WO2018079965A1 - Système de production d'énergie hybride et station de charge hybride d'hydrogène-électricité indépendante de l'énergie, qui utilisent un dispositif d'électrodialyse inverse capable de produire efficacement de l'hydrogène-électricité - Google Patents

Système de production d'énergie hybride et station de charge hybride d'hydrogène-électricité indépendante de l'énergie, qui utilisent un dispositif d'électrodialyse inverse capable de produire efficacement de l'hydrogène-électricité Download PDF

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WO2018079965A1
WO2018079965A1 PCT/KR2017/005702 KR2017005702W WO2018079965A1 WO 2018079965 A1 WO2018079965 A1 WO 2018079965A1 KR 2017005702 W KR2017005702 W KR 2017005702W WO 2018079965 A1 WO2018079965 A1 WO 2018079965A1
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water
hydrogen
cathode
reverse electrodialysis
chamber
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PCT/KR2017/005702
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English (en)
Korean (ko)
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김찬수
한지형
황교식
김한기
정남조
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한국에너지기술연구원
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Priority claimed from KR1020160141145A external-priority patent/KR101892692B1/ko
Priority claimed from KR1020170059428A external-priority patent/KR102041554B1/ko
Application filed by 한국에너지기술연구원 filed Critical 한국에너지기술연구원
Publication of WO2018079965A1 publication Critical patent/WO2018079965A1/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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02B90/10—Applications of fuel cells in buildings
    • 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

Definitions

  • the present invention relates to a hybrid power generation system, and more particularly, to a hybrid power generation system for producing electricity using a reverse electrodialysis apparatus and a fuel cell, and an energy-independent hydrogen-electric hybrid charging station.
  • the present invention was created by supporting the following two research projects.
  • the first research project is the core development technology development (2104.06.01 ⁇ 2017.05.03) for high efficiency RED stack with power generation efficiency of more than 15% for marine salt generation.
  • the second research project is funded by the Ministry of Trade, Industry & Energy, Republic of Korea, and the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KEPEP). ) It is a task.
  • Reverse electrodialysis is a technique for producing electricity by using salinity differences between seawater and fresh water. Energy is obtained by a process opposite to a general electrodialysis process in which electricity is generated to generate electrolyte concentration differences.
  • the reverse electrodialysis apparatus converts the chemical potential difference of the ion exchange membranes into the electrical potential difference using a redox couple material as the electrode solution.
  • Reverse electrodialysis devices are environmentally friendly and, unlike other renewable energy technologies, are not subject to climate and time constraints.
  • technology development is being made in the direction of suppressing the generation of gaseous substances which are by-products generated on the electrode side.
  • the electrode solution is prepared by using a minimum voltage necessary for causing a redox reaction, that is, a ferricyanide / ferrocyanide or a Fe 2 + / 3 +, which is a redox couple having a low overpotential. Most often used.
  • these redox species have a relatively high toxicity compared to brine or fresh water and cannot immediately discharge the electrode solution material from the reverse electrodialysis apparatus.
  • these redox species have low chemical stability, degrading the long-term performance of the reverse electrodialysis apparatus.
  • Perry When using a cyanide / ferrocyanide as reducing species oxidation, the oxidation reaction while up in the anode becomes lower the solution pH in the electrode interface broken and Perry cyanide / ferrocyanide free Perry ion (free ferric, Fe 3 +) or Faroe ion (free ferrous ion, Fe + 2) are made. This reaction product reacts with the unbreakable ferricyanide or ferrocyanide to produce a blue precipitate. This deposit sticks to the electrode surface to reduce the effective area of the electrode.
  • the concentration of redox species participating in the electrochemical reaction is reduced, and the power is reduced when the reverse electrodialysis apparatus is operated in the long term.
  • the solution pH of the electrode interface is increased by the water reduction reaction to form a ferric oxyhydroxide precipitate.
  • a fuel cell is a power generation device that generates electricity by using an electrochemical reaction of hydrogen and oxygen.
  • Known fuel cell stacks are supplied with hydrogen produced in a hydrogen generator, or with reformed gas (hydrogen rich gas) produced in a fuel processor comprising a reformer, a burner and a carbon monoxide reducer.
  • Hydrogen can be obtained by decomposing hydrocarbon fuels or by electrolyzing water.
  • the present disclosure seeks to provide a hybrid power generation system capable of producing electricity in both reverse electrodialysis equipment and fuel cells while producing hydrogen in real time and at low cost.
  • the present disclosure seeks to provide an energy independent hydrogen-electric composite charging station.
  • Hybrid power generation system is a cell stack consisting of a cation exchange membrane and an anion exchange membrane to alternately form a high concentration electrolyte solution flow path and a low concentration electrolyte solution flow path, and provides a membrane voltage for water decomposition reaction, disposed on one side of the cell stack
  • An anode chamber including a first water flow path and an anode
  • a cathode chamber including a second water flow path and a cathode disposed on the other side of the cell stack, wherein oxygen and electrons are formed by an oxidation reaction of water in the anode chamber.
  • hydrogen is generated by a reduction reaction of water in the cathode chamber, and the electron generated in the anode chamber is supplied to the cathode through a load to produce electric power, and the reverse electrodialysis apparatus.
