WO2019181662A1 - アルカリ水電解装置及びガス製造方法 - Google Patents
アルカリ水電解装置及びガス製造方法 Download PDFInfo
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- WO2019181662A1 WO2019181662A1 PCT/JP2019/010092 JP2019010092W WO2019181662A1 WO 2019181662 A1 WO2019181662 A1 WO 2019181662A1 JP 2019010092 W JP2019010092 W JP 2019010092W WO 2019181662 A1 WO2019181662 A1 WO 2019181662A1
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
- C25B1/044—Hydrogen or oxygen by electrolysis of water producing mixed hydrogen and oxygen gas, e.g. Brown's gas [HHO]
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- C25B15/00—Operating or servicing cells
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/13—Single electrolytic cells with circulation of an electrolyte
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- C—CHEMISTRY; METALLURGY
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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 an alkaline water electrolysis apparatus and a gas production method using an alkaline water electrolysis method.
- An alkaline water electrolysis method is known as a method for producing hydrogen gas and oxygen gas.
- hydrogen gas is generated from the cathode by electrolyzing water using a basic aqueous solution (alkaline water) in which an alkali metal hydroxide (eg, NaOH, KOH, etc.) is dissolved as an electrolytic solution.
- an electrolytic cell for alkaline water electrolysis includes an anode chamber and a cathode chamber separated by an ion-permeable diaphragm, and electrolysis is performed while circulating an electrolyte in the anode chamber and the cathode chamber, respectively.
- the electrolytic solution collected from each electrode chamber is once collected and stored in the circulation tank, and the electrolyte solution stored in the circulation tank is supplied to each electrode chamber again.
- Patent Document 1 discloses an anode chamber that contains an anode and generates anode gas, a cathode chamber that contains a cathode and generates hydrogen gas, the anode chamber, and the cathode chamber. And an anode-side circulation line that discharges the electrolytic solution from the anode chamber and returns the electrolyte solution to the anode chamber, wherein the anode-side circulation line removes the anode gas from the electrolyte solution.
- An anode-side gas-liquid separation means for separating, the anode chamber and the anode-side gas-liquid separation means are connected, and the electrolytic solution and the anode gas are discharged from the anode chamber to become the anode-side gas-liquid separation means.
- Anode-side supply line for connecting the anode-side discharge line to be fed, the anode chamber and the anode-side gas-liquid separation means, and discharging the electrolyte from the anode-side gas-liquid separation means and feeding it to the anode chamber Before the line and dissolved Hydrogen gas is present as a gas phase, and has an anode gas supply line that connects the gas phase region in which the hydrogen gas and the anode gas are mixed with the anode side gas-liquid separation means, and the anode gas supply line Supplies an anode gas to the gas phase region, and the hydrogen gas concentration in the gas phase region is less than an explosion limit lower limit.
- Patent Document 1 it is claimed that in the electrolysis process for generating hydrogen, the possibility that a small amount of gas gradually accumulates in the electrolyte circulation line and reaches the explosion limit of hydrogen can be reliably eliminated. Yes.
- the cited document 1 describes that the gas discharged from the gas phase region of the circulation tank is discharged out of the system as exhaust gas.
- the gas in the gas phase region of the circulation tank is pushed out (purged) using the anode gas, so that the gas discharged from the gas phase region of the circulation tank is in the gas phase region.
- cathode gas released from the electrolyte in the circulation tank to the gas phase region is mixed. Therefore, even if the gas discharged from the gas phase region of the circulation tank is recovered in the form described in the cited document 1, it is difficult to obtain a highly pure anode gas.
- a pipe communicating with the liquid-phase region of the anode-side circulation tank and the liquid-phase region of the cathode-side circulation tank
- the electrolyte flows into the other tank from one tank through the communication pipe, and at the same time, the electrolyte flowing in through the communication pipe also brings in dissolved gas, so the electrolyte flows in through the communication pipe.
- the gas composition in the gas phase region may reach the explosion limit in the side tank.
- the present invention produces both hydrogen gas and oxygen gas while preventing the gas composition in the gas phase region of the circulation tank from reaching the explosion limit and reducing the adverse effect of dissolved gas in the electrolyte on gas purity. It is an object of the present invention to provide an alkaline water electrolysis device that can be used. In addition, it prevents both the gas composition in the gas phase region of the circulation tank from reaching the explosion limit and produces both hydrogen gas and oxygen gas while reducing the adverse effect of dissolved gas in the electrolyte on gas purity.
- a method for producing oxygen gas and hydrogen gas is provided.
- the present invention includes the following forms [1] to [9].
- An electrolytic cell comprising an anode chamber that contains an anode and generates oxygen gas, a cathode chamber that contains a cathode and generates hydrogen gas, and an ion-permeable diaphragm that partitions the anode chamber and the cathode chamber
- a first gas-liquid separator connected to the anode chamber for gas-liquid separation of the electrolyte and oxygen gas flowing out of the anode chamber
- a second gas-liquid separator connected to the cathode chamber for gas-liquid separation of the electrolyte and hydrogen gas flowing out from the cathode chamber
- a first electrolyte tank connected to the first gas-liquid separator and receiving and storing the electrolyte separated by the first gas-liquid separator
- a second electrolyte tank connected to the second gas-liquid separator and receiving and storing the electrolyte separated by the second gas-liquid separator;
- the oxygen gas connected to the first gas-liquid
- a hydrogen gas blowing tube An oxygen gas discharge pipe connected to the first electrolyte solution tank and for causing oxygen gas to flow out of a gas phase region of the first electrolyte solution tank;
- a hydrogen gas discharge pipe connected to the second electrolyte solution tank and for causing hydrogen gas to flow out of a gas phase region of the second electrolyte solution tank;
- a circulation device for supplying an electrolyte from the first electrolyte tank and the second electrolyte tank to the anode chamber and the cathode chamber;
- the alkaline water electrolysis apparatus wherein the electrolytic solution is an alkaline aqueous solution.
