Hydrogen generating device

Abstract

A hydrogen generation device coats a solid hydrogen carrier on a surface 41a of a conveyor belt 41 by means of a powder coating device 12, and discharges a water-containing liquid onto the hydrogen carrier coated on the surface 41a by means of a liquid discharge device. Then, hydrogen generated by a reaction between the hydrogen carrier on the surface 41a and the liquid is collected by a hydrogen collection device. A byproduct generated by a reaction between the hydrogen carrier on the surface 41a and the liquid is collected by a byproduct collection device. A hydrogen carrier regulation amount holding unit (13) regulates the amount of hydrogen carrier supplied from a hydrogen carrier storage tank (11) to a storage unit (121) of a powder coating device (12) so as to hold the hydrogen carrier in the storage unit (121) within a predetermined range. As a result, it is possible to obtain a hydrogen generation device that easily promotes a reaction between a hydrogen carrier and a water-containing liquid.

Description

Technical Field

[0001] The present invention relates to a hydrogen generation device that generates hydrogen by using a hydrogen carrier as a raw material, and the hydrogen carrier has a property of generating hydrogen when an aqueous solution is poured thereon. Background Art

[0002] As a hydrogen generation device, a device that supplies water and a solvent to sodium borohydride and generates hydrogen by hydrolysis of sodium borohydride has been proposed (for example, Patent Document 1). Citation List Patent Document

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-114708 Summary of the Invention Technical Problem

[0004] Here, as a configuration for generating hydrogen by supplying an aqueous solution to a hydrogen carrier such as sodium borohydride, a configuration can be considered in which the hydrogen carrier is coated on a transfer member and the solution is supplied to the hydrogen carrier. In the case of this configuration, if the thickness of the hydrogen carrier on the surface of the transfer member is uneven, the progress of the reaction caused by the solution supply also becomes uneven.

[0005] An object of the present invention is to provide a hydrogen generation device that easily promotes the reaction between a hydrogen carrier and an aqueous solution. Solution to the Problem

[0006] The hydrogen generation device of the present invention includes: a transfer member capable of transferring a solid hydrogen carrier, a supply container for storing the hydrogen carrier for replenishment, a coating device including a storage unit and configured to coat the hydrogen carrier on the transfer member from the storage unit, the storage unit being configured to store the hydrogen carrier supplied from the supply container, a discharge device configured to discharge an aqueous solution onto the hydrogen carrier coated on the transfer member, a hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier and the solution on the transfer member, a by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier and the solution on the transfer member, and a hydrogen carrier control amount holding unit configured to adjust the supply amount of the hydrogen carrier from the supply container to the storage unit so as to keep the hydrogen carrier in the storage unit within a predetermined range.

[0007] In addition, the hydrogen generation device of the present invention includes: a conveying member capable of conveying a solid hydrogen carrier, a supply container storing the hydrogen carrier for replenishment, including an accumulation portion configured to temporarily accumulate the hydrogen carrier supplied from the supply container, a storage portion configured to store the hydrogen carrier, a supply portion configured to supply the hydrogen carrier from the accumulation portion to the storage portion, and a coating device configured to coat the hydrogen carrier on the conveying member from the storage portion, a discharging device configured to discharge an aqueous solution onto the hydrogen carrier coated on the conveying member, a hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier on the conveying member and the solution, a by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier on the conveying member and the solution, a supply container for the storage portion storing the hydrogen carrier to replenish the coating device, and a hydrogen carrier regulation amount holding portion configured to adjust the replenishment amount of the hydrogen carrier from the accumulation portion to the storage portion so as to maintain the hydrogen carrier in the storage portion within a predetermined range. Advantageous Effects of the Invention

[0008] According to the present invention, a hydrogen generation device can be provided that can easily promote the reaction between a hydrogen carrier and an aqueous solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 is a schematic structural cross-sectional view of a hydrogen generation device according to a first embodiment. Figure 2 is a control block diagram of a hydrogen generation device according to a first embodiment. Figure 3 is a schematic structural cross-sectional view showing an enlarged view near a powder coating device in a state where a gate of a hydrogen carrier storage container is closed in a hydrogen generation device according to a first embodiment. Figure 4 is a schematic structural cross-sectional view showing an enlarged view near a powder coating device in a state where a gate of a hydrogen carrier storage tank is open in a hydrogen generation device according to a first embodiment. Figure 5 is a schematic structural cross-sectional view showing an enlarged view near a powder coating device in a hydrogen generation device according to a second embodiment. DETAILED DESCRIPTION OF THE EMBODIMENTS <First Embodiment>

[0010] The following will refer to Figures 1 to 4Describe the first embodiment. First, as an energy source to replace fossil fuels, hydrogen is attracting attention. This is because, unlike fossil fuels, hydrogen does not produce, for example, carbon dioxide when burned, and carbon dioxide is a greenhouse gas that causes global warming. An example of a system that uses hydrogen as an energy source and is put into practical use is a fuel cell vehicle. A fuel cell vehicle is a vehicle that generates electricity by using hydrogen as a raw material and moves by driving an electric motor using the generated electricity. Most fuel cell vehicles store hydrogen, which serves as an energy source, in a hydrogen tank, and generate electricity by charging the hydrogen discharged from the hydrogen tank into a fuel cell. In the hydrogen tank, hydrogen is stored in a compressed state under a high pressure such as 70 MPa (700 times the atmospheric pressure).

[0011] The problem with hydrogen serving as an energy source is that its energy density is low. The volumetric energy density of hydrogen is about 1 / 3000 of that of gasoline, and even when using a 70 MPa hydrogen tank, only about 1 / 5 of the energy of the same volume of gasoline can be obtained. Therefore, typically, a fuel cell vehicle including a hydrogen tank needs to be refueled more frequently than a gasoline-powered vehicle.

[0012] Therefore, as materials that can carry hydrogen at a higher energy density than a hydrogen tank (i.e., hydrogen carriers), various materials have been considered. For example, ammonia, methylcyclohexane, etc. are known as hydrogen carriers, and when in use, the hydrogen carrier rather than hydrogen itself is transported and hydrogen is extracted from the hydrogen carrier.