  • the hydrogen from the oxygen and electrochemical reaction of oxygen and the hydrogen And a fuel cell to produce a group, and a reaction by-product water.
  • Hybrid power generation system is a cell stack consisting of a cation exchange membrane and an anion exchange membrane alternately formed between a high concentration electrolyte solution flow path and a low concentration electrolyte solution flow path, providing a membrane voltage required for water decomposition reaction, installed on both ends of the cell stack
  • a cathode chamber and an anode chamber each containing an aqueous solution, at least one linear cathode installed in the cathode chamber, and an anode installed in the anode chamber, wherein oxygen and electrons are generated by an oxidation reaction of water in the anode chamber;
  • a reverse electrodialysis apparatus that generates hydrogen by a reduction reaction of water in the cathode chamber, and generates power while the electrons generated in the anode chamber are supplied to the cathode through a load;
  • An energy self-supporting hydrogen-electric composite charging station uses a salt difference between a high concentration electrolyte solution and a low concentration electrolyte solution to generate hydrogen by water decomposition reaction, and at the same time, to generate electricity and reverse electricity. And a hydrogen charger supplied with hydrogen generated in the dialysis apparatus, and an electric charger supplied with electricity generated in the reverse electrodialysis apparatus.
  • the hybrid power generation system combines a reverse electrodialysis apparatus and a fuel cell to compensate for the low energy density of the reverse electrodialysis apparatus, and a storage facility that raises hydrogen production and safety issues of high energy consumption, which is a problem of a conventional fuel cell. Can solve the problem.
  • hydrogen required by the fuel cell can be supplied in real time, efficiency of the fuel cell can be improved.
  • the reverse electrodialysis apparatus can be used as a hydrogen source of a fuel cell since a sufficient amount of hydrogen can be produced. Therefore, it is possible to solve the problem of a storage facility that raises the hydrogen production and safety issues of high energy consumption, which is a problem of the conventional fuel cell. In addition, since hydrogen required by the fuel cell can be supplied in real time, efficiency of the fuel cell can be improved.
  • the reverse electrodialysis apparatus capable of producing hydrogen-electricity according to the present disclosure may implement an eco-friendly energy production apparatus because hydrogen-electricity is produced only by water redox reaction without using redox species having chemical toxicity.
  • the reverse electrodialysis apparatus can produce hydrogen at the same time as the electricity production, it is possible to implement an energy-independent hydrogen-electric complex charging station.
  • FIG. 1 is a block diagram of a hybrid power generation system according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of a fuel cell constituting a fuel cell stack of the hybrid power generation system shown in FIG. 1.
  • FIG. 3 is a block diagram of a hybrid power generation system according to another embodiment of the present invention.
  • FIG. 4 is a schematic diagram of an assembly of a reverse electrodialysis apparatus constituting a hybrid power generation system according to an embodiment of the present invention.
  • 5A and 5B are cross-sectional views and a top view of a reverse electrodialysis apparatus constituting a hybrid power generation system according to another embodiment of the present invention.
  • FIG. 6 is a schematic diagram of a method of operating a reverse electrodialysis apparatus constituting a hybrid power generation system according to another embodiment of the present invention.
  • Figure 7 is a graph showing the power according to the current of the conventional reverse electrodialysis apparatus and the reverse electrodialysis apparatus using a linear electrode.
  • FIG. 8 is a graph showing a relationship of energy generated according to a distance between an electrode tip and a cell stack.
  • FIG. 9 is a block diagram of an energy-independent hydrogen-electric composite charging station according to an embodiment of the present invention.
  • FIG. 1 is a configuration diagram of a hybrid power generation system 1 according to an embodiment of the present invention.
  • the hybrid power generation system 1 includes a reverse electrodialysis apparatus 100 and a fuel cell 50.
  • the hybrid power generation system 1 is a power generation system that generates energy in the fuel cell 50 by supplying hydrogen generated when generating energy in the reverse electrodialysis apparatus 100 to the fuel cell 50.
  • the reverse electrodialysis apparatus 100 includes a cell stack 10, an anode 42 positioned at one side of the cell stack 10 with the first water channel WCH1 interposed therebetween, and a second water channel WCH2.
  • the cathode 32 is positioned on the other side of the cell stack 10 in between.
  • the cell stack 10 includes a cation exchange membrane 11 and an anion exchange membrane 11 which alternately form a high concentration electrolyte solution HC such as a channel for supplying brine and a low concentration electrolyte solution LC such as a channel for supplying fresh water. 12). Two adjacent unit cells share a cation exchange membrane 11 or an anion exchange membrane 12.
  • the high concentration electrolyte solution may be a solution having a salt concentration of 35,000 mg / L or more
  • the low concentration electrolyte solution may be a solution having a salt concentration of 0 to 1,000 mg / L.
  • Seawater may be used as the high concentration electrolyte solution and fresh water may be used as the low concentration electrolyte solution.
  • the present invention is not limited thereto, and any combination of materials that allow exchange of cations and anions due to a difference in relative concentrations of ions may occur. Is also applicable. And if a variety of pretreatment facilities can be installed before entering the cell stack 10, industrial waste brine, seawater, artificial brine, etc. may be used as a high concentration electrolyte solution (saline).