- the circulation device is A collecting pipe connected to the first electrolyte tank and the second electrolyte tank;
- the circulation device is A first circulation pump for supplying an electrolytic solution from the first electrolytic solution tank to the anode chamber;
- a first gas composition detector for monitoring a gas composition in a gas phase region of the first electrolyte tank
- the alkaline water electrolysis device according to any one of [1] to [3], further comprising a second gas composition detector that monitors a gas composition in a gas phase region of the second electrolyte solution tank.
- An electrolytic cell comprising an anode chamber containing an anode and generating oxygen gas, a cathode chamber containing a cathode and generating hydrogen gas, and an ion-permeable diaphragm separating the anode chamber and the cathode chamber
- a method for producing oxygen gas and hydrogen gas by electrolyzing an electrolyte solution that is an alkaline aqueous solution (A) generating oxygen gas from the anode and generating hydrogen gas from the cathode by energizing between the anode and the cathode while supplying an electrolytic solution to the anode chamber and the cathode chamber; , (B) recovering a first gas-liquid mixture containing an electrolytic solution and oxygen gas from the anode chamber; (C) recovering a second gas-liquid mixture containing an electrolytic solution and hydrogen gas from the cathode chamber; (D) gas-liquid separation of the first gas-liquid mixture; (E) gas-liquid separation of the second gas-liquid mixture; (
- step (l) the mixture of the electrolytic solution stored in the first electrolytic solution tank and the electrolytic solution stored in the second electrolytic solution tank is converted into the anode chamber and the cathode chamber.
- step (l) Supplying the electrolyte stored in the first electrolyte tank to the anode chamber; and The method for producing oxygen gas and hydrogen gas according to [6], including supplying an electrolyte stored in the second electrolyte tank to the cathode chamber.
- the oxygen gas recovered from the anode chamber is guided to the gas phase region of the first electrolyte tank storing the electrolyte recovered from the anode chamber through an oxygen gas blowing pipe.
- the oxygen gas flows out from the gas phase region of the first electrolyte tank through the oxygen gas discharge pipe, and from the cathode chamber to the gas phase region of the second electrolyte tank that stores the electrolyte recovered from the cathode chamber.
- the recovered hydrogen gas is guided through the hydrogen gas blowing pipe, and the hydrogen gas flows out from the gas phase region of the second electrolyte tank through the hydrogen gas discharge pipe.
- an alkaline water electrolyzer capable of producing both hydrogen gas and oxygen gas can be provided.
- the hydrogen gas and oxygen gas production method of the present invention in particular, by providing the steps (f) to (k), in the gas phase region of the first electrolyte tank that stores the electrolyte recovered from the anode chamber, The oxygen gas recovered from the anode chamber is introduced, the oxygen gas is recovered from the gas phase region of the first electrolyte tank, and the gas in the second electrolyte tank that stores the electrolyte recovered from the cathode chamber is stored. Hydrogen gas recovered from the cathode chamber is introduced into the phase region, and hydrogen gas is recovered from the gas phase region of the second electrolyte tank.
- the method for producing hydrogen gas and oxygen gas of the present invention it is possible to prevent the gas composition in the gas phase region of the circulation tank from reaching the explosion limit and to adversely affect the gas purity of the dissolved gas in the electrolyte. It is possible to provide a method for producing oxygen gas and hydrogen gas capable of producing both hydrogen gas and oxygen gas while being reduced.
- FIG. 1 is a diagram schematically illustrating an alkaline water electrolysis apparatus 100 (hereinafter sometimes referred to as “electrolysis apparatus 100”) according to an embodiment of the present invention.
- the electrolysis apparatus 100 is an apparatus that uses oxygen water as an electrolyte and produces oxygen gas and hydrogen gas by electrolysis of alkali water.
- the electrolyzer 100 includes an electrolyzer 10, a first gas-liquid separator 20, a second gas-liquid separator 30, a first electrolyte tank 40, a second electrolyte tank 50, and a circulation device. 60.
- the arrow indicates the direction in which the substance flows.
- the electrolytic cell 10 includes an anode chamber 11 that contains an anode and generates oxygen gas, a cathode chamber 12 that contains a cathode and generates hydrogen gas, and an ion-permeable diaphragm 13 that partitions the anode chamber 11 and the cathode chamber 12. It has.
- an electrolytic cell of a form conventionally used for an alkaline water electrolysis apparatus can be employed without any particular limitation.
- the first gas-liquid separator 20 is connected to the anode chamber 11 through the anolyte / gas recovery pipe 21, and gas-liquid separates the electrolyte and oxygen gas flowing out from the anode chamber 11.
- the second gas / liquid separator 30 is connected to the cathode chamber 12 through the catholyte / gas recovery tube 31 and gas-liquid separates the electrolyte and hydrogen gas flowing out from the cathode chamber 12.
- the 1st gas-liquid separator 20 and the 2nd gas-liquid separator 30 the gas-liquid separator of the form conventionally used for the alkaline water electrolysis apparatus can be employ
- the first electrolyte tank 40 is connected to the first gas-liquid separator 20 and receives and stores the electrolyte separated by the first gas-liquid separator 20.
- the electrolytic solution separated by the first gas-liquid separator 20 is introduced into the first electrolytic solution tank 40 through the anolyte discharge pipe 22.
- Inside the first electrolytic solution tank 40 there are a liquid phase region 40a occupied by the stored electrolytic solution and a gas phase region 40b above the liquid phase region 40a.
- the second electrolyte tank 50 is connected to the second gas-liquid separator 30 and receives and stores the electrolyte separated by the second gas-liquid separator 30.
- the electrolytic solution separated by the second gas-liquid separator 30 is introduced into the second electrolytic solution tank 50 through the catholyte discharge pipe 32.
- the liquid phase region 40 a of the first electrolytic solution tank 40 and the liquid phase region 50 a of the second electrolytic solution tank 50 are connected by a communication pipe 80 so that the electrolytic solution can flow. That is, the electrolytic solution occupying the liquid phase region 40a of the first electrolytic solution tank 40 can move to the liquid phase region 50a of the second electrolytic solution tank 50 through the communication pipe 80, and the second electrolytic solution The electrolytic solution occupying the liquid phase region 50 a of the liquid tank 50 can move to the liquid phase region 40 a of the first electrolytic solution tank 40 through the communication pipe 80.
