DISPOSITIVO DE PRODUÇÃO DE HIDRETO ORGÂNICO

Description

1 / 29 Descriptive Report of the Invention Patent for ORGANIC HYDRIDE PRODUCTION DEVICE. FIELD OF TECHNIQUE

[0001] The present invention relates to an organic hydride production device, a water removal device, and a water removal method. BACKGROUND OF THE TECHNIQUE

[0002] Conventionally, an organic hydride production device comprising an electrolyzer having an anode electrode to generate water protons, a cathode electrode to hydrogenate an organic compound (substance to be hydrogenated) having an unsaturated bond, and a membrane to separate the anode electrode and the cathode electrode is known (see, for example, Patent Literature 1). In this organic hydride production device, protons are generated by oxidation of water at the anode electrode, the protons move to the cathode electrode side through the membrane, and the substance to be hydrogenated is hydrogenated by the protons at the cathode electrode, so that an organic hydride is produced. Prior Art Documents Patent Literature

[0003] Patent Literature 1 WO2012 / 091128A SUMMARY OF THE INVENTION TECHNICAL PROBLEM

[0004] According to the organic hydride production device described above, the generation of protons and the hydrogenation of the substance to be hydrogenated can be carried out by a one-step process. Therefore, the process for producing organic hydride can be simplified compared to a case where organic hydride is produced by a two-step process in which hydrogen is produced by electrolysis of water or similar substances and the substance to be hydrogenated is produced by electrolysis of water or similar substances. Petition 870240056494, dated 04 / 07 / 2024, page 6 / 41 2 / 29 hydrogenated is chemically hydrogenated in a reactor such as a power plant. Or, the production efficiency of organic hydride can be improved. Furthermore, since it is possible to omit a high-pressure container to store hydrogen, which is required in the case of producing hydrogen by water electrolysis or similar methods, it is expected that the equipment cost will be greatly reduced.

[0005] On the other hand, in the organic hydride production device described above, when protons move through the membrane, water at the anode electrode moves to the cathode electrode side along with the protons. As a result of intensive studies, the present inventors have discovered that the entrained water having moved to the cathode electrode side can be accumulated at the bottom of the gas-liquid separation tower provided on the downstream side of the electrolyzer after being fed into the electrolyzer along with the organic hydride. Furthermore, the present inventors have discovered that when a circulation flow path is provided between a tank for storing the substance to be hydrogenated and the electrolyzer, the entrained water can also be accumulated at the bottom of the tank.

[0006] When the amount of entrained water increases, the organic hydride or the substance to be hydrogenated may overflow from the gas-liquid separation tower or tank. To resolve this, it is conceivable to suppress the overflow of the organic hydride or the substance to be hydrogenated by increasing the volume of the gas-liquid separation tower or tank in consideration of the increase in entrained water. However, increasing the volume of the gas-liquid separation tower or tank causes an increase in the size of the organic hydride production device.

[0007] The present invention was made in view of such a situation, and one of its objects is to provide a technique for suppressing an overflow of an organic hydride or a substance to be hydrogenated while Petition 870240056494, dated 04 / 07 / 2024, page 7 / 41 3 / 29 suppressing an increase in size of an organic hydride production device. SOLUTION TO THE PROBLEM

[0008] One aspect of the present invention is an organic hydride production device. This device includes: an electrolyzer having an anode electrode that oxidizes water in an anolyte to generate protons, an anode chamber equipping the anode electrode, a cathode electrode that hydrogenates a substance to be hydrogenated in a catholyte with the protons to generate an organic hydride, a cathode chamber equipping the cathode electrode, and a membrane that separates the anode chamber and the cathode chamber and moves the protons along with the entrained water from the anode chamber side to the cathode chamber side; and a water removal device that removes the entrained water from the catholyte fed from the cathode chamber and that contains at least the organic hydride and the entrained water.The water removal device has a container that stores the catholyte fed from the cathode chamber, a drain pipe that is connected to the container and discharges the entrained water, a detector that detects that a predetermined amount of entrained water has accumulated in the container, and a switch that is provided in the drain pipe, can switch between a regulating state in which the drainage of the drain pipe is regulated and a running state in which the drainage is executed, and switches from the regulating state to the running state based on a detector detection result.

[0009] Another aspect of the present invention is a water removal device. This device includes: a container that holds a catholyte fed from a cathode chamber of an electrolyzer and containing at least one organic hydride and entrained water, the electrolyzer having an anode electrode that oxidizes water in an anolyte to generate protons, an anode chamber that equips the electrode Petition 870240056494, dated 04 / 07 / 2024, p. 8 / 41 4 / 29 of an anode, a cathode electrode that hydrogenates a substance to be hydrogenated in the catholyte with protons to generate the organic hydride, the cathode chamber that equips the cathode electrode, and a membrane that separates the anode chamber and the cathode chamber and moves the protons along with the entrained water from the anode chamber side to the cathode chamber side; a drain tube that is connected to the container and discharges the entrained water; a detector that detects that a predetermined amount of entrained water has accumulated in the container; and a switch that is provided in the drain tube, can switch between a regulating state in which the drainage of the drain tube is regulated and a running state in which the drainage is performed, and switches from the regulating state to the running state based on a detection result from the detector.

[0010] Another aspect of the present invention is a method for removing water. This method includes: storing, in a container, a catholyte fed from a cathode chamber of an electrolyzer and containing at least one organic hydride and entrained water, the electrolyzer having an anode electrode that oxidizes water in an anolyte to generate protons, an anode chamber equipping the anode electrode, a cathode electrode that hydrogenates a substance to be hydrogenated in the cathode with the protons to generate the organic hydride, the cathode chamber equipping the cathode electrode, and a membrane that separates the anode chamber and the cathode chamber and moves the protons along with the entrained water from the anode chamber side to the cathode chamber side; and when it is detected that a predetermined amount of entrained water has accumulated in the container, discharging the entrained water from the container.