  • the low concentration electrolyte solution fresh water
  • industrial cooling water sewage discharged water, river water, tap water, and the like
  • the salt water is used as the high concentration electrolyte solution HC
  • the fresh water is described as the low concentration electrolyte solution LC.
  • the flow directions of the high concentration electrolyte solution HC and the low concentration electrolyte solution LC are opposite to each other. However, the flow direction of the high concentration electrolyte solution HC and the low concentration electrolyte solution LC may be in the same direction.
  • the ions move from the high concentration electrolyte solution HC to the low concentration electrolyte solution LC.
  • the length of the flow path becomes longer, the larger amount of ions moves and the difference in concentration between the two solutions at the outlet side than at the inlet side. Will be reduced. Therefore, when the length of the flow path is long, it is advantageous to reverse the flow directions of the high concentration electrolyte solution HC and the low concentration electrolyte solution LC to each other so that the difference in concentration depending on the location is small, which may be advantageous in improving performance. That is, the potential is kept constant throughout the cathode 32 and the anode 42, which may be more advantageous for hydrogen generation.
  • the high concentration electrolyte solution HC may be a solution having a salt concentration of 35,000 mg / L or more
  • the low concentration electrolyte solution LC may be a solution having a salt concentration of 0 to 1,000 mg / L.
  • River water may be used as high concentration electrolyte solution (HC) and seawater (low concentration) electrolyte solution (LC), but is not limited thereto, and any combination of materials may allow the exchange of cations and anions due to the difference in relative ion concentrations. Is also applicable.
  • electrochemical potential is generated between the ion exchange membranes 11 and 12.
  • a reduction reaction occurs at the cathode 32 and an oxidation reaction occurs at the anode 42, whereby a flow of electrons is generated between the anode 42 and the cathode 32 to generate energy, that is, electricity.
  • the cell stack 10 may include a plurality of unit cells, for example, ten or more unit cells. Since the cell voltage increases as the number of unit cells increases, water may be used instead of a conventional redox couple as an electrode solution. That is, in the reverse electrodialysis apparatus 100 according to an embodiment of the present invention, the voltage of the cell stack 10 is about 1.23V or more, which is water electrolysis voltage, so that electrolysis of water at the anode 42 and the cathode 32 is performed. The reaction may occur.
  • each reaction of the pH of the cathode chamber 30 including the second water flow path (WCH2) in contact with the cathode 32 and the anode chamber 40 including the first water flow path (WCH1) in contact with the anode 42 It can be used by adjusting to an advantageous pH.
  • the solution of the second water channel WCH2 in which the reduction reaction occurs may be adjusted to an acidic solution
  • the solution of the first water channel WCH1 in which the oxidation reaction occurs may be adjusted to the basic solution.
  • the theoretical water decomposition voltage at this time may be about 0.4V. Therefore, if the voltage applied to the cell stack 10 is 0.4V or more, water electrolysis may occur.
  • the theoretical electrolysis voltage of water varies according to the pH of the cathode chamber 30 and the anode chamber 40. When a cell voltage having a voltage higher than this voltage is generated, water electrolysis reaction may occur to produce hydrogen gas. have.
  • the ratio of electrode resistance in the total resistance component of the reverse electrodialysis apparatus 100 is significantly reduced, so that pure water or fresh water is used as the electrode solution. Even when used, the amount of reduction in power and the amount of hydrogen produced by the electrode solution resistance is negligible. That is, when hydrogen is produced even with pure water, there are various advantages compared to the production of hydrogen by water electrolysis. In conventional water electrolysis, pure water cannot be used as an electrolyte because the effect of solution resistance is large, so pure water is not used as an electrolyte. On the other hand, in the reverse electrodialysis apparatus 100 of the present invention, since pure hydrogen is produced by supplying pure water without using the existing redox species, it is possible to produce even more pure hydrogen gas.
  • aqueous solution in which the salt is dissolved.
  • NaCl or Na 2 SO 4 end
  • an aqueous solution dissolved at 2.92 g / L to 5.8 g / L When the salt is dissolved, the resistance of the electrode solution can be reduced, but as described above, when the number of cells increases, the effect of the resistance of the electrode solution is insignificant, so pure water or fresh water can be used as the electrode solution.
  • oxygen and electrons may be generated by the oxidation reaction of water in the anode chamber 40 as shown in Formula (1).
  • chloride ions may be oxidized to generate chlorine gas as shown in Formula (2).
  • hydrogen and hydroxide ions may be generated by the reduction reaction of water in the cathode chamber 30 as in Chemical Formula (3).
  • the first water passage WCH1 and the second water passage WCH2 may be configured in a cyclic or acyclic manner.
  • the first water channel WCH1 is connected to the second water channel WCH2 through the connecting tube 63, and the oxygen and electrons generated at the anode 42 together with the second water. It may be transferred to the flow path WCH2.
  • an auxiliary gas-liquid separator 64 is installed in the connecting pipe 33. Oxygen gas can be removed.
  • the cation exchange membrane 11 and the anion exchange membrane 12 are preferably made of a material or structure which can lower resistance and thickness and increase permselectivity.