- the circulation device 60 supplies the electrolytic solution from the first electrolytic solution tank 40 and the second electrolytic solution tank 50 to the anode chamber 11 and the cathode chamber 12.
- the circulation device 60 is connected to the collective piping 62 connected to the liquid phase region 40a of the first electrolytic solution tank 40 and the liquid phase region 50a of the second electrolytic solution tank, to the collective piping 62 and the electrolytic cell 10, and
- a circulation pump 61 is provided for supplying the electrolytic solution guided through the pipe 62 to the anode chamber 11 and the cathode chamber 12 through the electrolytic solution supply pipe 63.
- the electrolytic solution supply pipe 63 is branched in the middle, and introduces the electrolytic solution sent from the circulation pump 61 into each of the anode chamber 11 and the cathode chamber 12.
- a circulation pump of a form conventionally used in an alkaline water electrolysis apparatus can be used without particular limitation.
- the electrolyzer 100 is connected to the first gas-liquid separator 20 and the first electrolyte tank 40, and oxygen gas separated by the first gas-liquid separator 20 is vaporized in the first electrolyte tank 40.
- the oxygen gas blowing pipe 23 that leads to the region 40b, the second gas-liquid separator 30 and the second electrolyte tank 50 are connected to the second gas-liquid separator 30 and the hydrogen gas separated by the second gas-liquid separator 30 is supplied to the second gas-liquid separator 30.
- a hydrogen gas blowing pipe 33 leading to the gas phase region 50b of the electrolyte tank 50 is further provided.
- the electrolyzer 100 is connected to the first electrolyte tank 40, and is connected to an oxygen gas discharge pipe 41 that discharges oxygen gas from the gas phase region 40 b of the first electrolyte tank 40, and the second electrolyte tank 50. And a hydrogen gas discharge pipe 51 for allowing hydrogen gas to flow out from the gas phase region 50b of the second electrolyte tank 50.
- the oxygen gas produced in the electrolyzer 100 is finally recovered from the oxygen gas discharge pipe 41, and the hydrogen gas produced in the electrolyzer 100 is finally recovered from the hydrogen gas 51.
- the electrolyzer 100 monitors the gas composition in the gas phase region 50b of the first gas solution detector 50 and the gas phase region 50b of the second electrolyte solution tank 50. And a second gas composition detector 72.
- the first gas composition detector 71 is connected to the gas outlet side of the first electrolyte tank 40 (that is, in the middle of the oxygen gas discharge pipe 41), and the second gas composition detector 72. Is connected to the gas outlet side of the second electrolyte tank 50 (that is, in the middle of the hydrogen gas discharge pipe 51).
- the first gas composition detector 71 a conventional gas composition detector capable of measuring the hydrogen gas concentration in a gas containing oxygen as a main component can be used without particular limitation, and the second gas composition detector 71 can be used.
- the detector 72 a conventional gas composition detector capable of measuring the oxygen gas concentration in the gas containing hydrogen as a main component can be used without any particular limitation.
- the anode chamber 11 While supplying an electrolytic solution to the anode chamber 11 and the cathode chamber 12 of the electrolytic cell 10, the anode chamber 11 is energized between the anode housed in the anode chamber 11 and the cathode housed in the cathode chamber 12. Oxygen gas is generated from the anode, and hydrogen gas is generated from the cathode in the cathode chamber 12 (step (a)).
- a first gas-liquid mixture containing the electrolytic solution and oxygen gas generated in the anode chamber 11 is recovered from the anode chamber 11 (step (b)).
- the first gas-liquid mixture recovered from the anode chamber 11 is guided to the first gas-liquid separator 20 through the anolyte / gas recovery pipe 21.
- a second gas-liquid mixture containing the electrolytic solution and hydrogen gas generated in the cathode chamber 12 is recovered (step (c)).
- the second gas-liquid mixture recovered from the cathode chamber 12 is guided to the second gas-liquid separator 30 through the catholyte / gas recovery tube 31.
- the first gas-liquid mixture guided from the anode chamber 11 through the anolyte / gas recovery pipe 21 is gas-liquid separated in the first gas-liquid separator 20 (step (d)).
- the first gas-liquid separator 20 causes the gas-liquid separated electrolyte (anolyte) to flow out to the anolyte discharge pipe 22, and causes the gas gas-liquid separated oxygen gas to flow out to the oxygen gas blowing pipe 23.
- the second gas-liquid mixture introduced from the cathode chamber 12 through the catholyte / gas recovery pipe 31 is gas-liquid separated in the second gas-liquid separator 30 (step (e)).
- the second gas-liquid separator 30 causes the electrolytic solution (catholyte) separated by gas-liquid to flow out to the catholyte discharge pipe 32 and causes the hydrogen gas separated from gas-liquid to flow out to the hydrogen gas blowing pipe 33.
- the electrolyte (anolyte) separated in the first gas-liquid separator 20 is guided to the first electrolyte tank 40 through the anolyte discharge pipe 22 and stored in the first electrolyte tank 40.
- the electrolytic solution (catholyte) separated in the second gas-liquid separator 30 is guided to the second electrolytic solution tank 50 through the catholyte discharge pipe 32 and stored in the second electrolytic solution tank 50. (Step (g)).
- the oxygen gas separated in the first gas-liquid separator 20 is introduced into the gas phase region 40b of the first electrolyte tank 40 through the oxygen gas blowing pipe 23 (step (h)).
- the hydrogen gas separated in the second gas-liquid separator 30 is introduced into the gas phase region 50b of the second electrolyte tank 50 through the hydrogen gas blowing pipe 33 (step (i)).
- the oxygen gas in the gas phase region 40b of the first electrolyte tank 40 is recovered from the gas phase region 40b through the oxygen gas discharge pipe 41 (step (j)).
- the gas recovered from the gas phase region 40b through the oxygen gas discharge pipe 41 is added to the liquid phase region 40a of the first electrolyte tank 40 in addition to the oxygen gas introduced into the gas phase region 40b through the oxygen gas blowing pipe 23.
- the dissolved gas released from the electrolyte solution occupying the gas phase region 40b is also included.