[0011] Any combinations of the above components and conversion of the expressions in the present description between methods, devices, systems, and the like are also effective as aspects Petition 870240056494, dated 04 / 07 / 2024, page 9 / 41 5 / 29 of the present description. ADVANTAGEOUS EFFECTS OF THE INVENTION

[0012] According to the present invention, it is possible to suppress an overflow of an organic hydride or a substance to be hydrogenated while suppressing an increase in the size of an organic hydride production device. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is a schematic view of an organic hydride production device according to one embodiment. Figure 2 is a schematic view of a part of an organic hydride production device according to a modification. DESCRIPTION OF MODALITIES

[0014] Hereafter, the present invention will be described based on preferred embodiments with reference to the drawings. The embodiments are illustrative rather than limiting of the invention, and all features described in the embodiments and their combinations are not necessarily essential to the invention. The same or equivalent components, members, and processes illustrated in the drawings are denoted by the same reference numbers, and redundant description will be omitted as appropriate. Furthermore, the scale and shape of each part illustrated in each drawing are defined for convenience to facilitate description and should not be interpreted in a limiting manner unless otherwise specified. Moreover, when the terms first, second, and the like are used in this specification or claims, the terms do not represent any order or importance but are used to distinguish one configuration from another configuration.Furthermore, in each drawing, some of the body parts that are not important for describing the sports are omitted. Petition 870240056494, dated 04 / 07 / 2024, page 10 / 41 6 / 29

[0015] Figure 1 is a schematic view of an organic hydride production device 1 according to one embodiment. The organic hydride production device 1 includes an electrolyzer 2, a power supply 4, a first circulation mechanism 6, a second circulation mechanism 8, a controller 10, and a water removal device 12.

[0016] Electrolyzer 2 is an electrolytic cell that generates an organic hydride β by hydrogenation of a substance to be hydrogenated α by an electrochemical reduction reaction. Electrolyzer 2 has an anode electrode 14, an anode chamber 16, a cathode electrode 18, a cathode chamber 20, and a membrane 22.

[0017] The anode electrode 14 is an electrode (anode) that oxidizes water in an anolyte La to generate protons (H+). The anode electrode 14 is arranged so as to be in contact with a major surface of the membrane 22. The anode electrode 14 has, for example, a metal such as iridium (Ir), ruthenium (Ru), or platinum (Pt), or one of their metal oxides as an anode catalyst. In the anode electrode 14, as an example, the anode catalyst is sparsely supported or coated on a base material that has electron conductivity. The base material includes a material containing, for example, a metal such as titanium (Ti) or stainless steel (SUS) as a major component. Examples of the base material form include a woven fabric sheet or a non-woven fabric sheet, a mesh, a porous sintered body, a foam-molded body (foam), and an expanded metal.

[0018] The thickness of the anode electrode 14, which includes the anode catalyst and the base material, is not specifically limited, but is, for example, 0.05 to 1 mm. By adjusting the thickness of the anode electrode 14 to 0.05 mm or more, the amount of catalyst required Petition 870240056494, dated 04 / 07 / 2024, page 11 / 41 7 / 29 for an electrolytic reaction can be more reliably obtained. Furthermore, by adjusting the thickness of the anode electrode 14 to 1 mm or less, it is possible to suppress an excessive decrease in the diffusivity of the La anolyte.

[0019] Note that the anode catalyst can be coated onto the base material to form a catalyst layer. In this case, the thickness of the catalyst layer is not specifically limited, but is, for example, 0.1 to 50 μm. The anode electrode 14 can have a layer structure that is obtained directly by coating a main surface of the membrane 22 with the anode catalyst. In this case, the thickness of the layer included on the anode electrode 14 is not specifically limited, but is, for example, 0.1 to 50 pm. By adjusting the layer thickness to 0.1 pm or more, the amount of catalyst required for the electrolytic reaction can be more reliably obtained. Furthermore, by adjusting the layer thickness to 50 pm or less, it is possible to suppress an excessive decrease in the diffusivity of the anolyte La.

[0020] Anode electrode 14 is fitted in the anode chamber 16. A space excluding the anode electrode 14 in the anode chamber 16 forms a flow path for the anolyte La and oxygen generated by an electrode reaction.

[0021] The cathode electrode 18 is an electrode (cathode) that hydrogenates the substance to be hydrogenated α in a catholyte Lc with protons to generate the organic hydride β. The cathode electrode 18 is arranged so as to be in contact with the other principal surface (principal surface opposite to the anode electrode 14) of the membrane 22. The cathode electrode 18 has a catalyst layer 18a and a diffusion layer 18b.

[0022] Catalyst layer 18a is arranged so as to be in contact with membrane 22. Catalyst layer 18a contains, Petition 870240056494, dated 04 / 07 / 2024, page 12 / 41 8 / 29 For example, platinum or ruthenium as a cathode catalyst. It is preferable that the catalyst layer 18a also have a catalyst support that supports the cathode catalyst. The catalyst support includes an electron-conducting material such as porous carbon, a porous metal, or a porous metal oxide. The thickness of the catalyst layer 18a is not specifically limited, but is, for example, 20 to 50 μm. By adjusting the thickness of the catalyst layer 18a to 20 pm or more, the amount of catalyst required for the electrolytic reaction can be more reliably obtained. Furthermore, by adjusting the thickness of the catalyst layer 18a to 50 pm or less, it is possible to suppress an excessive decrease in the diffusivity of the substance to be hydrogenated α.

[0023] The diffusion layer 18b is arranged to be in contact with a surface of the catalyst layer 18a on an opposite side of the membrane 22. The diffusion layer 18b is a layer that uniformly diffuses the liquid substance to be hydrogenated α supplied from the outside to the catalyst layer 18a. The organic hydride β generated in the catalyst layer 18a is discharged from the catalyst layer 18a through the diffusion layer 18b.

[0024] The diffusion layer 18b is formed from a conductive material such as carbon or a metal. Additionally, the diffusion layer 18b is a porous body such as a sintered body of fibers or particles or a molded foam body. Specific examples of the material forming the diffusion layer 18b include a carbon woven fabric (carbon cloth), a non-woven carbon fabric, and carbon paper. The thickness of the diffusion layer 18b is not specifically limited, but is, for example, 200 to 700 pm. By adjusting the thickness of the diffusion layer 18b to 200 pm or more, the diffusivity of the substance to be hydrogenated α can be more reliably improved. Furthermore, by adjusting the thickness of the Petition 870240056494, dated 04 / 07 / 2024, page 13 / 41 With a diffusion layer of 9 / 29 18b at 700 μm or less, it is possible to suppress the electrical resistance from becoming excessive.