  • the anode 42 and the cathode 32 may be formed of different materials or the same material.
  • the anode 42 and the cathode 32 may be made of different materials to optimize the respective reduction reaction.
  • the anode 42 may be made of iridium (Ir)
  • the cathode 32 may be made of ruthenium (Ru), but is not limited thereto.
  • the anode 42 and the cathode 32 may be formed of the same material so that the performance may be maintained even when a polarity change occurs during operation.
  • the anode 42 and the cathode 32 may be formed of electrodes coated with a platinum group catalyst material (Pt, Ir, Ru, Pd, etc.) on a titanium (Ti) base.
  • the anode 42 and the cathode 32 is preferably formed of a porous material to increase the specific surface area to provide a large number of reaction sites. It can also be made of a material that can improve corrosion resistance and improve capacity.
  • the anode 42 and the cathode 32 may be formed of a capacitive electrode formed with a porous structural material layer, for example, carbon cloth, carbon felt, or the like, on a metal support.
  • the metal support may be a Ti, Nb, Ta mesh.
  • a spacer (not shown) may be inserted into the high concentration electrolyte solution channel CH1 and the low concentration electrolyte solution channel CH2.
  • the spacers are inserted to maintain a constant mechanical distance between the cation exchange membrane 11 and the anion exchange membrane 12 and to cause turbulence of the supplied solution so that the solution is well supplied over the entire region of the flow paths CH1 and CH2. Can be. Therefore, it may be desirable for the spacer to have a high porosity.
  • the spacer may be composed of a mesh made of polypropylene or polyethylene, but is not limited thereto.
  • an electrode spacer (not shown) may also be provided in the first water channel WCH1 and the second water channel WCH2. Since the electrode spacer may be inserted to increase the electrical resistance, the electrode spacer may be formed of a material having good electrical conductivity. For example, the electrode spacer may be coated with a metal such as Pt to improve electrical conductivity.
  • the reverse electrodialysis apparatus 100 of this embodiment uses water as an electrode solution by increasing the number of cells, and actively generates hydrogen by electrolyzing water. That is, in the present embodiment, the reverse electrodialysis apparatus 100 functions as a hydrogen generator and at the same time a power generation apparatus.
  • Hydrogen generated in the reverse electrodialysis apparatus 100 is supplied to the fuel cell 50 to produce energy, that is, electricity in the fuel cell 50.
  • the hybrid power generation system 1 may further include a gas-liquid separator 70 to more smoothly supply hydrogen generated from the reverse electrodialysis apparatus 100.
  • the gas-liquid separator 70 is connected to the second water channel WCH2 of the reverse electrodialysis apparatus 100 to receive hydrogen and water therefrom. Thereafter, the gas-liquid separator 70 separates hydrogen, which is a gas, and water, which is a liquid.
  • the separated hydrogen is supplied to the fuel cell 50, and the gas-liquid separated water may be supplied again to the reverse electrodialysis apparatus 100 through the auxiliary pipe 71.
  • the gas-liquid separator 70 may be omitted.
  • the fuel cell 50 is a power generation device that generates electricity by using an electrochemical reaction between hydrogen and oxygen, and various types of known fuel cells may be applied.
  • the fuel cell 50 may be formed of any one of a phosphoric acid fuel cell, a molten carbonate fuel cell, a solid oxide fuel cell, and a polymer electrolyte fuel cell.
  • the fuel cell 50 largely includes a fuel cell stack 51, an air pump 52 for supplying air to the fuel cell stack 51, and an electric power for converting DC power from the fuel cell stack 51 into AC power. Transducer 53 and the like.
  • the fuel cell stack 51 includes a plurality of fuel cell cells connected in series, and is classified into the aforementioned types according to the type of catalyst and electrolyte and the operating temperature.
  • FIG. 2 is a schematic diagram of a fuel cell constituting a fuel cell stack of the hybrid power generation system shown in FIG. 1.
  • one fuel cell 54 includes an electrolyte 55, which is a medium material through which ions pass, a catalyst layer 56 positioned on both sides of the electrolyte 55, and one catalyst layer 56. And a cathode (anode) 57 in contact with and supplied with hydrogen, and a cathode (58) in contact with another catalyst layer 56 and provided with air.
  • the fuel electrode 57 hydrogen is separated into hydrogen ions and electrons, and electrons move electric wires to generate electricity.
  • the hydrogen ions moving through the electrolyte 55 react with oxygen sent to the cathode 58 and electrons introduced through the external wire to generate water.
  • the fuel cell 54 produces electricity from hydrogen and air and generates water as a byproduct.
  • the fuel cell stack 51 is connected to the first water flow path WCH1 of the reverse electrodialysis apparatus 100 through a water supply pipe 59 to reverse water generated as a byproduct. 100).
  • the auxiliary pipe 71 connected to the gas-liquid separator 70 may be connected to the water supply pipe 59.
  • Conventional fuel cells include a hydrogen production and storage facility for hydrogen supply, or a fuel processing device for reforming gas (hydrogen rich gas) production.
  • the fuel cell 50 of the present embodiment does not include a fuel processing apparatus including a separate hydrogen production and storage facility or a reformer, and generates power by receiving hydrogen produced by the reverse electrodialysis apparatus 100 as fuel.