- step (a) while supplying the electrolytic solution to the anode chamber 11 and the cathode chamber 12 of the electrolytic cell 10, the anode accommodated in the anode chamber 11 and the cathode accommodated in the cathode chamber 12.
- oxygen gas is generated from the anode in the anode chamber 11, and hydrogen gas is generated from the cathode in the cathode chamber 12.
- the anode chamber 11 and the cathode chamber 12 are partitioned by an ion-permeable diaphragm 13, but the gas barrier property of the diaphragm 13 is usually not perfect, so that the oxygen recovered from the anode chamber 11 is A small amount of hydrogen gas generated in the adjacent cathode chamber 12 is mixed in the gas. Similarly, a small amount of oxygen gas generated in the adjacent anode chamber 11 is mixed in the hydrogen gas recovered from the cathode chamber 12.
- the first gas-liquid separator 20 and the second gas-liquid separator 30 include a liquid contact portion including a metal material and a sacrificial electrode for suppressing electrolytic corrosion of the metal material.
- a small amount of hydrogen gas is generated in the first gas-liquid separator 20 (oxygen gas side), and the generated small amount of hydrogen gas is the first.
- the second gas-liquid separator 30 hydrogen gas side
- a small amount of oxygen gas is generated and the generated small amount of oxygen gas is mixed with the second gas-liquid separator 20. It mixes in the hydrogen gas flowing out from the gas-liquid separator 30.
- the dissolved gas in the electrolyte solution that occupies the liquid phase region 40a contains a small amount of hydrogen gas as well as oxygen gas.
- the hydrogen gas is discharged together with the oxygen gas introduced into the gas phase region 40b through the oxygen gas blowing tube 23 and the oxygen gas discharge pipe 41.
- the hydrogen gas concentration in the gas phase region 40b is prevented from rising until reaching the explosion limit.
- the electrolytic solution occupying the liquid phase region 40a of the first electrolytic solution tank 40 is an electrolytic solution (anolyte) recovered from the anode chamber 11, the main component of the dissolved gas in the electrolytic solution is oxygen. Gas.
- the hydrogen gas in the gas phase region 50b of the second electrolyte tank 50 is recovered from the gas phase region 50b through the hydrogen gas discharge pipe 51 (step (k)).
- the gas recovered from the gas phase region 50b through the hydrogen gas discharge pipe 51 is added to the hydrogen gas introduced into the gas phase region 50b through the hydrogen gas blowing pipe 33, and the liquid phase region 50a of the second electrolytic solution tank 50.
- the dissolved gas released from the electrolyte solution occupying the gas phase region 50b is also included.
- the dissolved gas contains a small amount of oxygen gas as well as hydrogen gas in a reverse relation to the case of the liquid phase region 40a in the first electrolyte tank 40 described above.
- the oxygen gas is introduced together with the hydrogen gas introduced into the gas phase region 50b through the hydrogen gas blowing tube 33 into the hydrogen gas discharge pipe 51.
- the oxygen gas concentration in the gas phase region 50b is prevented from rising until reaching the explosion limit.
- the electrolytic solution occupying the liquid phase region 50a of the second electrolytic solution tank 50 is the electrolytic solution (catholyte) recovered from the cathode chamber 12
- the main component of the dissolved gas in the electrolytic solution is hydrogen. Gas. That is, even if oxygen gas is contained as a dissolved gas in the electrolytic solution, the oxygen gas is only a subcomponent of the dissolved gas. Therefore, the influence of the dissolved gas released from the electrolyte solution occupying the liquid phase region 50a of the second electrolyte tank 50 into the gas phase region 50b on the purity of the hydrogen gas recovered from the hydrogen gas discharge pipe 51 is slight.
- the electrolytic solution stored in the first electrolytic solution tank 40 and the second electrolytic solution tank 50 is led to the circulation pump 61 through the collective piping 62, sent out from the circulation pump 61, and introduced from the first electrolyte solution tank 40.
- a mixture of the electrolyte solution thus introduced and the electrolyte solution guided from the second electrolyte solution tank 50 is supplied to the anode chamber 11 and the cathode chamber 12 through the electrolyte solution supply pipe 63 (step (l)).
- step (l) By continuously operating the electrolyzer 100, that is, the steps (a) to (l) are continuously performed simultaneously, the production of oxygen gas and hydrogen gas by electrolysis of alkaline water is continuously performed. .
- the liquid level difference occurs between the first electrolyte tank 40 and the second electrolyte tank 50 due to the difference in water consumption rate between the cathode reaction and the anode reaction during the operation of the electrolyzer 100.
- the liquid level difference is reduced or eliminated by moving the electrolytic solution from one electrolytic solution tank to the other electrolytic solution tank through the communication pipe 80.
- the electrolyte flows from one tank to the other tank through the communication pipe, and at the same time, the electrolyte flowing in through the communication pipe is also dissolved gas in the electrolyte.
- the gas composition in the gas phase region easily reaches the explosion limit in the tank on the side into which the electrolyte flows through the communication pipe.
- the electrolysis apparatus of the present invention it is possible to prevent the gas composition in the gas phase region of each electrolyte tank from reaching the explosion limit even when such a communication pipe is provided. Therefore, in the electrolysis apparatus having such a communication pipe, the effect of preventing the gas composition in the gas phase region of each electrolyte tank from reaching the explosion limit of the present invention is more remarkably exhibited. .
- the gas composition in the gas phase region 40b of the first electrolyte tank 40 is monitored by the first gas composition detector 71 arranged on the gas outlet side of the first electrolyte tank 40 (step (m)). . Since the gas composition observed on the gas outlet side of the first electrolyte tank 40 and the gas composition in the gas phase region 40b are the same, the gas composition arranged on the gas outlet side of the first electrolyte tank 40 The gas composition in the gas phase region 40b can be monitored by a detector.
- the gas composition in the gas phase region 50b of the second electrolyte tank 50 is monitored by the second gas composition detector 72 arranged on the gas outlet side of the second electrolyte tank 50 (step (n)). .
- the gas composition arranged on the gas outlet side of the second electrolyte tank 50 can be monitored by a detector.
