2H + + 2e ⁇ ⁇ H 2
  • the electrode reaction is the following electrode reaction (reduction reaction) at the cathode: Ag + + 2e - ⁇ Ag
  • Electrode reaction at the anode Ag ⁇ Ag + + 2e ⁇ No generation of hydrogen occurs.
  • hydrogen is usually generated in one main electrode chamber 7 (cathode chamber 7) by the electrode reaction described above, in the present invention, it is disposed between the electrode plate 1a (cathode) and the electrode plate 1b (anode). The same electrode reaction also occurs in the pseudo electrode chambers 15a and 15b in the water electrolysis unit 11 that is used.
  • the anions (Cl ⁇ ) move through the anion exchange membrane A into the adjacent dilute chamber 5, and accordingly, from the Na ions. Also, hydrogen ions having a low ionization tendency are reduced, and hydrogen is generated by an electrode reaction similar to that of the cathode chamber 7 described above.
  • the pseudo electrode chamber 15b having the anode surface 13b of the conductive plate 13 cations (Na + ) move through the cation exchange membrane C into the adjacent dilute chamber 5, and accordingly, anions ( Cl ⁇ ) is oxidized, and chlorine is generated by an electrode reaction similar to that of the anode chamber 9 described above.
  • the electroconductive board 13 which forms the water electrolysis unit 11 shows the function as a bipolar electrode. That is, the surface of the conductive plate 13 facing the main electrode chamber 9 (anode 1b) side functions as the cathode surface 13a, and the pseudo electrode chamber 15a functions as the cathode chamber, and the main electrode chamber.
  • the surface facing 7 (cathode 1a) shows the function as the anode surface 13b, and the pseudo electrode chamber 15b shows the function as the anode chamber.
  • the cathode 1a and the conductive plate 13 (anode surface 13b) and the anode 1b and the conductive plate 13 (cathode surface 13a) are unit units, respectively.
  • Electric power E is generated.
  • E n ⁇ 2 ⁇ ⁇ (RT / F) ⁇ ln (a 1 / a 2 )
  • n is the number of anion exchange membranes or cation exchange membranes present between the electrode plate 1a or 1b and the conductive plate 13.
  • ⁇ is the transport number through the ion exchange membranes A and C
  • a 1 and a 2 are the average activity (mol / dm 3 ) of the electrolyte flowing through the rich chamber 3 and the lean chamber 5, respectively.
  • R is a gas constant (J / (K ⁇ mol))
  • T is the absolute temperature (K)
  • F is the Faraday constant (C / mol).
  • the electromotive force ⁇ V1 generated between the anode chamber 9 and the pseudo electrode chamber 15a and the electromotive force ⁇ V1 ′ generated between the cathode chamber 7 and the pseudo electrode chamber 15b are respectively expressed by the above equations. expressed.
  • both high-concentration and dilute chambers flow high-concentration electrolyte solutions such as seawater and low-concentration electrolyte solutions such as river water in one pass. Is preferred.
  • the theoretical output increases as the electrolyte concentration difference between the rich chamber 3 and the lean chamber 5 increases.
  • the electrolyte concentration in the lean chamber 5 is too low, the internal resistance between the electrode plates increases. For this reason, the output voltage decreases, the current decreases, and the hydrogen generation efficiency decreases. Therefore, it is preferable to control the electrolyte concentration in the lean chamber 5 so as to be maintained in an appropriate range.
  • the polar solution E the high-concentration electrolyte solution H and the low-concentration electrolyte solution L described above can be circulated as they are. In this case, it is preferable to circulate the high concentration electrolyte solution H in order to increase the electric conductivity of the electrode chamber or the pseudo electrode chamber.
  • the polar solution E can be prepared separately from both the electrolyte solutions and circulated from the external tank to the electrode chamber or the pseudo electrode chamber. In this case, as described above, the salt concentration of the polar liquid E is relatively high, but as this concentration decreases, the potential difference between the adjacent lean chambers 5 decreases and the output decreases.
  • the concentration of the polar liquid E so as to be maintained in an appropriate range, for example, a level equal to or higher than the electrolyte concentration in the thick chamber 3.
  • concentration of the polar liquid E becomes lower than the electrolyte concentration in the dilute chamber 5, the anion will reversely diffuse from the dilute chamber 5 through the anion exchange membrane A, and a reverse potential is generated, which is not preferable.