[0013] Among these hydrogen carrier materials, metal hydrides such as sodium borohydride are well-known, and hydrogen can be easily extracted from them by pouring water thereon. As a method for obtaining hydrogen by hydrolyzing sodium borohydride, a method of dissolving sodium borohydride in water and using it as an aqueous solution is known. However, in the case of this method, there is a problem that the amount of water required is more than the amount required in the theory represented by the reaction formula, thereby reducing the substantial volumetric energy density.

[0014] Therefore, in the present embodiment, hydrogen is generated by pouring an aqueous liquid onto a solid hydrogen carrier by a hydrogen generation device configured as described below. In addition, by-products generated from the reaction between the hydrogen carrier and the liquid are collected. The by-products can be restored to the hydrogen carrier. [Hydrogen Generation Device]

[0015] The schematic configuration of the hydrogen generation device 1 will be described by using Figure 1 The hydrogen generation device 1 of the present embodiment is a device that places a solid hydrogen carrier (powder in the present embodiment) on a conveyor belt 41, discharges an aqueous liquid onto it, and causes the hydrogen carrier on the conveyor belt 41 to react with the aqueous liquid to generate hydrogen. The hydrogen generation device 1 mainly includes a conveyor belt 41, a powder coating device 12 that serves as a coating device, a liquid discharge device 22 that serves as a discharge device, a hydrogen collection device 31, and a by-product collection device 61.

[0016] The conveyor belt 41 rotates along the Figure 1 direction of the arrow in Figure 1 . The powder coating device 12 receives the supply of the hydrogen carrier stored in the hydrogen carrier storage tank 11 in the form of powder, and coats the hydrogen carrier on the surface 41a of the conveyor belt 41. In the rotation direction of the conveyor belt 41, the liquid discharging device 22 is arranged downstream of the powder coating device 12, receives the supply of the liquid from the liquid storage tank 21 storing the aqueous liquid, and discharges the liquid onto the hydrogen carrier coated on the surface 41a of the conveyor belt 41.

[0017] In the rotation direction of the conveyor belt 41, the hydrogen collection device 31 is arranged downstream of the liquid discharging device 22, and collects hydrogen generated by the reaction between the hydrogen carrier and the liquid on the surface 41a of the conveyor belt 41. The by-product collection device 61 collects the by-products generated by the reaction between the hydrogen carrier and the liquid on the surface 41a of the conveyor belt 41. The by-products mentioned here refer to the products other than hydrogen generated by the reaction between the hydrogen carrier and the liquid. In addition, the hydrogen generation device 1 of the present embodiment further includes a hydrogen carrier regulation amount holding unit 13 that holds the hydrogen carrier in the powder coating device 12 within a predetermined range.

[0018] The hydrogen generation device 1 can perform a series of steps on the conveyor belt 41, such as generating hydrogen by the reaction between the hydrogen carrier and the aqueous liquid, and collecting the by-products after the reaction. Therefore, the advantages of being able to continuously, stably and long-term generate hydrogen are achieved in a compact device structure.

[0019] The operation of the hydrogen generation device 1 is as follows. First, the conveyor belt 41 starts to operate, and when the conveying speed of the conveyor belt 41 is stabilized at a predetermined speed and the surface temperature of the conveyor belt 41 reaches the set temperature, the powder coating device 12 starts to operate to coat the hydrogen carrier on the conveyor belt 41. At the timing when the hydrogen carrier reaches below the liquid discharging device 22, the liquid is discharged from the liquid discharging device 22, thereby starting the reaction between the hydrogen carrier and the liquid, and the generated hydrogen is collected by the hydrogen collection device 31.

[0020] Then, the by-products generated after the reaction between the hydrogen carrier and the aqueous liquid are conveyed to the by-product collection device 61, and the by-product collection device 61 collects and sends the by-products to the by-product collection box 62. Next, each component will be described in detail. [Hydrogen Carrier]

[0021] The "hydrogen carrier" mentioned in this embodiment is not particularly limited as long as it is a solid hydrogen carrier that generates hydrogen when an aqueous liquid is poured thereon. For example, the following substances can be used alone or in combination: solid metal hydrides such as sodium borohydride, potassium borohydride, lithium borohydride, zinc borohydride, lithium aluminum hydride, sodium aluminum hydride, magnesium aluminum hydride, calcium aluminum hydride, magnesium hydride, lithium hydride, sodium hydride, and calcium hydride, and metal powders such as aluminum, zinc, calcium, and magnesium. In addition, additives such as reaction promoters or desiccants can be contained.

[0022] In addition, the hydrogen carrier of this embodiment is preferably a solid such as powder or granules, but sheets, pellets, and pastes can also be used. As the powder, powders with a particle size of about 10 μm or more and 10 mm or less, powders with a particle size of 10 μm or more and 3 mm or less, and powders with a particle size of 10 μm or more and 100 μm or less are more preferable. In addition, in the case of using in the form of a sheet or pellet, from the viewpoint of improving the reactivity with the aqueous liquid, it is preferable to perform surface roughening, pore-forming treatment, etc. to increase the surface area and increase the contact area with the aqueous liquid.

[0023] In this embodiment, sodium borohydride powder with an average particle size of 50 μm is used as the solid hydrogen carrier. It should be noted that the average particle size of the solid hydrogen carrier is not limited to this. The sodium borohydride powder reacts with water to generate hydrogen. After the reaction, the sodium borohydride is converted into sodium metaborate powder, which is a by-product. This reaction is represented by the following chemical formula. NaBH4 (sodium borohydride) + 2H2O (water) → NaBO2 (sodium metaborate) + 4H2 (hydrogen)... (1)

[0024] It is known that this reaction (chemical formula (1)) is promoted by a Raney catalyst, which is formed by a metal such as nickel, cobalt, or copper and an acidic solution such as citric acid or acetic acid. [Aqueous liquid]

[0025] The "aqueous liquid" mentioned in this embodiment is not particularly limited as long as the liquid reacts with the hydrogen carrier and generates hydrogen when poured. That is to say, the aqueous liquid can be simple water. In addition, two or more kinds of aqueous liquids can be prepared. By preparing two or more kinds of aqueous liquids, the hydrogen generation rate can be adjusted.