- the monitoring of the gas composition by the first gas composition detector 71 (step (m)) and the monitoring of the gas composition by the second gas composition detector 72 (step (n)) may be performed continuously. Although it may be performed intermittently, it is preferably performed continuously from the viewpoint of detecting an abnormality of the electrolysis apparatus 100 at an early stage.
- the first gas composition detector 71 arranged on the gas outlet side of the first electrolyte tank 40 and the second gas detector arranged on the gas outlet side of the second electrolyte tank 50.
- the electrolysis apparatus 100 having the gas composition detector 72 and the method for producing oxygen gas and hydrogen gas using the electrolysis apparatus 100 have been described as examples, the present invention is not limited to the form.
- the locations where the first gas composition detector and the second gas composition detector are disposed may be locations other than the gas outlet side of each electrolyte tank.
- each gas composition detector may be arranged in a gas phase region of each electrolyte tank.
- each gas composition detector may be arranged on the gas outlet side of each gas-liquid separator (upstream side of each electrolyte tank).
- each gas recovered from the electrolytic cell is taken out after passing through the gas phase region of each electrolyte tank. Therefore, even when each gas composition detector is arranged on the gas outlet side of each gas-liquid separator (upstream side of each electrolyte tank), the gas composition in the gas phase region of each electrolyte tank should be monitored. Is possible.
- the embodiment includes the communication pipe 80 that connects the liquid phase region 40a of the first electrolytic solution tank 40 and the liquid phase region 50a of the second electrolytic solution tank 50 so that the electrolytic solution can flow therethrough.
- the electrolysis apparatus 100 and the method for producing oxygen gas and hydrogen gas using the electrolysis apparatus is described as an example, the present invention is not limited to this form.
- an alkaline water electrolysis apparatus having a communication pipe that connects the liquid phase region of the first electrolytic solution tank and the liquid phase region of the second electrolytic solution tank may be provided.
- the circulation device 60 is connected to the collective pipe 62 connected to the first electrolytic solution tank 40 and the second electrolytic solution tank 50, the collective pipe 62 and the electrolytic cell 10, and the collective pipe 62.
- An electrolytic device 100 having a circulation pump 61 that supplies an electrolytic solution guided through the anode chamber 11 and the cathode chamber 12, and an oxygen gas and hydrogen gas manufacturing method using the electrolytic device 100 as an example.
- this invention is not limited to the said form.
- a circulation device includes a first circulation pump that supplies an electrolytic solution from a first electrolytic solution tank to the anode chamber, and a second circulating pump that supplies an electrolytic solution from the second electrolytic solution tank to the cathode chamber.
- an alkaline water electrolysis device in the form of being provided.
- FIG. 2 is a diagram schematically illustrating an alkaline water electrolysis apparatus 200 (hereinafter, also referred to as “electrolysis apparatus 200”) according to such another embodiment.
- electrolysis apparatus 200 the same elements as those already shown in FIG. 1 are denoted by the same reference numerals as those in FIG.
- the electrolyzer 200 is different from the electrolyzer 100 described above in that a circulator 260 is provided instead of the circulator 60.
- the circulation device 260 includes a first circulation pump 261 that supplies the electrolyte from the first electrolyte tank 40 to the anode chamber 11, and a second that supplies the electrolyte from the second electrolyte tank 50 to the cathode chamber 12.
- the circulation device 260 has a pipe 263 that guides the electrolyte from the liquid phase region 40 a of the first electrolyte tank 40 to the first circulation pump 261 and the electrolyte sent from the first circulation pump 261 to the anode chamber 11.
- a pipe 265 for guiding is further provided.
- the circulation device 260 also includes a pipe 264 that guides the electrolyte from the liquid phase region 50 a of the second electrolyte tank 50 to the second circulation pump 262 and the electrolyte sent from the second circulation pump 262 to the cathode chamber 12. And a pipe 266 leading to the pipe.
- the circulation pump of the form conventionally used for the alkaline water electrolysis apparatus can be especially used without a restriction
- step (l ) The operation of the electrolyzer 200 and the method for producing oxygen gas and hydrogen gas using the electrolyzer 200 will be further described with reference to FIG.
- the method for producing oxygen gas and hydrogen gas using the electrolyzer 200 is different only in step (l). That is, the electrolytic solution stored in the first electrolytic solution tank 40 is guided to the first circulation pump 261 through the pipe 263, sent out from the first circulation pump 261, and supplied to the anode chamber 11 through the pipe 265. .
- the electrolytic solution stored in the second electrolytic solution tank 50 is led to the second circulation pump 262 through the pipe 264, sent out from the second circulation pump 262, and supplied to the cathode chamber through the pipe 266 (step). (L ′)).
- oxygen gas and hydrogen gas can be produced by electrolysis of alkaline water. Done continuously.
- a liquid level difference occurs between the first electrolyte tank 40 and the second electrolyte tank 50 due to a difference in water consumption rate between the cathode reaction and the anode reaction while the electrolyzer 200 is operated.
- the liquid level difference is reduced or eliminated by moving the electrolytic solution from one electrolytic solution tank to the other electrolytic solution tank through the communication pipe 80.