  • the amount of hydrogen generated in the reverse electrodialysis apparatus 100 may be adjusted by changing the size, the number of cells, and the operating conditions of the reverse electrodialysis apparatus 100. Therefore, the hydrogen required for the fuel cell 50 can be produced and supplied in real time. In addition, hydrogen generated in the reverse electrodialysis apparatus 100 is additionally generated while producing electricity, and consumes less energy than electrolysis of existing water to produce hydrogen.
  • the above-described hybrid power generation system 1 combines the reverse electrodialysis apparatus 100 and the fuel cell 50 to compensate for the low energy density of the reverse electrodialysis apparatus 100, and the high energy consumption, which is a problem of the conventional fuel cell. It can solve the problem of storage facilities where hydrogen production and safety issues are raised. In addition, since the hydrogen required by the fuel cell 50 can be supplied in real time, the efficiency of the fuel cell 50 can be improved.
  • FIG 3 is a configuration diagram of a hybrid power generation system 2 according to another embodiment of the present invention.
  • the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 uses water as an electrode solution by increasing the number of unit cells, and increases the electrode interface resistance by reducing the electrode surface area to apply to the electrode interface. Loss is a device that can increase the voltage and thereby increase the rate of hydrogen evolution.
  • the electrode solution chambers 30 and 40 may be made wider to include a large amount of reactant water. That is, in the present embodiment, the reverse electrodialysis apparatus 200 functions as a hydrogen generator and at the same time a power generation apparatus.
  • Hydrogen generated in the reverse electrodialysis apparatus 200 may be directly supplied to the fuel cell 50 without a separate gas-liquid separator (70 of FIG. 1) to produce energy, that is, electricity in the fuel cell 50.
  • Reference numeral 53, the water supply pipe 59, and the like have substantially the same functions as the components described with reference to FIG.
  • Reverse electrodialysis apparatus 100 constituting the hybrid power generation system 1 may be assembled in a general form as shown in FIG.
  • the cathode 32 and the anode 42 are formed inside the end plates 221 and 222 in a mesh shape having a large surface area.
  • the cell stack 10 is formed in contact with a front surface of the cell stack 10 with a spacer having a thickness of about 100 to 200 ⁇ m and having a spacer having an open area ratio of about 50%.
  • the cathode chamber 30 forming the second water channel WCH2 and the anode chamber 40 forming the first water channel WCH1 may be formed to accommodate the cathode 32 and the anode 42.
  • the cathode 32 and the anode 42 are connected to an external rod (not shown) through the electrode connection 260.
  • the gasket 250 is to seal the space between the cell stack 10 and the end plates 221 and 222 to prevent leakage of the solution in the cathode chamber 30 and the anode chamber 40.
  • the width w of the cathode chamber 30 and the anode chamber 40 may be formed to be substantially equal to the width of the cathode 32 or the anode 42.
  • FIGS. 5A and 5B a cross-sectional view and a top view of the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 according to another embodiment are illustrated in FIGS. 5A and 5B.
  • the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 according to another embodiment includes a linear cathode 32W and a linear anode 42W.
  • the volume of the cathode chamber 30 and the anode chamber 40 compared to the reverse electrodialysis apparatus 100 shown in FIG. 4 is 10 times or more, preferably 25 times or more, more preferably 50 times or more. can do.
  • the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 includes a cell stack 10, a cathode chamber 30, and an anode chamber ( 40).
  • the cell stack 10 includes a cation exchange membrane 11 and an anion exchange membrane 11 which alternately form a high concentration electrolyte solution HC such as a channel for supplying brine and a low concentration electrolyte solution LC such as a channel for supplying fresh water. 12). Two adjacent unit cells share a cation exchange membrane 11 or an anion exchange membrane 12.
  • the flow directions of the high concentration electrolyte solution (HC, brine) and the low concentration electrolyte solution (LC, fresh water) are opposite to each other. However, the flow direction of the high concentration electrolyte solution (HC, brine) and the low concentration electrolyte solution (LC, fresh water) may be in the same direction.
  • End plates 21 and 22 are installed at both ends of the cell stack 10, respectively.
  • the end plates 21 and 22 are installed at both ends of the cell stack 10 to prevent the cation exchange membrane 11 and the anion exchange membrane 12 of the cell stack 10 from expanding due to the pumping pressure of the brine and fresh water. .
  • the end plates 21 and 22 communicate with each other through the opening with the neighboring cathode chamber 30 and the anode chamber 40, respectively.
  • the end plates 21, 22 have a constant open area like a mesh.
  • the end plates 21 and 22 are constructed in a mesh shape to prevent the cell stack 10 from expanding and allow the cell stack 10 to directly contact the solution of the cathode chamber 30 or the anode chamber 40.
  • the end plates 21 and 22 may be made of only plastic or may be made of metal. In the case of a metal mesh, a titanium mesh or the like may be used.
  • the cathode chamber 30 and the anode chamber 40 are disposed in contact with the end plates 21 and 22. As described above, it is suitable for hydrogen generation that at least one linear cathode 32W is disposed in the cathode chamber 30.