[0025] The cathode electrode 18 is fitted in the cathode chamber 20. A space excluding the cathode electrode 18 in the cathode chamber 20 forms a flow path for the substance to be hydrogenated α and the organic hydride β generated by the electrode reaction.

[0026] The anode chamber 16 and the cathode chamber 20 are separated by membrane 22. Membrane 22 is located between the anode electrode 14 and the cathode electrode 18. Membrane 22, as an example, is formed from a solid polymer electrolyte membrane that has proton conductivity. The solid polymer electrolyte membrane is not specifically limited as long as it is a proton-conductive material, and examples include a fluorine-based ion exchange membrane that has a sulfonic acid group such as Nafion (registered trademark).

[0027] Membrane 22 moves protons with water (H2O) from the anode chamber side 16 to the cathode chamber side 20. Hereafter, the water moving along with protons is referred to as entrained water W. The thickness of membrane 22 is not specifically limited, but is, for example, 5 to 300 pm. By adjusting the thickness of membrane 22 to 5 pm or more, the desired resistance of membrane 22 can be more reliably obtained. Furthermore, by adjusting the thickness of membrane 22 to 300 pm or less, it is possible to suppress the ion migration resistance from becoming excessive.

[0028] A reaction that occurs when toluene (TL) is used as an example of the α-hydrogenated substance in electrolyzer 2 is as follows. The β-organic hydride obtained in a case where toluene is used as the α-hydrogenated substance is methylcyclohexane (MCH). Electrode reaction at the anode electrode: 2H2O ^ O2 + 4H+ Petition 870240056494, dated 04 / 07 / 2024, page 14 / 41 10 / 29 + 4e Electrode reaction at the cathode electrode: TL + 6H++ 6e-^ MCH

[0029] That is, at the anode electrode 14, water is electrolyzed to generate oxygen gas, protons, and electrons. The protons move through the membrane 22 towards the cathode electrode 18. The electrons flow to a positive electrode of the power supply 4. The oxygen gas is discharged to the outside through the anode chamber 16. At the cathode electrode 18, methylcyclohexane is generated by the reaction of toluene, the electrons supplied from a negative electrode of the power supply 4, and the protons having reached through the membrane 22. Therefore, according to the organic hydride production device 1, the electrolysis of water and the hydrogenation reaction of the substance to be hydrogenated α can be performed in one step.

[0030] Power supply 4 is a DC power supply that supplies power to electrolyzer 2. By supplying power from power supply 4, a predetermined electrolytic voltage is applied between the anode electrode 14 and the cathode electrode 18 of electrolyzer 2. Power supply 4 receives power supplied from a power supplier 24 and supplies power to electrolyzer 2. The power supplier 24, as an example, may include a renewable energy generation device such as a wind power generation device 26, a solar power generation device 28, or similar.Note that energy provider 24 may include a power generation device that utilizes renewable energy other than wind and solar power, such as a geothermal power generation device, a wave power generation device, a temperature difference power generation device, or a biomass power generation device. Note that energy provider 24 is not limited to the power generation device. Petition 870240056494, dated 04 / 07 / 2024, page 15 / 41 11 / 29 which generates energy using renewable energy.

[0031] The first circulation mechanism 6 is a mechanism for allowing the anolyte La containing water to flow to an anode chamber 16. The first circulation mechanism 6 has an anolyte tank 30, an anolyte circulation path 32, an anolyte circulation device 34, and an anolyte gas-liquid separator 36. The anolyte tank 30 stores the anolyte La to be supplied to the anode chamber 16. Examples of the anolyte La include a solution that has a predetermined ion conductivity, such as an aqueous solution of sulfuric acid, an aqueous solution of nitric acid, or an aqueous solution of hydrochloric acid, pure water, and ion exchange water.

[0032] The anolyte tank 30 and the anode chamber 16 are connected in the anolyte circulation path 32. The anolyte circulation path 32 has an anode inlet tube 32a that supplies anolyte La in the anolyte tank 30 to the anode chamber 16, and an anode outlet tube 32b that returns the anolyte La fed from the anode chamber 16 to the anolyte tank 30.

[0033] As an example, the anolyte circulation device 34 is provided in the middle of the anode inlet tube 32a. By actuating the anolyte circulation device 34, the anolyte La flows into the anolyte circulation path 32. As a result, the anolyte La circulates between the anolyte tank 30 and the anode chamber 16. As with the anolyte circulation device 34, for example, various pumps such as a gear pump and a cylinder pump, a naturally descending flow type device or similar can be used.

[0034] The anolyte gas-liquid separator 36 is provided in the middle of the anode outlet tube 32b. At the anode electrode 14, oxygen is generated by an electrode reaction. Therefore, the anolyte La recovered from the anode chamber 16 contains gaseous oxygen and dissolved oxygen, in addition to unreacted water. The gaseous oxygen is separated from the anolyte La. Petition 870240056494, dated 04 / 07 / 2024, page 16 / 41 12 / 29 in the anolyte gas-liquid separator 36 and removed from the system. The La anolyte from which the oxygen was separated is recovered in anolyte tank 30.

[0035] In the first circulation mechanism 6, as an example, the anode inlet tube 32a is connected to a vertically lower portion of the anode chamber 16, and the anode outlet tube 32b is connected to a vertically upper portion of the anode chamber 16. The anolyte La in the anolyte tank 30 is pumped upwards by the anolyte circulation device 34 and enters the anode chamber 16. The anolyte La in the anode chamber 16 is pushed outwards to the anode outlet tube 32b by the flow of anolyte La entering the anode chamber 16, and flows downwards to the anolyte gas-liquid separator 36 by gravity. Anolyte La is placed under atmospheric pressure in anolyte gas-liquid separator 36. Anolyte La in anolyte gas-liquid separator 36 flows into anolyte tank 30 in a natural downward flow mode as the liquid level in anolyte tank 30 decreases.Note that the anode inlet tube 32a may be connected to the vertically upper portion of the anode chamber 16. In this case, the anolyte La enters the anode chamber 16 from the vertically upper portion. That is, the anolyte La may be supplied to the anode chamber 16 not as an upward flow but as a downward flow.