[0026] The aqueous liquid can include water-soluble organic solvents. Examples thereof can include alcohols, polyalkylene glycols, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds. Two or more selected from these can also be used in combination. By containing water-soluble organic solvents, the surface tension, boiling point, and melting point of the aqueous liquid can be adjusted to optimize the reaction with the hydrogen carrier.

[0027] A surfactant can be added to the aqueous liquid. By using the surfactant, the surface tension of the aqueous liquid can be reduced, the contact area with the hydrogen carrier can be increased, and thus an effective reaction can be carried out.

[0028] The aqueous liquid may contain a water-soluble acidic substance. This acidic substance acts as a positive catalyst in the reaction between the aqueous liquid and the hydrogen carrier. By adjusting the amount of the liquid containing the acidic substance, the hydrogen generation rate can be adjusted. In particular, by setting the pH value obtained from the aqueous liquid and the hydrogen carrier to be lower than 9.0, the hydrogen generation rate can be increased. Examples thereof include various acids such as chloric acid, sulfuric acid, nitric acid, boric acid, and organic acids, but are not limited thereto.

[0029] The aqueous liquid may include a water-soluble basic substance. The basic substance acts as a negative catalyst in the reaction between the aqueous liquid and the hydrogen carrier. By adjusting the amount of the liquid containing the basic substance, the hydrogen generation rate can be adjusted. In particular, by setting the pH value obtained from the aqueous liquid and the hydrogen carrier to be equal to or higher than 9.0, the hydrogen generation rate can be decreased. Examples thereof include bases such as sodium hydroxide, potassium hydroxide, and ammonia water, but are not limited thereto.

[0030] The aqueous liquid may include a buffer solution. The role of the buffer solution is to inhibit the pH fluctuation in the reaction between the aqueous liquid and the hydrogen carrier. By adjusting the amount of the liquid containing the buffer solution, the hydrogen generation rate can be adjusted. Examples thereof include various buffer solutions such as phosphate buffer solution, glycine buffer solution, Good’s buffer liquid, Tris buffer solution, and ammonia buffer solution, but are not limited thereto.

[0031] In addition to the above components, if necessary, the aqueous liquid may further contain various additives such as defoaming agents, pH regulators, viscosity regulators, rust inhibitors, preservatives, antifungal agents, antioxidants, and anti-reducing agents. [Conveyor belt]

[0032] The conveyor belt 41 serving as a conveying member is an endless belt and is capable of conveying a solid hydrogen carrier. The conveyor belt 41 is stretched by a driving roller 42 and a driven roller 43. The driving roller 42 is fixed, and the driven roller 43 is subjected to a force that pushes the driven roller 43 toward the front surface side of the conveyor belt, which is the applied force of a biasing spring (not shown), and due to this force, a certain tension is applied to the conveyor belt 41. In addition, the driving roller 42 is connected to a driving unit 41b (see Figure 2 ) such as an electric motor. Therefore, since the driving roller 42 is rotationally driven by the driving unit 41b, the conveyor belt 41 circulates (i.e., rotates) in the Figure 1 clockwise direction (arrow direction). Although the conveyor belt 41 is supported by two rollers in the present embodiment, there is no problem even if the conveyor belt 41 is supported by a plurality of rollers such as three rollers, for example.

[0033] In any case, the conveyor belt 41 is arranged such that the stretched surface stretched by two rollers (the drive roller 42 and the follower roller 43 in this embodiment), that is, the above-mentioned surface 41a is oriented in a substantially horizontal direction. In addition, the surface 41a is the upward-facing surface, and the powder coating device 12, the liquid discharge device 22, and the hydrogen collection device 31 provided above the conveyor belt 41 face the surface 41a.

[0034] The conveyor belt 41 configured in this way includes a mechanism for conveying the hydrogen carrier coated on the conveyor belt 41 by the powder coating device 12 in the order of the liquid discharge device 22 and the hydrogen collection device 31 toward the downstream side in the rotation direction. Thereafter, the reaction by-products are further conveyed downstream to the by-product collection device 61.

[0035] From the viewpoint of not causing static electricity, the conveyor belt 41 is preferably made conductive and can be formed of metal or resin. In the case of metal, aluminum, iron, copper, Ni, stainless steel (SUS), etc. can be used. In addition, in the case of resin, from the viewpoint of heat resistance, a resin with a high glass transition temperature is preferred. For example, engineering plastics with high heat resistance and high durability are preferred, such as polyimide, polyamideimide, and polyetheretherketone. In addition, in the case where the resin is not conductive, it is preferred that the resin contains an antistatic agent such as carbon black to impart conductivity. In addition, from the viewpoint of thermal conductivity, the thickness of the conveyor belt 41 is preferably about 30 μm or more and 200 μm or less. In this embodiment, an endless belt formed of a conductive resin (which is carbon-containing polyimide) is used as the conveyor belt 41.

[0036] The conveying speed (rotation speed) of the conveyor belt 41 is a predetermined speed set for each hydrogen carrier and aqueous liquid used. In addition, it is preferred that the conveying speed can be appropriately adjusted according to the required amount of hydrogen. Therefore, for example, in the case where the amount of hydrogen collected by the hydrogen collection device 31 does not reach the planned amount, the hydrogen generation amount can be adjusted by, for example, the following method: appropriately adjusting the conveying speed according to the amount of hydrogen measured by a flow sensor 32 (see Figure 2 ) etc., which measures the flow rate of hydrogen collected by the hydrogen collection device 31. It should be noted that the conveying member for conveying the hydrogen carrier in this way is not limited to a conveyor belt and can be, for example, different elements such as a rotatable drum or a movable table. [Powder Coating Device]

[0037] The powder coating device 12 is a device that receives the supply of the hydrogen carrier from the hydrogen carrier storage tank 11 and coats the hydrogen carrier on the conveyor belt 41. If the thickness of the hydrogen carrier coated on the conveyor belt 41 is about 50 μm or more and 3 mm or less, there is no problem, but it is preferable to set the thickness to 50 μm or more and 500 μm or less in order to improve the reactivity with the aqueous liquid.