  • the conductive plate 13 has an anode 13b surface (a surface facing the cathode 1a of the main electrode chamber 7) and a cathode 13a surface (a surface facing the anode 1b of the main electrode chamber 9). If it is configured so that electronic conductivity can be ensured between both surfaces, the structure and form can be used without limitation.
  • the anode 13b surface and the cathode 13a surface may be a single plate of the same material, and when the anode 13b and the cathode 13a surface are made of different materials, the plates forming the both surfaces are subjected to a method such as explosion or welding. It can also be configured by pasting together.
  • the electron conductive material may be any of simple metals or alloys of various metals, metal oxides or carbon materials. As a specific material, it is preferable to use Ni, Ag, Au, and platinum group metals such as Pt and Pd in terms of high hydrogen generation efficiency and high resistance to oxidation reaction.
  • the cathode 13a surface is preferably a metal material having a low hydrogen overvoltage from the viewpoint of increasing the amount of hydrogen generated.
  • a metal material having a low hydrogen overvoltage for example, Ni, Au, Ag, Pt, Pd, etc.
  • a single metal such as a platinum group, an alloy such as Ni—Sn or Ni—Fe—C, stainless steel, or the like can be used.
  • the surface of the anode 13b where oxygen and chlorine are generated preferably has a low overvoltage for oxygen and chlorine generation and is stable in these electrode reactions.
  • a single electrode of a platinum group such as Ni, Au, Ag, Pt, or Pd, or a metal oxide composite electrode in which RuO 2 , IrO 2 , or TiO 2 is formed on a Ti substrate is preferably used.
  • a platinum group such as Ni, Au, Ag, Pt, or Pd
  • a metal oxide composite electrode in which RuO 2 , IrO 2 , or TiO 2 is formed on a Ti substrate is preferably used.
  • the conductive plate 13 is formed by bonding the material on the anode 13b surface side or the cathode 13a surface side to a base material having electronic conductivity such as Ti, Ni, stainless steel, or carbon material, or by plating or coating. A coating layer can also be formed and configured.
  • the conductive plate 13 is not limited in the form of the anode 13b surface and the cathode 13a surface as long as the polar liquid E in the pseudo electrode chambers on both the anode side and the cathode side is separated so as not to mix. It is also possible to adopt a form in which a wire net-like anode 13b surface is bonded to the plate-like cathode 13a surface.
  • the reverse electrodialysis method of the present invention described above can be carried out in an arrangement other than the pattern described above, but the arrangement in the pattern of FIG. 1 is optimal. That is, in FIG. 1, the anion exchange membrane A and the cation exchange membrane C are alternately arranged in this order from the cathode 1a to the anode 1b.
  • the exchange membranes C and A may be alternately arranged in this order from the cation exchange membrane C and the anion exchange membrane A toward the anode 1b.
  • FIG. 1 the arrangement in the pattern of FIG. 1 is optimal. That is, in FIG. 1, the anion exchange membrane A and the cation exchange membrane C are alternately arranged in this order from the cathode 1a to the anode 1b.
  • the exchange membranes C and A may be alternately arranged in this order from the cation exchange membrane C and the anion exchange membrane A toward the anode 1b.
  • FIG. 1 in FIG.
  • the cathode chamber 7 is changed to a chamber formed by the cathode 1 a and the cation exchange membrane C, and the adjacent chamber is an anion exchange with the cation exchange membrane C forming the cathode chamber 7. Since the chamber is formed by the membrane A, the cation of the electrode solution having a higher salt concentration diffuses into the thick chamber. This cation flow is opposite to the original cation flow direction, which leads to a loss of electromotive force. Similarly, the anode chamber 9 is changed to a chamber formed by the anode 1b and the anion exchange membrane A, and adjacent chambers are formed by the anion exchange membrane A and the cation exchange membrane C forming the anode chamber 9. Therefore, the anion of the electrode solution having a higher salt concentration diffuses into the thick chamber. This anion flow is also opposite to the direction of the original anion flow, leading to a loss of electromotive force.
  • the number of ion-exchange membrane pairs existing between the conductive plate 13 and the electrode plate 1a or 1b is between the conductive plate 13 and the electrode plate 1a or 1b. It is necessary to set the generated electromotive force to be equal to or higher than the theoretical electrolysis voltage of water (1.23 V) + hydrogen overvoltage.