[0036] The second circulation mechanism 8 is a mechanism to allow the catholyte Lc containing the substance to be hydrogenated α to flow into the cathode chamber 20. The second circulation mechanism 8 has a catholyte tank 38, a catholyte circulation path 40, a catholyte circulation device 42, and a catholyte gas-liquid separator 44 (gas-liquid separation tower). The catholyte tank 38 stores the catholyte Lc supplied to the cathode chamber 20. The catholyte Lc stored in the catholyte tank Petition 870240056494, dated 04 / 07 / 2024, p. 17 / 41 13 / 29 contains at least the substance to be hydrogenated α before the operation of the organic hydride production device 1 is initiated. The substance to be hydrogenated α is a compound that is hydrogenated by an electrochemical reduction reaction in the electrolyzer 2 to become the organic hydride β, in other words, a dehydrogenated product of the organic hydride β. The substance to be hydrogenated α and the organic hydride β are preferably a liquid at 20°C and 1 atm.

[0037] The substance to be hydrogenated α and the organic hydride β are organic compounds capable of reversibly adding / removing hydrogen, causing a hydrogenation / dehydrogenation reaction. The substance to be hydrogenated α and the organic hydride β have specific gravities lower than that of water. Furthermore, the substance to be hydrogenated α and the organic hydride β have low compatibility with water, and form an IF interface with the entrained water W.

[0038] In the case where the detector 52 described below includes a sensor that detects the IF interface based on a difference in buoyancy (specific gravity) applied to a float, the substance to be hydrogenated α and the organic hydride β having a difference in specific gravity with respect to the entrained water W to such a degree that the sensor can perform detection are selected. In this case, examples of the substance to be hydrogenated α include an aromatic compound in which the specific gravity of the liquid is 0.6 to 0.9 g / cm3.

[0039] Furthermore, in a case where detector 52 includes a sensor that detects the IF interface based on a difference in capacitance (relative permittivity), the substance to be hydrogenated α and the organic hydride β having a difference in relative permittivity with respect to entrained water W to such a degree that the sensor can perform detection are selected. In this case, examples of the substance to be hydrogenated α include an aromatic compound in which the Petition 870240056494, dated 04 / 07 / 2024, p. 18 / 41 14 / 29 relative permissiveness is 1 to 50.

[0040] Specific examples of the substance to be α-hydrogenated include alkylbenzenes such as benzene and toluene, and nitrogen-containing aromatic compounds such as pyridine and pyrazine.

[0041] The catholyte tank 38 and the cathode chamber 20 are connected by the catholyte circulation path 40. The catholyte circulation path 40 has a cathode inlet tube 40a that supplies catholyte Lc in the catholyte tank 38 to the cathode chamber 20, and a cathode outlet tube 40b that returns the catholyte Lc fed from the cathode chamber 20 to the catholyte tank 38. In the catholyte Lc flowing through the catholyte circulation path 40, as the operating time of the organic hydride production device 1 elapses, in other words, as the number of circulations increases, the concentration of a substance to be hydrogenated α decreases, and the concentration of the organic hydride β increases.

[0042] As an example, the catholyte circulation device 42 is provided in the middle of the cathode inlet tube 40a. By actuating the catholyte circulation device 42, the catholyte Lc flows in the catholyte circulation path 40. As a result, the catholyte Lc circulates between the catholyte tank 38 and the cathode chamber 20. As with the catholyte circulation device 42, for example, various pumps such as a gear pump and a cylinder pump, a natural downflow type device, or similar devices can be used.

[0043] The catholyte gas-liquid separator 44 is provided in the middle of the cathode outlet tube 40b. At the cathode electrode 18, hydrogen is generated by a secondary reaction. As the concentration of the substance to be hydrogenated α supplied to the cathode electrode 18 decreases, the secondary reaction is more likely to occur. In other words, the ratio of the secondary reaction to the entire electrode reaction at the cathode electrode 18 increases. Therefore, the catholyte Petition 870240056494, dated 04 / 07 / 2024, page 19 / 41 15 / 29 The Lc recovered from cathode chamber 20 contains gaseous hydrogen and dissolved hydrogen, in addition to the unreacted hydrogenated substance α and the generated organic hydride β. The gaseous hydrogen is separated from the catholyte Lc in the catholyte gas-liquid separator 44 and removed from the system. The catholyte Lc from which the hydrogen was separated is recovered in the catholyte tank 38.

[0044] In the second circulation mechanism 8, as an example, the cathode inlet tube 40a is connected to the vertically lower portion of the cathode chamber 20, and the cathode outlet tube 40b is connected to the vertically upper portion of the cathode chamber 20. The catholyte Lc in the catholyte tank 38 is pumped upwards by the catholyte circulation device 42 and enters the cathode chamber 20. The catholyte Lc in the cathode chamber 20 is pushed outwards to the cathode outlet tube 40b by the flow of catholyte Lc entering the cathode chamber 20, and flows downwards to the catholyte gas-liquid separator 44 by gravity. The catholyte Lc is placed under atmospheric pressure in the catholyte gas-liquid separator 44. The catholyte Lc in the catholyte gas-liquid separator 44 flows to the catholyte tank 38 in a natural downward flow mode as the liquid level in the catholyte tank 38 decreases.Note that the inlet tube of cathode 40a may be connected to the vertically upper portion of cathode chamber 20. In this case, the catholyte Lc enters cathode chamber 20 from the vertically upper portion. That is, the catholyte Lc may be supplied to cathode chamber 20 not as an upward flow but as a downward flow.

[0045] Controller 10 controls the operation of the organic hydride production device 1. Controller 10 is implemented by an element or circuit such as a CPU or computer memory as a hardware configuration, and is implemented by a computer program or similar as a configuration of Petition 870240056494, dated 04 / 07 / 2024, p. 20 / 41 16 / 29 software, but is illustrated as a functional block realized through the cooperation between these in Figure 1. It should be understood by those skilled in the art that functional blocks can be implemented in various forms by a combination of hardware and software.