[0038] In addition, the hydrogen carrier storage tank 11 serving as a hydrogen carrier supply container stores the hydrogen carrier (hydrogen carrier for replenishment) for replenishing the storage section of the powder coating device 12. The hydrogen carrier storage tank 11 can be attached to the powder coating device 12 and separated from it. That is, the hydrogen carrier storage tank 11 is replaceable.

[0039] The powder coating device 12 coats the hydrogen carrier on the conveyor belt 41 only by gravity or by gravity and an external force, the external force being from the rotation of the paddle, roller, brush roller, spiral fin, etc. therein. When the powder coating device 12 becomes empty, the supply of the hydrogen generation substance to the conveyor belt 41 becomes stagnant. Therefore, preferably, a sensor for detecting the remaining amount of the hydrogen carrier is provided in the powder coating device 12. As this sensor, a piezoelectric sensor, an optical sensor, a capacitance sensor, an ultrasonic sensor, etc. can be considered. The detailed structure of the powder coating device 12 will be described later. [Liquid discharge device]

[0040] The liquid discharge device 22 is a liquid coating device that receives the supply of the aqueous liquid from the liquid storage tank 21 storing the aqueous liquid and coats the aqueous liquid on the hydrogen carrier on the conveyor belt 41. The liquid discharge device 22 can adjust the amount of the aqueous liquid relative to the amount of the hydrogen carrier. The liquid discharge device 22 can discharge the liquid onto the conveyor belt 41 in a non-contact manner or can discharge the liquid in a contact manner.

[0041] For the non-contact type liquid discharge device 22, there is no particular problem as long as the liquid discharge device 22 is a device capable of coating the aqueous liquid on the hydrogen carrier, such as a spraying system, a sprinkling system, or a dispenser system. Any of these systems can adjust the amount of the discharged liquid. In addition, as the contact type liquid discharge device 22, an intaglio offset roller, a rod coater, a die coater, a knife coater, a blade coater, etc. can be mentioned. Any of these systems can adjust the amount of the discharged liquid.

[0042] In addition, the liquid storage tank 21 serving as a liquid supply container stores the aqueous liquid to be supplied to the liquid discharge device 22. The liquid storage tank 21 can be attached to the liquid discharge device 22 and separated from it. That is, the liquid storage tank 21 is replaceable. [Hydrogen collection device]

[0043] A hydrogen collection device 31 is provided to collect hydrogen generated by the reaction between a hydrogen carrier and an aqueous liquid. As Figure 1 shown, in the sense of an exhaust device, it can be a canopy structure, or it can be a structure in which the upper outer wall of the hydrogen generation device 1 has an inclined shape and a discharge port is provided at the highest position. As long as the structure collects the hydrogen generated inside the hydrogen generation device 1, there is no particular problem. The hydrogen collection device 31 of the present embodiment is provided above the conveyor belt 41 and includes a collection portion 31a that collects the hydrogen generated on the conveyor belt 41 and a suction fan 31b that sucks the hydrogen collected by the collection portion 31a. The hydrogen sucked by the suction fan 31b is supplied to a supply destination, such as a fuel cell, through a pipe 31c.

[0044] In a fuel cell that serves as one of the supply destinations of hydrogen, dry hydrogen is desired. However, not only hydrogen but also water vapor or vapor of an alkaline substance generated by the reaction may be mixed into the collected gas. Therefore, it is preferable to provide a mechanism for removing substances other than hydrogen in a hydrogen flow path (such as the pipe 31c), such as a filter containing water, a filter containing silica gel, a steam trap incorporating a cooling device, etc. [By-product collection device]

[0045] The function of the by-product collection device 61 is to remove the by-products on the conveyor belt 41 from the conveyor belt 41 and send the by-products to the by-product collection box 62. In the case where the hydrogen carrier is sodium borohydride, the by-product is, for example, sodium metaborate. The by-product collection device 61 includes a collection blade 61a that contacts the conveyor belt 41 and a blade holding member (not shown in the figure) that holds the collection blade 61a.

[0046] The collection blade 61a preferably adjoins the outer peripheral surface of the conveyor belt 41 stretched by the roller of the stretched conveyor belt 41. In the present embodiment, the roller is the drive roller 42. In addition, the collection blade 61a preferably adjoins a surface other than the surface 41a, such as the lower surface in the vertical direction or the side surface in the horizontal direction of the conveyor belt 41. In addition, the by-product collection box 62 is preferably provided below the collection blade 61a in the vertical direction. Thus, the by-products collected by the collection blade 61a can fall by gravity and be collected by the by-product collection box 62.

[0047] There are no particular restrictions on the material of the collection blade 61a, and examples thereof include a rubber blade formed of rubber and used for cleaning an intermediate transfer belt in a copying machine or the like. It is formed of rubber such as silicone rubber or polyurethane rubber, molded into a plate shape, and connected so that its corners contact in the direction opposite to the moving direction of the conveyor belt 41, thereby removing by-products on the conveyor belt 41. In addition, there is no problem when using a blade formed of metal or glass in a trowel shape (so-called spatula) as the collection blade 61a.

[0048] The blade holding member has a function of supporting the collection blade 61a and applying a certain pressure to the collection blade 61a by the warping of the blade holding member. Although there are no particular restrictions on its material, metal is preferred because pressure is to be applied.

[0049] In addition, the by-product collection box 62 serving as a collection container is a box for collecting by-products collected from the conveyor belt 41 by the collection blade 61a. The by-product collection box 62 can be attached to the by-product collection device 61 and separated from it. That is, the by-product collection box 62 is replaceable. [Central control device]

[0050] Figure 2 is a block diagram showing the system of the hydrogen generation device 1 of the present embodiment. The central control device 101 includes: a controller 112, a random access memory (RAM) 111, a storage 113 storing programs, a communication interface, a signal transmission unit 114, and a signal reception unit 115. The controller 112 is composed of a central processing unit (CPU) or a CPU and a read-only memory (ROM), and issues control commands for the entire hydrogen generation device 1 by executing programs stored in the storage 113.