  • the electromotive force E is obtained as a value obtained by multiplying the value determined by the average activity, temperature, and transport number of the ion exchange membrane in the rich and lean chambers, the salt concentration in the rich and lean chambers. The difference is large, the transport number of the ion exchange membrane is high, and the logarithm is small if the temperature is high.
  • the number of ion exchange membrane pairs present between the conductive plate 13 and the electrode plate 1a or 1b is not generally determined, but is usually 10 to 1000 pairs, preferably 50 to 300 pairs.
  • the generated hydrogen and chlorine or oxygen are collected in a predetermined tank and used for various purposes.
  • the reverse electrodialysis method of the present invention by utilizing electromotive force generated by the concentration difference, water is electrolyzed at least in each of the pseudo electrode chambers, while effectively avoiding energy loss. , Hydrogen can be generated efficiently. Note that although the present invention is mainly intended to produce hydrogen, a part of the current obtained from the potential difference generated between the pair of electrode plates may be taken out and used for power generation.
  • Example 1 200 sheets of anion-exchange membrane conduction unit area is 10 dm 2 (Co. ASTOM Ltd. AMX) and 200 sheets of cation exchange membrane (Co. ASTOM Ltd. CMX), 4 sheets of electrode chamber gasket, 198 sheets A rubber gasket constituting the thick chamber 3 having a thickness of 0.6 mm and a rubber gasket constituting the thin chamber 5 having a thickness of 200 mm and having a thickness of 0.5 mm were prepared.
  • One electrode plate comprising a Pt plate as the cathode 1a and one Pt plate as the anode 1b was prepared.
  • the electrode chamber gasket, the anion exchange membrane A, the dilute chamber gasket 5, the cation exchange membrane C, and the rich chamber gasket 3 are stacked in this order, and the next to the 100th cation exchange membrane C
  • a platinum plate, a pseudo electrode chamber 15a, and an electrode gasket are laminated on the pseudo electrode chamber 15b and the conductive plate 13 through the electrode chamber gasket, and again the anion exchange membrane A, the lean chamber gasket 5, the cation exchange membrane C, and the rich Lamination was resumed in the order of the chamber gasket 3, and the anode side electrode chamber 9 was fixed via the electrode chamber gasket next to the 200th cation exchange membrane C.
  • a 2M sodium sulfate aqueous solution was supplied as an electrode solution to the electrode chambers 7 and 9 and the pseudo electrode chambers 15b and 15a.
  • the conductive plate was made of platinum.
  • Reverse electrodialysis was performed by supplying 0.5 M saline to the thick chamber 3 and 0.02 M saline to the dilute chamber 5 at a rate of 4.3 L / min on the membrane surface.
  • the liquid temperature was 28 ° C. for all.
  • Hydrogen was generated from a total of two cathodes, the main electrode chamber and the pseudo electrode chamber. The total generation amount was 30.0 cc / min.
  • Example 2 In Example 1, instead of 0.5M-saline solution as a concentrated solution, concentrated seawater (1.0M-saline solution equivalent, water temperature 32 ° C.) of a reverse osmosis membrane device is allowed to flow, and a dilute solution is treated at a sewage treatment plant Reverse electrodialysis was performed under the same conditions as in Example 1 except that water prepared by preparing sodium chloride so as to be 0.05 M was supplied to water (water temperature: 25 ° C.). Hydrogen was generated from a total of two cathodes, the main electrode chamber and the pseudo electrode chamber. The total generation amount was 54.2 cc / min.
  • Example 1 reverse electrodialysis was performed under the same conditions as in Example 1 except that the pseudo electrode chamber was not provided. Hydrogen was generated only from the main electrode chamber. The amount generated was 15.0 cc / min.
  • Example 3 In Example 1, the electrode chamber gasket, the cation exchange membrane C, the thick chamber gasket 3, the anion exchange membrane A, and the lean chamber gasket 5 are started in this order from the cathode side electrode chamber 7, and the 100th negative electrode After the ion exchange membrane A, the pseudo electrode chamber 15b, the conductive plate 13, the pseudo electrode chamber 15a, and the electrode gasket are laminated through the electrode chamber gasket, and again the cation exchange membrane C, the thick chamber gasket 3, and the anion exchange membrane. Lamination was resumed in the order of A and dilute chamber gasket 5, and reverse electricity was applied under the same conditions as in Example 1 except that the anode side electrode chamber 9 was fixed via the electrode chamber gasket next to the 200th anion exchange membrane A.
  • Example 1 Dialysis was performed.
  • the first anion exchange membrane A and the dilute chamber gasket 5 are removed from the cathode side, and the anode side also becomes the rich chamber 3, the anion exchange membrane A, the electrode gasket, and the anode electrode chamber 9. Will be replaced.