- Electrolyzer 100, 200 Electrolyzer 10 Electrolyzer 11 Anode chamber 12 Cathode chamber 13 (Ion permeable) diaphragm 20 First gas-liquid separator 21 Anode solution / gas recovery tube 22 Anode solution discharge tube 23 Oxygen gas blowing tube 30 2 gas-liquid separator 31 catholyte / gas recovery pipe 32 catholyte discharge pipe 33 hydrogen gas blowing pipe 40 first electrolyte tank 40a, 50a liquid phase area 40b, 50b gas phase area 41 oxygen gas discharge pipe 50 2 Electrolyte tank 51 Hydrogen gas discharge pipes 60, 260 Circulating device 61 Circulating pump 62 Collecting pipe 63 Electrolyte supply pipe 261 First circulating pump 262 Second circulating pump 263, 264, 265, 266 Pipe 71 First pipe Gas composition detector 72 Second gas composition detector 80 Communication piping
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Abstract
Description
[1] 陽極を収容し酸素ガスを発生する陽極室と、陰極を収容し水素ガスを発生する陰極室と、前記陽極室と前記陰極室とを区画するイオン透過性の隔膜とを備える電解槽と、
前記陽極室に接続され、前記陽極室から流出した電解液および酸素ガスを気液分離する、第1の気液分離器と、
前記陰極室に接続され、前記陰極室から流出した電解液および水素ガスを気液分離する、第2の気液分離器と、
前記第1の気液分離器に接続され、前記第1の気液分離器によって分離された電解液を受け容れ貯留する、第1の電解液タンクと、
前記第2の気液分離器に接続され、前記第2の気液分離器によって分離された電解液を受け容れ貯留する、第2の電解液タンクと、
前記第1の気液分離器および前記第1の電解液タンクに接続され、前記第1の気液分離器によって分離された酸素ガスを、前記第1の電解液タンクの気相領域に導く、酸素ガス吹込み管と、
前記第2の気液分離器および前記第2の電解液タンクに接続され、前記第2の気液分離器によって分離された水素ガスを、前記第2の電解液タンクの気相領域に導く、水素ガス吹込み管と、
前記第1の電解液タンクに接続され、前記第1の電解液タンクの気相領域から酸素ガスを流出させる、酸素ガス排出管と、
前記第2の電解液タンクに接続され、前記第2の電解液タンクの気相領域から水素ガスを流出させる、水素ガス排出管と、
前記第1の電解液タンク及び前記第2の電解液タンクから、前記陽極室及び前記陰極室に電解液を供給する、循環装置とを備え、
前記電解液はアルカリ水溶液であることを特徴とする、アルカリ水電解装置。
前記第1の電解液タンク及び前記第2の電解液タンクに接続された集合配管と、
前記集合配管及び前記電解槽に接続され、前記集合配管を通じて導かれた電解液を前記陽極室及び前記陰極室に供給する、循環ポンプとを備える、[1]に記載のアルカリ水電解装置。
前記第1の電解液タンクから前記陽極室に電解液を供給する、第1の循環ポンプと、
前記第2の電解液タンクから前記陰極室に電解液を供給する、第2の循環ポンプとを備える、[1]に記載のアルカリ水電解装置。
前記第2の電解液タンクの気相領域におけるガス組成を監視する、第2のガス組成検知器とをさらに備える、[1]~[3]のいずれかに記載のアルカリ水電解装置。
(a)前記陽極室および前記陰極室に電解液を供給しながら前記陽極と前記陰極との間に通電することにより、前記陽極から酸素ガスを発生させ且つ前記陰極から水素ガスを発生させる工程と、
(b)前記陽極室から電解液および酸素ガスを含む第1の気液混合物を回収する工程と、
(c)前記陰極室から電解液および水素ガスを含む第2の気液混合物を回収する工程と、
(d)前記第1の気液混合物を気液分離する工程と、
(e)前記第2の気液混合物を気液分離する工程と、
(f)前記第1の気液混合物の気液分離によって分離された電解液を、第1の電解液タンクに貯留する工程と、
(g)前記第2の気液混合物の気液分離によって分離された電解液を、第2の電解液タンクに貯留する工程と、
(h)前記第1の気液混合物の気液分離によって分離された酸素ガスを、前記第1の電解液タンクの気相領域に導入する工程と、
(i)前記第2の気液混合物の気液分離によって分離された水素ガスを、前記第2の電解液タンクの気相領域に導入する工程と、
(j)前記第1の電解液タンクの気相領域から酸素ガスを回収する工程と、
(k)前記第2の電解液タンクの気相領域から水素ガスを回収する工程と、
(l)前記第1の電解液タンク及び前記第2の電解液タンクから、前記陽極室および前記陰極室に電解液を供給する工程とを含む、酸素ガス及び水素ガスの製造方法。
前記第1の電解液タンクに貯留された電解液を、前記陽極室に供給すること、及び、
前記第2の電解液タンクに貯留された電解液を、前記陰極室に供給することを含む、[6]に記載の酸素ガス及び水素ガスの製造方法。
(n)前記第2の電解液タンクの気相領域中のガス組成を監視する工程とをさらに含む、[6]~[8]のいずれかに記載の酸素ガス及び水素ガスの製造方法。
図1は、本発明の一の実施形態に係るアルカリ水電解装置100(以下において「電解装置100」ということがある。)を模式的に説明する図である。電解装置100は、電解液としてアルカリ水を用い、アルカリ水の電気分解により酸素ガス及び水素ガスを製造する装置である。電解装置100は、電解槽10と、第1の気液分離器20と、第2の気液分離器30と、第1の電解液タンク40と、第2の電解液タンク50と、循環装置60とを備えている。図1中、矢印は物質の流れる向きを指している。
第2の電解液タンク50は、第2の気液分離器30に接続されており、第2の気液分離器30によって分離された電解液を受け容れ貯留する。第2の気液分離器30によって分離された電解液は、陰極液排出管32を通じて第2の電解液タンク50に導入される。第2の電解液タンク50の内部には、貯留された電解液で占められている液相領域50aと、液相領域50aの上側の気相領域50bとが存在する。