  • the anode chamber 40 may be any one of a mesh type electrode and a linear electrode. Although linear anode 42W is illustrated in FIG. 5A, a meshed anode may be disposed.
  • electrochemical potential is generated between the ion exchange membranes 11 and 12.
  • an oxidation reaction occurs at the anode 42
  • a reduction reaction occurs at the cathode 32
  • a flow of electrons (e ⁇ ) is generated between the anode 42 and the cathode 32 such that energy, that is, electricity is generated. Occurs.
  • Electrons generated in the anode chamber 40 may be transferred to the cathode chamber 30 through a load.
  • the cell stack 10 may include a plurality of unit cells, for example, ten or more unit cells. Since the cell voltage increases as the number of unit cells increases, water may be used as an electrode solution instead of the conventional redox species. That is, in the reverse electrodialysis apparatus 200 according to the embodiment of the present invention, the voltage of the cell stack 10 is about 1.23V or more, which is the water electrolysis voltage, so that the electrolysis of water at the anode 42 and the cathode 32 is performed. The reaction may occur. In addition, when the pH of the solution of the cathode chamber 30 and the pH of the solution of the anode chamber 40 are different, the water decomposition voltage may be further lowered.
  • the pH of the solution of the cathode chamber 30 and the solution of the anode chamber 40 may be adjusted to a pH favorable for each reaction.
  • the solution of the cathode chamber 30 in which the reduction reaction occurs is an acidic solution
  • the solution of the anode chamber 40 in which the oxidation reaction occurs can be adjusted to a basic solution.
  • the theoretical water decomposition voltage at this time may be about 0.4V. Therefore, if the voltage applied to the cell stack 10 is 0.4V or more, water electrolysis may occur.
  • the theoretical electrolysis voltage of water varies depending on the pH of the solution of the cathode chamber 30 and the solution of the anode chamber 40.
  • the water electrolysis reaction causes hydrogen. It can produce gas.
  • the ratio of electrode resistance in the total resistance component of the reverse electrodialysis apparatus 100 is significantly reduced, so that pure water or fresh water is used as the electrode solution. Even when used, the amount of reduction in power and the amount of hydrogen produced by the electrode solution resistance is negligible. That is, when hydrogen is produced even with pure water, there are various advantages compared to the production of hydrogen by water electrolysis. In conventional water electrolysis, pure water cannot be used as an electrolyte because the effect of solution resistance is large, so pure water is not used as an electrolyte.
  • the reverse electrodialysis apparatus 100 of the present invention since pure hydrogen is produced by supplying only pure water to the cathode chamber 30 without using the existing redox species, it is possible to produce even more pure hydrogen gas. Therefore, the fuel cell can be directly connected without an additional separation device such as a hydrogen separation membrane.
  • an aqueous solution in which salt is dissolved may be used.
  • NaCl or Na 2 SO 4 end It is also possible to use an aqueous solution dissolved at 2.92 g / L to 5.8 g / L.
  • the resistance of the electrode solution can be reduced, but as described above, when the number of cells increases, the effect of the resistance of the electrode solution is insignificant, so pure water or fresh water can be used as the electrode solution.
  • oxygen and electrons may be generated by the oxidation reaction of water in the linear anode 42W as shown in Chemical Formula 1.
  • chloride ions may be oxidized to generate chlorine gas as shown in Formula (2).
  • hydrogen and hydroxide ions may be generated by the reduction reaction of water in the linear cathode 32W as in Chemical Formula (3).
  • the electrochemically active area becomes small, thereby increasing the interfacial resistance. Since a large resistance is applied to a large resistance (Ohm's law), a large part of the film voltage of the cell stack 10 is caught at the linear cathode 32W interface, and the hydrogen generation rate can increase rapidly. Even in the case of the anode, the smaller the area, the greater the voltage across the anode interface, so that the rate of oxygen generation or chlorine gas generation may increase rapidly.
  • the anode may also use a linear anode 42W, but if oxygen generation or chlorine generation is not the main purpose and the main purpose of electricity production is a mesh type It may be more preferred to form it with an anode (see 42 in FIGS. 1 and 4).
  • the linear cathode 32W and the linear anode 42W are responsible for increasing the electrochemical reaction rate and current by increasing the voltage applied to the electrode interface by reducing the electrode area, only the precious metal such as Pt is used. It does not need to be formed.
  • precious metal such as Pt
  • non-noble metals such as carbon, titanium, nickel, manganese and copper can be used as the electrode.
  • reference numerals 35 and 45 are solution inlets of the cathode chamber 30 and the anode chamber 40, respectively.
  • Reference numerals 32a and 42a denote injection holes of the linear cathode 32W and the linear anode 42W, respectively.
  • the width W of the cathode chamber 30 and the anode chamber 40 of the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 is linear between the cathode 32W and the anode 42W. Since it is made of, it is not limited in width Accordingly, the width W of the cathode chamber 30 and the anode chamber 40 of the reverse electrodialysis apparatus 200 is equal to the cathode chamber 30 and the anode chamber 40 of the reverse electrodialysis apparatus 100 illustrated in FIG. 4. 10 times or more, preferably 25 times or more, more preferably 50 times or more than the width (w) of ().