  • Hydrogen was generated from a total of two cathodes, the main electrode chamber and the pseudo electrode chamber.
  • the total generation amount was 29.5 cc / min, which was a little smaller than 30.0 cc / min, which is the total generation amount of hydrogen in Example 1.
  • the water electrolysis unit is formed only in 200 alternately arranged anion exchange membranes and cation exchange membranes between a pair of electrode plates.
  • Example 4 In Example 1, the pseudo electrode chamber 15b, the conductive plate 13, the pseudo electrode chamber 15a, and the electrode gasket are stacked after the 100th cation exchange membrane C through the electrode chamber gasket, and again the anion exchange membrane A.
  • the anion exchange membrane A is intentionally placed one by one between the electrode gasket and the anion exchange membrane A.
  • Reverse electrodialysis was performed under the same conditions as in Example 1 except that the concentration chamber gasket 3 was added.
  • hydrogen was generated from a total of two cathodes of the main electrode chamber and the pseudo electrode chamber. The total generation amount was 29.6 cc / min.
  • the decrease in hydrogen generation amount in Example 4 is not large compared to Example 1, but when the number of water electrolysis units formed is increased at regular intervals, the amount of hydrogen generation is This is a significant difference that leads to efficiency from the viewpoint of industrial implementation.
  • Example 5 In Example 1, electrodialysis was performed under the same conditions as in Example 1 except that the conductive plate was placed after the 50th and 150th anion exchange membranes as well as the 100th plate. Hydrogen was generated from a total of four cathodes in the main electrode chamber and the pseudo electrode chamber. The total generated amount was 60.2 cc / min.
  • Example 6 Reverse electrodialysis was performed under the same conditions as in Example 5 except that a silver-silver chloride electrode was used as the electrode plate in Example 5. Hydrogen was not generated from the main electrode chamber, but hydrogen was generated only from the three cathodes of the pseudo electrode chamber. The total generation amount was 45.1 cc / min.
  • Electrode solution H High concentration electrolyte solution
  • L Low concentration electrolyte solution 1a: Electrode plate (cathode) 1b: Electrode plate (anode) 3: Rich chamber 5: Rare chamber 7: Main electrode chamber (cathode chamber) 9: Main electrode chamber (anode chamber) 11: Water electrolysis unit 13: Conductive plate 13a: Pseudo electrode (cathode) 13b: Pseudo electrode (anode) 15a: Pseudo electrode chamber (cathode chamber) 15b: Pseudo electrode chamber (anode chamber)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Urology & Nephrology (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne un procédé d'électrodialyse inverse dans lequel, entre des plaques d'électrode (1a, 1b) qui sont connectées par conduction l'une à l'autre, une pluralité de membranes d'échange d'anions (A) et de membranes d'échange de cations (C) sont disposées de manière alternée, des chambres formées entre les plaques d'électrode (1a, 1b) et l'une des membranes d'échange d'anions (A) ou l'une des membranes d'échange de cations (C) servant de chambres d'électrodes primaires (7, 9) dans lesquelles un liquide polaire (E) est amené à s'écouler, des chambres formées sur un côté des membranes d'échange d'anions (A) servant de chambres denses (3) dans lesquelles une solution d'électrolyte à concentration élevée (H) est amenée à s'écouler, et des chambres formées sur l'autre côté des membranes d'échange d'anions (A) servant de chambres de dilution (5) dans lesquelles une solution d'électrolyte à faible concentration (L) est amenée à s'écouler. La présente invention est caractérisée en ce qu'une unité d'électrolyse de l'eau (11) ayant une structure dans laquelle une plaque conductrice (13) est insérée entre une membrane d'échange d'anions (A) et une membrane d'échange de cations (C), qui sont disposées de manière alternée, est formée, les deux chambres étant formées individuellement entre les membranes d'échange d'ions (A, C) des deux côtés de la plaque conductrice (13) servent de chambres de pseudo-électrodes individuelles (15a, 15b), le liquide polaire (E) est amené à s'écouler dans les chambres de pseudo-électrodes individuelles (15a, 15b), et de l'hydrogène est également généré dans une chambre de pseudo-électrode (15a).
PCT/JP2017/041561 2016-11-21 2017-11-17 Procédé et appareil de génération d'hydrogène en utilisant une électrodialyse inverse WO2018092899A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-225692 2016-11-21
JP2016225692A JP6382915B2 (ja) 2016-11-21 2016-11-21 逆電気透析を利用して水素を発生させる方法及び装置