第1の電解液タンク40の液相領域40aと、第2の電解液タンク50の液相領域50aとは、連通配管80によって電解液が流通可能に接続されている。すなわち、第1の電解液タンク40の液相領域40aを占める電解液は、連通配管80を通じて第2の電解液タンク50の液相領域50aに移動することが可能であり、また第2の電解液タンク50の液相領域50aを占める電解液は、連通配管80を通じて第1の電解液タンク40の液相領域40aに移動することが可能である。
電解装置100は、第1の電解液タンク40に接続され、第1の電解液タンク40の気相領域40bから酸素ガスを流出させる酸素ガス排出管41と、第2の電解液タンク50に接続され、第2の電解液タンク50の気相領域50bから水素ガスを流出させる水素ガス排出管51とをさらに備えている。電解装置100において製造された酸素ガスは最終的に酸素ガス排出管41から回収され、電解装置100において製造された水素ガスは最終的に水素ガス51から回収される。
電解装置100は、第1の電解液タンク40の気相領域40bにおけるガス組成を監視する第1のガス組成検知器71と、第2の電解液タンク50の気相領域50bにおけるガス組成を監視する第2のガス組成検知器72とをさらに備えている。電解装置100において、第1のガス組成検知器71は第1の電解液タンク40のガス出側(すなわち、酸素ガス排出管41の途中)に接続されており、第2のガス組成検知器72は第2の電解液タンク50のガス出側(すなわち、水素ガス排出管51の途中)に接続されている。第1のガス組成検知器71としては、酸素を主成分とするガス中の水素ガス濃度を測定することが可能な従来のガス組成検知器を特に制限なく用いることができ、第2のガス組成検知器72としては、水素を主成分とするガス中の酸素ガス濃度を測定することが可能な従来のガス組成検知器を特に制限なく用いることができる。
電解装置100の動作、及び、電解装置100を用いる形態の酸素ガス及び水素ガスの製造方法について、図1を参照しつつさらに説明する。
陰極室12からは、電解液および陰極室12で発生した水素ガスを含む第2の気液混合物が回収される(ステップ(c))。陰極室12から回収された第2の気液混合物は、陰極液・ガス回収管31を通じて第2の気液分離器30に導かれる。
陰極液・ガス回収管31を通じて陰極室12から導かれた第2の気液混合物は、第2の気液分離器30において気液分離される(ステップ(e))。第2の気液分離器30は、気液分離した電解液(陰極液)を陰極液排出管32に流出させ、気液分離した水素ガスを水素ガス吹込み管33に流出させる。
第2の気液分離器30において気液分離された電解液(陰極液)は、陰極液排出管32を通じて第2の電解液タンク50に導かれ、第2の電解液タンク50に貯留される(ステップ(g))。
第2の気液分離器30において気液分離された水素ガスは、水素ガス吹込み管33を通じて、第2の電解液タンク50の気相領域50bに導入される(ステップ(i))。
第2の電解液タンク50のガス出側に配置された第2のガス組成検知器72により、第2の電解液タンク50の気相領域50bにおけるガス組成が監視される(ステップ(n))。第2の電解液タンク50のガス出側において観測されるガス組成と、気相領域50bにおけるガス組成とは同一であるので、第2の電解液タンク50のガス出側に配置されたガス組成検知器によって気相領域50bにおけるガス組成を監視することが可能である。
第1のガス組成検知器71によるガス組成の監視(ステップ(m))、及び、第2のガス組成検知器72によるガス組成の監視(ステップ(n))は、連続的に行ってもよく、間欠的に行ってもよいが、電解装置100の異常を早期に検知する観点からは連続的に行うことが好ましい。
本発明に関する上記説明では、循環装置60が、第1の電解液タンク40及び第2の電解液タンク50に接続された集合配管62と、集合配管62及び電解槽10に接続され、集合配管62を通じて導かれた電解液を陽極室11及び陰極室12に供給する循環ポンプ61とを備える形態の電解装置100、並びに、該電解装置100を用いる形態の酸素ガス及び水素ガスの製造方法を例に挙げたが、本発明は当該形態に限定されない。例えば、循環装置が、第1の電解液タンクから陽極室に電解液を供給する第1の循環ポンプと、第2の電解液タンクから陰極室に電解液を供給する第2の循環ポンプとを備える形態のアルカリ水電解装置とすることも可能である。図2は、そのような他の実施形態に係るアルカリ水電解装置200(以下において「電解装置200」ということがある。)を模式的に説明する図である。図2において、図1に既に表れた要素と同一の要素には図1における符号と同一の符号を付し、説明を省略することがある。
電解装置200の動作、及び、電解装置200を用いる形態の酸素ガス及び水素ガスの製造方法について、図2を参照しつつさらに説明する。電解装置200を用いる形態の酸素ガス及び水素ガスの製造方法は、上記ステップ(l)においてのみ異なっている。すなわち、第1の電解液タンク40に貯留された電解液は、配管263を通じて第1の循環ポンプ261に導かれて第1の循環ポンプ261から送出され、配管265を通じて陽極室11に供給される。また第2の電解液タンク50に貯留された電解液は、配管264を通じて第2の循環ポンプ262に導かれて第2の循環ポンプ262から送出され、配管266を通じて陰極室に供給される(ステップ(l’))。
10 電解槽
11 陽極室
12 陰極室
13 (イオン透過性の)隔膜
20 第1の気液分離器
21 陽極液・ガス回収管
22 陽極液排出管
23 酸素ガス吹込み管
30 第2の気液分離器
31 陰極液・ガス回収管
32 陰極液排出管
33 水素ガス吹込み管
40 第1の電解液タンク
40a、50a 液相領域
40b、50b 気相領域
41 酸素ガス排出管
50 第2の電解液タンク
51 水素ガス排出管
60、260 循環装置
61 循環ポンプ
62 集合配管
63 電解液供給管
261 第1の循環ポンプ
262 第2の循環ポンプ
263、264、265、266 配管
71 第1のガス組成検知器
72 第2のガス組成検知器
80 連通配管
Claims (9)
- 陽極を収容し酸素ガスを発生する陽極室と、陰極を収容し水素ガスを発生する陰極室と、前記陽極室と前記陰極室とを区画するイオン透過性の隔膜とを備える電解槽と、
前記陽極室に接続され、前記陽極室から流出した電解液および酸素ガスを気液分離する、第1の気液分離器と、
前記陰極室に接続され、前記陰極室から流出した電解液および水素ガスを気液分離する、第2の気液分離器と、
前記第1の気液分離器に接続され、前記第1の気液分離器によって分離された電解液を受け容れ貯留する、第1の電解液タンクと、
前記第2の気液分離器に接続され、前記第2の気液分離器によって分離された電解液を受け容れ貯留する、第2の電解液タンクと、
前記第1の気液分離器および前記第1の電解液タンクに接続され、前記第1の気液分離器によって分離された酸素ガスを、前記第1の電解液タンクの気相領域に導く、酸素ガス吹込み管と、
前記第2の気液分離器および前記第2の電解液タンクに接続され、前記第2の気液分離器によって分離された水素ガスを、前記第2の電解液タンクの気相領域に導く、水素ガス吹込み管と、
前記第1の電解液タンクに接続され、前記第1の電解液タンクの気相領域から酸素ガスを流出させる、酸素ガス排出管と、