[0046] A signal indicating a voltage of electrolyzer 2, a signal indicating a potential of anode electrode 14, or a signal indicating a potential of cathode electrode 18 is entered into the controller 10 of a sensor 46 provided in electrolyzer 2. The sensor 46 can detect the potential of each electrode and the voltage of electrolyzer 2 by a known method. The sensor 46, as an example, includes a known voltmeter or similar. Note that Figure 1 schematically illustrates the sensor 46. The sensor 46 may include a current detector that detects a current flowing between the anode electrode 14 and the cathode electrode 18. The controller 10 controls the power supply 4, the anolyte circulation device 34, the catholyte circulation device 42, and the like based on a detection result from the sensor 46.

[0047] The water removal device 12 is a device that removes entrained water W from the catholyte Lc. As described above, the entrained water W moves from the anode chamber side 16 to the cathode chamber 20. Therefore, the catholyte Lc fed from the cathode chamber 20 contains not only the substance to be hydrogenated α and the organic hydride β but also the entrained water W. The water removal device 12 removes the entrained water W from the catholyte Lc.

[0048] The water removal device 12 has a container 48, a drain tube 50, a detector 52 and a switch 54. Container 48 stores the catholyte Lc fed from the cathode chamber 20. Container 48 according to the present embodiment is provided in the middle of the cathode outlet tube 40b. Container 48 also serves Petition 870240056494, dated 04 / 07 / 2024, p. 21 / 41 17 / 29 as the catholyte gas-liquid separator 44. Therefore, a discharge port 48a for discharging hydrogen into the catholyte Lc is provided in a vertically upper portion of the container 48.

[0049] The catholyte Lc stored in container 48 contains the substance to be hydrogenated α, the organic hydride β, and the entrained water W. The substance to be hydrogenated α and the organic hydride β have specific gravities lower than that of the entrained water W and are incompatible with the entrained water W. Therefore, the catholyte Lc is divided into a lower layer (water layer) containing the entrained water W and an upper layer (oil layer) containing the substance to be hydrogenated α and the organic hydride β in container 48.

[0050] Drain pipe 50 is connected to container 48 to discharge entrained water W accumulated in container 48. One end of cathode outlet pipe 40b is connected to container 48. The other end of cathode outlet pipe 40b is connected to catholyte tank 38. One end of drain pipe 50 is connected to container 48. A connection position C1 of drain pipe 50 with respect to container 48 (catholyte gas-liquid separator 44) is arranged below a connection position C2 of cathode outlet pipe 40b with respect to container 48 in a vertical direction.

[0051] Detector 52 detects that a predetermined quantity of entrained water W has accumulated in container 48. The predetermined quantity can be appropriately defined based on empirical knowledge, experiment, or the like. Detector 52 according to the present embodiment includes an interface sensor that detects an interface IF between a layer containing the substance to be hydrogenated α and the organic hydride β in the catholyte Lc and a layer containing the entrained water W. In detector 52, an interface sensor Petition 870240056494, dated 04 / 07 / 2024, p. 22 / 41 18 / 29 known as a floating-type interface sensor, a capacitance-type interface sensor, or a conductivity-type interface sensor may be used. Furthermore, a person skilled in the art may appropriately select a combination of the types of substance to be hydrogenated α and organic hydride β and the type of detection of the interface sensor.

[0052] A detection position of the IF interface by detector 52 is defined below the connection position C2 of the cathode outlet tube 40b in the vertical direction. The detection position of the IF interface is defined above the connection position C1 of the drain tube 50 in the vertical direction. Detector 52 may be disposed inside container 48. Note that when container 48 does not inhibit detection of the IF interface (for example, when container 48 is made of a material capable of detecting capacitance inside the container from outside the container), detector 52 may be disposed outside container 48. Detector 52 may detect the accumulation of a predetermined amount of entrained water W in container 48 by detecting the IF interface. When detector 52 detects the IF interface, detector 52 transmits a control signal to switch 54.

[0053] The switch 54 is provided in the drain pipe 50. The switch 54 includes a mechanism capable of switching between a regulating state in which the drainage of the drain pipe 50 is regulated and a running state in which the drainage of the drain pipe 50 is performed. The switch 54 of the present embodiment includes a valve. As the valve included in the switch 54, for example, a known electromagnetic valve or similar may be used. Preferably, the valve included in the switch 54 is a normally closed type electromagnetic valve that is closed when not energized and open when energized. In a state where the switch 54 is closed, the discharge of water Petition 870240056494, dated 04 / 07 / 2024, p. 23 / 41 The flow of water carried away from drain pipe 50 (19 / 29) is regulated. When switch 54 is open, the discharge of water carried away from drain pipe 50 (W) is permitted (drainage of water carried away is performed). Switch 54 opens the valve based on the detection result of detector 52. That is, when the water level (IF interface) of the water carried away rises to a detection position of detector 52, switch 54 receives the control signal from detector 52, is energized, and opens the valve, and the water carried away is automatically discharged into container 48. The amount of water carried away accumulated in container 48 until switch 54 opens the valve is determined according to the size of container 48 or the detection position of the IF interface.

[0054] When a predetermined time elapses after the valve opens, the switch 54 closes the valve and regulates the drainage. For example, a valve opening time of the switch 54 is set so that the valve closes before the IF interface reaches the C1 connection position of the drain pipe 50. The valve opening time can be set in advance based on the amount of entrained water W accumulated in the container 48 when the switch 54 opens the valve, the drainage rate of the drain pipe 50, and similar factors. As a result, it is possible to suppress the hydrogenated substance α and the organic hydride β from being discharged from the drain pipe 50. The closing of the switch 54 valve (switching to the regulation state) can be performed by the control of the detector 52, or it can be performed by a timer or similar device that stops the energization of the switch 54 after a predetermined time has elapsed.

[0055] Note that the opening and closing of the switch valve can be controlled as follows. That is, detector 52 has two interface sensors, and one interface sensor is located below the other interface sensor. An IF interface detection position on the upper interface sensor is set below the connection position. Petition 870240056494, dated 04 / 07 / 2024, page 24 / 41 20 / 29 C2, and a detection position of the IF interface on the lower interface sensor is set above the connection position C1. When entrained water W gradually accumulates and the IF interface rises, the IF interface is detected by the upper interface sensor. As a result, switch 54 is opened, entrained water W is discharged, and the IF interface falls. When the IF interface is detected by the lower interface sensor, switch 54 is closed. This control can also suppress the hydrogenated substance α and the organic hydride β from being discharged from the drain pipe 50.