Publications (1)

Publication Number Publication Date
WO2018092899A1 true WO2018092899A1 (fr) 2018-05-24

Family

ID=62145447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/041561 WO2018092899A1 (fr) 2016-11-21 2017-11-17 Procédé et appareil de génération d'hydrogène en utilisant une électrodialyse inverse

Country Status (2)

Country Link
JP (1) JP6382915B2 (fr)
WO (1) WO2018092899A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408557A (zh) * 2020-11-11 2021-02-26 浙江浙能技术研究院有限公司 一种多极水循环电渗析系统及处理工艺

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018057566A1 (fr) 2016-09-22 2018-03-29 Cougeller Research Llc Collecteur de courant pour une conception de batterie empilée
CN110546790A (zh) 2017-04-21 2019-12-06 苹果公司 具有电解质扩散材料的电池单元
US11888112B2 (en) 2017-05-19 2024-01-30 Apple Inc. Rechargeable battery with anion conducting polymer
US11862801B1 (en) 2017-09-14 2024-01-02 Apple Inc. Metallized current collector for stacked battery
US11043703B1 (en) 2017-09-28 2021-06-22 Apple Inc. Stacked battery components and configurations
US11296351B1 (en) 2018-01-12 2022-04-05 Apple Inc. Rechargeable battery with pseudo-reference electrode
US11677120B2 (en) 2020-09-08 2023-06-13 Apple Inc. Battery configurations having through-pack fasteners
US11923494B2 (en) 2020-09-08 2024-03-05 Apple Inc. Battery configurations having through-pack fasteners
US11600891B1 (en) 2020-09-08 2023-03-07 Apple Inc. Battery configurations having balanced current collectors
US11588155B1 (en) 2020-09-08 2023-02-21 Apple Inc. Battery configurations for cell balancing