前記第2の電解液タンクに接続され、前記第2の電解液タンクの気相領域から水素ガスを流出させる、水素ガス排出管と、
前記第1の電解液タンク及び前記第2の電解液タンクから、前記陽極室及び前記陰極室に電解液を供給する、循環装置と
を備え、
前記電解液はアルカリ水溶液であることを特徴とする、
アルカリ水電解装置。 - 前記循環装置が、
前記第1の電解液タンク及び前記第2の電解液タンクに接続された集合配管と、
前記集合配管及び前記電解槽に接続され、前記集合配管を通じて導かれた電解液を前記陽極室及び前記陰極室に供給する、循環ポンプと
を備える、請求項1に記載のアルカリ水電解装置。 - 前記循環装置が、
前記第1の電解液タンクから前記陽極室に電解液を供給する、第1の循環ポンプと、
前記第2の電解液タンクから前記陰極室に電解液を供給する、第2の循環ポンプと
を備える、請求項1に記載のアルカリ水電解装置。 - 前記第1の電解液タンクの気相領域におけるガス組成を監視する、第1のガス組成検知器と、
前記第2の電解液タンクの気相領域におけるガス組成を監視する、第2のガス組成検知器と
をさらに備える、請求項1~3のいずれかに記載のアルカリ水電解装置。 - 前記第1の電解液タンクの液相領域と、前記第2の電解液タンクの液相領域とを、電解液が流通可能に接続する連通配管をさらに備える、
請求項1~4のいずれかに記載のアルカリ水電解装置。 - 陽極を収容し酸素ガスを発生する陽極室と、陰極を収容し水素ガスを発生する陰極室と、前記陽極室と前記陰極室とを区画するイオン透過性の隔膜とを備える電解槽を用いて、アルカリ水溶液である電解液を電解することにより酸素ガス及び水素ガスを製造する方法であって、
(a)前記陽極室および前記陰極室に電解液を供給しながら前記陽極と前記陰極との間に通電することにより、前記陽極から酸素ガスを発生させ且つ前記陰極から水素ガスを発生させる工程と、
(b)前記陽極室から電解液および酸素ガスを含む第1の気液混合物を回収する工程と、
(c)前記陰極室から電解液および水素ガスを含む第2の気液混合物を回収する工程と、
(d)前記第1の気液混合物を気液分離する工程と、
(e)前記第2の気液混合物を気液分離する工程と、
(f)前記第1の気液混合物の気液分離によって分離された電解液を、第1の電解液タンクに貯留する工程と、
(g)前記第2の気液混合物の気液分離によって分離された電解液を、第2の電解液タンクに貯留する工程と、
(h)前記第1の気液混合物の気液分離によって分離された酸素ガスを、前記第1の電解液タンクの気相領域に導入する工程と、
(i)前記第2の気液混合物の気液分離によって分離された水素ガスを、前記第2の電解液タンクの気相領域に導入する工程と、
(j)前記第1の電解液タンクの気相領域から酸素ガスを回収する工程と、
(k)前記第2の電解液タンクの気相領域から水素ガスを回収する工程と、
(l)前記第1の電解液タンク及び前記第2の電解液タンクから、前記陽極室および前記陰極室に電解液を供給する工程と、
を含む、酸素ガス及び水素ガスの製造方法。 - 前記工程(l)が、
前記第1の電解液タンクに貯留された電解液と、前記第2の電解液タンクに貯留された電解液との混合物を、前記陽極室および前記陰極室に供給すること
を含む、請求項6に記載の酸素ガス及び水素ガスの製造方法。 - 前記工程(l)が、
前記第1の電解液タンクに貯留された電解液を、前記陽極室に供給すること、及び、
前記第2の電解液タンクに貯留された電解液を、前記陰極室に供給すること
を含む、請求項6に記載の酸素ガス及び水素ガスの製造方法。 - (m)前記第1の電解液タンクの気相領域中のガス組成を監視する工程と、
(n)前記第2の電解液タンクの気相領域中のガス組成を監視する工程と
をさらに含む、請求項6~8のいずれかに記載の酸素ガス及び水素ガスの製造方法。
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| CA3093890A CA3093890A1 (en) | 2018-03-22 | 2019-03-12 | Apparatus for alkaline water electrolysis, and gas production method |
| EP19772146.7A EP3770304B1 (en) | 2018-03-22 | 2019-03-12 | Alkaline-water electrolysis apparatus and gas production method |
| JP2019542244A JP6594601B1 (ja) | 2018-03-22 | 2019-03-12 | アルカリ水電解装置及びガス製造方法 |
| MYPI2020003836A MY202881A (en) | 2018-03-22 | 2019-03-12 | Apparatus for alkaline water electrolysis, and gas production method |
| KR1020207021566A KR102611826B1 (ko) | 2018-03-22 | 2019-03-12 | 알칼리수 전해 장치 및 가스 제조 방법 |
| US16/965,150 US11220755B2 (en) | 2018-03-22 | 2019-03-12 | Apparatus for alkaline water electrolysis, and gas production method |
| PH12020551400A PH12020551400A1 (en) | 2018-03-22 | 2020-09-08 | Apparatus for alkaline water electrolysis, and gas production method |
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| EP3770304A1 (en) | 2021-01-27 |
| US20210040631A1 (en) | 2021-02-11 |
| PH12020551400A1 (en) | 2021-09-06 |
| CN111699279A (zh) | 2020-09-22 |
| KR20200133722A (ko) | 2020-11-30 |
| US11220755B2 (en) | 2022-01-11 |
| JP6594601B1 (ja) | 2019-10-23 |
| EP3770304B1 (en) | 2023-08-16 |
| MY202881A (en) | 2024-05-28 |
| CA3093890A1 (en) | 2019-09-26 |
| TW201940745A (zh) | 2019-10-16 |
| JPWO2019181662A1 (ja) | 2020-04-30 |
| TWI772629B (zh) | 2022-08-01 |
| KR102611826B1 (ko) | 2023-12-11 |
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