  • the volume can be increased to 10 times or more, preferably 25 times or more, and more preferably 50 times or more.
  • the size of the cathode chamber 30 illustrated in FIG. 4 is particularly 2.5 cm 3
  • the size of the cathode chamber 30 illustrated in FIG. 5A may be 125 cm 3.
  • Increasing the size of the cathode chamber 30 allows sufficient water decomposition reaction to occur, and it becomes easy to collect the hydrogen obtained as a result of the water decomposition reaction to the outside through the collecting pillar 50a connected to the upper portion of the chamber.
  • hydrogen generated in the reverse electrodialysis apparatus 200 simultaneously generates electricity, and consumes less energy than electrolysis of existing water to produce hydrogen. .
  • Seawater freshwater pumping energy is required when driving conventional reverse electrodialysis devices.
  • the power generated by the reverse electrodialysis apparatus minus the pumping energy is the net energy actually obtained. In small cells, the pumping energy is relatively large and the net energy is negative.
  • the reverse electrodialysis apparatuses 100 and 200 according to the embodiments of the present invention even if the output itself is increased and the pumping energy is subtracted, the positive value may obtain the net energy. Thus, hydrogen generation and power generation in large cells may not require additional energy.
  • the net energy including hydrogen production and power generation may decrease due to the increase in the total internal resistance by the distance resistance, but the existing external voltage may not be needed because additional external energy is not required.
  • water consumption can be much lower than water electrolysis, in which water is electrolyzed to produce hydrogen.
  • the sizes of the cathode chamber 30 and the anode chamber 40 can be made as large as possible.
  • the ends of the linear cathode 32W and the anode 42W may be brought into non-contact with the cell stack 10.
  • it may be located at least several millimeters to several centimeters or less.
  • the electrode solution of the cathode chamber 30 and the electrode solution of the anode chamber 40 may be configured in an acyclic manner so that the cathode chamber 30 and the anode chamber 40 may be independently configured.
  • the cathode chamber 30 and the anode chamber 40 are configured independently, the hydrogen generated in the cathode chamber 30 and the oxygen or chlorine gas generated in the anode chamber 40 are not mixed with each other and are collected again. There is no need for separation.
  • the hydrogen chamber 80 is installed in the cathode chamber 30 to collect hydrogen
  • the oxygen chamber or chlorine collector 90 is installed in the anode chamber 40 to collect oxygen or chlorine, respectively.
  • the electrode solution of the cathode chamber 30 and the anode chamber 40 may be formed to circulate.
  • the hydrogen ions H + generated at the linear anode 42W can be used at the linear cathode 32W.
  • oxygen is supplied together, hydrogen is prevented from being generated in the linear cathode 32W.
  • a gas-liquid separator (see 64 in FIG. 1) is installed in the connecting tube to separate oxygen gas, and the electrode includes only hydrogen ions.
  • the solution may be delivered to the cathode chamber 30.
  • FIG. 6 is a schematic diagram of a method of operating the reverse electrodialysis apparatus 200 constituting the hybrid power generation system 2 according to another embodiment of the present invention.
  • the overpotential of the reduction of hydronium ions at low pH and the oxidation of hydroxide ions at high pH is much lower than the overpotential of water redox at neutral pH, resulting in a smoother electrode reaction with reduced electrode interface impedance. This will happen. That is, by periodically switching between the brine and fresh water, it is possible to increase the hydrogen generation rate and oxygen generation rate while at the same time obtain the power of the reverse electrodialysis apparatus. As such, the method of periodically switching the brine and fresh water may be applied to the operation of the reverse electrodialysis apparatus 100 constituting the hybrid power generation system 1 according to an embodiment of the present invention.
  • FIG. 7 is a graph showing power according to current of the conventional reverse electrodialysis apparatus RED and the reverse electrodialysis apparatus 200 using the linear electrode. While the maximum output of the conventional reverse electrodialysis apparatus is 110 mW, the maximum output of the reverse electrodialysis apparatus 200 using the linear electrode is about 25 mW. The reason why the output of RED using linear electrode is lowered is largely for two reasons. First, the use of linear electrodes with small areas increases the amount of hydrogen gas generated at the cathodes with increased interfacial resistance, which converts part of the output reduction into hydrogen generation.
  • the increase in resistance as the distance between the cell stack and the linear electrode increases, and the increase in interfacial resistance as the area decreases increases the internal resistance of the reverse electrodialysis system itself.
  • Hydrogen gas was collected by running the reverse electrodialysis apparatus for an hour, and the energy yield of the reverse electrodialysis apparatus with the linear electrode was calculated.
  • the flow rate of the brine and fresh water was supplied to 50 mL / min per channel, subjected to a resistance of 82 ohms, 100 mM NaCl aqueous solution was used as the electrode solution.
  • the amount of hydrogen collected as a result of the operation was 30 mL and the amount of oxygen collected was 17 mL.
  • the generated power of the reverse electrodialysis apparatus was 24 mWh and 19 mWh.
  • the total energy production was 43 mWh, which was lower than that of the conventional 110 mWh of the reverse electrodialysis apparatus using the redox species. Therefore, it can be confirmed that a part of the RED power reduction has been converted to hydrogen production, and it can be confirmed that the increase in internal resistance by using the linear electrode reduced the total energy production.