[0051] The RAM 111 is the main memory for the operation of the controller 112. The storage 113 is a storage area for storing control programs and the like, and the controller 112 processes by reading control programs, temporarily stored timing data, log information, etc. from the RAM 111 and the storage 113.

[0052] Information from an external application 102 is input to the controller 112, and the external application is a fuel cell application such as a hydrogen application of a fuel cell supplied by the hydrogen generation device 1 or a fuel cell vehicle (FCV) using a fuel cell. In addition, the controller 112 receives information of the engine unit 103 of the hydrogen generation device 1 through the signal reception unit 115. As information of the engine unit 103, mention may be made of: the amount of hydrogen detected by the flow sensor 32 provided in the hydrogen collection device 31, information of the remaining amount detection sensors 11a, 12a, and 22a provided in the hydrogen carrier storage tank 11, the powder coating device 12, and the liquid discharge device 22, etc.

[0053] The remaining amount detection sensor 11a is a sensor provided in the hydrogen carrier storage tank 11 and detects the remaining amount of the hydrogen carrier in the hydrogen carrier storage tank 11. The remaining amount detection sensor 12a is a sensor provided in the powder coating device 12 and detects the remaining amount of the hydrogen carrier in the powder coating device 12. The remaining amount detection sensor 22a is a sensor provided in the liquid discharge device 22 and detects the remaining amount of the water-containing liquid in the liquid discharge device 22.

[0054] In addition, the controller 112 transmits the following signals via the signal transmission unit 114 as signals generated according to preset control information: a replenishment signal to the hydrogen carrier storage tank 11, a drive signal to the powder coating device 12 and the liquid discharge device 22, a drive signal to the conveyor belt 41, and the like.

[0055] The hydrogen carrier storage tank 11 includes a drive unit 11b for replenishing the powder coating device 12 with the hydrogen carrier. The powder coating device 12 includes a drive unit 12b for coating the hydrogen carrier on the conveyor belt 41. The liquid discharge device 22 includes a drive unit 22b for discharging the liquid onto the hydrogen carrier on the conveyor belt 41. In addition, the conveyor belt 41 is driven by the drive unit 41b as described above. The controller 112 controls the driving of the drive units 11b, 12b, 22b, and 41b.

[0056] Specifically, the drive unit 11b of the hydrogen carrier storage tank 11 is, for example, an electric motor or an electromagnetic coil, and the electric motor or the electromagnetic coil drives a shutter provided at a connection portion between the hydrogen carrier storage tank 11 and the powder coating device 12. The controller 112 performs, for example, a replenishment operation of the hydrogen carrier from the hydrogen carrier storage tank 11 to the powder coating device 12 or stops the replenishment operation by driving the drive unit 11b to open and close the shutter.

[0057] The drive unit 12b of the powder coating device 12 is, for example, an electric motor that drives a roller to coat the hydrogen carrier on the conveyor belt 41. The controller 112 drives the drive unit 12b to control the driving of the roller, thereby performing and stopping a coating operation of coating the hydrogen carrier from the powder coating device 12 onto the surface 41a of the conveyor belt 41.

[0058] The drive unit 22b of the liquid discharge device 22 is, for example, arranged to discharge the liquid onto the conveyor belt 41, and its drive structure varies according to its system. The controller 112 controls the driving of the drive unit 22b and thus performs and stops a liquid discharge operation from the liquid discharge device 22 to the surface 41a of the conveyor belt 41.

[0059] The drive unit 41b of the conveyor belt 41 is, for example, the above-mentioned electric motor. The controller 112 controls the driving of the drive unit 41b to drive and stop the conveyor belt 41 and further control its driving speed. [Hydrogen carrier regulation amount holding unit]

[0060] Next, by using Figure 3 and Figure 4 the hydrogen carrier regulation amount holding unit 13 that keeps the hydrogen carrier in the powder coating apparatus 12 within a predetermined range will be described. In the case where the thickness of the hydrogen carrier coated on the conveyor belt 41 by the powder coating apparatus 12 as described above is uneven, the reaction rate with the aqueous liquid on the belt becomes uneven. Although the hydrolysis reaction is not sufficiently carried out, there is a possibility of conveying the hydrogen carrier downstream. At this time, there is a possibility that unreacted hydrogen carrier mixes into the by-product collection device 61. As disadvantages of insufficient reaction progress, it can be mentioned that the amount of hydrogen that can be collected decreases, thereby reducing the energy efficiency, and unreacted hydrogen carrier mixes into the by-product collection device 61, thereby filling the by-product collection device 61 with hydrogen, and so on.

[0061] Here, if the change in the amount of the hydrogen carrier in the powder coating apparatus 12 is large, the change in the gravity and pressure on the hydrogen carrier near the coating port from the powder coating apparatus 12 to the conveyor belt 41 also becomes large. Thereby, there is a possibility that the coating amount of the hydrogen carrier from the powder coating apparatus 12 to the conveyor belt 41 becomes uneven. Therefore, in the present embodiment, the supply amount of the hydrogen carrier from the hydrogen carrier storage tank 11 to the powder coating apparatus 12 is adjusted so as to keep the hydrogen carrier in the powder coating apparatus 12 within a predetermined range.

[0062] First, the detailed structures of the powder coating apparatus 12 and the hydrogen carrier storage tank 11 will be described. The powder coating apparatus 12 includes a storage unit 121 that stores the hydrogen carrier supplied from the hydrogen carrier storage tank 11 (which serves as a supply container) and coats the hydrogen carrier on the conveyor belt 41 (on the conveying member). An opening 122 is formed at the lower end of the storage unit 121. The hydrogen carrier in the storage unit can be supplied to the surface 41a of the conveyor belt 41 by gravity through the opening 122.

[0063] The hydrogen carrier storage tank 11 is provided above the storage unit 121 of the powder coating apparatus 12 and includes an opening 11c that can supply the hydrogen carrier to the storage unit by gravity, and a gate 11d that can open and close the opening 11c. The gate 11d is provided as a supply unit to supply the storage unit 121 with the hydrogen carrier from the hydrogen carrier storage tank 11. The gate 11d is driven by a drive unit such as a motor or an electromagnetic coil (not shown) and opens and closes the opening 11c in response to the drive unit controlled by an instruction from the controller 112 (see Figure 2 ).