[0056] In the description above, the catholyte Lc circulates between the catholyte tank 38 and the cathode chamber 20. However, the present invention is not limited to this, and the catholyte Lc fed from the cathode chamber 20 may not be returned to the catholyte tank 38. In this case, the catholyte Lc fed from the cathode chamber 20 may be stored in an organic hydride tank (not shown in the drawings) after passing through the catholyte gas-liquid separator 44.

[0057] In the description above, the catholyte Lc fed to the cathode chamber 20 contains the unreacted substance to be hydrogenated α. However, the present invention is not limited to this, and there may exist a case where all the substance to be hydrogenated α supplied to the cathode chamber 20 is converted to the organic hydride β, and the substance to be hydrogenated α is not contained in the catholyte Lc fed to the cathode chamber 20.

[0058] Although only one electrolyzer 2 is illustrated in the Figure 1. The organic hydride production device 1 may have a plurality of electrolyzers 2. In this case, the respective electrolyzers 2 are arranged in the same direction so that the anode chamber 16 and the cathode chamber 20 are arranged in the same direction, and are stacked with an electrically conductive plate interposed between the adjacent electrolyzers 2. As a result, the Petition 870240056494, dated 04 / 07 / 2024, p. 25 / 41 21 / 29 Electrolyzers 2 are electrically connected in series. The electrical conduction plate includes a conductive material such as a metal. Note that the electrolyzers 2 may be connected in parallel, or it may be a combination of series and parallel connection. Furthermore, the switch 54 may include a pump. In this case, the switch 54 receives the control signal from the detector 52, is activated, and performs the drainage. Additionally, the switch 54 stops activating and regulates the drainage when a predetermined time has elapsed since the drainage execution.

[0059] As described above, the organic hydride production device 1 according to the present embodiment includes the electrolyzer 2 and the water removal device 12. The electrolyzer 2 has an anode electrode 14 that oxidizes water in the anolyte La to generate protons, the anode chamber 16 that equips the anode electrode 14, the cathode electrode 18 that hydrogenates the substance to be hydrogenated α in the catholyte Lc with the protons to generate the organic hydride β, the cathode chamber 20 that equips the cathode electrode 18, and the membrane 22 that separates the anode chamber 16 and the cathode chamber 20 and moves the protons together with the entrained water W from the side of the anode chamber 16 to the side of the cathode chamber 20.The water removal device 12 has container 48 that stores the catholyte Lc fed from the cathode chamber 20, drain tube 50 that is connected to container 48 and discharges entrained water W, detector 52 that detects that the predetermined quantity of entrained water W has accumulated in container 48, and switch 54 that is provided in drain tube 50, is capable of switching between a regulating state in which the drainage of drain tube 50 is regulated and a running state in which the drainage is performed, and switches from the regulating state to the running state based on a detection result from detector 52, and removes the entrained water W from the catholyte Lc which contains at least the. Petition 870240056494, dated 04 / 07 / 2024, p. 26 / 41 22 / 29 organic hydride β and entrained water W fed from cathode chamber 20.

[0060] As described above, the organic hydride production device 1 according to the present embodiment includes the water removal device 12 which detects that a predetermined quantity of entrained water W has accumulated in the container 48 and automatically discharges the entrained water W. When the detector 52 detects that the predetermined quantity of entrained water W has accumulated in the container 48, the entrained water W is discharged from the container 48. As a result, it is possible to suppress the organic hydride β or the substance to be hydrogenated α from overflowing from a container (downstream container), such as the catholyte gas-liquid separator 44, which is located downstream of the cathode chamber 20 and at least temporarily stores the catholyte Lc, due to an increase in entrained water W.

[0061] Furthermore, in a case where the overflow of organic hydride β and similar substances is suppressed by storing the entrained water W in the enlarged downstream container, it is necessary to increase the volume of the downstream container in order to store the entire amount of entrained water W generated by the operation of the organic hydride production device 1. On the other hand, since the water removal device 12 performs drainage each time the amount of entrained water W reaches the predetermined amount, the required size for the container 48 included in the water removal device 12 can be reduced. Furthermore, it is possible to avoid an increase in the size of the downstream container. Therefore, it is possible to suppress an increase in the size of the organic hydride production device 1.

[0062] Furthermore, in a case where entrained water W is stored in the downstream container, a removal treatment Petition 870240056494, dated 04 / 07 / 2024, page 27 / 41 23 / 29 of the entrained water W is required each time the operation of the organic hydride production device 1 is completed. On the other hand, since the water removal device 12 automatically performs drainage, such treatment is unnecessary. Therefore, the organic hydride β production process can be simplified and efficiency can be improved.

[0063] The organic hydride production device 1 of the present embodiment includes the catholyte tank 38 which stores the catholyte Lc supplied to the cathode chamber 20, the cathode inlet tube 40a which is connected to the catholyte tank 38 and to the cathode chamber 20 and supplies the catholyte Lc in the catholyte tank 38 to the cathode chamber 20, and the cathode outlet tube 40b which is connected to the cathode chamber 20 and to the catholyte tank 38 and returns the catholyte Lc fed from the cathode chamber 20 to the catholyte tank 38.

[0064] As described above, when the catholyte Lc repeatedly circulates between the catholyte tank 38 and the cathode chamber 20, the entrained water W can be fed to the cathode chamber 20 through the catholyte circulation path 40. When the entrained water W is fed to the cathode chamber 20, the amount of entrained water W that reaches the reaction field of the cathode electrode 18 increases, and the reduction reaction of the substance to be hydrogenated α can be inhibited. On the other hand, since the organic hydride production device 1 of the present embodiment includes the water removal device 12, it is possible to suppress the inhibition of the reduction reaction of the substance to be hydrogenated α by the entrained water W. Therefore, the organic hydride production efficiency can be effectively improved.