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011517012A (ja) * 2008-02-27 2011-05-26 レッドスタック・ベスローテン・フェンノートシャップ 逆電気透析プロセスを実行するためのデバイス及び方法
JP2014124561A (ja) * 2012-12-25 2014-07-07 Kuraray Co Ltd イオン交換膜、その製造方法および逆電気透析発電装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011517012A (ja) * 2008-02-27 2011-05-26 レッドスタック・ベスローテン・フェンノートシャップ 逆電気透析プロセスを実行するためのデバイス及び方法
JP2014124561A (ja) * 2012-12-25 2014-07-07 Kuraray Co Ltd イオン交換膜、その製造方法および逆電気透析発電装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408557A (zh) * 2020-11-11 2021-02-26 浙江浙能技术研究院有限公司 一种多极水循环电渗析系统及处理工艺
CN112408557B (zh) * 2020-11-11 2023-09-15 浙江浙能技术研究院有限公司 一种多极水循环电渗析系统及处理工艺

Also Published As

Publication number Publication date
JP2018083957A (ja) 2018-05-31
JP6382915B2 (ja) 2018-08-29

Similar Documents

Publication Publication Date Title
JP6382915B2 (ja) 逆電気透析を利用して水素を発生させる方法及び装置
CN110651068B (zh) 用于co2的电化学还原的双膜结构
Kang et al. Influence of flowrates to a reverse electro-dialysis (RED) stack on performance and electrochemistry of a microbial reverse electrodialysis cell (MRC)
Shi et al. Using reverse osmosis membranes to control ion transport during water electrolysis
CN101634035B (zh) 臭氧和过氧化氢在中性介质中协同电化学产生方法和装置
Scialdone et al. Investigation of electrode material–redox couple systems for reverse electrodialysis processes. Part II: Experiments in a stack with 10–50 cell pairs
JP5229756B2 (ja) 濃度差エネルギーを使用する塩水の脱塩方法、装置及びプラント
Zhu et al. Microbial reverse-electrodialysis chemical-production cell for acid and alkali production
JP2011525420A5 (fr)
JP6956953B2 (ja) 逆電気透析方法及びその利用
KR101311360B1 (ko) 폐순환 흐름전극을 이용한 농도차 발전장치
KR101394081B1 (ko) 고효율 역전기투석 발전장치
Lee et al. Porous carbon-coated graphite electrodes for energy production from salinity gradient using reverse electrodialysis
US11279637B2 (en) Electrodialysis cells based on the use of redox mediators
KR101863186B1 (ko) 고체염 역전기투석 장치
JP2005144240A (ja) 電解槽及び電解水生成装置
Veerman Reverse electrodialysis design and optimization by modeling and experimentation: Design and optimization by modeling and experimentation
Tehrani et al. Application of electrodeposited cobalt hexacyanoferrate film to extract energy from water salinity gradients
Lin et al. Ion transport channels in redox flow deionization enable ultra-high desalination performance
KR101506951B1 (ko) 레독스 흐름 전지 전해액 제조장치 및 그 제조방법
WO2005044738A1 (fr) Recipient d'electrolyse et appareil de generation d'eau electrolysee
JP3645636B2 (ja) ３室型電解槽
JPH01234585A (ja) ガス拡散電極を用いる電解方法及び装置
Susanto et al. The Role of Membrane, Feed Characteristic and Process Parameters on RED Power Generation
JPS63250480A (ja) 電解法によつてオゾンを発生させる方法の改良

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: 17871237

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17871237

Country of ref document: EP

Kind code of ref document: A1