[0064] Figure 3 The state where the gate 11d is closed is shown, Figure 4Shows the state where the gate 11d is open. As Figure 4 shown, since the gate 11d is open, the hydrogen carrier in the hydrogen carrier storage tank 11 is supplied to the storage unit 121 by gravity through the opening 11c and the supply port 121a formed at the upper end of the storage unit 121 of the powder coating device 12.

[0065] The hydrogen carrier regulation amount holding unit 13 includes: a hydrogen carrier amount detection unit 15 that can detect information related to the amount of the hydrogen carrier in the storage unit 121 of the powder coating device 12, and a controller 112 that controls the gate 11d based on the signal of the hydrogen carrier amount detection unit 15. The powder coating device 12 is disposed above the conveyor belt 41 as described above and can supply the hydrogen carrier to the conveyor belt 41 by gravity. Therefore, the hydrogen carrier amount detection unit 15 of the present embodiment is configured to detect information related to the height of the upper surface of the hydrogen carrier in the storage unit 121.

[0066] Specifically, the hydrogen carrier amount detection unit 15 is an optical detection sensor and includes a light emitting unit 15a composed of a light emitting element, window portions 15b1 and 15b2 that transmit light, and a light receiving unit 15c composed of a light receiving element. The window portions 15b1 and 15b2 are provided at positions on the side wall of the storage unit 121 opposite to the light emitting unit 15a and the light receiving unit 15b, respectively.

[0067] In the present embodiment, as Figure 3 shown, the height positions of the light emitting unit 15a and the light receiving unit 15c are different. Therefore, the light emitted from the light emitting unit 15a travels obliquely with respect to the horizontal direction, passes through the window portion 15b1 into the interior of the storage unit 121, and further travels through the window portion 15b2 to be received by the light receiving unit 15c. In addition, the controller 112 measures the ratio of the light transmission time from the light emitting unit 15a to the light receiving unit 15c, and thereby obtains the height information of the upper surface (surface) of the hydrogen carrier in the storage unit 121.

[0068] Here, the height position of the window portion 15b1 through which the light from the light emitting unit 15a enters the interior of the storage unit 121 will be represented by β, and the height position of the window portion 15b2 through which the light travels from the interior of the storage unit 121 toward the light receiving unit 15c will be represented by γ. The controller 112 controls the replenishment from the hydrogen carrier storage tank 11 so that the height position of the surface of the hydrogen carrier is maintained within a predetermined range of γ to β. That is, the controller 112 opens the gate 11d according to the signal from the hydrogen carrier amount detection unit 15 to allow the hydrogen carrier to fall in the direction of gravity, thereby supplying the hydrogen carrier to the storage unit 121 of the powder coating device 12.

[0069] Specifically, in a case where it is detected, in response to the height information of the surface of the hydrogen carrier received from the hydrogen carrier amount detection unit 15, that the height of the surface of the hydrogen carrier has decreased to a position equal to or lower than the position γ which is the first height, the controller 112 determines that the amount of the hydrogen carrier in the storage unit 121 has decreased to less than a predetermined amount. Then, as Figure 4 shown, the controller 112 opens the gate 11d and replenishes the storage unit 121 with the hydrogen carrier from the hydrogen carrier storage tank 11.

[0070] In contrast, in a case where it is detected, in response to the height information of the surface of the hydrogen carrier received from the hydrogen carrier amount detection unit 15, that the height of the surface of the hydrogen carrier has increased to a position equal to or higher than the position β which is the second height, the controller 112 determines that the amount of the hydrogen carrier in the storage unit 121 has increased to more than a predetermined amount. Then, as Figure 3 shown, the controller 112 closes the gate 11d to stop the supply of the hydrogen carrier from the hydrogen carrier storage tank 11.

[0071] According to the present embodiment configured in this way, by controlling the replenishment amount of the hydrogen carrier supplied from the hydrogen carrier storage tank 11 based on the surface height of the hydrogen carrier in the storage unit 121 detected by the hydrogen carrier amount detection unit 15, the amount of the hydrogen carrier in the powder coating device 12 can be maintained within a predetermined range. Thereby, a sudden change in the amount of the hydrogen carrier in the powder coating device 12 can be suppressed, and furthermore, changes in the gravity and pressure on the hydrogen carrier near the opening 122 from the powder coating device 12 to the conveyor belt 41 can be suppressed.

[0072] Thereby, the consistency of coating the hydrogen carrier from the powder coating device 12 onto the conveyor belt 41 can be stabilized. If the thickness of the hydrogen carrier coated on the conveyor belt 41 can be made uniform, the occurrence of non-uniform reaction due to the supply of the liquid to the hydrogen carrier can be suppressed. Therefore, according to the configuration of the present embodiment, the reaction between the hydrogen carrier on the conveyor belt 41 and the aqueous liquid can be easily promoted.

[0073] It should be noted that although the configuration of supplying the hydrogen carrier from the powder coating device 12 to the conveyor belt 41 by gravity has been described in the above description, a configuration such as the following can also be adopted: a rotating member such as a brush roll is provided at the opening 122, and the supply of the hydrogen carrier to the conveyor belt 41 is assisted by driving the rotating member. Also in the case of this configuration, the torque change caused by the difference between the case where the amount of the hydrogen carrier in the storage unit 121 is large and the case where the amount is small can be suppressed, and thus the consistency of coating the hydrogen carrier from the powder coating device 12 onto the conveyor belt 41 can be stabilized.

[0074] In addition, although the structure in which the light-emitting part 15a and the light-receiving part 15c are arranged at different height positions has been described above, the light-emitting part 15a and the light-receiving part 15c can be respectively provided at the β position and the γ position, and the height of the surface of the hydrogen carrier reaching the β position and the γ position can be detected.

[0075] In addition, as an alternative to the above optical sensor, a piezoelectric sensor, an electrostatic capacitance sensor, an ultrasonic sensor, etc. can be used as the hydrogen carrier amount detection part 15. In addition, a structure in which the amount of the hydrogen carrier in the storage part 121 is measured by detecting the weight of the powder coating device 12 can also be adopted.