[0065] As a method for suppressing entrained water entry In the cathode chamber 20, through the catholyte circulation path 40, it is conceivable to visually verify the water level of the entrained water. Petition 870240056494, dated 04 / 07 / 2024, page 28 / 41 24 / 29 In the catholyte tank 38, manually adjust the connection position of the cathode inlet tube 40a relative to the catholyte tank 38, according to the water level of the entrained water W. However, this method is very laborious. Furthermore, drainage treatment is necessary after the operation of the organic hydride production device 1 is completed. On the other hand, since the water removal device 12 automatically performs drainage, the organic hydride β production process can be simplified and efficiency improved.

[0066] The organic hydride production device 1 also includes the catholyte circulation device 42 provided in the middle of the cathode inlet tube 40a. The water removal device 12 container 48 is provided in the middle of the cathode outlet tube 40b. Compared with the cathode inlet tube 40a provided with the catholyte circulation device 42, in the cathode outlet tube 40b not provided with the catholyte circulation device 42, the catholyte flow Lc tends to be smooth. Therefore, according to the arrangement described above, the water removal device 12 can be installed in a region where the catholyte flow Lc is likely to be smoother, and the entrained water W can be more stably accumulated at the bottom of the container 48. Therefore, the removal efficiency of the entrained water W can be improved.

[0067] The container 48 of the present embodiment also serves as the gas-liquid separator of the catholyte 44. As a result, it is possible to eliminate an increase in cost associated with the installation of the water removal device 12 compared to the case where the container 48 is separately provided. Furthermore, it is possible to eliminate an increase in size of the organic hydride production device 1.

[0068] Detector 52 according to the present embodiment includes Petition 870240056494, dated 04 / 07 / 2024, page 29 / 41 25 / 29 an interface sensor that detects an IF interface between the layer containing at least the organic hydride β in the catholyte Lc and the layer containing the entrained water W (in a case where the catholyte Lc contains the substance to be hydrogenated α, an IF interface between the layer of the substance to be hydrogenated α and the organic hydride β and the layer of entrained water W). As a result, it is possible to easily detect the entrained water W accumulated in the container 48. Therefore, a configuration of the water removal device 12 can be simplified.

[0069] The embodiments of the present invention have been described in detail above. The embodiments described above are merely specific examples of carrying out the present invention. The content of the embodiments does not limit the technical scope of the present invention, and many design changes such as changes, additions, and deletions of components may be made without departing from the spirit of the invention defined in the claims. A new embodiment for which the design change is made has the combined effect of each of the embodiments and modifications. In the embodiment described above, the contents that may be subject to such design changes are emphasized with notations such as in the present embodiment and in the present embodiment, but design changes are permitted even in the contents without such notations. Any combination of the components described above is also effective as an aspect of the present invention. MODIFICATION

[0070] The present modification has a configuration common to the embodiment, except for the arrangement of the water removal device 12. Hereafter, the present modification will be described focusing on a configuration different from that of the embodiment, and the description of the common configuration will be omitted. Figure 2 is a view Petition 870240056494, dated 04 / 07 / 2024, pages 30 / 41 26 / 29 Schematic of a part of an organic hydride production device 1 according to the modification. An electrolyzer 2, a power supply 4, a first circulation mechanism 6, a controller 10 and a power supplier 24 in the present modification include configurations similar to those of the embodiment.

[0071] A second circulation mechanism 8 has a catholyte tank 38, a catholyte circulation path 40, a catholyte circulation device 42, and a catholyte gas-liquid separator 44. In the embodiment, the water removal device 12 is provided in the catholyte gas-liquid separator 44, but in the present modification, the water removal device 12 is provided in the catholyte tank 38. Except for this point, each configuration of the second circulation mechanism 8 is similar to that of the embodiment.

[0072] The water removal device 12 has a container 48, a drain tube 50, a detector 52 and a switch 54. The container 48 of the present modification also serves as the catholyte tank 38. The catholyte Lc stored in the container 48 contains the substance to be hydrogenated α, the organic hydride β, and the entrained water W. The catholyte Lc is divided into a lower layer containing the entrained water W and an upper layer containing the substance to be hydrogenated α and the organic hydride β in the container 48.

[0073] One end of drain pipe 50 is connected to container 48. One end of cathode inlet pipe 40a is connected to container 48. The other end of cathode inlet pipe 40a is connected to cathode chamber 20. A connection point C1 of drain pipe 50 with respect to container 48 (catholyte tank 38) is located below a connection point C3 of cathode inlet pipe 40a with respect to container 48 in a vertical direction. Naturally, connection point C1 is located below a connection point of cathode outlet pipe 40b with Petition 870240056494, dated 04 / 07 / 2024, pages 31 / 41 27 / 29 in relation to container 48 in the vertical direction.

[0074] Detector 52 detects that a predetermined quantity of entrained water W has accumulated in container 48. Detector 52, as an example, includes an interface sensor. An interface detection position IF by detector 52 is defined below the connection position C3 of the cathode inlet tube 40a in the vertical direction. The interface detection position IF is defined above the connection position C1 of the drain tube 50 in the vertical direction.

[0075] The switch 54 is provided in the drain pipe 50 and is capable of switching between a regulating state in which the drainage of the drain pipe 50 is regulated and a running state in which the drainage of the drain pipe 50 is executed. The switch 54 of the present modification includes a valve similarly to the embodiment, and opens the valve based on a detection result from the detector 52. That is, when the water level of the entrained water W rises to the detection position of the detector 52, the switch 54 receives a control signal from the detector 52, is energized, and opens the valve, and the entrained water W is automatically discharged from the container 48. In addition, the switch 54 as an example closes the valve when a predetermined time elapses from the opening of the valve. Similar to the embodiment, an opening and closing control of the switch 54 using two interface sensors can also be adopted. Additionally, switch 54 may include a pump.

[0076] The organic hydride production device 1 according to the present modification can also achieve effects similar to those of the organic hydride production device 1 according to the embodiment. Note that the container 48 included in the catholyte tank 38 can be provided with the discharge port 48a, and the container 48 of the water removal device 12 can also serve as the catholyte tank 38 and the catholyte gas-liquid separator 44. Also in Petition 870240056494, dated 04 / 07 / 2024, pages 32 / 41 28 / 29 first circulation mechanism 6, the anolyte gas-liquid separator 36 and the anolyte tank 30 can be integrated.