  • the distance between the linear electrode and the cell stack should be as short as possible, and the electrochemically active area in contact with the solution of the linear electrode should be as wide as possible.
  • 8 is a graph showing the relationship. That is, when the Pt linear electrode constituting the cathode and the anode is almost in contact with the Ti mesh which is the end plate (about 5 mm or less) ⁇ The distance between the Pt linear electrode constituting the cathode and the anode and the Ti mesh is about 1 If the distance is more than cm ⁇ The distance between the Pt linear electrode constituting the cathode and the anode and the Ti mesh is more than 4 cm apart in order to reduce the energy generation in order. In other words, it can be seen that the power increases as the electrode tip approaches the cell stack.
  • FIG. 9 is a block diagram of an energy-independent hydrogen-electric composite charging station according to an embodiment of the present invention.
  • the energy-independent hydrogen-electric composite charging station includes a hydrogen charger 170 and an electric charger 180 supplied with hydrogen and electricity, respectively, which are produced in a reverse electrodialysis apparatus 100 or 200 that simultaneously produces hydrogen and electricity.
  • the reverse electrodialysis apparatus 100 or 200 is a large capacity apparatus in which the number of unit cells constituting the cell stack is at least 50 or more, preferably 1000 cells or more.
  • the film voltage formed in the cell stack may be 7.5V or more and 100V or more, and sufficient water decomposition reaction may occur.
  • the specific configuration of the reverse electrodialysis apparatus 100 or 200 is the apparatus described with reference to FIGS. 1 to 7.
  • Hydrogen produced in the reverse electrodialysis apparatus 100 or 200 is supplied to the hydrogen charger 170.
  • the hydrogen charged in the hydrogen charger 170 may then be used to charge the fuel cell vehicle 175.
  • Hydrogen produced by the reverse electrodialysis apparatus 100 or 200 before being supplied to the hydrogen charger 170 may be supplied to the hydrogen charger 170 after passing through the hydrogen separation device 155.
  • the hydrogen separation device 155 When pure water is used as the electrode solution used in the reverse electrodialysis apparatus 100 or 200, the hydrogen separation device 155 is not required, and when using an aqueous solution containing salt, the hydrogen separation device 155 may be required. .
  • the electricity produced in the reverse electrodialysis apparatus 100 or 200 may be stored in the electric charger 180 and then used to charge the electric vehicle 185.
  • the electricity produced by the reverse electrodialysis apparatus 100 or 200 may convert power according to the type of the electric charger 180 through the power converter. Typically, fast chargers are powered by DC, while slow and home chargers are powered by AC.
  • the reverse electrodialysis apparatus 100 or 200 may be always supplied to the electric charging device because it is possible to produce power at any time, and the surplus generation amount may be supplied to the electric power grid 187.
  • the fresh water 103 and the brine 105 supplied to the reverse electrodialysis apparatus 100 or 200 may use the fresh water 103 and the brine 105 treated by the intake and pretreatment unit 101, and the intake and pretreatment.
  • the contamination monitoring unit (not shown) of the reverse electrodialysis apparatus 100 or 200, the membrane regeneration unit for chemically or physically cleaning the cell stack of the reverse electrodialysis apparatus 100 or 200 Not shown, the description of the applicant's prior application KR 10-2015-0161014.

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Abstract

Un système de production d'énergie hybride comprend un dispositif d'électrodialyse inverse et une pile à combustible. Lorsque de l'électricité est produite dans le dispositif d'électrodialyse inverse et que de l'hydrogène est généré simultanément par une réaction de décomposition d'eau, l'hydrogène généré est fourni à la pile à combustible de telle sorte que de l'électricité est produite par une réaction électrochimique d'hydrogène et d'oxygène dans la pile à combustible.
PCT/KR2017/005702 2016-10-27 2017-05-31 Système de production d'énergie hybride et station de charge hybride d'hydrogène-électricité indépendante de l'énergie, qui utilisent un dispositif d'électrodialyse inverse capable de produire efficacement de l'hydrogène-électricité WO2018079965A1 (fr)

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KR1020160141145A KR101892692B1 (ko) 2016-10-27 2016-10-27 역전기투석 장치와 연료전지를 이용한 하이브리드 발전 시스템
KR10-2016-0141145 2016-10-27
KR10-2017-0059428 2017-05-12
KR1020170059428A KR102041554B1 (ko) 2017-05-12 2017-05-12 효율적인 수소-전기 생산이 가능한 역전기 투석 장치를 이용한 하이브리드 발전 시스템 및 에너지 자립형 수소-전기 복합 충전 스테이션

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GB2589649A (en) * 2020-04-17 2021-06-09 Atom Industries Int Ltd Apparatus and method for production of hydrogen gas

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GB2589649A (en) * 2020-04-17 2021-06-09 Atom Industries Int Ltd Apparatus and method for production of hydrogen gas
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GB2589649B (en) * 2020-04-17 2022-02-23 Atom Industries Int Ltd Apparatus and method for production of hydrogen gas
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CN112436758B (zh) * 2020-11-10 2022-04-12 西安理工大学 一种反电渗析发电装置

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