[0076] In addition, although the structure in which the powder coating device 12 is replenished with the hydrogen carrier from the hydrogen carrier storage tank 11 by opening the gate 11d and relying on gravity has been described above, a structure in which replenishment is performed by using a roller or a screw, and a structure in which replenishment is performed by using a belt or air can be adopted. In the case of the structure in which the hydrogen carrier is replenished by driving different components as described above, it is preferable to arrange the hydrogen carrier storage tank 11 above the storage part 121 of the powder coating device 12 so as to effectively replenish the hydrogen carrier. However, the hydrogen carrier storage tank 11 does not have to be positioned above the powder coating device 12. <Second Embodiment>

[0077] The second embodiment will be described by using Figure 5 The hydrogen generation device 1A of this embodiment is different from that of the first embodiment in the structures of the powder coating device and the hydrogen carrier regulation amount holding part. Other elements and functions are similar to those of the above first embodiment. Therefore, similar elements are denoted by the same reference numerals, and their descriptions and illustrations are omitted or simplified, and the parts different from the first embodiment will be mainly described.

[0078] In the case of this embodiment, the powder coating device 12A includes a hydrogen carrier hopper 51 serving as an accumulation part for temporarily accumulating the hydrogen carrier supplied from the hydrogen carrier storage tank 11, a storage part 121A configured to store the hydrogen carrier, and a transfer screw 52 serving as a supply part for supplying the hydrogen carrier from the hydrogen carrier hopper 51 to the storage part 121A. Similar to the first embodiment, in the powder coating device 12A, an opening 122A is formed at the lower end part of the storage part 121A, and the hydrogen carrier in the storage part can be supplied to the surface 41a of the conveyor belt 41 by gravity through the opening 122A. It should be noted that, in the case of this embodiment, the opening 122A opens at the lower end part closer to the end of the storage part 121A in the horizontal direction. Therefore, a paddle 123 is provided in the storage part 121A to agitate the hydrogen carrier in the storage part 121A and transfer the hydrogen carrier to the opening 122A.

[0079] The hydrogen carrier regulation amount holding unit 13A of the present embodiment adjusts the supply amount of the hydrogen carrier from the hydrogen carrier hopper 51 to the storage unit 121 so as to keep the hydrogen carrier in the storage unit 121A within a predetermined range. The hydrogen carrier hopper 51 has a hopper function, in which the hydrogen carrier hopper 51 receives the supply of the hydrogen carrier from the hydrogen carrier storage tank 11, temporarily stores the hydrogen carrier, and supplies the storage unit 121A of the powder coating device 12A with the hydrogen carrier. A transfer screw 52 is provided in the hydrogen carrier hopper 51 to loosen the hydrogen carrier in the hydrogen carrier hopper 51 and transfer and supply the hydrogen carrier from the hydrogen carrier hopper 51 to the storage unit 121A.

[0080] The hydrogen carrier hopper 51 is provided at a position below the hydrogen carrier storage tank 11 and above the storage unit 121A. Due to the opening of the gate 11d of the hydrogen carrier storage tank 11, the hydrogen carrier is replenished from the hydrogen carrier storage tank 11 to the hydrogen carrier hopper 51. In addition, the transfer screw 52 is provided in a substantially horizontal direction and is located at the lower part of the hydrogen carrier hopper 51. Further, a communication part 53 that connects the hydrogen carrier hopper 51 and the storage unit 121A to each other is formed at the downstream end of the hydrogen carrier transfer direction of the transfer screw 52, and the transfer screw 52 rotates to replenish the storage unit 121A with the hydrogen carrier from the hydrogen carrier hopper 51 through the communication part 53. In the case of the present embodiment, the communication part 53 is formed at the lower end part of the hydrogen carrier hopper 51 so as to open downward, and the hydrogen carrier transferred by the transfer screw 52 is supplied to the storage unit 121A by gravity through the communication part 53.

[0081] The hydrogen carrier regulation amount holding unit 13A of the present embodiment includes a hydrogen carrier amount detection unit 15A that can detect information related to the amount of the hydrogen carrier in the storage unit 121A of the powder coating device 12A, and a controller 112 that controls the transfer screw 52 based on the signal of the hydrogen carrier amount detection unit 15A (see Figure 2 ). As described above, the powder coating device 12A is provided above the conveyor belt 41 and can supply the hydrogen carrier to the conveyor belt 41 by gravity. Therefore, the hydrogen carrier amount detection unit 15A of the present embodiment is configured to detect information related to the height of the upper surface (surface) of the hydrogen carrier in the storage unit 121.

[0082] Specifically, the hydrogen carrier amount detection unit 15A is a piezoelectric sensor. In a case where "lack of hydrogen carrier" is detected by the piezoelectric sensor, the controller 112 drives the transfer screw 52 for a predetermined time to supply the hydrogen carrier from the hydrogen carrier hopper 51 to the storage unit 121A. In contrast, in a case where "presence of hydrogen carrier" is detected by the piezoelectric sensor, the controller 112 stops driving the transfer screw 52 to stop the supply of the hydrogen carrier from the hydrogen carrier hopper 51. By driving and stopping the transfer screw 52 based on the signal of the piezoelectric sensor in this way, the height of the surface of the hydrogen carrier in the storage unit 121A can be maintained within the range from position γ' to position β', and the amount of the hydrogen carrier in the storage unit 121A can be maintained within a predetermined range.

[0083] It should be noted that the hydrogen carrier hopper 51 may be additionally provided with a sensor (not shown) capable of detecting information related to the amount of the hydrogen carrier therein, such as the height position of the surface of the hydrogen carrier. In this case, the controller 112 controls the opening and closing of the gate 11d of the hydrogen carrier storage tank 11 based on the signal of this sensor, thereby performing the supply and stop of the hydrogen carrier from the hydrogen carrier storage tank 11 to the hydrogen carrier hopper 51. Additionally, control may be performed such that the gate 11d opens when the transfer screw 52 is driven and closes when the drive is stopped, without providing such a sensor.