[0077] The modalities can also be specified as described below. ITEM 1 A 12-piece water removal device that includes: a container 48 that stores a catholyte Lc fed from a cathode chamber 20 of an electrolyzer 2 and containing at least one organic hydride β and entrained water W, the electrolyzer 2 having an anode electrode 14 that oxidizes water in an anolyte La to generate protons, an anode chamber 16 that equips the anode electrode 14, a cathode electrode 18 that hydrogenates a substance to be hydrogenated α in the catholyte Lc with the protons to generate the organic hydride β, the cathode chamber 20 that equips the cathode electrode 18, and the membrane 22 that separates the anode chamber 16 and the cathode chamber 20 and moves the protons together with the entrained water W from the side of the anode chamber 16 to the side of the cathode chamber 20; a drain pipe 50 that is connected to container 48 and discharges the entrained water W; a detector 52 that detects that a predetermined quantity of entrained water W has accumulated in the container 48; and a switch 54 that is provided in the drain pipe 50, can switch between a regulating state in which the drainage of the drain pipe 50 is regulated and a running state in which the drainage is carried out, and switches from the regulating state to the running state based on a detection result from the detector 52. ITEM 2 A method of water removal that includes: to store, in a container 48, a catholyte Lc fed from a cathode chamber 20 of an electrolyzer 2 and which contains at Petition 870240056494, dated 04 / 07 / 2024, pp. 33 / 41 29 / 29 minus an organic hydride β and entrained water W, the electrolyzer 2 having an anode electrode 14 that oxidizes water in an anolyte La to generate protons, an anode chamber 16 that equips the anode electrode 14, a cathode electrode 18 that hydrogenates a substance to be hydrogenated α in the catholyte Lc with the protons to generate the organic hydride β, the cathode chamber 20 that equips the cathode electrode 18, and the membrane 22 that separates the anode chamber 16 and the cathode chamber 20 and moves the protons together with the entrained water W from the side of the anode chamber 16 to the side of the cathode chamber 20; and when it is detected that a predetermined quantity of entrained water W has accumulated in the container 48, discharge the entrained water W from the container 48. INDUSTRIAL APPLICABILITY

[0078] The present invention can be used in an organic hydride production device, a water removal device, and a water removal method. LIST OF REFERENCE SYMBOLS

[0079] 1 organic hydride production device, 2 electrolyzer, 12 water removal device, 14 anode electrode, 16 anode chamber, 18 cathode electrode, 20 cathode chamber, 22 membrane, 30 anolyte tank, 32 anolyte circulation path, 34 anolyte circulation device, 36 anolyte gas-liquid separator, 38 catholyte tank, 40 catholyte circulation path, 40a cathode inlet tube, 40b cathode outlet tube, 42 catholyte circulation device, 44 catholyte gas-liquid separator, 48 container, 50 drain tube, 52 detector, 54 switch. Petition 870240056494, dated 04 / 07 / 2024, pages 34 / 41

Claims

1 / 3 CLAIMS 1. Organic hydride production device (1) characterized in that it comprises: an electrolyzer (2) having an anode electrode (14) that oxidizes water in an anolyte (La) to generate a proton, an anode chamber (16) equipping the anode electrode (14), a cathode electrode (18) that hydrogenates a substance to be hydrogenated (α) in a catholyte (Lc) with the proton to generate an organic hydride (β), a cathode chamber (20) equipping the cathode electrode (18), and a membrane (22) separating the anode chamber (16) and the cathode chamber (20) and moving the proton together with entrained water (W) from the side of the anode chamber (16) to the side of the cathode chamber (20); and a water removal device (12) structured to remove entrained water (W) from the catholyte (Lc) fed from the cathode chamber (20) and containing at least the organic hydride (β) and entrained water (W),wherein the water removal device (12) has a container (48) that stores the catholyte (Lc) fed from the cathode chamber (20), a drain pipe (50) that is connected to the container (48) and discharges the entrained water (W), a detector (52) that detects that a predetermined quantity of entrained water (W) has accumulated in the container (48), and a switch (54) that is provided in the drain pipe (50), is capable of switching between a regulating state in which the drainage of the drain pipe (50) is regulated and a running state in which the drainage is performed, and switches from the regulating state to the running state based on a detection result from the detector (52), the organic hydride production device (1) Petition 870240056494, dated 04 / 07 / 2024,pg. 35 / 41 2 / 3 comprising: a catholyte tank (38) structured to store the catholyte (Lc) supplied to the cathode chamber (20); an inlet tube (40a) connected to the catholyte tank (38) and to the cathode chamber (20) and structured to supply the catholyte (Lc) in the catholyte tank (38) to the cathode chamber (20); and an outlet tube (40b) connected to the cathode chamber (20) and to the catholyte tank (38) and structured to return the catholyte (Lc) fed from the cathode chamber (20) to the catholyte tank (38); a catholyte circulation device (42) provided in the middle of the inlet tube (40a), wherein the container (48) is provided in the middle of the outlet tube (40b), the container (48) also serves as a gas-liquid separator (44) from the catholyte (Lc), the container (48) includes a discharge port (48a) for discharging hydrogen into the catholyte (Lc) in a vertically upper portion of the container (48),A connection point (C1) of the drain pipe (50) with respect to the container (48) is arranged below a connection point (C2) of the outlet pipe (40b) with respect to the container (48) in a vertical direction, the catholyte (Lc) is placed under atmospheric pressure in the container (48) and flows into the catholyte tank (38) in a natural downward flow mode as the liquid level in the catholyte tank (38) decreases, and the catholyte (Lc) stored in the container (48) is divided into a lower layer containing entrained water (W) and an upper layer containing at least the organic hydride (β) according to a difference in specific gravity between the organic hydride (β) and the entrained water (W). Petition 870240056494, dated 04 / 07 / 2024, page 36 / 41 3 / 3, 2. Organic hydride production device (1), according to claim 1, characterized in that the container (48) also serves as a catholyte tank (38).

3. Organic hydride production device (1), according to claim 1 or 2, characterized in that the detector (52) includes an interface sensor that detects an interface (IF) between the upper layer and the lower layer. Petition 870240056494, dated 04 / 07 / 2024, p. 37 / 41

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