[0084] In the case of the present embodiment configured in this way, by providing the hydrogen carrier hopper 51, the amount of the hydrogen carrier in the storage unit 121A of the powder coating device 12A can be maintained at the necessary minimum value. Therefore, the hydrogen carrier in the storage unit 121A is not subjected to a large gravity or high pressure, so it is less likely to be blocked near the opening 122A of the storage unit 121A, and the consistency of the hydrogen carrier coating on the conveyor belt 41 can be stabilized.

[0085] In addition, since the hydrogen carrier is temporarily accumulated in the hydrogen carrier hopper 51, even when the hydrogen carrier storage tank 11 is being replaced, it is possible to continue coating hydrogen on the conveyor belt 41 by using the hydrogen carrier in the hydrogen carrier hopper 51. Therefore, even during the replacement of the hydrogen carrier storage tank 11, the operation of the hydrogen generation device 1A can continue, thus improving productivity.

[0086] It should be noted that although the structure of supplying the hydrogen carrier from the powder coating device 12A to the conveyor belt 41 by relying on gravity has been described above, similar to the first embodiment, for example, the following structure may be adopted: a rotating member such as a brush roll is provided at the opening 122A, and the supply of the hydrogen carrier to the conveyor belt 41 is assisted by driving this rotating member.

[0087] Alternatively, as an alternative to the piezoelectric sensor described above, an optical sensor, an electrostatic capacitance sensor, an ultrasonic sensor, etc. can be used as the hydrogen carrier amount detection unit 15A. Additionally, a configuration that measures the amount of hydrogen carrier in the storage unit 121 by detecting the weight of the storage unit 121A can also be adopted. Industrial applicability

[0088] The hydrogen generation device according to the present invention can preferably be applied to a hydrogen generation device that generates hydrogen by using a hydrogen carrier having the property of generating hydrogen in response to an aqueous liquid poured thereon as a raw material. List of reference numerals

[0089] 1, 1A: Hydrogen generation device 11: Hydrogen carrier storage tank (refueling container) 11c: Opening 11d: Gate (refueling unit) 12, 12A: Powder coating device (coating device) 13, 13A: Hydrogen carrier regulated amount holding unit 15, 15A: Hydrogen carrier amount detection unit 22: Liquid discharge device (discharge device) 31: Hydrogen collection device 41: Conveyor belt (transport component) 41a: Surface 51: Hydrogen carrier hopper (accumulation unit) 52: Transfer screw (supply unit) 61: By-product collection device 112: Controller 121, 121A: Storage unit 122, 122A: Opening

Claims

1. A hydrogen generation device, comprising: A conveying member capable of conveying a solid hydrogen carrier; A supply container for storing the hydrogen carrier for replenishment; A coating device, which includes a storage portion and is configured to coat the hydrogen carrier on the conveying member from the storage portion, and the storage portion is configured to store the hydrogen carrier supplied from the supply container; A discharging device configured to discharge an aqueous solution onto the hydrogen carrier coated on the conveying member; A hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier on the conveying member and the solution; A by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier on the conveying member and the solution; and A hydrogen carrier regulation amount holding portion configured to adjust the replenishment amount of the hydrogen carrier from the supply container to the storage portion so as to keep the hydrogen carrier in the storage portion within a predetermined range.

2. The hydrogen generation device according to claim 1, further comprising: A replenishment portion for replenishing the storage portion with the hydrogen carrier from the supply container, Among them, The hydrogen carrier regulation amount holding portion includes a hydrogen carrier amount detection portion capable of detecting information related to the amount of the hydrogen carrier in the storage portion, and a controller configured to control the replenishment portion based on a signal from the hydrogen carrier amount detection portion.

3. The hydrogen generation device according to claim 2, Among them, The supply container is disposed above the storage portion and has an opening portion, and the hydrogen carrier can be supplied to the storage portion through the opening portion by gravity, and wherein, the replenishment portion is a gate capable of opening and closing the opening portion.

4. The hydrogen generation device according to claim 2, Among them, The coating device is disposed above the conveying member, and the hydrogen carrier can be supplied to the conveying member by gravity, and wherein, the hydrogen carrier amount detection portion detects information related to the height of the upper surface of the hydrogen carrier in the storage portion.

5. A hydrogen generation device, comprising: A conveying member capable of conveying a solid hydrogen carrier; A supply container for storing the hydrogen carrier for replenishment; A coating device, which includes an accumulation portion configured to temporarily accumulate the hydrogen carrier supplied from the supply container, a storage portion configured to store the hydrogen carrier, a supply portion configured to supply the hydrogen carrier from the accumulation portion to the storage portion, and the coating device is configured to coat the hydrogen carrier on the conveying member from the storage portion; A discharging device configured to discharge an aqueous solution onto the hydrogen carrier coated on the conveying member; A hydrogen collection device configured to collect hydrogen generated by the reaction between the hydrogen carrier on the conveying member and the solution; A by-product collection device configured to collect by-products generated by the reaction between the hydrogen carrier on the conveying member and the solution; A supply container for storing the hydrogen carrier to replenish the storage portion of the coating device; And A hydrogen carrier regulation amount maintaining unit configured to adjust the supply amount of the hydrogen carrier from the accumulation unit to the storage unit so as to maintain the hydrogen carrier in the storage unit within a predetermined range.

6. The hydrogen generation device according to claim 5, wherein, The hydrogen carrier regulation amount maintaining unit includes a hydrogen carrier amount detection unit capable of detecting information related to the amount of the hydrogen carrier in the storage unit, and a controller configured to control the supply unit based on a signal from the hydrogen carrier amount detection unit.

7. The hydrogen generation device according to claim 5, wherein, The supply unit is a transfer screw configured to transfer the hydrogen carrier from the accumulation unit to the storage unit.

8. The hydrogen generation device according to claim 6, Among them, The coating device is disposed above the transfer member and capable of supplying the hydrogen carrier to the transfer member by gravity, and wherein the hydrogen carrier amount detection unit detects information related to the height of the upper surface of the hydrogen carrier in the storage unit.

9. The hydrogen generation device according to any one of claims 1 to 8, wherein, The supply container is replaceable.

10. The hydrogen generation device according to any one of claims 1 to 8, wherein, The transfer member is a conveyor belt.

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